CN105582915A - Catalyst for preparing glycolate through hydrogenating oxalate, preparation method for catalyst and use of catalyst - Google Patents
Catalyst for preparing glycolate through hydrogenating oxalate, preparation method for catalyst and use of catalyst Download PDFInfo
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Abstract
The invention relates to a catalyst for preparing glycolate through hydrogenating oxalate, a preparation method for the catalyst and use of the catalyst. The catalyst is mainly used for solving the problem in the prior art that catalysts are poor in activity and low in glycolate selectivity. Through adopting the technical scheme that the catalyst which contains the following ingredients in percentage by weight is prepared by in-situ synthesis: (1) 0.5-15wt% of silver or oxides thereof; (2) 0-4wt% of at least one metal of VIII-group metals or oxides thereof; (3) 0-3wt% of at least one element of VA-group elements or oxides thereof; and (4) 78-99.5wt% of at least one carrier selected from silica, alumina, zirconia, titania and molecular sieves, the problem is better solved, and the catalyst can be applied to the industrial production for preparing glycolate through hydrogenating oxalate.
Description
Technical field
The present invention relates to a kind of preparation method of oxalic ester hydrogenation synthesizing of glycolate catalyst, particularly about oxalic acid diformazanThe method for preparing catalyst of ester catalytic hydrogenation synthesizing methyl glycolate.
Background technology
Ethyl glycolate, due to its unique molecular structure, has the chemical property of alcohol and ester concurrently, and oxonation, water can occurSeparate reaction, oxidation reaction etc., become a kind of important industrial chemicals. Can be widely used in chemical industry, medicine, agricultural chemicals, feed,Many fields such as spices and fuel.
Because ethyl glycolate is widely used, market demand is high, also very many to its synthesising process research both at home and abroad, mainThere are glyoxal and methyl alcohol one-step synthesis, formaldehyde carbonylation one ester synthetic method, ester dimethoxym ethane and formic acid method, coupling method, chlorineAcetic, formaldehyde and hydrogen cyanide addition process, dimethoxym ethane and Formaldehyde Radical addition process, oxalate hydrogenating reduction method, biologyOxydasis method. Although synthetic method is more, all there is larger shortcoming in a lot of technique.
At present main production line is to adopt the carbonylation route that formaldehyde is raw material abroad, under about 70.9MPa and high temperature,By formalin and CO, under the catalyst action such as the concentrated sulfuric acid or boron trifluoride, first condensation generates glycolic. By ethanolAcid obtain methyl glycollate with methanol esterification. The shortcoming of this method be strong acid catalyst to consersion unit seriously corroded, and be highPress reaction, higher to equipment requirement, the disposable input of equipment is larger, cannot large-scale production. Domestic methyl glycollate andThe production of glycolic mainly adopts chloroactic acid method and formaldehyde and hydrogen cyanide addition process, and wherein chloroactic acid method is by monoxone and KeProperty sodium solution hybrid reaction resterification process route, it is raw material that this chloroacetic production adopts acetic acid, sulphur is catalyst,Chlorine method is produced, although process is simple, causes this method not thereby seriously corroded, pollution are greatly in production process, cost is highCan large-scale production. And impurity is more in the methyl glycollate of this kind of method production, affect its answering in fields such as polymerizationsWith. Hydrogen cyanide rule is under sulfuric acid catalysis, to obtain hydroxyacetonitrile taking formaldehyde and hydrogen cyanide as raw material, then hydrolysis, esterificationCan obtain gross production rate and be 80% methyl glycollate, the method is simple, but feed hydrogen cyanic acid toxicity is larger.
20 century 70s, are subject to the impact of world oil crisis, and various countries start to carry out a large amount of with natural gas and coal-based one after anotherRaw material is main C1 chemical research, and correlation technique has also obtained development fast in the nineties in last century, especially in researchObtain great breakthrough taking coal or natural gas as raw material production ethylene glycol aspect, with CO and methyl nitrite gas phase catalysisThis process route of synthesis of oxalate is ripe, and the pilot scale of existing many covers and industrialized unit build up at present. So exploitation withOxalate is that the method for raw material preparation of ethanol by hydrogenating acid methyl esters is significant.
Oxalate catalytic hydrogenation is a cascade reaction, and the first step obtains ethyl glycolate, and ethyl glycolate repeated hydrogenation can obtainEthylene glycol, how realizing the high conversion of oxalate and the high selectivity of ethyl glycolate is the key of this synthetic method. In recent yearsCome many enterprises and scientific research institution and all this catalyst is studied, also find adding of argent and other auxiliary agent of partBe conducive to the yield of ethyl glycolate in hydrogenation process. But there are many documents and patent mostly to collect the report of such catalystIn in the research of catalyst formulation, ignored the impact of catalyst duct structure on hydrogenation reaction, and this exactly reactsThe reaction of a structure sensitive property, thus need to consider formula and the pore passage structure of catalyst, otherwise cannot obtainHigher ethyl glycolate yield.
As patent CN101138730A discloses a kind of catalyst and preparation side thereof of oxalic ester hydrogenation synthesizing of glycolateMethod, this patent has been prepared taking metallic copper as main active component by infusion process, and silver is the catalyst of auxiliary agent, though this catalystSo can be in oxalic ester hydrogenation synthesizing of glycolate reaction, but dimethyl oxalate conversion ratio and selectively all lower pointBe not 85% and 83%.
