CN114163286B - Method and device for producing isododecane and co-producing triisobutene through oligomerization and hydrogenation of isobutene - Google Patents
Method and device for producing isododecane and co-producing triisobutene through oligomerization and hydrogenation of isobutene Download PDFInfo
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- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 103
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 90
- 238000000034 method Methods 0.000 title claims abstract description 32
- GTJOHISYCKPIMT-UHFFFAOYSA-N 2-methylundecane Chemical compound CCCCCCCCCC(C)C GTJOHISYCKPIMT-UHFFFAOYSA-N 0.000 title claims abstract description 16
- SGVYKUFIHHTIFL-UHFFFAOYSA-N Isobutylhexyl Natural products CCCCCCCC(C)C SGVYKUFIHHTIFL-UHFFFAOYSA-N 0.000 title claims abstract description 16
- VKPSKYDESGTTFR-UHFFFAOYSA-N isododecane Natural products CC(C)(C)CC(C)CC(C)(C)C VKPSKYDESGTTFR-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 111
- 239000003054 catalyst Substances 0.000 claims abstract description 104
- 238000000926 separation method Methods 0.000 claims abstract description 41
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims abstract description 20
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical compound CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims description 57
- 229910052739 hydrogen Inorganic materials 0.000 claims description 57
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 55
- 238000000605 extraction Methods 0.000 claims description 13
- 239000007791 liquid phase Substances 0.000 claims description 11
- 238000003860 storage Methods 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical group OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 4
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000013638 trimer Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 238000012856 packing Methods 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 230000009849 deactivation Effects 0.000 abstract description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 abstract 2
- 239000000047 product Substances 0.000 description 32
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 10
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- DRHABPMHZRIRAH-UHFFFAOYSA-N 2,4,4,6,6-pentamethylhept-2-ene Chemical group CC(C)=CC(C)(C)CC(C)(C)C DRHABPMHZRIRAH-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 238000005829 trimerization reaction Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- DFVOXRAAHOJJBN-UHFFFAOYSA-N 6-methylhept-1-ene Chemical compound CC(C)CCCC=C DFVOXRAAHOJJBN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000005586 carbonic acid group Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- 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
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/26—Catalytic processes with hydrides or organic compounds
- C07C2/28—Catalytic processes with hydrides or organic compounds with ion-exchange resins
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method and a device for producing isododecane and co-producing triisobutene by oligomerization and hydrogenation of isobutene, which comprise the following steps: a. the oligomerization catalyst and the hydrogenation catalyst are respectively filled in the reaction tower, and the raw material isobutene is polymerized by the oligomerization catalyst to produce diisobutene and triisobutene; b. extracting part of oligomerization products from the middle part of the reaction tower, separating the oligomerization products in a separation tower, circularly feeding tower top components of the separation tower into the reaction tower, and continuously reacting to obtain triisobutene products at the tower bottom; and (3) reacting part of oligomerization product triisobutene in a reaction tower through a hydrogenation catalyst to generate the isomerism dodecane. The method of the invention effectively improves the selectivity of the isobutanol, ensures that oligomerization and hydrogenation reactions are carried out in the same reactor, avoids the problem of easy deactivation of the catalyst and reduces the production cost.
Description
Technical Field
The invention relates to the field of oligomerization hydrogenation of isobutene, in particular to a method and a device for producing isododecane and co-producing triisobutene by oligomerization hydrogenation of isobutene.
Background
The isobutene oligomerization product is an important intermediate for preparing surfactants, detergents and plasticizers, and can also be used in the fields of essence, perfume, medicine, dye industry and the like. Meanwhile, the isobutene oligomerization product is adopted to produce the chemical raw material intermediate, so that the isobutene surplus can be effectively avoided.
The isobutene trimerization product is mainly used for producing intermediates of detergents, fragrances and lubricating oil, can also be used as raw materials for preparing regulators, pesticide emulsifiers and tertiary carbonic acid compounds, and can also be used in the fields of essence, medicines, dye industry and the like because the isobutene trimerization product meets the characteristic requirements of environmental protection and low toxicity in physiological toxicity.
