CN101993341A - Method for producing glycol through hydrogenation of oxalic ester - Google Patents

Method for producing glycol through hydrogenation of oxalic ester Download PDF

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CN101993341A
CN101993341A CN2009100578398A CN200910057839A CN101993341A CN 101993341 A CN101993341 A CN 101993341A CN 2009100578398 A CN2009100578398 A CN 2009100578398A CN 200910057839 A CN200910057839 A CN 200910057839A CN 101993341 A CN101993341 A CN 101993341A
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gas
effluent
ethylene glycol
gas phase
hydrogen
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CN101993341B (en
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谢在库
刘俊涛
王万民
孙凤侠
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Sinopec Shanghai Research Institute of Petrochemical Technology
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Sinopec Shanghai Research Institute of Petrochemical Technology
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Abstract

The invention relates to a method for producing glycol through hydrogenation of oxalic ester. The invention mainly solves the technical problems of low target product selectivity and low hydrogen use ratio in the prior art. The method adopts the oxalic ester as the raw material and comprises the following steps: (a) fresh hydrogen, recycle gas I, recycle gas II and first batch of oxalic ester raw materials firstly enter into a reactor I to be contacted with a copper-containing catalyst I to generate reaction effluent I containing glycol; (b) the effluent I is mixed with second batch of oxalic ester raw materials and then the mixture enters into a reactor II to be contacted with a copper-containing catalyst II to generate reaction effluent II; (c) after the reaction effluent II undergoes gas-liquid separation, the liquid phase effluent enters into a separation system to be separated to obtain the glycol product; the gas phase effluent is divided into gas phase effluent I and gas phase effluent II; and the gas phase effluent I is directly used as the recycle gas I; and (d) the gas phase effluent II enters into a hydrogen recovery system to obtain the recycle gas II and analytic gas, and the recycle gas II and the fresh hydrogen are mixed and recycled. The technical scheme better solves the problems and can be used in industrial production of glycol produced through hydrogenation of oxalic ester.

Description

The method of producing ethylene glycol from hydrogenation of oxalic ester
Technical field
The present invention relates to a kind of method of producing ethylene glycol from hydrogenation of oxalic ester, particularly produce the method for ethylene glycol about dimethyl oxalate hydrogenation or oxalic acid diethyl ester hydrogenation.
Background technology
Ethylene glycol (EG) is a kind of important Organic Chemicals, be mainly used in and produce trevira, frostproofer, unsaturated polyester resin, lubricant, softening agent, nonionogenic tenside and explosive etc., can be used for industries such as coating, soup, brake fluid and printing ink in addition, solvent and medium as ammonium pertorate, be used to produce special solvent glycol ether etc., purposes is very extensive.
At present, direct hydration method or the legal operational path of pressurized water are all adopted in domestic and international large-scale ethylene glycol production, this technology is that oxyethane and water are made into mixed aqueous solution by 1: 20～22 (mol ratios), in fixed-bed reactor in 130～180 ℃, 1.0～2.5MPa reacted 18～30 minutes down, oxyethane all is converted into alcohol mixture, the aqueous glycol solution content that generates is greatly about 10% (massfraction), carry through the multiple-effect evaporator dehydration then and obtain ethylene glycol dense the separation with rectification under vacuum, but production equipment need be provided with a plurality of vaporizers, consume lot of energy and be used for dehydration, cause the technological process of production long, equipment is many, the energy consumption height, directly influence the production cost of ethylene glycol.Since the seventies in 20th century, both at home and abroad some major companies that mainly produce ethylene glycol all are devoted to the Synthesis of Ethylene Glycol by Catalytic Hydration Study on Technology, mainly contain shell company, U.S. UCC company and Dow company, the Mitsubishi chemical company of Ying He, domestic Dalian University of Technology, Shanghai Petroleum Chemical Engineering Institute, Nanjing University of Technology etc.What representative was wherein arranged is the heterogeneous catalysis hydration method of Shell company and the homogeneous catalysis hydration method of UCC company.Shell company has reported that from 1994 quaternary ammonium type acid carbonate anionite-exchange resin carries out the exploitation of EO catalytic hydration technology as catalyzer, obtain EO transformation efficiency 96%～98%, the test-results of EG selectivity 97%～98%, develop the poly organic silicon alkane ammonium salt loaded catalyst of similar silicon dioxide skeleton and the epoxide hydrating process under the catalysis thereof in 1997 again, obtained better conversion rate and selectivity.The UCC company of the U.S. has mainly developed two kinds of hydration catalysts: a kind of is the anionic catalyst that is carried on the ion exchange resin, mainly is molybdate, tungstate, vanadate and triphenylphosphine complex catalyst; Another kind is the molybdate composite catalyst.In two kinds of Application of Catalyst examples, the TM catalyzer of spent ion exchange resin DOWEX WSA21 preparation is hydration under 9: 1 the condition in the mol ratio of water and EO, and the EG yield is 96%.Using the molybdate composite catalyst, is hydration under 5: 1 the condition in the mol ratio of water and EO, and the EG yield is 96.6%.Catalysis method greatly reduces the water ratio, simultaneously can obtain high EO transformation efficiency and high EG selectivity, but also there is certain problem aspect Preparation of Catalyst, regeneration and life-span, not enough as catalyst stability, preparation is quite complicated, be difficult to recycle, have also can be in product residual a certain amount of anionic metal, need to increase corresponding apparatus and separate.NSC 11801 method synthesizing glycol is by oxyethane and carbonic acid gas synthesizing ethylene carbonate, obtains ethylene glycol with the NSC 11801 hydrolysis again.The US4508927 patent proposes esterification and hydrolysis reaction are separately carried out.The two-step process that the US4500559 of U.S. Halcon-SD company proposes is that the mixture that comes from reactor is through resorber, again with the carbonic acid gas extracting oxyethane under the criticality, obtain oxyethane, carbonic acid gas, water mixture contacts synthetic BC with catalyst for esterification reaction such as Organohalogen compounds, sulfohalides, BC is admitted to hydrolysis reactor then, and hydrolysis obtains ethylene glycol and carbonic acid gas under same catalyst action, and the ethylene glycol yield is up to 99%.Japanese Patent JP571006631 has proposed the EO-EC-EG novel process of industrially scalable, patent introduces oxyethane and the carbonic acid gas esterification is in the presence of catalyzer KI, 160 ℃ are carried out esterification, transformation efficiency is 99.9%, the selectivity of ethylene glycol is 100%, the NSC 11801 legal system is equipped with the ethylene glycol technology no matter aspect transformation efficiency and selectivity, still all than present BO direct hydration method bigger advantage is being arranged aspect production process raw material consumption and the energy expenditure, technical in ethylene glycol is a kind of method that maintains the leading position.But this method still is raw material with the oil, and need build the ethylene glycol production equipment again, and this glycol unit to new construction is more suitable, and on original production unit was undergone technological transformation, it was favourable to be not so good as catalytic hydration.
