CN110407660A - A kind of pretreating process and pretreatment system of the material carbon four for solid acid alkylation processes - Google Patents
A kind of pretreating process and pretreatment system of the material carbon four for solid acid alkylation processes Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 103
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 95
- 230000008569 process Effects 0.000 title claims abstract description 91
- 239000000463 material Substances 0.000 title claims abstract description 87
- 239000011973 solid acid Substances 0.000 title abstract description 41
- 238000005804 alkylation reaction Methods 0.000 title description 38
- 239000002994 raw material Substances 0.000 claims abstract description 115
- 239000003054 catalyst Substances 0.000 claims abstract description 62
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 48
- 230000018044 dehydration Effects 0.000 claims abstract description 45
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 45
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 42
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 42
- 238000005406 washing Methods 0.000 claims abstract description 34
- 238000012545 processing Methods 0.000 claims abstract description 30
- 238000001179 sorption measurement Methods 0.000 claims abstract description 23
- 239000003053 toxin Substances 0.000 claims abstract description 6
- 231100000765 toxin Toxicity 0.000 claims abstract description 6
- 238000010521 absorption reaction Methods 0.000 claims description 86
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 73
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 72
- 239000006096 absorbing agent Substances 0.000 claims description 67
- 238000006477 desulfuration reaction Methods 0.000 claims description 48
- 230000023556 desulfurization Effects 0.000 claims description 48
- 150000004767 nitrides Chemical class 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 22
- 239000007800 oxidant agent Substances 0.000 claims description 22
- 230000001590 oxidative effect Effects 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 21
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 18
- 230000015572 biosynthetic process Effects 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 239000000945 filler Substances 0.000 claims description 18
- 238000003786 synthesis reaction Methods 0.000 claims description 18
- 238000011049 filling Methods 0.000 claims description 16
- 229910052573 porcelain Inorganic materials 0.000 claims description 12
- 230000003009 desulfurizing effect Effects 0.000 claims description 11
- 229910052785 arsenic Inorganic materials 0.000 claims description 10
- 150000001993 dienes Chemical class 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 239000011593 sulfur Substances 0.000 claims description 9
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 8
- 230000008676 import Effects 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 5
- 238000006317 isomerization reaction Methods 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 239000003223 protective agent Substances 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 24
- 238000004519 manufacturing process Methods 0.000 abstract description 17
- 239000000203 mixture Substances 0.000 abstract description 12
- 230000002152 alkylating effect Effects 0.000 abstract description 8
- 239000000047 product Substances 0.000 description 55
- 238000005984 hydrogenation reaction Methods 0.000 description 33
- 239000010410 layer Substances 0.000 description 31
- 230000029936 alkylation Effects 0.000 description 24
- 230000000694 effects Effects 0.000 description 19
- 230000002779 inactivation Effects 0.000 description 17
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 16
- 238000004581 coalescence Methods 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 239000005864 Sulphur Substances 0.000 description 10
- 239000002253 acid Substances 0.000 description 10
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 10
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 9
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 9
- 239000006227 byproduct Substances 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 8
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- 229910052801 chlorine Inorganic materials 0.000 description 8
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 230000008929 regeneration Effects 0.000 description 6
- 238000011069 regeneration method Methods 0.000 description 6
- 239000001282 iso-butane Substances 0.000 description 5
- 235000013847 iso-butane Nutrition 0.000 description 5
- 238000012797 qualification Methods 0.000 description 5
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 5
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 3
- 239000011162 core material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000007781 pre-processing Methods 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- ZALMZWWJQXBYQA-UHFFFAOYSA-N [N].[Cl] Chemical compound [N].[Cl] ZALMZWWJQXBYQA-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/11—Purification; Separation; Use of additives by absorption, i.e. purification or separation of gaseous hydrocarbons with the aid of liquids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
- C07C7/13—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers by molecular-sieve technique
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention provides a kind of pretreating process of material carbon four, include the following steps, first by material carbon four after washing and dehydration, obtain step processing product；Then step processing product above-mentioned steps obtained obtains the two steps processing product of removing toxin after adsorption treatment；The two steps processing product that above-mentioned steps are obtained again carries out hydroprocessing, after then removing lighter hydrocarbons and oxygenatedchemicals, after comprehensive adsorption treatment, obtains three step process product；After the three step process product that finally above-mentioned steps are obtained is dehydrated again, pretreated material carbon four is obtained.The comprehensive pretreatment technique of carbon four after raw material ether provided by the invention for solid acid alkylating, it effectively can reduce and remove harmful impurity, it is fully able to the requirement for meeting solid acid catalyst for material composition, quantity-produced stability is greatly improved, production cost has been significantly reduced.And simple process is easily-controllable, mild condition, is suitable for industrialization promotion and application.
Description
Technical field
The present invention relates to solid acid alkylation processes technical field, be related to a kind of material carbon four pretreating process and pre- place
Reason system more particularly to a kind of pretreating process and pretreatment system of the material carbon four for solid acid alkylation processes.
Background technique
Alkylate oil is the product of one of petroleum refining process hydrocarbon-containifirst, is a kind of very ideal the most clean
High-knock rating gasoline blend component, the isoparaffin and alkene that PETROLEUM PROCESSING (such as thermal cracking or catalytic cracking process) is generated
(mainly iso-butane and butylene) alkyl under the action of strong acid catalyst (sulfuric acid or hydrofluoric acid) is combined to, motor octane number
Up to 95 or more, it is a kind of non-aromatics, non-olefinic, low-sulfur, low Reid Vapour Pressure, high-octane alkanes blend component.Separately
Outside, the boiling range of alkylate oil is very wide, meets the multiple requirements of reformulated gasoline, the even more harsh national oil product of the following state six
Standard can make the effect of alkylate oil further obvious.
Alkylation mainstream technology is at present；With liquid acid (HF or H2SO4, ionic liquid) be catalyst alkylation process, by
In the strong corrosive and toxicity of acid, the alkaline residue and acid sludge of production process generation can cause environment seriously to pollute.Solid dialkylaminobenzoic acid
Environment-friendly type alkylation techniques of the change technology as a new generation, not using the concentrated sulfuric acid as catalyst, and using platinum as active carrier, In
Acid centre is formed in catalyst carrier, to complete the reaction of carbon tetra-alkylation, realizes on-line regeneration after catalyst inactivation.The technology
The alkylate oil of production is no sulphur, non-olefin-containing, without aromatic hydrocarbon product, research octane number (RON) (RON) is good state up to 95 or more
V high grade clean gasoline blend component.
Solid acid alkylation processes technology is compared with traditional sulfuric acid process alkylation process, without waste oil, useless in production process
Acid generates, and completely eliminates sour oil, spent acid to safety problem caused by the pollution of environment and spent acid leakage, is really green
Color process for cleanly preparing, the subversiveness for realizing worldwide petrochemical industry this technology are broken through.Solid acid alkylating technology will be not
Carry out the trend of alkylation techniques.But solid acid alkylation catalysts are expensive, and more harsh to ingredient requirement, so right
Seem particularly important in the pretreatment of raw material, the integrity of raw material pretreatment process will directly determine solid acid alkylating device
The cycle of operation.And at present in actual production, raw material for alkylation is mainly carbon four after ether, and impurity is more, the impurity content of raw material
Far from the requirement for meeting catalyst, harsh pretreatment of raw material is needed.And the pretreatment of common raw material mostly uses greatly purification
Device or using exchanger resin remove to the harmful substance of catalyst in subsequent reactions, and due to after the ether as raw material carbon four at
Divide complexity, this mode can only often remove one such specific toxic component, other are inhibited with the ingredient of catalyst activities
There is no removals, cause catalyst inactivation serious, more lead to not continue to regenerate, not only reduce quantity-produced stability,
Also production cost is increased.
Therefore, the preprocess method for how finding carbon four after a kind of ether for raw material, reduces and removes harmful impurity, protect
Demonstrate,prove the continuous and steady operation of solid acid alkylating device, it has also become one of associated production enterprise urgent problem to be solved in field.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that provide a kind of material carbon four pretreating process and pre- place
Reason system, the pretreating process and pretreatment system of especially a kind of material carbon four for solid acid alkylation processes, this hair
Carbon four after bright pretreated ether, poisonous and hazardous impurity content are substantially reduced and eliminate, and are fully able to meet solid acid catalysis
Requirement of the agent for material composition, greatly improves quantity-produced stability, also reduces production cost.
