CN102649706B - Method for preparing ethylene glycol through gas phase hydrogenation of oxalate - Google Patents
Method for preparing ethylene glycol through gas phase hydrogenation of oxalate Download PDFInfo
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Abstract
The invention relates to a method for preparing ethylene glycol through gas phase hydrogenation of oxalate, and mainly solves the technical problem in the prior art that in the reaction process of hydrogenation of oxalate to ethylene glycol, the selectivity of ethylene glycol is low. The method adopts oxalate as the raw material and methanol, alcohol or water as a terminator, and comprises the step that the raw material is in contact with a copper bearing catalyst in a fluidized bed reactor of an external cyclone separator to generate an effluent containing ethylene glycol under the conditions that the reaction temperature is 170-270 DEG C, the weight space velocity of oxalate is 0.2-5hours <-1>, the hydrogen/ester molar ratio is 40-200:1 and the reaction pressure is 1.5-10MPa. 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 the method for a kind of barkite by gas phase hydrogenation preparing ethylene glycol, particularly about employing external placed type cyclonic separator, be practically applicable in the reaction process of hydrogenation of oxalate for preparing ethylene glycol.
Background technology
Ethylene glycol (EG) is a kind of important Organic Chemicals, mainly for the production of poly-vinegar fiber, frostproofer, unsaturated polyester resin, lubricant, softening agent, nonionogenic tenside and explosive etc., can be used for the industries such as coating, soup, brake fluid and ink in addition, as solvent and the medium of ammonium pertorate, for the production of special solvent glycol ether etc., purposes is very extensive.
At present, China has exceeded the U.S. becomes the first in the world large ethylene glycol consumption big country, and within 2001 ~ 2006 years, domestic Apparent con-sumption average annual growth rate reaches 17.4%.Although China ethylene glycol capacity and output increases very fast, due to the powerful development of the industry such as polyester, still can not meet the growing market requirement, all need a large amount of import every year, and import volume is in growing trend year by year.
Current, the suitability for industrialized production of domestic and international large-scale ethylene glycol all adopts oxyethane direct hydration, the operational path that namely pressurized water is legal, and production technology monopolized by English lotus Shell, U.S. Halcon-SD and U.S. UCC tri-company substantially.In addition, the research-and-development activity of the new synthetic technology of ethylene glycol is also making progress always.As Shell company, UCC company, Moscow Mendelyeev chemical engineering institute, oil of SPC institute etc. develop 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 develop NSC 11801 legal system ethylene glycol production technology; The companies such as Dow chemistry develop 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 about 70%, directly affects the production cost of EG.Direct hydration method considerably reduces water ratio compared with catalytic hydration, obtains higher EO transformation efficiency and EG selectivity simultaneously.If catalyst stability and correlation engineering technical problem solve well, so EO catalytic hydration EG replace on-catalytic hydrating process to be trend of the times.NSC 11801 (EC) legal system no matter in EO transformation efficiency, EG selectivity, or all has larger advantage than EO direct hydration method for the technology of EG in raw material, energy expenditure, is a kind of method maintained the leading position.EG and DMC co-production technology can make full use of the CO of oxidation of ethylene by-product
2resource, in existing EO production equipment, only need increase the reactions steps of producing EC and just can produce two kinds of very value products, very attractive.
But the common drawback of aforesaid method needs consumption of ethylene resource, and for current ethene mainly by the refining of traditional petroleum resources, and when future, one period, global oil price was by long-term run at high level, oil production ethylene glycol (Non oil-based route is replaced with aboundresources, low-cost Sweet natural gas or coal, be again CO route), the advantage of competing mutually with traditional ethene route can be possessed.Wherein, synthetic gas synthesis EG new technology, may produce great impact to the innovation of EG production technique.Being that dimethyl oxalate prepared by raw material with carbon monoxide, is then a very attractive Coal Chemical Industry Route by preparation of ethanediol by dimethyl oxalate hydrogenation.Now domestic and international to being that the research that dimethyl oxalate prepared by raw material achieves good effect with carbon monoxide, industrial production is ripe.And by preparation of ethanediol by dimethyl oxalate hydrogenation, still have more need of work to further investigate, especially also well do not break through in the selectivity how effectively improving ethylene glycol and raising catalyst stability.
