CN103769090A - Ruthenium-palladium/carbon catalyst and preparation method thereof - Google Patents
Ruthenium-palladium/carbon catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a ruthenium-palladium/carbon catalyst and a preparation method thereof. A catalyst carrier is a carbon material, and active ingredients are Ru and Pd nanoparticles, wherein the load capacity of Ru is 0.5%-8.0%, the load capacity of Pd is 0.1%-2.0%, and the dispersity of ruthenium-palladium can achieve 30%-80%. The carrier is subjected to acid-base oxidization pretreatment, so that surface oxygen-containing functional groups can be increased, the property of ruthenium-palladium on the surface of the carbon material can be improved, the dispersity of ruthenium-palladium can be improved, the active ingredients can be firmly adsorbed on the functional groups, and the catalyst can show high activity in the reaction process. The prepared catalyst is applied to DMT (dimethyltryptamine) hydrogenation to prepare DMCD (dimethyl 1,4-cyclohexanedicarboxylate). The activity of the catalyst is not reduced after the catalyst is used for 20 times in an autoclave of 5000ml, the conversion rate of DMT can achieve 99.3%-100%, and the selectivity of DMCD can achieve 95.5%-96.4%. The purity of DMCD, which is simply distilled and purified, is greater than 99.5%. The preparation method has the advantages of being mild in technological conditions, simple in equipment, free from emission of three wastes, economic in investment, low in energy consumption, and feasible for industrialization.
Description
Technical field
The present invention relates to ruthenium palladium/carbon catalyst, method for making and the application thereof of a kind of DMT Hydrogenation DMCD of high activity and high stability, belong to the technical field of catalytic hydrogenation.
Background technology
Dimethyl terephthalate (DMT), is called for short DMT(Dimethyl terephthalate), white needle-like crystals, 140.7 ℃ of fusing points, 284 ℃ of boiling points, easily distillation.Be mainly used in synthetic polyester fibers, resin, film, Polyester Paint and engineering plastics etc.DMT mono-step hydrogenation products is Isosorbide-5-Nitrae-dimethyl hexahydrophthalate (being called for short DMCD), and two step hydrogenation products are 1,4-CHDM (being called for short CHDM).
DMCD is the important organic intermediate of a class and green chemical, can be used as the material modified of polymer, is also the important source material of producing CHDM.Heat endurance and chemical stability by materials such as both synthetic high-performance polyesters are good, containing phenyl ring, not nontoxic, are a kind of environmental protection plasticizer and green chemical.Particularly synthetic poly terephthalic acid 1,4-CHDM ester (PCT), polyethylene terephthalate cyclohexanedimethanol (PETG), copolyester (PCTA) are widely used in packaging for foodstuff, in infant's apparatus, toy, vessel etc.Therefore, the research and development of DMCD and CHDM, by effectively improving national food packaging safety problem, has great importance to children, child's healthy growth.
At present, people prepare Isosorbide-5-Nitrae-dimethyl hexahydrophthalate for dimethyl terephthalate (DMT) catalytic hydrogenation and have carried out a large amount of research.The hydrogenation catalyst using mainly contains two kinds, and one is noble metal catalyst, take ruthenium rhodium palladium as active component, take active carbon, aluminium oxide, silica etc. as carrier, becomes in recent years the focus of research; Another kind is non-precious metal catalyst, take thunder base nickel as representative.Have high energy consumption high pollution owing to producing thunder base Raney nickel, the accessory substance of hydrogenation is also many, is substituted gradually.
Patent US3334149, US3334149, the CN1099382 of the application of Yi Si Man of the U.S. have described take dimethyl terephthalate (DMT) as raw material and have prepared 1, the method of 4-dimethyl hexahydrophthalate, palladium/the aluminium oxide catalyst (palladium load capacity 0.5～1%) using is constantly improving, but the pressure using is all greater than 6.0MPa, higher hydroprocessing pressure is uneconomic on producing.
