CN102218274A - Method for mixing oxalate and hydrogen - Google Patents
Method for mixing oxalate and hydrogen Download PDFInfo
- Publication number
- CN102218274A CN102218274A CN2010101469244A CN201010146924A CN102218274A CN 102218274 A CN102218274 A CN 102218274A CN 2010101469244 A CN2010101469244 A CN 2010101469244A CN 201010146924 A CN201010146924 A CN 201010146924A CN 102218274 A CN102218274 A CN 102218274A
- Authority
- CN
- China
- Prior art keywords
- oxalate
- hydrogen
- packed bed
- mixing
- rotary packed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Abstract
The invention relates to a method for mixing oxalate and hydrogen, which mainly solves the technical problems of poor mixture effect of oxalate and hydrogen and high resolution ratio of oxalate in the prior art. Oxalate and hydrogen materials are induced into a supergravity device of a rotary packed bed and mixed under the conditions of a stay time of 0.001-2 seconds, a pressure of 0.5-8.0MPa and a temperature of 60-250 DEG C; and then the mixed materials leave the supergravity device of the rotary packed bed, wherein the supergravity device of the rotary packed bed comprises a gas inlet (1), rotary packing (2), a gas outlet (3), a liquid inlet (4), a motor shaft (5) and a liquid distributor (6). The technical scheme betters solves the problems, and the method for mixing oxalate and hydrogen can be used for industrial production for mixing oxalate and hydrogen.
Description
Technical field
The present invention relates to the method that a kind of oxalate mixes with hydrogen, particularly the method for mixing about the hydrogenation of oxalate for preparing ethylene glycol raw material.
Background technology
Ethylene glycol (EG) is a kind of important Organic Chemicals, be mainly used in and produce polyester fiber, antifreezing agent, unsaturated polyester resin, lubricant, plasticizer, non-ionic surface active agent 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, be used to produce special solvent glycol ether etc., purposes is very extensive.
At present, direct hydration method or the legal process route of pressure (hydraulic) water are all adopted in domestic and international large-scale ethylene glycol production, this technology is that oxirane and water are made into mixed aqueous solution by 1: 20～22 (mol ratios), in fixed bed reactors in 130～180 ℃, 1.0～2.5MPa reacted 18～30 minutes down, oxirane all is converted into mixed alcohol, the glycol water content that generates is greatly about 10% (mass fraction), carry through the multi-effect evaporator dehydration then and obtain ethylene glycol dense the separation with rectification under vacuum, but process units need be provided with a plurality of evaporimeters, consume lot of energy and be used for dehydration, cause the technological process of production long, equipment is many, the energy consumption height, directly influence the production cost of ethylene glycol.Since the seventies in 20th century, both at home and abroad some major companies that mainly produce ethylene glycol all are devoted to the Synthesis of Ethylene Glycol by Catalytic Hydration Study on Technology, mainly contain shell company, U.S. UCC company and Dow company, the Mitsubishi chemical company of Ying He, domestic Dalian University of Technology, Shanghai Petroleum Chemical Engineering Institute, Nanjing University of Technology etc.What representative was wherein arranged is the heterogeneous catalysis hydration method of Shell company and the homogeneous catalysis hydration method of UCC company.Shell company has reported that from 1994 quaternary ammonium type acid carbonate anion exchange resin carries out the exploitation of EO catalysis hydration technology as catalyst, obtain EO conversion ratio 96%～98%, the result of the test of EG selectivity 97%～98%, develop the poly-organosilicon alkane ammonium salt loaded catalyst of similar silicon dioxide skeleton and the epoxides hydrating process under the catalysis thereof in 1997 again, obtained better conversion rate and selectivity.The UCC company of the U.S. has mainly developed two kinds of hydration catalysts: a kind of is the anionic catalyst that is carried on the ion exchange resin, mainly is molybdate, tungstates, vanadate and triphenylphosphine complex catalyst; Another kind is the molybdate composite catalyst.In two kinds of Application of Catalyst examples, the TM catalyst of spent ion exchange resin DOWEX WSA21 preparation is hydration under 9: 1 the condition in the mol ratio of water and EO, and the EG yield is 96%.Using the molybdate composite catalyst, is hydration under 5: 1 the condition in the mol ratio of water and EO, and the EG yield is 96.6%.Catalysis method greatly reduces the water ratio, simultaneously can obtain high EO conversion ratio and high EG selectivity, but also there is certain problem aspect Preparation of Catalyst, regeneration and life-span, not enough as catalyst stability, preparation is quite complicated, be difficult to recycle, have also can be in product residual a certain amount of anionic metal, need to increase corresponding apparatus and separate.Ethylene carbonate method synthesizing glycol is by oxirane and carbon dioxide