CN117534571A - Method for producing 3-aminomethyl-3, 5-trimethylcyclohexylamine - Google Patents
Method for producing 3-aminomethyl-3, 5-trimethylcyclohexylamine Download PDFInfo
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- CN117534571A CN117534571A CN202311535855.XA CN202311535855A CN117534571A CN 117534571 A CN117534571 A CN 117534571A CN 202311535855 A CN202311535855 A CN 202311535855A CN 117534571 A CN117534571 A CN 117534571A
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- 238000004519 manufacturing process Methods 0.000 title description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 71
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000003054 catalyst Substances 0.000 claims abstract description 48
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 30
- JJDFVIDVSCYKDS-UHFFFAOYSA-N 1,3,3-trimethyl-5-oxocyclohexane-1-carbonitrile Chemical compound CC1(C)CC(=O)CC(C)(C#N)C1 JJDFVIDVSCYKDS-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 19
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical class [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 150000003608 titanium Chemical class 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 239000007868 Raney catalyst Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 238000009776 industrial production Methods 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 48
- 239000000047 product Substances 0.000 description 31
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 22
- 239000012295 chemical reaction liquid Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000000926 separation method Methods 0.000 description 6
- 238000005804 alkylation reaction Methods 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 230000011987 methylation Effects 0.000 description 5
- 238000007069 methylation reaction Methods 0.000 description 5
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- 238000007126 N-alkylation reaction Methods 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 230000029936 alkylation Effects 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910000564 Raney nickel Inorganic materials 0.000 description 3
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical group [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000004176 ammonification Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- -1 rare earth modified titanium-silicon Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/34—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a preparation method of 3-aminomethyl-3, 5-trimethylcyclohexane. The preparation method comprises the following steps: isophorone nitrile, ammonia and hydrogen peroxide react in the presence of a modified titanium silicon catalyst to generate an intermediate 1, and the obtained intermediate 1 undergoes hydrogenation reaction in the presence of a hydrogenation catalyst to generate 3-aminomethyl-3, 5-trimethylcyclohexylamine. The method can be operated under lower reaction pressure, has simple reaction steps and high yield, is easy to purify and separate, and is suitable for industrial production.
Description
Technical Field
The invention relates to a method for preparing 3-aminomethyl-3, 5-trimethyl cyclohexylamine, belonging to the field of organic synthesis.
Background
3-aminomethyl-3, 5-trimethylcyclohexylamine is abbreviated as IPDA, is cycloaliphatic diamine, has application in various industries, for example, can be used as a curing agent in the production of epoxy resin, can be used as a cross-linking agent, a coupling agent, a hydroxyl stabilizer and a special monomer in the production of polyurethane, and can also be used as a raw material for synthesizing isophorone diisocyanate.
The main production process of the IPDA at present is isophorone nitrile ammonification hydrogenation method: firstly, isophorone nitrile and ammonia are dehydrated to form isophorone nitrile imine, and then hydrogenated to IPDA:
DuPont (US 5491264) and BASF (US 5371292A, CN 1561260A) use liquid ammonia as an imidization reactant and a hydrogenation solvent. Because the whole system is introduced with liquid ammonia, the partial pressure of ammonia in the hydrogenation reaction system is higher, so that higher reaction pressure is needed to ensure the hydrogenation reaction effect.
Deggusa (US 5679860, US 4429157A) and Sumitomo company (US 5395972A, US 5589596A) are used for solving the problem of higher reaction pressure caused by partial pressure of ammonia, and solvent methanol is introduced into a reaction system, so that the operation pressure is reduced, the grade of material requirements is reduced, and the equipment investment is reduced. Meanwhile, the research shows that the methanol solvent is introduced, so that the methylation product of the IPDA appears in the hydrogenation product, and is difficult to separate from the IPDA, thereby increasing the separation energy consumption and reducing the product quality. The reaction pressure is still high, considering that the ammonia still has a certain partial pressure.
In short, the existing method for preparing the IPDA has the problems of high pressure, high content of difficult-to-separate impurities (the methylated product of the IPDA), introduction of methanol as a solvent and the like.
