CN109806883B - Catalyst, method for preparing 3-aminopropanol by using catalyst and system used by method - Google Patents
Catalyst, method for preparing 3-aminopropanol by using catalyst and system used by method Download PDFInfo
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- CN109806883B CN109806883B CN201910075213.3A CN201910075213A CN109806883B CN 109806883 B CN109806883 B CN 109806883B CN 201910075213 A CN201910075213 A CN 201910075213A CN 109806883 B CN109806883 B CN 109806883B
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- hydroxypropionitrile
- aminopropanol
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- hydrogen
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- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000003054 catalyst Substances 0.000 title abstract description 69
- 238000006243 chemical reaction Methods 0.000 claims abstract description 68
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 20
- 239000002638 heterogeneous catalyst Substances 0.000 claims abstract description 19
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- WSGYTJNNHPZFKR-UHFFFAOYSA-N 3-hydroxypropanenitrile Chemical compound OCCC#N WSGYTJNNHPZFKR-UHFFFAOYSA-N 0.000 claims description 77
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 66
- 229910052739 hydrogen Inorganic materials 0.000 claims description 43
- 239000001257 hydrogen Substances 0.000 claims description 42
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 40
- 238000005984 hydrogenation reaction Methods 0.000 claims description 37
- 239000007788 liquid Substances 0.000 claims description 33
- 239000007789 gas Substances 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 27
- 230000009467 reduction Effects 0.000 claims description 22
- 229910021529 ammonia Inorganic materials 0.000 claims description 19
- 238000005303 weighing Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 9
- 230000004913 activation Effects 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000000969 carrier Substances 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- 239000011343 solid material Substances 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052796 boron Inorganic materials 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 abstract description 2
- 239000002041 carbon nanotube Substances 0.000 abstract description 2
- 229910052802 copper Inorganic materials 0.000 abstract description 2
- 229910021389 graphene Inorganic materials 0.000 abstract description 2
- 229910002804 graphite Inorganic materials 0.000 abstract description 2
- 239000010439 graphite Substances 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- 239000002808 molecular sieve Substances 0.000 abstract description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052700 potassium Inorganic materials 0.000 abstract description 2
- 229910052702 rhenium Inorganic materials 0.000 abstract description 2
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004408 titanium dioxide Substances 0.000 abstract description 2
- 229910052725 zinc Inorganic materials 0.000 abstract description 2
- 229910052681 coesite Inorganic materials 0.000 description 16
- 229910052906 cristobalite Inorganic materials 0.000 description 16
- 238000004817 gas chromatography Methods 0.000 description 16
- 229910052682 stishovite Inorganic materials 0.000 description 16
- 229910052905 tridymite Inorganic materials 0.000 description 16
- 238000005086 pumping Methods 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- 238000005070 sampling Methods 0.000 description 13
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 239000003814 drug Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- -1 acyl azide Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- CMSMOCZEIVJLDB-UHFFFAOYSA-N Cyclophosphamide Chemical compound ClCCN(CCCl)P1(=O)NCCCO1 CMSMOCZEIVJLDB-UHFFFAOYSA-N 0.000 description 1
- SNPLKNRPJHDVJA-ZETCQYMHSA-N D-panthenol Chemical compound OCC(C)(C)[C@@H](O)C(=O)NCCCO SNPLKNRPJHDVJA-ZETCQYMHSA-N 0.000 description 1
- 229930003270 Vitamin B Natural products 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 229960004397 cyclophosphamide Drugs 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- SNPLKNRPJHDVJA-UHFFFAOYSA-N dl-panthenol Chemical compound OCC(C)(C)C(O)C(=O)NCCCO SNPLKNRPJHDVJA-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229940101267 panthenol Drugs 0.000 description 1
- 235000020957 pantothenol Nutrition 0.000 description 1
- 239000011619 pantothenol Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011720 vitamin B Substances 0.000 description 1
- 235000019156 vitamin B Nutrition 0.000 description 1
- 108010047303 von Willebrand Factor Proteins 0.000 description 1
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Abstract
The invention discloses a load type heterogeneous catalyst, which comprises a main active component, an auxiliary agent and a carrier, or comprises a main active component and a carrier, wherein the auxiliary agent is one or more than two simple substances of Fe, Cu, Ru, Re, K, Zn or B or oxides thereof; the carrier is one or more than two of graphite, active carbon, carbon nano tubes, graphene, silicon dioxide, aluminum oxide, molecular sieves, titanium dioxide and zirconium dioxide, and the supported heterogeneous catalyst is prepared by adopting an ultrasonic supporting method. The catalyst of the invention is used for preparing 3-aminopropanol, (1) the quality space-time yield of the 3-aminopropanol is improved, (2) the selectivity of the 3-aminopropanol is improved, (3) the reaction can be realized under lower reaction pressure, (4) the stability of a catalytic system is improved, (5) the flow operation is simple, convenient and feasible, the one-time investment and the production cost of production and subsequent separation devices are reduced, and the large-scale continuous industrial production is easy to realize.
Description
Technical Field
The invention relates to a catalyst, a method for preparing 3-aminopropanol by using the catalyst and used system equipment, belonging to the technical field of chemical synthesis.
