CN106554805A - Solvent and method that a kind of producing ethylene with acetylene hydrogenation is adopted - Google Patents
Solvent and method that a kind of producing ethylene with acetylene hydrogenation is adopted Download PDFInfo
- Publication number
- CN106554805A CN106554805A CN201611065574.2A CN201611065574A CN106554805A CN 106554805 A CN106554805 A CN 106554805A CN 201611065574 A CN201611065574 A CN 201611065574A CN 106554805 A CN106554805 A CN 106554805A
- Authority
- CN
- China
- Prior art keywords
- hydrogenation
- acetylene
- solvent
- oil
- producing ethylene
- 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
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 93
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 title claims abstract description 78
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000005977 Ethylene Substances 0.000 title claims abstract description 65
- 239000002904 solvent Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 238000009835 boiling Methods 0.000 claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 20
- 238000005292 vacuum distillation Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 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 22
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 13
- 239000012071 phase Substances 0.000 description 13
- 239000002738 chelating agent Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 239000007791 liquid phase Substances 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 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
- 238000010668 complexation reaction Methods 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 150000001345 alkine derivatives Chemical class 0.000 description 4
- 230000000694 effects Effects 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
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-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
- 230000000536 complexating effect Effects 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
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical class 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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 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
- 239000010779 crude oil Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect 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
- 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
- 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
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 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
- 238000000935 solvent evaporation Methods 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a kind of solvent that adopted of producing ethylene with acetylene hydrogenation and method.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 with ethylene product in hydrogenation reaction, it is to avoid increase the detached cost of subsequent cell；Heat stability is good, does not decompose under reaction temperature, does not produce impurity, it is ensured that ethylene product quality；The solvent dissolves a certain amount of green oil, and acetylene hydrogenation can be suppressed to generate the reaction of 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 adopted it is molten
Agent and method.
Background technology
One of ethylene is a kind of important basic material in modern industry, and the maximum chemicals of world wide production.Ethylene
Yield becomes the mark for weighing a national oil development of chemical industry level, and its production capacity is counted as a national economy reality
The embodiment of power.
Ethylene is mainly obtained by the method for cracking petroleum hydrocarbon, and oil is a kind of non-renewable resources, and its price is with the world
Environmental change fluctuation is very big.The current annual petroleum consumption ranking the second in the world of China, the oil pair of China in 2015 in 2014
Outer interdependency respectively reaches 59.6% and 60.4%, defines serious strategy for this China not enriched to petroleum resources
Threaten.Therefore, find another kind of new source and process prepares large basic organic chemical raw material-ethylene, it is raw in industry
Product field petroleum replacing raw material, can alleviate China to a certain extent for the dependency of oil.
Although acetylene hydrogenation technology is extensively applied in hydrocarbon pyrolysis ethylene process, which is mainly used in removing hot tearing
A small amount of acetylene (0.1-1.0vol%) in solution technical process.To the rare exploration of high concentration producing ethylene with acetylene hydrogenation, corresponding industrialization
Large-scale application is even more and has no report.
Patent《CN 103044179 A》In to acetylene hydrogenation solvent from N-Methyl pyrrolidone, dimethylformamide,
Tetrahydrofuran and dimethyl sulfoxide etc..Patent《CN 105152842 A》The middle solvent for adopting is pyridine, imidazoles, N- methylpyrroles
Alkanone, C12 alkane or its isomer, benzene, naphthalene and biphenyl etc..
The basic principle that two patents are selected to solvent is all intended to be had compared with highly dissoluble to acetylene, molten to ethylene
Solution property is little, it is ensured that the ethylene that reaction is generated can leave system as early as possible in the form of bubbles, it is to avoid excessive hydrogenation.But actual anti-
Middle should find, the two selected solvent only has dissolubility to acetylene, little to the dissolubility of hydrogen, this is converted to improving reaction
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 a kind of solvent and the method adopted by producing ethylene with acetylene hydrogenation, described second
Solvent that alkynes Hydrogenation ethylene is adopted while all there is good dissolubility to acetylene and hydrogen, while to the green oil for producing
There is good dissolubility, greatly reduce the probability that green oil is covered in catalyst surface, extend catalyst life and suppress acetylene simultaneously
The reaction of green oil is hydrogenated to, boiling point is high, and saturated vapor is forced down, do not steamed with ethylene product in hydrogenation reaction, it is to avoid after increase
The detached cost of continuous unit, decreases the loss that solvent evaporation is caused；Heat stability is good, does not decompose under reaction temperature, does not produce
Raw impurity, it is ensured that ethylene product quality.
