阅读说明：本技术 一种合成二元醇单叔丁基醚的催化剂、制备方法及应用 (Catalyst for synthesizing dihydric alcohol mono-tert-butyl ether, preparation method and application ) 是由 龚海燕 刘俊涛 张旭 于 2020-03-30 设计创作，主要内容包括：本发明公开了一种合成二元醇单叔丁基醚的催化剂、制备方法及应用。所述催化剂包括：β分子筛和粘结剂；以β分子筛和粘结剂总重为100重量份计,β分子筛40～90重量份；粘结剂10～60重量份；所述粘结剂为氧化硅；以催化剂总重计,所述催化剂酸量为130～700μmol/g。本发明选用β分子筛为醚化催化剂活性组分,并控制催化剂酸量和强酸比例可有效抑制高温区逆反应和二元醇双叔丁基醚的反应速率,提高异丁烯单程转化率和二元醇单叔丁基醚收率。(The invention discloses a catalyst for synthesizing dihydric alcohol mono-tertiary butyl ether, a preparation method and application thereof. The catalyst comprises: beta molecular sieve and binder; 40-90 parts by weight of beta molecular sieve based on 100 parts by weight of the total weight of the beta molecular sieve and the binder; 10-60 parts of a binder; the binder is silicon oxide; based on the total weight of the catalyst, the acid content of the catalyst is 130-700 mu mol/g. The invention selects beta molecular sieve as the active component of the etherification catalyst, and controls the acid amount of the catalyst and the proportion of strong acid, thereby effectively inhibiting the reverse reaction in a high temperature area and the reaction rate of the dihydric alcohol double tertiary butyl ether, and improving the single-pass conversion rate of isobutene and the yield of the dihydric alcohol single tertiary butyl ether.)

1. A catalyst for synthesizing glycol mono-t-butyl ether, characterized in that the catalyst comprises:

beta molecular sieve and binder;

based on 100 weight portions of the total weight of the beta molecular sieve and the binder,

40-90 parts of beta molecular sieve; preferably 50 to 80 parts by weight;

10-60 parts of a binder; preferably 20 to 50 parts by weight;

based on the total weight of the catalyst, the acid amount of the catalyst is 130-700 mu mol/g, preferably 300-600 mu mol/g.

2. The catalyst of claim 1, wherein:

the binder is silicon oxide.

3. The catalyst of claim 1, wherein:

the strong acid in the catalyst accounts for 10-45% of the total acid amount, and preferably 25-35%.

4. The catalyst of claim 1, wherein:

the catalyst also comprises at least one of Co, La, Ni and Sn;

based on the total weight of the beta molecular sieve and the binder as 100 parts by weight;

at least one of Co, La, Ni and Sn in an amount of 0.1 to 3 parts by weight.

5. The catalyst of claim 1, wherein:

the catalyst further comprises P;

based on the total weight of the beta molecular sieve and the binder as 100 parts by weight; the content of P is 0.1-3 parts by weight.

6. A process for preparing a catalyst as claimed in any one of claims 1 to 5, characterized in that it comprises:

mixing, kneading and tabletting or extruding strip forming, drying and roasting the beta molecular sieve, the pore-forming agent and the binder to obtain a catalyst precursor;

adding a catalyst precursor into an acid-containing aqueous solution, soaking for 4-20 hours at 70-100 ℃ in an excessive manner, washing, drying and roasting to obtain the catalyst; the acid-containing aqueous solution is an aqueous solution containing citric acid, nitric acid or acetic acid;

the roasting temperature is 400-600 ℃.

7. The method of claim 6, wherein:

the concentration of the acid-containing aqueous solution is 0.03-1 mol/l, preferably 0.03-0.25 mol/l.

8. The method of preparing a catalyst according to claim 6, wherein:

the method comprises the steps of (3) preparing a solution by using at least one soluble salt of Co, La, Ni and Sn and/or phosphoric acid or ammonium dihydrogen phosphate to impregnate the catalyst obtained in the step (2), and drying and roasting the catalyst to obtain the catalyst;

the roasting temperature is 400-600 ℃.