The present invention provides a kind of pretreating process of material carbon four, comprising the following steps:
1) by material carbon four after washing and dehydration, step processing product is obtained；
2) after adsorption treatment, the two steps processing for obtaining removing toxin produces the step processing product obtained above-mentioned steps
Object；
3) the two steps processing product obtained above-mentioned steps carries out hydroprocessing, then removes lighter hydrocarbons and oxygenatedchemicals
Afterwards, after using comprehensive adsorption treatment, three step process product is obtained；
4) after the three step process product for obtaining above-mentioned steps is dehydrated again, pretreated material carbon four is obtained.
Preferably, the material carbon four is carbon four after ether；
The washing is washing methanol；
The temperature of the washing is 0~50 DEG C；
The pressure of the washing is 1.1~1.7MPa；
The methanol content in material carbon four after the washing is less than or equal to 50ppm.
Preferably, the mode of the dehydration is the dehydration of coarse separation formula；
The temperature of the dehydration is 0~50 DEG C；
The pressure of the dehydration is 1.1~1.8MPa；
The flow of the dehydration is less than or equal to the 95% of metered flow；
Water content in the dewatered material carbon four is less than or equal to 10ppm；
It further include drying steps after the dehydration；
The mode of the drying is dehydration and drying.
Preferably, the absorption includes absorption desulfurization and absorption dearsenification；
The mode of the absorption desulfurization is to adsorb desulfurization using desulfurizing agent；
The temperature of the absorption desulfurization is 0~50 DEG C；
The pressure of the absorption desulfurization is 0.8~1.6MPa；
The sulfur content in material carbon four after the absorption desulfurization is less than or equal to 1ppm；
The mode of the absorption dearsenification is to adsorb dearsenification using Hydrodearsenic Catalyst；
The temperature of the absorption dearsenification is 0~50 DEG C；
The pressure of the absorption dearsenification is 0.8~1.6MPa；
The arsenic content in material carbon four after the absorption dearsenification is less than or equal to 1ppm.
Preferably, the temperature of the hydroprocessing is 50~150 DEG C；
The pressure of the hydroprocessing is 0.8~2.5MPa；
The diene content in material carbon four after the hydroprocessing is less than or equal to 50ppm；
The temperature of the removing lighter hydrocarbons and oxygenatedchemicals is 80~150 DEG C；
The pressure of the removing lighter hydrocarbons and oxygenatedchemicals is 1.1~1.8MPa；
The oxygenatedchemicals removal efficiency of the removing lighter hydrocarbons and oxygenatedchemicals is more than or equal to 70%；
The comprehensive absorption includes in adsorbing and removing oxygenatedchemicals, adsorbing and removing chloride and adsorbing and removing nitride
It is one or more.
Preferably, the temperature of the comprehensive absorption is 0~50 DEG C；
The pressure of the comprehensive absorption is 0.8~1.6MPa；
The synthesis is adsorbed as using deoxidier adsorbing and removing oxygenatedchemicals, using antichlor adsorbing and removing chloride and
Using denitrifier adsorbing and removing nitride；
The content of the oxygenatedchemicals in material carbon four after the comprehensive absorption is less than or equal to 30ppmw, and chloride contains
Amount is less than or equal to 1ppmw, and the content of nitride is less than or equal to 1ppmw.
Preferably, the step 3) can be with are as follows:
The two steps processing product that above-mentioned steps are obtained is after comprehensive adsorption treatment, then carries out hydroprocessing, then takes off
After lighter hydrocarbons and oxide, three step process product is obtained.
The present invention provides a kind of pretreatment systems of material carbon four, comprising:
Water scrubber；
The coalescer being connected is exported with the water scrubber；
The dewatering dryer being connected is exported with the coalescer；
The absorber being connected is exported with the dewatering dryer；
The hydrogenator being connected is exported with the absorber；
The raw material lightness-removing column being connected is exported with the hydrogenator；
The synthesis absorber being connected is exported with the raw material lightness-removing column；
The second coalescer being connected is exported with the comprehensive absorber.
Preferably, the water scrubber is board-like water scrubber；
The column plate quantity of the water scrubber is 30~80 pieces；
The coalescer is vertical coalescer；
The filler of the dewatering dryer includes porcelain ball and molecular sieve；
The filler of the dewatering dryer is multiple filling layers；
The absorber includes the desulfurization absorber being connected with dewatering dryer outlet and adsorbs with the desulfurization
Device exports the dearsenification absorber being connected.
Preferably, the filler of the hydrogenator includes porcelain ball, isomerization catalyst and protective agent；
Antichlor and denitrogenation oxidant layer, the first deoxidation oxidant layer and the second deoxidation oxidant layer are provided in the comprehensive absorber；
The outlet of the absorber is also connected with the import of the comprehensive absorber；
The outlet of the comprehensive absorber is also connected with the import of the hydrogenator.
The present invention provides a kind of pretreating process of material carbon four, include the following steps, first pass through material carbon four
After washing and dehydration, step processing product is obtained；Then step above-mentioned steps obtained handles product after adsorption treatment,
Obtain the two steps processing product of removing toxin；The two steps processing product that above-mentioned steps are obtained again carries out hydrogenation reaction, then takes off
After lighter hydrocarbons and oxygenatedchemicals, after comprehensive adsorption treatment, three step process product is obtained；Finally above-mentioned steps are obtained
Three step process product be dehydrated again after, obtain pretreated material carbon four.Compared with prior art, the present invention is for existing
Ether after there are a variety of poisonous and harmful impurity contents in carbon four, the impurity content of raw material is far from the catalyst for meeting solid acid alkylating
Requirement, and common removal of impurities means can only remove the specific toxic component of a certain kind therein, inhibit catalyst to other
Active ingredient when causing for solid acid alkylating, causes catalyst inactivation serious, but will can not continue again there is no removing
It is raw, the defects of reducing quantity-produced stability, increase production cost.
The invention provides a kind of pretreating process of material carbon four, is a kind of synthesis for carbon four after ether
Pretreatment impurity removal process can effectively reduce especially for the requirement of the catalyst of solid acid alkylating and removal has
Harmful impurity is fully able to the requirement for meeting solid acid catalyst for material composition, greatly improves quantity-produced and stablizes
Property, it has been significantly reduced production cost.And pretreating process provided by the invention is simple and easy to control, corresponding pre-processing device
Not using popularization and low-producing complex device is difficult to, mild condition is particularly suitable for industrialization promotion and application.
The experimental results showed that pretreating process provided by the invention, treated material carbon four, impurity content is substantially reduced
Or eliminate, it is fully able to the requirement for meeting solid acid catalyst for material composition, wherein impurity butadiene content is 0, tertiary fourth
Alcohol content is 0.05ppm, and MTBE content is 0, methanol content 0.11ppm, sulfur content 0.5ppm, and diformazan ether content is
0.03ppm, chlorinity 0ppm, water content 0.6ppm.
Detailed description of the invention
Fig. 1 is the process flow provided by the present invention for the pretreating process of the material carbon four of solid acid alkylation processes
Schematic diagram.
Specific embodiment
In order to further appreciate that the present invention, the preferred embodiments of the invention are described below with reference to embodiment, but
It is it should be appreciated that these descriptions only require the invention patent to further illustrate the features and advantages of the present invention
Limitation.
All raw materials of the present invention, are not particularly limited its source, buying on the market or according to those skilled in the art
The preparation of conventional method known to member.
All raw materials of the present invention, are not particularly limited its purity, and present invention preferably employs technical pure or solid dialkylaminobenzoic acids
Change the purity of preparation field routine.
The expression of all nouns of the present invention and referred to as belong to this field routine noun expression and referred to as, each noun expression and
Referred to as in its related application field be it is explicit, those skilled in the art express and referred to as according to noun, Neng Gouqing
Chu is accurately uniquely understood.