Document CN101138725A discloses a kind of Catalysts and its preparation method of oxalic ester hydrogenation synthesizing of ethylene glycol, it is active ingredient with the metallic copper, zinc is auxiliary agent, the preparation of employing coprecipitation method, but this catalyzer barkite transformation efficiency is lower, do not have simultaneously the catalyst stability report yet, do not mention the problem that hydrogen effectively utilizes yet.
Document " petrochemical complex " was rolled up the 340th～343 page of the 4th phase in 2007 the 36th and has been introduced a kind of employing Cu/SiO 2Carry out the research of hydrogenation of dimethyl oxalate to synthesizing ethylene glycol reaction, but there is poor selectivity in this catalyzer, and does not have the report of catalyst stability equally, also do not mention the problem that hydrogen effectively utilizes.
At present, world's oil price is not following according to height, and the resource general layout of China can be summarized as few oil, weak breath, many coals.Development carbon one chemical industry not only can make full use of Sweet natural gas and coal resource, reduces the dependence of petroleum import and can alleviate environmental stress, is unusual important field of research.With the carbon monoxide is the feedstock production barkite, is a very attractive Coal Chemical Industry route then with preparing glycol by hydrogenating oxalate.Now both at home and abroad to being that the research of feedstock production barkite has obtained good effect with the carbon monoxide, industrial production is ripe.And, still have more need of work further investigation with preparing glycol by hydrogenating oxalate.
Summary of the invention
Technical problem to be solved by this invention is to exist the purpose selectivity of product low in the prior art, and the technical problem that hydrogen utilization ratio is low provides a kind of method of new producing ethylene glycol from hydrogenation of oxalic ester.This method has glycol selectivity height, hydrogen utilization ratio advantages of higher.
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 of producing ethylene glycol from hydrogenation of oxalic ester is a raw material with the barkite, may further comprise the steps:
A) at first enter among the reactor I after fresh hydrogen, circulation gas I, circulation gas II and first strand of barkite raw material mix and contact with copper containing catalyst I, generation contains the reaction effluent I of ethylene glycol;
B) the reaction effluent I that contains ethylene glycol contact with copper containing catalyst II with entering among the reactor II after second strand of barkite raw material mixes, and generation contains the reaction effluent II of ethylene glycol;
C) contain the reaction effluent II of ethylene glycol after gas-liquid separation, the liquid phase effluent enters and obtains the ethylene glycol product after separation system is separated, the gas phase effluent is divided into gas phase effluent I and gas phase effluent II, and gas phase effluent I directly mixes with fresh hydrogen as circulation gas I;
D) gas phase effluent II enters hydrogen recovery system and obtains circulation gas II reconciliation gassing body, and circulation gas II and virgin gas hydrogen mixed cycle are used;
Wherein, the mol ratio of gas phase effluent I and virgin gas is 0.5～100: 1, and the mol ratio of gas phase effluent II and gas phase effluent I is 0.01～5: 1; First strand of barkite raw material and second strand of barkite material molar ratio are: 0.5～2: 1; Barkite is selected from dimethyl oxalate, oxalic acid diethyl ester or its mixture.
In the technique scheme, circulation gas II is the gas that is rich in hydrogen behind the hydrogen upgrading, and foreign gas concentration is higher in the parsing gas.Resolve gas and can directly send fuel system to make fuel usefulness, or emptying after further handling.
