CN104043457A - Catalyst and method for preparation of glycol by oxalate hydrogenation - Google Patents
Catalyst and method for preparation of glycol by oxalate hydrogenation Download PDFInfo
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- CN104043457A CN104043457A CN201310078824.6A CN201310078824A CN104043457A CN 104043457 A CN104043457 A CN 104043457A CN 201310078824 A CN201310078824 A CN 201310078824A CN 104043457 A CN104043457 A CN 104043457A
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Abstract
The invention relates to a catalyst and a method for preparation of glycol by oxalate hydrogenation, and aims at solving the problems of poor catalyst activity and low glycol selectivity in the prior art. The catalyst comprises the following components by weight: a) 5-50% of at least one substance selected from the group consisting of copper or copper oxide; b) greater than 0-10% of at least one metal or oxide selected from the group consisting of barium, chromium, zinc, calcium, magnesium, zirconium, silver, nickel or molybdenum; c) greater than 0-10% of at least one metal or oxide selected from the group consisting of cobalt, manganese, cerium, iron or lanthanum; and d) 30-94% of at least one substance selected from the group consisting of alumina, silica or zeolite, by use of the technical scheme of the catalyst, the problems of poor catalyst activity and low glycol selectivity in the prior art can be well solved, and the catalyst and the method can be used in industrial production for preparation of the glycol by oxalate hydrogenation.
Description
Technical field
The present invention relates to a kind of catalyst and method thereof of hydrogenation of oxalate for preparing ethylene glycol, particularly produce the Catalyst And Method of ethylene glycol about dimethyl oxalate or diethy-aceto oxalate catalytic hydrogenation.
Background technology
Ethylene glycol (EG) is a kind of important Organic Chemicals, mainly for the production of polyester fiber, antifreezing agent, unsaturated polyester resin, lubricant, plasticizer, non-ionic surface active agent and explosive etc., can be used in addition the industries such as coating, soup, brake-fluid and ink, as solvent and the medium of ammonium pertorate, also can be used for producing special solvent glycol ether etc., purposes is very extensive.
Over nearly 10 years, because polyester industrial is sought-after, domestic market keeps rapid growth situation to the demand of ethylene glycol.Nineteen ninety-five, the apparent consumption amount of China's ethylene glycol only had 65.69 ten thousand tons, within 2000, reached 195.71 ten thousand tons, and average growth rate per annum is up to 24.40%.Since entering 21 century, the apparent consumption amount of ethylene glycol continues to increase substantially, and within 2002, breaks through 3,000,000 tons of high pointes, reaches 301.99 ten thousand tons, becomes the large ethylene glycol of the first in the world country of consumption that exceedes the U.S..Although China's ethylene glycol capacity and output increases very fast, due to the powerful development of the industry such as polyester, still can not meet the growing market demand, the situation that import interdependency is higher will continue in a very long time.
Current, the suitability for industrialized production of domestic and international large-scale ethylene glycol mainly adopts oxirane direct hydration, i.e. the legal process route of pressure (hydraulic) water, and production technology is monopolized by English lotus Shell, U.S. Halcon-SD and U.S. UCC tri-companies substantially.In addition, the research-and-development activity of the new synthetic technology of ethylene glycol is also making progress always.As Shell company, UCC company, Moscow Mendeleev chemical engineering institute, oil of SPC research institute etc. have developed catalyzing epoxyethane hydration legal system ethylene glycol production technology etc. in succession.The common feature of said method is to consume valuable ethene resource, and at present ethene mainly by traditional petroleum resources refining, and following one period global oil price by long-term run at high level.