And for example patent CN101700496A disclose a kind of Hydrogenation of Dimethyl Oxalate synthesizing methyl glycolate catalyst andIts preparation method, described catalyst is taking metallic copper as main active component, and silver and manganese are for helping active component, and A1203 is carrier:Wherein metallic copper content is catalyst quality 25%～50%, and argent content is catalyst quality 5%～15%, goldTo belong to manganese content be catalyst quality 8%～20%, and A1203 content is catalyst quality 15%～40%. This invention is urgedAgent has very high reactivity in the reaction of Hydrogenation of Dimethyl Oxalate synthesizing methyl glycolate, and oxalate conversion ratio canReach 98%, but methyl glycollate selectively only has 75%.
Summary of the invention
One of technical problem to be solved by this invention be in prior art, exist poor catalyst activity and ethyl glycolate selectiveLow technical problem, provides a kind of catalyst of new preparing ethanol by oxalate hydrogenation acid esters. Technology to be solved by this inventionTwo of problem is to provide a kind of new preparing ethanol by oxalate hydrogenation acid esters method for preparing catalyst. The grass that adopts the method to prepareAcid esters preparation of ethanol by hydrogenating acid esters catalyst has active good, selective high feature. Technical problem to be solved by this inventionThree be to provide the side of a kind of catalyst corresponding with one of technical solution problem for preparing ethanol by oxalate hydrogenation acid estersMethod.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of preparing ethanol by oxalate hydrogenation acidThe catalyst of ester, by weight percentage, comprises following component: 1) 0.5～15wt% silver or its oxide; 2) 0～At least one metal or its oxide in 4wt% VIII family; 3) at least one element or its oxygen in 0～3wt% V A familyCompound; 4) 78～99.5wt% is selected from silica, aluminium oxide, zirconium dioxide, titanium dioxide, molecular sieve at least onePlant as carrier.
In technique scheme, catalyst pore volume is 0.9～2cm3/ g, inner aperture accounts for catalysis at the pore volume in 8～20nm ductThe more than 40% of the total pore volume of agent.
Component 2 in technique scheme) content is preferably 0.1～3%.
The element that is selected from V A family in technique scheme is preferably P, Sb or Bi.
In technique scheme, the preferred catalyst by weight percentage of catalyst also comprises the element that is selected from of 0.005～1wt%At least one element or its oxide in periodic table III A family.
In technique scheme, be selected from element in periodic table of elements group IIIA and be preferably B or its oxide.
In technique scheme the inner aperture of catalyst the pore volume in 8～20nm duct account for the total pore volume of catalyst 50% withOn.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: the system of synthesizing of glycolate ester catalystPreparation Method, comprises the following steps:
A) by active component silver and component 2), 3) soluble-salt wiring solution-forming I;
B) by a certain amount of masterplate agent and acetate dissolution in deionized water, stir, obtain solution II;
C) under stirring, a certain amount of esters of silicon acis is added drop-wise in solution II, obtains solution III;
D) under stirring, add a certain amount of titanium dioxide, aluminium oxide or Zirconium powder in solution III, stir 1～24Hour obtain slurry IV;
E) under stirring, solution I is joined in slurry IV;
F) by slurry IV as in crystallizing kettle 20～100 DEG C aging 5～48 hours;
G), after crystallization finishes, with ammonia hydrolysis section crystallizing kettle, interior pH is 4～8;
H), by gained slurries filtration, with the washing of ethanol and deionized water, then dry, obtain oxalate after roasting, reduction and addHydrogen ethyl glycolate catalyst processed.
In technique scheme, masterplate agent is preferably P123 or TMB.
In technique scheme, NaOH, sodium carbonate or ammoniacal liquor regulate pH in crystallizing kettle to be preferably 4.5～6.
Preferably temperature programming to 100～350 DEG C under hydrogen gas space velocity 300～4000 conditions of catalyst reduction in technique schemeReductase 12～30 hour.
For solve the problems of the technologies described above three, the technical solution used in the present invention is as follows: a kind of preparing ethanol by oxalate hydrogenation acidThe method of ester, taking oxalate and hydrogen as raw material, is 160～240 DEG C in reaction temperature, and reaction pressure is 0.5～4MPa,Oxalate weight space velocity is 0.1～2.5 hour-1, hydrogen and oxalate mol ratio be under 20～160:1 condition with the present inventionCatalyst haptoreaction, generates the effluent that contains methyl glycollate.
Oxalate hydrogenation is the reaction of a series connection, and the first step is that oxalate hydrogenation generates ethyl glycolate, and second stepTo be hydrogenated into ethylene glycol, if further reaction can generate ethanol. Calculation of thermodynamics, known these 3 reactions is flatWeighing apparatus conversion ratio is all higher, so must select the dynamics speed of suitable catalyst control reaction.
Key of the present invention is to utilize the synthetic method of original position to prepare silver/silicon dioxide catalyst, this kind of preparation methodCan make between active component, auxiliary agent and the carrier in catalyst effect more strong, and by masterplate agent and crystallization conditionRegulate catalyst duct structure Deng effectively, so this catalyst has higher oxalate in oxalate hydrogenation processConversion ratio and ethyl glycolate selective
The catalyst of preparing with the present invention, in the reacting of oxalate and hydrogen synthesizing alcohol acid esters, with dimethyl oxalate andHydrogen is raw material, is 160～240 DEG C in reaction temperature, and reaction pressure is 0.5～4MPa, dimethyl oxalate weight space velocityIt is 0.1～2.5 hour-1, hydrogen and dimethyl oxalate mol ratio are under 20～160:1 condition, the conversion ratio of oxalate canReach 99%, methyl glycollate selectively can reach 91%, obtain good technique effect.
