CN104045516B - The method improving quality of ethylene glycol product - Google Patents
The method improving quality of ethylene glycol product Download PDFInfo
- Publication number
- CN104045516B CN104045516B CN201310078821.2A CN201310078821A CN104045516B CN 104045516 B CN104045516 B CN 104045516B CN 201310078821 A CN201310078821 A CN 201310078821A CN 104045516 B CN104045516 B CN 104045516B
- Authority
- CN
- China
- Prior art keywords
- ethylene glycol
- hydrogen
- transmittance
- raw material
- catalyst
- 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.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
Abstract
The present invention relates to a kind of method improving quality of ethylene glycol product, the technical problem that mainly present in solution prior art, ethylene glycol product UV transmittance is low.The present invention, by using the defective ethylene glycol raw material and hydrogen that the UV transmittance that quality of glycol content is more than 99% is low, is 70 DEG C ~ 130 DEG C in reaction temperature, and reaction pressure is 0.05 ~ 1.0MPa, and ethylene glycol liquid hourly space velocity (LHSV) is 2 ~ 60h‑1Under conditions of the volume ratio of hydrogen and raw material is 1 ~ 50, by liquid phase fixed bed reactors, contact with the catalyst in reactor, obtaining polyester grade ethylene glycol product logistics, wherein catalyst is with aluminium oxide as carrier, with at least one in nickel or palladium as active component, technical scheme with at least one in magnesium, calcium, barium, molybdenum, cerium as auxiliary agent preferably solves this problem, can be used in the commercial production of raising quality of ethylene glycol product.
Description
Technical field
The present invention relates to a kind of method improving quality of ethylene glycol product, especially with regard to improving Hydrogenation of Dimethyl Oxalate or the method for ethyl oxalate Hydrogenation ethylene glycol product UV transmittance.
Background technology
Ethylene glycol (EG) is a kind of important basic petrochemical Organic Ingredients, and it can mix with water with arbitrary proportion, and boiling point is high, freezing point is low.Mainly for the production of polyester fiber, antifreezing agent, unsaturated polyester resin, lubricant, plasticizer, nonionic surfactant and explosive etc., additionally can be used for the industries such as coating, soup, brake-fluid and ink, solvent and medium as ammonium pertorate, for producing special solvent glycol ether etc., purposes is quite varied.
At present, the ethylene glycol of domestic and international large chemical complex produces the process route all using oxirane direct hydration method, i.e. first through petroleum path synthesizing ethylene, reoxidizes ethylene production oxirane, is finally obtained ethylene glycol by oxirane on-catalytic hydration reaction.Impact yet with oil crisis in recent years; researchers start with coal one after another for primary raw materials to produce the new method of ethylene glycol; i.e. by producing synthesis gas from coal oxidative coupling reaction producing oxalic ester; then the coal ethyl glycol process route of oxalate further Hydrogenation ethylene glycol; this is an ethylene glycol production technology route with bigger potentiality and preferably Technical Economy, and current domestic industry production technology is the most ripe.The application of coal ethyl glycol is identical with petroleum path ethylene glycol product, and the quality standard weighing coal ethyl glycol product is the most thus like.Currently, as a composite target, domestic and international commonly used product UV transmittance (UV value) judges that quality of ethylene glycol product, general method are to measure the impurity content that the UV transmittance of 220nm ~ 350nm wavelength is detected, controls in ethylene glycol product by ethylene glycol product.Excellent ethylene glycol product should be at least 75% to the UV transmittance of 220nm wavelength, and the UV transmittance to 275nm wavelength should be at least 92%, and the UV transmittance to 350nm wavelength should be at least 99%.The underproof ethylene glycol of UV transmittance prepare poly-to this naphthalate for follow-up prepare polyester fiber and polyester plastics time, the quality of fiber will be had a strong impact on, such as gloss, colourity, coloring and the intensity etc. of fiber.
