CN118079905A - Preparation of a modified carbon-supported ruthenium-based catalyst and its application in catalytic synthesis of pentamethylenediamine - Google Patents
Preparation of a modified carbon-supported ruthenium-based catalyst and its application in catalytic synthesis of pentamethylenediamine Download PDFInfo
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- CN118079905A CN118079905A CN202410225577.6A CN202410225577A CN118079905A CN 118079905 A CN118079905 A CN 118079905A CN 202410225577 A CN202410225577 A CN 202410225577A CN 118079905 A CN118079905 A CN 118079905A
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- lysine
- pentamethylenediamine
- catalyst
- ruthenium
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- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 title claims abstract description 144
- 239000003054 catalyst Substances 0.000 title claims abstract description 120
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 46
- 238000007036 catalytic synthesis reaction Methods 0.000 title claims abstract description 5
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 67
- 239000004472 Lysine Substances 0.000 claims abstract description 52
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims abstract description 50
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000006114 decarboxylation reaction Methods 0.000 claims abstract description 23
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 18
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 16
- 229960003646 lysine Drugs 0.000 claims description 49
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims description 48
- 235000018977 lysine Nutrition 0.000 claims description 47
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 44
- 238000000034 method Methods 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 25
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 21
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- BVHLGVCQOALMSV-JEDNCBNOSA-N L-lysine hydrochloride Chemical compound Cl.NCCCC[C@H](N)C(O)=O BVHLGVCQOALMSV-JEDNCBNOSA-N 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 229960005337 lysine hydrochloride Drugs 0.000 claims description 11
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 239000003575 carbonaceous material Substances 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 2
- WPLOVIFNBMNBPD-ATHMIXSHSA-N subtilin Chemical group CC1SCC(NC2=O)C(=O)NC(CC(N)=O)C(=O)NC(C(=O)NC(CCCCN)C(=O)NC(C(C)CC)C(=O)NC(=C)C(=O)NC(CCCCN)C(O)=O)CSC(C)C2NC(=O)C(CC(C)C)NC(=O)C1NC(=O)C(CCC(N)=O)NC(=O)C(CC(C)C)NC(=O)C(NC(=O)C1NC(=O)C(=C/C)/NC(=O)C(CCC(N)=O)NC(=O)C(CC(C)C)NC(=O)C(C)NC(=O)CNC(=O)C(NC(=O)C(NC(=O)C2NC(=O)CNC(=O)C3CCCN3C(=O)C(NC(=O)C3NC(=O)C(CC(C)C)NC(=O)C(=C)NC(=O)C(CCC(O)=O)NC(=O)C(NC(=O)C(CCCCN)NC(=O)C(N)CC=4C5=CC=CC=C5NC=4)CSC3)C(C)SC2)C(C)C)C(C)SC1)CC1=CC=CC=C1 WPLOVIFNBMNBPD-ATHMIXSHSA-N 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- VFAHXTJRZRHGDN-UHFFFAOYSA-N [Ru].[C]=O Chemical compound [Ru].[C]=O VFAHXTJRZRHGDN-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract description 9
- 239000002808 molecular sieve Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 229910052799 carbon Inorganic materials 0.000 abstract description 5
- 238000003837 high-temperature calcination Methods 0.000 abstract description 2
- 150000001721 carbon Chemical class 0.000 abstract 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 17
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 12
- 150000002431 hydrogen Chemical class 0.000 description 11
- 239000011259 mixed solution Substances 0.000 description 10
- 238000004811 liquid chromatography Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 4
- -1 L-lysine, lysine salt Chemical class 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000000855 fermentation Methods 0.000 description 3
- 230000004151 fermentation Effects 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 235000019766 L-Lysine Nutrition 0.000 description 2
- 108010048581 Lysine decarboxylase Proteins 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229920006118 nylon 56 Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- BHXBZLPMVFUQBQ-UHFFFAOYSA-K samarium(iii) chloride Chemical compound Cl[Sm](Cl)Cl BHXBZLPMVFUQBQ-UHFFFAOYSA-K 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910021524 transition metal nanoparticle Inorganic materials 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 101000827703 Homo sapiens Polyphosphoinositide phosphatase Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 102100023591 Polyphosphoinositide phosphatase Human genes 0.000 description 1
- 101100012902 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) FIG2 gene Proteins 0.000 description 1
- 101100233916 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) KAR5 gene Proteins 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
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- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
-
- 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)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种改性碳负载钌基催化剂的制备及其催化合成戊二胺的应用,多相化学催化赖氨酸脱羧制戊二胺备受关注,已报道的分子筛限域催化剂具有较高的戊二胺选择性,但催化剂活性较差无法工业化使用;碳基钌催化剂结构较为稳定,但其活性仍然较低。本发明通过稀土金属及高温焙烧的方式对碳基钌催化剂进行改性,制备出优良性能碳基钌催化剂。在赖氨酸脱羧制戊二胺反应中,与不改性碳基钌催化剂相比,改性碳基钌催化剂戊二胺的选择性有了明显的提升。这为化学法赖氨酸脱羧产戊二胺提供了新的工业化机会,具有良好的工业应用前景。
The present invention discloses the preparation of a modified carbon-supported ruthenium-based catalyst and its application in catalytic synthesis of pentamethylenediamine. Heterogeneous chemical catalysis of lysine decarboxylation to produce pentamethylenediamine has attracted much attention. The reported molecular sieve confined catalyst has a high selectivity for pentamethylenediamine, but the catalyst activity is poor and cannot be used industrially; the carbon-based ruthenium catalyst has a relatively stable structure, but its activity is still low. The present invention modifies the carbon-based ruthenium catalyst by rare earth metals and high-temperature calcination to prepare a carbon-based ruthenium catalyst with excellent performance. In the reaction of lysine decarboxylation to produce pentamethylenediamine, compared with the unmodified carbon-based ruthenium catalyst, the selectivity of the modified carbon-based ruthenium catalyst for pentamethylenediamine is significantly improved. This provides a new industrialization opportunity for the chemical decarboxylation of lysine to produce pentamethylenediamine, and has good industrial application prospects.