9. Use of a catalyst according to any one of claims 1 to 5 or prepared by a process according to any one of claims 6 to 8 in the synthesis of glycol mono-tert-butyl ether, wherein:

using a stream containing isobutene and dihydric alcohol as raw materials, wherein the conditions for contacting the stream containing isobutene and the dihydric alcohol with a catalyst comprise: the contact temperature is 80-140 DEG CThe pressure is 1-4.0 MPa, and the weight space velocity of the material flow containing isobutene is 1-15 hours^-1The molar ratio of the dihydric alcohol to the isobutene is 1.1-15: 1; the preferable contact temperature is 90-130 ℃, the pressure is 1-4.0 MPa, and the weight space velocity of the material flow containing isobutene is 3-10 hours^-1The molar ratio of the dihydric alcohol to the isobutene is 2-10: 1.

10. The use of claim 9, wherein:

the dihydric alcohol contains 0.1 wt% -10 wt% of water.

Technical Field

The invention relates to the technical field of chemical synthesis, in particular to a catalyst for synthesizing dihydric alcohol mono-tertiary butyl ether, a preparation method and application.

Background

The dihydric alcohol mono-tertiary butyl ether is a substance which has both hydroxyl and ether structures, and the two groups have hydrophilicity and lipophilicity respectively, so that the dihydric alcohol mono-tertiary butyl ether can dissolve hydrophobic and water-soluble compounds simultaneously, and is a universal solvent with excellent performance. It is mainly used as industrial solvent and has wide application in coating, cleaning, printing, leather and other fields.

The current route to ethylene oxide is the only method of industrial production of primary alcohol glycol ethers. However, when tertiary alcohol is used, the tertiary alcohol is difficult to react with ethylene oxide, the selectivity of the monoethylene glycol ether is particularly low, and ethylene oxide oligomers with higher molecular weight are mainly generated, so that the technological route of ethylene glycol mono-tert-butyl ether is a technical route which adopts dihydric alcohol and isobutene as raw materials instead of the reaction of tert-butyl alcohol and ethylene oxide. In the 60 s, U.S. Pat. No. 3,3170000 disclosed a process for preparing ethylene glycol mono-tert-butyl ether from Ethylene Glycol (EG) and Isobutylene (IB) in the presence of an acidic catalyst. In the 70 s, with the construction of large-scale cracking units, many countries began to focus on the production of ethylene glycol mono-t-butyl ether from EG and mixed C4 fractions as raw materials, starting from the comprehensive utilization of mixed C4 fractions extracted from butadiene. In the early 80 s, Nippon Wanshan oil company adopted the process route to build a 5000 ton/year ethylene glycol tert-butyl ether production device.

At present, strong acid resin is generally adopted as a catalyst in the technology, and most of the resin can not resist high temperature, and the reverse reaction of etherification can be accelerated at high temperature to influence the conversion rate, so that the reaction is carried out at a lower temperature. However, because the viscosity of the dihydric alcohol is very high at low temperature and the solubility of isobutene in the dihydric alcohol is low, the dihydric alcohol and the isobutene are difficult to mix, so that the reaction rate is slow, more byproducts such as isobutene oligomers or di-tert-butyl ether of the dihydric alcohol are generated, and the selectivity of the target product dihydric alcohol mono-tert-butyl ether is low.

For example, the document "petrochemical 1997, volume 26, pages 112-116, describes the synthesis of ethylene glycol mono-tert-butyl ether from isobutene and ethylene glycol under the catalysis of cation exchange resin at a reaction temperature of 45-65 ℃, but the selectivity of the ethylene glycol mono-tert-butyl ether under the optimal condition is 84%.

Therefore, the improvement of the selectivity and yield of the ethylene glycol mono-tert-butyl ether is a technical problem to be solved urgently at present.

Disclosure of Invention

In order to solve the problems in the prior art, the invention provides a catalyst for synthesizing dihydric alcohol mono-tertiary butyl ether, a preparation method and application thereof. The beta molecular sieve is used as an active component of the etherification catalyst, and the acid amount of the catalyst and the proportion of strong acid are controlled, so that the reverse reaction in a high-temperature area and the reaction rate of the dihydric alcohol double-tert-butyl ether can be effectively inhibited, and the single-pass conversion rate of isobutene and the yield of the dihydric alcohol single-tert-butyl ether are improved.

One of the objects of the present invention is to provide a catalyst for synthesizing glycol mono-t-butyl ether.

The catalyst comprises:

beta molecular sieve and binder;

based on 100 weight portions of the total weight of the beta molecular sieve and the binder,

40-90 parts of beta molecular sieve; preferably 50 to 80 parts by weight;

10-60 parts of a binder; preferably 20 to 50 parts by weight.

