CN102649702A - Method for improving stability of ethylene glycol catalyst synthesized by hydrogenation of oxalate - Google Patents
Method for improving stability of ethylene glycol catalyst synthesized by hydrogenation of oxalate Download PDFInfo
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- CN102649702A CN102649702A CN2011100464642A CN201110046464A CN102649702A CN 102649702 A CN102649702 A CN 102649702A CN 2011100464642 A CN2011100464642 A CN 2011100464642A CN 201110046464 A CN201110046464 A CN 201110046464A CN 102649702 A CN102649702 A CN 102649702A
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Abstract
The invention relates to a method for improving the stability of ethylene glycol catalyst synthesized by hydrogenation of oxalate, and mainly solves the technical problem in the prior art that the stability of the ethylene glycol catalyst synthesized by hydrogenation of oxalate is poor. The method comprises the following steps: (a) the hydrogen raw material enters a first reaction zone to be in contact with a cleanser at first, so as to obtain a first stream hydrogen effluent from which sulphur and chlorine impurities are removed; and (b) the first stream hydrogen effluent enters a second reaction zone to be in contact with a copper bearing catalyst after being mixed with the oxalate raw material, so as to produce a second stream reaction effluent containing ethylene glycol, wherein the oxalate raw material is selected from dimethyl oxalate, diethyl oxalate or a mixture of the both. By adopting the technical scheme, the 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 improves the oxalic ester hydrogenation synthesizing of ethylene glycol catalyst stability, particularly about improving the method for dimethyl oxalate hydrogenation or oxalic acid diethyl ester glycol catalyst synthesized by hydrogenating stability.
Background technology
Terepthaloyl moietie (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 are used to produce special solvent glycol ether etc., and purposes very extensively.
At present, the petroleum law route is mainly adopted in domestic and international large-scale terepthaloyl moietie production, and both oxidation of ethylene was an oxyethane; The legal operational path of oxyethane direct hydration method or pressurized water then; This technology is that oxyethane and water are made into mixed aqueous solution by 1: 20～22 (mol ratios), and in 130～180 ℃, 1.0～2.5MPa reacted 18～30 minutes down in fixed-bed reactor; Oxyethane all is converted into alcohol mixture; The aqueous glycol solution content that generates carry through the multiple-effect evaporator dehydration then and obtain terepthaloyl moietie dense the separation with rectification under vacuum, but production equipment need be provided with a plurality of vaporizers greatly about 10% (massfraction); Consume lot of energy and be used for dehydration, cause that the technological process of production is long, equipment is many, energy consumption is high.
Under situation about being becoming tight petroleum resources day, development oil replacement resource has become common recognition, 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 with preparing glycol by hydrogenating oxalate (coal-ethylene glycol) then.But in the preparing glycol by hydrogenating oxalate process, the stability of barkite hydrogenation catalyst is one of important factor of restriction coal-ethylene glycol skilled industryization, therefore, prolongs the stability of catalyzer, and meaning will be very great.
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, find that according to our test-results the stability of catalyzer is merely 1000 hours in this method, the stability of catalyzer is short.
Summary of the invention
Technical problem to be solved by this invention is the short problem of the oxalic ester hydrogenation synthesizing of ethylene glycol catalyst stability that exists in the method for document in the past, and a kind of method of new raising oxalic ester hydrogenation synthesizing of ethylene glycol catalyst stability is provided.This method has the long advantage of oxalic ester hydrogenation synthesizing of ethylene glycol catalyst stability.
In order to solve the problems of the technologies described above, the technical scheme that the present invention adopts is following: a kind of method that improves the oxalic ester hydrogenation synthesizing of ethylene glycol catalyst stability may further comprise the steps:
A) hydrogen feed at first gets in first reaction zone and contacts with scavenging agent, first strand of hydrogen effluent of be removed sulphur and chlorine impurity;
B) after first strand of hydrogen effluent and the barkite raw materials mix, get in second reaction zone and contact, generate the second strand of reaction effluent that contains terepthaloyl moietie with copper containing catalyst;
Wherein, scavenging agent in parts by weight comprise 30～98 parts be selected from least a in silicon oxide or the aluminum oxide be carrier and at least a active ingredient in Ca, Cu, Zn, Na, Fe, Ni, Mg, Pb or its oxide compound that is selected from of carrying on it 2～60 parts.