Description
技术领域Technical Field
本发明涉及化学合成领域,具体涉及一种改性碳负载钌基催化剂的制备及其催化合成戊二胺的应用。The invention relates to the field of chemical synthesis, and in particular to the preparation of a modified carbon-supported ruthenium-based catalyst and its application in catalytic synthesis of pentamethylenediamine.
背景技术Background technique
1,5-戊二胺,又称尸胺,和己二酸聚合后可生产尼龙56材料。尼龙56材料具有良好的综合性能,例如吸湿排汗率高、透气性好、柔软度及染色性能佳等,且耐磨损、耐化学药品,阻燃性好且易于加工,在尼龙材料系列中具有强有力的竞争优势。1,5-戊二胺报道较多的生产方法是生物发酵法。南京工业大学利用豆渣水解液发酵生产戊二胺(CN201810954086.X),然而戊二胺对微生物具有毒性,影响生产效率。上海凯赛生物技术研发中心有限公司申请了多篇戊二胺生物发酵法专利(CN201811506539.9、CN201710453415.8、CN201710011198.7等),专利内容指出,在赖氨酸发酵过程中接入赖氨酸脱羧酶菌株的种子液,有效改善了戊二胺对菌株的毒性问题。但是,生物发酵法仍然存在较大的困难,例如赖氨酸脱羧酶活性低、耐毒性差,产物浓度低,分离成本过高等。1,5-pentanediamine, also known as cadaverine, can be polymerized with adipic acid to produce nylon 56 material. Nylon 56 material has good comprehensive properties, such as high moisture absorption and perspiration rate, good air permeability, softness and good dyeing performance, etc. It is also wear-resistant, chemical-resistant, flame-retardant and easy to process, and has a strong competitive advantage in the nylon material series. The most reported production method of 1,5-pentanediamine is biological fermentation. Nanjing University of Technology uses soybean dregs hydrolyzate to ferment and produce pentamethylenediamine (CN201810954086.X), but pentamethylenediamine is toxic to microorganisms and affects production efficiency. Shanghai Cathay Biotechnology Research and Development Center Co., Ltd. has applied for multiple patents for pentamethylenediamine biofermentation methods (CN201811506539.9, CN201710453415.8, CN201710011198.7, etc.). The patent content points out that the seed liquid of lysine decarboxylase strains is introduced into the lysine fermentation process, which effectively improves the toxicity of pentamethylenediamine to the strain. However, the biofermentation method still has great difficulties, such as low lysine decarboxylase activity, poor toxicity resistance, low product concentration, and high separation cost.
相比于生物发酵脱羧法,化学脱羧法具有明显的优点,例如催化剂活性不受戊二胺毒性影响、产物易分离等。但目前报道的化学法制备戊二胺存在催化剂活性低不稳定的问题。中国专利申请号202110938327.3的专利公开了一种分子筛限域金属氧化物催化剂、制备方法及应用。该发明采用原位合成的方法制备了一种分子筛限域金属催化剂,该催化剂金属活性组分得到有效固载,避免活性组分团聚,且催化剂结构保持良好;将催化剂用于赖氨酸脱羧反应有效提高了戊二胺生产速率,缩短了反应工艺时间,但选择性有待提高。Compared with the biological fermentation decarboxylation method, the chemical decarboxylation method has obvious advantages, such as the catalyst activity is not affected by the toxicity of pentamethylenediamine and the product is easy to separate. However, the currently reported chemical method for preparing pentamethylenediamine has the problem of low and unstable catalyst activity. Chinese patent application No. 202110938327.3 discloses a molecular sieve confined metal oxide catalyst, preparation method and application. The invention adopts an in-situ synthesis method to prepare a molecular sieve confined metal catalyst, the metal active components of the catalyst are effectively immobilized, the active components are avoided from agglomerating, and the catalyst structure is well maintained; the use of the catalyst for the decarboxylation reaction of lysine effectively increases the production rate of pentamethylenediamine and shortens the reaction process time, but the selectivity needs to be improved.
中国专利申请号202211265811.5的专利公开了一种金属离子改性分子筛限域过渡金属纳米粒子及其催化合成戊二胺的方法,制备了一系列分子筛负载或限域的钌催化剂用于L-赖氨酸脱羧制备戊二胺,通过改变催化剂表面碱性,促进羧基的定向吸附,从而抑制副产物产生,提高选择性,高效合成戊二胺,通过改变催化剂表面碱性,有效提升赖氨酸羧基的定向吸附性,从源头上抑制副反应的发生,进而强化赖氨酸直接脱羧生成戊二胺过程,大幅提高了戊二胺选择性,采用金属离子改性分子筛限域过渡金属纳米粒子作为催化剂催化合成戊二胺的选择性高达77.4%,目前处于国际领先水平。然而,赖氨酸脱羧反应在高温、高压、酸性条件下进行反应,催化剂稳定性差仍是制约工业化生产的最大难题。例如,传统Ru/C催化剂中的碳发生甲烷化反应,催化剂结构发生坍塌,催化剂失活。以分子筛为载体的催化剂也存在催化剂在反应后失活现象,分子筛中的铝在脱落致使分子筛结构坍塌,因此,制备出兼具戊二胺选择性和稳定性的催化剂,对于赖氨酸脱羧制备戊二胺极其重要。The Chinese patent application No. 202211265811.5 discloses a metal ion modified molecular sieve confined transition metal nanoparticle and a method for catalytically synthesizing pentamethylenediamine. A series of molecular sieve-loaded or confined ruthenium catalysts are prepared for the decarboxylation of L-lysine to prepare pentamethylenediamine. By changing the alkalinity of the catalyst surface, the directional adsorption of carboxyl groups is promoted, thereby inhibiting the production of by-products, improving selectivity, and efficiently synthesizing pentamethylenediamine. By changing the alkalinity of the catalyst surface, the directional adsorption of lysine carboxyl groups is effectively improved, and the occurrence of side reactions is inhibited from the source, thereby strengthening the direct decarboxylation of lysine to produce pentamethylenediamine. The selectivity of pentamethylenediamine is greatly improved. The selectivity of pentamethylenediamine is as high as 77.4% using metal ion modified molecular sieve confined transition metal nanoparticles as catalysts, which is currently at the international leading level. However, the lysine decarboxylation reaction is carried out under high temperature, high pressure, and acidic conditions, and the poor stability of the catalyst is still the biggest problem restricting industrial production. For example, the carbon in the traditional Ru/C catalyst undergoes methanation reaction, the catalyst structure collapses, and the catalyst is deactivated. Catalysts based on molecular sieves also suffer from the phenomenon of catalyst deactivation after the reaction. The aluminum in the molecular sieve falls off, causing the molecular sieve structure to collapse. Therefore, it is extremely important to prepare a catalyst that has both pentamethylenediamine selectivity and stability for the decarboxylation of lysine to prepare pentamethylenediamine.
