CN110128251A - Hydroformylation process and equipment - Google Patents
Hydroformylation process and equipment Download PDFInfo
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- CN110128251A CN110128251A CN201910550807.5A CN201910550807A CN110128251A CN 110128251 A CN110128251 A CN 110128251A CN 201910550807 A CN201910550807 A CN 201910550807A CN 110128251 A CN110128251 A CN 110128251A
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- reaction kettle
- reaction
- gas
- inspiratory limb
- nozzle
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- 238000007037 hydroformylation reaction Methods 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 40
- 230000008569 process Effects 0.000 title abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 359
- 239000012530 fluid Substances 0.000 claims abstract description 90
- 239000007921 spray Substances 0.000 claims abstract description 87
- 239000003054 catalyst Substances 0.000 claims abstract description 77
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 71
- 230000003434 inspiratory effect Effects 0.000 claims abstract description 66
- 239000007788 liquid Substances 0.000 claims abstract description 47
- 238000002156 mixing Methods 0.000 claims abstract description 39
- 239000002994 raw material Substances 0.000 claims abstract description 33
- 238000004891 communication Methods 0.000 claims abstract description 16
- 150000001336 alkenes Chemical class 0.000 claims description 105
- 230000015572 biosynthetic process Effects 0.000 claims description 57
- 238000009826 distribution Methods 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 22
- 239000011541 reaction mixture Substances 0.000 claims description 22
- 238000004064 recycling Methods 0.000 claims description 13
- 230000005587 bubbling Effects 0.000 claims description 7
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 5
- -1 ethylene, propylene Chemical group 0.000 claims description 5
- ARGCQEVBJHPOGB-UHFFFAOYSA-N 2,5-dihydrofuran Chemical compound C1OCC=C1 ARGCQEVBJHPOGB-UHFFFAOYSA-N 0.000 claims description 4
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 claims description 4
- 238000009792 diffusion process Methods 0.000 claims description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 2
- 239000007789 gas Substances 0.000 description 256
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 56
- 239000000243 solution Substances 0.000 description 43
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 42
- 239000012071 phase Substances 0.000 description 39
- 150000001299 aldehydes Chemical class 0.000 description 37
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 36
- 239000000047 product Substances 0.000 description 34
- 239000010948 rhodium Substances 0.000 description 24
- 238000002347 injection Methods 0.000 description 23
- 239000007924 injection Substances 0.000 description 23
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 21
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 20
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 20
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 19
- 239000005977 Ethylene Substances 0.000 description 19
- 239000007791 liquid phase Substances 0.000 description 19
- 239000003446 ligand Substances 0.000 description 17
- 229910052703 rhodium Inorganic materials 0.000 description 14
- 238000010586 diagram Methods 0.000 description 12
- 230000006698 induction Effects 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 12
- 238000005507 spraying Methods 0.000 description 11
- CTFNJPHOILFHEL-UHFFFAOYSA-N CC1=C(C=CC=C1)[P] Chemical compound CC1=C(C=CC=C1)[P] CTFNJPHOILFHEL-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 230000009471 action Effects 0.000 description 8
- 239000012295 chemical reaction liquid Substances 0.000 description 7
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000006837 decompression Effects 0.000 description 6
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000007809 chemical reaction catalyst Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000007701 flash-distillation Methods 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 238000000819 phase cycle Methods 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 150000008301 phosphite esters Chemical class 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- KYLUAQBYONVMCP-UHFFFAOYSA-N (2-methylphenyl)phosphane Chemical class CC1=CC=CC=C1P KYLUAQBYONVMCP-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000010523 cascade reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 210000000867 larynx Anatomy 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J10/00—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor
- B01J10/002—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor carried out in foam, aerosol or bubbles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
Abstract
Disclose hydroformylation process and equipment.The method includes providing hydroformylation synthesis reaction vessel; its top is equipped with the lower self-priming reactor of spray; the reactor successively includes inspiratory limb, mixing section and the diffuser that nozzle is connected with fluid; the nozzle is located in inspiratory limb; the inspiratory limb and feed gas source and reaction kettle are in fluid communication, which further includes the gas distributor being connected in reaction kettle and with feed gas source fluid；The reaction solution containing catalyst is sprayed into the reaction kettle via the nozzle of the lower self-priming reactor of spray, the reaction solution rolls up the circulating air for inhaling a part of gas raw material and reaction kettle gas phase portion from gas source in inspiratory limb, and is mixed, reacted and spread in mixing section and diffuser；Gas raw material by another part from gas source send the gas distributor to reaction kettle through pipeline, by being bubbled and the solution haptoreaction containing catalyst in reaction kettle liquid.
Description
Technical field
The present invention relates to hydroformylation synthetic method and equipment, and in particular to one kind is by alkene and synthesis gas hydroformylation system
The method of standby aldehyde, consersion unit and reaction system for this method.Reaction can be improved using the method for the present invention and reaction system
Efficiency reduces equipment investment, has high economic benefit.
Background technique
Hydroformylation of olefin is important organic synthesis, and very important effect is played in modern industry.It is produced
Object aldehyde is very useful chemical intermediate, can synthesize a variety of important Chemical products, is production scale so far
Maximum homogeneous catalytic reaction process.[Trzeciak,A.M.；J.J.Coord.Chem.Rev.1999,
190-192,883-900.]。
Main method by olefin hydroformylation production aldehyde includes low pressure rhodium catalysed hydroformylation method, and high pressure cobalt is catalyzed hydrogen first
Acylated method.Under certain condition, raw material olefin and synthesis gas H2/ CO directly enters together in the catalyst solution of reaction kettle,
Liquid phase main body, which reacts, generates aldehydes.During using the olefin hydroformylation of ligand-modified homogeneous catalyst, reaction solution
Middle concentration and temperature it is uneven can to reaction conversion ratio, the space-time yield of aldehyde (STY, it is intended that the unit time, unit volume alkene
Inversion quantity, based on reaction total volume), the just different of product seriously affected than generating, thus most of device needs to increase by stirring
Contact between strong gas-liquid, is thoroughly mixed material uniformly.With the growth of reaction carbochain, the reactivity drop of olefin hydroformylation
Low, especially when the presence of internal olefin, reactivity reduction become apparent, reaction time is long, causes byproduct of reaction more,
Thus need to find a kind of method that reaction is strengthened, Lai Tisheng reaction efficiency improves the selectivity of main reaction.
A kind of method of modifying is with stirring come mixed reaction solution.Reaction kettle mixed effect with agitating paddle is preferable, but stirs
Device construction is complicated, and the blender material used in special circumstances is expensive.Blender is had another disadvantage that using stirred autoclave
Axis has to pass through the wall of compressive reaction kettle, higher to the seal request of equipment, while being influenced by agitating shaft rotation, to reaction
Kettle sealing and agitating paddle, which have, higher answers force request.Mixing plant is easy to happen equipment fault in day-to-day operation, seriously affects life
The continual and steady operation produced.The hydroformylation of olefin device overwhelming majority of industrial practical application is all made of autoclave and stirs at present
Device is mixed, due to factors such as mass transfers, reaction efficiency is relatively low, by taking the examples of industrial application of n-butene hydroformylation as an example, 70,000 tons/
The 2- propyl enanthol process units in year, needs 3 stirred autoclave tandem reactions, and the volume of each reaction kettle is in 105m3
(" mechanical engineer ", 2015 (6): 252-254).
As the substitution of stirring-type reaction kettle, industrially has and carry out hydroformylation of olefin using bubble tower reaction kettle
Case.Reaction gas is passed through from tower bottom is bubbled, and ensures that reaction gas is scattered in reaction solution to increase and pass by gas distributor
Matter surface area, bubble disperses to rise in reaction solution, so that reaction solution be made to mix.But in simple bubble tower reaction kettle, by
Hydroformylation reaction is participated in uphill process in reaction gas, is easy to form the concentration gradient and temperature of subrange in bubble tower
Unevenness is spent, to influence the space-time yield of reaction conversion ratio, aldehyde selectivity and aldehyde, production efficiency is also below stirred autoclave.
CN 101679173B discloses a kind of by by alkene and the system of reacting of the synthetic gas comprising carbon monoxide and hydrogen
The method and apparatus of standby aldehyde, it, to improve hydroformylation efficiency, obtains desirable height in such a way that injector reinforces gas-liquid mass transfer
Yield aldehyde.
CN102272079A discloses a kind of equipment for preparing alcohol by alkene, it includes hydroformylation reactor, described
Reactor includes for spraying the injection apparatus of alkene and synthesis gas in the catalyst mixed solution into reactor, for being discharged
The reactor outlet of the reaction mixture of the alkene and synthesis gas, for changing the alkene and synthesize flow of air distribution
Plate and circulation pipe for part reaction mixture to be recycled to injection apparatus.
