CN106391001B - Active carbon loaded ruthenium-platinum bimetallic composite catalyst, preparation method and application - Google Patents
Active carbon loaded ruthenium-platinum bimetallic composite catalyst, preparation method and application Download PDFInfo
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- CN106391001B CN106391001B CN201610734410.8A CN201610734410A CN106391001B CN 106391001 B CN106391001 B CN 106391001B CN 201610734410 A CN201610734410 A CN 201610734410A CN 106391001 B CN106391001 B CN 106391001B
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- activated carbon
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- CFQCIHVMOFOCGH-UHFFFAOYSA-N platinum ruthenium Chemical compound [Ru].[Pt] CFQCIHVMOFOCGH-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 239000002131 composite material Substances 0.000 title abstract description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 20
- 238000001914 filtration Methods 0.000 claims abstract description 20
- 239000002105 nanoparticle Substances 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 16
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012065 filter cake Substances 0.000 claims abstract description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 62
- 229910052707 ruthenium Inorganic materials 0.000 claims description 30
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 29
- 239000002905 metal composite material Substances 0.000 claims description 29
- 229910052697 platinum Inorganic materials 0.000 claims description 24
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 21
- NPAXBRSUVYCZGM-UHFFFAOYSA-N carbonic acid;propane-1,2-diol Chemical compound OC(O)=O.CC(O)CO NPAXBRSUVYCZGM-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 238000006722 reduction reaction Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000001354 calcination Methods 0.000 abstract description 2
- 238000002791 soaking Methods 0.000 abstract 2
- 150000001298 alcohols Chemical class 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 abstract 1
- 229910021641 deionized water Inorganic materials 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 abstract 1
- ZTWIEIFKPFJRLV-UHFFFAOYSA-K trichlororuthenium;trihydrate Chemical compound O.O.O.Cl[Ru](Cl)Cl ZTWIEIFKPFJRLV-UHFFFAOYSA-K 0.000 abstract 1
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical compound O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 description 12
- 238000013019 agitation Methods 0.000 description 10
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229960003767 alanine Drugs 0.000 description 3
- 235000004279 alanine Nutrition 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- GSDSWSVVBLHKDQ-UHFFFAOYSA-N 9-fluoro-3-methyl-10-(4-methylpiperazin-1-yl)-7-oxo-2,3-dihydro-7H-[1,4]oxazino[2,3,4-ij]quinoline-6-carboxylic acid Chemical compound FC1=CC(C(C(C(O)=O)=C2)=O)=C3N2C(C)COC3=C1N1CCN(C)CC1 GSDSWSVVBLHKDQ-UHFFFAOYSA-N 0.000 description 2
- 229910010084 LiAlH4 Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- ROBXZHNBBCHEIQ-BYPYZUCNSA-N ethyl (2s)-2-aminopropanoate Chemical compound CCOC(=O)[C@H](C)N ROBXZHNBBCHEIQ-BYPYZUCNSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000012280 lithium aluminium hydride Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 229960001699 ofloxacin Drugs 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 206010018612 Gonorrhoea Diseases 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 206010022678 Intestinal infections Diseases 0.000 description 1
- 229910010082 LiAlH Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910006124 SOCl2 Inorganic materials 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 229960003405 ciprofloxacin Drugs 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 229940124307 fluoroquinolone Drugs 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000006197 hydroboration reaction Methods 0.000 description 1
- VCRYGHPVKURQMM-UHFFFAOYSA-N methane;platinum Chemical compound C.[Pt] VCRYGHPVKURQMM-UHFFFAOYSA-N 0.000 description 1
- NCPHGZWGGANCAY-UHFFFAOYSA-N methane;ruthenium Chemical compound C.[Ru] NCPHGZWGGANCAY-UHFFFAOYSA-N 0.000 description 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene chloride Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- -1 propylene glycol ester Chemical class 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 150000007660 quinolones Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Substances ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- B01J32/00—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- 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
- B01J37/16—Reducing
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/30—Alkali metal phosphates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention provides an active carbon loaded ruthenium-platinum bimetallic composite catalyst, which is prepared by the following steps: adding activated carbon into nitric acid solution, stirring, soaking, filtering, washing filter cake to neutrality with deionized water, placing in a tube furnace, and soaking in N2Calcining under protection for later use; mixing ruthenium chloride trihydrate, chloroplatinic acid and propylene carbonateMixing alcohol esters, adding a reducing agent for reduction to obtain ruthenium-platinum nanoparticle sol, adding prepared pretreated activated carbon, stirring for adsorption, filtering, washing with water, washing with acetone, and drying in vacuum to obtain the catalyst; the catalyst has the advantages of simple preparation process, high catalytic activity, good stability and the like, can realize hydrogenation of the L-aminopropionic acid in a water phase at a lower temperature and a lower pressure to complete the preparation of the L-aminopropanol, has low cost, high yield and simple process, and conforms to the principle of green chemistry.
