CN108264929A - Sulfuric acid alkylation method - Google Patents
Sulfuric acid alkylation method Download PDFInfo
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- CN108264929A CN108264929A CN201611263054.2A CN201611263054A CN108264929A CN 108264929 A CN108264929 A CN 108264929A CN 201611263054 A CN201611263054 A CN 201611263054A CN 108264929 A CN108264929 A CN 108264929A
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- Prior art keywords
- sulfuric acid
- hydrocarbon
- iso
- butane
- acid
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 182
- 238000005804 alkylation reaction Methods 0.000 title claims abstract description 52
- 230000029936 alkylation Effects 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 40
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims abstract description 215
- 239000001282 iso-butane Substances 0.000 claims abstract description 106
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 87
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 87
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 78
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 239000002253 acid Substances 0.000 claims abstract description 31
- 150000001336 alkenes Chemical class 0.000 claims abstract description 31
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 235000013847 iso-butane Nutrition 0.000 claims description 100
- 239000003995 emulsifying agent Substances 0.000 claims description 50
- 238000010008 shearing Methods 0.000 claims description 47
- 238000004945 emulsification Methods 0.000 claims description 29
- 239000007788 liquid Substances 0.000 claims description 29
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 4
- 210000000481 breast Anatomy 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 abstract description 12
- 238000003756 stirring Methods 0.000 abstract description 11
- 238000012546 transfer Methods 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 5
- 230000001804 emulsifying effect Effects 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 20
- 230000000694 effects Effects 0.000 description 14
- 239000012071 phase Substances 0.000 description 14
- -1 isobutyl Alkane Chemical class 0.000 description 12
- 230000008569 process Effects 0.000 description 10
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 10
- 150000001335 aliphatic alkanes Chemical class 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 9
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 230000006835 compression Effects 0.000 description 5
- 238000007906 compression Methods 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000002309 gasification Methods 0.000 description 5
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- 230000003068 static effect Effects 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005057 refrigeration Methods 0.000 description 3
- 238000005728 strengthening Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000005504 petroleum refining Methods 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- UHZZMRAGKVHANO-UHFFFAOYSA-M chlormequat chloride Chemical compound [Cl-].C[N+](C)(C)CCCl UHZZMRAGKVHANO-UHFFFAOYSA-M 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000006206 glycosylation reaction Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003470 sulfuric acid monoesters Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
- C07C2/56—Addition to acyclic hydrocarbons
- C07C2/58—Catalytic processes
- C07C2/62—Catalytic processes with acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
- C07C2527/03—Acids of sulfur other than sulfhydric acid or sulfuric acid, e.g. halosulfonic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A sulfuric acid alkylation process comprising: introducing an isobutane raw material, circulating isobutane from an isobutane separation tower and sulfuric acid from an acid-hydrocarbon separator into an external-kettle circulating emulsifying device consisting of a stirring kettle and a shear-type emulsifying device for premixing to form an acid-hydrocarbon emulsion containing isobutane and sulfuric acid; one part of the acid hydrocarbon emulsion enters a stirring kettle for circulation, and the other part of the acid hydrocarbon emulsion enters an alkylation reactor for contact reaction with the mixed olefin in the alkylation reactor; recycling a part of reaction effluent after the acid hydrocarbon emulsion and the mixed olefin react to the stirring kettle, and enabling a part of reaction effluent to enter an acid hydrocarbon separator, wherein the acid hydrocarbon separator separates the reaction effluent into sulfuric acid and hydrocarbon components; and the separated hydrocarbon component enters an isobutane separation tower, the isobutane separation tower separates the hydrocarbon component into isobutane and alkylate oil, wherein the separated isobutane is circulated to the stirring kettle. The method of the invention enhances the mixing degree of acid and hydrocarbon, is beneficial to the mass transfer of isobutane from a hydrocarbon phase to an acid phase, and improves the product quality of alkylate.
Description
Technical field
The present invention relates to petroleum refining process, in particular to the alkylation reaction techniques that iso-butane is promoted to be mixed with sulfuric acid.
