CN1403425A - High-carbon alpha-olefine preparing process and apparatus - Google Patents
High-carbon alpha-olefine preparing process and apparatus Download PDFInfo
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- CN1403425A CN1403425A CN 02109869 CN02109869A CN1403425A CN 1403425 A CN1403425 A CN 1403425A CN 02109869 CN02109869 CN 02109869 CN 02109869 A CN02109869 A CN 02109869A CN 1403425 A CN1403425 A CN 1403425A
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims description 30
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 239000005977 Ethylene Substances 0.000 claims abstract description 19
- 238000005507 spraying Methods 0.000 claims abstract description 15
- 239000000839 emulsion Substances 0.000 claims abstract description 12
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 8
- -1 alkylaluminium compound Chemical class 0.000 claims description 38
- 239000007791 liquid phase Substances 0.000 claims description 37
- 239000004711 α-olefin Substances 0.000 claims description 37
- 239000003595 mist Substances 0.000 claims description 24
- 238000005649 metathesis reaction Methods 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 239000012071 phase Substances 0.000 claims description 7
- 210000004907 gland Anatomy 0.000 claims description 6
- 239000007921 spray Substances 0.000 claims description 6
- 241000282326 Felis catus Species 0.000 claims description 4
- 238000005194 fractionation Methods 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000012263 liquid product Substances 0.000 claims description 3
- 210000002445 nipple Anatomy 0.000 claims description 3
- 238000012856 packing Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 239000008384 inner phase Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 25
- 229910052782 aluminium Inorganic materials 0.000 abstract description 8
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 3
- 239000004411 aluminium Substances 0.000 abstract description 2
- 230000003139 buffering effect Effects 0.000 abstract 1
- 239000007792 gaseous phase Substances 0.000 abstract 1
- 238000006317 isomerization reaction Methods 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 238000007701 flash-distillation Methods 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000006384 oligomerization reaction Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XINQFOMFQFGGCQ-UHFFFAOYSA-L (2-dodecoxy-2-oxoethyl)-[6-[(2-dodecoxy-2-oxoethyl)-dimethylazaniumyl]hexyl]-dimethylazanium;dichloride Chemical compound [Cl-].[Cl-].CCCCCCCCCCCCOC(=O)C[N+](C)(C)CCCCCC[N+](C)(C)CC(=O)OCCCCCCCCCCCC XINQFOMFQFGGCQ-UHFFFAOYSA-L 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention is the preparation process and apparatus for substituting alkyl group in high-carbon aluminium alkyl with ethylene to prepare straight-chain C4-26 alpha-olefine. High-carbon aluminum alkyl after being preheated to 120-180 deg.c is made to enter into a single-stage spraying tubular reactor at a linear speed of 150-300 m/s while ethylene after being preheated to 280-300 deg.c is made to enter into a reactor in tangent direction, so that replacement reaction is performed at 230-300 deg.c and 0.5-1.8 MPa. The atomizing reaction product is cooled to 20-60 deg.c and then, the emulsion is made to enter into the buffering tank in a double-disc separating tower for filming and separating while the gaseous phase is separated in the tower top for reuse. The coarse high-carbon alpha-olefine is fractionationed to obtain the destination product.
Description
Technical field
The invention belongs to the Speciality Petrochemicals field, relate to the method and apparatus for preparing high-carbon alpha-olefin, particularly replace C with polymer grade ethylene
4-26Alkyl in the high alkylaluminium compound, preparation C
4-26The method and apparatus of high-carbon alpha-olefin.
Background technology
Straight chain alpha-C
4-8Alkene is the comonomer of high density polyethylene(HDPE), linear low density polyethylene, and consumption is big.Other linear alpha-olefin all is good fine chemical material, as straight chain alpha-C
8-12Alkene is the raw material of synthetic high gear lubricating oil.Straight chain alpha-C
12--16Alkene is the agent alive of synthesising biological degradation property surface of good, detergent raw material.So alpha-olefin is a product good in economic efficiency, extensive market, be fastest-rising in the world in recent years chemical industry.