Description
(1) technical field
The invention belongs to catalyst technical fields, and in particular to a kind of activated carbon supported ruthenium-platinum bimetallic composite catalyzing
Agent and preparation method thereof, and add hydrogen to prepare the application in L- aminopropanol in catalysis L- alanine.
(2) background technique
L- aminopropanol is the key intermediate for synthesizing lefofloxacin, lefofloxacin (levofxcain, DR-
3355) be Ofloxacin ofloxacin the left-handed optical isomer of S type, antibacterial activity is twice of the latter, and toxic side effect is small, water-soluble
Property is big, is one of extensive pedigree antibiotic outstanding in quinolones.The antibacterial activity of lefofloxacin be enantiomer 8~
128 times, be one of large drug of current clinical use to enteric infection, gonococcal infection effective percentage up to 100%.The product
It is succeeded in developing earliest by Japanese Daiichi Pharmaceutical Co., Ltd. in the beginning of the nineties in last century, nineteen ninety-five formally enters Chinese market,
Start within 1997 to realize production domesticization, then, the market sales revenue of lefofloxacin rises rapidly, leaps to domestic antibacterial within 2002
It is the first to contaminate pharmaceutical market, annual sales amount accounts for the 2.08% of medical market share, substitution Ciprofloxacin becomes should up to 124,470,000 yuan
The soldier at the head of a formation in market, annual average rate of increase is 10% or so.2007, lefofloxacin year consumption sum firmly in occupation of
The position of the market ranking first, the market share also take up the half of the country of fluoroquinolones, continue to take on leading product
The role of kind.
There are following several approach in the country to Stereoselective synthesizing process at present:
(1) direct-reduction process: LiAlH is utilized4It restores l-Alanine and produces L- aminopropanol, in 5%LiAlH4THF it is molten
It is heated to reflux in liquid, uses CH2Cl2Dilution, then a certain amount of water process is used, to remove inorganic salts, filter cake handles reachable twice for filtering
To promising result, yield is up to 75%.Restoring method process is simple, but reducing agent LiAlH4Expensive and operational hazards, in addition
Last handling process is too complicated, so method has rarely had use at present.
(2) it is esterified reduction method: using l-Alanine in SOCl2Ester is generated with reaction in dehydrated alcohol, in NaBH4Aqueous solution
In the ethanol solution 1h of l-Alanine ethyl ester (L-alanine ethyl ester) is continuously added dropwise, and continue to stir at room temperature
3h, reduction obtain L- aminopropanol, are evaporated under reduced pressure after being extracted with ethyl acetate, yield 67%.
The method of industrialized production L- aminopropanol is at present: being first esterified alanine, then uses metal hydroboration
Object makees reducing agent, and reducing agent dosage is big, expensive, and residue pollutes environment.