碳基材料由于良好的耐高温、耐酸性和大的比表面积,被用于赖氨酸脱羧制备戊二胺催化剂的载体。2017年,报道了使用Ru/C作为催化剂进行L-赖氨酸脱羧反应,戊二胺选择性32%。戊二胺的选择性仍然较低。因此,制备活性优良的碳基钌催化剂,对于赖氨酸脱羧制备戊二胺极其重要。Carbon-based materials are used as carriers for catalysts for the decarboxylation of lysine to produce pentamethylenediamine due to their good high temperature resistance, acid resistance and large specific surface area. In 2017, Ru/C was reported as a catalyst for the decarboxylation of L-lysine, with a pentamethylenediamine selectivity of 32%. The selectivity of pentamethylenediamine is still relatively low. Therefore, the preparation of carbon-based ruthenium catalysts with excellent activity is extremely important for the decarboxylation of lysine to produce pentamethylenediamine.
有鉴于此,特提出本发明。In view of this, the present invention is proposed.
发明内容Summary of the invention
针对现有技术中存在的问题,本发明提供一种改性碳负载钌基催化剂的制备及其催化合成戊二胺的应用,该催化剂在赖氨酸脱羧反应中,具有较高的戊二胺选择性,同时催化剂的稳定性良好,工业应用前景良好。In view of the problems existing in the prior art, the present invention provides a preparation method of a modified carbon-supported ruthenium-based catalyst and its application in catalytic synthesis of pentamethylenediamine. The catalyst has high selectivity for pentamethylenediamine in the decarboxylation reaction of lysine, and the catalyst has good stability and good industrial application prospects.
一种改性碳负载钌基催化剂的制备方法,将钌前驱体及稀土金属前驱体,依次加入到碳材料的水分散液中,在一定温度下搅拌,然后将混合物烘干,烘干后在一定的氛围和温度下焙烧,获得改性碳负载钌基催化剂。A method for preparing a modified carbon-supported ruthenium-based catalyst comprises the following steps: adding a ruthenium precursor and a rare earth metal precursor to an aqueous dispersion of a carbon material in sequence, stirring the mixture at a certain temperature, and then drying the mixture. After drying, the mixture is calcined at a certain atmosphere and temperature to obtain a modified carbon-supported ruthenium-based catalyst.
在一个优选实施方案中,所述钌前驱体为氯化钌、十二羰基合钌、六氨合钌中的任意一种,改性碳负载钌基催化剂中钌的质量分数为0.01~50%,优选为为0.1~10%。In a preferred embodiment, the ruthenium precursor is any one of ruthenium chloride, ruthenium dodecacarbonyl, and ruthenium hexaamine, and the mass fraction of ruthenium in the modified carbon-supported ruthenium-based catalyst is 0.01 to 50%, preferably 0.1 to 10%.
在一个优选实施方案中,所述稀土金属为钇(Y)、镧(La)、铈(Ce)、镨(Pr)、钕(Nd)、钐(Sm)中的一种或几种,改性碳负载钌基催化剂中稀土金属的质量分数为0.01~50%,优选为为0.1~5%。In a preferred embodiment, the rare earth metal is one or more of yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), and samarium (Sm), and the mass fraction of the rare earth metal in the modified carbon-supported ruthenium-based catalyst is 0.01 to 50%, preferably 0.1 to 5%.
在一个优选实施方案中,所述碳材料为活性炭、石墨烯、碳纳米管中的一种。In a preferred embodiment, the carbon material is one of activated carbon, graphene and carbon nanotubes.
在一个优选实施方案中,所述搅拌温度为30-80℃,焙烧氛围为氮气、氢气、氩气、氦气中的一种,焙烧温度为30-1000℃。In a preferred embodiment, the stirring temperature is 30-80°C, the calcination atmosphere is one of nitrogen, hydrogen, argon and helium, and the calcination temperature is 30-1000°C.
本发明还提供利用所述的改性碳负载钌基催化剂的制备方法制得的改性碳负载钌基催化剂。The present invention also provides a modified carbon-supported ruthenium-based catalyst prepared by the preparation method of the modified carbon-supported ruthenium-based catalyst.
本发明还提供所述的改性碳负载钌基催化剂在赖氨酸脱羧制戊二胺中的应用:赖氨酸脱羧合成戊二胺在高压反应釜中进行,将赖氨酸或赖氨酸盐、去离子水、磷酸和改性碳负载钌基催化剂加入高压反应釜中,反应得到戊二胺水溶液。The present invention also provides the use of the modified carbon-supported ruthenium-based catalyst in the decarboxylation of lysine to prepare pentamethylenediamine: the decarboxylation of lysine to synthesize pentamethylenediamine is carried out in a high-pressure reactor, lysine or lysine salt, deionized water, phosphoric acid and the modified carbon-supported ruthenium-based catalyst are added into the high-pressure reactor, and the pentamethylenediamine aqueous solution is obtained by reaction.
