CN102649703B - Method adopting oxalate to produce ethylene glycol - Google Patents
Method adopting oxalate to produce ethylene glycol Download PDFInfo
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- CN102649703B CN102649703B CN201110047172.0A CN201110047172A CN102649703B CN 102649703 B CN102649703 B CN 102649703B CN 201110047172 A CN201110047172 A CN 201110047172A CN 102649703 B CN102649703 B CN 102649703B
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Abstract
The invention relates to a method adopting oxalate to produce ethylene glycol, and mainly solves the problem in the prior art that the target product is low in selectivity. The method adopts oxalate as the raw material and comprises the following steps: (a) hydrogen and a first stream raw material enter a first reaction zone to be in contact with a copper-silver-silicon catalyst at first, so as to produce a first stream reaction effluent; and (b) the first stream reaction effluent and a second stream raw material enter at least a second reaction zone to be in contact with a copper-zinc-silicon catalyst, so as to produce a second stream reaction effluent containing ethylene glycol. By adopting the technical scheme, the above problem is better solved, and the method provided by the invention can be used for industrial increase production of ethylene glycol.
Description
Technical field
The present invention relates to a kind of method that adopts preparing ethylene glycol from oxalic ester, particularly about adopting Hydrogenation of Dimethyl Oxalate or oxalic acid diethyl ester hydrogenation to produce the method for ethylene glycol.
Background technology
Ethylene glycol (EG) is a kind of important Organic Chemicals, mainly for the production of poly-vinegar fiber, frostproofer, unsaturated polyester resin, lubricant, softening agent, nonionogenic tenside 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, for the production of special solvent glycol ether etc., purposes is very extensive.
At present, China has exceeded the U.S. becomes the large ethylene glycol consumption of the first in the world big country, and within 2001～2006 years, domestic apparent consumption amount average annual growth rate reaches 17.4%.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 requirement, all need every year a large amount of imports, and import volume is increase year after year situation.
Current, the suitability for industrialized production of domestic and international large-scale ethylene glycol all adopts oxyethane direct hydration, i.e. the legal operational path of pressurized 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 Mendelyeev chemical engineering institute, oil of SPC institute etc. have developed catalyzing epoxyethane hydration legal system ethylene glycol production technology in succession; The companies such as Halcon-SD, UCC, Dow chemistry, Japanese catalyst chemistry and Mitsubishi Chemical have developed NSC 11801 legal system ethylene glycol production technology in succession; The companies such as Dow chemistry have developed EG and methylcarbonate (DMC) coproduction preparing ethylene glycol production technology etc.
Reaction product water content for direct hydration method is high, follow-up equipment (vaporizer) long flow path, equipment is large, energy consumption is high, process total recovery only has 70% left and right, directly affects the production cost of EG.Direct hydration method has significantly reduced water ratio compared with catalytic hydration, has obtained higher EO transformation efficiency and EG selectivity simultaneously.If catalyst stability and correlation engineering technical problem solve well, EO catalytic hydration EG replacement processed on-catalytic hydrating process is trend of the times so.NSC 11801 (EC) legal system no matter aspect EO transformation efficiency, EG selectivity, or all has larger advantage than EO direct hydration method aspect raw material, energy expenditure for the technology of EG, is a kind of method maintaining the leading position.EG and DMC co-production technology can make full use of the CO of oxidation of ethylene by-product
2resource, in existing EO production equipment, only needs the reactions steps that increases production EC just can produce two kinds of very value products, very attractive.
But the common shortcoming of aforesaid method is to need consumption of ethylene resource, and mainly refine by traditional petroleum resources for current ethene, and following one period global oil price by the situation of long-term run at high level, replace oil production ethylene glycol (Non oil-based route with aboundresources, low-cost Sweet natural gas or coal, be again CO route), can possess the advantage of competing mutually with traditional ethene route.Wherein, synthetic gas synthesizes EG new technology, may produce great impact to the innovation of EG production technique.Preparing dimethyl oxalate taking carbon monoxide as raw material, is then a very attractive Coal Chemical Industry Route by preparation of ethanediol by dimethyl oxalate hydrogenation.Now the research of preparing dimethyl oxalate taking carbon monoxide as raw material has been obtained to good effect both at home and abroad, industrial production is ripe.And by preparation of ethanediol by dimethyl oxalate hydrogenation, still have the further investigation of more need of work, especially how effectively improve in the selectivity of ethylene glycol and also have more need of work research.
