CN105251482A - Ruthenium palladium/carbon catalyst of cyclohexanecarboxylic acid synthesized through benzoic acid hydrogenation and preparation method and application thereof - Google Patents
Ruthenium palladium/carbon catalyst of cyclohexanecarboxylic acid synthesized through benzoic acid hydrogenation and preparation method and application thereof Download PDFInfo
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 239000003054 catalyst Substances 0.000 title claims abstract description 86
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 61
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 239000005711 Benzoic acid Substances 0.000 title claims abstract description 35
- 235000010233 benzoic acid Nutrition 0.000 title claims abstract description 35
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 32
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 title claims abstract description 18
- VZFUCHSFHOYXIS-UHFFFAOYSA-N cycloheptane carboxylic acid Natural products OC(=O)C1CCCCCC1 VZFUCHSFHOYXIS-UHFFFAOYSA-N 0.000 title abstract 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 20
- 239000002105 nanoparticle Substances 0.000 claims abstract description 16
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 14
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 46
- 229910052799 carbon Inorganic materials 0.000 claims description 46
- 239000000047 product Substances 0.000 claims description 26
- 239000002253 acid Substances 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 16
- 239000012752 auxiliary agent Substances 0.000 claims description 13
- 150000003303 ruthenium Chemical class 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 12
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 238000009938 salting Methods 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000005470 impregnation Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- 241000370738 Chlorion Species 0.000 claims description 6
- 235000002595 Solanum tuberosum Nutrition 0.000 claims description 6
- 244000061456 Solanum tuberosum Species 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- 239000012265 solid product Substances 0.000 claims description 6
- 239000011592 zinc chloride Substances 0.000 claims description 6
- 235000005074 zinc chloride Nutrition 0.000 claims description 6
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 0.000 claims description 6
- 150000007513 acids Chemical class 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- NGIISMJJMXRCCT-UHFFFAOYSA-N [Ru].[N+](=O)(O)[O-] Chemical compound [Ru].[N+](=O)(O)[O-] NGIISMJJMXRCCT-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000003301 hydrolyzing effect Effects 0.000 claims description 3
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- SPDCFZAAMSXKTK-UHFFFAOYSA-N acetic acid;ruthenium Chemical compound [Ru].CC(O)=O SPDCFZAAMSXKTK-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 150000002940 palladium Chemical class 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 23
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FSVJFNAIGNNGKK-UHFFFAOYSA-N 2-[cyclohexyl(oxo)methyl]-3,6,7,11b-tetrahydro-1H-pyrazino[2,1-a]isoquinolin-4-one Chemical compound C1C(C2=CC=CC=C2CC2)N2C(=O)CN1C(=O)C1CCCCC1 FSVJFNAIGNNGKK-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241001442514 Schistosomatidae Species 0.000 description 1
- 208000012826 adjustment disease Diseases 0.000 description 1
- -1 after distillation Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- RSPWPAYFBOWLKA-UHFFFAOYSA-N cyclohexane;formic acid Chemical compound OC=O.C1CCCCC1 RSPWPAYFBOWLKA-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- ZQWPRMPSCMSAJU-UHFFFAOYSA-N methyl cyclohexanecarboxylate Chemical class COC(=O)C1CCCCC1 ZQWPRMPSCMSAJU-UHFFFAOYSA-N 0.000 description 1
- 239000002547 new drug Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229960002957 praziquantel Drugs 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a ruthenium palladium/carbon catalyst of cyclohexanecarboxylic acid synthesized through benzoic acid hydrogenation. The catalyst comprises a carbon material carrier, an active component of metal element Ru nanoparticles and an auxiliary of metal element Pd nanoparticles. The loading capacity of the Ru nanoparticles is 0.5-0.8%, and the loading capacity of the Pd nanoparticles is 0.05-2.0%. The invention further discloses a preparation method of the ruthenium palladium/carbon catalyst. Firstly, the carbon material carrier is prepared, then the active component ruthenium and the auxiliary palladium are loaded, a catalyst precursor is obtained, and finally the catalyst precursor is dried and reduced. The catalyst avoids use of a large amount of palladium, has high reaction activity, selectivity and stability, can be used circularly and remarkably reduces production cost. The catalyst is used for synthesizing cyclohexanecarboxylic acid through benzoic acid catalytic hydrogenation. The raw material conversion rate is 100%, the purity of a target product can be higher than 99.5%, process conditions are moderate, equipment is simple, three wastes are not emitted, and industrialization is easily achieved.
