CN106554805B - Solvent and method used by a kind of producing ethylene with acetylene hydrogenation - Google Patents
Solvent and method used by a kind of producing ethylene with acetylene hydrogenation Download PDFInfo
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- CN106554805B CN106554805B CN201611065574.2A CN201611065574A CN106554805B CN 106554805 B CN106554805 B CN 106554805B CN 201611065574 A CN201611065574 A CN 201611065574A CN 106554805 B CN106554805 B CN 106554805B
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- hydrogenation
- acetylene
- solvent
- oil
- producing ethylene
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 92
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 title claims abstract description 80
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000005977 Ethylene Substances 0.000 title claims abstract description 52
- 239000002904 solvent Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 238000009835 boiling Methods 0.000 claims abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 24
- 238000005292 vacuum distillation Methods 0.000 claims description 9
- 238000004939 coking Methods 0.000 claims description 3
- 230000003111 delayed effect Effects 0.000 claims description 3
- 239000002283 diesel fuel Substances 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 26
- 239000012535 impurity Substances 0.000 abstract description 6
- 229920006395 saturated elastomer Polymers 0.000 abstract description 6
- 239000003921 oil Substances 0.000 description 63
- 239000000047 product Substances 0.000 description 21
- 239000012071 phase Substances 0.000 description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 13
- 239000008139 complexing agent Substances 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 239000007791 liquid phase Substances 0.000 description 9
- 230000000536 complexating effect Effects 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229960001484 edetic acid Drugs 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 150000001345 alkine derivatives Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000003863 metallic catalyst Substances 0.000 description 4
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical group OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- -1 C12 alkane Chemical class 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
- C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
Abstract
Solvent and method used by the present invention provides a kind of producing ethylene with acetylene hydrogenation.The solvent is hydrogenation tail oil, and hydrogenation tail oil has good dissolubility as the solvent of pure producing ethylene with acetylene hydrogenation to green oil, greatly reduces the probability that green oil is covered in catalyst surface, extends catalyst life；Its boiling point is high, and saturated vapor is forced down, do not steamed in hydrogenation reaction with ethylene product, avoids the increase separated cost of subsequent cell；Heat endurance is good, is not decomposed under reaction temperature, does not produce impurity, ensures ethylene product quality；The solvent dissolves a certain amount of green oil, can suppress the reaction of acetylene hydrogenation generation green oil.
Description
Technical field
The present invention relates to technical field of petrochemical industry, in particular to a kind of producing ethylene with acetylene hydrogenation used by it is molten
Agent and method.
Background technology
Ethene is a kind of important basic material in modern industry, and one of chemicals of world wide production maximum.Ethene
Yield becomes the mark for weighing a national oil development of chemical industry level, its production capacity is counted as a national economy reality
The embodiment of power.
Ethene is mainly made by the method for cracking petroleum hydrocarbon, and oil is a kind of non-renewable resources, its price is with the world
Environmental change fluctuation is very big.The current annual petroleum consumption ranking the second in the world in China, the oil pair in China in 2015 in 2014
Outer interdependency respectively reaches 59.6% and 60.4%, and serious strategy is formd for this China not enriched to petroleum resources
Threaten.Therefore, find another new source and process prepares large basic organic chemical raw material-ethene, it is raw in industry
Production field substitutes petroleum, can alleviate dependence of the China for oil to a certain extent.
Although the extensive use in hydrocarbon pyrolysis ethylene process of acetylene hydrogenation technology, it is mainly used for removing hot tearing
Solve a small amount of acetylene (0.1-1.0vol%) in technical process.To the rare exploration of high concentration producing ethylene with acetylene hydrogenation, corresponding industrialization
Large-scale application is even more to have no report.
Patent《CN 103044179 A》In to acetylene hydrogenation solvent select 1-methyl-2-pyrrolidinone, dimethylformamide,
Tetrahydrofuran and dimethyl sulfoxide (DMSO) etc..Patent《CN 105152842 A》The middle solvent used is pyridine, imidazoles, N- methylpyrrole
Alkanone, C12 alkane or its isomers, benzene, naphthalene and biphenyl etc..
