Method for synthesizing monoethanolamine and diethanolamine
阅读说明：本技术 合成一乙醇胺和二乙醇胺的方法 (Method for synthesizing monoethanolamine and diethanolamine ) 是由 刘师前 王德举 钱斌 韩亚梅 于 2018-06-12 设计创作，主要内容包括：本发明涉及合成一乙醇胺和二乙醇胺的方法,主要解决以往技术中生产一乙醇胺(MEA)和二乙醇胺(DEA)时副产三乙醇胺(TEA)、产物分离能耗大的问题,通过采用合成一乙醇胺和二乙醇胺的方法,在催化剂存在下,EO与液NH<Sub>3</Sub>反应生成一乙醇胺和二乙醇胺,所述催化剂包括ZSM-5分子筛,和分子筛改性元素,所述改性元素包括La和Ca的技术方案较好地解决了该问题,可用于一乙醇胺和二乙醇胺的工业生产中。(The invention relates to a method for synthesizing monoethanolamine and diethanolamine, which mainly solves the problems of byproduct Triethanolamine (TEA) and large energy consumption for product separation when Monoethanolamine (MEA) and Diethanolamine (DEA) are produced in the prior art 3 Reaction to produce monoethanolamine and diethanolamine, said catalysisThe agent comprises a ZSM-5 molecular sieve and molecular sieve modification elements, and the technical scheme that the modification elements comprise La and Ca better solves the problem and can be used in the industrial production of monoethanolamine and diethanolamine.)
1. Method for synthesizing monoethanolamine and diethanolamine, in the presence of catalyst, EO and liquid NH3The catalyst comprises a ZSM-5 molecular sieve and molecular sieve modification elements, and the modification elements comprise La and Ca.
2. The method according to claim 1, wherein the reaction temperature is 60 to 100 ℃.
3. The method according to claim 1, wherein the reaction pressure is 5.0 to 12.0 MPa.
4. The method of claim 1, wherein the NH is present in a molar ratio3/EO＝5～30。
5. The method as set forth in claim 1, wherein the volume space velocity of the ethylene oxide liquid phase is 0.2 to 2.2 hours-1。
6. The method according to claim 1, wherein the content of the modifying element is more than 0 and not more than 50 g/L.
7. The process as set forth in claim 1 wherein the ZSM-5 molecular sieve is a hydrogen type molecular sieve.
8. The method of claim 1, wherein the molecular sieve has a silica to alumina molar ratio of SiO2/Al2O3Is 20 to 200.
9. The process of claim 1 wherein the catalyst is with or without a molecular sieve binder.
10. The method according to claim 1, characterized in that the catalyst is obtained by a preparation method comprising the following steps:
mixing the molecular sieve with a compound solution of a modifying element;
drying;
and (4) roasting.
Technical Field
The invention relates to a method for synthesizing monoethanolamine and diethanolamine.
Background
Ethanolamine (EA) is a generic name of products in which hydrogen atoms in ammonia molecules are respectively substituted by one, two or three hydroxyethanol, and is respectively called Monoethanolamine (MEA), Diethanolamine (DEA) and Triethanolamine (TEA). The ethanolamine compound contains two functional groups: hydroxyl and amine groups, and therefore have certain chemical properties and novel properties of alcohols and amines. The characteristics and the interaction of the bifunctional groups enable the compound to become an important organic intermediate and a chemical end product, and the application is very wide. One application of ethanolamine is to produce important basic raw materials of products such as surfactants, medicines, polyurethane aids, rubber processing aids, antifreeze aids and the like.
At present, the related enterprises engaged in ethanolamine production abroad mainly include Dow chemical, BASF company, Huntsman company, Nippon Shokubai company, and the like. Ethanolamine enterprises can be classified into four categories according to the concentration of ammonia in the raw material used: 1) the American SD company adopts low-concentration ammonia water as a reaction raw material, EO, 20-30 wt% of ammonia water (including fresh materials and circulating materials) and circulating MEA are reacted in a fixed bed reactor (the structure of a reaction product is adjusted by the MEA), and NH is generated3EO is 10:1, the reaction temperature is 100 ℃, the system pressure is 0.5MPa, the products after the reaction are separated and rectified to respectively obtain high-purity MEA, DEA and TEA, the relative contents of the MEA, the DEA and the TEA are respectively 69 wt%, 21 wt% and 10 wt%, the excessive ammonia in the reaction system is recovered by reduced pressure distillation, and the residual ammonia is repeatedly circulated in the form of ammonia water. Because the water content in the system is high, the energy consumption is high in the process of reaction temperature rise and temperature reduction, and the product is easy to dissolve in water and has high dehydration energy consumption. Therefore, although the reaction conditions of the low-concentration ammonia synthesis method are mild, the energy consumption is too high, and the method is gradually eliminated. 2) Dow chemical company adopts medium-high concentration ammonia water as a reaction raw material, the concentration of the ammonia water is 35-50 wt%, the system pressure is 3.5MPa, and the reaction temperature is 115-130 ℃. Dow chemical company adopts the method of high vacuum flash distillation for the first time to retrieve the ammonia in the system, and the product distribution is adjusted by the content of raw material ammonia, and this company adopts the coproduction device of EO and ethanolamine in production. 3) BASF company adopts high-concentration ammonia water as raw material, the concentration of the ammonia water is more than 90 wt%, the system pressure is 10MPa, and NH is generated3And (2) EO (ethylene oxide)/EO (ethylene oxide) is 15-25: 1, the residence time is 3-30 min, a four-stage heat-insulating pipe reactor is adopted, EO is placed at different nodes in batches and enters the reactor, the reacted materials are decompressed in a flash tower, most of ammonia is evaporated, ammonia is condensed into liquid ammonia and returns, residual ammonia is evaporated at 0.4MPa, and after the liquid ammonia is absorbed into dilute ammonia water by water in a dehydration tower, the dilute ammonia water and the liquid ammonia are prepared into 90% concentrated ammonia water to participate in the reaction. The adoption of high-concentration ammonia has become a trend of an ammonia water method process, and the ammonia water method can obtain a product with balanced composition, but has the problems of more by-products of the product, high separation difficulty, incapability of recovering reaction heat and the like. 4) Nippon Shokubai (Tsunekih, Moriya a, Baba h.us6169207; moriya a, Tsuneki h.ep0652207; moriya a, Tsuneki h.us 5880058; tsuneki H, Moriya a, Baba H.A EP 0941986; tsuneki H, Kirishiki M, Arita Y, hashimoto Y, Oku T, Shindou H, Urano Y, morishitaf.us 6559342; tsuneki h. us6455016) company uses liquid ammonia as a raw material and La-modified zeolite as a catalyst to generate diethanolamine with high selectivity, and has been applied industrially. The process conditions are as follows: the reaction temperature is 100-120 ℃, the pressure is 12-15 MPa, and the liquid phase space velocity is 8-10 hr-1When in use, a fixed bed reactor is adopted, and the single-pass weight selectivity of the diethanol amine is about 41 percent; by recycling monoethanolamine, the weight selectivity of diethanolamine can reach 81%, and ethylene oxide can be completely converted, but the product still contains about 7% of triethanolamine.
In recent years, the market demand of the market for products such as ethylenediamine, piperazine, triethylene diamine and the like is increased sharply, the yield increase of upstream products such as monoethanolamine and diethanolamine is obviously stimulated, the triethanolamine is co-produced in the prior art, and the separation and production cost can be greatly increased by separating the triethanolamine from the products and converting the triethanolamine into the monoethanolamine and the diethanolamine.
Disclosure of Invention
The invention aims to solve the technical problems that the prior art produces triethanolamine as a byproduct for producing monoethanolamine and diethanolamine, and separates and converts the triethanolamine into the monoethanolamine and diethanolamine with high energy consumption and high cost, and provides a method for synthesizing the monoethanolamine and diethanolamine, which has the advantages of high EO conversion rate, high total selectivity of the monoethanolamine and diethanolamine and low selectivity of the triethanolamine as a byproduct, and reduces the energy consumption for separating and converting the triethanolamine into the monoethanolamine and the diethanolamine.
In order to solve the technical problems, the technical scheme of the invention is as follows:
method for synthesizing monoethanolamine and diethanolamine, in the presence of catalyst, EO and liquid NH3The catalyst comprises a ZSM-5 molecular sieve and molecular sieve modification elements, and the modification elements comprise La and Ca.
In the technical scheme, the reaction temperature is preferably 60-100 ℃.
In the technical scheme, the reaction pressure is preferably 5.0-12.0 MPa. Unless otherwise specified, the pressures referred to herein are in terms of gauge pressure.
In the above-mentioned embodiment, NH is preferably used in terms of molar ratio3/EO＝5～30。
In the technical scheme, the preferred volume airspeed of the liquid phase of the ethylene oxide is 0.2-2.2 hours-1。
In comparison, the process conditions in the specific embodiment of the invention are as follows: the reaction temperature is 80 ℃, the reaction pressure is 6.0MPa, and the liquid NH is3The molar ratio of the EO to the EO is 8, the volume space velocity of the EO liquid phase is 1.2 hours-1。
La and Ca have synergistic effect in improving the conversion rate of EO and the selectivity of monoethanolamine and diethanolamine.
As a first preferred technical solution, the modifying element further preferably includes P. La and P have synergistic effect on the aspect of improving the selectivity of monoethanolamine and diethanolamine; ca and P have synergistic effect on the aspect of improving the selectivity of the monoethanolamine and the diethanolamine; meanwhile, La, Ca and P have ternary synergistic effect on the aspect of improving the selectivity of monoethanolamine and diethanolamine in the catalyst.
As a second preferred technical solution, the modifying element further preferably includes an alkali metal, and the alkali metal is preferably Na or K. La and alkali metal have synergistic effect on the aspect of improving the selectivity of monoethanolamine and diethanolamine; the alkali metal and Ca have a synergistic effect on the aspect of improving the selectivity of the monoethanolamine and the diethanolamine; meanwhile, La, alkali metal and Ca have ternary synergistic effect on the aspect of improving the selectivity of monoethanolamine and diethanolamine in the catalyst.
In the above technical solution, the ratio of La to the alkali metal is not particularly limited, and is, for example, 0.5 to 10 by weight, for example, but not limited to, 1.02, 1.52, 2.02, 2.52, 3.02, 3.52, 4.02, 4.52, 5.02, 5.52, 6.02, 7.02, 8.02, 9.02, and the like. For comparison, the ratio of 8.0 is commonly used in the embodiments of the present invention.
In the above technical solution, the ratio of La to P is not particularly limited, and is, for example, 0.5 to 10 by weight, for example, but not limited to, 1.02, 1.52, 2.02, 2.52, 3.02, 3.52, 4.02, 4.52, 5.02, 5.52, 6.02, 7.02, 8.02, 9.02, and the like. For comparison, the ratio of 8.0 is commonly used in the embodiments of the present invention.
In the above technical solution, the ratio of La to Ca is not particularly limited, and is, for example, 0.5 to 10 by weight, for example, but not limited to, 1.02, 1.52, 2.02, 2.52, 3.02, 3.52, 4.02, 4.52, 5.02, 5.52, 6.02, 7.02, 8.02, 9.02, and the like. For comparison, the ratio of 8.0 is commonly used in the embodiments of the present invention.
In the above technical means, the content of the modifying element is preferably more than 0 and not more than 50 g/L. For convenience, the content of the modifying element is generally 25g/L in the embodiment of the invention.
In the above technical scheme, the ZSM-5 molecular sieve is preferably a hydrogen type molecular sieve.
In the above technical scheme, the mole ratio of silicon to aluminum of the molecular sieve is preferably SiO2/Al2O3Is 20 to 200. For the sake of convenience, SiO is commonly used in the embodiments of the present invention2/Al2O3Is 50.
In the technical scheme, the catalyst can achieve comparable technical effects with or without a molecular sieve binder. In the case of a catalyst comprising a molecular sieve binder, the skilled person can rationally select the usual binder without inventive step, for example, the molecular sieve binders that can be selected are pseudo-boehmite, alumina, silica, etc.
When the catalyst is passivated by the method comprising the following steps, the selectivity of monoethanolamine and diethanolamine in a product is obviously improved, and the catalyst can achieve the purpose of not containing triethanolamine:
contacting the catalyst with a passivation material, and passivating for 2-24 hours at 40-100 ℃, wherein the passivation material comprises ethylene oxide and ammonia water, and NH in the passivation material3The molar ratio of the EO to the EO is 1 to 10.
The ammonia used in the reaction of the catalyst for producing the monoethanolamine and the diethanolamine is liquid ammonia, the catalyst is passivated by using ammonia water as a passivation raw material, and the selectivity of the catalyst is improved after the catalyst is passivated, but the liquid ammonia does not have the function.
In the passivation, the ammonia concentration in the ammonia water is preferably 20 to 95 w%, such as, but not limited to, 30 w%, 40 w%, 50 w%, 60 w%, 65 w%, 70 w%, 75 w%, 80 w%, 85 w%, 90 w%, 91 w%, 92 w%, 93 w%, 94 w%, 95 w%, and the like, and more preferably 60 to 95 w%.
