CN118079905A - Preparation of modified carbon-supported ruthenium-based catalyst and application of modified carbon-supported ruthenium-based catalyst in catalytic synthesis of pentanediamine - Google Patents
Preparation of modified carbon-supported ruthenium-based catalyst and application of modified carbon-supported ruthenium-based catalyst in catalytic synthesis of pentanediamine Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 128
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 72
- KJOMYNHMBRNCNY-UHFFFAOYSA-N pentane-1,1-diamine Chemical compound CCCCC(N)N KJOMYNHMBRNCNY-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000007036 catalytic synthesis reaction Methods 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 88
- 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
- 238000000034 method Methods 0.000 claims abstract description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000006114 decarboxylation reaction Methods 0.000 claims abstract description 22
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 19
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 17
- 150000001721 carbon Chemical class 0.000 claims abstract description 10
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims description 49
- 229960003646 lysine Drugs 0.000 claims description 49
- 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
- 239000000203 mixture Substances 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 28
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 claims description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- 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
- 238000001035 drying Methods 0.000 claims description 13
- 150000002431 hydrogen Chemical class 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 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
- -1 pentylene diamine Chemical class 0.000 claims description 11
- 230000001105 regulatory effect Effects 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 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 239000003575 carbonaceous material Substances 0.000 claims description 5
- 229910052786 argon Inorganic materials 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
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 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 3
- 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
- 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
- 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
- NQZFAUXPNWSLBI-UHFFFAOYSA-N carbon monoxide;ruthenium Chemical group [Ru].[Ru].[Ru].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] NQZFAUXPNWSLBI-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
- 229910052799 carbon Inorganic materials 0.000 abstract description 7
- 239000002808 molecular sieve Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 16
- 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
- 238000004090 dissolution Methods 0.000 description 9
- 238000004811 liquid chromatography Methods 0.000 description 9
- 238000001704 evaporation Methods 0.000 description 8
- 230000018044 dehydration Effects 0.000 description 7
- 238000006297 dehydration reaction Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 238000000855 fermentation Methods 0.000 description 5
- 230000004151 fermentation Effects 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 230000001988 toxicity Effects 0.000 description 4
- 231100000419 toxicity Toxicity 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 235000019766 L-Lysine Nutrition 0.000 description 2
- 108010048581 Lysine decarboxylase Proteins 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 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
- 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 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
- 238000001354 calcination Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 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
- 230000000911 decarboxylating effect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 230000006872 improvement Effects 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
- 238000003760 magnetic stirring Methods 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
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 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
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005406 washing Methods 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
The invention discloses a preparation method of a modified carbon supported ruthenium-based catalyst and application of the modified carbon supported ruthenium-based catalyst in catalytic synthesis of pentanediamine, which are focused on heterogeneous chemistry catalytic lysine decarboxylation to prepare the pentanediamine, wherein the reported molecular sieve limited-area catalyst has higher pentanediamine selectivity, but the catalyst activity is poor and cannot be industrially used; the carbon-based ruthenium catalyst has a relatively stable structure, but the activity of the catalyst is still relatively low. The invention prepares the carbon-based ruthenium catalyst with excellent performance by modifying the carbon-based ruthenium catalyst through rare earth metal and high-temperature roasting. In the reaction of preparing the pentanediamine by decarboxylation of the lysine, compared with the non-modified carbon-based ruthenium catalyst, the selectivity of the modified carbon-based ruthenium catalyst for the pentanediamine is obviously improved. The method provides a new industrialization opportunity for producing the pentanediamine by the decarboxylation of the lysine by a chemical method, and has good industrial application prospect.
Description
Technical Field
The invention relates to the field of chemical synthesis, in particular to preparation of a modified carbon-supported ruthenium-based catalyst and application of the catalyst in catalytic synthesis of pentanediamine.