The first reaction zone operational condition: 20～400 ℃ of temperature of reaction, volume space velocity are 1000～10000 hours
-1, reaction pressure is 0.5～8.0MPa; The first reaction zone preferred operations condition is: 100～300 ℃ of temperature of reaction, volume space velocity are 2000～8000 hours
-1, reaction pressure is 0.5～5.0MPa; The second reaction zone operational condition: 160～300 ℃ of temperature of reaction, weight space velocity are 0.08～8 hour
-1, reaction pressure is 1.0～6.0MPa, hydrogen/ester mol ratio 20～120: 1.The second reaction zone preferred operations condition: 170～260 ℃ of temperature of reaction, weight space velocity are 0.1～6 hour
-1, reaction pressure is 1.5～5.0MPa, hydrogen/ester mol ratio is 40～120: 1.
To preferably include 40～80 parts be selected from least a in silicon oxide or the aluminum oxide in parts by weight be carrier and at least a active ingredient in Cu, Zn, Ni, Mg, Pb or its oxide compound that is selected from of carrying on it 10～60 parts to scavenging agent in the technique scheme.The barkite raw material is preferably selected from dimethyl oxalate, oxalic acid diethyl ester or its mixture
Among the present invention: set up one before in the oxalate hydrogenation district and purify reaction zone; The hydrogen that gets into hydroconversion reaction zone is carried out the impurity deep removal; Guarantee that the hydrogen poisonous substance impurity that gets into hydroconversion reaction zone is reduced to lower level, thereby guarantee the stable performance of barkite activity of hydrocatalyst.
A large amount of researchs show that for the hydrogenation of oxalate for preparing ethylene glycol reaction process, Cu-series catalyst is better active; The catalyst system that selectivity is higher; And for Cu-series catalyst, in the life-time service process, assemble factor such as grow up except carbon distribution, crystal grain and cause the catalyst stability variation, outside the decay of activity; The poisonous substance of the trace in the raw material is the also greatly activity of accelerator activator reduction usually, and especially the sulphur or the chlorine of trace are fatal to copper catalyst.Among the present invention,, the hydrogen that gets into hydroconversion reaction zone is carried out the impurity deep removal through setting up a purification reaction zone; Emphasis be remove its Shen impurity such as sulphur or chlorine to 0.1ppm; Through test, be surprised to find, the stability of catalyzer prolongs greatly and adds.
Adopting technical scheme of the present invention, is raw material with the dimethyl oxalate, the first reaction zone operational condition: 20～400 ℃ of temperature of reaction, volume space velocity are 1000～10000 hours
-1, reaction pressure is 0.5～8.0MPa; The second reaction zone operational condition: 160～300 ℃ of temperature of reaction, weight space velocity are 0.08～8 hour
-1, reaction pressure is 1.0～6.0MPa, hydrogen/ester mol ratio 20～120: 1.The scavenging agent active ingredient is selected from least a in Ca, Cu, Zn, Na, Fe, Ni, Mg, Pb or its oxide compound, and carrier is selected from silicon oxide or the aluminum oxide at least a; The employing silicon oxide is that the copper containing catalyst of carrier is under the condition of catalyzer, and the transformation efficiency of dimethyl oxalate is greater than 98%, and the selectivity of terepthaloyl moietie is greater than 95%, and the stability of catalyzer obtained better technical effect greater than 5000 hours.
Through embodiment the present invention is done further elaboration below, but be not limited only to present embodiment.
Embodiment
[embodiment 1]
Sample B among the embodiment 1 among the scavenging agent employing patent CN97116288.3A.
Taking by weighing specific surface is silica support 500 grams of 350 meters squared per gram; According to 35 parts of reactive metal copper content configuration catalyzer; Its step is following: choose cupric nitrate; Be made into steeping fluid according to the Cu charge capacity, silica support is flooded 24 hours in this solution after, vacuum-drying at room temperature 12 hours solids.Solid was descended dry 12 hours at 120 ℃, 450 ℃ of roastings made required CuO/SiO in 4 hours afterwards again
2Catalyst precursor.