For how improving the ethylene glycol UV transmittance that conventional petroleum route prepares, researchers have done substantial amounts of research work, in prior art, general employing ion exchange resin improves ethylene glycol UV transmittance, as United States Patent (USP) US5770777 and US6525229 describe with anion exchange resin finished product ethylene glycol or the processing method of glycol water, make ethylene glycol UV transmittance reach polyester grade by ion exchange and require exchange and the absorption of resin, can preferably remove diones impurity, improve ethylene glycol UV transmittance, ethylene glycol UV transmittance is made to reach polyester grade requirement.It is obvious that resin method improves ethylene glycol UV transmittance effect, but, the exchange capacity of ion exchange resin is limited, for extensive ethylene glycol process units, not only need substantial amounts of ion exchange resin, also needing to often carry out the regeneration of resin, regeneration can produce more acid-base waste fluid, transition intermediate material etc..Additionally, catalytic hydrogenation method is improved the prepared ethylene glycol UV transmittance of conventional petroleum route and have also been made certain exploratory development work by researchers, intermittently or serially catalytic hydrogenation is carried out as Chinese patent CN200710021425.0 describes the glycol water using skeleton nickel or palladium-carbon catalyst to produce conventional petroleum route method, reduce aldehyde, the method improving the UV transmittance of ethylene glycol, aldehyde < the 3ug/g of the ethylene glycol product obtained after the processing of the method, UV transmittance is more than 90% at 220nm, 275nm is more than 95%, and 350nm is more than 99%.But the method the most effectively reduces the aldehyde in ethylene glycol, is not directed to other impurity how reduced in ethylene glycol, has some limitations.
About coal ethyl glycol process route while saving petroleum resources, have also been introduced the former unexistent impurity of petrochemical industry route, some double bond containing by-products can be produced as in coal ethyl glycol technique, including aldehyde, ketone, carbonyl acid, ester etc., the uv absorption wavelength of these by-products is mostly within 220 ~ 350nm.But the technique study report that the ethylene glycol prepared coal ethyl glycol process route the most both at home and abroad purifies is less, and in the method reported, all there is certain defect, being difficult to industrial applications, the quality (specifically how being effectively improved coal ethyl glycol product UV transmittance) how being effectively improved coal ethyl glycol product also has many job demand to study further.
Chinese patent 201110047173.5 describes the ethylene glycol using activated carbon and molecular sieve adsorption hydrogenation of oxalate for preparing to obtain, the method improving ethylene glycol ultraviolet permeability.But the adsorption capacity that the method exists activated carbon and adsorbent of molecular sieve is limited, after using a period of time, effect substantially reduces, and activated carbon is difficult to regenerate completely, and use cost is high, limits its industrial applications.
Chinese patent 201110045250.3 describes employing copper system, nickel system or palladium series catalyst, ethylene glycol raw material and hydrogen in temperature 20～280 DEG C, pressure 0.1～4.0MPa, air speed 0.2～100.0 hours-1, mol ratio is by rotary packed bed reactor, the method improving ethylene glycol UV transmittance under conditions of 0.01～40: 1.But the method reaction temperature is too high, can directly affect the quality of ethylene glycol product, and the rotary packed bed reactor used is equipment, maximize difficulty, limits its commercial Application.
Chinese patent 201110045256.0 describes employing cupric solid oxide catalyst, and ethylene glycol raw material and hydrogen are 100～260 DEG C in temperature, and pressure is 0.1～6.0MPa, and air speed is 0.2～50 hour-1, hydrogen/alcohol mol ratio be under conditions of 0.1～40:1 with catalyst haptoreaction, the method improving ethylene glycol UV transmittance.But it is too high that the method equally exists reaction temperature, the shortcoming that the quality of ethylene glycol product can be directly affected.
Chinese patent 200910053962.2 describes the purifying technique of a kind of coal glycol rude products, use the Pd/C catalyst that quality proportion by subtraction is 5% or the Ranney Ni catalyst of Pd, use trickle bed reactor or tank reactor, being 100～120 DEG C in reaction temperature, reaction pressure is that coal glycol rude products purifies to improve under conditions of 1.0～3.0MPa the UV transmittance of ethylene glycol.The shortcomings such as but it is high that the method exists Catalyst Production cost, reactor maximizes difficult, and operation is complicated.