synthesizing ethylene carbonate, obtains ethylene glycol with the ethylene carbonate hydrolysis again.The US4508927 patent proposes esterification and hydrolysis are separately carried out.The two-step process that the US4500559 of U.S. Halcon-SD company proposes is that the mixture that comes from reactor is through absorber, again with the carbon dioxide extracting oxirane under the supercriticality, obtain oxirane, carbon dioxide, aqueous mixtures contacts synthetic BC with catalyst for esterification reaction such as organohalogen compounds, sulfide, BC is admitted to hydrolysis reactor then, and hydrolysis obtains ethylene glycol and carbon dioxide under same catalyst action, and the ethylene glycol yield is up to 99%.Japan Patent JP571006631 has proposed the EO-EC-EG new technology of industrially scalable, patent introduces oxirane and the carbon dioxide esterification is in the presence of catalyst KI, 160 ℃ are carried out esterification, conversion ratio is 99.9%, the selectivity of ethylene glycol is 100%, the ethylene carbonate legal system is equipped with the ethylene glycol technology no matter aspect conversion ratio and selectivity, still all than present EO direct hydration method bigger advantage is being arranged aspect production process consumption of raw materials and the energy consumption, technical in ethylene glycol is a kind of method that maintains the leading position.But this method still is raw material with the oil, and need build the ethylene glycol process units again, and this glycol unit to new construction is more suitable, and on original production equipment was undergone technological transformation, it was favourable to be not so good as catalytic hydration.
Document CN101138725A discloses a kind of Catalysts and its preparation method of oxalic ester hydrogenation synthesizing of ethylene glycol, and it is active component with the metallic copper, and zinc is auxiliary agent, the preparation of employing coprecipitation, but this catalyst oxalate conversion ratio is lower, and glycol selectivity is not high, and the hydrogen ester ratio is best about 100.
Document " petrochemical industry " 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, but this catalyst exists glycol selectivity not high, the hydrogen ester ratio is greater than 100.
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 natural gas and coal resource, reduces the dependence of petroleum import and can alleviate environmental pressure, is unusual important field of research.With the carbon monoxide is the feedstock production oxalate, is a very attractive Coal Chemical Industry route then with preparing glycol by hydrogenating oxalate.But in the preparing glycol by hydrogenating oxalate process, how further to improve the selectivity of the purpose glycol product of oxalate hydrogenation, the treating capacity that effectively improves catalyst is to need the further problem of research, especially how further optimizes oxalate hydrogenation process from the equipment angle and rarely has report.
Summary of the invention
Technical problem to be solved by this invention is that the oxalate and the hydrogen mixed effect that exist in the document poor in the past, the technical problem that the oxalate resolution ratio is high, the method that provides a kind of new oxalate to mix with hydrogen.This method has oxalate and hydrogen good mixing effect, the advantage that the oxalate resolution ratio is low.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: the method that a kind of oxalate mixes with hydrogen, oxalate and hydrogen feed are introduced rotary packed bed hypergravity device, in the time of staying is 0.001～2 second, pressure is 0.5～8.0MPa, temperature is to mix under 60～250 ℃ the condition, and mixed material leaves rotary packed bed hypergravity device;
Wherein, used rotary packed bed hypergravity device comprises gas access (1), rotation filler (2), gas vent (3), inlet (4), motor shaft (5) and liquid distribution trough (6).
The preferred mixing condition of technique scheme medium-height grass acid esters and hydrogen feed is: incorporation time is 0.005～1 second, and pressure is 1.0～6.0MPa, and temperature is 80～240 ℃.
The rotating speed of rotary packed bed hypergravity device rotation filler is 100～8000 rev/mins in the technique scheme.The preferred range of speeds is 200～6000 rev/mins.Oxalate is preferably from dimethyl oxalate, diethy-aceto oxalate or its mixture.
As everyone knows, oxalate is a heat-sensitive substance, meets thermal capacitance and easily decomposes, especially under the situation that does not have hydrogen to exist, therefore the time of staying is long more, decomposes seriously more, and what how to guarantee hydrogen and oxalate efficiently contacts that to mix be the important technology key that prevents the oxalate decomposition.On the other hand, oxalate hydrogenation process is a course of reaction that is subjected to dynamics Controlling, and the difference of raw material mixed effect is remarkable to the motive force influence of reaction, and mixed effect is good more, and the efficient of catalyst is high more, and the purpose product selectivity is just high more.