Description
Technical field
The present invention relates to a kind of ruthenium Pd/carbon catalyst of synthesizing cyclohexyl formic acid by benzoic acid hydrogenation of high activity and high stability and method for making thereof and application, belong to technical field of catalytic hydrogenation.
Background technology
Hexahydrobenzoid acid is a kind of important organic synthesis intermediate, it itself is good light curing agent, can be used for the synthesis that medicine resists pregnant 392 and treatment blood fluke new drug praziquantel, its derivative is as cyclohexanecarboxylic acid methyl esters, and trans 1-4-isopropyl cyclohexanecarboxylic acid etc. is all the important intermediate of many chemical products and medicine synthesis.
CN101092349A discloses a kind of benzoic method of hydrotreating, its process is: under the existence of Pd/C catalyst and Ru/C auxiliary agent, the benzoic acid of melting and hydrogen carry out hydrogenation reaction in the reactor, after reaction, mixture is through rotary filter press and centrifugation, turbid liquid containing high concentration catalyst and auxiliary agent loops back reactor, isolated clear liquid enters evaporimeter and is separated further, isolated catalyst and the complete Returning reactor system of auxiliary agent.Weak point is that the benzoic acid activity of melting is low, and process conditions are harsh, and precious metals pd is expensive.
CN1749234A discloses a kind of method of synthesizing cyclohexyl formic acid by benzoic acid hydrogenation.Benzoic acid, under the existence of carrier-borne transition metal rhodium catalyst, solvent-free, in supercritical carbon dioxide and hexahydrobenzoid acid, contacts initial ring catalytic reaction with hydrogen under the condition of reaction pressure 8MPa; Utilize the solubility of hexahydrobenzoid acid in supercritical carbon dioxide to extract after reaction, make catalyst and product separation.Weak point is its reaction conversion ratio and selective not high, and supercritical carbon dioxide extracting needs the pressure of 10MPa simultaneously, and process is comparatively complicated, and investment energy consumption is higher, and catalyst activity component rhodium is rare metal, expensive.
CN103599795A discloses a kind of Catalysts and its preparation method and application of benzoic acid hydrogenation preparing cyclohexane formic acid, and described catalyst comprises carrier, auxiliary agent and active component, and carrier is nickel foam, and auxiliary agent is active carbon, and active component is metallic element Pd.This invention also provides preparation method and its application as integral catalyzer in fixed bed of described catalyst.Weak point is that the reactivity of nickel is high, but poor selectivity, accessory substance are many, separation difficulty, and active component Pd is expensive simultaneously.
Make a general survey of situation both domestic and external, benzoic acid hydrogenation synthesizing cyclohexane 1 alkane formic acid many employings noble metal makes catalyst, wherein in the majority with metallic element Pd, although good product performance, purposes is wide, and price is high, so not yet by large-scale promotion application.Simultaneously, because such reaction temperature is higher, complex procedures, catalyst and product length time of contact easily cause secondary response, cause reaction selectivity to decline, and catalyst is oxidizable poisoning, causes reactivity to reduce, reduce catalyst access times, so need development of new hydrogenation catalyst and synthesis technology.
For overcoming the weak point of above-mentioned technology, the invention provides that a kind of activity is high, the catalyst of the synthesizing cyclohexyl formic acid by benzoic acid hydrogenation of good stability, process conditions gentleness and method for making thereof and application.
Summary of the invention
The invention provides a kind of ruthenium Pd/carbon catalyst of synthesizing cyclohexyl formic acid by benzoic acid hydrogenation, described catalyst comprises carrier, active component and auxiliary agent, described carrier is impregnated with active component and auxiliary agent, described carrier is Carbon Materials, described active component is metallic element Ru nano particle, and described auxiliary agent is metallic element Pd nano particle; Wherein, the load capacity of described Ru nano particle is 0.5%-8.0%, and the load capacity of described Pd nano particle is 0.05%-2.0%.
Further, the load capacity of described Ru nano particle is preferably 3.0%-8.0%.