20 century 70s; be subject to the impact of world oil crisis; various countries begin one's study one after another and produce the method for ethylene glycol taking coal or natural gas as raw material; hope can adopt aboundresources, low-cost natural gas or coal to replace Petroleum Production ethylene glycol (Non oil-based route), and this route possesses the advantage of competing mutually with traditional ethene route.Ube Industries Ltd. and the cooperative development of union carbide corporation of the U.S. be the process route by the indirect synthesizing glycol of synthesis gas by dialkyl oxalate.This technique is reacted oxalic butyl ester taking CO and butanols as raw material by liquid-phase carbonylation, and then produces ethylene glycol through liquid-phase hydrogenatin reaction.The generating rate of this synthetic route carbonylation is low, side reaction is many, and hydrogenation pressure is high.The beginning of the eighties, ARCO chemical company of the U.S. and company of Ube Industries Ltd. have developed again alkyl nitrite method, in reaction, introduce alkyl nitrite, coupling reaction is carried out under anhydrous condition, this discovery has greatly promoted the research and development of gas-phase process technology.A lot of research at present is all carried out based on this, especially, with synthesis gas gas-phase reaction synthesis of oxalate, oxalate repeated hydrogenation is the process route most with application value realistic of generally acknowledging to the two-step mode technique route (oxalate method) of ethylene glycol, has economy and competitiveness.This technology reaction condition gentleness, selectively high is the main development direction that Non oil-based route is produced ethylene glycol technology.Now the research of preparing oxalate taking carbon monoxide as raw material has been obtained to good effect both at home and abroad, industrial production is ripe.And by preparing glycol by hydrogenating oxalate, still have more need of work further investigation, especially aspect raising oxalate conversion ratio and glycol selectivity.
Document CN102319581A discloses a kind of efficient oxalic ester hydrogenation catalyst method and preparation method thereof, and this catalyst is taking copper as main active constituent, ZnO, K
2o, MgO, Cr
2o
3, NiO, Co
2o
3, ZrO
2, Mo
2o
3for auxiliary agent, mesoporous silicon oxide is carrier.Adopt infusion process in two steps copper and auxiliary agent to be loaded on silica, but this catalyst exists oxalate low conversion rate, generally, below 96%, glycol selectivity is low, in 90% left and right.
Document CN101138725A discloses a kind of Catalysts and its preparation method of oxalic ester hydrogenation synthesizing of ethylene glycol.It is taking metallic copper as active component, and zinc is auxiliary agent, adopts coprecipitation preparation, but this catalyst exists conversion ratio and the low problem of glycol selectivity of transforming equally.
Summary of the invention
One of technical problem to be solved by this invention is in prior art, to have poor catalyst activity and the low problem of glycol selectivity, and a kind of catalyst of new hydrogenation of oxalate for preparing ethylene glycol is provided.Two of technical problem to be solved by this invention is to provide a kind of method of new hydrogenation of oxalate for preparing ethylene glycol.Adopt this hydrogenation of oxalate for preparing ethylene glycol catalyst to there is good catalyst activity, the advantage that glycol selectivity is high.
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 catalyst of hydrogenation of oxalate for preparing ethylene glycol, by weight percentage, comprises following component:
A) 5 ~ 50% at least one that are selected from the oxide of copper or copper;
B) >0 ~ 10% is selected from least one metal or the oxide in barium, zinc, chromium, calcium, magnesium, zirconium, silver, nickel or molybdenum;
C) >0 ~ 10% is selected from least one metal or the oxide in cobalt, manganese, cerium, iron or lanthanum;
D) 30～94% at least one carrier being selected from aluminium oxide, silica or molecular sieve.
In technique scheme, by weight percentage, component consumption preferable range a) is 10～30%, and component consumption preferable range b) is 0.1～7%, and component consumption preferable range c) is 0.03～7%, and component consumption preferable range d) is 60～89%.Component b) preferred version is at least one metal or the oxide being selected from barium, zinc, calcium, magnesium, silver, nickel or molybdenum.Component c) preferred version is at least one metal or the oxide being selected from cobalt, manganese or iron.Component is b) 0.3～10 with component metal total mole number c) than preferable range, and more preferably scope is 1 ~ 8.Described molecular sieve preferred version is at least one being selected from ZSM or MCM.Carrier preferred version is at least one being selected from aluminium oxide or silica, and more preferably scheme is the mixture that is selected from aluminium oxide and silica, and wherein the weight ratio preferable range of aluminium oxide and silica is 0.1～5, and more preferably scope is 0.5 ~ 4.
The preparation method of hydrogenation of oxalate for preparing ethylene glycol catalyst of the present invention, mainly comprise the following steps: a) soluble-salt of active constituent copper and component b) are made into mixed solution I with component soluble-salt c), wherein the soluble-salt concentration preferable range of active ingredient copper is 0.1～2.5 mol/L, component soluble-salt concentration preferable range b) is 0.01～2 mol/L, and component soluble-salt concentration preferable range c) is 0.005～2 mol/L; B) be mixed with solution II and make precipitating reagent being selected from least one in carbonate, bicarbonate, alkali-metal hydroxide or inorganic ammoniacal liquor; C) solution II is added to mixed liquor I, the pH value of controlling reaction end is 6～8.5, obtains slurry III and is reactive precursor; D) reactive precursor and carrier are mixed and obtain slurry IV; E) will after 80～120 DEG C of oven dry of the filter cake obtaining after slurry IV filtration washing, 300～500 DEG C of roastings, obtain described hydrogenation of oxalate for preparing ethylene glycol catalyst.