The basic principle that two patents select solvent is all intended to have compared with highly dissoluble acetylene, molten to ethene
Solution property is little, ensures the ethene of reaction generation and can leave system in the form of bubbles as early as possible, avoids excessive hydrogenation.But actual anti-
Middle it should find, the two selected solvent only has dissolubility to acetylene, little to the solubility of hydrogen, this is to improving reaction conversion
Rate does not have no great facilitation.
In view of this, it is special to propose the present invention.
The content of the invention
The first object of the present invention is to provide solvent and method used by a kind of producing ethylene with acetylene hydrogenation, the second
Solvent all has good dissolubility to acetylene and hydrogen at the same time used by alkynes Hydrogenation ethene, while to the green oil of generation
There is good dissolubility, greatly reduce the probability that green oil is covered in catalyst surface, extend catalyst life and suppress acetylene at the same time
The reaction of green oil is hydrogenated to, boiling point is high, and saturated vapor is forced down, do not steamed in hydrogenation reaction with ethylene product, after avoiding increase
The separated cost of continuous unit, decreases loss caused by evaporation of the solvent；Heat endurance is good, is not decomposed under reaction temperature, does not produce
Raw impurity, ensures ethylene product quality.
The second object of the present invention be to provide it is a kind of using the producing ethylene with acetylene hydrogenation used by solvent carry out
The method of producing ethylene with acetylene hydrogenation, this method technique is simple, can effectively suppress green oil and be covered in catalyst surface, further prevent
The only deep hydrogenation of acetylene, improves the selectivity of ethene, so as to add yield of ethene.
In order to realize the above-mentioned purpose of the present invention, spy uses following technical scheme：
Solvent used by a kind of producing ethylene with acetylene hydrogenation, the solvent are hydrogenation tail oil.
The present invention is in order to solve the problems in the existing technology, there is provided a kind of special producing ethylene with acetylene hydrogenation is used
Solvent, the selection theory of the solvent is different from traditional approach, it is main consider to suppress green oil generation, high temperature never degenerates and boiling point
High and heat-transfer effect it is good this some.Solvent at the same time all has very acetylene and hydrogen used by producing ethylene with acetylene hydrogenation of the present invention
Good dissolubility, while also have good dissolubility to the green oil of generation, greatly reduce green oil and be covered in the several of catalyst surface
Rate, extends the reaction that catalyst life suppresses acetylene hydrogenation generation green oil at the same time, boiling point is high, and saturated vapor forces down, hydrogenation reaction
In do not steamed with ethylene product, avoid increase the separated cost of subsequent cell；Heat endurance is good, is not decomposed under reaction temperature, no
Impurity is produced, ensures ethylene product quality.
Preferably, the hydrogenation tail oil includes the wax oil from atmospheric and vacuum distillation unit second line of distillation, from atmospheric and vacuum distillation
One or more in device subtracts three wax oil of line and the wax oil from atmospheric and vacuum distillation unit delayed coking unit, hydrogenated essence
The component for the ratio diesel oil weight made and be hydrocracked.
Preferably, the hydrogenation tail oil includes cut boiling range at 300 DEG C -600 DEG C.
It is further preferred that the hydrogenation tail oil includes cut boiling range at 320 DEG C -530 DEG C.
The method that producing ethylene with acetylene hydrogenation is carried out using above-mentioned solvent.
The method that solvent carries out producing ethylene with acetylene hydrogenation used by using producing ethylene with acetylene hydrogenation provided by the invention, this
Inventive method technique is simple, can effectively suppress green oil and be covered in catalyst surface, further prevent the deep hydrogenation of acetylene, carry
The high selectivity of ethene, so as to add yield of ethene.
Preferably, this method is carried out using paste state bed reactor.
Preferably, the molar ratio of hydrogen and acetylene is 5-6:1, it is preferably 5-5.5:1, more preferably 5:1.
Preferably, the overall flow rate of hydrogen and acetylene is 1500-2000mL/min, is preferably 1500mL/min-1600mL/
min。
Preferably, reaction temperature is 110-150 DEG C, is preferably 120-130 DEG C.
Preferably, operating pressure 0.4-1MPa, is preferably 0.4-0.6MPa, more preferably 0.5MPa.
