CN102276417B - Catalyst starting method - Google Patents
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Abstract
The invention relates to a catalyst starting method for mainly solving the technical problem of low selectivity of ethylene glycol in the initial starting period when oxalate is hydrogenated into the ethylene glycol in the prior art. In a technical scheme adopted by the invention, the catalyst starting method comprises the following steps of: (1) loading a copper-containing catalyst into a reactor, introducing a reducing gas to reduce the catalyst under a reduction condition; (b) placing the reduced catalyst in a hydrogen atmosphere by maintaining the volume velocity of hydrogen to be 50-5000 h<-1>, controlling the temperature to enable the temperature of the reactor to be 5-50 DEG C lower than a design temperature for normal reaction; and (c) maintaining system pressure to be 0.5-5.0MPa, and introducing an oxalate raw material for reaction to generate an effluent containing the ethylene, wherein after the oxalate raw material is introduced for reaction for 4-100 hours, the temperature is raised to a design condition for reaction. By means of the technical scheme, the problem is favorably solved, and the catalyst starting method is suitable for the industrial production of catalyst starting for hydrogenating the oxalate into the ethylene glycol.
Description
Technical field
The present invention relates to a kind of method of catalyst starting, the method for the catalyst starting that is particularly ethylene glycol about dimethyl oxalate or oxalic acid diethyl ester hydrogenation.
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 ink, solvent and medium as ammonium pertorate, for the production of special solvent glycol ether etc., purposes is very extensive.
At present, China has surpassed the U.S. becomes the large ethylene glycol consumption of the first in the world big country, and within 2001～2006 years, domestic apparent consumption amount average annual growth rate reaches 17.4%.Although China's ethylene glycol capacity and output increases very fast, the powerful development due to industry such as polyester, still can not meet the growing market requirement, all need every year a large amount of imports, and import volume is increase year after year situation.
Current, the suitability for industrialized production of domestic and international large-scale ethylene glycol all adopts oxyethane direct hydration, i.e. the legal operational path of pressurized water, and production technology is monopolized by English lotus Shell, U.S. Halcon-SD and U.S. UCCSan company substantially.In addition, the research-and-development activity of the new synthetic technology of ethylene glycol is also making progress always.As ,UCC company of Shell company, Moscow Mendelyeev chemical engineering institute, oil of SPC institute etc. have developed catalyzing epoxyethane hydration legal system ethylene glycol production technology in succession; The companies such as Halcon-SD, UCC, Dow chemistry, Japanese catalyst chemistry and Mitsubishi Chemical have developed NSC 11801 legal system ethylene glycol production technology in succession; The companies such as Dow chemistry have developed EG and methylcarbonate (DMC) coproduction preparing ethylene glycol production technology etc.
Reaction product water content for direct hydration method is high, follow-up equipment (vaporizer) long flow path, equipment is large, energy consumption is high, process total recovery only has 70% left and right, directly affects the production cost of EG.Direct hydration method is compared with catalytic hydration and has significantly been reduced water ratio, has obtained higher EO transformation efficiency and EG selectivity simultaneously.If catalyst stability and correlation engineering technical problem solve well, EO catalytic hydration EG replacement processed on-catalytic hydrating process is trend of the times so.NSC 11801 (EC) legal system no matter aspect EO transformation efficiency, EG selectivity, or all has larger advantage than EO direct hydration method aspect raw material, energy expenditure for the technology of EG, is a kind of method maintaining the leading position.EG and DMC co-production technology can make full use of the CO2 resource of oxidation of ethylene by-product, in existing EO production equipment, only need the reactions steps that increases production EC just can produce two kinds of very value products, very attractive.
But the common shortcoming of aforesaid method is to need consumption of ethylene resource, and mainly by traditional petroleum resources, refine for current ethene, and following one period global oil price by the situation of long-term run at high level, with aboundresources, low-cost Sweet natural gas or coal, replace oil production ethylene glycol (Non oil-based route, be again CO route), can possess the advantage of competing mutually with traditional ethene route.Wherein, synthetic gas synthesizes EG new technology, may produce great impact to the innovation of EG production technique.The carbon monoxide of take is prepared dimethyl oxalate as raw material, by preparation of ethanediol by dimethyl oxalate hydrogenation, is then a very attractive Coal Chemical Industry Route.Both at home and abroad to take the research that carbon monoxide prepares dimethyl oxalate as raw material, obtained good effect now, industrial production is ripe.And by preparation of ethanediol by dimethyl oxalate hydrogenation, still having the further investigation of more need of work, the driving scheme of barkite hydrogenation catalyst for example, improves the aspects such as the selectivity of ethylene glycol and stability and need further research and perfect.
