CN103361121A - Production method of high-octane gasoline blending component - Google Patents
Production method of high-octane gasoline blending component Download PDFInfo
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- CN103361121A CN103361121A CN2012100977775A CN201210097777A CN103361121A CN 103361121 A CN103361121 A CN 103361121A CN 2012100977775 A CN2012100977775 A CN 2012100977775A CN 201210097777 A CN201210097777 A CN 201210097777A CN 103361121 A CN103361121 A CN 103361121A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 239000003502 gasoline Substances 0.000 title claims abstract description 15
- 238000002156 mixing Methods 0.000 title claims abstract description 6
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 33
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 32
- 230000029936 alkylation Effects 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 24
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 17
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000001336 alkenes Chemical class 0.000 claims abstract description 13
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 11
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 7
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 238000011084 recovery Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000000567 combustion gas Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000011133 lead Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 239000011973 solid acid Substances 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 239000003921 oil Substances 0.000 claims 2
- 239000004411 aluminium Substances 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 31
- 238000000926 separation method Methods 0.000 abstract description 10
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 8
- 238000011160 research Methods 0.000 abstract description 8
- 239000002737 fuel gas Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 13
- 238000002474 experimental method Methods 0.000 description 8
- 238000012545 processing Methods 0.000 description 7
- -1 C 4 olefin Chemical class 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000009434 installation Methods 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
Images
Classifications
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- 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
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
- C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
- C10G69/12—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step
- C10G69/123—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step alkylation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
- C10L1/06—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for spark ignition
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/305—Octane number, e.g. motor octane number [MON], research octane number [RON]
-
- 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
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a production method of a high-octane gasoline blending component; C4-C8 mixed alkane and C4 olefin raw materials enter an isomerization reaction device and are subjected to an isomerization reaction under the hydrogen condition through an isomerization catalyst catalytic reaction; the isomerization material flow generated by the reaction enters a hydrogen separation device; the separated hydrogen and the supplemented fresh hydrogen are mixed and then return to the isomerization reaction device; the liquid hydrocarbon and the raw material isomeric C4 olefin are separated and enter an alkylation device; the alkylation material flow generated under the catalysis of the alkylation catalyst enters an alkylation catalyst recovery device, and C4-C6 light hydrocarbon, catalyst and C8-C12 alkylation product material flow are obtained through separation; the separated C4-C6 light hydrocarbon material flow is sent to fuel gas or is recycled after being separated; returning one part of the separated catalyst material flow to an alkylation device, and taking the other part out of the boundary area; the method widens the raw material source, reduces the production cost, and the research octane number of the obtained alkylate reaches 91.5.
Description
Technical field
The invention belongs to the production technique in refining of petroleum field, more particularly, is a kind of production method of stop bracket gasoline blend component.
Background technology
The future development of unleaded, the low aromatic hydrocarbons of gasoline quality standard forward, low-steam pressure, high-octane rating and elevated oxygen level.Isomerization and alkylation are widely used in petroleum refining process, and the gasoline blending component of high-octane rating and don't increase gasoline aromaticity content can be provided.
So-called isomerization is exactly under certain reaction conditions, and normal paraffin is converted into the formation of isoparaffin through the catalyzed reaction of catalyzer.Because the isomerized alkyl knock resistance is good, the more corresponding normal paraffin of general octane value is high, so be good stop bracket gasoline blend component.The part isoparaffin can also be as the raw material of alkylation process simultaneously.
So-called alkylation is exactly alkane and alkene generate macromole isomery chain hydrocarbon through addition reaction process.Alkylate is owing to often form tertiary carbon and side chain is many, and knock resistance is good, and octane value is higher, is extraordinary stop bracket gasoline blend component.Through development for many years, formed the one-tenth production art of comparative maturity.
Since this year raw material sources worse and worse and more and more higher oil quality requirement, to the exploitation of the research of above-mentioned production process and catalyzer of new generation be still oil-refining chemical hot fields it
The product of isomerization process is because also can be used as the raw material of alkylation process, and the simple series connection of two processes is also much like this.Owing to can on flow process, further simplify after two process series connection, reduced energy consumption, improved to a certain extent economic benefit.Some improvement on flow process are constantly by the work report.
Some work is sought to improve in sepn process, in C4 isomerization reaction product separation process, introduce the membrane sepn process such as patent CN200680015930.8, namely reduced energy consumption and improved separation efficiency, be conducive to again reduce isomerization catalyst and enter the interference that alkylated reaction partly brings.But this separation method only is confined to feed composition better simply the time, for then helpless such as the C5-C6 parallel feeding.
Some work is devoted to improve selectivity of product and yield by the control that improves reaction conditions.Reported a kind of method that in downflow reactor, prepares alkylate such as patent CN200710161288.0.Using such method, alkene oligomer play the alkene precursor and the effect of non-olefinic in reaction.