However, in a comparable manner, the catalyst deactivation in the embodiment of the present invention is carried out by the following method:
heating the catalyst bed to 80 deg.C, and reacting according to NH3Introducing ethylene oxide and ammonia water with the concentration of 90% into the EO (3) for catalyst passivation treatment, wherein the liquid phase volume space velocity of the ethylene oxide is 2.0 hours-1The deactivation time was 24 hours. After the passivation is finished, the airspeed is 10.0 hours-1Liquid ammonia was introduced into the reactor for 10 hours to displace the ammonia.
In the technical scheme, the catalyst is obtained by adopting a preparation method comprising the following steps:
mixing the molecular sieve with a compound solution of a modifying element;
drying;
and (4) roasting.
In the technical scheme, the drying temperature is preferably 60-150 ℃, and more preferably 80-120 ℃.
In the technical scheme, the drying time is preferably 4-24 hours, and more preferably 3-8 hours.
In the technical scheme, the roasting temperature is preferably 250-750 ℃, and more preferably 350-550 ℃.
In the above technical scheme, the roasting time is preferably 2-12 hours, and more preferably 2-8 hours.
In the technical scheme, the roasting atmosphere has no special requirement, and both oxidizing atmosphere and inert atmosphere can obtain comparable technical effects. Oxidizing atmosphere such as, but not limited to, optionally oxygen-containing atmosphere, preferably air atmosphere from the economical point of view; the inert gas atmosphere is selected from at least one of nitrogen or inert gas atmosphere, and the inert gas atmosphere can be nitrogen, helium, argon and the like. From an economic point of view, nitrogen is often used as the inert atmosphere. In a comparable manner, air atmospheres are used in embodiments of the invention.
In the above technical solutions, the compound of La element is not particularly limited, for example, but not limited to, lanthanum nitrate, lanthanum acetate, lanthanum oxalate, and the like.
In the above technical scheme, the compound of the element P is not particularly limited, such as but not limited to phosphoric acid, phosphorous acid, and the like.
In the above technical scheme, the compound of the K element is not particularly limited, and examples thereof include, but are not limited to, potassium hydroxide, potassium acetate, potassium nitrate, potassium carbonate, and the like.
In the above technical scheme, the compound of Na element is not particularly limited, such as but not limited to sodium hydroxide, sodium acetate, sodium nitrate, potassium carbonate, and the like.
In the above technical solution, the compound of Ca element is not particularly limited, such as but not limited to calcium nitrate and the like.
There is no particular limitation on the method for preparing the ZSM-5 molecular sieve, and those skilled in the art can make a reasonable choice without inventive effort. By way of example, the molecular sieves of embodiments of the invention can be prepared by a process comprising the steps of:
the ZSM-5 molecular sieve is preferably synthesized by the following method: at least one of water glass, silica sol or white carbon black is used as a silicon source, and aluminum is used asAt least one of sodium and aluminum sulfate is taken as an aluminum source, at least one of tetrapropylammonium bromide, tetrapropylammonium hydroxide or 1, 6-hexamethylene diamine is taken as a template agent, at least one of sodium hydroxide and potassium hydroxide is taken as an alkali source, and the raw materials of the mixture have the molar ratio of SiO2/Al2O3＝20～200，H2O/SiO2＝10～150，OH-/SiO2＝0.01～1，Cl-/SiO20.1 to 1 weight percent of a templating agent/SiO2Crystallizing at the crystallization temperature of 100-200 ℃ for 24-144 hours, and filtering, washing, drying and roasting a crystallized product to obtain the ZSM-5 molecular sieve. The preferred molar ratio of the raw materials is SiO2/Al2O3＝30～90，H2O/SiO2＝20～60，OH-/SiO2＝0.1～0.5，Cl-/SiO20.1 to 0.7 of a templating agent/SiO20.1 to 0.5. The preferable crystallization temperature is 120-180 ℃, and the preferable crystallization time is 24-120 hours.
However, for the sake of comparison, the molecular sieve in the embodiment of the present invention is generally prepared by the following method:
mixing 40 w% silica sol, sodium metaaluminate, tetrapropylammonium bromide (TPABr), sodium chloride, sodium hydroxide and water in sequence, stirring for 180 minutes, putting into a reaction kettle, and dynamically crystallizing at 170 ℃ (200 revolutions per minute) for 72 hours. And (3) carrying out sharp quenching, filtering and washing on the crystallized product until the pH value is 7, and drying for 12 hours at 120 ℃ to obtain the ZSM-5 molecular sieve raw powder. The molar ratio of each raw material in the reaction mixture is as follows: SiO 22/Al2O3＝50，H2O/SiO2＝25.83，NaCl/SiO2＝0.68，NaOH/SiO2＝0.15，TPABr/SiO2＝0.40。
The obtained sodium-containing molecular sieve can be converted into a hydrogen-containing molecular sieve by a method well known to those skilled in the art, and the conversion is performed at the raw powder stage or after the molding, which is not particularly limited, and comparable technical effects can be obtained.
By way of example, in one embodiment of the present invention the conversion of molecular sieve to hydrogen form molecular sieve is carried out at the raw meal stageThe method specifically comprises the following steps: 0.1 to 1.0 mol.L is used-1The solid-liquid ratio of the ammonium nitrate solution is 1: 10-1: 20, the solution is stirred for 1-5 hours at the temperature of 60-120 ℃, and then the solution is filtered and washed. The process is repeated for three times, the obtained sample is dried for 4-8 hours at the temperature of 60-150 ℃, and finally roasted for 2-12 hours at the temperature of 250-750 ℃ to obtain the hydrogen type ZSM-5 molecular sieve powder.
By way of comparison only, the steps for converting the molecular sieve to the hydrogen form of the molecular sieve in the embodiments of the present invention are as follows: use 0.2 mol. L-1The ammonium nitrate solution has a solid-to-liquid ratio of 1:15, is heated at 90 ℃ and stirred for 2 hours, and then is filtered, washed. The process is repeated three times, the obtained sample is dried for 6 hours at 120 ℃, and finally roasted for 5 hours at 550 ℃ to obtain the hydrogen type ZSM-5 molecular sieve powder.
Mixing hydrogen type ZSM-5 molecular sieve raw powder with boehmite, sesbania powder and water, wherein the weight part ratio of the raw materials is ZSM-5/Al2O3The powder/water of sesbania/sesbania is 55:19:1:25, extruded into strips, dried at 120 ℃ for 12 hours, and roasted at 550 ℃ for 5 hours to obtain the molecular sieve with the diameter of 1.0mm and the length of 3.0 mm.
The technical key of the invention is the selection of the catalyst, and the specific process conditions of the specific application can be reasonably selected by a person skilled in the art without creative labor.
By adopting the invention, the conversion rate of Ethylene Oxide (EO) can reach 95.86%, and the selectivity of monoethanolamine and diethanolamine can reach 95.48%, thus obtaining better technical effect.
Detailed Description
[ example 1 ]
1. Molecular sieve preparation
Mixing 40 w% silica sol, sodium metaaluminate, tetrapropylammonium bromide (TPABr), sodium chloride, sodium hydroxide and water in sequence, stirring for 180 minutes, putting into a reaction kettle, and dynamically crystallizing at 170 ℃ (200 revolutions per minute) for 72 hours. And (3) carrying out sharp quenching, filtering and washing on the crystallized product until the pH value is 7, and drying for 12 hours at 120 ℃ to obtain the ZSM-5 molecular sieve raw powder. The molar ratio of each raw material in the reaction mixture is as follows: SiO 22/Al2O3＝50，H2O/SiO2＝25.83，NaCl/SiO2＝0.68，NaOH/SiO2＝0.15，TPABr/SiO2＝0.40。
The prepared ZSM-5 molecular sieve raw powder is mixed by 0.2 mol.L-1Soaking in ammonium nitrate solution at solid-to-liquid ratio of 1:15, heating at 90 deg.C, stirring for 2 hr, filtering, and washing. The process is repeated three times, the obtained sample is dried for 6 hours at 120 ℃, and finally roasted for 5 hours at 550 ℃ to obtain the hydrogen type ZSM-5 molecular sieve powder.
Mixing the synthesized ZSM-5 molecular sieve raw powder with boehmite, sesbania powder and water, wherein the weight part ratio of the raw materials is ZSM-5/Al2O3And (3) extruding and forming the powder/water of sesbania/sesbania powder/water of 55:19:1:25, drying the powder at 120 ℃ for 12 hours, and roasting the powder at 550 ℃ for 5 hours to obtain the formed hydrogen type molecular sieve with the diameter of 1.0mm and the length of 3.0 mm.
2. Catalyst preparation
1L of hydrogen type molecular sieve is taken and mixed with 0.6L of lanthanum nitrate aqueous solution (containing 25g of La), and the mixture is dried for 6 hours at 110 ℃ and roasted for 4 hours at 450 ℃.
The catalyst contained 25g/L of La.
3. Catalyst passivation
The catalyst was not passivated.
4. Catalyst evaluation
Catalyst evaluation conditions: the reaction temperature is 80 ℃, the reaction pressure is 6.0MPa, and the liquid NH is3The molar ratio of the EO to the EO is 8, the volume space velocity of the EO liquid phase is 1.2 hours-1Then, catalyst evaluation was performed.
For comparison, the kinds and contents of the modifying elements, and the evaluation results of the catalyst are shown in Table 1.
[ example 2 ]
1. Molecular sieve preparation
Mixing 40 w% silica sol, sodium metaaluminate, tetrapropylammonium bromide (TPABr), sodium chloride, sodium hydroxide and water in sequence, stirring for 180 minutes, putting into a reaction kettle, and dynamically crystallizing at 170 ℃ (200 revolutions per minute) for 72 hours. And (3) carrying out sharp quenching, filtering and washing on the crystallized product until the pH value is 7, and drying for 12 hours at 120 ℃ to obtain the ZSM-5 molecular sieve raw powder. The molar ratio of each raw material in the reaction mixture is as follows: SiO 22/Al2O3＝50，H2O/SiO2＝25.83，NaCl/SiO2＝0.68，NaOH/SiO2＝0.15，TPABr/SiO2＝0.40。
The prepared ZSM-5 molecular sieve raw powder is mixed by 0.2 mol.L-1Soaking in ammonium nitrate solution at solid-to-liquid ratio of 1:15, heating at 90 deg.C, stirring for 2 hr, filtering, and washing. The process is repeated three times, the obtained sample is dried for 6 hours at 120 ℃, and finally roasted for 5 hours at 550 ℃ to obtain the hydrogen type ZSM-5 molecular sieve powder.
Mixing the synthesized ZSM-5 molecular sieve raw powder with boehmite, sesbania powder and water, wherein the weight part ratio of the raw materials is ZSM-5/Al2O3And (3) extruding and forming the powder/water of sesbania/sesbania powder/water of 55:19:1:25, drying the powder at 120 ℃ for 12 hours, and roasting the powder at 550 ℃ for 5 hours to obtain the formed hydrogen type molecular sieve with the diameter of 1.0mm and the length of 3.0 mm.
2. Catalyst preparation
1L of hydrogen type molecular sieve was mixed with 0.6L of phosphoric acid aqueous solution (containing P25 g), dried at 110 ℃ for 6 hours, and calcined at 450 ℃ for 4 hours.
The catalyst contained P25 g/L.
3. Catalyst passivation
The catalyst was not passivated.
4. Catalyst evaluation
Catalyst evaluation conditions: the reaction temperature is 80 ℃, the reaction pressure is 6.0MPa, and the liquid NH is3The molar ratio of the EO to the EO is 8, the volume space velocity of the EO liquid phase is 1.2 hours-1Then, catalyst evaluation was performed.
For comparison, the kinds and contents of the modifying elements, and the evaluation results of the catalyst are shown in Table 1.
[ example 3 ]
1. Molecular sieve preparation
Mixing 40 w% silica sol, sodium metaaluminate, tetrapropylammonium bromide (TPABr), sodium chloride, sodium hydroxide and water in sequence, stirring for 180 minutes, putting into a reaction kettle, and dynamically crystallizing at 170 ℃ (200 revolutions per minute) for 72 hours. And (3) carrying out sharp quenching, filtering and washing on the crystallized product until the pH value is 7, and drying for 12 hours at 120 ℃ to obtain the ZSM-5 molecular sieve raw powder. The molar ratio of each raw material in the reaction mixture is as follows: SiO 22/Al2O3＝50，H2O/SiO2＝25.83，NaCl/SiO2＝0.68，NaOH/SiO2＝0.15，TPABr/SiO2＝0.40。
The prepared ZSM-5 molecular sieve raw powder is mixed by 0.2 mol.L-1Soaking in ammonium nitrate solution at solid-to-liquid ratio of 1:15, heating at 90 deg.C, stirring for 2 hr, filtering, and washing. The process is repeated three times, the obtained sample is dried for 6 hours at 120 ℃, and finally roasted for 5 hours at 550 ℃ to obtain the hydrogen type ZSM-5 molecular sieve powder.
