CN210595857U - Oxo-synthesis spray kettle, reaction system and bottom spray self-suction type sprayer - Google Patents
Oxo-synthesis spray kettle, reaction system and bottom spray self-suction type sprayer Download PDFInfo
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- CN210595857U CN210595857U CN201920960454.1U CN201920960454U CN210595857U CN 210595857 U CN210595857 U CN 210595857U CN 201920960454 U CN201920960454 U CN 201920960454U CN 210595857 U CN210595857 U CN 210595857U
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Abstract
An injection still, reaction system and lower-spray self-sucking sprayer are disclosed. The oxo-synthesis spray tank comprises one or more lower spray self-priming sprayers arranged at the top of the spray tank, each lower spray self-priming sprayer comprises a nozzle and a suction section, a mixing section and a diffusion section which are communicated with each other in a fluid mode, the nozzle is positioned in the suction section, and the suction section is communicated with a raw material gas source in a fluid mode; each air suction section is also in fluid communication with the part above the liquid phase line of the spraying kettle through a pipeline.
Description
Technical Field
The utility model relates to the field of oxo synthesis, in particular to a reaction device and a reaction system for preparing aldehyde by carbonylation of unsaturated compounds (such as olefin) and synthesis gas. Adopt the utility model discloses reaction system can improve reaction efficiency, reduce equipment investment, has high economic benefits.
Background
The olefin carbonyl reaction is an important organic synthesis reaction and plays a very important role in modern industry. The product aldehyde is a very useful chemical intermediate, can synthesize various important chemical products, and is a homogeneous catalytic reaction process with the largest production scale so far. [ Trzeciak, A.M.; zi Lou lkowski, J.J. coord.chem.Rev.1999,190-192,883-900.
The main processes for the production of aldehydes from olefinic carbonyls include the low pressure rhodium catalyzed carbonyl process, the high pressure cobalt catalyzed carbonyl process. Under certain conditions, raw material olefin and synthesis gas H2the/CO directly enters the catalyst solution of the reaction kettle together and reacts in the liquid phase main body to generate aldehydes. In the process of using the ligand modified homogeneous catalyst for the carbonyl of olefins, the reaction conversion rate, the space-time yield of aldehyde (STY, which means the conversion amount of olefins per unit time and unit volume based on the total volume of the reaction) and the positive-to-differential ratio of the product can be seriously affected by the unevenness of the concentration and temperature in the reaction solution, so that most devices need to enhance the contact between gas and liquid by stirring, and the materials are thoroughly and uniformly mixed. With the increase of the reaction carbon chain, the reactivity of the alkene carbonyl group is reduced, especially when the internal alkene exists, the reduction of the reactivity is more obvious, the reaction residence time is long, and a plurality of reaction byproducts are generated, so 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 leads the reaction kettle to have better mixing effect under special conditionsThe stirrer used is expensive. Another disadvantage of using a stirred tank reactor is that the stirrer shaft must penetrate the wall of the pressurized tank reactor, which requires high equipment sealing, and also requires high stress on the tank seals and the stirring paddles due to the rotation of the stirring shaft. In daily operation, equipment failure of stirring equipment easily occurs, and continuous and stable operation of production is seriously influenced. At present, most of olefin carbonyl reaction devices which are industrially and practically applied adopt a kettle type stirrer, the reaction efficiency is relatively low due to factors such as mass transfer and the like, taking an industrial application example of n-butene carbonyl as an example, a 2-propyl heptanol production device with 7 ten thousand tons/year needs 3 stirring reaction kettles for series reaction, and the volume of each reaction kettle is 105m3(mechanical Engineers, 2015 (6): 252-.
As an alternative to the stirred tank reactor, there is a case of industrially carrying out an olefin carbonyl reaction using a bubble column reactor. The reaction gas is introduced from the bottom of the bubbling tower, the reaction gas is ensured to be dispersed in the reaction liquid through the gas distributor so as to increase the mass transfer surface area, and the bubbles are dispersed and raised in the reaction liquid, so that the reaction liquid is mixed. However, since the reaction gas participates in the carbonyl reaction during the rising process, a local concentration gradient and temperature unevenness are easily formed in the bubble column, thereby affecting the reaction conversion rate, the aldehyde selectivity and the space-time yield of the aldehyde, and the production efficiency is lower than that of a stirred tank reactor.
CN 101679173B discloses a method and apparatus for producing aldehydes by reacting olefins with synthesis gas comprising carbon monoxide and hydrogen, using an ejector to enhance the gas-liquid mass transfer, thereby improving the hydroformylation efficiency and obtaining the desired high yield of aldehydes.
CN102272079A discloses an apparatus for producing an alcohol from an olefin, which comprises a carbonyl addition reactor comprising an injection means for injecting an olefin and a synthesis gas into a catalyst mixed solution in the reactor, a reactor outlet for discharging a reaction mixture of the olefin and the synthesis gas, a distribution plate for changing the flow of the olefin and the synthesis gas, and a circulation pipe for circulating a part of the reaction mixture to the injection means through a pipe disposed outside the reactor.
Wanxiao et al "model and application of a jet gas-liquid reactor" ("chemical industry and engineering technology" 2002, vol 23, No. 2) describe jet gas-liquid reactors. It refers to a bottom-spray self-priming sprayer typically used in the industry, which consists of four parts, namely a nozzle, a suction chamber, a mixing chamber and a diffusion chamber. When a reaction liquid having a certain pressure is downwardly sprayed through a nozzle, a high flow velocity is generated, a pressure drop is formed around the nozzle, and a laterally supplied raw material gas is sucked into a suction chamber and then sufficiently mixed in a mixing chamber to form a turbulent flow while performing a reaction. The flow velocity of the product in the diffusion chamber is gradually reduced, the product is sent out by using increased static pressure, and a large amount of gas can be automatically sucked without gas supply equipment such as a compressor, so that the energy consumption is greatly reduced. And the material forms stable turbulence at the nozzle, thus strengthening the mixing of gas and liquid and being very beneficial to the gas-liquid phase transient reaction controlled by diffusion.
In the chemical industry, the reaction efficiency is improved by one percent to generate huge economic efficiency. Thus, although the introduction of a jet gas-liquid reactor improves the efficiency of the olefin carbonylation reaction, there is still room for further improvement in this process.
Disclosure of Invention
The object of the present invention is to further improve the efficiency of the olefin carbonylation reaction.
Therefore, one aspect of the present invention relates to an oxo process spray tank, comprising a bottom spray self-priming sprayer disposed on the top of the spray tank, the bottom spray self-priming sprayer sequentially comprising a nozzle and a suction section, a mixing section and a diffusion section which are in fluid communication with each other, the nozzle being located in the suction section, the suction section being in fluid communication with a feed gas source;
the device is characterized in that the air suction section is communicated with the part above the liquid phase line of the spraying kettle through a pipeline.
The utility model discloses an on the other hand relates to a lower spraying is from inhaling formula sprayer, and it includes suction segment, mixing section and the diffuser that nozzle and fluid link to each other in proper order, the nozzle is located the suction segment, the suction segment has the gas inlet who introduces feed gas and circulating gas.
Another aspect of the utility model relates to a reaction system of oxo reaction, it includes the utility model oxo sprays the cauldron, it includes to spray the cauldron:
the lower spraying self-suction type ejector is arranged at the top of the ejector and sequentially comprises a nozzle, and a suction section, a mixing section and a diffusion section which are connected with each other in a fluid manner, wherein the nozzle is positioned in the suction section, and the suction section is communicated with a raw material gas source in a fluid manner and is communicated with a part of the fluid above a liquid phase line of the spraying kettle;
a jet kettle outlet mounted at the lower portion thereof for discharging the reaction mixture of the synthesis gas and olefins; and
a distributor plate mounted inside the spray tank and between the lower spray self-priming injector and the spray tank outlet for altering the flow of the olefins and syngas;
the system also includes a circulation tube for recovering the reaction mixture from the jet kettle outlet and then supplying it to the lower jet self-priming ejector nozzle.