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 patent does not have the play-by-play of catalyst starting technical scheme, this catalyzer barkite transformation efficiency is lower, and glycol selectivity is low.
Document CN200710061390.3 discloses a kind of Catalysts and its preparation method of oxalic ester hydrogenation synthesizing of ethylene glycol, and catalyzer of the present invention be take metallic copper as main active ingredient, take zinc as promotor, by coprecipitation method, is prepared from.Its carrier is the silicon sol carrier of modification.Wherein metallic copper content is preferably 5%～45% of vehicle weight, and the best is 10%～40%; Metallic zinc content is 0.1%～15% of vehicle weight, and the best is 1%～8%.But this invention catalyzer is in barkite reacts with hydrogen synthesizing glycol, barkite low conversion rate, if dimethyl oxalate low conversion rate is in 93%, glycol selectivity is lower than 93%, and the driving scheme of catalyzer is not mentioned yet.
Summary of the invention
There is the technical problem that glycol selectivity is low in the driving initial stage that technical problem to be solved by this invention is is ethylene glycol catalyst in barkite hydrogenation in previous literature, a kind of method of new catalyst starting is provided.In the startup procedure that it is ethylene glycol catalyst that the method has in barkite hydrogenation, the advantage that glycol selectivity is high.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of catalyst starting, comprises the steps:
A) copper containing catalyst is packed in reactor, pass into reducing gas and under reductive condition, catalyzer is reduced;
B) catalyzer after reduction being kept to hydrogen volume air speed under atmosphere of hydrogen is 50～5000 hours
-1, control temperature and make temperature of reactor lower 5～50 ℃ than normal reaction design temperature;
C) maintaining system pressure is 0.5～5.0MPa, passes into barkite raw material and reacts the effluent that generation contains ethylene glycol;
Wherein, pass into barkite raw material reaction after 4～100 hours, be warming up to design conditions and react.
In technique scheme, reducing gas is selected from least one in CO or hydrogen, preferably from hydrogen; Reductive condition preferable range is: volume space velocity is 100～4000 hours
-1, reduction pressure is 0～5.0MPa, reduction temperature is 20～400 ℃; Reductive condition more preferably scope is: volume space velocity is 200～3000 hours
-1; Reduction pressure is 0～3.0MPa; Reduction temperature is 80～350 ℃.
In technique scheme, passing into the barkite raw material reaction time was preferably after 6～80 hours, was warming up to design conditions and reacted.Copper containing catalyst design reaction conditions is: 120～250 ℃ of temperature of reaction, barkite weight space velocity is 0.1～1.5 hour
-1, reaction pressure is 0.5～6.0MPa, hydrogen ester mol ratio is 30～150: 1.Copper containing catalyst preferred design reaction conditions is: 130～230 ℃ of temperature of reaction; Barkite weight space velocity is 0.2～0.8 hour
-1; Reaction pressure is 1.0～3.5MPa; Hydrogen ester mol ratio is 40～120: 1.Copper containing catalyst more preferably designs reaction conditions: 140～230 ℃ of temperature of reaction; Barkite weight space velocity is 0.2～0.7 hour
-1; Reaction pressure is 1.5～3.5MPa; Hydrogen ester mol ratio is 50～100: 1.
In technique scheme, the metal simple-substance copper of copper containing catalyst and the content of metal oxide thereof, the catalyst weight umber preferable range of take is 20～60%, more preferably weight range is 20～50%.The auxiliary agent preferred version of copper containing catalyst is selected from least one in K, Mg, Ba, V, Mn, Zn, Al, La or Ce compound, and in catalyst weight umber, the preferable range of auxiliary element content is 0.01～15 part.Auxiliary agent more preferably scheme is selected from least one in K, Ba, Mn, Zn, La or Ce compound, and auxiliary element content more preferably scope is 0.02～12 part, and most preferred range is 0.05～10 part.Carrier preferred version is selected from silicon oxide, aluminum oxide or molecular sieve at least one for carrier, the preferred autoxidation silicon of carrier.
In the inventive method, catalyzer to be restored adopts conventional pickling process, coprecipitation method or the preparation of other method, active ingredient can be flooded with random order with auxiliary agent, can first on carrier, flood active ingredient, and then dipping auxiliary agent, also can first flood auxiliary agent, then flood active ingredient, also can active ingredient and auxiliary agent flood simultaneously, while adopting coprecipitation method to prepare, carrier and active ingredient and auxiliary agent also can add in any way.
