CN104492429A - Catalyst and method for synthesizing methyl glycollate and ethylene glycol by virtue of dimethyl oxalate hydrogenation - Google Patents
Catalyst and method for synthesizing methyl glycollate and ethylene glycol by virtue of dimethyl oxalate hydrogenation Download PDFInfo
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- CN104492429A CN104492429A CN201410785366.4A CN201410785366A CN104492429A CN 104492429 A CN104492429 A CN 104492429A CN 201410785366 A CN201410785366 A CN 201410785366A CN 104492429 A CN104492429 A CN 104492429A
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Abstract
The invention relates to a catalyst and a method for synthesizing methyl glycollate and ethylene glycol by virtue of dimethyl oxalate hydrogenation, and mainly aims to solve the problems that the catalyst in the prior art is low in activity and poor in stability. The invention adopts a technical scheme that the catalyst for synthesizing methyl glycollate and ethylene glycol by virtue of dimethyl oxalate hydrogenation comprises the following components in percentage by mass: 0.01-30% of an active component Ag, 0-10% of an auxiliary agent and the balance of a carrier, wherein the carrier is at least one of titanium dioxide and a carbon carrier, the active component is Ag, and the auxiliary agent is at least one of Cu, Ca, Ba, Mg, Au, Ru, Rh, Pd, Pt, Ni, Zn and Zr; and the method for synthesizing methyl glycollate and ethylene glycol by virtue of dimethyl oxalate hydrogenation is also adopted. Therefore, the problems are well solved by the technical scheme, and the technical scheme can be used in a process for synthesizing methyl glycollate and ethylene glycol by virtue of dimethyl oxalate hydrogenation.
Description
Technical field
The present invention relates to the Catalyst And Method of a kind of Hydrogenation of Dimethyl Oxalate synthesizing methyl glycolate and ethylene glycol.
Background technology
Methyl glycollate (HOCH
2cOOCH
3, MG) and be the important chemical products of a class and intermediate, be widely used in many fields such as chemical industry, medicine, agricultural chemicals, feed, dyestuff and spices.Mainly comprise: 1) as the fine solvent of fiber, resin and rubber; 2) further hydrogenating reduction preparing ethylene glycol; 3) carbonylation malonic acid (list) methyl esters; 4) ammonia solution glycine; 5) oxidative dehydrogenation glyoxalic acid methylester; 6) glycolic processed etc. is hydrolyzed.Wherein, the potential market of glycolic is particularly important, and what at present the synthesis of external glycolic mainly adopted is take formaldehyde as the carbonylation route of raw material or formaldehyde and hydrogen cyanide reaction scheme, and equipment is corrosion-resistant and high pressure resistant requirement is higher, disposablely have high input, large-scale production has difficulties; And domestic process route producing and ethanol in next life acid of also always continuing to use monoxone and soda lye hybrid reaction resterification, and chloroacetic production adopts acetic acid to be raw material, sulphur is catalyst, chlorine method is produced, although process is simple, but seriously corroded in production process, pollute large, cost is high, thus causes this method can not heavy industrialization application.Therefore exploitation eco-friendly synthetic route is needed badly.
Along with the growing tension of petroleum resources, to carry out with natural gas or coal be raw material, and C1 chemical industry has more and more important realistic meaning.Produce dimethyl oxalate (DMO) by synthesis gas and then be an important route of C1 chemical industry by DMO preparation of ethanol by hydrogenating acid methyl esters.
Prepare methyl glycollate by Hydrogenation of Dimethyl Oxalate route, current emphasis is still in the exploitation of high performance catalyst.Other routes relatively, the advantage of this route is that hydrogenating materials can be prepared with the synthesis gas of C1 route, the route that Fixed Bed Gas Phase hydrogenation generates methyl glycollate easily realizes continuous prodution, and the ethylene glycol of hydrogenation by-product is also the bulk chemical that a kind of added value is higher.Therefore, in catalyst R&D process, improve methyl glycollate optionally simultaneously, need the formation reducing other non-ethylene glycol accessory substances further.