At present, the process for producing triisobutene by oligomerization of isobutene has the current situations of low single-pass conversion rate of reaction, low selectivity of triisobutene as a product, and the like. In addition, in the prior art, the oligomerization and hydrogenation of isobutene are usually carried out in two different reactors, the selectivity of the oligomerization reaction of isobutene to triisobutene is not high, and the diisobutene produced is hydrogenated to produce low-added-value products such as isooctane. Since the oligomerization reaction of isobutene is usually a gaseous catalytic reaction, the oligomerization and hydrogenation processes are not easy to control, the problems of low selectivity of target products and the like possibly caused by direct hydrogenation of isobutene can exist, and since the oligomerization reaction of isobutene is an exothermic reaction, the service life of a hydrogenation catalyst can be influenced by overheated triisobutene products, so the oligomerization and hydrogenation reactions are not recorded in the prior art for the same reactor.
U.S. patent No. 6274783B reports a technique for preparing isooctane from isobutene through a superposition reaction and a hydrogenation reaction in a catalytic rectifying tower, wherein the superposition catalyst and the hydrogenation catalyst can be alternately packed in two or more layers or can be mixed and packed, the superposition catalyst is an acidic cation exchange resin or a molecular sieve, and the hydrogenation catalyst is a VIII metal loaded on alumina or a carbon material. The technical scheme mainly produces iso Xin Wanting and a small amount of isododecane, and does not have the function of producing triisobutene at the same time.
Chinese patent CN111217661a reports a process for the preparation of isooctane by the superposition-hydrogenation of isobutene comprising contacting hydrogen and a feedstock comprising isobutene with a superposition-hydrogenation bifunctional solid acid catalyst in a reactor to effect a superposition-hydrogenation reaction to prepare isooctane; wherein the dual function solid acid catalyst comprises an inert or acidic support, a hydrogenation active component and an acidic component. The technical scheme introduces a catalyst with polymerization and hydrogenation functions, and the catalyst is applied to the production of isooctane and has lower selectivity of isomerism dodecane.
U.S. patent No. 2131806 reports a technology for preparing isooctane by superposition-hydrogenation of isobutene, wherein solid phosphoric acid (pyrophosphoric acid/diatomite) is added into a kettle-type reactor to serve as a superposition catalyst, reduced Fe and NiO are added into the kettle-type reactor to serve as hydrogenation catalysts, raw materials isobutene and the catalysts are stirred under the hydrogen atmosphere of 8MPa at the temperature of 250 ℃ to perform superposition reaction of isobutene and hydrogenation reaction of isooctene to generate isooctane. The technical scheme is carried out at high temperature and high pressure, the requirement on a reaction system is high, the catalyst is not easy to recycle, the catalyst loss is serious, and meanwhile, the scheme is mainly applied to the production of isooctane and the selectivity of isomerically dodecane is low.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a method and a device for producing isododecane and co-producing triisobutene by oligomerization and hydrogenation of isobutene, which solve the problems that the triisobutene of an oligomerization product is low in selectivity, oligomerization and hydrogenation cannot be carried out in the same equipment, and the like.
In order to achieve the above object, the present invention has the following technical scheme:
a method for producing isododecane and co-producing triisobutene by oligomerization and hydrogenation of isobutene comprises the following steps:
a. the oligomerization catalyst and the hydrogenation catalyst are respectively filled in the reaction tower, and the raw material isobutene is polymerized by the oligomerization catalyst to produce diisobutene and triisobutene;
b. extracting part of oligomerization products from the middle part of the reaction tower, separating the oligomerization products in a separation tower, circularly feeding tower top components of the separation tower into the reaction tower, and continuously reacting to obtain triisobutene products at the tower bottom; and (3) reacting part of oligomerization product triisobutene in a reaction tower through a hydrogenation catalyst to generate the isomerism dodecane.