The operational condition of reactor I is in the technique scheme: temperature of reaction is 190 ℃～300 ℃, and reaction pressure is 1.5～8.0MPa, and weight space velocity is 0.05～5 hour -1, hydrogen/ester mol ratio is 30～200: 1; The preferred operations condition of reactor I is: temperature of reaction is 200 ℃～260 ℃, and reaction pressure is 2.0～7.0MPa, and weight space velocity is 0.1～3 hour -1, hydrogen/ester mol ratio is 40～150: 1; Reactor II operational condition: temperature of reaction is 180～280 ℃, and weight space velocity is 0.05～5 hour -1, hydrogen/ester mol ratio is 30～200: 1, reaction pressure is 1.5～8.0MPa.Reactor II preferred operations condition is: temperature of reaction is 190～260 ℃, and weight space velocity is 0.08～3 hour -1, hydrogen/ester mol ratio is 40～150: 1, reaction pressure is 2.0～7.0Mpa
The preferred molar ratio scope of gas phase effluent I and fresh hydrogen is 1～50: 1 in the technique scheme, and the preferred molar ratio scope of gas phase effluent II and gas phase effluent I is 0.05～2: 1; The preferred molar ratio scope of first strand of barkite raw material and second strand of barkite raw material is: 0.8～1.5: 1.Copper containing catalyst I and copper containing catalyst II are carrier with at least a in silicon oxide or the aluminum oxide all, it preferably is carrier with the silicon oxide, in simple substance copper consumption is 10～80% of catalyst weight, and preferred weight range is for being 20～60% of catalyst weight in simple substance copper consumption.Copper containing catalyst can add auxiliary element, auxiliary agent is selected from least a in alkali earth metal, transition metal or the thulium, auxiliary agent is preferably from alkali earth metal Mg, Ca and Ba, the metallic element K of IA family, Na, the V of transition metal, Ti, Mn, Fe, Co, Ni and Zn, perhaps at least a among rare-earth metals La, Eu, Gd and the Tb.In total catalyst weight is 100 parts, and the content of auxiliary element is greater than 0～20 part, and preferable range is 0.01～15 part.Barkite is selected from dimethyl oxalate or oxalic acid diethyl ester.
Among the present invention: adopt the reaction end gas circulation, and part tail gas is after hydrogen purification, again with fresh hydrogen blended technical scheme.Discover, the barkite hydrogenation generates in the reaction process of ethylene glycol, except that the main reaction that generates the purpose glycol product, also exist barkite to decompose, side reactions such as dehydration of alcohols, cause except that hydrogen, also containing in the reaction end gas methane, ethane, dme, gases such as CO, in Industrial processes, because hydrogenation process hydrogen is excessive greatly, therefore, most of hydrogen need recycle, but discovers the methane in the recycled offgas, ethane, dme, gases such as CO are understood the transformation efficiency of remarkably influenced barkite after concentration runs up to a certain degree, the selectivity of ethylene glycol and the stability of catalyzer.For this reason, regularly discharge cycle hydrogen is very necessary with the transition accumulation that prevents impurity in the gas phase, but considers that hydrogen is important material in the hydrogenation reaction, therefore the present invention adopts hydrogen recovery system, with most of hydrogen recovery, all the other impure higher a small amount of gaseous emissions, or the gas that acts as a fuel enters fuel system, not only can significantly improve the utilization ratio of hydrogen, reduce cost,, also improved the selectivity of ethylene glycol simultaneously owing to the raising of hydrogen purity.
We also find under study for action, oxalate hydrogenation is thermopositive reaction, and catalyzer is relatively more responsive to temperature, the optimum temps interval is narrower, in addition, hydrogen/ester is than high more favourable to the purpose selectivity of product, and the present invention adopts raw material barkite segmentation injecting scheme to ensure that not only local reaction atmosphere hydrogen/ester is than higher favourable condition for this reason, optimize the temperature of reactor distribution simultaneously, can effectively improve glycol selectivity.
The hydrogen utilization ratio of indication of the present invention obtains by following account form:
Hydrogen utilization ratio=(entering the amounts of hydrogen of the fresh hydrogen tolerance-emptying from system of system)/enter fresh hydrogen tolerance * 100% of system.
Adopting technical scheme of the present invention, is raw material with the dimethyl oxalate, and adopting copper load silicon oxide is catalyst I and catalyst I I, and counting its consumption in simple substance copper is 20～60% of catalyst weight.The operational condition of reactor I is: temperature of reaction is 200 ℃～260 ℃, and reaction pressure is 2.0～7.0MPa, and weight space velocity is 0.1～3 hour -1, hydrogen/ester mol ratio is 30～200: 1; Reactor II operational condition: temperature of reaction is 190～260 ℃, and weight space velocity is 0.08～3 hour -1, hydrogen/ester mol ratio is 40～150: 1, reaction pressure is 2.0～7.0Mpa; The mol ratio of gas phase effluent I and fresh hydrogen is 1～50: 1, and the mol ratio of gas phase effluent II and gas phase effluent I is 0.05～2: 1; First strand of dimethyl oxalate raw material and second strand of dimethyl oxalate material molar ratio are: under 0.8～1.5: 1 the condition, the transformation efficiency of dimethyl oxalate is greater than 98%, the selectivity of ethylene glycol is greater than 90%, and hydrogen utilization ratio has been obtained better technical effect greater than 95%.
The invention will be further elaborated below by embodiment, but be not limited only to present embodiment.
Embodiment
[embodiment 1]
Taking by weighing specific surface is silica support 200 grams of 280 meters squared per gram, according to 35 parts of reactive metal copper and 10 parts of metallic zinc content configuration catalyzer, its step is as follows: choose cupric nitrate, and zinc nitrate, be made into steeping fluid according to Cu and Zn charge capacity, silica support flooded 18 hours in this solution after, vacuum-drying at room temperature 10 hours solids.Solid was descended dry 10 hours at 120 ℃, 450 ℃ of roastings made required CuO+ZnO/SiO in 4 hours afterwards again 2Catalyst precursor.