Background
Nylon 56 materials can be produced from polymerization of 1, 5-pentanediamine, also known as cadaverine, and adipic acid. The nylon 56 material has good comprehensive properties, such as high moisture absorption and sweat release rate, good air permeability, good softness and dyeing property, and the like, is resistant to abrasion, chemicals, good in flame retardance and easy to process, and has strong competitive advantages in nylon material series. A more reported production method of 1, 5-pentanediamine is a biological fermentation method. The industrial university of Nanjing utilizes bean dreg hydrolysate to ferment and produce the pentanediamine (CN201810954086. X), however, the pentanediamine has toxicity to microorganisms and affects the production efficiency. A plurality of patent (CN 201811506539.9, CN201710453415.8, CN201710011198.7 and the like) of the pentanediamine biological fermentation method are applied by Shanghai Kaiser biotechnology research and development center, and the patent content indicates that seed liquid of a lysine decarboxylase strain is inoculated in the lysine fermentation process, so that the toxicity problem of the pentanediamine to the strain is effectively improved. However, the biological fermentation method still has great difficulties such as low lysine decarboxylase activity, poor toxicity resistance, low product concentration, excessively high separation cost, and the like.
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 the pentanediamine, the product is easy to separate, and the like. However, the chemical method for preparing the pentanediamine reported at present has the problem of low and unstable catalyst activity. The patent of China patent application number 202110938327.3 discloses a molecular sieve domain-limited metal oxide catalyst, a preparation method and application. The invention adopts an in-situ synthesis method to prepare a molecular sieve domain-limited metal catalyst, wherein the metal active components of the catalyst are effectively immobilized, the agglomeration of the active components is avoided, and the catalyst structure is kept good; the catalyst is used for lysine decarboxylation reaction, so that the production rate of the pentanediamine is effectively improved, the reaction process time is shortened, and the selectivity is required to be improved.
The patent of China patent application number 202211265811.5 discloses a metal ion modified molecular sieve limited transition metal nanoparticle and a method for synthesizing the pentanediamine by catalysis, a series of molecular sieve supported or limited ruthenium catalysts are prepared for preparing the pentanediamine by decarboxylation of L-lysine, the surface alkalinity of the catalysts is changed, the directional adsorption of carboxyl is promoted, thereby inhibiting the generation of byproducts, improving the selectivity, efficiently synthesizing the pentanediamine, the surface alkalinity of the catalysts is changed, the directional adsorption of lysine carboxyl is effectively improved, the side reaction is inhibited from the source, the process of directly decarboxylating the lysine to generate the pentanediamine is further enhanced, the selectivity of the pentanediamine is greatly improved, and the selectivity of synthesizing the pentanediamine by catalysis of the metal ion modified molecular sieve limited transition metal nanoparticle serving as the catalyst is as high as 77.4 percent, so that the selectivity of the pentanediamine is at the international leading level at present. However, the decarboxylation reaction of lysine is carried out under the conditions of high temperature, high pressure and acidity, and the poor stability of the catalyst is still the biggest difficulty in restricting industrial production. For example, carbon in a conventional Ru/C catalyst undergoes methanation, the catalyst structure collapses, and the catalyst deactivates. The catalyst taking the molecular sieve as a carrier also has the phenomenon of deactivation of the catalyst after reaction, and aluminum in the molecular sieve falls off to cause collapse of the molecular sieve structure, so that the catalyst with the selectivity and stability of the pentanediamine is prepared, and the catalyst is extremely important for preparing the pentanediamine by decarboxylation of lysine.
Carbon-based materials are used as supports for the preparation of pentylene diamine catalysts by lysine decarboxylation due to good high temperature resistance, acid resistance and large specific surface area. In 2017, it was reported that L-lysine decarboxylation reaction using Ru/C as catalyst was performed with a pentandiamine selectivity of 32%. The selectivity to pentamethylenediamine is still low. Therefore, the preparation of a carbon-based ruthenium catalyst having excellent activity is extremely important for the preparation of pentylene diamine by decarboxylation of lysine.
In view of this, the present invention has been made.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the preparation of the modified carbon-supported ruthenium-based catalyst and the application of the catalyst in the catalytic synthesis of the pentanediamine, wherein the catalyst has higher pentanediamine selectivity in the lysine decarboxylation reaction, and meanwhile, the catalyst has good stability and good industrial application prospect.
A preparation method of a modified carbon-supported ruthenium-based catalyst comprises the steps of sequentially adding a ruthenium precursor and a rare earth metal precursor into an aqueous dispersion of a carbon material, stirring at a certain temperature, drying the mixture, and roasting at a certain atmosphere and temperature after drying to obtain the modified carbon-supported ruthenium-based catalyst.