In some preferred embodiments of the present invention, the reaction column feed composition comprises a separation column overhead component having a mass concentration of from 10 to 30wt% and a feed isobutylene having a mass concentration of from 70 to 90 wt%; by adjusting the raw material composition at the inlet of the reaction tower, the yield ratio of the byproduct diisobutylene can be reduced, and the triisobutylene product obtained at the tower bottom of the reaction tower is separated.
In some preferred embodiments of the invention, the oligomerization catalyst is disposed in the upper portion of the reaction column to form an oligomerization catalyst loading zone, the hydrogenation catalyst is disposed in the lower portion of the reaction column to form a hydrogenation catalyst loading zone, the middle extraction port of the reaction column is disposed between the oligomerization catalyst loading zone and the hydrogenation catalyst loading zone, and the isobutylene is fed from above the oligomerization catalyst loading zone.
In some preferred embodiments of the invention, the hydrogen is fed at a temperature of 10-40 ℃.
In some preferred embodiments of the invention, the reaction column hydrogenation zone hydrogen to oil ratio, i.e., the molar ratio of hydrogen feed to olefin flow into the hydrogenation zone, is from 1.2 to 12:1, preferably 2 to 5:1.
in some preferred embodiments of the invention, the lower hydrogenation catalyst loading zone of the reaction column is fed with hydrogen, and the hydrogen feed is split into three streams in order to ensure the conversion of the hydrogenation reaction. The upper hydrogen feeding accounts for 40-60% of the total volume of the hydrogen feeding, the middle hydrogen feeding accounts for 20-30% of the total feeding volume, and the lower hydrogen feeding accounts for 20-30% of the total feeding volume. According to the invention, through reasonably distributing hydrogen feeding, the full reaction of olefin and hydrogen can be ensured, and the hydrogenation conversion rate of triisobutene is improved; meanwhile, the temperature of the triisobutene in the hydrogenation catalyst bed layer of the oligomerization reaction product can be effectively neutralized by adjusting the feeding position and the flow rate of the hydrogen, so that the catalyst deactivation caused by overhigh temperature of the triisobutene is prevented, the activity of the catalyst is ensured, and the service cycle of the catalyst is prolonged.
In some preferred embodiments of the invention, the upper section of the hydrogenation catalyst loading zone refers to the location where the hydrogenation catalyst loading zone begins to a location 1/3 of the length of the entire loading zone (preferably excluding 1/3 location), the middle section of the hydrogenation catalyst loading zone refers to the location 1/3 of the length of the hydrogenation catalyst loading zone to a location 2/3 of the length of the entire loading zone (preferably excluding 2/3 location), and the lower section of the hydrogenation catalyst loading zone refers to the location 2/3 of the length of the hydrogenation catalyst loading zone to the end location of the entire loading zone. In some preferred embodiments of the invention, a recycle hydrogen outlet is also arranged at the top of the reaction tower, and unreacted hydrogen can be recycled to the hydrogen feeding line for recycling. In some preferred embodiments of the present invention, the oligomerization catalyst is a benzenesulfonic acid resin catalyst; the hydrogenation catalyst is one or more of copper, iron and nickel catalysts, preferably copper catalysts.
In some preferred embodiments of the invention, the reaction feed is preheated prior to entering the reaction column. The reaction raw materials can be mixed by a storage tank, then enter a preheater for preheating and enter a reaction tower.
In some preferred embodiments of the invention, the reaction column feed temperature is 60 to 90℃and the reaction pressure is 2 to 4MPa.
In some preferred embodiments of the invention, the isobutylene is a liquid phase feed.
In some preferred embodiments of the invention, the isobutylene feed is at a volumetric space velocity relative to the oligomerization catalyst of from 0.5 to 8 hours -1 The volume space velocity of the oligomerization product relative to the hydrogenation catalyst is 0.5-12 h -1 ，
In some preferred embodiments of the invention, the oligomerization catalyst loading volume is 2 to 4 times the hydrogenation catalyst loading volume.
