CN105061130B - A kind of liquid phase solvent for producing ethylene with acetylene hydrogenation slurry bed system - Google Patents
A kind of liquid phase solvent for producing ethylene with acetylene hydrogenation slurry bed system Download PDFInfo
- Publication number
- CN105061130B CN105061130B CN201510484952.XA CN201510484952A CN105061130B CN 105061130 B CN105061130 B CN 105061130B CN 201510484952 A CN201510484952 A CN 201510484952A CN 105061130 B CN105061130 B CN 105061130B
- Authority
- CN
- China
- Prior art keywords
- parts
- liquid phase
- phase solvent
- solvent
- 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
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of liquid phase solvent for producing ethylene with acetylene hydrogenation slurry bed system, include the component of following parts by weight：2 0.5 15 parts of methylcyclohexyl acetates, 50 85 parts of selective solvent, 0.5 15 parts of ionic liquid, 0.3 10 parts of hydrogen supply agent.Catalyst can be not only dispersed in liquid phase solvent by gained liquid phase solvent, remove heat of reaction in time, prevent the phenomenons such as sintering of catalyst, inactivation, and after reacting gas enters liquid phase solvent, the acetylene hydrogenation that efficiently can be adsorbed for catalyst active center provides hydroperoxyl radical, improve the efficiency of catalyst, it is to avoid covering of the acetylene autohemagglutination generation green oil polymer to catalyst, extend catalyst life；Meanwhile, the boiling point of liquid phase solvent system is improved, it is ensured that the concentration and viscosity of solvent needed for reactor, is reduced the load of solvent recovery in next step process, is significantly reduced the energy consumption level of device.
Description
Technical field
The present invention relates to a kind of liquid phase solvent for producing ethylene with acetylene hydrogenation slurry bed system, belong to ethene technology of preparing neck
Domain.
Background technology
In coal chemical technology, pass through Non-catalytic partial oxygen by calcium carbide technique or by raw material of natural gas by raw material of coal
Chemical industry skill produces acetylene, then using acetylene as raw material, under selective hydrocatalyst effect, by Hydrogenation for ethylene product.
Because acetylene hydrogenation reaction is moment strong exothermal reaction, experiment both at home and abroad shows anti-using fixed bed reactors progress acetylene hydrogenation
At once, a large amount of accumulation of heat moment occur in reaction, cause " temperature runaway " phenomenon.Therefore acetylene hydrogenation reaction is inclined both at home and abroad
To in employing reactor of the preferable slurry bed system of mass transfer, heat transfer property as selective hydrogenation of acetylene.
Experiment at present discloses the optimum temperature of producing ethylene with acetylene hydrogenation reaction at 160 DEG C or so, just in the solvent system
Boiling range within, with the progress of course of reaction, NMP, DMF equal solvent in solvent constantly evaporate, can with purpose product second
The effusion of alkene gas departs from reaction system, causes the concentration and viscosity of reactor solvent system constantly to increase, the effusion meeting of solvent
Also increase the load of solvent recovery process, cause production cost significantly to rise.
The content of the invention
It is an object of the invention to provide a kind of multi component liquid phase solvent for producing ethylene with acetylene hydrogenation slurry bed system, it has
Good hydroperoxyl radical absorption functions of physical supply and the ability of raising solvent system boiling point.
To achieve these goals, the present invention is adopted the following technical scheme that：
A kind of liquid phase solvent for producing ethylene with acetylene hydrogenation slurry bed system, includes the component of following parts by weight：2- methyl rings
0.5-15 parts of hexyl acetate (MCHA), 50-85 parts of selective solvent, 0.5-15 parts of ionic liquid, 0.3-10 parts of hydrogen supply agent.
