CN102649705B - Ethylene glycol production method - Google Patents
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- CN102649705B CN102649705B CN201110047192.8A CN201110047192A CN102649705B CN 102649705 B CN102649705 B CN 102649705B CN 201110047192 A CN201110047192 A CN 201110047192A CN 102649705 B CN102649705 B CN 102649705B
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention relates to an ethylene glycol production method, and mainly solves the technical problem in the prior art that ethylene glycol is low in selectivity. The method adopts oxalate as the raw material and at least one of the matters selected from water and C2-C5 alcohol as a terminator, and comprises the following steps: (a) the raw material enters to be in contact reaction with a catalyst from the bottom of a fluidized bed reactor to form an effluent I containing both ethylene glycol and catalyst; (b) the effluent I formed in the step (a) is in contact with the terminator at the bottom of a gas-solid quick separation area at the upper part of a transition zone of the fluidized bed reactor, so as to form an effluent II which is subjected to gas-solid separation after entering the gas-solid quick separation area at the upper part of the fluidized bed reactor, and then a solid catalyst enters an activator for activation; and (c) an activated catalyst from the activator returns to a dense-phase zone at the bottom of the fluidized bed reactor for continuous reaction. 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 production method of ethylene glycol, particularly react the method for generating glycol about dimethyl oxalate or oxalic acid diethyl ester catalysis by fluidized bed catalytic.
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 in the selectivity how effectively improving ethylene glycol, also have the research of more need of work.
Document " spectrographic laboratory " 27 volume 2 phase 616-619 pages in 2010 disclose the research of one section of ethylene glycol catalyst prepared by dimethyl oxalate plus hydrogen, and it has prepared Cu-B/ γ-Al by chemical reduction-deposition
2o
3, Cu-B/SiO
2amorphous alloy catalyst, its evaluation result shows, but this catalyzer barkite transformation efficiency is lower, and glycol selectivity is lower than 90%.
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%.
The subject matter that above-mentioned document exists is that glycol selectivity is lower, needs to improve further and improve.
Summary of the invention
Technical problem to be solved by this invention is the problem that the glycol selectivity that exists in conventional art is low.A kind of production method of new ethylene glycol is provided.The method has the high advantage of glycol selectivity.
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 production method of ethylene glycol, take barkite as raw material, to be selected from water, C
2~ C
5at least one in alcohol is terminator, comprises the following steps:
A first () raw material enters bottom fluidized-bed reactor, react in fluidized-bed reactor emulsion zone and zone of transition and catalyst exposure, forms the effluent I containing ethene and catalyzer;
B () contacts with terminator bottom the gas-solid sharp separation district on fluidized-bed reactor zone of transition top from the effluent I of (a) step, form effluent II, effluent II enters the gas-solid sharp separation district on fluidized-bed reactor top after gas solid separation, gas enters follow-up workshop section and is separated, and solid catalyst enters activator activation;
C () returns to fluidized-bed reactor bottom dense from the deactivated catalyst of activator and proceeds reaction.
In technique scheme, in fluidized-bed reactor, emulsion zone is connected with gas-solid sharp separation district by the zone of transition of undergauge structure.The reaction conditions of fluidized-bed reactor is preferably: temperature of reaction is 170 ~ 270 DEG C, and barkite weight space velocity is 0.2 ~ 5 hour
-1, hydrogen/ester mol ratio is 40 ~ 200: 1, and reaction pressure is 1.5 ~ 10MPa.The reaction conditions of fluidized-bed reactor is more preferably: temperature of reaction is 180 ~ 260 DEG C, and barkite weight space velocity is 0.3 ~ 3 hour
-1, hydrogen/ester mol ratio is 50 ~ 150: 1, and reaction pressure is 2.0 ~ 6.0MPa.Catalyzer preferred version is in total catalyst weight number, the Cu and its oxides that catalyzer comprises 5 ~ 80 parts be active ingredient, 10 ~ 90 parts silicon oxide, at least one is carrier in molecular sieve or aluminum oxide, and the bismuth of 0.01 ~ 30 part and tungsten metallic element or its oxide compound are auxiliary agent; The average particulate diameter preferable range of catalyzer is 20 ~ 300 microns.Catalyzer more preferably scheme in total catalyst weight number, the Cu and its oxides that catalyzer comprises 10 ~ 60 parts is active ingredient, at least one is carrier in the silicon oxide of 15 ~ 90 parts or aluminum oxide, and the bismuth of 0.05 ~ 20 part and tungsten metallic element or its oxide compound are auxiliary agent; The average particulate diameter of catalyzer is 30 ~ 200 microns.