In catalyst, the particle diameter of described Ru, Pd nano particle is 2-5nm; The decentralization of described Ru, Pd is 30%-80%; The specific area of described Carbon Materials is 500-2500m
2/ g, is preferably 1000-2000m
2/ g, most probable pore size is 2-10nm.
The present invention also provides a kind of preparation method of ruthenium Pd/carbon catalyst of synthesizing cyclohexyl formic acid by benzoic acid hydrogenation, and concrete steps are as follows:
Step 1, the preparation of Carbon Materials, mixes rear heating and to be hydrolyzed polymerization by mealy potato, resorcinol, zinc chloride and water, it is dry and carbonize to have reacted rear taking-up mixture, then by the washing of the solid product of charing to without chlorion post-drying;
Step 2, the ruthenium salt of preparation solubility and palladium salting liquid, then adopt vacuum equivalent impregnation method to flood step ruthenium salt and palladium salting liquid respectively by Carbon Materials, obtain ruthenium Pd/carbon catalyst precursor after dry process;
Step 3, adds aqueous slkali in the ruthenium Pd/carbon catalyst precursor that step 2 obtains, and after regulating pH to alkalescence, precipitates and leaves standstill;
Step 4, adopts the product that reducing agent reduction step 3 is obtained, obtains the activated ruthenium Pd/carbon catalyst of tool.
In the preparation method of ruthenium Pd/carbon catalyst of the present invention, preferred technical scheme is:
In step 1, hydrolytic polymerization temperature is preferably 95-100 DEG C, and hydrolysis time is preferably 24-36h; Baking temperature is preferably 200-250 DEG C, and drying time is preferably 2-8h; Carbonization temperature is preferably 500-700 DEG C, and carbonization time is preferably 10-15h.
In step 2, described ruthenium salt is selected from one or more in the ruthenic chloride of solubility, acetic acid ruthenium and nitric acid ruthenium; Described palladium salt is selected from one or more in the palladium bichloride of solubility, palladium and palladium nitrate, and the dip time of ruthenium salt and palladium salting liquid is preferably 2-10h, and baking temperature is preferably 80 DEG C-150 DEG C, and drying time is preferably 2-8h.
In step 3, described aqueous slkali is preferably NaOH solution, and pH value is preferably 9-13; Sedimentation time is 0.5-6h, and time of repose is 0.5-3h.
In step 4, described reducing agent is formaldehyde or sodium borohydride solution, and reducing agent consumption is preferably more than 100% of theoretical amount, and the recovery time is preferably 0.5-6h.
The present invention also provides a kind of method above-mentioned ruthenium Pd/carbon catalyst being applied to benzoic acid hydrogenation and preparing hexahydrobenzoid acid, concrete steps are: by benzoic acid solvent-free or under having solvent existent condition, face hydrogen to contact with ruthenium Pd/carbon catalyst, carry out hydrogenation reaction, normal temperature and pressure is down to after reaction terminates, isolated by filtration product and catalyst, namely filtrate obtain target product after distillation.
Described solvent is selected from water, acids, alcohols or hydro carbons; Wherein, preferred acids reacts as solvent, and preferably the target product hexahydrobenzoid acid of hydrogenation is solvent further.
The reaction pressure of described hydrogenation reaction is preferably 2.0-6.0MPa, and reaction temperature is preferably 100-180 DEG C, and the reaction time is preferably 2-64h.
Catalyst of the present invention adopts Carbon Materials to be carrier, and being active component with ruthenium, take palladium as auxiliary agent, avoid a large amount of uses of palladium, catalyst of the present invention has high reactivity, selective and stability simultaneously, and catalyst can be recycled, and significantly reduces production cost.Simply, decentralization is high, and carrier material is cheap and easy to get for Catalyst Production of the present invention and recovery process, through process of simply making charcoal, i.e. recyclable active component ruthenium, palladium, the production of catalyst, use, cost recovery all significantly reduce, and significantly can reduce environmental pollution.Adopt catalyst of the present invention and preferred process conditions to be applied to Synthesis of CyclohexanecarboxyliAcid Acid by Hydrogenation of Benzoic Acid, feed stock conversion 100%, the purity of target product can be greater than 99.5%, process conditions are gentle, equipment is simple, and three-waste free discharge, easily realizes industrialization.