The second object of the present invention is that offer is a kind of to be carried out using the solvent adopted by described producing ethylene with acetylene hydrogenation
The method of producing ethylene with acetylene hydrogenation, the method process is simple can effectively suppress green oil to be covered in catalyst surface, further prevent
Only the deep hydrogenation of acetylene, improves the selectivity of ethylene, so as to increased yield of ethene.
In order to realize the above-mentioned purpose of the present invention, spy employs the following technical solutions：
A kind of solvent adopted by producing ethylene with acetylene hydrogenation, the solvent are hydrogenation tail oil.
The present invention is in order to solve problems of the prior art, there is provided a kind of special producing ethylene with acetylene hydrogenation is adopted
Solvent, the selection theory of the solvent is different from traditional approach, main to consider to suppress that green oil is generated, high temperature never degenerates and boiling point
High and heat-transfer effect it is good this some.The solvent adopted by producing ethylene with acetylene hydrogenation of the present invention is while all have very to acetylene and hydrogen
Good dissolubility, while the green oil to producing also has good dissolubility, greatly reduces green oil and is covered in the several of catalyst surface
Rate, extends catalyst life and suppresses acetylene hydrogenation to generate the reaction of green oil simultaneously, and boiling point is high, and saturated vapor is forced down, hydrogenation reaction
In do not steam with ethylene product, it is to avoid increase the detached cost of subsequent cell；Heat stability is good, does not decompose under reaction temperature, no
Produce impurity, it is ensured that ethylene product quality.
Preferably, the hydrogenation tail oil include wax oil from atmospheric and vacuum distillation unit second line of distillation, from atmospheric and vacuum distillation
The wax oil of device subtracts three line and one or more in the wax oil of atmospheric and vacuum distillation unit delayed coking unit, hydrogenated essence
Make and be hydrocracked the component of the ratio diesel oil weight for obtaining.
Preferably, the hydrogenation tail oil includes boiling range in 300 DEG C -600 DEG C of fraction.
It is further preferred that the hydrogenation tail oil includes boiling range in 320 DEG C -530 DEG C of fraction.
The method that producing ethylene with acetylene hydrogenation is carried out using above-mentioned solvent.
The method that the solvent adopted by the producing ethylene with acetylene hydrogenation provided using the present invention carries out producing ethylene with acetylene hydrogenation, this
Inventive method process is simple, can effectively suppress green oil to be covered in catalyst surface, further prevent the deep hydrogenation of acetylene, carry
The high selectivity of ethylene, so as to increased yield of ethene.
Preferably, the method is carried out using paste state bed reactor.
Preferably, the mol ratio of hydrogen and acetylene is 5-6:1, preferably 5-5.5:1, more preferably 5:1.
Preferably, the overall flow rate of hydrogen and acetylene is 1500-2000mL/min, preferably 1500mL/min-1600mL/
min。
Preferably, reaction temperature is 110-150 DEG C, preferably 120-130 DEG C.
Preferably, operating pressure is 0.4-1MPa, 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 problems of the prior art, there is provided a kind of special producing ethylene with acetylene hydrogenation is adopted
Solvent, the selection theory of the solvent is different from traditional approach, main to consider to suppress that green oil is generated, high temperature never degenerates and boiling point
High and heat-transfer effect it is good this some.The solvent adopted by producing ethylene with acetylene hydrogenation of the present invention is while all have very to acetylene and hydrogen
Good dissolubility, while the green oil to producing also has good dissolubility, greatly reduces green oil and is covered in the several of catalyst surface
Rate, extends catalyst life and suppresses acetylene hydrogenation to generate the reaction of green oil simultaneously, and boiling point is high, and saturated vapor is forced down, hydrogenation reaction
In do not steam with ethylene product, it is to avoid increase the detached cost of subsequent cell；Heat stability is good, does not decompose under reaction temperature, no
Produce impurity, it is ensured that ethylene product quality.