Method of testing
1) catalyst component is recorded by ICP.
2) utilize nitrogen physisorphtion to measure pore volume and pore-size distribution.
Detailed description of the invention
[embodiment 1]
The solution I of the silver acetate of preparation 50ml argentiferous 4.5%, then 35gP123 is dissolved in to 1.2L containing 1.5mol/L acetic acidIn the aqueous solution, stir, obtain solution II, then under stirring, 75ml ethyl orthosilicate is added drop-wise to solution IIIn, obtain solution III, stir and obtain slurry IV after 20 hours. Under stirring, the solution I preparing is joined to slurryIn IV, after stirring, slurry is transferred in crystallizing kettle 50 DEG C aging 12 hours, after crystallization finishes, use NaOH solutionIn joint crystallizing kettle, pH is 5. Taking-up product filters, then with ethanol and deionized water washing worry cake, 120 DEG C of oven dry, 500 DEG CRoasting, gets 200 DEG C of the temperature programmings under hydrogen gas space velocity 1000 conditions of roast rear catalyst, reduces and within 10 hours, also obtains oxalic acidEster through hydrogenation ethyl glycolate catalyst processed cat-A1. Get catalyst sample and do ICP and BET characterization test, test result is shown inTable 1.
[embodiment 2]
Preparation 50ml argentiferous 4.5%, the silver acetate of cobalt 0.045% and the solution I of cobalt nitrate, then 35gP123 is dissolved in1.2L, containing in 1.5mol/L aqueous acetic acid, stirs, and obtains solution II, then under stirring by 75ml justSilester is added drop-wise in solution II, obtains solution III, stirs and obtains slurry IV after 14 hours. Under stirring, will prepareGood solution I joins in slurry IV, after stirring, slurry is transferred in crystallizing kettle 40 DEG C aging 12 hours, crystallizationAfter end, regulating pH in crystallizing kettle with NaOH is 5. Taking-up product filters, then washs and consider by ethanol and deionized waterCake, 120 DEG C of oven dry, 500 DEG C of roastings, get 200 DEG C of the temperature programmings under hydrogen gas space velocity 1000 conditions of roast rear catalyst,Reduce and within 10 hours, also obtain preparing ethanol by oxalate hydrogenation acid esters catalyst cat-A2. Get catalyst sample and be ICP and BETCharacterization test, test result is in table 1.
[embodiment 3]
Preparation 50ml argentiferous 4.5%, the silver acetate of nickel 0.22% and the solution I of nickel nitrate, then 35gP123 is dissolved in to 1.2LContaining in 1.5mol/L aqueous acetic acid, stir, obtain solution II, then under stirring by positive 69ml silicic acid secondEster is added drop-wise in solution II, obtains solution III, then adds 2g aluminium oxide, stirring to obtain slurry IV after 4 hours. Stir shapeUnder state, the solution I preparing is joined in slurry IV, after stirring, slurry is transferred in crystallizing kettle 100 DEG C aging12 hours, after crystallization finishes, with NaOH crystallizing kettle, interior pH was 5. Taking-up product filters, then uses ethanol and deionizationCake is considered in water washing, and 120 DEG C of oven dry, 500 DEG C of roastings, get the temperature programming under hydrogen gas space velocity 1000 conditions of roast rear catalyst200 DEG C, reduce and within 10 hours, also obtain preparing ethanol by oxalate hydrogenation acid esters catalyst cat-A3. Get catalyst sample and be ICPWith BET characterization test, test result is in table 1.
[embodiment 4]
Preparation 50ml argentiferous 0.2%, the silver acetate of palladium 0.8% and the solution I of palladium nitrate, then 35gP123 is dissolved in to 1.2LContaining in 1.5mol/L aqueous acetic acid, stir, obtain solution II, then under stirring by positive 69ml silicic acid secondEster is added drop-wise in solution II, obtains solution III, then adds 0.45gZSM-5 powder, stirring to obtain slurry IV after 4 hours.Under stirring, the solution I preparing is joined in slurry IV, after stirring, slurry is transferred in crystallizing kettle to 70 DEG CAging 12 hours, after crystallization finishes, with ammonia hydrolysis section crystallizing kettle, interior pH was 5. Taking-up product filter, then use ethanol andCake is considered in deionized water washing, and 120 DEG C of oven dry, 500 DEG C of roastings, get roast rear catalyst journey under hydrogen gas space velocity 1000 conditionsOrder heats up 200 DEG C, reduces and within 10 hours, also obtains preparing ethanol by oxalate hydrogenation acid esters catalyst cat-A4. Get catalyst sampleProduct do ICP and BET characterization test, and test result is in table 1.
[embodiment 5]
Preparation 50ml argentiferous 2.2%, the silver acetate of nickel 1.7% and the solution I of nickel nitrate, then 35gP123 is dissolved in to 1.2LContaining in 1.5mol/L aqueous acetic acid, stir, obtain solution II, then under stirring by positive 71ml silicic acid secondEster is added drop-wise in solution II, obtains solution III, then adds 1g aluminium oxide, stirring to obtain slurry IV after 20 hours. StirUnder state, the solution I preparing is joined in slurry IV, after stirring, slurry is transferred in crystallizing kettle 20 DEG C aging12 hours, after crystallization finishes, regulating pH in crystallizing kettle with NaOH was 5. Taking-up product filter, then with ethanol with goCake is considered in ionized water washing, and 120 DEG C of oven dry, 500 DEG C of roastings, get roast rear catalyst program under hydrogen gas space velocity 1000 conditionsHeat up 200 DEG C, reduce and within 10 hours, also obtain preparing ethanol by oxalate hydrogenation acid esters catalyst cat-A5. Get catalyst sampleDo ICP and BET characterization test, test result is in table 1.