Japan Patent JP 06135895 comparatively early reports prepared by dimethyl oxalate plus hydrogen methyl glycollate, with Cu-Ag/SiO
2catalyst, adopt copper ammonia complexation ammonia still process legal system standby, the yield of methyl glycollate is lower than 70%, and DMO does not transform completely when high yield, and this will be separated to later product and bring difficulty; University Of Tianjin also illustrates the research to this reaction at patent CN101138730A, employing be improved silica dip loading copper silver catalyst, the result that catalytic performance and Japan Patent are reported is suitable.
United States Patent (USP) (US4409395A) adopts silica or alumina load silver or palladium as the catalyst of preparing ethanol by oxalate hydrogenation acid esters, this catalyst has higher hydrogenation activity, but selective still the treating of ethyl glycolate is improved, the generation of accessory substance need be reduced by further optimization of catalysts preparation, improve the economy of application in the future; Meanwhile, be active component relatively with copper, active component is catalyst more easy-sintering in course of reaction of silver, thus causes the easy inactivation of catalyst.For this reason, other auxiliary agents need generally be introduced to improve the stability of silica supported silver catalyst.Therefore in view of alumina support and the comparatively strong interaction of silver, the silver catalyst reported also has employing aluminium oxide to be carrier, but because oxalate hydrogenation can not be too high to acidity of catalyst requirement, need be generally carrier with Alpha's aluminium oxide that specific area is minimum, and will be suppressed at the low temperature active of loading type silver catalyst in such cases, thus affect the hydrogenation efficiency of catalyst.
In addition, existing patent (US4628129) and research paper (Chem.Commun., 2013,49,5195-5197) confirm, silica support at high temperature can with the formation of methanol methyl silicate, and in Hydrogenation of Dimethyl Oxalate course of reaction, just produce methyl alcohol, therefore, when silver catalyst adopts silica to be carrier, the methyl silicate that course of reaction is formed will easily mix in the product, and this can bring higher extra cost (mainly purification of products) to the application of product (as cosmetics).
Summary of the invention
One of technical problem to be solved by this invention is the problem of lower, the less stable of catalyst activity in prior art, provides the catalyst of a kind of new Hydrogenation of Dimethyl Oxalate synthesizing methyl glycolate and ethylene glycol.This catalyst is used in Hydrogenation of Dimethyl Oxalate synthesizing methyl glycolate and ethylene glycol technique, has that activity is higher, the good advantage of stability.Two of technical problem to be solved by this invention is to provide a kind of method of Hydrogenation of Dimethyl Oxalate synthesizing methyl glycolate corresponding with one of technical solution problem and ethylene glycol.
For one of solving the problem, the technical solution used in the present invention is as follows: the catalyst of a kind of Hydrogenation of Dimethyl Oxalate synthesizing methyl glycolate and ethylene glycol, comprise that mass fraction is 0.01 ~ 30% active component A g, mass fraction is the auxiliary agent of 0 ~ 10%, all the other are carrier; Described carrier is at least one in titanium dioxide and carbon carrier, and described active component is Ag, and described auxiliary agent is at least one in Cu, Ca, Ba, Mg, Au, Ru, Rh, Pd, Pt, Ni, Zn, Zr.
In technique scheme, preferably, described catalyst comprises that mass fraction is 1 ~ 15% active component A g, mass fraction is the auxiliary agent of 0.1 ~ 5%; Described titanium dioxide comprises dense phase and porous titanium oxide and regular type titanium oxide, and carbon carrier comprises active carbon, CNT, carbon fiber.
In technique scheme, preferably, described catalyst needs in use through H
2activation, activation temperature 100 ~ 400 DEG C, soak time 0.5 ~ 8 hour, air speed is 500 ~ 10000h
-1.
In technique scheme, preferably, described catalyst adopts infusion process or deposition-precipitation method preparation.
In technique scheme, preferably, when described catalyst adopts infusion process to prepare, comprise the following steps:
1) maceration extract will be mixed with containing soluble silver salt or other metal salt precursor deionized waters or ammonia solvent;
2) carrier is shaping in advance, carrier forming method comprises spray shaping, forming oil column, rotational forming, extruded moulding and compression molding;
3) then the carrier of forming is put into maceration extract to soak, soaking temperature is 10-35 DEG C, and soak time is 1 ~ 10 hour;
4) separated from maceration extract by solid, drying 1 ~ 24 hour at 80 ~ 140 DEG C, more namely 300 ~ 800 DEG C of roastings obtain catalyst in 1 ~ 24 hour in Muffle furnace, calcination atmosphere is air or nitrogen.