Disclosure of Invention
The invention aims to provide a preparation method of IPDA, by adopting the method, reaction liquid with low content of impurities difficult to separate can be obtained under low reaction pressure, the reaction steps are simple, the yield is high, and the product is easy to purify and separate.
As can be seen from the technical analysis of the industrial production at present, the imidization reaction of isophorone nitrile and ammonia is an equilibrium reaction, and in order to move the imidization reaction towards the direction beneficial to the positive reaction, the usage amount of ammonia is greatly excessive, which leads to higher partial pressure of ammonia in the whole reaction system and improves the pressure required by the reaction. Also we have studied on the introduction of a methanol solvent, and found that both the N-methylated product and the methylated product are produced in an imidization stage, wherein methanol and liquid ammonia are subjected to imidization reaction in the presence of an imidization catalyst to produce methylamine, and methylamine and IPN are subjected to imidization reaction in the presence of an imidization catalyst to further undergo hydrogenation reaction to produce the N-methylated product of IPDA; the methylation product is the methylation product of IPN generated by alkylation reaction of IPN and methanol in the presence of imidization catalyst, then imidization reaction of IPN and liquid ammonia is generated to generate the methylation product of IPNI, and further hydrogenation reaction is performed to generate the methylation product of IPDA. The specific reaction process is as follows:
since the N-methylated and methylated products of IPDA are structurally similar to IPDA, the separation is difficult during actual operation, and thus the formation of these two compounds needs to be avoided.
According to our findings, to achieve the above object, we changed the c=o group into c—no by reaction 2 The influence of imidization reaction balance on the reaction is not needed to be considered, the ammonia content in the hydrogenation reaction stage is low or ammonia is not contained, the partial pressure of ammonia is low or even zero, the reaction pressure is greatly reduced, in addition, the imidization reaction is not involved, the generation of N-alkylation products and alkylation products of IPDA can be avoided, and the separation difficulty is reduced.
The invention adopts the following technical scheme:
a method for preparing IPDA, comprising the steps of:
(1) Isophorone nitrile, ammonia and hydrogen peroxide react in the presence of a modified titanium silicon catalyst to generate an intermediate 1;
(2) The obtained intermediate 1 undergoes hydrogenation reaction in the presence of a hydrogenation catalyst to generate 3-aminomethyl-3, 5-trimethylcyclohexylamine.
The reaction equation of this reaction is shown as follows:
in view of the fact that intermediate 1 is insoluble in water, step (1) of the present invention is required to be carried out in the presence of a solvent, preferably a C1-4 alcohol, more preferably methanol or ethanol, in order to ensure that the reaction system is not phase separated.
Further, the mass ratio of isophorone nitrile to solvent in step (1) is 1:1 to 20, preferably 1:5 to 10.
Further, the reaction temperature adopted in the step (1) is 30-90 ℃, preferably 40-70 ℃; the reaction pressure used is 0.1 to 1.0MPa, preferably 0.1 to 0.3MPa.
Further, in the step (1), ammonia is liquid ammonia, and the molar ratio of isophorone nitrile, ammonia and hydrogen peroxide is 1:1-3:1.2-2.5, preferably 1:1.1-2.0:2-2.5.
Further, the reaction in the step (1) is carried out in a fixed bed filled with a modified titanium silicon catalyst, isophorone nitrile, liquid ammonia, hydrogen peroxide and a solvent are mixed and then continuously pass through the fixed bed filled with the modified titanium silicon catalyst from bottom to top;
the modified titanium-silicon catalyst is zinc and rare earth modified titanium-silicon catalyst, and the preparation method can be seen in patent CN115845915A, for example:
(1) Hydrolysis: mixing a titanium source, a silicon source, a template agent and water, and performing hydrolysis reaction to obtain a hydrolysis product;
(2) Rare earth metal and zinc modification: adding a rare earth metal source and a zinc source into the hydrolysate obtained in the step (1), and performing hydrothermal crystallization reaction to obtain a crystallized product;
(3) Alkali metal modification: adding an alkali metal source into the crystallized product obtained in the step (2), and uniformly mixing to obtain an alkali metal modified product;
(4) And (3) forming: drying and molding the alkali metal modified product obtained in the step (3) to obtain a catalyst molded product;
(5) Roasting: and (3) roasting the catalyst molding product obtained in the step (4) to obtain the modified titanium-silicon catalyst.