The present invention provides a kind of pretreating process of material carbon four, comprising the following steps:
1) by material carbon four after washing and dehydration, step processing product is obtained；
2) after adsorption treatment, the two steps processing for obtaining removing toxin produces the step processing product obtained above-mentioned steps
Object；
3) the two steps processing product obtained above-mentioned steps carries out hydroprocessing, then removes lighter hydrocarbons and oxygenatedchemicals
Afterwards, after using comprehensive adsorption treatment, three step process product is obtained；
4) after the three step process product for obtaining above-mentioned steps is dehydrated again, pretreated material carbon four is obtained.
The present invention obtains step processing product first by material carbon four after washing and dehydration.
The material carbon four is not particularly limited in the present invention, with carbon four well known to those skilled in the art, mainly
Including normal butane and iso-butane, those skilled in the art can according to practical condition, raw material condition and product requirement into
Row selection and adjustment, material carbon four of the present invention are preferably carbon four after ether, i.e. etherification reaction falls the remaining carbon four of isobutene, main
If butene-1, butane, suitable anti-butene-2 etc., more preferably for carbon four after the ether of solid acid alkylation processes, concrete content
It may refer to table 1.Table 1 is carbon four after the raw material ether produced conventionally used for solid acid alkylation processes.
Table 1
The process and parameter of the washing is not particularly limited in the present invention, with well known to those skilled in the art water washed
Journey and parameter, those skilled in the art can select according to practical condition, raw material condition and product requirement
And adjustment, washing of the present invention preferably refer to washing methanol, i.e. washing removal methanol.The temperature of washing of the present invention is preferred
It is 0~50 DEG C, more preferably 10~40 DEG C, more preferably 20~30 DEG C.The pressure of the washing is preferably 1.1~1.7MPa,
More preferably 1.12~1.4MPa, more preferably 1.15~1.25MPa.
The present invention is to further increase pretreated effect, reduces solid acid alkylation catalysts inactivation rate, the washing
The methanol content in material carbon four afterwards is preferably smaller than equal to 50ppm, more preferably less than or equal to 40ppm, more preferably less than or equal to
30ppm。
The process and parameter of the dehydration is not particularly limited in the present invention, with well known to those skilled in the art dehydrated
Journey and parameter, those skilled in the art can select according to practical condition, raw material condition and product requirement
And adjustment, the mode of dehydration of the present invention are preferably the dehydration of coarse separation formula.The temperature of dehydration of the present invention is preferably 0~
50 DEG C, more preferably 30~50 DEG C, more preferably 35~45 DEG C.The pressure of the dehydration is preferably 1.1~1.8MPa, more preferably
For 1.1~1.7MPa, more preferably 1.12~1.4MPa, more preferably 1.15~1.25MPa.The flow of the dehydration is preferably small
In being equal to the 95% of metered flow, more preferably less than it is equal to the 90% of metered flow, is more preferably less than equal to metered flow
85%.
The present invention is to further increase pretreated effect, reduces solid acid alkylation catalysts inactivation rate, the dehydration
The water content in material carbon four afterwards is preferably smaller than equal to 10ppm, more preferably less than or equal to 8ppm, more preferably less than or equal to
5ppm。
The present invention is to further increase pretreated effect, reduces solid acid alkylation catalysts inactivation rate, complete and thin
Change technical process, it is also preferable to include drying steps after the dehydration.The mode of the drying is not particularly limited in the present invention, with
Drying mode well known to those skilled in the art, those skilled in the art can be according to practical conditions, raw material condition
And product requirement is selected and is adjusted, the mode of drying of the present invention is dehydration and drying, i.e., using dewatering dryer into
Row drying.The parameter of the drying is not particularly limited in the present invention, with drying parameter well known to those skilled in the art,
Those skilled in the art can select and adjust according to practical condition, raw material condition and product requirement, the present invention
The temperature of the drying is preferably 0~50 DEG C, more preferably 10~40 DEG C, more preferably 30~50 DEG C.The pressure of the drying
Preferably 1.1~1.8MPa, more preferably 1.3~1.6MPa, more preferably 1.45~1.55MPa.
The present invention is to further increase pretreated effect, reduces solid acid alkylation catalysts inactivation rate, the drying
The water content in material carbon four afterwards is preferably smaller than equal to 1ppm, more preferably less than or equal to 0.8ppm, more preferably less than or equal to
0.5ppm。
The step processing product that the present invention then obtains above-mentioned steps obtains the two of removing toxin after adsorption treatment
Step processing product.
The detailed process of the adsorption treatment is not particularly limited in the present invention, with absorption well known to those skilled in the art
The process of processing, those skilled in the art can select according to practical condition, raw material condition and product requirement
It selects and adjusts, absorption of the present invention preferably includes absorption desulfurization and adsorbs dearsenification.
The detailed process and parameter of the absorption desulfurization is not particularly limited in the present invention, known to those skilled in the art
Absorption desulfurization process and parameter, those skilled in the art can be according to practical condition, raw material condition and production
Product require to be selected and adjusted, and the mode of absorption desulfurization of the present invention preferably uses desulfurizing agent to adsorb desulfurization.The present invention
The temperature of the absorption desulfurization is preferably 0~50 DEG C, more preferably 10~40 DEG C, more preferably 20~30 DEG C.The absorption is de-
The pressure of sulphur is preferably 0.8~1.6MPa, more preferably 0.85~1.3MPa, more preferably 0.9~1.1MPa.
The present invention is to further increase pretreated effect, reduces solid acid alkylation catalysts inactivation rate, the absorption
The sulfur content in material carbon four after desulfurization is preferably smaller than equal to 1ppm, more preferably less than or equal to 0.8ppm, more preferably less than etc.
In 0.5ppm.
The detailed process and parameter of the absorption dearsenification is not particularly limited in the present invention, known to those skilled in the art
Absorption dearsenification process and parameter, those skilled in the art can be according to practical condition, raw material condition and production
Product require to be selected and adjusted, and the mode of absorption desulfurization of the present invention preferably uses Hydrodearsenic Catalyst to adsorb dearsenification.The present invention
The temperature of the absorption dearsenification is preferably 0~50 DEG C, more preferably 10~40 DEG C, more preferably 20~30 DEG C.The absorption is de-
The pressure of arsenic is preferably 0.8~1.6MPa, more preferably 0.85~1.3MPa, more preferably 0.9~1.1MPa.
The present invention is to further increase pretreated effect, reduces solid acid alkylation catalysts inactivation rate, the absorption
The arsenic content in material carbon four after dearsenification is preferably smaller than equal to 1ppb, more preferably less than or equal to 0.8ppb, more preferably less than etc.
In 0.5ppb.
The two steps processing product that the present invention again obtains above-mentioned steps carries out hydrogenation reaction, then removes lighter hydrocarbons and containing oxidation
After closing object, after comprehensive adsorption treatment, three step process product is obtained.
The detailed process and parameter of the hydrogenation reaction is not particularly limited in the present invention, known to those skilled in the art
Hydrogenation reaction process and parameter, those skilled in the art can be according to practical condition, raw material condition and production
Product require to be selected and adjusted, and the mode of absorption desulfurization of the present invention preferably uses Hydrodearsenic Catalyst to adsorb dearsenification.The present invention
The temperature of the hydrogenation reaction is preferably 50~150 DEG C, more preferably 60~140 DEG C, more preferably 65~125 DEG C.It is described to add
The pressure of hydrogen reaction is preferably 0.8~2.5MPa, more preferably 1.0~2.3MPa, more preferably 1.45~2.05MPa.
The present invention is to further increase pretreated effect, reduces solid acid alkylation catalysts inactivation rate, described plus hydrogen
The diene content in material carbon four after reaction is preferably smaller than equal to 50ppm, more preferably small more preferably less than or equal to 40ppm
In equal to 30ppm.The absorptivity of monoolefine in the hydrogenation process in material carbon four is preferably 100%.