Background
3-aminopropanol is an important drug intermediate, has wide application in the aspects of medicines, pesticides, dyes and the like, is used for synthesizing medicaments such as cyclophosphamide, cardioclonine and the like, and is a raw material for synthesizing vitamin B (DL-panthenol). With the improvement of social development level in recent years, the application of panthenol in daily chemical products is continuously improved, especially in cosmetics and shampoo products, and the market demand of 3-aminopropanol is greatly promoted.
Chinese patent application 201110289735.7 reports a process for producing 3-aminopropanol by ring-opening of 1, 4-butyrolactone as raw material under the action of hydrazine hydrate, adding aqueous solution of sodium nitrite to produce acyl azide, and then carrying out rearrangement. The method has complex flow and low yield of the target product 3-aminopropanol, and is not suitable for practical application and popularization. Von Willebrand discloses a method for preparing 3-aminopropanol by synthesizing cyclohexanone oxime by using cyclohexanone as a raw material, then condensing the cyclohexanone oxime with acrylonitrile and then carrying out catalytic hydrocracking. The method also has the problems of complicated steps, poor selectivity of target products and low product yield.
Patents CH-B-244837, DE-B-2655794, EP- ｃA1-1132371, JP- ｃA-2002201164, etc. report ｃA process for producing 3-aminopropanol by reacting 3-hydroxypropionitrile as ｃA starting material with hydrogen gas under ammoniｃA-critical conditions. The method can directly synthesize the target product 3-aminopropanol by one step, but still has the problem of low selectivity of the target product. JP-A-05163213 discloses ｃA Raney cobalt catalyst used in the reaction of 3-hydroxypropionitrile in the synthesis of 3-aminopropanol by hydrogenation of ammoniｃA, and the catalyst system has high risk and is not easy to realize industrial application. Patent CN-A-103261148 reports A process for the production and purification of 3-aminopropanol with A selectivity of up to 93% but with A reaction pressure of up to 18MPA and A mass space-time yield of only 0.3 Kg/Kg.h-1. There is no report of catalyst life in the above patent for the synthesis of 3-aminopropanol. Therefore, the above reported catalysts have problems of difficulty in continuous production or low activity, short life and severe reaction conditions, and have low industrial application value.
The process for directly synthesizing the 3-aminopropanol by one step through hydrogenation under the condition of 3-hydroxypropionitrile and ammonia is simple, the target product selectivity is high, and the method is a relatively green and environment-friendly path for preparing the 3-aminopropanol. The main problems existing at present are one or more of harsh reaction conditions, poor catalyst stability, low activity and the like.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a catalyst, the catalyst is prepared by an ultrasonic loading method, the activity is high, the selectivity is good, the preparation of 3-aminopropanol by using the catalyst can be carried out under lower pressure, the conversion rate is high, and the system ensures the smooth reaction.
In order to solve the technical problems, the invention firstly discloses a supported heterogeneous catalyst which comprises a main active component, an auxiliary agent and a carrier, or comprises a main active component and a carrier, wherein the main active component is Ni and/or Co, and the auxiliary agent is one or more than two simple substances or oxides thereof in Fe, Cu, Ru, Re, K, Zn or B; the carrier is one or more than two of insoluble solid materials of graphite, active carbon, carbon nano tubes, graphene, silicon dioxide, aluminum oxide, molecular sieves, titanium dioxide and zirconium dioxide, the supported heterogeneous catalyst is prepared by adopting an ultrasonic supporting method, and the steps comprise:
(1) dissolving the main active component and soluble salt of the auxiliary agent or the soluble salt of the main active component by deionized water to obtain a salt solution, wherein the ion concentration is 0.05-2.0 mol/L;
(2) weighing a quantitative carrier, placing the quantitative carrier in the salt solution obtained in the step (1), transferring the quantitative carrier into an ultrasonic reactor for treatment for t hours at 5-120KHz, wherein t is more than 0 and less than or equal to 10, and preferably, t is more than or equal to 0.1 and less than or equal to 2;
(3) adding an ammonia water solution into the solution obtained in the step (2) to adjust the pH value to 9-11, and continuing ultrasonic treatment for t2 hours, wherein t2 is more than 0 and less than or equal to 8, and preferably t2 is more than 0.1 and less than or equal to 1.5;
(4) evaporating ammonia from the mixture obtained in the step (3) after ultrasonic treatment at the temperature of 60-100 ℃ until the pH value of the mixture is 5-7;
(5) performing suction filtration, washing the product obtained in the step (4) with deionized water or ethanol, and then drying at 60-120 ℃ for 3-24 h; and then roasting the mixture for 2 to 10 hours in a muffle furnace at the temperature of 350 to 700 ℃ to obtain the supported heterogeneous catalyst subjected to ultrasonic load treatment.
Further, the mass fraction of the main active component is 0.5-50%, preferably 5-25%; the mass fraction of the auxiliary agent is 0-20%, preferably 0-5%; the balance being carriers.
Further, the carrier is one or two of silicon dioxide or aluminum oxide.