In technique scheme, preferably, when described catalyst adopts deposition-precipitation method to prepare, comprise the following steps:
1) carrier is joined in deionized water, in stirred at ambient temperature 0 ~ 24 hour, be prepared into suspension;
2) metallic solution will be mixed with containing soluble silver salt or other metal salt precursor deionized waters or ammonia solvent;
3) metallic solution is joined in above-mentioned suspension, at room temperature stir 0 ~ 12 hour, obtain mixed liquor;
4) NaOH of 0.01 ~ 1mol/L or sodium carbonate liquor are added drop-wise in above-mentioned mixed liquor, at room temperature stir 0 ~ 24 hour continuously, sample is through filtering, washing, drying 1 ~ 24 hour at 80 ~ 140 DEG C, in Muffle furnace, 300 ~ 800 DEG C of roastings obtain catalyst in 1 ~ 24 hour again, and calcination atmosphere is air or nitrogen;
5) by shaping of catalyst, shaping of catalyst method comprises spray shaping, forming oil column, rotational forming, extruded moulding and compression molding.
In technique scheme, more preferably, described soluble silver salt comprises silver nitrate, silver sulfate or actol, and described Cu, Ca, Ba, Mg, Au, Ru, Rh, Pd, Pt, Ni, Zn or Zr metal salt precursor is water-soluble slaine, comprises nitrate, organic salt.
In technique scheme, more preferably, adopt different impregnation sequence to support active component A g and auxiliary agent, comprise carrier and first flood Ag, after catalyst drying, then impregnation aids, then drying and roasting; Carrier first floods Ag, after catalyst drying and roasting, then impregnation aids, then drying and roasting; The first impregnation aids of carrier, after catalyst drying, then floods Ag; The first impregnation aids of carrier, after catalyst drying and roasting, then floods Ag; Carrier floods Ag and auxiliary agent simultaneously.
For solve the problem two, the technical solution used in the present invention is as follows: a kind of method of Hydrogenation of Dimethyl Oxalate synthesizing methyl glycolate and ethylene glycol, use described catalyst, reaction temperature be 150 ~ 350 DEG C, reaction pressure is 0 ~ 4MpaG, hydrogen ester mol ratio is 2 ~ 100, dimethyl oxalate liquid hourly space velocity (LHSV) is 0.1 ~ 2h
-1condition under, dimethyl oxalate is generated by hydrogenation and comprises the product of methyl glycollate and ethylene glycol.
In technique scheme, preferably, described reaction temperature is 160 ~ 250 DEG C, reaction pressure is 0.1 ~ 2MpaG, hydrogen ester mol ratio is 25 ~ 50.
The catalyst that the present invention is used for Hydrogenation of Dimethyl Oxalate synthesizing methyl glycolate and ethylene glycol adopts titanium dioxide, carbon carrier or both combinations as carrier, active high, selective good, reaction condition is gentle, catalyst stability is good, for the catalyst preparing high stability provides a kind of effective way, thus effectively solve prior art Problems existing, achieve good technique effect.
Detailed description of the invention
The activity rating of catalyst carries out in fixed bed stainless steel pressurized reactor, and reaction tube is internal diameter 15mm, long 600mm.Reaction pressure is controlled by front and back pressure maintaining valve and counterbalance valve, and reaction temperature fluctuation range is at ± 0.5 DEG C.Load 2 gram of 20 ~ 30 object catalyst in reactor, bed loads inert stone sand up and down to be prevented from managing interior gas channel.Dimethyl oxalate or its methanol solution are squeezed into gasifier by measuring pump vaporize, from steel cylinder hydrogen through pressure maintaining valve decompression after, controlled by high pressure mass flowmenter and measure its flow, enter gasifier and the dimethyl oxalate from high-pressure metering pump fully mix after and flow to and carry out hydrogenation reaction into reactor.Product is collected and is analyzed after cooling.