The binder is silicon oxide;

based on the total weight of the catalyst, the acid amount of the catalyst is 130-700 mu mol/g, preferably 300-600 mu mol/g;

wherein the content of the first and second substances,

the strong acid in the catalyst accounts for 10-45% of the total acid amount, and preferably accounts for 25-35%.

In the invention, the ratio of strong acid to total acid is the peak area ratio of NH3 TPD during characterization, and the test method is shown in the example.

Since the reaction of isobutylene and glycol is a series reaction, the formation of glycol mono-tertiary-butyl ether as the main reaction is only the first step of the reaction, and the inventors have a breakthrough discovery that: the strength of the acid in the catalyst and the total amount of the acid affect the selectivity of the reaction, and the strength and the total amount of the acid must be controlled within a certain range to improve the yield of the target product.

In a preferred embodiment of the present invention,

the catalyst also comprises at least one of Co, La, Ni and Sn;

based on the total weight of the beta molecular sieve and the binder as 100 parts by weight;

at least one of Co, La, Ni and Sn in an amount of 0.1 to 3 parts by weight.

In a preferred embodiment of the present invention,

the catalyst further comprises P;

based on the total weight of the beta molecular sieve and the binder as 100 parts by weight; the content of P is 0.1-3 parts by weight.

The addition of the above-mentioned auxiliaries during the preparation of the catalyst is advantageous for optimizing the acid quantity and the strong acid ratio.

The second purpose of the invention is to provide a preparation method of the catalyst for synthesizing the glycol mono-tertiary butyl ether.

The method comprises the following steps:

mixing, kneading and tabletting or extruding strip forming, drying and roasting the beta molecular sieve, the pore-forming agent and the binder to obtain a catalyst precursor;

the pore-foaming agent is a pore-foaming agent commonly used in the prior art, such as: sesbania powder, methyl cellulose, hydroxymethyl cellulose, urea ammonium bicarbonate and the like, and the skilled person can select the sesbania powder, the methyl cellulose, the hydroxymethyl cellulose, the urea ammonium bicarbonate and the like according to actual conditions.

And (2) adding the catalyst precursor into an acid-containing solution, soaking for 4-20 hours at the temperature of 90-110 ℃ in an excessive manner, washing, drying and roasting to obtain the catalyst.

The acid-containing aqueous solution is an aqueous solution containing citric acid, nitric acid or acetic acid. The concentration of the acid-containing aqueous solution is preferably 0.03 mol/1-1 mol/l; more preferably 0.03mol/1 to 0.25 mol/l.

The washing may be performed with deionized water.

In a preferred embodiment of the present invention,

the method comprises the step (3) of preparing a solution by using at least one soluble salt of Co, La, Ni and Sn and/or phosphoric acid or ammonium dihydrogen phosphate to impregnate the catalyst obtained in the step (2), and drying and roasting the catalyst to obtain the catalyst.

In a preferred embodiment of the present invention,

in the preparation method, the roasting temperature in the step (1), the step (2) and the step (3) is 400-600 ℃.

The third object of the present invention is to provide a catalyst according to the first object of the present invention or a catalyst obtained by the preparation method according to the second object of the present invention.

The isobutene-containing material flow and dihydric alcohol are used as raw materials, and the contact conditions of the isobutene-containing material flow and the dihydric alcohol with a catalyst comprise the following conditions: the contact temperature is 80-140 ℃, the pressure is 1-4.0 MPa, and the weight space velocity of the material flow containing isobutene is 1-15 hours^-1The molar ratio of the dihydric alcohol to the isobutene is 1.1-15: 1; the preferable contact temperature is 90-130 ℃, the pressure is 1-4.0 MPa, and the weight space velocity of the material flow containing isobutene is 3-10 hours^-1The molar ratio of the dihydric alcohol to the isobutene is 2-10: 1.

The dihydric alcohol is at least one of ethylene glycol, propylene glycol or butanediol.

In a preferred embodiment:

the dihydric alcohol preferably contains 0.1 to 10 percent of water, and the dihydric alcohol contains part of water, so that the reaction selectivity is improved.

The stream containing isobutene is derived from a refinery catalytic cracking unit, an ethylene plant steam cracking unit or a coal-to-olefin unit byproduct mixed C-IV stream, and preferably derived from a refinery catalytic cracking unit, an ethylene plant steam cracking unit or a coal-to-olefin unit byproduct mixed C-IV stream subjected to 1, 3-butadiene removal.