Background technology
Alkylation refers to introduce the chemical reaction process of alkyl group, in alkylated various commercial Applications, with isobutyl
Alkane is alkylating reagent, the various low-carbon alkenes such as C3~C5 is alkylated with reaction, and to produce high-knock rating gasoline reconciliation
Isobutane alkylation for the purpose of component is one of most important alkylation commercial Application.Isobutane alkylation technology evolution
In, it is main that two kinds of liquid acids of sulfuric acid or hydrofluoric acid is used also to have ionic liquid, solid acid etc. to be used as alkyl in recent years as catalyst
Change catalyst, but technology is still immature, there are no large-scale applications.It is a small amount of that skeleton is produced since hydrofluoric acid is volatile
Raw irreversible injury, therefore today increasingly increased in environmental requirement of hydrofluoric acid alkylation technology is by very big system
About, although in contrast there are the problems such as spent acid processing, be more preferably to select for sulfuric acid alkylation.Sulfuric acid alkylation reacts
In, butylene dissolving enters in sulfuric acid catalyst comparatively easily, the equilibrium composition of formation alkene and sulfuric acid monoester, and iso-butane
Solubility in sulfuric acid is very low, and hydrocarbon phase is formed together with product alkylate oil, and the mixability of sour hydrocarbon two-phase determines isobutyl
For alkane from the mass transfer rate of hydrocarbon phase sour in opposite directions, this is also that the rate determining step that sulfuric acid alkylation reacts is rapid.If iso-butane can not in time into
Enter sour hydrocarbon interface and generate ideal C8 components with olefine reaction, then the byproduct of alkene meeting autohemagglutination generation low octane rating, causes most
Whole alkylate oil octane number reduces.Common practice is to use very high iso-butane/butylene ratio, the alkane alkene in actual reaction zone
It is more tens of or even hundreds of than that can reach, so as to make up the dissolving of iso-butane limitation, inhibit the side reaction of butylene, but improve alkane alkene ratio
The increase of follow-up iso-butane separating energy consumption is directly resulted in, influences the economic benefit of device.
The reactor of sulfuric acid alkylation mainstream is as horizontal stirred with what water conservancy diversion was set disclosed in United States Patent (USP) US3759318
Kettle is mixed, mechanical agitation is set as eccentric structure by improvement thereafter.Iso-butane, butylene and sulfuric acid catalyst are under stirring blade effect
Flow to dispersion of the diffusion sheet so as to fulfill liquid phase.Chinese patent CN200880011181.0 discloses a kind of high shear formula reaction
Hydrocarbon including isoparaffin and alkene and liquid acid catalyst can be cut into hydrocarbonization in sour continuous phase by device
The emulsion that object average droplet is less than 5 μm is closed, promotes the mass transfer of reaction system.The mixing intensity of mechanical stirring kettle is by stirring work(
The limitation of rate, and reaction temperature generally at 10 DEG C or so, although lower temperature is conducive to reaction selectivity, but sulphur under low temperature
Sour viscosity raising, reaches equal stirring extent motor power consumption and increased dramatically.
Du Pont has reported a series of its transformation on horizontal eccentric stirred tank in international petroleum refining annual meeting in 2007,
Including the premixing for adding iso-butane and butylene, mixed again with sulfuric acid later, so as to strengthen iso-butane to reaction interface
Mass transport process.The premixing of reaction raw materials, it has also become one of focus of sulfuric acid alkylation technological improvement, including iso-butane
The premixing of premixing and iso-butane and sulfuric acid catalyst with butylene.
United States Patent (USP) US5443799 discloses a kind of vertical upstriker injection reactor, employs a kind of with distributor pipe
Iso-butane and sulfuric acid premixing structure, iso-butane are ejected from distributor pipe, and the sulfuric acid entered with annular space is mixed, and is pre-mixed it
Iso-butane afterwards/sulfuric acid emulsion enters reaction zone, and alkylated reaction occurs with the alkene that reaction zone axial segmentation enters.In addition to
Premixing effect is outer, and since volume of the reaction zone than pre-mix zone increases, flow volume expansion can absorb a part of heat.