In technique scheme, the soluble-salt of active constituent copper is selected at least one in copper nitrate, Schweinfurt green or cupric oxalate.Carbonate in precipitating reagent or bicarbonate are selected from carbonate or the bicarbonate of alkali metal or alkaline-earth metal; Alkali-metal hydroxide is selected from NaOH or potassium hydroxide; Inorganic ammonia is selected from liquefied ammonia or ammoniacal liquor.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: a kind of method of hydrogenation of oxalate for preparing ethylene glycol, be included under hydrogenation conditions, oxalate raw material is contacted with above-mentioned catalyst.
In technique scheme, described hydrogenation conditions comprises: 170～260 DEG C of reaction temperatures, weight space velocity 0.1～1.5 hour
-1, hydrogen ester is than 30～200, reaction pressure 1.5～4MPa.Described oxalate raw material is dimethyl oxalate or diethy-aceto oxalate.
In technique scheme, described catalyst before use, can be handled as follows: heat up and reduce at the gaseous mixture Program of hydrogen or hydrogen and nitrogen.Wherein, the volume space velocity of the gaseous mixture of hydrogen or hydrogen and nitrogen is 500～3000 hours
-1, preferable range is 1000～2000 hours
-1; Temperature programming to 150～350 DEG C, preferable range is 200～280 DEG C.
As everyone knows, oxalate hydrogenation is the reaction of a series connection, target product ethylene glycol is an intermediate product in this cascade reaction, want to improve the selective of the activity of catalyst and ethylene glycol, just raw material oxalate all must be converted into ethylene glycol, the excessive hydrogenation that suppresses again ethylene glycol becomes ethanol.The present invention is selected from barium by interpolation, zinc, chromium, calcium, magnesium, zirconium, silver, at least one metal in nickel or molybdenum or oxide improve the decentralization of active constituent precipitation, effectively improve catalyst activity, be selected from cobalt by interpolation simultaneously, manganese, cerium, at least one metal in iron or lanthanum or oxide suppress the hydrogenation reaction of oxalate hydrogenation intermediate product ethylene glycol, effectively improve the selective of ethylene glycol, and controlling component is b) 0.3～10 with component metal total mole number ratio c), making this catalyst is 100% at the conversion ratio of oxalate hydrogenation medium-height grass acid esters, ethylene glycol be selectively greater than 95%, obtain good technique effect.
Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[embodiment 1]
Contain 0.5 mol/L copper nitrate by 1 liter, the solution of 0.05 mol/L nickel nitrate and 0.05 mol/L manganese nitrate is as solution I, under stirring, join in slurry I the ammonium hydrogencarbonate of 3 mol/L as precipitating reagent II, controlling terminal PH is 6.5, the copper obtaining thus, nickel, manganese reactive precursor, then 65g silica and 5g aluminium oxide are joined after stirring in reactive precursor and filter, washing, 80～120 DEG C of oven dry of filter cake that obtain 10 hours, again 350 DEG C of roastings 5 hours, catalyst tablet forming after roasting is catalyst, it consists of 30%CuO+3%NiO+2.5%Mn after tested
2o
3/ 60%SiO
2+ 4.5%Al
2o
3.
By 10 restrain catalyst to pack diameter into be that in the tubular reactor of 25 millimeters, passing into hydrogen is 1000 hours at volume space velocity
-1under condition, temperature programming to 200 DEG C is reduced and is obtained Cu-contained catalyst.
Sample after reduction, taking dimethyl oxalate as raw material, methyl alcohol is solvent, 205 DEG C of reaction temperatures, weight space velocity 0.3 hour
-1, hydrogen/ester mol ratio is 80:1, reaction pressure is 2.8MPa, reacts dimethyl oxalate conversion ratio 100%, glycol selectivity 97% under the condition that dimethyl oxalate mass percent is 20%.