In selective catalytic hydrogenation reaction, the performance of catalyst is to influence the principal element of reaction, patent:
CN101648879B has invented a kind of synthetic method of L- aminopropanol, uses L- alanine and H2For primary raw material, ruthenium
Charcoal is catalyst, carries out plus hydrogen directly synthesizes L- aminopropanol, be disadvantageous in that l-Alanine and sulfuric acid mass ratio (1~
1.2): 1, the mass ratio (4.8~5) of ruthenium Pd/carbon catalyst and L- alanine: 1, i.e., production process to consume a large amount of sulfuric acid and
Catalyst and reaction pressure is higher, operating process is dangerous easily to occur accident.Patent: the preparation L- amino of CN102344378B invention
The method of propyl alcohol, be water phase, organic phase blending agent acidic environment in, realize the catalytic hydrogenation of alanine, but receive
Rate is not more than 80%.Patent: CN103769211A is invented a kind of for synthesizing the hybrid inorganic-organic materials of L- aminopropanol
Supported ruthenium catalyst, catalyst preparation process is complicated and needs using organic matters such as a large amount of concentrated sulfuric acid, concentrated nitric acid and toluene, right
Environment causes largely to pollute, and does not meet the principle of Green Chemistry.
(3) summary of the invention
Activated carbon supported ruthenium catalyst and platinum catalyst has good Hydrogenation and is widely used for as adding
The catalyst of hydrogen reaction.Therefore, carrying out developmental research to activated carbon supported ruthenium and platinum catalyst has important theory significance
And prospects for commercial application.
It is an object of the invention to solve in the prior art, by catalytic hydrogenation synthesize L- aminopropanol when reaction pressure and
Temperature provides a kind of for synthesizing L- aminopropan compared with the problem that high, catalyst consumption is big, selectivity is low, at high cost and low yield
Activated carbon supported ruthenium-platinum double-metal composite catalyst of alcohol and the preparation method and application thereof, the catalyst is in lower pressure
(1.5~2.5Mpa) has high activity and highly selective under lower temperature (80~100 DEG C), can reduce synthesis L- aminopropan
The cost of alcohol simultaneously improves its yield.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of activated carbon supported ruthenium-platinum double-metal composite catalyst, preparation method are as follows:
(1) Activated Carbon Pretreatment:
Active carbon is added in 15wt%~25wt% nitric acid solution with feed liquid mass ratio 1:2~4, stirring 2~4h of dipping,
It filters later, filter cake is washed with deionized to neutrality, is subsequently placed in tube furnace, in N2Under protection, forged in 450~650 DEG C
3~5h is burnt, pretreated active carbon is obtained, it is spare;
(2) ruthenium, platinum are loaded:
Three chloride hydrate rutheniums, chloroplatinic acid, propylene glycol carbonate are mixed, reducing agent reduction is added, obtains ruthenium-platinum nanometer
Particle colloidal sols;Step (1) ready pretreated active carbon is added in gained ruthenium-Pt nanoparticle colloidal sol, stirring is inhaled
Attached 2~4h, later filter, wash, acetone wash, be dried in vacuo (200~400 DEG C, 2~4h), obtain described in it is activated carbon supported
Ruthenium-platinum double-metal composite catalyst;
The quality dosage of the three chloride hydrates ruthenium is calculated as 0.5~5mg/mL with the volume of propylene glycol carbonate;
The quality dosage of the chloroplatinic acid is calculated as 0.0025~0.025mg/mL with the volume of propylene glycol carbonate;
The reducing agent is H2、C2H5OH、N2H4·H2O or CH2OH-CH2OH;
When reducing agent is H2When, the H of reduction reaction2Pressure is 1~4MPa, and reaction temperature is 50~100 DEG C, the reaction time
For 2~5h;
When reducing agent is C2H5OH、N2H4·H2O or CH2OH-CH2When OH, the body of the reducing agent and propylene glycol carbonate
Product is than being 1.5~2:1, and reaction temperature is 40~80 DEG C, and the reaction time is 1~2h;
The quality of the pretreated active carbon and theoretical matter of the three chloride hydrate rutheniums in terms of ruthenium with chloroplatinic acid in terms of platinum
Measuring the ratio between summation is 100:1~15, preferably 100:5~10.
In activated carbon supported ruthenium-platinum double-metal composite catalyst made from preparation method according to the present invention, gold
The load capacity for belonging to ruthenium is 1wt%~10wt% (particularly preferably 5wt%), and the load capacity of metal platinum is 0.1wt%~1wt%
(particularly preferably 0.25wt%).
