CN106187687A - The post-processing approach of dihydroxylic alcohols in a kind of coal-ethylene glycol process by-product residual liquid - Google Patents
The post-processing approach of dihydroxylic alcohols in a kind of coal-ethylene glycol process by-product residual liquid Download PDFInfo
- Publication number
- CN106187687A CN106187687A CN201610554148.9A CN201610554148A CN106187687A CN 106187687 A CN106187687 A CN 106187687A CN 201610554148 A CN201610554148 A CN 201610554148A CN 106187687 A CN106187687 A CN 106187687A
- Authority
- CN
- China
- Prior art keywords
- ethylene glycol
- residual liquid
- coal
- product
- post
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by elimination of -OH groups, e.g. by dehydration
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
- C07C29/172—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with the obtention of a fully saturated alcohol
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides the post-processing approach of dihydroxylic alcohols in a kind of coal-ethylene glycol process by-product residual liquid, the method is by carrying out catalytic hydrogenation dehydration to the dihydroxylic alcohols in residual liquid, make ethylene glycol and 1,2 butanediols are separately converted to ethanol and butanol, then by simple rectification, ethanol and butanol are separated and are collected.The method has been abandoned ethylene glycol and 1,2 butanediols are the fraction tradition high energy consumption rectification separation process of main component, ethylene glycol and 1 has effectively been broken by hydrogenation dehydration, 2 butanediol azeotropic balances, achieve extraction high-quality ethanol, butanol chemicals from residual liquid, reduce energy consumption of rectification, decrease the wasting of resources, it is greatly improved value of the product, it is achieved that coal-ethylene glycol technique residual liquid resource recycles；Present invention process condition is relatively mild, it is easy to industrial applications.
Description
Technical field
The invention belongs to chemical products separate and catalysis technical field, residual particularly to a kind of coal-ethylene glycol process by-product
The post-processing approach of dihydroxylic alcohols in liquid.
Technical background
End in December, 2015, the Chinese coal-ethylene glycol project totally 10 run and succeed in the test run of having gone into operation, formed total
Count 1,700,000 tons/year of ethylene glycol production capacities.In the coming years, the coal-ethylene glycol production capacity of China is up to 10,260,000 tons/year, and this will
Alleviate China's inlet pressure to ethylene glycol to a certain extent.In coal-ethylene glycol production process, about 10% can be produced
By-product residual liquid, if the production load of these coal-ethylene glycol projects is by 90% calculation, every year by about more than 90 ten thousand tons of by-product residual liquids of generation.
According to analyzing test, in these residual liquids in addition to water, be mainly composed of ethylene glycol, 1, the dihydroxylic alcohols such as 2-butanediol, be limited by ethylene glycol
With 1,2-butanediol boiling point is close, there is azeotropic balance, is difficult to be effectively separated the two by rectification.These residual liquids at present
Sell mainly as cheap solvent.If these coal-ethylene glycol process by-product residual liquids reasonably can be utilized, will significantly
Reduce the wasting of resources, increase enterprise income.
Patent 103666389,103694966 and CN203498300U discloses a kind of coal-ethylene glycol waste material preparation and starts
The process of machine coolant and device, be limited by coal-ethylene glycol process by-product residual liquid complicated components and conversion frequently, to
This proposes the highest requirement for material allocation engine coolant, is difficult to find a pervasive cooling liquid formulation.Additionally, send out
Motivation coolant is sold extremely strong seasonal characteristics, significantly limit the economy of project.To coal-ethylene glycol technique
In by-product residual liquid, dihydroxylic alcohols carries out the post-processing approach of catalytic hydrogenation dehydration there is not been reported, by ethylene glycol and 1,2-butanediol
Catalytic hydrogenation dehydration is changed into ethanol and butanol, then breaks azeotropic composition, solves to achieve work while the two separates a difficult problem
The resource recycling of skill by-product residual liquid.
Summary of the invention
The invention provides the post-processing approach of a kind of coal-ethylene glycol process by-product residual liquid dihydroxylic alcohols, the method can have
Effect breaks ethylene glycol and 1, and 2-butanediol azeotropic balances, and reduces rectification cost, reduces the wasting of resources, simultaneously by ethylene glycol and 1,2-
The dihydroxylic alcohols Efficient Conversion that butanediol is main is ethanol and butanol, and improving product is worth, and increases enterprise income.