Document " spectrographic laboratory " 27 2 phase of volume 616-619 pages in 2010 disclose the research of one section of ethylene glycol catalyst prepared by dimethyl oxalate plus hydrogen, and it has prepared Cu B/ γ-Al by chemical reduction sedimentation
2o
3, Cu-B/SiO
2amorphous alloy catalyst, its evaluation result shows, but this catalyzer barkite transformation efficiency is lower, and glycol selectivity is lower than 90%.
Document CN200710061390.3 discloses a kind of Catalysts and its preparation method of oxalic ester hydrogenation synthesizing of ethylene glycol, and the barkite transformation efficiency of this catalyzer and technique thereof is lower, and generally in 96% left and right, the selectivity of ethylene glycol is about 92% left and right.
The subject matter that above-mentioned document exists is that glycol selectivity is lower, needs further improve and improve.
Summary of the invention
Technical problem to be solved by this invention is the low technical problem of glycol selectivity existing in the method for previous literature, and a kind of method of new employing preparing ethylene glycol from oxalic ester is provided.The method has, the advantage that glycol selectivity is high.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method that adopts preparing ethylene glycol from oxalic ester, taking barkite as raw material, comprises the following steps:
A) first hydrogen enter in the first reaction zone and contact with copper-Yin-Si catalyst with first strand of raw material, generates the first strand of reaction effluent that contains ethylene glycol;
B) first strand of reaction effluent enters at least one second reaction zone and contacts with copper-zinc-Si catalyst with second strand of raw material, generates the second strand of reaction effluent that contains ethylene glycol;
Wherein, first strand of raw material and second strand of material molar ratio are 0.1～10: 1; The mol ratio of hydrogen and first strand of raw material and second burst of raw material sum is 20～300: 1; First strand of raw material is selected from dimethyl oxalate, oxalic acid diethyl ester or its mixture, and second strand of raw material is selected from dimethyl oxalate, oxalic acid diethyl ester or its mixture.
The first reactor operating condition in technique scheme: 100～260 DEG C of temperature of reaction, weight space velocity is 0.05～10 hour
-1, hydrogen/ester mol ratio is 30～200: 1, reaction pressure is 0.2～5.0MPa; The first reactor preferred operations condition: 130～230 DEG C of temperature of reaction, weight space velocity is 0.08～6 hour
-1, hydrogen/ester mol ratio is 40～150: 1, reaction pressure is 0.5～3.0MPa; The second reactor operating condition: 180～300 DEG C of temperature of reaction, weight space velocity is 0.08～8 hour
-1, reaction pressure is 1.0～10.0MPa, first strand of raw material and second strand of material molar ratio are 0.2～8: 1.The second reactor preferred operations condition: 180～260 DEG C of temperature of reaction, weight space velocity is 0.1～5 hour
-1, reaction pressure is 1.5～6.0MPa, first strand of raw material and second burst of material molar ratio preferable range are 0.3～6: 1.Copper-Yin-Si catalyst is taking catalyst weight as benchmark, and its weight of copper content preferable range is 5～60%, and more preferably scope is 10～40%, silver weight content preferable range be 1～20% more preferably scope be 1～10%; Copper-zinc-Si catalyst, taking catalyst weight as benchmark, its weight of copper content preferable range is 5～60%, and more preferably scope is 10～50%, and the weight content preferable range of zinc is 1～30%, and more preferably scope is 1～20%.
The present invention adopts at least two reactors in series, and raw material segmentation is injected, and the first reactor is at cold operation, and the second reactor at high temperature operates.As everyone knows, hydrogenation reaction is thermopositive reaction, and oxalate hydrogenation is no exception equally.Large quantity research shows, be used for the catalyzer of barkite hydrogenation in reaction process, the concentrated heat release of hydrogenation process can cause the temperature rise that catalyzer is higher, especially the temperature of catalyst active center may exceed catalyzer apparent temperature tens and spends even more than 100 DEG C, and too high local temperature rise is disadvantageous to the selectivity that improves ethylene glycol in catalyst reaction process.Study and also show, oxalate hydrogenation, is typical cascade reaction, and reaction intermediate is in the favourable generation of low temperature, under high temperature, can further generate object glycol product.In the present invention, adopt on the one hand tandem reactor, and the first reactor adopts cold operation to concentrate thermal discharge by mild hydrogenation, avoid local temperature rise too high, in the second reactor, adopt the intermediate product generating compared with High Operating Temperature principal security the first reactor reaction to be converted to comparatively completely object glycol product, thereby improve selectivity and the yield of object glycol product.On the other hand; the mode of injecting by raw material segmentation; can ensure in situation that total amounts of hydrogen is certain; hydrogen/ester suitable under actual response chemical atmosphere is than high, and meanwhile, the segmentation of raw material is injected the heat effect of optimization reaction process favourable; further optimize on the whole the operation operating mode of reaction; reduce the operation temperature rise of reactor, effectively protected the reactivity worth of catalyzer, can reach the object of maximized glycol selectivity.In addition, need be ben, reactors in series number can be 2,3 or multiple.