The invention also discloses a method for preparing 3-aminopropanol by using the supported heterogeneous catalyst, which comprises the steps of taking 3-hydroxypropionitrile as a raw material to perform hydrogenation reaction in the presence of liquid ammonia to prepare 3-aminopropanol, mixing the 3-hydroxypropionitrile and the liquid ammonia in proportion, mixing the mixture with hydrogen, and then performing hydrogenation reaction at the temperature of 60-230 ℃, preferably 80-120 ℃, under the reaction pressure of 1.0-30.0 MPa, preferably 2.0-18.0 MPa; the product is obtained by reaction in a reactor in the presence of a supported heterogeneous catalyst prepared by an ultrasonic supported method.
Further, the adding molar ratio of the liquid ammonia to the 3-hydroxypropionitrile is 1: 1-30: 1, preferably 2: 1-15: 1.
Further, the molar ratio of the hydrogen to the 3-hydroxypropionitrile is 1:1 to 10:1, preferably 2:1 to 5: 1.
Further, the liquid mass space velocity of the 3-hydroxypropionitrile is 0.1-1.0 h-1Preferably 0.9 to 1.0 hour-1。
Further, the reactor is one of a fixed bed, a fluidized bed or a slurry bed reactor, preferably a fixed bed reactor.
Further, the supported heterogeneous catalyst is subjected to hydrogen reduction activation treatment before use, and the hydrogen reduction activation treatment is carried out under the conditions that the temperature is 300-450 ℃, the pressure is 0.1-1.0 MPa, and the volume space velocity is 500-3000 h-1Reducing the hydrogen flow for 1 to 24 hours, preferably 2 to 8 hours.
The invention also discloses a system used in the method for preparing 3-aminopropanol by adopting the catalyst, wherein a raw material mixing container for mixing 3-hydroxypropionitrile and liquid ammonia is communicated with a mixer sequentially through a raw material mixture filter and a high-pressure pump; the hydrogen tank is communicated with the mixer through the purification tank, the hydrogen filter and the one-way valve in sequence; the discharge port of the mixer is communicated with a reactor filled with a supported heterogeneous catalyst, and the discharge port of the reactor is communicated with a collecting tank; the collecting tank is also connected with a gas chromatograph through a back pressure valve; an emergency evacuation pipe is arranged between the high-pressure pump and the mixer, and an evacuation pipe is arranged at one end of the gas chromatograph; a pressure gauge, a pressure regulating valve and a mass flow meter are also arranged between the hydrogen tank and the mixer, a rotor flow meter is also arranged in front of the gas chromatograph, and a plurality of stop valves are also arranged on the system pipeline.
The catalyst is prepared by an ultrasonic loading method and is a high-dispersion catalyst. In the supported catalyst, Co is higher in catalytic activity when being used as a main active component, but is more expensive; while Ni is relatively cheap, but has less effect as the main active component than Co, the invention adopts the ultrasonic load method and reasonable preparation parameters to ensure that the Ni achieves the same catalytic activity as Co when the Ni is used as the main active component. The catalyst of the invention is used for preparing 3-aminopropanol, which (1) improves the quality space-time yield of 3-aminopropanol on the whole, (2) improves the selectivity of the target product 3-aminopropanol, (3) enables the 3-hydroxypropionitrile ammonia hydrogenation reaction to be realized under lower reaction pressure, (4) improves the stability of a catalytic system, (5) has simple flow operation, is convenient and feasible, reduces the one-time investment and production cost of production and subsequent separation devices, and is easy to realize large-scale continuous industrial production. The reaction pressure range during the preparation of the 3-aminopropanol is larger, and particularly, compared with the prior art, the reaction pressure lower than 18.0MPa can be realized, so that the safety is greatly improved.
Drawings
FIG. 1 shows a schematic flow diagram according to an embodiment of the invention.
In the figure: 1, a stop valve; 2-a pressure gauge; 3-purifying the tank; 4-a stop valve; 5-pressure regulating valve; 6-a stop valve; 7-a hydrogen filter; 8-mass flow meter; 9-a one-way valve; 10-a mixer; 11-a stop valve; 12-a high pressure pump; 13-raw mixture filter; 14-a shut-off valve; 15-a reactor; 16-a stop valve; 17-a collection tank; 18-a shut-off valve; 19-back pressure valve; 20-a stop valve; 21-a stop valve; 22-a rotameter; 23-gas chromatography; 24-a hydrogen tank; 25-raw material mixing container.
Detailed Description
The present invention will be described more specifically with reference to examples. The practice of the present invention is not limited to the following examples, and any modification or variation of the present invention is within the scope of the present invention.
The invention is further illustrated by the following specific examples.
The system used in the invention
As shown in fig. 1, a hydrogen tank 24 containing hydrogen is connected to the mixer 10 through a pipeline, and a stop valve 1, a pressure gauge 2, a purge tank 3, a stop valve 4, a pressure regulating valve 5, a stop valve 6, a hydrogen filter 7, a mass flow meter 8, and a check valve 9 are sequentially provided on the pipeline between the hydrogen tank and the mixer 10.