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, and zinc is auxiliary agent, adopts coprecipitation method preparation, but this catalyzer barkite transformation efficiency is lower, the selectivity of ethylene glycol is lower simultaneously.
Document CN200710061390.3 discloses a kind of Catalysts and its preparation method of oxalic ester hydrogenation synthesizing of ethylene glycol, and the barkite transformation efficiency of this catalyzer and technique thereof is lower, and generally about 96%, the selectivity of ethylene glycol is about about 92%.
Involved by above-mentioned document subject matter be that glycol selectivity is low.
Summary of the invention
Technical problem to be solved by this invention be in previous literature technology in hydrogenation of oxalate for preparing ethylene glycol reaction process, there is the technical problem that glycol selectivity is low, provide a kind of new barkite by the method for gas phase hydrogenation preparing ethylene glycol.The method is used for, in hydrogenation of oxalate for preparing ethylene glycol reaction process, having 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 barkite, by the method for gas phase hydrogenation preparing ethylene glycol, take barkite as raw material, with methyl alcohol, ethanol or water for terminator, be 170 ~ 270 DEG C in temperature of reaction, barkite weight space velocity is 0.2 ~ 5 hour
-1, hydrogen/ester mol ratio is 40 ~ 200: 1, reaction pressure is under 1.5 ~ 10MPa condition, raw material contacts with the copper containing catalyst in fluidized-bed reactor, generate the effluent containing ethylene glycol, wherein fluidized-bed reactor is substantially by settling vessel (5), stripper (11), interchanger (3) and external placed type cyclonic separator (8) composition, comprise emulsion zone (A), zone of transition (B), negative area (C), material inlet (1), sparger or grid distributor (2), interchanger (3), riser tube (4), fast separating device (6), airway (7), external placed type cyclonic separator (8), collection chamber (9), product gas outlet (10), stripper (11), regenerator sloped tube (12) and inclined tube to be generated (13), wherein emulsion zone (A) is connected with riser tube (4) after the zone of transition (B) of undergauge structure, riser tube (4) upper end or end are provided with fast separating device (6), the spiral arm of fast separating device (6) is positioned at riser tube (4) outward, in the airway (7) coaxially communicated with riser tube (4), airway (7) is connected with collection chamber (9) but does not communicate for the integral part on settling vessel (5) top, its upper end, and its lower end is positioned at riser tube (4) outward, zone of transition (B) outer upper ends, it is outside that external placed type cyclonic separator (8) is positioned at settling vessel (5), its upper inlet port is connected with airway (7) top, its air outlet communicates with collection chamber (9), and the dipleg of external placed type cyclonic separator (8) stretches in the negative area (C) of settling vessel (5), collection chamber (9) is positioned at airway (7) and is connected with product gas outlet (10) above, stripper (11) one end is connected with the bottom of settling vessel (5), and the other end of stripper (11) is connected with inclined tube to be generated (13), interchanger (3) is set between the bottom of settling vessel (5) and emulsion zone (A) hypomere, one end of interchanger (3) is connected with the bottom of settling vessel (5), and the other end of interchanger (3) is connected with emulsion zone (A), sparger or grid distributor (2) are positioned at emulsion zone (A) bottom, and the bottom of sparger or grid distributor (2) is provided with material inlet (1).
In technique scheme, preferred version for arrange terminator inlet 15 near riser tube 4 lower region, and terminator inlet 15 is 0 ~ 4/5 of riser tube 4 height apart from the vertical range bottom riser tube 4; Terminator inlet 15 distributes ringwise along riser tube 4 lower region; The internal diameter of riser tube 4 is 1/15 ~ 1/2 of emulsion zone A external diameter, and the height of riser tube 4 is 1/5 ~ 5/1 of emulsion zone A height; Regenerator sloped tube 12 is 1/10 ~ 1/2 of emulsion zone A vertical height with emulsion zone A Link Port distance emulsion zone A bottom vertical distance; The vertical height of zone of transition B is 1/20 ~ 1/2 of emulsion zone A vertical height.
