阅读说明：本技术 间歇式催化胺化制备聚醚胺的方法 (Method for preparing polyether amine by intermittent catalytic amination ) 是由 王国强 见方田 周国栋 于 2020-12-31 设计创作，主要内容包括：本发明属于精细化工原料制造合成技术领域,具体涉及一种间歇式催化胺化制备聚醚胺的方法,运用间歇式方法以聚醚为原料,在负载镍催化剂及改性助剂存在下与氢气和液氨发生还原胺化反应,制得聚醚胺。本发明中采用间歇式工艺生产可以使生产更加灵活,可根据产品淡旺季调整产品种类,可根据需求定制产品,生产线切换方便,可实现24小时切换产品。本发明原料转化率可高达99％以上,胺化产品收率95％以上,副产物小于5％,产品分离简单,无需循环回用未反应的原料与中间体,降低能耗,最终降低生产成本。(The invention belongs to the technical field of fine chemical raw material manufacturing and synthesis, and particularly relates to a method for preparing polyether amine by intermittent catalytic amination. The invention adopts the intermittent process production, so that the production is more flexible, the product types can be adjusted according to light and busy seasons of the products, the products can be customized according to the requirements, the production line is convenient to switch, and the products can be switched in 24 hours. The conversion rate of the raw materials can reach more than 99 percent, the yield of aminated products is more than 95 percent, the by-products are less than 5 percent, the product separation is simple, the unreacted raw materials and intermediates are not required to be recycled, the energy consumption is reduced, and the production cost is finally reduced.)

1. A method for preparing polyether amine by intermittent catalytic amination is characterized in that: polyether is used as a raw material to react with hydrogen and liquid ammonia in the presence of a supported nickel catalyst and a modification auxiliary agent by an intermittent method to prepare polyether amine.

2. The process for preparing polyetheramines by batch catalytic amination according to claim 1, characterized in that: polyether is used as a raw material, a supported nickel catalyst is filled in a reaction kettle, then polyether, a modification auxiliary agent, hydrogen and liquid ammonia are added into the reaction kettle to carry out catalytic amination reaction, a crude product is obtained after the reaction is finished, and then the crude product is degassed and dehydrated to obtain polyetheramine.

3. The process for preparing polyetheramines by batch catalytic amination according to claim 2, characterized in that: the reaction kettle is internally provided with a self-suction stirring paddle.

4. The process for preparing polyetheramines by batch catalytic amination according to claim 2, characterized in that: the degassing and the dehydration are both carried out in a dehydration kettle, and the degassing kettle is heated by steam to remove hydrogen and ammonia in the materials; and after degassing is finished, removing the water in the materials by using a vacuum pump under vacuum negative pressure.

5. The process for preparing polyetheramines by batch catalytic amination according to claim 1, characterized in that: the reaction temperature is 100 ℃ and 260 ℃, the reaction pressure is 4.0-15.0MPa, and the reaction time is 10-25 h.

6. The process for preparing polyetheramines by batch catalytic amination according to claim 1, characterized in that: the supported nickel catalyst has an active component nickel content of 0.5-10 wt% based on the total weight of the catalyst, and the carrier is one or more of alumina, silica or titanium oxide.

7. The process for preparing polyetheramines by batch catalytic amination according to claim 1, characterized in that: the molecular weight of the polyether is 400-2000.

8. The process for preparing polyetheramines by batch catalytic amination according to claim 1, characterized in that: the catalyst is prepared by the addition polymerization reaction of an initiator and ethylene oxide, propylene oxide or butylene oxide in the presence of a catalyst.

9. The process for preparing polyetheramines by batch catalytic amination according to claim 1, characterized in that: the modifying assistant is one or more of sodium hydroxide, potassium hydroxide or cesium hydroxide, the concentration is 1-60 wt%, and the dosage is 0.1-10% of the weight of the polyether.

10. The process for preparing polyetheramines by batch catalytic amination according to claim 1, characterized in that: the molar ratio of hydrogen to polyether is 4:1, and the space velocity of the catalyst is 0.01-1 kg/h.

Technical Field

The invention belongs to the technical field of fine chemical raw material manufacturing and synthesis, and particularly relates to a method for preparing polyether amine through intermittent catalytic amination.

Background

Polyether polyamines (Polyether polyamines) are compounds having a flexible Polyether backbone and terminated at the end with amino or amino groups (typically secondary, primary or Polyamine groups containing active hydrogen), and the structural changes of the Polyether backbone include polyoxyethylene diamine, polyoxypropylene diamine, polyoxyethylene/oxypropylene diamine, polyoxypropylene triamine, polytetramethylene ether diamine, and the like.