United States Patent (USP) US5785933 discloses a kind of alkylated reaction device of static mixer form, raw material iso-butane
Merge with the acid hydrocarbon emulsification liquid of reactor bottom outflow, then after being mixed with the sulfuric acid from settling tank by static mixer into one
Step mixing, then enter reaction zone after being mixed with butylene by static mixer.The main purpose of the technology is to reduce dynamic equipment
Use, preferentially iso-butane and sulfuric acid are mixed in the selection of mixing, and add acid hydrocarbon emulsification liquid, improve mixing effect
Rate.
Chinese patent 201510738217.7 discloses a kind of sulfuric acid alkylation reaction method, devises a kind of special construction
Double feeding spray nozzles sulfuric acid and iso-butane are pre-mixed, it is mixed acid hydrocarbon mixture again with mix carbon four simultaneously enter instead
It answers and reaction is alkylated inside device.Inside reactor step-by-step arrangement the structured packing with mixed effect, sour hydrocarbon mixture
It further mixes and reacts in packing layer.The process employs from refrigeration heat taking method, alkane is taken away using the partial gasification of hydro carbons
Glycosylation reaction heat, keeps reaction to carry out at a lower temperature.
Chinese patent 201310503473.9 discloses a kind of sulfuric acid alkylation reaction process, and iso-butane is first passed through with sulfuric acid
Colloid mill is pre-mixed, and enters back into rotary drill reactor and another strand of iso-butane, olefin feedstock hybrid reaction, the technique later
The mixing mass transfer of reaction mass is realized by the sectional feeding, colloid mill, ejector mixing of iso-butane.
Analysis above-mentioned technical proposal in order to solve mass transfer of the iso-butane into sulfuric acid in sulfuric acid alkylation reaction it is found that ask
Topic, strengthening the premixing effect of iso-butane and sulfuric acid has become one of direction of technological improvement.Said program is different from traditional
Alkane alkene be pre-mixed, the substantial concentrated sulfuric acid can to alkane alkene mixed liquor generate extracting effect, most alkene is dissolved in, alkane alkene it is pre-
It is mixed not satisfactory to the effect of mass transmitting effect of iso-butane.Iso-butane is integrally mixed with the premixing of sulfuric acid with strengthening raw material for alkylation
Technology also there is apparent technology to distinguish, with rotary packed bed a kind of disclosed in Chinese patent CN201310503460.1 etc.,
Stream of pulses and filling-material structure disclosed in United States Patent (USP) US7319180, Chinese patent CN0381334 1.5 etc., above-mentioned Chinese patent
The technologies such as shearing reactor disclosed in CN20088001 1181.0, it is preferred that emphasis is the immixture of reaction mass entirety, due to
During micromixing to microcosmic mixing, part, of short duration non-uniform areas are certainly existed, when reaction mass integrally mixes
Side reaction is likely to occur, and the premixing of iso-butane and sulfuric acid is only physical process, does not generate by-product, be can be used various
Technical solution is to realize sufficient mixing and emulsifying.But the major programme of presently disclosed iso-butane and sulfuric acid pre-mixed technology
It is that the accessory structure of alkylation reactor is belonged to simply once by form using such as static mixer, injection head-on collision, it is right
Still there is certain limitation to the mass transfer of sulfuric acid in strengthening iso-butane.
Invention content
The purpose of the present invention is to provide a kind of sulfuric acid alkylation methods.
To achieve the above object, the present invention provides a kind of sulfuric acid alkylation method, includes the following steps：
Step 1, by isobutane feedstock, the recycle isobutane from iso-butane knockout tower and the sulphur from sour hydrocarbon separator
Acid is passed through the kettle outer circulation type emulsifier unit being made of stirred tank and shearing emulsifier unit and is pre-mixed, and is formed comprising isobutyl
The acid hydrocarbon emulsification liquid of alkane and sulfuric acid；
Step 2, an acid hydrocarbon emulsification liquid part enter stirred tank cycle, a part enter alkylation reactor with wherein
Mixed olefins haptoreaction；
Step 3, the reaction effluent part after acid hydrocarbon emulsification liquid has been reacted with mixed olefins are recycled to stirred tank, and one
Part enters sour hydrocarbon separator, and reaction effluent is separated into sulfuric acid and the hydrocarbon component by sour hydrocarbon separator；And
Step 4, the hydrocarbon component separated in step 3 enter iso-butane knockout tower, and iso-butane knockout tower is by the hydrocarbon component
Iso-butane and alkylate oil are separated into, wherein, the iso-butane isolated is recycled to stirred tank.