Summary of the invention
The technical problem to be solved is the technical problem that ethylene glycol product UV transmittance is low present in prior art, it is provided that a kind of method of new raising quality of ethylene glycol product.The method has the advantage that ethylene glycol product UV transmittance is high.
For solving above-mentioned technical problem, the present invention uses technical scheme as follows: a kind of method improving quality of ethylene glycol product, use ethylene glycol raw material and hydrogen that the UV transmittance that quality of glycol content is more than 99% is low, it it is 70 DEG C ~ 130 DEG C in reaction temperature, reaction pressure is 0.05 ~ 1.0MPa, and ethylene glycol liquid hourly space velocity (LHSV) is 2 ~ 60 hours-1Under conditions of the volume ratio of hydrogen and raw material is 1 ~ 50, by gas and liquid phase fixed bed reactors, contact with the catalyst in reactor, obtain polyester grade ethylene glycol product logistics, wherein catalyst is with aluminium oxide as carrier, with at least one in nickel or palladium as active component, with at least one in magnesium, calcium, barium, molybdenum, cerium as auxiliary agent；Described UV transmittance is low refers to that ethylene glycol UV transmittance at 220nm is less than 75%, or the UV transmittance at 275nm is less than 92%.
In technique scheme, reaction temperature is preferably 75 DEG C ~ 120 DEG C, more preferably 80 DEG C ~ 120 DEG C；Reaction pressure is preferably 0.05 ~ 0.8MPa, more preferably 0.05 ~ 0.6MPa；Ethylene glycol liquid hourly space velocity (LHSV) is preferably 5 ~ 50h-1, more preferably 5 ~ 40h-1；Hydrogen is preferably 2 ~ 40 with the volume ratio of raw material, and more preferably 5 ~ 40.
When the active component of catalyst is nickel, metallic nickel content is preferably the 10%～50% of vehicle weight, more preferably 15%～40%；When the active component of catalyst is palladium, Metal Palladium content is preferably the 0.1%～1% of vehicle weight, more preferably 0.1%～0.8%.Catalyst is with at least one in magnesium, calcium, barium, molybdenum, cerium as auxiliary agent, and metal promoter content is preferably the 0.05～2% of vehicle weight.
Catalyst needs to use the reducibility gas containing hydrogen to carry out reduction treatment before use.Reduction treatment condition is the hydrogen with hydrogen volume content >=70% and the mixed gas of nitrogen, is 0.1～0.6MPa at pressure, and maximum temperature is 450 DEG C ~ 500 DEG C, and volume space velocity is 800 ~ 1500h- 1Under conditions of, reduction treatment catalyst 8 ~ 16 hours.In gas and liquid phase fixed bed reactors defective ethylene glycol raw material and hydrogen for and stream flows up or and stream flow downward.Defective ethylene glycol raw material is from hydrogenation of oxalate for preparing ethylene glycol product.
nullIt is known that，In the course of reaction of hydrogenation of oxalate for preparing ethylene glycol，In addition to ethylene glycol target product，Also has a certain amount of by-product，Ethanol such as constant、Butanediol、Propylene glycol and the compound containing unsaturated double-bond of other trace，And separated by routine or the method for other special extract rectifications can remove the compound of most constant，The purity making ethylene glycol product reaches more than 99.8%，But，Typically，Although the purity of ethylene glycol is the highest，But ethylene glycol product is to 220nm、The UV transmittance of 275nm and 350nm wavelength is still not up to required value, and (requirement of GB_T 4649-2008 standard industry spent glycol top grade product is ethylene glycol product 220nm、UV transmittance at 275nm and 350nm should be the most at least 75%、92% and 99%)，The uv absorption wavelength of the compound of the unsaturated double-bond of the trace of the even ppm level being trace of tracing it to its cause is mostly within 220 ~ 350nm，Notable on the impact of ethylene glycol UV transmittance，Particularly have a strong impact on ethylene glycol product 220nm、UV transmittance at 275nm，And the trace impurity of these ppm levels is generally difficult to be removed by conventional separation method.