Catalyst can be dispersed in liquid phase solvent by gained liquid phase solvent of the invention, when reacting gas is molten into liquid phase
After agent, the acetylene hydrogenation that efficiently can be adsorbed for catalyst active center provides hydroperoxyl radical, and constantly adds to catalyst work
Property center, promote the progress of acetylene hydrogenation positive reaction, substantially increase the efficiency of hydrogenation catalyst, it is to avoid acetylene is from consor
Into covering of the green oil polymer to catalyst, so as to reduce catalyst carbon deposition and inactivation, extend catalyst life；Meanwhile, liquid phase
Thus the boiling point of solvent system is improved to 218 DEG C for preceding 160-208 DEG C, substantially reduces entrainment of the ethene to solvent, it is ensured that anti-
The concentration and viscosity of solvent needed for answering device, it is to avoid the saturated vapor pressure of liquid phase solvent system is relatively low, it is volatile and cause ethene
Middle solvent is higher, reduces the load of solvent recovery in next step process, significantly reduces the energy consumption level of device.
In liquid phase solvent of the present invention, the selective solvent is selected from 1-METHYLPYRROLIDONE (NMP), 2- methyl first
One or more in acid amides (DMF), monomethyl amine (MMA) or cyclohexanone；It is preferred that 1-METHYLPYRROLIDONE (NMP), 2- methyl first
The combination of acid amides (DMF) and monomethyl amine (MMA).
In liquid phase solvent of the present invention, the ionic liquid is [BMIM] [BF4], [BMIM] [PF6], [BMIM]
[SbF6]、[BMIM]Cl、[BMIM]Br、[BMIM](MeO)2PO2, one or more in [BMIM] DMP；It is preferred that [BMIM]
(MeO)2PO2.Experiments verify that, under identical catalyst action, add the 2- methylcyclohexyl acetates of ionic liquid
(MCHA) liquid phase solvent compares the liquid phase solvent for not adding ionic liquid, and its reaction rate improves 5 times.
In liquid phase solvent of the present invention, the hydrogen supply agent is cycloalkyl aromatic hydrocarbons or/and the high aromatic hydrocarbons of oil coal tar
Distillate；Wherein, the cycloalkyl aromatic hydrocarbons are selected from 2,6- naphthoquinones, hexahydroxy-Isosorbide-5-Nitrae-naphthalenedione etc..
As the preferred embodiment of the present invention, the liquid phase solvent is made by the component of following parts by weight：2- methyl rings
0.5-15 parts of hexyl acetate (MCHA), 3-8 parts of 2- NMFs (DMF), 0.5-4 parts of methyl methacrylate (MMA), N-
50-85 parts of methyl pyrrolidone (NMP), ionic liquid [BMIM] (MeO)2PO20.5-15 parts, hydrogen supply agent 2,6- naphthoquinones 0.3-10
Part.
Further preferably, the liquid phase solvent is made by the component of following parts by weight：2- methylcyclohexyl acetates
(MCHA) 8-15 parts, 8 parts of 2- NMFs (DMF), 2 parts of methyl methacrylate (MMA), 1-METHYLPYRROLIDONE (NMP)
55-65 parts, ionic liquid [BMIM] (MeO)2PO22-5 parts, hydrogen supply agent 2,0.3 part of 6- naphthoquinones.
Still more preferably, the liquid phase solvent is made by the component of following parts by weight：2- methylcyclohexyl acetates
(MCHA) 8 parts, 8 parts of 2- NMFs (DMF), 2 parts of methyl methacrylate (MMA), 1-METHYLPYRROLIDONE (NMP) 65
Part, ionic liquid [BMIM] (MeO)2PO22 parts, hydrogen supply agent 2,0.3 part of 6- naphthoquinones.
Liquid phase solvent of the present invention can be mixed each component in proportion using the conventional hybrid mode in this area
It is made.
Scheme of the present invention has the beneficial effect that：
(1) present invention gained liquid phase solvent has relatively high solvability to acetylene, and acetylene content can be from original 40g/L
Bring up to 50~150g/L；It is small to ethylene dissolution degree and density contrast is big；To catalyst Non-toxic act on, small toxicity and it is inexpensive easily
.