A raw material mixing container 25 for mixing 3-hydroxypropionitrile and liquid ammonia is communicated with the mixer 10 through a pipeline, a raw material filter 13, a high-pressure pump 12 and a stop valve 11 are sequentially arranged on the pipeline between the raw material mixing container 25 and the mixer 10, the mixed liquid of 3-hydroxypropionitrile and liquid ammonia is pumped into the mixer 10 by the high-pressure pump 12, an emergency vent pipe is connected between the stop valve 11 and the high-pressure pump 12, and the stop valve 14 is arranged on the emergency vent pipe.
A discharge port of the mixer 10 is connected with a reactor 15, a stop valve 16 and a collecting tank 17 in sequence through a pipeline, the reactor 15 is filled with a supported heterogeneous catalyst prepared by the ultrasonic supporting method, hydrogen, 3-hydroxypropionitrile and liquid ammonia are mixed in the mixer 10 and then react in the reactor 15, and the reactor 15 of the following examples 1 to 15 adopts a fixed bed reactor, and has the length of 60mm and the inner diameter of 10 mm. The inlet of the collection tank 17 is arranged at the top for collecting the liquid product obtained from the reaction, which is discharged by the shut-off valve 16. The top of the collection tank 17 is also connected with a gas chromatograph 23 through a pipeline, and the gas passes through a back pressure valve 19, a stop valve 20 and a rotor flow meter 22 which are arranged on the pipeline from the top of the collection tank 17 in sequence and reaches the gas chromatograph 23 to analyze gaseous products. A stop valve 21 is provided in parallel with the rotameter 22 and the gas chromatograph 23, and the gas emptying absorption or recycling can be controlled by the stop valve 21.
A sampling pipe with a stop valve 18 is arranged at the bottom of the collecting tank 17, and the reaction product can be analyzed on line through a gas chromatograph 23 after being sampled.
The composition is 20Ni-3Re/SiO2Preparation of the catalyst of (1):
weighing 7.432gNi (NO)3)2·6H2O and 0.432g NH4·ReO4Dissolving in 150mL of deionized water; then 10.0g of SiO were weighed2Placing the mixture into the mixed solution, stirring, transferring the mixture into an ultrasonic reactor, and carrying out ultrasonic treatment for 1h at 50 KHz; measuring 17mL of ammonia water solution with the mass concentration of 28%, adding the ammonia water solution into the mixed solution, and continuously performing ultrasonic treatment for 1h at the original frequency of 50 KHz; then mixing the aboveDistilling ammonia at 90 deg.C until pH value of the mixture is about 6.5; performing suction filtration, washing the obtained product by deionized water, and then drying for 4h at 120 ℃; then the mixture is roasted for 4 hours in a muffle furnace at 450 ℃. The catalyst is crushed to 20-40 meshes for later use, and other catalysts can be prepared by the same method according to different proportions.
The catalyst loading of the invention is 5mL, and the catalyst is activated by hydrogen reduction treatment before use, and the preferred hydrogen reduction activation condition is in hydrogen flow at 390 ℃ (normal pressure, volume space velocity of 1500 h)-1) And reducing for 6 hours.
Preparation of 3-aminopropanol:
the product obtained by the invention is analyzed by Agilent7890B, DB-35 capillary chromatographic column and FID detector.
Example 1
Weighing the 20Ni-3Re/SiO22.6g (about 5ml) of catalyst was charged into the fixed bed reactor. Before use, the catalyst is activated by hydrogenation treatment under the following conditions: the temperature T is 390 ℃; the pressure P is 0.3MPa, and the gas volume space velocity GHSV is 1500h-1And the reduction time is 6 hours. And when the temperature in the reactor is naturally reduced to 100 ℃, the pressure is increased to 8MPa, and the system is waited to be stable. Mixing liquid ammonia and 3-hydroxypropionitrile according to a molar ratio of 5:1, pumping the mixed liquid into a mixer 10 through a high-pressure pump 12 after a fixed bed reaction system is stabilized, adjusting the liquid mass airspeed of the 3-hydroxypropionitrile to be 1.03-hydroxypropionitrile g/catalyst g.h, and the molar ratio of hydrogen to the 3-hydroxypropionitrile in the reaction system to be 2.0:1, carrying out reaction for 48 hours, sampling from a collection tank 17, and analyzing by gas chromatography. 3-hydroxypropionitrile undergoes an ammonia hydrogenation reaction, the conversion rate is 90%, and the selectivity is 93%.
Example 2
Weighing the 20Ni-3Re/SiO22.6g (about 5ml) of catalyst was charged into the fixed bed reactor. Before use, the catalyst is activated by hydrogenation treatment under the following conditions: the temperature T is 390 ℃; the pressure P is 0.3MPa, and the gas volume space velocity GHSV is 1500h-1And the reduction time is 6 hours. And when the temperature in the reactor is naturally reduced to 100 ℃, the pressure is increased to 8MPa, and the system is waited to be stable. Reacting liquid ammonia with 3-hydroxypropionitrileMixing at a molar ratio of 5:1, pumping the mixed liquid into a mixer 10 through a high-pressure pump 12 after a fixed bed reaction system is stabilized, adjusting the liquid mass space velocity of 3-hydroxypropionitrile to be 1.03-hydroxypropionitrile g/catalyst g.h, and the molar ratio of hydrogen to 3-hydroxypropionitrile in the reaction system to be 2.2:1, carrying out reaction for 48 hours, sampling from a collection tank 17, and analyzing by gas chromatography. 3-hydroxypropionitrile undergoes an ammonia hydrogenation reaction, the conversion rate is 93 percent, and the selectivity is 92 percent.