Present inventor finds under study for action, uses the nickeliferous and/or catalyst of palladium, processes ethylene glycol in presence of hydrogen, the UV transmittance that can make ethylene glycol product significantly improves, and the inventive method technique is simple, catalyst life is long, it is easy to industrialized production is applied.
Using technical scheme, the ethylene glycol obtained with hydrogenation of oxalate for preparing, as raw material, is 75 DEG C ~ 120 DEG C in reaction temperature, and reaction pressure is 0.05 ~ 0.8MPa, and ethylene glycol liquid hourly space velocity (LHSV) is 5 ~ 50h-1Under conditions of the volume ratio of hydrogen and raw material is 2 ~ 40, ethylene glycol raw material and hydrogen are by gas and liquid phase fixed bed reactors, contact with the catalyst in reactor, obtain polyester grade ethylene glycol product logistics, wherein catalyst is with aluminium oxide as carrier, with at least one in nickel or palladium as active component, metallic nickel content is the 10%～50% of vehicle weight, Metal Palladium content is the 0.1%～1% of vehicle weight, with at least one in magnesium, calcium, barium, molybdenum, cerium as auxiliary agent, metal promoter content is the 0.05～2% of vehicle weight.After after its hydrogenation, ethylene glycol product of obtaining is separated, its UV transmittance at 220nm >=80%, at 275nm >=95%, at 350nm >=99%, achieve preferable technique effect.
Below by embodiment, the invention will be further elaborated, but is not limited only to the present embodiment.
Detailed description of the invention
[embodiment 1]
By with aluminium oxide as carrier, metallic nickel content as vehicle weight 20%, metal promoter content of magnesium as vehicle weight 1.5% catalyst load in gas and liquid phase fixed bed reactors, it is passed through hydrogen and the mixed gas of nitrogen that hydrogen volume content is 90%, it is 0.3MPa at pressure, maximum temperature is 450 DEG C, and volume space velocity is 1000h- 1Under conditions of, reduction treatment 12 hours, reduction is down to reaction temperature after terminating, then each led into, by the bottom of reactor, ethylene glycol product raw material (UV transmittance of raw material is as shown in table 1) and the hydrogen that the prepared by dimethyl oxalate plus hydrogen that purity is 99.8% obtains, reaction temperature 80 DEG C, reaction pressure 0.4MPa, ethylene glycol liquid hourly space velocity (LHSV) is 15h-1, the volume ratio of hydrogen and raw material be under conditions of 10 with catalyst haptoreaction, obtain ethylene glycol UV transmittance result after purification as shown in table 1.
[embodiment 2]
By with aluminium oxide as carrier, metallic nickel content as vehicle weight 10%, Metal Palladium content as vehicle weight 0.8%, metal promoter barium content as vehicle weight 0.8% catalyst load in gas and liquid phase fixed bed reactors, it is passed through pure hydrogen, it is 0.1MPa at pressure, maximum temperature is 500 DEG C, and volume space velocity is 800h- 1Under conditions of, reduction treatment 8 hours, reduction is down to reaction temperature after terminating, then each led into, by the top of reactor, ethylene glycol product raw material (UV transmittance of raw material is as shown in table 1) and the hydrogen that the prepared by dimethyl oxalate plus hydrogen that purity is 99.2% obtains, reaction temperature 90 DEG C, reaction pressure 0.6MPa, ethylene glycol liquid hourly space velocity (LHSV) is 10h-1, the volume ratio of hydrogen and raw material be under conditions of 50 with catalyst haptoreaction, obtain ethylene glycol UV transmittance result after purification as shown in table 1.
[embodiment 3]
By with aluminium oxide as carrier, metallic nickel content as vehicle weight 40%, metal promoter content of magnesium as vehicle weight 1%, metal promoter molybdenum content as vehicle weight 0.1% catalyst load in gas and liquid phase fixed bed reactors, it is passed through hydrogen and the mixed gas of nitrogen that hydrogen volume content is 70%, it is 0.6MPa at pressure, maximum temperature is 480 DEG C, and volume space velocity is 1500h- 1Under conditions of, reduction treatment 16 hours, reduction is down to reaction temperature after terminating, then each led into, by the base portion of reactor, ethylene glycol product raw material (UV transmittance of raw material is as shown in table 1) and the hydrogen that the prepared by dimethyl oxalate plus hydrogen that purity is 99.9% obtains, reaction temperature 95 DEG C, reaction pressure 0.5MPa, ethylene glycol liquid hourly space velocity (LHSV) is 40h-1, the volume ratio of hydrogen and raw material be under conditions of 2 with catalyst haptoreaction, obtain ethylene glycol UV transmittance result after purification as shown in table 1.