[embodiment 2]
According to each step and the condition of [embodiment 1], be the 20%CuO+5%Cu+2%BaO+CoO3.5%MoO that consists of of catalyst
3/ 69 SiO
2+ 0.5%Al
2o
3.
By 10 restrain catalyst to pack diameter into be that in the tubular reactor of 25 millimeters, passing into hydrogen is 1500 hours at volume space velocity
-1temperature programming to 230 DEG C is reduced and is obtained Cu-contained catalyst.
Sample after reduction, taking dimethyl oxalate as raw material, methyl alcohol is solvent, 210 DEG C of reaction temperatures, weight space velocity 0.8 hour
-1, hydrogen/ester mol ratio is 80:1, reaction pressure is 2.8MPa, and under the condition that dimethyl oxalate mass percent is 20%, dimethyl oxalate conversion ratio 100%, glycol selectivity 96%.
[embodiment 3]
According to each step and the condition of [embodiment 1], be the 10%CuO+15%Cu+3%ZnO+3%Fe that consists of of catalyst
2o
3/ 60%SiO
2+ 8%Al
2o
3.
By 10 restrain catalyst to pack diameter into be that in the tubular reactor of 25 millimeters, passing into hydrogen is 2000 hours at volume space velocity
-1temperature programming to 260 DEG C is reduced and is obtained Cu-contained catalyst.
Sample after reduction, taking dimethyl oxalate as raw material, methyl alcohol is solvent, 215 DEG C of reaction temperatures, weight space velocity 1 hour
-1, hydrogen/ester mol ratio is 70:1, reaction pressure is 2.8MPa, and under the condition that dimethyl oxalate mass percent is 20%, dimethyl oxalate conversion ratio 100%, glycol selectivity 96%.
[embodiment 4]
According to each step and the condition of [embodiment 1], just catalyst consists of 10%CuO+10%Cu+1.5%Mo
2o
3+ 0.1% Fe
2o
3/ 10.5%Al
2o
3+ 68% SiO
2.
By 10 restrain catalyst to pack diameter into be that in the tubular reactor of 25 millimeters, passing into hydrogen is 1500 hours at volume space velocity
-1temperature programming to 280 DEG C is reduced and is obtained Cu-contained catalyst.
Sample after reduction, taking dimethyl oxalate as raw material, methyl alcohol is solvent, 218 DEG C of reaction temperatures, weight space velocity 1.5 hours
-1, hydrogen/ester mol ratio is 60:1, reaction pressure is 2.8MPa, and under the condition that dimethyl oxalate mass percent is 20%, dimethyl oxalate conversion ratio 100%, glycol selectivity 95%.
[embodiment 5]
According to each step and the condition of [embodiment 1], just catalyst consists of 10%CuO+20%Cu+3%Fe
2o
3+ 2%CaO/ 63%SiO
2+ 2% Al
2o
3.
By 10 restrain catalyst to pack diameter into be that in the tubular reactor of 25 millimeters, passing into hydrogen is 1500 hours at volume space velocity
-1temperature programming to 220 DEG C is reduced and is obtained Cu-contained catalyst.
Sample after reduction, taking dimethyl oxalate as raw material, methyl alcohol is solvent, 215 DEG C of reaction temperatures, weight space velocity 1 hour
-1, hydrogen/ester mol ratio is 100:1, reaction pressure is 2.8MPa, and under the condition that dimethyl oxalate mass percent is 20%, dimethyl oxalate conversion ratio 100%, glycol selectivity 95%.
[embodiment 6]
According to each step and the condition of [embodiment 1], just catalyst consists of 20%CuO+5%Cu+2%MgO+3%Mn
2o
3/ 20% SiO
2+ 50% Al
2o
3.
By 10 restrain catalyst to pack diameter into be that in the tubular reactor of 25 millimeters, passing into hydrogen is 1500 hours at volume space velocity
-1temperature programming to 220 DEG C is reduced and is obtained Cu-contained catalyst.
Sample after reduction, taking diethy-aceto oxalate as raw material, methyl alcohol is solvent, 220 DEG C of reaction temperatures, weight space velocity 1 hour
-1, hydrogen/ester mol ratio is 80:1, reaction pressure is 2.8MPa, and under the condition that diethy-aceto oxalate mass percent is 20%, dimethyl oxalate conversion ratio 99%, glycol selectivity 96%.