Adopt technical scheme of the present invention, taking dimethyl oxalate as raw material, at the first reactor operating condition: 130～230 DEG C of temperature of reaction, weight space velocity is 0.08～6 hour
-1, hydrogen/ester mol ratio is 40～150: 1, reaction pressure is 0.5～3.0MPa, adopts copper-Yin-Si catalyst; The second reactor operating condition: 180～260 DEG C of temperature of reaction, weight space velocity is 0.1～5 hour
-1, reaction pressure is 1.5～6.0MPa, and employing copper-zinc-silicon is catalyzer, and first strand of raw material and second strand of material molar ratio are 0.3～6: 1; The mol ratio of hydrogen and first strand of raw material and second burst of raw material sum is 20～300: 1, adopts under the condition of copper containing catalyst, and the transformation efficiency of dimethyl oxalate can reach 100%, and the selectivity of ethylene glycol can be greater than 95%, has obtained good technique effect.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
[embodiment 1]
Take specific surface and be 100 grams of the silica supports of 200 meters squared per gram, according to 25%Cu-2%Ag/SiO
2content configuration catalyzer, its step is as follows: choose cupric nitrate, and Silver Nitrate, be made into steeping fluid according to Cu and silver-colored charge capacity, silica support to be flooded in this solution after 20 hours, at room temperature vacuum-drying obtains solids for 8 hours.Again solid is dried to 10 hours at 120 DEG C, 500 DEG C of roastings make required Cu-Ag/SiO for 6 hours afterwards
2catalyzer.
Prepare 25%Cu-10%Zn/SiO according to above-mentioned same method
2cu-Zn/SiO2 catalyzer (taking weight as benchmark, as follows).
Taking respectively the catalyzer making is respectively charged into diameter is in the desired amount in the tubular reactor of 18 millimeters, reaction procatalyst is in 100 ml/min, and hydrogen molar content 20%, under nitrogen molar content 80% condition, be raised to 450 DEG C from room temperature with 3 DEG C/min, constant temperature activates for 4 hours.
Taking hydrogen and dimethyl oxalate as raw material, dimethyl oxalate raw material is divided into first strand of raw material and second strand of raw material, first strand of raw material and second strand of material molar ratio are 0.5: 1, total mol ratio of hydrogen and first strand of raw material and second burst of raw material sum is 100: 1, and first strand of raw material and second strand of raw material are all selected from dimethyl oxalate.First hydrogen enter in the first reactor and contact with copper-Yin-Si catalyst with first strand of raw material, generates the first strand of reaction effluent that contains ethylene glycol; First strand of reaction effluent and second strand of raw material, enter in the second reactor and contact with copper-zinc-Si catalyst, generates the second strand of reaction effluent that contains ethylene glycol; Wherein, at the first reactor operating condition: 150 DEG C of temperature of reaction, weight space velocity is 0.1 hour
-1, hydrogen/ester mol ratio is 100: 1, reaction pressure is 0.5MPa; The second reactor operating condition: 230 DEG C of temperature of reaction, weight space velocity is 0.2 hour
-1, reaction pressure is 3.5MPa, and its reaction result is: the transformation efficiency of dimethyl oxalate is 100%, and the selectivity of ethylene glycol is 94.4%.
[embodiment 2]
Each Step By Condition according to embodiment 1 makes 35%Cu+10%Ag/SiO
2catalyzer and 20%Cu+5%Zn/SiO
2catalyzer.