[embodiment 4]
By with aluminium oxide as carrier, Metal Palladium content as vehicle weight 1%, metal promoter cerium content as vehicle weight 0.6%, metal promoter calcium content as vehicle weight 0.05% catalyst load in gas and liquid phase fixed bed reactors, it is passed through pure hydrogen, it is 0.3MPa at pressure, maximum temperature is 480 DEG C, and volume space velocity is 1200h- 1Under conditions of, reduction treatment 10 hours, reduction is down to reaction temperature after terminating, then each led into, by the bottom of reactor, ethylene glycol product raw material (UV transmittance of raw material is as shown in table 1) and the hydrogen that the ethyl oxalate Hydrogenation that purity is 99.9% obtains, reaction temperature 75 DEG C, reaction pressure 0.05MPa, ethylene glycol liquid hourly space velocity (LHSV) is 50h-1, the volume ratio of hydrogen and raw material be under conditions of 5 with catalyst haptoreaction, obtain ethylene glycol UV transmittance result after purification as shown in table 1.
[embodiment 5]
By with aluminium oxide as carrier, metallic nickel content as vehicle weight 15%, Metal Palladium content as vehicle weight 0.1%, the catalyst of the metal promoter cerium content 1.2 % as vehicle weight load in gas and liquid phase fixed bed reactors, it is passed through pure hydrogen, it is 0.5MPa at pressure, maximum temperature is 450 DEG C, and volume space velocity is 1000h- 1Under conditions of, reduction treatment 12 hours, reduction is down to reaction temperature after terminating, then each led into, by the top of reactor, ethylene glycol product raw material (UV transmittance of raw material is as shown in table 1) and the hydrogen that the ethyl oxalate Hydrogenation that purity is 99.3% obtains, reaction temperature 120 DEG C, reaction pressure 0.8MPa, ethylene glycol liquid hourly space velocity (LHSV) is 5h-1, the volume ratio of hydrogen and raw material be under conditions of 40 with catalyst haptoreaction, obtain ethylene glycol UV transmittance result after purification as shown in table 1.
[embodiment 6]
By with aluminium oxide as carrier, metallic nickel content as vehicle weight 25%, metal promoter content of magnesium as vehicle weight 1.8%, metal promoter cerium content as vehicle weight 0.1% catalyst load in gas and liquid phase fixed bed reactors, it is passed through pure hydrogen, it is 0.5MPa at pressure, maximum temperature is 460 DEG C, and volume space velocity is 1200h- 1Under conditions of, reduction treatment 12 hours, reduction is down to reaction temperature after terminating, then each led into, by the bottom of reactor, ethylene glycol product raw material (UV transmittance of raw material is as shown in table 1) and the hydrogen that the prepared by dimethyl oxalate plus hydrogen that purity is 99.7% obtains, reaction temperature 100 DEG C, reaction pressure 0.5MPa, ethylene glycol liquid hourly space velocity (LHSV) is 20h-1, the volume ratio of hydrogen and raw material be under conditions of 15 with catalyst haptoreaction, obtain ethylene glycol UV transmittance result after purification as shown in table 1.
[embodiment 7]
Use catalyst, reducing condition, feeding manner and reaction condition same as in Example 6, the ethylene glycol product raw material (UV transmittance of raw material is as shown in table 1) obtaining the ethyl oxalate Hydrogenation that purity is 99.8% is purified process, obtains ethylene glycol UV transmittance result after purification as shown in table 1.
Table 1
[comparative example 1]
Using ethylene glycol product raw material in the same manner as in Example 1, simply use ion exchange resin to process ethylene glycol product, after process, the UV transmittance at ethylene glycol product 220nm, 275nm and 350nm is respectively 62%, and 80%, 99.4%.