Mixing the synthesized ZSM-5 molecular sieve raw powder with boehmite, sesbania powder and water, wherein the weight part ratio of the raw materials is ZSM-5/Al2O3And (3) extruding and forming the powder/water of sesbania/sesbania powder/water of 55:19:1:25, drying the powder at 120 ℃ for 12 hours, and roasting the powder at 550 ℃ for 5 hours to obtain the formed hydrogen type molecular sieve with the diameter of 1.0mm and the length of 3.0 mm.
2. Catalyst preparation
1L of hydrogen type molecular sieve is taken and mixed with 0.6L of potassium hydroxide solution (containing 25g of K), dried for 6 hours at 110 ℃ and roasted for 4 hours at 450 ℃.
The catalyst contained K25 g/L.
3. Catalyst passivation
The catalyst was not passivated.
4. Catalyst evaluation
Catalyst evaluation conditions: the reaction temperature is 80 ℃, the reaction pressure is 6.0MPa, and the liquid NH is3The molar ratio of the EO to the EO is 8, the volume space velocity of the EO liquid phase is 1.2 hours-1Then, catalyst evaluation was performed.
For comparison, the kinds and contents of the modifying elements, and the evaluation results of the catalyst are shown in Table 1.
[ example 4 ]
1. Molecular sieve preparation
Mixing 40 w% silica sol, sodium metaaluminate, tetrapropylammonium bromide (TPABr), sodium chloride, sodium hydroxide and water in sequence, stirring for 180 minutes, putting into a reaction kettle, and dynamically crystallizing at 170 ℃ (200 revolutions per minute) for 72 hours. And (3) carrying out sharp quenching, filtering and washing on the crystallized product until the pH value is 7, and drying for 12 hours at 120 ℃ to obtain the ZSM-5 molecular sieve raw powder. The molar ratio of each raw material in the reaction mixture is as follows: SiO 22/Al2O3＝50，H2O/SiO2＝25.83，NaCl/SiO2＝0.68，NaOH/SiO2＝0.15，TPABr/SiO2＝0.40。
The prepared ZSM-5 molecular sieve raw powder is mixed by 0.2 mol.L-1Soaking in ammonium nitrate solution at solid-to-liquid ratio of 1:15, heating at 90 deg.C, stirring for 2 hr, filtering, and washing. The process is repeated three times, the obtained sample is dried for 6 hours at 120 ℃, and finally roasted for 5 hours at 550 ℃ to obtain the hydrogen type ZSM-5 molecular sieve powder.
Mixing the synthesized ZSM-5 molecular sieve raw powder with boehmite, sesbania powder and water, wherein the weight part ratio of the raw materials is ZSM-5/Al2O3And (3) extruding and forming the powder/water of sesbania/sesbania powder/water of 55:19:1:25, drying the powder at 120 ℃ for 12 hours, and roasting the powder at 550 ℃ for 5 hours to obtain the formed hydrogen type molecular sieve with the diameter of 1.0mm and the length of 3.0 mm.
2. Catalyst preparation
1L of hydrogen type molecular sieve was mixed with 0.6L of sodium hydroxide solution (containing 25g of Na), dried at 110 ℃ for 6 hours, and calcined at 450 ℃ for 4 hours.
The catalyst contained Na 25 g/L.
3. Catalyst passivation
The catalyst was not passivated.
4. Catalyst evaluation
Catalyst evaluation conditions: the reaction temperature is 80 ℃, the reaction pressure is 6.0MPa, and the liquid NH is3The molar ratio of the EO to the EO is 8, the volume space velocity of the EO liquid phase is 1.2 hours-1Then, catalyst evaluation was performed.
For comparison, the kinds and contents of the modifying elements, and the evaluation results of the catalyst are shown in Table 1.
[ example 5 ]
1. Molecular sieve preparation
Mixing 40 w% silica sol, sodium metaaluminate, tetrapropylammonium bromide (TPABr), sodium chloride, sodium hydroxide and water in sequence, stirring for 180 minutes, putting into a reaction kettle, and dynamically crystallizing at 170 ℃ (200 revolutions per minute) for 72 hours. And (3) carrying out sharp quenching, filtering and washing on the crystallized product until the pH value is 7, and drying for 12 hours at 120 ℃ to obtain the ZSM-5 molecular sieve raw powder. The molar ratio of the raw materials in the reaction mixture is：SiO2/Al2O3＝50，H2O/SiO2＝25.83，NaCl/SiO2＝0.68，NaOH/SiO2＝0.15，TPABr/SiO2＝0.40。
The prepared ZSM-5 molecular sieve raw powder is mixed by 0.2 mol.L-1Soaking in ammonium nitrate solution at solid-to-liquid ratio of 1:15, heating at 90 deg.C, stirring for 2 hr, filtering, and washing. The process is repeated three times, the obtained sample is dried for 6 hours at 120 ℃, and finally roasted for 5 hours at 550 ℃ to obtain the hydrogen type ZSM-5 molecular sieve powder.
Mixing the synthesized ZSM-5 molecular sieve raw powder with boehmite, sesbania powder and water, wherein the weight part ratio of the raw materials is ZSM-5/Al2O3And (3) extruding and forming the powder/water of sesbania/sesbania powder/water of 55:19:1:25, drying the powder at 120 ℃ for 12 hours, and roasting the powder at 550 ℃ for 5 hours to obtain the formed hydrogen type molecular sieve with the diameter of 1.0mm and the length of 3.0 mm.
2. Catalyst preparation
1L of hydrogen type molecular sieve was mixed with 0.6L of calcium nitrate solution (containing 25g of Ca), dried at 110 ℃ for 6 hours, and calcined at 450 ℃ for 4 hours.
The catalyst contained 25g/L Ca.
3. Catalyst passivation
The catalyst was not passivated.
4. Catalyst evaluation
Catalyst evaluation conditions: the reaction temperature is 80 ℃, the reaction pressure is 6.0MPa, and the liquid NH is3The molar ratio of the EO to the EO is 8, the volume space velocity of the EO liquid phase is 1.2 hours-1Then, catalyst evaluation was performed.
For comparison, the kinds and contents of the modifying elements, and the evaluation results of the catalyst are shown in Table 1.
[ example 6 ]
1. Molecular sieve preparation
Mixing 40 w% silica sol, sodium metaaluminate, tetrapropylammonium bromide (TPABr), sodium chloride, sodium hydroxide and water in sequence, stirring for 180 minutes, putting into a reaction kettle, and dynamically crystallizing at 170 ℃ (200 revolutions per minute) for 72 hours. And (3) carrying out sharp quenching, filtering and washing on the crystallized product until the pH value is 7, and drying for 12 hours at 120 ℃ to obtain the ZSM-5 molecular sieve raw powder. Reaction mixingThe molar ratio of the raw materials in the product is as follows: SiO 22/Al2O3＝50，H2O/SiO2＝25.83，NaCl/SiO2＝0.68，NaOH/SiO2＝0.15，TPABr/SiO2＝0.40。
The prepared ZSM-5 molecular sieve raw powder is mixed by 0.2 mol.L-1Soaking in ammonium nitrate solution at solid-to-liquid ratio of 1:15, heating at 90 deg.C, stirring for 2 hr, filtering, and washing. The process is repeated three times, the obtained sample is dried for 6 hours at 120 ℃, and finally roasted for 5 hours at 550 ℃ to obtain the hydrogen type ZSM-5 molecular sieve powder.
Mixing the synthesized ZSM-5 molecular sieve raw powder with boehmite, sesbania powder and water, wherein the weight part ratio of the raw materials is ZSM-5/Al2O3And (3) extruding and forming the powder/water of sesbania/sesbania powder/water of 55:19:1:25, drying the powder at 120 ℃ for 12 hours, and roasting the powder at 550 ℃ for 5 hours to obtain the formed hydrogen type molecular sieve with the diameter of 1.0mm and the length of 3.0 mm.
2. Catalyst preparation
1L of hydrogen type molecular sieve is mixed with 0.6L of nickel nitrate solution (containing 25g of Ni), dried at 110 ℃ for 6 hours and roasted at 450 ℃ for 4 hours.
The catalyst contained Ni 25 g/L.
3. Catalyst passivation
The catalyst was not passivated.
4. Catalyst evaluation
Catalyst evaluation conditions: the reaction temperature is 80 ℃, the reaction pressure is 6.0MPa, and the liquid NH is3The molar ratio of the EO to the EO is 8, the volume space velocity of the EO liquid phase is 1.2 hours-1Then, catalyst evaluation was performed.
For comparison, the kinds and contents of the modifying elements, and the evaluation results of the catalyst are shown in Table 1.
[ example 7 ]
1. Molecular sieve preparation
Mixing 40 w% silica sol, sodium metaaluminate, tetrapropylammonium bromide (TPABr), sodium chloride, sodium hydroxide and water in sequence, stirring for 180 minutes, putting into a reaction kettle, and dynamically crystallizing at 170 ℃ (200 revolutions per minute) for 72 hours. The crystallized product is quenched, filtered and washed with water until the pH value is 7, and dried for 12 hours at 120 ℃ to obtain ZSM-5Molecular sieve raw powder. The molar ratio of each raw material in the reaction mixture is as follows: SiO 22/Al2O3＝50，H2O/SiO2＝25.83，NaCl/SiO2＝0.68，NaOH/SiO2＝0.15，TPABr/SiO2＝0.40。
The prepared ZSM-5 molecular sieve raw powder is mixed by 0.2 mol.L-1Soaking in ammonium nitrate solution at solid-to-liquid ratio of 1:15, heating at 90 deg.C, stirring for 2 hr, filtering, and washing. The process is repeated three times, the obtained sample is dried for 6 hours at 120 ℃, and finally roasted for 5 hours at 550 ℃ to obtain the hydrogen type ZSM-5 molecular sieve powder.
Mixing the synthesized ZSM-5 molecular sieve raw powder with boehmite, sesbania powder and water, wherein the weight part ratio of the raw materials is ZSM-5/Al2O3And (3) extruding and forming the powder/water of sesbania/sesbania powder/water of 55:19:1:25, drying the powder at 120 ℃ for 12 hours, and roasting the powder at 550 ℃ for 5 hours to obtain the formed hydrogen type molecular sieve with the diameter of 1.0mm and the length of 3.0 mm.
2. Catalyst preparation
1L of hydrogen type molecular sieve is taken and mixed with 0.6L of mixed solution of lanthanum acetate and phosphoric acid (containing 20g of La and 5g of P), dried for 6 hours at 110 ℃, and roasted for 4 hours at 450 ℃.
The catalyst contains 20g/L of La and 5g/L of P.
3. Catalyst passivation
The catalyst was not passivated.
4. Catalyst evaluation
Catalyst evaluation conditions: the reaction temperature is 80 ℃, the reaction pressure is 6.0MPa, and the liquid NH is3The molar ratio of the EO to the EO is 8, the volume space velocity of the EO liquid phase is 1.2 hours-1Then, catalyst evaluation was performed.
For comparison, the kinds and contents of the modifying elements, and the evaluation results of the catalyst are shown in Table 1.
[ example 8 ]
1. Molecular sieve preparation
Mixing 40 w% silica sol, sodium metaaluminate, tetrapropylammonium bromide (TPABr), sodium chloride, sodium hydroxide and water in sequence, stirring for 180 minutes, putting into a reaction kettle, and dynamically crystallizing at 170 ℃ (200 revolutions per minute) for 72 hours. The crystallized product is quenched and filteredFiltering and washing the mixture until the pH value is 7, and drying the mixture for 12 hours at the temperature of 120 ℃ to obtain ZSM-5 molecular sieve raw powder. The molar ratio of each raw material in the reaction mixture is as follows: SiO 22/Al2O3＝50，H2O/SiO2＝25.83，NaCl/SiO2＝0.68，NaOH/SiO2＝0.15，TPABr/SiO2＝0.40。
The prepared ZSM-5 molecular sieve raw powder is mixed by 0.2 mol.L-1Soaking in ammonium nitrate solution at solid-to-liquid ratio of 1:15, heating at 90 deg.C, stirring for 2 hr, filtering, and washing. The process is repeated three times, the obtained sample is dried for 6 hours at 120 ℃, and finally roasted for 5 hours at 550 ℃ to obtain the hydrogen type ZSM-5 molecular sieve powder.
Mixing the synthesized ZSM-5 molecular sieve raw powder with boehmite, sesbania powder and water, wherein the weight part ratio of the raw materials is ZSM-5/Al2O3And (3) extruding and forming the powder/water of sesbania/sesbania powder/water of 55:19:1:25, drying the powder at 120 ℃ for 12 hours, and roasting the powder at 550 ℃ for 5 hours to obtain the formed hydrogen type molecular sieve with the diameter of 1.0mm and the length of 3.0 mm.
