CN102641735B - Oxalate hydrogenated Au-Ag bimetallic catalyst and preparation method thereof - Google Patents
Oxalate hydrogenated Au-Ag bimetallic catalyst and preparation method thereof Download PDFInfo
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Abstract
Disclosed are an oxalate hydrogenation Au-Ag bimetallic catalyst and a preparation method thereof, which relate to catalysts. The oxalate hydrogenated Au-Ag bimetallic catalyst comprises, by mass percentage, 2-12% of Au, 0.5-5% of Ag and the balance being carriers. The formula of the catalyst is x%Au-y%Ag/carriers, wherein the x% is the mass percentage of Au of the catalyst, and the y% is the massage percentage of Ag of the catalyst. The preparation method includes: modifying the carriers with high polymer, preparing a precursor of the catalyst by adding components of Au and Ag, reducing the precursor of the catalyst at an hydrogen-containing atmosphere, and finally obtaining the oxalate hydrogenated loaded Au-Ag bimetallic catalyst. With the preparation method, methyl glycollate or ethylene glycol can be prepared selectively by controlling reaction temperature. The catalyst prepared by the preparation method has the advantages of excellent low-temperature catalytic activity, fine catalytic stability, long service life and the like.
Description
Technical field
The present invention relates to a kind of catalyst, especially a kind of catalyst for the synthesis of methyl glycollate or ethylene glycol.
Background technology
Methyl glycollate (MG) is a kind of multiduty industrial chemicals, synthetic intermediate and good solvent, is widely used in the fields such as chemical industry, medicine, agricultural chemicals, feed, spices and fuel.In its molecular structure, contain the functional groups such as α-hydrogen, hydroxyl and ester group simultaneously, have the chemical property of alcohol and ester concurrently, it is the fine solvent of many celluloses, resin and rubber, be soluble in NC Nitroncellulose, cellulose acetate, cellulose acetate propionate and polyvinyl acetate, the reactions such as carbonylation, hydrolysis, alcoholysis and oxidation can occur.Methyl glycollate is the synthetic important intermediate with isoharringtonin and the analog thereof of active anticancer, is also the raw material that improves the anti-carrier additives of lubricating oil crushing resistance and wearability; The ethylene glycol that methyl glycollate hydrogenation generates, the glycolic that hydrolysis generates, can be used for producing polyester fiber and is used as cleaning agent; The diester malonate that carbonylation makes and acetaldehyde ethyl acetate, be used to the fields such as medicine and agricultural chemicals; The glycine that ammonia solution generates, of many uses at aspects such as food, feed addictive, herbicide, plant growth regulator and multi-medicament synthesize; The glyoxylic ester that oxidative dehydrogenation generates, and then hydrolysis generation glyoxalic acid, can be used for producing important fine chemicals and the medicines such as vanillic aldehyde, oral penicillin and allantoin.Visible, the downstream product centered by methyl glycollate has broad application prospects.The method of synthesizing methyl glycolate mainly contains formaldehyde carbonylation esterification process, by ethylene glycol and methyl alcohol one-step synthesis and methyl formate and formaldehyde coupling method.The early stage technology path of formaldehyde carbonylation esterification process is corrosion-resistant and high voltage bearing having relatively high expectations to equipment, after the eighties in 20th century, because catalyst performance improves, this method made a breakthrough, and reaction pressure reduces.Mitsubishi changes into Industrial Co., Ltd and German Hirst company philosophy, and to adopt heteropoly molybdic acid, assorted many wolframic acids and storng-acid cation exchange resin etc. be catalyst, oxonation pressure drops to 5.9MPa, and make selectively greatly to improve, but reaction condition is still comparatively harsh, and the problem of catalyst recovery recycling still exists.By ethylene glycol and methyl alcohol one-step synthesis, adopting aluminum nitrate is catalyst, and reaction condition is comparatively gentle, but owing to adopting homogeneous catalysis system, and catalyst and product separated brought to very large problem.And methyl formate and formaldehyde coupling method employing solid heteropoly acid are catalyst, yield is lower, is unfavorable for large-scale industrial production application.