In a preferred embodiment, the ruthenium precursor is any one of ruthenium chloride, ruthenium dodecacarbonyl and ruthenium hexammoniate, and the mass fraction of ruthenium in the modified carbon-supported ruthenium-based catalyst is 0.01-50%, preferably 0.1-10%.
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 0.01-50%, preferably 0.1-5%.
In a preferred embodiment, the carbon material is one of activated carbon, graphene, and carbon nanotubes.
In a preferred embodiment, the stirring temperature is 30-80 ℃, the roasting atmosphere is one of nitrogen, hydrogen, argon and helium, and the roasting temperature is 30-1000 ℃.
The invention also provides the modified carbon-supported ruthenium-based catalyst prepared by the preparation method of the modified carbon-supported ruthenium-based catalyst.
The invention also provides application of the modified carbon-supported ruthenium-based catalyst in preparing pentanediamine through lysine decarboxylation: the synthesis of the pentanediamine by decarboxylation of the lysine is carried out in a high-pressure reaction kettle, lysine or lysine salt, deionized water, phosphoric acid and a modified carbon supported ruthenium-based catalyst are added into the high-pressure reaction kettle, and the water solution of the pentanediamine is obtained by reaction.
In a preferred embodiment, the autoclave reaction conditions are: the reaction temperature is 120-250 ℃, the pressure is 0.5-6 MPa, the concentration of lysine or lysine salt in the reaction solution is 0.01-3M, the molar ratio of the catalyst to the lysine or lysine salt is 1 (0.1-10), the pH value of the reaction solution is regulated to be 1-8, preferably 1-5 by adopting phosphoric acid, the reaction time is 0-3 h, the reaction atmosphere is any one of nitrogen, hydrogen, argon, helium or carbon monoxide, the lysine is L-lysine, and the lysine salt is any one of lysine hydrochloride and lysine sulfate.
Compared with the prior art, the invention has the beneficial effects that: the invention adopts rare earth metal as electronic auxiliary agent and structural auxiliary agent, and improves the activity and structural stability of the catalyst by doping various rare earth auxiliary agents. The rare earth modified catalyst is used in lysine decarboxylation reaction, has high pentylene diamine selectivity, good catalyst stability and good industrial application prospect.
Drawings
FIG. 1 XRD patterns of the catalysts of comparative examples 1-2 and examples 1-2.
Figure 2 XRD patterns of example 2 before and after the catalyst reaction.
Figure 3 XRD patterns of example 4 before and after the catalyst reaction.
Figure 4 XRD patterns of example 5 before and after the catalyst reaction.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without any inventive effort, are within the scope of the present invention.
Comparative example 1 (unmodified Ru/C catalyst)
Comparative example 1 is a preparation method of a 5% Ru/C catalyst, comprising the following steps:
0.02g of ruthenium trichloride is added into 20g of deionized water, evenly mixed, 1g of active carbon is added, and the mixture is magnetically stirred for 12 hours at room temperature. Then evaporating water at 105 ℃, drying at 100 ℃ for 4 hours, and further dehydrating to obtain the comparative catalyst 1.
The 5% Ru/C catalyst prepared in comparative example 1 (comparative catalyst 1) was used for catalytic synthesis of pentamethylenediamine by the following method:
0.1826g of lysine hydrochloride is taken and put into a 25ml reaction kettle liner, 10ml of water is added for dissolution, then 0.101g of catalyst is added, the mixture is stirred until the mixture is completely and uniformly mixed, and the pH value of the mixed solution is regulated to 2.0 by phosphoric acid; installing a reaction kettle, replacing air in the kettle with nitrogen, replacing the nitrogen with hydrogen, and pressurizing to 2MPa after the replacement is completed; and (3) starting the reaction kettle to react at 200 ℃ and the stirring speed of 800 r/min. The reaction was carried out within 0-3 hours. And detecting the concentration of lysine and pentanediamine in the reacted solution by adopting liquid chromatography after the reaction solution is derived. It was found that at 2.5h of reaction, the lysine conversion reached 70%. The pentylene diamine selectivity was 30%.