Example 3
Weighing the 20Ni-3Re/SiO22.6g (about 5ml) of catalyst was charged into the fixed bed reactor. Before use, the catalyst is activated by hydrogenation treatment under the following conditions: the temperature T is 390 ℃; the pressure P is 0.3MPa, and the gas volume space velocity GHSV is 1500h-1And the reduction time is 6 hours. And when the temperature in the reactor is naturally reduced to 100 ℃, the pressure is increased to 8MPa, and the system is waited to be stable. Mixing liquid ammonia and 3-hydroxypropionitrile according to a molar ratio of 5:1, pumping the mixed liquid into a mixer 10 through a high-pressure pump 12 after a fixed bed reaction system is stabilized, adjusting the liquid mass airspeed of the 3-hydroxypropionitrile to be 1.03-hydroxypropionitrile g/catalyst g.h, and the molar ratio of hydrogen to the 3-hydroxypropionitrile in the reaction system to be 2.5:1, carrying out reaction for 48 hours, sampling from a collection tank 17, and analyzing by gas chromatography. The 3-hydroxypropionitrile undergoes an ammonia hydrogenation reaction, the conversion rate is 96 percent, and the selectivity is 90 percent.
Example 4
Weighing the 20Ni-3Re/SiO22.6g (about 5ml) of catalyst was charged into the fixed bed reactor. Before use, the catalyst is activated by hydrogenation treatment under the following conditions: the temperature T is 390 ℃; the pressure P is 0.3MPa, and the gas volume space velocity GHSV is 1500h-1And the reduction time is 6 hours. And when the temperature in the reactor is naturally reduced to 100 ℃, the pressure is increased to 8MPa, and the system is waited to be stable. Mixing liquid ammonia and 3-hydroxypropionitrile according to a molar ratio of 5:1, pumping the mixed liquid into a mixer 10 through a high-pressure pump 12 after a fixed bed reaction system is stabilized, adjusting the liquid mass space velocity of the 3-hydroxypropionitrile to be 1.03-hydroxypropionitrile g/catalyst g.h, and the molar ratio of hydrogen to the 3-hydroxypropionitrile in the reaction system to be 3.0:1, carrying out reaction, and reactingTime 48 hours, and a sample was taken from the collection tank 17 and analyzed by gas chromatography. The conversion rate of the 3-hydroxypropionitrile through the ammonia hydrogenation reaction is 99.8 percent, and the selectivity is 88 percent.
Example 5
Weighing the 20Ni-3Re/SiO22.6g (about 5ml) of catalyst was charged into the fixed bed reactor. Before use, the catalyst is activated by hydrogenation treatment under the following conditions: the temperature T is 390 ℃; the pressure P is 0.3MPa, and the gas volume space velocity GHSV is 1500h-1And the reduction time is 6 hours. And when the temperature in the reactor is naturally reduced to 100 ℃, the pressure is increased to 8MPa, and the system is waited to be stable. Mixing liquid ammonia and 3-hydroxypropionitrile according to a molar ratio of 5:1, pumping the mixed liquid into a mixer 10 through a high-pressure pump 12 after a fixed bed reaction system is stabilized, adjusting the liquid mass space velocity of the 3-hydroxypropionitrile to be 1.03-hydroxypropionitrile g/catalyst g.h, and the molar ratio of hydrogen to the 3-hydroxypropionitrile in the reaction system to be 5.0:1, carrying out reaction for 48 hours, sampling from a collection tank 17, and analyzing by gas chromatography. The 3-hydroxypropionitrile undergoes an ammonia hydrogenation reaction, the conversion rate is 100 percent, and the selectivity is 85 percent.
Example 6
Weighing the 20Ni-3Re/SiO22.6g (about 5ml) of catalyst was charged into the fixed bed reactor. Before use, the catalyst is activated by hydrogenation treatment under the following conditions: the temperature T is 390 ℃; the pressure P is 3.0MPa, and the gas volume space velocity GHSV is 1500h-1And the reduction time is 6 hours. And when the temperature in the reactor is naturally reduced to 105 ℃, the pressure is increased to 8MPa, and the system is waited to be stable. Mixing liquid ammonia and 3-hydroxypropionitrile in a molar ratio of 5:1, pumping the mixed liquid into a mixer 10 through a high-pressure pump 12 after a fixed bed reaction system is stabilized, adjusting the liquid mass space velocity of the 3-hydroxypropionitrile to be 1.03 g/g.g.h of the catalyst, and the molar ratio of hydrogen to the 3-hydroxypropionitrile in the reaction system to be 2.0:1, reacting for 48 hours, and sampling from a collection tank 17 to analyze through gas chromatography. The conversion rate of the 3-hydroxypropionitrile through the ammonia hydrogenation reaction is 96 percent, and the selectivity is 88 percent.
