CN105498761A - Preparation method of nano Ru/C supported catalyst - Google Patents
Preparation method of nano Ru/C supported catalyst Download PDFInfo
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- CN105498761A CN105498761A CN201510974077.3A CN201510974077A CN105498761A CN 105498761 A CN105498761 A CN 105498761A CN 201510974077 A CN201510974077 A CN 201510974077A CN 105498761 A CN105498761 A CN 105498761A
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- ruthenium
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- carbon
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- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 42
- 238000003756 stirring Methods 0.000 claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000007864 aqueous solution Substances 0.000 claims abstract description 20
- 239000012298 atmosphere Substances 0.000 claims abstract description 19
- 239000012065 filter cake Substances 0.000 claims abstract description 16
- 239000011268 mixed slurry Substances 0.000 claims abstract description 15
- 238000007598 dipping method Methods 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 150000003303 ruthenium Chemical class 0.000 claims abstract description 6
- 230000007935 neutral effect Effects 0.000 claims abstract description 5
- 239000000047 product Substances 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 241000370738 Chlorion Species 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- NCPHGZWGGANCAY-UHFFFAOYSA-N methane;ruthenium Chemical compound C.[Ru] NCPHGZWGGANCAY-UHFFFAOYSA-N 0.000 claims description 6
- BIXNGBXQRRXPLM-UHFFFAOYSA-K ruthenium(3+);trichloride;hydrate Chemical group O.Cl[Ru](Cl)Cl BIXNGBXQRRXPLM-UHFFFAOYSA-K 0.000 claims description 6
- 239000002250 absorbent Substances 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 239000003610 charcoal Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- SPDCFZAAMSXKTK-UHFFFAOYSA-N acetic acid;ruthenium Chemical compound [Ru].CC(O)=O SPDCFZAAMSXKTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000007833 carbon precursor Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 239000008187 granular material Substances 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- SIEBMRITFODZNV-UHFFFAOYSA-N Cl.[K].[Ru] Chemical compound Cl.[K].[Ru] SIEBMRITFODZNV-UHFFFAOYSA-N 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 230000036571 hydration Effects 0.000 claims description 2
- 238000006703 hydration reaction Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 20
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 3
- 239000002440 industrial waste Substances 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 abstract 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 17
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 16
- 229930016911 cinnamic acid Natural products 0.000 description 16
- 235000013985 cinnamic acid Nutrition 0.000 description 16
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000005984 hydrogenation reaction Methods 0.000 description 11
- 230000009467 reduction Effects 0.000 description 11
- 239000012299 nitrogen atmosphere Substances 0.000 description 10
- 238000012546 transfer Methods 0.000 description 10
- 241000234671 Ananas Species 0.000 description 9
- 235000007119 Ananas comosus Nutrition 0.000 description 9
- HJZLEGIHUQOJBA-UHFFFAOYSA-N cyclohexane propionic acid Chemical compound OC(=O)CCC1CCCCC1 HJZLEGIHUQOJBA-UHFFFAOYSA-N 0.000 description 9
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- NASFKTWZWDYFER-UHFFFAOYSA-N sodium;hydrate Chemical compound O.[Na] NASFKTWZWDYFER-UHFFFAOYSA-N 0.000 description 3
- YYMCVDNIIFNDJK-XFQWXJFMSA-N (z)-1-(3-fluorophenyl)-n-[(z)-(3-fluorophenyl)methylideneamino]methanimine Chemical compound FC1=CC=CC(\C=N/N=C\C=2C=C(F)C=CC=2)=C1 YYMCVDNIIFNDJK-XFQWXJFMSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 230000001147 anti-toxic effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- MAZOHJVAXBNBPX-UHFFFAOYSA-N ruthenium hydrochloride Chemical compound Cl.[Ru] MAZOHJVAXBNBPX-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- NAORGNSYBDQEPT-UHFFFAOYSA-N 3-phenylprop-2-enoic acid Chemical compound OC(=O)C=CC1=CC=CC=C1.OC(=O)C=CC1=CC=CC=C1 NAORGNSYBDQEPT-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229940124226 Farnesyltransferase inhibitor Drugs 0.000 description 1
- 229910002061 Ni-Cr-Al alloy Inorganic materials 0.000 description 1
- 244000061176 Nicotiana tabacum Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- -1 cyclohexyl allyl propionate Chemical compound 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000003528 protein farnesyltransferase inhibitor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 230000002194 synthesizing effect 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
-
- B01J35/393—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/36—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by hydrogenation of carbon-to-carbon unsaturated bonds
Abstract
The invention discloses a preparation method of a nano Ru/C supported catalyst. The method comprises steps as follows: treated activated carbon is added to a ruthenium slat aqueous solution, stirring and dipping are performed for 0.5-4 h, then an alkaline compound aqueous solution is used for adjusting the pH of mixed slurry of activated carbon and ruthenium salt to 7-12, the mixed slurry is stirred continuously for 1-6 h, left to stand for 2-4 h and filtered, a filter cake is washed with water to be neutral and free of chloride ions and dried at the temperature of 80-120 DEG C for 4-12 h, and a treated Ru/C precursor is obtained; the treated Ru/C precursor is subjected to sectioned calcination in the inert atmosphere; a product after calcination is reduced, and then the nano Ru/C supported catalyst with high dispersion is obtained. The particle size of ruthenium particles of the catalyst is 1-4 nm. The method is low in production cost, has mild preparation conditions and causes few three industrial wastes, and the catalyst has advantages of long service life and the like.