CN102476052A discloses a kind of load ruthenium catalyst and preparation method thereof, it is characterized in that: take aluminium oxide as carrier, first with the alkali salt pretreatment carrier of solubility, take carrier quality as basis, the quality of the alkali salt of solubility is carrier 0.1～20%.Take metal Ru as main active component, any one or several for helping catalyst component with in metallic nickel, cobalt, palladium, platinum, the carrier that dipping was processed through alkali salt, the quality of the 0.1～5%, second metallic nickel that wherein quality of metal Ru is carrier, cobalt, palladium, platinum is carrier 0.01～5%.
CN103007962A discloses auxiliary palladium-carbon catalyst of a kind of metal oxide and preparation method thereof, it is characterized in that: active carbon is carrier, described absorbent charcoal carrier area load layer of metal oxide, form metal oxide-active carbon complexes carrier, supported palladium nano particle on described complexes carrier.The conversion ratio of DMT reaction is that 99%, DMCD is selectively 92%.
Summary of the invention
The object of the invention is to applying nano technology, a kind of ruthenium Pd/carbon catalyst and Catalyst Production method more simple, energy-conserving and environment-protective of not adding the alkali metal such as promoter potassium, barium, cobalt, caesium, iron or alkali metal salt is provided, and this catalyst is applied to DMT hydrogenation production DMCD.
The technical solution that realizes the object of the invention is: a kind of ruthenium palladium/carbon catalyst, and described catalyst carrier is Carbon Materials, and active component is Ru and Pd nano particle, and wherein, the load capacity of Ru is 0.5-8.0%, and the load capacity of Pd is 0.1-2.0%.In described catalyst, the decentralization of ruthenium palladium can reach 30%-80%.
Described carrier specific area is 1000-2500m
2/ g, the most several apertures are 2-10nm.
The particle diameter of described Ru and Pd nano particle is 2-5nm.
Ruthenium palladium/carbon catalyst disclosed in this invention and preparation method thereof step is as follows:
(1) in advance carrier Carbon Materials is carried out to pretreatment, and be washed with water to neutrality, dry; Degassed processing 0.5-4h under 50-150 ℃, vacuum condition, for subsequent use again;
(2) the ruthenium salt of solubility and palladium salt are mixed with respectively to the solution that concentration is 0.5-10mol/L, 0.1-2mol/;
(3) pretreated Carbon Materials is adopted vacuum equivalent impregnation method first flood ruthenium solution 2-10h, dry 2-4h at 80 ℃, dry 2-6h at 120 ℃; Adopt the palladium-impregnated solution 4h in 50-80 ℃ of water-bath that uses the same method, dry 2-4h, obtains ruthenium palladium-Pd/carbon catalyst precursor at 80 ℃ again;
(4) in above-mentioned ruthenium palladium-Pd/carbon catalyst precursor, add aqueous slkali, adjusting PH is 8-14; Precipitation 0.5-6h, leaves standstill 0.5-2h, is precipitated thing;
(5) product that adopts reducing agent reduction step (4) to make, obtains the activated ruthenium palladium/carbon catalyst of tool;
(6) cooling, filtration, deionized water are washed till without Cl
-, band is wet to be saved backup.
In above ruthenium Pd/carbon catalyst preparation process, further preferred technical scheme is:
In step (1), described Carbon Materials is mesoporous carbon or active carbon; Described pretreatment is acid treatment, alkali treatment or oxidation processes, wherein acid solution is that mass concentration is the hydrochloric acid solution of 1-38% or the salpeter solution that molar concentration is 1-14.6M, aqueous slkali is that PH is the sodium bicarbonate solution of 8-14, and oxidant is hydrogen peroxide or nitric acid, and pretreatment time is 1-48h.
In step (2), described ruthenium salt is selected from one or more in ruthenic chloride, acetic acid ruthenium, nitric acid ruthenium or the ruthenium hydrochloride sodium of solubility; Described palladium salt is selected from one or more in palladium bichloride, palladium or the palladium nitrate of solubility.
In step (2), the solvent of described ruthenium solution or palladium solution is water or hydrochloric acid.