Ethylene glycol (EG) claims again glycol, ethylene glycol, it is a kind of important Organic Chemicals, at present in China mainly for the production of polyester, anti-icing fluid, adhesive, paint solvent, Everlube, nonionic surface active agent, explosive and plasticizer etc., wherein polyester is the main consumer field of ethylene glycol, is the principal element that pulls ethylene glycol production and consumption.In addition, ethylene glycol is also widely used in the industries such as coating, soup, brake-fluid and ink, and can be used as having the solvent, cement grinding aid etc. of specific use, and be also often used to replace glycerine to use in process hides and pharmaceuticals industry, be used separately as hydrating agents and solvent.At present, the key industry production method of ethylene glycol is that the epoxyethane water of traditional petrochemical industry route is legal.Whole world Ethylene Oxide Production Technology majority is by U.S. Shell Co. Ltd (Shell), U.S. Scientific Design Company, Inc. (SD) and the monopolization of three companies of U.S. Union Carbide Corp (UCC); The main flow technique of hydration of epoxy ethane to prepare ethandiol is pressurization direct hydration method, the greatest problem of direct hydration method is that the concentration of the glycol product aqueous solution is low, the process units of this technique need arrange a plurality of evaporimeters, lot of energy, for product separation, makes the shortcoming that this technological process is long, equipment is many, energy consumption is high very outstanding simultaneously.Catalytic hydration has good prospect because significantly having reduced water content in reactant, but this method is still to exist some problems to have aspect catalyst preparation, life-span and regeneration to be solved, as bad in catalyst stability, preparation is complicated, be difficult to recycle etc., make that this method is applied to industrial production and need time.In addition the technology of, having developed or having developed comprises that the ethylene carbonate method preparing ethylene glycol of company's research and development such as the ethylene glycol of Tao Shi (DOW) and dimethyl carbonate coproduction preparing ethylene glycol, Japanese catalyst chemistry and Mitsubishi Chemical and emerging coal are through oxalate preparing ethylene glycol technique etc.Wherein, Coal Chemical Industry Route by synthesis gas, through oxalate diester, produce methyl glycollate and ethylene glycol is a reaction that Atom economy is higher in theory, there is no waste discharge, meet environmentally friendly technology requirement, have a extensive future.
In short supply along with petroleum resources, develop China compared with the coal of horn of plenty and natural gas resource, development carbon one chemical industry has important strategy and economic implications, and wherein, CO and nitrites gas-phase dimethyloxalate synthesis (DMO) are the important breakthrough of carbon one chemical industry synthesis of chemicals.At present, the process upstream technology of producing dimethyl oxalate has both at home and abroad become to stablizing maturation, further develops the chain of dimethyl oxalate downstream product and study hotspot and the emphasis that production technology becomes this field.
The dimethyl oxalate selective hydrogenation first step obtains methyl glycollate, and methyl glycollate further hydrogenation can obtain ethylene glycol.If can realize dimethyl oxalate high conversion and highly selective synthesizing methyl glycolate or ethylene glycol by appropriate change reaction condition on a kind of catalyst, be of great immediate significance.