Take by weighing the CuO+ZnO/SiO that to make respectively 2It is in two placed in-line tubular reactors of 24 millimeters that catalyst precursor is respectively charged into diameter in the desired amount, the reaction procatalyst is in 200 ml/min, hydrogen molar content 20%, under nitrogen molar content 80% condition, be raised to 450 ℃ from room temperature with 3 ℃/minute, constant temperature activated and obtains forming identical catalyst I and catalyst I I in 6 hours, reduced to temperature of reaction then and fed intake.
With the dimethyl oxalate is raw material, at first enters among the reactor I after fresh hydrogen, circulation gas I, circulation gas II and first strand of dimethyl oxalate raw material mix to contact with copper containing catalyst I, and generation contains the reaction effluent I of ethylene glycol; The reaction effluent I that contains ethylene glycol contact with copper containing catalyst II with entering among the reactor II after second strand of dimethyl oxalate raw material mixes, and generation contains the reaction effluent II of ethylene glycol; The reaction effluent II that contains ethylene glycol is after gas-liquid separation, the liquid phase effluent enters and obtains the ethylene glycol product after separation system is separated, the gas phase effluent is divided into gas phase effluent I and gas phase effluent II, and gas phase effluent I directly mixes with fresh hydrogen as circulation gas I; Gas phase effluent II enters hydrogen recovery system and obtains circulation gas II and conciliate the gassing body, resolves gas and send fuel system to make fuel usefulness, and circulation gas II mixes with fresh hydrogen and continues to recycle.Wherein, the mol ratio of gas phase effluent I and fresh hydrogen is 10: 1, and the mol ratio of gas phase effluent II and gas phase effluent I is 5: 1, and first strand of dimethyl oxalate raw material and second strand of dimethyl oxalate material molar ratio are: 1: 1.The operational condition of reactor I is: 210 ℃ of temperature of reaction, reaction pressure 2.5MPa, weight space velocity 0.2 hour -1, hydrogen/ester mol ratio is 100: 1; Reactor II operational condition: 220 ℃ of temperature of reaction, weight space velocity are 0.33 hour -1, hydrogen/ester mol ratio is 100: 1, reaction pressure is 2.5MPa.Hydrogen recovery system adopts the embrane method recovery technology, and its result is: hydrogen utilization ratio is 91% condition, and the transformation efficiency of dimethyl oxalate is 99.7%, and the selectivity of ethylene glycol is 91.6%.
[embodiment 2]
The 40%Cu+8%Zn+0.2%Ce/SiO that makes according to each Step By Condition of embodiment 1 2Catalyst I and 30%Cu+1%Tb+0.1%Li/Al 2O 3Catalyst I I.
With the dimethyl oxalate is raw material, at first enters among the reactor I after fresh hydrogen, circulation gas I, circulation gas II and first strand of dimethyl oxalate raw material mix to contact with copper containing catalyst I, and generation contains the reaction effluent I of ethylene glycol; The reaction effluent I that contains ethylene glycol contact with copper containing catalyst II with entering among the reactor II after second strand of dimethyl oxalate raw material mixes, and generation contains the reaction effluent II of ethylene glycol; The reaction effluent II that contains ethylene glycol is after gas-liquid separation, the liquid phase effluent enters and obtains the ethylene glycol product after separation system is separated, the gas phase effluent is divided into gas phase effluent I and gas phase effluent II, and gas phase effluent I directly mixes with fresh hydrogen as circulation gas I; Gas phase effluent II enters hydrogen recovery system and obtains circulation gas II and conciliate the gassing body, resolves gas and send fuel system to make fuel usefulness, and circulation gas II mixes with fresh hydrogen and continues to recycle.Wherein, the mol ratio of gas phase effluent I and fresh hydrogen is 50: 1, and the mol ratio of gas phase effluent II and gas phase effluent I is 2: 1, and first strand of dimethyl oxalate raw material and second strand of dimethyl oxalate material molar ratio are: 1.8: 1.The operational condition of reactor I is: 260 ℃ of temperature of reaction, reaction pressure 6.5MPa, weight space velocity 3 hours -1, hydrogen/ester mol ratio is 100: 1; Reactor II operational condition: 240 ℃ of temperature of reaction, weight space velocity are 0.5 hour -1, hydrogen/ester mol ratio is 150: 1, reaction pressure is 6.5MPa.Hydrogen recovery system adopts the embrane method recovery technology, and its result is: hydrogen utilization ratio is 93%, and the transformation efficiency of dimethyl oxalate is 99.7%, and the selectivity of ethylene glycol is 96.7%.
[embodiment 3]
The 60%Cu+5%Zn+1%Fe/SiO that makes according to each Step By Condition of embodiment 1 2Catalyst I and 20%Cu+1%Ba+0.1%Li/Al 2O 3Catalyst I I.
With the dimethyl oxalate is raw material, at first enters among the reactor I after fresh hydrogen, circulation gas I, circulation gas II and first strand of dimethyl oxalate raw material mix to contact with copper containing catalyst I, and generation contains the reaction effluent I of ethylene glycol; The reaction effluent I that contains ethylene glycol contact with copper containing catalyst II with entering among the reactor II after second strand of dimethyl oxalate raw material mixes, and generation contains the reaction effluent II of ethylene glycol; The reaction effluent II that contains ethylene glycol is after gas-liquid separation, the liquid phase effluent enters and obtains the ethylene glycol product after separation system is separated, the gas phase effluent is divided into gas phase effluent I and gas phase effluent II, and gas phase effluent I directly mixes with fresh hydrogen as circulation gas I; Gas phase effluent II enters hydrogen recovery system and obtains circulation gas II and conciliate the gassing body, resolves gas and send fuel system to make fuel usefulness, and circulation gas II mixes with fresh hydrogen and continues to recycle.Wherein, the mol ratio of gas phase effluent I and fresh hydrogen is 5: 1, and the mol ratio of gas phase effluent II and gas phase effluent I is 0.5: 1, and first strand of dimethyl oxalate raw material and second strand of dimethyl oxalate material molar ratio are: 0.5: 1.The operational condition of reactor I is: 200 ℃ of temperature of reaction, reaction pressure 3.0MPa, weight space velocity 0.5 hour -1, hydrogen/ester mol ratio is 80: 1; Reactor II operational condition: 210 ℃ of temperature of reaction, weight space velocity are 0.5 hour -1, hydrogen/ester mol ratio is 120: 1, reaction pressure is 3.0MPa.Hydrogen recovery system adopts the embrane method recovery technology, and its result is: hydrogen utilization ratio is 89.8%, and the transformation efficiency of dimethyl oxalate is 100%, and the selectivity of ethylene glycol is 95.4%.