In technique scheme, Optimal reaction conditions is: temperature of reaction is 180 ~ 250 DEG C, and barkite weight space velocity is 0.2 ~ 3 hour
-1, hydrogen/ester mol ratio is 40 ~ 100: 1, and reaction pressure is 1.5 ~ 5MPa, and support of the catalyst is preferably selected from least one in silicon oxide or aluminum oxide, and catalyst particle diameter average preferred range is 30 ~ 180 microns.
As everyone knows, hydrogenation of oxalate for preparing ethylene glycol reaction is thermopositive reaction, and hydrogenation of oxalate for preparing ethylene glycol reaction is cascade reaction, and ethylene glycol is the intermediate product of reaction process, if excessive hydrogenation can generate ethanol.Research also finds, the best speech " form " of hydrogenation of oxalate for preparing ethylene glycol reaction is very narrow, temperature low reaction low conversion rate, during temperature height, the selectivity of ethylene glycol is low, control reaction bed uniformity of temperature profile most important, the temperature distribution of beds is more even, and the selection of ethylene glycol more easily controls, and easily keeps higher selectivity.Adopt fluidized-bed reactor in the present invention, make full use of fluidized-bed reactor heat transfer evenly, and the feature of uniformity of temperature profile, guarantee that the selectivity of ethylene glycol is higher.Research also finds to adopt in hydrogenation of oxalate for preparing ethylene glycol fluidized-bed reaction process, raw material contacts in situation with long-lasting catalytic, still can continue to transform, especially at the settling zone of hydrogenation of oxalate for preparing ethylene glycol fluidized-bed reactor, a large amount of unsegregated catalyzer can continue to react at high operating temperatures, cause barkite rate of loss high, glycol selectivity is low.The present invention also injects terminator by the region, outlet position leaving catalytic bed at catalyzer and reaction product, on the one hand, the terminator that temperature is lower and pyroreaction mixture and catalyst exposure, significantly can reduce the temperature of reaction mixture and catalyzer, this can accelerate the sharply temperature-fall period of pyroreaction mixture and catalyzer further, after the reaction mixture that temperature sharply reduces and catalyzer leave reaction zone, side reaction is few, continue reaction odds little, reduce the rate of loss of raw material, improve the selectivity of ethylene glycol.
The present invention's Fig. 1 shown device, adopt copper oxide fluid catalyst, methyl alcohol, ethanol or water are terminator, take barkite as raw material, are 170 ~ 270 DEG C in temperature of reaction, and barkite weight space velocity is 0.2 ~ 5 hour
-1hydrogen/ester mol ratio is 40 ~ 200: 1, reaction pressure is under 1.5 ~ 10MPa condition, raw material contacts with the copper containing catalyst in fluidized-bed reactor, generate the effluent containing ethylene glycol, its result is, the transformation efficiency of barkite can be reached for 100%, the selectivity of ethylene glycol can be greater than 98%, achieves good technique effect.
Accompanying drawing explanation
Fig. 1 is fluidized-bed reactor schematic diagram of the present invention.
In Fig. 1, A is emulsion zone, B is zone of transition, C be negative area, 1 is material inlet, and 2 is sparger or grid distributor, and 3 is interchanger, 4 is riser tubes, and 5 is settling vessels, and 6 is fast separating devices, 7 is airways, and 8 is external placed type cyclonic separators, and 9 is collection chambers, 10 product gas outlet, 11 is strippers, and 12 is regenerator sloped tubes, and 13 is inclined tubes to be generated, 14 is stripped vapor entrances, and 15 is terminator inlets.