[comparative example 2]
Use according to 20wt%Cu+5wt%Ni/SiO in document CN201110045256.0 embodiment 192The catalyst of content preparation, uses the ethylene glycol product raw material identical with in embodiment 6 and reaction condition to process ethylene glycol product, and after process, the UV transmittance at ethylene glycol product 220nm, 275nm and 350nm is respectively 66%, and 85%, 100%.
Claims (4)
1. the method improving quality of ethylene glycol product, uses the purple that quality of glycol content is more than 99%
Ethylene glycol raw material that outer light transmittance is low and hydrogen, be 70 DEG C～100 DEG C in reaction temperature, and reaction pressure is
0.5～1.0MPa, ethylene glycol liquid hourly space velocity (LHSV) is 20～60 hours-1, hydrogen is 15～50 with the volume ratio of raw material
Under the conditions of, by gas and liquid phase fixed bed reactors, contact with the catalyst in reactor, obtain polyester grade second
Glycol product stream, wherein catalyst is with aluminium oxide as carrier, with nickel as active component, with magnesium and cerium as auxiliary agent,
Metallic nickel content is the 25% of vehicle weight, and metal promoter content of magnesium is the 1.8% of vehicle weight, metal promoter
Cerium content is the 0.1% of vehicle weight；Described UV transmittance is low refers to that ethylene glycol ultraviolet at 220nm is saturating
Light rate is less than 75%, or the UV transmittance at 275nm is less than 92%；
Catalyst needs to use the reducibility gas containing hydrogen to carry out reduction treatment before use.
The method of raising quality of ethylene glycol product the most according to claim 1, it is characterised in that reaction temperature
Degree is 75 DEG C～100 DEG C, and reaction pressure is 0.5～0.8MPa, and ethylene glycol liquid hourly space velocity (LHSV) is 20～50 hours-1, hydrogen
Gas is 15～40 with the volume ratio of raw material.
The method of raising quality of ethylene glycol product the most according to claim 2, it is characterised in that reaction temperature
Degree is 80 DEG C～100 DEG C, and reaction pressure is 0.5～0.6MPa, and ethylene glycol liquid hourly space velocity (LHSV) is 20～40 hours-1, hydrogen
Gas is 15～40 with the volume ratio of raw material.
The method of raising quality of ethylene glycol product the most according to claim 1, it is characterised in that also original place
Reason condition be with hydrogen volume content more than 70% hydrogen and the mixed gas of nitrogen, pressure be 0.1～
0.6MPa, maximum temperature is 450 DEG C～500 DEG C, and volume space velocity is 800～1500 hours-1Under conditions of, also
Original place reason catalyst 8～16 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310078821.2A CN104045516B (en) | 2013-03-13 | 2013-03-13 | The method improving quality of ethylene glycol product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310078821.2A CN104045516B (en) | 2013-03-13 | 2013-03-13 | The method improving quality of ethylene glycol product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104045516A CN104045516A (en) | 2014-09-17 |
| CN104045516B true CN104045516B (en) | 2016-08-24 |
Family
ID=51498963
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310078821.2A Active CN104045516B (en) | 2013-03-13 | 2013-03-13 | The method improving quality of ethylene glycol product |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104045516B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107970892B (en) * | 2016-10-21 | 2020-08-14 | 上海浦景化工技术股份有限公司 | Refining agent and preparation method and application thereof |
| CN112439425A (en) * | 2019-09-02 | 2021-03-05 | 中国石油化工股份有限公司 | Hydrofining method and hydrofining agent for crude ethylene glycol |
| CN111644172B (en) * | 2019-09-09 | 2023-12-01 | 上海浦景化工技术股份有限公司 | Catalyst for liquid phase hydrogenation and preparation method and application thereof |
| CN111686737A (en) * | 2020-07-24 | 2020-09-22 | 中国科学院兰州化学物理研究所 | Auxiliary agent modified supported nickel-based catalyst and preparation method and application thereof |