[embodiment 4]
Each Step By Condition according to embodiment 1 makes 50%Cu+5%Zn/SiO 2Catalyst I and 25%Cu+3%Ba/SiO 2Catalyst I I.
With the oxalic acid diethyl ester is raw material, at first enters among the reactor I after fresh hydrogen, circulation gas I, circulation gas II and first strand of oxalic acid diethyl ester raw material mix to contact with copper containing catalyst I, and generation contains the reaction effluent I of ethylene glycol; The reaction effluent I that contains ethylene glycol contact with copper containing catalyst II with entering among the reactor II after second strand of oxalic acid diethyl ester raw material mixes, and generation contains the reaction effluent II of ethylene glycol; The reaction effluent II that contains ethylene glycol is after gas-liquid separation, the liquid phase effluent enters and obtains the ethylene glycol product after separation system is separated, the gas phase effluent is divided into gas phase effluent I and gas phase effluent II, and gas phase effluent I directly mixes with fresh hydrogen as circulation gas I; Gas phase effluent II enters hydrogen recovery system and obtains circulation gas II and conciliate the gassing body, resolves gas and send fuel system to make fuel usefulness, and circulation gas II mixes with fresh hydrogen and continues to recycle.Wherein, the mol ratio of gas phase effluent I and fresh hydrogen is 1: 1, and the mol ratio of gas phase effluent II and gas phase effluent I is 0.2: 1, and first strand of oxalic acid diethyl ester raw material and second strand of oxalic acid diethyl ester material molar ratio are: 2: 1.The operational condition of reactor I is: 180 ℃ of temperature of reaction, reaction pressure 4.0MPa, weight space velocity 0.3 hour -1, hydrogen/ester mol ratio is 60: 1; Reactor II operational condition: 230 ℃ of temperature of reaction, weight space velocity are 0.2 hour -1, hydrogen/ester mol ratio is 140: 1, reaction pressure is 4.0MPa.Hydrogen recovery system adopts the embrane method recovery technology, and its result is: hydrogen utilization ratio is 89.7%, and the transformation efficiency of oxalic acid diethyl ester is 100%, and the selectivity of ethylene glycol is 95.8%.
[embodiment 5]
Each Step By Condition according to embodiment 1 makes 30%Cu+15%Zn/SiO 2Catalyst I and 50%Cu+0.8%Ni+0.2%V/SiO 2Catalyst I I.
With the dimethyl oxalate is raw material, at first enters among the reactor I after fresh hydrogen, circulation gas I, circulation gas II and first strand of dimethyl oxalate raw material mix to contact with copper containing catalyst I, and generation contains the reaction effluent I of ethylene glycol; The reaction effluent I that contains ethylene glycol contact with copper containing catalyst II with entering among the reactor II after second strand of dimethyl oxalate raw material mixes, and generation contains the reaction effluent II of ethylene glycol; The reaction effluent II that contains ethylene glycol is after gas-liquid separation, the liquid phase effluent enters and obtains the ethylene glycol product after separation system is separated, the gas phase effluent is divided into gas phase effluent I and gas phase effluent II, and gas phase effluent I directly mixes with fresh hydrogen as circulation gas I; Gas phase effluent II enters hydrogen recovery system and obtains circulation gas II and conciliate the gassing body, resolves gas and send fuel system to make fuel usefulness, and circulation gas II mixes with fresh hydrogen and continues to recycle.Wherein, the mol ratio of gas phase effluent I and fresh hydrogen is 20: 1, and the mol ratio of gas phase effluent II and gas phase effluent I is 0.1: 1, and first strand of dimethyl oxalate raw material and second strand of dimethyl oxalate material molar ratio are: 1: 1.The operational condition of reactor I is: 230 ℃ of temperature of reaction, reaction pressure 2.8MPa, weight space velocity 0.4 hour -1, hydrogen/ester mol ratio is 110: 1; Reactor II operational condition: 210 ℃ of temperature of reaction, weight space velocity are 0.8 hour -1, hydrogen/ester mol ratio is 80: 1, reaction pressure is 2.8MPa.Hydrogen recovery system adopts transformation absorption recovery technology, and its result is: hydrogen utilization ratio is 92%, and the transformation efficiency of dimethyl oxalate is 100%, and the selectivity of ethylene glycol is 96.1%.
[embodiment 6]
Each Step By Condition according to embodiment 1 makes 40%Cu+5%Zn+0.3%K/SiO 2Catalyst I and 30%Cu+5%Mn+0.1%Mg/SiO 2Catalyst I I.