The partial conversion rate of oligomerization is above 99%, the selectivity of diisobutylene is about 20-30%, the selectivity of triisobutene is about 70-80%, the selectivity of tetramer is about 0-5%, and the feeding quantity is preferably 2-4 h relative to the volume space velocity of oligomerization catalyst in order to avoid by-producing too much tetramer -1 。
The yield of triisobutene and isododecane can be flexibly adjusted by adjusting the extraction flow in the reaction tower.
Preferably, the extraction flow in the reaction tower can be 20% -80% of the total feeding amount of the reaction tower.
In some preferred embodiments of the invention, the separation column bottom operating temperature is 150-190 ℃, the column top operating temperature is 30-80 ℃, the operating pressure is 5-30 kPaA, the reflux ratio is 0.5-8, the number of column plates in the rectifying column section is 10-25, and the number of column plates in the stripping section is 10-20. The separation tower is conventional equipment, the top of the tower is provided with a condenser and a reflux pump, and the bottom of the tower is provided with a reboiler and a circulating pump, which are not described in detail. The tower top component of the separation tower is mainly diisobutylene, the feeding composition of the reaction tower can be adjusted by circularly entering the reaction tower, diisobutylene and isobutene are polymerized again in the reaction tower to obtain triisobutylene, through the operation, the yield of the by-product diisobutylene is reduced, the selectivity of the product triisobutylene and the isomeric dodecane is improved, and the co-production of the triisobutylene and the isomeric dodecane is realized.
The invention also provides a device for producing the isododecane and the co-producing triisobutene by oligomerization and hydrogenation of isobutene, which comprises an isobutene storage tank, a feed preheater, a reaction tower and a separation tower, wherein the isobutene storage tank is connected with the feed preheater through a feed pump, the discharge of the feed preheater is connected with a feed inlet above the reaction tower, an oligomerization catalyst is loaded at the upper part of the reaction tower, a hydrogenation catalyst is loaded at the lower part of the reaction tower, a hydrogen feed inlet is arranged in a hydrogenation catalyst loading area, the hydrogen feed inlet is divided into three parts and is respectively positioned at the upper part, the middle part and the lower part of the hydrogenation catalyst loading area, a middle extraction outlet is arranged between the oligomerization catalyst loading area and the hydrogenation catalyst loading area, and the middle extraction outlet is connected with the separation tower through a pipeline.
Preferably, the upper end of the reaction tower is provided with a circulating hydrogen outlet, and circulating hydrogen enters a hydrogen feeding pipeline in a circulating way through a compressor.
And a tower top extraction port is arranged above the separation tower, and the tower top extraction port enters an isobutene storage tank through a pipeline.
The separation tower is filled with high-efficiency separation structured packing or sieve plates.
The invention also provides application of the method, and the method can be suitable for olefin oligomerization hydrogenation processes of ethylene oligomerization products, propylene dimers, propylene trimers, propylene tetramers, isobutene dimers, isobutene trimers, isobutene tetramers and the like, and can be used for producing corresponding products such as olefin, isoparaffin and the like.
Compared with the prior art, the application has the following beneficial effects:
the invention innovatively realizes that oligomerization and hydrogenation are carried out in the same reactor, meanwhile, the raw material isobutene adopts liquid-phase feeding, so that the reaction condition is easier to control, partial oligomerization products are extracted by arranging the reaction tower, so that diisobutene products can be recycled, the conversion rate of isobutene and the selectivity of triisobutene are improved, the feeding amount of oligomerization and hydrogenation can be regulated, the triisobutene and the isododecane productivity can be flexibly regulated, and the two reactions are better balanced and controlled to be carried out simultaneously.
In addition, the invention effectively solves the problems that the direct hydrogenation temperature of the oligomerization product is too high and the service life of the hydrogenation catalyst is influenced, reasonably rationalizes the heat of the oligomerization product, has mild reaction conditions, reduces equipment investment and saves energy.