In step (5), when the formaldehyde that described reducing agent is 38wt% or the sodium borohydride solution of 10wt%, it is more than 130% that reducing agent is theoretical consumption, and the recovery time is 0.5-5h; When reducing agent is hydrogen, reduction temperature is 150-450 ℃, recovery time 1-6h, heating rate 2-10 ℃/min.
In step (5), in described catalyst, ruthenium load capacity is 0.5-8.0%, and the load capacity of palladium is 0.1%-2.0%.
An application for ruthenium palladium/carbon catalyst, described catalyst is prepared DMCD for DMT low-voltage hydrogenation.
Concrete step is: dimethyl terephthalate (DMT) is dissolved in solvent, under the condition of facing hydrogen, contacts with ruthenium palladium/carbon catalyst, carry out hydrogenation reaction.
Described hydrogenation solvent comprises alcohols, ester class, hydro carbons; Alcohols solvent is selected from the one in methyl alcohol, ethanol, isopropyl alcohol or n-butanol, preferably isopropyl alcohol; Esters solvent is selected from the one in methyl formate, ethyl acetate, Ethyl formate, methyl acetate or Isosorbide-5-Nitrae-dimethyl hexahydrophthalate, preferably Isosorbide-5-Nitrae-dimethyl hexahydrophthalate; Varsol is selected from the one in benzinum, hexane, cyclohexane, benzene, toluene or ethylbenzene.
Described hydroconversion condition is reaction pressure 2.0-10.0MPa, 80 ℃-250 ℃ of reaction temperatures, preferred reaction pressure 3.0-5.0MPa, 100 ℃-150 ℃ of reaction temperatures.
Beneficial effect of the present invention is: the present invention selects the Carbon Materials of high surface as carrier, by soda acid oxidation pre-treatment, effectively remove objectionable impurities, increase oxygen-containing functional group, improve ruthenium palladium at charcoal material surface character, pore-size distribution, improve the decentralization of ruthenium palladium, active component is adsorbed in functional group securely, thereby make catalyst existing high activity of meeting, selective in course of reaction, have again high stability.The catalyst of preparation, does not add alkali metal or alkaline-earth metal, and decentralization is high, and production and recovery process are simple, and support material is cheap and easy to get.The processing of the simple burning of catalyst process carbon, i.e. recyclable active component palladium ruthenium, thus production, recovery, the use cost of catalyst are significantly reduced, can significantly reduce environmental pollution simultaneously; The catalyst of preparation is applied to DMT Hydrogenation for DMCD, process conditions gentleness, equipment is simple, three-waste free discharge, reduced investment, energy consumption be low, easily realize industrialization.
Accompanying drawing explanation
Fig. 1 is method for making and the technique for applying block diagram of ruthenium palladium/carbon catalyst of the present invention.
Fig. 2 is the BJH-absorption-graph of pore diameter distribution of embodiment 1 ruthenium Pd/carbon catalyst (RuPd/C).
Fig. 3 is embodiment 1 ruthenium Pd/carbon catalyst XRD spectra.
Fig. 4 is embodiment 1 ruthenium Pd/carbon catalyst TEM figure.
Fig. 5 is the product distribution map of embodiment 1 ruthenium Pd/carbon catalyst for DMT Hydrogenation DMCD.
Fig. 6 is the high-purity DMCD distribution map after embodiment 1 hydrogenation products is purified.