2. Catalyst preparation
1L of hydrogen type molecular sieve is taken and mixed with 0.6L of mixed solution of lanthanum oxalate and potassium acetate (containing 20g of La and 5g of K), dried for 6 hours at 110 ℃ and roasted for 4 hours at 450 ℃.
The catalyst contains 20g/L of La and 5g/L of K.
3. Catalyst passivation
The catalyst was not passivated.
4. Catalyst evaluation
Catalyst evaluation conditions: the reaction temperature is 80 ℃, the reaction pressure is 6.0MPa, and the liquid NH is3The molar ratio of the EO to the EO is 8, the volume space velocity of the EO liquid phase is 1.2 hours-1Then, catalyst evaluation was performed.
For comparison, the kinds and contents of the modifying elements, and the evaluation results of the catalyst are shown in Table 1.
[ example 9 ]
1. Molecular sieve preparation
Mixing 40 w% silica sol, sodium metaaluminate, tetrapropylammonium bromide (TPABr), sodium chloride, sodium hydroxide and water in sequence, stirring for 180 minutes, putting into a reaction kettle, and 1Dynamic (200 rpm) crystallization at 70 ℃ for 72 hours. And (3) carrying out sharp quenching, filtering and washing on the crystallized product until the pH value is 7, and drying for 12 hours at 120 ℃ to obtain the ZSM-5 molecular sieve raw powder. The molar ratio of each raw material in the reaction mixture is as follows: SiO 22/Al2O3＝50，H2O/SiO2＝25.83，NaCl/SiO2＝0.68，NaOH/SiO2＝0.15，TPABr/SiO2＝0.40。
The prepared ZSM-5 molecular sieve raw powder is mixed by 0.2 mol.L-1Soaking in ammonium nitrate solution at solid-to-liquid ratio of 1:15, heating at 90 deg.C, stirring for 2 hr, filtering, and washing. The process is repeated three times, the obtained sample is dried for 6 hours at 120 ℃, and finally roasted for 5 hours at 550 ℃ to obtain the hydrogen type ZSM-5 molecular sieve powder.
Mixing the synthesized ZSM-5 molecular sieve raw powder with boehmite, sesbania powder and water, wherein the weight part ratio of the raw materials is ZSM-5/Al2O3And (3) extruding and forming the powder/water of sesbania/sesbania powder/water of 55:19:1:25, drying the powder at 120 ℃ for 12 hours, and roasting the powder at 550 ℃ for 5 hours to obtain the formed hydrogen type molecular sieve with the diameter of 1.0mm and the length of 3.0 mm.
2. Catalyst preparation
1L of hydrogen type molecular sieve is taken and mixed with 0.6L of mixed solution of lanthanum nitrate and sodium acetate (containing 20g of La and 5g of Na), dried for 6 hours at 110 ℃, and roasted for 4 hours at 450 ℃.
The catalyst contained 20g/L of La and 5g/L of Na.
3. Catalyst passivation
The catalyst was not passivated.
4. Catalyst evaluation
Catalyst evaluation conditions: the reaction temperature is 80 ℃, the reaction pressure is 6.0MPa, and the liquid NH is3The molar ratio of the EO to the EO is 8, the volume space velocity of the EO liquid phase is 1.2 hours-1Then, catalyst evaluation was performed.
For comparison, the kinds and contents of the modifying elements, and the evaluation results of the catalyst are shown in Table 1.
[ example 10 ]
1. Molecular sieve preparation
Sequentially mixing 40 w% silica sol, sodium metaaluminate, tetrapropylammonium bromide (TPABr) and sodium chlorideMixing with sodium hydroxide and water, stirring for 180 min, loading into a reaction kettle, and dynamically crystallizing at 170 deg.C (200 rpm) for 72 hr. And (3) carrying out sharp quenching, filtering and washing on the crystallized product until the pH value is 7, and drying for 12 hours at 120 ℃ to obtain the ZSM-5 molecular sieve raw powder. The molar ratio of each raw material in the reaction mixture is as follows: SiO 22/Al2O3＝50，H2O/SiO2＝25.83，NaCl/SiO2＝0.68，NaOH/SiO2＝0.15，TPABr/SiO2＝0.40。
The prepared ZSM-5 molecular sieve raw powder is mixed by 0.2 mol.L-1Soaking in ammonium nitrate solution at solid-to-liquid ratio of 1:15, heating at 90 deg.C, stirring for 2 hr, filtering, and washing. The process is repeated three times, the obtained sample is dried for 6 hours at 120 ℃, and finally roasted for 5 hours at 550 ℃ to obtain the hydrogen type ZSM-5 molecular sieve powder.
Mixing the synthesized ZSM-5 molecular sieve raw powder with boehmite, sesbania powder and water, wherein the weight part ratio of the raw materials is ZSM-5/Al2O3And (3) extruding and forming the powder/water of sesbania/sesbania powder/water of 55:19:1:25, drying the powder at 120 ℃ for 12 hours, and roasting the powder at 550 ℃ for 5 hours to obtain the formed hydrogen type molecular sieve with the diameter of 1.0mm and the length of 3.0 mm.
2. Catalyst preparation
1L of hydrogen type molecular sieve is taken and mixed with 0.6L of mixed solution of lanthanum nitrate and calcium nitrate (containing 20g of La and 5g of Ca), dried for 6 hours at 110 ℃ and roasted for 4 hours at 450 ℃.
The catalyst contains 20g/L of La and 5g/L of Ca.
3. Catalyst passivation
The catalyst was not passivated.
4. Catalyst evaluation
Catalyst evaluation conditions: the reaction temperature is 80 ℃, the reaction pressure is 6.0MPa, and the liquid NH is3The molar ratio of the EO to the EO is 8, the volume space velocity of the EO liquid phase is 1.2 hours-1Then, catalyst evaluation was performed.
For comparison, the kinds and contents of the modifying elements, and the evaluation results of the catalyst are shown in Table 1.
[ example 11 ]
1. Molecular sieve preparation
In turn willMixing 40 w% silica sol, sodium metaaluminate, tetrapropylammonium bromide (TPABr), sodium chloride, sodium hydroxide and water, stirring for 180 minutes, loading into a reaction kettle, and dynamically crystallizing at 170 ℃ (200 revolutions per minute) for 72 hours. And (3) carrying out sharp quenching, filtering and washing on the crystallized product until the pH value is 7, and drying for 12 hours at 120 ℃ to obtain the ZSM-5 molecular sieve raw powder. The molar ratio of each raw material in the reaction mixture is as follows: SiO 22/Al2O3＝50，H2O/SiO2＝25.83，NaCl/SiO2＝0.68，NaOH/SiO2＝0.15，TPABr/SiO2＝0.40。
The prepared ZSM-5 molecular sieve raw powder is mixed by 0.2 mol.L-1Soaking in ammonium nitrate solution at solid-to-liquid ratio of 1:15, heating at 90 deg.C, stirring for 2 hr, filtering, and washing. The process is repeated three times, the obtained sample is dried for 6 hours at 120 ℃, and finally roasted for 5 hours at 550 ℃ to obtain the hydrogen type ZSM-5 molecular sieve powder.
Mixing the synthesized ZSM-5 molecular sieve raw powder with boehmite, sesbania powder and water, wherein the weight part ratio of the raw materials is ZSM-5/Al2O3And (3) extruding and forming the powder/water of sesbania/sesbania powder/water of 55:19:1:25, drying the powder at 120 ℃ for 12 hours, and roasting the powder at 550 ℃ for 5 hours to obtain the formed hydrogen type molecular sieve with the diameter of 1.0mm and the length of 3.0 mm.
2. Catalyst preparation
1L of hydrogen type molecular sieve is taken and mixed with 0.6L of mixed solution of lanthanum nitrate and nickel acetate (containing 20g of La and 5g of Ni), dried for 6 hours at 110 ℃, and roasted for 4 hours at 450 ℃.
The catalyst contains 20g/L of La and 5g/L of Ni.
3. Catalyst passivation
The catalyst was not passivated.
4. Catalyst evaluation
Catalyst evaluation conditions: the reaction temperature is 80 ℃, the reaction pressure is 6.0MPa, and the liquid NH is3The molar ratio of the EO to the EO is 8, the volume space velocity of the EO liquid phase is 1.2 hours-1Then, catalyst evaluation was performed.
For comparison, the kinds and contents of the modifying elements, and the evaluation results of the catalyst are shown in Table 1.
[ example 12 ]
1. Molecular sieve preparation
Mixing 40 w% silica sol, sodium metaaluminate, tetrapropylammonium bromide (TPABr), sodium chloride, sodium hydroxide and water in sequence, stirring for 180 minutes, putting into a reaction kettle, and dynamically crystallizing at 170 ℃ (200 revolutions per minute) for 72 hours. And (3) carrying out sharp quenching, filtering and washing on the crystallized product until the pH value is 7, and drying for 12 hours at 120 ℃ to obtain the ZSM-5 molecular sieve raw powder. The molar ratio of each raw material in the reaction mixture is as follows: SiO 22/Al2O3＝50，H2O/SiO2＝25.83，NaCl/SiO2＝0.68，NaOH/SiO2＝0.15，TPABr/SiO2＝0.40。
The prepared ZSM-5 molecular sieve raw powder is mixed by 0.2 mol.L-1Soaking in ammonium nitrate solution at solid-to-liquid ratio of 1:15, heating at 90 deg.C, stirring for 2 hr, filtering, and washing. The process is repeated three times, the obtained sample is dried for 6 hours at 120 ℃, and finally roasted for 5 hours at 550 ℃ to obtain the hydrogen type ZSM-5 molecular sieve powder.
Mixing the synthesized ZSM-5 molecular sieve raw powder with boehmite, sesbania powder and water, wherein the weight part ratio of the raw materials is ZSM-5/Al2O3And (3) extruding and forming the powder/water of sesbania/sesbania powder/water of 55:19:1:25, drying the powder at 120 ℃ for 12 hours, and roasting the powder at 550 ℃ for 5 hours to obtain the formed hydrogen type molecular sieve with the diameter of 1.0mm and the length of 3.0 mm.
2. Catalyst preparation
1L of hydrogen type molecular sieve is taken and mixed with 0.6L of mixed solution (containing 20g of La, 2.5g of P and 2.5g of K) of lanthanum nitrate, phosphoric acid and potassium carbonate, dried for 6 hours at 110 ℃ and roasted for 4 hours at 450 ℃.
The catalyst contains 20g/L of La, 2.5g/L of P and 2.5g/L of K.
3. Catalyst passivation
The catalyst was not passivated.
4. Catalyst evaluation
Catalyst evaluation conditions: the reaction temperature is 80 ℃, the reaction pressure is 6.0MPa, and the liquid NH is3The molar ratio of the EO to the EO is 8, the volume space velocity of the EO liquid phase is 1.2 hours-1Then, catalyst evaluation was performed.
For comparison, the kinds and contents of the modifying elements, and the evaluation results of the catalyst are shown in Table 1.
[ example 13 ]
1. Molecular sieve preparation
Mixing 40 w% silica sol, sodium metaaluminate, tetrapropylammonium bromide (TPABr), sodium chloride, sodium hydroxide and water in sequence, stirring for 180 minutes, putting into a reaction kettle, and dynamically crystallizing at 170 ℃ (200 revolutions per minute) for 72 hours. And (3) carrying out sharp quenching, filtering and washing on the crystallized product until the pH value is 7, and drying for 12 hours at 120 ℃ to obtain the ZSM-5 molecular sieve raw powder. The molar ratio of each raw material in the reaction mixture is as follows: SiO 22/Al2O3＝50，H2O/SiO2＝25.83，NaCl/SiO2＝0.68，NaOH/SiO2＝0.15，TPABr/SiO2＝0.40。
The prepared ZSM-5 molecular sieve raw powder is mixed by 0.2 mol.L-1Soaking in ammonium nitrate solution at solid-to-liquid ratio of 1:15, heating at 90 deg.C, stirring for 2 hr, filtering, and washing. The process is repeated three times, the obtained sample is dried for 6 hours at 120 ℃, and finally roasted for 5 hours at 550 ℃ to obtain the hydrogen type ZSM-5 molecular sieve powder.
Mixing the synthesized ZSM-5 molecular sieve raw powder with boehmite, sesbania powder and water, wherein the weight part ratio of the raw materials is ZSM-5/Al2O3And (3) extruding and forming the powder/water of sesbania/sesbania powder/water of 55:19:1:25, drying the powder at 120 ℃ for 12 hours, and roasting the powder at 550 ℃ for 5 hours to obtain the formed hydrogen type molecular sieve with the diameter of 1.0mm and the length of 3.0 mm.
2. Catalyst preparation
1L of hydrogen type molecular sieve is taken and mixed with 0.6L of mixed solution of lanthanum nitrate, phosphoric acid and calcium carbonate (containing 20g of La, 2.5g of P and 2.5g of Ca), dried for 6 hours at 110 ℃ and roasted for 4 hours at 450 ℃.
The catalyst contained 20g/L of La, 2.5g/L of P and 2.5g/L of Ca.
3. Catalyst passivation
The catalyst was not passivated.