With the dimethyl oxalate is raw material, at first enters among the reactor I after fresh hydrogen, circulation gas I, circulation gas II and first strand of dimethyl oxalate raw material mix to contact with copper containing catalyst I, and generation contains the reaction effluent I of ethylene glycol; The reaction effluent I that contains ethylene glycol contact with copper containing catalyst II with entering among the reactor II after second strand of dimethyl oxalate raw material mixes, and generation contains the reaction effluent II of ethylene glycol; The reaction effluent II that contains ethylene glycol is after gas-liquid separation, the liquid phase effluent enters and obtains the ethylene glycol product after separation system is separated, the gas phase effluent is divided into gas phase effluent I and gas phase effluent II, and gas phase effluent I directly mixes with fresh hydrogen as circulation gas I; Gas phase effluent II enters hydrogen recovery system and obtains circulation gas II and conciliate the gassing body, resolves gas and send fuel system to make fuel usefulness, and circulation gas II mixes with fresh hydrogen and continues to recycle.Wherein, the mol ratio of gas phase effluent I and fresh hydrogen is 80: 1, and the mol ratio of gas phase effluent II and gas phase effluent I is 1: 1, and first strand of dimethyl oxalate raw material and second strand of dimethyl oxalate material molar ratio are: 0.5: 1.The operational condition of reactor I is: 220 ℃ of temperature of reaction, reaction pressure 8.0MPa, weight space velocity 4 hours -1, hydrogen/ester mol ratio is 180: 1; Reactor II operational condition: 260 ℃ of temperature of reaction, weight space velocity are 4 hours -1, hydrogen/ester mol ratio is 120: 1, reaction pressure is 8.0MPa.Hydrogen recovery system adopts the embrane method recovery technology, and its result is: hydrogen utilization ratio is 94%, and the transformation efficiency of dimethyl oxalate is 100%, and the selectivity of ethylene glycol is 88.4%.
[embodiment 7]
Each Step By Condition according to embodiment 1 makes 30%Cu+2%Co+0.2%La/SiO 2Catalyst I and 40%Cu+5%Ni+2%Zn/SiO 2Catalyst I I.
With the dimethyl oxalate is raw material, at first enters among the reactor I after fresh hydrogen, circulation gas I, circulation gas II and first strand of dimethyl oxalate raw material mix to contact with copper containing catalyst I, and generation contains the reaction effluent I of ethylene glycol; The reaction effluent I that contains ethylene glycol contact with copper containing catalyst II with entering among the reactor II after second strand of dimethyl oxalate raw material mixes, and generation contains the reaction effluent II of ethylene glycol; The reaction effluent II that contains ethylene glycol is after gas-liquid separation, the liquid phase effluent enters and obtains the ethylene glycol product after separation system is separated, the gas phase effluent is divided into gas phase effluent I and gas phase effluent II, and gas phase effluent I directly mixes with fresh hydrogen as circulation gas I; Gas phase effluent II enters hydrogen recovery system and obtains circulation gas II and conciliate the gassing body, resolves gas and send fuel system to make fuel usefulness, and circulation gas II mixes with fresh hydrogen and continues to recycle.Wherein, the mol ratio of gas phase effluent I and fresh hydrogen is 65: 1, and the mol ratio of gas phase effluent II and gas phase effluent I is 0.08: 1, and first strand of dimethyl oxalate raw material and second strand of dimethyl oxalate material molar ratio are: 1: 1.The operational condition of reactor I is: 170 ℃ of temperature of reaction, reaction pressure 2.0MPa, weight space velocity 1 hour -1, hydrogen/ester mol ratio is 150: 1; Reactor II operational condition: 240 ℃ of temperature of reaction, weight space velocity are 2 hours -1, hydrogen/ester mol ratio is 110: 1, reaction pressure is 2.0MPa.Hydrogen recovery system adopts the embrane method recovery technology, and its result is: hydrogen utilization ratio is 90.5%, and the transformation efficiency of dimethyl oxalate is 100%, and the selectivity of ethylene glycol is 95.6%.
[embodiment 8]
Each Step By Condition according to embodiment 1 makes 28%Cu+6%Zn/SiO 2Catalyst I and 30%Cu+8%Zn+1%K/Al 2O 3Catalyst I I.
With the dimethyl oxalate is raw material, at first enters among the reactor I after fresh hydrogen, circulation gas I, circulation gas II and first strand of dimethyl oxalate raw material mix to contact with copper containing catalyst I, and generation contains the reaction effluent I of ethylene glycol; The reaction effluent I that contains ethylene glycol contact with copper containing catalyst II with entering among the reactor II after second strand of dimethyl oxalate raw material mixes, and generation contains the reaction effluent II of ethylene glycol; The reaction effluent II that contains ethylene glycol is after gas-liquid separation, the liquid phase effluent enters and obtains the ethylene glycol product after separation system is separated, the gas phase effluent is divided into gas phase effluent I and gas phase effluent II, and gas phase effluent I directly mixes with fresh hydrogen as circulation gas I; Gas phase effluent II enters hydrogen recovery system and obtains circulation gas II and conciliate the gassing body, resolves gas and send fuel system to make fuel usefulness, and circulation gas II mixes with fresh hydrogen and continues to recycle.Wherein, the mol ratio of gas phase effluent I and fresh hydrogen is 40: 1, and the mol ratio of gas phase effluent II and gas phase effluent I is 0.3: 1, and first strand of dimethyl oxalate raw material and second strand of dimethyl oxalate material molar ratio are: 2: 1.The operational condition of reactor I is: 240 ℃ of temperature of reaction, reaction pressure 3.0MPa, weight space velocity 4 hours -1, hydrogen/ester mol ratio is 100: 1; Reactor II operational condition: 235 ℃ of temperature of reaction, weight space velocity are 0.35 hour -1, hydrogen/ester mol ratio is 140: 1, reaction pressure is 3.0MPa.Hydrogen recovery system adopts the embrane method recovery technology, and its result is: hydrogen utilization ratio is 91.5%, and the transformation efficiency of dimethyl oxalate is 100%, and the selectivity of ethylene glycol is 96.1%.
