CN101993344B - Method for preparing ethylene glycol from synthesis gas - Google Patents
Method for preparing ethylene glycol from synthesis gas Download PDFInfo
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- CN101993344B CN101993344B CN200910057842XA CN200910057842A CN101993344B CN 101993344 B CN101993344 B CN 101993344B CN 200910057842X A CN200910057842X A CN 200910057842XA CN 200910057842 A CN200910057842 A CN 200910057842A CN 101993344 B CN101993344 B CN 101993344B
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Abstract
The invention relates to a method for preparing ethylene glycol from synthesis gas and mainly solves the technical problems of the previous technologies that the selectivity of the target product is low and the utilization rates of H2 and CO in synthesis gas are low. The method uses synthesis gas as the raw material and comprises the following steps: a) synthesis gas firstly enters a gas separation unit and is separated to obtain CO gaseous effluent I and H2 effluent II; b) the CO gaseous effluent I and nitrite enter a carbonyl synthesis unit to obtain reaction effluent III; c) the reaction effluent III is separated to obtain oxalate effluent V, gaseous effluent VI and gaseous effluent VII, the gaseous effluent VII is directly returned to the carbonyl synthesis unit for recycling; d) the oxalate effluent V and the H2 effluent II enter a hydrogenation reaction unit to obtain ethylene glycol product effluent IX, gaseous effluent XI with H2 and gaseous effluent XII with H2, the gaseous effluent XII is directly returned to the hydrogenation reaction unit and is reused in the hydrogenation reactor; and e) the gaseous effluent VI and the gaseous effluent XI are returned to the gas separation unit to be separated for recycling. The technical scheme of the invention better solves the technical problems and can be used in the industrial production for increasing the yield of ethylene glycol.
Description
Technical field
The present invention relates to a kind of synthetic gas and produce the method for ethylene glycol, particularly about by coal or producing synthesis gas from natural gas, synthetic gas is isolated to CO and hydrogen, and CO makes barkite, and the barkite repeated hydrogenation is produced the method for ethylene glycol to the two-step approach of ethylene glycol by synthetic gas.
Background technology
Ethylene glycol (EG) is a kind of important Organic Chemicals, mainly for the production of trevira, 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 printing ink, solvent and medium as ammonium pertorate, for the production of special solvent glycol ether etc., purposes is very extensive.
At present, domestic and international large-scale ethylene glycol production all adopts direct hydration method or the legal operational path of pressurized water, this technique is that oxyethane and water are made into to mixed aqueous solution by 1: 20～22 (mol ratios), in fixed-bed reactor in 130～180 ℃, 1.0 react under～2.5MPa 18～30 minutes, oxyethane all is converted into alcohol mixture, the aqueous glycol solution content generated is greatly about 10% (massfraction), then separate and obtain ethylene glycol with rectification under vacuum through multiple-effect evaporator dehydration concentrate, but production equipment need arrange a plurality of vaporizers, consume a large amount of energy for dehydration, cause the technological process of production long, equipment is many, energy consumption is high, directly affect the production cost of ethylene glycol.Since 20 century 70s, both at home and abroad some major companies that mainly produce ethylene glycol all are devoted to the research of Synthesis of Ethylene Glycol by Catalytic Hydration 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 Catalytic 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 technique as catalyzer, obtain EO transformation efficiency 96%～98%, the test-results of EG selectivity 97%～98%, within 1997, develop again the poly organic silicon alkane ammonium salt loaded catalyst of similar silicon dioxide skeleton and the epoxide hydrating process under catalysis thereof, obtained transformation efficiency and selectivity preferably.The UCC company of the U.S. has mainly developed two kinds of hydration catalysts: a kind of is the anionic catalyst be carried on ion exchange resin, is mainly molybdate, tungstate, vanadate and triphenylphosphine complex catalyst; Another kind is the molybdate composite catalyst.In the example application of two kinds of catalyzer, TM catalyzer prepared by spent ion exchange resin DOWEX WSA21, the Water Under that is 9: 1 in the mol ratio of water and EO closes, and the EG yield is 96%.Application molybdate composite catalyst, the Water Under that is 5: 1 in the mol ratio of water and EO closes, and the EG yield is 96.6%.Catalysis method greatly reduces the water ratio, can obtain high EO transformation efficiency and high EG selectivity simultaneously, but also there is certain problem aspect catalyzer preparation, regeneration and life-span, as catalyst stability not, prepare very complex, be difficult to recycle, have also can be in product residual a certain amount of anionic metal, need to increase corresponding equipment and separate.NSC 11801 method synthesizing glycol is by oxyethane and carbonic acid gas synthesizing ethylene carbonate, then obtains ethylene glycol with the NSC 11801 hydrolysis.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 criticality, obtain oxyethane, carbonic acid gas, water mixture contacts synthetic BC with catalyst for esterification reaction such as Organohalogen compounds, sulfohalides, then BC is admitted to hydrolysis reactor, and under same catalyst action, hydrolysis obtains ethylene glycol and carbonic acid gas, and the ethylene glycol yield is up to 99%.Japanese Patent JP571006631 has proposed the EO-EC-EG novel process of industrially scalable, patent Introduction oxyethane and carbonic acid gas esterification are under catalyzer KI exists, 160 ℃ are carried out esterification, transformation efficiency is 99.9%, the selectivity of ethylene glycol is 100%, the standby ethylene glycol technology of NSC 11801 legal system is no matter aspect transformation efficiency and selectivity, or all than current BO direct hydration method, larger advantage is being arranged aspect production process raw material consumption and energy expenditure, be a kind of method maintained the leading position on the ethylene glycol technology of preparing.But this method still be take oil as raw material, and need to again build the ethylene glycol production equipment, this glycol unit to new construction is more suitable, and, on original production unit is undergone technological transformation, is not so good as catalytic hydration favourable.