Fig. 1 Raw is introduced by material inlet 1, through gas distributor or grid distributor 2 distribute laggard enter the emulsion zone A of fluidized-bed and catalyst exposure react, catalyzer and reaction mixture enter riser tube 4 through zone of transition B; After vortex quick separation device 6 sharp separation of riser tube 4 upper end (end), major part catalyzer enters the lower region of settling vessel C, the partially catalyzed agent that reaction mixture is carried secretly enters through airway 7 carries out secondary separation through external placed type cyclonic separator 8, gas product after separation enters collection chamber 9 through the outlet of external placed type cyclonic separator 8, is drawn by product gas outlet 10.Catalyzer after being separated from external placed type cyclonic separator 8 returns the lower region of settling vessel 5 through the dipleg of external placed type cyclonic separator 8.The reclaimable catalyst of the C bottom, negative area in settling vessel 5 enters stripper 11, through from after the stripped vapor stripping of stripped vapor entrance 14, enter revivifier (in figure, revivifier omits) through inclined tube 12 to be generated, regenerator enters the fluidized-bed reactor emulsion zone A of hydrogenation of oxalate for preparing ethylene glycol through regenerator sloped tube 12.In addition, continue to react bottom the fluidized-bed reactor emulsion zone A that the partially catalyzed agent in settling vessel 5 enters hydrogenation of oxalate for preparing ethylene glycol after interchanger 3 heat exchange with catalyst mix, whole process circulation is carried out.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
With the fluidized-bed reactor of Fig. 1, wherein, the vertical range bottom terminator inlet distance riser tube is 1/5 of riser tube length, and the internal diameter of riser tube is 1/10 of emulsion zone external diameter, and the height of riser tube is 1/4 of emulsion zone height.Fluidized-bed reactor regenerator sloped tube and emulsion zone Link Port distance emulsion zone bottom vertical distance are 1/5 of emulsion zone vertical heights, and the vertical height of fluidized-bed reactor zone of transition is 1/10 of emulsion zone vertical height.Its particle diameter average out to 80 microns, adopts and consists of 30wt%Cu+10wt%Zn+1wt%W/SiO
2fluid catalyst, methyl alcohol is terminator, is raw material with dimethyl oxalate, and the weight ratio of raw material and terminator is 10: 1, and terminator feeding temperature is 40 DEG C, is 240 DEG C in temperature of reaction, and weight space velocity is 1 hour
-1, hydrogen/ester mol ratio is 100: 1, and reaction pressure is under the condition of 3.0MPa, and the transformation efficiency of dimethyl oxalate is 100%, and the selectivity of ethylene glycol is 98.6%.
[embodiment 2]
With the fluidized-bed reactor of Fig. 1, wherein, the vertical range bottom terminator inlet distance riser tube is 1/8 of riser tube length, and the internal diameter of riser tube is 1/12 of emulsion zone external diameter, and the height of riser tube is 1/2 of emulsion zone height.Fluidized-bed reactor regenerator sloped tube and emulsion zone Link Port distance emulsion zone bottom vertical distance are 1/3 of emulsion zone vertical heights, and the vertical height of fluidized-bed reactor zone of transition is 1/5 of emulsion zone vertical height.Employing consists of 40wt%Cu+5wt%Zn+1wt%Ni/SiO
2fluid catalyst, its particle diameter average out to 100 microns, ethanol is terminator, is raw material with oxalic acid diethyl ester, and the weight ratio of raw material and terminator is 10: 1, and terminator feeding temperature is 40 DEG C, is 220 DEG C in temperature of reaction, and weight space velocity is 0.8 hour
-1, hydrogen/ester mol ratio is 70: 1, and reaction pressure is under the condition of 2.0MPa, and the transformation efficiency of oxalic acid diethyl ester is 100%, and the selectivity of ethylene glycol is 97.9%.