Some documents disclose the catalyst formulation of prepared by dimethyl oxalate plus hydrogen methyl glycollate.For example, when adopting supported silver or silver-copper to be catalyst, dimethyl oxalate can selective hydrogenation obtain methyl glycollate (as, Chinese patent CN 101138730A, CN 101700496A, CN 101954288A, CN 101816934A); While adopting the very approaching Au-Cu bimetallic catalyst of gold and the atomic ratio of copper for oxalate hydrogenation, also can obtain the result that hydrogenation principal product is methyl glycollate (J.Mater.Chem.2011,21,8997～8999).Yet the low temperature active of these catalyst and stability wait to improve.On the other hand, because vapor phase method preparing ethylene glycol by using dimethyl oxalate plus hydrogen is important step in " coal-ethylene glycol " technology path, in document and patent, there is the more report about oxalate catalytic hydrogenation synthesizing glycol used catalyst, and be object mainly with realizing high activity, high stability and highly selective synthesizing glycol, develop different catalyst and preparation technology thereof, almost all usingd copper as main active component in the formula of these catalyst.Related U.S. patent U.S.4 the earliest, 112,245, the active component of catalyst mainly comprises copper and chromium, carrier is aluminium oxide and silica etc.; The outstanding feature of copper/chrome catalysts is stability and better active, optimum catalytic activity is not less than 1134h (Industrial Catalysis stationary phase, 1996,4,24～29), but chromium (especially high valence state chromium) has larger biological toxicity, use chromium-containing catalyst to increase the insecurity of production link and product, chromium processing cost in spent catalyst is high, therefore, and exploitation and use chromium-less, eco-friendly catalyst very active.Wherein, by selecting chromium the second preparation of metals chromium-less copper bimetallic catalyst in addition can improve its catalytic performance, in the copper-based catalysts formula of published hydrogenation of oxalate for preparing ethylene glycol, the second metal is except adopting Cr, also have and adopt other as alkali metal K, Na, alkali earth metal Mg, Ca and Ba, rare-earth metals La, Eu, Gd and Tb, transition metal Ti, V, Mn, Mo, Fe, Co, Ni, Zn, Pd and Ag etc. (as, Chinese patent CN 10134289A, CN 101138725A, CN 101462061A, CN 101474561A, CN 101474562A, CN101433847A, CN 101444735A, CN 101524646A, CN 101700496A, CN 101445426A), to promote the performance of copper-based catalysts hydrogenation of oxalate for preparing ethylene glycol.
Summary of the invention
Object of the present invention is intended to provide a kind of oxalate hydrogenation gold-silver bimetal Catalysts and its preparation method, and this catalyst has the outstanding features such as excellent low-temperature catalytic activity, good catalytic stability and long service life.
Described oxalate hydrogenation gold-silver bimetal catalyst is comprised of the gold of active constituent and silver and carrier, catalyst composition is expressed as: x%Au-y%Ag/ carrier, in formula, x% represents the mass percent of gold in catalyst, y% represents the mass percent of silver in catalyst, described catalyst components content is Au:2%～12% by mass percentage, Ag:0.5%～6%, surplus is carrier.
Described catalyst components content is preferably Au:4%～8% by mass percentage, Ag:0.5%～3%, and surplus is carrier.
Described gold derives from gold chloride etc.
Described silver derives from the acetate of silver-colored nitrate or silver etc.
Described carrier is silica or silicon-based mesoporous molecular sieve SBA-15 etc.
The preparation method of described oxalate hydrogenation gold-silver bimetal catalyst is as follows:
1) organic polymer is dissolved in organic solvent and obtains Polymer Solution, add after the carrier of catalyst composition and ratio standingly, after filtration, deionized water washing and dry, then add complexing agent to reflux, obtain support type complexing agent-polymeric solid powders A;
2) prepare the chlorauric acid solution of 0.005～0.015g/mL, by catalyst composition and ratio, join in support type complexing agent-polymeric solid powders A, then add reducing agent reduction, after filtration, washing, obtain pressed powder B;
3) prepare the silver salt solution of 0.005～0.015g/mL, by catalyst composition and ratio, join in pressed powder B, then add reducing agent reduction, after filtration, after washing, oven dry, roasting, obtain catalyst precursor;
4) catalyst precursor is reduced under hydrogeneous atmosphere, obtain oxalate hydrogenation gold-silver bimetal catalyst;
In step 1) in, described organic polymer is optional from polyvinyl alcohol (PVA) or polystyrene propylene fine (SAN) etc.; Described organic solvent can be selected from oxolane (THF) or dimethyl formamide (DMF) etc.; The concentration of described Polymer Solution can be 5～15mg/mL; Described complexing agent can be selected from a kind of in ethylenediamine (ED), monoethanolamine (EA), dicyandiamide (DC) etc.; In described complexing agent-polymeric solid powder, complexing agent and polymeric solid powder quality ratio can be 0.1; The described standing time can be 0.5～12h, and the temperature of described backflow can be 70～110 ℃, and the time of backflow can be 12～14h.
In step 2) in, the time of described reduction can be 0.5～2h, and described reducing agent can adopt the NaBH of 0.003～0.008g/mL
4the aqueous solution.
In step 3) in, the time of described reduction can be 0.5～2h, and described reducing agent can adopt the NaBH of 0.003～0.008g/mL
4the aqueous solution; The condition of described oven dry can be vacuum drying 6～12h at 60～120 ℃; The condition of described roasting is 400～550 ℃ of roasting 4～12h in air atmosphere.