| CN112142564A (en) * | 2020-09-28 | 2020-12-29 | 合肥江新化工科技有限公司 | Device and method for improving quality of ethylene glycol product obtained by side production of ethylene glycol product tower |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101342489A (en) * | 2007-07-12 | 2009-01-14 | 上海焦化有限公司 | Hydrogenation reaction catalyst, preparation and application thereof |
| CN101993345A (en) * | 2009-08-31 | 2011-03-30 | 中国石油化工股份有限公司 | Method for improving selectivity of glycol prepared by adding hydrogen into oxalate |
| CN102218320A (en) * | 2011-04-15 | 2011-10-19 | 上海浦景化工技术有限公司 | Catalyst for hydrogenation, preparation method and application thereof |
| CN102649687A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for improving quality of ethylene glycol product |
| CN102649688A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for purifying ethylene glycol product |
-
2013
- 2013-03-13 CN CN201310078821.2A patent/CN104045516B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101342489A (en) * | 2007-07-12 | 2009-01-14 | 上海焦化有限公司 | Hydrogenation reaction catalyst, preparation and application thereof |
| CN101993345A (en) * | 2009-08-31 | 2011-03-30 | 中国石油化工股份有限公司 | Method for improving selectivity of glycol prepared by adding hydrogen into oxalate |
| CN102649687A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for improving quality of ethylene glycol product |
| CN102649688A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for purifying ethylene glycol product |
| CN102218320A (en) * | 2011-04-15 | 2011-10-19 | 上海浦景化工技术有限公司 | Catalyst for hydrogenation, preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104045516A (en) | 2014-09-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104045516B (en) | The method improving quality of ethylene glycol product | |
| CN101138725B (en) | Catalyzer for the oxalic ester hydrogenation synthesizing of ethylene glycol and method of preparing the same | |
| CN101138730B (en) | Catalyzer for oxalic ester hydrogenation for synthesizing glycolate and method of preparing the same | |
| CN102617518B (en) | One-step preparation method for tetrahydrofuran by employing maleic anhydride gas phase hydrogenation | |
| CN104109081B (en) | Improve the method for synthetic gas preparing ethylene glycol quality product | |
| US9051236B2 (en) | Method for improving the quality of ethylene glycol products | |
| CN102911013B (en) | Ethylene-glycolrefining method | |
| CN102649704B (en) | Method for purifying ethylene glycol product | |
| CN111333520B (en) | Method for preparing N, N-dimethyl cyclohexylamine | |
| CN102816045A (en) | Method for synthesizing chloromethane by tail gas generated during chloroacetic acid production | |
| CN103964997A (en) | Treatment method for butylene oxydehydrogenation products | |
| CN105152842B (en) | A kind of acetylene hydrogenation prepares the reaction system and method for ethene | |
| JP7032612B2 (en) | Catalyst for producing isoprene glycol and method for producing isoprene glycol | |
| CN101407466A (en) | Method for purifying ethylenediamine | |
| CN102219641B (en) | Method for purifying ethylene glycol | |
| CN103936574A (en) | Method for preparing high-purity methyl isobutyl ketone from industrial by-product acetone waste liquid | |
| CN102649692B (en) | Improve the method for quality of glycol | |
| CN102211036A (en) | Modified molecular sieve catalyst, and precursor and preparation method thereof | |
| CN114369006B (en) | Method for preparing isohexide and methyl isobutyl carbinol | |
| CN102276418B (en) | Ethylene glycol purification method | |
| CN103272579A (en) | Catalyst for oriented synthesis of isobutanol by synthesis gas as well as preparation method and application of catalyst | |
| CN102807481B (en) | Method for preparing methyl ethyl ketone by oxidizing normal butane | |
| CN107778151B (en) | Method for preparing methyl ethyl ketone by sec-butyl alcohol dehydrogenation | |
| CN103450028B (en) | Method for preparing cyclohexylamine and dicyclohexylamine from nitrobenzene through one-step catalytic hydrogenation | |
| CN115709065B (en) | Catalyst for preparing ethylene glycol by hydrogenating dimethyl oxalate, and preparation method and application thereof |
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 |