Drawings
FIG. 1 is a schematic diagram of an apparatus for producing isododecane and co-producing triisobutene by oligomerization and hydrogenation of isobutene according to the present invention.
Wherein 1 is an isobutene storage tank, 2 is a feed pump, 3 is a feed preheater, 4 is a reaction tower, 5 is a separation tower, and 6 is a compressor.
FIG. 2 is a schematic diagram of a comparative example apparatus.
Wherein 1 is an isobutene storage tank, 2 is a feed pump, 3 is a feed preheater, 5 is a separation tower, 6 is a compressor, 7 is an oligomerization tower, 8 is a hydrogenation tower, 9 is a hydrogen preheater, and 10 is a triisobutene preheater.
The specific implementation method comprises the following steps:
the invention is further described below with reference to the accompanying drawings, but the invention is not limited thereto.
The raw material sources are as follows:
the hydrogen is derived from industrial park to produce hydrogen with purity of 99.9%.
Isobutylene was purchased from ortraceae with a purity of 99.9% or more.
The invention is further described by the following examples:
examples analytical instruments and methods are as follows:
gas chromatograph: agilent-7820;
gas chromatographic column: DB-5 capillary column with the thickness of 0.25mm multiplied by 30m, detector FID, vaporizing chamber temperature of 280 ℃, column box temperature of 280 ℃, FID detector temperature of 300 ℃, argon current-carrying capacity of 2.1mL/min, hydrogen flow of 30mL/min, air flow of 400mL/min and sample injection amount of 1.0 mu L. The conversion of the alkene and the selectivity of the product were calculated using an area normalization method. Heating program: preheating to 40 deg.C, maintaining for 5min, and heating from 40 deg.C to 280 deg.C at 15 deg.C/min for 2min.
Example 1
Referring to fig. 1, the device for producing isododecane and co-producing triisobutene by oligomerization and hydrogenation of isobutene comprises an isobutene storage tank 1, a feed preheater 3, a reaction tower 4 and a separation tower 5, wherein the isobutene storage tank 1 is connected with the feed preheater 3 through a feed pump 2, the discharge of the feed preheater 3 is connected with a feed inlet above the reaction tower 4, an oligomerization catalyst is loaded at the upper part of the reaction tower, a hydrogenation catalyst is loaded at the lower part of the reaction tower, a hydrogen feed inlet is arranged in a hydrogenation catalyst loading area, the hydrogen feed inlet is divided into three parts, namely, the upper part, the middle part and the lower part of the hydrogenation catalyst loading area, a middle extraction outlet is arranged between the oligomerization catalyst loading area and the hydrogenation catalyst loading area, and the middle extraction outlet is connected with the separation tower through a pipeline.
Preferably, a recycle hydrogen outlet is arranged at the upper end of the reaction tower, and recycle hydrogen enters a hydrogen feeding pipeline through a compressor 6 in a recycle way.
The upper part of the reactor is an oligomerization catalyst loading area filled with benzenesulfonic acid resin (manufacturer: dow), the lower part is a hydrogenation catalyst loading area filled with a copper-based hydrogenation catalyst (manufacturer: quick Kai new material), and the loading volume of the oligomerization catalyst is 2 times of that of the hydrogenation catalyst. The temperature of the isobutene raw material is 15 ℃, the pressure is 0.4MPa, the flow is 80kg/h, the diisobutene returned from the top of the separation tower is 23kg/h, after the raw material isobutene and the recovered diisobutene are mixed, the pressure is increased to 2.0MPa by an isobutene feeding pump, an isobutene preheater is heated to 60 ℃, and the isobutene enters from the top of the reaction tower to carry out oligomerization reaction and hydrogenation reaction respectively. Wherein, the space velocity of the feeding volume of the oligomerization section of the reaction tower is 4.12h -1 The reaction pressure was 2.0MPa, and the inside of the reaction column was a liquid phase reaction.