Document CN101138725A discloses a kind of Catalysts and its preparation method of oxalic ester hydrogenation synthesizing of ethylene glycol, it take metallic copper as active ingredient, zinc is auxiliary agent, the preparation of employing coprecipitation method, but this catalyzer barkite transformation efficiency is lower, there is no the catalyst stability report yet, do not mention the problem that hydrogen effectively utilizes yet simultaneously.
340th～343 pages of document " petrochemical complex " the 36th the 4th phases of volume in 2007 have 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 there is no equally the report of catalyst stability, also do not mention the problem that hydrogen effectively utilizes.
At present, the World oil price fluctuation is larger, and is becoming tight petroleum resources day, and the resource general layout of China can be summarized as few oil, weak breath, the energy general layout of many coals.Development carbon one chemical industry not only can take full advantage of Sweet natural gas and coal resource, reduces the dependence of petroleum import and can alleviate environmental stress, is unusual important field of research.Take synthetic gas as raw material, first separate and obtain carbon monoxide, CO prepares barkite by linked reaction, by preparing glycol by hydrogenating oxalate, is then a very attractive Coal Chemical Industry Route.
Summary of the invention
Technical problem to be solved by this invention is that the purpose selectivity of product existed in prior art is low, hydrogen and the low technical problem of CO utilization ratio in synthetic gas, a kind of method that provides new synthetic gas to produce ethylene glycol.It is high that the method has glycol selectivity, hydrogen and CO utilization ratio advantages of higher in synthetic gas.
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 synthetic gas is produced the method for ethylene glycol, take synthetic gas as raw material, comprises the following steps:
A) at first raw material of synthetic gas enters gas separation unit and obtain CO gaseous effluent I and hydrogen effluent II after separating;
B) CO gaseous effluent I enters the oxo process unit with nitrous acid ester and contacts with palladium-containing catalyst in the CO coupler reactor, and reaction generates the reaction effluent III that contains NO and barkite;
C) reaction effluent III, after separating, obtains gas phase effluent IV and barkite effluent V, and gas phase effluent IV is divided into gas phase effluent VI and gas phase effluent VII, and gas phase effluent VII directly returns to the oxo process unit and recycles;
D) barkite effluent V is with from step, the hydrogen effluent II in a) enters the hydrogenation reaction unit, in hydrogenator, with copper containing catalyst, contact, reaction generates the effluent VIII containing ethylene glycol, and effluent VIII obtains ethylene glycol product effluent IX and contains H after separating
2gas phase effluent X, the gas phase effluent is divided into gas phase effluent XI and gas phase effluent XII, gas phase effluent XII directly returns to the hydrogenation reaction unit, in hydrogenator, recycles;
E) from step c) in gas phase effluent VI with from steps d) in gas phase effluent XI return step a) in gas separation unit after separating, recycle;
Wherein, step c), the mol ratio of gas phase effluent VII and gas phase effluent VI is 1～120: 1; Steps d) in, the mol ratio of gas phase effluent XII and gas phase effluent XI is 1～120: 1.