4. Catalyst evaluation
Catalyst evaluation conditions: the reaction temperature is 80 ℃, the reaction pressure is 6.0MPa, and the liquid NH is3The molar ratio of the EO to the EO is 8, the volume space velocity of the EO liquid phase is 1.2 hours-1Then, catalyst evaluation was performed.
For comparison, the kinds and contents of the modifying elements, and the evaluation results of the catalyst are shown in Table 1.
[ example 14 ]
1. Molecular sieve preparation
Mixing 40 w% silica sol, sodium metaaluminate, tetrapropylammonium bromide (TPABr), sodium chloride, sodium hydroxide and water in sequence, stirring for 180 minutes, putting into a reaction kettle, and dynamically crystallizing at 170 ℃ (200 revolutions per minute) for 72 hours. And (3) carrying out sharp quenching, filtering and washing on the crystallized product until the pH value is 7, and drying for 12 hours at 120 ℃ to obtain the ZSM-5 molecular sieve raw powder. The molar ratio of each raw material in the reaction mixture is as follows: SiO 22/Al2O3＝50，H2O/SiO2＝25.83，NaCl/SiO2＝0.68，NaOH/SiO2＝0.15，TPABr/SiO2＝0.40。
The prepared ZSM-5 molecular sieve raw powder is mixed by 0.2 mol.L-1Soaking in ammonium nitrate solution at solid-to-liquid ratio of 1:15, heating at 90 deg.C, stirring for 2 hr, filtering, and washing. The process is repeated three times, the obtained sample is dried for 6 hours at 120 ℃, and finally roasted for 5 hours at 550 ℃ to obtain the hydrogen type ZSM-5 molecular sieve powder.
Mixing the synthesized ZSM-5 molecular sieve raw powder with boehmite, sesbania powder and water, wherein the weight part ratio of the raw materials is ZSM-5/Al2O3And (3) extruding and forming the powder/water of sesbania/sesbania powder/water of 55:19:1:25, drying the powder at 120 ℃ for 12 hours, and roasting the powder at 550 ℃ for 5 hours to obtain the formed hydrogen type molecular sieve with the diameter of 1.0mm and the length of 3.0 mm.
2. Catalyst preparation
1L of hydrogen type molecular sieve is taken and mixed with 0.6L of mixed solution of lanthanum nitrate, phosphoric acid and nickel nitrate (containing 20g of La, 2.5g of P and 2.5g of Ni), dried at 110 ℃ for 6 hours and roasted at 450 ℃ for 4 hours.
The catalyst contains 20g/L of La, 2.5g/L of P and 2.5g/L of Ni.
3. Catalyst passivation
The catalyst was not passivated.
4. Catalyst evaluation
Catalyst evaluation conditions: the reaction temperature is 80 ℃, the reaction pressure is 6.0MPa, and the liquid NH is3The molar ratio of the EO to the EO is 8, the volume space velocity of the EO liquid phase is 1.2 hours-1Then, catalyst evaluation was performed.
For comparison, the kinds and contents of the modifying elements, and the evaluation results of the catalyst are shown in Table 1.
[ example 15 ]
1. Molecular sieve preparation
Mixing 40 w% silica sol, sodium metaaluminate, tetrapropylammonium bromide (TPABr), sodium chloride, sodium hydroxide and water in sequence, stirring for 180 minutes, putting into a reaction kettle, and dynamically crystallizing at 170 ℃ (200 revolutions per minute) for 72 hours. And (3) carrying out sharp quenching, filtering and washing on the crystallized product until the pH value is 7, and drying for 12 hours at 120 ℃ to obtain the ZSM-5 molecular sieve raw powder. The molar ratio of each raw material in the reaction mixture is as follows: SiO 22/Al2O3＝50，H2O/SiO2＝25.83，NaCl/SiO2＝0.68，NaOH/SiO2＝0.15，TPABr/SiO2＝0.40。
The prepared ZSM-5 molecular sieve raw powder is mixed by 0.2 mol.L-1Soaking in ammonium nitrate solution at solid-to-liquid ratio of 1:15, heating at 90 deg.C, stirring for 2 hr, filtering, and washing. The process is repeated three times, the obtained sample is dried for 6 hours at 120 ℃, and finally roasted for 5 hours at 550 ℃ to obtain the hydrogen type ZSM-5 molecular sieve powder.
Mixing the synthesized ZSM-5 molecular sieve raw powder with boehmite, sesbania powder and water, wherein the weight part ratio of the raw materials is ZSM-5/Al2O3And (3) extruding and forming the powder/water of sesbania/sesbania powder/water of 55:19:1:25, drying the powder at 120 ℃ for 12 hours, and roasting the powder at 550 ℃ for 5 hours to obtain the formed hydrogen type molecular sieve with the diameter of 1.0mm and the length of 3.0 mm.
2. Catalyst preparation
1L of hydrogen type molecular sieve was taken, mixed with 0.6L of a mixed solution of lanthanum nitrate, sodium hydroxide and calcium nitrate (containing 20g of La, 2.5g of Na and 2.5g of Ca), dried at 110 ℃ for 6 hours, and calcined at 450 ℃ for 4 hours.
The catalyst contained 20g/L of La, 2.5g/L of Na and 2.5g/L of Ca.
3. Catalyst passivation
The catalyst was not passivated.
4. Catalyst evaluation
Catalyst evaluation conditions: the reaction temperature is 80 ℃, the reaction pressure is 6.0MPa, and the liquid NH is3The molar ratio of the EO to the EO is 8, the volume space velocity of the EO liquid phase is 1.2 hours-1Then, catalyst evaluation was performed.
For comparison, the kinds and contents of the modifying elements, and the evaluation results of the catalyst are shown in Table 1.
[ example 1' ]
1. Molecular sieve preparation
Mixing 40 w% silica sol, sodium metaaluminate, tetrapropylammonium bromide (TPABr), sodium chloride, sodium hydroxide and water in sequence, stirring for 180 minutes, putting into a reaction kettle, and dynamically crystallizing at 170 ℃ (200 revolutions per minute) for 72 hours. And (3) carrying out sharp quenching, filtering and washing on the crystallized product until the pH value is 7, and drying for 12 hours at 120 ℃ to obtain the ZSM-5 molecular sieve raw powder. The molar ratio of each raw material in the reaction mixture is as follows: SiO 22/Al2O3＝50，H2O/SiO2＝25.83，NaCl/SiO2＝0.68，NaOH/SiO2＝0.15，TPABr/SiO2＝0.40。
Mixing the synthesized ZSM-5 molecular sieve raw powder with boehmite, sesbania powder and water, wherein the weight part ratio of the raw materials is ZSM-5/Al2O3And (3) extruding and forming the powder/water of sesbania/sesbania powder/water of 55:19:1:25, drying the powder at 120 ℃ for 12 hours, and roasting the powder at 550 ℃ for 5 hours to obtain the formed hydrogen type molecular sieve with the diameter of 1.0mm and the length of 3.0 mm.
2. Catalyst preparation
1L of hydrogen type molecular sieve is taken and mixed with 0.6L of lanthanum nitrate aqueous solution (containing 25g of La), and the mixture is dried for 6 hours at 110 ℃ and roasted for 4 hours at 450 ℃.
The catalyst contained 25g/L of La.
3. Catalyst passivation
Heating the catalyst bed to 80 deg.C, and reacting according to NH3Introducing ethylene oxide and ammonia water with the concentration of 90% into the EO (3) for catalyst passivation treatment, wherein the liquid phase volume space velocity of the ethylene oxide is 2.0 hours-1The deactivation time was 24 hours. After the passivation is finished, the volume airspeed is 10.0 hours-1Liquid ammonia was introduced into the reactor for 10 hours to displace the ammonia.
4. Catalyst evaluation
Catalyst evaluation conditions: the reaction temperature is 80 ℃, the reaction pressure is 6.0MPa, and the liquid NH is3The molar ratio of the EO to the EO is 8, the volume space velocity of the EO liquid phase is 1.2 hours-1Then, catalyst evaluation was performed.
For comparison, the kinds and contents of the modifying elements, and the evaluation results of the catalyst are shown in Table 1.
[ example 2' ]
1. Molecular sieve preparation
Mixing 40 w% silica sol, sodium metaaluminate, tetrapropylammonium bromide (TPABr), sodium chloride, sodium hydroxide and water in sequence, stirring for 180 minutes, putting into a reaction kettle, and dynamically crystallizing at 170 ℃ (200 revolutions per minute) for 72 hours. And (3) carrying out sharp quenching, filtering and washing on the crystallized product until the pH value is 7, and drying for 12 hours at 120 ℃ to obtain the ZSM-5 molecular sieve raw powder. The molar ratio of each raw material in the reaction mixture is as follows: SiO 22/Al2O3＝50，H2O/SiO2＝25.83，NaCl/SiO2＝0.68，NaOH/SiO2＝0.15，TPABr/SiO2＝0.40。
The prepared ZSM-5 molecular sieve raw powder is mixed by 0.2 mol.L-1Soaking in ammonium nitrate solution at solid-to-liquid ratio of 1:15, heating at 90 deg.C, stirring for 2 hr, filtering, and washing. The process is repeated three times, the obtained sample is dried for 6 hours at 120 ℃, and finally roasted for 5 hours at 550 ℃ to obtain the hydrogen type ZSM-5 molecular sieve powder.
Mixing the synthesized ZSM-5 molecular sieve raw powder with boehmite, sesbania powder and water, wherein the weight part ratio of the raw materials is ZSM-5/Al2O3And (3) extruding and forming the powder/water of sesbania/sesbania powder/water of 55:19:1:25, drying the powder at 120 ℃ for 12 hours, and roasting the powder at 550 ℃ for 5 hours to obtain the formed hydrogen type molecular sieve with the diameter of 1.0mm and the length of 3.0 mm.
2. Catalyst preparation
1L of hydrogen type molecular sieve was mixed with 0.6L of phosphoric acid aqueous solution (containing P25 g), dried at 110 ℃ for 6 hours, and calcined at 450 ℃ for 4 hours.
The catalyst contained P25 g/L.
3. Catalyst passivation
Heating catalystThe catalyst bed reaches 80 ℃, and after the temperature is constant, the catalyst bed is treated according to NH3Introducing ethylene oxide and ammonia water with the concentration of 90% into the EO (3) for catalyst passivation treatment, wherein the liquid phase volume space velocity of the ethylene oxide is 2.0 hours-1The deactivation time was 24 hours. After the passivation is finished, the volume airspeed is 10.0 hours-1Liquid ammonia was introduced into the reactor for 10 hours to displace the ammonia.
4. Catalyst evaluation
Catalyst evaluation conditions: the reaction temperature is 80 ℃, the reaction pressure is 6.0MPa, and the liquid NH is3The molar ratio of the EO to the EO is 8, the volume space velocity of the EO liquid phase is 1.2 hours-1Then, catalyst evaluation was performed.
For comparison, the kinds and contents of the modifying elements, and the evaluation results of the catalyst are shown in Table 1.
[ example 3' ]
1. Molecular sieve preparation
Mixing 40 w% silica sol, sodium metaaluminate, tetrapropylammonium bromide (TPABr), sodium chloride, sodium hydroxide and water in sequence, stirring for 180 minutes, putting into a reaction kettle, and dynamically crystallizing at 170 ℃ (200 revolutions per minute) for 72 hours. And (3) carrying out sharp quenching, filtering and washing on the crystallized product until the pH value is 7, and drying for 12 hours at 120 ℃ to obtain the ZSM-5 molecular sieve raw powder. The molar ratio of each raw material in the reaction mixture is as follows: SiO 22/Al2O3＝50，H2O/SiO2＝25.83，NaCl/SiO2＝0.68，NaOH/SiO2＝0.15，TPABr/SiO2＝0.40。
The prepared ZSM-5 molecular sieve raw powder is mixed by 0.2 mol.L-1Soaking in ammonium nitrate solution at solid-to-liquid ratio of 1:15, heating at 90 deg.C, stirring for 2 hr, filtering, and washing. The process is repeated three times, the obtained sample is dried for 6 hours at 120 ℃, and finally roasted for 5 hours at 550 ℃ to obtain the hydrogen type ZSM-5 molecular sieve powder.
Mixing the synthesized ZSM-5 molecular sieve raw powder with boehmite, sesbania powder and water, wherein the weight part ratio of the raw materials is ZSM-5/Al2O3And (3) extruding and forming the powder/water of sesbania/sesbania powder/water of 55:19:1:25, drying the powder at 120 ℃ for 12 hours, and roasting the powder at 550 ℃ for 5 hours to obtain the formed hydrogen type molecular sieve with the diameter of 1.0mm and the length of 3.0 mm.
2. Catalyst preparation
1L of hydrogen type molecular sieve is taken and mixed with 0.6L of potassium hydroxide solution (containing 25g of K), dried for 6 hours at 110 ℃ and roasted for 4 hours at 450 ℃.
The catalyst contained K25 g/L.