1966, U.S. Gulf company took the lead in using the patent of Ziegler, and exploitation is under triethyl aluminum catalysis, by the preparing alpha-olefin by ethane oligomerisation technology.Nineteen eighty-three, Chevron company adopts one-step technology with this skilled industryization.Compressed and the preheating of ethylene raw material gas feeds in five placed in-line tubular reactors that fill triethylaluminium catalyst solution (it can be coiled pipe or U type pipe) after reaching 23Mpa and 180 ℃, carries out ethylene oligomerization and replacement(metathesis)reaction, and reaction time is 15min.The reaction product that generates enters gas-liquid separator.Isolated ethylene recycle is used, and liquid product is separated after using NaOH-aqueous solution termination reaction again.The NaAlO of lower floor
2Waste liquid is transported to the waste water processing station, and the thick product on upper strata is delivered in the rectifying tower and separated through overcooling, drying, obtains containing the alpha-olefin product of different carbon numbers.
Ethyl company (now belonging to Bp-Amoco) finishes ethylene oligomerization (transfer reaction) and replacement(metathesis)reaction respectively in two kinds of four reactors, claim two step method (USP3906053).Triethylaluminium catalyst solution is parallel enters two oligomerisation reaction devices.First oligomerisation reaction device, ethene carries out oligomerisation under 160-275 ℃, 10.0-25.0Mpa, obtain α-C
4-10Alkene is mainly as displacer.Second oligomerisation reaction device, ethene carries out oligomerisation under 60-100 ℃, 10.0-20.0Mpa.Product enters first metathesis reactor, under 245-300 ℃, 0.7-2.0Mpa, and the α-C that generates with first excessive oligomerisation reaction device
4-10Alkene is replaced, and obtains α-C
12-18Alkene and C
4-10Aluminum alkyls.Aluminum alkyls continues the catalyzed ethylene oligomerisation reaction through returning after separating in the first or second oligomerisation reaction device.α-C
12-18Alkene separates, purifies, and obtains product.In second metathesis reactor, the aluminum alkyls of generation α-C
12Alkene carries out replacement(metathesis)reaction, generates α-C
4-10Alkene and C
12Aluminum alkyls.The former can be used as the displacer of first metathesis reactor, and the latter then is used to produce n-dodecanol.Do not relate to reactor in the patent.
Chinese patent application numbers 95117459.2, " method for preparing low-carbon alpha-alkene " of disclosed Daqing Petrochemical main office.The low-carbon alkyl aluminium that this invention obtains with the oligomerisation of triethyl aluminum catalyzed ethylene.With ethene and/or butene-1 displacement alkyl wherein, produce target product 1-hexene then.Nozzle to the metathesis reactor of this invention in the literary composition is described as: " metathesis reactor is a spray reaction, and liquid jet, gas jet spray simultaneously, forms the atomizing system ".Like this, make spouting of liquid need high pressure, and nozzle diameter is very thin, stops up easily.The reactor of this application Figure of description 3 expressions is a kind of jars with the awl end, is injected in the spray rotation easily in jar in the jar, causes back-mixing, to reacting unfavorable.
Summary of the invention
The object of the present invention is to provide and a kind ofly replace C with polymer grade ethylene
4-26Alkyl in the high alkylaluminium compound prepares C
4-26The method of high-carbon alpha-olefin, and spraying tubular reactor, the double plate knockout tower of this method of realization.
A kind of method for preparing high-carbon alpha-olefin is characterized in that, this method mainly may further comprise the steps:
(1) high alkylaluminium compound of requirement is pumped into is preheated to 120-180 ℃ in the preheater,, enter single-stage spraying tubular reactor with the linear velocity of 1-4cm/s; Simultaneously,
(2) with after the excessive ethene metering, send the ethene preheating oven to and be heated to 280-300 ℃, send in the above-mentioned reactor with tangential direction, ethene and high alkylaluminium compound mol ratio are 30-50, linear velocity with 150-300cm/s atomizes high alkylaluminium compound at the nozzle place, spray into then in the reaction tubes in 230-300 ℃, 0.5-1.8Mpa and carry out replacement(metathesis)reaction, obtain vaporific reaction product;
(3) above-mentioned vaporific reaction product is cooled to 20-60 ℃ after, obtain emulsion.
(4) this emulsion enters the double plate knockout tower and separates, and it is compressed with fresh ethylene that cat head is told ethene, sends into described single-stage spraying tubular reactor; Liquid product enters in the basin at the bottom of tower, then through fractionation, just makes high-carbon alpha-olefin.