[embodiment 6]
Preparation 50ml argentiferous 8%, the silver nitrate of iron 1.5% and the solution I of ferric nitrate, then 35gP123 is dissolved in to 1.2LContaining in 1.5mol/L aqueous acetic acid, stir, obtain solution II, then under stirring by positive 60ml silicic acid secondEster is added drop-wise in solution II, obtains solution III, then adds 4g zirconia, stirring to obtain slurry IV after 4 hours. Stir shapeUnder state, the solution I preparing is joined in slurry IV, after stirring, slurry is transferred in crystallizing kettle 100 DEG C aging12 hours, after crystallization finishes, regulating pH in crystallizing kettle with NaOH was 5. Taking-up product filter, then with ethanol with goCake is considered in ionized water washing, and 120 DEG C of oven dry, 500 DEG C of roastings, get roast rear catalyst program under hydrogen gas space velocity 1000 conditionsHeat up 200 DEG C, reduce and within 10 hours, also obtain preparing ethanol by oxalate hydrogenation acid esters catalyst cat-A6. Get catalyst sampleDo ICP and BET characterization test, test result is in table 1.
[embodiment 7]
Preparation 50ml contains the solution I of silver nitrate, nickel nitrate and the phosphoric acid of Ag4.5%, Ni0.22% and 0.12%P, then35gP123 is dissolved in to 1.2L containing in 1.5mol/L aqueous acetic acid, stirs, obtain solution II, then stirringUnder state, 69ml ethyl orthosilicate is added drop-wise in solution II, obtains solution III, then add 2g aluminium oxide, stir 4 littleTime after obtain slurry IV. Under stirring, the solution I preparing is joined in slurry IV, after stirring, slurry is turnedMove on in crystallizing kettle 100 DEG C aging 12 hours, after crystallization finishes, regulating pH in crystallizing kettle with ammoniacal liquor is 5. Take out productFilter, then consider cake with ethanol and deionized water washing, 120 DEG C of oven dry, 500 DEG C of roastings, get roast rear catalyst at hydrogen200 DEG C of temperature programmings under air speed 1000 conditions, reduce and within 10 hours, also obtain preparing ethanol by oxalate hydrogenation acid esters catalyst cat-A7. Get catalyst sample and do ICP and BET characterization test, test result is in table 1.
[embodiment 8]
Preparation 50ml is molten containing silver nitrate, cobalt acetate and the sodium antimonate of Ag4.5%, 0.045%Co and 0.003%SbLiquid I, then 35gP123 is dissolved in to 1.2L containing in 1.5mol/L aqueous solution of nitric acid, stir, obtain solution II, soAfter under stirring, 69ml ethyl orthosilicate is added drop-wise in solution II, obtain solution III, then add 2g aluminium oxide,Stir and obtain slurry IV after 4 hours. Under stirring, the solution I preparing is joined in slurry IV, after stirringBy slurry transfer in crystallizing kettle 100 DEG C aging 12 hours, after crystallization finishes, regulating pH in crystallizing kettle with sodium carbonate is 5.Taking-up product filters, then with ethanol and deionized water washing worry cake, and catalysis after roast is got in 120 DEG C of oven dry, 500 DEG C of roastingsAgent 200 DEG C of temperature programmings under hydrogen gas space velocity 1000 conditions, reduce and within 10 hours, also obtain preparing ethanol by oxalate hydrogenation acid esters and urgeAgent cat-A8. Get catalyst sample and do ICP and BET characterization test, test result is in table 1.
[embodiment 9]
Preparation 50ml contains the solution I of silver nitrate, nickel nitrate and the bismuth nitrate of Ag4.5%, 0.22%Ni and 0.45%Bi,Again 35gP123 is dissolved in to 1.2L containing in 1.5mol/L aqueous acetic acid, stirs, obtain solution II, then stirringMix under state 69ml ethyl orthosilicate is added drop-wise in solution II, obtain solution III, then add 2g aluminium oxide, stirring 4After hour, obtain slurry IV. Under stirring, the solution I preparing is joined in slurry IV, after stirring by slurryTransfer in crystallizing kettle 100 DEG C aging 12 hours, after crystallization finishes, with NaOH crystallizing kettle, interior pH is 5. Take out and produceThing filters, then considers cake with ethanol and deionized water washing, and 120 DEG C of oven dry, 500 DEG C of roastings, get roast rear catalyst at hydrogen200 DEG C of temperature programmings under gas air speed 1000 conditions, reduce and within 10 hours, also obtain preparing ethanol by oxalate hydrogenation acid esters catalystCat-A9. Get catalyst sample and do ICP and BET characterization test, test result is in table 1.