Wherein the molar ratio of zinc to rare earth is 0.1-10 (e.g., 0.2,0.5,0.6,0.8,1,1.5,2,2.5,3,3.5,4,5, etc.), other conditions may be found in CN115845915A and will not be described in detail herein. The catalyst of the invention obviously improves the conversion rate of the reaction in the step (1);
further, in the step (1) of the present invention, the treatment amount of the modified titanium silicalite catalyst is 0.01 to 1g isophorone nitrile/(g catalyst.hr), preferably 0.1 to 0.2g isophorone nitrile/(g catalyst.hr).
Further, the reaction liquid obtained in the step (1) can be separated by rectification to obtain the intermediate 1 for the reaction in the step (2), or the reaction liquid containing the intermediate 1 can be directly used for the reaction in the step (2) without separation. From the viewpoints of energy saving and reduction of investment, it is preferable that the reaction solution containing the intermediate 1 is directly used for the reaction in the step (2) without separation.
The reaction temperature in the step (2) is 60-150 ℃, preferably 100-120 ℃, and the reaction pressure is 1-12 MPa, preferably 5-8 MPa.
Further, the molar ratio of intermediate 1 to hydrogen in step (2) of the present invention is 1:10 to 200, preferably 1:40 to 100.
Further, the hydrogenation catalyst in the step (2) is a nickel-based or cobalt-based catalyst, and is selected from a supported catalyst or a Raney catalyst or a combination of the two; preferably, the catalyst is a Raney nickel catalyst.
Preferably, the hydrogenation reaction in step (2) is performed in a fixed bed filled with a hydrogenation catalyst, and the reaction liquid containing intermediate 1 and hydrogen obtained in step (1) pass through the fixed bed filled with the hydrogenation catalyst from top to bottom.
Further, the hydrogenation catalyst in step (2) of the present invention has a throughput of 0.01 to 1g of intermediate 1/(g of catalyst.hr), preferably 0.05 to 0.2g of intermediate 1/(g of catalyst.hr).
In the preparation method of the invention, the IPDA product can be obtained after the hydrogenation reaction liquid is separated and purified. In a specific embodiment, the specific separation steps are: the hydrogenation reaction liquid is firstly completely or partially separated from hydrogen, inert gas, ammonia, solvent, low-boiling impurities and part of water in one or more rectifying towers, wherein the solvent and liquid ammonia (a small amount) can be recycled; other low-boiling impurities, water and high-boiling impurities are completely or partly separated in the rectification column and IPDA is obtained.
By adopting the method, isophorone nitrile can be efficiently converted into IPDA under lower reaction pressure, the total conversion rate of the reaction can reach 99.9 percent, and the total selectivity is not less than 95.0 percent (calculated by isophorone nitrile).
The preparation method of the invention has the main advantages that:
can be operated under lower reaction pressure, and has simple reaction steps and high yield; the N-alkylation and alkylation products are not generated, the products are easy to purify and separate, and the method is suitable for industrial production.
Detailed Description
The invention is further illustrated by the following examples, which are not to be construed as limiting the scope of the invention as claimed.
The main raw materials related to the invention are all purchased through commercial paths.
The test instrument used in this embodiment is: GC was tested using Agilent7820 and samples were diluted 3-fold with chromatographic methanol.
Preparation of modified titanium silicon catalyst
The preparation process of the modified titanium-silicon catalyst comprises the following steps: 2083.0g of tetraethyl silicate and 91.0g of tetraethyl titanate were mixed uniformly, added dropwise to a solution containing 51.0g of tetrapropylammonium hydroxide (TPAOH) and 3600.0g of water, hydrolyzed at 45℃for 3 hours, and then 22gCe (NO) 3 ) 3 ·6H 2 O and 10gZn (NO) 3 ) 2 ·6H 2 O, stirring at 40℃for 36 hours. Transferring the solution into a hydrothermal kettle, and carrying out hydrothermal reaction for 2 hours at 200 ℃ to obtain a crystallization reaction product. After transferring the crystallization reaction product to a beaker, 3.5g KNO was added 3 Stirred at 50℃for 8 hours. And finally, drying and forming the modified crystallization product, and roasting for 4 hours at 550 ℃ to obtain the modified microsphere titanium-silicon catalyst.