" pattern and application of injecting type gas-liquid reaction device " (" chemical industry and the engineering technology " 2002 of Wang little Fu etc.
The 2nd phase of volume 23) describe injecting type gas-liquid reactor.It mentions the self-priming reactor of spray under industrial typically used as having,
The lower self-priming reactor of spray is made of nozzle, induction chamber, mixing chamber and four part of diffuser casing.When with the anti-of certain pressure
The unstripped gas for when liquid being answered to spray downwards through nozzle, generating very high flow velocity, forming pressure drop around nozzle, and side is supplied
Induction chamber is sucked, turbulent flow is then thoroughly mixed to form in mixing chamber, while being reacted.Flow velocity is gradually in diffuser casing for product
It reduces, is seen off product using increased static pressure, can voluntarily suck a large amount of gas because not needing the equipment of supplying gas such as compressor
Body greatly reduces energy consumption.And material forms stable turbulent flow at nozzle, enhances the mixing between gas-liquid, controls to diffusion
The gas and liquid phase moment reaction of system is highly beneficial.
In chemical engineering industry, reaction efficiency will generate huge economic benefit even improving 1%.Although introducing injecting type
Gas-liquid reaction device improves the efficiency of hydroformylation of olefin, but there are also further improved leeway for this method.
Summary of the invention
The object of the invention is to further improve the efficiency of hydroformylation of olefin.
Therefore, one aspect of the present invention is related to a kind of hydroformylation synthesis reaction vessel, it includes being placed in the reaction kettle
The self-priming reactor of lower spray at top, the self-priming reactor of the lower spray successively include nozzle be connected with fluid inspiratory limb, mix
It closes section and diffuser, the nozzle is located in inspiratory limb, the inspiratory limb and feed gas source are in fluid communication；
It is characterized in that the inspiratory limb also passes through pipeline and the reaction kettle liquidus curve above section is in fluid communication, and
The reaction kettle further includes the gas distributor being connected inside reaction kettle and with the feed gas source fluid.
Another aspect of the present invention relates to a kind of reaction systems of hydroformylation synthetic reaction, it includes hydrogen of the present invention
Formylated synthesis reaction vessel, the reaction kettle include:
The self-priming reactor of lower spray being mounted at the top of it, the reactor successively include the air-breathing that nozzle is connected with fluid
Section, mixing section and diffuser, the nozzle are located in inspiratory limb, and the inspiratory limb is connected with feed gas source fluid, and described
Inspiratory limb also passes through pipeline and the reaction kettle liquidus curve above section is in fluid communication；
The gas distributor being connected in reaction kettle and with the feed gas source fluid；
Its underpart is mounted on for the reaction kettle outlet of reaction mixture and catalyst solution to be discharged；With
It is mounted between the self-priming reactor of the lower spray and reaction kettle outlet for changing the alkene and synthesis gas
The distribution plate of flowing；
The system also includes be then supplied to the lower self-priming reaction of spray for exporting recycling reaction mixture from reaction kettle
The nozzle of device is so that the circulation pipe that reaction mixture and catalyst solution recycle.
Another aspect of the present invention relates to a kind of methods for preparing aldehyde by alkene, it includes the following steps:
Hydroformylation synthesis reaction vessel is provided, the top of the reaction kettle is equipped with the lower self-priming reactor of spray, the lower spray
Self-priming reactor successively includes inspiratory limb, mixing section and the diffuser that nozzle is connected with fluid, and the nozzle is located at inspiratory limb
Interior, the inspiratory limb and feed gas source are in fluid communication, and the inspiratory limb also pass through pipeline and the reaction kettle liquidus curve with
Upper segment fluid flow communicates, which further includes the gas distributor being connected with feed gas source fluid；
The reaction solution containing catalyst is sprayed into the reaction kettle via the nozzle of the lower self-priming reactor of spray, this is anti-
Answer liquid to roll up the circulating air for inhaling a part of gas raw material and reaction kettle gas phase portion from gas source in inspiratory limb, and in mixing section and
Diffuser is mixed, is reacted and spread；
Gas raw material by another part from gas source send the gas distributor to reaction kettle through pipeline, in reaction kettle liquid
In by be bubbled with the solution haptoreaction containing catalyst.
Another aspect of the invention is related to the hydroformylation synthesis reaction vessel and is preparing the purposes in aldehyde by alkene.
Detailed description of the invention
The present invention is further illustrated below by attached drawing.In attached drawing:
Fig. 1 is the structural schematic diagram for the self-priming reactor of lower spray that the present invention uses；
Fig. 2 is the process flow diagram of an example of the invention；
Fig. 3 is the process flow diagram of another example of the invention；
Fig. 4 is the process flow diagram of another example of the invention；
Fig. 5 is the concatenated process flow diagram of double injection kettles in an example of the invention；
Fig. 6 is the process flow diagram of an example of the invention, wherein the self-priming reactor of lower spray passes through a Y type air inlet
Pipe is connected with feed gas source and reaction kettle gas phase portion fluid respectively.
Specific embodiment
The present inventor carefully studies existing hydroformylation synthesis reaction vessel, is found that while lower spray certainly
Suction reactor has the power that will be pushed away under reactant, is allowed to move downwardly into bottom liquid phases catalyst solution, but was running
The part Cheng Zhongyou reaction raw materials, the especially synthesis gas of lighter in weight can be suspended in the top of reaction kettle, such as the top of reaction kettle
Portion, to influence reaction efficiency.Based on the discovery that the present inventor proposes to follow the gas of reaction kettle gas phase portion
Ring introduces the inspiratory limb of the lower self-priming reactor of spray, is allowed to be recycled to lower spray reactor and be reacted, to further increase instead
Answer efficiency.
In addition, present inventor has further discovered that, if spraying self-priming reactor simultaneously under introducing in bubble tower reaction kettle
Gaseous feed is passed through to the self-priming reactor of lower spray simultaneously and gas distributor introduces reaction kettle, due to the lower self-priming reactor of spray
Jet power more or less play the role of agitation or stirring, can disappear while being advantageously employed bubble tower reaction kettle advantage
Except such as subrange concentration gradient and the defects of temperature unevenness existing for conventional bubble column reaction kettle.
Therefore, the present invention relates to a kind of hydroformylation synthesis reaction vessel, the shape, material, sizes of described reaction kettle itself
Etc. being not particularly limited, a kind of conventional reactor known in the art can be.It is described anti-in an example of the present invention
Answering kettle is vertical response kettle.In another example of the invention, the reaction kettle is horizontal reacting kettle.
Reaction kettle of the present invention includes the self-priming reactor of lower spray being placed at the top of the reaction kettle, and the lower spray is self-priming anti-
Device is answered successively and includes inspiratory limb, mixing section and the diffuser that nozzle is connected with fluid, the nozzle is located in inspiratory limb, and institute
Inspiratory limb and feed gas source is stated to be in fluid communication, the inspiratory limb also pass through pipeline and the reaction kettle liquidus curve above section or
Gas phase portion is in fluid communication.
In the present invention, the position that term " nozzle is located in inspiratory limb " is not limited to nozzle is physically located at suction
In gas section.Nozzle can keep various positions relationship with inspiratory limb, as long as ejecta can roll up suction while spraying into inspiratory limb
Gaseous feed and gas from reaction kettle gas phase portion.For example, nozzle can be located at the edge of inspiratory limb, the pressure of injection
Power is enough to volume and inhales gaseous feed.
In the present invention, " inspiratory limb also passes through pipeline and the reaction kettle liquidus curve above section or gas to term
Phase segment fluid flow communicates " in " pipeline " refer to any pipeline in addition to the routinely lower self-priming reactor body pipeline of spray.It should
Pipeline is located at outside reaction kettle.
In the present invention, term " reaction kettle liquidus curve above section " refers to higher than reaction kettle liquidus curve and follows in gas phase
The reaction kettle position of liquid will not be sucked during ring.In an example of the present invention, the reaction kettle liquidus curve is with top
Divide and refers to the close and position including reaction kettle kettle top.It is described " more than reaction kettle liquidus curve in another example of the invention
Part " refers to reaction kettle kettle top.
In the present invention, term " the lower self-priming reactor of spray includes connected inspiratory limb, mixing section and the diffuser of fluid "
Refer to that the reactor includes three functional sections with air-breathing, mixing and diffusion function, the functional section can be can physics
(such as induction chamber, mixing chamber and the diffuser casing) distinguished, be also possible to it is physically undistinguishable (a such as segment pipe, no
Respectively there is air-breathing, mixing or diffusion function with position).