The specific embodiment
In following embodiment, adopt gas chromatograph Agilent7820 analytical reactions thing conversion ratio, productive rate, selective; Adopt full-automatic specific area and the pore analysis instrument V-Sorb2800P that Beijing Jin Aipu Science and Technology Ltd. produces to measure specific surface area of catalyst, pore volume and aperture; The X'TRA X-ray diffractometer (XRD) of Arl Inc. of employing Switzerland carries out microstructure to catalyst and characterizes; Adopt pattern, the microstructure of the JEM-200CX transmission electron microscope observation sample of Japanese JEOL company.Ruthenium palladium/carbon catalyst of the present invention and preparation method thereof and application, technical process is as shown in Figure 1: the carbonaceous material that the 1st step in Fig. 1 is catalyst carrier, the pretreatment that the 2nd step is carbonaceous material, the 3rd step is the load of catalyst activity component, the reduction that the 4th step is catalyst precarsor, the 5th step is DMT Hydrogenation DMCD, and concrete technical process is as follows:
1, the selection of Carbon Materials: adopt the carbonaceous material of high surface, specific area is 100-2500m
2/ g, the most a few aperture 2-10nm.
2, the pretreatment of Carbon Materials: it is a kind of preferred embodiment of the present invention that Carbon Materials is carried out to soda acid oxidation pre-treatment, but be not to implement steps necessary of the present invention.Than not carrying out pretreated carrier, carry out pretreatment and can make active component be loaded to more equably charcoal material surface, thereby improve decentralization, activity and the stability of ruthenium palladium on carrier.
3, the load of active component ruthenium palladium: ruthenium, palladium solution are loaded on charcoal carrier.
4, the reduction dry run of precursor: the method that can adopt liquid-phase reduction or vapour phase reduction.
5, DMT Hydrogenation DMCD: the high pressure autoclave hydrogenation plant that adopts 100ml-5000ml, charging feedstock DMT(35wt%), solvent and ruthenium Pd/carbon catalyst (m (DMT): m (RuPd/C)=100:3), adopt nitrogen replacement deoxidation or vacuumize the method for deoxidation, first the oxygen of reaction system is got rid of, again to reactor introduce hydrogen, adjust reaction pressure to 3.0-5.0MPa, evenly be warming up to 100-150 ℃, reaction 1-6h, be down to normal temperature and pressure, take out reactant, after filtration catalizer, analyze.The catalyst separating can repeatedly recycle.Described solvent has C
1-C
4alcohols, ester class, the hydrogenation products DMCD of hydro carbons or DMT.
Embodiment 1-3 makes meso-porous carbon material by oneself with reference to patent 200610156120.5, and specific area is 1730m
2/ g, the most a few aperture 2-10nm.
Embodiment
Embodiment 1
(1) take homemade mesoporous carbon 20g as support material, be positioned in 80ml5mol/L aqueous solution of nitric acid, in the water-bath of 80 ℃, flood 12h, cooling, filter, be washed to neutrality, dry; Degassed processing 2h under 120 ℃, vacuum condition;
(2) by active component ruthenium load capacity be 5.00%, palladium load capacity is 0.05% to configure respectively the ruthenic chloride solution of 3mol/L and the palladium chloride solution of 1.0mol/L;
(3) adopt vacuum equivalent impregnation method the mesoporous carbon after acid treatment first to be flooded to ruthenium solution 4h, 80 ℃ of dry 4h, 120 ℃ of dry 6h; Adopt same method palladium-impregnated solution, leave standstill 4h in 80 ℃ of water-baths, 80 ℃ of dry 4h, obtain ruthenium palladium-Pd/carbon catalyst precursor;
(4) with the NaOH aqueous solution of 10wt%, adjusting pH value is 11-12, and precipitation 2h, leaves standstill 2h;
(5) with the above-mentioned solution of the molten reduction of formaldehyde of 37wt%, consumption be the more than 130% of theoretical consumption, standing 2h after reductase 12 h;
(6) cooling, filtration, deionized water are washed till without Cl
-, band is wet to be saved backup;
Catalyst is numbered CAT-1/MC.The characterization data of this catalyst is seen Fig. 2-Fig. 4, and this catalyst is shown in Fig. 5 for DMT Hydrogenation for DMCD product distribution map, and after simple distillation purification, high-purity DMCD distribution map is shown in Fig. 6.
Embodiment 2
Prepare ruthenium, palladium load capacity with the same method of embodiment 1 and be respectively 8.0%, 1.0% ruthenium palladium/carbon catalyst; Catalyst is numbered CAT-2/MC.