Because rotary packed bed extra gravity field device can strengthening transfer process, in super gravity field, mix, can strengthen the mass transfer between the material, shorten incorporation time greatly, make the material hybird environment that speeds away, reach the raising mixing efficiency, reduce the generation of accessory substance such as decompositions grade, reduce equipment volume, the effect that cuts down the consumption of energy.Simultaneously, because the reinforcement of diabatic process more evenly and is steadily carried out mixed process.
Method of the present invention has the following advantages:
1, owing in rotary packed bed extra gravity field device, mixes, greatly strengthened mass transport process, thereby shortened incorporation time, make the disposal ability of unit interval improve tens times and even hundreds of times, mixing efficiency improves widely, the size of equipment reduces widely, has reduced energy consumption, has reduced the investment of equipment.
2, because the time of staying of mixed material in rotary packed bed extra gravity field device shortens (less than 0.5 second), obviously reduce so the probability of side reactions such as decomposition takes place, raw material availability obviously improves, and the quality of product obviously improves.
3, owing in rotary packed bed super gravity field, strengthened the mass transport process of gas-liquid phase, gas can fully be mixed on microcosmic with liquid, gas more is soluble in the liquid phase, thereby can reduce reaction pressure, some high pressure, High Temperature Gas liquid phase reactor can be carried out under lower pressure and temperature, and then cut down the consumption of energy, solved the material problem and the engineering scale-up problem of high pressure-temperature reaction, can save great amount of investment.
Description of drawings
Fig. 1 is that gas-liquid phase adverse current is mixed rotary packed bed extra gravity field device schematic diagram.
Fig. 2 is that gas-liquid also flows the rotary packed bed extra gravity field device schematic diagram of mixing mutually.
1-gas access 2-rotation filler 3-gas vent 4-inlet 5-motor shaft 6-liquid distribution trough 7-liquid outlet 8-inlet pipeline 9-fluid pipeline among Fig. 1.
1-gas vent 2-rotation filler 3-gas access 4-inlet 5-motor shaft 6-liquid distribution trough 7-liquid outlet 8-inlet pipeline 9-fluid pipeline among Fig. 2.
The invention will be further elaborated below by embodiment, but be not limited only to present embodiment.
The specific embodiment
Describe method of the present invention in detail below in conjunction with accompanying drawing.
As shown in Figure 1, oxalate and hydrogen gas-liquid two-phase adopt the mode of counter current contacting to mix.The gas that contains reaction mass is tangentially introduced rotary packed bed extra gravity field device by gas access 1, under action of pressure, pass the rotation filler 2 and the liquid phase counter current contacting that contains reaction mass that sprays by the liquid distribution trough 6 that places rotary packed bed extra gravity field device center of rotation at a high speed, gas-liquid two-phase strong mixing with turbulence in the rotary filler layer of rotation at a high speed carried out mass transfer reaction, mixed gas phase is drawn by the gas vent 3 of extra gravity field device reactor, mixed liquid phase is thrown away at a high speed after liquid outlet 7 is drawn, and gas-liquid two-phase enters after-treatment system separately or does it and use.
As shown in Figure 2, oxalate mixes with the mode that the hydrogen gas-liquid two-phase adopts and stream contacts.Gas-liquid two-phase is introduced by the gas access 3 and the inlet 4 at the center of rotary packed bed extra gravity field device respectively, pass the rotation filler 2 of rotation at a high speed jointly, gas-liquid two-phase mixes strongly in the rotation filler of rotation at a high speed and mass transfer is carried out in turbulence, mixed gas phase is drawn by the gas vent 1 of rotary packed bed extra gravity field device, mixed liquid phase is thrown away at a high speed after liquid outlet 7 is drawn, and gas, liquid two-phase enter after-treatment system respectively or do it and use.
[embodiment 1]
In rotary packed bed extra gravity field device, carry out mixing of dimethyl oxalate and hydrogen, and be used for the reaction of preparing ethylene glycol by using dimethyl oxalate plus hydrogen.Adopt the rotary packed bed extra gravity field device shown in the accompanying drawing 1.