Detailed description of the invention
Be described in detail to the specific embodiment of the present invention below, reagent used in embodiment is all from being purchased.
Specific embodiment is as follows:
The preparation of ruthenium Pd/carbon catalyst:
Step 1, the preparation of Carbon Materials, mealy potato, resorcinol, zinc chloride and water are mixed after rear heating in 95-100 DEG C of hydrolytic polymerization 24-36h, react rear taking-up mixture in 200-250 DEG C of dry 2-8h, afterwards at 500-700 DEG C of charing 10-15h, then the solid product of charing is washed extremely without chlorion post-drying;
Step 2, the ruthenium salt of preparation solubility and palladium salting liquid, then adopt vacuum equivalent impregnation method to flood ruthenium salt and palladium salting liquid respectively by Carbon Materials, dipping 2-10h, obtains ruthenium Pd/carbon catalyst precursor after dry 2-8h afterwards at 80 DEG C-150 DEG C;
Step 3, adds NaOH solution in the ruthenium Pd/carbon catalyst precursor that step 2 obtains, and after regulating pH to 9-13, precipitation 0.5-6h also leaves standstill 0.5-3h;
Step 4, adopt the product that formaldehyde or sodium borohydride solution reduction step 3 obtain, reducing agent consumption is preferably more than 100% of theoretical amount, and reduction 0.5-6h, obtains the activated ruthenium Pd/carbon catalyst of tool.
The application of catalyst:
Catalyst is used for synthesizing cyclohexyl formic acid by benzoic acid hydrogenation, adopt the pressure autoclave type hydrogenation plant of 100ml-5000ml, charging feedstock successively, solvent and catalyst, wherein (m (raw material): m (catalyst)=100:5), adopt hydrogen exchange or vacuumize the method for deoxidation, oxygen in reaction system is got rid of, again to reactor introduce hydrogen, adjustment reaction pressure is to 2.0-6.0MPa, evenly be warming up to 100-180 DEG C, reaction 2-64h, reactant mixture is taken out after being down to normal temperature and pressure, isolated by filtration product and catalyst, after distillation, product is analyzed.The catalyst be separated can repeatedly recycle.
The computing formula of conversion of benzoic acid is as follows: benzoic acid molal quantity × 100% that the benzoic acid molal quantity that conversion ratio=reaction consumes/reaction drops into;
Benzoic acid optionally computing formula is as follows: benzoic acid molal quantity × 100% that hexahydrobenzoid acid molal quantity/reaction that selective=reaction generates consumes.
Embodiment 1
The preparation of ruthenium Pd/carbon catalyst:
Step 1, the preparation of Carbon Materials, 20g mealy potato, 5g resorcinol, 65g zinc chloride and water are mixed in the oil bath being placed on 96 DEG C the polymerization that is hydrolyzed, mixture dry 8h in the baking oven of 220 DEG C is taken out after reaction 30h, transfer to 650 DEG C of constant temperature charing 12h in retort, finally the washing of gained solid product existed to without chlorion, dry stand-by, obtained high-area carbon specific area is 1460m
2/ g, most probable pore size are 7.8nm;
Step 2, prepares the ruthenic chloride solution of 3mol/L and the palladium chloride solution of 1.0mol/L respectively by active component ruthenium load capacity 5.0%, palladium load capacity 0.5%;
Step 3, gets 5g Carbon Materials, adopts vacuum equivalent impregnation method to flood the ruthenium, the palladium solution that have prepared respectively, leaves standstill 4h, 100 DEG C of dry 4h, can obtain ruthenium Pd/carbon catalyst precursor in 80 DEG C of water-baths;
Step 4, with the NaOH aqueous solution of 10wt%, regulates pH value to be 11, and precipitation 2h, leaves standstill 2h;
Step 5, reduce above-mentioned solution by the formalin of 37wt%, formaldehyde consumption is more than 100% of theoretical amount, leaves standstill 2h after reductase 12 h, cooling, filter, deionized water is washed till without Cl
oneafter namely obtain ruthenium Pd/carbon catalyst.