[embodiment 10]
Preparation 50ml is containing silver nitrate, nickel nitrate, the bismuth nitrate of Ag4.5%, 0.22%Ni, 0.15%Bi and 0.22%BWith the solution I of boric acid, then 35gP123 is dissolved in to 1.2L containing in 1.5mol/L aqueous acetic acid, stirs, obtainSolution II is then added drop-wise to 69ml ethyl orthosilicate in solution II under stirring, obtains solution III, then adds2g aluminium oxide, stirring obtained slurry IV after 4 hours. Under stirring, the solution I preparing is joined in slurry IV,After stirring, slurry is transferred in crystallizing kettle 100 DEG C aging 12 hours, after crystallization finishes, regulate brilliant with NaOHChanging pH in still is 5. Taking-up product filters, then washs and consider cake by ethanol and deionized water, 120 DEG C of oven dry, 500 DEG C of roastings,Get 200 DEG C of the temperature programmings under hydrogen gas space velocity 1000 conditions of roast rear catalyst, reduce and within 10 hours, also obtain oxalate hydrogenationEthyl glycolate catalyst cat-A10 processed. Get catalyst sample and do ICP and BET characterization test, test result is in table 1.[embodiment 11]
Preparation 50ml contains the solution I of silver nitrate, nickel nitrate and the phosphoric acid of Ag4.5%, 0.22%Ni and 0.45P, then35gP123 is dissolved in to 1.2L containing in 1.5mol/L aqueous acetic acid, stirs, obtain solution II, then stirringUnder state, 69ml ethyl orthosilicate is added drop-wise in solution II, obtains solution III, then add 2g aluminium oxide, stir 4 littleTime after obtain slurry IV. Under stirring, the solution I preparing is joined in slurry IV, after stirring, slurry is turnedMove on in crystallizing kettle 100 DEG C aging 12 hours, after crystallization finishes, regulating pH in crystallizing kettle with NaOH is 5. Take outProduct filters, then considers cake with ethanol and deionized water washing, and 120 DEG C of oven dry, 500 DEG C of roastings, get roast rear catalyst and exist200 DEG C of temperature programmings under hydrogen gas space velocity 1000 conditions, reduce and within 10 hours, also obtain preparing ethanol by oxalate hydrogenation acid esters catalystCat-A11. Get catalyst sample and do ICP and BET characterization test, test result is in table 1.
[embodiment 12]
According to the formula of embodiment 10 and preparation method, just changing masterplate agent P123 consumption is 20g, that is: preparation 50mlContain the solution I of silver nitrate, nickel nitrate, bismuth nitrate and the boric acid of Ag4.5%, 0.22%Ni, 0.15%Bi and 0.22%B,Change 20gP123 is dissolved in to 1.2L containing in 1.5mol/L aqueous acetic acid, stir, obtain solution II, then stirringMix under state 69ml ethyl orthosilicate is added drop-wise in solution II, obtain solution III, then add 2g aluminium oxide, stirring 4After hour, obtain slurry IV. Under stirring, the solution I preparing is joined in slurry IV, after stirring by slurryTransfer in crystallizing kettle 100 DEG C aging 12 hours, after crystallization finishes, regulating pH in crystallizing kettle with NaOH is 5. GetGo out product and filter, then consider cake with ethanol and deionized water washing, 120 DEG C of oven dry, 500 DEG C of roastings, get roast rear catalyst200 DEG C of temperature programmings under hydrogen gas space velocity 1000 conditions, reduce and within 10 hours, also obtain the catalysis of preparing ethanol by oxalate hydrogenation acid estersAgent cat-A12. Get catalyst sample and do ICP and BET characterization test, test result is in table 1.
[embodiment 13]
According to the formula of embodiment 10 and preparation method, just changing masterplate agent P123 consumption is 45g, that is: preparation 50mlContain the solution I of silver nitrate, nickel nitrate, bismuth nitrate and the boric acid of Ag4.5%, 0.22%Ni, 0.15%Bi and 0.22%B,Change 45gP123 is dissolved in to 1.2L containing in 1.5mol/L aqueous acetic acid, stir, obtain solution II, then stirringMix under state 69ml ethyl orthosilicate is added drop-wise in solution II, obtain solution III, then add 2g aluminium oxide, stirring 4After hour, obtain slurry IV. Under stirring, the solution I preparing is joined in slurry IV, after stirring by slurryTransfer in crystallizing kettle 100 DEG C aging 12 hours, after crystallization finishes, regulating pH in crystallizing kettle with NaOH is 5. GetGo out product and filter, then consider cake with ethanol and deionized water washing, 120 DEG C of oven dry, 500 DEG C of roastings, get roast rear catalyst200 DEG C of temperature programmings under hydrogen gas space velocity 1000 conditions, reduce and within 10 hours, also obtain the catalysis of preparing ethanol by oxalate hydrogenation acid estersAgent cat-A13. Get catalyst sample and do ICP and BET characterization test, test result is in table 1.
[embodiment 14]
According to the formula of embodiment 10 and preparation method, just change masterplate agent and be TMB: preparation 50ml is containing Ag4.5The solution I of silver nitrate, nickel nitrate, bismuth nitrate and the boric acid of %, 0.22%Ni, 0.15%Bi and 0.22%B, changes mouldVersion agent is that 35gTMB is dissolved in 1.2L containing in 1.5mol/L aqueous acetic acid, stirs, and obtains solution II, is then stirringMix under state 69ml ethyl orthosilicate is added drop-wise in solution II, obtain solution III, then add 2g aluminium oxide, stirring 4After hour, obtain slurry IV. Under stirring, the solution I preparing is joined in slurry IV, after stirring by slurryTransfer in crystallizing kettle 80 DEG C aging 12 hours, after crystallization finishes, regulating pH in crystallizing kettle with NaOH is 5. GetGo out product and filter, then consider cake with ethanol and deionized water washing, 120 DEG C of oven dry, 500 DEG C of roastings, get roast rear catalyst200 DEG C of temperature programmings under hydrogen gas space velocity 1000 conditions, reduce and within 10 hours, also obtain the catalysis of preparing ethanol by oxalate hydrogenation acid estersAgent cat-A14. Get catalyst sample and do ICP and BET characterization test, test result is in table 1.