Compared with prior art, beneficial effects of the present invention are：
The present invention is in order to solve the problems in the existing technology, there is provided a kind of special producing ethylene with acetylene hydrogenation is used
Solvent, the selection theory of the solvent is different from traditional approach, it is main consider to suppress green oil generation, high temperature never degenerates and boiling point
High and heat-transfer effect it is good this some.Solvent at the same time all has very acetylene and hydrogen used by producing ethylene with acetylene hydrogenation of the present invention
Good dissolubility, while also have good dissolubility to the green oil of generation, greatly reduce green oil and be covered in the several of catalyst surface
Rate, extends the reaction that catalyst life suppresses acetylene hydrogenation generation green oil at the same time, boiling point is high, and saturated vapor forces down, hydrogenation reaction
In do not steamed with ethylene product, avoid increase the separated cost of subsequent cell；Heat endurance is good, is not decomposed under reaction temperature, no
Impurity is produced, ensures ethylene product quality.
The method that solvent carries out producing ethylene with acetylene hydrogenation used by using producing ethylene with acetylene hydrogenation provided by the invention, this
Inventive method technique is simple, can effectively suppress green oil and be covered in catalyst surface, further prevent the deep hydrogenation of acetylene, carry
The high selectivity of ethene, so as to add yield of ethene.
Embodiment
Technical scheme is clearly and completely described below in conjunction with embodiment, but ability
Field technique personnel will be understood that following described embodiment is part of the embodiment of the present invention, instead of all the embodiments,
The present invention is merely to illustrate, and is not construed as limiting the scope of the invention.Based on the embodiments of the present invention, the common skill in this area
Art personnel all other embodiments obtained without making creative work, belong to the model that the present invention protects
Enclose.The person that is not specified actual conditions in embodiment, the condition suggested according to normal condition or manufacturer carry out.Agents useful for same or instrument
Production firm person is not specified, is the conventional products that can be obtained by commercially available purchase.
Solvent used by the present invention provides a kind of producing ethylene with acetylene hydrogenation, the solvent are hydrogenation tail oil.
Hydrogenation tail oil is one of byproduct of hydrogenation crude cracking, is called and does that " unconverted oil or UCO ", refer to split in hydrogenation
Uncracked saturated hydrocarbons during change.In the prior art, the purposes of hydrogenation tail oil mainly includes following several：
1st, available for preparing ethylene by steam cracking raw material；
2nd, catalytic cracking feeds；
3rd, the lube base oil of the high viscous index of production.
The present invention is in order to solve the problems in the existing technology, there is provided a kind of special producing ethylene with acetylene hydrogenation is used
Solvent, the selection theory of the solvent is different from traditional approach, it is main consider to suppress green oil generation, high temperature never degenerates and boiling point
High and heat-transfer effect it is good this some.Solvent at the same time all has very acetylene and hydrogen used by producing ethylene with acetylene hydrogenation of the present invention
Good dissolubility, while also have good dissolubility to the green oil of generation, greatly reduce green oil and be covered in the several of catalyst surface
Rate, extends the reaction that catalyst life suppresses acetylene hydrogenation generation green oil at the same time, boiling point is high, and saturated vapor forces down, hydrogenation reaction
In do not steamed with ethylene product, avoid increase the separated cost of subsequent cell；Heat endurance is good, is not decomposed under reaction temperature, no
Impurity is produced, ensures ethylene product quality.
Preferably, the hydrogenation tail oil includes the wax oil from atmospheric and vacuum distillation unit second line of distillation, from atmospheric and vacuum distillation
One or more in device subtracts three wax oil of line and the wax oil from atmospheric and vacuum distillation unit delayed coking unit, hydrogenated essence
The component for the ratio diesel oil weight made and be hydrocracked.
Preferably, the hydrogenation tail oil includes cut boiling range at 300 DEG C -600 DEG C.
It is further preferred that the hydrogenation tail oil includes cut boiling range at 320 DEG C -530 DEG C.
Solvent used by the present invention selects the cut of hydrogenation tail oil at a certain temperature as producing ethylene with acetylene hydrogenation, has
Help improve dissolubility of the gained solvent to acetylene, hydrogen and green oil, further reducing green oil is covered in the several of catalyst surface
Rate, extends the reaction that catalyst life suppresses acetylene hydrogenation generation green oil at the same time.