77.25kg/h (75% of the total feeding amount) of oligomerization reaction products are extracted to a separation tower through a middle pipeline of the reaction tower for separation, 23kg/h of diisobutylene as a tower top material is recycled to an inlet of the reaction tower, and the material components at the inlet of the reaction tower are adjusted. The bottom of the separation column yields about 54.25kg/h of triisobutene product. The bottom of the reaction column gave 25.75kg/h of hydrogenated product (wherein dodecane was isomerised 17.8 kg/h).
The number of the tower plates of the separation tower is 15, and the number of the tower plates of the stripping section is 15; the operation temperature of the tower bottom is 160 ℃, and the operation temperature of the tower top is 50 ℃; operating pressure 15kPaA; reflux ratio 2.
Hydrogenation reaction section, hydrogen feed 6Nm 3 And/h, divided into three feeds, the upper feed 3Nm 3 And the feeding rate of the middle section and the lower end is 1.5Nm respectively 3 And/h. Based on the feeding and discharging of the components of the reaction, the space velocity of the liquid phase feeding volume is about 2.1h -1 The hydrogen to oil ratio was about 1.5.
Example 2
The same reaction apparatus as in example 1 was used in this example, except that the hydrogenation catalyst was a supported nickel catalyst (manufacturer: haitai technology), and the oligomerization catalyst loading volume was 3.5 times the hydrogenation catalyst loading volume. Isobutene with the temperature of 15 ℃ and the pressure of 0.4MPa and the flow rate of 80kg/h is mixed with diisobutene returned from the top of the separation tower of about 11.88kg/h, the pressure is increased to 2.0MPa by an isobutene feeding pump, an isobutene preheater is heated to 60 ℃ and enters from the top of the reaction tower, and oligomerization reaction and hydrogenation reaction are respectively carried out. Wherein, the space velocity of the feeding volume of the oligomerization section of the reaction tower is 3.67h -1 The reaction pressure is controlled to be 2.0MPa, and the liquid phase reaction is carried out in the reaction tower.
46.17kg/h (50% of total feed) of oligomerization reaction products are extracted to a separation tower through a middle pipeline of the reaction tower for separation, 11.88kg/h of diisobutylene as a tower top material is recycled to an inlet of the reaction tower, and the material components at the inlet of the reaction tower are adjusted. The bottom of the separation tower is about 33.82kg/h of triisobutene product. The bottom of the reaction column gave 46.18kg/h of hydrogenated product (wherein dodecane was isomerised 33.82 kg/h).
The number of the column plates of the separation column is 15, and the number of the column plates of the stripping section is 15. The tower bottom operation temperature is 160 ℃, and the tower top operation temperature is 50 ℃. The operating pressure was 15kPaA. Reflux ratio 2.
Hydrogenation reaction section, hydrogen feed rate 42Nm 3 And/h, divided into three feeds, the upper feed 18Nm 3 /h, mid-stage feed 12Nm 3 /h, lower feed 12Nm 3 And/h. Based on the feeding and discharging of the reaction components, the space velocity of the liquid phase feeding volume is about 6.5h -1 The hydrogen to oil ratio was 6.
Example 3
The same reaction apparatus as in example 1 was used in this example, except that the hydrogenation catalyst was a supported iron-based catalyst (manufacturer: haitai technology), and the oligomerization catalyst loading volume was 3.5 times the hydrogenation catalyst loading volume. Isobutene with the temperature of 15 ℃ and the pressure of 0.4MPa and the flow rate of 80kg/h is mixed with diisobutene returned from the top of the separation tower of about 6kg/h, the pressure is increased to 2.0MPa by an isobutene feeding pump, an isobutene preheater is heated to 60 ℃ and enters from the top of the reaction tower, and oligomerization reaction and hydrogenation reaction are respectively carried out. Wherein, the space velocity of the feeding volume of the oligomerization section of the reaction tower is 3.43h -1 The reaction pressure is controlled to be 2.0MPa, and the liquid phase reaction is carried out in the reaction tower.
