CN111072493A - Method for preparing 1, 5-pentanediamine by one-step method - Google Patents
Method for preparing 1, 5-pentanediamine by one-step method Download PDFInfo
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- CN111072493A CN111072493A CN201911317144.9A CN201911317144A CN111072493A CN 111072493 A CN111072493 A CN 111072493A CN 201911317144 A CN201911317144 A CN 201911317144A CN 111072493 A CN111072493 A CN 111072493A
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- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 238000006114 decarboxylation reaction Methods 0.000 claims abstract description 23
- 235000001014 amino acid Nutrition 0.000 claims abstract description 18
- 150000001413 amino acids Chemical class 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000012298 atmosphere Substances 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims description 10
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 235000019766 L-Lysine Nutrition 0.000 claims description 5
- 239000004472 Lysine Substances 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- IDIFPUPZOAXKOV-UHFFFAOYSA-N azane ruthenium Chemical compound N.[Ru] IDIFPUPZOAXKOV-UHFFFAOYSA-N 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 238000001514 detection method Methods 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 2
- FGHSTPNOXKDLKU-UHFFFAOYSA-N nitric acid;hydrate Chemical compound O.O[N+]([O-])=O FGHSTPNOXKDLKU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000005453 pelletization Methods 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 230000002950 deficient Effects 0.000 claims 1
- 239000011148 porous material Substances 0.000 claims 1
- 238000010189 synthetic method Methods 0.000 claims 1
- BVHLGVCQOALMSV-JEDNCBNOSA-N L-lysine hydrochloride Chemical compound Cl.NCCCC[C@H](N)C(O)=O BVHLGVCQOALMSV-JEDNCBNOSA-N 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000005984 hydrogenation reaction Methods 0.000 abstract 1
- 229940024606 amino acid Drugs 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 229910019891 RuCl3 Inorganic materials 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 229960003646 lysine Drugs 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- AGPKZVBTJJNPAG-WHFBIAKZSA-N L-isoleucine Chemical compound CC[C@H](C)[C@H](N)C(O)=O AGPKZVBTJJNPAG-WHFBIAKZSA-N 0.000 description 3
- 229960000310 isoleucine Drugs 0.000 description 3
- VJROPLWGFCORRM-UHFFFAOYSA-N 2-methylbutan-1-amine Chemical compound CCC(C)CN VJROPLWGFCORRM-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- AGPKZVBTJJNPAG-UHFFFAOYSA-N isoleucine Natural products CCC(C)C(N)C(O)=O AGPKZVBTJJNPAG-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229930182844 L-isoleucine Natural products 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910010298 TiOSO4 Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/66—Pore distribution
- B01J35/695—Pore distribution polymodal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for preparing 1, 5-pentanediamine by a one-step method, which aims to solve the problems that the existing raw materials are difficult to obtain, the process conditions are complex and the like. The method takes L-lysine hydrochloride as a raw material, and hydrogenation reduction decarboxylation is carried out under the high-pressure heating condition. By using a self-made high selectivity amino acid decarboxylation catalyst. The selectivity can be stabilized at more than 90 percent, and the method has good industrial application value.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a synthetic route for preparing 2-methylbutylamine by decarboxylation of isoleucine by using a catalyst.
Background
The decarboxylation of L-lysine to prepare 1, 5-pentanediamine is an ideal synthetic route, theoretically, only CO is available2A by-product. However, the preparation of chemicals by catalytic conversion using amino acids as raw materials faces many challenges, and the amino acids have a plurality of functional groups, i.e. a special structure of one amino group and one carboxyl group, so that the amino acids generate different products under different reaction conditions.
According to the literature, the current common route for the preparation of 1, 5-pentanediamine is reported to be enzymatic conversion (EP1482055), and microbial fermentation production (Biotechnology and Bioengineering, 2011, 108 (1): 93-103.), as well as more novel whole-cell catalysis (Journal of Anhui Agri.Sci., 2011, 39 (4): 1917-. However, the existing methods have the defects of harsh operating conditions, difficult separation and the like. The chemical method for preparing 1, 5-pentanediamine is a development direction, the common method is to prepare the 1, 5-pentanediamine by catalytic hydrogenation of a corresponding dinitrile compound, and the used catalyst is a nickel catalyst (Appl Catal, A,2009,352 (1-2); 193-201).
Disclosure of Invention
The invention aims to solve the technical problems of low yield, complex process and the like in the process of preparing 1, 5-pentanediamine in the prior art, and provides a method for preparing 1, 5-pentanediamine with high conversion rate and high selectivity.