The preparation of hexahydrobenzoid acid:
Above-mentioned ruthenium Pd/carbon catalyst 8g (weight containing water in catalyst), benzoic acid 40g and the hexahydrobenzoid acid 40g prepared is loaded in 200mL autoclave, under the condition of facing hydrogen, reaction pressure 4.0MPa, reaction temperature 140 DEG C carries out hydrogenation reaction, reaction time is 6h, be down to normal temperature and pressure, isolated by filtration product and catalyst after reaction terminates, namely filtrate obtain target product after distillation.
Embodiment 2
The preparation of ruthenium Pd/carbon catalyst:
Step 1, the preparation of Carbon Materials, 20g mealy potato, 5g resorcinol, 65g zinc chloride and water are mixed in the oil bath being placed on 95 DEG C the polymerization that is hydrolyzed, mixture dry 8h in the baking oven of 200 DEG C is taken out after reaction 36h, transfer to 700 DEG C of constant temperature charing 10h in retort, finally the washing of gained solid product existed to without chlorion, dry stand-by, obtained high-area carbon specific area is 1580m
2/ g, most probable pore size are 7.2nm;
Step 2, configures the ruthenium acetate solution of 3mol/L and the palladium solution of 1.0mol/L respectively by active component ruthenium load capacity 5.0%, palladium load capacity 0.1%;
Step 3, gets 5g Carbon Materials, adopts vacuum equivalent impregnation method to flood the ruthenium, the palladium solution that have prepared respectively, leaves standstill 2h, 80 DEG C of dry 8h, can obtain ruthenium Pd/carbon catalyst precursor in 80 DEG C of water-baths;
Step 4, with the NaOH aqueous solution of 10wt%, regulates pH value to be 9, and precipitation 6h, leaves standstill 0.5h;
Step 5, reduce above-mentioned solution with 20% sodium borohydride solution, consumption is more than 100% of theoretical amount, leaves standstill 2h after reduction 6h, cooling, filter, deionized water is washed till without Cl
oneafter namely obtain ruthenium Pd/carbon catalyst.
The preparation of hexahydrobenzoid acid:
Above-mentioned ruthenium Pd/carbon catalyst 8g, benzoic acid 40g and the hexahydrobenzoid acid 40g prepared is loaded in 200mL autoclave, under the condition of facing hydrogen, reaction pressure 6.0MPa, reaction temperature 100 DEG C carries out hydrogenation reaction, reaction time is 64h, be down to normal temperature and pressure, isolated by filtration product and catalyst after reaction terminates, namely filtrate obtain target product after distillation.
Embodiment 3
The preparation of ruthenium Pd/carbon catalyst:
Step 1, the preparation of Carbon Materials, 20g mealy potato, 5g resorcinol, 65g zinc chloride and water are mixed in the oil bath being placed on 100 DEG C the polymerization that is hydrolyzed, mixture dry 2h in the baking oven of 250 DEG C is taken out after reaction 24h, transfer to 500 DEG C of constant temperature charing 15h in retort, finally the washing of gained solid product existed to without chlorion, dry stand-by, obtained high-area carbon specific area is 1380m
2/ g, most probable pore size are 6.8nm;
Step 2, configures the nitric acid ruthenium solution of 3mol/L and the palladium nitrate solution of 1.0mol/L respectively by active component ruthenium load capacity 5.0%, palladium load capacity 1.0%;
Step 3, gets 5g Carbon Materials, adopts vacuum equivalent impregnation method to flood the ruthenium, the palladium solution that have prepared respectively, leaves standstill 10h, 150 DEG C of dry 2h, can obtain ruthenium Pd/carbon catalyst precursor in 80 DEG C of water-baths;
Step 4, with the NaOH aqueous solution of 10wt%, regulates pH value to be 13, and precipitation 0.5h, leaves standstill 3h;
Step 5, reduce above-mentioned solution by the formalin of 37wt%, consumption is more than 100% of theoretical amount, leaves standstill 2h after reduction 0.5h, cooling, filter, deionized water is washed till without Cl
oneafter namely obtain ruthenium Pd/carbon catalyst.
The preparation of hexahydrobenzoid acid:
Above-mentioned ruthenium Pd/carbon catalyst 8g, the benzoic acid 40g prepared is loaded in 200mL autoclave, under the condition of facing hydrogen, reaction pressure 2.0MPa, reaction temperature 180 DEG C carries out hydrogenation reaction, reaction time is 2h, be down to normal temperature and pressure, isolated by filtration product and catalyst after reaction terminates, namely filtrate obtain target product after distillation.