3. Catalyst passivation
Heating the catalyst bed to 80 deg.C, and reacting according to NH3Introducing ethylene oxide and ammonia water with the concentration of 90% into the EO (3) for catalyst passivation treatment, wherein the liquid phase volume space velocity of the ethylene oxide is 2.0 hours-1The deactivation time was 24 hours. After the passivation is finished, the volume airspeed is 10.0 hours-1Liquid ammonia was introduced into the reactor for 10 hours to displace the ammonia.
4. Catalyst evaluation
Catalyst evaluation conditions: the reaction temperature is 80 ℃, the reaction pressure is 6.0MPa, and the liquid NH is3The molar ratio of the EO to the EO is 8, the volume space velocity of the EO liquid phase is 1.2 hours-1Then, catalyst evaluation was performed.
For comparison, the kinds and contents of the modifying elements, and the evaluation results of the catalyst are shown in Table 1.
[ example 4' ]
1. Molecular sieve preparation
Mixing 40 w% silica sol, sodium metaaluminate, tetrapropylammonium bromide (TPABr), sodium chloride, sodium hydroxide and water in sequence, stirring for 180 minutes, putting into a reaction kettle, and dynamically crystallizing at 170 ℃ (200 revolutions per minute) for 72 hours. And (3) carrying out sharp quenching, filtering and washing on the crystallized product until the pH value is 7, and drying for 12 hours at 120 ℃ to obtain the ZSM-5 molecular sieve raw powder. The molar ratio of each raw material in the reaction mixture is as follows: SiO 22/Al2O3＝50，H2O/SiO2＝25.83，NaCl/SiO2＝0.68，NaOH/SiO2＝0.15，TPABr/SiO2＝0.40。
The prepared ZSM-5 molecular sieve raw powder is mixed by 0.2 mol.L-1Soaking in ammonium nitrate solution at solid-to-liquid ratio of 1:15, heating at 90 deg.C, stirring for 2 hr, filtering, and washing. This procedure was repeated three times, and the samples were dried at 120 ℃ for 6 hours and finally calcined at 550 ℃ for 5 hours to obtain hydrogenType ZSM-5 molecular sieve powder.
Mixing the synthesized ZSM-5 molecular sieve raw powder with boehmite, sesbania powder and water, wherein the weight part ratio of the raw materials is ZSM-5/Al2O3And (3) extruding and forming the powder/water of sesbania/sesbania powder/water of 55:19:1:25, drying the powder at 120 ℃ for 12 hours, and roasting the powder at 550 ℃ for 5 hours to obtain the formed hydrogen type molecular sieve with the diameter of 1.0mm and the length of 3.0 mm.
2. Catalyst preparation
1L of hydrogen type molecular sieve was mixed with 0.6L of sodium hydroxide solution (containing 25g of Na), dried at 110 ℃ for 6 hours, and calcined at 450 ℃ for 4 hours.
The catalyst contained Na 25 g/L.
3. Catalyst passivation
Heating the catalyst bed to 80 deg.C, and reacting according to NH3Introducing ethylene oxide and ammonia water with the concentration of 90% into the EO (3) for catalyst passivation treatment, wherein the liquid phase volume space velocity of the ethylene oxide is 2.0 hours-1The deactivation time was 24 hours. After the passivation is finished, the volume airspeed is 10.0 hours-1Liquid ammonia was introduced into the reactor for 10 hours to displace the ammonia.
4. Catalyst evaluation
Catalyst evaluation conditions: the reaction temperature is 80 ℃, the reaction pressure is 6.0MPa, and the liquid NH is3The molar ratio of the EO to the EO is 8, the volume space velocity of the EO liquid phase is 1.2 hours-1Then, catalyst evaluation was performed.
For comparison, the kinds and contents of the modifying elements, and the evaluation results of the catalyst are shown in Table 1.
[ example 5' ]
1. Molecular sieve preparation
Mixing 40 w% silica sol, sodium metaaluminate, tetrapropylammonium bromide (TPABr), sodium chloride, sodium hydroxide and water in sequence, stirring for 180 minutes, putting into a reaction kettle, and dynamically crystallizing at 170 ℃ (200 revolutions per minute) for 72 hours. And (3) carrying out sharp quenching, filtering and washing on the crystallized product until the pH value is 7, and drying for 12 hours at 120 ℃ to obtain the ZSM-5 molecular sieve raw powder. The molar ratio of each raw material in the reaction mixture is as follows: SiO 22/Al2O3＝50，H2O/SiO2＝25.83，NaCl/SiO2＝0.68，NaOH/SiO2＝0.15，TPABr/SiO2＝0.40。
The prepared ZSM-5 molecular sieve raw powder is mixed by 0.2 mol.L-1Soaking in ammonium nitrate solution at solid-to-liquid ratio of 1:15, heating at 90 deg.C, stirring for 2 hr, filtering, and washing. The process is repeated three times, the obtained sample is dried for 6 hours at 120 ℃, and finally roasted for 5 hours at 550 ℃ to obtain the hydrogen type ZSM-5 molecular sieve powder.
Mixing the synthesized ZSM-5 molecular sieve raw powder with boehmite, sesbania powder and water, wherein the weight part ratio of the raw materials is ZSM-5/Al2O3And (3) extruding and forming the powder/water of sesbania/sesbania powder/water of 55:19:1:25, drying the powder at 120 ℃ for 12 hours, and roasting the powder at 550 ℃ for 5 hours to obtain the formed hydrogen type molecular sieve with the diameter of 1.0mm and the length of 3.0 mm.
2. Catalyst preparation
1L of hydrogen type molecular sieve was mixed with 0.6L of calcium nitrate solution (containing 25g of Ca), dried at 110 ℃ for 6 hours, and calcined at 450 ℃ for 4 hours.
The catalyst contained 25g/L Ca.
3. Catalyst passivation
Heating the catalyst bed to 80 deg.C, and reacting according to NH3Introducing ethylene oxide and ammonia water with the concentration of 90% into the EO (3) for catalyst passivation treatment, wherein the liquid phase volume space velocity of the ethylene oxide is 2.0 hours-1The deactivation time was 24 hours. After the passivation is finished, the volume airspeed is 10.0 hours-1Liquid ammonia was introduced into the reactor for 10 hours to displace the ammonia.
4. Catalyst evaluation
Catalyst evaluation conditions: the reaction temperature is 80 ℃, the reaction pressure is 6.0MPa, and the liquid NH is3The molar ratio of the EO to the EO is 8, the volume space velocity of the EO liquid phase is 1.2 hours-1Then, catalyst evaluation was performed.
For comparison, the kinds and contents of the modifying elements, and the evaluation results of the catalyst are shown in Table 1.
[ example 6' ]
1. Molecular sieve preparation
Sequentially mixing 40 w% silica sol, sodium metaaluminate, tetrapropylammonium bromide (TPABr), sodium chloride, sodium hydroxide and waterMixing, stirring for 180 min, loading into reactor, dynamic crystallizing at 170 deg.C (200 rpm) for 72 hr. And (3) carrying out sharp quenching, filtering and washing on the crystallized product until the pH value is 7, and drying for 12 hours at 120 ℃ to obtain the ZSM-5 molecular sieve raw powder. The molar ratio of each raw material in the reaction mixture is as follows: SiO 22/Al2O3＝50，H2O/SiO2＝25.83，NaCl/SiO2＝0.68，NaOH/SiO2＝0.15，TPABr/SiO2＝0.40。
The prepared ZSM-5 molecular sieve raw powder is mixed by 0.2 mol.L-1Soaking in ammonium nitrate solution at solid-to-liquid ratio of 1:15, heating at 90 deg.C, stirring for 2 hr, filtering, and washing. The process is repeated three times, the obtained sample is dried for 6 hours at 120 ℃, and finally roasted for 5 hours at 550 ℃ to obtain the hydrogen type ZSM-5 molecular sieve powder.
Mixing the synthesized ZSM-5 molecular sieve raw powder with boehmite, sesbania powder and water, wherein the weight part ratio of the raw materials is ZSM-5/Al2O3And (3) extruding and forming the powder/water of sesbania/sesbania powder/water of 55:19:1:25, drying the powder at 120 ℃ for 12 hours, and roasting the powder at 550 ℃ for 5 hours to obtain the formed hydrogen type molecular sieve with the diameter of 1.0mm and the length of 3.0 mm.
2. Catalyst preparation
1L of hydrogen type molecular sieve is mixed with 0.6L of nickel nitrate solution (containing 25g of Ni), dried at 110 ℃ for 6 hours and roasted at 450 ℃ for 4 hours.
The catalyst contained Ni 25 g/L.
3. Catalyst passivation
Heating the catalyst bed to 80 deg.C, and reacting according to NH3Introducing ethylene oxide and ammonia water with the concentration of 90% into the EO (3) for catalyst passivation treatment, wherein the liquid phase volume space velocity of the ethylene oxide is 2.0 hours-1The deactivation time was 24 hours. After the passivation is finished, the volume airspeed is 10.0 hours-1Liquid ammonia was introduced into the reactor for 10 hours to displace the ammonia.
4. Catalyst evaluation
Catalyst evaluation conditions: the reaction temperature is 80 ℃, the reaction pressure is 6.0MPa, and the liquid NH is3The molar ratio of the EO to the EO is 8, the volume space velocity of the EO liquid phase is 1.2 hours-1Then, catalyst evaluation was performed.
For comparison, the kinds and contents of the modifying elements, and the evaluation results of the catalyst are shown in Table 1.
[ example 7' ]
1. Molecular sieve preparation
Mixing 40 w% silica sol, sodium metaaluminate, tetrapropylammonium bromide (TPABr), sodium chloride, sodium hydroxide and water in sequence, stirring for 180 minutes, putting into a reaction kettle, and dynamically crystallizing at 170 ℃ (200 revolutions per minute) for 72 hours. And (3) carrying out sharp quenching, filtering and washing on the crystallized product until the pH value is 7, and drying for 12 hours at 120 ℃ to obtain the ZSM-5 molecular sieve raw powder. The molar ratio of each raw material in the reaction mixture is as follows: SiO 22/Al2O3＝50，H2O/SiO2＝25.83，NaCl/SiO2＝0.68，NaOH/SiO2＝0.15，TPABr/SiO2＝0.40。
The prepared ZSM-5 molecular sieve raw powder is mixed by 0.2 mol.L-1Soaking in ammonium nitrate solution at solid-to-liquid ratio of 1:15, heating at 90 deg.C, stirring for 2 hr, filtering, and washing. The process is repeated three times, the obtained sample is dried for 6 hours at 120 ℃, and finally roasted for 5 hours at 550 ℃ to obtain the hydrogen type ZSM-5 molecular sieve powder.
Mixing the synthesized ZSM-5 molecular sieve raw powder with boehmite, sesbania powder and water, wherein the weight part ratio of the raw materials is ZSM-5/Al2O3And (3) extruding and forming the powder/water of sesbania/sesbania powder/water of 55:19:1:25, drying the powder at 120 ℃ for 12 hours, and roasting the powder at 550 ℃ for 5 hours to obtain the formed hydrogen type molecular sieve with the diameter of 1.0mm and the length of 3.0 mm.
2. Catalyst preparation
1L of hydrogen type molecular sieve is taken and mixed with 0.6L of mixed solution of lanthanum acetate and phosphoric acid (containing 20g of La and 5g of P), dried for 6 hours at 110 ℃, and roasted for 4 hours at 450 ℃.
The catalyst contains 20g/L of La and 5g/L of P.
3. Catalyst passivation
Heating the catalyst bed to 80 deg.C, and reacting according to NH3Introducing ethylene oxide and ammonia water with the concentration of 90% into the EO (3) for catalyst passivation treatment, wherein the liquid phase volume space velocity of the ethylene oxide is 2.0 hours-1The passivation time is 24 hoursThen (c) is performed. After the passivation is finished, the volume airspeed is 10.0 hours-1Liquid ammonia was introduced into the reactor for 10 hours to displace the ammonia.
4. Catalyst evaluation
Catalyst evaluation conditions: the reaction temperature is 80 ℃, the reaction pressure is 6.0MPa, and the liquid NH is3The molar ratio of the EO to the EO is 8, the volume space velocity of the EO liquid phase is 1.2 hours-1Then, catalyst evaluation was performed.
For comparison, the kinds and contents of the modifying elements, and the evaluation results of the catalyst are shown in Table 1.
[ example 8' ]
1. Molecular sieve preparation
Mixing 40 w% silica sol, sodium metaaluminate, tetrapropylammonium bromide (TPABr), sodium chloride, sodium hydroxide and water in sequence, stirring for 180 minutes, putting into a reaction kettle, and dynamically crystallizing at 170 ℃ (200 revolutions per minute) for 72 hours. And (3) carrying out sharp quenching, filtering and washing on the crystallized product until the pH value is 7, and drying for 12 hours at 120 ℃ to obtain the ZSM-5 molecular sieve raw powder. The molar ratio of each raw material in the reaction mixture is as follows: SiO 22/Al2O3＝50，H2O/SiO2＝25.83，NaCl/SiO2＝0.68，NaOH/SiO2＝0.15，TPABr/SiO2＝0.40。
The prepared ZSM-5 molecular sieve raw powder is mixed by 0.2 mol.L-1Soaking in ammonium nitrate solution at solid-to-liquid ratio of 1:15, heating at 90 deg.C, stirring for 2 hr, filtering, and washing. The process is repeated three times, the obtained sample is dried for 6 hours at 120 ℃, and finally roasted for 5 hours at 550 ℃ to obtain the hydrogen type ZSM-5 molecular sieve powder.