The detailed process and parameter of the removing lighter hydrocarbons and oxygenatedchemicals is not particularly limited in the present invention, with this field
The process and parameter of removing lighter hydrocarbons and oxygenatedchemicals known to technical staff, those skilled in the art can be according to reality
The condition of production, raw material condition and product requirement are selected and are adjusted, removing lighter hydrocarbons and oxygenatedchemicals of the present invention
Temperature is preferably 80~150 DEG C, more preferably 90~140 DEG C, more preferably 100~120 DEG C.The removing lighter hydrocarbons and containing oxidation
The pressure for closing object is preferably 1.1~1.8MPa, more preferably 1.3~1.75MPa, more preferably 1.6~1.7MPa.
The present invention is to further increase pretreated effect, reduces solid acid alkylation catalysts inactivation rate, the removing
The removal efficiency of the oxygenatedchemicals of material carbon four is preferably greater than or equal to 70% during lighter hydrocarbons and oxygenatedchemicals, more preferably big
In being equal to 75%, more preferably greater than it is equal to 80%.
The detailed process and parameter of the comprehensive absorption is not particularly limited in the present invention, known to those skilled in the art
Comprehensive absorption process and parameter, those skilled in the art can be according to practical condition, raw material condition and production
Product require to be selected and adjusted, and comprehensive absorption of the present invention preferably includes adsorbing and removing oxygenatedchemicals, adsorbing and removing chlorine
One of compound and adsorbing and removing nitride are a variety of, more preferably adsorbing and removing oxygenatedchemicals, adsorbing and removing chloride
With it is a variety of in adsorbing and removing nitride, more preferably using deoxidier adsorbing and removing oxygenatedchemicals, adsorbed using antichlor
Chloride is removed and using a variety of in denitrifier adsorbing and removing nitride, most preferably using deoxidier adsorbing and removing containing oxidation
Close object, using antichlor adsorbing and removing chloride and using denitrifier adsorbing and removing nitride.
The oxygenatedchemicals is not particularly limited in the present invention, with carbon four after raw material ether well known to those skilled in the art
In the oxygenatedchemicals that contains or the issuable oxygenatedchemicals in above-mentioned treatment process, it is of the present invention to contain compound
It mainly include DME and MTBE.
The temperature of comprehensive absorption of the present invention is preferably 0~50 DEG C, more preferably 10~40 DEG C, more preferably 20~30
℃.The pressure of the comprehensive absorption is preferably 0.8~1.6MPa, more preferably 0.9~1.4MPa, more preferably 1.1~
1.3MPa。
The present invention is to further increase pretreated effect, reduces solid acid alkylation catalysts inactivation rate, the synthesis
The content of the oxygenatedchemicals in material carbon four after absorption is preferably smaller than equal to 30ppmw, more preferably less than or equal to 25ppmw,
More preferably less than or equal to 20ppmw；The content of the chloride in material carbon four after the comprehensive absorption is preferably smaller than equal to
1ppmw, more preferably less than or equal to 0.8ppmw, more preferably less than or equal to 0.5ppmw；In material carbon four after the comprehensive absorption
Nitride content preferably smaller than be equal to 1ppmw, more preferably less than or equal to 0.8ppmw, more preferably less than or equal to 0.5ppmw.
The process and parameter of the dehydration is not particularly limited in the present invention, with well known to those skilled in the art dehydrated
Journey and parameter, those skilled in the art can select according to practical condition, raw material condition and product requirement
And adjustment, the mode of dehydration of the present invention are preferably the dehydration of coarse separation formula.The temperature of dehydration of the present invention is preferably 0~
50 DEG C, more preferably 10~45 DEG C, more preferably 20~40 DEG C.The pressure of the dehydration is preferably 1.1~1.8MPa, more preferably
For 1.1~1.7MPa, more preferably 1.15~1.4MPa, more preferably 1.2~1.3MPa.The flow of the dehydration is preferably smaller than
Equal to the 95% of metered flow, more preferably less than it is equal to the 90% of metered flow, more preferably less than equal to metered flow
85%.
The present invention is to further increase pretreated effect, reduces solid acid alkylation catalysts inactivation rate, complete and thin
Change technical process, the step 3) can be with are as follows:
The two steps processing product that above-mentioned steps are obtained is after comprehensive adsorption treatment, then carries out hydrogenation reaction, then takes off
After lighter hydrocarbons and oxide, three step process product is obtained.
The above-mentioned detailed process by comprehensive adsorption treatment and parameter is not particularly limited in the present invention, with art technology
The process and parameter of comprehensive absorption known to personnel, those skilled in the art can be according to practical condition, raw material feelings
Condition and product requirement are selected and are adjusted, and comprehensive absorption of the present invention preferably includes adsorbing and removing oxygenatedchemicals, inhales
One of attached removing chloride and adsorbing and removing nitride are a variety of, and more preferably adsorbing and removing oxygenatedchemicals, absorption is de-
Except a variety of in chloride and adsorbing and removing nitride, more preferably using deoxidier adsorbing and removing oxygenatedchemicals, using de-
It is a variety of in chlorine agent adsorbing and removing chloride and use denitrifier adsorbing and removing nitride, it is most preferably de- using deoxidier absorption
Except oxygenatedchemicals, using antichlor adsorbing and removing chloride and using denitrifier adsorbing and removing nitride.
The temperature of the above-mentioned comprehensive absorption of the present invention is preferably 0~50 DEG C, more preferably 10~40 DEG C, more preferably 20~30
℃.The pressure of the comprehensive absorption is preferably 0.8~1.6MPa, more preferably 1.0~1.4MPa, more preferably 1.1~
1.3MPa。
The present invention is to further increase pretreated effect, reduces oxygenatedchemicals, nitride and chlorination in material carbon four
Influence of the object to subsequent handling reduces solid acid alkylation catalysts inactivation rate, the material carbon four after the comprehensive adsorption treatment
In oxygenatedchemicals content preferably smaller than be equal to 30ppmw, more preferably less than or equal to 25ppmw, more preferably less than or equal to
20ppmw；The content of the chloride in material carbon four after the comprehensive absorption is preferably smaller than equal to 1ppmw, more preferably less than etc.
In 0.8ppmw, more preferably less than or equal to 0.5ppmw；The content of the nitride in material carbon four after the comprehensive absorption is preferred
Less than or equal to 1ppmw, more preferably less than or equal to 0.8ppmw, more preferably less than or equal to 0.5ppmw.
The process being dehydrated again and parameter is not particularly limited in the present invention, with well known to those skilled in the art de-
Water process and parameter, those skilled in the art can carry out according to practical condition, raw material condition and product requirement
Selection and adjustment, the mode of the present invention being dehydrated again are preferably the dehydration of coarse separation formula.It is of the present invention to be again dehydrated
Temperature is preferably 0~50 DEG C, more preferably 10~45 DEG C, more preferably 20~40 DEG C.The pressure being dehydrated again is preferably
1.1~1.8MPa, more preferably 1.1~1.7MPa, more preferably 1.15~1.4MPa, more preferably 1.2~1.3MPa.It is described
The flow being dehydrated again is preferably smaller than equal to the 95% of metered flow, more preferably less than 90% equal to metered flow, more excellent
It is selected as 85% less than or equal to metered flow.
The present invention is to further increase pretreated effect, reduces solid acid alkylation catalysts inactivation rate, it is described again
Water content in dewatered material carbon four is preferably smaller than equal to 10ppm, more preferably less than or equal to 8ppm, more preferably less than or equal to
5ppm。
Specifically, the pretreating process of above-mentioned raw materials carbon four of the present invention can be as follows:
Washing methanol → coalescence dehydration → drying and dehydrating → absorption desulfurization → absorption dearsenification → hydrogenation dialkene removal → de- light
Hydrocarbon → synthesis absorption (deoxidation, chlorine, nitrogen) → coalescence dehydration → reaction system.
If the content of oxygenatedchemicals, chloride or nitride is higher in raw material, to ensure that hydrogenation dialkene removal is urged
Requirement of the agent to raw material, then the pretreating process process of above-mentioned raw materials carbon four can be as follows: washing methanol → coalescence is de-
Water → drying and dehydrating → absorption desulfurization → absorption dearsenification → synthesis absorption (deoxidation, chlorine, nitrogen) → hydrogenation dialkene removal → de- lighter hydrocarbons
→ coalescence dehydration → reaction system.