Take by weighing the CuO/SiO that makes
2The catalyst precursor diameter of packing in the desired amount is in 24 millimeters the tubular reactor; The reaction procatalyst is in 200 ml/min, and hydrogen molar content 20% is under nitrogen molar content 80% condition; Be raised to 450 ℃ from room temperature with 3 ℃/minute, constant temperature carried out activation in 6 hours and obtains copper containing catalyst.
With the dimethyl oxalate is raw material, and hydrogen feed (chlorinity is 10ppm) at first gets in first reaction zone and contacts with scavenging agent, first strand of hydrogen effluent of the chlorine impurity that is removed; After first strand of hydrogen effluent and the barkite raw materials mix, get in second reaction zone and contact, generate the second strand of reaction effluent that contains terepthaloyl moietie with copper containing catalyst.The first reaction zone operational condition: 200 ℃ of temperature of reaction, volume space velocity are 1500 hours
-1, reaction pressure is 2.5MPa; The second reaction zone operational condition: 200 ℃ of temperature of reaction, weight space velocity are 0.3 hour
-1, hydrogen/ester mol ratio is 120: 1, reaction pressure is under the condition of 2.5MPa; Its reaction result is: the transformation efficiency of dimethyl oxalate is 99.7%; The selectivity of terepthaloyl moietie is 93.4%, and the stability of catalyzer is 3000 hours (be lower than 90% with feed stock conversion and be benchmark, be as follows).
[embodiment 2]
Sample L among the embodiment 4 among the scavenging agent employing patent CN97116288.3A.
The 40%Cu+8%Zn+0.2%K/SiO that makes according to each Step By Condition of embodiment 1
2Copper containing catalyst.
With the dimethyl oxalate is raw material, and hydrogen feed (chlorinity is 5ppm) at first gets in first reaction zone and contacts with scavenging agent, first strand of hydrogen effluent of the chlorine impurity that is removed; After first strand of hydrogen effluent and the barkite raw materials mix, get in second reaction zone and contact, generate the second strand of reaction effluent that contains terepthaloyl moietie with copper containing catalyst.The first reaction zone operational condition: 50 ℃ of temperature of reaction, volume space velocity are 3000 hours
-1, reaction pressure is 5.0MPa; The second reaction zone operational condition: 240 ℃ of temperature of reaction, weight space velocity are 0.2 hour
-1, hydrogen/ester mol ratio is 100: 1, and reaction pressure is under the condition of 5.0MPa, and its reaction result is: the transformation efficiency of dimethyl oxalate is 100%, and the selectivity of terepthaloyl moietie is 95.2%, the stability of catalyzer is 5000 hours.
[embodiment 3]
Sample L among the embodiment 4 among the scavenging agent employing patent CN97116288.3A.
Each Step By Condition according to embodiment 1 makes 60%Cu+5%Zn+1%Fe/SiO
2Copper containing catalyst.
With the oxalic acid diethyl ester is raw material, and hydrogen feed (chlorinity is 30ppm) at first gets in first reaction zone and contacts with scavenging agent, first strand of hydrogen effluent of the chlorine impurity that is removed; After first strand of hydrogen effluent and the barkite raw materials mix, get in second reaction zone and contact, generate the second strand of reaction effluent that contains terepthaloyl moietie with copper containing catalyst.The first reaction zone operational condition: 120 ℃ of temperature of reaction, volume space velocity are 4000 hours
-1Reaction pressure is 0.5MPa; The second reaction zone operational condition: 230 ℃ of temperature of reaction, weight space velocity are 0.2 hour
-1, hydrogen/ester mol ratio is 80: 1, and reaction pressure is under the condition of 3.0MPa, and its reaction result is: the transformation efficiency of oxalic acid diethyl ester is 99.8%, and the selectivity of terepthaloyl moietie is 95.8%, the stability of catalyzer is 3500 hours.
[embodiment 4]
Sample G among the embodiment 3 among the scavenging agent employing patent CN96118137.0A.
Each Step By Condition according to embodiment 1 makes 50%Cu+5%Zn/SiO
2Copper containing catalyst.