21.6kg/h (25% of total feed amount) of oligomerization reaction products are extracted to a separation tower through a middle pipeline of the reaction tower for separation, 5.94kg/h of diisobutylene as a tower top material is recycled to an inlet of the reaction tower, and the material components at the inlet of the reaction tower are adjusted. The bottom of the separation column yields about 15.66kg/h of triisobutene product. The bottom of the reaction column gave 63.54kg/h of hydrogenated product (wherein dodecane 47.47kg/h was isomerised).
The number of the column plates of the separation column is 15, and the number of the column plates of the stripping section is 15. The tower bottom operation temperature is 160 ℃, and the tower top operation temperature is 50 ℃. The operating pressure was 15kPaA. Reflux ratio 2.
In the hydrogenation reaction section, the hydrogen feed rate was 87Nm 3 And/h, divided into three feeds, the upper feed 43.5Nm 3 Feeding 21.75Nm at the middle and lower ends 3 And/h. Based on the feeding and discharging of the components of the reaction, the space velocity of the liquid phase feeding volume is about 8.9h -1 The hydrogen to oil ratio was about 9.
Comparative example 1
At present, the oligomerization and hydrogenation reactions are carried out in two reactors or towers by the common method, and can be seenFIG. 2 shows that the oligomerization tower is filled with benzenesulfonic acid resin (manufacturer: dow), the hydrogenation tower is filled with copper-based hydrogenation catalyst (manufacturer: quick Kai new material), the oligomerization feeding amount is 80kg/h, and the feeding volume space velocity is 3.2h -1 The reaction pressure is 2MPa, the temperature is 70 ℃, the reaction conversion rate is 80%, the DIB selectivity in the product is 60%, and the TIB selectivity is 40%. In the hydrogenation reaction stage, hydrogen is preheated to 100-120 ℃ for feeding, the liquid phase feeding temperature is 100-120 ℃, and the liquid phase feeding airspeed is 2h -1 The hydrogen-oil ratio is 3: after hydrogenation in a hydrogenation reactor, the reaction conversion rate is 90%, the isododecane is about 23kg, and the isooctane is about 34.5kg.
Comparing examples 1 to 3 with comparative example 1 above, it was found that the products in the comparative examples were isooctane and isododecane, and triisobutene could not be co-produced at the same time, and the product yield did not have flexibility. Meanwhile, the equipment investment in comparative example 1 is higher than that in examples 1 to 3.
Claims (19)
1. The method for producing isododecane and co-producing triisobutene by oligomerization and hydrogenation of isobutene is characterized by comprising the following steps:
a. the oligomerization catalyst and the hydrogenation catalyst are respectively filled in the reaction tower, and the raw material isobutene is polymerized by the oligomerization catalyst to produce diisobutene and triisobutene;
b. extracting part of oligomerization products from the middle part of the reaction tower, separating the oligomerization products in a separation tower, circularly feeding tower top components of the separation tower into the reaction tower, and continuously reacting to obtain triisobutene products at the tower bottom; part of oligomerization product triisobutene reacts in a reaction tower through a hydrogenation catalyst to generate isomerism dodecane;
the oligomerization catalyst is a benzenesulfonic acid resin catalyst; the hydrogenation catalyst is one or more of copper, iron and nickel catalysts;
in the reaction tower, oligomerization catalyst is arranged at the upper part of the reaction tower to form an oligomerization catalyst loading area, hydrogenation catalyst is arranged at the lower part of the reaction tower to form a hydrogenation catalyst loading area, a middle extraction port of the reaction tower is positioned between the oligomerization catalyst loading area and the hydrogenation catalyst loading area, and isobutene is fed from above the oligomerization catalyst loading area;
hydrogen is introduced into a hydrogenation catalyst loading area at the lower part of the reaction tower, and hydrogen feeding is divided into three strands;
the upper hydrogen feeding accounts for 40-60% of the total volume of the hydrogen feeding, the middle hydrogen feeding accounts for 20-30% of the total feeding volume, and the lower hydrogen feeding accounts for 20-30% of the total feeding volume.