The present invention is achieved by the following technical solutions: in a kind of coal-ethylene glycol process by-product residual liquid after dihydroxylic alcohols
Processing method, the steps include:
(1) coal-ethylene glycol process by-product residual liquid is carried out rectification process, the light component such as methanol removal, second alcohol and water, remaining set
Dividing is based on ethylene glycol and the diol component of 1,2-butanediol；
(2) diol component that step (1) obtains carries out being hydrogenated with dehydration, reaction condition under conditions of catalyst exists
Being: temperature is 50-550 DEG C that pressure is 0.5-5MPa, liquid hourly space velocity (LHSV) is 0.1-2h-1, it being passed through hydrogen during reaction, hydrogen volume is empty
Speed is 1000-10000h-1, product is with ethanol, butanol as key component；
(3) ethanol, the butanol that step (2) are obtained are that the component led carries out rectification.
Described by-product residual liquid is 100-1000:1 with the mass ratio of catalyst.
The chemical formula of catalyst and the formula of composition of described step (2) are expressed as aMbX/cYdZ；M in described catalyst
For the one in metallic nickel, copper, platinum, palladium, X is at least one in Pd, Pt, Ni, Co, Zn, La, Ce, and Y is in Ti, Zr, Al
One or more, Z is the one in silicon oxide, molecular sieve, activated carbon.
In described catalyst, a, b, c, d are respectively the percent mass that metal component M, X, Y and carrier Z are shared in the catalyst
Ratio, wherein a:10-40%, b:0-20%, c:0-20%, d:20-90%.
Described coal-ethylene glycol process by-product residual liquid with ethylene glycol, 1,2-butanediol, water are main, the most also methanol, second
The various ingredients such as alcohol, methyl formate, dimethoxym ethane.
In described catalyst, X is as active component auxiliary agent, and Y is as support modification agent.
The invention has the beneficial effects as follows: (1) processing method of the present invention is simple, and cost of investment is low, it is easy to industrialization should
With；(2) present invention is by the enforcement of catalytic hydrogenation dehydration post-processing approach, has effectively broken ethylene glycol and 1, being total to of 2-butanediol
Boiling balance, reduces energy consumption of rectification, decreases the wasting of resources, obtain ethanol and butanol simultaneously, it is achieved that coal-ethylene glycol technique
Residual liquid resource recycles；(3) the catalytic hydrogenation dehydration post-processing approach process conditions that the present invention provides are relatively mild, it is easy to work
Industryization is applied；(4) the catalytic hydrogenation dehydration post processing that the present invention provides is effective, can realize coal-ethylene glycol process by-product residual liquid
The conversion ratio 98-100% of middle ethylene glycol, the conversion ratio of 1,2-butanediol is not less than 90%.
Accompanying drawing explanation
Fig. 1 is the process chart of the present invention.
Detailed description of the invention
The invention is further illustrated by the following examples, but not thereby limiting the invention.
Embodiment 1
In the coal-ethylene glycol process by-product residual liquid of the present embodiment, the post-processing approach step of dihydroxylic alcohols is as follows:
Take 100Kg coal-ethylene glycol process by-product residual liquid, isolate the light groups such as water therein, methanol, ethanol through simple rectification
Point, remaining ingredient analyzes wherein ethylene glycol content 60% through gas chromatography, and 1,2-butanediol content 35%, between pumping into this component
Have a rest in tank reactor, add 1Kg palladium Modified Nickel zirconium Si catalyst (30wt%Ni+20wt%Pd/10wt%ZrO in a kettle.2+
40wt%SiO2), catalyst uses sol-gal process to prepare, and closed reactor is slowly introducing hydrogen, hydrogen volume air speed 2000h-1, system is warming up to 300 DEG C, reaction pressure 3.0MPa, liquid hourly space velocity (LHSV) 0.5h-1Under conditions of react, be subsequently cooled to room
Temperature, analyzes wherein ethylene glycol content 0.05% by product through gas chromatography, and 1,2-butanediol content 0.2%, through simple
Rectification, obtaining purity of alcohol is 99.5%, and butanol purity is 99%.