Above-mentioned steps of the present invention provide a kind of pretreating process of material carbon four, and material carbon four washes technique by methanol-water
It is washed, removes the methanol (< 50ppm) in raw material, into coalescence dewatering process dehydration (< 10ppm), be again introduced into dehydration
Drying process further dehydrates (< 1ppm), subsequently enters the sulphur in the desulfurization absorbing process abjection raw material with desulfurizing agent
(< 1ppm), raw material is again introduced into the dearsenification absorbing process with Hydrodearsenic Catalyst and carries out dearsenification (< 1ppb) after desulfurization, by processing
Raw material afterwards has reached impurity requirement of the hydrogenation catalyst to raw material, and the hydrogenation reaction technique that raw material enters removing alkadienes adds
Hydrogen removes alkadienes (< 50ppm), and the raw material after adding hydrogen enters de- light industry skill removing lighter hydrocarbons byproduct and most of oxide, then
It is secondary to be directed to oxide, chloride, nitride progress one by one into the synthesis absorbing process equipped with deoxidier, antichlor, denitrifier
Adsorbing and removing, the raw material after removing are again introduced into the water (< 10ppm) that coalescence dewatering process removing hydrogenation reaction generates, finally reach
Raw material after to qualification enters alkylated reaction system and is reacted.
The present invention also provides a kind of pretreatment systems of material carbon four, comprising:
Water scrubber；
The coalescer being connected is exported with the water scrubber；
The dewatering dryer being connected is exported with the coalescer；
The absorber being connected is exported with the dewatering dryer；
The hydrogenator being connected is exported with the absorber；
The raw material lightness-removing column being connected is exported with the hydrogenator；
The synthesis absorber being connected is exported with the raw material lightness-removing column；
The second coalescer being connected is exported with the comprehensive absorber.
The present invention is to the range of choice and optimum principle of route in the pretreatment system and parameter, with aforementioned pretreatment work
Route and the range of choice of parameter are consistent with optimum principle in skill, and this is no longer going to repeat them.
The mode being connected is not particularly limited in the present invention, with the side well known to those skilled in the art being connected
Formula, those skilled in the art can select and adjust according to practical condition, raw material condition and product requirement,
It is of the present invention be connected preferably refer to that the outlet of a certain equipment is connected with the import of another equipment, can be to be directly connected to,
Or it is connected by devices such as pipelines.
The selection of the water scrubber and parameter is not particularly limited in the present invention, with washing well known to those skilled in the art
Tower, those skilled in the art can select and adjust according to practical condition, raw material condition and product requirement,
Water scrubber of the present invention is preferably board-like water scrubber, more preferably single overflow sieve-plate tower.The number of plates of the board-like water scrubber
Preferably 30~80 pieces of amount, more preferably 40~70 pieces, more preferably 50~60 pieces.
The tower top temperature of water scrubber of the present invention is preferably 0~50 DEG C, and more preferably 10~40 DEG C, more preferably 20~
30 DEG C, the bottom temperature of the water scrubber is preferably 0~50 DEG C, more preferably 10~40 DEG C, more preferably 20~30 DEG C.It is described
The tower top pressure of water scrubber is preferably 1.1~1.7MPa, more preferably 1.12~1.4MPa, more preferably 1.15~1.25MPa.
The tower reactor pressure of the water scrubber is preferably 1.45~1.65MPa, more preferably 1.47~1.63MPa, more preferably 1.5~
1.6MPa。
The selection of the coalescer and parameter is not particularly limited in the present invention, with coalescence well known to those skilled in the art
Device, those skilled in the art can select and adjust according to practical condition, raw material condition and product requirement,
Coalescer of the present invention is preferably vertical coalescer.The filter core material of coalescer of the present invention is preferably polyester fiber.
The selection of the dewatering dryer and parameter is not particularly limited in the present invention, with well known to those skilled in the art
Dewatering dryer, those skilled in the art can select according to practical condition, raw material condition and product requirement
It selects and adjusts, dewatering dryer of the present invention is preferably material filling type dewatering dryer, more preferably filling out including multiple filling layers
Material formula dewatering dryer is specifically as follows 2 layers of filler.The filler of dewatering dryer of the present invention preferably includes porcelain ball and molecule
Sieve, is specifically as follows porcelain ball, 3A molecular sieve and 13X molecular sieve.
The selection of the absorber and parameter is not particularly limited in the present invention, with absorption well known to those skilled in the art
Device, those skilled in the art can select and adjust according to practical condition, raw material condition and product requirement,
Absorber of the present invention preferably includes desulfurization absorber and dearsenification absorber, is more preferably followed successively by desulfurization absorber and dearsenification is inhaled
Adnexa exports the desulfurization absorber being connected with the dewatering dryer and is connected with desulfurization absorber outlet de-
Arsenic absorber.
Desulfurization absorber of the present invention is preferably material filling type desulfurization absorber, more preferably includes the material filling type of multiple filling layers
Desulfurization absorber is specifically as follows 2 layers of filler.The filler of desulfurization absorber of the present invention preferably includes porcelain ball and desulfurizing agent.
Dearsenification absorber of the present invention is preferably material filling type dearsenification absorber, and the more preferably material filling type dearsenification including multiple filling layers is adsorbed
Device is specifically as follows 2 layers of filler.The filler of dearsenification absorber of the present invention preferably includes porcelain ball and Hydrodearsenic Catalyst.
The selection of the hydrogenator and parameter is not particularly limited in the present invention, with well known to those skilled in the art
Hydrogenator, those skilled in the art can select according to practical condition, raw material condition and product requirement
It selects and adjusts, hydrogenator of the present invention preferably uses II class container, more preferably material filling type hydrogenator, more preferably
Material filling type hydrogenator including single-layer or multi-layer filler.The filler of hydrogenator of the present invention preferably include porcelain ball,
Isomerization catalyst and protective agent.
The selection of the comprehensive absorber and parameter is not particularly limited in the present invention, with well known to those skilled in the art
Comprehensive absorber, those skilled in the art can select according to practical condition, raw material condition and product requirement
It selects and adjusts, comprehensive absorber of the present invention is preferably material filling type dewatering dryer, more preferably filling out including multiple filling layers
Material formula integrates absorber, is specifically as follows 3 layers of filler.
The present invention is to further increase pretreated effect, reduces solid acid alkylation catalysts inactivation rate, complete and thin
Change technical process, is preferably provided with antichlor and denitrogenation oxidant layer, the first deoxidation oxidant layer and the second deoxidation in the comprehensive absorber
Oxidant layer is more preferably preferably disposed with antichlor and denitrogenation oxidant layer, the first deoxidation oxidant layer and the second deoxidier along feedstock direction
Layer.Antichlor of the present invention and the filler of denitrogenation oxidant layer preferably include porcelain ball, antichlor and denitrifier.First deoxidier
The filler of layer preferably includes porcelain ball and deoxidier.The filler of the second deoxidation oxidant layer preferably includes porcelain ball and deoxidier.
The selection of second coalescer and parameter is not particularly limited in the present invention, with well known to those skilled in the art
Coalescer, those skilled in the art can be selected according to practical condition, raw material condition and product requirement and
Adjustment, the second coalescer of the present invention is preferably vertical coalescer.The filter core material of second coalescer of the present invention is preferred
For polyester fiber.
The present invention is to further increase pretreated effect, reduces solid acid alkylation catalysts inactivation rate, complete and thin
Change technical process, it is corresponding with the process route of aforementioned optimization, the outlet of the absorber also with the comprehensive absorber into
Mouth is connected；The outlet of the comprehensive absorber is also connected with the import of the hydrogenator.When in the material carbon four
Oxygenatedchemicals, chloride or nitride content it is higher when, two steps can be handled product and first passed through at comprehensive absorber
After reason, follow-up hydrogenation reactor is entered back into.
Above-mentioned steps of the present invention provide a kind of pretreatment system, in order to further increase pretreated effect, reduce solid
Body acid alkylation rate of catalyst deactivation, complete and process for refining process, specifically, the pretreatment system of above-mentioned raw materials carbon four of the present invention
System can be with are as follows:
1. material carbon four is washed tower by methanol-water and contacted with washing water progress vapour-liquid, the methanol in raw material is dissolved into washing water
In, to remove the methanol (< 50ppm) in raw material.