Invention also provides a kind of method that producing ethylene with acetylene hydrogenation is carried out using above-mentioned solvent.
The method that solvent carries out producing ethylene with acetylene hydrogenation used by using producing ethylene with acetylene hydrogenation provided by the invention, this
Inventive method technique is simple, can effectively suppress green oil and be covered in catalyst surface, further prevent the deep hydrogenation of acetylene, carry
The high selectivity of ethene, so as to add yield of ethene.
Preferably, the method that producing ethylene with acetylene hydrogenation is carried out using above-mentioned solvent that the specific embodiment of the invention provides
Carried out using paste state bed reactor.
Paste state bed reactor is a kind of " gas-liquid phase " two-phase haptoreaction system, and wherein gas phase is primarily as raw material
Hydrogen and acetylene, liquid phase includes hydrogenation tail oil as solvent, further includes catalyst, solid catalysis may be selected in wherein catalyst
Agent or liquid-phase catalyst, its dosage can account for the 1%-10% of liquid phase gross mass, preferably account for the 1%-3% of liquid phase gross mass.
Preferably, catalyst used in the specific embodiment of the invention includes complex state metallic catalyst, includes activity
Metal center and complexing agent.
The active metal centre includes：One in tungsten W, molybdenum Mo, manganese Mn, iron Fe, palladium Pd, platinum Pt, silver-colored Ag and lanthanum La etc.
Kind is a variety of, is preferably the one or more in palladium, manganese, iron.
The complexing agent is nitrilotriacetic acid, the one or more in ethylenediamine tetra-acetic acid, diethylenetriamine pentacarboxylic acid, preferably
For nitrilotriacetic acid or ethylenediamine tetra-acetic acid.
In the preparation process of the complex state metallic catalyst, since metal ion is also easy to produce hydroxide at a high ph
Thing precipitates, and can add stabilizer so as to prevent the generation of precipitation, and therefore, the complex state metallic catalyst can also include few
The stabilizer of amount.
Preferably, the stabilizer includes the one or more in anhydrous sorbitol, glucose and fructose.The stabilizer
Dosage to ensure that metal ion does not produce precipitation, the property of the complex state metallic catalyst is kept in the reaction system
Stabilization.
Preferably, the molar ratio of hydrogen and acetylene is 5-6:1, it is preferably 5-5.5:1, more preferably 5:1.
Preferably, the overall flow rate of hydrogen and acetylene is 1500-2000mL/min, is preferably 1500mL/min-1600mL/
min。
Preferably, reaction temperature is 110-150 DEG C, is preferably 120-130 DEG C.
Preferably, operating pressure 0.4-1MPa, is preferably 0.4-0.6MPa, more preferably 0.5MPa.
Acetylene hydrogenation second is carried out as solvent using the hydrogenation tail oil that above-mentioned special reaction condition is used in conjunction with the invention
The method of alkene, peomotes reaction and carries out, improve conversion of alkyne and easy absorptivity.
Preferably, hydrogenation tail oil used in the specific embodiment of the invention is Beijing Huafu Engineering Co., Ltd to crude oil
The byproduct of generation is hydrocracked, its property is as shown in table 1：
1 specific embodiment of the invention hydrogenation tail oil property of table
| Project | Hydrogenation tail oil |
| Density (20 DEG C)/kgm-3 | 832.1 |
| Appearance | It is yellowish green |
| Boiling range (ASTM D1160)/DEG C | |
| IBP/10% | 300/393 |
| 30%/50% | 401/413 |
| 70%/90% | 431/461 |
| 95%/EBP | 496/600 |
| Sulfur content/μ gg-1 | 6.5 |
| Nitrogen content/μ gg-1 | 1.0 |
| Condensation point/DEG C | +35 |
| Color (D1500)/number | ＜ 2.0 |
| Viscosity (40 DEG C)/mm2·s-1 | 13.20 |
| Viscosity (100 DEG C)/mm2·s-1 | 4.11 |
| Carbon residue, wt% | ＜ 0.01 |
| Asphalitine/μ gg-1 | 0 |
| Wax content, wt% | 19.2 |
| Alkane, wt% | 51.5 |
| Cycloalkane, wt% | 46.7 |
| Arene content, wt% | 1.6 |
| Flash-point (opening)/DEG C | 225 |
| Average molecular weight | 462 |
Embodiment 1
A kind of method of producing ethylene with acetylene hydrogenation：
Using one section of paste state bed reactor, hydrogen and acetylene are included in the gas phase；
The liquid phase is made of following raw material：Hydrogenation tail oil cut 99g of the boiling range at 300 DEG C -600 DEG C, with nitrilotriacetic acid
For the complexing palladium 1g of complexing agent configuration；
Operation temperature：110℃；
Operating pressure：0.4MPa；
Gas phase flow velocity：1500mL/min；
Hydrogen and acetylene molar ratio：5:1；
Successive reaction, from paste state bed reactor collected overhead gas-phase product, both obtains product.