A small amount of work of being devoted to integrated isomerousization and alkylation engineering does not have to break away from the dependence for forming comparatively simple raw material yet, in other words for C4, particularly the above petroleum naphtha component of the C5 process of producing as raw material does not provide further Optimizing Flow.Disclose the combined method of a kind of isomerization and alkylation process such as patent US7439410, but be confined to the C3-C4 raw material.Because may cause such as systemic problems such as inert component accumulative totals, and can't be applicable to the above raw material of C5.
Sum up above-mentioned improvement on alkylation and isomerization process, still have the following disadvantages:
1. mainly towards the C4 raw material.The appearance of alkylation process had once been found a good outlet for refining plant C 4, and the alkylate oil that can be used as the stop bracket gasoline blend component is more much higher than the economic worth that liquefied gas has.Therefore often the research work of this respect stresses the utilization of C4 component, and the C5-C6 component is only accomplished to take into account.
2. to the parallel feeding poor processing effect.Existing procedure only adapts to the narrow fraction charging, is not suitable with the parallel feeding of C4-C8 wide fraction.When processing the wide fraction parallel feeding, to only part utilization of unreacting material, energy consumption is high, and the alkylate oil octane value is low.
3. flow process is complicated.Isomerization and alkylation as two independently technological process grow up.Existing research often is conceived to the research of existing apparatus, fails fundamentally to integrate the angle of two processes and works.Therefore technical process is still aobvious complicated.
Along with increasing of carbonatoms, the isomer number that begins hydro carbons from C6 sharply increases.And for such as the parallel feeding of petroleum naphtha component, because the ingredient kind is complicated, can not be applied simply in the technique of the comparative maturity aspect C4 isomerization, the alkylation.Particularly normal paraffin has brought very large difficulty with the product separation that separates to isomerization process of isoparaffin in the blending ingredients.The enrichment of some inert component also is unexistent in the C4 process.
For above problem, only carry out the work in independent process, be helpless to solution of problem.Integrating and improve from the source then is thinking preferably.
Summary of the invention
The production method that the purpose of this invention is to provide a kind of stop bracket gasoline blend component is take C4-C8 mixed alkanes and C4 alkene as raw material.Raw material is through once generating alkylate oil by isomerization and alkylation process, and only unreacted hydrogen and a small amount of C3-C4 light constituent need through simple separation therebetween.Technical process is oversimplified most.Particularly solve the processing problem of wide fraction parallel feeding, adopt Reaction Separation, a small amount of unreacting material is reusable edible both, also can directly enter product.Adapt to the refinery and produce reality, widened raw material sources, greatly reduce production costs.Product alkylate oil octane value is high simultaneously, has guaranteed good economic benefit.
Olefin(e) centent should be lower than 10% in the C4-C8 paraffinic feedstock, and oxygenate is limited in 50ppm or lower, and general sulphur content is less than 20ppm.C4-C8 mixed alkanes and C4 olefin feed stream 101 enter isomerization reaction device 10.Under hydro condition, carry out isomerization reaction through the isomerization catalyst catalyzed reaction.Catalyzer is the loaded catalyst of VIII family metal, and the VIII precious metal is platinum especially.Charge capacity is that 0.01-5% (quality percentage composition) preferably is no more than 0.50% with at least 0.15%.Comprise one or more in the promoter metal, for example: tin, lead, iron, cobalt, tungsten, molybdenum, plug with molten metal, copper, silver, cadmium, bismuth, or multiple lucium, the quality percentage composition is 0.01～1%.The processing condition that adopt are that the hydrogen dividing potential drop is 0.5-2.5MPa, and temperature is 150-280 ℃, and mass space velocity is 0.2-5.5 hour
-1, hydrogen to oil volume ratio is 400-600, system pressure is 4-12MPa.The isomerization logistics 102 that reaction generates enters hydrogen tripping device 20.Separating obtained hydrogen logistics 103 mixes rear 114 with the fresh hydrogen 113 that replenishes and returns isomerization unit 10.Separating obtained liquid hydrocarbon 104 and raw material isomery C4 alkene 105 enter alkyl plant 30.Iso-butylene content is greater than 75% in the isomery C4 alkene, and sulphur content is less than 20ppm.The alkylation logistics 106 that generates under alkylation catalyst catalysis enters alkylation catalyst retrieving arrangement 40.Separate and obtain C4-C6 lighter hydrocarbons 107, catalyzer 108, C8-C12 alkylate logistics 109.Combustion gas or recycle after separating are sent in separating obtained C4-C6 lighter hydrocarbons logistics 107.The part 116 of separating obtained catalyst stream is returned alkyl plant 30, and another part 115 goes out the battery limit (BL).Alkylation catalyst is a kind of in sulfuric acid, hydrofluoric acid or the chloride solid acid, acid hydrocarbon ratio 1.45; Temperature of reaction is-10～25 ℃.