Realization prepares the single-stage spraying tubular reactor of the method for high-carbon alpha-olefin, it is characterized in that this reactor mainly comprises:
A, be the reaction tubes that the short tube of truncated cone-shaped is connected with the base lower inner wall;
Be provided with the conical cavity of outer mix nozzle in B, the base, on the same horizontal plane of this conical cavity, correspondence is provided with two inlet pipe that are tangential direction, and this two inlet pipe is connected with two gas phase inlet tubes of base downside;
C, be in the liquid phase outlet cone in the above-mentioned conical cavity, the annular space under it and the conical cavity between the vertical aperture constitutes above-mentioned outer mix nozzle;
D, the outside by its underpart barrel and this liquid phase outlet cone, with the liquid phase conduit that screw thread is connected, liquid phase exports between the suitable for reading and liquid phase conduit lower end cylindrical shell of cone and is provided with gasket;
E, by upper inner and liquid phase conduit middle part, the seat of honour that is connected with screw thread;
F, the nut that the seat of honour and base are connected as a single entity;
G, the gland that is connected with screw thread by its outer wall and seat of honour inwall are provided with lock packing between the round platform in gland lower port and top, the seat of honour tube.
Above-described reactor, pipe nipple is provided with nut on its liquid phase conduit.
Realization prepares the double plate knockout tower of the method for high-carbon alpha-olefin, it is characterized in that this tower mainly comprises:
A, with the cylindrical shell that is provided with the A flange on the feed-pipe that is connected of middle part, be in the tower the vertically pipeline section outside, tapered surge tank in the reverse bottom at this feed-pipe;
B, the A upper flange center of passing that links to each other with the outer top of this surge tank tapered bottom, and the coupled mist post of catching, this is caught and has many eyelets on the mist post;
C, the following rack on outside above-mentioned surge tank tapered bottom, and between the last rack of A upper flange below, around catch the mist post oneself outside to inside, be provided with the inside more more little mist catching net layer of its mesh successively;
D, be positioned at below the surge tank, central authorities are provided with the dish post in the cylindrical shell that is provided with the B upper flange, and it passes B lower flange centre hole and coupled;
E, on above-mentioned dish post, from top to bottom between the discharge nozzle horizontal section of cylindrical shell inner underside, be provided with by the many group double plates that are used for solution-air separation of emulsions of its center borehole jack on this dish post, be provided with support ring between each dish, every group of double plate is by mouth deep bid up, the shallow bid composition of a mouth down, in the support ring outside, have a plurality of circular holes of the shallow bid of liquid phase stream under it in each deep bid central hole.
Above-mentioned knockout tower on its described large and small dish upper surface, is respectively equipped with and makes liquid phase become liquid film mobile roller flower, or the drum side be equipped with make liquid phase become the liquid film mobile several with the concentric circular groove of dish.
Above-described knockout tower, its dish post is a round tube, is provided with coaxial pipe in it, pipe tower outer segment is provided with cooling but inlet pipe, the outlet pipe of medium in this, its outer sealing nut that is provided with; Be provided with clamping nut in this tubular dish post upper end.
Below prepare high-carbon alpha-olefin with regard to the present invention method be described as follows:
As the polymer grade ethylene of displacer, be the product of Jilin Petrochemical company, high alkylaluminium compound is the intermediate product that Jihua Group Co produces higher alcohols, is C
4-26The mixture of aluminum alkyls, the alkyl carbon number distributes by Possion and contains solvent; Aluminium content=4.44%; Measure the viscosity and the proportion of high alkylaluminium compound respectively with known Ubbelohde viscometer and specific gravity hydrometer, the pass of the proportion (d) that records high alkylaluminium compound and temperature (t, ℃) is:
d＝-10
-6×t
2-5×10
-4t+0.8536
Record high alkylaluminium compound viscosity (η, Cp) pass with temperature (t, ℃) is:
η＝17.683×e
-0.0171t
The analytical procedure that the present invention relates to, open in " vapor-phase chromatography and chemical method are measured total speed of alkyl replacement(metathesis)reaction in the mixture of alkyl aluminum " (Li Baojun etc. analyze chemistry 2001,8 (29) 913 chemical press).