Description
Technical field
The present invention relates to a kind of for the preparation method of cinnamic acid Hydrogenation for the nano ruthenium carbon-supported type catalyst of high activity and high stability of 3-cyclohexylpropionic acid, belong to catalysis technical field.
Background technology
3-cyclohexylpropionic acid, also known as pineapple acid, is important organic synthesis and medical synthetic intermediate, is widely used in the synthesis etc. of spices, farnesyl transferase inhibitor and ferroelectric liquid crystal material.Industrially be mainly used in synthesizing cyclohexyl allyl propionate (being commonly called as allyl cyclohexyl propionate).Allyl cyclohexyl propionate is a kind of additive with strong sweet pineapple fruits fragrance, is widely used in the fields such as food, cosmetics and tobacco.The preparation method of current pineapple acid mainly contains benzaldehyde method and cyclohexanol method.Cyclohexanol method is that di-tert-butyl peroxide is initator with methyl acrylate and cyclohexanol for raw material, and through ester exchange reaction synthesis γ, γ-cyclopenta butyrolactone, then hydrogenation obtains pineapple acid.Although the operation of this method is simple, pineapple acid selective lower (69-80%).Benzaldehyde method be by benzaldehyde and aceticanhydride through Perkin react obtained cinnamic acid (3-phenylacrylic acid) again catalytic hydrogenation synthesize 3-cyclohexylpropionic acid, overall reaction yield about 60%.This method is simple to operate, and energy consumption is low, and by cinnamic acid Hydrogenation for the selective height of pineapple acid.Therefore industrial generally employing benzaldehyde method, namely cinnamic acid catalytic hydrogenation legal system is for pineapple acid.
The catalyst for this reaction of current report mainly contains nickel, platinum and ruthenium catalyst etc.Ni catalyst price is relatively cheap, therefore applies more in the industrial production.Ding Desheng etc. find cinnamic acid can be made containing chromium Raney's nickel W-7 type catalyst (Ni-Cr-Al alloy, its ratio is 38.6:60.1:1.13) to be converted into pineapple acid at middle pressure two benches hydrogenation, yield 90%.Ni method for preparing catalyst is simple, workable, but need carry out at high temperature under high pressure, and hydroconversion condition is harsh, and the antitoxin poor-performing of Ni catalyst, easy in inactivation, need improve further.The initial activity of Pt catalyst is higher, and reaction condition is gentle, and antitoxin performance is good.The PtO that Wang Wennan etc. adopt infusion process to prepare
2/ SiO
2react 3-5h at normal temperatures and pressures cinnamic acid almost to be transformed completely, pineapple acid purity reaches 95%, and this catalyst uses 5 activity slightly to decline.Although Pt catalyst performance is better than Ni catalyst, on this catalyst, hydrogenation product yields is not very high, and cost is higher, and domestic industry application is not very extensive.And Ru catalyst shows high cinnamic acid hydrogenation activity and selective, and price comparatively Pt catalyst is cheap.Japan Patent JPH10204022A adopts Ru/C catalyst to react the 3-cyclohexylpropionic acid yield that 5h can obtain 96% at middle pressure 1.0-3.0MPa, 100-170 DEG C.But this Ru catalyst based reaction time is longer, and reaction temperature is higher, and therefore reaction condition is relatively harsh, and the stability of catalyst is not mentioned.Therefore in cinnamic acid hydrogenation process, still there is following subject matter: how control to make phenyl ring complete hydrogenation under more leniently condition; Catalyst apply mechanically the problems such as number of times, separation losses and loss of active component.These factors limit applying of this process for cleanly preparing of catalytic hydrogenation.Therefore the key technology that the catalyst simultaneously with high activity, high selectivity and high stability is cinnamic acid hydrogenation reaction is developed.Patent CN101502798B, CN101549292B and CN101966457B adopt the precipitation method to prepare ruthenium carbon-supported type catalyst in conjunction with liquid phase reduction, although catalytic activity is high, with short production cycle, active component and carrier interact not strong, active component is caused easily to run off, the shortcomings such as the life-span is low.