The method that the solvent adopted by the producing ethylene with acetylene hydrogenation provided using the present invention carries out producing ethylene with acetylene hydrogenation, this
Inventive method process is simple, can effectively suppress green oil to be covered in catalyst surface, further prevent the deep hydrogenation of acetylene, carry
The high selectivity of ethylene, so as to increased yield of ethene.
Specific embodiment
Technical scheme is clearly and completely described below in conjunction with specific embodiment, but ability
Field technique personnel will be understood that, following described embodiment is a part of embodiment of the invention, rather than the embodiment of whole,
The present invention is merely to illustrate, and is not construed as limiting the scope of the present invention.Based on the embodiment in the present invention, the common skill in this area
The every other embodiment obtained under the premise of creative work is not made by art personnel, belongs to the model of present invention protection
Enclose.Unreceipted actual conditions person in embodiment, the condition advised according to normal condition or manufacturer are carried out.Agents useful for same or instrument
Unreceipted production firm person, is the conventional products that can pass through that commercially available purchase is obtained.
The invention provides a kind of solvent adopted by producing ethylene with acetylene hydrogenation, the solvent is hydrogenation tail oil.
Hydrogenation tail oil is one of side-product of hydrogenation crude cracking, is called and does " unconverted oil or UCO ", refers to and split in hydrogenation
Uncracked saturated hydrocarbons during change.In prior art, the purposes of hydrogenation tail oil is mainly including following several：
1st, can be used for preparing ethylene by steam cracking raw material；
2nd, catalytic cracking feeds；
3rd, produce the lube base oil of high viscous index.
The present invention is in order to solve problems of the prior art, there is provided a kind of special producing ethylene with acetylene hydrogenation is adopted
Solvent, the selection theory of the solvent is different from traditional approach, main to consider to suppress that green oil is generated, high temperature never degenerates and boiling point
High and heat-transfer effect it is good this some.The solvent adopted by producing ethylene with acetylene hydrogenation of the present invention is while all have very to acetylene and hydrogen
Good dissolubility, while the green oil to producing also has good dissolubility, greatly reduces green oil and is covered in the several of catalyst surface
Rate, extends catalyst life and suppresses acetylene hydrogenation to generate the reaction of green oil simultaneously, and boiling point is high, and saturated vapor is forced down, hydrogenation reaction
In do not steam with ethylene product, it is to avoid increase the detached cost of subsequent cell；Heat stability is good, does not decompose under reaction temperature, no
Produce impurity, it is ensured that ethylene product quality.
Preferably, the hydrogenation tail oil include wax oil from atmospheric and vacuum distillation unit second line of distillation, from atmospheric and vacuum distillation
The wax oil of device subtracts three line and one or more in the wax oil of atmospheric and vacuum distillation unit delayed coking unit, hydrogenated essence
Make and be hydrocracked the component of the ratio diesel oil weight for obtaining.
Preferably, the hydrogenation tail oil includes boiling range in 300 DEG C -600 DEG C of fraction.
It is further preferred that the hydrogenation tail oil includes boiling range in 320 DEG C -530 DEG C of fraction.
The present invention selects the solvent adopted as producing ethylene with acetylene hydrogenation by hydrogenation tail oil fraction at a certain temperature, has
Help improve gained dissolubility of the solvent to acetylene, hydrogen and green oil, further reduce green oil and be covered in the several of catalyst surface
Rate, extends catalyst life and suppresses acetylene hydrogenation to generate the reaction of green oil simultaneously.
Invention also provides a kind of method for carrying out producing ethylene with acetylene hydrogenation using above-mentioned solvent.
The method that the solvent adopted by the producing ethylene with acetylene hydrogenation provided using the present invention carries out producing ethylene with acetylene hydrogenation, this
Inventive method process is simple, can effectively suppress green oil to be covered in catalyst surface, further prevent the deep hydrogenation of acetylene, carry
The high selectivity of ethylene, so as to increased yield of ethene.
Preferably, the method that the above-mentioned solvent of the employing of specific embodiment of the invention offer carries out producing ethylene with acetylene hydrogenation
Carried out using paste state bed reactor.