In step 4) in, the temperature of described reduction can be 250～550 ℃, and the time of reduction can be 2～12h.
The activity of described oxalate hydrogenation gold-silver bimetal catalyst and stability adopt following methods evaluation: use high pressure fixed bed reaction system thinking catalyst activity.Catalyst precursor after roasting is sized to 40～60 orders through compressing tablet and packs in reaction tube, and bed packs up and down enough inertia quartz sand into and prevents from managing interior gas channel.By certain condition, catalyst is carried out to online reduction activation, then regulate reaction temperature, pressure, hydrogen flow rate and dimethyl oxalate charging rate to carry out activity rating.Dimethyl oxalate is mixed with the methanol solution that concentration is 0.02～0.1g/mL, by high pressure constant flow pump, squeezed in reaction system, hydrogen is controlled flow by high pressure mass flowmenter after pressure maintaining valve decompression, reaction pressure scope is 1～4MPa, range of reaction temperature is 140～230 ℃, hydrogen ester mol ratio is 40～150, and dimethyl oxalate mass space velocity is 0.1～5h
-1.For investigating the stability of catalyst, under the condition of fixation reaction temperature, reaction pressure, dimethyl oxalate mass space velocity and hydrogen ester ratio, catalyst is carried out to long time running, assaying reaction conversion ratio and optionally situation of change.
The present invention is by adopting the macromolecule modified so that better load of metal and being dispersed in carrier surface to carrier, in loading type silver catalyst, introduce appropriate gold, effectively promoted the dispersion of metal, prepared Au-Ag bimetallic catalyst, not containing poisonous elements such as chromium, has good oxalate and selects preparation of ethanol by hydrogenating acid methyl esters or ethylene glycol activity.Catalyst after compositional optimization has the following advantages: (1), under 140 ℃ of low reaction temperatures, dimethyl oxalate conversion ratio is greater than 97%, and methyl glycollate is selectively greater than 98%, and methyl glycollate quality space-time yield is greater than 300mg/g-cat/h; (2) at 230 ℃ of reaction temperatures, dimethyl oxalate conversion ratio approaches 100%, and glycol selectivity is not less than 95%, and quality of glycol space-time yield is greater than 300mg/g-cat/h.Catalyst performance stabilised, preparation technology is simple, reproducible, and the scale that is easy to carry out is amplified production.Load type gold-silver bimetal the catalyst that uses this method to prepare, take dimethyl oxalate as raw material, carry out catalytic hydrogenation, hydrogenation products is included as ethylene glycol (EG), methyl glycollate (MG), 1,-propane diols (1,2-PDO), 1,2-butanediol (1,2-BDO) and ethanol (EtOH).
Accompanying drawing explanation
Fig. 1 be the 8%Au-0.75%Ag/ED-P-SBA-15 catalyst of embodiment 1 preparation at 140 ℃ of reaction temperatures, the study on the stability schematic diagram of reaction 300h.In Fig. 1, abscissa is the time (h) of dimethyl oxalate gas phase hydrogenation reaction, the conversion ratio that ordinate is dimethyl oxalate or selective (%); Mark zero represents the conversion ratio of dimethyl oxalate; ■ represents the selective of methyl glycollate; △ represents the selective of ethylene glycol.
Fig. 2 be the 8%Au-5.5%Ag/ED-P-SBA-15 catalyst of embodiment 4 preparation at 200 ℃ of reaction temperatures, the catalyst stability reacting 200 hours is investigated schematic diagram.In Fig. 2, abscissa is the time (h) of dimethyl oxalate gas phase hydrogenation reaction, the conversion ratio that ordinate is dimethyl oxalate or selective (%); Mark zero represents the conversion ratio of dimethyl oxalate; ■ represents the selective of methyl glycollate; △ represents the selective of ethylene glycol.
The specific embodiment
Below by embodiment, the invention will be further described.
Embodiment 1
1) taking the surface area of preparing in laboratory is 833m
2the SBA-15 carrier 3.0g of/g.
2) PVA 0.5g is dissolved in the oxolane of 30mL completely, above-mentioned carrier is poured in this solution, after standing 4h, filter, wash and be dried, obtain P-SBA-15 product, standby.