[embodiment 3]
With the fluidized-bed reactor of Fig. 1, adopt and consist of 28wt%Cu+3wt%Al/SiO
2fluid catalyst, catalyst particle diameter average out to 120 microns, water is terminator, and the vertical range bottom terminator inlet distance riser tube is 1/10 of riser tube length, the internal diameter of riser tube is 1/6 of emulsion zone external diameter, and the height of riser tube is 1/8 of emulsion zone height.Regenerator sloped tube and emulsion zone Link Port distance emulsion zone bottom vertical distance are 1/6 of emulsion zone vertical heights.The vertical height of zone of transition is 1/7 of emulsion zone vertical height.The gas inlet distance set air chamber plan vertical distance of cyclonic separator is 1/4 of settling vessel diameter.Be raw material with dimethyl oxalate, the weight ratio of raw material and terminator is 40: 1, and terminator feeding temperature is 35 DEG C, is 220 DEG C in temperature of reaction, and weight space velocity is 1.2 hours
-1, hydrogen/ester mol ratio is 80: 1, and reaction pressure is under the condition of 2.8MPa, and the transformation efficiency of dimethyl oxalate is 100%, and the selectivity of ethylene glycol is 98.3%.
[embodiment 4]
With the fluidized-bed reactor of Fig. 1, adopt and consist of 25wt%Cu+3wt%Ni/SiO
2fluid catalyst, catalyst particle diameter average out to 110 microns, methyl alcohol is terminator, and the vertical range bottom terminator inlet distance riser tube is 1/5 of riser tube length, the internal diameter of riser tube is 1/4 of emulsion zone external diameter, and the height of riser tube is 1/8 of emulsion zone height.Regenerator sloped tube and emulsion zone Link Port distance emulsion zone bottom vertical distance are 1/10 of emulsion zone vertical heights.The vertical height of zone of transition is 1/6 of emulsion zone vertical height.The gas inlet distance set air chamber plan vertical distance of cyclonic separator is 1/6 of settling vessel diameter.Be raw material with dimethyl oxalate, the weight ratio of raw material and terminator is 60: 1, and terminator feeding temperature is 25 DEG C, is 190 DEG C in temperature of reaction, and weight space velocity is 0.4 hour
-1, hydrogen/ester mol ratio is 70: 1, and reaction pressure is under the condition of 2.2MPa, and the transformation efficiency of dimethyl oxalate is 99.8%, and the selectivity of ethylene glycol is 98.8%.
[comparative example 1]
With reference to each step and the reaction conditions of embodiment 1, just the reactor of hydrogenation of oxalate for preparing ethylene glycol adopts fixed-bed reactor, and does not add terminator, and reaction result is: the transformation efficiency of dimethyl oxalate is 96.5%, and the selectivity of ethylene glycol is 91.2%.
[comparative example 2]
With reference to each step and the reaction conditions of embodiment 2, just the reactor of hydrogenation of oxalate for preparing ethylene glycol adopts fixed-bed reactor, and does not add terminator, and reaction result is: the transformation efficiency of oxalic acid diethyl ester is 95.4%, and the selectivity of ethylene glycol is 90.3%.