Drawings
The invention is further illustrated by the following figures. In the drawings:
fig. 1 is a schematic structural view of a bottom-spray self-priming sprayer used in the present invention;
FIG. 2 is a simplified process flow diagram of an embodiment of the present invention;
FIG. 3 is a simplified process flow diagram of another embodiment of the present invention;
FIG. 4 is a simplified process flow diagram of another embodiment of the present invention;
FIG. 5 is a schematic view of a process flow of a double-injection kettle series connection in one embodiment of the present invention;
fig. 6 is a simplified process flow diagram of an embodiment of the present invention.
Detailed Description
The inventor of the utility model has conducted careful research on the existing oxo reactor, and found that although the bottom-spraying self-priming injector has the force to push down the reactant, making it move downward to enter the bottom liquid phase catalyst solution, there is part of the reaction raw material, especially the synthesis gas with lighter weight, which can be suspended upward on the upper part of the spraying kettle, such as the top of the spraying kettle, thereby affecting the reaction efficiency. Based on the discovery, the inventor of the utility model provides a gas circulation of spraying cauldron gaseous phase part is introduced the suction segment of bottom sprag from inhaling formula sprayer, makes it circulate to the bottom sprag reactor and reacts, can further improve reaction efficiency.
Accordingly, the present invention relates to an oxo process spray tank, the shape, material, size, etc. of which are not particularly limited and may be known in the art. In one example of the present invention, the spray tank is a vertical reactor. In another example of the present invention, the spray tank is a horizontal reactor.
The utility model discloses the injection cauldron is including arranging in the lower of injection cauldron top portion is from inhaling formula sprayer, it includes suction segment, mixing section and the diffuser that nozzle and fluid link to each other in proper order to spout from inhaling formula sprayer down, the nozzle is located the suction segment, and the suction segment communicates with each other with the feed gas fluid, the suction segment still through the pipeline with partial or gaseous phase fluid communication above the injection cauldron liquid phase line.
In the present invention, the term "the air suction section is further communicated with the portion above the liquid phase line of the spraying kettle or the portion of the gas phase in the fluid communication" through a pipeline "means a pipeline except the conventional lower spraying self-suction type sprayer body pipeline. The conduit is located outside the spray tank.
In the present invention, the term "portion above the spray pot liquidus line" refers to a spray pot position higher than the spray pot liquidus line and not sucking liquid during the gas phase circulation. In one embodiment of the present invention, the portion above the spray still liquidus is a position near and including the top of the spray still. In another embodiment of the present invention, the "part above the spray kettle liquidus" refers to the spray kettle top.
In the present invention, the term "downward-spraying self-priming sprayer includes a suction section, a mixing section and a diffusion section which are connected with each other by fluid" means that the sprayer includes three functional sections having functions of suction, mixing and diffusion, which may be physically distinguishable (for example, a suction chamber, a mixing chamber and a diffusion chamber) or physically indistinguishable (for example, a section of a pipe, each having a suction, mixing or diffusion function at a different position).
In the present invention, the term "the nozzle is located in the air suction section" does not refer to that the position of the nozzle is physically located in the air suction section, but means that the entrainment force generated by the jet flow formed by the nozzle is sufficient to entrain the gaseous material regardless of the physical position thereof.
The terms "in fluid communication" and "fluidly connected" are used interchangeably in the present application to mean that two parts are connected to each other and that fluid can flow between the two parts.
In one embodiment of the present invention, the suction section has two gas inlets, one of which is fluidly connected to the source gas and the other of which is fluidly connected to the top of the spray tank via a conduit.
In an embodiment of the present invention, the suction section has a gas inlet, and the inlet is in fluid communication with the raw material gas source and the upper portion of the spray tank liquid phase line through a Y-shaped pipe.
In a preferred embodiment of the present invention, the suction section has two gas inlets, one of which is fluidly connected to the source gas and the other of which is fluidly connected to the upper portion of the spray tank liquid phase line via a conduit. In one example of the present invention, the two gas inlets are of equal height, and the nozzle opening is lower than the gas inlets.
In an example of the present invention, the suction segment has two gas inlets, one of which is fluidly connected to the raw material gas source, the other of which is fluidly connected to the upper portion of the liquid phase line of the spray tank through a pipe, the two gas inlets have the same height, and the nozzle opening is lower than the lowest point of the gas inlet by 0.5-500mm, preferably 10-350mm, more preferably 20-250 mm. Preferably 50-200mm lower.
The structure of the bottom-spray self-priming ejector of the present invention is not particularly limited, and may be a conventional structure known in the art, for example, a bottom-spray self-priming ejector described in "type and application of jet gas-liquid reactor" in waning volt et al (chemical industry and engineering technology, vol. 23, No. 2 of 2002), except that the suction section has two gas inlets or the gas inlet of the suction chamber is fluidly connected to two gas streams through a Y-shaped pipe.
In one embodiment of the present invention, the downflow reactor disclosed in FIG. 1b of Chinese patent CN102272079A is used, except that the gas inlet section has two gas inlets or the gas inlet of the gas suction chamber is fluidly connected to two gas streams through a Y-shaped pipe.
Fig. 1 is a schematic structural view of a bottom-spray self-priming sprayer according to an embodiment of the present invention. As shown in the figure, the utility model discloses lower spraying is from inhaling formula sprayer includes nozzle 1, aspiration chamber 2, mixing chamber 3 and diffusion chamber 4 in proper order, nozzle 1 is located in aspiration chamber 2, aspiration chamber 2 has gas inlet 6 that links to each other with gas source fluid and with the gas inlet 7 that sprays the fluid phase line of cauldron above part (better spraying cauldron kettle top) fluid and link to each other.
In operation, a liquid stream 5 containing a catalyst is sprayed downward through the nozzle 1, and the sprayed pressure entrains the raw material gas introduced through the raw material gas inlet 6 and the gas from the gas phase part of the spray kettle introduced through the circulating gas inlet 7, and the raw material gas and the gas are fully mixed and reacted in the moving path from the gas suction chamber 2 to the mixing chamber 3, and then are diffused into the spray kettle through the diffusion chamber 4.
In one example of the present 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 air suction chamber 2 is connected with the nozzle 1, the lower part of the air suction chamber is a tapered pipe contraction section, the mixing chamber 3 forms the throat of the Venturi tube, and the diffusion chamber 4 forms the diffusion section of the Venturi tube.
In one embodiment of the present invention, the diameter D of the inlet section of the suction chamber 2 to which the nozzle 1 is connected is 0.8 to 500mm, preferably 1 to 400mm, more preferably 1.5 to 300mm, preferably 1.75 to 250mm, preferably 2 to 100 mm; the cone angle of the nozzle spray cone is about 10 to 90 degrees, preferably 15 to 75 degrees, and more preferably 20 to 60 degrees. The diameter of the throat is 1.0-3.0D, and the length is 5.0-100.0 times, preferably 20.0-60.0 times of the diameter of the throat. The cone angle of the diffuser section is about 5 to 30 degrees, preferably 9 to 20 degrees, more preferably 10 to 15 degrees, and the diameter at the exit of the diffuser section is about 1.0 to 20 times, preferably 1.2 to 18 times, more preferably 1.5 to 15 times, and preferably 2 to 10 times the diameter of the throat.
In one embodiment of the present invention, the total length of the injection pipe is 0.01 to 1.5 times, preferably 0.05 to 1.4 times, more preferably 0.08 to 1.2 times, still more preferably 0.1 to 1.1 times, still more preferably 0.2 to 1.0 times, and most preferably 0.5 to 0.95 times the inner height of the injection tank.
In an example of the present invention, the olefin used in the oxo reaction of the present invention is gaseous olefin, and at this time the liquid stream 5 containing the catalyst comprises fresh catalyst solution and/or recycled catalyst solution, the raw gas introduced by entrainment through the raw gas inlet 6 comprises olefin and synthesis gas, and the gas introduced by entrainment through the recycle gas inlet 7 is gas derived from the gas phase part of the injection reactor.