Hydrogen enters rotary packed bed super gravity field mixing arrangement by gas access 1, under differential pressure action, diffuses into rotation filler 2, and rotation filler rotating speed transfers to 2000rpm.Dimethyl oxalate solution is introduced the inboard of liquid distribution trough 6 and rotation filler 2 through inlet 4 by inlet pipeline 8, the mol ratio of hydrogen and dimethyl oxalate is 100: 1, mixing temperature is 190 ℃, pressure is 3.0MPa, the time of staying is 0.1 second, gas and liquid counter current contacting in filler, mixed effluent are gas, and (hydrogenation catalyst is the Cu/SiO of silica supported cupric oxide to escape and enter the oxalate hydrogenation device by gas vent 3
2Catalyst is 40% in vehicle weight percentage cupric oxide content), 190 ℃ of temperature, pressure 3.0MPa, air speed 0.8 hour
-1React under the condition, its result is: the conversion ratio of dimethyl oxalate is 100%, and the selectivity of ethylene glycol is 96%, and the resolution ratio of dimethyl oxalate is 0 behind the rotary packed bed extra gravity field device of process.
[embodiment 2]
In rotary packed bed extra gravity field device, carry out mixing of diethy-aceto oxalate and hydrogen, and be used for the reaction of diethy-aceto oxalate hydrogenation preparing ethylene glycol.Adopt the rotary packed bed extra gravity field device shown in the accompanying drawing 2.
Hydrogen enters rotary packed bed super gravity field mixing arrangement by gas access 3, under differential pressure action, diffuses into rotation filler 2, and rotation filler rotating speed transfers to 5000rpm.Diethy-aceto oxalate solution is introduced the inboard of liquid distribution trough 6 and rotation filler 2 through inlet 4 by inlet pipeline 8, the mol ratio of hydrogen and diethy-aceto oxalate is 80: 1, mixing temperature is 195 ℃, pressure is 2.5MPa, the time of staying is 0.08 second, gas also flows in filler with liquid and contacts, and mixed effluent is a gas, and gaseous effluent escapes and enter the oxalate hydrogenation device by gas vent 1, and (hydrogenation catalyst is the Cu/SiO of silica supported cupric oxide
2Catalyst is 40% in vehicle weight percentage cupric oxide content), 195 ℃ of temperature, pressure 2.5MPa, air speed 1.0 hours
-1React under the condition, its result is: the conversion ratio of diethy-aceto oxalate is 100%, and the selectivity of ethylene glycol is 95%, and the resolution ratio of diethy-aceto oxalate is 0 behind the rotary packed bed extra gravity field device of process.
[comparative example 1]
According to embodiment 1 identical condition and reaction raw materials, just adopt static mixing gas, its result is: the conversion ratio of dimethyl oxalate is 98.8%, the selectivity of ethylene glycol is 85%, is 2% through the resolution ratio of dimethyl oxalate behind the static mixing gas.
[comparative example 2]
According to embodiment 2 identical condition and reaction raw materials, just adopt static mixing gas, its result is: the conversion ratio of diethy-aceto oxalate is 97%, and the selectivity of ethylene glycol is 86%, and the resolution ratio of diethy-aceto oxalate is 3% behind the rotary packed bed extra gravity field device of process.
Claims (5)
1. method that oxalate mixes with hydrogen, oxalate and hydrogen feed are introduced rotary packed bed hypergravity device, in the time of staying is 0.001～2 second, pressure is 0.5～8.0MPa, temperature is to mix under 60～250 ℃ the condition, and mixed material leaves rotary packed bed hypergravity device;
Wherein, used rotary packed bed hypergravity device comprises gas access (1), rotation filler (2), gas vent (3), inlet (4), motor shaft (5) and liquid distribution trough (6).
2. the method for mixing with hydrogen according to the described oxalate of claim 1, the incorporation time that it is characterized in that oxalate and hydrogen feed is 0.005～1 second, and pressure is 1.0～6.0MPa, and temperature is 80～240 ℃.
3. the method for mixing with hydrogen according to the described oxalate of claim 1 is characterized in that the rotating speed of rotary packed bed hypergravity device rotation filler is 100～8000 rev/mins.
4. the method for mixing with hydrogen according to the described oxalate of claim 3 is characterized in that the rotating speed of rotary packed bed hypergravity device rotation filler is 200～6000 rev/mins.