In preparation method of the present invention, the preparation of the ruthenium-Pt nanoparticle does not need stabilizer, only in carbonic acid
Ruthenium-Pt nanoparticle can be prepared in propylene glycol ester solution.Obtained ruthenium nano-particle size in 2~10nm, receive by platinum
Rice grain size is in 5~8nm.
Activated carbon supported ruthenium-platinum double-metal composite catalyst of the present invention can be applied to the catalysis of L- alanine
Hydrogenation reaction, the method for the application are as follows:
By L- alanine, water, 85wt% phosphoric acid, activated carbon supported ruthenium of the present invention-platinum bimetallic composite catalyzing
Agent mixing, 70~100 DEG C, Hydrogen Vapor Pressure be 1.5~4MPa under conditions of react 3~8h, filter later, filtrate with NaOH into
Row neutralizes, and after filtering out the phosphate for neutralizing and generating, first removes moisture under reduced pressure, then carry out rectifying, obtains product L- aminopropanol;
The mass ratio of the L- alanine and water, 85wt% phosphoric acid, catalyst of the present invention is 1:5~8.5:1~1.5:
0.1~0.35.
In application method of the present invention, the conversion ratio of L- alanine is up to 99%, and selectivity is up to 98%.
Compared with the prior art, the beneficial effects of the present invention are embodied in: for the present invention using active carbon as carrier, carrier is cheaply easy
?.And the advantages that catalyst of the present invention has preparation process simple, and catalytic activity is high, and stability is good, can lower temperature, compared with
The hydrogenation that L- alanine is realized in water phase under low-pressure, completes the preparation of L- aminopropanol, and at low cost, yield is high and technique
Simply, while during being somebody's turn to do the byproduct phosphoric acid hydrogen sodium generated is a kind of important raw material of industry, meets the principle of Green Chemistry.
(4) specific embodiment
Below by specific embodiment, invention is further explained, but protection scope of the present invention is not limited in
This.
Used active carbon is pre-processed through following method in following embodiment:
Active carbon is added in 20wt% nitric acid solution with feed liquid mass ratio 1:3, stirring dipping 3h is filtered, filter cake later
It is washed with deionized to neutrality, is subsequently placed in tube furnace, in N2Under protection, in 550 DEG C of calcining 4h, obtain pretreated
Active carbon, it is spare;
Embodiment 1
By tri- chloride hydrate ruthenium of 0.0260g, 2.6 × 10-4The magnetic agitation of g chloroplatinic acid addition propylene glycol carbonate containing 26ml
In kettle, it is filled with Hydrogen Vapor Pressure and reacts 2h at 80 DEG C to 4MPa, obtain Ru-Pt nano particle colloidal sol;It is added into the colloidal sol
Then (50mL × 3), acetone washing (20mL × 3) is washed with water in the pretreated active carbon of 1g, stirring and adsorbing 2h, filtering,
300 DEG C of vacuum drying 3h are to get arriving activated carbon supported ruthenium-platinum double-metal composite catalyst, in gained catalyst, ruthenium load capacity
For 1wt%, platinum load capacity is 0.1wt%.
Embodiment 2
By tri- chloride hydrate ruthenium of 0.0780g, 7.8 × 10-4The magnetic agitation of g chloroplatinic acid addition propylene glycol carbonate containing 78ml
In kettle, it is filled with Hydrogen Vapor Pressure and reacts 2h at 80 DEG C to 4MPa, obtain Ru-Pt nano particle colloidal sol;It is added into the colloidal sol
Then (50mL × 3), acetone washing (20mL × 3) is washed with water in the pretreated active carbon of 1g, stirring and adsorbing 2h, filtering,
300 DEG C of vacuum drying 3h are to get arriving activated carbon supported ruthenium-platinum double-metal composite catalyst, in gained catalyst, ruthenium load capacity
For 3wt%, platinum load capacity is 0.3wt%.