CO coupler reactor operational condition in technique scheme: temperature of reaction is 80～180 ℃, and reaction contact time is 0.1～50 second, and reaction pressure is-0.05～1.5MPa, and CO and nitrous acid ester mol ratio are 1～5: 1; CO coupler reactor operational condition preferable range is: temperature of reaction is 90～160 ℃, and reaction contact time is 0.2～30 second, and reaction pressure is 0.01～1.0MPa, and CO and nitrous acid ester mol ratio are 1～3: 1.The hydrogenator operational condition: temperature of reaction is 170 ℃～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.Hydrogenator operational condition preferable range is: temperature of reaction is 190 ℃～260 ℃, and reaction pressure is 2.0～6.0MPa, and weight space velocity is 0.05～3 hour
-1, hydrogen/ester mol ratio is 50～150: 1.
Palladium-containing catalyst active component palladium in technique scheme, the simple substance consumption of take is catalyst weight 0.02～1%, preferred weight range is 0.02～0.6%; Palladium-containing catalyst also comprises auxiliary agent and carrier, auxiliary agent is selected from least one in basic metal, alkaline-earth metal or transition metal element compound, the simple substance consumption of take is catalyst weight 0.01～15%, the auxiliary agent preferred version is selected from least one in K, Fe, Ce or Sn compound, and the simple substance consumption preferable range of take is catalyst weight 0.05～10%; Carrier is selected from α-Al
2o
3, γ-Al
2o
3, δ-Al
2o
3, η-Al
2o
3, θ-Al
2o
3, at least one in silica/alumina, zeolite, non-zeolite molecular sieve, titanium oxide or zirconium white, count 86～99.7% with catalyst weight, the carrier preferred version is selected from α-Al
2o
3, the catalyst weight preferable range of take is catalyst weight 89.4～99.0%.
In technique scheme, copper containing catalyst also comprises active ingredient, auxiliary agent and carrier, and carrier is selected from least one in silicon oxide or aluminum oxide, preferably autoxidation silicon; Active ingredient is selected from oxide compound or its mixture of metallic copper, copper, and preferably from the mixture of metallic copper or Red copper oxide, the simple substance consumption of take is catalyst weight 10～70%, and the simple substance consumption preferable range of take is catalyst weight 15～60%; Auxiliary agent is selected from least one in alkali earth metal, transition metal or thulium, preferably from alkali earth metal Mg, Ca and Ba, alkali metal element K, Na, the V of transition metal, Ti, Mn, Fe, Co, Ni and Zn, perhaps at least one in rare-earth metals La, Eu, Gd and Tb, the simple substance amount ranges of take is catalyst weight 0.01～20%, and the simple substance consumption preferable range of take is catalyst weight 0.01～15%.
In technique scheme, from gasification or Sweet natural gas, conversion makes synthetic gas, and the synthetic gas preferably made from gasification, from step c in claim 1) in the mol ratio preferable range of gas phase effluent VII and gas phase effluent VI be 2～100: 1; Steps d) in, the mol ratio preferable range of gas phase effluent XII and gas phase effluent XI is 2～100: 1.
In the present invention: adopt CO coupling producing oxalic ester reaction emptying end gas is introduced to synthetic gas separating unit entrance, CO in recycling use emptying, simultaneously, the oxalate hydrogenation emptying end gas is also introduced to synthetic gas separating unit entrance, reclaim most of hydrogen and a small amount of CO, further fully recycle.Research shows, in the reaction process of barkite hydrogenation generating glycol, except the main reaction that generates the purpose glycol product, also exist barkite to decompose, the side reactions such as dehydration of alcohols, cause in reaction end gas also containing methane except hydrogen, ethane, dme, the gases such as CO, in Industrial processes, because hydrogenation process hydrogen is greatly excessive, therefore, most of hydrogen need recycle, but the methane in recycled offgas is found in research, ethane, dme, the gases such as CO are after concentration runs up to a certain degree, the transformation efficiency of meeting remarkably influenced barkite, the selectivity of ethylene glycol and the stability of catalyzer.For this reason, regularly discharge cycle hydrogen, be very necessary with the transition accumulation that prevents impurity in gas phase, but consider that hydrogen is raw material important in hydrogenation reaction, if in discharge gas, hydrogen can't reclaim and causes the energy consumption of producing ethylene glycol large, cost is high.At first adopt first step hydrogen recovery system in the present invention, by most of hydrogen recovery, all the other are impure relatively high, but main ingredient is still the emission of hydrogen, introduce synthetic gas separating unit unstripped gas entrance, after further separation, can, by most of hydrogen purification, enter in turn the follow-up hydrogenation unit and continue to use.In addition, decomposing by barkite the CO gas produced in emission also can be recycled by flow process of the present invention.