Embodiment 2
A kind of method of producing ethylene with acetylene hydrogenation：
Using one section of paste state bed reactor, hydrogen and acetylene are included in the gas phase；
The liquid phase is made of following raw material：Hydrogenation tail oil cut 95g of the boiling range at 300 DEG C -600 DEG C, with ethylenediamine tetraacetic
Acetic acid is the complexing palladium 3g of complexing agent configuration, and ethylenediamine tetra-acetic acid is the complexing manganese 1g of complexing agent configuration, and ethylenediamine tetra-acetic acid is
The Complexing Iron 1g of complexing agent configuration；
Operation temperature：150℃；
Operating pressure：1.0MPa；
Gas phase flow velocity：2000mL/min；
Hydrogen and acetylene molar ratio：6:1；
Successive reaction, from paste state bed reactor collected overhead gas-phase product, both obtains product.
Embodiment 3
A kind of method of producing ethylene with acetylene hydrogenation：
Using one section of paste state bed reactor, hydrogen and acetylene are included in the gas phase；
The liquid phase is made of following raw material：Hydrogenation tail oil cut 99g of the boiling range at 320 DEG C -530 DEG C, with nitrilotriacetic acid
For the complexing palladium 1g of complexing agent configuration；
Operation temperature：120℃；
Operating pressure：0.6MPa；
Gas phase flow velocity：1500mL/min；
Hydrogen and acetylene molar ratio：5.5:1；
Successive reaction, from paste state bed reactor collected overhead gas-phase product, both obtains product.
Embodiment 4
A kind of method of producing ethylene with acetylene hydrogenation：
Using one section of paste state bed reactor, hydrogen and acetylene are included in the gas phase；
The liquid phase is made of following raw material：Hydrogenation tail oil cut 95g of the boiling range at 320 DEG C -530 DEG C, with ethylenediamine tetraacetic
Acetic acid is the complexing palladium 3g of complexing agent configuration, and ethylenediamine tetra-acetic acid is the complexing manganese 1g of complexing agent configuration, and ethylenediamine tetra-acetic acid is
The Complexing Iron 1g of complexing agent configuration；
Operation temperature：130℃；
Operating pressure：0.5MPa；
Gas phase flow velocity：1600mL/min；
Hydrogen and acetylene molar ratio：5:1；
Successive reaction, from paste state bed reactor collected overhead gas-phase product, both obtains product.
Using the gas chromatography detection embodiment of the present invention and comparative example, (comparative example 1 and comparative example 2 are successively respectively according to special
Technical solution described in the embodiment 3 and embodiment 4 of sharp CN201510485015.6 carries out producing ethylene with acetylene hydrogenation) gained production
Product, calculate the green oil content adhered on conversion of alkyne, yield of ethene, catalyst life and catalyst, the testing result such as institute of table 2
Show：
The product testing result of the present invention of table 2
| Embodiment | Conversion of alkyne % | Yield of ethene % | Catalyst life h | Green oil content % |
| Embodiment 1 | 99.9 | 90.3 | 600 | 0.10 |
| Embodiment 2 | 99.9 | 91.6 | 674 | 0.09 |
| Embodiment 3 | 99.9 | 94.2 | 763 | 0.06 |
| Embodiment 4 | 99.9 | 95.7 | 809 | 0.04 |
| Comparative example 1 | 99.5 | 82.1 | 291 | 1.35 |
| Comparative example 2 | 99.7 | 88.7 | 400 | 0.15 |
It can be seen from Table 2 that compared with using the comparative example of Conventional solvents, the present invention is using hydrogenation tail oil as molten
Agent, greatly reduces the probability that green oil is covered in catalyst surface, extends catalyst life and suppresses acetylene hydrogenation generation green oil at the same time
Reaction, the selectivity of ethene is improved, so as to add yield of ethene.