Term " fluid communication " is used interchangeably with " fluid is connected " in the present invention, refer to two part be connected with each other and
Fluid can flow between the two parts.
In an example of the present invention, inspiratory limb tool is there are two gas access, one of those and feed gas source
Fluid is connected, and therein another passes through pipeline and reaction kettle liquidus curve above section, preferably at the top of reaction kettle, fluid phase
Even.
In an example of the present invention, the inspiratory limb have a gas access, the entrance by Y-piece respectively with
Feed gas source and reaction kettle liquidus curve above section are in fluid communication.
In an example of the present invention, inspiratory limb tool is there are two gas access, one of those and feed gas source
Fluid is connected, and therein another is connected by pipeline with reaction kettle liquidus curve above section fluid.In an example, nozzle
The height of mouth is lower than at least one described gas access, is preferably lower than two gas accesses simultaneously.
In an example of the present invention, inspiratory limb tool is there are two contour gas access, one of those and original
Expect that gas source fluid is connected, therein another is connected by pipeline with reaction kettle liquidus curve above section fluid, the height of jet hole
Degree is lower than the gas access.
In an example of the present invention, inspiratory limb tool is there are two gas access, one of those and feed gas source
Fluid is connected, and therein another is connected by pipeline with reaction kettle liquidus curve above section fluid.Jet hole is than at least one
The low 0.5-500mm of the minimum point of the gas access, preferable low 10-350mm, more preferable low 20-250mm, preferably low 50-200mm.
In an example of the present invention, jet hole is 0.5-30mm lower than the minimum point of gas access described at least one, preferably low
0.8-20mm, more preferable low 1-10mm.It is preferred that low 1.1-5mm.
In an example of the present invention, the height difference of described two gas accesses is less than 100mm.Preferably less than
50mm, more preferably less than 10mm, preferably less than 5mm, preferably smaller than 1mm.
It is without particular limitation that self-priming reactor configuration is sprayed under the present invention, can be conventional configurations known in the art, example
Such as reference can be made to " pattern and application of injecting type gas-liquid reaction device " (" chemical industry and the engineering technology " 2002 of Wang little Fu
The 2nd phase of volume 23) the self-priming reactor of lower spray introduced, in addition to there are two the gas of gas input port or induction chamber for inspiratory limb tool
Other than body input port is connected by a Y-piece with two strands of air-flow fluids.
In an example of the present invention, using following spray reactor disclosed in Chinese patent CN102272079A Fig. 1 b,
In addition to there are two the gas input ports of gas input port or induction chamber to pass through a Y-piece and two strands of air-flow fluids for inspiratory limb tool
Other than being connected.
Fig. 1 is the structural schematic diagram of the self-priming reactor of lower spray of an example of the invention.As shown, being sprayed under the present invention
Self-priming reactor successively includes nozzle 1, induction chamber 2, mixing chamber 3 and diffuser casing 4, and the nozzle 1 is located at the induction chamber 2
Interior, the induction chamber 2 has the gas access 6 being connected with gas source fluid and (preferably reacts with reaction kettle liquidus curve above section
Kettle kettle top) the connected gas access 7 of fluid.
When operation, the liquid stream 5 containing catalyst is sprayed downwards through nozzle 1, and the pressure volume of injection is inhaled to be drawn through unstrpped gas entrance 6
The unstrpped gas that enters and the gas from reaction kettle gas phase portion introduced through recyclegas entrance 7, three is in induction chamber 2 to mixing
It closes in 3 running path of room and is sufficiently mixed and reacts, diffuse into reaction kettle through diffuser casing 4 after.
In an example of the present invention, the gas compartment 2, mixing chamber 3 and diffuser casing 4 constitute a Venturi tube.Such as
Shown in Fig. 1.The entrance of induction chamber 2 is connected with nozzle 1, and the lower part of induction chamber is conical pipe contraction section, and mixing chamber 3 constitutes text
The venturi of venturi, diffuser casing 4 constitute the diffuser of Venturi tube.
In an example of the present invention, the 2 entrance diameter D of induction chamber that nozzle 1 is connected is 0.8-500mm, preferably
For 1-400mm, more preferably 1.5-300mm, preferably 1.75-250mm, preferably 2-100mm；Nozzle cone pipe cone angle is about 10-90
Degree, preferable 15-75 degree, more preferable 20-60 degree.The diameter of venturi is 1.0-3.0D, and length is 5-100 times of throat diameter, preferably
It is 20-60 times.The cone angle of diffuser about 5-30 degree, preferable 9-20 degree, more preferable 10-15 degree, diffuser exit diameter is about larynx
1.0-20 times of road diameter, preferably 1.2-18 times, more preferably 1.5-15 times, preferably 2-10 times.
In an example of the present invention, the overall length of the Venturi tube is 0.01-1.5 times of reaction kettle internal height,
Preferably 0.05-1.4 times, more preferably 0.08-1.2 times, preferably 0.1-1.1 times, more preferably 0.2-1 times, preferably 0.2-0.95
Times.
Reaction kettle of the present invention includes the gas distributor being connected in reaction kettle with unstrpped gas fluid, for containing catalysis
It is bubbled in the reaction solution of agent, so that unreacted material is anti-in the continuous progress of reaction kettle liquid relaying in the lower self-priming reactor of spray
It answers, further increases reaction efficiency.
In preferably embodiment of the invention, the unstripped gas scale of construction for being input to gas distributor accounts for the total amount of unstripped gas and is
30%-95%, preferable 40%-90%, more preferable 50%-85%, preferably 60%-85%.
The position of gas distributor is without particular limitation in the reaction kettle, as long as it can be in the reaction solution containing catalyst
In be bubbled.After having read present disclosure, those skilled in the art be can easily determine suitably
Gas distributor position.
Gas distributor suitable for reaction kettle of the present invention is without particular limitation, can be gas distribution known in the art
Device.After having read present disclosure, the common timely personnel of this field can easily determine suitable gas distribution
Device and its installation dimension, for example, those skilled in the art can be according to " the gas distributor design in bubbling bed of the iron of fine quality etc.
And its influence to hydraulics " (" coal chemical industry ", 2 months nineteen ninety-fives) selected works select applicable gas distributor.
In an example of the present invention, alkene 100% enters gas distributor, the unreacted reacted kettle gas of unstripped gas
Injector is mutually drawn to by volume, under the effect of the catalyst further reaction.
In an example of the present invention, the alkene of hydroformylation synthetic reaction of the present invention is together with catalyst solution
Inspiratory limb is sprayed by nozzle, volume inhales the gas of unstrpped gas and reaction kettle gas phase portion while spraying into, and three's mixing is simultaneously anti-
It answers, reaction product needed for being formed.
In an example of the present invention, the alkene for hydroformylation synthetic reaction of the present invention is gaseous olefin,
The liquid stream 5 containing catalyst includes the catalyst solution and optional raw material olefin of fresh catalyst solution and/or circulation at this time,
It include synthesis gas and optional raw material olefin through unstrpped gas entrance unstrpped gases being attracted into of volume 6, through recyclegas entrance volume 7
The gas being attracted into is the gas from reaction kettle gas phase portion, and the air-flow introduced in gas distributor includes synthesis gas
And/or gaseous olefin.
In another example of the invention, the alkene for hydroformylation synthetic reaction of the present invention is liquid olefinic
Hydrocarbon, liquid stream 5 includes the catalyst solution of alkene, fresh catalyst solution and/or circulation at this time, through unstrpped gas entrance volume 6
The unstrpped gas being attracted into includes synthesis gas, is from reaction kettle gas phase portion through recyclegas entrance gases being attracted into of volume 7
Gas, and the air-flow introduced in gas distributor includes synthesis gas.
In the present invention, the synthesis gas is CO/H2Mixed gas, it can easily with conventional method be made, such as
It is made with conventional water-gas synthetic method.
The invention further relates to the reaction systems for hydroformylation synthetic reaction, it includes that hydroformylation of the present invention is closed
At reaction kettle, the reaction kettle includes being mounted on its top to be used for raw material olefin, synthesis gas (CO/H2), catalyst solution with
And self-priming reactor is sprayed under the present invention of reaction kettle gas phase cycle stock injection reaction kettle；Be mounted on its underpart for be discharged reaction
The outlet of the reaction kettle of mixture and catalyst solution；It is mounted between the self-priming reactor of the lower spray and reaction kettle outlet and is used for
Change the alkene and synthesizes the distribution plate of flow of air；For from reaction kettle export recycling reaction mixture and catalyst solution and
Be supplied to the nozzle of the self-priming reactor of lower spray afterwards so that reaction mixture circulation circulation pipe, and be mounted on reaction kettle liquid phase
It is connected with feed gas source fluid for generating the gas distributor being bubbled below line.