Embodiment 3
Prepare ruthenium, palladium load capacity with the same method of embodiment 1 and be respectively 3.0%, 0.1% ruthenium palladium/carbon catalyst; Catalyst is numbered CAT-3/MC.
Embodiment 4
Prepare ruthenium, palladium load capacity with the same method of embodiment 1 and be respectively 0.5%, 2.0% ruthenium palladium/carbon catalyst; Catalyst is numbered CAT-4/MC.
Embodiment 5
The pretreatment condition that changes carrier mesoporous carbon in embodiment 1 step (1), is positioned over homemade mesoporous carbon 20g in the hydrogen peroxide solution of 80ml20%, in the water-bath of 40 ℃, floods 24h, cooling, filter, vacuum drying treatment 2h at 120 ℃; Load capacity and other step are with embodiment 1.Catalyst is numbered CAT-5/MC.
Embodiment 6
Change the pretreatment condition of carrier mesoporous carbon in embodiment 1 step (1), will in the homemade mesoporous carbon 20g NaOH aqueous solution that to be positioned at PH be 12, flood 24h, vacuum drying treatment 2h at washing and filtering, 120 ℃; Load capacity and other step are with embodiment 1.Catalyst is numbered CAT-6/MC.
Embodiment 7
Changing carrier mesoporous carbon in embodiment 1 step (1) is commercially available active carbon (Zhuxi, Jiangsu active carbon factory), weigh 2000g, in the NaOH aqueous solution that is 12 at PH, flood 24h, the salt acid soak 24h that is 10% by mass concentration again, finally uses 10% hydrogen peroxide solution oxidation processes 24h; Wash, be filtered to without Cl
-, 80 ℃ of vacuum drying 8h; Degassed processing 2h under 120 ℃, vacuum condition; Load capacity and other step are with embodiment 1.Catalyst is numbered CAT-1/AC.
The above-mentioned controlling catalyst CAT-1/MC to CAT5/MC of institute is BET and analyzes, and made specific surface area of catalyst is 1526-1708m
2/ g, bore dia are 2-50nm.Process XRD and TEM phenetic analysis, the particle diameter of Ru and Pd is 2-5nm.CAT-6/MC catalyst CAT-1/AC specific area is 1520m
2/ g, pore volume 0.65ml/g, bore dia is 2-50nm.
Above-mentioned homemade catalyst is reacted for DMCD for DMT Hydrogenation, adopt 100ml autoclave to carry out activity rating to it, operating procedure, with technical process 5, the results are shown in Table 1.
Comparative example
Comparative example 1
Change embodiment 1 step (1), Carbon Materials is not carried out to pretreatment, load capacity and other step are with embodiment 1.
Comparative example 2
Change active component in embodiment 1 step (2), the only ruthenium of load 5%, palladium no longer adulterates.Other step is with embodiment 1.
Comparative example 3
Change embodiment 1 step (2), be respectively 5.00%, 0.05% configuration ruthenic chloride, palladium bichloride mixed solution 150ml by active component ruthenium, palladium load capacity; Change embodiment 1 step (3), adopt an excessive step dipping method, acid-treated mesoporous carbon is first flooded to the mixed solution of putting into ruthenium, palladium and flood 6h, 80 ℃ of dry 4h, 120 ℃ of dry 6h; Other step is with embodiment 1.
Comparative example 4
Method with reference to patent CN103007962A palladium carbon catalyst for the embodiment 1 of DMT catalytic hydrogenation DMCD processed, the Pd/Fe-AC catalyst that preparation quality percentage composition is 5.0wt%.
Above-mentioned catalyst is reacted for DMCD for DMT Hydrogenation, adopt 100ml autoclave to carry out activity rating to it, operating procedure, with technical process 5, the results are shown in Table 1.