在一个优选实施方案中,所述高压釜反应条件为:反应温度为120~250℃,压力为0.5~6MPa,反应溶液中赖氨酸或赖氨酸盐浓度为0.01~3M,催化剂与赖氨酸或赖氨酸盐的摩尔比为1:(0.1~10),采用磷酸调节反应溶液的pH值在1~8,优选1~5,反应时间为0~3h,反应气氛为氮气、氢气、氩气、氦气或一氧化碳中的任意一种,所述赖氨酸为L-赖氨酸,赖氨酸盐为赖氨酸盐酸盐、赖氨酸硫酸盐中的任意一种。In a preferred embodiment, the autoclave reaction conditions are as follows: reaction temperature is 120-250° C., pressure is 0.5-6 MPa, concentration of lysine or lysine salt in the reaction solution is 0.01-3 M, molar ratio of catalyst to lysine or lysine salt is 1:(0.1-10), phosphoric acid is used to adjust pH value of the reaction solution to 1-8, preferably 1-5, reaction time is 0-3 h, reaction atmosphere is any one of nitrogen, hydrogen, argon, helium or carbon monoxide, lysine is L-lysine, lysine salt is any one of lysine hydrochloride and lysine sulfate.
相对于现有技术,本发明的有益效果:本发明采用稀土金属为电子助剂和结构助剂,通过多种稀土助剂掺杂,以提升催化剂活性和结构稳定性。讲稀土改性后的催化剂用于赖氨酸脱羧反应中,具有较高的戊二胺选择性,催化剂稳定性良好,工业应用前景良好。Compared with the prior art, the present invention has the following beneficial effects: the present invention uses rare earth metals as electronic additives and structural additives, and dopes with a variety of rare earth additives to improve the activity and structural stability of the catalyst. The rare earth-modified catalyst is used in the decarboxylation reaction of lysine, has a high selectivity for pentamethylenediamine, good catalyst stability, and good industrial application prospects.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1对比例1-2和实施例1-2催化剂的XRD图。Figure 1 shows XRD patterns of the catalysts of Comparative Example 1-2 and Example 1-2.
图2实施例2催化剂反应前后的XRD图。FIG2 is an XRD diagram of the catalyst of Example 2 before and after reaction.
图3实施例4催化剂反应前后的XRD图。FIG3 is an XRD diagram of the catalyst of Example 4 before and after reaction.
图4实施例5催化剂反应前后的XRD图。FIG4 is an XRD diagram of the catalyst of Example 5 before and after reaction.
具体实施方式Detailed ways
下面将结合本发明实施例,对本发明的技术方案进行清楚、完整的描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有付出创造性劳动前提下所获得的所有其他实施列,均属于本发明保护的范围。The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solution of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
对比例1(未改性的Ru/C催化剂)Comparative Example 1 (Unmodified Ru/C Catalyst)
对比例1为一种5%Ru/C催化剂的制备方法,步骤如下:Comparative Example 1 is a method for preparing a 5% Ru/C catalyst, and the steps are as follows:
将0.02g三氯化钌加入到20g去离子水混合均匀,加入活性炭1g,在室温条件下磁力搅拌12h。之后在105℃下蒸发水分,100℃下烘干4h进一步脱水得到对比催化剂1。0.02 g of ruthenium trichloride was added to 20 g of deionized water and mixed evenly, and 1 g of activated carbon was added, and magnetic stirring was performed at room temperature for 12 h. Then, the water was evaporated at 105° C., and further dehydrated by drying at 100° C. for 4 h to obtain comparative catalyst 1.
将对比例1制得的5%Ru/C催化剂(对比催化剂1)用于催化合成戊二胺,方法如下:The 5% Ru/C catalyst (Comparative Catalyst 1) prepared in Comparative Example 1 was used to catalyze the synthesis of pentamethylenediamine in the following manner:
取0.1826g赖氨酸盐酸盐放入25ml的反应釜内衬中,加入10ml水溶解,然后加入0.101g催化剂,搅拌至完全混合均匀,用磷酸调节混合溶液pH至2.0;安装反应釜,用氮气置换釜中的空气,之后用氢气置换氮气,置换完成后加压至2MPa;开启反应釜在200℃,搅拌速度为800r/min条件下进行反应。在0-3小时内进行反应。反应液衍生后采用液相色谱对反应后溶液中赖氨酸及戊二胺浓度进行检测。发现在反应为2.5h时,赖氨酸转化率达到70%。戊二胺选择性为30%。Take 0.1826g of lysine hydrochloride and put it into the inner lining of a 25ml reactor, add 10ml of water to dissolve it, then add 0.101g of catalyst, stir until completely mixed, and adjust the pH of the mixed solution to 2.0 with phosphoric acid; install the reactor, replace the air in the reactor with nitrogen, and then replace the nitrogen with hydrogen, and pressurize it to 2MPa after the replacement is completed; open the reactor and react at 200℃ and a stirring speed of 800r/min. The reaction is carried out within 0-3 hours. After the reaction solution is derivatized, the concentrations of lysine and pentamethylenediamine in the solution after the reaction are detected by liquid chromatography. It was found that the lysine conversion rate reached 70% when the reaction was 2.5h. The selectivity of pentamethylenediamine was 30%.
对比例2(不进行焙烧)Comparative Example 2 (without calcination)
一种改性碳负载钌基催化剂的制备方法,方法如下:A method for preparing a modified carbon-supported ruthenium-based catalyst, the method is as follows:
将0.02g三氯化钌和0.023g硝酸铈加入到20g去离子水混合均匀,加入1g活性炭,在室温条件下磁力搅拌12h。之后在105℃下蒸发水分,100℃下烘干4h进一步脱水,得到改性碳负载钌基催化剂1%Ce-5%Ru/C,记为对比催化剂2。0.02g of ruthenium trichloride and 0.023g of cerium nitrate were added to 20g of deionized water and mixed evenly, and 1g of activated carbon was added, and magnetic stirring was performed at room temperature for 12h. Then, the water was evaporated at 105°C, and further dehydrated at 100°C for 4h to obtain a modified carbon-supported ruthenium-based catalyst 1% Ce-5% Ru/C, which was recorded as comparative catalyst 2.