Paste state bed reactor is a kind of " gas-liquid phase " biphase haptoreaction system, and wherein gas phase is primarily as raw material
Hydrogen and acetylene, liquid phase includes the hydrogenation tail oil as solvent, also including catalyst, wherein catalyst may be selected solid catalysis
Agent or liquid-phase catalyst, its consumption can account for the 1%-10% of liquid phase gross mass, preferably account for the 1%-3% of liquid phase gross mass.
Preferably, the catalyst used by the specific embodiment of the invention includes complex state metallic catalyst, comprising activity
Metal center and chelating agent.
The active metal centre includes：Tungsten W, molybdenum Mo, manganese Mn, ferrum Fe, palladium Pd, platinum Pt, in silver-colored Ag and lanthanum La etc.
Plant or various, one or more preferably in palladium, manganese, ferrum.
The chelating agent is nitrilotriacetic acid, ethylenediaminetetraacetic acid, one or more in diethylenetriamine pentacarboxylic acid, preferably
For nitrilotriacetic acid or ethylenediaminetetraacetic acid.
In the preparation process of the complex state metallic catalyst, as metal ion is also easy to produce hydroxide at a high ph
Thing is precipitated, and can add stabilizer so as to the generation for preventing from precipitating, therefore, the complex state metallic catalyst can also be comprising few
The stabilizer of amount.
Preferably, the stabilizer includes one or more in anhydrous sorbitol, glucose and Fructose.The stabilizer
Consumption guaranteeing that metal ion does not produce precipitation, the property of the complex state metallic catalyst is kept in the response system
It is stable.
Preferably, the mol ratio of hydrogen and acetylene is 5-6:1, preferably 5-5.5:1, more preferably 5:1.
Preferably, the overall flow rate of hydrogen and acetylene is 1500-2000mL/min, preferably 1500mL/min-1600mL/
min。
Preferably, reaction temperature is 110-150 DEG C, preferably 120-130 DEG C.
Preferably, operating pressure is 0.4-1MPa, preferably 0.4-0.6MPa, more preferably 0.5MPa.
The hydrogenation tail oil being used in conjunction with the invention using above-mentioned special reaction condition carries out acetylene hydrogenation second as solvent
The method of alkene, helping lend some impetus to reaction is carried out, and improves conversion of alkyne and easy absorbance.
Preferably, the hydrogenation tail oil used by the specific embodiment of the invention is Beijing Huafu Engineering Co., Ltd to crude oil
The side-product 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 |
| Outward 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 |
| Mean molecule quantity | 462 |
Embodiment 1
A kind of method of producing ethylene with acetylene hydrogenation：
Using one section of paste state bed reactor, hydrogen and acetylene in the gas phase, are included；
The liquid phase is made up of following raw material：Boiling range in 300 DEG C -600 DEG C of hydrogenation tail oil fraction 99g, with nitrilotriacetic acid
For the complexation palladium 1g of chelating 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, had both obtained product.
Embodiment 2
A kind of method of producing ethylene with acetylene hydrogenation：
Using one section of paste state bed reactor, hydrogen and acetylene in the gas phase, are included；
The liquid phase is made up of following raw material：Boiling range in 300 DEG C -600 DEG C of hydrogenation tail oil fraction 95g, with ethylenediamine tetraacetic
Acetic acid is the complexation palladium 3g of chelating agent configuration, and ethylenediaminetetraacetic acid is the complexation manganese 1g of chelating agent configuration, and ethylenediaminetetraacetic acid is
The Complexing Iron 1g of chelating 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, had both obtained product.
Embodiment 3
A kind of method of producing ethylene with acetylene hydrogenation：
Using one section of paste state bed reactor, hydrogen and acetylene in the gas phase, are included；
The liquid phase is made up of following raw material：Boiling range in 320 DEG C -530 DEG C of hydrogenation tail oil fraction 99g, with nitrilotriacetic acid
For the complexation palladium 1g of chelating 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, had both obtained product.
Embodiment 4
A kind of method of producing ethylene with acetylene hydrogenation：
Using one section of paste state bed reactor, hydrogen and acetylene in the gas phase, are included；
The liquid phase is made up of following raw material：Boiling range in 320 DEG C -530 DEG C of hydrogenation tail oil fraction 95g, with ethylenediamine tetraacetic
Acetic acid is the complexation palladium 3g of chelating agent configuration, and ethylenediaminetetraacetic acid is the complexation manganese 1g of chelating agent configuration, and ethylenediaminetetraacetic acid is
The Complexing Iron 1g of chelating 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, had both obtained product.