The selectivity of high-carbon alpha-olefin is:
The high alkylaluminium compound transformation efficiency:
High alkylaluminium compound is carried with the double plunger volume pump, after stopping valve, check valve enter preheating oven and are preheated to 120-180 ℃, by liquid phase conduit top continuously, the stable single-stage spraying tubular reactor that enters, its linear velocity is 1-4cm/s; Meanwhile, fresh ethylene and cyclic ethylene are joined, and through mass-flow gas meter, precision pressure gauge after entering tubular type electrical heater (controlling from setting parameter PID instrument with intelligence) and being heated to 280-300 ℃, enters this reactor with tangential direction.Ethene is 150-300m/s in nozzle place linear velocity, forms the downward ethylene stream of high speed rotating, and high alkylaluminium compound is disperseed, atomizes.Pipe nipple on rotation liquid phase conduit can make the liquid phase outlet cone of its lower end upper and lower mobile, can change fogdrop diameter, makes it to become the micron order droplet.Atomizing back high alkylaluminium compound sprays into reaction tubes, in 230-300 ℃, carries out replacement(metathesis)reaction under the 0.5-1.8Mpa and makes vaporific reaction product.This reactor solution-air contact area is very big, and reaction is fast, and the residence time was less than 1 second.The high alkylaluminium compound transformation efficiency is more than 80% after testing, and high-carbon alpha-olefin selectivity＞99% is not found the product isomerization.
Vaporific as mentioned above reaction product, be cooled to 20-60 ℃ through heat-eliminating medium and form emulsion, enter the double plate knockout tower by liquid phase conduit upper end then and separate, splash when preventing that emulsion from advancing tower, vertical tapered, jar mouthful surge tank of inwardly receiving in the reverse bottom of the section outside in the feed-pipe tower.Emulsion is sprayed onto at the bottom of the surge tank inner conical, flow to the many groups double plate that is used for the solution-air separation of emulsions under it along inwall, roller flower or groove on each dish upper surface become membrane flow, help the solution-air flash separation, can improve its separating effect, the gas phase entrainment that flashes off is behind mist catching net layer, and gas phase is separated by cat head through catching on the mist post eyelet, and compressed machine and fresh ethylene are joined and returned to single-stage spraying tubular reactor.And thick product enters basin at the bottom of by tower, makes purpose product high-carbon alpha-olefin through fractionation then, and the rectifying tower bottoms is produced C through oxydrolysis
10-16Higher alcohols.1-butylene content is less than 1.0% in the ethene, and ethylene content is less than 1.0% in the thick product.Do the displacer economical rationality with ethene; Ethene and high-carbon alpha-olefin vapour pressure deficit are big, separate easily.Adopt single-stage spraying tubular reactor, the table of equipment number is few, and reactor nozzle is difficult for stopping up, no back-mixing, and the reaction times is less than 1 second, no product isomerization, technology is succinct, and reactor and knockout tower are simple and compact for structure reasonable, and the three wastes are few.
Technical solution of the present invention provides α-C in the high-carbon alpha-olefin product
20-24Alkene further is not processed into low-carbon alkene as commodity.α-C wherein
4-18The alkene technical specification sees the following form:
| Project is the state smell in the time of 20 ℃ | α-C 4 ＝ | ?α-C 6 ＝ | ??α-C 8 ＝To α-C 10 ＝The colourless transparent liquid nonirritant | ?α-C 12 ＝ | ?α-C 14 ＝ | α-C 16 ＝ | |||