Fluidized-bed reactor preferred version is selected from bubbling fluidized bed, turbulent fluidized bed, fast fluidized bed or riser reactor.Fluidized-bed reactor more preferably scheme is selected from fast fluidized bed.The weight ratio of raw material and terminator is 5 ~ 1000: 1, and terminator feeding temperature is 10 ~ 200 DEG C.
Adopt in hydrogenation of oxalate for preparing ethylene glycol 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 injects terminator by the region, outlet position leaving catalytic bed at catalyzer and reaction product, the terminator making temperature lower and pyroreaction mixture and catalyst exposure, significantly can reduce the temperature of reaction mixture and catalyzer, the sharply reduction of temperature, after making reaction mixture and catalyzer leave reaction zone, side reaction is few, continues reaction odds little, reduces the rate of loss of raw material.On the other hand, reacted catalyzer, after Hydrogen activation, can further improve the selectivity of ethylene glycol.
The present invention adopts fluidized-bed reactor to be used for hydrogenation of oxalate for preparing ethylene glycol reaction, use Fig. 1 shown device, adopt copper oxide fluid catalyst, water or alcohol are terminator, taking barkite as raw material, is 160 ~ 260 DEG C in temperature of reaction, and reaction pressure is 1.0 ~ 8.0MPa, hydrogen ester mol ratio is 20 ~ 200: 1, and reaction velocity is 0.1 ~ 5 hour
-1condition under, raw material contacts with fluid catalyst, and reaction generates containing the effluent of ethylene glycol, and wherein, the transformation efficiency of barkite can be reached for 100%, and the selectivity of ethylene glycol can be greater than 95%, achieves good technique effect.
Accompanying drawing explanation
Fig. 1 is the fluidized-bed reactor schematic diagram adopted in the production method of ethylene glycol 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 cyclonic separators, and 9 is collection chambers, 10 product gas outlet, 11 is strippers, and 12 is activation inclined tubes, and 13 is inclined tubes to be activated, 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 settling vessel 5 top dilute phase space and carries out secondary separation through cyclonic separator 8, gas product after separation enters collection chamber 9 through the outlet of cyclonic separator 8, is drawn by product gas outlet 10.Catalyzer after being separated from cyclonic separator 8 returns the lower region of settling vessel 5 through the dipleg of cyclonic separator 8.The catalyzer to be activated 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 activator (in figure, activator omits) through inclined tube 12 to be activated, the activated inclined tube 12 of activator enters fluidized-bed reactor emulsion zone A.In addition, the partially catalyzed agent in settling vessel 5 enters to continue to react with catalyst mix bottom fluidized-bed reactor emulsion zone A through interchanger 3 heat exchange is laggard, and whole process circulation is carried out.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
[embodiment 1]
According to the content preparation catalyzer of the silicon oxide of 20 parts of Cu, 5 parts of Bi and 2 part W and surplus, its step is as follows: (a) configures mixed nitrate solution and the sodium carbonate solution of the copper of desired concn, bismuth and tungsten; B the co-precipitation at 70 DEG C of () above-mentioned solution, constantly stirs in precipitation process, PH=6 when precipitation stops; (c) by above-mentioned sediment slurry deionized water repetitive scrubbing, until without Na
+after add the silica sol binder making beating that silica support (specific surface area 150 meters squared per gram) and concentration are 10%; D () carries out spray shaping with press spray moisture eliminator, control catalyst particle diameter average out to 100 microns, particle is ball-type; (e) 120 DEG C of dryings 6 hours, roasting 4 hours at 450 DEG C.I.e. obtained fluid catalyst A.
Test adopts fluidized bed reactor arrangement shown in accompanying drawing 1, and taking dimethyl oxalate as raw material, is 220 DEG C in temperature of reaction, and weight space velocity is 0.5 hour
-1, hydrogen/ester mol ratio is 80: 1, and reaction pressure is that under the condition of 2.8MPa, raw material contacts with catalyst A, and reaction generates the effluent containing ethylene glycol, and its reaction result is: the transformation efficiency of dimethyl oxalate is 100%, and the selectivity of ethylene glycol is 94.5%.
[embodiment 2]
According to each step and the condition of embodiment 1, just shaping of catalyst time control controlling catalyst particle diameter average out to 150 microns, particle is ball-type, and its carrier average specific surface area is 280 meters squared per gram, and catalyst B obtained is thus 30 parts of Cu, 10 parts of Bi and 1 part W and surplus silicon oxide.Test adopts fluidized bed reactor arrangement shown in accompanying drawing 1, and taking dimethyl oxalate as raw material, is 250 DEG C in temperature of reaction, and weight space velocity is 6 hours
-1, hydrogen/ester mol ratio is 100: 1, and reaction pressure is under the condition of 35% of 3.0MPa, and the transformation efficiency of dimethyl oxalate is 100%, and the selectivity of ethylene glycol is 96.3%.