Further, in acid hydrocarbon emulsification liquid sulfuric acid be continuous phase, the hydro carbons comprising iso-butane be dispersant liquid drop, dispersant liquid drop
Average diameter be less than 50 μm.
Further, shearing emulsifier unit includes stator and rotor, realizes the mixing of logistics by the rotation of rotor, turns
300-5000 revs/min of rotor speed range.
Further, the acid hydrocarbon emulsification liquid outlet temperature that shearing emulsifier unit is formed is -5~10 DEG C.
Further, alkylation reactor carries rotational structure.
Further, shearing emulsifier unit and alkylation reactor are coaxially connected.
Further, the alkylation reactor with rotational structure be rotary packed bed or rotor supergravity reactor in
One kind.
Further, mixed olefins are C3-C5 alkene.
Further, mixed olefins are C4 alkene.
The beneficial effects of the invention are as follows：
(1) degree of scatter of sour hydrocarbon in alkylated reaction is enhanced, iso-butane is promoted to the mass transfer of sour phase, reduces sour phase
The generation of the side reaction of middle alkene improves the selectivity of antiknock component in alkylate oil.
(2) iso-butane/sulfuric acid emulsion that premixing is formed can reduce mixing intensity in reactor, be conducive to be alkylated
Reaction zone mass transfer and the design of heat transfer.
Description of the drawings
Fig. 1 is the alkylation process flow diagram of the shearing emulsifier unit premix of pipeline.
Fig. 2 is the alkylation process flow diagram of the shearing emulsifier unit premix of kettle outer circulation type.
Fig. 3 is the refrigeration alkylation process flow diagram certainly with shearing premix.
Wherein, reference numeral：
1 isobutane feedstock
2 shearing emulsifier units
3 mixed butenes
4 reactors
5 reaction effluents
6 sour hydrocarbon separators
7 sulfuric acid
8 sour hydrocarbon mixture streams
9 hydrocarbon
10 iso-butane knockout towers
11 alkylate oils
12 recycle isobutanes
13 iso-butanes/sulfuric acid emulsion
Kettle is mixed in 14 iso-butanes/sulfuric acid
15 kettle outer circulation emulsification pretreatment logistics
16 propane
17 compression condensation tanks
18 coolers
19 gas compressors
20 compression condensation liquid
21 reactor outlet gas hydro carbons
22 sour hydrocarbon separator gas hydro carbons
Specific embodiment
With reference to legend, the present invention is further described.
A kind of sulfuric acid alkylation method, includes the following steps：
Step 1, by isobutane feedstock, the recycle isobutane from iso-butane knockout tower and the sulphur from sour hydrocarbon separator
Acid is passed through the kettle outer circulation type emulsifier unit being made of stirred tank and shearing emulsifier unit and is pre-mixed, and is formed comprising isobutyl
The acid hydrocarbon emulsification liquid of alkane and sulfuric acid；
Step 2, an acid hydrocarbon emulsification liquid part enter stirred tank cycle, a part enter alkylation reactor with wherein
Mixed olefins haptoreaction；
Step 3, the reaction effluent part after acid hydrocarbon emulsification liquid has been reacted with mixed olefins are recycled to stirred tank, and one
Part enters sour hydrocarbon separator, and reaction effluent is separated into sulfuric acid and the hydrocarbon component by sour hydrocarbon separator；And
Step 4, the hydrocarbon component separated in step 3 enter iso-butane knockout tower, and iso-butane knockout tower is by the hydrocarbon component
Iso-butane and alkylate oil are separated into, wherein, the iso-butane isolated is recycled to stirred tank.
Further, in acid hydrocarbon emulsification liquid sulfuric acid be continuous phase, the hydro carbons comprising iso-butane be dispersant liquid drop, dispersant liquid drop
Average diameter be less than 50 μm.
Further, shearing emulsifier unit includes stator and rotor, realizes the mixing of logistics by the rotation of rotor, turns
300-5000 revs/min of rotor speed range.
Further, the acid hydrocarbon emulsification liquid outlet temperature that shearing emulsifier unit is formed is -5~10 DEG C.