In another embodiment of the present invention, the olefin used in the oxo reaction of the present invention is a liquid olefin, and the liquid stream 5 comprises olefin, fresh catalyst solution and/or recycled catalyst solution, the raw gas introduced by entrainment through the raw gas inlet 6 comprises syngas, and the gas introduced by entrainment through the recycle gas inlet 7 is gas originating from the gas phase portion of the injection still.
In the present invention, the synthesis gas is CO/H2Can be easily prepared by a conventional method, for example, by a conventional water gas synthesis method.
The utility model discloses still relate to a reaction system for oxo reaction, it includes the oxo sprays the cauldron, it is used for raw materials alkene and synthetic gas (CO/H) including installing at its top to spray the cauldron2) The utility model discloses a bottom spray self-suction type sprayer, wherein the catalyst solution and the gas phase circulation material of the spraying kettle are injected into the spraying kettle; a jet kettle outlet mounted at the lower portion thereof for discharging the reaction mixture of the synthesis gas and olefins; a distributor plate mounted inside the spray tank and between the lower spray self-priming injector and the spray tank outlet for altering the flow of the olefins and syngas; for discharging from jet kettlesA circulation pipe for recovering the reaction mixture and supplying it to a nozzle of a lower spray self-priming ejector to circulate the reaction mixture.
In the present invention, the term "lower part of the spray tank" refers to a position below the liquidus line of the spray tank. In one example of the present invention, the "injection pot lower part" includes an injection pot bottom.
The distribution plate installed in the spraying kettle is used for changing the flow of the spraying flow of the lower spraying self-suction type sprayer so as to adjust the residence time of the reaction raw materials in the spraying kettle. One of ordinary skill in the art can readily determine the location and shape of the distributor plate in the spray tank according to the particular reaction requirements. For example, one of ordinary skill in the art can determine the location and shape of the distribution plate in the spray tank based on the shape and placement requirements of the distribution plate as disclosed in the specific reaction in conjunction with chinese patent CN 102272079A.
Figure 2 is a schematic diagram of a reaction scheme of an embodiment of the present invention. As shown in fig. 2, the reaction system for oxo reaction of the present invention comprises the oxo spray reactor 100 of the present invention, the spray reactor 100 comprises a bottom spray self-suction type sprayer 104, the reactor 104 is installed on the top of the spray reactor, its suction chamber has two gas inlets respectively, one is used for sucking the gas phase raw material input through the pipeline 111 to the suction chamber, the other is used for sucking the gas phase circulating material of the spray reactor circulating through the pipeline 107 to the suction chamber; the lines 122 and 115 inject the circulating catalyst-containing solution into the spray tank and simultaneously entrain the gas-phase feedstock for reaction; a spray pot outlet installed at the lower connection pipe 113 of the spray pot for discharging a reaction mixture containing a catalyst solution; a distribution plate 101 installed inside the spray tank between the lower spray self-priming sprayer 104 and the spray tank outlet for changing the flow of the olefins and the synthesis gas; circulation pipes 114 and 115 for recovering the reaction mixture from the outlet of the injection tank through a pipe 113 and then supplying to the nozzle of the lower spray self-suction type ejector 104 to circulate the reaction mixture.
In one embodiment of the present invention, the reaction system further comprises a reduced-pressure flash tank 108 fluidly connected to the outlet of the injection still, and an aldehyde evaporator 109 fluidly connected to the reduced-pressure flash tank 108, wherein the bottom of the aldehyde evaporator 109 is fluidly connected to the nozzle 105 of the lower-injection self-priming injector 104 of the injection still 100 via pipes 120 and 122.
In use, the nozzle 105 of the lower spray self-suction type ejector 104 sprays the olefin and the catalyst solution (if necessary) fed through the pipe 111, the reaction circulation liquid from the injection tank 100 circulated through the pipe 115, and the catalyst-containing recovery liquid from the aldehyde evaporator 109 circulated through the pipes 120 and 122 into the injection tank 100 while entraining the synthesis gas (CO/H) fed through the pipe 1102) And a gas phase part of the gas in the injection kettle is conveyed through a pipeline 107, and the injection is mixed, reacted and diffused through the diffusion section 106, is blocked by the baffle plate 101 and is further distributed and reacted in the injection kettle. The reaction mixture is conveyed by the action of a jet circulation pump 102 through outlets at the lower part (preferably the bottom) of the jet kettle through pipelines 113 and 114, a part of the reaction mixture is sent to a nozzle 105 through a pipeline 115 after heat exchange by a circulating liquid heat exchanger 103, the other part of the reaction mixture is sent to a reduced-pressure flash tank 108 through a pipeline 116, tail gas of the reduced-pressure flash tank 108 is emptied through a pipeline 118, a flash product enters an aldehyde evaporator 109 through a pipeline 117, the obtained final aldehyde product is recovered through a pipeline 119, and distillation residues (a solution containing a catalyst) are conveyed to the nozzle 105 through a pipeline 120 and are recycled.
In an example of the present invention, when the olefin raw material is in a gaseous state, the nozzle 105 of the lower spray self-suction type sprayer 104 sprays the catalyst solution (if necessary) fed through the pipe 111, the reaction circulation liquid from the spray tank circulating through the pipe 115, and the catalyst-containing recovery liquid from the aldehyde evaporator 109 circulating through the pipe 120 into the spray tank 100 while entraining the synthesis gas (CO/H) fed through the pipe 1102) And gaseous olefins and the gas phase part of the jet reactor gas delivered by the pipeline 107, the jet is mixed, reacted and diffused by the diffusion section 106, and is further distributed and reacted in the jet reactor after being blocked by the baffle plate 101. The reaction mixture is conveyed by the action of the jet circulation pump 102 through the lower (preferably bottom) outlet of the jet kettle via the pipes 113 and 114, a part of the reaction mixture is sent to the nozzle 105 via the pipe 115 after heat exchange by the circulating liquid heat exchanger 103, the other part is sent to the reduced-pressure flash tank 108 via the pipe 116, and the tail gas of the reduced-pressure flash tank 108Is evacuated via line 118, the flash product is fed via line 117 to the aldehyde evaporator 109, the final aldehyde product obtained is recovered via line 119, and the distillation residue (catalyst-containing solution) is conveyed via line 120 to the nozzle 105 for recycling.
In one example of the present invention, the reaction system of the present invention comprises 1-2 oxo spray kettles 100, each spray kettle comprises 1-2 down spray self-priming sprayers 104, and all are provided with a gas phase circulation line 107 and liquid phase circulation lines 113, 114, 115 and 120; the nozzle 105 of the lower spraying self-suction ejector 104 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 ejection kettle into the ejection kettle, most of the raw material olefin carbonylation reaction is completed in the lower spraying self-suction ejector 104, and the rest of the raw material olefin carbonylation reaction is completed in the ejection kettle outside the lower spraying self-suction ejector. Each injection kettle is provided with an independent heat transfer or heating heat exchange device which is arranged on a circulating pipe.
In one example of the present invention, a catalyst is used that includes a group viii metal element and a phosphorus-containing ligand.
In one embodiment of the present invention, the reaction system includes 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 starting olefin is selected from the group consisting of ethylene, propylene, 1-butene, 2-butene, isobutylene, pentene, 2, 5-dihydrofuran, C6-C18At least one of olefinic compounds.
In an example of the present invention, the volume flow rate of the injection liquid is circulated per hour: the effective loading volume ratio of the spray tank is 10-90, preferably 20-80.
In an example of the present invention, a gas phase circulation is formed between the injection kettle and the lower injection self-priming injector through the pipe 107, wherein the volume flow of the self-circulation gas: the flow ratio of the volume flow of the circulating injection liquid is 0.5-4; preferably 0.7-2.
In an example of the present invention, each spraying kettle is configured with one or two lower spraying self-suction type sprayers, and is configured with 1-2 heat exchange devices for heat transfer or heating of the reaction system, and the heat exchange devices are installed on the circulation pipe, and the position is between the lower spraying self-suction type sprayer 104 and the spraying circulation pump 102.
In one embodiment of the invention, the catalyst composition selected is a rhodium acetylacetonate carbonyl compound precursor and the phosphorus ligand selected is a combination of tris (o-methylphenyl) phosphine and a bisphosphite; the selected phosphorus ligand is a composition of tri (o-methylphenyl) phosphine and monophosphite; wherein the structure of the diphosphite is as follows:
wherein the monophosphonite has the structure:
in one embodiment of the invention, the catalyst composition is a triphenylphosphine acetylacetonate rhodium carbonyl compound precursor and the phosphorus ligand is triphenylphosphine.
In one example of the present invention, the evaporator can be a tubular heat exchanger, a falling film evaporator, a wiped film evaporator, or the like to accomplish the reuse of the catalyst and the separation of the aldehyde products. When the boiling point of the aldehyde product is high, the separation of the catalyst and the aldehyde product can be realized by a decompression mode.
In one example of the present invention, when the reaction system comprises two or more oxo reactors, the reactors are connected in series.
Fig. 3 is a schematic diagram of a reaction system according to an embodiment of the present invention, wherein the injection tank 100 comprises two bottom-injection self-priming injectors arranged in parallel. As shown in FIG. 3, the reaction mixture discharged from the lower part of the spray tank is divided into 2 streams through a pipe 112, and the streams are subjected to heat exchange by circulating pumps 102A and 102B and circulating liquid heat exchangers 103A and 103B, respectively, to form circulating liquids 115A and 115B. The circulating liquid 115A, the raw material olefin 111A and the circulating catalyst 122A are mixed and then enter a nozzle of a lower-spraying self-suction type sprayer, and the synthesis gas 110 and the gas-phase component at the top of the spraying kettle are sucked while spraying; the circulating liquid 115B is mixed with the raw material olefin 111B and the circulating catalyst 122B and then enters another parallel-connected lower-spraying self-suction type sprayer for spraying, and the synthesis gas 110 and the gas-phase component at the top of the spraying kettle are sucked while spraying.
In one embodiment of the present invention, the feed olefin is in a gaseous state, and the olefin is entrained with the syngas 110 in the reaction system rather than injected from a nozzle.
Fig. 4 is a schematic diagram of an example of the present invention, wherein the injection tank 100 of the reaction system comprises two bottom-injection self-priming injectors arranged in parallel. As shown in FIG. 4, the circulating liquid from the lower part of the injection tank 100 via the pipe 112 passes through the circulating pump 102, the circulating heat exchanger 103 and the pipe 115, mixes with the raw olefin 111 and the circulating catalyst 122, and then is divided into 2 streams, which enter the nozzles 105 of two parallel lower-injection self-priming injectors 104. Each lower-spraying self-suction type ejector independently sucks raw material synthetic gas and sucks mixed gas phase at the top of the injection kettle through a gas phase circulating pipeline, and gas-liquid phases at the nozzle are fully contacted to form micro bubbles which enter a diffusion section of the lower-spraying self-suction type ejector. Most of the reaction is completed in a bottom-spray self-suction type sprayer.
Fig. 5 is a schematic view of a reaction system according to another embodiment of the present invention. As shown in FIG. 5, the reaction system comprises two spray tanks 100A, 100B arranged in series, the gas phase portions of the two spray tanks being fluidly connected via a conduit 114. When in use, a reaction mixture output from the lower part of the first spraying kettle 100A is divided into two parts through a pipeline 112A and a circulating pump 102A, one part is mixed with a raw material 111 and a circulating catalyst 122 through a circulating heat exchanger 103A and a pipeline 115A and then enters a nozzle 105A of a lower spraying self-suction type sprayer 104A of the spraying kettle 100A, and the nozzle 105A sprays the mixture to the spraying kettle 100A and sucks gas phase gas of the spraying kettle conveyed through a pipeline 107A and synthesis gas conveyed through a pipeline 110A; the other stream is recycled to the injection tank 100B. In the injection tank 100B, the reaction mixture output from the outlet at the lower part of the injection tank through the pipe 112B is divided into two flows by the circulation pump 102B. One is input into a nozzle 105B of a lower spraying self-suction type sprayer 104B through a pipeline 115B after passing through a circulating heat exchanger 103B, and the nozzle 105B sucks and sucks the gas-forming gas 110B and the gas-phase components of the spraying kettle conveyed through a pipeline 107B when spraying the gas-forming gas into the spraying kettle 100B; the other is conveyed to a reduced-pressure flash tank 108 through a pipeline 116, and enters an aldehyde evaporator 109 for separation and recovery after flash separation.
Figure 6 is a schematic of a reaction scheme of an embodiment of the present invention. As shown in FIG. 6, the reaction system for oxo reaction of the present invention comprises the oxo spraying reactor 100, the spraying reactor 100 comprises a bottom spraying self-suction type sprayer 104, the sprayer 104 is installed on the top of the spraying reactor for inputting raw material olefin and synthesis gas (CO/H) through pipelines 110 and 1112) The jet reactor gas phase circulation material circulating through the pipe 107 and the catalyst solution circulating through the pipes 122 and 115 are injected into the jet reactor and simultaneously react; a spray pot outlet installed at the lower connection pipe 112 of the spray pot for discharging a reaction mixture containing a catalyst solution; a distribution plate 101 installed inside the spray tank between the lower spray self-priming sprayer and the spray tank outlet for changing the flow of the olefins and the synthesis gas; a circulation pipe 115 for recovering the reaction mixture from the outlet of the injection tank through a pipe 112 and then supplying to the nozzle of the lower spray self-suction type injector 104 to circulate the reaction mixture. As shown in FIG. 6, the jet tank injects syngas (CO/H)2) And the gas phase circulating material of the injection kettle is combined into a whole through a Y-shaped pipe and enters the injector.
The utility model discloses use above-mentioned device and system to prepare the method of aldehyde by alkene includes following step:
providing an oxo-synthesis spray kettle, wherein a lower spray self-suction type sprayer is arranged at the top of the spray kettle, the lower spray self-suction type sprayer comprises a nozzle, a suction section, a mixing section and a diffusion section, the suction section is connected with a fluid, the suction section is communicated with a raw material gas source, and the suction section is also communicated with the part of the fluid above a liquid phase line of the spray kettle;
and (3) spraying a jet flow containing the catalyst into the spraying kettle through a nozzle of the lower spraying self-suction sprayer, entraining the gas-phase raw material from a gas source and the components of the gas-phase part of the spraying kettle in a suction section, and mixing, reacting and diffusing in a mixing section and a diffusion section to obtain an aldehyde product.
In one embodiment of the present invention, the method for preparing aldehydes from gaseous olefins comprises the steps of:
providing an oxo-synthesis spray kettle, wherein a lower spray self-suction type sprayer is arranged at the top of the spray kettle, the lower spray self-suction type sprayer comprises a nozzle, a suction section, a mixing section and a diffusion section, the suction section is connected with a fluid, the suction section is communicated with a raw material gas source, and the suction section is also communicated with the part of the fluid above a liquid phase line of the spray kettle;
and (3) spraying liquid containing the catalyst into the spraying kettle through a nozzle of the lower spraying self-suction sprayer, entraining the synthesis gas, the gaseous olefin and the components of the gas phase part of the spraying kettle from a gas source in a suction section, and mixing, reacting and diffusing in a mixing section and a diffusion section to obtain an aldehyde product.
In the process of the present invention, the conditions for the carbonyl reaction are not particularly limited, and may be reaction conditions known in the art. In one example of the present invention, the carbonyl reaction conditions described in chinese patent CN102272079A, which is incorporated herein by reference, are used.
The utility model discloses an in an example, raw materials alkene is liquid, spout down and inhale formula sprayer from being located the injection cauldron top, and circulation liquid, raw materials alkene, circulation catalyst liquid three mix the back, roll up in spouting down and inhale raw materials synthetic gas and injection cauldron top mixed gas phase from inhaling formula sprayer, vapour liquid fully contacts, spouts through the diffuser section in the reaction liquid.
The utility model discloses an in the example, raw materials alkene is the gaseous state, spout down from inhaling formula sprayer and be located the injection kettle top, and the circulation liquid, the two back that mixes of circulation catalyst liquid, roll up in spouting down from inhaling formula sprayer and inhale raw materials synthetic gas, raw materials alkene and injection kettle top mixed gas phase, vapour-liquid fully contacts, spouts through the diffuser in the reaction liquid.
The utility model discloses a spraying jet entrainment gaseous phase, spraying cauldron gas phase space and down have formed the gaseous phase circulation from inhaling between the formula sprayer, raw materials synthetic gas, spraying cauldron gas phase component, catalyst solution and olefin raw materials fully contact in spraying the reactor. It was found through experiments that the reaction rate was accelerated due to the large amount of hydrogen gas being sufficiently contacted with the reaction liquid containing the catalyst composition.
In addition, the conversion rate relative to the feeding propylene in a narrow space in the ejector can reach more than 70 percent, and unexpected experimental results are obtained, the conversion rate of olefin is further improved by the reaction of unreacted olefin in the ejector kettle, and because the reaction is strengthened, the ejector kettle with the gas phase circulation loop and the liquid phase circulation loop can realize high conversion rate of olefin, and the olefin stripping separation process of a post-system is omitted. Because the reaction efficiency is improved, the volume and the number of the injection 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 utility model can form smaller bubbles and larger vapor-liquid contact area; compare with traditional stirred tank reation kettle, have higher synthetic gas concentration in the spray tube formation liquid phase, the better mixed effect of vapour-liquid, faster reaction rate, nozzle simple structure and safe and reliable, investment cost is low, has eliminated the unstable factor that mechanical stirring brought moreover.
Examples
The present invention is further illustrated by the following examples.
Example 1
A test was conducted using 1-butene as an olefin feedstock in the reaction system shown in FIG. 2, wherein the concentration of rhodium as a catalyst was 200ppm, and the ligand was a composition of tris (o-methylphenyl) phosphorus L0 and L4, wherein the molar ratio of Rh: L0: L4 was 1:10:4, the temperature of the spray tank was maintained at 95 ℃, the reaction pressure was 1.5MPa, the effective reaction liquid volume of the spray tank 100 was 10L, the height of the spray tank was 900mm, the lower spray self-priming sprayer 104 provided at the top of the spray tank had a nozzle orifice diameter of 2.5mm, a spray angle of 30 degrees, a spray extension pipe diameter of 20mm, and a spray extension pipe length of 850 mm.
The circulating liquid is taken from the bottom of the spraying kettle through a pipeline 113, mixed with 1-butene feeding 111 and a subsequent circulating catalyst 122 after passing through a circulating pump 102 and a circulating heat exchanger 103, and then enters a lower spraying self-suction type sprayer 104, the liquid phase can also largely suck a mixed gas phase consisting of unreacted 1-butene, synthesis gas and partial products at the upper part of the spraying kettle through a gas circulating pipe 107 besides the entrainment of the synthesis gas 110, a vapor-liquid two-phase full contact is formed in the sprayer, and the liquid phase carries a large amount of micro bubbles to enter a sprayer diffusion section. Most of the reaction is completed in a bottom-spraying self-sucking sprayer.
The flow rate of the syngas 110 is 2010NL/H, with a CO: H2 molar ratio of 1: the flow rate of the 1, 1-butene feed 111 was 2.5kg/h, the volume flow rate of the circulating liquid was 300L/h, and the gas circulation amount was 350L/h. The yield of valeraldehyde was 3.76kg/h, the conversion of 1-butene to valeraldehyde was 98.0% and the conversion to butane was 1%. The valeraldehyde space-time yield STY was found to be 4.35mol/(l h) with a product positive iso ratio of 38.
Comparative example 1
A test was conducted using 1-butene as an olefin feedstock using the reaction system shown in FIG. 2, with a catalyst rhodium concentration of 200ppm, and a ligand of a composition of tris (o-methylphenyl) phosphorus L0 and L4, wherein the molar ratio of Rh: L0: L4 was 1:10:4, the temperature of the reaction vessel was maintained at 95 ℃, the reaction pressure was 1.5MPa, the effective reaction liquid volume of the injection vessel 100 was 10L, the height of the injection vessel was 900mm, in the lower spray self-priming ejector 104 provided at the top of the injection vessel, the nozzle diameter was 2.5mm, the spray angle was 30 °, the spray extension tube diameter was 20mm, and the spray tube length was 850 mm.
The circulating liquid is taken from the bottom of the spray kettle through a pipeline 113, passes through a circulating pump 102 and a circulating heat exchanger 103, is mixed with a butylene feed 111 and a subsequent circulating catalyst 122, and then enters a lower spray self-suction type sprayer 104. The gas circulation quantity of the gas phase circulating from the jet kettle is adjusted by closing a valve to be displayed at 0L/h, so that the liquid phase only sucks the synthesis gas 110, the gas phase and the liquid phase are fully contacted in a vapor-liquid phase in the ejector, and the liquid phase carries a large amount of micro bubbles to enter a diffusion section of the ejector. Most of the reaction is accomplished in the bottom spray self-priming eductor 104.
The flow rate of the syngas 110 is 2010NL/H, with a CO: H2 molar ratio of 1: the flow rate of the 1, 1-butene feed 111 was 2.5kg/h and the volume flow rate of the circulating liquid was 300L/h. The yield of valeraldehyde was 2.88kg/h, the conversion of 1-butene to valeraldehyde was 75.0% and the conversion to butane was 2%. The valeraldehyde space-time yield STY was found to be 3.35mol/(l h) with a product positive iso ratio of 30.
Example 2
A test was conducted using 2-butene as an olefin feedstock in the reaction system shown in FIG. 2, with a catalyst rhodium concentration of 200ppm and a ligand of a composition of tris (o-methylphenyl) phosphorus L0 and L5, wherein the molar ratio of Rh: L0: L5 was 1:10:4, the temperature of the spray tank was maintained at 95 ℃, the reaction pressure was 1.5MPa, the effective reaction liquid volume of the spray tank 100 was 10L, the height of the spray tank was 900mm, the top of the spray tank was provided with a lower spray self-priming sprayer 104 having a nozzle orifice diameter of 2.5mm, a spray angle of 30 °, a spray expansion pipe diameter of 20mm, and a spray pipe length of 700 mm.
The circulating liquid is taken from the bottom of the spraying kettle through a pipeline 113, passes through a circulating pump 102 and a circulating heat exchanger 103, is mixed with 2-butene feeding 111 and a subsequent circulating catalyst 122, and then enters a lower spraying self-suction type sprayer 104, the liquid phase sucks the synthesis gas 110, and also sucks a large amount of mixed gas phase consisting of unreacted 2-butene in the gas phase part of the spraying kettle, the synthesis gas and part of products through a gas circulating pipe 107, so that gas-liquid two-phase full contact is formed in the sprayer, and the liquid phase carries a large amount of micro bubbles to enter a diffusion section of the lower spraying self-suction type sprayer. Most of the reaction is completed in a bottom-spraying self-sucking sprayer.
The syngas 110 in this example was 1610NL/H, with a CO: H2 molar ratio of 1: the 1, 2-butene feed 111 was 2.0kg/h, the circulating liquid volume flow was 300L/h, and the gas circulation was 350L/h. The yield of valeraldehyde is 2.92kg/h, the conversion rate of 2-butene converted into valeraldehyde is 95.0 percent, and the conversion rate of 2-butene converted into butane is 1.2 percent. The valeraldehyde space-time yield STY was found to be 3.39mol/(l h) with a product positive iso ratio of 28.
Example 3
A test is carried out by using isobutene as an olefin raw material by using a reaction system shown in FIG. 2, the concentration of rhodium in the catalyst is 200ppm, a ligand is a composition of tris (o-methylphenyl) phosphorus L0 and L7, wherein the molar ratio of Rh to L0 to L7 is 1:10:10, the temperature of a spray kettle is maintained at 100 ℃, the reaction pressure is 1.5MPa, the volume of an effective reaction liquid of the spray kettle 100 is 10L, the height of the spray kettle is 900mm, the top of the spray kettle is provided with a lower spray self-suction type sprayer 104, the nozzle orifice diameter is 2.5mm, the spray angle is 30 degrees, the spray expansion pipe diameter is 20mm, and the spray pipe length is 850 mm.
The circulating liquid is taken from the bottom of the spraying kettle through a pipeline 113, passes through a circulating pump 102 and a circulating heat exchanger 103, is mixed with an isobutene feed 111 and a subsequent circulating catalyst 122, and then enters a lower spraying self-suction type sprayer 104, the liquid phase sucks the synthesis gas 110, and also sucks a large amount of mixed gas phase consisting of unreacted isobutene, synthesis gas and partial products in the gas phase part of the spraying kettle through a gas circulating pipe 107, so that gas-liquid two-phase full contact is formed in the sprayer, and the liquid phase carries a large amount of micro bubbles to enter a diffusion section of the lower spraying self-suction type sprayer. Most of the reaction is completed in a bottom-spraying self-sucking sprayer.
The syngas 110 was 1770NL/H with a CO: H2 molar ratio of 1:1, the isobutene feed 111 was 2.2kg/h, the circulating liquid volume flow was 300L/h and the gas circulation was 350L/h. The yield of the isovaleraldehyde is 3.28kg/h, the conversion rate of converting isobutene into isovaleraldehyde is 97.0 percent, and the conversion rate of converting isobutene into isobutane is 1.2 percent. The isovaleraldehyde space-time yield, STY, was found to be 3.81mol/(l h).
Example 4
Using the reaction system shown in FIG. 2, a test was conducted using 2, 5-dihydrofuran as the olefin feed, with a catalyst rhodium concentration of 200ppm and a ligand of triphenylphosphine composition, wherein Rh: the mol ratio of TPP is 1:20, the temperature of the injection kettle is maintained at 90 ℃, the reaction pressure is 2.0MPa, the effective reaction liquid volume of the injection kettle 100 is 10L, the height of the injection kettle is 900mm, the top of the injection kettle is provided with a lower injection self-suction type injector 104, the diameter of a nozzle orifice of the injector is 2.5mm, the injection angle is 30 degrees, the diameter of an injection expanding pipe is 20mm, and the length of the injection pipe is 850 mm.
The circulating liquid is taken from the bottom of the spraying kettle through a pipeline 113, mixed with 2, 5-dihydrofuran feeding 111 and a subsequent circulating catalyst 120 after passing through a circulating pump 102 and a circulating heat exchanger 103, and then enters a lower spraying self-suction type sprayer 104, the liquid phase can also suck a large amount of unreacted synthesis gas in the gas phase part of the spraying kettle and mixed gas phase consisting of partial products through a gas circulating pipe 107 besides the entrainment of the synthesis gas 110, so that the gas phase and the liquid phase are fully contacted with each other, and the liquid phase carries a large amount of micro bubbles to enter a diffusion section of the lower spraying self-suction type sprayer. Most of the reaction is completed in a bottom-spraying self-sucking sprayer.
The syngas 110 flow rate is 1460NL/H, with a CO: H2 molar ratio of 1: the feed 111 flow rate of the 1, 2, 5-dihydrofuran is 2.2kg/h, the volume flow rate of the circulating liquid is 300L/h, and the gas circulation amount is 350L/h. The yield of 3-formaldehyde tetrahydrofuran and 2-formaldehyde tetrahydrofuran is 3.10kg/h, the conversion rate of 2, 5-dihydrofuran converted into aldehyde is 98%, and the conversion rate of 2, 5-dihydrofuran into tetrahydrofuran is lower than 0.2%. The observed aldehyde space-time yield STY was 3.10 mol/(l × h), the product 3-formaldehyde tetrahydrofuran: the molar ratio of 2-formaldehyde to tetrahydrofuran was 25.
Example 5
A test was conducted using 1-pentene as an olefin raw material using the reaction system shown in FIG. 2, and the catalyst rhodium concentration was 200ppm, and the ligand was a composition of tris (o-methylphenyl) phosphorus L0 and L5, wherein the molar ratio of Rh: L0: L5 was 1:10:4, the temperature of the spray tank was maintained at 100 ℃, the reaction pressure was 1.5MPa, the effective reaction liquid volume of the spray tank 100 was 10L, the height of the spray tank was 900mm, the top of the spray tank was provided with a lower spray self-priming sprayer 104 having a nozzle orifice diameter of 2.5mm, a spray angle of 30 °, a spray expansion pipe diameter of 20mm, and a spray pipe length of 850 mm.
The circulating liquid is taken from the bottom of the spraying kettle through a pipeline 113, mixed with 1-pentene feeding 111 and a subsequent circulating catalyst 122 after passing through a circulating pump 102 and a circulating heat exchanger 103, and then enters a lower spraying self-suction type sprayer 104, the liquid phase can also suck a large amount of mixed gas phase consisting of unreacted 1-pentene, synthesis gas and part of products in the gas phase part of the spraying kettle through a gas circulating pipe 107 besides the entrainment of the synthesis gas 110, a gas-liquid two-phase full contact is formed in the sprayer, and the liquid phase carries a large amount of micro bubbles to enter a diffusion section of the lower spraying self-suction type sprayer. Most of the reaction is completed in a bottom-spraying self-sucking sprayer.
The syngas 110 in this example was 1420NL/H with a CO: H2 molar ratio of 1: the 1, 1-pentene feed 111 was 2.2kg/h, the circulating liquid volume flow was 300L/h, and the gas circulation amount was 350L/h. The yield of pentanal is 3.02kg/h, the conversion rate of 1-pentene into hexanal is 98.0 percent, and the conversion rate into pentane is 1.1 percent. The valeraldehyde space-time yield STY was found to be 3.08mol/(l h) with a product positive iso ratio of 28.
Example 6
A test was conducted using 1-heptene as an olefin feedstock using the reaction system shown in FIG. 2, with a catalyst rhodium concentration of 200ppm and a ligand of a composition of tris (o-methylphenyl) phosphorus L0 and L8, wherein the molar ratio of Rh: L0: L8 was 1:10:10, the temperature of the spray tank was maintained at 105 ℃, the reaction pressure was 1.5MPa, the effective reaction liquid volume of the spray tank 100 was 10L, the height of the spray tank was 900mm, the top of the spray tank was provided with a lower spray self-priming sprayer 104 having a nozzle orifice diameter of 2.5mm, a spray angle of 30 °, a spray expansion pipe diameter of 20mm, and a spray pipe length of 850 mm.
The circulating liquid is taken from the bottom of the spraying kettle through a pipeline 113, mixed with 1-heptene feeding 111 and a subsequent circulating catalyst 122 after passing through a circulating pump 102 and a circulating heat exchanger 103, and then enters a lower spraying self-suction type sprayer 104, the liquid phase can also suck a large amount of mixed gas phase consisting of unreacted 1-pentene, synthesis gas and part of products in the gas phase part of the spraying kettle through a gas circulating pipe 107 besides the synthesis gas 110, a gas-liquid two-phase full contact is formed in the sprayer, and the liquid phase carries a large amount of micro bubbles to enter a diffusion section of the lower spraying self-suction type sprayer. Most of the reaction is completed in a bottom-spraying self-sucking sprayer.
The syngas 110 was 1840NL/H with a molar ratio of CO: H2 of 1: the 1, 1-heptene feed 111 was 4.0kg/h, the circulating liquid volume flow was 300L/h, and the gas circulation amount was shown at (350L/h). The yield of octanal is 5.12kg/h, the conversion of 1-heptene to octanal is 98.0%, and the conversion to heptane is 1.2%. The octanal space-time yield STY was found to be 4.0mol/(l × h) with a product positive iso ratio of 1.
Example 7
A test was conducted using 1-heptene as an olefin feedstock using the reaction system shown in FIG. 2, with a catalyst rhodium concentration of 200ppm and a ligand of a composition of tris (o-methylphenyl) phosphorus L0 and L5, wherein the molar ratio of Rh: L0: L5 was 1:10:4, the temperature of the spray tank was maintained at 105 ℃, the reaction pressure was 1.5MPa, the effective reaction liquid volume of the spray tank 100 was 10L, the height of the spray tank was 900mm, the top of the spray tank was provided with a lower spray self-priming sprayer 104 having a nozzle orifice diameter of 2.5mm, a spray angle of 30 °, a spray expansion pipe diameter of 20mm, and a spray pipe length of 850 mm.
The circulating liquid is taken from the bottom of the spraying kettle through a pipeline 113, mixed with 1-heptene feeding 111 and a subsequent circulating catalyst 122 after passing through a circulating pump 102 and a circulating heat exchanger 103, and then enters a lower spraying self-suction type sprayer 104, the liquid phase can also suck a large amount of mixed gas phase consisting of unreacted 1-heptene, synthesis gas and part of products in the gas phase part of the spraying kettle through a gas circulating pipe 107 besides sucking the synthesis gas 110, a gas-liquid two-phase full contact is formed in the sprayer, and the liquid phase carries a large amount of micro bubbles to enter a diffusion section of the lower spraying self-suction type sprayer. Most of the reaction is completed in a bottom-spraying self-sucking sprayer.
The syngas 110 was 1610NL/H with a molar ratio of CO: H2 of 1: the 1, 1-heptene feed 111 was 3.5kg/h, the circulating liquid volume flow was 300L/h, and the gas circulation amount was 350L/h. The yield of octanal was 4.43kg/h, the conversion of 1-heptene to octanal was 97.0% and to heptane was 1.1%. The octanal space-time yield STY was found to be 3.46mol/(l × h) and the product positive iso ratio was 20.
Example 8
A test is carried out by using the reaction system shown in FIG. 2 and taking 1-decene as an olefin raw material, the concentration of rhodium as a catalyst is 200ppm, a ligand is triphenylphosphine, the molar ratio of Rh to TPP is 1:100, the temperature of a spray kettle is maintained at 105 ℃, the reaction pressure is 1.5MPa, the effective reaction liquid volume of the spray kettle 100 is 10L, the height of the spray kettle is 900mm, the top of the spray kettle is provided with a lower spray self-suction type sprayer 104, the diameter of a nozzle orifice of the sprayer is 2.5mm, the spray angle is 30 degrees, the diameter of a spray expanding pipe is 20mm, and the length of the spray pipe is 850 mm.
The circulating liquid is taken from the bottom of the spraying kettle through a pipeline 113, mixed with 1-decene feeding 111 and a subsequent circulating catalyst 122 after passing through a circulating pump 102 and a circulating heat exchanger 103, and then enters a lower spraying self-suction type sprayer 104, the liquid phase can also suck a large amount of mixed gas phase consisting of unreacted 1-decene, synthesis gas and part of products in the gas phase of the spraying kettle through a gas circulating pipe 107 besides sucking the synthesis gas 110, the gas phase and the liquid phase are fully contacted with each other in a gas-liquid two-phase manner in the sprayer, and the liquid phase carries a large amount of micro bubbles to enter a diffusion section of the lower spraying self-suction type. Most of the reaction is completed in a bottom-spraying self-sucking sprayer.
The syngas 110 was 1290NL/H with a molar ratio of CO: H2 of 1: the 1, 1-decene feed 111 was 4.0kg/h, the circulating liquid volume flow was 300L/h, and the gas circulation amount was shown at (350L/h). The yield of the undecyl aldehyde was 4.65kg/h, the conversion rate of 1-decene into undecyl aldehyde was 96.0% and the conversion rate into decane was 1.0%. The undecanal space-time yield STY was found to be 2.75mol/(l × h) with a product positive iso ratio of 24.
Example 9
A reaction system shown in FIG. 3 is used for carrying out a test on an n-butene raw material with a 1:2 mol ratio of 1-butene to 2-butene, the concentration of rhodium in a catalyst is 200ppm, a ligand is a composition of tris (o-methylphenyl) phosphorus L0 and L5, the mol ratio of Rh to L0 to L5 is 1:10:4, the temperature of a jet kettle is maintained at 95 ℃, the reaction pressure is 1.5MPa, the effective reaction liquid volume of the jet kettle 100 is 10L, the height of the jet kettle is 900mm, two lower jet self- suction type ejectors 104A and 104B are arranged at the top of the jet kettle, the nozzle diameters of the lower jet self-suction type ejectors are both 2.5mm, the jet angle is 30 degrees, the jet expansion pipe diameter is 20mm, and the jet pipe length is 850 mm.
The circulating liquid 113 is divided into two parts after being taken from the bottom of the spraying kettle, and is respectively mixed with n- butene feeding materials 111A and 111B and subsequent circulating catalysts 120A and 120B after passing through circulating pumps 102A and 102B and circulating heat exchangers 103A and 103B, and then respectively enters lower spraying self-priming ejectors 104A and 104B, the liquid phase sucks synthesis gas 111A and 111B, and also sucks a large amount of mixed gas phase consisting of unreacted n-butene, synthesis gas and partial products in the gas phase part of the spraying kettle through a gas circulating pipe 107, so that a gas-liquid two-phase full contact is formed in the ejectors, and the liquid phase carries a large amount of micro bubbles to enter a diffusion section of the lower spraying self-priming ejectors. Most of the reaction is completed in a bottom-spraying self-sucking sprayer.
The syngas 110 was 1770NL/H with a CO: H2 molar ratio of 1:1, the n-butene feed 111 was 2.2kg/h, the circulating liquid flow rates were 280L/h, and the gas circulation rates were 320L/h, respectively. The yield of valeraldehyde was 3.31kg/h, the conversion of n-butene to valeraldehyde was 98.0% and the conversion to butane was 1.3%. The valeraldehyde space-time yield STY was found to be 3.85mol/(l h) with a product positive iso ratio of 29.
Example 10
A reaction system shown in FIG. 4 is used for carrying out a test on an n-butene raw material with a 1:2 mol ratio of 1-butene to 2-butene, the concentration of rhodium in a catalyst is 200ppm, a ligand is a composition of tris (o-methylphenyl) phosphorus L0 and L5, the mol ratio of Rh to L0 to L5 is 1:10:4, the temperature of a jet kettle is maintained at 95 ℃, the reaction pressure is 1.5MPa, the effective reaction liquid volume of the jet kettle 100 is 10L, the height of the jet kettle is 900mm, two lower jet self- suction type ejectors 104A and 104B are arranged at the top of the jet kettle, the nozzle diameters of the lower jet self-suction type ejectors are both 2.5mm, the jet angle is 30 degrees, the jet expansion pipe diameter is 20mm, and the jet pipe length is 850 mm.
The circulating liquid 113 is taken from the bottom of the spraying kettle, passes through a circulating pump 103, is mixed with n-butene feeding 111 and a subsequent circulating catalyst 120, and then enters a lower spraying self- suction type sprayer 104A and 104B respectively in two paths, the liquid phase sucks the synthesis gas 110, and also sucks a large amount of mixed gas phase consisting of unreacted n-butene, synthesis gas and partial products in the gas phase of the spraying kettle through a gas circulating pipe 107, so that the gas phase and the liquid phase are fully contacted with each other in the sprayer, and the liquid phase carries a large amount of micro bubbles to enter a diffusion section of the lower spraying self-suction type sprayer. Most of the reaction is completed in a bottom-spraying self-sucking sprayer.
The syngas 110 was 1770NL/H with a CO: H2 molar ratio of 1:1, the n-butene feed 111 was 2.2kg/h, the total volumetric flow rate of the circulating liquid was 400L/h, and the total gas circulation was shown to be 450L/h. The yield of valeraldehyde was 3.28kg/h, the conversion of n-butene to valeraldehyde was 97.0% and the conversion to butane was 1.3%. The valeraldehyde space-time yield STY was found to be 3.81mol/(l h) with a product positive iso ratio of 28.