Summary of the invention
The present invention is directed to existing catalyst and generate for cinnamic acid hydrogenation the shortcoming that 3-cyclohexylpropionic acid exists that catalytic activity is low, stability is low and active component easily runs off etc., a kind of preparation method for cinnamic acid hydrogenation reaction with the nano ruthenium carbon-supported type catalyst of efficient catalytic activity and stability is provided.
For solving above technical problem, the technical solution used in the present invention is: high activity and high stability nano ruthenium carbon-supported type catalyst adopts dipper precipitation standby in conjunction with baking inphases legal system, the preparation method of this catalyst is specially: active carbon is after salpeter solution process, spend deionized water extremely neutral and dry, join in the ruthenium salt precursor body aqueous solution and stir dipping, then the pH value of mixed slurry is regulated with the alkali compounds aqueous solution, continue to stir certain hour, after leaving standstill a period of time again, filter, filter cake is washed with water to neutrality and without after chlorion, be transferred in baking oven dry, low-temperature bake under inert atmosphere conditions again, then raised temperature roasting certain hour again, catalyst after roasting is reduced at a certain temperature, namely the nano ruthenium carbon-supported type catalyst of high dispersive is obtained, this catalyst composition is by weight percentage: metal Ru 1-6%, absorbent charcoal carrier accounts for 94-99%, and the ruthenium particle granules of this catalyst is of a size of 1-4nm.
A preparation method for nano ruthenium carbon-supported type catalyst, is characterized in that the method comprises the following steps:
1) be 80-300 order by granular size, specific area is 900-1200m
2g
-1absorbent charcoal carrier to join concentration be 0.1-1.0molL
-1hNO
3at 30-60 DEG C, stir 1-4h in solution, then spend deionized water to neutral, filter and dry 4-12h, obtain the active carbon that pretreatment is good;
2) active carbon handled well is joined in ruthenium saline solution and stir dipping 0.5-4h, then the mixed slurry pH to 7-12 of active carbon and ruthenium salt is regulated with the alkali compounds aqueous solution, continue to stir 1-6h, leave standstill 2-4h, filter, filter cake is washed with water to neutrality and without after chlorion, namely filter cake dry 4-12h at temperature is 80-120 DEG C is obtained the ruthenium carbon precursor handled well;
3) the ruthenium carbon precursor handled well is carried out baking inphases under inert atmosphere conditions;
4) reduced by step 3) products therefrom, namely obtain the nano ruthenium carbon-supported type catalyst of high dispersive, the ruthenium particle granules of this catalyst is of a size of 1-4nm.
Described ruthenium salt is hydrate ruthenium trichloride, acetic acid ruthenium, ruthenium hydrochloride potassium, ammonium hexachlororuthenate or hydration pentachloro-ruthenic acid ammonium.
Described alkali compounds is Na
2cO
3, NaHCO
3, NaOH, KOH or ammoniacal liquor.
Baking inphases in described step 3) is at N
2prior to 120-200 DEG C of roasting 2-10h under atmosphere, be then elevated to 400-600 DEG C and continue roasting 2-4h.
Reducing condition in described step 4) is 120-350 DEG C of reductase 12-10h under the mixed atmosphere of pure hydrogen or hydrogen and nitrogen.
The volume ratio of described hydrogen and nitrogen is 1:9 ~ 3:7.
Catalyst of the present invention is particularly suitable for cinnamic acid catalytic hydrogenation reaction synthesis 3-cyclohexylpropionic acid.Namely add water, cinnamic acid, NaOH and catalyst in a kettle., this catalyst is 70-120 DEG C in reaction temperature, and Hydrogen Vapor Pressure is 1.0-3.0MPa, reaction time is 1-3h, 3-cyclohexylpropionic acid yield reaches more than 96%, and purity reaches electron level, and catalyst can at least recycled 30 times.The advantages such as therefore this catalyst has long service life, production cost is low, reaction condition is gentle, product purity is high and three industrial wastes are few.