Need make with extra care product, shown in figure-2, enter lighter hydrocarbons recovery part 50 in the 40 separating obtained alkylate logistics 109 of alkylation catalyst retrieving arrangement.Separating obtained heavier C8-C12 alkylate oil logistics 112 goes out the battery limit (BL) as product.The part 118 of separating obtained lighter rich C5-C7 alkane logistics 111 is returned isomerization unit 10, and another part 117 goes out the battery limit (BL).
Shown in figure-3, enter alkylation reactor 30 after additional alkylation catalyst logistics 119 and recycling catalyst logistics 116 pre-mixings 120.
Product is had particular requirement, shown in figure-4, go out the battery limit (BL) in light ends unit 50 separating obtained heavier C8-C12 alkylate oil logistics 112 parts as product, another part 121 is through 52 times light ends units 50 of reboiler.The part 118 of separating obtained lighter rich C5-C7 alkane logistics 111 is returned isomerization unit 10, and another part advances condenser 51.After condensation, non-condensable gas 124 send combustion gas, 122 times light ends units 50 of a phlegma part, and another part 123 is sent the battery limit (BL).
The method disclosed in the present towards C5-C6 alkane, is taken into account C4 alkane on raw material.Raw material is through once generating alkylate oil by isomerization and alkylation process, and only unreacted hydrogen and a small amount of C3-C4 light constituent need through simple separation therebetween.Technical process is oversimplified most.Particularly solve the processing problem of wide fraction parallel feeding, adopt Reaction Separation, a small amount of unreacting material is reusable edible both, also can directly enter product.Adapt to the refinery and produce reality, widened raw material sources, greatly reduce production costs.Product alkylate oil octane value is high simultaneously, has guaranteed good economic benefit.
Description of drawings
This production method of Fig. 1 schema
The simple rectification flow of Fig. 2 product
Replenishing of Fig. 3 catalyzer
Fig. 4 product depth rectification flow
Embodiment
Embodiment 1
For verifying effect of the present invention, adopt the technical process shown in the figure-1, carry out industrial experiment at certain experimental installation.
The raw material that this experiment is adopted is the part of the petroleum naphtha in certain petro-chemical corporation's straight-run spirit and isomery C 4 olefin.Raw material straight(-run) tops typical properties sees Table-1.Consisting of of isomery C 4 olefin: iso-butylene 91%, other C 4 olefins 9%.
The typical properties of table-1 certain petro-chemical corporation's straight(-run) tops
| Project | Project | ||
| The raw material index | Group composition | ||
| Olefin(e) centent, wt% | ＜10 | Carbon is below four, % | 0 |
| Sulphur content, ppm | ＜50 | Carbon four, % | 3.7 |
| H 2O content, ppm | ＜50 | Carbon five, % | 37.5 |
| Nitrogen content, ppm | ＜5 | Carbon six, % | 42.6 |
| Arsenic content, ppb | ＜5 | Carbon is more than six, % | 16.2 |
| Copper content, ppb | ＜50 | Distillating property | |
| Benzene content, wt% | ＜5 | Initial boiling point, ℃ | 24 |
| 10％，℃ | 41 | ||
| 50％，℃ | 58 |
| 90％，℃ | 93 |
The processing condition that adopt are that isomerization unit hydrogen dividing potential drop is 1.8MPa, and temperature is 270 ℃, and mass space velocity is 1.2 hours
-1, hydrogen to oil volume ratio is 520, system pressure is 5.5MPa.The agent of alkylation partially catalyzed is sulfuric acid, and temperature of reaction is 12 ℃, reaction pressure 0.55MPa, acid hydrocarbon ratio 1.45.Experiment gained alkylate oil research octane number (RON) is 88.9.
Embodiment 2
Gained alkylate oil among the embodiment 1 is simply made with extra care, adopted the technical process shown in the figure-2, make with extra care experiment at certain experimental installation.Experimental temperature is 75 ℃, experimental pressure 50kPa, and experiment gained alkylate oil research octane number (RON) is 91.5.
Embodiment 3
For verifying effect of the present invention, adopt the technical process shown in the figure-4, carry out industrial experiment at certain experimental installation.
The raw material that this experiment is adopted is certain petro-chemical corporation's pentane oil and isomery C 4 olefin.Raw material pentane oil character sees Table-2.Consisting of of isomery C 4 olefin: iso-butylene 91%, other C 4 olefins 9%.
Table-2 certain petro-chemical corporation's pentane oil properties
The processing condition that adopt are that isomerization unit hydrogen dividing potential drop is 1.8M Pa, and temperature is 270 ℃, and mass space velocity is 1.2 hours
-1, hydrogen to oil volume ratio is 520, system pressure is 5.5MPa.The agent of alkylation partially catalyzed is sulfuric acid, and temperature of reaction is 12 ℃, reaction pressure 0.55MPa, acid hydrocarbon ratio 1.45.Experiment gained alkylate oil research octane number (RON) is 91.5.