Embodiment 2
In the coal-ethylene glycol process by-product residual liquid of the present embodiment, the post-processing approach step of dihydroxylic alcohols is as follows:
Take 750Kg coal-ethylene glycol process by-product residual liquid, isolate the light groups such as water therein, methanol, ethanol through simple rectification
Point, remaining ingredient analyzes wherein ethylene glycol content 50%, 1,2-butanediol content 40% through gas chromatography, this component is pumped into solid
In fixed bed reactor, adding 1.5Kg carried by active carbon copper catalyst (40wt%Cu/60wt%C) in a kettle., catalyst uses and steams
Prepared by ammonia process, closed reactor is slowly introducing hydrogen, hydrogen volume air speed 5000h-1, system is warming up to 550 DEG C, reaction pressure
5.0MPa, liquid hourly space velocity (LHSV) 0.1h-1Under conditions of react, be then cooled to room temperature, product divided through gas chromatography
Analysing wherein ethylene glycol content 0.03%, 1,2-butanediol content 0.5%, through simple rectification, obtaining purity of alcohol is 99.2%, fourth
Alcohol purity is 98.5%.
Embodiment 3
In the coal-ethylene glycol process by-product residual liquid of the present embodiment, the post-processing approach step of dihydroxylic alcohols is as follows:
Take 200Kg coal-ethylene glycol process by-product residual liquid, isolate the light groups such as water therein, methanol, ethanol through simple rectification
Point, remaining ingredient analyzes wherein ethylene glycol content 65% through gas chromatography, and 1,2-butanediol content 25%, between pumping into this component
Have a rest in tank reactor, add 0.5Kg carrying alumina platinum palladium catalyst (10wt%Pt+5wt%Pd/85wt% in a kettle.
Al2O3), catalyst uses infusion process to prepare, and closed reactor is slowly introducing hydrogen, hydrogen volume air speed 1000h-1, system liter
Warm to 50 DEG C, reaction pressure 0.5MPa, liquid hourly space velocity (LHSV) 2h-1Under conditions of react, be then cooled to room temperature, by product
Analyze wherein ethylene glycol content 0.1%, 1,2-butanediol content 0.3% through gas chromatography, through simple rectification, obtain ethanol pure
Degree is 99.8%, and butanol purity is 98.9%.
Embodiment 4
In the coal-ethylene glycol process by-product residual liquid of the present embodiment, the post-processing approach step of dihydroxylic alcohols is as follows:
150Kg coal-ethylene glycol process by-product residual liquid is carried out simple rectification process, the light component such as methanol removal, second alcohol and water,
Remaining ingredient is with ethylene glycol and 1, and 2-butanediol is main diol component, analyzes wherein ethylene glycol content through gas chromatography
64%, 1,2-butanediol content 26%；Infusion process is utilized to prepare the catalyst of 10wt%Ni+20wt%Co/70wt% molecular sieve composition,
Carry out the diol component obtained under conditions of this 0.15Kg catalyst exists being hydrogenated with dehydration, described catalyst reaction
Condition is: temperature is 50 DEG C, and pressure is 5MPa, and liquid hourly space velocity (LHSV) is 2h-1, it being passed through hydrogen during reaction, hydrogen volume air speed is
10000h-1, product is with ethanol, butanol as key component；The component that the ethanol obtained, butanol are main is carried out simple rectification.Will
Product analyzes wherein ethylene glycol content 0.2%, 1,2-butanediol content 0.3% through gas chromatography, through simple rectification, obtains
Being 99.8% to purity of alcohol, butanol purity is 98.9%.