将对比例2制得改性碳负载钌基催化剂1%Ce-5%Ru/C(对比催化剂2)用于催化合成戊二胺,方法如下:The modified carbon-supported ruthenium-based catalyst 1% Ce-5% Ru/C (Comparative Catalyst 2) prepared in Comparative Example 2 was used to catalyze the synthesis of pentamethylenediamine in the following manner:
取0.1826g赖氨酸盐酸盐放入25ml的反应釜内衬中,加入10ml水溶解,然后加入0.101g对比催化剂2,搅拌至完全混合均匀,用磷酸调节混合溶液pH至2.0;安装反应釜,用氮气置换釜中的空气,之后用氢气置换氮气,置换完成后加压至2MPa;开启反应釜在200℃,搅拌速度为800r/min条件下进行反应。在0-3小时内进行反应。反应液衍生后采用液相色谱对反应后溶液中赖氨酸及戊二胺浓度进行检测。发现在反应为1.5h时,赖氨酸转化率达到85%。戊二胺选择性达为34.2%。Take 0.1826g of lysine hydrochloride and put it into the inner lining of a 25ml reactor, add 10ml of water to dissolve it, then add 0.101g of comparative catalyst 2, stir until completely mixed, and adjust the pH of the mixed solution to 2.0 with phosphoric acid; install the reactor, replace the air in the reactor with nitrogen, and then replace the nitrogen with hydrogen, and pressurize it to 2MPa after the replacement is completed; open the reactor and react at 200℃ and a stirring speed of 800r/min. The reaction is carried out within 0-3 hours. After the reaction solution is derivatized, the concentrations of lysine and pentamethylenediamine in the solution after the reaction are detected by liquid chromatography. It was found that the lysine conversion rate reached 85% when the reaction was 1.5h. The selectivity of pentamethylenediamine reached 34.2%.
对比例3(提高稀土金属含量)Comparative Example 3 (Increasing rare earth metal content)
一种改性碳负载钌基催化剂15%Ce-5%Ru/C的制备方法,步骤如下:A method for preparing a modified carbon-supported ruthenium-based catalyst 15% Ce-5% Ru/C, comprising the following steps:
将0.02g三氯化钌和0.345g硝酸铈加入到20g去离子水混合均匀,加入1g活性炭,在室温条件下磁力搅拌12h。之后在105℃下蒸发水分,100℃下烘干4h进一步脱水。然后将干燥后的固体,得到对比催化剂3。0.02g of ruthenium trichloride and 0.345g of cerium nitrate were added to 20g of deionized water and mixed evenly, and 1g of activated carbon was added. The mixture was stirred magnetically for 12h at room temperature. The water was then evaporated at 105°C and further dehydrated at 100°C for 4h. The dried solid was then used to obtain comparative catalyst 3.
将对比例3制得的改性碳负载钌基催化剂15%Ce-5%Ru/C(对比催化剂3)用于赖氨酸脱羧制备戊二胺,方法如下:The modified carbon-supported ruthenium-based catalyst 15% Ce-5% Ru/C (comparative catalyst 3) prepared in Comparative Example 3 was used for decarboxylation of lysine to prepare pentamethylenediamine, and the method was as follows:
取0.1826g赖氨酸盐酸盐放入25ml的反应釜内衬中,加入10ml水溶解,然后加入0.101g对比催化剂3,搅拌至完全混合均匀,用磷酸调节混合溶液pH至2.0;安装反应釜,用氮气置换釜中的空气,之后用氢气置换氮气,置换完成后加压至2MPa;开启反应釜在200℃,搅拌速度为800r/min条件下进行反应。在不同0-3小时内进行反应。反应液衍生后采用液相色谱对反应后溶液中赖氨酸及戊二胺浓度进行检测。发现在反应为1h时,赖氨酸转化率达到90%。戊二胺选择性为25%。Take 0.1826g of lysine hydrochloride and put it into the inner lining of a 25ml reactor, add 10ml of water to dissolve it, then add 0.101g of comparative catalyst 3, stir until completely mixed, and adjust the pH of the mixed solution to 2.0 with phosphoric acid; install the reactor, replace the air in the reactor with nitrogen, and then replace the nitrogen with hydrogen, and pressurize it to 2MPa after the replacement is completed; open the reactor and react at 200℃ and a stirring speed of 800r/min. The reaction was carried out within different 0-3 hours. After the reaction solution was derivatized, the concentrations of lysine and pentamethylenediamine in the solution after the reaction were detected by liquid chromatography. It was found that the lysine conversion rate reached 90% when the reaction was 1h. The selectivity of pentamethylenediamine was 25%.
实施例1Example 1
本实施例为稀土金属和焙烧联合改性催化剂1%Ce-5%Ru/C的制备,方法如下:This example is the preparation of a rare earth metal and calcined combined modified catalyst 1% Ce-5% Ru/C, the method is as follows:
将0.02g三氯化钌和0.023g硝酸铈加入到20g去离子水混合均匀,加入1g活性炭,在室温条件下磁力搅拌12h,之后在105℃下蒸发水分,100℃下烘干4h进一步脱水。然后将干燥后的固体在氮气氛围下400℃焙烧3h,得到催化剂1。0.02 g of ruthenium trichloride and 0.023 g of cerium nitrate were added to 20 g of deionized water and mixed evenly, and 1 g of activated carbon was added. The mixture was magnetically stirred at room temperature for 12 h, and then the water was evaporated at 105 ° C. and further dehydrated at 100 ° C. for 4 h. The dried solid was then calcined at 400 ° C. for 3 h in a nitrogen atmosphere to obtain catalyst 1.