Claims (4)
1. the production method of a stop bracket gasoline blend component is characterized in that:
1) C4-C8 mixed alkanes and C4 olefin feedstock enter the isomerization reaction device, carry out isomerization reaction through the isomerization catalyst catalyzed reaction under hydro condition; Catalyzer is silicon or aluminium load platinum catalyst, and platinum load quality percentage composition is 0.01～5% of catalyzer; Promotor is tin, lead, iron, cobalt, tungsten, molybdenum, plug with molten metal, copper, silver, cadmium, bismuth or multiple lucium, the quality percentage composition is 0.01～1% of catalyzer, the hydrogen dividing potential drop is 0.5～2.5MPa, and temperature is 150～280 ℃, and mass space velocity is 0.2～5.5 hour
-1, hydrogen to oil volume ratio is 400～600, system pressure is 4～12Mpa;
2) isomerate of reaction generation flows to into the hydrogen tripping device;
3) separating obtained hydrogen with return the isomerization reaction device after the fresh hydrogen that replenishes mixes;
4) separating obtained liquid hydrocarbon and raw material isomery C4 alkene enter alkyl plant; Alkylation catalyst is a kind of in sulfuric acid, hydrofluoric acid or the chloride solid acid, acid hydrocarbon ratio 1.45; Temperature of reaction is-10～25 ℃;
5) alkylide that generates under alkylation catalyst catalysis flows to into the alkylation catalyst retrieving arrangement, separates to obtain C4-C6 lighter hydrocarbons, catalyzer, the logistics of C8-C12 alkylate;
6) combustion gas or recycle after separating are sent in the logistics of separating obtained C4-C6 lighter hydrocarbons;
7) part of separating obtained catalyst stream is returned alkyl plant, and another part goes out the battery limit (BL).
2. the production method of stop bracket gasoline blend component according to claim 1 is characterized in that: enter the lighter hydrocarbons recovery part in the separating obtained alkylate logistics of alkylation catalyst retrieving arrangement; The part of separating obtained C5-C7 alkane logistics is returned the isomerization reaction device, and another part goes out the battery limit (BL); The logistics of separating obtained C8-C12 alkylate goes out the battery limit (BL) as product.
3. the production method of stop bracket gasoline blend component according to claim 1 is characterized in that: enter alkylation reactor after replenishing alkylation catalyst logistics and recycling catalyst logistics pre-mixing.
4. the production method of stop bracket gasoline blend component according to claim 1, it is characterized in that: an alkylate oil logistics part separating obtained at light ends unit goes out the battery limit (BL) as product, and another part returns light ends unit through reboiler; The part of separating obtained C5-C7 alkane logistics is returned the isomerization reaction device, and another part advances condenser; After condensation, non-condensable gas send combustion gas, and a phlegma part is returned light ends unit, and another part is sent the battery limit (BL).
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| CN2012100977775A CN103361121A (en) | 2012-04-05 | 2012-04-05 | Production method of high-octane gasoline blending component |
| PCT/CN2012/000747 WO2013149365A1 (en) | 2012-04-05 | 2012-05-30 | Method for producing gasoline blended component with high octane number |
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| CN2012100977775A CN103361121A (en) | 2012-04-05 | 2012-04-05 | Production method of high-octane gasoline blending component |
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| CN104711022A (en) * | 2013-12-16 | 2015-06-17 | 中国石油化工股份有限公司 | Two-stage catalytic gasoline upgrading method for increasing gasoline yield and producing ultra-low sulfur gasoline |
| WO2020242961A1 (en) * | 2019-05-24 | 2020-12-03 | Lummus Technology Llc | Flexible production of gasoline and jet fuel in alkylation reactor |
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| CN1339424A (en) * | 2000-08-18 | 2002-03-13 | 中国石油化工股份有限公司 | Isomeric paraffin and olefine alkylating method |
| CN101137604A (en) * | 2005-03-11 | 2008-03-05 | 环球油品公司 | Isomerization process |
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| CN104711022A (en) * | 2013-12-16 | 2015-06-17 | 中国石油化工股份有限公司 | Two-stage catalytic gasoline upgrading method for increasing gasoline yield and producing ultra-low sulfur gasoline |
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| WO2020242961A1 (en) * | 2019-05-24 | 2020-12-03 | Lummus Technology Llc | Flexible production of gasoline and jet fuel in alkylation reactor |
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| TWI790441B (en) * | 2019-05-24 | 2023-01-21 | 美商拉莫斯科技有限公司 | Flexible production of gasoline and jet fuel in alkylation reactor |
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