3) above-mentioned P-SBA-15 product is added in 0.3g ethylenediamine (ED) and 30 ml deionized water, heat 12h at 90 ℃, be cooled to room temperature, use deionized water drip washing, 60 ℃ of vacuum drying obtain functionalization ED-P-SBA-15 pressed powder A, standby.
4) under room temperature condition, with pipette, pipette the chlorauric acid solution that 18.5mL concentration is 0.01g/mL, add the dilution of 50ml deionized water to obtain orange-yellow solution, under agitation add 1.0g functionalization ED-P-SBA-15 pressed powder A, the sodium borohydride aqueous solution 20mL that drips while stirring 0.005g/mL after stirring 10min, after 10min, solution becomes brownish red from yellow, and vacuum filtration also washs sediment to filtrate and exists without chlorion by deionized water, obtain pressed powder B, standby.
5) measure the liquor argenti nitratis ophthalmicus that 1.27mL concentration is 0.01g/mL, by 50mL deionized water, be diluted to colourless transparent solution, pour in pressed powder B, after stirring 10min, add 0.005g/mL sodium borohydride solution 20mL, continue again to stir 10min, vacuum filtration with deionized water washing 8～10 times, obtains pressed powder C afterwards, and after ICP-OES detects washing 8 times, in the washing lotion of gained, Na content is less than 0.5 μ g/mL.
6) after pressed powder C is dried in the electric heating convection oven of 60 ℃ spending the night, be placed in Muffle furnace and rise to 500 ℃ of roasting 6h with the heating rate of 1 ℃/min, obtain catalyst precarsor.
7) compressing tablet sieves out 40～60 order particles, packs in pipe reaction pipe, at 5%H
2in/Ar atmosphere, with 2 ℃/min, be warming up to 350 ℃ of reduction 4h, make 8%Au-0.75%Ag/ED-P-SBA-15 catalyst, ICP-MS quantitative analysis results shows that golden and silver-colored content is in the error range of theoretical load capacity; Through nitrogen adsorption test, specific area is 545m
2/ g, pore volume is 0.77mL/g, average pore size is 5.4nm.
Performance with Hydrogenation of Dimethyl Oxalate reaction evaluating catalyst.Concrete operations are, adopt straight pipe type high-pressure micro-device, loaded catalyst is 0.1g, with 2 ℃/min, make beds be warming up to 140 ℃, and in reactor, pump into dimethyl oxalate-methanol solution that concentration is 0.1g/mL with high pressure constant flow pump, flow rate of liquid is 0.02mL/min, and now dimethyl oxalate mass space velocity is 0.6h
-1, it is 100 that control hydrogen flow rate makes hydrogen ester mol ratio, and reactant is collected product liquid after gas-liquid separator separates, and interval 1h samples quantitative analysis in gas-chromatography.
Chromatographiccondition: chromatographic column KB-Wax 30m * 0.25mm * 0.32 μ m, 50 ℃ to 200 ℃ of temperature programmings, 20 ℃/min of heating rate.According to the ratio of each component in product, adopt correction factor normalization method to calculate the selective of the conversion ratio of dimethyl oxalate and various products.
Reaction 2～3h rear catalyst activity data reaches stable state, the results are shown in Table 1.Now, dimethyl oxalate conversion ratio 97.2%, glycol selectivity is 1.1%, and methyl glycollate is selectively 98.9%, and methyl glycollate quality space-time yield is 440mg/g-cat/h.The catalyst stability that this catalyst carries out 300 hours under above-mentioned reaction condition investigate in (Fig. 1), show good low-temperature catalyzed stability and life-span, meet the requirement of the high yield high stability of low temperature of modern industry.
Embodiment 2
The preparation method of catalyst is with embodiment 1, and the liquor argenti nitratis ophthalmicus that changes 0.01g/mL is 0.85mL, and other composition is constant, makes 8%Au-0.5%Ag/ED-P-SBA-15 catalyst.