Taking hydrogen and dimethyl oxalate as raw material, dimethyl oxalate raw material is divided into first strand of raw material and second strand of raw material, first strand of raw material and second strand of material molar ratio are 1: 1, total mol ratio of hydrogen and first strand of raw material and second burst of raw material sum is 60: 1, and first strand of raw material and second strand of raw material are all selected from dimethyl oxalate.First hydrogen enter in the first reactor and contact with copper-Yin-Si catalyst with first strand of raw material, generates the first strand of reaction effluent that contains ethylene glycol; First strand of reaction effluent and second strand of raw material, enter in the second reactor and contact with copper-zinc-Si catalyst, generates the second strand of reaction effluent that contains ethylene glycol; Wherein, at the first reactor operating condition: 140 DEG C of temperature of reaction, weight space velocity is 0.2 hour
-1, hydrogen/ester mol ratio is 40: 1, reaction pressure is 0.5MPa; The second reactor operating condition: 190 DEG C of temperature of reaction, weight space velocity is 0.3 hour
-1, reaction pressure is 3.5MPa, and its reaction result is: the transformation efficiency of dimethyl oxalate is 100%, and the selectivity of ethylene glycol is 96.1%.
[embodiment 3]
Each Step By Condition according to embodiment 1 makes 15%Cu+3%Ag/SiO
2catalyzer and 20%Cu+20%Zn/SiO
2catalyzer.
Taking hydrogen and barkite as raw material, barkite is the mixture that dimethyl oxalate and oxalic acid diethyl ester mol ratio are 1: 1, barkite raw material is divided into first strand of raw material and second strand of raw material, first strand of raw material and second strand of material molar ratio are 3: 1, total mol ratio of hydrogen and first strand of raw material and second burst of raw material sum is 160: 1, and first strand of raw material and second strand of raw material are all selected from the mixture that dimethyl oxalate and oxalic acid diethyl ester mol ratio are 1: 1.First hydrogen enter in the first reactor and contact with copper-Yin-Si catalyst with first strand of raw material, generates the first strand of reaction effluent that contains ethylene glycol; First strand of reaction effluent and second strand of raw material, enter in the second reactor and contact with copper-zinc-Si catalyst, generates the second strand of reaction effluent that contains ethylene glycol; Wherein, at the first reactor operating condition: 180 DEG C of temperature of reaction, weight space velocity is 1 hour
-1, hydrogen/ester mol ratio is 130: 1, reaction pressure is 1.5MPa; The second reactor operating condition: 230 DEG C of temperature of reaction, weight space velocity is 0.9 hour
-1, reaction pressure is 1.8MPa, and its reaction result is: the transformation efficiency of barkite is 100%, and the selectivity of ethylene glycol is 97.3%.
[embodiment 4]
Each Step By Condition according to embodiment 1 makes 40%Cu+1.5%Ag/SiO
2catalyzer and 10%Cu+25%Zn/SiO
2catalyzer.
Taking hydrogen and barkite as raw material, barkite is the mixture that dimethyl oxalate and oxalic acid diethyl ester mol ratio are 2: 1, barkite raw material is divided into first strand of raw material and second strand of raw material, first strand of raw material and second strand of material molar ratio are 8: 1, total mol ratio of hydrogen and first strand of raw material and second burst of raw material sum is 200: 1, and first strand of raw material and second strand of raw material are all selected from the mixture that dimethyl oxalate and oxalic acid diethyl ester mol ratio are 2: 1.First hydrogen enter in the first reactor and contact with copper-Yin-Si catalyst with first strand of raw material, generates the first strand of reaction effluent that contains ethylene glycol; First strand of reaction effluent and second strand of raw material, enter in the second reactor and contact with copper-zinc-Si catalyst, generates the second strand of reaction effluent that contains ethylene glycol; Wherein, at the first reactor operating condition: 200 DEG C of temperature of reaction, weight space velocity is 3 hours
-1, hydrogen/ester mol ratio is 200: 1, reaction pressure is 2.2MPa; The second reactor operating condition: 240 DEG C of temperature of reaction, weight space velocity is 2.5 hours
-1, reaction pressure is 2.2MPa, and its reaction result is: the transformation efficiency of barkite is 100%, and the selectivity of ethylene glycol is 96.8%.
[embodiment 5]
Each Step By Condition according to embodiment 1 makes 50%Cu+8%Ag/SiO
2catalyzer and 45%Cu+10%Zn/SiO
2catalyzer.