[embodiment 3]
By the content preparation catalyzer of the silicon oxide of 40 parts of Cu, 3 parts of Bi and 15 part W and surplus and aluminum oxide, its step is as follows: (a) configures mixed nitrate solution and the sodium carbonate solution of the copper of desired concn, bismuth and tungsten; B the co-precipitation at 65 DEG C of () above-mentioned solution, constantly stirs in precipitation process, PH=7 when precipitation stops; (c) by above-mentioned sediment slurry deionized water repetitive scrubbing, until without Na
+after add the silica sol binder making beating that alumina supporter (specific surface area 300 meters squared per gram) and concentration are 15%; D () carries out spray shaping with press spray moisture eliminator, control catalyst particle diameter average out to 150 microns, particle is ball-type; (e) 120 DEG C of dryings 6 hours, roasting 4 hours at 450 DEG C.I.e. obtained fluid catalyst C.
Test adopts fluidized bed reactor arrangement shown in accompanying drawing 1, and taking oxalic acid diethyl ester as raw material, is 200 DEG C in temperature of reaction, and weight space velocity is 0.5 hour
-1, hydrogen/ester mol ratio is 100: 1, and reaction pressure is under the condition of 2.8MPa, and the transformation efficiency of oxalic acid diethyl ester is 99%, and the selectivity of ethylene glycol is 93.5%.
[embodiment 4]
By the content preparation catalyzer of the silicon oxide of 30 parts of Cu, 1 part of Bi and 8 part W and surplus and aluminum oxide, its step is as follows: (a) configures mixed nitrate solution and the sodium carbonate solution of the copper of desired concn, bismuth and tungsten; B the co-precipitation at 65 DEG C of () above-mentioned solution, constantly stirs in precipitation process, PH=7 when precipitation stops; (c) by above-mentioned sediment slurry deionized water repetitive scrubbing, until without Na
+after add the silica sol binder making beating that alumina supporter (specific surface area 100 meters squared per gram) and concentration are 6%; D () carries out spray shaping with press spray moisture eliminator, control catalyst particle diameter average out to 120 microns, particle is ball-type; (e) 120 DEG C of dryings 6 hours, roasting 4 hours at 450 DEG C.I.e. obtained fluid catalyst D.
Test adopts fluidized bed reactor arrangement shown in accompanying drawing 1, and taking oxalic acid diethyl ester as raw material, is 240 DEG C in temperature of reaction, and weight space velocity is 4 hours
-1, hydrogen/ester mol ratio is 60: 1, and reaction pressure is under the condition of 3.8MPa, and the transformation efficiency of oxalic acid diethyl ester is 99%, and the selectivity of ethylene glycol is 96.7%.
[embodiment 5]
By the content preparation catalyzer of the ZSM-5 molecular sieve of 45 parts of Cu, 8 parts of Bi and 2 part W and surplus, its step is as follows: (a) configures mixed nitrate solution and the sodium carbonate solution of the copper of desired concn, bismuth and tungsten; B the co-precipitation at 65 DEG C of () above-mentioned solution, constantly stirs in precipitation process, PH=5 when precipitation stops; (c) by above-mentioned sediment slurry deionized water repetitive scrubbing, until without Na
+after add ZSM-5 molecular sieve carrier (specific surface area 450 meters squared per gram) making beating; D () carries out spray shaping with press spray moisture eliminator, control catalyst particle diameter average out to 140 microns, particle is ball-type; (e) 120 DEG C of dryings 6 hours, roasting 4 hours at 450 DEG C.I.e. obtained fluid catalyst E.
Test adopts fluidized bed reactor arrangement shown in accompanying drawing 1, and taking dimethyl oxalate as raw material, is 230 DEG C in temperature of reaction, and weight space velocity is 0.3 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 100%, and the selectivity of ethylene glycol is 97.2%.
[embodiment 6]
By the content preparation catalyzer of the ZSM-5 molecular sieve of 25 parts of Cu, 0.8 part of Bi and 4 part W and surplus, its step is as follows: (a) configures mixed nitrate solution and the sodium carbonate solution of the copper of desired concn, bismuth and tungsten; B the co-precipitation at 65 DEG C of () above-mentioned solution, constantly stirs in precipitation process, PH=5 when precipitation stops; (c) by above-mentioned sediment slurry deionized water repetitive scrubbing, until without Na
+after add ZSM-5 molecular sieve carrier (specific surface area 400 meters squared per gram) making beating; D () carries out spray shaping with press spray moisture eliminator, control catalyst particle diameter average out to 140 microns, particle is ball-type; (e) 120 DEG C of dryings 6 hours, roasting 4 hours at 450 DEG C.I.e. obtained fluid catalyst.