Further, alkylation reactor carries rotational structure.
Further, shearing emulsifier unit and alkylation reactor are coaxially connected.
Further, the alkylation reactor with rotational structure be rotary packed bed or rotor supergravity reactor in
One kind.
Further, mixed olefins are C3-C5 alkene.
Further, mixed olefins are C4 alkene.
Isobutane feedstock of the present invention, refers to the hydrocarbon material rich in iso-butane, and the mixed olefins refer to richness
The hydrocarbon material of the alkene containing C3-C5 is particularly preferably rich in the mixed butene material of 1- butylene, cis/trans 2- butylene and isobutene.It is rich
It is reacted again with mixed butene after logistics containing iso-butane and the premix of sulfuric acid, the technical solution existing report in disclosed technological document
Lead, generate must effect, but used premix mode is limited to static mixer, nozzle, distributor etc., and incorporation time is very
It is short, and iso-butane only has subparticipation premixing, and mixing intensity is relatively low.Method selection additionaling power proposed by the present invention
Shearing emulsifier unit by all materials containing iso-butane into reactor, including fresh feed iso-butane and recycles isobutyl
Alkane fully enters pre-mixing process, is mixed with the catalyst of sulfur acid, can realize the abundant of iso-butane and sulfuric acid two-phase
Emulsion is mixed into, is suitble to the sour hydrocarbon two-phase proportion of wider range.
Iso-butane and sulfuric acid are pre-mixed using shearing emulsifier unit, may be used one-pass mode into
Row, i.e., by being directly entered subsequent reactor after shearing emulsifier unit, the art is generally referred to as iso-butane and sulfuric acid
It is emulsified for pipeline.If required up higher emulsification degree, institute's wasted work rate is very big, disguises applied to large size for pipeline emulsification
It puts relatively difficult.The method of the present invention is preferably emulsified using outer circulation type, i.e., iso-butane and sulfuric acid pass through shearing emulsifier unit
The mixing of logistics is realized in combination with stirred tank, in stirred tank logistics outer circulation is formed by shearing emulsifier unit, it is shearing
An emulsifier unit outlet streams part enters stirred tank cycle, and a part is reacted into alkylation reactor with mixed butene.Outside
The shearing emulsifier unit of lower-wattage may be used in circulating emulsification method, and certain residence time is controlled to reach mixing effect
Fruit, because not containing alkene in mixed material, side reaction also do not occur for mixing for a long time, thus circulating emulsification may be used compared with
Long residence time, the method for the present invention preferred residence time are 0.1-1h.
Sulfuric acid alkylation is reacted, the preferably suitable acid hydrocarbon ratio of the present invention makes sulfuric acid for continuous phase, and iso-butane is dispersion
Phase.By outer circulation type emulsifier unit of the present invention, the dispersed phase drop average diameter of formation is less than 50 μm.As one kind
Preferred embodiment, the present invention select the high-shear emulsifier unit for including stator and rotor structure, pass through the high speed rotation of rotor
Realize the mixing of logistics, 300-5000 revs/min of rotor speed range, preferred range is 600-2000 revs/min, forms dispersion
Phase mean drop diameter is less than 30 μm.Conventional equipment can be selected in shearing emulsifier unit, pumped including emulsification pretreatment machine, glue mill etc.,
Special designing is not needed to, is conducive to the operation and maintenance of equipment, and some shearing emulsifier units have adherence pressure simultaneously
Effect, can be used as delivery pump.
Method proposed by the present invention is suitble to cryogenic alkylation to react, and usually the viscosity increase of sulfuric acid causes at a lower temperature
Stirring is difficult, mixing dispersion efficiency reduces, and the premixing of iso-butane and sulfuric acid is realized using shearing emulsifier unit, can compared with
It is carried out under high viscosity, the preferably shearing emulsifier unit outlet temperature of the method for the present invention is -5~10 DEG C, this temperature and alkylation
The temperature of reaction is identical, controls the temperature of shearing emulsifier unit outlet and reactor that cooling jacket, coil pipe, gasification can be used
Etc. scheme well-known in the art.