| Molecular-weight average | 56 | ?84 | ?112 | 140 | ?168 | ?196 | 225 | ||
| Density in the time of 20 ℃ | ?0.67 | ?0.71 | 0.74 | ?0.76 | ?0.77 | 0.78 | |||
| Refractive index nD20 | ?1.3879 | ?1.4087 | 1.4215 | ?1.4300 | ?1.4364 | 1.441 | |||
| Freezing point ℃ | ?-140 | ?-102 | -66 | ?-36 | ?-14 | 3 | |||
| Kinematic viscosity cst in the time of 20 ℃ | ?0.40 | ?0.70 | 1.10 | ?1.80 | ?2.75 | 4.00 | |||
| Flash-point PMC ℃ | ?-26 | ?15 | 46 | ?77 | ?102 | 130 | |||
| | ?60 ?66 | ?122 ?126 | 158 168 | ?210 ?213 | ?245 ?251 | 280 290 | |||
| Water-content mg/kg | ?20 | ?50 | ?100 | 100 | ?100 | ?100 | 100 | ||
| Carbon monoxide content ppm | ?1 | ?5 | ?10 | 10 | ?15 | ?15 | 15 | ||
| Peroxide level ppm | ?1 | ?2 | ?3 | 1 | ?3 | ?3 | 3 | ||
| Carbon number distribution % | ?C 4 | ?＞99.0 | ?＜0.5 | ||||||
| ?C 6 | ?＜0.00 ?5 | ?＞99.5 | ?＜1 | ||||||
| ?C 8 | ?＜0.2 | ?＞98.5 | ＜1 | ||||||
| ?C 10 | ?＜0.1 | ?＜0.5 | ＞97.5 | ?＜1 | |||||
| ?C 12 | ＜2 | ?＞97 | ?＜2 | ||||||
| ?C 14 | ?＜2 | ?＞95 | ＞5 | ||||||
| ?C 16 | ?＜4 | ＞92 | |||||||
| ?C 18 | ＜5 | ||||||||
| Hydrocarbon content %W | The n-alpha-olefin | ＞99.0 | ?＞96.0 | ?＞95.5 | ＞96.0 | ?＞95.0 | ?＞94.0 | ＞94.0 | |
| Branched-chain alkene | ＜1.0 | ?＜3.7 | ?＜3.5 | ＜3.0 | ?＜3.0 | ?＜4.0 | ＜4.0 | ||
| β-alkene | ＜1.0 | ＜2.5 | ?＜2.5 | ?＜2.5 | ＜2.5 | ||||
| Alkane | 0.005 | ?＜0.1 | ?＜0.1 | ＜0.2 | ?＜0.2 | ?＜0.2 | ＜0.2 | ||
| Conjugated diene | ＜0.02 | ?＜0.1 | ?＜0.1 | ＜0.1 | ?＜0.1 | ?＜0.1 | ＜0.1 | ||
| Aromatic hydrocarbons | ?＜0.1 | ?＜0.1 | ＜0.1 | ?＜0.1 | ?＜0.1 | ＜0.1 | |||
| Total single hydrocarbon hydrocarbon | ?＞99.0 | ?98.5 | ?99.0 | ?99.0 | ?99.0 | 99.0 | |||
Description of drawings Fig. 1, be preparation high-carbon alpha-olefin process flow diagram; Fig. 2, for spraying tubular type structure of reactor synoptic diagram wherein
1-reaction tubes 2-liquid phase outlet cone 3-base 4-clamping nut
5-liquid phase conduit 6-seat of honour 7-gland 8-nut Fig. 3, be double plate knockout tower structural representation wherein
1-sealing nut 2-B lower flange 3-B upper flange 4-cylindrical shell
5-discharge nozzle 6-support ring 7-dish post 8-shallow bid
Rack under the 9-deep bid 10-clamping nut 11-feed-pipe 12-
13-mist extractor-1 14-mist extractor-2 15-mist extractor-3 16-mist extractor post
The positive and negative wire connection head of the last rack 18-A of 17-lower flange 19-A upper flange 20-
The 21-surge tank
Embodiment
One, the method for preparing high-carbon alpha-olefin
Below in conjunction with accompanying drawing and example, the method that the present invention is prepared high-carbon alpha-olefin further specifies as follows:
See accompanying drawing 1, prepare the method for high-carbon alpha-olefin, comprise the steps:
High alkylaluminium compound is sent into the high alkylaluminium compound preheating oven with the double plunger volume pump with the 0.25mol/h flow, and temperature out is 120 ℃, and it directly enters metathesis reactor.Ethene is sent into the ethene preheating oven through mass-flow gas meter with the 12.5mol/h flow, and temperature out is 300 ℃, reaction pressure 1Mpa, temperature of reaction is 260 ℃, high alkylaluminium compound per pass conversion 84%, alpha-olefin selectivity＞99% is not found the product isomerization.
High alkylaluminium compound is sent into the high alkylaluminium compound preheating oven with the double plunger volume pump with the 0.25mol/h flow, and temperature out is 120 ℃, and it directly enters metathesis reactor.Ethene is sent into the ethene preheating oven through mass-flow gas meter with the 12.5mol/h flow, and temperature out is 280 ℃, reaction pressure 1Mpa, temperature of reaction is 220 ℃, high alkylaluminium compound per pass conversion 39%, alpha-olefin selectivity＞99% is not found the product isomerization.