[embodiment 7]
According to each step and the condition of [embodiment 1], just catalyst consists of 20%CuO+5%Cu+2%AgO+3%Mn
2o
3/ 70%SiO
2
By 10 restrain catalyst to pack diameter into be that in the tubular reactor of 25 millimeters, the gaseous mixture that passes into hydrogen and nitrogen is 1500 hours at volume space velocity
-1temperature programming to 220 DEG C is reduced and is obtained Cu-contained catalyst.
Sample after reduction, taking dimethyl oxalate as raw material, methyl alcohol is solvent, 220 DEG C of reaction temperatures, weight space velocity 1 hour
-1, hydrogen/ester mol ratio is 80:1, reaction pressure is 2.8MPa, and under the condition that dimethyl oxalate mass percent is 20%, dimethyl oxalate conversion ratio 99%, glycol selectivity 95.2%.
[embodiment 8]
According to each step and the condition of [embodiment 1], be the 20%CuO+5%Cu+2%BaO+CoO3.5%MoO that consists of of catalyst
3/ 69.5%ZSM-5.
By 10 restrain catalyst to pack diameter into be that in the tubular reactor of 25 millimeters, passing into hydrogen is 1500 hours at volume space velocity
-1temperature programming to 230 DEG C is reduced and is obtained Cu-contained catalyst.
Sample after reduction, taking dimethyl oxalate as raw material, methyl alcohol is solvent, 210 DEG C of reaction temperatures, weight space velocity 0.7 hour
-1, hydrogen/ester mol ratio is 80:1, reaction pressure is 2.8MPa, and under the condition that dimethyl oxalate mass percent is 20%, dimethyl oxalate conversion ratio 100%, glycol selectivity 95%.
[comparative example 1]
According to each step and the condition of [embodiment 1], be the 35.5%CuO/60%SiO that consists of of catalyst
2+ 4.5%Al
2o
3.
10 restrain catalyst to pack diameter into be that in the tubular reactor of 25 millimeters, passing into hydrogen is 1500 hours at volume space velocity
-1temperature programming to 200 DEG C is reduced and is obtained Cu-contained catalyst.
Sample after reduction, taking dimethyl oxalate as raw material, methyl alcohol is solvent, 230 DEG C of reaction temperatures, weight space velocity 0.6 hour
-1, hydrogen/ester mol ratio is 80:1, reaction pressure is 2.8MPa, and under the condition that dimethyl oxalate mass percent is 20%, dimethyl oxalate conversion ratio 97%, glycol selectivity 83%.
[comparative example 2]
According to each step and the condition of [embodiment 1], be the 35%CuO+0.5%BaO/60%SiO that consists of of catalyst
2+ 4.5%Al
2o
3.
10 restrain catalyst to pack diameter into be that in the tubular reactor of 25 millimeters, passing into hydrogen is 1500 hours at volume space velocity
-1temperature programming to 200 DEG C is reduced and is obtained Cu-contained catalyst.
Sample after reduction, taking dimethyl oxalate as raw material, methyl alcohol is solvent, 232 DEG C of reaction temperatures, weight space velocity 0.6 hour
-1, hydrogen/ester mol ratio is 80:1, reaction pressure is 2.8MPa, and under the condition that dimethyl oxalate mass percent is 20%, dimethyl oxalate conversion ratio 100%, glycol selectivity 85%.
[comparative example 3]
According to each step and the condition of [embodiment 1], be the 20%CuO+15Cu+0.5%NiO/60%SiO that consists of of catalyst
2+ 4.5%Al
2o
3.
10 restrain catalyst to pack diameter into be that in the tubular reactor of 25 millimeters, passing into hydrogen is 1500 hours at volume space velocity
-1temperature programming to 200 DEG C is reduced and is obtained Cu-contained catalyst.
Sample after reduction, taking dimethyl oxalate as raw material, methyl alcohol is solvent, 232 DEG C of reaction temperatures, weight space velocity 0.6 hour
-1, hydrogen/ester mol ratio is 80:1, reaction pressure is 2.8MPa, and under the condition that dimethyl oxalate mass percent is 20%, dimethyl oxalate conversion ratio 97%, glycol selectivity 82%.
[comparative example 4]
According to each step and the condition of [embodiment 1], be the 20%CuO+14Cu+1.5%Mn that consists of of catalyst
2o
3/ 60%SiO
2+ 4.5%Al
2o
3.