The etherification reaction of the dihydric alcohol and the isobutene is a reversible reaction and a series reaction, wherein the dihydric alcohol mono-tertiary butyl ether is generated firstly in the reaction process, and then the dihydric alcohol di-tertiary butyl ether is generated, so that a proper catalyst is selected to control the kinetic speed of the reaction and increase the selectivity of the dihydric alcohol mono-tertiary butyl ether. At the same time, because isobutylene and the diol are immiscible, the mixing of the raw materials also affects the rate of the reaction and the amount of polyisobutylene as a by-product.

The key point of the invention is that the beta molecular sieve is selected as the active component of the etherification catalyst, and the acid amount of the catalyst and the proportion of strong acid are controlled to effectively inhibit the reverse reaction in a high-temperature area and the reaction rate of the dihydric alcohol di-tert-butyl ether. The viscosity of the raw material dihydric alcohol is reduced, so that the mixing effect of isobutene and the dihydric alcohol is improved, the dimerization of isobutene and the generation of dihydric alcohol double tertiary butyl ether are reduced, and the reaction selectivity is improved. By adopting the method, the single-pass conversion rate of the isobutene can be up to 90.8%, the selectivity of the dihydric alcohol mono-tertiary butyl ether is up to 97.13%, and the yield of the dihydric alcohol mono-tertiary butyl ether is up to 88.19% under the optimal conditions, so that better technical effects are achieved.

Detailed Description

While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.

In the examples of the invention, the test and characterization methods used were as follows:

the invention adopts a temperature programmed adsorption instrument to carry out temperature programmed desorption analysis (NH) of the molecular sieve₃TPD) characterizing the amount of catalyst acid. The test conditions were: the carrier gas flow rate was 50 ml/min. Weighing 0.1g of catalyst sample, placing the catalyst sample into a quartz adsorption tube, introducing carrier gas, raising the temperature to 550 ℃ at the speed of 20 ℃/min, keeping the temperature for 2 hours, and removing impurities adsorbed on the molecular sieve sample. Then reducing the temperature to 100 ℃ at the speed of 20 ℃/min, and keeping the temperature for 30 min; switching the carrier gas to NH₃Keeping the temperature for 30min by using the mixed gas of-He so as to enable the catalyst sample to adsorb NH₃Saturation is achieved; reacting NH₃The mixed gas of-He and high-purity He is switched into carrier gas of high-purity He, the carrier gas is purged for 1h, and NH is adsorbed₃(ii) a Then the temperature is raised to 600 ℃ at the speed of 10 ℃/min, and a temperature programmed desorption curve is obtained. The desorbed ammonia is detected by a thermal conductivity cell. Converting the temperature programmed desorption curve into NH₃Following the desorption rate-temperature profile, the acid amount and strong acid ratio can be obtained by resolution of the peak pattern, as is well known in the art.

In the present invention, the XRF (X-ray fluorescence) method is used to analyze the composition of the catalyst. XRF test conditions were: a Rigaku ZSX 100e type XRF instrument is adopted, a rhodium target is used as an excitation source, the maximum power is 3600W, the tube voltage is 60KV, and the tube current is 120 mA.

In the present invention, the product composition is determined by gas chromatography. Liquid phase product test conditions: chromatography model Agilent 7890A, with FID detector, separation on HP-Innowax capillary chromatography column with programmed temperature start 60 ℃ for 5 minutes, followed by 10 ℃/min ramp up to 240 ℃ for 10 minutes. Gas phase product test conditions: the chromatography model is Agilent 7890A, and is separated by FID detector and alumina capillary chromatography column, wherein the chromatography column is maintained at 50 deg.C for 10 min, and then heated to 220 deg.C at a rate of 10 deg.C/min for 10 min.

In the present invention, the reaction pressure refers to gauge pressure.

Example 1

Step 1: and uniformly mixing 70g of beta molecular sieve powder, 5g of sesbania powder and 75ml of silica sol, adding water, kneading, extruding into strips, forming, drying at 120 ℃, and roasting at 500 ℃ for 4 hours to obtain a catalyst precursor I.

Step 2: preparing 1L of 0.2mol/L citric acid aqueous solution II, soaking the catalyst precursor I in the aqueous solution II at 90 ℃ for 8 hours, washing with deionized water, drying at 120 ℃ and roasting at 500 ℃.