With the same method of embodiment one, improve the high alkylaluminium compound preheating temperature, the temperature that makes the high alkylaluminium compound that enters metathesis reactor is 160 ℃, the result, high alkylaluminium compound per pass conversion 85.6%, alpha-olefin selectivity＞99% is not found the product isomerization.
Embodiment 4
With the same method of embodiment one, improve the high alkylaluminium compound preheating temperature, the temperature that makes the high alkylaluminium compound that enters metathesis reactor is 180 ℃, the result, high alkylaluminium compound per pass conversion 86%, alpha-olefin selectivity＞99% is not found the product isomerization.
With the same method of embodiment one, reducing the ethene flow is 10.0mol/h, the result, and high alkylaluminium compound per pass conversion 78%, alpha-olefin selectivity＞99% is not found the product isomerization.
With the same method of embodiment one, reducing the ethene flow is 7.5mol/h, the result, and high alkylaluminium compound per pass conversion 78%, alpha-olefin selectivity＞99% is not found the product isomerization.
With the same method of embodiment one, improve reaction pressure to 1.8Mpa, the result, high alkylaluminium compound per pass conversion 78%, alpha-olefin selectivity＞99% is not found the product isomerization.
With the same method of embodiment one, reduce reaction pressure to 0.7Mpa, the result, high alkylaluminium compound per pass conversion 81%, alpha-olefin selectivity＞99% is not found the product isomerization.
High alkylaluminium compound is sent into the high alkylaluminium compound preheating oven with the double plunger volume pump with the 0.25mol/h flow, and temperature out is 140 ℃, and it directly enters metathesis reactor.Ethene is sent into the ethene preheating oven through mass-flow gas meter with the 12.5mol/h flow, and temperature out is 300 ℃, temperature is 240 ℃ in the reaction pressure 1Mpa, tubular reactor, high alkylaluminium compound per pass conversion 54.4%, alpha-olefin selectivity＞99% is not found the product isomerization.
Two, realization prepares the spraying tubular reactor of the method for high-carbon alpha-olefin.
Now it is further specified as follows with example in conjunction with the accompanying drawings:
Embodiment: see accompanying drawing 2.Spraying tubular reactor provided by the present invention comprises: be the truncated cone-shaped short tube with base 3 lower inner wall, with the hollow reaction tubes 1 that is threaded; In this base 3, be provided with the conical cavity of outer mix nozzle, on the same horizontal plane of this cavity, correspondence is provided with two inlet pipe that are the tangential direction air inlet, and this two inlet pipe links to each other with two gas phase inlet tubes of base 3 downsides; Liquid phase outlet cone 2 in described conical cavity with the annular space between the vertical small sircle hole under the conical cavity, has constituted described outer mix nozzle; By its underpart tube inwall and this liquid phase outlet cone 2 outsides, with the liquid phase conduit 5 that is threaded; The nut 8 that is connected with the adapter of liquid phase conduit 5 upper ends is tightened promptly rotatable liquid phase conduit 5 with this nut 8 with it, make its upper and lower moving, change the annular space area of nozzle, thereby change the gas phase spouting velocity, promptly change the diameter of drop, make it to become the micron order droplet.Suitable for reading in liquid phase outlet cone 2, and between the liquid phase conduit bottom cylindrical shell bottom, be provided with gasket; By the upper inner wall and the seat of honour 6 of liquid phase conduit 5 middle parts to be threaded; By its outer wall and the seat of honour 6 inwalls gland 7 that is threaded; Between the round platform, be provided with lock packing in the tube on these gland 7 lower port and loam cake 7 tops; The nut 4 that the seat of honour 6 and base 3 are connected as a single entity.
This reactor still can be used for the system reaction that other gas phase can not be dissolved in liquid phase preferably.
Three, realization prepares the double plate knockout tower of the method for high-carbon alpha-olefin.
Now in conjunction with the accompanying drawings with example to this knockout tower, be described in detail as follows.