ICP-MS quantitative analysis results shows that Au and Ag content are in the error range of theoretical load capacity; Through nitrogen adsorption test, specific area is 564m
2/ g, pore volume is 0.80ml/g, average pore size is 5.3nm.Catalyst with embodiment 1, the results are shown in Table 1 to the performance evaluation of Hydrogenation of Dimethyl Oxalate and analysis condition.
Embodiment 3
The preparation method of catalyst is with embodiment 1, and the liquor argenti nitratis ophthalmicus that changes 0.01g/mL is 2.55mL, and other composition is constant, makes 8%Au-1.5%Ag/ED-P-SBA-15 catalyst.
ICP-MS quantitative analysis results shows that Au and Ag content are in the error range of theoretical load capacity; Through nitrogen adsorption test, specific area is 555m
2/ g, pore volume is 0.76ml/g, average pore size is 5.4nm.Catalyst with embodiment 1, the results are shown in Table 1 to the performance evaluation of Hydrogenation of Dimethyl Oxalate and analysis condition.
The preparation method of catalyst is with embodiment 1, and the liquor argenti nitratis ophthalmicus that changes 0.01g/mL is 9.35mL, and other composition is constant, makes 8%Au-5.5%Ag/ED-P-SBA-15 catalyst.
ICP-MS quantitative analysis results shows that Au and Ag content are in the error range of theoretical load capacity; Through nitrogen adsorption test, specific area is 455m
2/ g, pore volume is 0.67ml/g, average pore size is 5.5nm.Catalyst with embodiment 1, the results are shown in Table 1 to the performance evaluation of Hydrogenation of Dimethyl Oxalate and analysis condition.In reaction temperature, be 200 ℃, the catalyst stability that catalyst is carried out 200 hours investigate in (Fig. 2), show good catalytic stability and life-span, meet the requirement of the high yield high stability of modern industry.
Embodiment 5
The preparation method of catalyst is with embodiment 1, and the chlorauric acid solution that changes 0.01g/mL is 18.6mL, and the liquor argenti nitratis ophthalmicus of 0.01g/mL is 5.1mL, and other composition and condition are constant, make 4.5%Au-5.5%Ag/ED-P-SBA-15 catalyst.
ICP-MS quantitative analysis results shows that Au and Ag content are in the error range of theoretical load capacity; Through nitrogen adsorption test, specific area is 497m
2/ g, pore volume is 0.68ml/g, average pore size is 5.5nm.Catalyst with embodiment 1, the results are shown in Table 1 to the performance evaluation of Hydrogenation of Dimethyl Oxalate and analysis condition.
Embodiment 6
The preparation method of catalyst is with embodiment 1, and the chlorauric acid solution that changes 0.01g/mL is 24.20mL, and other composition and condition are constant, make 12%Au-0.75%Ag/ED-P-SBA-15 catalyst.
ICP-MS quantitative analysis results shows that gold content is 2.69wt%, and silver content is 2.56wt%; Through nitrogen adsorption test, specific area is 458m
2/ g, pore volume is 0.66ml/g, average pore size is 5.4nm.Catalyst with embodiment 1, the results are shown in Table 1 to the performance evaluation of Hydrogenation of Dimethyl Oxalate and analysis condition.
Embodiment 7
Get commercially available specific area 330m
2the SiO of/g
2carrier 1.0g, all the other preparation methods, with embodiment 1, make and are labeled as 8%Au-0.75%Ag/ED-P-SiO
2catalyst.
Catalyst with embodiment 1, the results are shown in Table 1 to the performance evaluation of preparing ethylene glycol by using dimethyl oxalate plus hydrogen and product analysis condition.
Embodiment 8
The preparation method of P-SBA-15 is with embodiment 1.At above-mentioned P-SBA-15 product, add 0.3g complexing agent dicyandiamide (DC) and 30 ml deionized water, 90 ℃ of backflow 12h, are cooled to room temperature, use deionized water drip washing, and 60 ℃ of oven dry obtain functionalization DC-P-SBA-15 pressed powder A.All the other steps, with embodiment 1, make and are labeled as 8%Au-0.75%Ag/DC-P-SBA-15 catalyst.
Catalyst with embodiment 1, the results are shown in Table 1 to the performance evaluation of Hydrogenation of Dimethyl Oxalate and product analysis condition.