And step 3: 3.3g of tin tetrachloride pentahydrate and 2.4g of phosphoric acid are dissolved in deionized water to obtain a solution III, the solution III is soaked on the catalyst prepared in the step 2, and then the catalyst A1 is obtained after drying at 100 ℃ and roasting at 520 ℃ for 4 hours.

The catalyst composition, total acid amount and strong acid ratio are shown in table 1 a.

Example 2

Step 1: and uniformly mixing 70g of beta molecular sieve powder, 5g of sesbania powder and 75ml of silica sol, adding water, kneading, extruding into strips, forming, drying at 120 ℃, and roasting at 500 ℃ for 4 hours to obtain a catalyst precursor I.

Step 2: preparing 1L of 0.2mol/L citric acid aqueous solution II, soaking the catalyst precursor I in the aqueous solution II at 90 ℃ for 8 hours, washing with deionized water, drying at 120 ℃ and roasting at 500 ℃ for 4 hours.

And step 3: 3.3g of pentahydrate stannic chloride is dissolved in deionized water to obtain a solution III, the solution III is soaked on the catalyst prepared in the step 2, and then the catalyst A2 is obtained after drying at 100 ℃ and roasting at 520 ℃ for 4 hours.

The catalyst composition, total acid amount and strong acid ratio are shown in table 1 a.

Example 3

Step 1: and uniformly mixing 70g of beta molecular sieve powder, 5g of sesbania powder and 75ml of silica sol, adding water, kneading, extruding into strips, forming, drying at 120 ℃, and roasting at 500 ℃ for 4 hours to obtain a catalyst precursor I.

Step 2: preparing 1L of 0.2mol/L citric acid aqueous solution II, soaking the catalyst precursor I in the aqueous solution II at 90 ℃ for 8 hours, washing with deionized water, drying at 120 ℃ and roasting at 500 ℃ for 4 hours to obtain the catalyst A3.

The catalyst composition, total acid amount and strong acid ratio are shown in table 1 a.

Example 4

Step 1: mixing 75g beta molecular sieve powder, 5g ammonium bicarbonate and 63ml silica sol uniformly, adding water, kneading, extruding into strips, forming, drying at 120 ℃, and roasting at 500 ℃ for 4 hours to obtain a catalyst precursor I.

Step 2: preparing 1L of nitric acid aqueous solution II with the concentration of 0.15mol/L, soaking the catalyst precursor I in the aqueous solution II for 8 hours at 90 ℃, washing with deionized water, drying at 120 ℃, and roasting at 500 ℃ for 4 hours to obtain the catalyst A4.

The catalyst composition, total acid amount and strong acid ratio are shown in table 1 a.

Example 5

Step 1: uniformly mixing 90g of beta molecular sieve powder, 5g of sesbania powder and 40ml of silica sol, adding water, kneading, extruding into strips, forming, drying at 120 ℃, and roasting at 500 ℃ for 4 hours to obtain a catalyst precursor I.

Step 2: preparing 1L of acetic acid aqueous solution II with the concentration of 1mol/L, immersing the catalyst precursor I into the aqueous solution II, immersing for 8 hours at 90 ℃, washing with deionized water, drying at 120 ℃, and roasting for 4 hours at 500 ℃ to obtain the catalyst A5.

The catalyst composition, total acid amount and strong acid ratio are shown in table 1 a.

Example 6

Step 1: and uniformly mixing 50g of beta molecular sieve powder, 5g of sesbania powder, 125g of silicon oxide and 75ml of silica sol, adding water, kneading, extruding into strips, molding, drying at 120 ℃, and roasting at 600 ℃ for 4 hours to obtain a catalyst precursor I.

Step 2: preparing 1L of 0.2mol/L citric acid aqueous solution II, soaking the catalyst precursor I in the aqueous solution II at 90 ℃ for 8 hours, washing with deionized water, drying at 120 ℃ and roasting at 500 ℃ for 4 hours to obtain the catalyst A6.

The catalyst composition, total acid amount and strong acid ratio are shown in table 1 a.

Example 7

Step 1: uniformly mixing 40g of beta molecular sieve powder, 5g of sesbania powder, 30g of silicon oxide and 75ml of silica sol, adding water, kneading, extruding into strips, molding, drying at 120 ℃, and roasting at 400 ℃ for 4 hours to obtain a catalyst precursor I.

Step 2: preparing 1L of 0.2mol/L citric acid aqueous solution II, soaking the catalyst precursor I in the aqueous solution II at 90 ℃ for 8 hours, washing with deionized water, drying at 120 ℃ and roasting at 500 ℃ for 4 hours to obtain the catalyst A7.