The invention uses cheap and easily obtained L-lysine as a raw material, uses a self-made decarboxylation catalyst, and carries out a one-step reaction in a pressure vessel.
(1) Dissolving L-lysine in deionized water, adding the deionized water into a reaction kettle with a polytetrafluoroethylene lining, adding a proper amount of decarboxylation catalyst, sealing the reaction kettle, detecting leakage, replacing air in the kettle with nitrogen for about 6 times, and considering complete replacement;
(2) slowly introducing hydrogen to reach the initial set pressure, and controlling the pressure range to be 2-10 MPa;
(3) after leakage detection is finished, stirring and heating are started, the rotating speed of a stirring paddle is 400rpm, and the heating rate is 6 ℃/min;
(4) heating to a specific temperature, keeping for 2-6 h, and keeping stirring;
(5) stopping heating and keeping stirring after the set reaction time is reached, and naturally cooling to room temperature;
(6) slowly decompressing, and filtering the catalyst to obtain the 1, 5-pentanediamine aqueous solution.
The amino acid decarboxylation catalyst used in the invention uses an impregnation method to load a precursor on nano TiO2The precursor is ruthenium metal salt, the mass percentage of the precursor is 0.1-10%, and the balance is TiO2(ii) a The nano TiO is2The particle size is 10-50 nm; the ruthenium metal salt is one of ruthenium chloride, ruthenium ammonia complex or chlorine ruthenate complex salt; the TiO is2Is Ti with high specific surface area prepared by adopting a low-temperature liquid phase method3+The anatase phase carrier with a defect structure has a spherical geometric structure or a multi-level hole structure.
The preparation method specifically comprises the following steps:
(1) adding TiOSO into nitric acid water solution4Ultrasonic dissolving to form transparent solution;
(2) stirring the transparent solution obtained in the step (1), adding a polyethylene glycol-2000 dispersing agent, continuously stirring for 1h, and carrying out water bath at the temperature of 50-90 ℃ for 2-6 h to obtain a suspension;
(3) centrifuging and filtering the suspension obtained in the step (2), washing with water and alcohol for 3 times respectively, drying at 50 ℃ for 12h, and roasting at 350-450 ℃ in an air atmosphere for 4h to obtain anatase type nano TiO with high specific surface area2；
(4) Adding ruthenium metal salt into deionized water or absolute ethyl alcohol, dispersing for 1-4 h by using ultrasonic, and adding the nano TiO prepared in the step (3)2Stirring for 6-24 h to obtain a material;
(5) centrifuging, washing and drying the material obtained in the step (4), and roasting for 4-8 h at the temperature of 650 ℃ in an air atmosphere; is arranged at H2Reducing at 100-650 deg.c in atmosphere, pelletizing, forming and drying to obtain the decarboxylation catalyst for amino acid.
The invention has the beneficial effects that:
(1) compared with the background literature, the synthesis process of the 1, 5-pentanediamine has no special requirement on pH and does not need to add extra acid.
(2) Compared with the background literature, the conversion rate and the selectivity of the 1, 5-pentanediamine are higher and can reach more than 85 percent.
(3) Compared with the background literature, the synthetic steps of the 1, 5-pentanediamine are simple.
Detailed Description
The present invention is further illustrated by the following examples, but is not limited thereto.
The catalyst evaluation was carried out using an autoclave reactor equipped with a polytetrafluoroethylene liner and a stirring paddle. The reaction was carried out at high temperature and high pressure with the catalyst accounting for 5 wt% of the reaction substrate. After the reaction kettle is sealed, N is firstly used2The air in the autoclave was replaced 6 times and pressurized to a specific initial pressure by introducing hydrogen. The stirring was turned on and the temperature was started. Keeping the temperature at 180 ℃ for reaction for 4-8 h, stopping heating and naturally cooling, and sampling and analyzing.
The analytical instruments are Shimadzu GC-2014 gas chromatography, hydrogen flame ion detector and DB-1701 chromatographic column. The selectivity and conversion were calculated according to the formula.