In like manner, in CO coupling producing oxalic ester unit, because the accumulation of rare gas element needs the tail gas containing CO gas of discharge, also introduce synthetic gas separating unit unstripped gas entrance, after further separation, most of CO can be purified, enter in turn follow-up oxo process unit and continue to use.In the present invention, hydrogen recovery system can adopt pressure swing adsorption, also can adopt the embrane method recovery technology, or adopts the advanced isolation technique such as membrane separating technology and pressure swing adsorption combination, has energy consumption low, and floor space is little, hydrogen and CO utilization ratio advantages of higher.
The hydrogen of indication of the present invention and CO utilization ratio obtain by following account form:
The fresh hydrogen tolerance of hydrogen utilization ratio=(entering the amounts of hydrogen of the fresh hydrogen tolerance of system-emptying from system)/enter system * 100%.
The fresh hydrogen tolerance of CO utilization ratio=(entering the CO amount of the fresh CO amount-emptying from system of system)/enter system * 100%.
Adopt technical scheme of the present invention, synthetic gas obtains CO and hydrogen after separating, CO and methyl nitrite enter the oxo process unit, in the CO coupler reactor, with palladium-containing catalyst, contact, reaction oxalic dimethyl ester, dimethyl oxalate enters hydrogenator with after the hydrogen mixing obtained after separating from synthetic gas, contact with copper containing catalyst and obtain flowing out thing containing ethylene glycol, obtain the ethylene glycol product after separating, wherein the emission from oxo process unit and hydrogenation unit returns to synthetic gas separating unit unstripped gas entrance, after separating, recycles.In CO coupler reactor operational condition: temperature of reaction is 90～160 ℃, and reaction contact time is 0.2～30 second, and reaction pressure is 0.01～1.0MPa; The hydrogenator operational condition: temperature of reaction is 190 ℃～260 ℃, and reaction pressure is 2.0～6.0MPa, and weight space velocity is 0.05～3 hour
-1, under the condition that hydrogen/the ester mol ratio is 50～150: 1, hydrogen and CO utilization ratio are greater than 97%, and the selectivity of ethylene glycol is greater than 95%, has obtained technique effect preferably.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
[embodiment 1]
Contain the preparation of the CO coupling producing oxalic ester catalyzer of palladium:
Iron nitrate is dissolved in water, is heated to 80 ℃, vacuum rotating is immersed in the α-Al of 5 millimeters
2o
3on bead, then in 120 ℃ of dryings 4 hours.Saltpetre and Palladous nitrate are dissolved in the water respectively, and making its pH value with the HCl regulator solution is 4 left and right, then this solution is heated to 80 ℃, is immersed in the α-Al of 5 millimeters
2o
3on bead, then in 140 ℃ of dryings 4 hours, then 450 ℃ of roastings 4 hours, be down to room temperature, obtain required palladium-containing catalyst, its weight consists of: 0.45%Pd+0.40%K+0.22%Fe/ α-Al
2o
3.
The preparation of the hydrogenation of oxalate for preparing ethylene glycol catalyzer of cupric:
Silica support 200 grams that to take specific surface be 300 meters squared per gram, according to 35% reactive metal copper and 2% auxiliary agent 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, after silica support is flooded to 24 hours in this solution, at room temperature vacuum-drying obtains solids in 12 hours.Again by solid under 120 ℃ dry 12 hours, 450 ℃ of roastings made required copper containing catalyst after 4 hours, and its weight consists of 35%Cu+2%Zn/SiO
2.
Take the above-mentioned palladium-containing catalyst made of 10 grams, the diameter of packing into is in the tubular type coupler reactor of 18 millimeters, the reaction procatalyst is in 100 ml/min, hydrogen molar content 20%, under nitrogen molar content 80% condition, be raised to 300 ℃ from room temperature with 3 ℃/minute, constant temperature, after 3 hours, is down to temperature of reaction and is fed intake.
Take the above-mentioned copper containing catalyst made of 30 grams, in the tubular reactor that the diameter of packing into is 18 millimeters, 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 is activated in 6 hours, then is down to temperature of reaction and feeds intake.