In the present invention, term " reaction kettle lower part " refers to reaction kettle liquidus curve position below.At of the invention one
In example, " the reaction kettle lower part " includes reactor bottom.
The distribution plate in reaction kettle is mounted on for changing the flowing of the lower self-priming reactor injection stream of spray, so as to adjust anti-
Answer the residence time of raw material in a kettle.Those skilled in the art easily can require determining point according to specific reaction
The location and shape of matching board in a kettle.For example, those skilled in the art can be according to specific reaction bonded China specially
The disclosed distribution plate shape of sharp CN102272079A and setting requirements determine the location and shape of distribution plate in a kettle.
Fig. 2 is the reaction process schematic diagram of an example of the invention.As shown in Fig. 2, the present invention is synthesized for hydroformylation
The reaction system of reaction includes hydroformylation synthesis reaction vessel 10 of the present invention, and the reaction kettle 10 includes that lower spray is self-priming anti-
Device 16 is answered, there are two independent gas access, the gas phase portions of one of those and reaction kettle for the inspiratory limb tool of the reactor 16
Fluid is connected, another is connected with feed gas source fluid.Reactor 16 is mounted at the top of reaction kettle, for that will pass through pipeline 110
It is recycled with raw material olefin, synthesis gas (CO/H2) and the fresh catalyst solution (if necessary) of 111B input, by pipeline 19
Reaction kettle gas phase cycle stock and by pipeline 113 and 114 recycle containing catalyst solution by nozzle 17 inject reaction kettle simultaneously
It is reacted simultaneously；Reaction kettle lower connection pipe road 112 is mounted on for the anti-of the reaction mixture containing catalyst solution to be discharged
Kettle is answered to export；It is mounted between the self-priming reactor 16 of the lower spray and reaction kettle outlet for changing the alkene and synthesis gas
The distribution plate 12 of flowing；The lower spray self-priming is then supplied to for recycling reaction mixture through pipeline 113 from reaction kettle outlet
The nozzle 17 of formula reactor 16 is so that the circulation pipe 114 that reaction mixture recycles.
In an example of the present invention, the reaction system further includes the vacuum flashing being connected with reaction kettle outlet fluid
Tank 22, and the aldehydes evaporator 23 being connected with 22 fluid of vacuum flashing pipe, the bottom of the aldehydes evaporator 23 and reaction kettle
The nozzle 17 of the self-priming reactor 16 of lower spray be connected through pipeline 124,125,113 with 114 fluids.
In use, when olefin feedstock is in a liquid state, the nozzle 17 of the lower self-priming reactor 16 of spray will be inputted through pipeline 110
Liquefied olefines solution and fresh catalyst solution (if necessary) contain catalyst from reaction kettle through what pipeline 112 recycled
Solution and the penetrating reaction kettle 10 of recovered liquid containing catalyst from aldehydes evaporator 23 recycled through pipeline 125, while rolling up suction warp
The synthesis gas (CO/H2) of pipeline 111B input and the reaction kettle gas phase portion gas conveyed through pipeline 19, ejecta is through spreading
18 mixing of section reacts and spreads and further distribute in a kettle after the blocking of baffle 12, reaction.Another gang of synthesis gas 111A
The gas distributor 11 below of liquidus curve in reaction kettle is directly inputted without decompression, reaction solution is bubbled so that unreacted
Alkene further reacts under the action of catalyst.Reaction mixture reacted kettle lower part under the action of spraying cycle pump 13 is (excellent
Select bottom) by the conveying of pipeline 113 and 114, part of it, which is sent into after the heat exchange of circulation fluid heat exchanger 14 by pipeline 114, to be sprayed for outlet
Mouth 17, another part are sent into reduced-pressure flash tank 22 through pipeline 120, and the tail gas of reduced-pressure flash tank 22 is emptied by pipeline 121, and flash distillation produces
Object enters aldehydes evaporator 23 through pipeline 122, and obtained final aldehyde product is recycled through pipeline 123, and bottoms (contain catalyst
Solution) under the action of circulating pump 24 through pipeline 124 and 125 be delivered to nozzle 17 be recycled.
When olefin feedstock is in gaseous state, the nozzle 17 of the self-priming reactor 16 of lower spray fresh is urged what is inputted through pipeline 110
Agent solution (if necessary) and optional raw material olefin, through pipeline 112 recycle be originated from reaction kettle containing catalyst solution and
Reaction kettle 10 is sprayed into through the recovered liquid containing catalyst from aldehydes evaporator 23 that pipeline 125 recycles, while rolling up suction through pipeline
Synthesis gas (CO/H2), optional gaseous olefin and the reaction kettle gas phase portion gas conveyed through pipeline 19 of 111B input, spray
It penetrates object and mixes, reacts and spread and further distributed in a kettle after the blocking of baffle 12, reaction through diffuser 18.Another stock
Synthesis gas 111A and/or gaseous olefin without decompression directly input the gas distributor 11 below of liquidus curve in reaction kettle, right
Reaction solution is bubbled so that unreacted alkene further reacts under the action of catalyst.Reaction mixture is pumped in spraying cycle
Reacted kettle lower part (preferably bottom) outlet is conveyed by pipeline 113 and 114 under the action of 13, and part of it exchanges heat through circulation fluid
Nozzle 17 is sent by pipeline 114 after the heat exchange of device 14, another part is sent into reduced-pressure flash tank 22, reduced-pressure flash tank 22 through pipeline 120
Tail gas emptied by pipeline 121, flash distillation product through pipeline 122 enter aldehydes evaporator 23, obtained final aldehyde product is through pipeline
123 recycling, bottoms (solution containing catalyst) are delivered to nozzle 17 through pipeline 124 under the action of circulating pump 24 and recycle
It uses.
In an example of the present invention, reaction system of the present invention includes 1-2 hydroformylation synthesis reaction vessel 10, each
Reaction kettle includes the 1-2 self-priming reactors 16 of lower spray, and is respectively both provided with gas phase pipeloop 19 and liquid phase circulation pipe
Line 113,114,125；The nozzle 17 of the lower self-priming reactor 16 of spray sprays reaction solution, raw material alkene containing catalyst into reaction kettle
The complete raw mixture of unreacted at the top of hydrocarbon, synthesis gas and reaction kettle, and major part is completed in the lower self-priming reactor 16 of spray
The reaction of raw material olefin hydroformylation, the synthesis gas and/or alkene (when alkene is gaseous state) that another part does not depressurize are conveyed
Gas is distributed to reaction kettle liquidus curve gas below, is bubbled in reaction kettle liquid phase, thus in the lower self-priming reactor of spray
The reaction of further progress raw material olefin hydroformylation in outer reaction kettle.Each reaction kettle is equipped with independent shifting heat or heating
Heat-exchanger rig, be mounted on circulation pipe.
In an example of the present invention, the catalyst used includes the 8th race's metallic element and phosphorus-containing ligand.
In an example of the present invention, the reaction system includes at least one evaporator, completes the reuse of catalyst
With the separation of aldehyde product.
In an example of the present invention, the raw material olefin be selected from ethylene, propylene, 1- butylene, 2- butylene, isobutene,
Amylene, 2,5-dihydrofuran, C6-C18At least one of olefinic compounds.
In an example of the present invention, the volume flow of cyclic spray liquid per hour: the efficient loading volume of reaction kettle
The ratio between ratio be 10-60, preferably 20-40.
In an example of the present invention, gas phase is formd through pipeline 19 between reaction kettle and the lower self-priming reactor of spray and is followed
Ring, wherein self-circulating gas volume flow: the ratio between cyclic spray liquid volume flow is 0.5-4；Preferably 1-2.
In an example of the present invention, each reaction kettle configures one or two lower self-priming reactors of spray, and
1-2 heat exchange equipment is configured, heat is moved for reaction system or heating, the heat exchange equipment is mounted on circulation pipe, position is between institute
It states between the self-priming reactor 16 of lower spray and spraying cycle pump 13.
In an example of the present invention, the carbon monoxide-olefin polymeric of selection is acetylacetone,2,4-pentanedione rhodium carbonyl compound precursor, choosing
Phosphorus ligand is the composition of three (o-methyl-phenyl) phosphines and bis-phosphite；The phosphorus ligand of selection is three (o-methyl-phenyls)
The composition of phosphine and single phosphite ester；Wherein the structure of bis-phosphite is as follows:
The wherein structure of single phosphinate are as follows:
In an example of the present invention, the carbon monoxide-olefin polymeric of selection is triphenylphosphine acetylacetone,2,4-pentanedione rhodium carbonyl compound
Precursor, the phosphorus ligand of selection are triphenylphosphine.