Comparative example 2 (no calcination)
The preparation method of the modified carbon supported ruthenium-based catalyst comprises the following steps:
0.02g of ruthenium trichloride and 0.023g of cerium nitrate were added to 20g of deionized water, mixed well, 1g of activated carbon was added, and magnetically stirred at room temperature for 12 hours. Then evaporating water at 105 ℃, drying at 100 ℃ for 4 hours, and further dehydrating to obtain the modified carbon supported ruthenium-based catalyst 1% Ce-5% Ru/C, which is denoted as comparative catalyst 2.
The modified carbon-supported ruthenium-based catalyst 1% Ce-5% Ru/C (comparative catalyst 2) prepared in comparative example 2 was used for catalytic synthesis of pentamethylene diamine by the following method:
0.1826g of lysine hydrochloride is put into a 25ml reaction kettle liner, 10ml of water is added for dissolution, then 0.101g of comparative catalyst 2 is added, and the mixture is stirred until the mixture is completely and uniformly mixed, and the pH value of the mixture is regulated to 2.0 by phosphoric acid; installing a reaction kettle, replacing air in the kettle with nitrogen, replacing the nitrogen with hydrogen, and pressurizing to 2MPa after the replacement is completed; and (3) starting the reaction kettle to react at 200 ℃ and the stirring speed of 800 r/min. The reaction was carried out within 0-3 hours. And detecting the concentration of lysine and pentanediamine in the reacted solution by adopting liquid chromatography after the reaction solution is derived. It was found that at 1.5h of reaction, the lysine conversion reached 85%. The selectivity of the pentanediamine reaches 34.2 percent.
Comparative example 3 (improvement of rare earth metal content)
The preparation method of the modified carbon supported ruthenium-based catalyst 15% Ce-5% Ru/C comprises the following steps:
0.02g of ruthenium trichloride and 0.345g of cerium nitrate are added to 20g of deionized water, and uniformly mixed, 1g of active carbon is added, and the mixture is magnetically stirred for 12 hours at room temperature. Then evaporating water at 105 ℃, and drying at 100 ℃ for 4 hours for further dehydration. The dried solid was then subjected to drying to give comparative catalyst 3.
The modified carbon-supported ruthenium-based catalyst prepared in comparative example 3, 15% Ce-5% Ru/C (comparative catalyst 3), was used for lysine decarboxylation to prepare pentylene diamine by the following method:
0.1826g of lysine hydrochloride is taken and put into a 25ml reaction kettle liner, 10ml of water is added for dissolution, then 0.101g of contrast catalyst 3 is added, and the mixture is stirred until the mixture is completely and uniformly mixed, and the pH value of the mixture is regulated to 2.0 by phosphoric acid; installing a reaction kettle, replacing air in the kettle with nitrogen, replacing the nitrogen with hydrogen, and pressurizing to 2MPa after the replacement is completed; and (3) starting the reaction kettle to react at 200 ℃ and the stirring speed of 800 r/min. The reaction was carried out in different 0-3 hours. And detecting the concentration of lysine and pentanediamine in the reacted solution by adopting liquid chromatography after the reaction solution is derived. It was found that at 1h of reaction, the lysine conversion reached 90%. Pentanediamine selectivity was 25%.
Example 1
The embodiment is the preparation of rare earth metal and roasting combined modified catalyst 1% Ce-5% Ru/C, and the method is as follows:
0.02g of ruthenium trichloride and 0.023g of cerium nitrate were added to 20g of deionized water, mixed uniformly, 1g of activated carbon was added, magnetically stirred at room temperature for 12 hours, then water was evaporated at 105 ℃, and dried at 100 ℃ for 4 hours for further dehydration. And then roasting the dried solid for 3 hours at 400 ℃ in a nitrogen atmosphere to obtain the catalyst 1.
The 1% Ce-5% Ru/C catalyst prepared in this example 1 (catalyst 1) was used to catalyze the synthesis of pentamethylenediamine by the following method:
0.1826g of lysine hydrochloride is taken and put into a 25ml reaction kettle liner, 10ml of water is added for dissolution, then 0.101g of catalyst 1 is added, the mixture is stirred until the mixture is completely and uniformly mixed, and the pH value of the mixed solution is regulated to 2.0 by phosphoric acid; installing a reaction kettle, replacing air in the kettle with nitrogen, replacing the nitrogen with hydrogen, and pressurizing to 2MPa after the replacement is completed; and (3) starting the reaction kettle to react at 200 ℃ and the stirring speed of 800 r/min. The reaction was carried out within 0-3 hours. And detecting the concentration of lysine and pentanediamine in the reacted solution by adopting liquid chromatography after the reaction solution is derived. It was found that at 1.5h of reaction, the lysine conversion reached 87%. The selectivity of the pentanediamine reaches 40 percent.