At first raw material of synthetic gas enters gas separation unit and obtain CO gaseous effluent I and hydrogen effluent II after separating; CO gaseous effluent I enters the oxo process unit with methyl nitrite and contacts with palladium-containing catalyst in the CO coupler reactor, and reaction generates the reaction effluent III that contains NO and dimethyl oxalate; Reaction effluent III, after separating, obtains gas phase effluent IV and dimethyl oxalate effluent V, and gas phase effluent IV is divided into gas phase effluent VI and gas phase effluent VII, and gas phase effluent VII directly returns to the oxo process unit and recycles; Dimethyl oxalate effluent V is with from step, the hydrogen effluent II in a) enters the hydrogenation reaction unit, in hydrogenator, with copper containing catalyst, contact, reaction generates the effluent VIII containing ethylene glycol, and effluent VIII obtains ethylene glycol product effluent IX and contains H after separating
2gas phase effluent X, the gas phase effluent is divided into gas phase effluent XI and gas phase effluent XII, gas phase effluent XII directly returns to the hydrogenation reaction unit, in hydrogenator, recycles; Gas phase effluent VI returns to gas separation unit with gas phase effluent XI and recycles after separating; Wherein, the mol ratio of gas phase effluent VII and gas phase effluent VI is 100: 1; The mol ratio of gas phase effluent XII and gas phase effluent XI is 100: 1.CO coupler reactor operational condition: temperature of reaction is 120 ℃, and reaction contact time is 40 seconds, and reaction pressure is-0.056MPa that CO and methyl nitrite mol ratio are 1.2: 1; The hydrogenator operational condition: temperature of reaction is 190 ℃, and reaction pressure is 1.5MPa, and weight space velocity is 0.05 hour
-1, hydrogen/ester mol ratio is 50: 1, its result is: the CO utilization ratio is 99.4%, hydrogen utilization ratio is 98.1%, the selectivity of oxo process unit dimethyl oxalate is 97.4%, and the transformation efficiency that barkite adds the hydrogen partial dimethyl oxalate is 99.5%, and the selectivity of ethylene glycol is 88.0%.
[embodiment 2]
Each Step By Condition according to embodiment 1 makes 0.2%Pd+0.22%Fe/ α-Al
2o
3palladium-containing catalyst and 48%Cu+8%Zn+0.2%K/SiO
2copper containing catalyst, reductive condition and reaction process are with embodiment 1.Just, in corresponding process, the mol ratio of gas phase effluent VII and gas phase effluent VI is 60: 1; The mol ratio of gas phase effluent XII and gas phase effluent XI is 60: 1.CO coupler reactor operational condition: temperature of reaction is 90 ℃, and reaction contact time is 20 seconds, and reaction pressure is 0.01MPa, and CO and methyl nitrite mol ratio are 2: 1; The hydrogenator operational condition: temperature of reaction is 210 ℃, and reaction pressure is 2.5MPa, and weight space velocity is 1 hour
-1, hydrogen/ester mol ratio is 80: 1, its result is: the CO utilization ratio is 99.1%, hydrogen utilization ratio is 98.5%, the selectivity of oxo process unit dimethyl oxalate is 99.2%, and the transformation efficiency of hydrogenation reaction unit dimethyl oxalate is 99.8%, and the selectivity of ethylene glycol is 95.7.0%.
[embodiment 3]
Each Step By Condition according to embodiment 1 makes 0.17%Pd+0.12%Fe/ α-Al
2o
3palladium-containing catalyst and 48%Cu+8%Zn+0.2%K/SiO
2copper containing catalyst, reductive condition and reaction process are with embodiment 1.Just, in corresponding step process, the mol ratio of gas phase effluent VII and gas phase effluent VI is 50: 1; The mol ratio of gas phase effluent XII and gas phase effluent XI is 60: 1.CO coupler reactor operational condition: temperature of reaction is 100 ℃, and reaction contact time is 9 seconds, and reaction pressure is 0.2MPa, and CO and methyl nitrite mol ratio are 1.1: 1; The hydrogenator operational condition: temperature of reaction is 230 ℃, and reaction pressure is 3.0MPa, and weight space velocity is 0.8 hour
-1, hydrogen/ester mol ratio is 150: 1, its result is: the CO utilization ratio is 98.8%, hydrogen utilization ratio is 99.1%, the selectivity of oxo process unit dimethyl oxalate is 98.1%, and the transformation efficiency of hydrogenation reaction unit dimethyl oxalate is 100%, and the selectivity of ethylene glycol is 95.40%.
[embodiment 4]
Each Step By Condition according to embodiment 1 makes 0.34%Pd+1.0%K+0.46%Mn/ α-Al
2o
3palladium-containing catalyst and the copper containing catalyst of 30%Cu+3%Mn+1%Li/ZSM-5, reductive condition and reaction process are with embodiment 1.Just, in corresponding process, the mol ratio of gas phase effluent VII and gas phase effluent VI is 10: 1; The mol ratio of gas phase effluent XII and gas phase effluent XI is 10: 1.CO coupler reactor operational condition: temperature of reaction is 140 ℃, and reaction contact time is 6 seconds, and reaction pressure is 0.5MPa, and CO and methyl nitrite mol ratio are 1.5: 1; The hydrogenator operational condition: temperature of reaction is 260 ℃, and reaction pressure is 6.0MPa, and weight space velocity is 3.0 hours
-1, hydrogen/ester mol ratio is 200: 1, its result is: the CO utilization ratio is 98.2%, hydrogen utilization ratio is 98.6%, the selectivity of oxo process unit dimethyl oxalate is 97.9%, and the transformation efficiency of hydrogenation reaction unit dimethyl oxalate is 100%, and the selectivity of ethylene glycol is 97.20%.