With the dimethyl oxalate is raw material, and hydrogen feed (chlorinity is 50ppm) at first gets in first reaction zone and contacts with scavenging agent, first strand of hydrogen effluent of the chlorine impurity that is removed; After first strand of hydrogen effluent and the barkite raw materials mix, get in second reaction zone and contact, generate the second strand of reaction effluent that contains terepthaloyl moietie with copper containing catalyst.The first reaction zone operational condition: 285 ℃ of temperature of reaction, volume space velocity are 6000 hours
-1, reaction pressure is 1.0MPa; The second reaction zone operational condition: 260 ℃ of temperature of reaction, weight space velocity are 0.4 hour
-1, hydrogen/ester mol ratio is 70: 1, and reaction pressure is under the condition of 2.5MPa, and its reaction result is: the transformation efficiency of dimethyl oxalate is 100%, and the selectivity of terepthaloyl moietie is 97.3%, the stability of catalyzer is 5300 hours.
[embodiment 5]
Sample L among the embodiment 4 among the scavenging agent employing patent CN96118137.0A.
Each Step By Condition according to embodiment 1 makes 30%Cu+15%Zn/SiO
2Copper containing catalyst.
With the dimethyl oxalate is raw material, and hydrogen feed (chlorinity is 5ppm) at first gets in first reaction zone and contacts with scavenging agent, first strand of hydrogen effluent of the chlorine impurity that is removed; After first strand of hydrogen effluent and the barkite raw materials mix, get in second reaction zone and contact, generate the second strand of reaction effluent that contains terepthaloyl moietie with copper containing catalyst.The first reaction zone operational condition: 125 ℃ of temperature of reaction, volume space velocity are 8000 hours
-1, reaction pressure is 2.0MPa; The second reaction zone operational condition: 180 ℃ of temperature of reaction, weight space velocity are 0.3 hour
-1, hydrogen/ester mol ratio is 60: 1, and reaction pressure is under the condition of 1.8MPa, and its reaction result is: the transformation efficiency of dimethyl oxalate is 98%, and the selectivity of terepthaloyl moietie is 94.3%, the stability of catalyzer is 6000 hours.
[embodiment 6]
Sample L among the embodiment 4 among the scavenging agent employing patent CN96118137.0A.
Each Step By Condition according to embodiment 1 makes 40%Cu+5%Zn+K0.3%/SiO
2Copper containing catalyst.
With the dimethyl oxalate is raw material, and hydrogen feed (chlorinity is 2ppm) at first gets in first reaction zone and contacts with scavenging agent, first strand of hydrogen effluent of the chlorine impurity that is removed; After first strand of hydrogen effluent and the barkite raw materials mix, get in second reaction zone and contact, generate the second strand of reaction effluent that contains terepthaloyl moietie with copper containing catalyst.The first reaction zone operational condition: 265 ℃ of temperature of reaction, volume space velocity are 2000 hours
-1, reaction pressure is 6.0MPa; The second reaction zone operational condition: 200 ℃ of temperature of reaction, weight space velocity are 3 hours
-1, hydrogen/ester mol ratio is 80: 1, and reaction pressure is under the condition of 6.0MPa, and its reaction result is: the transformation efficiency of dimethyl oxalate is 96%, and the selectivity of terepthaloyl moietie is 96.3%, the stability of catalyzer is 6800 hours.
[Comparative Examples 1]
According to embodiment 5 identical catalyzer, reaction raw materials and condition, just there is not scavenging agent, its reaction result is: the transformation efficiency of dimethyl oxalate is 96%, and the selectivity of terepthaloyl moietie is 89.3%, and the stability of catalyzer is 2000 hours.
[Comparative Examples 2]
According to embodiment 4 identical catalyzer, reaction raw materials and condition, just there is not scavenging agent, its reaction result is: the transformation efficiency of dimethyl oxalate is 97%, and the selectivity of terepthaloyl moietie is 92.3%, and the stability of catalyzer is 500 hours.