Preparation of modified titanium silicon catalyst
The preparation of the modified titanium silicalite catalyst differs from preparation example 1 in that: NO Zn (NO) is added 3 ) 2 ·6H 2 O。
Example 1
(1) Preparing a stainless steel tube type fixed bed reactor, wherein the inner diameter is 15mm, and the length is 500mm; 50g of the modified titanium silicalite catalyst prepared in preparation example 1 was charged therein;
controlling the mass ratio of isophorone nitrile to methanol to be 1:5, preparing isophorone nitrile and methanol into a mixed solution, and respectively and continuously entering a reactor with liquid ammonia and hydrogen peroxide water solution through a feed pump, wherein the feed flow rates are respectively as follows: 30g/h of isophorone nitrile methanol solution, 0.57g/h of liquid ammonia, 5.89g/h of hydrogen peroxide aqueous solution (35 wt%); the reaction temperature was controlled at 40℃and the reaction pressure at 0.1MPa. And (3) intermittently sampling to perform GC analysis on the reaction liquid, and reacting for 6 hours to enter a stable state, wherein the conversion rate reaches 99.9%, and the selectivity of the intermediate 1 reaches 97.2%.
(2) Preparing a stainless steel tube type fixed bed reactor, wherein the inner diameter is 15mm, and the length is 500mm; 50g of Raney nickel catalyst (purchased from Grace) was packed therein;
continuously feeding the reaction solution containing the intermediate 1 obtained in the step (1) into a reactor by using a feed pump at a speed of 15.78g/h, controlling the flow rate of hydrogen to 11.4L/h, and controlling the reaction temperature to 100 ℃ and the reaction pressure to 5MPa. The reaction solution was intermittently sampled and subjected to GC analysis, and after 4 hours of reaction, it was found that the reaction was in a steady state, wherein the conversion rate reached 99.9%, the IPDA selectivity reached 99.2%, and no N-alkylation and alkylation products were detected.
The crude hydrogenation reaction liquid is rectified and separated, the number of tower plates of a rectifying tower is 30, firstly, low boiling point compounds such as methanol, water and the like are subjected to pressure of 20Kpa, then the pressure is reduced to 2.0kPa, and the product with the purity of more than or equal to 99.7% is collected.
Example 2
(1) As in example 1, a stainless steel tube type fixed bed reactor was prepared, having an inner diameter of 15mm and a length of 500mm; 50g of the modified titanium silicalite catalyst prepared in preparation example 1 was charged therein;
controlling the mass ratio of isophorone nitrile to ethanol to be 1:10, preparing isophorone nitrile and ethanol into a mixed solution, and respectively and continuously entering a reactor with liquid ammonia and hydrogen peroxide water solution through a feed pump, wherein the feed flow rates are respectively as follows: 110g/h of isophorone nitrile methanol solution, 2.05g/h of liquid ammonia, and 14.66g/h of hydrogen peroxide aqueous solution (35 wt%); the reaction temperature was controlled at 70℃and the reaction pressure at 0.3MPa. And (3) intermittently sampling to perform GC analysis on the reaction liquid, and reacting for 6 hours to enter a stable state, wherein the conversion rate reaches 99.9%, and the selectivity of the intermediate 1 reaches 97.8%.
(2) As in example 1, a stainless steel tube type fixed bed reactor was prepared, having an inner diameter of 15mm and a length of 500mm; 50g of Raney nickel catalyst (purchased from Grace) was packed therein;
continuously feeding the reaction solution containing the intermediate 1 obtained in the step (1) into a reactor by a 109g/h feed pump, controlling the flow of hydrogen to 114L/h, and controlling the reaction temperature to 120 ℃ and the reaction pressure to 8MPa. The reaction solution was intermittently sampled and subjected to GC analysis, and it was found that the reaction was brought into a steady state after 2 hours, wherein the conversion rate reached 99.9%, the IPDA selectivity reached 99.3%, and no N-alkylation and alkylation products were detected.