Embodiment, see accompanying drawing 3, double plate knockout tower provided by the present invention mainly comprises: the middle part is welded with feed-pipe 11 on the cylindrical shell 4 of A lower flange 18 being welded with upper port, and it is in the vertical pipeline section outside of central authorities in the tower, tapered in the reverse bottom, jar mouthful worn-out mouthful surge tank of inwardly receiving 21; Catch mist post 16 by what screw thread linked to each other with these surge tank 21 tapered bottom tops, it passes A upper flange 19 centers and weldering thereon.This is caught and has many eyelets on the mist post 16, and there is positive and negative wire connection 20 its upper end; On below the following rack 12 on the surge tank tapered bottom, the A upper flange 19 between the rack 17, around catching mist post 16 certainly outside to inside, be provided with the inside more more little three layers of mist extractor 13,14,15 of its mesh successively: mist extractor-1, mist extractor-2, mist extractor-3, their available bolts are separately fixed on the upper and lower rack.
Be positioned at below the above-mentioned surge tank 21, central authorities are provided with tubular dish post 7 in its lower port is welded with the cylindrical shell 4 of B upper flange 3; This dish post 7 passes B lower flange 2, and is welded on the B flange 2, and its top links to each other with clamping nut 10.In this circular discs post 7, can be provided with interior pipe, its tower is provided with water coolant (gas) inlet pipe, outlet pipe outward, and sealing nut 1 is arranged outside it.On dish post 7, from top to bottom between discharge nozzle 5 horizontal sections that cylindrical shell 4 inner undersides are provided with, by the many groups of double plates that are used to separate the solution-air emulsion of its center borehole jack on this dish post 7.Every group of double plate formed by up deep bid 9 of a mouth, the shallow bid 8 of a mouth down.Also be furnished with support ring 6 between each dish; Near outside the support ring 6, have a plurality of liquid on the deep bid 9 that supply in each big center hole, flow to the circular hole of shallow bid 8; At deep bid 9 internal surfaces, shallow bid 8 outside surfaces are (promptly big, the upper surface of shallow bid) on, be provided with several and the concentric shallow trench of dish around its card respectively, make liquid phase greatly, become liquid film to flow on the little panel surface, from deep bid 9 near the orifice flow in support ring 6 outsides to shallow bid 8, shallow bid again the film forming flash distillation separate, flow on the deep bid 9 along shallow bid 8 edges then, become membrane flow again, flash distillation also separates, so repeat, thereby with solution ethene in high-carbon alpha-olefin, tell and remove mist through above-mentioned mist extractor, ethene aperture from the mist extractor post 16 is separated by cat head, the compressed junction with fresh ethylene enters in the aforesaid single-stage spraying tubular reactor, carries out replacement(metathesis)reaction.Thick product enters in the basin from double plate knockout tower bottom, just makes the purpose product through fractionation then.
Claims (6)
1, a kind of method for preparing high-carbon alpha-olefin is characterized in that; This method mainly may further comprise the steps:
(1) high alkylaluminium compound with requirement pumps into preheating oven, is preheated to 120-180 ℃, with the linear velocity of 1-4cm/s, enters single-stage spraying tubular reactor; Simultaneously
(2) be heated to 280-300 ℃ in the ethene preheating oven with sending to after the excessive ethene metering, enter in the above-mentioned reactor with tangential direction, ethene and high alkylaluminium compound mol ratio are 30-50, the linear velocity of sentencing 150-300m/s at nozzle atomizes high alkylaluminium compound, spray into then in the reaction tubes under 230-300 ℃, 0.5-1.8Mpa and carry out replacement(metathesis)reaction, obtain vaporific reaction product;
(3) after should vaporific reaction product being cooled to 20-60 ℃, obtain emulsion;
(4) this emulsion enters the double plate knockout tower and separates, and it is compressed with fresh ethylene that cat head is told ethene, sends into described single-stage spraying tubular reactor, and liquid product enters in the basin at the bottom of tower, then through fractionation, just makes high-carbon alpha-olefin.