Example 2
The embodiment is the preparation of rare earth metal and roasting combined modified catalyst 1% Ce-5% Ru/C, and the method is as follows:
0.02g of ruthenium trichloride and 0.023g of cerium nitrate were added to 20g of deionized water, mixed well, 1g of activated carbon was added, and magnetically stirred at room temperature for 12 hours. Then evaporating water at 105 ℃, and drying at 100 ℃ for 4 hours for further dehydration. And then roasting the dried solid for 3 hours at 800 ℃ in a nitrogen atmosphere to obtain the catalyst 2.
The 1% Ce-5% Ru/C catalyst prepared in this example 2 (catalyst 2) was used to catalyze the synthesis of pentamethylenediamine by the following method:
0.1826g of lysine hydrochloride is taken and put into a 25ml reaction kettle liner, 10ml of water is added for dissolution, then 0.101g of catalyst 2 is added, and the mixture is stirred until the mixture is completely and uniformly mixed, and the pH value of the mixture is regulated to 2.0 by phosphoric acid; installing a reaction kettle, replacing air in the kettle with nitrogen, replacing the nitrogen with hydrogen, and pressurizing to 2MPa after the replacement is completed; and (3) starting the reaction kettle to react at 200 ℃ and the stirring speed of 800 r/min. The reaction was carried out within 0-3 hours. And detecting the concentration of lysine and pentanediamine in the reacted solution by adopting liquid chromatography after the reaction solution is derived. It was found that at 2h of reaction, the lysine conversion reached 90%. The selectivity of the pentanediamine reaches 41.2 percent.
Example 3
The embodiment is the preparation of rare earth metal and roasting combined modified catalyst 1% La-5% Ru/C, and the method is as follows:
0.02g of ruthenium trichloride and 0.017g of lanthanum chloride are added to 20g of deionized water, and the mixture is uniformly mixed, 1g of activated carbon is added, and the mixture is magnetically stirred for 12 hours at room temperature. Then evaporating water at 105 ℃, and drying at 100 ℃ for 4 hours for further dehydration. And then roasting the dried solid for 3 hours at 800 ℃ in a nitrogen atmosphere to obtain the catalyst 3.
The 1% La-5% Ru/C catalyst (catalyst 3) prepared in this example 3 was used to catalyze the synthesis of pentamethylenediamine by the following method:
0.1826g of lysine hydrochloride is taken and put into a 25ml reaction kettle liner, 10ml of water is added for dissolution, then 0.101g of catalyst 3 is added, and the mixture is stirred until the mixture is completely and uniformly mixed, and the pH value of the mixture is regulated to 2.0 by phosphoric acid; installing a reaction kettle, replacing air in the kettle with nitrogen, replacing the nitrogen with hydrogen, and pressurizing to 2MPa after the replacement is completed; and (3) starting the reaction kettle to react at 200 ℃ and the stirring speed of 800 r/min. The reaction was carried out within 0-3 hours. And detecting the concentration of lysine and pentanediamine in the reacted solution by adopting liquid chromatography after the reaction solution is derived. It was found that at 2h of reaction, the lysine conversion reached 82%. The selectivity of the pentanediamine reaches 36.4 percent.
Example 4
The embodiment is the preparation of 1% Sm-5% Ru/C of rare earth metal and roasting combined modified catalyst, and the method is as follows:
0.02g of ruthenium trichloride and 0.016g of samarium chloride are added into 20g of deionized water, and the mixture is uniformly mixed, activated carbon is added, and the mixture is magnetically stirred for 12 hours at room temperature. Then evaporating water at 105 ℃, and drying at 100 ℃ for 4 hours for further dehydration. And then roasting the dried solid for 3 hours at 800 ℃ in a nitrogen atmosphere to obtain the catalyst 4.