In an example of the present invention, evaporator can be tubular heat exchanger, falling film evaporator etc. to complete catalyst
Reuse and aldehyde product separation.When product aldehyde boiling point is high, it can realize that catalyst and aldehydes produce by way of decompression
The separation of product.
It is described when reaction system includes two or more hydroformylation reaction kettle in an example of the present invention
Reaction kettle connects in a series arrangement.
Fig. 3 is the reaction system schematic diagram of an example of the invention, and the reaction kettle 100 of the reaction system includes two parallel connections
The self-priming reactor of lower spray of arrangement.As shown in figure 3, in an example of the present invention, by 100 lower part of reaction kettle through pipeline
The reaction mixture of 113 outputs is divided into 2 strands, changes respectively by circulating pump 102A, 102B and circulation fluid heat exchanger 103A, 103B
Heat forms circulation fluid 115A, 115B.Circulation fluid 115A and raw material olefin 111A (for example, when raw material olefin is liquid) and
Enter the nozzle that self-priming reactor 105 is sprayed under one after recycling catalyst 120A mixing, and volume inhales first while injection
Stock synthesis gas 110 and the reaction kettle top gas phase component through pipeline；Circulation fluid 115B and raw material olefin 111B is (for example, work as
When raw material olefin is liquid) and recycling catalyst 120B mixing after enter the spray of another self-priming reactor of lower spray in parallel
Mouth, and the reaction kettle top gas phase component that volume is inhaled synthesis gas 110 and conveyed through pipeline 107 while injection.Second burst of synthesis
Gas 110A (not shown) is sent directly into the gas distributor 11 in reaction kettle 100, it be bubbled while and reaction kettle
Catalysis reaction occurs for unreacted alkene in liquid.
A part of alkene is inhaled by volume together with synthesis gas 110 when raw material olefin is gaseous state, in above-mentioned reaction system is added
And it is nonessential sprayed by nozzle, another part synthesis gas 110A is admitted to gas distributor together with optional alkene and is bubbled
Reaction.
In use, being divided into 2 strands by the reaction mixture that 100 lower part of reaction kettle is exported through pipeline 113, respectively by circulation
102A and 102B, pipeline 114A and 114B, circulation fluid heat exchanger 103A and 103B heat exchange are pumped, circulation fluid 115A, 115B are formed.Portion
Reaction mixture is divided to send through pipeline 116 to reduced-pressure flash tank 108, the tail gas of reduced-pressure flash tank 108 is emptied by pipeline 118.Flash distillation
Product enters aldehydes evaporator 109 through pipeline 117, and obtained final aldehyde product is recycled through pipeline 119.Bottoms are (containing urging
The solution of agent) through pipeline 120 be delivered to reaction kettle be recycled.
Fig. 4 is the schematic diagram of an example of the invention, and the reaction kettle 100 of the example reaction system includes two parallel arrangements
The self-priming reactor of lower spray.As shown in figure 4, by the circulation fluid 113 of 100 lower part of reaction kettle output by circulating pump 102, circulation
Heat exchanger 103, with raw material olefin 111 (when raw material olefin is liquid), optional fresh catalyst agent solution and recycling catalyst
After 120 mixing, 2 strands are further divided into, the nozzle of the self-priming reactor 104,105 of two lower sprays in parallel is respectively enterd.Each lower spray
Self-priming reactor individual volume is inhaled material synthesis gas (when raw material olefin is gaseous state, also optionally including raw material olefin) and is passed through
Gas phase pipeloop volume 107 gas phases inhaled at the top of reaction kettle, vehicle repair major sufficiently connects in the lower self-priming reactor mixing section of spray
Touching forms microvesicle, into the lower self-priming reactor diffuser of spray.Most of reaction is completed in the lower self-priming reactor of spray.Together
Sample, partially synthetic gas and optional alkene are admitted to the gas distributor 11 in reaction kettle and carry out blistering reaction.
Fig. 5 is the reaction system schematic diagram of another example of the invention.As shown in figure 5, reaction system includes two series connection
The gas phase portion of reaction kettle 100A, 100B of arrangement, two reaction kettles are connected through 114 fluid of pipeline.It is anti-by first when use
The reaction mixture for answering the lower part kettle 100A to export is divided into two strands after pipeline 112A and circulating pump 102A, a stock-traders' know-how circulation heat exchanger
Enter the lower spray of reaction kettle 100A after mixing after 103A with raw material 111 (for example, when alkene is liquid) and recycling catalyst 122
The nozzle 105A of self-priming reactor 104A, another stock are recycled to reaction kettle 100B.It is equipped in reaction kettle 100A and feed gas source
The connected gas distributor 11 of fluid, partially synthetic gas and optional alkene are admitted to the gas distributor and carry out blistering reaction.
In reaction kettle 100B, the reaction mixture that reaction kettle lower part outlet is exported through pipeline 112B is divided to two strands after circulating pump 102B.One
Input the nozzle 105B of the lower self-priming reactor 104B of spray after stock-traders' know-how circulation heat exchanger 103B by pipeline 115B, nozzle 105B by its
The reaction kettle gaseous component that volume is inhaled synthesis gas 110B and conveyed through pipeline 107B when spraying into reaction kettle 100B；Another stock-traders' know-how pipeline
116 are delivered to reduced-pressure flash tank 108, are separated and recovered by pipeline 117 into aldehydes evaporator 109 after flash separation.It is reacting
Gas distributor 11 can be optionally set in kettle 110B, and part material device can be fed directly to the gas distributor and carry out blistering reaction.
Fig. 6 is the reaction process schematic diagram of an example of the invention.Compared with Fig. 2, the inspiratory limb of reactor 16 only has one
A gas access, it is connected with gas source and reaction kettle Top fluidic respectively by a Y-piece.Remaining structure function and Fig. 2 phase
Together.
The invention further relates to a kind of methods for preparing aldehyde by alkene, it includes the following steps:
Hydroformylation synthesis reaction vessel is provided, the top of the reaction kettle is equipped with the lower self-priming reactor of spray, the lower spray
Self-priming reactor successively includes inspiratory limb, mixing section and the diffuser that nozzle is connected with fluid, and the nozzle is in inspiratory limb
Interior, the inspiratory limb and feed gas source are in fluid communication, and the inspiratory limb also pass through pipeline and the reaction kettle liquidus curve with
Upper segment fluid flow is connected, and the reaction kettle further includes the gas distributor being connected in reaction kettle and with feed gas source fluid；
The solution containing catalyst, the solution are sprayed into the reaction kettle via the nozzle of the lower self-priming reactor of spray
The component for inhaling a part of unstrpped gas and reaction kettle gas phase portion from gas source is rolled up in inspiratory limb, and in mixing section and diffuser
It mixed, reacted and spread；
Another part unstrpped gas is sent into the gas distributor in reaction kettle, is allowed to be bubbled in reaction kettle liquid, urge
Further progress hydroformylation reaction under the action of agent.
In the method for the present invention, the condition of hydroformylation reaction is without particular limitation, can be reaction item known in the art
Part.In an example of the present invention, using hydroformylation reaction condition described in Chinese patent CN102272079A, the China
Patent application is inserted into herein by reference as a part of the invention.
In an example of the present invention, the raw material olefin is liquid, and the lower self-priming reactor of spray is located at reaction
Kettle top portion, it is mixed containing catalyst recycle liquid, raw material olefin, the recycling catalyst liquid three from aldehydes evaporator from reaction kettle
After conjunction, is inhaled in the lower self-priming reactor curls inward of spray and mix gas phase at the top of material synthesis gas and reaction kettle, vapour-liquid comes into full contact with, and passes through
Diffuser sprays into reaction liquid；A part of synthesis gas is sent to gas distributor simultaneously, is bubbled in reaction kettle liquid, and surplus
Remaining alkene further reacts under the effect of the catalyst.
In an example of the present invention, the raw material olefin is gaseous state, and the lower self-priming reactor of spray is located at reaction
Kettle top portion, from reaction kettle containing catalyst recycle liquid, the recycling catalyst liquid from aldehydes evaporator and optional alkene three
After person's mixing, the gaseous mixture at the top of the self-priming reactor curls inward suction material synthesis gas of lower spray, optional raw material olefin and reaction kettle
Phase, vapour-liquid come into full contact with, and are sprayed into reaction liquid by diffuser；A part of synthesis gas and optional some olefin are sent simultaneously
To gas distributor, it is bubbled in reaction kettle liquid, is further reacted under the effect of the catalyst with remaining alkene.