Claims (1)
1. barkite is by a method for gas phase hydrogenation preparing ethylene glycol, with fluidized-bed reactor, adopts and consists of 30wt%Cu+10wt%Zn+1wt%W/SiO
2, particle diameter average out to 80 microns fluid catalyst, methyl alcohol is terminator, is raw material with dimethyl oxalate, and the weight ratio of raw material and terminator is 10: 1, and terminator feeding temperature is 40 DEG C, is 240 DEG C in temperature of reaction, and weight space velocity is 1 hour
-1, hydrogen/ester mol ratio is 100: 1, and reaction pressure is under the condition of 3.0MPa, and the transformation efficiency of dimethyl oxalate is 100%, and the selectivity of ethylene glycol is 98.6%, wherein, described fluidized-bed reactor is substantially by settling vessel (5), stripper (11), interchanger (3) and external placed type cyclonic separator (8) composition, comprise emulsion zone (A), zone of transition (B), negative area (C), material inlet (1), sparger or grid distributor (2), interchanger (3), riser tube (4), fast separating device (6), airway (7), external placed type cyclonic separator (8), collection chamber (9), product gas outlet (10), stripper (11), regenerator sloped tube (12) and inclined tube to be generated (13), wherein emulsion zone (A) is connected with riser tube (4) after the zone of transition (B) of undergauge structure, riser tube (4) upper end or end are provided with fast separating device (6), the spiral arm of fast separating device (6) is positioned at riser tube (4) outward, in the airway (7) coaxially communicated with riser tube (4), airway (7) is connected with collection chamber (9) but does not communicate for the integral part on settling vessel (5) top, its upper end, and its lower end is positioned at riser tube (4) outward, zone of transition (B) outer upper ends, it is outside that external placed type cyclonic separator (8) is positioned at settling vessel (5), its upper inlet port is connected with airway (7) top, its air outlet communicates with collection chamber (9), and the dipleg of external placed type cyclonic separator (8) stretches in the negative area (C) of settling vessel (5), collection chamber (9) is positioned at airway (7) and is connected with product gas outlet (10) above, stripper (11) one end is connected with the bottom of settling vessel (5), and the other end of stripper (11) is connected with inclined tube to be generated (13), interchanger (3) is set between the bottom of settling vessel (5) and emulsion zone (A) hypomere, one end of interchanger (3) is connected with the bottom of settling vessel (5), and the other end of interchanger (3) is connected with emulsion zone (A), sparger or grid distributor (2) are positioned at emulsion zone (A) bottom, and the bottom of sparger or grid distributor (2) is provided with material inlet (1), terminator inlet (15) is set near riser tube (4) lower region, the vertical range of terminator inlet (15) distance riser tube (4) bottom is 1/5 of riser tube (4) length, and terminator inlet (15) distributes ringwise along riser tube (4) lower region, the internal diameter of riser tube (4) is 1/10 of emulsion zone (A) external diameter, and the height of riser tube (4) is 1/4 of emulsion zone (A) height, regenerator sloped tube (12) is 1/5 of emulsion zone (A) vertical height with emulsion zone (A) Link Port distance emulsion zone (A) bottom vertical distance, the vertical height of zone of transition (B) is 1/10 of emulsion zone (A) vertical height.
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| CN105478175B (en) * | 2015-12-27 | 2018-01-16 | 安徽淮化股份有限公司 | A kind of catalyst regeneration system suitable for synthesis gas preparing ethylene glycol hydrogenation reaction |
| CN106861710A (en) * | 2017-02-20 | 2017-06-20 | 宁波中科远东催化工程技术有限公司 | Catalyst of dimethyl oxalate preparing ethylene glycol and preparation method thereof |
| CN106928021B (en) * | 2017-02-20 | 2020-04-24 | 宁波中科远东催化工程技术有限公司 | Method for preparing ethylene glycol by dimethyl oxalate hydrogenation |
| CN112479814A (en) * | 2019-09-12 | 2021-03-12 | 南京延长反应技术研究院有限公司 | Reaction system and process for strengthening hydrogenation of dimethyl oxalate in coal-to-ethylene glycol |
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| US6166282A (en) * | 1999-08-20 | 2000-12-26 | Uop Llc | Fast-fluidized bed reactor for MTO process |
| CN101164685A (en) * | 2006-10-20 | 2008-04-23 | 中国石油化工股份有限公司 | Combined quickly fluidized bed reactor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6166282A (en) * | 1999-08-20 | 2000-12-26 | Uop Llc | Fast-fluidized bed reactor for MTO process |
| CN101164685A (en) * | 2006-10-20 | 2008-04-23 | 中国石油化工股份有限公司 | Combined quickly fluidized bed reactor |
Non-Patent Citations (1)
| Title |
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| 《草酸二甲酯加氢制乙二醇Cu/SiO2催化剂的制备与改性》;黄维捷等;《工业催化》;20080630;第16卷(第6期);第13-17页 * |
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