Embodiment 5
In the coal-ethylene glycol process by-product residual liquid of the present embodiment, the post-processing approach step of dihydroxylic alcohols is as follows:
300Kg coal-ethylene glycol process by-product residual liquid is carried out simple rectification process, the light component such as methanol removal, second alcohol and water,
Remaining ingredient is with ethylene glycol and 1, and 2-butanediol is main diol component, analyzes wherein ethylene glycol content through gas chromatography
60%, 1,2-butanediol content 30%；Infusion process is utilized to prepare the catalyst of 20wt%Pt+15wt%Zn/10wt%Zr+55%C composition,
Carry out the diol component obtained under conditions of this catalyst of 0.8Kg exists being hydrogenated with dehydration, described catalyst reaction
Condition is: temperature is 100 DEG C, and pressure is 4MPa, and liquid hourly space velocity (LHSV) is 1.5h-1, it being passed through hydrogen during reaction, hydrogen volume air speed is
8000h-1, product is with ethanol, butanol as key component；The component that the ethanol obtained, butanol are main is carried out simple rectification.Will be anti-
Answer product to analyze wherein ethylene glycol content 0.2%, 1,2-butanediol content 0.3% through gas chromatography, through simple rectification, obtain
Purity of alcohol is 99.5%, and butanol purity is 99.5%.
Embodiment 6
In the coal-ethylene glycol process by-product residual liquid of the present embodiment, the post-processing approach step of dihydroxylic alcohols is as follows:
200Kg coal-ethylene glycol process by-product residual liquid is carried out simple rectification process, the light component such as methanol removal, second alcohol and water,
Remaining ingredient is with ethylene glycol and 1, and 2-butanediol is main diol component, analyzes wherein ethylene glycol content through gas chromatography
63%, 1,2-butanediol content 30%；Infusion process is utilized to prepare 30wt%Cu+10wt%Ce/20wt%Al+40%SiO2The catalysis of composition
Agent, carries out the diol component obtained under conditions of this catalyst of 0.3Kg exists being hydrogenated with dehydration, and described catalyst is anti-
The condition is answered to be: temperature is 200 DEG C, and pressure is 3MPa, and liquid hourly space velocity (LHSV) is 1h-1, it being passed through hydrogen during reaction, hydrogen volume air speed is
6000h-1, product is with ethanol, butanol as key component；The component that the ethanol obtained, butanol are main is carried out simple rectification.Will be anti-
Answer product to analyze wherein ethylene glycol content 0.5%, 1,2-butanediol content 0.4% through gas chromatography, through simple rectification, obtain
Purity of alcohol is 99.3%, and butanol purity is 99.1%.
Embodiment 7
In the coal-ethylene glycol process by-product residual liquid of the present embodiment, the post-processing approach step of dihydroxylic alcohols is as follows:
120Kg coal-ethylene glycol process by-product residual liquid is carried out simple rectification process, the light component such as methanol removal, second alcohol and water,
Remaining ingredient is with ethylene glycol and 1, and 2-butanediol is main diol component, analyzes wherein ethylene glycol content through gas chromatography
67%, 1,2-butanediol content 27%；Infusion process is utilized to prepare the catalyst of 40wt%Cu+20wt%La/20wt%Ti+20%C composition,
Carry out the diol component obtained under conditions of this catalyst of 0.9Kg exists being hydrogenated with dehydration, described catalyst reaction
Condition is: temperature is 400 DEG C, and pressure is 1.5MPa, and liquid hourly space velocity (LHSV) is 0.5h-1, it being passed through hydrogen during reaction, hydrogen volume air speed is
4000h-1, product is with ethanol, butanol as key component；The component that the ethanol obtained, butanol are main is carried out simple rectification.Will be anti-
Answer product to analyze wherein ethylene glycol content 0.4%, 1,2-butanediol content 0.3% through gas chromatography, through simple rectification, obtain
Purity of alcohol is 99.9%, and butanol purity is 98.9%.
Embodiment 8
In the coal-ethylene glycol process by-product residual liquid of the present embodiment, the post-processing approach step of dihydroxylic alcohols is as follows:
100Kg coal-ethylene glycol process by-product residual liquid is carried out simple rectification process, the light component such as methanol removal, second alcohol and water,
Remaining ingredient is with ethylene glycol and 1, and 2-butanediol is main diol component, analyzes wherein ethylene glycol content through gas chromatography
66%, 1,2-butanediol content 33%；Infusion process is utilized to prepare the catalyst of 10wt%Pd/90wt% molecular sieve composition, by obtain
Diol component carries out being hydrogenated with dehydration under conditions of this catalyst of 1Kg exists, and described catalyst reaction condition is: temperature
Being 550 DEG C, pressure is 0.5MPa, and liquid hourly space velocity (LHSV) is 0.1h-1, it being passed through hydrogen during reaction, hydrogen volume air speed is 1000h-1, produce
Thing is with ethanol, butanol as key component；The component that the ethanol obtained, butanol are main is carried out simple rectification.By product warp
Gas chromatography analyzes wherein ethylene glycol content 0.1%, 1,2-butanediol content 0.5%, through simple rectification, obtains purity of alcohol
Being 99.6%, butanol purity is 99.4%.