[embodiment 9]
Each Step By Condition according to embodiment 1 makes 40%Cu+15%Zn/SiO 2Catalyst I, 30%Cu+3%Mn+1%K/SiO 2Catalyst I I and 25%Cu+3%Ni/SiO 2Catalyst I II.
With the dimethyl oxalate is raw material, at first enters among the reactor I after fresh hydrogen, circulation gas I, circulation gas II and first strand of dimethyl oxalate raw material mix to contact with copper containing catalyst I, and generation contains the reaction effluent I of ethylene glycol; The reaction effluent I that contains ethylene glycol contact with copper containing catalyst II with entering among the reactor II after second strand of dimethyl oxalate raw material mixes, and generation contains the reaction effluent II of ethylene glycol; The reaction effluent II that contains ethylene glycol contact with copper containing catalyst III with entering among the reactor III after the 3rd strand of dimethyl oxalate raw material mixes, and generation contains the reaction effluent III of ethylene glycol; The reaction effluent III that contains ethylene glycol is after gas-liquid separation, the liquid phase effluent enters and obtains the ethylene glycol product after separation system is separated, the gas phase effluent is divided into gas phase effluent I and gas phase effluent II, and gas phase effluent I directly mixes with fresh hydrogen as circulation gas I; Gas phase effluent II enters hydrogen recovery system and obtains circulation gas II and conciliate the gassing body, resolves gas and send fuel system to make fuel usefulness, and circulation gas II mixes with fresh hydrogen and continues to recycle.Wherein, the mol ratio of gas phase effluent I and fresh hydrogen is 30: 1, the mol ratio of gas phase effluent II and gas phase effluent I is 0.2: 1, first strand of dimethyl oxalate raw material and second strand of dimethyl oxalate raw material with the 3rd strand of dimethyl oxalate material molar ratio be: 1: 1: 1.The operational condition of reactor I is: 210 ℃ of temperature of reaction, reaction pressure 2.5MPa, weight space velocity 0.4 hour -1, hydrogen/ester mol ratio is 100: 1; Reactor II operational condition: 225 ℃ of temperature of reaction, weight space velocity are 0.35 hour -1, hydrogen/ester mol ratio is 95: 1, reaction pressure is 3.5MPa.Reactor III operational condition: 220 ℃ of temperature of reaction, weight space velocity are 0.25 hour -1, hydrogen/ester mol ratio is 90: 1, reaction pressure is 3.5MPa.Hydrogen recovery system adopts the embrane method recovery technology, and its result is: hydrogen utilization ratio is 91.7%, and the transformation efficiency of dimethyl oxalate is 100%, and the selectivity of ethylene glycol is 94.5%.
[embodiment 10]
Each Step By Condition according to embodiment 1 makes 40%Ni+15%Zn/SiO 2Catalyst I, 30%Ni+3%Mn+1%K/SiO 2Catalyst I I and 25%Cu+3%Ni/SiO 2Catalyst I II.
With the dimethyl oxalate is raw material, at first enters among the reactor I after fresh hydrogen, circulation gas I, circulation gas II and first strand of dimethyl oxalate raw material mix to contact with copper containing catalyst I, and generation contains the reaction effluent I of ethylene glycol; The reaction effluent I that contains ethylene glycol contact with copper containing catalyst II with entering among the reactor II after second strand of dimethyl oxalate raw material mixes, and generation contains the reaction effluent II of ethylene glycol; The reaction effluent II that contains ethylene glycol contact with copper containing catalyst III with entering among the reactor III after the 3rd strand of dimethyl oxalate raw material mixes, and generation contains the reaction effluent III of ethylene glycol; The reaction effluent III that contains ethylene glycol is after gas-liquid separation, the liquid phase effluent enters and obtains the ethylene glycol product after separation system is separated, the gas phase effluent is divided into gas phase effluent I and gas phase effluent II, and gas phase effluent I directly mixes with fresh hydrogen as circulation gas I; Gas phase effluent II enters hydrogen recovery system and obtains circulation gas II and conciliate the gassing body, resolves gas and send fuel system to make fuel usefulness, and circulation gas II mixes with fresh hydrogen and continues to recycle.Wherein, the mol ratio of gas phase effluent I and fresh hydrogen is 35: 1, the mol ratio of gas phase effluent II and gas phase effluent I is 0.25: 1, first strand of dimethyl oxalate raw material and second strand of dimethyl oxalate raw material with the 3rd strand of dimethyl oxalate material molar ratio be: 1: 1: 1.The operational condition of reactor I is: 210 ℃ of temperature of reaction, reaction pressure 3.5MPa, weight space velocity 0.4 hour -1, hydrogen/ester mol ratio is 100: 1; Reactor II operational condition: 225 ℃ of temperature of reaction, weight space velocity are 0.35 hour -1, hydrogen/ester mol ratio is 95: 1, reaction pressure is 3.5MPa.Reactor III operational condition: 220 ℃ of temperature of reaction, weight space velocity are 0.25 hour -1, hydrogen/ester mol ratio is 90: 1, reaction pressure is 3.5MPa.Hydrogen recovery system adopts the embrane method recovery technology, and its result is: hydrogen utilization ratio is 92.7%, and the transformation efficiency of dimethyl oxalate is 100%, and the selectivity of ethylene glycol is 84.5%.