The catalyst composition, total acid amount and strong acid ratio are shown in table 1 a.

Example 8

Step 1: and uniformly mixing 70g of beta molecular sieve powder, 5g of sesbania powder and 75ml of silica sol, adding water, kneading, extruding into strips, forming, drying at 120 ℃, and roasting at 500 ℃ for 4 hours to obtain a catalyst precursor I.

Step 2: preparing 1L of nitric acid aqueous solution II with the concentration of 0.03mol/L, immersing the catalyst precursor I into the aqueous solution II for 8 hours at 90 ℃, washing with deionized water, drying at 120 ℃ and roasting at 500 ℃.

And step 3: and (3) dissolving 3.4g of lanthanum nitrate and 2.4g of phosphoric acid in deionized water to obtain a solution III, soaking the solution III on the catalyst prepared in the step (2), drying at 100 ℃, and roasting at 520 ℃ for 4 hours to obtain the catalyst A8.

The catalyst composition, total acid amount and strong acid ratio are shown in table 1 a.

Example 9

Step 1: and uniformly mixing 70g of beta molecular sieve powder, 5g of sesbania powder and 75ml of silica sol, adding water, kneading, extruding into strips, forming, drying at 120 ℃, and roasting at 500 ℃ for 4 hours to obtain a catalyst precursor I.

Step 2: preparing 1L of 0.2mol/L acetic acid aqueous solution II, immersing the catalyst precursor I in the aqueous solution II for 8 hours at 90 ℃, washing with deionized water, drying at 120 ℃ and roasting at 500 ℃.

And step 3: 3.3g of cobalt acetate and 2.4g of phosphoric acid are dissolved in deionized water to obtain a solution III, the solution III is soaked on the catalyst prepared in the step 2, and then the catalyst A1 is obtained by drying at 100 ℃ and roasting at 520 ℃ for 4 hours.

The catalyst composition, total acid amount and strong acid ratio are shown in table 1 a.

Example 10

Step 1: and uniformly mixing 70g of beta molecular sieve powder, 5g of sesbania powder and 75ml of silica sol, adding water, kneading, extruding into strips, forming, drying at 120 ℃, and roasting at 500 ℃ for 4 hours to obtain a catalyst precursor I.

Step 2: preparing 1L of 0.2mol/L citric acid aqueous solution II, soaking the catalyst precursor I in the aqueous solution II at 100 ℃ for 4 hours, washing with deionized water, drying at 120 ℃ and roasting at 500 ℃.

And step 3: 3.3g of nickel nitrate and 2.4g of phosphoric acid are dissolved in deionized water to obtain a solution III, the solution III is soaked on the catalyst prepared in the step 2, and then the catalyst A10 is obtained by drying at 100 ℃ and roasting at 520 ℃ for 4 hours.

The catalyst composition, total acid amount and strong acid ratio are shown in table 1 a.

Example 11

Step 1: and uniformly mixing 70g of beta molecular sieve powder, 5g of sesbania powder and 75ml of silica sol, adding water, kneading, extruding into strips, forming, drying at 120 ℃, and roasting at 500 ℃ for 4 hours to obtain a catalyst precursor I.

Step 2: preparing 1L of 0.2mol/L citric acid aqueous solution II, soaking the catalyst precursor I in the aqueous solution II at 95 ℃ for 20 hours, washing with deionized water, drying at 120 ℃ and roasting at 500 ℃.

And step 3: 3.3g of nickel nitrate, 0.7g of lanthanum nitrate and 2.4g of phosphoric acid are dissolved in deionized water to obtain a solution III, the solution III is soaked on the catalyst prepared in the step 2, and then the catalyst A11 is obtained by drying at 100 ℃ and roasting at 520 ℃ for 4 hours.

The catalyst composition, total acid amount and strong acid ratio are shown in table 1 a.

Example 12

Step 1: and uniformly mixing 70g of beta molecular sieve powder, 5g of sesbania powder and 75ml of silica sol, adding water, kneading, extruding into strips, forming, drying at 120 ℃, and roasting at 500 ℃ for 4 hours to obtain a catalyst precursor I.

Step 2: preparing 1L of 0.2mol/L citric acid aqueous solution II, soaking the catalyst precursor I in the aqueous solution II at 90 ℃ for 8 hours, washing with deionized water, drying at 120 ℃ and roasting at 500 ℃.