Embodiment 4
The preparation of ruthenium Pd/carbon catalyst:
The present embodiment prepares the ruthenic chloride solution of 3mol/L and the palladium chloride solution of 1.0mol/L by active component ruthenium load capacity 0.5%, palladium load capacity 0.05% in step 2 as different from Example 1 respectively, and the preparation process of other ruthenium Pd/carbon catalysts is identical with embodiment 1.
The preparation of hexahydrobenzoid acid:
Above-mentioned ruthenium Pd/carbon catalyst 1.2g, benzoic acid 6g and the water 120g prepared is loaded in 200mL autoclave, under the condition of facing hydrogen, reaction pressure 6.0MPa, reaction temperature 100 DEG C carries out hydrogenation reaction, reaction time is 48h, be down to normal temperature and pressure, isolated by filtration product and catalyst after reaction terminates, after distillation, namely obtain target product.
Embodiment 5
The preparation of ruthenium Pd/carbon catalyst:
The present embodiment prepares the ruthenic chloride solution of 3mol/L and the palladium chloride solution of 1.0mol/L by active component ruthenium load capacity 3.0%, palladium load capacity 2.0% in step 2 as different from Example 1 respectively, and the preparation process of other ruthenium Pd/carbon catalysts is identical with embodiment 1.
The preparation of hexahydrobenzoid acid:
The present embodiment as different from Example 1 solvent is methyl alcohol, and reaction pressure is 5.0MPa, reaction temperature 120 DEG C, reaction time 36h, and the preparation process of all the other hexahydrobenzoid acids is identical with embodiment 1.
Embodiment 6
The preparation of ruthenium Pd/carbon catalyst:
The present embodiment prepares the ruthenic chloride solution of 3mol/L and the palladium chloride solution of 1.0mol/L by active component ruthenium load capacity 8.0%, palladium load capacity 0.5% in step 2 as different from Example 1 respectively, and the preparation process of other ruthenium Pd/carbon catalysts is identical with embodiment 1.
The preparation of hexahydrobenzoid acid:
The present embodiment as different from Example 1 solvent is toluene, and reaction pressure is 4.0MPa, reaction temperature 130 DEG C, reaction time 4h, and the preparation process of all the other hexahydrobenzoid acids is identical with embodiment 1.
Comparative example 1
The ruthenium of only load 5% in catalyst prepared by this comparative example, no longer adulterate palladium, and other step is with embodiment 1.
Comparative example 2
Be active component with palladium in catalyst prepared by this comparative example, ruthenium is auxiliary agent, ruthenium, palladium load capacity are respectively 0.5%, 5.0%, and other step is with embodiment 1.
Comparative example 3
With reference to the method for the embodiment 9 of the method for a patent CN1749234A synthesizing cyclohexyl formic acid by benzoic acid hydrogenation, preparation quality percentage composition is the rhodium catalyst of 5.0%.
Chromatography embodiment 1 ~ 6 and benzoic conversion ratio under different catalysts in comparative example 1 ~ 3 and selective, the results are shown in Table 1.
Conversion ratio under table 1 different catalysts and selective
From experiment, the present invention adopts Carbon Materials carrier, by vacuum equivalent impregnation method carried metal active component, make chain carrier disperse evenly, effectively improve the reactivity of catalyst, gained target product has higher selective, under the preferred conditions, make the conversion ratio of raw material reach 100%, the selective of target product reaches 99.8%.In addition, the catalytic activity after 15 times and selective applied mechanically by the catalyst detected in embodiment 1, its benzoic conversion ratio is 99.5%, the selective of target product hexahydrobenzoid acid generated is 99.2%, visible the present invention catalyst used still can maintain higher reactivity and selective after use repeatedly, and namely catalyst stability used in the present invention is good.
In sum, catalyst of the present invention has better activity, selective and stability, and preparation method is simple, and removal process simplifies, and reduces production cost.Be applied to benzoic acid hydrogenation and prepare hexahydrobenzoid acid, appointed condition is simple, and process conditions are gentle, and energy consumption and industrialization investment significantly reduce, and easily realize industrialization.