The present invention by dipper precipitation in conjunction with the method for baking inphases by active component ruthenium with hydroxide form uniform deposition and anchor on absorbent charcoal carrier, enhance the interaction of active component and carrier, avoid desorption and the migration of active component in course of reaction, solve the difficult problem that liquid-phase reduction mode active component easily runs off.Preparation method provided by the invention can obtain the high nano ruthenium carbon-supported type catalyst of decentralization, the active metal particles size of this catalyst at 1-4nm, even particle size distribution.
Accompanying drawing explanation
Fig. 1 is the TEM figure of nano ruthenium carbon-supported type catalyst, and as can be seen from the figure ruthenium nano particle size is at 1-4nm, even particle size distribution.
Detailed description of the invention
In order to illustrate advance and the innovative point of the technology of the present invention, make the technology of the present invention feature be more readily apparent from understanding, spy is further described in conjunction with instantiation.According to following embodiment, the present invention may be better understood.But concrete material ratio, process conditions and result thereof described by embodiment only for illustration of the present invention, and should can not limit the present invention described in detail in claims yet.
The pretreatment of active carbon: select domain size distribution at 120-200 order, specific area is 950m
2g
-1absorbent charcoal carrier, being joined concentration is 1.0molL
-1hNO
3stir in solution and soak 3h, then spend deionized water active carbon to neutral and filter, dry 8h, obtain the active carbon that pretreatment is good.
Embodiment 1
Accurately take the active carbon 50.00g that pretreatment is good, join 300mL and contain stirring dipping 3h in the 5.56g hydrate ruthenium trichloride aqueous solution, then use 1.0molL
-1aqueous sodium carbonate regulates the pH to 9 of mixed slurry, continues to stir 4h, leaves standstill 2h, filters, and filter cake is washed with water to neutrality and without after chlorion, to transfer in baking oven dry 4h at 100 DEG C, at N
2atmosphere prior to 150 DEG C at roasting 4h, then in 400 DEG C of roasting 4h, finally in H
2: N
2=1:9(v/v) the lower 300 DEG C of reduction 3h of atmosphere, the ruthenium load capacity namely obtaining high dispersive is the nano ruthenium carbon-supported type catalyst of 4.0%.
Embodiment 2
Accurately take the active carbon 50.00g that pretreatment is good, join 300mL and contain stirring dipping 3h in the 4.13g hydrate ruthenium trichloride aqueous solution, then use 1.0molL
-1aqueous sodium carbonate regulates the pH to 9 of mixed slurry, continues to stir 4h, leaves standstill 1h, filters, and filter cake is washed with water to neutrality and without after chlorion, to transfer in baking oven dry 4h at 100 DEG C, at N
2atmosphere prior to 150 DEG C at roasting 4h, then in 400 DEG C of roasting 4h, finally in H
2: N
2=1:9(v/v) the lower 300 DEG C of reduction 3h of atmosphere, the ruthenium load capacity namely obtaining high dispersive is the nano ruthenium carbon-supported type catalyst of 3.0%.
Embodiment 3
Accurately take the active carbon 50.00g that pretreatment is good, join 300mL and contain stirring dipping 3h in the 7.02g hydrate ruthenium trichloride aqueous solution, then use 1.0molL
-1aqueous sodium carbonate regulates the pH to 9 of mixed slurry, continues to stir 4h, leaves standstill 1h, filters, and filter cake is washed with water to neutrality and without after chlorion, to transfer in baking oven dry 6h at 100 DEG C, first at N
2atmosphere prior to 150 DEG C at roasting 4h, then in 400 DEG C of roasting 2h, finally in H
2: N
2=3:7(v/v) the lower 120 DEG C of reduction 10h of atmosphere, the ruthenium load capacity namely obtaining high dispersive is the nano ruthenium carbon-supported type catalyst of 5.0%.
Embodiment 4
Accurately take the active carbon 50.00g that pretreatment is good, join 300mL and contain stirring dipping 2h in the 5.56g hydrate ruthenium trichloride aqueous solution, then use 1.0molL
-1sodium hydrate aqueous solution regulates the pH to 8 of mixed slurry, continues to stir 2h, leaves standstill 2h, filters, and filter cake is washed with water to neutrality and without after chlorion, to transfer in baking oven dry 8h at 100 DEG C, first at N
2atmosphere prior to 150 DEG C at roasting 6h, then in 500 DEG C of roasting 4h, finally in H
2: N
2=1:9(v/v) the lower 250 DEG C of reduction 3h of atmosphere, the ruthenium load capacity namely obtaining high dispersive is the nano ruthenium carbon-supported type catalyst of 4.0%.