Example 1
A2% dilute nitric acid solution containing 100mL was placed in a 50 ℃ water bath. While stirring, 8g of TiOSO was added4Wherein TiOSO4The volume ratio of the nitric acid to the aqueous solution was 1: 20. While maintaining stirring, 6mL of polyethylene glycol-2000 was added dropwise. The resulting mixture was stirred at 50 ℃ for 6h, and the suspension was centrifuged and filtered. Then washing with water and ethanol for three times, drying at 50 deg.C for 12h, and calcining at 450 deg.C in air atmosphere for 4h to obtain 3.52g of the prepared TiO2And obtaining the target quantity through multiple accumulation.
1.3g of RuCl3·3H2Dissolving O in 80ml absolute ethyl alcohol, ultrasonic dissolving, adding 20g TiO21, soaking for 16 hours under strong stirring; removing the solvent from the obtained material, drying, fully washing with deionized water, drying at 100 ℃, roasting at 350 ℃ for 4h in an air atmosphere, and cooling to room temperature in a dry environment. After granulation, molding and drying again, the sample is placed in a hydrogen atmosphere and reduced for 3 hours at 400 ℃ to obtain the amino acid decarboxylation catalyst.
Dissolving 1.21g L-lysine hydrochloride in 100ml deionized water, ultrasonic dissolving, adding 0.6g of amino acid decarboxylation catalyst, and placing the mixed solution in a reaction kettle. After sealing, nitrogen gas is used for replacing 6 times, and then hydrogen gas is slowly introduced until the initial pressure reaches 4 Mpa. Heating and stirring are started, timing is started when the temperature is 150 ℃, heating is stopped after 4 hours, and the mixture is naturally cooled to the room temperature. After slowly decompressing, taking the reaction solution, filtering, and taking the supernatant for testing.
Example 2
TiO2-1 preparation same as example 1. 3.6g of RuCl3·3H2Dissolving O in deionized water, ultrasonic dissolving, and adding 20g of TiO2-1, soaking for 24h under vigorous stirring; removing the solvent from the obtained material, drying, fully washing with deionized water, drying at 100 ℃, granulating, molding, drying again, roasting at 450 ℃ for 8h in an air atmosphere, and cooling to room temperature in a dry environment. And then placing the sample in a hydrogen atmosphere, and reducing for 3h at 500 ℃ to obtain the amino acid decarboxylation catalyst.
Dissolving 0.48g L-lysine hydrochloride in 40ml deionized water, ultrasonic dissolving, adding 0.24g of amino acid decarboxylation catalyst, and placing the mixed solution in a reaction kettle. After sealing, nitrogen gas is used for replacing 6 times, and then hydrogen gas is slowly introduced until the initial pressure reaches 4 Mpa. Heating and stirring are started, timing is started when the temperature is 180 ℃, heating is stopped after 2 hours, and the mixture is naturally cooled to the room temperature. After slowly decompressing, taking the reaction solution, filtering, and taking the supernatant for testing.
Example 3
TiO2-1 preparation same as example 1. 3.9g of RuCl3·3H2Dissolving O in deionized water, ultrasonic dissolving, and adding 20g of commercially available anatase TiO2Strongly stirring and soaking for 24 hours; removing the solvent from the obtained material, drying, fully washing with deionized water, drying at 100 ℃, granulating, molding, drying again, roasting at 350 ℃ for 8h in an air atmosphere, and cooling to room temperature in a dry environment. And then placing the sample in a hydrogen atmosphere, and reducing for 3h at 500 ℃ to obtain the amino acid decarboxylation catalyst.
Dissolving 0.48g L-lysine hydrochloride in 40ml deionized water, ultrasonic dissolving, adding 0.24g of amino acid decarboxylation catalyst, and placing the mixed solution in a reaction kettle. After sealing, nitrogen gas is used for replacing 6 times, and then hydrogen gas is slowly introduced until the initial pressure reaches 8 Mpa. Heating and stirring are started, timing is started when the temperature is 180 ℃, heating is stopped after 4 hours, and the mixture is naturally cooled to the room temperature. After slowly decompressing, taking the reaction solution, filtering, and taking the supernatant for testing.
Example 4
TiO2-1 preparation same as example 1. 0.6g of RuCl3·3H2Dissolving O in deionized water, ultrasonic dissolving, and adding 20g of commercially available anatase TiO2Strongly stirring and soaking for 24 hours; removing the solvent from the obtained material, drying, fully washing with deionized water, drying at 100 ℃, granulating, molding, drying again, roasting at 350 ℃ for 8h in an air atmosphere, and cooling to room temperature in a dry environment. Then the sample is put in hydrogen atmosphere and reduced for 3h at 500 ℃ to obtain decarboxylation of amino acidA catalyst;
dissolving 0.26g L-isoleucine in 40ml deionized water, ultrasonic dissolving, adding 0.24g of amino acid decarboxylation catalyst, and placing the mixed solution in a reaction kettle. After sealing, nitrogen gas is used for replacing 6 times, and then hydrogen gas is slowly introduced until the initial pressure reaches 2 Mpa. Heating and stirring are started, timing is started when the temperature is 180 ℃, heating is stopped after 8 hours, and the mixture is naturally cooled to the room temperature. After slowly decompressing, taking the reaction solution, filtering, and taking the supernatant for testing.