Embodiment 3
By tri- chloride hydrate ruthenium of 0.1300g, 1.3 × 10-3The magnetic force that the propylene glycol carbonate containing 130ml is added in g chloroplatinic acid stirs
It mixes in kettle, is filled with Hydrogen Vapor Pressure and reacts 2h at 80 DEG C to 4MPa, obtain Ru-Pt nano particle colloidal sol;Add into the colloidal sol
Entering the pretreated active carbon of 1g, stirring and adsorbing 2h, then (50mL × 3), acetone washing (20mL × 3) is washed with water in filtering,
300 DEG C of vacuum drying 3h are to get arriving activated carbon supported ruthenium-platinum double-metal composite catalyst, in gained catalyst, ruthenium load capacity
For 5wt%, platinum load capacity is 0.5wt%.
Embodiment 4
By tri- chloride hydrate ruthenium of 0.1820g, 1.82 × 10-3The magnetic force that the propylene glycol carbonate containing 182ml is added in g chloroplatinic acid stirs
It mixes in kettle, is filled with Hydrogen Vapor Pressure and reacts 2h at 80 DEG C to 4MPa, obtain Ru-Pt nano particle colloidal sol;Add into the colloidal sol
Entering the pretreated active carbon of 1g, stirring and adsorbing 2h, then (50mL × 3), acetone washing (20mL × 3) is washed with water in filtering,
300 DEG C of vacuum drying 3h are to get arriving activated carbon supported ruthenium-platinum double-metal composite catalyst, in gained catalyst, ruthenium load capacity
For 7wt%, platinum load capacity is 0.7wt%.
Embodiment 5
By tri- chloride hydrate ruthenium of 0.2600g, 2.6 × 10-3The magnetic force that the propylene glycol carbonate containing 260ml is added in g chloroplatinic acid stirs
It mixes in kettle, is filled with Hydrogen Vapor Pressure and reacts 2h at 80 DEG C to 4MPa, obtain Ru-Pt nano particle colloidal sol;Add into the colloidal sol
Entering the pretreated active carbon of 1g, stirring and adsorbing 2h, then (50mL × 3), acetone washing (20mL × 3) is washed with water in filtering,
300 DEG C of vacuum drying 3h are to get arriving activated carbon supported ruthenium-platinum double-metal composite catalyst, in gained catalyst, ruthenium load capacity
For 10wt%, platinum load capacity is 1wt%.
Embodiment 6
By tri- chloride hydrate ruthenium of 0.130g, 6.5 × 10-4The magnetic agitation of g chloroplatinic acid addition propylene glycol carbonate containing 26ml
In kettle, it is filled with Hydrogen Vapor Pressure and reacts 2h at 80 DEG C to 4MPa, obtain Ru-Pt nano particle colloidal sol;It is added into the colloidal sol
Then (50mL × 3), acetone washing (20mL × 3) is washed with water in the pretreated active carbon of 1g, stirring and adsorbing 2h, filtering,
300 DEG C of vacuum drying 3h are to get arriving activated carbon supported ruthenium-platinum double-metal composite catalyst, in gained catalyst, ruthenium load capacity
For 5wt%, platinum load capacity is 0.25wt%.
Embodiment 7
By tri- chloride hydrate ruthenium of 0.130g, 8.6 × 10-4The magnetic agitation of g chloroplatinic acid addition propylene glycol carbonate containing 43ml
In kettle, it is filled with Hydrogen Vapor Pressure and reacts 2h at 80 DEG C to 4MPa, obtain Ru-Pt nano particle colloidal sol;It is added into the colloidal sol
Then (50mL × 3), acetone washing (20mL × 3) is washed with water in the pretreated active carbon of 1g, stirring and adsorbing 2h, filtering,
300 DEG C of vacuum drying 3h are to get arriving activated carbon supported ruthenium-platinum double-metal composite catalyst, in gained catalyst, ruthenium load capacity
For 5wt%, platinum load capacity is 0.35wt%.