The 1% Sm-5% Ru/C catalyst (catalyst 4) prepared in this example 4 was used to catalyze the synthesis of pentamethylenediamine by the following procedure:
0.1826g of lysine hydrochloride is taken and put into a 25ml reaction kettle liner, 10ml of water is added for dissolution, then 0.101g of catalyst 4 is added, and the mixture is stirred until the mixture is completely and uniformly mixed, and the pH value of the mixture is regulated to 2.0 by phosphoric acid; installing a reaction kettle, replacing air in the kettle with nitrogen, replacing the nitrogen with hydrogen, and pressurizing to 2MPa after the replacement is completed; and (3) starting the reaction kettle to react at 200 ℃ and the stirring speed of 800 r/min. The reaction was carried out within 0-3 hours. And detecting the concentration of lysine and pentanediamine in the reacted solution by adopting liquid chromatography after the reaction solution is derived. It was found that at 2h of reaction, the lysine conversion reached 92.4%. The selectivity of the pentanediamine reaches 42.3 percent.
Example 5
The embodiment is the preparation of rare earth metal and roasting combined modified catalyst 1% Ce-0.5% Sm-5% Ru/C, and the method is as follows:
0.02g of ruthenium trichloride, 0.008g of samarium chloride and 0.023g of cerium nitrate are added into 20g of deionized water, and are uniformly mixed, 1g of activated carbon is added, and the mixture is magnetically stirred for 12 hours at room temperature. Then evaporating water at 105 ℃, and drying at 100 ℃ for 4 hours for further dehydration. And then roasting the dried solid for 3 hours at 800 ℃ in a nitrogen atmosphere to obtain the catalyst 5.
The 1% Ce-0.5% Sm-5% Ru/C catalyst (catalyst 5) prepared in this example 5 was used to catalyze the synthesis of pentamethylene diamine by the following method:
0.1826g of lysine hydrochloride is taken and put into a 25ml reaction kettle liner, 10ml of water is added for dissolution, then 0.101g of catalyst 5 is added, and the mixture is stirred until the mixture is completely and uniformly mixed, and the pH value of the mixture is regulated to 2.0 by phosphoric acid; installing a reaction kettle, replacing air in the kettle with nitrogen, replacing the nitrogen with hydrogen, and pressurizing to 2MPa after the replacement is completed; and (3) starting the reaction kettle to react at 200 ℃ and the stirring speed of 800 r/min. The reaction was carried out within 0-3 hours. And detecting the concentration of lysine and pentanediamine in the reacted solution by adopting liquid chromatography after the reaction solution is derived. It was found that at 2h of reaction, the lysine conversion reached 91.24%. The selectivity of the pentanediamine reaches 61.3 percent.
Example 6
The embodiment is the preparation of rare earth metal and roasting combined modified catalyst 1% Ce-0.5% La-5% Ru/C, and the method is as follows:
0.02g of ruthenium trichloride, 0.023g of cerium nitrate and 0.017g of lanthanum chloride are added into 20g of deionized water, uniformly mixed, activated carbon is added, the solid-to-liquid ratio is 1:5, and magnetic stirring is carried out for 12h at room temperature. Then evaporating water at 105 ℃, and drying at 100 ℃ for 4 hours for further dehydration. And then roasting the dried solid for 3 hours at 800 ℃ in a nitrogen atmosphere to obtain the catalyst 6.
The 1% Ce-0.5% La-5% Ru/C catalyst (catalyst 6) prepared in this example 7 was used to catalyze the synthesis of pentamethylene diamine by the following method:
0.1826g of lysine hydrochloride is taken and put into a 25ml reaction kettle liner, 10ml of water is added for dissolution, then 0.101g of catalyst 6 is added, the mixture is stirred until the mixture is completely and uniformly mixed, and the pH value of the mixed solution is regulated to 2.0 by phosphoric acid; installing a reaction kettle, replacing air in the kettle with nitrogen, replacing the nitrogen with hydrogen, and pressurizing to 2MPa after the replacement is completed; and (3) starting the reaction kettle to react at 200 ℃ and the stirring speed of 800 r/min. The reaction was carried out within 0-3 hours. And detecting the concentration of lysine and pentanediamine in the reacted solution by adopting liquid chromatography after the reaction solution is derived. It was found that at 2h of reaction, the lysine conversion reached 90%. The selectivity of the pentanediamine reaches 56.5 percent.