Mixing the synthesized ZSM-5 molecular sieve raw powder with boehmite, sesbania powder and water, wherein the weight part ratio of the raw materials is ZSM-5/Al2O3And (3) extruding and forming the powder/water of sesbania/sesbania powder/water of 55:19:1:25, drying the powder at 120 ℃ for 12 hours, and roasting the powder at 550 ℃ for 5 hours to obtain the formed hydrogen type molecular sieve with the diameter of 1.0mm and the length of 3.0 mm.
2. Catalyst preparation
1L of hydrogen type molecular sieve is taken and mixed with 0.6L of mixed solution of lanthanum oxalate and potassium acetate (containing 20g of La and 5g of K), dried for 6 hours at 110 ℃ and roasted for 4 hours at 450 ℃.
The catalyst contains 20g/L of La and 5g/L of K.
3. Catalyst passivation
Heating the catalyst bed to 80 deg.C, and reacting according to NH3Introducing ethylene oxide and ammonia water with the concentration of 90% into the EO (3) for catalyst passivation treatment, wherein the liquid phase volume space velocity of the ethylene oxide is 2.0 hours-1The deactivation time was 24 hours. After the passivation is finished, the volume airspeed is 10.0 hours-1Liquid ammonia was introduced into the reactor for 10 hours to displace the ammonia.
4. Catalyst evaluation
Catalyst evaluation conditions: the reaction temperature is 80 ℃, the reaction pressure is 6.0MPa, and the liquid NH is3The molar ratio of the EO to the EO is 8, the volume space velocity of the EO liquid phase is 1.2 hours-1Then, catalyst evaluation was performed.
For comparison, the kinds and contents of the modifying elements, and the evaluation results of the catalyst are shown in Table 1.
[ example 9' ]
1. Molecular sieve preparation
Mixing 40 w% silica sol, sodium metaaluminate, tetrapropylammonium bromide (TPABr), sodium chloride, sodium hydroxide and water in sequence, stirring for 180 minutes, putting into a reaction kettle, and dynamically crystallizing at 170 ℃ (200 revolutions per minute) for 72 hours. And (3) carrying out sharp quenching, filtering and washing on the crystallized product until the pH value is 7, and drying for 12 hours at 120 ℃ to obtain the ZSM-5 molecular sieve raw powder. The molar ratio of each raw material in the reaction mixture is as follows: SiO 22/Al2O3＝50，H2O/SiO2＝25.83，NaCl/SiO2＝0.68，NaOH/SiO2＝0.15，TPABr/SiO2＝0.40。
The prepared ZSM-5 molecular sieve raw powder is mixed by 0.2 mol.L-1Soaking in ammonium nitrate solution at solid-to-liquid ratio of 1:15, heating at 90 deg.C, stirring for 2 hr, filtering, and washing. The process is repeated three times, the obtained sample is dried for 6 hours at 120 ℃, and finally roasted for 5 hours at 550 ℃ to obtain the hydrogen type ZSM-5 molecular sieve powder.
Mixing the synthesized ZSM-5 molecular sieve raw powder with boehmite, sesbania powder and water, wherein the weight part ratio of the raw materials is ZSM-5/Al2O3And (3) extruding and forming the powder/water of sesbania/sesbania powder/water of 55:19:1:25, drying the powder at 120 ℃ for 12 hours, and roasting the powder at 550 ℃ for 5 hours to obtain the formed hydrogen type molecular sieve with the diameter of 1.0mm and the length of 3.0 mm.
2. Catalyst preparation
1L of hydrogen type molecular sieve is taken and mixed with 0.6L of mixed solution of lanthanum nitrate and sodium acetate (containing 20g of La and 5g of Na), dried for 6 hours at 110 ℃, and roasted for 4 hours at 450 ℃.
The catalyst contained 20g/L of La and 5g/L of Na.
3. Catalyst passivation
Heating the catalyst bed to 80 deg.C, and reacting according to NH3Introducing ethylene oxide and ammonia water with the concentration of 90% into the EO (3) for catalyst passivation treatment, wherein the liquid phase volume space velocity of the ethylene oxide is 2.0 hours-1The deactivation time was 24 hours. After the passivation is finished, the volume airspeed is 10.0 hours-1Liquid ammonia was introduced into the reactor for 10 hours to displace the ammonia.
4. Catalyst evaluation
Catalyst evaluation conditions: the reaction temperature is 80 ℃, the reaction pressure is 6.0MPa, and the liquid NH is3The molar ratio of the EO to the EO is 8, the volume space velocity of the EO liquid phase is 1.2 hours-1Then, catalyst evaluation was performed.
For comparison, the kinds and contents of the modifying elements, and the evaluation results of the catalyst are shown in Table 1.
[ example 10' ]
1. Molecular sieve preparation
Mixing 40 w% silica sol, sodium metaaluminate, tetrapropylammonium bromide (TPABr), sodium chloride, sodium hydroxide and water in sequence, stirring for 180 minutes, putting into a reaction kettle, and dynamically crystallizing at 170 ℃ (200 revolutions per minute) for 72 hours. And (3) carrying out sharp quenching, filtering and washing on the crystallized product until the pH value is 7, and drying for 12 hours at 120 ℃ to obtain the ZSM-5 molecular sieve raw powder. The molar ratio of each raw material in the reaction mixture is as follows: SiO 22/Al2O3＝50，H2O/SiO2＝25.83，NaCl/SiO2＝0.68，NaOH/SiO2＝0.15，TPABr/SiO2＝0.40。
The prepared ZSM-5 molecular sieve raw powder is mixed by 0.2 mol.L-1Soaking in ammonium nitrate solution at solid-to-liquid ratio of 1:15, heating at 90 deg.C, stirring for 2 hr, filtering, and washing. The process is repeated three times, the obtained sample is dried for 6 hours at 120 ℃, and finally roasted for 5 hours at 550 ℃ to obtain the hydrogen type ZSM-5 molecular sieve powder.
Mixing the synthesized ZSM-5 molecular sieve raw powder with boehmite, sesbania powder and water, wherein the weight part ratio of the raw materials is ZSM-5/Al2O3And (3) extruding and forming the powder/water of sesbania/sesbania powder/water of 55:19:1:25, drying the powder at 120 ℃ for 12 hours, and roasting the powder at 550 ℃ for 5 hours to obtain the formed hydrogen type molecular sieve with the diameter of 1.0mm and the length of 3.0 mm.
2. Catalyst preparation
1L of hydrogen type molecular sieve is taken and mixed with 0.6L of mixed solution of lanthanum nitrate and calcium nitrate (containing 20g of La and 5g of Ca), dried for 6 hours at 110 ℃ and roasted for 4 hours at 450 ℃.
The catalyst contains 20g/L of La and 5g/L of Ca.
3. Catalyst passivation
Heating the catalyst bed to 80 deg.C, and reacting according to NH3Introducing ethylene oxide and ammonia water with the concentration of 90% into the EO (3) for catalyst passivation treatment, wherein the liquid phase volume space velocity of the ethylene oxide is 2.0 hours-1The deactivation time was 24 hours. After the passivation is finished, the volume airspeed is 10.0 hours-1Liquid ammonia was introduced into the reactor for 10 hours to displace the ammonia.
4. Catalyst evaluation
Catalyst evaluation conditions: the reaction temperature is 80 ℃, the reaction pressure is 6.0MPa, and the liquid NH is3The molar ratio of the EO to the EO is 8, the volume space velocity of the EO liquid phase is 1.2 hours-1Then, catalyst evaluation was performed.
For comparison, the kinds and contents of the modifying elements, and the evaluation results of the catalyst are shown in Table 1.
[ example 11' ]
1. Molecular sieve preparation
Mixing 40 w% silica sol, sodium metaaluminate, tetrapropylammonium bromide (TPABr), sodium chloride, sodium hydroxide and water in sequence, stirring for 180 minutes, putting into a reaction kettle, and dynamically crystallizing at 170 ℃ (200 revolutions per minute) for 72 hours. Quenching and filtering crystallized productWashing with water until the pH value is 7, and drying at 120 ℃ for 12 hours to obtain ZSM-5 molecular sieve raw powder. The molar ratio of each raw material in the reaction mixture is as follows: SiO 22/Al2O3＝50，H2O/SiO2＝25.83，NaCl/SiO2＝0.68，NaOH/SiO2＝0.15，TPABr/SiO2＝0.40。
The prepared ZSM-5 molecular sieve raw powder is mixed by 0.2 mol.L-1Soaking in ammonium nitrate solution at solid-to-liquid ratio of 1:15, heating at 90 deg.C, stirring for 2 hr, filtering, and washing. The process is repeated three times, the obtained sample is dried for 6 hours at 120 ℃, and finally roasted for 5 hours at 550 ℃ to obtain the hydrogen type ZSM-5 molecular sieve powder.
Mixing the synthesized ZSM-5 molecular sieve raw powder with boehmite, sesbania powder and water, wherein the weight part ratio of the raw materials is ZSM-5/Al2O3And (3) extruding and forming the powder/water of sesbania/sesbania powder/water of 55:19:1:25, drying the powder at 120 ℃ for 12 hours, and roasting the powder at 550 ℃ for 5 hours to obtain the formed hydrogen type molecular sieve with the diameter of 1.0mm and the length of 3.0 mm.
2. Catalyst preparation
1L of hydrogen type molecular sieve is taken and mixed with 0.6L of mixed solution of lanthanum nitrate and nickel acetate (containing 20g of La and 5g of Ni), dried for 6 hours at 110 ℃, and roasted for 4 hours at 450 ℃.
The catalyst contains 20g/L of La and 5g/L of Ni.
3. Catalyst passivation
Heating the catalyst bed to 80 deg.C, and reacting according to NH3Introducing ethylene oxide and ammonia water with the concentration of 90% into the EO (3) for catalyst passivation treatment, wherein the liquid phase volume space velocity of the ethylene oxide is 2.0 hours-1The deactivation time was 24 hours. After the passivation is finished, the volume airspeed is 10.0 hours-1Liquid ammonia was introduced into the reactor for 10 hours to displace the ammonia.
4. Catalyst evaluation
Catalyst evaluation conditions: the reaction temperature is 80 ℃, the reaction pressure is 6.0MPa, and the liquid NH is3The molar ratio of the EO to the EO is 8, the volume space velocity of the EO liquid phase is 1.2 hours-1Then, catalyst evaluation was performed.
For comparison, the kinds and contents of the modifying elements, and the evaluation results of the catalyst are shown in Table 1.
[ example 12' ]
1. Molecular sieve preparation
Mixing 40 w% silica sol, sodium metaaluminate, tetrapropylammonium bromide (TPABr), sodium chloride, sodium hydroxide and water in sequence, stirring for 180 minutes, putting into a reaction kettle, and dynamically crystallizing at 170 ℃ (200 revolutions per minute) for 72 hours. And (3) carrying out sharp quenching, filtering and washing on the crystallized product until the pH value is 7, and drying for 12 hours at 120 ℃ to obtain the ZSM-5 molecular sieve raw powder. The molar ratio of each raw material in the reaction mixture is as follows: SiO 22/Al2O3＝50，H2O/SiO2＝25.83，NaCl/SiO2＝0.68，NaOH/SiO2＝0.15，TPABr/SiO2＝0.40。
The prepared ZSM-5 molecular sieve raw powder is mixed by 0.2 mol.L-1Soaking in ammonium nitrate solution at solid-to-liquid ratio of 1:15, heating at 90 deg.C, stirring for 2 hr, filtering, and washing. The process is repeated three times, the obtained sample is dried for 6 hours at 120 ℃, and finally roasted for 5 hours at 550 ℃ to obtain the hydrogen type ZSM-5 molecular sieve powder.
Mixing the synthesized ZSM-5 molecular sieve raw powder with boehmite, sesbania powder and water, wherein the weight part ratio of the raw materials is ZSM-5/Al2O3And (3) extruding and forming the powder/water of sesbania/sesbania powder/water of 55:19:1:25, drying the powder at 120 ℃ for 12 hours, and roasting the powder at 550 ℃ for 5 hours to obtain the formed hydrogen type molecular sieve with the diameter of 1.0mm and the length of 3.0 mm.
2. Catalyst preparation
1L of hydrogen type molecular sieve is taken and mixed with 0.6L of mixed solution (containing 20g of La, 2.5g of P and 2.5g of K) of lanthanum nitrate, phosphoric acid and potassium carbonate, dried for 6 hours at 110 ℃ and roasted for 4 hours at 450 ℃.