And step 3: 0.34g of tin tetrachloride pentahydrate and 2.4g of phosphoric acid are dissolved in deionized water to obtain a solution III, the solution III is soaked on the catalyst prepared in the step 2, and then the catalyst A12 is obtained after drying at 100 ℃ and roasting at 520 ℃ for 4 hours.

The catalyst composition, total acid amount and strong acid ratio are shown in table 1 a.

Example 13

Step 1: and uniformly mixing 70g of beta molecular sieve powder, 5g of sesbania powder and 75ml of silica sol, adding water, kneading, extruding into strips, forming, drying at 120 ℃, and roasting at 500 ℃ for 4 hours to obtain a catalyst precursor I.

Step 2: preparing 1L of 0.2mol/L citric acid aqueous solution II, soaking the catalyst precursor I in the aqueous solution II at 90 ℃ for 8 hours, washing with deionized water, drying at 120 ℃ and roasting at 500 ℃.

And step 3: and (3) dissolving 10g of tin tetrachloride pentahydrate and 2.4g of phosphoric acid in deionized water to obtain a solution III, soaking the solution III on the catalyst prepared in the step (2), drying at 100 ℃, and roasting at 520 ℃ for 4 hours to obtain the catalyst A13.

The catalyst composition, total acid amount and strong acid ratio are shown in table 1 a.

Example 14

Step 1: and uniformly mixing 70g of beta molecular sieve powder, 5g of sesbania powder and 75ml of silica sol, adding water, kneading, extruding into strips, forming, drying at 120 ℃, and roasting at 500 ℃ for 4 hours to obtain a catalyst precursor I.

Step 2: preparing 1L of 0.25mol/L citric acid aqueous solution II, soaking the catalyst precursor I in the aqueous solution II at 90 ℃ for 8 hours, washing with deionized water, drying at 120 ℃ and roasting at 500 ℃.

And step 3: 3.3g of tin tetrachloride pentahydrate and 0.4g of ammonium dihydrogen phosphate are dissolved in deionized water to obtain a solution III, the solution III is soaked on the catalyst prepared in the step 2, and then the catalyst A14 is obtained after drying at 100 ℃ and roasting at 520 ℃ for 4 hours.

The catalyst composition, total acid amount and strong acid ratio are shown in table 1 a.

Example 15

Step 1: and uniformly mixing 70g of beta molecular sieve powder, 5g of sesbania powder and 75ml of silica sol, adding water, kneading, extruding into strips, forming, drying at 120 ℃, and roasting at 500 ℃ for 4 hours to obtain a catalyst precursor I.

Step 2: preparing 1L of 0.2mol/L citric acid aqueous solution II, soaking the catalyst precursor I in the aqueous solution II at 90 ℃ for 8 hours, washing with deionized water, drying at 120 ℃ and roasting at 500 ℃.

And step 3: and (3) dissolving 16g of nickel nitrate and 2.3g of 70% phosphoric acid in deionized water to obtain a solution III, soaking the solution III on the catalyst prepared in the step (2), drying at 100 ℃, and roasting at 520 ℃ for 4 hours to obtain the catalyst A14.

The catalyst composition, total acid amount and strong acid ratio are shown in table 1 a.

Application example 1

The catalysts obtained in examples 1 to 15 were charged in a fixed bed reactor to obtain a mixed C containing 5.5% by weight of n-butane, 58.7% by weight of 2-butene, 29.7% by weight of 1-butene and 6.1% by weight of isobutene₄And ethylene glycol containing 0.6 wt% of water as raw materials, at the reaction temperature of 95 ℃, the reaction pressure of 2MPa and the weight space velocity of the mixed C4 of 5 g/g.h^-1The ethylene glycol and isobutene were contacted with a catalyst at a molar ratio of 5 to produce an effluent containing ethylene glycol mono-t-butyl ether, and after the reaction had stabilized for 2 hours, a sample of the product was taken for gas chromatographic analysis, the results of which are shown in Table 1 a.

Application example 2

The catalyst obtained in example 1 was evaluated in the same manner as in application example 1 except that 15.8% by weight of n-butane, 40.1% by weight of isobutane, 18.5% by weight of 2-butene and 12.8% by weight of 1-butene as raw materials of mixed C4 were used% and 12.8% by weight of isobutylene₄The results are shown in Table 1 b.