2. The process according to claim 1, wherein the reaction column feed comprises a separation column overhead component in a mass concentration of 10 to 30 wt.% and a feed isobutene in a mass concentration of 70 to 90 wt.%.
3. The method of claim 1, wherein the hydrogen is fed at a temperature of 10 to 40 ℃.
4. The process according to claim 1, wherein the reaction column hydrogenation zone hydrogen to oil ratio, i.e. the molar ratio of the hydrogen feed to the olefin flow into the hydrogenation zone is from 1.2 to 12:1.
5. the process according to claim 4, wherein the reaction column hydrogenation zone hydrogen to oil ratio, i.e. the molar ratio of the hydrogen feed to the olefin flow into the hydrogenation zone is from 2 to 5:1.
6. the method according to claim 1, wherein the top of the reaction tower is further provided with a circulating hydrogen outlet, and unreacted hydrogen can be recycled to the hydrogen feeding line for recycling.
7. The process of claim 1, wherein the hydrogenation catalyst is a copper catalyst.
8. The method according to claim 1, wherein the feeding temperature of the reaction tower is 60-90 ℃ and the reaction pressure is 2-4 MPa.
9. The process of claim 1, wherein the isobutylene is a liquid phase feed.
10. The process according to claim 1, wherein the volumetric space velocity of the isobutene feedstock relative to the oligomerization catalyst is from 0.5 to 8 hours -1 。
11. The process according to claim 10, wherein the volumetric space velocity of the isobutylene feed relative to the oligomerization catalyst is from 2 to 4 hours -1 。
12. The process according to claim 1, wherein the volume space velocity of the oligomerization product relative to the hydrogenation catalyst is from 0.5 to 12 hours -1 。
13. The process of claim 1 wherein the oligomerization catalyst loading volume is from 2 to 4 times the hydrogenation catalyst loading volume.
14. The method according to claim 1, wherein the extraction flow rate in the reaction tower is 20-80% of the total feed rate in the reaction tower.
15. The method according to claim 1, wherein the separation column has a column bottom operation temperature of 150-190 ℃, a column top operation temperature of 30-80 ℃, an operation pressure of 5-30 kPaA, a reflux ratio of 0.5-8, a rectifying column stage tray number of 10-25, and a stripping column stage tray number of 10-20.
16. The method according to claim 1, wherein the device for producing the isododecane and the co-producing triisobutene by oligomerization and hydrogenation of isobutene comprises an isobutene storage tank, a feed preheater, a reaction tower and a separation tower, wherein the isobutene storage tank is connected with the feed preheater through a feed pump, the discharge of the feed preheater is connected with a feed inlet above the reaction tower, the upper part of the reaction tower is loaded with oligomerization catalyst, the lower part of the reaction tower is loaded with hydrogenation catalyst, a hydrogenation catalyst loading area is provided with a hydrogen feed inlet, the hydrogen feed inlet is divided into three parts, and a middle extraction outlet is respectively arranged at the upper part, the middle part and the lower part of the hydrogenation catalyst loading area, and the middle extraction outlet is connected with the separation tower through a pipeline.
17. The method according to claim 16, wherein the reaction tower is provided at an upper end thereof with a recycle hydrogen outlet, and recycle hydrogen is circulated into the hydrogen feed line through a compressor.
18. The method of claim 16, wherein a top take off is provided above the separation column, the top take off being via a pipeline into an isobutylene storage tank;
the separation tower is filled with high-efficiency separation structured packing or sieve plates.
19. Use of a process according to any one of claims 1 to 18 for the oligomerization hydrogenation of ethylene oligomerization products, propylene dimers, propylene trimers, propylene tetramers, isobutylene dimers, isobutylene trimers, isobutylene tetramers.
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