The present invention rolls up inspiratory phase by liquid phase, forms gas between reaction kettle gas-phase space and the lower self-priming reactor of spray
It mutually recycles, material synthesis gas, reaction kettle gaseous component, catalyst solution and olefin feedstock come into full contact in injection reactor.
It is found through experiments that, since a large amount of hydrogen and the reaction solution containing carbon monoxide-olefin polymeric come into full contact with, accelerates reaction rate.Together
When, partially synthetic gas is added by bubbling mode while spraying self-priming reactor under use, with conventional simple bubbling
Tower reaction kettle is compared, and the synthesis gas flow-reduction of input is bubbled, and helps to slow down concentration gradient and temperature gradient is unevenly brought
Adverse effect；On the other hand, the jet flow of the lower self-priming reactor of spray more or less plays stirring action, helps to eliminate temperature
The adverse effect that degree gradient unevenly generates.
In addition, the conversion ratio in injection reactor in small space relative to feed olefin (such as propylene) can achieve
70% or more, unexpected experimental result is obtained, unreacted alkene carries out blistering reaction by being injected in kettle, into one
Step improve the conversion ratio of alkene, due to reaction strengthened, with setting gas phase circulation loop and liquid phase circulation circuit and
High olefin conversion may be implemented in the injection stream reaction kettle of gas distributor, eliminates the alkene stripping separation work of rear system
Skill.Since reaction efficiency is promoted, the volume and quantity of reaction kettle can be reduced, and reaction time shortens, the selection of product aldehyde
Property also further promoted, the disposable investment of catalyst is reduced.Compared with blistering reaction kettle, the present invention can eliminate concentration gradient
With the uneven bring adverse effect of temperature gradient；Compared with traditional stirred tank reaction kettle, being formed in liquid phase in injection pipe has more
High synthetic gas density, the better mixed effect of vapour-liquid, faster reaction speed, nozzle arrangements are simple and safe and reliable, investment
It is at low cost, and eliminate mechanical stirring bring unstable factor.
Present invention mainly solves reaction kettle volume is big in the prior art, quantity is more, power consumption is high, reaction efficiency is low, reaction
The technical problem of process flow complexity.The present invention designs bubbling+injection combined type reaction kettle device, by utilizing synthesis
The high pressure of gas source head is passed directly into reaction kettle liquid by gas distributor and forms more excellent bubbling effect, while certainly using gas phase
Circulation loop and liquid phase spraying cycle combine, and further enhance gas-liquid mass transfer, greatly improve reaction efficiency.Bubbling bed is completed
The hydroformylation reaction of part material alkene, unconverted complete alkene further complete residual olefin in a smaller injector
Hydroformylation reaction, so that olefin conversion is effectively improved, and reduce spraying cycle pump unit consumption.
It is molten with aldehyde under conditions of reaction pressure 1.0-6.0MPa at 60-130 DEG C in an example of the present invention
The catalyst synthesis of aldehyde by hydroformylation of olefins that agent, the 8th race's metallic element and phosphorus-containing ligand are formed；The alkene be propylene,
Ethylene, butylene, amylene, hexene, heptene, at least one of olefinic compounds of carbon atom from 6 to 18.The conversion ratio of alkene
It can reach 99% or more, realize to hydroformylation of olefin process intensification, technical solution preferably solves the above problem,
During can be used for hydroformylation of olefin production aldehyde, and the disposable input cost of catalyst is reduced, the consumption phase of ligand
It should reduce.
Embodiment
The present invention will be further described below by way of examples.
Embodiment 1
It is tested using reaction system shown in Fig. 2 by olefin feedstock of propylene, catalyst rhodium concentration 80ppm, ligand
For the composition of three (o-methyl-phenyl) phosphorus L0 and L4, wherein the molar ratio of Rh:L0:L4 is 1:10:4, and temperature of reaction kettle maintains
At 90 DEG C, reaction pressure is in 1.6MPa, and the effecting reaction liquid product of reaction kettle 10 is 10L, and reaction kettle height 900mm, top is set
Lower spray self-adsorption ejector 16 is set, nozzle vent diameter 2.5mm, 30 ° of jet angle, injection expands pipe diameter 20mm, injection pipe
Expand length of tube 850mm.The inspiratory limb of injector 16 there are two gas access, respectively with gas source and reaction kettle Top fluidic phase
Even.
One injector 16 is set at the top of reaction kettle, and circulation fluid 112 takes liquid from reactor bottom, with recycling catalyst solution
125 mixing mix after circulating pump 13 and circulation heat exchanger 14 with propylene feed 110, subsequently into injector 16, liquid phase in addition to
Volume inhales feed synthesis gas 111B, can also by gas circulating tube 19 largely volume inhale unreacted propylene at the top of reaction kettles, synthesis gas,
The mixing gas phase of portioned product composition forms coming into full contact with for gas-liquid two-phase in nozzle interior, and liquid phase carries a large amount of small gas
Bubble enters injector diffuser.
Synthesis gas feeds 111A and is admitted to gas distributor 11 without decompression, in the liquid phase containing catalyst and reaction mixture
Carry out blistering reaction.For reaction product 120 through reduced-pressure flash tank 22, liquid-phase product removes aldehyde product evaporator separating catalyst, circulation
Catalyst 125 returns to reaction kettle 10.
Synthesis gas 111A is 1540NL/h in the present embodiment, and feed pressure 5.5MPa is depressurized to by gas distribution tube
1.6MPa；111B is 380NL/h, and feed pressure 2.0MPa, propylene feed 110 is 1.8kg/h, and circulation fluid volume flow is
150L/h, gas internal circulating load are 170L/h.Butyraldehyde output capacity is 3.06kg/h, and the conversion ratio of conversion propylene conversion butyraldehyde is
99.1%.It surveys butyraldehyde space-time yield STY=4.25mol/ (l*h), product is just different than being 35.Since reaction is strengthened, catalyst
Concentration is low, it is only necessary to which an evaporator realizes the separation of catalyst and product aldehyde, and alkene is substantially free of in product aldehyde.
Embodiment 2
It is tested using reaction system shown in Fig. 2 by olefin feedstock of propylene, catalyst rhodium concentration 80ppm, ligand
For the composition of three (o-methyl-phenyl) phosphorus L0 and L5, wherein the molar ratio of Rh:L0:L5 is 1:10:4, and temperature of reaction kettle maintains
At 90 DEG C, reaction pressure is in 1.6MPa, and the effecting reaction liquid product of reaction kettle 10 is 10L, and reaction kettle height 900mm, top is set
Lower spray self-adsorption ejector 16 is set, nozzle vent diameter 2.5mm, 30 ° of jet angle, injection expands pipe diameter 20mm, injection pipe
Expand length of tube 850mm.The inspiratory limb of injector 16 there are two gas access, respectively with gas source and reaction kettle Top fluidic phase
Even.
One injector 16 is set at the top of reaction kettle, and circulation fluid 112 takes liquid from reactor bottom, with recycling catalyst solution
125 mixing mix after circulating pump 13 and circulation heat exchanger 14 with propylene feed 110, subsequently into injector 16, liquid phase in addition to
Volume inhales feed synthesis gas 111B, can also by gas circulating tube 19 largely volume inhale unreacted propylene at the top of reaction kettles, synthesis gas,
The mixing gas phase of portioned product composition forms coming into full contact with for gas-liquid two-phase in nozzle interior, and liquid phase carries a large amount of small gas
Bubble enters injector diffuser.
Synthesis gas feeds 111A and is admitted to gas distributor 11 without decompression, in the liquid phase containing catalyst and reaction mixture
Carry out blistering reaction.For reaction product 120 through reduced-pressure flash tank 22, liquid-phase product removes aldehyde product evaporator separating catalyst, circulation
Catalyst 125 returns to reaction kettle 10.
Synthesis gas 111A is 1540NL/h in the present embodiment, and feed pressure 5.5MPa is depressurized to by gas distribution tube
1.6MPa；111B is 380NL/h, and feed pressure 2.0MPa, propylene feed 110 is 1.8kg/h, and circulation fluid volume flow is
150L/h, gas internal circulating load are 170L/h.Butyraldehyde output capacity is 3.06kg/h, and the conversion ratio of conversion propylene conversion butyraldehyde is
99.2%.It surveys butyraldehyde space-time yield STY=4.25mol/ (l*h), product is just different than being 32.