将本实施例1制得的1%Ce-5%Ru/C催化剂(催化剂1)用于催化合成戊二胺,方法如下:The 1% Ce-5% Ru/C catalyst (catalyst 1) prepared in Example 1 was used to catalyze the synthesis of pentamethylenediamine in the following manner:
取0.1826g赖氨酸盐酸盐放入25ml的反应釜内衬中,加入10ml水溶解,然后加入0.101g催化剂1,搅拌至完全混合均匀,用磷酸调节混合溶液pH至2.0;安装反应釜,用氮气置换釜中的空气,之后用氢气置换氮气,置换完成后加压至2MPa;开启反应釜在200℃,搅拌速度为800r/min条件下进行反应。在0-3小时内进行反应。反应液衍生后采用液相色谱对反应后溶液中赖氨酸及戊二胺浓度进行检测。发现在反应为1.5h时,赖氨酸转化率达到87%。戊二胺选择性达到40%。Take 0.1826g of lysine hydrochloride and put it into the inner lining of a 25ml reactor, add 10ml of water to dissolve it, then add 0.101g of catalyst 1, stir until it is completely mixed, and adjust the pH of the mixed solution to 2.0 with phosphoric acid; install the reactor, replace the air in the reactor with nitrogen, and then replace the nitrogen with hydrogen, and pressurize it to 2MPa after the replacement is completed; open the reactor and react at 200℃ and a stirring speed of 800r/min. The reaction is carried out within 0-3 hours. After the reaction solution is derivatized, the concentrations of lysine and pentamethylenediamine in the solution after the reaction are detected by liquid chromatography. It is found that the lysine conversion rate reaches 87% when the reaction is 1.5h. The selectivity of pentamethylenediamine reaches 40%.
实施例2Example 2
本实施例为稀土金属和焙烧联合改性催化剂1%Ce-5%Ru/C的制备,方法如下:This example is the preparation of a rare earth metal and calcined combined modified catalyst 1% Ce-5% Ru/C, the method is as follows:
将0.02g三氯化钌和0.023g硝酸铈加入到20g去离子水混合均匀,加入1g活性炭,在室温条件下磁力搅拌12h。之后在105℃下蒸发水分,100℃下烘干4h进一步脱水。然后将干燥后的固体在氮气氛围下800℃焙烧3h,得到催化剂2。0.02 g of ruthenium trichloride and 0.023 g of cerium nitrate were added to 20 g of deionized water and mixed evenly. 1 g of activated carbon was added and magnetically stirred at room temperature for 12 h. The water was then evaporated at 105 ° C and further dehydrated at 100 ° C for 4 h. The dried solid was then calcined at 800 ° C for 3 h in a nitrogen atmosphere to obtain catalyst 2.
将本实施例2制得的1%Ce-5%Ru/C催化剂(催化剂2)用于催化合成戊二胺,方法如下:The 1% Ce-5% Ru/C catalyst (catalyst 2) prepared in Example 2 was used to catalyze the synthesis of pentamethylenediamine in the following manner:
取0.1826g赖氨酸盐酸盐放入25ml的反应釜内衬中,加入10ml水溶解,然后加入0.101g催化剂2,搅拌至完全混合均匀,用磷酸调节混合溶液pH至2.0;安装反应釜,用氮气置换釜中的空气,之后用氢气置换氮气,置换完成后加压至2MPa;开启反应釜在200℃,搅拌速度为800r/min条件下进行反应。在0-3小时内进行反应。反应液衍生后采用液相色谱对反应后溶液中赖氨酸及戊二胺浓度进行检测。发现在反应为2h时,赖氨酸转化率达到90%。戊二胺选择性达到41.2%。Take 0.1826g of lysine hydrochloride and put it into the inner lining of a 25ml reactor, add 10ml of water to dissolve it, then add 0.101g of catalyst 2, stir until completely mixed, and adjust the pH of the mixed solution to 2.0 with phosphoric acid; install the reactor, replace the air in the reactor with nitrogen, and then replace the nitrogen with hydrogen, and pressurize it to 2MPa after the replacement is completed; open the reactor and react at 200℃ and a stirring speed of 800r/min. The reaction is carried out within 0-3 hours. After the reaction solution is derivatized, the concentrations of lysine and pentamethylenediamine in the solution after the reaction are detected by liquid chromatography. It is found that when the reaction is 2h, the lysine conversion rate reaches 90%. The selectivity of pentamethylenediamine reaches 41.2%.
实施例3Example 3
本实施例为稀土金属和焙烧联合改性催化剂1%La-5%Ru/C的制备,方法如下:This example is the preparation of a rare earth metal and calcined combined modified catalyst 1% La-5% Ru/C, the method is as follows:
将0.02g三氯化钌和0.017g氯化镧加入到20g去离子水混合均匀,加入1g活性炭,在室温条件下磁力搅拌12h。之后在105℃下蒸发水分,100℃下烘干4h进一步脱水。然后将干燥后的固体在氮气氛围下800℃焙烧3h,得到催化剂3。0.02 g of ruthenium trichloride and 0.017 g of lanthanum chloride were added to 20 g of deionized water and mixed evenly. 1 g of activated carbon was added and magnetically stirred at room temperature for 12 h. The water was then evaporated at 105 ° C and further dehydrated at 100 ° C for 4 h. The dried solid was then calcined at 800 ° C for 3 h in a nitrogen atmosphere to obtain catalyst 3.
将本实施例3制得的1%La-5%Ru/C催化剂(催化剂3)用于催化合成戊二胺,方法如下:The 1% La-5% Ru/C catalyst (catalyst 3) prepared in Example 3 was used to catalyze the synthesis of pentamethylenediamine in the following manner:
取0.1826g赖氨酸盐酸盐放入25ml的反应釜内衬中,加入10ml水溶解,然后加入0.101g催化剂3,搅拌至完全混合均匀,用磷酸调节混合溶液pH至2.0;安装反应釜,用氮气置换釜中的空气,之后用氢气置换氮气,置换完成后加压至2MPa;开启反应釜在200℃,搅拌速度为800r/min条件下进行反应。在0-3小时内进行反应。反应液衍生后采用液相色谱对反应后溶液中赖氨酸及戊二胺浓度进行检测。发现在反应为2h时,赖氨酸转化率达到82%。戊二胺选择性达到36.4%。Take 0.1826g of lysine hydrochloride and put it into the inner lining of a 25ml reactor, add 10ml of water to dissolve it, then add 0.101g of catalyst 3, stir until it is completely mixed, and adjust the pH of the mixed solution to 2.0 with phosphoric acid; install the reactor, replace the air in the reactor with nitrogen, and then replace the nitrogen with hydrogen, and pressurize it to 2MPa after the replacement is completed; open the reactor and react at 200℃ and a stirring speed of 800r/min. The reaction is carried out within 0-3 hours. After the reaction solution is derivatized, the concentrations of lysine and pentamethylenediamine in the solution after the reaction are detected by liquid chromatography. It is found that when the reaction is 2h, the lysine conversion rate reaches 82%. The selectivity of pentamethylenediamine reaches 36.4%.