Embodiment 9
Except complexing agent changes monoethanolamine (EA) into, all the other preparation methods are with embodiment 8, and gained catalyst is designated as 8%Au-0.75%Au/EA-P-SBA-15.
Catalyst with embodiment 1, the results are shown in Table 1 to the performance evaluation of Hydrogenation of Dimethyl Oxalate and product analysis condition.
Embodiment 10
Get specific area 783m prepared by laboratory
2the SBA-15 carrier 3.0g of/g, is dissolved in SAN 0.5g in 20mL dimethyl formamide (DMF) completely, and above-mentioned carrier is poured in this solution, after standing 4h, filters, washs and is dried, and obtains S-SBA-15 product, standby.At above-mentioned S-SBA-15 product, add 0.3g ethylenediamine and 30 ml deionized water, backflow 12h, is cooled to room temperature, uses deionized water drip washing, and 60 ℃ of oven dry obtain functionalization ED-S-SBA-15 pressed powder A, standby.All the other steps, with embodiment 1, make the catalyst that is labeled as 8%Au-0.75%Au/ED-S-SBA-15.
Catalyst with embodiment 1, the results are shown in Table 1 to the performance evaluation of Hydrogenation of Dimethyl Oxalate and product analysis condition.
Comparative example 1
Functionalization ED-P-SBA-15 preparation method is with embodiment 1.Getting concentration is the liquor argenti nitratis ophthalmicus 7.65mL of 0.01g/mL, by 50ml deionized water, is diluted to colourless transparent solution, under stirring condition, the functionalization ED-P-SBA-15 obtaining is scattered in this solution, drips while stirring the NaBH of 0.005g/mL after stirring 10min
420mL, dropwise rear continuation and stir 1h, vacuum filtration with deionized water washing 8～10 times afterwards, after the solid obtaining is dried in the electric heating convection oven of 60 ℃ spending the night, be placed in Muffle furnace and rise to 500 ℃ of roasting 6h with the heating rate of 1 ℃/min, obtain catalyst precursor.Compressing tablet sieves out 40～60 order particles, catalyst is packed in reactor, at normal pressure 5%H
2/ N
2under atmosphere, with 2 ℃/min, be warming up to 350 ℃ of reduction 4h, make 4.5%Ag/ED-P-SBA-15 catalyst, ICP-MS quantitative analysis results shows that Ag content is in the error range of theoretical load capacity; Through nitrogen adsorption test, specific area is 474m
2/ g, pore volume is 0.73ml/g, average pore size is 5.6nm.Catalyst with embodiment 1, the results are shown in Table 1 to the performance evaluation of Hydrogenation of Dimethyl Oxalate and product analysis condition.
Comparative example 2
Functionalization ED-P-SBA-15 preparation method is with embodiment 1.After pressed powder B in embodiment 1 is dried in the electric heating convection oven of 60 ℃ spending the night, be placed in Muffle furnace and rise to 500 ℃ of roasting 6h with the heating rate of 1 ℃/min, obtain catalyst precursor.Compressing tablet sieves out 40～60 order particles, catalyst is packed in reactor, at normal pressure 5%H
2/ N
2under atmosphere, with 2 ℃/min, be warming up to 350 ℃ of reduction 4h, make 8%Ag/ED-P-SBA-15 catalyst, ICP-MS quantitative analysis results shows that Au content is in the error range of theoretical load capacity; Through nitrogen adsorption test, specific area is 474m
2/ g, pore volume is 0.73ml/g, average pore size is 5.6nm.Catalyst with embodiment 1, the results are shown in Table 1 to the performance evaluation of Hydrogenation of Dimethyl Oxalate and product analysis condition.
Comparative example 3
Take specific area 833m prepared by 1.0g laboratory
2the SBA-15 of/g, does not carry out functionalization directly as carrier, according to the inventory of embodiment 1 and preparation method, make 8%Au-0.75%Ag/SBA-15 catalyst, ICP-MS quantitative analysis results shows that Au content is 3.34wt%, and Ag content is 0.59wt%, a little less than theoretical negative carrying capacity; Through nitrogen adsorption test, specific area is 358m
2/ g, pore volume is 0.71ml/g, average pore size is 6.5nm.Catalyst with embodiment 1, the results are shown in Table 1 to the performance evaluation of Hydrogenation of Dimethyl Oxalate and product analysis condition.