Claims (5)
1. method that improves the oxalic ester hydrogenation synthesizing of ethylene glycol catalyst stability may further comprise the steps:
A) hydrogen feed at first gets in first reaction zone and contacts with scavenging agent, first strand of hydrogen effluent of be removed sulphur and chlorine impurity;
B) after first strand of hydrogen effluent and the barkite raw materials mix, get in second reaction zone and contact, generate the second strand of reaction effluent that contains terepthaloyl moietie with copper containing catalyst;
Wherein, scavenging agent in parts by weight comprise 30～98 parts be selected from least a in silicon oxide or the aluminum oxide be carrier and at least a active ingredient in Ca, Cu, Zn, Na, Fe, Ni, Mg, Pb or its oxide compound that is selected from of carrying on it 2～60 parts.
2. according to the method for the said raising oxalic ester hydrogenation synthesizing of ethylene glycol of claim 1 catalyst stability, it is characterized in that the first reaction zone operational condition: 20～400 ℃ of temperature of reaction, volume space velocity are 1000～10000 hours
-1, reaction pressure is 0.5～8.0MPa; The second reaction zone operational condition: 160～300 ℃ of temperature of reaction, weight space velocity are 0.08～8 hour
-1, reaction pressure is 1.0～6.0MPa, hydrogen/ester mol ratio 20～120: 1.
3. according to the method for the said raising oxalic ester hydrogenation synthesizing of ethylene glycol of claim 2 catalyst stability, it is characterized in that the first reaction zone operational condition: 100～300 ℃ of temperature of reaction, volume space velocity are 2000～8000 hours
-1, reaction pressure is 0.5～5.0MPa; The second reaction zone operational condition: 170～260 ℃ of temperature of reaction, weight space velocity are 0.1～6 hour
-1, reaction pressure is 1.5～5.0MPa, hydrogen/ester mol ratio is 40～120: 1.
4. according to the method for the said raising oxalic ester hydrogenation synthesizing of ethylene glycol of claim 1 catalyst stability, it is characterized in that scavenging agent in parts by weight comprise 40～80 parts be selected from least a in silicon oxide or the aluminum oxide be carrier and at least a active ingredient in Cu, Zn, Ni, Mg, Pb or its oxide compound that is selected from of carrying on it 10～60 parts.
5. according to the method for the said raising oxalic ester hydrogenation synthesizing of ethylene glycol of claim 1 catalyst stability, it is characterized in that the barkite raw material is selected from dimethyl oxalate, oxalic acid diethyl ester or its mixture.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4614728A (en) * | 1984-01-27 | 1986-09-30 | Ube Industries, Ltd. | Catalyst composition for producing ethylene glycol and process for producing the catalyst composition |
| EP0310189B1 (en) * | 1987-09-29 | 1994-09-07 | Union Carbide Corporation | Process for refining ethylene glycol |
| CN1147977A (en) * | 1996-04-26 | 1997-04-23 | 湖北省化学研究所 | Refined antichlor and method for preparing same |
| CN1178133A (en) * | 1997-09-10 | 1998-04-08 | 中国石油化工总公司 | High performance dechloridizing agent and preparation thereof |
| CN101927200A (en) * | 2010-08-26 | 2010-12-29 | 河南煤业化工集团有限责任公司 | Method for activating and reducing catalyst for hydrogenation of dimethyl oxalate to prepare glycol |
-
2011
- 2011-02-25 CN CN201110046464.2A patent/CN102649702B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4614728A (en) * | 1984-01-27 | 1986-09-30 | Ube Industries, Ltd. | Catalyst composition for producing ethylene glycol and process for producing the catalyst composition |
| EP0310189B1 (en) * | 1987-09-29 | 1994-09-07 | Union Carbide Corporation | Process for refining ethylene glycol |
| CN1147977A (en) * | 1996-04-26 | 1997-04-23 | 湖北省化学研究所 | Refined antichlor and method for preparing same |
| CN1178133A (en) * | 1997-09-10 | 1998-04-08 | 中国石油化工总公司 | High performance dechloridizing agent and preparation thereof |
| CN101927200A (en) * | 2010-08-26 | 2010-12-29 | 河南煤业化工集团有限责任公司 | Method for activating and reducing catalyst for hydrogenation of dimethyl oxalate to prepare glycol |
Non-Patent Citations (1)
| Title |
|---|
| 张启云等: "草酸二甲酯加氢合成乙二醇反应的研究", 《石油化工》 * |
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