5. the method for mixing with hydrogen according to the described oxalate of claim 1 is characterized in that oxalate is selected from dimethyl oxalate, diethy-aceto oxalate or its mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101469244A CN102218274B (en) | 2010-04-15 | 2010-04-15 | Method for mixing oxalate and hydrogen |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101469244A CN102218274B (en) | 2010-04-15 | 2010-04-15 | Method for mixing oxalate and hydrogen |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102218274A true CN102218274A (en) | 2011-10-19 |
| CN102218274B CN102218274B (en) | 2013-07-31 |
Family
ID=44775127
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101469244A Active CN102218274B (en) | 2010-04-15 | 2010-04-15 | Method for mixing oxalate and hydrogen |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102218274B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1116146A (en) * | 1995-05-26 | 1996-02-07 | 北京化工大学 | Preparing method for ultromicro granule |
| CN1507940A (en) * | 2002-12-16 | 2004-06-30 | 中国石油化工股份有限公司 | Catalytic reaction method |
| WO2005039731A2 (en) * | 2003-10-24 | 2005-05-06 | Cleveland Gas Systems Llc | Spinning impingement multiphase contacting device |
| CN1895766A (en) * | 2005-07-14 | 2007-01-17 | 中国石油化工股份有限公司 | Catalytic selective hydrogenation |
| CN101104595A (en) * | 2007-04-26 | 2008-01-16 | 宁波万华聚氨酯有限公司 | Process for preparing isocyanate |
| 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
- 2010-04-15 CN CN2010101469244A patent/CN102218274B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1116146A (en) * | 1995-05-26 | 1996-02-07 | 北京化工大学 | Preparing method for ultromicro granule |
| CN1507940A (en) * | 2002-12-16 | 2004-06-30 | 中国石油化工股份有限公司 | Catalytic reaction method |
| WO2005039731A2 (en) * | 2003-10-24 | 2005-05-06 | Cleveland Gas Systems Llc | Spinning impingement multiphase contacting device |
| CN1895766A (en) * | 2005-07-14 | 2007-01-17 | 中国石油化工股份有限公司 | Catalytic selective hydrogenation |
| CN101104595A (en) * | 2007-04-26 | 2008-01-16 | 宁波万华聚氨酯有限公司 | Process for preparing isocyanate |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102218274B (en) | 2013-07-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101138725B (en) | Catalyzer for the oxalic ester hydrogenation synthesizing of ethylene glycol and method of preparing the same | |
| CN101475441B (en) | Method for preparing ethylene glycol from oxalic ester | |
| CN101475443B (en) | Method for preparing ethylene glycol | |
| CN102372596B (en) | Method for producing glycol product by separating synthetic gas | |
| CN101475442A (en) | Method for preparing ethylene glycol from oxalic ester | |
| CN101993344A (en) | Method for preparing ethylene glycol from synthesis gas | |
| CN102372600B (en) | Separation method for glycol, propylene glycol and butylene glycol | |
| CN102372597B (en) | Method for separating glycol product produced from syngas | |
| CN109970511B (en) | Method for synthesizing 1, 3-propylene glycol by resource utilization of HPPO byproduct | |
| CN102219640A (en) | Method for improving selectivity for making glycol by adding hydrogen in oxalate | |
| CN102219641B (en) | Method for purifying ethylene glycol | |
| CN101993343B (en) | Multi-stage synthesis method of ethylene glycol | |
| CN102219639B (en) | Method for preparing glycol by virtue of hydrogenation of oxalate | |
| CN107652263A (en) | Catalytic distillation device prepares the industrialization continuation method of solketal | |
| CN101993345A (en) | Method for improving selectivity of glycol prepared by adding hydrogen into oxalate | |
| CN102218274B (en) | Method for mixing oxalate and hydrogen | |
| CN112266320B (en) | Method and system for producing 1,3-propylene glycol by multi-step method | |
| CN102276418B (en) | Ethylene glycol purification method | |
| CN101993341B (en) | Method for producing glycol through hydrogenation of oxalic ester | |
| CN102442976B (en) | Method for epoxidizing olefinic hydrocarbon | |
| CN102649689B (en) | Method for parking reactor | |
| CN102649691B (en) | Method for improving selectivity of ethylene glycol prepared through hydrogenation reaction by oxalic ester | |
| CN102649693B (en) | Method for preparing ethylene glycol through catalytic hydrogenation by oxalic ester | |
| CN102649684B (en) | Improve barkite shortening preparing ethylene glycol optionally method | |
| CN102649701B (en) | Method for stopping reactor in hydrogenation of oxalate to ethylene glycol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |