CN110128251B - Hydroformylation process and apparatus - Google Patents
Hydroformylation process and apparatus Download PDFInfo
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- CN110128251B CN110128251B CN201910550807.5A CN201910550807A CN110128251B CN 110128251 B CN110128251 B CN 110128251B CN 201910550807 A CN201910550807 A CN 201910550807A CN 110128251 B CN110128251 B CN 110128251B
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- 238000000034 method Methods 0.000 title claims abstract description 37
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 276
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- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 21
- 238000004891 communication Methods 0.000 claims abstract description 14
- 150000001336 alkenes Chemical class 0.000 claims description 103
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- 150000001299 aldehydes Chemical class 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 12
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- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 7
- -1 ethylene, propylene, 1-butene Chemical class 0.000 claims description 5
- ARGCQEVBJHPOGB-UHFFFAOYSA-N 2,5-dihydrofuran Chemical compound C1OCC=C1 ARGCQEVBJHPOGB-UHFFFAOYSA-N 0.000 claims description 4
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- 150000001875 compounds Chemical class 0.000 claims description 3
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- 239000007789 gas Substances 0.000 description 260
- 230000015572 biosynthetic process Effects 0.000 description 52
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 42
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 40
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- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 21
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- 229910052703 rhodium Inorganic materials 0.000 description 12
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 12
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
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- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 description 6
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- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
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- 238000007789 sealing Methods 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 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
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
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- 239000011259 mixed solution Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- YLQLIQIAXYRMDL-UHFFFAOYSA-N propylheptyl alcohol Chemical compound CCCCCC(CO)CCC YLQLIQIAXYRMDL-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- GBXQPDCOMJJCMJ-UHFFFAOYSA-M trimethyl-[6-(trimethylazaniumyl)hexyl]azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCCCCC[N+](C)(C)C GBXQPDCOMJJCMJ-UHFFFAOYSA-M 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Hydroformylation processes and apparatus are disclosed. The method comprises the steps of providing a hydroformylation synthesis reaction kettle, wherein a lower spraying self-priming reactor is arranged at the top of the reaction kettle, the reactor sequentially comprises a nozzle, an air suction section, a mixing section and a diffusion section which are in fluid connection, the nozzle is positioned in the air suction section, the air suction section is in fluid communication with a raw material air source and the reaction kettle, and the reaction kettle further comprises a gas distributor which is positioned in the reaction kettle and is in fluid connection with the raw material air source; spraying a reaction liquid containing a catalyst into the reaction kettle through a nozzle of the lower spraying self-priming reactor, wherein the reaction liquid is used for sucking a part of gas raw materials from a gas source and circulating gas of a gas phase part of the reaction kettle in a suction section, and mixing, reacting and diffusing in a mixing section and a diffusion section; and (3) delivering the other part of the gas raw material from the gas source to a gas distributor in the reaction kettle through a pipeline, and carrying out contact reaction with the catalyst-containing solution in the reaction kettle liquid through bubbling.
Description
Technical Field
The invention relates to a hydroformylation synthesis method and equipment, in particular to a method for preparing aldehyde by hydroformylation of olefin and synthesis gas, and a reaction equipment and a reaction system used for the method. The method and the reaction system can improve the reaction efficiency, reduce the equipment investment and have high economic benefit.
Background
Olefin hydroformylation is an important organic synthesis reaction that plays a significant role in the modern industry. The aldehyde product is a useful chemical intermediate, can synthesize a plurality of important chemical products, and is a homogeneous catalytic reaction process with the maximum production standard so far.[Trzeciak,A.M.；J.J.Coord.Chem.Rev.1999,190-192,883-900.]。
The main method for producing aldehyde by olefin hydroformylation comprises a low-pressure rhodium-catalyzed hydroformylation method and a high-pressure cobalt-catalyzed hydroformylation method. Under certain conditions, raw material olefin and synthesis gas H 2 And (3) directly introducing the/CO into a catalyst solution of a reaction kettle, and reacting in a liquid phase main body to generate aldehydes. In the olefin hydroformylation process using a ligand-modified homogeneous catalyst, the concentration and temperature of the reaction solution are not uniform, so that the reaction conversion rate, the space-time yield of aldehyde (STY, meaning the conversion amount of olefin per unit time and unit volume based on the total reaction volume) and the normal-to-iso ratio of the product are seriously affected, and most devices need to enhance the contact between gas and liquid by stirring, so that materials are thoroughly and uniformly mixed. Along with the growth of the reaction carbon chain, the reaction activity of the olefin hydroformylation is reduced, particularly when internal olefin exists, the reaction activity is obviously reduced, the reaction residence time is long, and the reaction byproducts are more, so that a reaction strengthening method is needed to be found to improve the reaction efficiency and the selectivity of the main reaction.
One modification method is to mix the reaction solution with stirring. The reaction kettle with the stirring paddle has better mixing effect, but the stirrer has complex structure and the materials of the stirrer used under special conditions are expensive. Another disadvantage of using stirred tanks is that the stirrer shaft must pass through the wall of the pressurized tank and the sealing requirements for the equipment are high, while the stirring shaft rotation affects the sealing and stirring paddles of the tank. In daily operation, equipment faults easily occur in stirring equipment, and continuous and stable operation of production is seriously influenced. Most of the olefin hydroformylation reaction devices in practical application in industry at present adopt kettle type stirrers, the reaction efficiency is relatively low due to factors such as mass transfer, and taking an industrial application example of n-butene hydroformylation as an example, a 7-ten thousand ton/year 2-propyl heptanol production device needs 3 stirring reaction kettles to carry out series connection reaction, and the volume of each reaction kettle is 105m 3 ("mechanical Engineers", 2015 (6): 25)2-254)。
As an alternative to stirred tanks, there are cases in industry where olefin hydroformylation reactions are carried out using bubble column reactors. The reaction gas is introduced from the bottom of the bubbling tower, and the reaction gas is ensured to be dispersed in the reaction liquid through a gas distributor so as to increase the mass transfer surface area, and the bubbles are dispersed and lifted in the reaction liquid, so that the reaction liquid is mixed. However, in a simple bubble column reactor, because the reaction gas participates in the hydroformylation reaction in the rising process, a local concentration gradient and temperature non-uniformity are easily formed in the bubble column, so that the reaction conversion rate, aldehyde selectivity and aldehyde space time yield are affected, and the production efficiency is lower than that of a stirring reactor.
CN 101679173B discloses a process and apparatus for producing aldehydes by reacting olefins with synthesis gas comprising carbon monoxide and hydrogen, which employs an ejector to enhance gas-liquid mass transfer, thereby improving hydroformylation efficiency and yielding desirable high yields of aldehydes.
CN102272079a discloses an apparatus for producing alcohols from olefins comprising a hydroformylation reactor, said reactor comprising injection means for injecting olefins and synthesis gas into a catalyst mixed solution in the reactor, a reactor outlet for discharging a reaction mixture of said olefins and synthesis gas, a distribution plate for changing the flow of said olefins and synthesis gas, and a circulation pipe for circulating part of the reaction mixture to the injection means.
Wang Xiaofu et al, "spray gas-liquid reactor type and application" ("chemical industry and engineering technology", 2002, volume 23, phase 2) describe spray gas-liquid reactors. It mentions that there are typically used in industry downspray self-priming reactors consisting of four parts of a nozzle, a suction chamber, a mixing chamber and a diffusion chamber. When the reaction liquid having a certain pressure is sprayed downward through the nozzle, a high flow rate is generated, a pressure drop is formed around the nozzle, and the raw material gas supplied from the side is sucked into the suction chamber, and then sufficiently mixed in the mixing chamber to form turbulence, while the reaction is performed. The flow velocity of the product in the diffusion chamber is gradually reduced, the product is sent out by utilizing the increased static pressure, and a large amount of gas can be automatically sucked without air supply equipment such as a compressor and the like, so that the energy consumption is greatly reduced. And the material forms stable turbulence at the nozzle, so that the mixing between gas and liquid is enhanced, and the method is very beneficial to the diffusion-controlled gas-liquid phase transient reaction.
In the chemical industry, even a 1% improvement in reaction efficiency can produce great economic benefits. While the introduction of a sparged gas-liquid reactor improves the efficiency of the olefin hydroformylation reaction, there is room for further improvement in this process.
Disclosure of Invention
It is an object of the present invention to further improve the efficiency of olefin hydroformylation reactions.
Accordingly, one aspect of the invention relates to a hydroformylation synthesis reaction vessel comprising a down-draft self-priming reactor disposed at the top of the reaction vessel, the down-draft self-priming reactor comprising in sequence a nozzle and a suction section, a mixing section and a diffusion section fluidly connected, the nozzle being located within the suction section, the suction section being in fluid communication with a source of feed gas;
the reaction kettle is characterized in that the air suction section is also in fluid communication with a part above the liquidus line of the reaction kettle through a pipeline, and the reaction kettle further comprises a gas distributor which is arranged inside the reaction kettle and is in fluid connection with the raw material gas source.
Another aspect of the invention relates to a reaction system for a hydroformylation synthesis reaction, which comprises the hydroformylation synthesis reaction kettle provided by the invention, wherein the reaction kettle comprises:
the bottom-spraying self-priming reactor is arranged on the top of the reactor and comprises a nozzle, an air suction section, a mixing section and a diffusion section which are in fluid connection in sequence, wherein the nozzle is positioned in the air suction section, the air suction section is in fluid connection with a raw material air source, and the air suction section is also in fluid communication with a part above the liquidus line of the reaction kettle through a pipeline;
A gas distributor in the reaction kettle and fluidly connected to the source gas source;
a reaction vessel outlet installed at a lower portion thereof for discharging a reaction mixture and a catalyst solution; and
a distributor plate mounted between the downspray self-priming reactor and the reactor outlet for altering the flow of the olefins and synthesis gas;
the system also includes a circulation tube for recovering the reaction mixture from the outlet of the reaction vessel and then supplying it to the nozzle of the downdraft self-priming reactor to circulate the reaction mixture and the catalyst solution.
Another aspect of the invention relates to a process for preparing aldehydes from olefins, comprising the steps of:
providing a hydroformylation synthesis reaction kettle, wherein a lower spraying self-priming reactor is arranged at the top of the reaction kettle, the lower spraying self-priming reactor sequentially comprises a nozzle, an air suction section, a mixing section and a diffusion section which are in fluid connection, the nozzle is positioned in the air suction section, the air suction section is in fluid communication with a raw material air source, the air suction section is also in fluid communication with a part above the liquidus line of the reaction kettle through a pipeline, and the reaction kettle further comprises a gas distributor which is in fluid connection with the raw material air source;
spraying a reaction liquid containing a catalyst into the reaction kettle through a nozzle of the lower spraying self-priming reactor, wherein the reaction liquid is used for sucking a part of gas raw materials from a gas source and circulating gas of a gas phase part of the reaction kettle in a suction section, and mixing, reacting and diffusing in a mixing section and a diffusion section;
And (3) delivering the other part of the gas raw material from the gas source to a gas distributor in the reaction kettle through a pipeline, and carrying out contact reaction with the catalyst-containing solution in the reaction kettle liquid through bubbling.
Yet another aspect of the invention relates to the use of the hydroformylation synthesis reaction vessel in the preparation of aldehydes from olefins.
Drawings
The invention is further illustrated by the following figures. In the accompanying drawings:
FIG. 1 is a schematic diagram of a downspray self-priming reactor used in the present invention;
FIG. 2 is a schematic process flow diagram of one example of the present invention;
FIG. 3 is a schematic process flow diagram of another example of the present invention;
FIG. 4 is a schematic process flow diagram of another example of the present invention;
FIG. 5 is a schematic flow diagram of a process in which dual jet kettles are connected in series in one example of the present invention;
FIG. 6 is a schematic process flow diagram of an example of the present invention in which a downjet self-priming reactor is fluidly connected to a source of feed gas and a gas phase portion of a reaction vessel, respectively, via a Y-type inlet.
Detailed Description
The inventor of the present invention conducted a careful study on the existing hydroformylation synthetic reaction vessel, and found that although the down-jet self-priming reactor has a force to push down the reactants so as to move down into the bottom liquid phase catalyst solution, during operation, part of the reaction raw materials, particularly the synthesis gas with lighter weight, may be suspended in the upper part of the reaction vessel, such as the top of the reaction vessel, thereby affecting the reaction efficiency. Based on such findings, the inventors of the present invention proposed that the gas of the gas phase portion of the reaction vessel be circulated to the suction section of the downdraft self-priming reactor and circulated to the downdraft reactor for reaction, thereby further improving the reaction efficiency.
In addition, the inventors of the present invention have also found that if a downdraft self-priming reactor is introduced into a bubble column reactor and gaseous raw materials are introduced into the reactor through the downdraft self-priming reactor and a gas distributor simultaneously, defects such as local range concentration gradient and temperature unevenness, etc., which exist in a conventional bubble column reactor can be eliminated while advantageously utilizing the advantages of the bubble column reactor, since the injection force of the downdraft self-priming reactor more or less plays a role of stirring or stirring.
Accordingly, the present invention relates to a hydroformylation synthesis reaction vessel, the shape, material, size, etc. of which is not particularly limited, and may be a conventional reaction vessel known in the art. In one example of the invention, the reaction vessel is a vertical reaction vessel. In another example of the invention, the reaction vessel is a horizontal reaction vessel.
The reaction kettle comprises a lower spraying self-priming reactor arranged at the top of the reaction kettle, wherein the lower spraying self-priming reactor sequentially comprises a nozzle, an air suction section, a mixing section and a diffusion section which are in fluid connection, the nozzle is positioned in the air suction section, the air suction section is in fluid communication with a raw material air source, and the air suction section is also in fluid communication with a part above the liquidus line or a gas phase part of the reaction kettle through a pipeline.
In the present invention, the term "the nozzle is located within the suction section" is not limited to the location of the nozzle being physically located within the suction section. The nozzle may be maintained in various positional relationships with the gas-suction section as long as the jet is capable of entraining the gaseous raw material and the gas originating from the gas-phase portion of the reaction vessel while being injected into the gas-suction section. For example, the nozzles may be located at the edge of the suction section and spray at a pressure sufficient to entrain the gaseous feed.
In the present invention, the term "conduit" in "the suction section is also in fluid communication with the portion above the liquidus line or the gas phase portion of the reaction vessel through a conduit" means any conduit other than the conventional downspray self-priming reactor body conduit. The pipeline is positioned outside the reaction kettle.
In the present invention, the term "part above the liquidus of the reaction vessel" refers to a position of the reaction vessel which is higher than the liquidus of the reaction vessel and does not suck in liquid during the gas phase circulation. In one example of the invention, the portion above the liquidus line of the reactor refers to a location near and including the top of the reactor. In another example of the invention, the "portion above the liquidus line of the reaction vessel" refers to the top of the reaction vessel.
In the present invention, the term "downjet self-priming reactor comprises a suction section, a mixing section and a diffusion section which are fluidly connected" means that the reactor comprises three functional sections with suction, mixing and diffusion functions, which may be physically distinguishable (e.g. suction chamber, mixing chamber and diffusion chamber) or physically indistinguishable (e.g. a section of piping with suction, mixing or diffusion functions at different positions, respectively).
The terms "fluid communication" and "fluid connection" are used interchangeably herein to refer to two portions being connected to one another and fluid being able to flow between the two portions.
In one embodiment of the invention, the suction section has two gas inlets, one of which is fluidly connected to a source of feed gas and the other of which is fluidly connected to a portion of the reactor above the liquidus line, preferably the top of the reactor, by a conduit.
In one embodiment of the invention, the suction section has a gas inlet in fluid communication with the source of feed gas and the portion of the reactor above the liquidus line through Y-tubes, respectively.
In one embodiment of the invention, the suction section has two gas inlets, one of which is fluidly connected to a source of feed gas and the other of which is fluidly connected to a portion of the reactor above the liquidus line by a conduit. In one example, the nozzle opening has a height below at least one of the gas inlets, preferably below both of the gas inlets.
In one embodiment of the invention, the suction section has two gas inlets of equal height, one of which is in fluid connection with the source of raw material gas, the other of which is in fluid connection with the portion of the reactor above the liquidus line by a pipe, and the nozzle opening has a height lower than that of the gas inlet.
In one embodiment of the invention, the suction section has two gas inlets, one of which is fluidly connected to a source of feed gas and the other of which is fluidly connected to a portion of the reactor above the liquidus line by a conduit. The nozzle opening is 0.5-500mm, preferably 10-350mm, more preferably 20-250mm, preferably 50-200mm lower than the lowest point of at least one of said gas inlets. In one embodiment of the invention the nozzle opening is 0.5-30mm, preferably 0.8-20mm, more preferably 1-10mm lower than the lowest point of at least one of said gas inlets. Preferably 1.1-5mm lower.
In one example of the invention, the two gas inlets differ in height by less than 100mm. Preferably less than 50mm, more preferably less than 10mm, preferably less than 5mm, and most preferably less than 1mm.
The construction of the downjet self-priming reactor of the present invention is not particularly limited and may be of conventional construction known in the art, for example, the type and application of the "jet gas-liquid reactor" as described in Wang Xiaofu et al (volume 23, 2 nd of the chemical industry and engineering technology 2002), except that the gas inlet of the suction section has two gas inlets or chambers fluidly connected to the two gas streams by a Y-tube.
In one example of the present invention, a downflow reactor disclosed in fig. 1b of chinese patent CN102272079a was used, except that the gas inlet of the gas suction section, which has two gas inlets or chambers, was fluidly connected to two gas streams by a Y-pipe.
FIG. 1 is a schematic diagram of a downspray self-priming reactor according to one embodiment of the present invention. As shown in the figure, the downspray self-priming reactor of the invention sequentially comprises a nozzle 1, an air suction chamber 2, a mixing chamber 3 and a diffusion chamber 4, wherein the nozzle 1 is positioned in the air suction chamber 2, and the air suction chamber 2 is provided with a gas inlet 6 which is in fluid connection with an air source and a gas inlet 7 which is in fluid connection with a part above the liquidus line of the reaction kettle (preferably the top of the reaction kettle).
In operation, a liquid stream 5 containing catalyst is sprayed downwardly through nozzle 1, the sprayed pressure entrains feed gas introduced through feed gas inlet 6 and gas from the gas phase portion of the reactor introduced through recycle gas inlet 7, the three being thoroughly mixed and reacted in the path of movement from suction chamber 2 to mixing chamber 3 and subsequently diffused into the reactor through diffusion chamber 4.
In one example of the invention, the gas chamber 2, the mixing chamber 3 and the diffusion chamber 4 constitute a venturi. As shown in fig. 1. The inlet section of the suction chamber 2 is connected with the nozzle 1, the lower part of the suction chamber is a conical pipe contraction section, the mixing chamber 3 forms the throat of the venturi pipe, and the diffusion chamber 4 forms the diffusion section of the venturi pipe.
In one embodiment of the invention, the diameter D of the inlet section of the suction chamber 2 to which the nozzle 1 is connected is 0.8-500mm, preferably 1-400mm, more preferably 1.5-300mm, preferably 1.75-250mm, preferably 2-100mm; the cone angle of the nozzle cone is about 10-90 degrees, preferably 15-75 degrees, more preferably 20-60 degrees. The diameter of the throat is 1.0-3.0D, and the length is 5-100 times, preferably 20-60 times, the diameter of the throat. The angle of taper of the diffuser is about 5 to 30 degrees, preferably 9 to 20 degrees, more preferably 10 to 15 degrees, and the diameter at the outlet of the diffuser is about 1.0 to 20 times, preferably 1.2 to 18 times, more preferably 1.5 to 15 times, more preferably 2 to 10 times the diameter of the throat.
In one embodiment of the invention, the overall length of the venturi tube is 0.01 to 1.5 times, preferably 0.05 to 1.4 times, more preferably 0.08 to 1.2 times, most preferably 0.1 to 1.1 times, most preferably 0.2 to 1 times, most preferably 0.2 to 0.95 times the height of the interior of the reaction vessel.
The reaction kettle comprises a gas distributor which is in fluid connection with raw material gas in the reaction kettle and is used for bubbling in reaction liquid containing a catalyst so as to continuously react unreacted materials in the self-priming reactor in the reaction kettle liquid by downward spraying, thereby further improving the reaction efficiency.
In a preferred embodiment of the invention, the amount of feed gas fed to the gas distributor is 30% to 95%, preferably 40% to 90%, more preferably 50% to 85%, and most preferably 60% to 85% of the total amount of feed gas.
The position of the gas distributor in the reaction vessel is not particularly limited as long as it can bubble in the catalyst-containing reaction liquid. Suitable gas distributor locations can be readily determined by one of ordinary skill in the art after reading this disclosure.
The gas distributor suitable for the reaction vessel of the present invention is not particularly limited and may be a gas distributor known in the art. Suitable gas distributors and their mounting dimensions can be readily determined by one of ordinary skill in the art after reading this disclosure, e.g., one of ordinary skill in the art can select a suitable gas distributor based on the "bubbling bed gas distributor design and its impact on hydraulics" of Zhang et al (coal chemical industry, 1995, month 2).
In one example of the invention, 100% of the olefin enters the gas distributor and unreacted feed gas is entrained to the eductor through the reactor vapor phase for further reaction under the influence of the catalyst.
In one embodiment of the invention, the olefin and the catalyst solution are sprayed into an air suction section through a nozzle, and the raw material gas and the gas in the gas phase part of the reaction kettle are sucked up and mixed and reacted simultaneously to form the required reaction product.
In one example of the invention, the olefin used in the hydroformylation synthesis reaction of the invention is a gaseous olefin, where the catalyst-containing liquid stream 5 comprises fresh catalyst solution and/or recycled catalyst solution and optionally feed olefin, the feed gas introduced via feed gas inlet 6 comprises synthesis gas and optionally feed olefin, the gas introduced via recycle gas inlet 7 is a gas originating from the gas phase portion of the reaction vessel, and the gas stream introduced in the gas distributor comprises synthesis gas and/or gaseous olefin.
In another example of the invention, the olefin used in the hydroformylation synthesis reaction of the invention is a liquid olefin, where stream 5 comprises olefin, fresh catalyst solution and/or recycled catalyst solution, the feed gas introduced by entrainment through feed gas inlet 6 comprises synthesis gas, the gas introduced by entrainment through recycle gas inlet 7 is gas originating from the gas phase portion of the reaction vessel, and the gas stream introduced in the gas distributor comprises synthesis gas.
In the present invention, the synthesis gas is CO/H 2 It can be easily prepared by conventional methods, for example by conventional water gas synthesis.
The invention also relates to a reaction system for hydroformylation synthesis reaction, comprising the hydroformylation synthesis reaction kettle, wherein the reaction kettle comprises a catalyst layer arranged on the top of the reaction kettle and used for preparing raw material olefin and synthesis gas (CO/H) 2 ) The catalyst solution and the gas-phase circulating material of the reaction kettle are injected into the lower spraying self-priming reactor of the invention of the reaction kettle; a reaction vessel outlet installed at a lower portion thereof for discharging a reaction mixture and a catalyst solution; a distribution plate installed between the downspray self-priming reactor and the outlet of the reaction kettle for changing the flow of the olefin and the synthesis gas; a circulation pipe for recovering the reaction mixture and the catalyst solution from the outlet of the reaction vessel and then supplying to the nozzle of the downdraft self-priming reactor to circulate the reaction mixture, and a gas distributor installed below the liquidus line of the reaction vessel and fluidly connected to a source gas for generating bubbling.
In the present invention, the term "lower part of the reaction vessel" means a position below the liquidus line of the reaction vessel. In one example of the present invention, the "reactor lower portion" includes the reactor bottom.
A distributor plate is mounted in the reaction kettle for changing the flow of the jet of the down-jet self-priming reactor, thereby adjusting the residence time of the reaction raw materials in the reaction kettle. One of ordinary skill in the art can readily determine the location and shape of the distribution plate in the reactor based on the specific reaction requirements. For example, one of ordinary skill in the art can determine the location and shape of the distribution plate in the reactor based on the specific reaction in combination with the distribution plate shape and placement requirements disclosed in chinese patent CN102272079 a.
FIG. 2 is a schematic reaction scheme of one embodiment of the present invention. As shown in fig. 2, the reaction system for hydroformylation synthesis reaction of the present invention comprises a hydroformylation synthesis reaction vessel 10 of the present invention, wherein the reaction vessel 10 comprises a downdraft self-priming reactor 16, and the gas suction section of the reactor 16 is provided with two independent gas inlets, one of which is in fluid connection with the gas phase part of the reaction vessel, and the other of which is in fluid connection with a raw material gas source. A reactor 16 is installed at the top of the reaction vessel for injecting raw olefin, synthesis gas (CO/H2) and fresh catalyst solution (if necessary) fed through lines 110 and 111B, a reaction vessel gas-phase recycle material circulated through line 19, and catalyst-containing solution circulated through lines 113 and 114 into the reaction vessel through a nozzle 17 and simultaneously carrying out a reaction; a reaction vessel outlet installed at the lower portion of the reaction vessel for discharging a reaction mixture containing a catalyst solution; a distributor plate 12 mounted between the downspray self-priming reactor 16 and the reactor outlet for altering the flow of the olefins and synthesis gas; a circulation pipe 114 for recovering the reaction mixture from the outlet of the reaction vessel through a pipe 113 and then supplying to the nozzle 17 of the downdraft self-priming reactor 16 to circulate the reaction mixture.
In one example of the invention, the reaction system further comprises a reduced pressure flash tank 22 fluidly connected to the outlet of the reaction vessel, and an aldehyde evaporator 23 fluidly connected to the reduced pressure flash tube 22, the bottom of the aldehyde evaporator 23 being fluidly connected to the nozzle 17 of the downspray self-priming reactor 16 of the reaction vessel via lines 124, 125, 113 and 114.
In use, when the olefin feedstock is in the liquid state, the nozzle 17 of the downspray self-priming reactor 16 sprays the liquid olefin solution and fresh catalyst solution (if necessary) fed through the line 110, the catalyst-containing solution from the reaction vessel circulated through the line 112 and the catalyst-containing recovery liquid from the aldehyde evaporator 23 circulated through the line 125 into the reaction vessel 10 while entraining the synthesis gas (CO/H2) fed through the line 111B and the partial gas of the gas phase of the reaction vessel fed through the line 19, and the spray is mixed, reacted and diffused by the diffusion section 18 and then further distributed and reacted in the reaction vessel after being blocked by the baffle 12. The other stream of synthesis gas 111A is directly fed into the gas distributor 11 below the liquidus line in the reaction vessel without depressurizing, and the reaction solution is bubbled to further react the unreacted olefin under the action of the catalyst. The reaction mixture is conveyed by the jet circulation pump 13 through the lower (preferably bottom) outlet of the reaction kettle through the pipelines 113 and 114, one part of the reaction mixture is conveyed into the nozzle 17 through the pipeline 114 after heat exchange by the circulating liquid heat exchanger 14, the other part of the reaction mixture is conveyed into the decompression flash tank 22 through the pipeline 120, the tail gas of the decompression flash tank 22 is emptied through the pipeline 121, the flash product enters the aldehyde evaporator 23 through the pipeline 122, the obtained final aldehyde product is recovered through the pipeline 123, and the distillation residue (solution containing the catalyst) is conveyed to the nozzle 17 through the pipelines 124 and 125 for recycling under the action of the circulating pump 24.
When the olefin feedstock is in the gaseous state, the nozzle 17 of the downdraft self-priming reactor 16 injects fresh catalyst solution (if necessary) and optionally feed olefin(s) fed via line 110, catalyst-containing solution from the reactor via line 112 and catalyst-containing recovery liquid from aldehyde evaporator 23 via line 125 into the reactor 10 while entraining synthesis gas (CO/H2) fed via line 111B, optionally gaseous olefin(s) and part of the reactor gas phase fed via line 19, the jets being mixed, reacted and diffused by diffuser 18 and blocked by baffle 12 before further distribution and reaction in the reactor. The other stream of non-depressurized synthesis gas 111A and/or gaseous olefins is directly fed into a gas distributor 11 below the liquidus line in the reactor, and the reaction solution is bubbled to further react the unreacted olefins under the action of the catalyst. The reaction mixture is conveyed through the lower (preferably bottom) outlet of the reaction kettle by the jet circulation pump 13 through the pipelines 113 and 114, one part of the reaction mixture is conveyed into the nozzle 17 through the pipeline 114 after heat exchange by the circulating liquid heat exchanger 14, the other part of the reaction mixture is conveyed into the decompression flash tank 22 through the pipeline 120, the tail gas of the decompression flash tank 22 is emptied through the pipeline 121, the flash product enters the aldehyde evaporator 23 through the pipeline 122, the obtained final aldehyde product is recovered through the pipeline 123, and the distillation residue (solution containing the catalyst) is conveyed to the nozzle 17 for recycling through the pipeline 124 under the action of the circulating pump 24.
In one example of the present invention, the reaction system of the present invention comprises 1-2 hydroformylation synthesis reaction vessels 10, each comprising 1-2 downflow self-priming reactors 16, each provided with a gas phase recycle line 19 and liquid phase recycle lines 113, 114, 125; the nozzle 17 of the down-jet self-priming reactor 16 sprays the reaction liquid containing the catalyst, the raw material olefin, the synthesis gas and the unreacted raw material mixture at the top of the reaction kettle into the reaction kettle, and the reaction of the hydroformylation of most of the raw material olefin is completed in the down-jet self-priming reactor 16, and the other part of the synthesis gas and/or olefin (when the olefin is in a gaseous state) which is not decompressed is conveyed to the gas distribution gas below the liquidus line of the reaction kettle, bubbling is carried out in the liquid phase of the reaction kettle, so that the reaction of the hydroformylation of the raw material olefin is further carried out in the reaction kettle outside the down-jet self-priming reactor. Each reaction kettle is provided with an independent heat transfer device for transferring heat or heating, and is arranged on the circulating pipe.
In one example of the invention, a catalyst is used that includes a group viii metal element and a phosphorus-containing ligand.
In one embodiment of the invention, the reaction system comprises at least one evaporator to accomplish the recycling of the catalyst and the separation of the aldehyde product.
In one embodiment of the present invention, the feed olefin is selected from the group consisting of ethylene, propylene, 1-butene, 2-butene, isobutylene, pentene, 2, 5-dihydrofuran, C 6 -C 18 At least one of the olefinic compounds.
In one example of the invention, the volume flow rate of the circulating injection liquid per hour: the ratio of the effective loading volume ratio of the reaction kettle is 10-60, preferably 20-40.
In one embodiment of the invention, a gas phase circulation is formed between the reactor and the downjet self-priming reactor via line 19, wherein the self-circulating gas volume flow: the ratio of the volume flow of the circulating jet liquid is 0.5-4; preferably 1-2.
In one example of the invention, each reactor is provided with one or two down-jet self-priming reactors, and 1-2 heat exchange devices are provided for heat transfer or heating of the reaction system, and the heat exchange devices are arranged on a circulating pipe and are positioned between the down-jet self-priming reactors 16 and the jet circulating pump 13.
In one embodiment of the invention, the catalyst composition is selected from the group consisting of rhodium acetylacetonate carbonyl compound precursor, and the phosphorus ligand is selected from the group consisting of tris (o-methylphenyl) phosphine and bisphosphite; the selected phosphorus ligand is a combination of tri (o-methylphenyl) phosphine and monophosphite; wherein the bisphosphite has the following structure:
Wherein the monophosphonite has the structure:
in one embodiment of the present invention, the catalyst composition selected is a triphenylphosphine acetylacetonato rhodium carbonyl compound precursor and the phosphorus ligand selected is triphenylphosphine.
In one example of the invention, the evaporator may be a tube heat exchanger, a falling film evaporator, or the like to accomplish the reuse of the catalyst and the separation of the aldehyde product. When the boiling point of the product aldehyde is high, the separation of the catalyst and the aldehyde product can be realized by a decompression mode.
In one example of the invention, when the reaction system comprises two or more hydroformylation reaction vessels, the reaction vessels are connected in series.
FIG. 3 is a schematic illustration of a reaction system of an example of the present invention, wherein the reaction vessel 100 comprises two downjet self-priming reactors arranged in parallel. As shown in FIG. 3, in one example of the present invention, the reaction mixture outputted from the lower portion of the reaction vessel 100 through the pipe 113 is divided into 2 streams, and heat-exchanged by the circulation pumps 102A, 102B and the circulation liquid heat exchangers 103A, 103B, respectively, to form circulation liquids 115A, 115B. The recycle liquid 115A is mixed with the feed olefin 111A (e.g., when the feed olefin is in a liquid state) and the recycle catalyst 120A, and then enters a nozzle of a downjet self-priming reactor 105, and entrains the first synthesis gas 110 and the overhead gas phase components of the reactor conveyed via the pipe while being injected; the recycle liquid 115B is mixed with the feed olefin 111B (e.g., when the feed olefin is in a liquid state) and the recycle catalyst 120B and then enters the nozzle of another parallel downjet self-priming reactor and entrains the synthesis gas 110 and the reactor overhead gas phase components conveyed via the pipe 107 while being injected. The second stream of synthesis gas 110A (not shown) is fed directly into the gas distributor 11 in the reactor 100, which is bubbled and simultaneously catalytically reacted with unreacted olefins in the reactor effluent.
When the feedstock olefins are in the gaseous state, a portion of the olefins in the reaction system described above are entrained with the synthesis gas 110 rather than having to be injected through nozzles, and another portion of the synthesis gas 110A is fed into a gas distributor with optional olefins for bubbling.
In use, the reaction mixture output from the lower portion of the reaction vessel 100 via line 113 is split into 2 streams, and is subjected to heat exchange by circulation pumps 102A and 102B, lines 114A and 114B, and circulation heat exchangers 103A and 103B, respectively, to form circulation liquids 115A and 115B. Part of the reaction mixture is sent via line 116 to reduced pressure flash tank 108 and the tail gas from reduced pressure flash tank 108 is vented via line 118. The flash product is passed via line 117 to aldehyde evaporator 109 and the resulting final aldehyde product is recovered via line 119. The distillation residue (catalyst-containing solution) is transported via line 120 to the reaction vessel for recycling.
Fig. 4 is a schematic diagram of an example of the present invention, in which the reaction vessel 100 of the reaction system comprises two downjet self-priming reactors arranged in parallel. As shown in fig. 4, the circulating liquid 113 outputted from the lower part of the reaction vessel 100 is mixed with the raw olefin 111 (when the raw olefin is in a liquid state), optional fresh catalyst solution and the circulating catalyst 120 by the circulating pump 102 and the circulating heat exchanger 103, and then divided into 2 streams, and enters the nozzles of the two parallel down-jet self-priming reactors 104 and 105 respectively. Each downspray self-priming reactor independently entrains feed synthesis gas (and optionally feed olefin when the feed olefin is in the gaseous state) and entrains the gas phase at the top of the reactor via gas phase recycle line 107 where the gas phase and liquid phase fully contact to form microbubbles into the downspray self-priming reactor diffuser. Most of the reaction was completed in a downflow self-priming reactor. Also, a portion of the synthesis gas and optionally olefins is fed to a gas distributor 11 in the reaction vessel for bubbling.
FIG. 5 is a schematic diagram of a reaction system according to another embodiment of the present invention. As shown in fig. 5, the reaction system includes two reaction vessels 100A, 100B arranged in series, the gas phase portions of the two reaction vessels being fluidly connected via a conduit 114. In use, the reaction mixture output from the lower portion of the first reaction vessel 100A is split into two streams via the pipe 112A and the circulation pump 102A, one stream is passed through the circulation heat exchanger 103A and mixed with the feedstock 111 (e.g., when the olefin is in a liquid state) and the circulation catalyst 122 before entering the nozzle 105A of the downjet self-priming reactor 104A of the reaction vessel 100A, and the other stream is circulated to the reaction vessel 100B. The reactor 100A has a gas distributor 11 fluidly connected to a source of feed gas and into which a portion of the synthesis gas and optionally olefins are fed for bubbling reactions. In the reaction vessel 100B, the reaction mixture outputted from the outlet of the lower part of the reaction vessel through the pipe 112B is split into two streams after passing through the circulation pump 102B. One is input into a nozzle 105B of the lower spraying self-priming reactor 104B through a pipeline 115B after passing through a circulating heat exchanger 103B, and the nozzle 105B sucks the synthesis gas 110B and gas phase components of the reaction kettle conveyed through a pipeline 107B when spraying the gas phase components into the reaction kettle 100B; the other is sent to the decompression flash tank 108 through a pipeline 116, and is separated by flash evaporation and then enters the aldehyde evaporator 109 through a pipeline 117 for separation and recovery. A gas distributor 11 may be optionally disposed in the reaction vessel 110B, and a part of the raw materials may be directly sent to the gas distributor for bubbling reaction.
FIG. 6 is a schematic of a reaction scheme according to one embodiment of the present invention. In contrast to FIG. 2, the suction section of the reactor 16 has only one gas inlet, which is fluidly connected to a gas source and the top of the reactor, respectively, via a Y-tube. The remaining structural functions are the same as in fig. 2.
The invention also relates to a process for preparing aldehydes from olefins, comprising the steps of:
providing a hydroformylation synthesis reaction kettle, wherein a lower spraying self-priming reactor is arranged at the top of the reaction kettle, the lower spraying self-priming reactor sequentially comprises a nozzle, an air suction section, a mixing section and a diffusion section which are in fluid connection, the nozzle is arranged in the air suction section, the air suction section is in fluid communication with a raw material air source, the air suction section is also in fluid connection with a part above the liquidus line of the reaction kettle through a pipeline, and the reaction kettle also comprises a gas distributor which is arranged in the reaction kettle and is in fluid connection with the raw material air source;
spraying a solution containing a catalyst into the reaction kettle through a nozzle of the lower spraying self-priming reactor, wherein the solution is used for sucking a part of raw material gas from a gas source and components of a gas phase part of the reaction kettle in a suction section, and mixing, reacting and diffusing in a mixing section and a diffusion section;
and (3) sending the other part of raw material gas into a gas distributor in the reaction kettle, bubbling the raw material gas in the reaction kettle liquid, and further carrying out hydroformylation reaction under the action of a catalyst.
In the process of the present invention, the conditions for the hydroformylation reaction are not particularly limited and may be reaction conditions known in the art. In one example of the present invention, the hydroformylation reaction conditions described in chinese patent CN102272079a, which is incorporated herein by reference as part of the present invention, are employed.
In one embodiment of the invention, the raw material olefin is in a liquid state, the down-injection self-priming reactor is positioned at the top of the reaction kettle, after the catalyst-containing circulating liquid from the reaction kettle, the raw material olefin and the circulating catalyst liquid from the aldehyde evaporator are mixed, the raw material synthesis gas and the mixed gas phase at the top of the reaction kettle are coiled in the down-injection self-priming reactor, the gas and the liquid are fully contacted, and the gas and the liquid are sprayed into the reaction liquid through a diffusion section; at the same time, a part of the synthesis gas is sent to a gas distributor, bubbling in the reaction kettle liquid and further reacting with the rest olefin under the action of a catalyst.
In one embodiment of the invention, the raw material olefin is in a gaseous state, the down-injection self-priming reactor is positioned at the top of the reaction kettle, after the catalyst-containing circulating liquid from the reaction kettle, the circulating catalyst liquid from the aldehyde evaporator and the optional olefin are mixed, raw material synthesis gas, the optional raw material olefin and mixed gas phase at the top of the reaction kettle are sucked in the down-injection self-priming reactor in a rolling way, and the gas and the liquid are fully contacted and are sprayed into the reaction liquid through a diffusion section; while a portion of the synthesis gas and optionally a portion of the olefins is sent to a gas distributor, which bubbles in the reaction tank liquor to further react with the remaining olefins under the influence of a catalyst.
The invention forms gas phase circulation between the gas phase space of the reaction kettle and the lower spraying self-priming reactor by liquid phase entrainment gas phase, and raw material synthesis gas, reaction kettle gas phase components, catalyst solution and olefin raw materials fully contact in the spraying reactor. It was found through experiments that the reaction rate was accelerated due to the sufficient contact of a large amount of hydrogen with the reaction liquid containing the catalyst composition. Meanwhile, part of synthesis gas is added in a bubbling mode while a down-spraying self-priming reactor is used, and compared with a conventional pure bubbling tower reaction kettle, the bubbling input synthesis gas flow is reduced, so that adverse effects caused by concentration gradient and temperature gradient non-uniformity are reduced; on the other hand, the jet of the down-jet self-priming reactor plays a more or less stirring role, helping to eliminate the adverse effect caused by uneven temperature gradient.
In addition, the conversion rate of the olefin (such as propylene) fed in a narrow space in the jet reactor can reach more than 70%, unexpected experimental results are obtained, unreacted olefin is subjected to bubbling reaction in the kettle through jet, the conversion rate of the olefin is further improved, the reaction is enhanced, the high conversion rate of the olefin can be realized by the jet reaction kettle provided with a gas-phase circulation loop, a liquid-phase circulation loop and a gas distributor, and the olefin stripping and separating process of a rear system is omitted. As the reaction efficiency is improved, the volume and the number of the reaction kettles can be reduced, the reaction residence time is shortened, the selectivity of the product aldehyde is further improved, and the one-time investment of the catalyst is reduced. Compared with a bubbling reaction kettle, the invention can eliminate adverse effects caused by concentration gradient and temperature gradient non-uniformity; compared with the traditional stirred tank reactor, the jet pipe has higher concentration of synthesis gas in liquid phase, better mixing effect of vapor and liquid, faster reaction speed, simple structure, safety and reliability, low investment cost and eliminates unstable factors caused by mechanical stirring.
The invention mainly solves the technical problems of large volume, large quantity, high power consumption, low reaction efficiency and complex reaction process flow of the reaction kettle in the prior art. The invention designs a bubbling and spraying combined reaction kettle device, which directly connects into reaction kettle liquid through a gas distributor by utilizing the high pressure of a synthetic gas source to form a better bubbling effect, and simultaneously adopts the combination of a gas phase self-circulation loop and a liquid phase spraying circulation, thereby further strengthening gas-liquid mass transfer and greatly improving reaction efficiency. The bubbling bed completes the hydroformylation of partial raw material olefin, and the unconverted olefin further completes the hydroformylation of the residual olefin in a smaller ejector, so that the conversion rate of the olefin is effectively improved, and the unit consumption of an ejector circulating pump is reduced.
In one example of the invention, under the condition of 60-130 ℃ and 1.0-6.0MPa of reaction pressure, using aldehyde as a solvent, catalyzing olefin hydroformylation to synthesize aldehyde by using a catalyst formed by an eighth group metal element and a phosphorus-containing ligand; the olefin is at least one of propylene, ethylene, butene, pentene, hexene, heptene, olefinic compounds of from 6 to 18 carbon atoms. The conversion rate of the olefin can reach more than 99%, the strengthening of the hydroformylation reaction process of the olefin is realized, the technical scheme well solves the problems, the catalyst can be used in the process of producing aldehyde by the hydroformylation reaction of the olefin, the one-time input cost of the catalyst is reduced, and the consumption of the ligand is correspondingly reduced.
Examples
The invention is further illustrated by the following examples.
Example 1
The experiment was conducted using propylene as an olefin raw material using the reaction system shown in FIG. 2, the rhodium concentration of the catalyst was 80ppm, the ligand was a composition of tri (o-methylphenyl) phosphorus L0 and L4, wherein the molar ratio of Rh: L0: L4 was 1:10:4, the reaction vessel temperature was maintained at 90 ℃, the reaction pressure was 1.6MPa, the effective reaction liquid volume of the reaction vessel 10 was 10L, the reaction vessel height was 900mm, the top was provided with a downward-spraying self-priming injector 16, the nozzle orifice diameter thereof was 2.5mm, the injection angle was 30 °, the injection expansion pipe diameter was 20mm, and the injection pipe expansion pipe length was 850mm. The suction section of the eductor 16 has two gas inlets fluidly connected to a gas source and the top of the reactor, respectively.
The top of the reaction kettle is provided with an ejector 16, the circulating liquid 112 is taken from the bottom of the reaction kettle, is mixed with the circulating catalyst solution 125, passes through the circulating pump 13 and the circulating heat exchanger 14, is mixed with the propylene feed 110, and then enters the ejector 16, the liquid phase, besides the entrainment of the feed synthesis gas 111B, also a large amount of mixed gas phase composed of unreacted propylene, synthesis gas and partial products at the top of the reaction kettle is entrained by the gas circulation pipe 19, the full contact of gas-liquid two phases is formed in the nozzle, and a large amount of tiny bubbles carried by the liquid phase enter the ejector diffusion section.
The synthesis gas feed 111A is fed into the gas distributor 11 without depressurisation and the bubbling reaction is carried out in the liquid phase comprising the catalyst and the reaction mixture. The reaction product 120 is passed through a reduced pressure flash tank 22, the catalyst is separated by a liquid product dealdehyder evaporator, and the recycle catalyst 125 is returned to the reactor 10.
In the embodiment, the synthetic gas 111A is 1540NL/h, the feeding pressure is 5.5MPa, and the pressure is reduced to 1.6MPa through a gas distribution pipe; 111B is 380NL/h, the feed pressure is 2.0MPa, the propylene feed 110 is 1.8kg/h, the circulating liquid volumetric flow rate is 150L/h, and the gas circulating amount is 170L/h. The yield of butyraldehyde is 3.06kg/h, and the conversion rate of converted propylene into butyraldehyde is 99.1%. The butyraldehyde space-time yield sty=4.25 mol/(l×h) was measured, the product-to-iso ratio being 35. Because of the reaction enhancement, the catalyst concentration is low, only one evaporator is needed to realize the separation of the catalyst and the product aldehyde, and the product aldehyde basically contains no olefin.
Example 2
The experiment was conducted using propylene as an olefin raw material using the reaction system shown in FIG. 2, the rhodium concentration of the catalyst was 80ppm, the ligand was a composition of tri (o-methylphenyl) phosphorus L0 and L5, wherein the molar ratio of Rh: L0: L5 was 1:10:4, the reaction vessel temperature was maintained at 90 ℃, the reaction pressure was 1.6MPa, the effective reaction liquid volume of the reaction vessel 10 was 10L, the reaction vessel height was 900mm, the top was provided with a downward-spraying self-priming injector 16, the nozzle orifice diameter thereof was 2.5mm, the injection angle was 30 °, the injection expansion pipe diameter was 20mm, and the injection pipe expansion pipe length was 850mm. The suction section of the eductor 16 has two gas inlets fluidly connected to a gas source and the top of the reactor, respectively.
The top of the reaction kettle is provided with an ejector 16, the circulating liquid 112 is taken from the bottom of the reaction kettle, is mixed with the circulating catalyst solution 125, passes through the circulating pump 13 and the circulating heat exchanger 14, is mixed with the propylene feed 110, and then enters the ejector 16, the liquid phase, besides the entrainment of the feed synthesis gas 111B, also a large amount of mixed gas phase composed of unreacted propylene, synthesis gas and partial products at the top of the reaction kettle is entrained by the gas circulation pipe 19, the full contact of gas-liquid two phases is formed in the nozzle, and a large amount of tiny bubbles carried by the liquid phase enter the ejector diffusion section.
The synthesis gas feed 111A is fed into the gas distributor 11 without depressurisation and the bubbling reaction is carried out in the liquid phase comprising the catalyst and the reaction mixture. The reaction product 120 is passed through a reduced pressure flash tank 22, the catalyst is separated by a liquid product dealdehyder evaporator, and the recycle catalyst 125 is returned to the reactor 10.