10 restrain catalyst to pack diameter into be that in the tubular reactor of 25 millimeters, passing into hydrogen is 1500 hours at volume space velocity
-1temperature programming to 200 DEG C is reduced and is obtained Cu-contained catalyst.
Sample after reduction, taking dimethyl oxalate as raw material, methyl alcohol is solvent, 232 DEG C of reaction temperatures, weight space velocity 0.6 hour
-1, hydrogen/ester mol ratio is 80:1, reaction pressure is 2.8MPa, and under the condition that dimethyl oxalate mass percent is 20%, dimethyl oxalate conversion ratio 96%, glycol selectivity 80%.
[comparative example 5]
According to each step and the condition of [embodiment 1], be the 10%CuO+20%Cu+0.3%Fe that consists of of catalyst
2o
3+ 6%CaO+65% SiO
2, wherein the mol ratio of auxiliary agent iron and auxiliary agent calcium is 0.018.
10 restrain catalyst to pack diameter into be that in the tubular reactor of 25 millimeters, passing into hydrogen is 1500 hours at volume space velocity
-1temperature programming to 200 DEG C is reduced and is obtained Cu-contained catalyst.
Sample after reduction, taking dimethyl oxalate as raw material, methyl alcohol is solvent, 232 DEG C of reaction temperatures, weight space velocity 0.6 hour
-1, hydrogen/ester mol ratio is 80:1, reaction pressure is 2.8MPa, and under the condition that dimethyl oxalate mass percent is 20%, dimethyl oxalate conversion ratio 100%, glycol selectivity 85%.
[comparative example 6]
According to each step and the condition of [embodiment 1], be the 10%CuO+20%Cu+4.7%Fe that consists of of catalyst
2o
3+ 0.3%CaO+65% SiO
2, wherein the mol ratio of auxiliary agent iron and auxiliary agent calcium is 11.4.
10 restrain catalyst to pack diameter into be that in the tubular reactor of 25 millimeters, passing into hydrogen is 1500 hours at volume space velocity
-1temperature programming to 200 DEG C is reduced and is obtained Cu-contained catalyst.
Sample after reduction, taking dimethyl oxalate as raw material, methyl alcohol is solvent, 232 DEG C of reaction temperatures, weight space velocity 0.6 hour
-1, hydrogen/ester mol ratio is 80:1, reaction pressure is 2.8MPa, and under the condition that dimethyl oxalate mass percent is 20%, dimethyl oxalate conversion ratio 99%, glycol selectivity 80%.
[comparative example 7]
Use the catalyst of [embodiment 1] just to change reaction condition.
By 10 restrain catalyst to pack diameter into be that in the tubular reactor of 25 millimeters, passing into hydrogen is 800 hours at volume space velocity
-1temperature programming to 350 DEG C is reduced and is obtained Cu-contained catalyst.
Sample after reduction, taking dimethyl oxalate as raw material, methyl alcohol is solvent, 210 DEG C of reaction temperatures, weight space velocity 0.8 hour
-1, hydrogen/ester mol ratio is 50:1, reaction pressure is 2.8MPa, and under the condition that dimethyl oxalate mass percent is 20%, dimethyl oxalate conversion ratio 92%, glycol selectivity 76%.
Claims (10)
1. a catalyst for hydrogenation of oxalate for preparing ethylene glycol, by weight percentage, comprises following component:
A) 5 ~ 50% at least one that are selected from the oxide of copper or copper;
B) >0 ~ 10% is selected from least one metal or the oxide in barium, zinc, chromium, calcium, magnesium, zirconium, silver, nickel or molybdenum;
C) >0 ~ 10% is selected from least one metal or the oxide in cobalt, manganese, cerium, iron or lanthanum;
D) 30～94% at least one carrier being selected from aluminium oxide, silica or molecular sieve.
2. the catalyst of hydrogenation of oxalate for preparing ethylene glycol according to claim 1, it is characterized in that by weight percentage, component consumption a) is 10～30%, and component consumption b) is 0.1～7%, component consumption c) is 0.03～7%, and component consumption d) is 60～89%.
3. the catalyst of hydrogenation of oxalate for preparing ethylene glycol according to claim 1, is characterized in that component b) is selected from least one metal or the oxide in barium, zinc, calcium, magnesium, silver, nickel or molybdenum; Component c) is selected from least one metal or the oxide in cobalt, manganese or iron.