As everyone knows, in the process of oxalic ester hydrogenation synthesizing of ethylene glycol, oxide compound of copper, copper and composition thereof is that main active ingredient, especially copper and Red copper oxide are the active centre of reaction, and the two synergy completes catalytic reaction process; But, generally, in catalyst preparation process, the valence state of copper is divalent,, in use procedure, need to reduce to catalyzer for this reason, what need concern is to a certain extent, the reactivity worth of different method of reducing to catalyzer, comprises the transformation efficiency of raw material, and the selectivity of product and the stability influence of catalyzer are remarkable.In addition, catalyst starting process is typical strong exothermic process, if driving scheme is improper, will cause the bed temperature difference larger, occurs excessive temperature focus, temperature runaway phenomenon even, and then cause forfeiture or the decay of catalyst activity position.Present inventor finds in research process, adopting under normal design reaction conditions, barkite hydrogenation catalyst is fed intake, within for some time at initial stage that feeds intake, the selectivity of ethylene glycol is lower, after analysis, thinks, this is because the initial stage feeding intake after catalyst reduction, the active sites of catalyst surface, character is active, and reactive behavior is higher, in addition, react needed active sites and reach needed state initial reaction stage is also more difficult, and then cause side reaction to increase, glycol selectivity is on the low side.And present inventor further finds after further investigation; if the initial temperature feeding intake is controlled at than feeding intake under the condition of low 5～50 ℃ of common design temperature; conventionally can avoid glycol selectivity situation on the low side; after treating that just current in the past; temperature adjustment is to normal design temperature again; can guarantee whole feeding intake and reaction process, catalyst reaction is steadily active, and glycol selectivity is higher.
Adopt the inventive method, copper containing catalyst packs in reactor, and passing into hydrogen reducing gas is 100～4000 hours at volume space velocity
-1, reduction pressure is 0～5.0MPa, and reduction temperature is under 80～400 ℃ of conditions, catalyzer to be reduced, and after catalyst reduction, under atmosphere of hydrogen, keeping hydrogen volume air speed is 50～5000 hours
-1, control temperature and make temperature of reactor lower 5～50 ℃ than normal reaction design temperature, pass into barkite raw material and react the effluent that generation contains ethylene glycol; Wherein, copper containing catalyst design reaction conditions is: 120～250 ℃ of temperature of reaction, barkite weight space velocity is 0.1～1.5 hour
-1, reaction pressure is 0.5～6.0MPa, hydrogen ester mol ratio is 30～150: 1.Wait passing into after the barkite raw material reaction time is 4～100 hours, be warming up to design conditions and react, the transformation efficiency that its result is barkite can reach 100%, and the selectivity of ethylene glycol is the highest is greater than 95%, has obtained good technique effect.
Below by embodiment and comparative example, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
[embodiment 1]
Catalyzer preparation:
Take specific surface and be 200 grams of the silica supports of 280 meters squared per gram, according to 35 parts of active metal copper and 10 parts of metallic zinc content configuration catalyzer, its step is as follows: choose cupric nitrate, and zinc nitrate, according to Cu and Zn charge capacity, be made into steeping fluid, silica support is flooded in this solution after 18 hours, at room temperature vacuum-drying obtains solids for 10 hours.Again solid is dried to 10 hours at 120 ℃, 450 ℃ of roastings make required 30%CuO+10%ZnO/SiO for 4 hours afterwards
2catalyst precursor.
Take the 30%CuO+10%ZnO/SiO making
2catalyst precursor is 50 grams, packs diameter into and is in the tubular reactor of 18 millimeters, and employing hydrogen is reducing gas.At volume space velocity, it is 2000 hours
-1, reduction pressure is 0.5MPa, and reduction temperature is under 300 ℃ of conditions, reduces after 12 hours, is cooled to 180 ℃ in atmosphere of hydrogen, and at pressure 2.5MPa, dimethyl oxalate weight space velocity is 0.5 hour
-1, under the condition that hydrogen ester mol ratio is 100: 1, dimethyl oxalate is dropped into reactor, stablize and after 12 hours, temperature is warming up to 200 ℃ of catalyzer well-defined reaction temps and continues reaction, in whole reaction process, the transformation efficiency of dimethyl oxalate is 100%, and the selectivity of ethylene glycol is 95.2%.
[embodiment 2]
Adopt the identical catalyzer of embodiment 1, just the reductive condition of catalyzer is that volume space velocity is 3500 hours
-1, reduction pressure is 2.5MPa, and reduction temperature is under 200 ℃ of conditions, reduces after 8 hours, is cooled to 185 ℃ in atmosphere of hydrogen, and at pressure 2.5MPa, dimethyl oxalate weight space velocity is 0.8 hour
-1, under the condition that hydrogen ester mol ratio is 80: 1, dimethyl oxalate is dropped into reactor, stablize and after 18 hours, temperature is warming up to 200 ℃ of catalyzer well-defined reaction temps and continues reaction, in whole reaction process, the transformation efficiency of dimethyl oxalate is 100%, and the selectivity of ethylene glycol is 95.8%.