实施例4Example 4
本实施例为稀土金属和焙烧联合改性催化剂1%Sm-5%Ru/C的制备,方法如下:This example is the preparation of a rare earth metal and calcined combined modified catalyst 1% Sm-5% Ru/C, the method is as follows:
将0.02g三氯化钌和0.016g氯化钐加入到20g去离子水混合均匀,加入活性炭,在室温条件下磁力搅拌12h。之后在105℃下蒸发水分,100℃下烘干4h进一步脱水。然后将干燥后的固体在氮气氛围下800℃焙烧3h,得到催化剂4。0.02 g of ruthenium trichloride and 0.016 g of samarium chloride were added to 20 g of deionized water and mixed evenly. Activated carbon was added and magnetically stirred at room temperature for 12 h. The water was then evaporated at 105 °C and further dehydrated at 100 °C for 4 h. The dried solid was then calcined at 800 °C for 3 h under a nitrogen atmosphere to obtain catalyst 4.
将本实施例4制得的1%Sm-5%Ru/C催化剂(催化剂4)用于催化合成戊二胺,方法如下:The 1% Sm-5% Ru/C catalyst (catalyst 4) prepared in Example 4 was used to catalyze the synthesis of pentamethylenediamine in the following manner:
取0.1826g赖氨酸盐酸盐放入25ml的反应釜内衬中,加入10ml水溶解,然后加入0.101g催化剂4,搅拌至完全混合均匀,用磷酸调节混合溶液pH至2.0;安装反应釜,用氮气置换釜中的空气,之后用氢气置换氮气,置换完成后加压至2MPa;开启反应釜在200℃,搅拌速度为800r/min条件下进行反应。在0-3小时内进行反应。反应液衍生后采用液相色谱对反应后溶液中赖氨酸及戊二胺浓度进行检测。发现在反应为2h时,赖氨酸转化率达到92.4%。戊二胺选择性达到42.3%。Take 0.1826g of lysine hydrochloride and put it into the inner lining of a 25ml reactor, add 10ml of water to dissolve it, then add 0.101g of catalyst 4, stir until it is completely mixed, and adjust the pH of the mixed solution to 2.0 with phosphoric acid; install the reactor, replace the air in the reactor with nitrogen, and then replace the nitrogen with hydrogen, and pressurize it to 2MPa after the replacement is completed; open the reactor and react at 200℃ and a stirring speed of 800r/min. The reaction is carried out within 0-3 hours. After the reaction solution is derivatized, the concentrations of lysine and pentamethylenediamine in the solution after the reaction are detected by liquid chromatography. It is found that when the reaction is 2h, the lysine conversion rate reaches 92.4%. The selectivity of pentamethylenediamine reaches 42.3%.
实施例5Example 5
本实施例为稀土金属和焙烧联合改性催化剂1%Ce-0.5%Sm-5%Ru/C的制备,方法如下:This example is the preparation of a rare earth metal and calcined combined modified catalyst 1% Ce-0.5% Sm-5% Ru/C, the method is as follows:
将0.02g三氯化钌、0.008g氯化钐和0.023g硝酸铈加入到20g去离子水混合均匀,加1g入活性炭,在室温条件下磁力搅拌12h。之后在105℃下蒸发水分,100℃下烘干4h进一步脱水。然后将干燥后的固体在氮气氛围下800℃焙烧3h,得到催化剂5。0.02 g of ruthenium trichloride, 0.008 g of samarium chloride and 0.023 g of cerium nitrate were added to 20 g of deionized water and mixed evenly. 1 g of activated carbon was added and magnetically stirred at room temperature for 12 h. The water was then evaporated at 105 ° C and further dehydrated at 100 ° C for 4 h. The dried solid was then calcined at 800 ° C for 3 h in a nitrogen atmosphere to obtain catalyst 5.
将本实施例5制得的1%Ce-0.5%Sm-5%Ru/C催化剂(催化剂5)用于催化合成戊二胺,方法如下:The 1% Ce-0.5% Sm-5% Ru/C catalyst (catalyst 5) prepared in Example 5 was used to catalyze the synthesis of pentamethylenediamine in the following manner:
取0.1826g赖氨酸盐酸盐放入25ml的反应釜内衬中,加入10ml水溶解,然后加入0.101g催化剂5,搅拌至完全混合均匀,用磷酸调节混合溶液pH至2.0;安装反应釜,用氮气置换釜中的空气,之后用氢气置换氮气,置换完成后加压至2MPa;开启反应釜在200℃,搅拌速度为800r/min条件下进行反应。在0-3小时内进行反应。反应液衍生后采用液相色谱对反应后溶液中赖氨酸及戊二胺浓度进行检测。发现在反应为2h时,赖氨酸转化率达到91.24%。戊二胺选择性达到61.3%。Take 0.1826g of lysine hydrochloride and put it into the inner lining of a 25ml reactor, add 10ml of water to dissolve it, then add 0.101g of catalyst 5, stir until it is completely mixed, and adjust the pH of the mixed solution to 2.0 with phosphoric acid; install the reactor, replace the air in the reactor with nitrogen, and then replace the nitrogen with hydrogen, and pressurize it to 2MPa after the replacement is completed; open the reactor and react at 200℃ and a stirring speed of 800r/min. The reaction is carried out within 0-3 hours. After the reaction solution is derivatized, the concentrations of lysine and pentamethylenediamine in the solution after the reaction are detected by liquid chromatography. It is found that when the reaction is 2h, the lysine conversion rate reaches 91.24%. The selectivity of pentamethylenediamine reaches 61.3%.