In the embodiment, the synthetic gas 111A is 1540NL/h, the feeding pressure is 5.5MPa, and the pressure is reduced to 1.6MPa through a gas distribution pipe; 111B is 380NL/h, the feed pressure is 2.0MPa, the propylene feed 110 is 1.8kg/h, the circulating liquid volumetric flow rate is 150L/h, and the gas circulating amount is 170L/h. The yield of butyraldehyde is 3.06kg/h, and the conversion rate of converted propylene into butyraldehyde is 99.2%. The butyraldehyde space-time yield sty=4.25 mol/(l×h) was measured, the product-to-iso ratio being 32.
Example 3
The experiment was conducted using propylene as an olefin raw material using the reaction system shown in FIG. 2, the rhodium concentration of the catalyst was 80ppm, the ligand was a composition of tris (o-methylphenyl) phosphorus L0 and monophosphite L7, wherein the molar ratio of Rh: L0: L7 was 1:10:4, the reaction vessel temperature was maintained at 90 ℃, the reaction pressure was 1.6MPa, the effective reaction liquid volume of the reaction vessel 10 was 10L, the reaction vessel height was 900mm, the top was provided with a downward-jet self-priming injector 16, the nozzle orifice diameter thereof was 2.5mm, the injection angle was 30℃and the injection expansion pipe diameter was 20mm, and the injection pipe expansion pipe length was 850mm. The suction section of the eductor 16 has two gas inlets fluidly connected to a gas source and the top of the reactor, respectively.
The operation of this example was the same as that of example 1 and example 2, in which the synthesis gas 111A was 1540NL/h, the feed pressure was 5.5MPa, and the pressure was reduced to 1.6MPa by means of a gas distribution pipe; 111B is 380NL/h, the feed pressure is 2.0MPa, the propylene feed 110 is 1.8kg/h, the circulating liquid volumetric flow rate is 150L/h, and the gas circulating amount is 170L/h. The yield of butyraldehyde is 3.06kg/h, and the conversion rate of converted propylene into butyraldehyde is 99.2%. The butyraldehyde space-time yield sty=4.25 mol/(l×h) was measured, the product-to-iso ratio being 37.
Example 4
Using the procedure described in example 1, the catalyst had a rhodium concentration of 60ppm and the ligand was a combination of tris (o-methylphenyl) phosphorus L0 and L4, with a molar ratio of Rh to L0 to L4 of 1:10:4. Experiments were conducted using ethylene as the olefin feed.
In the embodiment, the synthetic gas 111A is 2250NL/h, the feeding pressure is 5.5MPa, and the pressure is reduced to 1.6MPa through a gas distribution pipe; 111B is 400NL/h, and the feeding pressure is 2.0MPa; ethylene feed 110 was 1.65kg/h, the recycle liquid volumetric flow rate was 150L/h, and the gas recycle amount was 170L/h. The yield of propanal was 3.40kg/h and the conversion of ethylene to propanal was 99.3%. The observed propanal space-time yield sty=5.86 mol/(l×h).
Example 5
Using the procedure described in example 2, the catalyst had a rhodium concentration of 60ppm and the ligand was a combination of tris (o-methylphenyl) phosphorus L0 and L5, with a molar ratio of Rh to L0 to L5 of 1:10:4. Experiments were conducted using ethylene as the olefin feed.
In the embodiment, the synthetic gas 111A is 2250NL/h, the feeding pressure is 5.5MPa, and the pressure is reduced to 1.6MPa through a gas distribution pipe; 111B is 400NL/h, and the feeding pressure is 2.0MPa; ethylene feed 110 was 1.65kg/h, the recycle liquid volumetric flow rate was 150L/h, and the gas recycle amount was 170L/h. The yield of propanal was 3.40kg/h and the conversion of ethylene to propanal was 99.3%. The observed propanal space-time yield sty=5.86 mol/(l×h).
Example 6
Using the procedure described in example 2, the catalyst rhodium concentration was 150ppm, the ligand was triphenylphosphine and the ethylene was used as the olefin feed.
In the embodiment, the synthetic gas 111A is 2250NL/h, the feeding pressure is 5.5MPa, and the pressure is reduced to 1.6MPa through a gas distribution pipe; 111B is 400NL/h, and the feeding pressure is 2.0MPa; ethylene feed 110 was 1.65kg/h, the recycle liquid volumetric flow rate was 150L/h, and the gas recycle amount was 170L/h. The propionaldehyde yield was 2.80kg/h and the conversion of ethylene to propionaldehyde was 82%. The observed space-time yield of propanal sty=4.83 mol/(l×h).
Example 7
The procedure of example 1 was employed, but using an ethylene-propylene mixture gas as the olefin feedstock, wherein the ethylene-propylene mixture ratio was 1:4.
In the embodiment, the synthetic gas 111A is 1950NL/h, the feeding pressure is 5.5MPa, and the pressure is reduced to 1.6MPa through a gas distribution pipe; 111B is 350NL/h, and the feeding pressure is 2.0MPa; the ethylene content of the mixed olefin feed 110 was 0.75kg/h, the propylene content was 1.0kg/h, the circulating liquid volume flow rate was 150L/h, and the gas circulation rate was 170L/h. The yield of propanal was 1.54kg/h and the conversion of ethylene to propanal was 99.4%. The observed propanal space-time yield sty=2.66 mol/(l×h); the yield of butyraldehyde is 1.70kg/h, and the conversion rate of converted propylene into butyraldehyde is 99.3%. The butyraldehyde space-time yield sty=2.36 mol/(l×h) was measured, the product-to-iso ratio being 30.
Comparative example 1
The same procedure as in example 1 was used, but the connection 19 of the sparger 16 to the top of the reactor was closed.
In this example, the synthesis gas 111A was 1540NL/h, the feed pressure was 5.5MPa, and the pressure was reduced to 1.6MPa by a gas distribution pipe; 111B is 380NL/h, and the feeding pressure is 2.0MPa; propylene feed 110 was 1.8kg/h, the circulating liquid volume flow was 150L/h, and gas circulation line 19 was closed, and the gas circulation amount was shown at (0L/h). The butyraldehyde yield was 2.45kg/h and the conversion of converted propylene to butyraldehyde was 79.5%. The butyraldehyde space-time yield sty=3.40 mol/(l×h) was measured, the product-to-iso ratio being 30.
Comparative example 2
The same procedure as in comparative example 1 was used while closing the connection pipe 111B of the ejector to the air source. As a result, all of the synthesis gas was fed to the gas distributor 11 without depressurizing, and bubbling reaction was performed in the liquid phase containing the catalyst and the reaction mixture.
In the embodiment, the ejector is used for liquid circulation and propylene feeding, the synthesis gas is fed from the bottom of the reaction kettle, 111A is 1920NL/h, and the pressure of the feed distributor is 2.0MPa;111B is 0NL/h; propylene feed 110 was 1.8kg/h, the circulating liquid volume flow was 150L/h, and gas circulation line 19 was closed, and the gas circulation amount was shown at (0L/h). The butyraldehyde yield was 2.35kg/h and the conversion of converted propylene to butyraldehyde was 78%. The butyraldehyde space-time yield sty=3.24 mol/(l×h) was measured, the product-to-iso ratio being 25.
Comparative example 3
Using the procedure described in example 1, the catalyst had a rhodium concentration of 60ppm and the ligand was a combination of tris (o-methylphenyl) phosphorus L0 and L4, with a molar ratio of Rh to L0 to L4 of 1:10:4. Experiments were conducted using ethylene as the olefin feed. The connection line 19 of the injector 16 to the top of the reaction vessel and the connection line 111B of the injector to the gas source are closed.
In the embodiment, the synthetic gas 111A is 2400NL/h, the feeding pressure is 5.5MPa, and the pressure is reduced to 1.6MPa through a gas distribution pipe; 111B flow is 0NL/h; ethylene feed 110 was 1.5kg/h and the recycle liquid volumetric flow rate was 150L/h, gas recycle line 19 was closed and the gas recycle was shown at (0L/h). The yield of propanal was 2.73kg/h and the conversion of converted ethylene to propanal was 88.0%. The observed space-time yield of propanal sty=4.71 mol/(l×h) with a product normal-to-iso ratio of 30.