[embodiment 1]
Getting silver nitrate 23.6g is dissolved in 100mL water, is immersed by the 100g titanium dioxide of forming in the solution of joining, and soaks 2 hours, after fully absorbing, isolate solid, drying 4 hours at 80 DEG C, then roasting obtained this catalyst after 5 hours at 400 DEG C.Get 20 ~ 30 object particles after being sieved by this catalyst, filled in fixed bed reactors, pass into hydrogen and reduce 4 hours at 300 DEG C, then at reaction temperature 250 DEG C, pressure 2.5Mpa, hydrogen ester mol ratio 50, feeding liquid hourly space velocity 0.7h
-1condition under carry out hydrogenation reaction, the reaction result obtained: dimethyl oxalate conversion ratio is 98.3%, methyl glycollate selective 94.1%, and the selective of ethylene glycol is 5.1%, methyl glycollate yield 92.5%, and does not detect carrier component in the product.
[embodiment 2]
Getting silver nitrate 23.6g is dissolved in 90mL water, is immersed by the 100g titanium dioxide of forming in the solution of joining, and soaks 2 hours, after absorbing completely, by solid at 80 DEG C dry 4 hours, then at 300 DEG C roasting this catalyst obtained after 4 hours.Get 20 ~ 30 object particles after being sieved by this catalyst, filled in fixed bed reactors, pass into hydrogen and reduce 4 hours at 300 DEG C, then at reaction temperature 240 DEG C, pressure 2.5Mpa, hydrogen ester mol ratio 50, feeding liquid hourly space velocity 0.7h
-1condition under carry out hydrogenation reaction, the reaction result obtained: dimethyl oxalate conversion ratio is 98.2%, methyl glycollate selective 93.1%, and the selective of ethylene glycol is 6.1%, methyl glycollate yield 91.4%, and does not detect carrier component in the product.
[embodiment 3]
Getting silver nitrate 23.6g is dissolved in 100mL water, is immersed by 100g CNT in the solution of joining, and soaks 2 hours, after fully absorbing, isolate solid, drying 4 hours at 80 DEG C, then roasting obtained this catalyst after 5 hours at 400 DEG C.Get 20 ~ 30 object particles after being sieved by this catalyst, filled in fixed bed reactors, pass into hydrogen and reduce 4 hours at 300 DEG C, then at reaction temperature 250 DEG C, pressure 2.5Mpa, hydrogen ester mol ratio 50, feeding liquid hourly space velocity 0.7h
-1condition under carry out hydrogenation reaction, the reaction result obtained: dimethyl oxalate conversion ratio is 99.3%, methyl glycollate selective 97.1%, and the selective of ethylene glycol is 2.1%, methyl glycollate yield 96.4%, and does not detect carrier component in the product.
[embodiment 4]
20g active carbon is added in deionized water, stirs 2 hours, obtain suspension.After 5g silver nitrate is dissolved completely, join in suspension, stir 2 hours.The sodium hydroxide solution of 0.1mol/L is dropwise added drop-wise in above-mentioned solution, at room temperature fully stirs 8 hours, filtrations, lotion, at 80 DEG C dry 6 hours, then roasting obtained this catalyst after 4 hours at 400 DEG C.Get 20 ~ 30 object particles after being sieved by this catalyst, filled in fixed bed reactors, at 240 DEG C, activate 4 hours, then at reaction temperature 250 DEG C, pressure 3Mpa, hydrogen ester mol ratio 25, feeding liquid hourly space velocity 1h
-1condition under carry out hydrogenation reaction, the reaction result obtained: dimethyl oxalate conversion ratio is 99.3%, methyl glycollate selective 92.4%, and the selective of ethylene glycol is 6.7%, methyl glycollate yield 91.8%.