实施例6Example 6
本实施例为稀土金属和焙烧联合改性催化剂1%Ce-0.5%La-5%Ru/C的制备,方法如下:This example is the preparation of a rare earth metal and calcined combined modified catalyst 1% Ce-0.5% La-5% Ru/C, the method is as follows:
将0.02g三氯化钌、0.023g硝酸铈和0.017g氯化镧加入到20g去离子水混合均匀,加入活性炭,固液比为1:5,在室温条件下磁力搅拌12h。之后在105℃下蒸发水分,100℃下烘干4h进一步脱水。然后将干燥后的固体在氮气氛围下800℃焙烧3h,得到催化剂6。0.02g of ruthenium trichloride, 0.023g of cerium nitrate and 0.017g of lanthanum chloride were added to 20g of deionized water and mixed evenly. Activated carbon was added with a solid-liquid ratio of 1:5, and magnetic stirring was performed at room temperature for 12h. After that, the water was evaporated at 105°C and further dehydrated at 100°C for 4h. The dried solid was then calcined at 800°C for 3h under a nitrogen atmosphere to obtain catalyst 6.
将本实施例7制得的1%Ce-0.5%La-5%Ru/C催化剂(催化剂6)用于催化合成戊二胺,方法如下:The 1% Ce-0.5% La-5% Ru/C catalyst (catalyst 6) prepared in Example 7 was used to catalyze the synthesis of pentamethylenediamine in the following manner:
取0.1826g赖氨酸盐酸盐放入25ml的反应釜内衬中,加入10ml水溶解,然后加入0.101g催化剂6,搅拌至完全混合均匀,用磷酸调节混合溶液pH至2.0;安装反应釜,用氮气置换釜中的空气,之后用氢气置换氮气,置换完成后加压至2MPa;开启反应釜在200℃,搅拌速度为800r/min条件下进行反应。在0-3小时内进行反应。反应液衍生后采用液相色谱对反应后溶液中赖氨酸及戊二胺浓度进行检测。发现在反应为2h时,赖氨酸转化率达到90%。戊二胺选择性达到56.5%。Take 0.1826g of lysine hydrochloride and put it into the inner lining of a 25ml reactor, add 10ml of water to dissolve it, then add 0.101g of catalyst 6, stir until completely mixed, and adjust the pH of the mixed solution to 2.0 with phosphoric acid; install the reactor, replace the air in the reactor with nitrogen, and then replace the nitrogen with hydrogen, and pressurize it to 2MPa after the replacement is completed; open the reactor and react at 200℃ and a stirring speed of 800r/min. The reaction is carried out within 0-3 hours. After the reaction solution is derivatized, the concentrations of lysine and pentamethylenediamine in the solution after the reaction are detected by liquid chromatography. It is found that when the reaction is 2h, the lysine conversion rate reaches 90%. The selectivity of pentamethylenediamine reaches 56.5%.
实施例7Example 7
对对比例1、实施例1和2制备的催化剂进行XRD分析,可以看到高温焙烧对催化剂结构有明显影响。800℃下发现钌单质和氧化铈存在(如图1)。并对反应前后的实施例2、4、5催化剂进行XRD分析,发现反应前后催化剂结构保持稳定(如图2,3,4)。XRD analysis was performed on the catalysts prepared in Comparative Example 1, Examples 1 and 2, and it was found that high temperature calcination had a significant effect on the catalyst structure. Ruthenium and cerium oxide were found to exist at 800°C (as shown in Figure 1). XRD analysis was performed on the catalysts of Examples 2, 4 and 5 before and after the reaction, and it was found that the catalyst structure remained stable before and after the reaction (as shown in Figures 2, 3 and 4).
实施例8Example 8
本实施例为催化剂5重复性实验,方法如下:This example is a repeatability experiment of catalyst 5, and the method is as follows:
将赖氨酸脱羧反应后的催化剂分离并用蒸馏水离心洗涤3次后加入到反应器中,之后加入0.1mol/L L-赖氨酸溶液10mL,通过添加磷酸溶液调节混合溶液的pH等于2,将反应器密封在200℃,2MPa氢气下进反2h。该过程重复进行5次反应后,催化剂活性仍然能达到赖氨酸转化率90%,戊二胺选择性60%。The catalyst after the lysine decarboxylation reaction was separated and washed three times by centrifugation with distilled water before being added to the reactor. Then, 10 mL of 0.1 mol/L L-lysine solution was added, and the pH of the mixed solution was adjusted to 2 by adding phosphoric acid solution. The reactor was sealed and reacted at 200°C and 2 MPa of hydrogen for 2 hours. After the process was repeated for 5 times, the catalyst activity could still reach a lysine conversion rate of 90% and a pentamethylenediamine selectivity of 60%.
本发明提供了稀土金属改性钌碳催化剂的制备及其催化合成戊二胺的方法。稀土金属改性钌碳催化剂有效提升了赖氨酸脱羧制备戊二胺反应中戊二胺选择性,为化学法赖氨酸脱羧产戊二胺提供了新的工业化机会,具有良好的工业应用前景。The present invention provides a method for preparing a rare earth metal modified ruthenium carbon catalyst and catalytically synthesizing pentamethylenediamine. The rare earth metal modified ruthenium carbon catalyst effectively improves the selectivity of pentamethylenediamine in the reaction of preparing pentamethylenediamine by decarboxylation of lysine, provides a new industrialization opportunity for the chemical decarboxylation of lysine to produce pentamethylenediamine, and has good industrial application prospects.
以上已对本发明进行了详细描述,但本发明并不局限于本文所描述具体实施方式。本领域技术人员理解,在不背离本发明范围的情况下,可以作出其他更改和变形。本发明的范围由所附权利要求限定。The present invention has been described in detail above, but the present invention is not limited to the specific embodiments described herein. It is understood by those skilled in the art that other changes and modifications may be made without departing from the scope of the present invention. The scope of the present invention is defined by the appended claims.
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