2. contacted since raw material has carried out vapour-liquid with water, from water scrubber come out raw material have a certain amount of water, by into
Enter to coalesce dehydrator and be dehydrated (< 10ppm), be again introduced into dewatering dryer and further dehydrate, ensures water content
≯1ppm。
3. dewatered raw material enters the desulfurization absorber with desulfurizing agent, the sulfide in raw material is adsorbed by desulfurizing agent
(< 1ppm).
4. raw material is again introduced into the dearsenification absorber with Hydrodearsenic Catalyst after desulfurization, absorption dearsenification (< is carried out by Hydrodearsenic Catalyst
1ppb)。
5. raw material after treatment, which has been removed water, sulphur, arsenic etc., influences the impurity of hydrogenation catalyst, reach hydrogenation catalyst
Impurity requirement of the agent to raw material, enters hydrogenator, under the pressure of 1.5mpa, hydrogenation and removing alkadienes after raw material boosting
(< 50ppm), and retain alkene.
6. plus the product after hydrogen has part lighter hydrocarbons byproduct, removes lighter hydrocarbons byproduct into lightness-removing column, while also removing
Most of oxide.
7. the raw material after removing lighter hydrocarbons be again introduced into equipped with deoxidier, antichlor, denitrifier synthesis adsorption tower needle one by one
Adsorbing and removing is carried out to oxide, chloride, nitride.The synthesis absorber can operate for double tower, mutually switching absorption (1
A absorption, 1 regeneration are spare).Raw material after removing is again introduced into the water (< that coalescence dehydrator removing hydrogenation reaction generates
10ppm), the raw material after finally reaching qualification enters alkylated reaction system and is reacted.
Referring to the pretreating process that Fig. 1, Fig. 1 are provided by the present invention for the material carbon four of solid acid alkylation processes
Process flow diagram.
Referring to table 2, table 2 is requirement of the typical solid acid catalyst to carbon four after raw material ether.Table 2
Above-mentioned steps of the present invention provide the pretreating process and pretreatment system of carbon four after a kind of raw material ether, and the present invention is special
Deoxidier, antichlor, denitrifier layering grading loading adsorption effect has not only been ensured into, but also save and set in a container
Standby investment and land occupation.And after hydrogenation dialkene removal, it is provided with lightness-removing column, which can remove lighter hydrocarbons and 70% or more simultaneously
Oxide can make the deoxidier service life of comprehensive absorber below extend 3 times or more；It is particularly provided with to be directed to and adds hydrogen de- two
Safeguard measure (separating methanol → coalescence dehydration → drying and dehydrating → desulfurization → dearsenification) before alkene, effective guarantee preprocessing process
In, the activity of the catalyst (noble metal) of hydrogenation dialkene removal is unaffected.In addition, also at the end of entire pretreatment of raw material process
Tail, then a coalescence dehydrator is set up, it, will when effectivelying prevent because of the comprehensive absorber steam regeneration switching maloperation in front or failure
Water brings way of escape alkylation reactor into, impacts to catalyst.The present invention be directed to wanting for the catalyst of solid acid alkylating
It asks, effectively can reduce and remove harmful impurity, be fully able to the requirement for meeting solid acid catalyst for material composition,
Quantity-produced stability is greatly improved, production cost has been significantly reduced.And pretreating process letter provided by the invention
Single easily-controllable, corresponding pre-processing device also is difficult to promote without use and low-producing complex device, mild condition are especially suitable for
In industrialization promotion and application.
The experimental results showed that pretreating process provided by the invention, treated material carbon four, impurity content is substantially reduced
Or eliminate, it is fully able to the requirement for meeting solid acid catalyst for material composition, wherein impurity butadiene content is 0, tertiary fourth
Alcohol content is 0.05ppm, and MTBE content is 0, methanol content 0.11ppm, sulfur content 0.5ppm, and diformazan ether content is
0.03ppm, chlorinity 0ppm, water content 0.6ppm.
In order to further illustrate the present invention, with reference to embodiments to a kind of pretreatment of material carbon four provided by the invention
Technique and pretreatment system are described in detail, but it is to be understood that these embodiments are before being with technical solution of the present invention
It puts and is implemented, the detailed implementation method and specific operation process are given, only the spy of the invention for further explanation
It seeks peace advantage, rather than limiting to the claimed invention, protection scope of the present invention are also not necessarily limited to following embodiments.
Embodiment 1
1 material composition
It include: propane 0.04% referring to raw material for alkylation C in table 1；Iso-butane 34.56%；11.8% pentane 0 of normal butane；
1- butylene 14.05%；Isobutene 0.14%；Along 2 butylene 15.38%；Butadiene 0；The tert-butyl alcohol 1.1%；MTBE 0.47%；First
Alcohol 2.83%；Sulphur 15.9ppm；Dimethyl ether 0；Chlorine is 0, As content 10ppb, water 2.3ppm.
2 treatment process
1. above-mentioned raw materials carbon four is washed tower by methanol-water to contact with washing water progress vapour-liquid, the methanol in raw material is dissolved into
In washing water, to remove the methanol (< 50ppm) in raw material.
Wherein, water scrubber is single overflow sieve-plate tower, and column plate quantity is 69, and the temperature of the tower top of water scrubber is 30 DEG C, washing
The pressure of the tower top of tower is 1.15MPa, and the temperature of the tower reactor of water scrubber is 25 DEG C, and the pressure of the tower reactor of water scrubber is 1.22MPa,
2. contacted since raw material has carried out vapour-liquid with water, from water scrubber come out raw material have a certain amount of water, by into
Enter to coalesce dehydrator and be dehydrated (< 10ppm), be again introduced into dewatering dryer and further dehydrate, ensures water content
≯1ppm。
Wherein, the temperature of dehydration is 30 DEG C, and the pressure of dehydration is 1.1MPa.
3. dewatered raw material enters the desulfurization absorber with desulfurizing agent, the sulfide in raw material is adsorbed by desulfurizing agent
(< 1ppm).
Wherein, the temperature of desulfurization is 25 DEG C, and the pressure of desulfurization is 0.9MPa.
4. raw material is again introduced into the dearsenification absorber with Hydrodearsenic Catalyst after desulfurization, absorption dearsenification (< is carried out by Hydrodearsenic Catalyst
1ppm)。
Wherein, the temperature of dearsenification is 25 DEG C, and the pressure of dearsenification is 0.9MPa.
5. raw material after treatment, which has been removed water, sulphur, arsenic etc., influences the impurity of hydrogenation catalyst, reach hydrogenation catalyst
Impurity requirement of the agent to raw material, enters hydrogenator, under the pressure of 1.5mpa, hydrogenation and removing alkadienes after raw material boosting
(< 50ppm), and retain alkene.
Wherein, the temperature of hydroprocessing is 53 DEG C, and the pressure of hydroprocessing is 1.95MPa.
6. plus the product after hydrogen has part lighter hydrocarbons byproduct, removes lighter hydrocarbons byproduct into lightness-removing column, while also removing
Most of oxide.
Wherein, the temperature for removing lighter hydrocarbons and oxygenatedchemicals is 103 DEG C, and the pressure for removing lighter hydrocarbons and oxygenatedchemicals is
1.67MPa。
7. the raw material after removing lighter hydrocarbons be again introduced into equipped with deoxidier, antichlor, denitrifier synthesis adsorption tower needle one by one
Adsorbing and removing is carried out to oxide, chloride, nitride.The synthesis absorber can operate for double tower, mutually switching absorption (1
A absorption, 1 regeneration are spare).
Wherein, comprehensive absorber is disposed with antichlor and denitrogenation oxidant layer, the first deoxidation oxidant layer and the along feedstock direction
Dideoxy oxidant layer.The temperature of comprehensive absorption is 25 DEG C, and the pressure of comprehensive absorption is 1.0MPa.
Raw material after removing is again introduced into the water (< 10ppm) that coalescence dehydrator removing hydrogenation reaction generates, and finally reaches
Raw material after qualification enters alkylated reaction system and is reacted.