2, realize the single-stage spraying tubular reactor of the described method of claim 1, it is characterized in that this reactor mainly comprises:
(A) be the reaction tubes (1) that the short tube of truncated cone-shaped is connected with base (3) lower inner wall;
(B) be provided with the conical cavity of outer mix nozzle in the base (3), on the same horizontal plane of this conical cavity, correspondence is provided with two and is the tangential direction inlet pipe, and this two inlet pipe is connected with two gas phase inlet tubes of base (3) downside;
(C) liquid phase that is in the above-mentioned conical cavity exports cone (2), and the annular space under this liquid phase outlet cone (2) and the conical cavity between the vertical aperture constitutes above-mentioned outer mix nozzle;
(D) outside by its underpart barrel and this liquid phase outlet cone (2), with the liquid phase conduit (5) that screw thread is connected, liquid phase exports between suitable for reading and this liquid phase conduit (5) lower end cylindrical shell of cone (2) and is provided with gasket;
(E) seat of honour (6) that is connected with screw thread by upper inner and liquid phase conduit (5) middle part;
(F) nut (4) that the seat of honour (6) and base (3) are connected as a single entity.
(G),, be provided with lock packing between the round platform in this gland (7) lower port and top, the seat of honour (6) tube with the gland (7) that screw thread is connected by its outer wall and the seat of honour (6) inwall.
3, reactor according to claim 2 is characterized in that the last pipe nipple of described liquid phase conduit (5) is provided with nut (8).
4, realize the double plate knockout tower of the described method of claim 1, it is characterized in that this tower mainly comprises:
(A) going up the feed-pipe (11) that the middle part is connected with the cylindrical shell that is provided with lower flange (18) (4), be in the vertical pipeline section outside in the tower, tapered surge tank (21) in the reverse bottom at this feed-pipe (11);
(B) link to each other with the outer top of this surge tank (21) tapered bottom, pass A upper flange (19) center, and the coupled mist post (16) of catching, this is caught on the mist post (16) and has many eyelets;
Between the last rack (17) of (C) the following rack (12) on above-mentioned surge tank (21) tapered bottom, and A upper flange (19) below,, be provided with its mesh successively more to the more little mist catching net layer of internal layer around catching mist post (16) from outside to inside;
(D) be positioned at below the surge tank (21), central authorities in the cylindrical shell that is provided with B upper flange (3) (4) are provided with dish post (7), and it passes B lower flange (2) center and is connected with it;
(E) on above-mentioned dish post (7), from top to bottom between discharge nozzle (5) horizontal section that cylindrical shell (4) inner underside is provided with, be provided with by the many group double plates that are used for solution-air separation of emulsions of its center borehole jack on this dish post, be provided with support ring (6) between each dish, every group of double plate is by mouth deep bid (9) up, shallow bid (8) composition of a mouth down, outside support ring, have a plurality of circular holes of the shallow bid of liquid phase stream under it in each deep bid central hole.
5, knockout tower according to claim 4 is characterized in that on the upper surface of described large and small dish, is respectively equipped with to make liquid phase become liquid film mobile roller flower or drum side to be equipped with to make liquid phase to become liquid film flow several and the concentric circular groove of dish.
6, knockout tower according to claim 4, it is characterized in that described dish post (7) is a round tube, be provided with coaxial pipe in it, the tower outer segment of pipe in being somebody's turn to do, be provided with cooling but inlet pipe, the outlet pipe of medium, its outer sealing nut (1) that is provided with is provided with clamping nut (10) in this tubular dish post (7) upper end.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021098697A CN1164537C (en) | 2002-05-24 | 2002-05-24 | High-carbon alpha-olefine preparing process and apparatus |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021098697A CN1164537C (en) | 2002-05-24 | 2002-05-24 | High-carbon alpha-olefine preparing process and apparatus |
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| Publication Number | Publication Date |
|---|---|
| CN1403425A true CN1403425A (en) | 2003-03-19 |
| CN1164537C CN1164537C (en) | 2004-09-01 |
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| CNB021098697A Expired - Fee Related CN1164537C (en) | 2002-05-24 | 2002-05-24 | High-carbon alpha-olefine preparing process and apparatus |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114377644A (en) * | 2022-01-13 | 2022-04-22 | 万华化学集团股份有限公司 | Device for producing alpha-olefin and method for preparing alpha-olefin by using device |
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2002
- 2002-05-24 CN CNB021098697A patent/CN1164537C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114377644A (en) * | 2022-01-13 | 2022-04-22 | 万华化学集团股份有限公司 | Device for producing alpha-olefin and method for preparing alpha-olefin by using device |
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| Publication number | Publication date |
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| CN1164537C (en) | 2004-09-01 |
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