Table 1 different catalysts conversion ratio and selective
| ` catalyst | Ru/wt% | Pd/wt% | Conversion ratio % | Selective % |
| CAT1/MC | 5 | 0.5 | 100 | 96.5 |
| CAT2/MC | 8 | 1 | 99.9 | 95.2 |
| CAT3/MC | 3 | 0.1 | 92.2 | 94.8 |
| CAT4/MC | 0.5 | 2 | 65.3 | 95.1 |
| CAT5/MC | 5 | 0.5 | 99.5 | 95.9 |
| CAT6/MC | 5 | 0.5 | 99.6 | 94.2 |
| CAT1/AC | 5 | 0.5 | 99.6 | 95.4 |
| Comparative example 1 | ? | ? | 92.6 | 92.3 |
| Comparative example 2 | 5 | - | 95.8 | 92.4 |
| Comparative example 3 | ? | ? | 93.5 | 94.3 |
| Comparative example 4 | ? | ? | 95.6 | 95.2 |
Catalyst CAT-1/AC 1000ml autoclave prepared by embodiment 7 is prepared DMCD.Operating procedure is with technical process 5.The results are shown in Table 2.
Catalyst CAT-1/AC 5000ml autoclave prepared by embodiment 7 is prepared DMCD, and catalyst is applied mechanically 20 times.Operating procedure is with technical process 5.The results are shown in Table 2.
The conversion ratio of table 2 different scales catalysts and selective
| ` catalyst | Still specification/ml | Conversion ratio % | Selective % |
| CAT1/ |
100 | 99.6 | 95.4 |
| CAT1/ |
1000 | 99.9 | 96.2 |
| CAT1/AC(applies mechanically 20 times) | 5000 | 99.3-100 | 95.5-96.4 |
From experiment, by the pretreatment to catalyst carrier, can increase quantity and its adhering to the time on carrier in activated centre; Adopt vacuum equivalent impregnation method, can allow metal active center disperse more even, can effectively improve the activity of catalyst.And expansion reaction scale, catalyst activity is slightly improved, and particularly, in the autoclave of 5000ml, catalyst is applied mechanically more than 20 times, and catalyst activity does not selectively subtract.After simple distillation is purified, product purity reaches 99.5%.
In sum, catalyst of the present invention has better activity, selectively and longer service life, for DMT Hydrogenation DMCD, and process conditions gentleness, appointed condition is simple, and the investment of industrialization and energy consumption are significantly reduced.And preparation method is simple, do not add alkali metal or alkaline-earth metal, removal process is simplified, and has reduced production cost simultaneously.
Claims (10)
1. a ruthenium palladium/carbon catalyst, is characterized in that described catalyst carrier is Carbon Materials, and active component is Ru and Pd nano particle, and wherein, the load capacity of Ru is 0.5-8.0%, and the load capacity of Pd is 0.1-2.0%.
2. ruthenium palladium/carbon catalyst according to claim 1, is characterized in that the decentralization of ruthenium palladium in described catalyst can reach 30%-80%.
3. ruthenium palladium/carbon catalyst according to claim 1, is characterized in that described carrier specific area is 1000-2500m
2/ g, the most several apertures are 2-10nm.
4. ruthenium palladium/carbon catalyst according to claim 1, is characterized in that described Ru and the particle diameter of Pd nano particle are 2-5nm.
5. a method for making for ruthenium palladium/carbon catalyst, is characterized in that described method for preparing catalyst is as follows:
(1) in advance carrier Carbon Materials is carried out to pretreatment, and be washed with water to neutrality, dry; Degassed processing 0.5-4h under 50-150 ℃, vacuum condition, for subsequent use again;
(2) the ruthenium salt of solubility and palladium salt are mixed with respectively to the solution that concentration is 0.5-10mol/L, 0.1-2mol/;
(3) pretreated Carbon Materials is adopted vacuum equivalent impregnation method first flood ruthenium solution 2-10h, dry 2-4h at 80 ℃, dry 2-6h at 120 ℃; Adopt the palladium-impregnated solution 4h in 50-80 ℃ of water-bath that uses the same method, dry 2-4h, obtains ruthenium palladium-Pd/carbon catalyst precursor at 80 ℃ again;
(4) in above-mentioned ruthenium palladium-Pd/carbon catalyst precursor, add aqueous slkali, adjusting PH is 8-14; Precipitation 0.5-6h, leaves standstill 0.5-2h, is precipitated thing;
(5) product that adopts reducing agent reduction step (4) to make, obtains the activated ruthenium palladium/carbon catalyst of tool.