[embodiment 15]
According to the formula of embodiment 10 and preparation method, just changing masterplate agent is F127, that is: preparation 50ml is containing Ag4.5The solution I of silver nitrate, nickel nitrate, bismuth nitrate and the boric acid of %, 0.22%Ni, 0.15%Bi and 0.22%B, changes mouldVersion agent is that 35GF127 is dissolved in 1.2L containing in 1.5mol/L aqueous acetic acid, stirs, and obtains solution II, then existsUnder stirring, 69ml ethyl orthosilicate is added drop-wise in solution II, obtains solution III, then add 2g aluminium oxide, stirringAfter 4 hours, obtain slurry IV. Under stirring, the solution I preparing is joined in slurry IV, after stirring by slurryTransfer in crystallizing kettle 80 DEG C aging 12 hours, after crystallization finishes, regulating pH in crystallizing kettle with NaOH is 5. GetGo out product and filter, then consider cake with ethanol and deionized water washing, 120 DEG C of oven dry, 500 DEG C of roastings, get roast rear catalyst200 DEG C of temperature programmings under hydrogen gas space velocity 1000 conditions, reduce and within 10 hours, also obtain the catalysis of preparing ethanol by oxalate hydrogenation acid estersAgent cat-A15. Get catalyst sample and do ICP and BET characterization test, test result is in table 1.
[embodiment 16]
According to the formula of embodiment 10 and preparation method, just changing PH in adjusting crystallizing kettle is 4, that is: preparation 50mlContain the solution I of silver nitrate, nickel nitrate, bismuth nitrate and the boric acid of Ag4.5%, 0.22%Ni, 0.15%Bi and 0.22%B,Again 35gP123 is dissolved in to 1.2L containing in 1.5mol/L aqueous acetic acid, stirs, obtain solution II, then stirringMix under state 69ml ethyl orthosilicate is added drop-wise in solution II, obtain solution III, then add 2g aluminium oxide, stirring 4After hour, obtain slurry IV. Under stirring, the solution I preparing is joined in slurry IV, after stirring by slurryTransfer in crystallizing kettle 80 DEG C aging 12 hours, after crystallization finishes, regulating pH in crystallizing kettle with NaOH is 4. GetGo out product and filter, then consider cake with ethanol and deionized water washing, 120 DEG C of oven dry, 500 DEG C of roastings, get roast rear catalyst200 DEG C of temperature programmings under hydrogen gas space velocity 1000 conditions, reduce and within 10 hours, also obtain the catalysis of preparing ethanol by oxalate hydrogenation acid estersAgent cat-A16. Get catalyst sample and do ICP and BET characterization test, test result is in table 1.
[embodiment 17]
According to the formula of embodiment 10 and preparation method, just changing pH in adjusting crystallizing kettle is 6, prepares 50ml and containsThe solution I of silver nitrate, nickel nitrate, bismuth nitrate and the boric acid of Ag4.5%, 0.22%Ni, 0.15%Bi and 0.22%B,Changing masterplate agent is that 35gP123 is dissolved in 1.2L containing in 1.5mol/L aqueous acetic acid, stirs, and obtains solution II,Then under stirring, 69ml ethyl orthosilicate is added drop-wise in solution II, obtains solution III, then add 2g aluminium oxide,Stir and obtain slurry IV after 4 hours. Under stirring, the solution I preparing is joined in slurry IV, after stirringBy slurry transfer in crystallizing kettle 80 DEG C aging 12 hours, after crystallization finishes, regulate pH in crystallizing kettle to be with NaOH6. Taking-up product filters, then with ethanol and deionized water washing worry cake, and 120 DEG C of oven dry, 500 DEG C of roastings are urged after getting roastAgent 200 DEG C of temperature programmings under hydrogen gas space velocity 1000 conditions, reduce and within 10 hours, also obtain preparing ethanol by oxalate hydrogenation acid estersCatalyst cat-A17. Get catalyst sample and do ICP and BET characterization test, test result is in table 1.
[embodiment 18]
According to the formula of embodiment 10 and preparation method, just changing pH in adjusting crystallizing kettle is 8, prepares 50ml and containsThe solution I of silver nitrate, nickel nitrate, bismuth nitrate and the boric acid of Ag4.5%, 0.22%Ni, 0.15%Bi and 0.22%B,Changing masterplate agent is that 35gP123 is dissolved in 1.2L containing in 1.5mol/L aqueous acetic acid, stirs, and obtains solution II,Then under stirring, 69ml ethyl orthosilicate is added drop-wise in solution II, obtains solution III, then add 2g aluminium oxide,Stir and obtain slurry IV after 4 hours. Under stirring, the solution I preparing is joined in slurry IV, after stirringBy slurry transfer in crystallizing kettle 80 DEG C aging 12 hours, after crystallization finishes, regulate pH in crystallizing kettle to be with NaOH8. Taking-up product filters, then with ethanol and deionized water washing worry cake, and 120 DEG C of oven dry, 500 DEG C of roastings are urged after getting roastAgent 200 DEG C of temperature programmings under hydrogen gas space velocity 1000 conditions, reduce and within 10 hours, also obtain preparing ethanol by oxalate hydrogenation acid estersCatalyst cat-A18. Get catalyst sample and do ICP and BET characterization test, test result is in table 1.
