CN103319310A - Technology for efficiently purifying glycol obtained through oxalate hydrogenation - Google Patents
Technology for efficiently purifying glycol obtained through oxalate hydrogenation Download PDFInfo
- Publication number
- CN103319310A CN103319310A CN2013102636036A CN201310263603A CN103319310A CN 103319310 A CN103319310 A CN 103319310A CN 2013102636036 A CN2013102636036 A CN 2013102636036A CN 201310263603 A CN201310263603 A CN 201310263603A CN 103319310 A CN103319310 A CN 103319310A
- Authority
- CN
- China
- Prior art keywords
- ethylene glycol
- heat exchange
- glycol
- crude product
- temperature
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a technology for efficiently purifying glycol obtained through oxalate hydrogenation. The technology is characterized in that LNG (Liquefied Natural Gas) low-temperature liquid is subjected to heat exchange through a heat exchange unit, after the temperature of the LNG low-temperature liquid rises to a room temperature, the LNG low-temperature liquid is liquefied, and then the liquefied LNG low-temperature liquid is conveyed to a natural gas application place outside battery limit through a natural gas conveying pipeline; a glycol crude product prepared through high-temperature high-pressure oxalate hydrogenation passes through the heat exchange unit in a direction opposite to the conveying direction of the LNG low-temperature liquid through the conveying pipeline, is precooled through the heat exchange unit and is subjected to auxiliary refrigeration through auxiliary refrigeration equipment, and after the temperature of the crude product is reduced to minus 5 DEG C to 5 DEG C, the crude product is conveyed to a separation unit through the pipeline; after the temperature of the crude product in the separation unit is reduced to minus 20 DEG C to minus 40 DEG C through freezing-separation equipment, liquefied 1, 2-propylene glycol and 1,2-butanediol serve as byproducts to be separated and recycled, and the solid glycol is directly collected, or after the glycol is heated to liquid state, the liquid glycol pure product is collected. According to the technology, the impurities, namely the 1,2-propylene glycol and the 1,2-butanediol in the glycol are separated by virtue of the characteristics of difference in solidifying points, the high-purity glycol is obtained, the productivity is high, and the cold energy of LNG is fully utilized.
Description
Technical field
The present invention relates to a kind of technique of efficiently utilizing LNG cold energy purification barkite hydrogenation gained ethylene glycol, the higher-grade cold energy of emitting when by heat exchange mode LNG being gasified specifically is used for the refining ethylene glycol of freezing method of purification, the by product such as separating propylene glycol and butyleneglycol, replace present azeotropic distillation Methods For Purification ethylene glycol, solve the problem that the preparing ethylene glycol energy consumption is too high, purity is low.Simultaneously also help to solve the step problem of complex utilization of present LNG cold energy.
Background technology
Ethylene glycol (EG) is as a kind of large Chemicals and basic chemical industry raw material, and its development and use market outlook are wide.Can be used for producing unsaturated polyester vinegar resin, trevira, coating, frostproofer, printing ink lubricant, explosive etc.In addition, some special solvents for example the production of glycol ether also need ethylene glycol.
Many large-scale ethylene glycol production projects are still to adopt oxyethane (EO) direct hydration method at present, although this production technique comparative maturity, stable but still have many shortcomings, for example flow process is tediously long, equipment is more, energy consumption is very high, and its raw material ethene cost has accounted for product ethylene glycol cost greatly.And this production technique still relies on petroleum resources, and along with the day by day shortage of petroleum resources, this kind production technique will be subject to serious challenge future.