The embodiment of the present invention and comparative example are detected using gas chromatography, and (comparative example 1 and comparative example 2 are successively respectively according to special
Technical scheme described in the embodiment 3 and embodiment 4 of sharp CN201510485015.6 carries out producing ethylene with acetylene hydrogenation) obtained by produce
Product, calculate the green oil content adhered on conversion of alkyne, yield of ethene, catalyst life and catalyst, testing result such as 2 institute of table
Show：
2 Product checking result of the present invention of table
| 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 the comparative example using 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 to generate green oil simultaneously
Reaction, improve the selectivity of ethylene, so as to increased yield of ethene.
Hydrogenation tail oil used in the present invention is as shown in table 3 with the boiling point of conventional producing ethylene with acetylene hydrogenation solvent：
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 adopts hydrogenation tail oil as the solvent of producing ethylene with acetylene hydrogenation, and its boiling point is high,
Saturated vapor is forced down, and will not be steamed with ethylene product in hydrogenation reaction, it is to avoid increase the detached cost of subsequent cell；Heat stability
It is good, do not decompose under reaction temperature, do not produce impurity, it is ensured that the quality of ethylene product；Additionally, hydrogenation tail oil is simultaneously to acetylene and hydrogen
Gas all has good dissolubility, while the green oil to producing also has good dissolubility, greatly reduces green oil and is covered in catalysis
The probability on agent surface, extends catalyst life and suppresses acetylene hydrogenation to generate the reaction of green oil simultaneously.
Although with specific embodiment illustrate and describing the present invention, but it will be appreciated that various embodiments above is only used
To illustrate technical scheme, rather than a limitation；It will be understood by those within the art that：Without departing substantially from this
In the case of bright spirit and scope, the technical scheme described in foregoing embodiments can be modified, or to wherein
Some or all of technical characteristic carries out equivalent；And these modifications or replacement, do not make the essence of appropriate technical solution
Depart from the scope of various embodiments of the present invention technical scheme；It is, therefore, intended that including in the following claims belonging to the present invention
In the range of all these substitutions and modifications.
Claims (10)
1. the solvent adopted by a kind of producing ethylene with acetylene hydrogenation, it is characterised in that the solvent is hydrogenation tail oil.
2. a kind of solvent adopted by producing ethylene with acetylene hydrogenation according to claim 1, it is characterised in that the hydrogenation tail
Oil includes wax oil from atmospheric and vacuum distillation unit second line of distillation, the wax oil from the atmospheric and vacuum distillation unit line that subtracts three and subtracts from often
One or more in the wax oil of pressure distilling apparatus delayed coking unit, it is hydrogenated refined and be hydrocracked obtain than diesel oil weight
Component.
3. a kind of solvent adopted by producing ethylene with acetylene hydrogenation according to claim 1, it is characterised in that the hydrogenation tail
Oil includes boiling range in 300 DEG C -600 DEG C of fraction.
4. a kind of solvent adopted by producing ethylene with acetylene hydrogenation according to claim 3, it is characterised in that the hydrogenation tail
Oil includes boiling range in 320 DEG C -530 DEG C of fraction.
5. the method for producing ethylene with acetylene hydrogenation being carried out using the arbitrary described solvent of claim 1-4.
6. method according to claim 5, it is characterised in that the method is carried out using paste state bed reactor.
7. method according to claim 5, it is characterised in that the mol ratio of hydrogen and acetylene is 5-6:1, preferably 5-
5.5:1, more preferably 5:1.
8. method according to claim 5, it is characterised in that the overall flow rate of hydrogen and acetylene is 1500-2000mL/min,
Preferably 1500mL/min-1600mL/min.
9. method according to claim 5, it is characterised in that reaction temperature is 110-150 DEG C, preferably 120-130 DEG C.