6. the method for making of ruthenium palladium/carbon catalyst according to claim 5, is characterized in that the Carbon Materials described in step (1) is mesoporous carbon or active carbon; Described pretreatment is acid treatment, alkali treatment or oxidation processes, wherein acid solution is that mass concentration is the hydrochloric acid solution of 1-38% or the salpeter solution that molar concentration is 1-14.6M, aqueous slkali is that PH is the sodium bicarbonate solution of 8-14, and oxidant is hydrogen peroxide or nitric acid, and pretreatment time is 1-48h.
7. the method for making of ruthenium palladium/carbon catalyst according to claim 5, is characterized in that the ruthenium salt described in step (2) is selected from one or more in the ruthenic chloride of solubility, acetic acid ruthenium, nitric acid ruthenium or ruthenium hydrochloride sodium; Described palladium salt is selected from one or more in palladium bichloride, palladium or the palladium nitrate of solubility.
8. the method for making of ruthenium palladium/carbon catalyst according to claim 5, the solvent that it is characterized in that the ruthenium solution described in step (2) or palladium solution is water or hydrochloric acid.
9. the method for making of ruthenium palladium/carbon catalyst according to claim 5, while it is characterized in that the sodium borohydride solution of formaldehyde that the reducing agent described in step (5) is 38wt% or 10wt%, reducing agent is the more than 130% of theoretical consumption, and the recovery time is 0.5-5h; When reducing agent is hydrogen, reduction temperature is 150-450 ℃, recovery time 1-6h, heating rate 2-10 ℃/min.
10. the method for making of ruthenium palladium/carbon catalyst according to claim 5, the load capacity that it is characterized in that ruthenium in the catalyst described in step (5) is 0.5-8.0%, the load capacity of palladium is 0.1%-2.0%.
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| CN105251482A (en) * | 2015-10-14 | 2016-01-20 | 南京大学连云港高新技术研究院 | Ruthenium palladium/carbon catalyst of cyclohexanecarboxylic acid synthesized through benzoic acid hydrogenation and preparation method and application thereof |
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| CN109894131A (en) * | 2017-12-07 | 2019-06-18 | 中国科学院大连化学物理研究所 | A kind of dimethyl terephthalate (DMT) (DMT) hydrogenation catalyst and preparation method thereof |
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| CN109894131B (en) * | 2017-12-07 | 2022-03-08 | 中国科学院大连化学物理研究所 | Dimethyl terephthalate (DMT) hydrogenation catalyst and preparation method thereof |
| CN111082074A (en) * | 2019-11-28 | 2020-04-28 | 安徽元琛环保科技股份有限公司 | Porous platinum fuel cell catalyst and preparation method thereof |
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| CN111330580A (en) * | 2020-03-10 | 2020-06-26 | 中国科学院山西煤炭化学研究所 | Acid-resistant catalyst, preparation method thereof and application of acid-resistant catalyst in water-phase hydrogenation production of succinic acid |
| CN111330580B (en) * | 2020-03-10 | 2021-05-28 | 中国科学院山西煤炭化学研究所 | Acid-resistant catalyst, preparation method thereof and application of acid-resistant catalyst in water-phase hydrogenation production of succinic acid |
| CN111987322A (en) * | 2020-08-11 | 2020-11-24 | 广东能创科技有限公司 | Novel Pt-Co/NC catalyst and preparation method and application thereof |
| CN114276261A (en) * | 2021-12-31 | 2022-04-05 | 浙江工业大学 | Preparation method of procaine |
| CN114276261B (en) * | 2021-12-31 | 2023-11-17 | 浙江工业大学 | Preparation method of procaine |
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