(2) effectively hydrogenation catalyst can be dispersed in liquid phase solvent using liquid phase solvent of the present invention, institute
The hydroperoxyl radical and acetylene of absorption improve hydrogenation efficiency close around in catalyst active center, being conducive to reaction forward to carry out.
(3) because the boiling point of liquid phase solvent is improved, entrainment of the purpose product ethylene gas to solvent can be substantially reduced, it is ensured that
The concentration and viscosity of solvent needed for reactor, it is to avoid the saturated vapor pressure of liquid phase solvent system is relatively low, it is volatile and cause
Solvent is higher in ethene, reduces the load of solvent recovery in next step process, significantly reduces the energy consumption level of device,
So that the producing ethylene with acetylene hydrogenation process units of same scale uses device capbility after novel dissolvent system to improve 30%.Using new
Type dicyandiamide solution is compared with using current dicyandiamide solution, and general item investment reduces more than 20%.
Embodiment
Following examples are used to illustrate the present invention, but are not limited to the scope of the present invention.
Embodiment 1
A kind of liquid phase solvent, is made by the component of following parts by weight：8 parts of 2- methylcyclohexyls acetate (MCHA), 2- first
8 parts of base formamide (DMF), 2 parts of methyl methacrylate (MMA), 65 parts of 1-METHYLPYRROLIDONE (NMP), ionic liquid
[BMIM](MeO)2PO22 parts, hydrogen supply agent 2,0.3 part of 6- naphthoquinones.
Embodiment 2
A kind of liquid phase solvent, is made by the component of following parts by weight：10 parts of 2- methylcyclohexyls acetate (MCHA), 2- first
8 parts of base formamide (DMF), 2 parts of methyl methacrylate (MMA), 60 parts of 1-METHYLPYRROLIDONE (NMP), ionic liquid
[BMIM](MeO)2PO25 parts, hydrogen supply agent 2,0.3 part of 6- naphthoquinones.
Embodiment 3
A kind of liquid phase solvent, is made by the component of following parts by weight：15 parts of 2- methylcyclohexyls acetate (MCHA), 2- first
8 parts of base formamide (DMF), 2 parts of methyl methacrylate (MMA), 55 parts of 1-METHYLPYRROLIDONE (NMP), ionic liquid
[BMIM](MeO)2PO25 parts, hydrogen supply agent 2,0.3 part of 6- naphthoquinones.
Comparative example 1
A kind of liquid phase solvent, is made by the component of following parts by weight：8 parts of 2- NMFs (DMF), methyl methacrylate
2 parts of ester (MMA), 75 parts of 1-METHYLPYRROLIDONE (NMP), hydrogen supply agent 2,0.3 part of 6- naphthoquinones.
Compliance test result
Example 1-3, the gained liquid phase solvent 85.3g of comparative example 1 are respectively charged into the slurry bed system containing palladium catalyst 0.2g,
Catalyst granules is in be dispersed in liquid phase solvent；It is passed through after acetylene is mixed with hydrogen from slurry bed system bottom, operating pressure
0.1MPa, 160 DEG C of reaction temperature, hydrogen is 4 with acetylene volume ratio:1, air speed be 1800mL/ (gcat.h), reactor product gas from
Flowed out at the top of paste state bed reactor.
Detection method：GC7900, fid detector, capillary column and gas chromatograph.
Testing result is as shown in the table.
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | |
| Conversion of alkyne % | 98 | 97 | 95 | 92 |
| Yield of ethene % | 86.5 | 85 | 84.5 | 73.4 |
| Catalyst life h | 347 | 352 | 353 | 232 |
| Green oil content % | 0.02 | 0.04 | 0.04 | 1.67 |
As seen from the above table, under identical experiment condition, using liquid phase solvent Hydrogenation of the present invention for ethene, second
Alkyne conversion rate, yield of ethene are above comparative example, and green oil content is far below comparative example, and catalyst service life is able to substantially
Extension, achieves significant technique effect.