The catalytic performance of table 1 prepared by dimethyl oxalate plus hydrogen methyl glycollate
Embodiment 11
Adopt the catalyst of embodiment 1～4 and comparative example 1 and 2 to carry out Hydrogenation of Dimethyl Oxalate reaction, 230 ℃ of reaction temperatures, all the other evaluations and product analysis condition, with embodiment 1, the results are shown in Table 2.
The catalytic performance of table 2 preparing ethylene glycol by using dimethyl oxalate plus hydrogen
Claims (8)
1. the preparation method of oxalate hydrogenation gold-silver bimetal catalyst, it is characterized in that, described oxalate hydrogenation gold-silver bimetal catalyst is comprised of active constituent gold and silver and carrier, catalyst composition is expressed as: x%Au-y%Ag/ carrier, in formula, x% represents the mass percent of gold in catalyst, and y% represents the mass percent of silver in catalyst, and described catalyst components content is Au:2%～12% by mass percentage, Ag:0.5%～6%, surplus is carrier; Described gold derives from gold chloride; Described silver derives from the acetate of silver-colored nitrate or silver; Described carrier is silica or silicon-based mesoporous molecular sieve SBA-15;
Described preparation method's concrete steps are as follows:
1) organic polymer is dissolved in organic solvent and obtains Polymer Solution, add after the carrier of catalyst composition and ratio standingly, after filtration, deionized water washing and dry, then add complexing agent to reflux, obtain support type complexing agent-polymeric solid powders A; Described organic polymer is selected from polyvinyl alcohol or polystyrene acrylonitrile; Described organic solvent is selected from oxolane or dimethyl formamide; Described complexing agent is selected from a kind of in ethylenediamine, monoethanolamine, dicyandiamide; The temperature of described backflow is 70～110 ℃, and the time of backflow is 12～14h;
2) prepare the chlorauric acid solution of 0.005～0.015g/mL, by catalyst composition and ratio, join in support type complexing agent-polymeric solid powders A, then add reducing agent reduction, after filtration, washing, obtain pressed powder B;
3) prepare the silver salt solution of 0.005～0.015g/mL, by catalyst composition and ratio, join in pressed powder B, then add reducing agent reduction, after filtration, after washing, oven dry, roasting, obtain catalyst precursor; The condition of described oven dry is vacuum drying 6～12h at 60～120 ℃; The condition of described roasting is 400～550 ℃ of roasting 4～12h in air atmosphere;
4) catalyst precursor is reduced under hydrogeneous atmosphere, obtain oxalate hydrogenation gold-silver bimetal catalyst.
2. a kind of preparation method of oxalate hydrogenation gold-silver bimetal catalyst as claimed in claim 1, is characterized in that described catalyst components content is Au:4%～8% by mass percentage, Ag:0.5%～3%, and surplus is carrier.
3. a kind of preparation method of oxalate hydrogenation gold-silver bimetal catalyst as claimed in claim 1, is characterized in that in step 1), and the concentration of described Polymer Solution is 5～15mg/mL.
4. a kind of preparation method of oxalate hydrogenation gold-silver bimetal catalyst as claimed in claim 1, is characterized in that in step 1), and in described complexing agent-polymeric solid powder, complexing agent and polymeric solid powder quality ratio are 0.1.
5. a kind of preparation method of oxalate hydrogenation gold-silver bimetal catalyst as claimed in claim 1, is characterized in that in step 1), and the described standing time is 0.5～12h.
6. a kind of preparation method of oxalate hydrogenation gold-silver bimetal catalyst as claimed in claim 1, is characterized in that in step 2) or step 3) in, the time of described reduction is 0.5～2h.
7. a kind of preparation method of oxalate hydrogenation gold-silver bimetal catalyst as claimed in claim 1, is characterized in that in step 2) or step 3) in, described reducing agent adopts the NaBH4 aqueous solution of 0.003～0.008g/mL.
8. a kind of preparation method of oxalate hydrogenation gold-silver bimetal catalyst as claimed in claim 1, is characterized in that in step 4), and the temperature of described reduction is 250～550 ℃, and the time of reduction is 2～12h.
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