The polyether amine is a polymer with a polyether structure as a main chain and an amino group as a terminal active functional group, and is widely applied to the fields of epoxy resin curing, polyurethane polyurea elastomers, gasoline detergents, lubricating oil, sealants and the like. At present, the synthesis methods of polyether amine mainly include a catalytic reductive amination method, a leaving group method, an amino butenoate method, a polyether nitrile alkylation method and the like.

In U.S. Pat. Nos. 3128311 and 3654370, polyether amine is produced by catalytic amination, and hydroxyl groups in polyether polyol are subjected to ammonolysis reaction with ammonia in the presence of a catalyst (such as a Ni-containing catalyst, a Ni/Cu/Cr catalyst, and a Raney Ni/Al catalyst). The method has harsh reaction conditions and needs to be carried out under the conditions of high temperature and high pressure, so the investment, operation and maintenance costs of equipment are higher, and in addition, the preparation process of the catalyst is more complicated.

In the patent US4313004 and US4352919A, polyether amine is produced by polyether nitrile alkylation, polyether and acrylonitrile are subjected to addition reaction under the action of an alkaline catalyst, and then catalytic hydrogenation is carried out in an autoclave to obtain polyether amine. The method has the disadvantages of high toxicity of acrylonitrile as a reaction raw material and high production cost.

Patent CN108017782A adopts a leaving group method, which generally comprises two steps, wherein the first step is esterification, starting from active hydrogen of terminal hydroxyl of polyether polyol, a compound (p-toluenesulfonic acid vinyl, acyl chloride, halogen, carboxyl, aldehyde group and the like) with an easy-to-leave group or an unsaturated group reacts with the active hydrogen to carry out end capping, and the second step is amination, and the product obtained in the first step reacts with amine (mono-amine or polyamine to obtain ATPE). The method has the disadvantages of high requirements on equipment and complex preparation of the catalyst.

Therefore, in the above patent, the process flow is complex, the reaction process is difficult to control, the product quality repeatability of different batches is poor, and the production line switching is not flexible enough. The problems of long process route and low product yield and selectivity exist in the prior disclosed method for producing polyether amine, so a technical scheme which is simple in process flow, improves amination yield and reduces byproducts needs to be developed.

Disclosure of Invention

The technical problem to be solved by the invention is as follows: the method overcomes the defects of the prior art, provides a method for preparing polyether amine by intermittent catalytic amination, has the advantages of high raw material conversion rate of more than 99 percent, amination product yield of more than 95 percent, less than 5 percent of by-products, simple product separation, no need of recycling unreacted raw materials and intermediates, reduced energy consumption and finally reduced production cost.

In order to achieve the above purpose, the invention adopts the following technical scheme:

the method for preparing polyether amine by intermittent catalytic amination provided by the invention is characterized in that polyether is used as a raw material by an intermittent method, and the polyether is subjected to reductive amination reaction with hydrogen and liquid ammonia in the presence of a supported nickel catalyst and a modification auxiliary agent to prepare polyether amine.

Preferably, polyether is used as a raw material, a batch fixed bed catalytic amination device is adopted for production, a supported nickel catalyst is filled in a reaction kettle, then polyether, a modification auxiliary agent, hydrogen and liquid ammonia are added into the reaction kettle for catalytic amination reaction, the reaction temperature is 100-260 ℃, preferably 110-230 ℃, the reaction pressure is 4.0-15.0MPa, preferably 5.0-10.0MPa, and the reaction time is 10-25h, a crude product is obtained after the reaction is finished, and then the crude product is degassed and dehydrated to obtain polyetheramine.

Preferably, a self-suction stirring paddle is arranged in the reaction kettle. The self-suction stirring paddle can enhance material mass transfer and reduce side reaction, the traditional batch method reaction catalyst is in a suspension method in a reaction kettle, the mass transfer is dispersed by stirring, the power of a motor is high, and the catalyst needs to be separated in the later period, so that the danger is high. According to the intermittent fixed bed catalytic amination device, the catalyst is filled in the reaction kettle, and after the reaction is finished, the catalyst is not required to be separated, so that the risk is reduced. Because the catalyst is not contacted with the stirring, the catalyst loss is less, and the service life is long and can reach 4 to 5 years. The material excess ratio is small, and the liquid ammonia consumption is low.

Preferably, the degassing and the dehydration are both carried out in a dehydration kettle, the degassing kettle is heated by steam at first, hydrogen and ammonia in the materials are removed, and the degassing time is preferably 5 hours; and after the degassing is finished, removing the water in the material by using a vacuum pump under vacuum negative pressure, wherein the dewatering time is preferably 15 hours. NH generated by degassing₃The condensate liquid after the waste gas generated in the dehydration process is condensed is a partThe ammonia is recycled for ammonia spraying, and part of the ammonia is discharged into a sewage treatment station for treatment.