Embodiment 5
Accurately take the active carbon 50.00g that pretreatment is good, join 300mL and contain stirring dipping 2h in 8.50g ruthenium hydrochloride aqueous solutions of potassium, then use 1.0molL
-1sodium hydrate aqueous solution regulates the pH to 9 of mixed slurry, continues to stir 5h, leaves standstill 2h, filters, and filter cake is washed with water to neutrality and without after chlorion, to transfer in baking oven dry 10h at 100 DEG C, first at N
2atmosphere prior to 150 DEG C at roasting 8h, then in 600 DEG C of roasting 4h, finally in H
2: N
2=1:9(v/v) the lower 300 DEG C of reduction 3h of atmosphere, the ruthenium load capacity namely obtaining high dispersive is the nano ruthenium carbon-supported type catalyst of 4.0%.
Embodiment 6
Accurately take the active carbon 50.00g that pretreatment is good, join 300mL and contain stirring dipping 2h in 8.50g ruthenium hydrochloride aqueous solutions of potassium, then use 1.0molL
-1ammonia spirit regulates the pH to 10 of mixed slurry, continues to stir 2h, leaves standstill 3h, filters, and filter cake is washed with water to neutrality and without after chlorion, to transfer in baking oven dry 4h at 100 DEG C, first at N
2atmosphere prior to 120 DEG C at roasting 8h, then in 400 DEG C of roasting 2h, finally in H
2: N
2=2:8(v/v) the lower 150 DEG C of reduction 8h of atmosphere, the ruthenium load capacity namely obtaining high dispersive is the nano ruthenium carbon-supported type catalyst of 4.0%.
Embodiment 7
Accurately take the active carbon 50.00g that pretreatment is good, join 300mL and contain stirring dipping 2h in the 5.74g acetic acid ruthenium aqueous solution, then use 1.0molL
-1sodium bicarbonate aqueous solution regulates the pH to 9 of mixed slurry, continues to stir 3h, leaves standstill 2h, filters, and filter cake is washed with water to neutrality and without after chlorion, to transfer in baking oven dry 6h at 100 DEG C, first at N
2atmosphere prior to 180 DEG C at roasting 4h, then in 600 DEG C of roasting 3h, finally in H
2: N
2=1:9(v/v) the lower 200 DEG C of reduction 3h of atmosphere, the ruthenium load capacity namely obtaining high dispersive is the nano ruthenium carbon-supported type catalyst of 4.0%.
Embodiment 8
Accurately take the active carbon 50.00g that pretreatment is good, join 300mL and contain stirring dipping 4h in the 7.34g ammonium hexachlororuthenate aqueous solution, then use 1.0molL
-1potassium hydroxide solution regulates the pH to 9 of mixed slurry, continues to stir 1h, leaves standstill 2h, filters, and filter cake is washed with water to neutrality and without after chlorion, to transfer in baking oven dry 6h at 120 DEG C, first at N
2atmosphere prior to 120 DEG C at roasting 4h, then in 500 DEG C of roasting 3h, finally in H
2: N
2=1:9(v/v) the lower 250 DEG C of reduction 3h of atmosphere, the ruthenium load capacity namely obtaining high dispersive is the nano ruthenium carbon-supported type catalyst of 4.0%.
Embodiment 9
Accurately take the active carbon 50.00g that pretreatment is good, join 300mL and contain stirring dipping 3h in the 7.34g ammonium hexachlororuthenate aqueous solution, then use 1.0molL
-1potassium hydroxide solution regulates the pH to 11 of mixed slurry, continues to stir 2h, leaves standstill 2h, filters, and filter cake is washed with water to neutrality and without after chlorion, to transfer in baking oven dry 8h at 80 DEG C, first at N
2atmosphere prior to 200 DEG C at roasting 2h, then in 450 DEG C of roasting 4h, finally in the lower 200 DEG C of reductase 12 h of pure hydrogen atmosphere, the ruthenium load capacity namely obtaining high dispersive is the nano ruthenium carbon-supported type catalyst of 4.0%.