4. the catalyst of hydrogenation of oxalate for preparing ethylene glycol according to claim 1, is characterized in that component is b) 0.3～10 with component metal total mole number ratio c).
5. the catalyst of hydrogenation of oxalate for preparing ethylene glycol according to claim 1, is characterized in that at least one in ZSM or MCM molecular sieve of described molecular screening.
6. the catalyst of hydrogenation of oxalate for preparing ethylene glycol according to claim 1, is characterized in that carrier is selected from least one in aluminium oxide or silica.
7. the catalyst of hydrogenation of oxalate for preparing ethylene glycol according to claim 6, is characterized in that carrier is selected from the mixture of aluminium oxide and silica, and wherein the weight ratio of aluminium oxide and silica is 0.1～5.
8. a method for hydrogenation of oxalate for preparing ethylene glycol, is included under hydrogenation conditions, and oxalate raw material is contacted with catalyst claimed in claim 1.
9. the method for hydrogenation of oxalate for preparing ethylene glycol according to claim 8, is characterized in that described hydrogenation conditions comprises: 170～260 DEG C of reaction temperatures, weight space velocity 0.1～1.5 hour
-1, hydrogen ester is than 30～200, reaction pressure 1.5～4MPa.
10. the method for hydrogenation of oxalate for preparing ethylene glycol according to claim 8, is characterized in that oxalate raw material is dimethyl oxalate or diethy-aceto oxalate.
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| CN108273509A (en) * | 2017-01-06 | 2018-07-13 | 平顶山市汇通达科技开发有限公司 | A kind of catalyst and preparation method thereof for preparing glycol by hydrogenating oxalate |
| CN108654617A (en) * | 2017-03-28 | 2018-10-16 | 中国科学院大连化学物理研究所 | Hydrogenation of oxalate for preparing ethylene glycol catalyst carrier method of modifying and catalyst and application |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475442A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Method for preparing ethylene glycol from oxalic ester |
| CN101992127A (en) * | 2009-08-31 | 2011-03-30 | 中国石油化工股份有限公司 | Catalyst reduction method |
| CN101993342A (en) * | 2009-08-31 | 2011-03-30 | 中国石油化工股份有限公司上海石油化工研究院 | Method for preparing glycol by using oxalic ester |
| CN102649062A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Catalyst for production of hydroxyacetic acid ester by oxalate through hydrogenation |
| CN102649699A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for preparing ethylene glycol through catalytic hydrogenation reaction by oxalic ester |
| US20120298554A1 (en) * | 2011-05-26 | 2012-11-29 | Uop Llc | Fibrous substrate-based hydroprocessing catalysts and associated methods |
-
2013
- 2013-03-13 CN CN201310078824.6A patent/CN104043457A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475442A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Method for preparing ethylene glycol from oxalic ester |
| CN101992127A (en) * | 2009-08-31 | 2011-03-30 | 中国石油化工股份有限公司 | Catalyst reduction method |
| CN101993342A (en) * | 2009-08-31 | 2011-03-30 | 中国石油化工股份有限公司上海石油化工研究院 | Method for preparing glycol by using oxalic ester |
| CN102649062A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Catalyst for production of hydroxyacetic acid ester by oxalate through hydrogenation |
| CN102649699A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for preparing ethylene glycol through catalytic hydrogenation reaction by oxalic ester |
| US20120298554A1 (en) * | 2011-05-26 | 2012-11-29 | Uop Llc | Fibrous substrate-based hydroprocessing catalysts and associated methods |
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| CN109180429A (en) * | 2018-08-03 | 2019-01-11 | 沂州科技有限公司 | A method of ethylene glycol is prepared with coke-stove gas, coal gas of converter |
| CN109180429B (en) * | 2018-08-03 | 2019-08-09 | 沂州科技有限公司 | A method of ethylene glycol is prepared with coke-stove gas, coal gas of converter |
| CN111346638A (en) * | 2018-12-20 | 2020-06-30 | 万华化学集团股份有限公司 | Catalyst for preparing α -phenethyl alcohol by acetophenone hydrogenation |
| CN111346638B (en) * | 2018-12-20 | 2022-11-04 | 万华化学集团股份有限公司 | Catalyst for preparing alpha-phenethyl alcohol by acetophenone hydrogenation |
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