10. method according to claim 5, it is characterised in that operating pressure is 0.4-1MPa, preferably 0.4-
0.6MPa, more preferably 0.5MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611065574.2A CN106554805B (en) | 2016-11-28 | 2016-11-28 | Solvent and method used by a kind of producing ethylene with acetylene hydrogenation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611065574.2A CN106554805B (en) | 2016-11-28 | 2016-11-28 | Solvent and method used by a kind of producing ethylene with acetylene hydrogenation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106554805A true CN106554805A (en) | 2017-04-05 |
| CN106554805B CN106554805B (en) | 2018-04-20 |
Family
ID=58445380
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611065574.2A Active CN106554805B (en) | 2016-11-28 | 2016-11-28 | Solvent and method used by a kind of producing ethylene with acetylene hydrogenation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106554805B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115414865A (en) * | 2022-09-27 | 2022-12-02 | 溢通环保科技（莆田）有限公司 | Anti-settling polymerization inhibitor for diesel oil tail gas treatment fluid and production process thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2552078A1 (en) * | 1983-09-19 | 1985-03-22 | Inst Francais Du Petrole | PROCESS FOR SELECTIVE HYDROGENATION OF ACETYLENE CONTAINED IN A MIXTURE OF ACETYLENE AND ETHYLENE |
| US20090234167A1 (en) * | 2008-03-14 | 2009-09-17 | Catalytic Distillation Technologies | Process for converting methane to ethylene |
| FR2932177B1 (en) * | 2008-06-06 | 2012-11-30 | Inst Francais Du Petrole | METHOD FOR SELECTIVE HYDROGENATION ON A CATALYST CONTAINING GOLD. |
| 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 |
| CN104829406A (en) * | 2015-05-15 | 2015-08-12 | 北京神雾环境能源科技集团股份有限公司 | Method for preparing ethylene by heterogeneous reaction |
| CN105061130A (en) * | 2015-08-07 | 2015-11-18 | 北京神雾环境能源科技集团股份有限公司 | Liquid phase solvent for acetylene hydrogenation to ethylene slurry state bed |
| CN105152836A (en) * | 2015-08-28 | 2015-12-16 | 北京神雾环境能源科技集团股份有限公司 | Method using acetylene hydrogenation to produce ethylene |
| CN105152842A (en) * | 2015-08-07 | 2015-12-16 | 北京神雾环境能源科技集团股份有限公司 | Reaction system and method for preparing ethylene through acetylene hydrogenation |
| CN105859501A (en) * | 2016-06-08 | 2016-08-17 | 北京神雾环境能源科技集团股份有限公司 | Reaction system and method for preparing ethylene by means of solvent reclamation |
-
2016
- 2016-11-28 CN CN201611065574.2A patent/CN106554805B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2552078A1 (en) * | 1983-09-19 | 1985-03-22 | Inst Francais Du Petrole | PROCESS FOR SELECTIVE HYDROGENATION OF ACETYLENE CONTAINED IN A MIXTURE OF ACETYLENE AND ETHYLENE |
| US20090234167A1 (en) * | 2008-03-14 | 2009-09-17 | Catalytic Distillation Technologies | Process for converting methane to ethylene |
| FR2932177B1 (en) * | 2008-06-06 | 2012-11-30 | Inst Francais Du Petrole | METHOD FOR SELECTIVE HYDROGENATION ON A CATALYST CONTAINING GOLD. |
| 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 |
| CN104829406A (en) * | 2015-05-15 | 2015-08-12 | 北京神雾环境能源科技集团股份有限公司 | Method for preparing ethylene by heterogeneous reaction |
| CN105061130A (en) * | 2015-08-07 | 2015-11-18 | 北京神雾环境能源科技集团股份有限公司 | Liquid phase solvent for acetylene hydrogenation to ethylene slurry state bed |
| CN105152842A (en) * | 2015-08-07 | 2015-12-16 | 北京神雾环境能源科技集团股份有限公司 | Reaction system and method for preparing ethylene through acetylene hydrogenation |
| CN105152836A (en) * | 2015-08-28 | 2015-12-16 | 北京神雾环境能源科技集团股份有限公司 | Method using acetylene hydrogenation to produce ethylene |
| CN105859501A (en) * | 2016-06-08 | 2016-08-17 | 北京神雾环境能源科技集团股份有限公司 | Reaction system and method for preparing ethylene by means of solvent reclamation |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115414865A (en) * | 2022-09-27 | 2022-12-02 | 溢通环保科技（莆田）有限公司 | Anti-settling polymerization inhibitor for diesel oil tail gas treatment fluid and production process thereof |