The catalyst contains 20g/L of La, 2.5g/L of P and 2.5g/L of K.
3. Catalyst passivation
Heating the catalyst bed to 80 deg.C, and reacting according to NH3Introducing ethylene oxide and ammonia water with the concentration of 90% into the EO (3) for catalyst passivation treatment, wherein the liquid phase volume space velocity of the ethylene oxide is 2.0 hours-1The deactivation time was 24 hours. After the passivation is finished, the volume airspeed is 10.0 hours-1Liquid ammonia was introduced into the reactor for 10 hours to displace the ammonia.
4. Catalyst evaluation
Catalyst evaluation conditions: the reaction temperature is 80 ℃, the reaction pressure is 6.0MPa, and the liquid NH is3The molar ratio of the EO to the EO is 8, the volume space velocity of the EO liquid phase is 1.2 hours-1Then, catalyst evaluation was performed.
For comparison, the kinds and contents of the modifying elements, and the evaluation results of the catalyst are shown in Table 1.
[ example 13' ]
1. Molecular sieve preparation
Mixing 40 w% silica sol, sodium metaaluminate, tetrapropylammonium bromide (TPABr), sodium chloride, sodium hydroxide and water in sequence, stirring for 180 minutes, putting into a reaction kettle, and dynamically crystallizing at 170 ℃ (200 revolutions per minute) for 72 hours. And (3) carrying out sharp quenching, filtering and washing on the crystallized product until the pH value is 7, and drying for 12 hours at 120 ℃ to obtain the ZSM-5 molecular sieve raw powder. The molar ratio of each raw material in the reaction mixture is as follows: SiO 22/Al2O3＝50，H2O/SiO2＝25.83，NaCl/SiO2＝0.68，NaOH/SiO2＝0.15，TPABr/SiO2＝0.40。
The prepared ZSM-5 molecular sieve raw powder is mixed by 0.2 mol.L-1Soaking in ammonium nitrate solution at solid-to-liquid ratio of 1:15, heating at 90 deg.C, stirring for 2 hr, filtering, and washing. The process is repeated three times, the obtained sample is dried for 6 hours at 120 ℃, and finally roasted for 5 hours at 550 ℃ to obtain the hydrogen type ZSM-5 molecular sieve powder.
Mixing the synthesized ZSM-5 molecular sieve raw powder with boehmite, sesbania powder and water, wherein the weight part ratio of the raw materials is ZSM-5/Al2O3And (3) extruding and forming the powder/water of sesbania/sesbania powder/water of 55:19:1:25, drying the powder at 120 ℃ for 12 hours, and roasting the powder at 550 ℃ for 5 hours to obtain the formed hydrogen type molecular sieve with the diameter of 1.0mm and the length of 3.0 mm.
2. Catalyst preparation
1L of hydrogen type molecular sieve is taken and mixed with 0.6L of mixed solution of lanthanum nitrate, phosphoric acid and calcium carbonate (containing 20g of La, 2.5g of P and 2.5g of Ca), dried for 6 hours at 110 ℃ and roasted for 4 hours at 450 ℃.
The catalyst contained 20g/L of La, 2.5g/L of P and 2.5g/L of Ca.
3. Catalyst passivation
Heating the catalyst bed to 80 deg.C, and reacting according to NH3Introducing ethylene oxide and ammonia water with the concentration of 90% into the EO (3) for catalyst passivation treatment, wherein the liquid phase volume space velocity of the ethylene oxide is 2.0 hours-1The deactivation time was 24 hours. After the passivation is finished, the volume airspeed is 10.0 hours-1Liquid ammonia was introduced into the reactor for 10 hours to displace the ammonia.
4. Catalyst evaluation
Catalyst evaluation conditions: the reaction temperature is 80 ℃, the reaction pressure is 6.0MPa, and the liquid NH is3The molar ratio of the EO to the EO is 8, the volume space velocity of the EO liquid phase is 1.2 hours-1Then, catalyst evaluation was performed.
For comparison, the kinds and contents of the modifying elements, and the evaluation results of the catalyst are shown in Table 1.
[ example 14' ]
1. Molecular sieve preparation
Mixing 40 w% silica sol, sodium metaaluminate, tetrapropylammonium bromide (TPABr), sodium chloride, sodium hydroxide and water in sequence, stirring for 180 minutes, putting into a reaction kettle, and dynamically crystallizing at 170 ℃ (200 revolutions per minute) for 72 hours. And (3) carrying out sharp quenching, filtering and washing on the crystallized product until the pH value is 7, and drying for 12 hours at 120 ℃ to obtain the ZSM-5 molecular sieve raw powder. The molar ratio of each raw material in the reaction mixture is as follows: SiO 22/Al2O3＝50，H2O/SiO2＝25.83，NaCl/SiO2＝0.68，NaOH/SiO2＝0.15，TPABr/SiO2＝0.40。
The prepared ZSM-5 molecular sieve raw powder is mixed by 0.2 mol.L-1Soaking in ammonium nitrate solution at solid-to-liquid ratio of 1:15, heating at 90 deg.C, stirring for 2 hr, filtering, and washing. The process is repeated three times, the obtained sample is dried for 6 hours at 120 ℃, and finally roasted for 5 hours at 550 ℃ to obtain the hydrogen type ZSM-5 molecular sieve powder.
Mixing the synthesized ZSM-5 molecular sieve raw powder with boehmite, sesbania powder and water, wherein the weight part ratio of the raw materials is ZSM-5/Al2O3A preparation method of a medicated dietAnd (3) extruding and forming the green coke powder/water (55: 19:1: 25), drying at 120 ℃ for 12 hours, and roasting at 550 ℃ for 5 hours to obtain the formed hydrogen type molecular sieve with the diameter of 1.0mm and the length of 3.0 mm.
2. Catalyst preparation
1L of hydrogen type molecular sieve is taken and mixed with 0.6L of mixed solution of lanthanum nitrate, phosphoric acid and nickel nitrate (containing 20g of La, 2.5g of P and 2.5g of Ni), dried at 110 ℃ for 6 hours and roasted at 450 ℃ for 4 hours.
The catalyst contains 20g/L of La, 2.5g/L of P and 2.5g/L of Ni.
3. Catalyst passivation
Heating the catalyst bed to 80 deg.C, and reacting according to NH3Introducing ethylene oxide and ammonia water with the concentration of 90% into the EO (3) for catalyst passivation treatment, wherein the liquid phase volume space velocity of the ethylene oxide is 2.0 hours-1The deactivation time was 24 hours. After the passivation is finished, the volume airspeed is 10.0 hours-1Liquid ammonia was introduced into the reactor for 10 hours to displace the ammonia.
4. Catalyst evaluation
Catalyst evaluation conditions: the reaction temperature is 80 ℃, the reaction pressure is 6.0MPa, and the liquid NH is3The molar ratio of the EO to the EO is 8, the volume space velocity of the EO liquid phase is 1.2 hours-1Then, catalyst evaluation was performed.
For comparison, the kinds and contents of the modifying elements, and the evaluation results of the catalyst are shown in Table 1.
[ example 15' ]
1. Molecular sieve preparation
Mixing 40 w% silica sol, sodium metaaluminate, tetrapropylammonium bromide (TPABr), sodium chloride, sodium hydroxide and water in sequence, stirring for 180 minutes, putting into a reaction kettle, and dynamically crystallizing at 170 ℃ (200 revolutions per minute) for 72 hours. And (3) carrying out sharp quenching, filtering and washing on the crystallized product until the pH value is 7, and drying for 12 hours at 120 ℃ to obtain the ZSM-5 molecular sieve raw powder. The molar ratio of each raw material in the reaction mixture is as follows: SiO 22/Al2O3＝50，H2O/SiO2＝25.83，NaCl/SiO2＝0.68，NaOH/SiO2＝0.15，TPABr/SiO2＝0.40。
The prepared ZSM-5 molecular sieveThe raw powder is added in an amount of 0.2 mol.L-1Soaking in ammonium nitrate solution at solid-to-liquid ratio of 1:15, heating at 90 deg.C, stirring for 2 hr, filtering, and washing. The process is repeated three times, the obtained sample is dried for 6 hours at 120 ℃, and finally roasted for 5 hours at 550 ℃ to obtain the hydrogen type ZSM-5 molecular sieve powder.
Mixing the synthesized ZSM-5 molecular sieve raw powder with boehmite, sesbania powder and water, wherein the weight part ratio of the raw materials is ZSM-5/Al2O3And (3) extruding and forming the powder/water of sesbania/sesbania powder/water of 55:19:1:25, drying the powder at 120 ℃ for 12 hours, and roasting the powder at 550 ℃ for 5 hours to obtain the formed hydrogen type molecular sieve with the diameter of 1.0mm and the length of 3.0 mm.
2. Catalyst preparation
1L of hydrogen type molecular sieve was taken, mixed with 0.6L of a mixed solution of lanthanum nitrate, sodium hydroxide and calcium nitrate (containing 20g of La, 2.5g of Na and 2.5g of Ca), dried at 110 ℃ for 6 hours, and calcined at 450 ℃ for 4 hours.
The catalyst contained 20g/L of La, 2.5g/L of Na and 2.5g/L of Ca.
3. Catalyst passivation
Heating the catalyst bed to 80 deg.C, and reacting according to NH3Introducing ethylene oxide and ammonia water with the concentration of 90% into the EO (3) for catalyst passivation treatment, wherein the liquid phase volume space velocity of the ethylene oxide is 2.0 hours-1The deactivation time was 24 hours. After the passivation is finished, the volume airspeed is 10.0 hours-1Liquid ammonia was introduced into the reactor for 10 hours to displace the ammonia.
4. Catalyst evaluation
Catalyst evaluation conditions: the reaction temperature is 80 ℃, the reaction pressure is 6.0MPa, and the liquid NH is3The molar ratio of the EO to the EO is 8, the volume space velocity of the EO liquid phase is 1.2 hours-1Then, catalyst evaluation was performed.
For comparison, the kinds and contents of the modifying elements, and the evaluation results of the catalyst are shown in Table 1.
[ example 16' ]
1. Molecular sieve preparation
Mixing 40 w% silica sol, sodium metaaluminate, tetrapropylammonium bromide (TPABr), sodium chloride, sodium hydroxide and water in sequence, stirring for 180 minutes, putting into a reaction kettle, and 170Dynamic crystallization at 200 rpm for 72 hours. And (3) carrying out sharp quenching, filtering and washing on the crystallized product until the pH value is 7, and drying for 12 hours at 120 ℃ to obtain the ZSM-5 molecular sieve raw powder. The molar ratio of each raw material in the reaction mixture is as follows: SiO 22/Al2O3＝50，H2O/SiO2＝25.83，NaCl/SiO2＝0.68，NaOH/SiO2＝0.15，TPABr/SiO2＝0.40。
The prepared ZSM-5 molecular sieve raw powder is mixed by 0.2 mol.L-1Soaking in ammonium nitrate solution at solid-to-liquid ratio of 1:15, heating at 90 deg.C, stirring for 2 hr, filtering, and washing. The process is repeated three times, the obtained sample is dried for 6 hours at 120 ℃, and finally roasted for 5 hours at 550 ℃ to obtain the hydrogen type ZSM-5 molecular sieve powder.
Mixing the synthesized ZSM-5 molecular sieve raw powder with boehmite, sesbania powder and water, wherein the weight part ratio of the raw materials is ZSM-5/Al2O3And (3) extruding and forming the powder/water of sesbania/sesbania powder/water of 55:19:1:25, drying the powder at 120 ℃ for 12 hours, and roasting the powder at 550 ℃ for 5 hours to obtain the formed hydrogen type molecular sieve with the diameter of 1.0mm and the length of 3.0 mm.
2. Catalyst preparation
1L of hydrogen type molecular sieve was taken, mixed with 0.6L of a mixed solution of lanthanum nitrate, sodium hydroxide and calcium nitrate (containing 20g of La, 2.5g of Na and 2.5g of Ca), dried at 110 ℃ for 6 hours, and calcined at 450 ℃ for 4 hours.
The catalyst contained 20g/L of La, 2.5g/L of Na and 2.5g/L of Ca.
3. Catalyst passivation
Heating the catalyst bed to 80 deg.C, and reacting according to NH3Introducing ethylene oxide and liquid ammonia in the proportion of EO (3) for catalyst passivation treatment, wherein the liquid phase volume space velocity of the ethylene oxide is 2.0 hours-1The deactivation time was 24 hours.
4. Catalyst evaluation
Catalyst evaluation conditions: the reaction temperature is 80 ℃, the reaction pressure is 6.0MPa, and the liquid NH is3The molar ratio of the EO to the EO is 8, the volume space velocity of the EO liquid phase is 1.2 hours-1Then, catalyst evaluation was performed.
For comparison, the kinds and contents of the modifying elements, and the evaluation results of the catalyst are shown in Table 1.
TABLE 1
Note: example 16 'is the same as example 15' except that the aqueous ammonia in the passivation mass is replaced by liquid ammonia.
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