Embodiment 3
It is tested using reaction system shown in Fig. 2 by olefin feedstock of propylene, catalyst rhodium concentration 80ppm, ligand
For the composition of three (o-methyl-phenyl) phosphorus L0 and single phosphite ester L7, wherein the molar ratio of Rh:L0:L7 is 1:10:4, reaction
Kettle temperature degree maintains 90 DEG C, and for reaction pressure in 1.6MPa, the effecting reaction liquid product of reaction kettle 10 is 10L, reaction kettle height
900mm, top setting is lower to spray self-adsorption ejector 16, and nozzle vent diameter 2.5mm, 30 ° of jet angle, injection expands pipe diameter
20mm, injection pipe expand length of tube 850mm.The inspiratory limb of injector 16 there are two gas access, respectively with gas source and reaction kettle
Top fluidic is connected.
This implementation operation is with embodiment 1 and embodiment 2, and synthesis gas 111A is 1540NL/h, feed pressure in the present embodiment
For 5.5MPa, 1.6MPa is depressurized to by gas distribution tube；111B is 380NL/h, feed pressure 2.0MPa, propylene feed 110
For 1.8kg/h, circulation fluid volume flow is 150L/h, and gas internal circulating load is 170L/h.Butyraldehyde output capacity is 3.06kg/h, conversion
The conversion ratio that propylene converts butyraldehyde is 99.2%.It surveys butyraldehyde space-time yield STY=4.25mol/ (l*h), the just different ratio of product is
37。
Embodiment 4
Using method described in embodiment 1, catalyst rhodium concentration 60ppm, ligand is three (o-methyl-phenyl) phosphorus L0 and L4
Composition, wherein the molar ratio of Rh:L0:L4 be 1:10:4.Carried out using ethylene as olefin feedstock and is tested.
Synthesis gas 111A is 2250NL/h in the present embodiment, and feed pressure 5.5MPa is depressurized to by gas distribution tube
1.6MPa；111B is 400NL/h, feed pressure 2.0MPa；Ethylene feed 110 is 1.65kg/h, and circulation fluid volume flow is
150L/h, gas internal circulating load are 170L/h.Propionic aldehyde output capacity is 3.40kg/h, and the conversion ratio that conversion ethylene is converted into propionic aldehyde is
99.3%.It surveys propionic aldehyde space-time yield STY=5.86mol/ (l*h).
Embodiment 5
Using method as described in example 2, catalyst rhodium concentration 60ppm, ligand is three (o-methyl-phenyl) phosphorus L0 and L5
Composition, wherein the molar ratio of Rh:L0:L5 be 1:10:4.Carried out using ethylene as olefin feedstock and is tested.
Synthesis gas 111A is 2250NL/h in the present embodiment, and feed pressure 5.5MPa is depressurized to by gas distribution tube
1.6MPa；111B is 400NL/h, feed pressure 2.0MPa；Ethylene feed 110 is 1.65kg/h, and circulation fluid volume flow is
150L/h, gas internal circulating load are 170L/h.Propionic aldehyde output capacity is 3.40kg/h, and the conversion ratio that conversion ethylene is converted into propionic aldehyde is
99.3%.It surveys propionic aldehyde space-time yield STY=5.86mol/ (l*h).
Embodiment 6
Using method as described in example 2, catalyst rhodium concentration 150ppm, ligand is triphenylphosphine, using ethylene as alkene
Raw material carries out experiment.
Synthesis gas 111A is 2250NL/h in the present embodiment, and feed pressure 5.5MPa is depressurized to by gas distribution tube
1.6MPa；111B is 400NL/h, feed pressure 2.0MPa；Ethylene feed 110 is 1.65kg/h, and circulation fluid volume flow is
150L/h, gas internal circulating load are 170L/h.Propionic aldehyde output capacity is 2.80kg/h, and the conversion ratio that conversion ethylene is converted into propionic aldehyde is
82%.It surveys propionic aldehyde space-time yield STY=4.83mol/ (l*h).
Embodiment 7
Using the method for embodiment 1, but using ethylene-propylene mixed gas is olefin feedstock, and wherein ethylene-propylene is mixed
Composition and division in a proportion is 1:4.
Synthesis gas 111A is 1950NL/h in the present embodiment, and feed pressure 5.5MPa is depressurized to by gas distribution tube
1.6MPa；111B is 350NL/h, feed pressure 2.0MPa；Ethylene 0.75kg/h in mixed olefins charging 110, propylene are
1.0kg/h, circulation fluid volume flow are 150L/h, and gas internal circulating load is 170L/h.Propionic aldehyde output capacity is 1.54kg/h, converts second
The conversion ratio that alkene is converted into propionic aldehyde is 99.4%.It surveys propionic aldehyde space-time yield STY=2.66mol/ (l*h)；Butyraldehyde output capacity is
The conversion ratio of 1.70kg/h, conversion propylene conversion butyraldehyde are 99.3%.It surveys butyraldehyde space-time yield STY=2.36mol/ (l*h),
Product is just different than being 30.
Comparative example 1
Using the identical method of embodiment 1, but close the connecting pipe 19 at the top of injector 16 and reaction kettle.
Synthesis gas 111A is 1540NL/h in the present embodiment, feed pressure 5.5MPa is depressurized to by gas distribution tube
1.6MPa；111B is 380NL/h, feed pressure 2.0MPa；Propylene feed 110 is 1.8kg/h, and circulation fluid volume flow is
150L/h, closes gas circulating tube line 19, and gas internal circulating load is shown in (0L/h).Butyraldehyde output capacity is 2.45kg/h, conversion third
The conversion ratio that alkene converts butyraldehyde is 79.5%.It surveys butyraldehyde space-time yield STY=3.40mol/ (l*h), product is just different than being 30.
Comparative example 2
Using the identical method of comparative example 1, the connecting pipe 111B of injector and gas source is simultaneously closed off.As a result all synthesis
Gas is admitted to gas distributor 11 without decompression, carries out blistering reaction in the liquid phase containing catalyst and reaction mixture.
Injector only does liquid circulation and propylene feed and uses in the present embodiment, synthesis gas all from reactor bottom into
Material, 111A 1920NL/h, the pressure into distributor are 2.0MPa；111B is 0NL/h；Propylene feed 110 is 1.8kg/h, is followed
Ring liquid volume flow is 150L/h, closes gas circulating tube line 19, and gas internal circulating load is shown in (0L/h).Butyraldehyde output capacity is
The conversion ratio of 2.35kg/h, conversion propylene conversion butyraldehyde are 78%.It surveys butyraldehyde space-time yield STY=3.24mol/ (l*h), produces
Object is just different than being 25.
Comparative example 3
Using method described in embodiment 1, catalyst rhodium concentration 60ppm, ligand is three (o-methyl-phenyl) phosphorus L0 and L4
Composition, wherein the molar ratio of Rh:L0:L4 be 1:10:4.Carried out using ethylene as olefin feedstock and is tested.Close injector 16 with
Connecting pipe 19 at the top of reaction kettle and the connecting pipe 111B for closing injector and gas source.
Synthesis gas 111A is 2400NL/h in the present embodiment, and feed pressure 5.5MPa is depressurized to by gas distribution tube
1.6MPa；111B flow is 0NL/h；Ethylene feed 110 is 1.5kg/h, and circulation fluid volume flow is 150L/h, closes gas and follows
Endless tube line 19, gas internal circulating load are shown in (0L/h).Propionic aldehyde output capacity is 2.73kg/h, the conversion ratio of conversion ethylene conversion propionic aldehyde
It is 88.0%.It surveys propionic aldehyde space-time yield STY=4.71mol/ (l*h), product is just different than being 30.
Embodiment 8
Carried out using ethylene as olefin feedstock using reaction system shown in fig. 5 and is tested, catalyst rhodium concentration 60ppm, ligand
For the composition of three (o-methyl-phenyl) phosphorus L0 and L4, wherein the molar ratio of Rh:L0:L4 is 1:10:4.Temperature of reaction kettle maintains
At 90 DEG C, for reaction pressure in 1.6MPa, the effecting reaction liquid product of single reaction kettle is 10L, and double total autoclave body products of kettles series connection are 20L,
Reaction kettle height 900mm, top setting is lower to spray self-adsorption ejector 16, and nozzle vent diameter 2.5mm, sprays by 30 ° of jet angle
Expand pipe diameter 20mm, injection pipe expands length of tube 850mm.The inspiratory limb of injector 16 there are two gas access, respectively with gas
Source is connected with reaction kettle Top fluidic.