Application example 3

Catalyst obtained in example 1 the catalyst obtained in example 1 was charged in a fixed bed reactor to obtain a mixed C containing 5.5% by weight of n-butane, 58.7% by weight of 2-butene, 29.7% by weight of 1-butene and 6.1% by weight of isobutene₄The starting material was reacted in contact with a catalyst under the conditions given in Table 2 with a glycol starting material to produce an effluent containing glycol mono-t-butyl ether, and the product was analyzed by gas chromatography, the results of which are given in Table 2.

Application example 4

A3500-hour stability evaluation was carried out on catalyst A1 under the reaction conditions [ application example 1 ] starting from a mixed C4 comprising 5.5% by weight of n-butane, 58.7% by weight of 2-butene, 29.7% by weight of 1-butene and 6.1% by weight of isobutene and from 0.6% by weight of ethylene glycol at a reaction temperature of 95 ℃ and a reaction pressure of 2MPa and a mixed C4 weight space velocity of 5g/g h^-1The ethylene glycol and isobutene contact and react with the catalyst under the condition that the molar ratio of the ethylene glycol to the isobutene is 5 to generate an effluent containing ethylene glycol mono-tert-butyl ether, and the product is subjected to gas chromatography analysis, and the stability test data are shown in a table 3.

After 3500 hours, the conversion of isobutene was 90.1% and the selectivity to ethylene glycol mono-tert-butyl ether was 91.6%. Compared with the initial reaction stage, the conversion rate of isobutene and the selectivity of ethylene glycol tert-butyl ether are basically unchanged, which shows that the catalyst stability is good.

Comparative example 1

Step 1: 70g of beta molecular sieve powder, 5g of sesbania powder, 30g of alumina and nitric acid aqueous solution are kneaded, extruded into strips, molded, dried at 120 ℃ and roasted at 500 ℃ for 4 hours to obtain a catalyst precursor I.

Step 2: preparing 1L of 0.2mol/L citric acid aqueous solution II, soaking the catalyst precursor I in the aqueous solution II at 90 ℃ for 8 hours, washing with deionized water, drying at 120 ℃ and roasting at 500 ℃.

And step 3: 3.3g of tin tetrachloride pentahydrate and 2.4g of phosphoric acid are dissolved in deionized water to obtain a solution III, the solution III is soaked on the catalyst prepared in the step 2, and then the catalyst B1 is obtained by drying at 100 ℃ and roasting at 520 ℃ for 4 hours.

The catalyst composition, total acid amount and strong acid ratio are shown in table 1 a.

The catalyst obtained in comparative example 1 was charged in a fixed bed reactor to obtain a mixed C containing 5.5% by weight of n-butane, 58.7% by weight of 2-butene, 29.7% by weight of 1-butene and 6.1% by weight of isobutene₄And ethylene glycol containing 0.6 wt% of water as raw materials, at the reaction temperature of 95 ℃, the reaction pressure of 2MPa and the weight space velocity of the mixed C4 of 5 g/g.h^-1The ethylene glycol and isobutene were contacted with a catalyst at a molar ratio of 5 to produce an effluent containing ethylene glycol mono-t-butyl ether, and after the reaction had stabilized for 2 hours, a sample of the product was taken for gas chromatographic analysis, the results of which are shown in Table 1 a.

Comparative example 2

Stability evaluation was performed under the reaction conditions [ application example 1 ] using macroporous cationic resin as a catalyst. Taking mixed C4 containing 5.5 weight percent of n-butane, 58.7 weight percent of 2-butylene, 29.7 weight percent of 1-butylene and 6.1 weight percent of isobutene and ethylene glycol containing 0.6 weight percent as raw materials, reacting at the temperature of 95 ℃, the reaction pressure of 2MPa and the weight space velocity of mixed C4 of 5 g/g.h^-1The ethylene glycol and isobutene contact and react with the catalyst under the condition that the molar ratio of the ethylene glycol to the isobutene is 5 to generate an effluent containing ethylene glycol mono-tert-butyl ether, the product is analyzed by gas chromatography, and the stability test data are shown in a table 4.

The conversion of isobutylene at the initial stage of the test was 85.1%, and the selectivity of ethylene glycol mono-t-butyl ether was 83.6%. After 500 hours, the conversion of isobutylene was 20.1% and the selectivity to ethylene glycol mono-t-butyl ether was 85.7%.

Table 3 catalyst a1 stability evaluation data

TABLE 4 evaluation data for stability of resin catalyst