The hydrogenation of oxalate for preparing ethylene glycol process is to generate synthetic gas, synthetic gas (CO+H by gasification
2) through the linked reaction synthesis of oxalate, barkite is further hydrogenation generating glycol again.The feed coal aboundresources, price is cheap than oil, and technique is simple, and energy consumption is less, and to the requirement of the reaction conditions also very gentle many advantages that waits, this technological line will have competitive power and development prospect in ethylene glycol market.But the discharging of product liquid phase mainly comprises the compositions such as methyl alcohol, ethanol, water, methyl glycolate, dimethyl oxalate, propylene glycol, ethylene glycol and butyleneglycol, wherein 1,2-propylene glycol (187 ℃ of boiling points), ethylene glycol (197.3 ℃ of boiling points) and 1,2-butyleneglycol (191～192 ℃ of boiling points) is difficult to use conventional distillation to separate because boiling point approaches, affect performance and the marketable value of the finished product, separate simultaneously and also have the high shortcoming of energy consumption.Such as ethylene glycol market (ethylene glycol content 〉=99.8%) price of polyester grade probably about 9000～10000 yuan/tons, and the ethylene glycol of deicing fluid level (ethylene glycol content 〉=98%, containing the foreign matter contents such as butyleneglycol, propylene glycol higher) only about 6000 yuan/tons, the purity of product will directly have influence on the final marketable value of product to market value.
Conventional gas is processed through purification and very low temperature after gas-field exploitation, the rapid contracting 600 times of volume changed super-low liquid (162 ℃) into, form natural gas liquids (LNG), can greatly save storage and transportation space, and have that calorific value is large, the performance high.And the required heat of LNG gasification was by providing with seawater to make heat exchange or the mode by the gas-firing supplementary heating in the past.So the cold energy of flood tide is not only by the utilization of science, and destroyed the marine eco-environment even consumed natural gas source.The LNG cold energy use of China also just is in the starting stage, and LNG cold energy use technology is still immature, requires to seek more rational cold energy cascade utilization mode, improves the added value of cold energy, to reduce the derived product cost of LNG.
Summary of the invention
The cold energy of emitting when reasonably utilizing natural gas gasifying and further reduce the energy consumption of separating ethylene glycol, propylene glycol and butyleneglycol in the oxalic acid fat preparing ethylene glycol method, improve ethylene glycol purity, the present invention proposes technique and system thereof that the barkite hydrogenation method prepares high-purity ethylene glycol.
The present patent application has adopted following technical scheme:
The barkite hydrogenation method prepares the system of high-purity ethylene glycol, comprise heat exchange unit, replenish refrigeration equipment, separating unit, the transport pipe of LNG storage tank is through heat exchange unit, hydrogenation of oxalate for preparing ethylene glycol crude product transport pipe and LNG carry oppositely and are connected to additional refrigeration equipment through behind the heat exchange unit, replenish refrigeration equipment and be connected to separating unit in parallel through pipeline, the liquid transmission pipeline of separating unit, Solid Conveying and Melting pipeline and LNG are connected to respectively by-product recovery device and glycol recovery device after carrying equidirectional process heat exchange unit.
The barkite hydrogenation method prepares the technique of high-purity ethylene glycol:
(1) after the LNG cryogenic liquid was warming up to room temperature gasification by the heat exchange unit heat exchange, Sweet natural gas was delivered to natural gas motorcar place outside the battery limit (BL) by natural-gas transfer pipeline;
(2) traditional High Temperature High Pressure barkite hydrogenation technique preparing ethylene glycol crude product is passed through heat exchange unit on the contrary through transport pipe and LNG cryogenic liquid throughput direction, through heat exchange unit precooling, auxiliary cooling equipment auxiliary cooling, crude product is cooled to-5 ℃～5 ℃ and is delivered to separating unit through pipeline;
The temperature of hydrogenation of oxalate for preparing ethylene glycol crude product is 50～200 ℃, and pressure is 25-30bar; The massfraction of each component is: ethylene glycol 60～99%, propylene glycol 0～15%, butyleneglycol 0～25%;
(3) according to 1,2-propylene glycol, ethylene glycol and 1,2-butyleneglycol freezing point temperature scope is cooled to-20～-40 ℃ at separating unit by subzero fractionation equipment, makes ethylene glycol be solid-state, 1,2-propylene glycol and 1,2-butyleneglycol are in a liquid state, and liquid 1,2-propylene glycol and 1,2-butyleneglycol after remaining cold recovery as the separated recovery of by product; Collect solid-state ethylene glycol, heat into liquid state after, through the hydrogenation of oxalate for preparing ethylene glycol crude product heat exchange of heat exchange unit and High Temperature High Pressure, for crude product provides cold energy, realize the cold energy reuse, collect simultaneously ethylene glycol sterling (ethylene glycol content 〉=99.8%).