Carbon four after the pretreated raw material ether of the embodiment of the present invention 1 is detected, the results showed that, pretreated raw material
In, butadiene content 0, t butanol content 0, MTBE content be 0, methanol content 0.43ppm, sulfur content 0.5ppm,
Diformazan ether content is 0, chlorinity 0, water content 0.6ppm, content of beary metal 0.
Embodiment 2
1 material composition
It include: propane 0.02% referring to raw material for alkylation A in table 1；Iso-butane 51.08%；Normal butane 8.73%；Pentane 0；
1- butylene 0%；Isobutene 0.01%；Along 2 butylene 11.09%；Anti- dibutene 18.88%；Butadiene 0；The tert-butyl alcohol 0；MTBE
8.58%；Methanol 1.7%；Sulphur 21.8ppm；Dimethyl ether 0；Chlorine is 0, water 0.8ppm.
2 treatment process
1. above-mentioned raw materials carbon four is washed tower by methanol-water to contact with washing water progress vapour-liquid, the methanol in raw material is dissolved into
In washing water, to remove the methanol (< 50ppm) in raw material.
Wherein, water scrubber is single overflow sieve-plate tower, and column plate quantity is 69, and the temperature of the tower top of water scrubber is 31 DEG C, washing
The pressure of the tower top of tower is 1.16MPa, and the temperature of the tower reactor of water scrubber is 26 DEG C, and the pressure of the tower reactor of water scrubber is 1.24MPa,
2. contacted since raw material has carried out vapour-liquid with water, from water scrubber come out raw material have a certain amount of water, by into
Enter to coalesce dehydrator and be dehydrated (< 10ppm), be again introduced into dewatering dryer and further dehydrate, ensures water content
≯1ppm。
Wherein, the temperature of dehydration is 31 DEG C, and the pressure of dehydration is 1.12MPa.
3. dewatered raw material enters the desulfurization absorber with desulfurizing agent, the sulfide in raw material is adsorbed by desulfurizing agent
(< 1ppm).
Wherein, the temperature of desulfurization is 26 DEG C, and the pressure of desulfurization is 0.92MPa.
4. raw material is again introduced into the dearsenification absorber with Hydrodearsenic Catalyst after desulfurization, absorption dearsenification (< is carried out by Hydrodearsenic Catalyst
1ppm)。
Wherein, the temperature of dearsenification is 25.5 DEG C, and the pressure of dearsenification is 0.91MPa.
5. raw material after treatment, which has been removed water, sulphur, arsenic etc., influences the impurity of hydrogenation catalyst, reach hydrogenation catalyst
Impurity requirement of the agent to raw material, enters hydrogenator, under the pressure of 1.5mpa, hydrogenation and removing alkadienes after raw material boosting
(< 50ppm), and retain alkene.
Wherein, the temperature of hydroprocessing is 54 DEG C, and the pressure of hydroprocessing is 1.96MPa.
6. plus the product after hydrogen has part lighter hydrocarbons byproduct, removes lighter hydrocarbons byproduct into lightness-removing column, while also removing
Most of oxide.
Wherein, the temperature for removing lighter hydrocarbons and oxygenatedchemicals is 104 DEG C, and the pressure for removing lighter hydrocarbons and oxygenatedchemicals is
1.68MPa。
7. the raw material after removing lighter hydrocarbons be again introduced into equipped with deoxidier, antichlor, denitrifier synthesis adsorption tower needle one by one
Adsorbing and removing is carried out to oxide, chloride, nitride.The synthesis absorber can operate for double tower, mutually switching absorption (1
A absorption, 1 regeneration are spare).
Wherein, comprehensive absorber is disposed with antichlor and denitrogenation oxidant layer, the first deoxidation oxidant layer and the along feedstock direction
Dideoxy oxidant layer.The temperature of comprehensive absorption is 26 DEG C, and the pressure of comprehensive absorption is 1.1MPa.
Raw material after removing is again introduced into the water (< 10ppm) that coalescence dehydrator removing hydrogenation reaction generates, and finally reaches
Raw material after qualification enters alkylated reaction system and is reacted.
Carbon four after the pretreated raw material ether of the embodiment of the present invention 2 is detected, the results showed that, pretreated raw material
In, butadiene content 0, t butanol content 0, MTBE content be 0, methanol content 0.43ppm, sulfur content 0.9ppm,
Diformazan ether content is 0, chlorinity 0, water content 0.6ppm, content of beary metal 0.
Embodiment 3
1 material composition
It include: propane 0.01% referring to raw material for alkylation B in table 1；Iso-butane 41.38%；Normal butane 10.81%；Pentane
0；1- butylene 0；Isobutene 0.01%；Along 2 butylene 14.21%；Anti- dibutene 20.35%；Butadiene 0；The tert-butyl alcohol 0.57；MTBE
0；Methanol 2.53%；Sulphur 20.9ppm；Dimethyl ether 0.91；Water 0.8ppm；Further include chlorine be 0.9ppm, nitrogen 1.0ppm.
2 treatment process
1. raw material after treatment, which has been removed water, sulphur, arsenic etc., influences the impurity of hydrogenation catalyst, reach hydrogenation catalyst
Agent is less than 0.5ppm nitrogen to chlorine maximum permissible concentration and is less than 1ppm to the requirement of the impurity of raw material, hydrogenation catalyst, thus need again into
The removing to chlorine nitrogen is carried out before entering hydrogenator.Technique requirement at this time is introduced into comprehensive absorber and adsorbs to chlorine nitrogen.
It it is directed to oxide, chloride, nitride is one by one adsorbed into the synthesis adsorption tower equipped with deoxidier, antichlor, denitrifier
Removing.The synthesis absorber can operate for double tower, mutually switching absorption (1 absorption, 1 regeneration are spare).
Wherein, comprehensive absorber is disposed with antichlor and denitrogenation oxidant layer, the first deoxidation oxidant layer and the along feedstock direction
Dideoxy oxidant layer.The temperature of comprehensive absorption is 26.5 DEG C, and the pressure of comprehensive absorption is 1.15MPa.
It is required that being to enter hydrogenator, under the pressure of 1.5mpa, hydrogenation and removing alkadienes (< after raw material boosts
50ppm), and retain alkene.
Wherein, the temperature of hydroprocessing is 55 DEG C, and the pressure of hydroprocessing is 1.99MPa.
2. plus the product after hydrogen has part lighter hydrocarbons byproduct, removes lighter hydrocarbons byproduct into lightness-removing column, while also removing
Most of oxide.
Wherein, the temperature for removing lighter hydrocarbons and oxygenatedchemicals is 103.5 DEG C, and the pressure for removing lighter hydrocarbons and oxygenatedchemicals is
1.64MPa。
3. the raw material after removing lighter hydrocarbons is again introduced into the water (< 10ppm) that coalescence dehydrator removing hydrogenation reaction generates, most
Raw material after reaching qualification afterwards enters alkylated reaction system and is reacted.
Carbon four after carrying out raw material ether before 3 pre-hydrogenator of the embodiment of the present invention is detected, after pretreated raw material ether
Carbon four is detected, the results showed that chlorinity 0.01ppm, nitrogen content 0.05ppm.In pretreated raw material, butadiene contains
Amount is 0, t butanol content 0, and MTBE content is 0, methanol content 0.23ppm, sulfur content 0.2ppm, and diformazan ether content is
0, chlorinity 0.01ppm, nitrogen content 0.05ppm, water content 0.6ppm, content of beary metal 0.
Pretreating process to a kind of material carbon four for solid acid alkylation processes provided by the invention and pre- above
Processing system is described in detail, and specific case used herein explains the principle of the present invention and embodiment
It states, the above description of the embodiment is only used to help understand the method for the present invention and its core ideas, including best mode, and
But also any person skilled in the art can practice the present invention, including any device or system of manufacture and use, and real
The method for applying any combination.It should be pointed out that for those skilled in the art, not departing from the principle of the invention
Under the premise of, it can be with several improvements and modifications are made to the present invention, these improvement and modification also fall into the claims in the present invention
Protection scope in.The range of the invention patent protection is defined by the claims, and may include those skilled in the art's energy
The other embodiments enough expected.If there is these other embodiments the structure for being not different from claim character express to want
Element, or if they include the equivalent structural elements with the character express of claim without essence difference, these other
Embodiment should also be included in the scope of the claims.