[embodiment 5]
Each Step By Condition according to embodiment 1 makes the magnesian palladium-containing catalyst of 0.11%Pd+0.6%Ba+0.2%Fe/ and 60%Cu+0.5%Ni+1%Ba/Al
2o
3copper containing catalyst, reductive condition and reaction process are with embodiment 1.Just, in corresponding process, the mol ratio of gas phase effluent VII and gas phase effluent VI is 30: 1; The mol ratio of gas phase effluent XII and gas phase effluent XI is 20: 1.CO coupler reactor operational condition: temperature of reaction is 160 ℃, and reaction contact time is 1 second, and reaction pressure is 1.0MPa, and CO and methyl nitrite mol ratio are 2.5: 1; The hydrogenator operational condition: temperature of reaction is 240 ℃, and reaction pressure is 7.5MPa, and weight space velocity is 2.0 hours
-1, hydrogen/ester mol ratio is 100: 1, its result is: the CO utilization ratio is 98.9%, hydrogen utilization ratio is 98.6%, the selectivity of oxo process unit dimethyl oxalate is 99.1%, and the transformation efficiency of hydrogenation reaction unit dimethyl oxalate is 100%, and the selectivity of ethylene glycol is 96.20%.
[embodiment 6]
Each Step By Condition according to embodiment 1 makes 0.8%Pd+10%Ce+0.003%Zr+0.507%Fe/TiO
2palladium-containing catalyst and 18%Cu+15%Mn+0.08%Ce/SiO
2copper containing catalyst, reductive condition and reaction process are with embodiment 1.Just, in corresponding process, the mol ratio of gas phase effluent VII and gas phase effluent VI is 2: 1; The mol ratio of gas phase effluent XII and gas phase effluent XI is 30: 1.CO coupler reactor operational condition: temperature of reaction is 130 ℃, and reaction contact time is 3 seconds, and reaction pressure is normal pressure, and CO and methyl nitrite mol ratio are 1.05: 1; The hydrogenator operational condition: temperature of reaction is 230 ℃, and reaction pressure is 4.0MPa, and weight space velocity is 0.5 hour
-1, hydrogen/ester mol ratio is 80: 1, its result is: the CO utilization ratio is 98.7%, hydrogen utilization ratio is 98.3%, the selectivity of oxo process unit dimethyl oxalate is 98.9%, and the transformation efficiency of hydrogenation reaction unit dimethyl oxalate is 100%, and the selectivity of ethylene glycol is 95.10%.
[embodiment 7]
Each Step By Condition according to embodiment 1 makes 0.6%Pd+0.2%Cu+0.08%Fe/ α-Al
2o
3palladium-containing catalyst and 38%Cu+0.1%V+0.05%La+0.2%Zr/SiO
2copper containing catalyst, reductive condition and reaction process are with embodiment 1.Just, in corresponding process, the mol ratio of gas phase effluent VII and gas phase effluent VI is 20: 1; The mol ratio of gas phase effluent XII and gas phase effluent XI is 5: 1.CO coupler reactor operational condition: temperature of reaction is 140 ℃, and reaction contact time is 5 seconds, and reaction pressure is-0.02MPa that CO and methyl nitrite mol ratio are 1.3: 1; The hydrogenator operational condition: temperature of reaction is 180 ℃, and reaction pressure is 3.0MPa, and weight space velocity is 0.08 hour
-1, hydrogen/ester mol ratio is 70: 1, its result is: the CO utilization ratio is 98.1%, hydrogen utilization ratio is 98.3%, the selectivity of oxo process unit dimethyl oxalate is 97.8%, and the transformation efficiency of hydrogenation reaction unit dimethyl oxalate is 98.7%, and the selectivity of ethylene glycol is 90.01%.