The batch process that is formed by subzero fractionation and solid collection of (4) carrying out in the separating unit, two groups of subzero fractionation systems by parallel connection hocket subzero fractionation, solid collection process, make separating unit make the purpose that can reach continuous purification ethylene glycol product, high productivity.
The present invention utilizes 1,2-propylene glycol (zero pour-60 ℃), ethylene glycol (zero pour-11.5 ℃) and 1,2-butyleneglycol (zero pour-50 ℃) characteristics that zero pour is different, the cold energy of LNG is coupled in the subzero fractionation purification process flow process, the higher-grade cold energy of emitting when by heat exchange mode LNG being gasified is used for the refining ethylene glycol of freezing method of purification, removes 1,2-PD and 1, the impurity such as 2-butyleneglycol have been broken through the traditional way by impurity in the boiling point separating ethylene glycol.Take the cold energy use of LNG as main, the technique of compressor, decompressor auxiliary cooling is compared with the azeotropic rectificating method, will significantly reduce energy consumption at the subzero fractionation clean unit.Can fully utilize simultaneously the cold energy of LNG, when alleviating the LNG gasification to the negative impact of environment.
Description of drawings
Fig. 1 is process flow sheet of the present invention;
Among the figure, 1.LNG storage tank, 2. heat exchange unit, 3. auxiliary cooling equipment, 4. ethylene glycol, 1,2-PD and 1,2-butyleneglycol separating unit;
101.LNG transport pipe, 102. natural-gas transfer pipeline, 103. hydrogenation of oxalate for preparing ethylene glycol crude product transport pipe, 104. heat exchange ethylene glycol crude product transport pipes, 105. advance separating unit ethylene glycol crude product transport pipe, 106. ethylene glycol product transport pipe, 107.1,2-propylene glycol and 1,2-butyleneglycol recovery channel, 108. ethylene glycol product feeding pipe road, 109. by-product recovery device feed pipes.
Embodiment
Below with reference to embodiment the application's technical scheme is further elaborated:
Embodiment 1
Fig. 1 is process flow sheet of the present invention, and with reference to shown in Figure 1, the device that adopts comprises heat exchange unit 2, replenishes refrigeration equipment 3, ethylene glycol, 1,2-PD and 1,2-butyleneglycol separating unit 4.Heat exchange unit 2 links to each other by pipeline 101 with LNG storage tank 1, and-162 ℃ LNG cryogenic liquid is warming up to the room temperature gasification by heat exchange unit 2 heat exchange.Sweet natural gas is delivered to natural gas motorcar place outside the battery limit (BL) by natural-gas transfer pipeline 102 after the gasification.Temperature is 180 ℃, pressure is that (massfraction of ethylene glycol is 70% to 30bar hydrogenation of oxalate for preparing ethylene glycol crude product, 1, the massfraction of 2-propylene glycol is 15%, the massfraction of 1,2-butyleneglycol is 15%) enter heat exchange unit 2 heat exchange with the flow velocity of 2500Kg/h through crude product transport pipe 103 and be cooled to 0 ℃.Crude product after the cooling is delivered to auxiliary cooling equipment 3 by heat exchange ethylene glycol crude product transport pipe 104, crude product further is cooled to-5 ℃ and is delivered to ethylene glycol, 1 by advancing separating unit ethylene glycol crude product transport pipe 105 in auxiliary cooling equipment 3,2-propylene glycol and 1,2-butyleneglycol separating unit 4.
At separating unit 4 by subzero fractionation equipment ethylene glycol, 1 in the separating ethylene glycol crude product under-25 ℃ of conditions, 2-propylene glycol and 1, the products such as 2-butyleneglycol, wherein liquid product 1,2-propylene glycol massfraction is 49.6%, 1,2-butyleneglycol massfraction is 49.6% to be delivered to heat exchange unit 2 by 1,2-PD and 1,2-butyleneglycol recovery channel 107 and to carry out Yu Leng and reclaim.By product after Yu Leng reclaims can enter the by-product recovery device by by-product recovery device feed pipe 109.