Although above the present invention is described in detail with a general description of the specific embodiments,
On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause
This, these modifications or improvements, belong to the scope of protection of present invention without departing from theon the basis of the spirit of the present invention.
Claims (4)
1. a kind of liquid phase solvent for producing ethylene with acetylene hydrogenation slurry bed system, it is characterised in that include the component of following parts by weight：
0.5-15 parts of 2- methylcyclohexyl acetates, 50-85 parts of selective solvent, 0.5-15 parts of ionic liquid, 0.3-10 parts of hydrogen supply agent；
Wherein, the selective solvent is the combination of 1-METHYLPYRROLIDONE, 2- NMFs and methyl methacrylate；
The ionic liquid is [BMIM] (MeO)2PO2；
The hydrogen supply agent is 2,6- naphthoquinones or hexahydroxy -1,4- naphthalenediones.
2. liquid phase solvent according to claim 1, it is characterised in that be made by the component of following parts by weight：2- methyl rings
0.5-15 parts of hexyl acetate, 3-8 parts of 2- NMFs, 0.5-4 parts of methyl methacrylate, 1-METHYLPYRROLIDONE 50-
85 parts, ionic liquid [BMIM] (MeO)2PO20.5-15 parts, hydrogen supply agent 2,0.3-10 parts of 6- naphthoquinones.
3. liquid phase solvent according to claim 2, it is characterised in that be made by the component of following parts by weight：2- methyl rings
8-15 parts of hexyl acetate, 8 parts of 2- NMFs, 2 parts of methyl methacrylate, 55-65 parts of 1-METHYLPYRROLIDONE, ion
Liquid [BMIM] (MeO)2PO22-5 parts, hydrogen supply agent 2,0.3 part of 6- naphthoquinones.
4. liquid phase solvent according to claim 3, it is characterised in that be made by the component of following parts by weight：2- methyl rings
8 parts of hexyl acetate, 8 parts of 2- NMFs, 2 parts of methyl methacrylate, 65 parts of 1-METHYLPYRROLIDONE, ionic liquid
[BMIM](MeO)2PO22 parts, hydrogen supply agent 2,0.3 part of 6- naphthoquinones.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510484952.XA CN105061130B (en) | 2015-08-07 | 2015-08-07 | A kind of liquid phase solvent for producing ethylene with acetylene hydrogenation slurry bed system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510484952.XA CN105061130B (en) | 2015-08-07 | 2015-08-07 | A kind of liquid phase solvent for producing ethylene with acetylene hydrogenation slurry bed system |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105061130A CN105061130A (en) | 2015-11-18 |
| CN105061130B true CN105061130B (en) | 2017-08-08 |
Family
ID=54490706
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510484952.XA Active CN105061130B (en) | 2015-08-07 | 2015-08-07 | A kind of liquid phase solvent for producing ethylene with acetylene hydrogenation slurry bed system |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105061130B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106554805B (en) * | 2016-11-28 | 2018-04-20 | 霍尔果斯道科特环能科技有限公司 | Solvent and method used by a kind of producing ethylene with acetylene hydrogenation |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7045670B2 (en) * | 2003-09-03 | 2006-05-16 | Synfuels International, Inc. | Process for liquid phase hydrogenation |
| US7141709B2 (en) * | 2003-11-13 | 2006-11-28 | Chevron Phillips Chemical Company Lp | Methods and systems of producing monoolefins by the extraction-hydrogenation of highly unsaturated hydrocarbons |
| CN102876377B (en) * | 2011-07-11 | 2015-06-17 | 中国石油化工股份有限公司 | Hydrotreatment and catalytic cracking combined method of heavy hydrocarbon raw material |
| CN103044179A (en) * | 2012-12-19 | 2013-04-17 | 清华大学 | Method for preparing ethylene through liquid-phase selective hydrogenation of acetylene in slurry reactor |
-
2015