| CN115414865B (en) * | 2022-09-27 | 2023-09-19 | 溢通环保科技（莆田）有限公司 | Anti-settling polymerization inhibitor for diesel exhaust treatment fluid and production process thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106554805B (en) | 2018-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106753549B (en) | A kind of method that the phenolic product hydrotreating of lignin depolymerization lightweight prepares HC fuel | |
| CN107235829B (en) | Method for preparing 4-ethylphenol by selective hydrogenolysis of lignin | |
| CN102614870B (en) | Vinylacetylene hydrogenation catalyst and preparation method thereof | |
| CN101940959A (en) | Regeneration method of catalyst for dehydrogenation of low-carbon alkanes | |
| CN104496943A (en) | Method for preparing dihydroxymethyl tetrahydrofuran | |
| CN110551278B (en) | Supported catalyst and preparation method and application thereof | |
| CN101920199B (en) | Fischer-Tropsch synthesis cobalt-based catalyst using modified silica gel as carrier and preparation method thereof | |
| CN106669799B (en) | The hydrocracking catalyst preparation method of maximum production low-coagulation diesel oil | |
| CN105566032A (en) | Alkyne-rich C4 selective hydrogenation technology | |
| CN107417485A (en) | A kind of method that hanging type tetrahydrochysene dicyclopentadiene is directly prepared by dicyclopentadiene | |
| CN105080563B (en) | A kind of hydrogenation catalyst and preparation method thereof | |
| CN105152842B (en) | A kind of acetylene hydrogenation prepares the reaction system and method for ethene | |
| CN109608304B (en) | Method for directly producing 1, 2-pentanediol by furfural hydrogenation | |
| CN106495991B (en) | A kind of method that industry dibenzofuran hydrofinishing prepares biphenyl and o-phenyl phenol | |
| CN106554805B (en) | Solvent and method used by a kind of producing ethylene with acetylene hydrogenation | |
| CN105732285A (en) | Selective hydrogenation method for C3 fraction | |
| CN102861583B (en) | Cobalt-based Fischer-Tropasch synthetic catalyst and preparation method | |
| CN102908957A (en) | Method for Fischer-Tropsch synthesis | |
| CN111514926A (en) | Molecular sieve catalyst, and preparation method and application thereof | |
| CN102211036A (en) | Modified molecular sieve catalyst, and precursor and preparation method thereof | |
| CN101768070A (en) | Method for synthesizing crylic acid by catalyzing acetylene carbonyl through palladium | |
| CN105727989A (en) | Preparation method of Pd-Ni-series supported hydrogenation catalyst | |
| CN111482177A (en) | Catalyst for preparing hydrogenated terphenyl and preparation method and application thereof | |
| CN102703118B (en) | Preparation method of diesel | |
| CN104725187A (en) | Technology for directly preparing ethyl alcohol and co-generating methane from synthesis gas |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20180104 Address after: Room 227, 2 floor, administrative service center, Huoerguosi City, Yili, the Xinjiang Uygur Autonomous Region, the Xinjiang Uygur Autonomous Region Applicant after: Huoerguosi road Cote ring Energy Technology Co.,Ltd. Address before: 102200 Beijing City, Changping District science and Technology Park Fukang Road No. 18 Applicant before: BEIJING HUAFU ENGINEERING Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20181114 Address after: 102200 No. 18 Fukang Road, Changping District science and Technology Park, Beijing Patentee after: BEIJING HUAFU ENGINEERING Co.,Ltd. Address before: 835000 the Xinjiang Uygur Autonomous Region Yili Kazakhstan Autonomous Prefecture, Huoerguosi administrative service center, 2 floor, 227 room. Patentee before: Huoerguosi road Cote ring Energy Technology Co.,Ltd. |
|
| PP01 | Preservation of patent right | ||
| PP01 | Preservation of patent right |
Effective date of registration: 20190625 Granted publication date: 20180420 |
|
| PD01 | Discharge of preservation of patent | ||
| PD01 | Discharge of preservation of patent |
Date of cancellation: 20220625 Granted publication date: 20180420 |
|
| PP01 | Preservation of patent right | ||
| PP01 | Preservation of patent right |
Effective date of registration: 20220625 Granted publication date: 20180420 |