Example 7
Weighing the 20Ni-3Re/SiO2Catalyst 2.6g (about 5ml) was charged in a solidIn a fixed bed reactor. Before use, the catalyst is activated by hydrogenation treatment under the following conditions: the temperature T is 390 ℃; the pressure P is 0.3MPa, and the gas volume space velocity GHSV is 1500h-1And the reduction time is 6 hours. And when the temperature in the reactor is naturally reduced to 110 ℃, the pressure is increased to 8MPa, and the system is waited to be stable. Mixing liquid ammonia and 3-hydroxypropionitrile according to a molar ratio of 5:1, pumping the mixed liquid into a mixer 10 through a high-pressure pump 12 after a fixed bed reaction system is stabilized, adjusting the liquid mass space velocity of the 3-hydroxypropionitrile to be 1.03-hydroxypropionitrile g/catalyst g.h, and the molar ratio of hydrogen to the 3-hydroxypropionitrile in the reaction system to be 2.0:1, carrying out reaction for 48 hours, sampling from a collection tank 17, and analyzing by gas chromatography. The 3-hydroxypropionitrile undergoes an ammonia hydrogenation reaction, the conversion rate is 98 percent, and the selectivity is 83 percent.
Example 8
Weighing the 20Ni-3Re/SiO22.6g (about 5ml) of catalyst was charged into the fixed bed reactor. Before use, the catalyst is activated by hydrogenation treatment under the following conditions: the temperature T is 390 ℃; the pressure P is 0.3MPa, and the gas volume space velocity GHSV is 1500h-1And the reduction time is 6 hours. And when the temperature in the reactor is naturally reduced to 100 ℃, the pressure is increased to 8MPa, and the system is waited to be stable. Mixing liquid ammonia and 3-hydroxypropionitrile in a molar ratio of 5:1, pumping the mixed liquid into a mixer 10 through a high-pressure pump 12 after a fixed bed reaction system is stabilized, adjusting the liquid mass space velocity of the 3-hydroxypropionitrile to be 1.03 g/g.g.h of the catalyst, and the molar ratio of hydrogen to the 3-hydroxypropionitrile in the reaction system to be 2.0:1, reacting for 48 hours, and sampling from a collection tank 17 to analyze through gas chromatography. The conversion rate of the 3-hydroxypropionitrile through the ammonia hydrogenation reaction is 96 percent, and the selectivity is 83 percent.
Example 9
Weighing the 20Ni-3Re/SiO22.6g (about 5ml) of catalyst was charged into the fixed bed reactor. Before use, the catalyst is activated by hydrogenation treatment under the following conditions: the temperature T is 390 ℃; the pressure P is 0.3MPa, and the gas volume space velocity GHSV is 1500h-1And the reduction time is 6 hours. And when the temperature in the reactor is naturally reduced to 100 ℃, the pressure is increased to 8MPa, and the system is waited to be stable. Mixing liquid ammonia with3-hydroxypropionitrile in a molar ratio of 5:1, pumping the mixed liquid into a mixer 10 through a high-pressure pump 12 after a fixed bed reaction system is stabilized, adjusting the liquid mass space velocity of the 3-hydroxypropionitrile to be 1.03 g/g.g.h of the catalyst, and the molar ratio of hydrogen to the 3-hydroxypropionitrile in the reaction system to be 3.0:1, reacting for 48 hours, and sampling from a collection tank 17 to analyze through gas chromatography. The 3-hydroxypropionitrile undergoes an ammonia hydrogenation reaction, the conversion rate is 98.5 percent, and the selectivity is 82 percent.
Example 10
Weighing the 20Ni-3Re/SiO22.6g (about 5ml) of catalyst was charged into the fixed bed reactor. Before use, the catalyst is activated by hydrogenation treatment under the following conditions: the temperature T is 390 ℃; the pressure P is 0.3MPa, and the gas volume space velocity GHSV is 1500h-1And the reduction time is 6 hours. And when the temperature in the reactor is naturally reduced to 100 ℃, the pressure is increased to 8MPa, and the system is waited to be stable. Mixing liquid ammonia and 3-hydroxypropionitrile in a molar ratio of 5:1, pumping the mixed liquid into a mixer 10 through a high-pressure pump 12 after a fixed bed reaction system is stabilized, adjusting the liquid mass airspeed of the 3-hydroxypropionitrile to be 0.93-hydroxypropionitrile g/catalyst g.h, and H in the reaction system2The reaction was carried out with a hydrogen/3-hydroxypropionitrile molar ratio of 2.5:1 for 48 hours, and a sample was taken from the collection tank 17 and analyzed by gas chromatography. The 3-hydroxypropionitrile undergoes an ammonia hydrogenation reaction, the conversion rate is 100 percent, and the selectivity is 90 percent.