The supported nickel catalyst comprises an active component nickel, a carrier and an optional auxiliary agent, wherein the active component nickel content is 0.5-10 wt%, preferably 1-5 wt% based on the total weight of the catalyst, and the carrier is one or more of alumina, silica or titanium oxide. The catalyst of the invention has higher activity for ammonia decomposition reaction. The catalyst system is suitable for direct reductive amination of polyether, and in the research process of applying the catalyst system to reductive amination reaction, the active metal component Ni shows excellent activity to the reductive amination reaction of polyether, but when the content of the introduced Ni in the catalyst is less than 0.5%, the selectivity of the catalyst is obviously reduced in the reductive amination process; when the Ni content is more than 10%, the increase of the Ni content does not contribute to the improvement of the activity and selectivity of the catalyst, and even increases by-products.

The molecular weight of the polyether is 400-2000. Prepared by addition polymerization of an initiator (active hydrogen group-containing compound) with Ethylene Oxide (EO), Propylene Oxide (PO) or Butylene Oxide (BO) in the presence of a catalyst.

The modifying assistant is one or more of sodium hydroxide, potassium hydroxide or cesium hydroxide, and the general formula R is⁺OH, wherein R is Na⁺、K⁺、Cs⁺A metal ion. Preferably, the modifying assistant is added in the form of an aqueous solution, at a concentration of 1 to 60% by weight, preferably 5 to 15% by weight, in an amount of 0.1 to 10% by weight of the polyether. The addition of the modification auxiliary agent can be used for reducing the polyether amine (including intermolecular and intramolecular) by-products in the reductive amination process, and the selectivity of the polyether amine main product is ensured.

In the reductive amination process, no solvent is used, hydrogen is used as a protective agent of the supported nickel catalyst, the molar ratio of the hydrogen to the polyether is 4:1, and the airspeed of the catalyst is 0.01-1 kg/h.

Compared with the prior art, the invention has the following beneficial effects:

1. the invention adopts the intermittent process production, so that the production is more flexible, the product types can be adjusted according to light and busy seasons of the products, the products can be customized according to the requirements, the production line is convenient to switch, and the products can be switched in 24 hours.

2. The conversion rate of the raw materials can reach more than 99 percent, the yield of aminated products is more than 95 percent, the by-products are less than 5 percent, the product separation is simple, the unreacted raw materials and intermediates are not required to be recycled, the energy consumption is reduced, and the production cost is finally reduced.

Detailed Description

The present invention will be further illustrated with reference to the following examples, but the present invention is not limited to the examples.

Method for determining total amine value: titrating the product by adopting 0.5mol/L hydrochloric acid solution, and calculating the total amine value of the product through the volume number of consumed hydrochloric acid.

The ammoniation conversion rate is total amine value/hydroxyl value × 100%.

Method for determining secondary/tertiary amine value: and mixing and stirring the product and salicylaldehyde with equal mass for 2 hours, titrating the product by adopting 0.5mol/L hydrochloric acid solution, and calculating the sum of secondary amine and tertiary amine values of the product through the volume number of consumed hydrochloric acid.

Primary amine selectivity ═ (total amine number-secondary/tertiary amine number)/total amine number × 100%.

Example 1

Filling a loaded nickel catalyst into a reaction kettle with a jacket and a coil, wherein the loaded nickel catalyst comprises an active component nickel, a carrier and a copper, lanthanum and magnesium aluminum composite oxide auxiliary agent, the active component nickel content is 1 wt% based on the total weight of the catalyst, the carrier is alumina, polyether, liquid ammonia, hydrogen and potassium hydroxide modification auxiliary agent are added into the reaction kettle, and the molar ratio of the liquid ammonia to the polyether is 3: 1, the molar ratio of hydrogen to polyether is 4:1, first use N₂Replacement three times with H₂Replacing for three times, wherein the replacement pressure is more than or equal to 0.02 MPa. N is a radical of₂，H₂After the replacement is finished, slowly heating, controlling the temperature at 150 ℃, the reaction pressure at 8MPa, and the reaction time at 20 hours, obtaining a crude product after the reaction is finished, then degassing and dehydrating the crude product in a dehydration kettle, firstly heating the degassing kettle by steam, removing hydrogen and ammonia in the materials, and degassing for 5 hours; after degassing, removing the material by vacuum negative pressure of a vacuum pumpWater content, dehydration time 15 hours, NH produced during degassing₃And recycling the waste gas generated in the dehydration process after the condensation in the ammonia spraying process, discharging part of the waste gas into a sewage treatment station for treatment, degassing and dehydrating to obtain the polyether amine product. Sending to the laboratory to measure the amine value and the primary amine rate.