Wherein solid phase prod quality of glycol mark is 99.9% to heat to 0 ℃ after collecting, deliver to heat exchange unit and 180 ℃ with the flow velocity of 1745kg/h by ethylene glycol product transport pipe 106, pressure is the heat exchange of 30bar hydrogenation of oxalate for preparing ethylene glycol crude product, for crude product provides cold energy, realize the cold energy reuse, make simultaneously the ethylene glycol product enter ethylene glycol product unit (purity is 99.9%) through ethylene glycol product feeding pipe road 108.
The batch process that separating unit is comprised of subzero fractionation and solid collection, two groups of subzero fractionation systems by parallel connection hocket subzero fractionation, solid collection process make separating unit make the purpose that can reach continuous purification ethylene glycol product, high productivity.
The above only is the preferred embodiment of this patent, and all equalizations of doing according to this patent scope change and modify, and all should belong to this patent covering scope.
Claims (4)
1. the technique of the barkite hydrogenation method gained ethylene glycol of efficiently purifying is characterized in that:
(1) after the LNG cryogenic liquid was warming up to room temperature gasification by the heat exchange unit heat exchange, Sweet natural gas was delivered to natural gas motorcar place outside the battery limit (BL) by natural-gas transfer pipeline;
(2) the hydrogenation of oxalate for preparing ethylene glycol crude product of High Temperature High Pressure passes through heat exchange unit on the contrary through transport pipe and LNG cryogenic liquid throughput direction, through heat exchange unit precooling, auxiliary cooling equipment auxiliary cooling, crude product is cooled to-5 ℃～5 ℃ and is delivered to separating unit through pipeline;
(3) be cooled to-20～-40 ℃ at separating unit by subzero fractionation equipment, make ethylene glycol be solid-state, 1,2-PD and 1,2-butyleneglycol are in a liquid state, liquid 1,2-PD and 1,2-butyleneglycol after remaining cold recovery as the separated recovery of by product; Directly collect solid-state ethylene glycol, perhaps solid-state ethylene glycol is heated into liquid state after, collect the ethylene glycol sterling.
2. the technique of efficient purification barkite hydrogenation method gained ethylene glycol according to claim 1, the temperature that it is characterized in that the hydrogenation of oxalate for preparing ethylene glycol crude product is 50～200 ℃, pressure is 25-30bar; The massfraction of each component is: ethylene glycol 60～99%, propylene glycol 0～15%, butyleneglycol 0～25%.
3. the technique of efficient purification barkite hydrogenation method gained ethylene glycol according to claim 1, it is characterized in that in the step (3), after solid-state ethylene glycol is heated into liquid state, before collecting through the hydrogenation of oxalate for preparing ethylene glycol crude product heat exchange of heat exchange unit and High Temperature High Pressure, for crude product provides cold energy.