The boiling point of hydrogenation tail oil used in the present invention and conventional producing ethylene with acetylene hydrogenation solvent is as shown in table 3：
3 solvent of the present invention of table is contrasted with Conventional solvents boiling point
It can be seen from Table 3 that the present invention uses solvent of the hydrogenation tail oil as producing ethylene with acetylene hydrogenation, its boiling point is high,
Saturated vapor forces down, and will not be steamed in hydrogenation reaction with ethylene product, avoids the increase separated cost of subsequent cell；Heat endurance
It is good, do not decomposed under reaction temperature, do not produce impurity, ensure the quality of ethylene product；In addition, hydrogenation tail oil is at the same time to acetylene and hydrogen
Gas all has good dissolubility, while also has good dissolubility to the green oil of generation, greatly reduces green oil and is covered in catalysis
The probability on agent surface, extends the reaction that catalyst life suppresses acetylene hydrogenation generation green oil at the same time.
Although being illustrated and the invention has been described with specific embodiment, but it will be appreciated that various embodiments above is only used
To illustrate technical scheme, rather than its limitations；It will be understood by those of ordinary skill in the art that：Without departing substantially from this hair
In the case of bright spirit and scope, it can modify to the technical solution described in foregoing embodiments, or to wherein
Some or all of technical characteristic carries out equivalent substitution；And these are changed or are replaced, the essence of appropriate technical solution is not made
Depart from the scope of various embodiments of the present invention technical solution；It is, therefore, intended that include belonging to the present invention in the following claims
In the range of all these substitutions and modifications.
Claims (11)
1. solvent used by a kind of producing ethylene with acetylene hydrogenation, it is characterised in that the solvent is hydrogenation tail oil；
The hydrogenation tail oil includes the wax oil from atmospheric and vacuum distillation unit second line of distillation, from the atmospheric and vacuum distillation unit line that subtracts three
One or more in wax oil and wax oil from atmospheric and vacuum distillation unit delayed coking unit, it is hydrogenated refined and be hydrocracked
The component of obtained ratio diesel oil weight.
2. solvent used by a kind of producing ethylene with acetylene hydrogenation according to claim 1, it is characterised in that the hydrogenation tail
Oil includes cut boiling range at 300 DEG C -600 DEG C.
3. solvent used by a kind of producing ethylene with acetylene hydrogenation according to claim 2, it is characterised in that the hydrogenation tail
Oil includes cut boiling range at 320 DEG C -530 DEG C.
4. the method that producing ethylene with acetylene hydrogenation is carried out using any solvents of claim 1-3；
Wherein, the molar ratio of hydrogen and acetylene is 5-6:1；
The overall flow rate of hydrogen and acetylene is 1500-2000mL/min；
Reaction temperature is 110-150 DEG C；
Operating pressure is 0.4-1MPa.
5. according to the method described in claim 4, it is characterized in that, this method is carried out using paste state bed reactor.
6. according to the method described in claim 4, it is characterized in that, the molar ratio of hydrogen and acetylene is 5-5.5:1.
7. according to the method described in claim 6, it is characterized in that, the molar ratio of hydrogen and acetylene is 5:1.
8. according to the method described in claim 4, it is characterized in that, the overall flow rate of hydrogen and acetylene is 1500mL/min-
1600mL/min。
9. according to the method described in claim 4, it is characterized in that, reaction temperature is 120-130 DEG C.
10. according to the method described in claim 4, it is characterized in that, operating pressure is 0.4-0.6MPa.
11. according to the method described in claim 10, it is characterized in that, operating pressure is 0.5MPa.
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