Iso-butane is mixed with sulfuric acid reach preferable emulsified state after, the separation of sour hydrocarbon needs longer time, thus
In the case of iso-butane and sulfuric acid premixing effect are preferable, the intensity mixed in reactor can be reduced, such as stirring motor
Design height and flow velocity of power or filler etc..The stable state of acid hydrocarbon emulsification liquid has certain association with the composition of hydro carbons,
In hydro carbons containing heavier alkylate oil then emulsion stability improve.Therefore, as a preferred method of the present invention, draw
Enter the logistics being pre-mixed in the shearing emulsifier unit of outer circulation type and include isobutane feedstock, recycle isobutane, recycle sulfuric acid, reaction
Device exports the logistics containing sulfuric acid and alkylate oil, and several logistics enter reaction after being pre-mixed by shearing emulsifier unit
Device is reacted with C 4 olefin.The logistics that reactor outlet contains sulfuric acid and alkylate oil is introduced into shearing emulsifier unit and isobutyl
Alkane mixes, and alkylate oil and sulfuric ester therein is made further to be come into full contact with iso-butane, can also reduce the generation of side reaction,
The product quality of alkylate oil is improved, while increases the degree of freedom of reactor operation.
Method of the invention it is achieved that the abundant premixing of iso-butane and sulfuric acid, reduces the mixing of subsequent reactions process
Intensity requirement, the reactor of the method for the present invention can select conventional stirred tank, filling batch or existing interior cycle
Horizontal bias stirred tank.Present invention preferably uses a kind of reactor with rotational structure, shearing emulsifier unit and rotation are tied
The reactor of structure is coaxially connected, and power is provided by same motor, using well known to a person skilled in the art drive mechanisms point
Not Kong Zhi both rotating speed.The device structure of the program is compact, can save equipment investment.As a kind of preferred scheme, institute
The reactor with rotational structure stated be rotary packed bed or rotor supergravity reactor in one kind.
Alkylation process flow of the present invention is shown in Fig. 2, this figure only marks main equipment and logistics route, to say
Bright technical solution of the present invention, content well known in the art have been omitted from.Isobutane feedstock 1 from 10 tower top of iso-butane knockout tower with going out
The recycle isobutane 12 of mouth, sulfuric acid 7 and the outflow of 4 bottom of reactor from sour 6 bottom of hydrocarbon separator contain alkylate oil, isobutyl
The reaction effluent 5 of alkane and sulfuric acid merges the sour hydrocarbon mixture stream 8 formed, is mixed into iso-butane/sulfuric acid stirred tank 14
It closes, the effect of stirring is to maintain the disturbance of logistics in kettle, and the kettle outer circulation of iso-butane/14 outlet at bottom of sulfuric acid stirred tank is cut
Cut emulsification logistics 15 and enter shearing emulsifier unit 2 and carry out emulsification pretreatment, the logistics part that shearing emulsifier unit 2 exports into
Enter iso-butane/14 circulating emulsion of sulfuric acid stirred tank, the entrance object of a part of (iso-butane/sulfuric acid emulsion 13) as reactor 4
Stream, reacts with mixed butene 3.4 effluent of reactor, which enters in sour hydrocarbon separator 6, to be detached, and top hydro carbons enters iso-butane
Knockout tower 10 is further separated into iso-butane 12 and alkylate oil 11.
The method of the invention is shown in Fig. 3 with the example that rotating packed-bed reactor and gasification solutions for refrigeration are combined.It cuts
Cut type emulsifier unit 2 and rotary packed bed formula reactor 4 can be coaxially connected, using identical power source, can also independently move
Power source.Isobutane feedstock 1, compression condensation liquid 20, recycle isobutane 12 are with sour hydrocarbon mixture stream 8 in shearing emulsifier unit 2
It after emulsification pretreatment, reacts into reactor 4 with mixed butene 3, the pressure of control reactor 4 can make hydrocarbon in reactor 4
Class partial gasification, so as to control the reaction temperature in reactor 4.Reactor outlet gas hydro carbons 21 enters gas compressor 19,
It is condensed with compressing together with a small amount of gas from sour 6 top of hydrocarbon separator and passing through cooler 18,17 bottom of compression condensation tank pressure
Contracting condensate liquid 20 is recycled back to shearing emulsifier unit 2, and a small amount of gas in 17 top of compression condensation tank is used as rig for propane 16
Stream discharge.Example shown in Fig. 3 be to illustrate to be pre-mixed iso-butane and sulfuric acid using shearing emulsifier unit, easily with from
Cooling flow is combined, and similary those skilled in the art is it can be deduced that the method for the present invention is also easily mutually tied with effluent cooling flow
It closes.