Embodiment 10
Accurately take the active carbon 50.00g that pretreatment is good, join 300mL and contain stirring dipping 2h in the 5.74g acetic acid ruthenium aqueous solution, then use 1.0molL
-1sodium hydrate aqueous solution regulates the pH to 12 of mixed slurry, continues to stir 2h, leaves standstill 2h, filters, and filter cake is washed with water to neutrality and without after chlorion, to transfer in baking oven dry 4h at 120 DEG C, first at N
2atmosphere prior to 150 DEG C at roasting 2h, then in 400 DEG C of roasting 4h, finally in H
2: N
2=1:9(v/v) the lower 180 DEG C of reduction 3h of atmosphere, the ruthenium load capacity namely obtaining high dispersive is the nano ruthenium carbon-supported type catalyst of 4.0%.
By the concrete reaction condition that nano ruthenium carbon catalyst prepared by method described in embodiment 1 to embodiment 10 is used for cinnamic acid catalytic hydrogenation reaction be: be 70-120 DEG C in temperature, Hydrogen Vapor Pressure 1.0-3.0MPa, 500mL water, 100g cinnamic acid, 29g NaOH and 3.0g catalyst is added in 1.0L reactor, reaction time is 3h, and catalyst performance test result is as table 1:
Table 1
The concrete reaction condition that nano ruthenium carbon catalyst embodiment 1 prepared is used for cinnamic acid catalytic hydrogenation stability test is: be 70-120 DEG C in temperature, Hydrogen Vapor Pressure 1.0-3.0MPa, 500mL water, 100g cinnamic acid, 29g NaOH and 3.0g catalyst is added in 1.0L reactor, reaction time is after 3h, proceed to react by rejoining after catalyst filtration in reactor, catalyst stability test result is as follows next time:
Table 2
As can be seen from Table 1, the catalyst using the inventive method to prepare has higher 3-cyclohexylpropionic acid yield.As can be seen from Table 2, after catalyst reaction applies mechanically 30 times, 3-cyclohexylpropionic acid yield is without obvious decline, and the catalyst therefore using the inventive method to prepare has good stability.
Claims (6)
1. a preparation method for nano ruthenium carbon-supported type catalyst, it is characterized in that this catalyst adopts dipper precipitation standby in conjunction with baking inphases legal system, concrete steps are as follows:
1) be 80-300 order by granular size, specific area is 900-1200m
2g
-1absorbent charcoal carrier to join concentration be 0.1-1.0molL
-1hNO
3at 30-60 DEG C, stir 1-4h in solution, then spend deionized water to neutral, filter and dry 4-12h, obtain the active carbon that pretreatment is good;
2) active carbon handled well is joined in ruthenium saline solution and stir dipping 0.5-4h, then the mixed slurry pH to 7-12 of active carbon and ruthenium salt is regulated with the alkali compounds aqueous solution, continue to stir 1-6h, leave standstill 2-4h, filter, filter cake is washed with water to neutrality and without after chlorion, namely filter cake dry 4-12h at temperature is 80-120 DEG C is obtained the ruthenium carbon precursor handled well;
3) the ruthenium carbon precursor handled well is carried out baking inphases under condition under inert atmosphere;
4) reduced by step 3) products therefrom, namely obtain the nano ruthenium carbon-supported type catalyst of high dispersive, the ruthenium particle granules of this catalyst is of a size of 1-4nm.
2. preparation method as claimed in claim 1, is characterized in that described ruthenium salt is hydrate ruthenium trichloride, acetic acid ruthenium, ruthenium hydrochloride potassium, ammonium hexachlororuthenate or hydration pentachloro-ruthenic acid ammonium.
3. preparation method as claimed in claim 1, is characterized in that described alkali compounds is Na
2cO
3, NaHCO
3, NaOH, KOH or ammoniacal liquor.
4. preparation method as claimed in claim 1, is characterized in that the baking inphases in described step 3) is at N
2prior to 120-200 DEG C of roasting 2-10h under atmosphere, be then elevated to 400-600 DEG C and continue roasting 2-4h.
5. preparation method as claimed in claim 1, is characterized in that the reducing condition in described step 4) is 120-350 DEG C of reductase 12-10h under the mixed atmosphere of pure hydrogen or hydrogen and nitrogen.
6. preparation method as claimed in claim 5, is characterized in that the volume ratio of hydrogen and nitrogen in the mixed atmosphere of described hydrogen and nitrogen is 1:9 ~ 3:7.
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