- 2015-08-07 CN CN201510484952.XA patent/CN105061130B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105061130A (en) | 2015-11-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Gil et al. | Carbon adsorbents for CO2 capture from bio-hydrogen and biogas streams: Breakthrough adsorption study | |
| CN102701896B (en) | Composite solvent for purifying acetylene and purification method thereof | |
| CN102516006B (en) | Method and device for recovering ethylene in vinyl acetate production process | |
| CN105330512A (en) | Method for preparing chloroethylene from acetylene and hydrogen chloride in mercuration-free mode | |
| CN107778125A (en) | The sorption extraction separation of high alkynes and purification method in a kind of thick acetylene gas | |
| CN102430367A (en) | Coal-bed gas deoxidization method applying tube array fixed bed reactor | |
| CN105061130B (en) | A kind of liquid phase solvent for producing ethylene with acetylene hydrogenation slurry bed system | |
| CN105363406A (en) | Multifunctional deoxidizer, preparation and applications thereof | |
| CN106883091A (en) | A kind of method by 4- methyl -3- hexamethylene cyclohexene carboxaldehyde selectivity synthesis paraxylene | |
| Zhang et al. | Coconut shell activated carbon tethered ionic liquids for continuous cycloaddition of CO2 to epichlorohydrin in packed bed reactor | |
| CA2517882A1 (en) | Method of manufacturing acetic acid | |
| CN107445923B (en) | process for preparing furfuryl alcohol by hydrogenation of furfural | |
| CN107185542B (en) | Supported Fe-Zn/CNTs catalyst and preparation method thereof | |
| CN103936549B (en) | The recovery method of tail gas useful constituent in acetic acid plant | |
| CN109701574B (en) | Preparation of nitrogen-modified carbon-supported noble metal hydrogenation catalyst and application of nitrogen-modified carbon-supported noble metal hydrogenation catalyst in hydrogenation reaction of pyridine ring compounds | |
| CN204342435U (en) | The hydrogenation fluidized-bed reactor of anthraquinone legal system hydrogen peroxide | |
| CN107774083A (en) | A kind of purification method of the full temperature journey sorption extraction deep dehydration removal of impurities of alkene | |
| CN107649158B (en) | Catalyst for preparing dimethyl carbonate and method for preparing dimethyl carbonate | |
| CN105032125A (en) | Method for recycling cyclohexane oxidation exhaust gas in process of producing cyclohexanone through cyclohexane air oxidation method | |
| CN105060255A (en) | Method for recycling and treating heavy aromatics in oxidized tail gas obtained after oxidation of hydrogenated liquid in technology for producing hydrogen peroxide with anthraquinones process | |
| CN107973716A (en) | A kind of method of dimethyl ether carbonyl synthesis of acetic methyl esters | |
| CN112028017B (en) | Dehydrogenation separation purification process for carbon monoxide raw material gas | |
| CN108096996B (en) | MDEA selective desulfurization process and system | |
| CN113214148B (en) | Synthesis method and device of 2/3-cyanopyridine | |
| CN109081308A (en) | A method of by glycerol and methane co-producing hydrogen and synthesis gas |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20161010 Address after: 102200 Beijing City, Changping District science and Technology Park Fukang Road No. 18 Applicant after: Beijing Huafu Engineering Co., Ltd. Address before: 102200 Beijing city Changping District Machi Town cow Road No. 18 Applicant before: Beijing Shenwu Environment Energy Technology Group Co., Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200527 Address after: 100121 1105, floor 1, building 1, yard 18, Shuangqiao East Road, Chaoyang District, Beijing Patentee after: Beijing Jintai Chengrui Technology Development Co., Ltd Address before: 102200 No. 18 Fukang Road, Changping District science and Technology Park, Beijing Patentee before: BEIJING HUAFU ENGINEERING Co.,Ltd. |