4. the technique of efficient purification barkite hydrogenation method gained ethylene glycol according to claim 1, what it is characterized in that carrying out in the separating unit of described step (3) is that two groups of subzero fractionation and solid collection process by parallel connection hockets the ethylene glycol of can purifying continuously.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310263603.6A CN103319310B (en) | 2013-06-26 | 2013-06-26 | Technology for efficiently purifying glycol obtained through oxalate hydrogenation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310263603.6A CN103319310B (en) | 2013-06-26 | 2013-06-26 | Technology for efficiently purifying glycol obtained through oxalate hydrogenation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103319310A true CN103319310A (en) | 2013-09-25 |
| CN103319310B CN103319310B (en) | 2015-01-21 |
Family
ID=49188407
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310263603.6A Active CN103319310B (en) | 2013-06-26 | 2013-06-26 | Technology for efficiently purifying glycol obtained through oxalate hydrogenation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103319310B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104634065A (en) * | 2015-01-12 | 2015-05-20 | 江苏苏青水处理工程集团有限公司 | System and process for treating organic waste gas generated in ion resin production process |
| CN115073269A (en) * | 2022-06-02 | 2022-09-20 | 新疆中天力扬航空新材料科技有限公司 | Method for low-temperature freezing separation of glycol aqueous solution |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101993348A (en) * | 2009-08-31 | 2011-03-30 | 中国石油化工股份有限公司 | Method for preparing glycol from oxalate |
| CN102649704A (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
- 2013-06-26 CN CN201310263603.6A patent/CN103319310B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101993348A (en) * | 2009-08-31 | 2011-03-30 | 中国石油化工股份有限公司 | Method for preparing glycol from oxalate |
| CN102649704A (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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104634065A (en) * | 2015-01-12 | 2015-05-20 | 江苏苏青水处理工程集团有限公司 | System and process for treating organic waste gas generated in ion resin production process |
| CN115073269A (en) * | 2022-06-02 | 2022-09-20 | 新疆中天力扬航空新材料科技有限公司 | Method for low-temperature freezing separation of glycol aqueous solution |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103319310B (en) | 2015-01-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN204285888U (en) | A kind of LNG satellite station cold energy utilization device | |
| CN107940893A (en) | Using the LNG cold energy stepped utilization methods of cold energy lighter hydrocarbons recovery | |
| CN103496813A (en) | Method and device for steam stripping coal chemical industry wastewater through single tower without side line | |
| CN103319310B (en) | Technology for efficiently purifying glycol obtained through oxalate hydrogenation | |
| CN101852075A (en) | Oil-gas gathering and transferring treatment process of marine marginal oilfield | |
| CN204007197U (en) | The retracting device of steam condensate in synthesis gas preparing ethylene glycol industrial production | |
| CN110173961B (en) | Hydrogen and light hydrocarbon cryogenic separation device based on high-efficiency plate-fin heat exchanger | |
| CN104784953A (en) | Reaction product separation system for preparing propylene with methanol and quenching system of reaction product separation system | |
| CN104083888A (en) | Process method for producing octanol through vacuum rectification | |
| CN108826833B (en) | Natural gas impurity separation and recovery device | |
| CN203382692U (en) | System for efficiently purifying ethylene glycol obtained by using oxalic ester hydrogenation method | |
| CN103213946A (en) | Method for synthesizing ammonia by comprehensively utilizing liquefied natural gas | |
| CN203877912U (en) | Device for preparing and purifying H2 from LNG (liquefied natural gas) | |
| CN109608299B (en) | Petroleum light hydrocarbon separation device and method based on inter-tower heat integration technology | |
| CN101623574A (en) | Method for filtering Fischer-Tropsch synthesized heavy wax | |
| CN106477577A (en) | A kind of heat pump distillation produces device and the production method of ultra-high purity carbon dioxide | |
| CN104567275A (en) | High-yield natural gas liquidation and light dydrocarbon recovery device and recovery method | |
| CN103043609B (en) | Liquid nitrogen washing device with function of producing natural gas | |
| CN211078974U (en) | Purification device of high-purity methane | |
| CN110090543B (en) | Continuous CH separation by fluidized bed4/CO2Method (2) | |
| CN103754894A (en) | Novel method for recycling ammonia synthesis cold energy in synthetic ammonia system | |
| CN204097404U (en) | A kind of high-volatile feed coal segmentation pyrolysis sub-prime without discharge utilizes device | |
| CN103935959B (en) | Utilize LNG to produce and purify H2device and technique | |
| CN113004120A (en) | Water-saving emission-reducing methanol thermal coupling rectification system and rectification method | |
| CN203545965U (en) | Remote well associated gas recycling device |
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 | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 210019 Yunlong road 79, Jianye District, Jiangsu, Nanjing Patentee after: CHINA NUCLEAR HUAWEI ENGINEERING DESIGN AND RESEARCH Co.,Ltd. Address before: 210019 Yunlong road 79, Jianye District, Jiangsu, Nanjing Patentee before: JIANGSU CHINA NUCLEAR INDUSTRY HUAWEI ENGINEERING DESIGN AND RES Co.,Ltd. |