The explanation of above example, is only intended to help to understand method and the core concept thereof of the present invention.It is right to it should be pointed out that,
For those of ordinary skill in the art, on the premise of the principle of the invention, it is also possible to the present invention is suitably modified, this
Being suitably modified also should be within the scope of the invention as claimed.
Claims (4)
1. the post-processing approach of dihydroxylic alcohols in a coal-ethylene glycol process by-product residual liquid, it is characterised in that the steps include:
(1) coal-ethylene glycol process by-product residual liquid is carried out rectification process, the light component such as methanol removal, second alcohol and water, remaining set
Dividing is based on ethylene glycol and the diol component of 1,2-butanediol；
(2) diol component that step (1) obtains carries out being hydrogenated with dehydration, reaction condition under conditions of catalyst exists
Being: temperature is 50-550 DEG C that pressure is 0.5-5MPa, liquid hourly space velocity (LHSV) is 0.1-2h-1, it being passed through hydrogen during reaction, hydrogen volume is empty
Speed is 1000-10000h-1, product is with ethanol, butanol as key component；
(3) ethanol, the butanol that step (2) are obtained are that the component led carries out rectification.
The post-processing approach of dihydroxylic alcohols in coal-ethylene glycol process by-product residual liquid the most according to claim 1, its feature exists
In: described by-product residual liquid is 100-1000:1 with the mass ratio of catalyst.
The post-processing approach of dihydroxylic alcohols in coal-ethylene glycol process by-product residual liquid the most according to claim 1, its feature exists
In: the chemical formula of catalyst and the formula of composition of described step (2) are expressed as aMbX/cYdZ；In described catalyst, M is metal
One in Ni, Cu, Pt, Pd, X is at least one in Pd, Pt, Ni, Co, Zn, La, Ce, Y be the one in Ti, Zr, Al or
Multiple, Z is the one in silicon oxide, molecular sieve, activated carbon.
The post-processing approach of dihydroxylic alcohols in coal-ethylene glycol process by-product residual liquid the most according to claim 3, its feature exists
In: in described catalyst, a, b, c, d are respectively the mass percent that metal component M, X, Y and carrier Z are shared in the catalyst, its
Middle a:10-40%, b:0-20%, c:0-20%, d:20-90%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610554148.9A CN106187687B (en) | 2016-07-14 | 2016-07-14 | The post-processing approach of dihydric alcohol in a kind of coal-ethylene glycol process by-product raffinate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610554148.9A CN106187687B (en) | 2016-07-14 | 2016-07-14 | The post-processing approach of dihydric alcohol in a kind of coal-ethylene glycol process by-product raffinate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106187687A true CN106187687A (en) | 2016-12-07 |
| CN106187687B CN106187687B (en) | 2018-03-30 |
Family
ID=57474416
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610554148.9A Expired - Fee Related CN106187687B (en) | 2016-07-14 | 2016-07-14 | The post-processing approach of dihydric alcohol in a kind of coal-ethylene glycol process by-product raffinate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106187687B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103254030A (en) * | 2013-05-17 | 2013-08-21 | 天津天中福大科技发展有限公司 | Device and method for recycling byproduct residual liquid in coal-to-ethylene-glycol production process |
| CN103265401A (en) * | 2013-04-24 | 2013-08-28 | 河南朝歌日光新能源股份有限公司 | Method for recovering coal-to-glycol technology byproduct raffinate |
-
2016
- 2016-07-14 CN CN201610554148.9A patent/CN106187687B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103265401A (en) * | 2013-04-24 | 2013-08-28 | 河南朝歌日光新能源股份有限公司 | Method for recovering coal-to-glycol technology byproduct raffinate |