[embodiment 8]
Each Step By Condition according to embodiment 1 makes 0.30%Pd+0.2%Bi+0.02%Fe/ α-Al
2o
3palladium-containing catalyst and 38%Cu+0.1%W+0.05%La/SiO
2copper containing catalyst, reductive condition and reaction process are with embodiment 1.Just, in corresponding process, the mol ratio of gas phase effluent VII and gas phase effluent VI is 50: 1; The mol ratio of gas phase effluent XII and gas phase effluent XI is 60: 1.CO coupler reactor operational condition: temperature of reaction is 160 ℃, and reaction contact time is 0.1 second, and reaction pressure is 0.02MPa, and CO and methyl nitrite mol ratio are 1.25: 1; The hydrogenator operational condition: temperature of reaction is 220 ℃, and reaction pressure is 3.0MPa, and weight space velocity is 0.2 hour
-1, hydrogen/ester mol ratio is 100: 1, its result is: the CO utilization ratio is 98.9%, hydrogen utilization ratio is 98.9%, the selectivity of oxo process unit dimethyl oxalate is 98.9%, and the transformation efficiency of hydrogenation reaction unit dimethyl oxalate is 100%, and the selectivity of ethylene glycol is 96.01%.
[embodiment 9]
Each Step By Condition according to embodiment 1 makes 0.30%Pd+0.2%Bi+0.02%Fe/ α-Al
2o
3palladium-containing catalyst and 38%Cu+0.1%W+0.05%La/SiO
2copper containing catalyst, reductive condition and reaction process are with embodiment 1.Just, in corresponding process, the mol ratio of gas phase effluent VII and gas phase effluent VI is 50: 1; The mol ratio of gas phase effluent XII and gas phase effluent XI is 60: 1.CO coupler reactor operational condition: temperature of reaction is 160 ℃, and reaction contact time is 0.1 second, and reaction pressure is 0.02MPa, and CO and methyl nitrite mol ratio are 1.25: 1; The hydrogenator operational condition: temperature of reaction is 220 ℃, and reaction pressure is 3.0MPa, and weight space velocity is 0.2 hour
-1, hydrogen/ester mol ratio is 100: 1, its result is: the CO utilization ratio is 98.9%, hydrogen utilization ratio is 98.9%, the selectivity of oxo process unit dimethyl oxalate is 98.9%, and the transformation efficiency of hydrogenation reaction unit dimethyl oxalate is 100%, and the selectivity of ethylene glycol is 96.01%.
[embodiment 10]
Each Step By Condition according to embodiment 1 makes 0.3%Pd+6%W+0.50%Fe+0.7%Mo/ α-Al
2o
3palladium-containing catalyst and 35%Cu+2%Sn+0.3%Mg/SiO
2copper containing catalyst, reductive condition and reaction process are with embodiment 1.Just, in corresponding process, the mol ratio of gas phase effluent VII and gas phase effluent VI is 20: 1; The mol ratio of gas phase effluent XII and gas phase effluent XI is 40: 1.CO coupler reactor operational condition: temperature of reaction is 150 ℃, and reaction contact time is 5 seconds, and reaction pressure is normal pressure, and CO and ethyl nitrite mol ratio are 1.25: 1; The hydrogenator operational condition: temperature of reaction is 240 ℃, and reaction pressure is 3.0MPa, and weight space velocity is 0.6 hour
-1, hydrogen/ester mol ratio is 80: 1, its result is: the CO utilization ratio is 99.3%, hydrogen utilization ratio is 99.1%, the selectivity of oxo process unit oxalic acid diethyl ester is 98.9%, and the transformation efficiency of hydrogenation reaction unit oxalic acid diethyl ester is 100%, and the selectivity of ethylene glycol is 96.70%.
[comparative example 1]
Condition and catalyzer that employing is identical with embodiment 6, just tail gas is not introduced the gas separation unit recycling, keep in situation that reaction process CO is identical with hydrogen purity, its result is: the CO utilization ratio is 90.1%, hydrogen utilization ratio is 83.3%, the selectivity of oxo process unit dimethyl oxalate is 97.4%, and the transformation efficiency of hydrogenation reaction unit dimethyl oxalate is 99.7%, and the selectivity of ethylene glycol is 88.01%.
Obviously, the utilization ratio of this aspect method hydrogen and CO is high, and the glycol selectivity advantages of higher has remarkable technical superiority.