Embodiment 8
By tri- chloride hydrate ruthenium of 0.130g, 6.5 × 10-4The magnetic agitation of g chloroplatinic acid addition propylene glycol carbonate containing 260ml
In kettle, it is filled with Hydrogen Vapor Pressure and reacts 2h at 80 DEG C to 4MPa, obtain Ru-Pt nano particle colloidal sol;It is added into the colloidal sol
Then (50mL × 3), acetone washing (20mL × 3) is washed with water in 1g active carbon, stirring and adsorbing 2h, filtering, 300 DEG C of vacuum are dry
Dry 3h is to get activated carbon supported ruthenium-platinum double-metal composite catalyst is arrived, and in gained catalyst, ruthenium load capacity is 5wt%, platinum
Load capacity is 0.25wt%.
Embodiment 9
By tri- chloride hydrate ruthenium of 0.130g, 6.5 × 10-4The magnetic agitation of g chloroplatinic acid addition propylene glycol carbonate containing 130ml
In kettle, it is filled with Hydrogen Vapor Pressure and reacts 2h at 100 DEG C to 4MPa, obtain Ru-Pt nano particle colloidal sol;It is added into the colloidal sol
Then (50mL × 3), acetone washing (20mL × 3) is washed with water in the pretreated active carbon of 1g, stirring and adsorbing 2h, filtering,
300 DEG C of vacuum drying 3h are to get arriving activated carbon supported ruthenium-platinum double-metal composite catalyst, in gained catalyst, ruthenium load capacity
For 5wt%, platinum load capacity is 0.25wt%.
Embodiment 10
By tri- chloride hydrate ruthenium of 0.130g, 6.5 × 10-4The magnetic agitation of g chloroplatinic acid addition propylene glycol carbonate containing 130ml
In kettle, it is filled with Hydrogen Vapor Pressure and reacts 2h at 50 DEG C to 4MPa, obtain Ru-Pt nano particle colloidal sol;It is added into the colloidal sol
Then (50mL × 3), acetone washing (20mL × 3) is washed with water in the pretreated active carbon of 1g, stirring and adsorbing 2h, filtering,
300 DEG C of vacuum drying 3h are to get arriving activated carbon supported ruthenium-platinum double-metal composite catalyst, in gained catalyst, ruthenium load capacity
For 5wt%, platinum load capacity is 0.25wt%.
Embodiment 11
By tri- chloride hydrate ruthenium of 0.130g, 6.5 × 10-4The magnetic agitation of g chloroplatinic acid addition propylene glycol carbonate containing 130ml
In kettle, it is filled with Hydrogen Vapor Pressure and reacts 2h at 80 DEG C to 3MPa, obtain Ru-Pt nano particle colloidal sol;It is added into the colloidal sol
Then (50mL × 3), acetone washing (20mL × 3) is washed with water in the pretreated active carbon of 1g, stirring and adsorbing 2h, filtering,
300 DEG C of vacuum drying 3h are to get arriving activated carbon supported ruthenium-platinum double-metal composite catalyst, in gained catalyst, ruthenium load capacity
For 5wt%, platinum load capacity is 0.25wt%.
Embodiment 12
By tri- chloride hydrate ruthenium of 0.130g, 6.5 × 10-4The magnetic agitation of g chloroplatinic acid addition propylene glycol carbonate containing 130ml
In kettle, it is filled with Hydrogen Vapor Pressure and reacts 2h at 80 DEG C to 2MPa, obtain Ru-Pt nano particle colloidal sol;It is added into the colloidal sol
Then (50mL × 3), acetone washing (20mL × 3) is washed with water in the pretreated active carbon of 1g, stirring and adsorbing 2h, filtering,
300 DEG C of vacuum drying 3h are to get arriving activated carbon supported ruthenium-platinum double-metal composite catalyst, in gained catalyst, ruthenium load capacity
For 5wt%, platinum load capacity is 0.25wt%.