Claims (10)
1. a kind of pretreating process of material carbon four, which comprises the following steps:
1) by material carbon four after washing and dehydration, step processing product is obtained；
2) step processing product obtained above-mentioned steps obtains the two steps processing product of removing toxin after adsorption treatment；
3) the two steps processing product obtained above-mentioned steps carries out hydroprocessing, after then removing lighter hydrocarbons and oxygenatedchemicals, then
After comprehensive adsorption treatment, three step process product is obtained；
4) after the three step process product for obtaining above-mentioned steps is dehydrated again, pretreated material carbon four is obtained.
2. pretreating process according to claim 1, which is characterized in that the material carbon four is carbon four after ether；
The washing is washing methanol；
The temperature of the washing is 0~50 DEG C；
The pressure of the washing is 1.1~1.7MPa；
The methanol content in material carbon four after the washing is less than or equal to 50ppm.
3. pretreating process according to claim 1, which is characterized in that the mode of the dehydration is de- for coarse separation formula
Water；
The temperature of the dehydration is 0~50 DEG C；
The pressure of the dehydration is 1.1~1.8MPa；
The flow of the dehydration is less than or equal to the 95% of metered flow；
Water content in the dewatered material carbon four is less than or equal to 10ppm；
It further include drying steps after the dehydration；
The mode of the drying is dehydration and drying.
4. pretreating process according to claim 1, which is characterized in that the absorption includes that absorption desulfurization and absorption are de-
Arsenic；
The mode of the absorption desulfurization is to adsorb desulfurization using desulfurizing agent；
The temperature of the absorption desulfurization is 0~50 DEG C；
The pressure of the absorption desulfurization is 0.8~1.6MPa；
The sulfur content in material carbon four after the absorption desulfurization is less than or equal to 1ppm；
The mode of the absorption dearsenification is to adsorb dearsenification using Hydrodearsenic Catalyst；
The temperature of the absorption dearsenification is 0~50 DEG C；
The pressure of the absorption dearsenification is 0.8~1.6MPa；
The arsenic content in material carbon four after the absorption dearsenification is less than or equal to 1ppm.
5. pretreating process according to claim 1, which is characterized in that the temperature of the hydroprocessing is 50~150 DEG C；
The pressure of the hydroprocessing is 0.8~2.5MPa；
The diene content in material carbon four after the hydroprocessing is less than or equal to 50ppm；
The temperature of the removing lighter hydrocarbons and oxygenatedchemicals is 80~150 DEG C；
The pressure of the removing lighter hydrocarbons and oxygenatedchemicals is 1.1~1.8MPa；
The oxygenatedchemicals removal efficiency of the removing lighter hydrocarbons and oxygenatedchemicals is more than or equal to 70%；
The comprehensive absorption includes one of adsorbing and removing oxygenatedchemicals, adsorbing and removing chloride and adsorbing and removing nitride
Or it is a variety of.
6. pretreating process according to claim 5, which is characterized in that the temperature of the comprehensive absorption is 0~50 DEG C；
The pressure of the comprehensive absorption is 0.8~1.6MPa；
The synthesis is adsorbed as using deoxidier adsorbing and removing oxygenatedchemicals, using antichlor adsorbing and removing chloride and use
Denitrifier adsorbing and removing nitride；
The content of the oxygenatedchemicals in material carbon four after the comprehensive absorption is less than or equal to 30ppmw, and the content of chloride is small
In being equal to 1ppmw, the content of nitride is less than or equal to 1ppmw.
7. pretreating process according to claim 1, which is characterized in that the step 3) can be with are as follows:
The two steps processing product that above-mentioned steps are obtained is after comprehensive adsorption treatment, then carries out hydroprocessing, and then removing is light
After hydrocarbon and oxide, three step process product is obtained.
8. a kind of pretreatment system of material carbon four characterized by comprising
Water scrubber；
The coalescer being connected is exported with the water scrubber；
The dewatering dryer being connected is exported with the coalescer；
The absorber being connected is exported with the dewatering dryer；
The hydrogenator being connected is exported with the absorber；
The raw material lightness-removing column being connected is exported with the hydrogenator；
The synthesis absorber being connected is exported with the raw material lightness-removing column；
The second coalescer being connected is exported with the comprehensive absorber.
9. pretreatment system according to claim 8, which is characterized in that the water scrubber is board-like water scrubber；
The column plate quantity of the water scrubber is 30~80 pieces；
The coalescer is vertical coalescer；
The filler of the dewatering dryer includes porcelain ball and molecular sieve；
The filler of the dewatering dryer is multiple filling layers；
The absorber includes the desulfurization absorber being connected with dewatering dryer outlet and goes out with the desulfurization absorber
The dearsenification absorber that mouth is connected.
10. pretreatment system according to claim 8, which is characterized in that the filler of the hydrogenator include porcelain ball,
Isomerization catalyst and protective agent；
Antichlor and denitrogenation oxidant layer, the first deoxidation oxidant layer and the second deoxidation oxidant layer are provided in the comprehensive absorber；
The outlet of the absorber is also connected with the import of the comprehensive absorber；
The outlet of the comprehensive absorber is also connected with the import of the hydrogenator.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111892480A (en) * | 2020-08-07 | 2020-11-06 | 浙江三美化工股份有限公司 | Preparation method of 1-chloro-3, 3, 3-trifluoropropene |
| CN114426884A (en) * | 2020-09-27 | 2022-05-03 | 中国石油化工股份有限公司 | Dechlorination method of unsaturated C4 hydrocarbon raw material |
| CN115253430A (en) * | 2022-07-27 | 2022-11-01 | 安徽益沣石化有限公司 | Pretreatment device in carbon four production process |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1639089A (en) * | 2002-02-28 | 2005-07-13 | 斯东及韦伯斯特公司 | Production of alkyl aromatic compounds |
| CN105152840A (en) * | 2015-09-14 | 2015-12-16 | 中国成达工程有限公司 | Process for refining C-4 hydrocarbon fluid |
| CN105601460A (en) * | 2015-12-21 | 2016-05-25 | 中国石油大学(北京) | Refining method of alkylation feedstock |
| CN112143518A (en) * | 2019-06-27 | 2020-12-29 | 中国石油化工股份有限公司 | Solid acid alkylation method for producing gasoline |
| CN112143519A (en) * | 2019-06-27 | 2020-12-29 | 中国石油化工股份有限公司 | Solid acid alkylation of isoparaffin with olefin |
-
2018
- 2018-04-28 CN CN201810399472.7A patent/CN110407660B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1639089A (en) * | 2002-02-28 | 2005-07-13 | 斯东及韦伯斯特公司 | Production of alkyl aromatic compounds |
| CN105152840A (en) * | 2015-09-14 | 2015-12-16 | 中国成达工程有限公司 | Process for refining C-4 hydrocarbon fluid |
| CN105601460A (en) * | 2015-12-21 | 2016-05-25 | 中国石油大学(北京) | Refining method of alkylation feedstock |
| CN112143518A (en) * | 2019-06-27 | 2020-12-29 | 中国石油化工股份有限公司 | Solid acid alkylation method for producing gasoline |
| CN112143519A (en) * | 2019-06-27 | 2020-12-29 | 中国石油化工股份有限公司 | Solid acid alkylation of isoparaffin with olefin |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111892480A (en) * | 2020-08-07 | 2020-11-06 | 浙江三美化工股份有限公司 | Preparation method of 1-chloro-3, 3, 3-trifluoropropene |
| CN114426884A (en) * | 2020-09-27 | 2022-05-03 | 中国石油化工股份有限公司 | Dechlorination method of unsaturated C4 hydrocarbon raw material |
| CN114426884B (en) * | 2020-09-27 | 2024-02-13 | 中国石油化工股份有限公司 | Dechlorination method of unsaturated C4 hydrocarbon raw material |
| CN115253430A (en) * | 2022-07-27 | 2022-11-01 | 安徽益沣石化有限公司 | Pretreatment device in carbon four production process |
| CN115253430B (en) * | 2022-07-27 | 2023-04-07 | 安徽益沣石化有限公司 | Pretreatment device in carbon four production process |
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