Claims (5)
1. the method that synthetic gas is produced ethylene glycol, take synthetic gas as raw material, comprises the following steps:
A) at first raw material of synthetic gas enters gas separation unit and obtain CO gaseous effluent I and hydrogen effluent II after separating;
B) CO gaseous effluent I enters the oxo process unit with nitrous acid ester and contacts with palladium-containing catalyst in the CO coupler reactor, and reaction generates the reaction effluent III that contains NO and barkite;
C) reaction effluent III, after separating, obtains gas phase effluent IV and barkite effluent V, and gas phase effluent IV is divided into gas phase effluent VI and gas phase effluent VII, and gas phase effluent VII directly returns to the oxo process unit and recycles;
D) barkite effluent V is with from step, the hydrogen effluent II in a) enters the hydrogenation reaction unit, in hydrogenator, with copper containing catalyst, contact, reaction generates the effluent VIII containing ethylene glycol, and effluent VIII obtains ethylene glycol product effluent IX and contains H after separating
2gas phase effluent X, the gas phase effluent is divided into gas phase effluent XI and gas phase effluent XII, gas phase effluent XII directly returns to the hydrogenation reaction unit, in hydrogenator, recycles;
E) from step c) in gas phase effluent VI with from steps d) in gas phase effluent XI return step a) in gas separation unit after separating, recycle;
Wherein, step c), the mol ratio of gas phase effluent VII and gas phase effluent VI is 1～120: 1; Steps d) in, the mol ratio of gas phase effluent XII and gas phase effluent XI is 1～120: 1;
The palladium-containing catalyst active component palladium, the simple substance consumption of take is catalyst weight 0.02～0.6%; Also comprise auxiliary agent and carrier, auxiliary agent is selected from least one in K, Fe compound, and the simple substance consumption of take is catalyst weight 0.05～10%; Carrier is selected from α-A1
2o
3, with catalyst weight, count 89.4～99.0%;
Copper containing catalyst comprises active ingredient, auxiliary agent and carrier, and carrier is selected from silicon oxide; Active ingredient all is selected from the mixture of metallic copper or Red copper oxide, and the simple substance consumption of take is catalyst weight 15～60%; Auxiliary agent is selected from alkali metal element K, transition metal V, or at least one in rare-earth metals La, and the simple substance consumption of take is catalyst weight 0.01～15%.
2. the method that synthetic gas is produced ethylene glycol according to claim 1, it is characterized in that CO coupler reactor operational condition: temperature of reaction is 80～180 ℃, reaction contact time is 0.1～50 second, and reaction pressure is-0.05～1.5MPa, and CO and nitrous acid ester mol ratio are 1～5: 1; The hydrogenator operational condition: temperature of reaction is 170 ℃～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.
3. the method that synthetic gas is produced ethylene glycol according to claim 2, it is characterized in that CO coupler reactor operational condition: temperature of reaction is 90～160 ℃, reaction contact time is 0.2～30 second, and reaction pressure is 0.01～1.0MPa, and CO and nitrous acid ester mol ratio are 1～3: 1; The hydrogenator operational condition: temperature of reaction is 190 ℃～260 ℃, and reaction pressure is 2.0～6.0MPa, and weight space velocity is 0.05～3 hour
-1, hydrogen/ester mol ratio is 50～150: 1.
4. the method that synthetic gas is produced ethylene glycol according to claim 1, is characterized in that synthetic gas makes from gasification or Sweet natural gas conversion.
5. the method that synthetic gas is produced ethylene glycol according to claim 1, is characterized in that step c) in the mol ratio of gas phase effluent VII and gas phase effluent VI be 2～100: 1; Steps d) in, the mol ratio of gas phase effluent XII and gas phase effluent XI is 2～100: 1.
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| CN102218320B (en) * | 2011-04-15 | 2013-04-17 | 上海浦景化工技术有限公司 | Catalyst for hydrogenation, preparation method and application thereof |
| CN102218330B (en) * | 2011-04-15 | 2013-02-13 | 上海浦景化工技术有限公司 | Supported catalyst used in selective synthesis, and preparation method and purpose thereof |
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| CN104341266B (en) * | 2014-10-22 | 2016-02-17 | 安徽淮化股份有限公司 | A kind of synthetic gas preparing ethylene glycol hydrogenation unit surveys the device and method of hydrogen ester ratio |
| CN107626320A (en) * | 2017-09-30 | 2018-01-26 | 内蒙古科技大学 | Oxalic ester hydrogenation synthesizing of ethylene glycol catalyst and preparation method and application |
| CN110922401B (en) * | 2018-09-19 | 2022-07-26 | 广东东阳光药业有限公司 | Preparation method of quinuclidone derivative |
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| CN109762602A (en) * | 2019-01-30 | 2019-05-17 | 浙江天禄环境科技有限公司 | A method of ethylene glycol is prepared using low-order coal multipath |
| CN109761747A (en) * | 2019-01-30 | 2019-05-17 | 浙江天禄环境科技有限公司 | A method of utilizing volatile matter preparing ethylene glycol in low-order coal |
| CN113372542A (en) * | 2021-05-17 | 2021-09-10 | 俏东方生物燃料集团有限公司 | Preparation method of bio-based polyethylene glycol oxalate resin |
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