The crude hydrogenation reaction liquid is rectified and separated, the number of tower plates of a rectifying tower is 30, firstly, low boiling point compounds such as methanol, water and the like are subjected to pressure of 20Kpa, then the pressure is reduced to 2.0kPa, and the product with the purity of more than or equal to 99.7% is collected.
Comparative example 1
The only difference from example 1 is that the catalyst in step (1) is the modified titanium silicalite catalyst prepared in preparation example 2, resulting in a conversion of 86.5% of intermediate 1.
Comparative example 2
The imidization reactor and the hydrogenation reactor used a fixed bed 25mm in diameter and 1000mm in length, wherein the imidization reactor was packed with 100g of activated alumina pellets (purchased from Haixin, daidan) and the hydrogenation reactor was packed with 200g of Raney cobalt catalyst (purchased from Grace).
Mixing raw materials IPN, liquid ammonia and methanol, continuously feeding the mixture into an imidization reactor at a feeding speed of 20g/h, controlling the mass ratio of the liquid ammonia to the IPN to the methanol to be 3:1:4, controlling the imidization temperature to be 30 ℃, and controlling the reaction pressure to be 12Mpa. And (3) introducing imidization reaction liquid obtained from the outlet of the imidization reactor into a hydrogenation reactor, and controlling the hydrogenation reaction temperature to be 130 ℃ and the reaction pressure to be 12MPa. Sampling GC analysis during feeding, and after 9 hours, the reaction reaches equilibrium, the conversion rate of IPN ammonification hydrogenation to IPDA is calculated to be 99.9%, the selectivity of IPDA is calculated to be 97.3%, and the content of the methylated product of IPDA is calculated to be 0.785%.
Claims (10)
1. A process for the preparation of 3-aminomethyl-3, 5-trimethylcyclohexylamine, said process comprising the steps of:
(1) Isophorone nitrile, ammonia and hydrogen peroxide react in the presence of zinc and rare earth element modified titanium silicon catalyst to generate an intermediate 1;
(2) The obtained intermediate 1 undergoes hydrogenation reaction in the presence of a hydrogenation catalyst to generate 3-aminomethyl-3, 5-trimethylcyclohexylamine;
2. the process according to claim 1, wherein step (1) is carried out in the presence of a solvent, preferably a C1-4 alcohol, preferably isophorone nitrile to solvent in a mass ratio of 1:1-20.
3. The process according to any one of claims 1 to 2, wherein the reaction temperature in step (1) is 30 to 90 ℃ and the reaction pressure is 0.1 to 1.0MPa.
4. A process according to any one of claims 1 to 3, wherein the ammonia in step (1) is liquid ammonia and the molar ratio of isophorone nitrile, ammonia and hydrogen peroxide is 1:1 to 3:1.2 to 2.5.
5. The process according to any one of claims 1 to 4, wherein the modified titanium silicalite catalyst of step (1) has a throughput of 0.01 to 1g isophorone nitrile/(g catalyst.h).
6. The method according to claim 1, wherein the reaction temperature in the step (2) is 60 to 150 ℃ and the reaction pressure is 1 to 12MPa.
7. The process of claim 1 or 6, wherein the molar ratio of intermediate 1 to hydrogen in step (2) is 1:10 to 200, preferably 1:40 to 100.
8. The process according to claim 1 or 6 or 7, wherein the hydrogenation catalyst of step (2) is a nickel-based or cobalt-based catalyst.
9. The process of claim 8, wherein the hydrogenation catalyst of step (2) is selected from a supported catalyst or a rani catalyst or a combination of both; raney catalysts are preferred.
10. The process according to any one of claims 1 to 9, wherein the catalyst of step (2) has a throughput of 0.01 to 1g of intermediate 1/(g of catalyst per hour).
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