The ammoniation conversion rate is 99.5%, and the aminated product yield is 98.3%.

Example 2

Filling a loaded nickel catalyst into a reaction kettle with a jacket and a coil, wherein the loaded nickel catalyst comprises an active component nickel, a carrier and a copper, lanthanum and magnesium aluminum composite oxide auxiliary agent, the active component nickel content is 2 wt% based on the total weight of the catalyst, the carrier is alumina, polyether, liquid ammonia, hydrogen and potassium hydroxide modification auxiliary agent are added into the reaction kettle, and the molar ratio of the liquid ammonia to the polyether is 3: 1, the molar ratio of hydrogen to polyether is 4:1, first use N₂Replacement three times with H₂Replacing for three times, wherein the replacement pressure is more than or equal to 0.02 MPa. N is a radical of₂，H₂After the replacement is finished, slowly heating, controlling the temperature at 180 ℃, the reaction pressure at 10MPa, and the reaction time at 18 hours, obtaining a crude product after the reaction is finished, then degassing and dehydrating the crude product in a dehydration kettle, firstly heating the degassing kettle by steam, removing hydrogen and ammonia in the materials, and degassing for 5 hours; after the degassing is finished, removing the water in the materials by using a vacuum pump under vacuum negative pressure, wherein the dehydration time is 15 hours, and NH generated in the degassing process₃And recycling the waste gas generated in the dehydration process after the condensation in the ammonia spraying process, discharging part of the waste gas into a sewage treatment station for treatment, degassing and dehydrating to obtain the polyether amine product. Sending to the laboratory to measure the amine value and the primary amine rate.

The ammoniation conversion rate is 99.6%, and the aminated product yield is 98.5%.

Example 3

A reaction kettle with a jacket and a coil is filled with a supported nickel catalyst, and the supported nickel catalyst comprises an active component nickel, a carrier and a copper, lanthanum and magnesium aluminum composite oxide auxiliary agentBased on the total weight of the catalyst, the content of active component nickel is 3 wt%, the carrier is alumina, polyether, liquid ammonia, hydrogen and potassium hydroxide modification auxiliary agent are added into a reaction kettle, and the molar ratio of the liquid ammonia to the polyether is 3: 1, the molar ratio of hydrogen to polyether is 4:1, first use N₂Replacement three times with H₂Replacing for three times, wherein the replacement pressure is more than or equal to 0.02 MPa. N is a radical of₂，H₂After the replacement is finished, slowly heating, controlling the temperature at 200 ℃, the reaction pressure at 5MPa, and the reaction time at 15 hours, obtaining a crude product after the reaction is finished, then degassing and dehydrating the crude product in a dehydration kettle, firstly heating the degassing kettle by steam, removing hydrogen and ammonia in the materials, and degassing for 5 hours; after the degassing is finished, removing the water in the materials by using a vacuum pump under vacuum negative pressure, wherein the dehydration time is 15 hours, and NH generated in the degassing process₃And recycling the waste gas generated in the dehydration process after the condensation in the ammonia spraying process, discharging part of the waste gas into a sewage treatment station for treatment, degassing and dehydrating to obtain the polyether amine product. Sending to the laboratory to measure the amine value and the primary amine rate.

The ammoniation conversion rate is 99.3%, and the aminated product yield is 97.9%.

Example 4

Filling a loaded nickel catalyst into a reaction kettle with a jacket and a coil, wherein the loaded nickel catalyst comprises an active component nickel, a carrier and a copper, lanthanum and magnesium aluminum composite oxide auxiliary agent, the active component nickel content is 4 wt% based on the total weight of the catalyst, the carrier is alumina, polyether, liquid ammonia, hydrogen and potassium hydroxide modification auxiliary agent are added into the reaction kettle, and the molar ratio of the liquid ammonia to the polyether is 3: 1, the molar ratio of hydrogen to polyether is 4:1, first use N₂Replacement three times with H₂Replacing for three times, wherein the replacement pressure is more than or equal to 0.02 MPa. N is a radical of₂，H₂After the replacement is finished, slowly heating, controlling the temperature at 210 ℃, the reaction pressure at 6MPa, and the reaction time at 14 hours, obtaining a crude product after the reaction is finished, then degassing and dehydrating the crude product in a dehydration kettle, firstly heating the degassing kettle by steam, removing hydrogen and ammonia in the materials, and degassing for 5 hours; after the degassing is finished, removing the substances by vacuum negative pressure of a vacuum pumpWater content in the material, dehydration time 15 hours, NH produced in the degassing process₃And recycling the waste gas generated in the dehydration process after the condensation in the ammonia spraying process, discharging part of the waste gas into a sewage treatment station for treatment, degassing and dehydrating to obtain the polyether amine product. Sending to the laboratory to measure the amine value and the primary amine rate.