Application Example
L- ammonia is used for according to activated carbon supported ruthenium-platinum double-metal composite catalyst of embodiment 1-12 the method preparation
The catalytic hydrogenation reaction of base propionic acid, application method are as follows:
12g L- alanine, 100ml water, the phosphoric acid of 12g mass fraction 85%, 4g implementation are added in magnetic agitation kettle
The catalyst of one of example 1-12 preparation, at 90 DEG C, hydrogen pressure reacts 3h under the conditions of being 1.8MPa.After reaction, it filters, filtrate
It is neutralized with NaOH, after filtering out the phosphate for neutralizing and generating, first removes moisture under reduced pressure, then carry out rectifying, collect 72~78 DEG C
Fraction, obtain product L- aminopropanol.
Catalytic performance result such as following table (TOF in below table indicates transformation frequency):
Embodiment | Feed stock conversion/% | Selectivity of product/% | Product yield/% | TOF/min-1 |
1 | 62.4 | 99.4 | 62.0 | 38 |
2 | 93.3 | 98.8 | 92.2 | 52 |
3 | 92.1 | 98.2 | 90.4 | 188 |
4 | 97,4 | 97.6 | 95.1 | 211 |
5 | 98.5 | 96.2 | 94.8 | 240 |
6 | 50.1 | 99.5 | 49.8 | 32 |
7 | 74.5 | 98.9 | 73.7 | 44 |
8 | 98.9 | 98.3 | 97.2 | 182 |
9 | 82.3 | 98.5 | 81.1 | 49 |
10 | 60.3 | 99.4 | 59.9 | 37 |
11 | 96.5 | 98.4 | 95.0 | 146 |
12 | 95.8 | 98.6 | 94.5 | 88 |
Activated carbon supported ruthenium-platinum double-metal composite catalyst of 8 the method for embodiment preparation is used for L- alanine
Catalytic hydrogenation reaction, catalyst recycling the result is as follows:
Cycle-index | 1 | 5 | 10 | 15 | 20 | 25 | 30 |
Conversion ratio | 99.6% | 98.3% | 98.7% | 97.1% | 96.6% | 94.5% | 93.1% |
As can be seen from the table, the stability with higher of catalyst prepared by the method for the present invention can be recycled repeatedly
It uses, is beneficial to economize on resources, reduces cost.With the increase of number of use, the decline of conversion ratio is by catalyst in table
Caused by relative loss factor.
The ruthenium Pd/carbon catalyst of individual 5%Ru is used for the catalytic hydrogenation reaction knot of L- alanine under same application method
Fruit:
Reaction group number | Feed stock conversion/% | Selectivity of product/% | Product yield/% | TOF/min-1 |
1 | 48.4 | 89.9 | 43.5 | 38 |
2 | 52.3 | 88.5 | 46.3 | 64 |
3 | 50.5 | 87.6 | 44.2 | 76 |
The platinum carbon catalyst of individual 0.25%Pt is used for the catalytic hydrogenation reaction of L- alanine under same application method
As a result:
Reaction group number | Feed stock conversion/% | Selectivity of product/% | Product yield/% | TOF/min-1 |
1 | trace | trace | trace | trace |
2 | trace | trace | trace | trace |
3 | trace | trace | trace | trace |
As can be seen from the table, individual ruthenium Pd/carbon catalyst conversion ratio and selectivity are substantially reduced, and individually platinum charcoal is urged
Agent is not reacted but.Result above is compared it is recognised that the catalyst made from the method for the present invention has preparation process letter
The advantages that list, catalytic activity is high, and stability is good, can realize alanine in the water phase under lower temperature, lower pressure
Hydrogenation, completes the preparation of L- aminopropanol, and at low cost, yield is high and simple process, has and realizes industrialized prospect.