[embodiment 19]
According to the formula of embodiment 10 and preparation method, just changing carrier silicon was methyl silicate originally, prepared 50ml and containedThe solution I of silver nitrate, nickel nitrate, bismuth nitrate and the boric acid of Ag4.5%, 0.22%Ni, 0.15%Bi and 0.22%B,Changing masterplate agent is that 35gP123 is dissolved in 1.2L containing in 1.5mol/L aqueous acetic acid, stirs, and obtains solution II,Then under stirring, 45ml methyl silicate is added drop-wise in solution II, obtains solution III, then add 2g aluminium oxide,Stir and obtain slurry IV after 4 hours. Under stirring, the solution I preparing is joined in slurry IV, after stirringBy slurry transfer in crystallizing kettle 80 DEG C aging 12 hours, after crystallization finishes, regulate pH in crystallizing kettle to be with NaOH4. Taking-up product filters, then with ethanol and deionized water washing worry cake, and 120 DEG C of oven dry, 500 DEG C of roastings are urged after getting roastAgent 200 DEG C of temperature programmings under hydrogen gas space velocity 1000 conditions, reduce and within 10 hours, also obtain preparing ethanol by oxalate hydrogenation acid estersCatalyst cat-A19. Get catalyst sample and do ICP and BET characterization test, test result is in table 1.
[comparative example 1]
According to the formula of embodiment 10, then prepare synthesizing methyl glycolate by the method for patent CN101138730A and urgeAgent, gets catalyst sample and does ICP and BET characterization test, and test result is in table 1.
[comparative example 2]
According to the formula of embodiment 10 and preparation method, just in preparation process, do not add masterplate agent, prepare 50mlContain the solution I of silver nitrate, nickel nitrate, bismuth nitrate and the boric acid of Ag4.5%, 0.22%Ni, 0.15%Bi and 0.22%B,Then 69ml ethyl orthosilicate is added drop-wise to 1.2L under stirring containing in 1.5mol/L acetum II, obtains solutionIII, then add 2g aluminium oxide, stirring to obtain slurry IV after 4 hours. Under stirring, the solution I preparing is joinedIn slurry IV, after stirring, slurry is transferred in crystallizing kettle 80 DEG C aging 12 hours, after crystallization finishes, use hydroxideIt is 4 that sodium regulates pH in crystallizing kettle. Taking-up product filters, then with ethanol and deionized water washing worry cake, 120 DEG C of oven dry,500 DEG C of roastings, get 200 DEG C of the temperature programmings under hydrogen gas space velocity 1000 conditions of roast rear catalyst, and reducing 10 hours mustTo preparing ethanol by oxalate hydrogenation acid esters catalyst cat-B2. Get catalyst sample and do ICP and BET characterization test, testThe results are shown in Table 1.
[comparative example 3]
According to the formula of embodiment 10 and preparation method, just changing PH in adjusting crystallizing kettle is 9, prepares 50mlContain the solution I of silver nitrate, nickel nitrate, bismuth nitrate and the boric acid of Ag4.5%, 0.22%Ni, 0.15%Bi and 0.22%B,Changing masterplate agent is that 35gP123 is dissolved in 1.2L containing in 1.5mol/L aqueous acetic acid, stirs, and obtains solution II,Then under stirring, 69ml ethyl orthosilicate is added drop-wise in solution II, obtains solution III, then add 2g aluminium oxide,Stir and obtain slurry IV after 4 hours. Under stirring, the solution I preparing is joined in slurry IV, after stirringBy slurry transfer in crystallizing kettle 80 DEG C aging 12 hours, after crystallization finishes, regulate pH in crystallizing kettle to be with NaOH9. Taking-up product filters, then with ethanol and deionized water washing worry cake, and 120 DEG C of oven dry, 500 DEG C of roastings are urged after getting roastAgent 200 DEG C of temperature programmings under hydrogen gas space velocity 1000 conditions, reduce and within 10 hours, also obtain preparing ethanol by oxalate hydrogenation acid estersCatalyst cat-B3. Get catalyst sample and do ICP and BET characterization test, test result is in table 1.
[comparative example 4]
According to the formula of embodiment 10 and preparation method, just finally do not regulate pH in crystallizing kettle, prepare 50ml and containThe solution I of silver nitrate, nickel nitrate, bismuth nitrate and the boric acid of Ag4.5%, 0.22%Ni, 0.15%Bi and 0.22%B,Changing masterplate agent is that 35gP123 is dissolved in 1.2L containing in 1.5mol/L aqueous acetic acid, stirs, and obtains solution II,Then under stirring, 69ml ethyl orthosilicate is added drop-wise in solution II, obtains solution III, then add 2g aluminium oxide,Stir and obtain slurry IV after 4 hours. Under stirring, the solution I preparing is joined in slurry IV, after stirringBy slurry transfer in crystallizing kettle 80 DEG C aging 12 hours, after crystallization finishes, take out product and filter, then with ethanol with go fromCake is considered in sub-water washing, and 120 DEG C of oven dry, 500 DEG C of roastings, get roast rear catalyst program liter under hydrogen gas space velocity 1000 conditions200 DEG C of temperature, reduce and within 10 hours, also obtain preparing ethanol by oxalate hydrogenation acid esters catalyst cat-B4. Getting catalyst sample doesICP and BET characterization test, test result is in table 1.