The ammoniation conversion rate is 99.8%, and the aminated product yield is 98.1%.

Example 5

Filling a loaded nickel catalyst into a reaction kettle with a jacket and a coil, wherein the loaded nickel catalyst comprises an active component nickel, a carrier and a copper, lanthanum and magnesium aluminum composite oxide auxiliary agent, the active component nickel content is 5 wt% based on the total weight of the catalyst, the carrier is alumina, polyether, liquid ammonia, hydrogen and potassium hydroxide modification auxiliary agent are added into the reaction kettle, and the molar ratio of the liquid ammonia to the polyether is 3: 1, the molar ratio of hydrogen to polyether is 4:1, first use N₂Replacement three times with H₂Replacing for three times, wherein the replacement pressure is more than or equal to 0.02 MPa. N is a radical of₂，H₂After the replacement is finished, slowly heating, controlling the temperature at 230 ℃, the reaction pressure at 6MPa, and the reaction time at 10 hours, obtaining a crude product after the reaction is finished, then degassing and dehydrating the crude product in a dehydration kettle, firstly heating the degassing kettle by steam, removing hydrogen and ammonia in the materials, and degassing for 5 hours; after the degassing is finished, removing the water in the materials by using a vacuum pump under vacuum negative pressure, wherein the dehydration time is 15 hours, and NH generated in the degassing process₃And recycling the waste gas generated in the dehydration process after the condensation in the ammonia spraying process, discharging part of the waste gas into a sewage treatment station for treatment, degassing and dehydrating to obtain the polyether amine product. Sending to the laboratory to measure the amine value and the primary amine rate.

The ammoniation conversion rate is 99.5%, and the aminated product yield is 98.2%.

Example 6

A reaction kettle with a jacket and a coil is filled with a supported nickel catalyst, and the supported nickel catalyst comprises an active component nickel, a carrier and a copper, lanthanum and magnesium aluminum composite oxide assistantThe catalyst comprises an active component nickel content of 7 wt% and a carrier of alumina, wherein polyether, liquid ammonia, hydrogen and a potassium hydroxide modification auxiliary agent are added into a reaction kettle, and the molar ratio of the liquid ammonia to the polyether is 3: 1, the molar ratio of hydrogen to polyether is 4:1, first use N₂Replacement three times with H₂Replacing for three times, wherein the replacement pressure is more than or equal to 0.02 MPa. N is a radical of₂，H₂After the replacement is finished, slowly heating, controlling the temperature at 230 ℃, the reaction pressure at 6MPa, and the reaction time at 10 hours, obtaining a crude product after the reaction is finished, then degassing and dehydrating the crude product in a dehydration kettle, firstly heating the degassing kettle by steam, removing hydrogen and ammonia in the materials, and degassing for 5 hours; after the degassing is finished, removing the water in the materials by using a vacuum pump under vacuum negative pressure, wherein the dehydration time is 15 hours, and NH generated in the degassing process₃And recycling the waste gas generated in the dehydration process after the condensation in the ammonia spraying process, discharging part of the waste gas into a sewage treatment station for treatment, degassing and dehydrating to obtain the polyether amine product. Sending to the laboratory to measure the amine value and the primary amine rate.

The ammoniation conversion rate is 99.15%, and the aminated product yield is 98.0%.

It can be seen from examples 1 to 6 that the type of catalyst is determined by the batch method, and the yield of the product can be influenced by changing physical factors such as reaction temperature, reaction pressure, reaction time, etc. In conclusion, the method for synthesizing the polyetheramine has the advantages of mild reaction conditions, easiness in control, few byproducts, low preparation cost, short reaction period, convenience in post-treatment, higher conversion rate of the obtained polyetheramine, high primary amine selectivity and low product color, and can be used for flexibly selecting the amino types at two ends of the polyether, so that the obtained polyetheramine has higher activity and wider application.

Of course, the foregoing is only a preferred embodiment of the invention and should not be taken as limiting the scope of the embodiments of the invention. The present invention is not limited to the above examples, and equivalent changes and modifications made by those skilled in the art within the spirit and scope of the present invention should be construed as being included in the scope of the present invention.