The performance evaluation of the catalyst for decarboxylation of isoleucine to 2-methylbutylamine of the invention:
the reaction products obtained in examples 1 to 4 were respectively characterized, and the results are shown in the following table.
TABLE 1 results of the reaction
| Examples | Conversion rate/% | Selectivity/%) |
| 1 | 99.9 | 80.3 |
| 2 | 99.9 | 86.5 |
| 3 | 99.9 | 83.2 |
| 4 | 99.9 | 85.4 |
And (4) conclusion: the process route for preparing the 1, 5-pentanediamine by decarboxylation of the L-lysine is simple, the selectivity of the 1, 5-pentanediamine is high, the reaction can be carried out for 5 hours under the reaction conditions of 4Mpa and 180 ℃, the conversion rate is kept at 99.9%, and the selectivity is kept at more than 85%.
Claims (3)
1. A synthetic method for preparing 1, 5-pentanediamine by a one-step method is characterized in that an amino acid decarboxylation catalyst is adopted in the reaction, and the method comprises the following steps:
(1) dissolving L-lysine in deionized water, adding into a reaction kettle with a polytetrafluoroethylene lining, adding a proper amount of an amino acid decarboxylation catalyst, sealing the reaction kettle, detecting leakage, and replacing air in the kettle with nitrogen for more than 6 times;
(2) slowly introducing hydrogen to reach the initial set pressure, and controlling the pressure range to be 2-4 MPa;
(3) after leakage detection is finished, stirring and heating are started, the rotating speed of a stirring paddle is 400rpm, and the heating rate is 6 ℃/min;
(4) heating to a specific temperature, keeping for 2-6 h, and keeping stirring;
(5) stopping heating and keeping stirring after the set reaction time is reached, and naturally cooling to room temperature;
(6) slowly decompressing, and filtering the catalyst to obtain the 1, 5-pentanediamine aqueous solution.
2. The one-step method for preparing 1, 5-pentanediamine according to claim 1, wherein the amino acid decarboxylation catalyst in the step (1) is prepared by loading a precursor on nano TiO by using an impregnation method2The precursor is ruthenium metal salt, the mass percentage of the precursor is 0.1-10%, and the balance is TiO2(ii) a The nano TiO is2The particle size is 10-50 nm; the ruthenium metal salt is one of ruthenium chloride, ruthenium ammonia complex or chlorine ruthenate complex salt; the TiO is2Is Ti with high specific surface area prepared by adopting a low-temperature liquid phase method3+Of defective structuresThe anatase phase carrier has a spherical geometric structure or a multi-stage pore structure.
3. The one-step method for preparing 1, 5-pentanediamine according to claim 2, wherein the amino acid decarboxylation catalyst is prepared by the following steps:
(1) adding TiOSO into nitric acid water solution4Ultrasonic dissolving to form transparent solution;
(2) stirring the transparent solution obtained in the step (1), adding a polyethylene glycol-2000 dispersing agent, continuously stirring for 1h, and carrying out water bath at the temperature of 50-90 ℃ for 2-6 h to obtain a suspension;
(3) centrifuging and filtering the suspension obtained in the step (2), washing with water and alcohol for 3 times respectively, drying at 50 ℃ for 12h, and roasting at 350-450 ℃ in an air atmosphere for 4h to obtain anatase type nano TiO with high specific surface area2；
(4) Adding ruthenium metal salt into deionized water or absolute ethyl alcohol, dispersing for 1-4 h by using ultrasonic, and adding the nano TiO prepared in the step (3)2Stirring for 6-24 h to obtain a material;
(5) centrifuging, washing and drying the material obtained in the step (4), and roasting for 4-8 h at the temperature of 650 ℃ in an air atmosphere; is arranged at H2Reducing at 100-650 deg.c in atmosphere, pelletizing, forming and drying to obtain the decarboxylation catalyst for amino acid.
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