Test adopts fluidized bed reactor arrangement shown in accompanying drawing 1, and taking dimethyl oxalate as raw material, is 230 DEG C in temperature of reaction, and weight space velocity is 0.2 hour
-1, hydrogen/ester mol ratio is 100: 1, and reaction pressure is 2.8MPa, and the mass percentage of dimethyl oxalate is under the condition of 14.5%, and the transformation efficiency of dimethyl oxalate is 100%, and the selectivity of ethylene glycol is 98.1%.
[comparative example 1]
Test adopts fixed-bed reactor, and according to condition and the catalyzer of embodiment 1, its reaction result is: the transformation efficiency of dimethyl oxalate is 98%, and the selectivity of ethylene glycol is 88%.
Claims (8)
1. a production method for ethylene glycol take barkite as raw material, to be selected from water, C
2~ C
5at least one in alcohol is terminator, comprises the following steps:
A first () raw material enters bottom fluidized-bed reactor, react in fluidized-bed reactor emulsion zone and zone of transition and catalyst exposure, forms the effluent I containing ethylene glycol and catalyzer;
B () contacts with terminator bottom the gas-solid sharp separation district on fluidized-bed reactor zone of transition top from the effluent I of (a) step, form effluent II, effluent II enters the gas-solid sharp separation district on fluidized-bed reactor top after gas solid separation, gas enters follow-up workshop section and is separated, and solid catalyst enters activator activation;
C () returns to fluidized-bed reactor bottom dense from the deactivated catalyst of activator and proceeds reaction;
In total catalyst weight number, described catalyzer is composed of the following components: the Cu and its oxides of 5 ~ 80 parts be active ingredient, 10 ~ 90 parts silicon oxide, at least one is carrier in molecular sieve or aluminum oxide, and the bismuth of 0.01 ~ 30 part and tungsten metallic element or its oxide compound are auxiliary agent; The average particulate diameter of catalyzer is 20 ~ 300 microns.
2. the production method of ethylene glycol according to claim 1, is characterized in that in fluidized-bed reactor, emulsion zone is connected with gas-solid sharp separation district by the zone of transition of undergauge structure.
3. the production method of ethylene glycol according to claim 1, it is characterized in that the temperature of reaction of fluidized-bed reactor is 170 ~ 270 DEG C, barkite weight space velocity is 0.2 ~ 5 hour
-1, hydrogen/ester mol ratio is 40 ~ 200: 1, and reaction pressure is 1.5 ~ 10MPa.
4. the production method of ethylene glycol according to claim 3, it is characterized in that fluidized-bed reactor temperature of reaction is 180 ~ 260 DEG C, barkite weight space velocity is 0.3 ~ 3 hour
-1, hydrogen/ester mol ratio is 50 ~ 150: 1, and reaction pressure is 2.0 ~ 6.0MPa.
5. the production method of ethylene glycol according to claim 1, it is characterized in that in total catalyst weight number, catalyzer is composed of the following components: the Cu and its oxides of 10 ~ 60 parts is active ingredient, at least one is carrier in the silicon oxide of 15 ~ 90 parts or aluminum oxide, and the bismuth of 0.05 ~ 20 part and tungsten metallic element or its oxide compound are auxiliary agent; The average particulate diameter of catalyzer is 30 ~ 200 microns.
6. the production method of ethylene glycol according to claim 1, is characterized in that fluidized-bed reactor is selected from bubbling fluidized bed, turbulent fluidized bed, fast fluidized bed or riser reactor.
7. the production method of ethylene glycol according to claim 6, is characterized in that fluidized-bed reactor is selected from fast fluidized bed.
8. the production method of ethylene glycol according to claim 1, it is characterized in that the weight ratio of raw material and terminator is 5 ~ 1000: 1, terminator feeding temperature is 10 ~ 100 DEG C.
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| CN107848921B (en) * | 2015-07-29 | 2022-01-25 | 巴斯夫欧洲公司 | Process for the production of monoethylene glycol |
| CN108383982A (en) * | 2018-01-23 | 2018-08-10 | 浙江省现代纺织工业研究院 | A kind of preparation method of hydridization ethylene glycol |
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| 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 |
| CN101475442A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Method for preparing ethylene glycol from oxalic ester |
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| 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 |
| CN101475442A (en) * | 2008-12-18 | 2009-07-08 | 中国石油化工股份有限公司 | Method for preparing ethylene glycol from oxalic ester |
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