Example 11
Weighing the 20Ni-3Re/SiO22.6g (about 5ml) of catalyst was charged into the fixed bed reactor. Before use, the catalyst is activated by hydrogenation treatment under the following conditions: the temperature T is 390 ℃; the pressure P is 0.3MPa, and the gas volume space velocity GHSV is 1500h-1And the reduction time is 6 hours. And when the temperature in the reactor is naturally reduced to 100 ℃, the pressure is increased to 8MPa, and the system is waited to be stable. Mixing liquid ammonia and 3-hydroxypropionitrile in a molar ratio of 6: 1, pumping the mixed liquid into a mixer 10 through a high-pressure pump 12 after a fixed bed reaction system is stabilized, adjusting the liquid mass airspeed of the 3-hydroxypropionitrile to be 0.93-hydroxypropionitrile g/catalyst g.h, and adjusting the molar ratio of hydrogen to the 3-hydroxypropionitrile in the reaction system to be2.5:1, the reaction was carried out for 48 hours, and samples were taken from the collection pot 17 and analyzed by gas chromatography. The conversion rate of the 3-hydroxypropionitrile through the ammonia hydrogenation reaction is 100 percent, and the selectivity is 92 percent.
Example 12
Weighing the 20Ni-3Re/SiO22.6g (about 5ml) of catalyst was charged into the fixed bed reactor. Before use, the catalyst is activated by hydrogenation treatment under the following conditions: the temperature T is 390 ℃; the pressure P is 0.3MPa, and the gas volume space velocity GHSV is 1500h-1And the reduction time is 6 hours. And when the temperature in the reactor is naturally reduced to 100 ℃, the pressure is increased to 8MPa, and the system is waited to be stable. Mixing liquid ammonia and 3-hydroxypropionitrile in a molar ratio of 8: 1, pumping the mixed liquid into a mixer 10 through a high-pressure pump 12 after a fixed bed reaction system is stabilized, adjusting the liquid mass space velocity of the 3-hydroxypropionitrile to be 0.93 g/g.g.h of the catalyst, and the molar ratio of hydrogen to the 3-hydroxypropionitrile in the reaction system to be 2.5:1, reacting for 48 hours, and sampling from a collection tank 17 to analyze through gas chromatography. The conversion rate of the 3-hydroxypropionitrile through the ammonia hydrogenation reaction is 100 percent, and the selectivity is 94 percent.
Example 13
Weighing the 20Ni-3Re/SiO22.6g (about 5ml) of catalyst was charged into the fixed bed reactor. Before use, the catalyst is activated by hydrogenation treatment under the following conditions: the temperature T is 390 ℃; the pressure P is 0.3MPa, and the gas volume space velocity GHSV is 1500h-1And the reduction time is 6 hours. And when the temperature in the reactor is naturally reduced to 100 ℃, the pressure is increased to 8MPa, and the system is waited to be stable. Mixing liquid ammonia and 3-hydroxypropionitrile in a molar ratio of 8: 1, pumping the mixed liquid into a mixer after a fixed bed reaction system is stabilized, adjusting the liquid mass airspeed of the 3-hydroxypropionitrile to be 0.93-hydroxypropionitrile g/catalyst g.h, adjusting the molar ratio of hydrogen to the 3-hydroxypropionitrile in the reaction system to be 2.5:1, reacting for 48 hours, sampling from a collection tank 17, and analyzing by gas chromatography. The conversion rate of the 3-hydroxypropionitrile through the ammonia hydrogenation reaction is 100 percent, and the selectivity is 97 percent.
Example 14
Weighing the 20Ni-3Re/SiO2Catalysis2.6g (about 5ml) of the agent was charged into a fixed bed reactor. Before use, the catalyst is activated by hydrogenation treatment under the following conditions: the temperature T is 390 ℃; the pressure P is 0.3MPa, and the gas volume space velocity GHSV is 1500h-1And the reduction time is 6 hours. And when the temperature in the reactor is naturally reduced to 100 ℃, the pressure is increased to 8MPa, and the system is waited to be stable. Mixing liquid ammonia and 3-hydroxypropionitrile in a molar ratio of 10:1, pumping the mixed liquid into a mixer 10 through a high-pressure pump 12 after a fixed bed reaction system is stabilized, adjusting the liquid mass space velocity of the 3-hydroxypropionitrile to be 0.93 g/g.g.h of the catalyst, and the molar ratio of hydrogen to the 3-hydroxypropionitrile in the reaction system to be 2.5:1, reacting for 48 hours, and sampling from a collection tank 17 to analyze through gas chromatography. The conversion rate of the 3-hydroxypropionitrile through the ammonia hydrogenation reaction is 100 percent, and the selectivity is 98.5 percent.
Example 15
Weighing the 20Ni-3Re/SiO22.6g (about 5ml) of catalyst was charged into the fixed bed reactor. Before use, the catalyst is activated by hydrogenation treatment under the following conditions: the temperature T is 390 ℃; the pressure P is 0.3MPa, and the gas volume space velocity GHSV is 1500h-1And the reduction time is 6 hours. And when the temperature in the reactor is naturally reduced to 100 ℃, the pressure is increased to 8MPa, and the system is waited to be stable. Mixing liquid ammonia and 3-hydroxypropionitrile in a molar ratio of 10:1, pumping the mixed liquid into a mixer 10 through a high-pressure pump 12 after a fixed bed reaction system is stabilized, adjusting the liquid mass space velocity of the 3-hydroxypropionitrile to be 0.93 g/g.g.h of the catalyst, and the molar ratio of hydrogen to the 3-hydroxypropionitrile in the reaction system to be 2.5:1, reacting for 1000 hours, sampling from a collection tank 17 every 24 hours, and analyzing by gas chromatography. The conversion rate of the 3-hydroxypropionitrile through the ammonia hydrogenation reaction is 100 percent, and the selectivity is 98.5 percent.