[embodiment 5]
Get silver nitrate 5g, copper nitrate 1g be dissolved in 20mL water, the 20g titanium dioxide of forming is immersed in the solution of joining, soak 4 hours, after fully absorbing, isolate solid, dry 3 hours at 100 DEG C, then at 500 DEG C roasting this catalyst obtained after 2 hours.Get 20 ~ 30 object particles after being sieved by this catalyst, filled in fixed bed reactors, at 250 DEG C, activate 2 hours, then at reaction temperature 240 DEG C, pressure 3Mpa, hydrogen ester mol ratio 50, feeding liquid hourly space velocity 1h
-1condition under carry out hydrogenation reaction, the reaction result obtained: dimethyl oxalate conversion ratio is 99.3%, methyl glycollate selective 85.1%, selective 14.0% of ethylene glycol, methyl glycollate yield 84.5%.
[embodiment 6]
Getting silver nitrate 5g is dissolved in 20mL water, is immersed by the 20g titanium dioxide of forming in the solution of joining, and soaks 4 hours, after fully absorbing, isolate solid, dries 3 hours at 100 DEG C; Then getting copper nitrate 1g is dissolved in 20ml water, dried solid is immersed institute and joins in solution.Soak 4 hours, after fully absorbing, isolate solid, then roasting obtained this catalyst after 2 hours at 500 DEG C.Get 20 ~ 30 object particles after being sieved by this catalyst, filled in fixed bed reactors, at 250 DEG C, activate 2 hours, then at reaction temperature 240 DEG C, pressure 3Mpa, hydrogen ester mol ratio 50, feeding liquid hourly space velocity 1h
-1condition under carry out hydrogenation reaction, the reaction result obtained: dimethyl oxalate conversion ratio is 99.2%, methyl glycollate selective 88.1%, selective 11.0% of ethylene glycol, methyl glycollate yield 87.4%.
[embodiment 7]
Adopt the catalyst prepared by method for preparing catalyst in embodiment 1, by 2g Catalyst packing in fixed bed reactors, at 300 DEG C, activate 4 hours, then at reaction temperature 250 DEG C, pressure 2.5Mpa, hydrogen ester mol ratio 50, feeding liquid hourly space velocity 0.7h
-1condition under carry out hydrogenation reaction, catalyst stabilization run 300h, have no obvious inactivation, concrete reaction result is in table 1.
Table 1
[comparative example 1]
Get silver nitrate 23.6g to be dissolved in 100mL water, add ammoniacal liquor and make silver ammino solution, 100g silica is immersed in the solution of joining, makes catalyst precursor.Get 20 ~ 30 object particles after being sieved by this catalyst, filled in fixed bed reactors, pass into hydrogen and reduce 4 hours at 300 DEG C, then at reaction temperature 250 DEG C, pressure 2.5Mpa, hydrogen ester mol ratio 50, feeding liquid hourly space velocity 0.7h
-1condition under carry out hydrogenation reaction, the reaction result obtained: dimethyl oxalate conversion ratio is 96.2%, methyl glycollate selective 91.6%, and the selective of ethylene glycol is 6.6%, methyl glycollate yield 88.1%, and detects carrier component in the product.
Claims (10)
1. for a catalyst for Hydrogenation of Dimethyl Oxalate synthesizing methyl glycolate and ethylene glycol, comprise that mass fraction is 0.01 ~ 30% active component A g, mass fraction is the auxiliary agent of 0 ~ 10%, all the other are carrier; Described carrier is at least one in titanium dioxide and carbon carrier, and described active component is Ag, and described auxiliary agent is at least one in Cu, Ca, Ba, Mg, Au, Ru, Rh, Pd, Pt, Ni, Zn, Zr.
2. the catalyst of Hydrogenation of Dimethyl Oxalate synthesizing methyl glycolate and ethylene glycol according to claim 1, is characterized in that described catalyst comprises that mass fraction is 1 ~ 15% active component A g, mass fraction is the auxiliary agent of 0.1 ~ 5%; Described titanium dioxide comprises dense phase and porous titanium oxide and regular type titanium oxide, and carbon carrier comprises active carbon, CNT, carbon fiber.
3. the catalyst of Hydrogenation of Dimethyl Oxalate synthesizing methyl glycolate and ethylene glycol according to claim 1, it is characterized in that described catalyst needs to activate through H2 in use, activation temperature 100 ~ 400 DEG C, soak time 0.5 ~ 8 hour, air speed is 500 ~ 10000h
-1.