Claims (8)
1. a kind of activated carbon supported ruthenium-platinum double-metal composite catalyst, which is characterized in that the activated carbon supported ruthenium-platinum
Double-metal composite catalyst is prepared as follows to obtain:
(1) Activated Carbon Pretreatment:
Active carbon is added in 15wt%~25wt% nitric acid solution with feed liquid mass ratio 1:2~4, stirring 2~4h of dipping, later
Filtering, filter cake is washed with deionized to neutrality, is subsequently placed in tube furnace, in N2Under protection, in 450~650 DEG C calcine 3~
5h obtains pretreated active carbon, spare;
(2) ruthenium, platinum are loaded:
Three chloride hydrate rutheniums, chloroplatinic acid, propylene glycol carbonate are mixed, reducing agent reduction is added, obtains ruthenium-Pt nanoparticle
Colloidal sol;Addition step (1) ready pretreated active carbon in gained ruthenium-Pt nanoparticle colloidal sol, stirring and adsorbing 2~
4h, filtering later, washing, acetone are washed, are dried in vacuo, and the activated carbon supported ruthenium-platinum double-metal composite catalyst is obtained;
The quality dosage of the three chloride hydrates ruthenium is calculated as 0.5~5mg/mL with the volume of propylene glycol carbonate;
The quality dosage of the chloroplatinic acid is calculated as 0.0025~0.025mg/mL with the volume of propylene glycol carbonate;
The reducing agent is H2、C2H5OH、N2H4·H2O or CH2OH-CH2OH;
The quality of the pretreated active carbon is total with Theoretical Mass of the chloroplatinic acid in terms of platinum in terms of ruthenium with three chloride hydrate rutheniums
With the ratio between be 100:1~15.
2. activated carbon supported ruthenium-platinum double-metal composite catalyst as described in claim 1, which is characterized in that step (2)
In, the reducing agent is H2, the H of reduction reaction2Pressure is 1~4MPa, and reaction temperature is 50~100 DEG C, the reaction time 2
~5h.
3. activated carbon supported ruthenium-platinum double-metal composite catalyst as described in claim 1, which is characterized in that step (2)
In, the reducing agent is C2H5OH、N2H4·H2O or CH2OH-CH2OH, the volume ratio of the reducing agent and propylene glycol carbonate
For 1.5~2:1, reaction temperature is 40~80 DEG C, and the reaction time is 1~2h.
4. activated carbon supported ruthenium-platinum double-metal composite catalyst as described in claim 1, which is characterized in that step (2)
In, the quality of the pretreated active carbon and Theoretical Mass summation of the three chloride hydrate rutheniums in terms of ruthenium with chloroplatinic acid in terms of platinum
The ratio between be 100:5~10.
5. activated carbon supported ruthenium-platinum double-metal composite catalyst as described in claim 1, which is characterized in that step (2)
In, the vacuum drying temperature is 200~400 DEG C, and the time is 2~4h.
6. activated carbon supported ruthenium-platinum double-metal composite catalyst as described in claim 1 adds in the catalysis of L- alanine
Application in hydrogen reaction.
7. application as claimed in claim 6, which is characterized in that the method for the application are as follows:
By ruthenium activated carbon supported described in L- alanine, water, 85wt% phosphoric acid, claim 1-platinum double-metal composite catalyst
Mixing is filtered, filtrate is carried out with NaOH later in 70~100 DEG C, Hydrogen Vapor Pressure to react 3~8h under conditions of 1.5~4MPa
It neutralizes, after filtering out the phosphate for neutralizing and generating, first removes moisture under reduced pressure, then carry out rectifying, obtain product L- aminopropanol.
8. the use as claimed in claim 7, which is characterized in that the L- alanine and water, 85wt% phosphoric acid, claim
The mass ratio of 1 catalyst is 1:5~8.5:1~1.5:0.1~0.35.
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CN109174091B (en) * | 2018-10-10 | 2022-02-25 | 湖南高鑫铂业有限公司 | Ru-Rh/C bimetallic catalyst and preparation method and application thereof |
CN111628187A (en) * | 2020-05-05 | 2020-09-04 | 江苏大学 | Carbon-supported ruthenium oxide catalyst and preparation method thereof |
CN113121368A (en) * | 2021-03-29 | 2021-07-16 | 安徽华恒生物科技股份有限公司 | Method for preparing gamma-aminopropanol by one-step catalytic hydrogenation and application thereof |
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CN115178257B (en) * | 2022-06-13 | 2024-06-07 | 浙江工业大学 | Preparation method and application of Pt-Ru-La/C multi-metal catalyst |
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