Example 7
XRD analysis was performed on the catalysts prepared in comparative example 1 and examples 1 and 2, and it was found that high-temperature calcination had a significant effect on the catalyst structure. The presence of elemental ruthenium and cerium oxide was found at 800 c (see 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 (see FIGS. 2,3 and 4).
Example 8
This example is a catalyst 5 repeatability test, and is performed as follows:
Separating the catalyst after lysine decarboxylation reaction, centrifugally washing 3 times by using distilled water, adding into a reactor, adding 10mL of 0.1mol/L L-lysine solution, adjusting the pH value of the mixed solution to be equal to 2 by adding phosphoric acid solution, sealing the reactor at 200 ℃, and reacting under 2MPa of hydrogen for 2 hours. After the process is repeatedly carried out for 5 times, the activity of the catalyst can still reach 90% of lysine conversion rate and 60% of pentylene diamine selectivity.
The invention provides a preparation method of a rare earth metal modified ruthenium-carbon catalyst and a method for synthesizing pentylene diamine by catalysis. The rare earth metal modified ruthenium-carbon catalyst effectively improves the selectivity of the pentanediamine in the reaction of preparing the pentanediamine by lysine decarboxylation, provides a new industrialization opportunity for producing the pentanediamine by the chemical lysine decarboxylation, and has good industrial application prospect.
The invention has been described in detail above but is not limited to the specific embodiments described herein. Those skilled in the art will appreciate that other modifications and variations may be made without departing from the scope of the invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. A preparation method of a modified carbon supported ruthenium-based catalyst is characterized by comprising the following steps: sequentially adding a ruthenium precursor and a rare earth metal precursor into the aqueous dispersion of the carbon material, stirring at a certain temperature, drying the mixture, and roasting at a certain atmosphere and temperature after drying to obtain the modified carbon-supported ruthenium-based catalyst.
2. The method for preparing a modified carbon-supported ruthenium-based catalyst according to claim 1, wherein: the ruthenium precursor is any one or more of ruthenium chloride, ruthenium carbonyl and ruthenium hexammoniate.
3. The method for preparing a modified carbon-supported ruthenium-based catalyst according to claim 1, wherein: the rare earth metal is one or more of yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd) and samarium (Sm).
4. The method for preparing a modified carbon-supported ruthenium-based catalyst according to claim 1, wherein: the carbon material is one of activated carbon, graphene and carbon nano tube.
5. The method for preparing a modified carbon-supported ruthenium-based catalyst according to claim 1, wherein: the mass fraction of ruthenium in the modified carbon-supported ruthenium-based catalyst is 0.01-50%, and the mass fraction of rare earth metal in the modified carbon-supported ruthenium-based catalyst is 0.01-50%.
6. The method for preparing a modified carbon-supported ruthenium-based catalyst according to claim 1, wherein: the stirring temperature is 30-80 ℃, the roasting atmosphere is one of nitrogen, hydrogen, argon and helium, and the roasting temperature is 30-1000 ℃.
7. The modified carbon-supported ruthenium-based catalyst produced by the production method of a modified carbon-supported ruthenium-based catalyst according to any one of claims 1 to 6.
8. The use of the modified carbon-supported ruthenium-based catalyst of claim 7 in the preparation of pentylene diamine by decarboxylation of lysine.
9. The use according to claim 8, characterized in that: the synthesis of the pentanediamine by decarboxylation of the lysine is carried out in a high-pressure reaction kettle, lysine or lysine salt, deionized water, phosphoric acid and a modified carbon supported ruthenium-based catalyst are added into the high-pressure reaction kettle, and the water solution of the pentanediamine is obtained by reaction.
10. The method for catalytic synthesis of pentamethylenediamine according to claim 9, wherein: the reaction temperature is 120-250 ℃, the pressure is 0.5-6 MPa, the concentration of lysine or lysine salt in the reaction solution is 0.01-3M, the molar ratio of the catalyst to the lysine or lysine salt is 1 (0.1-10), the pH value of the reaction solution is regulated to 1-8 by adopting phosphoric acid, the reaction time is 0-3 h, the reaction atmosphere is any one of nitrogen, hydrogen, argon, helium or carbon monoxide, the lysine is L-lysine, and the lysine salt is any one of lysine hydrochloride and lysine sulfate.
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