4. the catalyst of Hydrogenation of Dimethyl Oxalate synthesizing methyl glycolate and ethylene glycol according to claim 1, is characterized in that described catalyst adopts infusion process or deposition-precipitation method preparation.
5. the catalyst of Hydrogenation of Dimethyl Oxalate synthesizing methyl glycolate and ethylene glycol according to claim 4, when it is characterized in that described catalyst adopts infusion process to prepare, comprises the following steps:
1) maceration extract will be mixed with containing soluble silver salt or other metal salt precursor deionized waters or ammonia solvent;
2) carrier is shaping in advance, carrier forming method comprises spray shaping, forming oil column, rotational forming, extruded moulding and compression molding;
3) then the carrier of forming is put into maceration extract to soak, soaking temperature is 10-35 DEG C, and soak time is 1 ~ 10 hour;
4) separated from maceration extract by solid, drying 1 ~ 24 hour at 80 ~ 140 DEG C, more namely 300 ~ 800 DEG C of roastings obtain catalyst in 1 ~ 24 hour in Muffle furnace, calcination atmosphere is air or nitrogen.
6. the catalyst of Hydrogenation of Dimethyl Oxalate synthesizing methyl glycolate and ethylene glycol according to claim 4, when it is characterized in that described catalyst adopts deposition-precipitation method to prepare, comprises the following steps:
1) carrier is joined in deionized water, in stirred at ambient temperature 0 ~ 24 hour, be prepared into suspension;
2) metallic solution will be mixed with containing soluble silver salt or other metal salt precursor deionized waters or ammonia solvent;
3) metallic solution is joined in above-mentioned suspension, at room temperature stir 0 ~ 12 hour, obtain mixed liquor;
4) NaOH of 0.01 ~ 1mol/L or sodium carbonate liquor are added drop-wise in above-mentioned mixed liquor, at room temperature stir 0 ~ 24 hour continuously, sample is through filtering, washing, drying 1 ~ 24 hour at 80 ~ 140 DEG C, in Muffle furnace, 300 ~ 800 DEG C of roastings obtain catalyst in 1 ~ 24 hour again, and calcination atmosphere is air or nitrogen;
5) by shaping of catalyst, shaping of catalyst method comprises spray shaping, forming oil column, rotational forming, extruded moulding and compression molding.
7. the catalyst of Hydrogenation of Dimethyl Oxalate synthesizing methyl glycolate and ethylene glycol according to claim 1,5,6, it is characterized in that described soluble silver salt comprises silver nitrate, silver sulfate or actol, described Cu, Ca, Ba, Mg, Au, Ru, Rh, Pd, Pt, Ni, Zn or Zr metal salt precursor is water-soluble slaine, comprises nitrate, organic salt.
8. according to claim 5 for the catalyst of Hydrogenation of Dimethyl Oxalate synthesizing methyl glycolate and ethylene glycol, it is characterized in that adopting different impregnation sequence to support active component A g and auxiliary agent, comprise carrier and first flood Ag, after catalyst drying, impregnation aids again, then drying and roasting; Carrier first floods Ag, after catalyst drying and roasting, then impregnation aids, then drying and roasting; The first impregnation aids of carrier, after catalyst drying, then floods Ag; The first impregnation aids of carrier, after catalyst drying and roasting, then floods Ag; Carrier floods Ag and auxiliary agent simultaneously.
9. the method for a Hydrogenation of Dimethyl Oxalate synthesizing methyl glycolate and ethylene glycol, use catalyst described in claim 1, reaction temperature be 150 ~ 350 DEG C, reaction pressure is 0 ~ 4MpaG, hydrogen ester mol ratio is 2 ~ 100, dimethyl oxalate liquid hourly space velocity (LHSV) is 0.1 ~ 2h
-1condition under, dimethyl oxalate is generated by hydrogenation and comprises the product of methyl glycollate and ethylene glycol.
10. the method for Hydrogenation of Dimethyl Oxalate synthesizing methyl glycolate and ethylene glycol according to claim 9, is characterized in that described reaction temperature is 160 ~ 250 DEG C, reaction pressure is 0.1 ~ 2MpaG, hydrogen ester mol ratio is 25 ~ 50.
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