Embodiment 1
Using flow shown in Fig. 1, belong to pipeline emulsifying manner, isobutane feedstock 1 is with coming from 10 tower of iso-butane knockout tower
The recycle isobutane 12 of ejection mouth merges, and sulfuric acid 7 and the outflow of 4 bottom of reactor from sour 6 bottom of hydrocarbon separator contain alkyl
The sour hydrocarbon mixing effluent 5 of carburetion, iso-butane and sulfuric acid merges, and the two entrances of shearing emulsifier unit 2 is respectively enterd, through breast
Enter reactor 4 after change with entering 3 haptoreaction of olefin-containing raw material therein.Device is the pilot plant test of 2kg butylene/h scales
Device, raw material are refinery isobutane, purity 96v%, and C4, wherein mixed butene content 48v% after refinery's ether, 92wt%'s is dense
Sulfuric acid.Shearing 1200 revs/min of emulsifier unit rotating speed, temperature rise 2 DEG C, and outlet temperature control is 8 DEG C, pressure 0.5MPa, reactor
For stirred tank, 200 revs/min of speed of agitator, logistics mean residence time is 15min, is 8 by cooling jacket controlling reaction temperature
℃.The iso-butane and sulfuric acid molar ratio of premixing are 0.9:1, the alkane alkene molar ratio into reactor is 12:1, reactor outlet
Logistics 5 fully enters sour hydrocarbon knockout drum, is not involved in sour hydrocarbon premixing.Shearing emulsifier unit is analyzed by local laser particle size analyzer
The average grain diameter of outlet material is 35 μm.Alkylate oil is made up of chromatography, and it is 95.6 to calculate research octane number (RON).Alkyl
Change the target product of reaction as C8 alkane, selectivity can reflect the efficiency of mixing and reaction process, and C8 paraffin selectivities
There is correspondence with octane number, the effect for mixing and reacting can be judged by octane number.
Reference Example
Process conditions are same as Example 1, and iso-butane, recycle sulfuric acid be not by shearing emulsifier unit, with mixed butene
Stirred tank reactor is directly entered together to be reacted.The research octane number (RON) of alkylate oil is 94.
Embodiment 2
Using technological parameter same as Example 1, a part for reaction effluent 5 introduces shearing emulsifier unit and isobutyl
The common emulsification pretreatment of alkane, sulfuric acid, institute's primer stream are 1 with the mass ratio for entering sour hydrocarbon separator logistics:6, gained alkylate oil
Research octane number (RON) is 96.1.
Embodiment 3
Using flow shown in Fig. 2, raw material is same as Example 1, makes pipeline emulsification pretreatment scheme into pilot-plant
Currently preferred circulation-type emulsifies scheme, is made of a stirred tank with shearing emulsifier unit.Pass through cooling jacket
Control stirring temperature in the kettle is -3 DEG C, pressure 0.5MPa, recycle ratio 8:1, shearing 850 revs/min of emulsifier unit rotating speed calculates flat
Equal residence time 18min.Iso-butane is 0.85 with sulfuric acid molar ratio:1, reactor uses wire packing bed, and coil pipe takes heat, instead
- 3 DEG C of temperature, mean residence time 7min are answered, reaction zone alkane alkene ratio is 15:1, reactor outlet stream portions are recycled to premix
It closes, flow-rate ratio is same as Example 2.The average grain diameter of online granularmetric analysis display premixing lotion is 25 μm, alkylate oil
Research octane number (RON) is 97.2.
Embodiment 4
Process conditions are identical with 3 part of embodiment, and reactor makes rotary packed bed, 600 revs/min of rotating speed, residence time into
About 5s, it is 3 that reactor outlet logistics, which is recycled to premixing flow with the mass ratio for entering sour hydrocarbon separator,：1, shearing emulsification dress
It puts outlet pressure and is adjusted to 0.3MPa, rotary packed bed outer clip extracts heat, and temperature is controlled at 5 DEG C.The organon of alkylate oil is pungent
Alkane value is 96.2.