Table 1
[embodiment 20]
The present embodiment explanation embodiment 1～19 gained catalyst answering in the reaction of prepared by dimethyl oxalate plus hydrogen methyl glycollateWith.
Get the embodiment of the present invention 1～19 gained catalyst and react examination. Taking dimethyl oxalate and hydrogen as raw material,205 DEG C of reaction temperatures, weight space velocity 0.9g/g.h-1, hydrogen ester, than 80:1, is checked and rated catalysis under reaction pressure 2.8MPa conditionAgent, reaction result is in table 2.
[embodiment 21]
The present embodiment explanation embodiment 1,10 gained catalyst answering in the reaction of diethy-aceto oxalate preparation of ethanol by hydrogenating acetoacetic esterWith.
Get the embodiment of the present invention 1,10 gained catalyst and react examination. Taking diethy-aceto oxalate and hydrogen as raw material,205 DEG C of reaction temperatures, weight space velocity 0.9g/g.h-1, hydrogen ester, than 80:1, is checked and rated catalysis under reaction pressure 2.8MPa conditionAgent, reaction result is in table 2.
[comparative example 5]
Get comparative example 1～4 gained catalyst and react examination, adopt the raw material identical with embodiment 20 and reaction barPart. Reaction result is in table 2.
Table 2
Can be found out the prepared by dimethyl oxalate plus hydrogen methyl glycollate catalyst activity of preparing by the inventive method by test resultProperty and selectively all apparently higher than reference sample. Show that catalyst prepared by the inventive method has obvious progress and advantage.
[embodiment 22]
The present embodiment explanation embodiment 10 gained catalyst change work in the reaction of prepared by dimethyl oxalate plus hydrogen methyl glycollateThe result of the test of skill condition.
Get the embodiment of the present invention 10 gained catalyst and react examination, change process conditions test, reaction condition withAnd the results are shown in Table 3.
Table 3
Claims (10)
1. a catalyst for preparing ethanol by oxalate hydrogenation acid esters, by weight percentage, comprises following component: 1)0.5～15wt% silver or its oxide; 2) at least one metal or its oxide in 0～4wt% VIII family; 3) 0～3wtAt least one element or its oxide in % V A family; 4) 78～99.5wt% is selected from silica, aluminium oxide, dioxyIn change zirconium, titanium dioxide, molecular sieve, at least one is carrier.
2. the catalyst of preparing ethanol by oxalate hydrogenation acid esters according to claim 1, is characterized in that catalyst poresAppearance is 0.9～2cm3/ g, inner aperture accounts for the more than 40% of the total pore volume of catalyst at the pore volume in 8～20nm duct.
3. the catalyst of preparing ethanol by oxalate hydrogenation acid esters according to claim 1, is characterized in that component 2)Content is 0.1～3%.
4. the catalyst of preparing ethanol by oxalate hydrogenation acid esters according to claim 1, is characterized in that being selected fromElement in V A family is P, Sb or Bi.
5. the catalyst of preparing ethanol by oxalate hydrogenation acid esters according to claim 1, is characterized in that with weight hundredProportion by subtraction meter catalyst also comprises that 0.005～1wt% is selected from least one element or its oxide in periodic table of elements III A family.
6. the catalyst of preparing ethanol by oxalate hydrogenation acid esters according to claim 5, is characterized in that being selected from elementIn periodic table group IIIA, element is B or its oxide.
7. the preparation method of the catalyst of preparing ethanol by oxalate hydrogenation acid esters described in claim 1～6 any one, bagDraw together following steps:
A) by active component silver and component 2), 3) soluble-salt wiring solution-forming I;
B) by a certain amount of masterplate agent and acetate dissolution in deionized water, stir, obtain solutionⅡ；
C) under stirring, a certain amount of esters of silicon acis is added drop-wise in solution II, obtains solution III;
D) under stirring, add a certain amount of titanium dioxide, aluminium oxide or Zirconium powder in solution III, stir 1～24Hour obtain slurry IV;
E) under stirring, solution I is joined in slurry IV;
F) by slurry IV as in crystallizing kettle 20～100 DEG C aging 5～48 hours;
G), after crystallization finishes, regulating pH in crystallizing kettle with NaOH, sodium carbonate or ammoniacal liquor is 4～8;
H), by gained slurries filtration, with the washing of ethanol and deionized water, then dry, obtain oxalate after roasting, reduction and addHydrogen ethyl glycolate catalyst processed.
8. the preparation method of the catalyst of preparing ethanol by oxalate hydrogenation acid esters according to claim 7, its feature existsBe P123 or TMB in masterplate agent.
9. the preparation method of the catalyst of described preparing ethanol by oxalate hydrogenation acid esters according to claim 7, its spyLevy and be that it is 4.5～6 that ammoniacal liquor regulates pH in crystallizing kettle.
10. a method for preparing ethanol by oxalate hydrogenation acid esters, taking oxalate and hydrogen as raw material, in reaction temperature is160～240 DEG C, reaction pressure is 0.5～4MPa, and oxalate weight space velocity is 0.1～2.5 hour-1, hydrogen and oxalateMol ratio be under 20～160:1 condition with catalyst haptoreaction described in claim 1～6 any one, generate and contain secondThe effluent of carboxylic ester.
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