[comparative example 1]
Employing is with embodiment 2 identical condition and catalyzer, just do not introduce hydrogen recovery system and the not segmentation of raw material dimethyl oxalate and inject, keep under the situation of identical hydrogen purity, the utilization ratio of hydrogen is 80%, the transformation efficiency of dimethyl oxalate is 96.5%, and the selectivity of ethylene glycol is 85.1%.
Obviously, the inventive method compared with prior art has the hydrogen utilization ratio height, and the glycol selectivity advantages of higher has remarkable technical superiority.

Claims (7)

1. the method for a producing ethylene glycol from hydrogenation of oxalic ester is a raw material with the barkite, may further comprise the steps:
A) at first enter among the reactor I after fresh hydrogen, circulation gas I, circulation gas II and first strand of barkite raw material mix and contact with copper containing catalyst I, generation contains the reaction effluent I of ethylene glycol;
B) the reaction effluent I that contains ethylene glycol contact with copper containing catalyst II with entering among the reactor II after second strand of barkite raw material mixes, and generation contains the reaction effluent II of ethylene glycol;
C) contain the reaction effluent II of ethylene glycol after gas-liquid separation, the liquid phase effluent enters and obtains the ethylene glycol product after separation system is separated, the gas phase effluent is divided into gas phase effluent I and gas phase effluent II, and gas phase effluent I directly mixes with fresh hydrogen as circulation gas I;
D) gas phase effluent II enters hydrogen recovery system and obtains circulation gas II and conciliate the gassing body, and circulation gas II mixes with fresh hydrogen and continues to recycle;
Wherein, the mol ratio of gas phase effluent I and fresh hydrogen is 0.5～100: 1, and the mol ratio of gas phase effluent II and gas phase effluent I is 0.01～5: 1; First strand of barkite raw material and second strand of barkite material molar ratio are: 0.5～2: 1; Barkite is selected from dimethyl oxalate, oxalic acid diethyl ester or its mixture.
2. according to the method for the described producing ethylene glycol from hydrogenation of oxalic ester of claim 1, it is characterized in that the operational condition of reactor I is: 190 ℃～300 ℃ of temperature of reaction, reaction pressure 1.5～8.0MPa, weight space velocity 0.05～5 hour -1, hydrogen/ester mol ratio is 30～200: 1; Reactor II operational condition: 180～280 ℃ of temperature of reaction, weight space velocity are 0.05～5 hour -1, hydrogen/ester mol ratio is 30～200: 1, reaction pressure is 1.5～8.0MPa.
3. according to the method for the described producing ethylene glycol from hydrogenation of oxalic ester of claim 2, it is characterized in that the operational condition of reactor I is: 200 ℃～260 ℃ of temperature of reaction, reaction pressure 2.0～7.0MPa, weight space velocity 0.1～3 hour hour -1, hydrogen/ester mol ratio is 40～150: 1; Reactor II operational condition: 190～260 ℃ of temperature of reaction, weight space velocity are 0.08～3 hour -1, hydrogen/ester mol ratio is 40～150: 1, reaction pressure is 2.0～7.0MPa.
4. according to the method for the described producing ethylene glycol from hydrogenation of oxalic ester of claim 1, the mol ratio that it is characterized in that gas phase effluent I and virgin gas is 1～50: 1, and the mol ratio of gas phase effluent II and gas phase effluent I is 0.05～2: 1; First strand of barkite raw material and second strand of barkite material molar ratio are: 0.8～1.5: 1.
5. according to the method for the described producing ethylene glycol from hydrogenation of oxalic ester of claim 1, it is characterized in that copper containing catalyst I and copper containing catalyst II all with silicon oxide, at least a in the aluminum oxide is carrier, is 10～80% of catalyst weight in simple substance copper consumption.
6. according to the method for the described producing ethylene glycol from hydrogenation of oxalic ester of claim 5, it is characterized in that copper containing catalyst I and copper containing catalyst II all are carrier with the silicon oxide, is 20～60% of catalyst weight in simple substance copper consumption.
7. according to the method for the described producing ethylene glycol from hydrogenation of oxalic ester of claim 1, it is characterized in that barkite is selected from dimethyl oxalate or oxalic acid diethyl ester.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107848921A (en) * 2015-07-29 2018-03-27 巴斯夫欧洲公司 Method for producing monoethylene glycol
CN111302895A (en) * 2019-10-31 2020-06-19 上海开荣化工科技有限公司 Synthesis method of high-purity ethylene glycol

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CN101462961A (en) * 2008-01-28 2009-06-24 上海戊正工程技术有限公司 Process flow for producing ethylene glycol with coproduction product dimethyl carbonate
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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Publication number Priority date Publication date Assignee Title
CN101462961A (en) * 2008-01-28 2009-06-24 上海戊正工程技术有限公司 Process flow for producing ethylene glycol with coproduction product dimethyl carbonate
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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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107848921A (en) * 2015-07-29 2018-03-27 巴斯夫欧洲公司 Method for producing monoethylene glycol
CN107848921B (en) * 2015-07-29 2022-01-25 巴斯夫欧洲公司 Process for the production of monoethylene glycol
CN111302895A (en) * 2019-10-31 2020-06-19 上海开荣化工科技有限公司 Synthesis method of high-purity ethylene glycol

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