Claims (10)
1. the ruthenium Pd/carbon catalyst of a synthesizing cyclohexyl formic acid by benzoic acid hydrogenation, it is characterized in that, described catalyst comprises carrier, active component and auxiliary agent, described carrier is impregnated with active component and auxiliary agent, described carrier is Carbon Materials, described active component is metallic element Ru nano particle, and described auxiliary agent is metallic element Pd nano particle; Wherein, the load capacity of described Ru nano particle is 0.5%-8.0%, and the load capacity of described Pd nano particle is 0.05%-2.0%.
2. the ruthenium Pd/carbon catalyst of synthesizing cyclohexyl formic acid by benzoic acid hydrogenation according to claim 1, is characterized in that, the load capacity of described Ru nano particle is 3.0%-8.0%.
3. the ruthenium Pd/carbon catalyst of synthesizing cyclohexyl formic acid by benzoic acid hydrogenation according to claim 1, is characterized in that, the particle diameter of described Ru, Pd nano particle is 2-5nm; The decentralization of described Ru, Pd is 30%-80%; The specific area of described Carbon Materials is 500-2500m
2/ g, most probable pore size is 2-10nm.
4. a preparation method for the ruthenium Pd/carbon catalyst of synthesizing cyclohexyl formic acid by benzoic acid hydrogenation as claimed in claim 1, concrete steps are as follows:
Step 1, the preparation of Carbon Materials, mixes rear heating and to be hydrolyzed polymerization by mealy potato, resorcinol, zinc chloride and water, it is dry and carbonize to have reacted rear taking-up mixture, then by the washing of the solid product of charing to without chlorion post-drying;
Step 2, the ruthenium salt of preparation solubility and palladium salting liquid, then adopt vacuum equivalent impregnation method to flood ruthenium salt and palladium salting liquid respectively by Carbon Materials, obtain ruthenium Pd/carbon catalyst precursor after dry process;
Step 3, adds aqueous slkali in the ruthenium Pd/carbon catalyst precursor that step 2 obtains, and after regulating pH to alkalescence, precipitates and leaves standstill;
Step 4, adopts the product that reducing agent reduction step 3 is obtained, obtains the activated ruthenium Pd/carbon catalyst of tool.
5. preparation method according to claim 4, is characterized in that, in step 1, hydrolytic polymerization temperature is 95-100 DEG C, and hydrolysis time is 24-36h, and baking temperature is 200-250 DEG C, drying time is 2-8h, and carbonization temperature is 500-700 DEG C, and carbonization time is 10-15h.
6. preparation method according to claim 4, it is characterized in that, in step 2, described ruthenium salt is selected from one or more in the ruthenic chloride of solubility, acetic acid ruthenium and nitric acid ruthenium, and described palladium salt is selected from one or more in the palladium bichloride of solubility, palladium and palladium nitrate; The dip time of ruthenium salt and palladium salting liquid is 2-10h, and baking temperature is 80 DEG C-150 DEG C, and drying time is 2-8h.
7. preparation method according to claim 4, is characterized in that, in step 3, described aqueous slkali is NaOH solution, and pH value is 9-13, and the sedimentation time is 0.5-6h, and time of repose is 0.5-3h; In step 4, described reducing agent is formaldehyde or sodium borohydride solution, and the recovery time is 0.5-6h.
8. one kind as arbitrary in claims 1 to 3 as described in ruthenium Pd/carbon catalyst prepare application in hexahydrobenzoid acid at benzoic acid hydrogenation, it is characterized in that, concrete steps are as follows: by benzoic acid solvent-free or under having solvent existent condition, face hydrogen to contact with ruthenium Pd/carbon catalyst, carry out hydrogenation reaction, be down to normal temperature and pressure, isolated by filtration product and catalyst after reaction terminates, namely filtrate obtain target product after distillation.
9. application according to claim 8, is characterized in that, described solvent is selected from water, acids, alcohols or hydro carbons, and the reaction pressure of described hydrogenation reaction is 2.0-6.0MPa, and reaction temperature is 100-180 DEG C, and the reaction time is 2-64h.
10. application according to claim 9, is characterized in that, described solvent is hexahydrobenzoid acid.
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