Synthesis gas 5450NL/h in the present embodiment, wherein first reactor distribution 80% is 4360NL/h, all from distribution
Device 11 enters 100A, and 110A is shown as 0NL/h；Second reactor distribution 20% is 1090NL/h, is all entered from distributor 11
100B, 110B are shown as 0NL/h；Feed pressure is 5.5MPa, is depressurized to 1.6MPa by gas distribution tube；Ethylene feed
111 be 3.4kg/h, and circulation fluid volume flow is 150L/h, and gas internal circulating load is 170L/h.Propionic aldehyde output capacity is 7.0kg/h, folding
Calculating ethylene and being converted into the conversion ratio of propionic aldehyde is 99.5%.It surveys propionic aldehyde space-time yield STY=6.03mol/ (l*h).
Embodiment 9
Carried out using ethylene as olefin feedstock using reaction system shown in fig. 6 and is tested, catalyst rhodium concentration 60ppm, ligand
For the composition of three (o-methyl-phenyl) phosphorus L0 and L4, wherein the molar ratio of Rh:L0:L4 is 1:10:4.Temperature of reaction kettle maintains
At 90 DEG C, reaction pressure is in 1.6MPa, and the effecting reaction liquid product of reaction kettle 10 is 10L, and reaction kettle height 900mm, top is set
Lower spray self-adsorption ejector 16 is set, nozzle vent diameter 2.5mm, 30 ° of jet angle, injection expands pipe diameter 20mm, injection pipe
Expand length of tube 850mm.The inspiratory limb of injector 16 only has a gas access, it by a Y-piece respectively with gas source and
Reaction kettle Top fluidic is connected.
Synthesis gas 111A is 2250NL/h in the present embodiment, and feed pressure 5.5MPa is depressurized to by gas distribution tube
1.6MPa；111B is 400NL/h, feed pressure 2.0MPa；Ethylene feed 110 is 1.65kg/h, and circulation fluid volume flow is
150L/h, gas internal circulating load are 170L/h.Propionic aldehyde output capacity is 3.22kg/h, and the conversion ratio that conversion ethylene is converted into propionic aldehyde is
94.5%.It surveys propionic aldehyde space-time yield STY=5.55mol/ (l*h).
Embodiment 10
Using method as described in example 2, select n-butene for olefin feedstock, wherein 1- butylene: 2- butylene quality is 1:
2；Catalyst rhodium concentration 200ppm, ligand are the composition of three (o-methyl-phenyl) phosphorus L0 and L5, wherein mole of Rh:L0:L5
Than for 1:10:4.Temperature of reaction kettle maintains 95 DEG C, and reaction pressure is in 1.5MPa.
Synthesis gas 111A is 1430NL/h in the present embodiment, and feed pressure 5.5MPa is depressurized to by gas distribution tube
1.6MPa；111B is 350NL/h, feed pressure 2.0MPa；Mixed butene charging 110 is 2.2kg/h, and circulation fluid volume flow is
150L/h, gas internal circulating load are 170L/h.Valeral output capacity is 3.26kg/h, and conversion mixed butene is converted into the conversion ratio of valeral
It is 96.5%.It surveys valeral space-time yield STY=3.79mol/ (l*h).
Embodiment 11
Using method as described in example 2, select 1- amylene for olefin feedstock,；Catalyst rhodium concentration 200ppm, ligand are
The composition of three (o-methyl-phenyl) phosphorus L0 and L5, wherein the molar ratio of Rh:L0:L4 is 1:10:4.Temperature of reaction kettle maintains
100 DEG C, reaction pressure is in 1.5MPa.
Synthesis gas 111A is 1150NL/h in the present embodiment, and feed pressure 5.5MPa is depressurized to by gas distribution tube
1.6MPa；111B is 270NL/h, feed pressure 2.0MPa；1- amylene feedstocks 110 are 2.2kg/h, and circulation fluid volume flow is
150L/h, gas internal circulating load are 170L/h.Hexanal output capacity is 3.01kg/h, and the conversion ratio that conversion amylene is converted into hexanal is
96.0%.It surveys hexanal space-time yield STY=3.00mol/ (l*h).
Claims (10)
1. a kind of method of preparing aldehyde by alkene hydroformylation, it includes the following steps:
Hydroformylation synthesis reaction vessel is provided, the top of the reaction kettle is equipped with the lower self-priming reactor of spray, the lower spray self-priming
Formula reactor successively includes inspiratory limb, mixing section and the diffuser that nozzle is connected with fluid, and the nozzle is located in inspiratory limb, institute
It states inspiratory limb and feed gas source is in fluid communication, and the inspiratory limb also passes through pipeline and the reaction kettle liquidus curve above section
It is in fluid communication, which further includes the gas distributor being connected in reaction kettle and with feed gas source fluid；
The reaction solution containing catalyst, the reaction solution are sprayed into the reaction kettle via the nozzle of the lower self-priming reactor of spray
The circulating air for inhaling a part of gas raw material and reaction kettle gas phase portion from gas source is rolled up in inspiratory limb, and in mixing section and diffusion
Duan Jinhang mixing is reacted and is spread；
Gas raw material by another part from gas source send the gas distributor to reaction kettle through pipeline, leads in reaction kettle liquid
Cross bubbling and the solution haptoreaction containing catalyst.
2. the method as described in claim 1, it is characterised in that there are two gas for the inspiratory limb tool of the lower self-priming reactor of spray
Body entrance is connected with gas source and reaction kettle liquidus curve above section fluid respectively.
3. the method as described in claim 1, it is characterised in that the alkene is selected from ethylene, propylene, 1- butylene, 2- butylene, different
Butylene, amylene, 2,5- dihydrofuran, C6-18Olefinic compounds or its two or more mixture.
4. a kind of hydroformylation synthesis reaction vessel, it includes the self-priming reactor of lower spray being placed at the top of the reaction kettle, described
The lower self-priming reactor of spray successively includes inspiratory limb, mixing section and the diffuser that nozzle is connected with fluid, and the nozzle, which is located at, to be inhaled
In gas section, the inspiratory limb and feed gas source are in fluid communication；
It is characterized in that the inspiratory limb also passes through pipeline and the reaction kettle liquidus curve above section is in fluid communication, and described
Reaction kettle further includes the gas distributor being connected in reaction kettle and with feed gas source fluid.
5. a kind of reaction system of hydroformylation synthetic reaction, it includes:
Reaction kettle, the reaction kettle include the self-priming reactor of lower spray being mounted at the top of it, which successively includes nozzle
Inspiratory limb, mixing section and the diffuser being connected with fluid, the nozzle are located in inspiratory limb, the inspiratory limb and unstripped gas source stream
Body communicates, and the inspiratory limb also passes through pipeline and the reaction kettle liquidus curve above section is in fluid communication, and the reaction kettle is also
Including the gas distributor being connected in reaction kettle and with feed gas source fluid, its underpart is mounted on for reaction mixture to be discharged
Exported with the reaction kettle of catalyst solution, and be mounted between the self-priming reactor of the lower spray and reaction kettle outlet for changing
The distribution plate of the flowing of the alkene and synthesis gas；With
Then it is supplied to the nozzle of the lower self-priming reactor of spray so that reaction is mixed for exporting recycling reaction mixture from reaction kettle
Close the circulation pipe of object and catalyst solution circulation.
6. reaction system as claimed in claim 5, it is characterised in that it includes two reaction kettles, the gas of described two reaction kettles
Mutually part is connected by pipeline fluid.
7. reaction kettle as claimed in claim 3 or reaction system as claimed in claim 5, it is characterised in that each reaction
Kettle includes two self-priming reactors of lower spray in parallel, and each lower self-priming reactor of spray successively includes nozzle and fluid phase
Inspiratory limb, mixing section and diffuser even, the nozzle is each located in inspiratory limb, the inspiratory limb respectively with unstripped gas source stream
Body communicates；And the inspiratory limb is respectively also in fluid communication by pipeline and the reaction kettle liquidus curve above section.
8. reaction kettle as claimed in claim 3 or reaction system as claimed in claim 5, it is characterised in that the air-breathing
Section, mixing section and diffuser respectively form a Venturi tube.
9. reaction kettle as claimed in claim 3 or reaction system as claimed in claim 5, it is characterised in that the lower spray
The inspiratory limb tool of self-priming reactor there are two gas access, respectively with gas source and reaction kettle liquidus curve above section fluid phase
Even.
10. hydroformylation synthesis reaction vessel as claimed in claim 5 is being prepared the purposes in aldehyde by alkene.
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| CN111170839A (en) * | 2020-01-16 | 2020-05-19 | 江苏诺盟化工有限公司 | Method for preparing nonanal by adopting loop reactor and Venturi ejector for preparing nonanal |
| CN111217686A (en) * | 2020-01-16 | 2020-06-02 | 江苏诺盟化工有限公司 | Preparation method of n-valeraldehyde and special Venturi ejector |
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