Example 8
Experiments were conducted using the reaction system shown in FIG. 5 with ethylene as the olefin feed, a rhodium catalyst concentration of 60ppm, and a ligand composition of tris (o-methylphenyl) phosphorus L0 and L4, wherein the molar ratio of Rh to L0 to L4 was 1:10:4. The temperature of the reaction kettle is maintained at 90 ℃, the reaction pressure is 1.6MPa, the volume of the effective reaction liquid of the single reaction kettle is 10L, the total volume of the double-kettle serial connection is 20L, the height of the reaction kettle is 900mm, the top is provided with a lower spraying self-priming sprayer 16, the diameter of a nozzle opening of the lower spraying self-priming sprayer is 2.5mm, the spraying angle is 30 degrees, the diameter of a spraying expansion pipe is 20mm, and the length of the spraying pipe is 850mm. The suction section of the eductor 16 has two gas inlets fluidly connected to a gas source and the top of the reactor, respectively.
In this example, synthesis gas 5450NL/h, wherein the first reactor split 80% 4360NL/h, all from distributor 11 into 100A,110A shown as 0NL/h; the second reactor was assigned 20% 1090NL/h, all from distributor 11 into 100B,110B shown as 0NL/h; the feeding pressure is 5.5MPa, and the pressure is reduced to 1.6MPa through a gas distribution pipe; ethylene feed 111 was 3.4kg/h, the recycle liquid volume flow was 150L/h and the gas recycle was 170L/h. The yield of propanal was 7.0kg/h and the conversion of ethylene to propanal was 99.5%. The observed space-time yield of propanal sty=6.03 mol/(l×h).
Example 9
Experiments were conducted using the reaction system shown in FIG. 6 with ethylene as the olefin feed, a rhodium catalyst concentration of 60ppm, and a ligand composition of tris (o-methylphenyl) phosphorus L0 and L4, wherein the molar ratio of Rh to L0 to L4 was 1:10:4. The temperature of the reaction kettle is maintained at 90 ℃, the reaction pressure is 1.6MPa, the volume of the effective reaction liquid of the reaction kettle 10 is 10L, the height of the reaction kettle is 900mm, a lower spraying self-priming sprayer 16 is arranged at the top, the nozzle opening diameter of the lower spraying self-priming sprayer is 2.5mm, the spraying angle is 30 degrees, the diameter of a spraying expansion pipe is 20mm, and the length of the spraying expansion pipe is 850mm. The suction section of eductor 16 has only one gas inlet which is fluidly connected to the gas source and the top of the reactor via a Y-tube, respectively.
In the embodiment, the synthetic gas 111A is 2250NL/h, the feeding pressure is 5.5MPa, and the pressure is reduced to 1.6MPa through a gas distribution pipe; 111B is 400NL/h, and the feeding pressure is 2.0MPa; ethylene feed 110 was 1.65kg/h, the recycle liquid volumetric flow rate was 150L/h, and the gas recycle amount was 170L/h. The propionaldehyde yield was 3.22kg/h and the conversion of ethylene to propionaldehyde was 94.5%. The observed propanal space-time yield sty=5.55 mol/(l×h).
Example 10
Using the method described in example 2, n-butene was selected as the olefin feedstock, wherein 1-butene: the mass of the 2-butene is 1:2; the rhodium catalyst concentration was 200ppm and the ligand was a combination of tris (o-methylphenyl) phosphorus L0 and L5, wherein the molar ratio of Rh to L0 to L5 was 1:10:4. The temperature of the reaction kettle is maintained at 95 ℃ and the reaction pressure is 1.5MPa.
In the embodiment, the synthetic gas 111A is 1430NL/h, the feeding pressure is 5.5MPa, and the pressure is reduced to 1.6MPa through a gas distribution pipe; 111B is 350NL/h, and the feeding pressure is 2.0MPa; the mixed butene feed 110 was 2.2kg/h, the circulating liquid volume flow was 150L/h, and the gas circulation volume was 170L/h. The valeraldehyde yield was 3.26kg/h and the conversion of mixed butenes to valeraldehyde was 96.5%. The valeraldehyde space-time yield sty=3.79 mol/(l×h) was measured.
Example 11
Using the method described in example 2, 1-pentene was selected as the olefin feed; the rhodium catalyst concentration was 200ppm and the ligand was a combination of tris (o-methylphenyl) phosphorus L0 and L5, wherein the molar ratio of Rh to L0 to L4 was 1:10:4. The temperature of the reaction kettle is maintained at 100 ℃, and the reaction pressure is 1.5MPa.
In the embodiment, the synthetic gas 111A is 1150NL/h, the feeding pressure is 5.5MPa, and the pressure is reduced to 1.6MPa through a gas distribution pipe; 111B is 270NL/h, and the feeding pressure is 2.0MPa; the 1-pentene feed 110 was 2.2kg/h, the recycle liquid volume flow rate was 150L/h, and the gas recycle volume was 170L/h. The hexanal yield was 3.01kg/h and the conversion of converted pentene to hexanal was 96.0%. The hexanal space-time yield sty=3.00 mol/(l×h) was measured.
Claims (3)
1. A process for the hydroformylation of olefins to produce aldehydes comprising the steps of:
providing a hydroformylation synthesis reaction kettle, wherein a lower spraying self-priming reactor is arranged at the top of the reaction kettle, the lower spraying self-priming reactor sequentially comprises a nozzle, an air suction section, a mixing section and a diffusion section which are in fluid connection, the nozzle is positioned in the air suction section, the air suction section is in fluid communication with a raw material air source, the air suction section is also in fluid communication with a part above the liquidus line of the reaction kettle through a pipeline, and the reaction kettle further comprises a gas distributor which is positioned in the reaction kettle and is in fluid connection with the raw material air source;
Spraying a reaction liquid containing a catalyst into the reaction kettle through a nozzle of the lower spraying self-priming reactor, wherein the reaction liquid is used for sucking a part of gas raw materials from a gas source and circulating gas of a gas phase part of the reaction kettle in a suction section, and mixing, reacting and diffusing in a mixing section and a diffusion section;
and (3) delivering the other part of the gas raw material from the gas source to a gas distributor in the reaction kettle through a pipeline, and carrying out contact reaction with the catalyst-containing solution in the reaction kettle liquid through bubbling.
2. The method of claim 1, wherein the suction section of the downdraft self-priming reactor has two gas inlets fluidly connected to the gas source and to the portion of the reactor above the liquidus line, respectively.
3. The process according to claim 1, wherein the olefin is selected from the group consisting of ethylene, propylene, 1-butene, 2-butene, isobutene, pentene, 2, 5-dihydrofuran, C 6-18 An olefinic compound or a mixture of two or more thereof.
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| CN102272079A (en) * | 2009-01-16 | 2011-12-07 | Lg化学株式会社 | Apparatus for producing alcohols from olefins |
| CN102826974A (en) * | 2011-06-17 | 2012-12-19 | 中国石油化工股份有限公司 | Method for preparing butyraldehyde through hydroformylation of propylene |
| CN103025695A (en) * | 2010-07-14 | 2013-04-03 | Lg化学株式会社 | An apparatus for coproduction of iso type aldehydes and alcohols from olefins, and a method for coproduction using the apparatus |
| CN203291868U (en) * | 2013-05-22 | 2013-11-20 | 中国石油化工股份有限公司 | Jet reaction device |
| CN104030901A (en) * | 2013-04-11 | 2014-09-10 | 中石化上海工程有限公司 | Light olefins hydroformylation method |
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| CN102272079A (en) * | 2009-01-16 | 2011-12-07 | Lg化学株式会社 | Apparatus for producing alcohols from olefins |
| CN103025695A (en) * | 2010-07-14 | 2013-04-03 | Lg化学株式会社 | An apparatus for coproduction of iso type aldehydes and alcohols from olefins, and a method for coproduction using the apparatus |
| CN102826974A (en) * | 2011-06-17 | 2012-12-19 | 中国石油化工股份有限公司 | Method for preparing butyraldehyde through hydroformylation of propylene |
| CN104030901A (en) * | 2013-04-11 | 2014-09-10 | 中石化上海工程有限公司 | Light olefins hydroformylation method |
| CN203291868U (en) * | 2013-05-22 | 2013-11-20 | 中国石油化工股份有限公司 | Jet reaction device |
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