Taking hydrogen and barkite as raw material, barkite is selected from dimethyl oxalate and oxalic acid diethyl ester, barkite raw material is divided into first strand of raw material and second strand of raw material, first strand of raw material and second strand of material molar ratio are 8: 1, total mol ratio of hydrogen and first strand of raw material and second burst of raw material sum is 200: 1, and first strand of raw material and second strand of raw material are selected from respectively dimethyl oxalate and oxalic acid diethyl ester.First hydrogen enter in the first reactor and contact with copper-Yin-Si catalyst with first strand of raw material, generates the first strand of reaction effluent that contains ethylene glycol; First strand of reaction effluent and second strand of raw material, enter in the second reactor and contact with copper-zinc-Si catalyst, generates the second strand of reaction effluent that contains ethylene glycol; Wherein, at the first reactor operating condition: 210 DEG C of temperature of reaction, weight space velocity is 5 hours
-1, hydrogen/ester mol ratio is 100: 1, reaction pressure is 3.5MPa; The second reactor operating condition: 210 DEG C of temperature of reaction, weight space velocity is 5 hours
-1, reaction pressure is 3.5MPa, and its reaction result is: the transformation efficiency of barkite is 100%, and the selectivity of ethylene glycol is 97.6%.
[comparative example 1]
According to embodiment 5 the same terms and reaction raw materials, just only adopt second reactor, in the case of the reaction conditionss such as total air speed and hydrogen ester ratio are identical, reaction result is: the transformation efficiency of barkite is 100%, the selectivity of ethylene glycol is 92.2%.
Claims (1)
1. a method that adopts preparing ethylene glycol from oxalic ester, step is as follows:
Take specific surface and be 100 grams of the silica supports of 200 meters squared per gram, according to 50%Cu+8%Ag/SiO
2content configuration catalyzer, its step is as follows: choose cupric nitrate, and Silver Nitrate, be made into steeping fluid according to Cu and silver-colored charge capacity, silica support to be flooded in this solution after 20 hours, at room temperature vacuum-drying obtains solids for 8 hours; Again solid is dried to 10 hours at 120 DEG C, 500 DEG C of roastings make required Cu-Ag/SiO for 6 hours afterwards
2catalyzer;
Prepare taking weight as benchmark 45%Cu-10%Zn/SiO according to above-mentioned same method
2cu-Zn/SiO
2catalyzer;
Taking hydrogen and barkite as raw material, barkite is selected from dimethyl oxalate and oxalic acid diethyl ester, barkite raw material is divided into first strand of raw material and second strand of raw material, first strand of raw material and second strand of material molar ratio are 8: 1, total mol ratio of hydrogen and first strand of raw material and second burst of raw material sum is 200: 1, first strand of raw material and second strand of raw material are selected from respectively dimethyl oxalate and oxalic acid diethyl ester, first hydrogen enter in the first reactor and contact with copper-Yin-Si catalyst with first strand of raw material, generates the first strand of reaction effluent that contains ethylene glycol; First strand of reaction effluent and second strand of raw material, enter in the second reactor and contact with copper-zinc-Si catalyst, generates the second strand of reaction effluent that contains ethylene glycol; Wherein, at the first reactor operating condition: 210 DEG C of temperature of reaction, weight space velocity is 5 hours
-1, hydrogen/ester mol ratio is 100: 1, reaction pressure is 3.5MPa; The second reactor operating condition: 210 DEG C of temperature of reaction, weight space velocity is 5 hours
-1, reaction pressure is 3.5MPa, and its reaction result is: the transformation efficiency of barkite is 100%, and the selectivity of ethylene glycol is 97.6%.
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| CN101475441A (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 |
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| CN101475441A (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 |
Non-Patent Citations (4)
| Title |
|---|
| Baowei Wang,et al.,.Synthesis of Methyl Glycolate by Hydrogenation of Dimethyl Oxalate over Cu-Ag/SiO2 Catalyst.《Journal of Natural Gas Chemistry》.2007,第16卷(第1期),第78-80页. |
| Synthesis of Methyl Glycolate by Hydrogenation of Dimethyl Oxalate over Cu-Ag/SiO2 Catalyst;Baowei Wang,et al.,;《Journal of Natural Gas Chemistry》;20071231;第16卷(第1期);第78-80页 * |
| 张旭.草酸二乙酯气相加氢催化剂助剂的研究.《中国优秀硕士学位论文全文数据库 工程科技I辑》.2009,第18页. |
| 草酸二乙酯气相加氢催化剂助剂的研究;张旭;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20090720;第18页 * |
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