[embodiment 3]
Each Step By Condition according to embodiment 1 makes 40%CuO+8%ZnO+0.2%CeO
2/ SiO
2catalyst precursor, and pack in reactor with identical loadings, the reductive condition of catalyzer is that volume space velocity is 1000 hours
-1, reduction pressure is 1.5MPa, and reduction temperature is under 250 ℃ of conditions, and reductase 12, after 0 hour, is cooled to 170 ℃ in atmosphere of hydrogen, and at pressure 2.8MPa, dimethyl oxalate weight space velocity is 0.4 hour
-1, under the condition that hydrogen ester mol ratio is 120: 1, dimethyl oxalate is dropped into reactor, stablize and after 40 hours, temperature is warming up to 210 ℃ of catalyzer well-defined reaction temps and continues reaction, in whole reaction process, the transformation efficiency of dimethyl oxalate is 100%, and the selectivity of ethylene glycol is 96.5%.
[embodiment 4]
Each Step By Condition according to embodiment 1 makes 30%CuO+2%BaO+0.2%La
2o
3/ SiO
2catalyst precursor, and pack in reactor with identical loadings, the reductive condition of catalyzer is that volume space velocity is 500 hours
-1, reduction pressure is 0.2MPa, and reduction temperature is under 350 ℃ of conditions, reduces after 6 hours, is cooled to 190 ℃ in atmosphere of hydrogen, and at pressure 3.5MPa, oxalic acid diethyl ester weight space velocity is 1.4 hours
-1, under the condition that hydrogen ester mol ratio is 70: 1, oxalic acid diethyl ester is dropped into reactor, stablize and after 60 hours, temperature is warming up to 220 ℃ of catalyzer well-defined reaction temps and continues reaction, in whole reaction process, the transformation efficiency of oxalic acid diethyl ester is 99.5%, and the selectivity of ethylene glycol is 94.3%.
[embodiment 5]
Each Step By Condition according to embodiment 1 makes 30%Cu
2o+5%MnO+0.1%MgO/Al
2o
3catalyst precursor, and pack in reactor with identical loadings, the reductive condition of catalyzer is that volume space velocity is 200 hours
-1, reduction pressure is 0.1MPa, and reduction temperature is under 180 ℃ of conditions, reduces after 48 hours, is cooled to 175 ℃ in atmosphere of hydrogen, and at pressure 3.0MPa, oxalic acid diethyl ester weight space velocity is 0.3 hour
-1, under the condition that hydrogen ester mol ratio is 50: 1, oxalic acid diethyl ester is dropped into reactor, stablize and after 80 hours, temperature is warming up to 205 ℃ of catalyzer well-defined reaction temps and continues reaction, in whole reaction process, the transformation efficiency of oxalic acid diethyl ester is 100%, and the selectivity of ethylene glycol is 93.8%.
[embodiment 6]
Each Step By Condition according to embodiment 1 makes 50%CuO+0.8%NiO+0.2%VO
2/ SiO
2catalyst precursor, and pack in reactor with identical loadings, the reductive condition of catalyzer is that volume space velocity is 100 hours
-1, reduction pressure is 0.2MPa, and reduction temperature is under 250 ℃ of conditions, reduces after 18 hours, is cooled to 200 ℃ in atmosphere of hydrogen, and at pressure 2.0MPa, dimethyl oxalate weight space velocity is 0.4 hour
-1, under the condition that hydrogen ester mol ratio is 80: 1, dimethyl oxalate is dropped into reactor, stablize and after 100 hours, temperature is warming up to 210 ℃ of catalyzer well-defined reaction temps and continues reaction, in whole reaction process, the transformation efficiency of dimethyl oxalate is 100%, and the selectivity of ethylene glycol is 97.1%.
[embodiment 7]
Each Step By Condition according to embodiment 1 makes 20%CuO+1%BaO/SiO
2catalyst precursor, and pack in reactor with identical loadings, the reductive condition of catalyzer is that volume space velocity is 400 hours
-1, reduction pressure is 1.0MPa, and reduction temperature is under 280 ℃ of conditions, reduces after 30 hours, is cooled to 170 ℃ in atmosphere of hydrogen, and at pressure 1.5MPa, dimethyl oxalate weight space velocity is 0.3 hour
-1, under the condition that hydrogen ester mol ratio is 60: 1, dimethyl oxalate is dropped into reactor, stablize and after 40 hours, temperature is warming up to 190 ℃ of catalyzer well-defined reaction temps and continues reaction, in whole reaction process, the transformation efficiency of dimethyl oxalate is 100%, and the selectivity of ethylene glycol is 96.9%.