Embodiment 5
Using flow shown in Fig. 3,1600 revs/min of rotating speed, temperature rises 4 DEG C, and outlet temperature control is 6 DEG C, pressure 0.5MPa, instead
Answering device, iso-butane is 0.85 with sulfuric acid molar ratio with embodiment 4:1, reaction zone alkane alkene ratio is 15:1, reactor outlet logistics follows
Ring is 5 to flow is pre-mixed with the mass ratio for entering sour hydrocarbon separator：1, reactor does not use chuck to take heat, is reacted by adjusting
Pressure controlling reaction temperature is 8 DEG C, and the gasification of hydro carbons occurs for reaction zone, absorbs partial reaction heat.The organon of alkylate oil is pungent
Alkane value is 96.4.
Embodiment 6
Process conditions are identical with 5 part of embodiment, and shearing emulsifier unit outlet temperature and reaction temperature are adjusted to -5
DEG C, the research octane number (RON) of alkylate oil is 97.3.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and deformation, but these corresponding changes and deformation can be made according to the present invention by knowing those skilled in the art
The protection domain of the claims in the present invention should all be belonged to.
Claims (9)
- A kind of 1. sulfuric acid alkylation method, which is characterized in that include the following steps：Step 1 leads to isobutane feedstock, the recycle isobutane from iso-butane knockout tower and the sulfuric acid from sour hydrocarbon separator Enter the kettle outer circulation type emulsifier unit being made of stirred tank and shearing emulsifier unit to be pre-mixed, formed comprising iso-butane and The acid hydrocarbon emulsification liquid of sulfuric acid；Step 2, an acid hydrocarbon emulsification liquid part enter stirred tank cycle, and a part enters alkylation reactor with being mixed with therein Close alkene haptoreaction；Step 3, the reaction effluent part after acid hydrocarbon emulsification liquid has been reacted with mixed olefins are recycled to stirred tank, a part Into sour hydrocarbon separator, reaction effluent is separated into sulfuric acid and the hydrocarbon component by sour hydrocarbon separator；AndStep 4, the hydrocarbon component separated in step 3 enter iso-butane knockout tower, and iso-butane knockout tower detaches the hydrocarbon component For iso-butane and alkylate oil, wherein, the iso-butane isolated is recycled to stirred tank.
- 2. sulfuric acid alkylation method according to claim 1, which is characterized in that sulfuric acid is continuous phase in acid hydrocarbon emulsification liquid, Hydro carbons comprising iso-butane is dispersant liquid drop, and the average diameter of dispersant liquid drop is less than 50 μm.
- 3. sulfuric acid alkylation method according to claim 1, which is characterized in that shearing emulsifier unit includes stator and turns Son realizes the mixing of logistics, 300-5000 revs/min of rotor speed range by the rotation of rotor.
- 4. sulfuric acid alkylation method according to claim 1, which is characterized in that the sour hydrocarbon breast that shearing emulsifier unit is formed It is -5~10 DEG C to change liquid outlet temperature.
- 5. sulfuric acid alkylation method according to claim 1, which is characterized in that alkylation reactor carries rotational structure.
- 6. sulfuric acid alkylation method according to claim 1, which is characterized in that shearing emulsifier unit and alkylated reaction Device is coaxially connected.
- 7. sulfuric acid alkylation method according to claim 1, which is characterized in that the alkylation reactor with rotational structure Rotary packed bed or rotor supergravity reactor in one kind.
- 8. sulfuric acid alkylation method according to claim 1, which is characterized in that mixed olefins are C3-C5 alkene.
- 9. sulfuric acid alkylation method according to claim 1, which is characterized in that mixed olefins are C4 alkene.
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| CN111589407A (en) * | 2020-05-20 | 2020-08-28 | 中石化南京工程有限公司 | Sulfuric acid alkylation system and method for producing isooctane by using same |
| CN111589406A (en) * | 2019-02-21 | 2020-08-28 | 中国石油化工股份有限公司 | Alkylation reaction device, reaction system and liquid acid catalyzed alkylation reaction method |
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