The present invention has been described in detail above, but the present invention is not limited to the specific embodiments described herein.
Claims (9)
1. A load type heterogeneous catalyst for preparing 3-aminopropanol by taking 3-hydroxypropionitrile as a raw material and carrying out hydrogenation reaction in the presence of liquid ammonia comprises a main active component, an auxiliary agent and a carrier, and is characterized in that: the main active component is Ni, and the auxiliary agent is a simple substance of Re or an oxide thereof; the carrier is one or two of insoluble solid materials of silicon dioxide and aluminum oxide, the supported heterogeneous catalyst is prepared by adopting an ultrasonic supporting method, and the method comprises the following steps:
(1) dissolving soluble salts of the main active component and the auxiliary agent by deionized water to obtain a salt solution, wherein the ion concentration is 0.05-2.0 mol/L;
(2) weighing a quantitative carrier, placing the quantitative carrier in the salt solution obtained in the step (1), transferring the quantitative carrier into an ultrasonic reactor, and treating for t1 hours at 5-120KHz, wherein t1 is more than 0 and less than or equal to 10;
(3) adding an ammonia water solution into the solution obtained in the step (2) to adjust the pH value to 9-11, and continuing ultrasonic treatment for t2 hours, wherein t2 is more than 0 and less than or equal to 8;
(4) evaporating ammonia from the mixture obtained in the step (3) after ultrasonic treatment at the temperature of 60-100 ℃ until the pH value of the mixture is 5-7;
(5) performing suction filtration, washing the product obtained in the step (4) with deionized water or ethanol, and then drying at 60-120 ℃ for 3-24 h; then roasting the mixture for 2 to 10 hours in a muffle furnace at the temperature of 350 to 700 ℃ to obtain the supported heterogeneous catalyst after ultrasonic load treatment,
the supported heterogeneous catalyst is subjected to hydrogen reduction activation treatment before use.
2. The supported heterogeneous catalyst of claim 1, wherein: the mass fraction of the main active component is 0.5-50%; the mass fraction of the auxiliary agent is 0-20% but not 0%; the balance being carriers.
3. A method for preparing 3-aminopropanol by using the supported heterogeneous catalyst of any one of claims 1 to 2, which takes 3-hydroxypropionitrile as a raw material to perform hydrogenation reaction in the presence of liquid ammonia to prepare 3-aminopropanol, and is characterized in that: mixing 3-hydroxypropionitrile and liquid ammonia in proportion, mixing with hydrogen, and reacting in a reactor at 60-230 ℃ and under the reaction pressure of 1.0-30.0 MPa in the presence of a supported heterogeneous catalyst prepared by an ultrasonic supported method to obtain a product.
4. The process for the preparation of 3-aminopropanol according to claim 3, wherein: the adding molar ratio of the liquid ammonia to the 3-hydroxypropionitrile is 1: 1-30: 1.
5. The process for the preparation of 3-aminopropanol according to claim 3, wherein: the adding molar ratio of the hydrogen to the 3-hydroxypropionitrile is 1: 1-10: 1.
6. The process for the preparation of 3-aminopropanol according to claim 3, wherein: the liquid mass space velocity of the 3-hydroxypropionitrile is 0.1-1.0 h-1。
7. The process for the preparation of 3-aminopropanol according to claim 3, wherein: the reactor is one of a fixed bed, a fluidized bed or a slurry bed reactor.
8. The process for the preparation of 3-aminopropanol according to claim 3, wherein: the supported heterogeneous catalyst is subjected to hydrogen reduction activation treatment before use, and the hydrogen reduction activation treatment is carried out under the conditions that the temperature is 300-450 ℃, the pressure is 0.1-1.0 MPa, and the volume space velocity is 500-3000 h-1Reducing the hydrogen flow for 1-24 h.
9. The process for preparing 3-aminopropanol according to any of claims 3 to 8 wherein: the system used in the method is that a raw material mixing container for mixing 3-hydroxypropionitrile and liquid ammonia is communicated with a mixer through a raw material mixture filter and a high-pressure pump in sequence; the hydrogen tank is communicated with the mixer through the purification tank, the hydrogen filter and the one-way valve in sequence; the discharge port of the mixer is communicated with a reactor filled with a supported heterogeneous catalyst, and the discharge port of the reactor is communicated with a collecting tank; the collecting tank is also connected with a gas chromatograph through a back pressure valve; an emergency evacuation pipe is arranged between the high-pressure pump and the mixer, and an evacuation pipe is arranged at one end of the gas chromatograph; a pressure gauge, a pressure regulating valve and a mass flow meter are also arranged between the hydrogen tank and the mixer, a rotor flow meter is also arranged in front of the gas chromatograph, and a plurality of stop valves are also arranged on the system pipeline.
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| CN111253269A (en) * | 2020-03-16 | 2020-06-09 | 安庆市鑫富化工有限责任公司 | Crude steaming process of 3-aminopropanol |
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