[comparative example 1]
According to the identical catalyzer of embodiment 5, reductive condition and reaction raw materials, while just feeding intake, the temperature of reactor remains on 205 ℃ of reactions of catalytic design temperature, in initial reaction stage 30 hours, the transformation efficiency of oxalic acid diethyl ester is 100%, and the selectivity of ethylene glycol is 85.8%.
[comparative example 2]
According to the identical catalyzer of embodiment 6, reductive condition and reaction raw materials, while just feeding intake, the temperature of reactor remains on 210 ℃ of reactions of catalytic design temperature, in initial reaction stage 50 hours, the transformation efficiency of dimethyl oxalate is 100%, and the selectivity of ethylene glycol is 83.4%.
[comparative example 3]
According to the identical catalyzer of embodiment 7, reductive condition and reaction raw materials, while just feeding intake, the temperature of reactor remains on 190 ℃ of reactions of catalytic design temperature, in initial reaction stage 20 hours, the transformation efficiency of dimethyl oxalate is 100%, and the selectivity of ethylene glycol is 86.3%.
Claims (5)
1. a method for catalyst starting, comprises the steps:
A) copper containing catalyst is packed in reactor, pass into reducing gas and under reductive condition, catalyzer is reduced;
B) catalyzer after reduction being kept to hydrogen volume air speed under atmosphere of hydrogen is 50～5000 hours
-1, control temperature and make temperature of reactor lower 5～50 ℃ than normal reaction design temperature;
C) maintaining system pressure is 1.0～3.5MPa, passes into barkite raw material and reacts the effluent that generation contains ethylene glycol;
Wherein, pass into barkite raw material reaction after 4～100 hours, be warming up to design conditions and react; Copper containing catalyst design reaction conditions is: 130～230 ℃ of temperature of reaction, barkite weight space velocity is 0.2～0.8 hour
-1, hydrogen ester mol ratio is 40～120:1.
2. the method for catalyst starting according to claim 1, is characterized in that reducing gas is selected from least one in CO or hydrogen; Reduction volume space velocity is 100～4000 hours
-1; Reduction pressure is 0～5.0MPa; Reduction temperature is 20～400 ℃.
3. the method for catalyst starting according to claim 2, is characterized in that reducing gas is selected from hydrogen; Reduction volume space velocity is 200～3000 hours
-1; Reduction pressure is 0～3.0MPa; Reduction temperature is 80～350 ℃.
4. the method for catalyst starting according to claim 1, is characterized in that passing into barkite raw material reaction after 6～80 hours, was warming up to design conditions and reacted.
5. the method for catalyst starting according to claim 1, is characterized in that copper containing catalyst design reaction conditions is: 140～230 ℃ of temperature of reaction; Barkite weight space velocity is 0.2～0.7 hour
-1; Reaction pressure is 1.5～3.5MPa; Hydrogen ester mol ratio is 50～100:1.
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| CN111348987B (en) * | 2018-12-20 | 2023-09-26 | 上海华谊能源化工有限公司 | Reduction method of catalyst in preparation of ethylene glycol by gas-phase hydrogenation of dimethyl oxalate |
Citations (4)
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|---|---|---|---|---|
| US4614728A (en) * | 1984-01-27 | 1986-09-30 | Ube Industries, Ltd. | Catalyst composition for producing ethylene glycol and process for producing the catalyst composition |
| US4628128A (en) * | 1985-02-04 | 1986-12-09 | Union Carbide Corporation | Process for the preparation of ethylene glycol by catalytic hydrogenation |
| CN101444735A (en) * | 2008-12-19 | 2009-06-03 | 上海工程技术大学 | Ethylene glycol catalyst prepared by dimethyl oxalate plus hydrogen and preparation method and application thereof |
| 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 |
-
2010
- 2010-06-11 CN CN201010200029.6A patent/CN102276417B/en active Active
Patent Citations (4)
| 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 |
| US4628128A (en) * | 1985-02-04 | 1986-12-09 | Union Carbide Corporation | Process for the preparation of ethylene glycol by catalytic hydrogenation |
| 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 |
| CN101444735A (en) * | 2008-12-19 | 2009-06-03 | 上海工程技术大学 | Ethylene glycol catalyst prepared by dimethyl oxalate plus hydrogen and preparation method and application thereof |
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