| CN103254030A (en) * | 2013-05-17 | 2013-08-21 | 天津天中福大科技发展有限公司 | Device and method for recycling byproduct residual liquid in coal-to-ethylene-glycol production process |
Non-Patent Citations (1)
| Title |
|---|
| YING-YING ZHU ET AL.: "The Influence of Copper Particle Dispersion in Cu/SiO2 Catalysts on the Hydrogenation Synthesis of Ethylene Glycol", 《CATAL LETT.》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106187687B (en) | 2018-03-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101693703B (en) | Energy-saving and emission-reducing technique for producing propane epoxide by using hydrogen peroxide epoxidation propylene | |
| CN103372453A (en) | Catalyst for synthesis of methyl glycolate and preparation method thereof | |
| CN101757917A (en) | Low nickel-content benzene hydrogenation catalyst and preparation method thereof | |
| CN100548972C (en) | A kind of method of separation of methanol acetonitrile azeotrope | |
| CN106349011A (en) | Method for producing cyclohexanol | |
| CN103787830A (en) | Method for producing ethanol by acetic acid hydrogenation | |
| CN111333520A (en) | Method for preparing N, N-dimethyl cyclohexylamine | |
| CN103254038B (en) | Method for preparing cyclohexanol by using benzene | |
| CN102463115B (en) | Method for producing isopropylbenzene | |
| CN102895974B (en) | Method for synthesizing N-methyl piperidine and supported catalyst used by the method | |
| CN102451674B (en) | Catalyst for preparing isobutene by methyl tert-butyl ether cracking, preparation method, and application thereof | |
| CN101733124B (en) | Catalyst for fixed bed hydrogenation for continuous production of fatty alcohol, preparation method thereof and application thereof | |
| CN102372599B (en) | Method for separating glycol and butylene glycol | |
| CN106117025A (en) | Sec-butyl alcohol Dichlorodiphenyl Acetate secondary butyl ester transfer hydrogenation produces the process of butanone simultaneously | |
| CN106187687A (en) | The post-processing approach of dihydroxylic alcohols in a kind of coal-ethylene glycol process by-product residual liquid | |
| CN104557454B (en) | A kind of method of acetic acid Hydrogenation for high-quality ethanol | |
| CN105195210B (en) | A kind of sec-butyl alcohol dehydrogenizing preparing ethyl methyl ketone catalyst and preparation method thereof | |
| CN106866373B (en) | Method for rectifying and refining ethylene glycol | |
| CN102372598A (en) | Method for separating glycol from butanediol | |
| CN107398273A (en) | Catalyst and process for hydrogenating cyclobutanedione compounds | |
| CN102924286A (en) | A preparation method of N1-(2-aminoethyl)-1, 2-ethylenediamine | |
| CN103772330B (en) | Method for recovery of furfural and acetic acid from furfural stripping steam condensate | |
| CN102757298B (en) | Method for preparing cyclohexane by benzene hydrogenation | |
| CN105198704A (en) | Method for low-energy consumption acetic acid hydrogenation production of ethanol | |
| CN103772329B (en) | Method for simultaneous extraction and recovery of furfural and acetic acid from furfural stripping steam condensate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 475000 No. 1 Songcheng Road, Kaifeng Development Zone, Henan Province Patentee after: HENAN ENERGY CHEMICAL GROUP ADVANCED EQUIPMENT INSTITUTE Co.,Ltd. Address before: 450046 Zhengzhou, Zheng Dong, Henan New District business outside the ring road, No. 6 Patentee before: HENAN ENERGY AND CHEMICAL INDUSTRY GROUP RESEARCH INSTITUTE CO.,LTD. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190903 Address after: The 12th Floor of Newton International B Block, 97 Xuzhuang Road, Jinshui District, Zhengzhou City, Henan Province, 450000 Patentee after: HENAN ENERGY AND CHEMICAL INDUSTRY GROUP RESEARCH INSTITUTE CO.,LTD. Address before: 475000 No. 1 Songcheng Road, Kaifeng Development Zone, Henan Province Patentee before: HENAN ENERGY CHEMICAL GROUP ADVANCED EQUIPMENT INSTITUTE Co.,Ltd. |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180330 Termination date: 20200714 |