Example 11
A reaction system shown in FIG. 5 is used for carrying out a test on an n-butene raw material with a 1:2 mol ratio of 1-butene to 2-butene, the concentration of rhodium in a catalyst is 200ppm, a ligand is a composition of tris (o-methylphenyl) phosphorus L0 and L5, the mol ratio of Rh to L0 to L5 is 1:10:4, the temperature of each injection kettle is maintained at 95 ℃, the reaction pressure is 1.5MPa, two injection kettles 100A/100B are connected through a pipeline 114, the effective reaction liquid volume of each injection kettle is 10L, the height of each injection kettle is 900mm, the top of each injection kettle is provided with a downward injection self-suction injector 104A/104B, the nozzle orifice diameter is 2.5mm, the injection angle is 30 degrees, the injection expansion pipe diameter is 20mm, and the injection pipe length is 850 mm.
The circulating liquid 112A is taken from the bottom of the injection kettle 100A, and is divided into two parts after passing through a circulating pump 102A, one part of the circulating liquid passes through a circulating heat exchanger 103A, and is mixed with n-butene feeding 111 and a subsequent circulating catalyst 122, and then enters a lower-injection self-suction type injector 104A of the injection kettle 100A, the liquid phase sucks the synthesis gas 110, and also sucks a large amount of mixed gas phase consisting of unreacted n-butene, synthesis gas and part of products through a gas circulating pipe 107, so that the vapor-liquid two phases are fully contacted in the injector, and the liquid phase carries a large amount of micro bubbles to enter an expansion section of the injector. Most of the reaction is completed in the injection tube.
In the embodiment, the synthesis gas 110 is divided into two paths of inlet gas, the total amount is 2010NL/H, and the molar ratio of CO to H2 is 1:1, the gas inlet ratio of the first reaction kettle to the second reaction kettle is 4:1, the n-butene feeding 111 is 2.5kg/h, the total volume flow rate of the circulating liquid is 300L/h, and the total gas circulation is shown at 350L/h. The yield of valeraldehyde was 3.80kg/h, the conversion of n-butene to valeraldehyde was 99.0% and butane was 0.8%, the time-space yield STY of valeraldehyde was found to be 4.41mol/(l x h) and the product positive iso-ratio was 29. The long-period stable operation is carried out for 3000h, and the addition amount of the ligand is about 4.0g of L5 added per 100kg of aldehyde.
Comparative example 2
A traditional kettle type stirring reaction kettle is selected, a three-kettle series process is selected, the effective reaction liquid volume of each kettle is 10L, n-butene raw material with the molar ratio of 1-butene to 2-butene being 1:2 is selected for testing, the concentration of rhodium in the catalyst is 200ppm, the ligand is a composition of tri (o-methylphenyl) phosphorus L0 and L5, the molar ratio of Rh to L0 to L5 is 1:10:4, the temperature of the reaction kettle is maintained at 95 ℃, and the reaction pressure is 1.5 MPa.
In the embodiment, the synthesis gas 110 is divided into three paths of inlet gas, the total amount is 2010NL/H, and the molar ratio of CO to H2 is 1:1, the air inlet ratio of the first reaction kettle, the second reaction kettle and the third reaction kettle is 7:2:1, and the n-butene feeding amount 111 is 2.5 kg/h. The valeraldehyde yield was 3.53kg/h, the conversion of n-butenes to valeraldehyde was 92.0% and to butane was 2.5%, and the valeraldehyde space-time yield, STY, was found to be 4.1mol/(l x h) with a product normal to iso ratio of 25. The long-period stable operation is carried out for 3000h, and the addition amount of the ligand is about 6.0g of L5 added per 100kg of aldehyde.
Example 12
A test was conducted using 1-butene as an olefin feedstock using the reaction system shown in FIG. 6, with a catalyst rhodium concentration of 200ppm, and a ligand of a composition of tris (o-methylphenyl) phosphorus L0 and L4, wherein the molar ratio of Rh: L0: L4 was 1:10:4, the temperature of the spray tank was maintained at 95 ℃, the reaction pressure was 1.5MPa, the effective reaction liquid volume of the spray tank 100 was 10L, the height of the spray tank was 900mm, the lower spray self-priming ejector 104 provided at the top of the spray tank had a nozzle orifice diameter of 2.5mm, a spray angle of 30 degrees, a spray expansion pipe diameter of 20mm, and a spray expansion pipe length of 850 mm.
The circulating liquid is taken from the bottom of the spraying kettle through a pipeline 113, passes through a circulating pump 102 and a circulating heat exchanger 103, is mixed with 1-butene feeding 111 and a subsequent circulating catalyst 122, and then enters a nozzle 105 of a lower spraying self-suction type sprayer 104, a suction chamber of the lower spraying self-suction type sprayer 104 is only provided with one gas inlet, and the gas inlet is respectively connected with a gas phase part of the spraying kettle and a gas source through a Y-shaped pipe. The jet flow formed by the nozzle 105 sucks the synthesis gas 110 and the mixed gas phase consisting of unreacted 1-butene, synthesis gas and partial products at the upper part of the jet kettle through a Y-shaped pipe simultaneously, the gas phase and the liquid phase are fully contacted, and the liquid phase carries a large amount of micro bubbles to enter a diffusion section of the jet kettle. Most of the reaction is completed in a bottom-spraying self-sucking sprayer.
The flow rate of the syngas 110 is 2010NL/H, with a CO: H2 molar ratio of 1: the flow rate of the 1, 1-butene feed 111 was 2.5kg/h, the volume flow rate of the circulating liquid was 300L/h, and the gas circulation amount was 350L/h. The yield of valeraldehyde was 3.66kg/h, the conversion of 1-butene to valeraldehyde was 96.0% and the conversion to butane was 1.8%. The valeraldehyde space-time yield STY was found to be 4.30mol/(l h) with a product positive iso ratio of 38.
Example 13：
A test was conducted using propylene as an olefin raw material in the reaction system shown in FIG. 2, and the catalyst rhodium concentration was 80ppm, and the ligand was a composition of tris (o-methylphenyl) phosphorus L0 and L4, wherein the molar ratio of Rh: L0: L4 was 1:10:4, the temperature of the spray tank was maintained at 90 ℃, the reaction pressure was 1.6MPa, the effective reaction liquid volume of the spray tank 100 was 10L, the height of the spray tank was 900mm, the lower spray self-priming ejector 104 provided at the top of the spray tank had a nozzle orifice diameter of 2.5mm, an ejection angle of 30 degrees, an ejection extension tube diameter of 20mm, and an ejection tube extension length of 850 mm.
The circulating liquid is taken from the bottom of the spraying kettle through a pipeline 113, mixed with propylene feeding 111 and a subsequent circulating catalyst 122 after passing through a circulating pump 102 and a circulating heat exchanger 103, and then enters a lower spraying self-suction type sprayer 104, the liquid phase can also greatly suck a mixed gas phase consisting of unreacted propylene, synthesis gas and partial products at the upper part of the spraying kettle through a gas circulating pipe 107 besides sucking the synthesis gas 110, a vapor-liquid two-phase full contact is formed in the sprayer, and the liquid phase carries a large amount of micro bubbles to enter a sprayer diffusion section. Most of the reaction is completed in a bottom-spraying self-sucking sprayer.
Example 14
A test was conducted using propylene as an olefin raw material in the reaction system shown in FIG. 2, and the catalyst rhodium concentration was 80ppm, and the ligand was a composition of tris (o-methylphenyl) phosphorus L0 and L5, wherein the molar ratio of Rh: L0: L5 was 1:10:4, the temperature of the spray tank was maintained at 90 ℃, the reaction pressure was 1.6MPa, the effective reaction liquid volume of the spray tank 100 was 10L, the height of the spray tank was 900mm, the lower spray self-priming ejector 104 provided at the top of the spray tank had a nozzle orifice diameter of 2.5mm, an ejection angle of 30 degrees, an ejection extension tube diameter of 20mm, and an ejection tube extension length of 850 mm.
The circulating liquid is taken from the bottom of the spraying kettle through a pipeline 113, mixed with propylene feeding 111 and a subsequent circulating catalyst 122 after passing through a circulating pump 102 and a circulating heat exchanger 103, and then enters a lower spraying self-suction type sprayer 104, the liquid phase can also greatly suck a mixed gas phase consisting of unreacted propylene, synthesis gas and partial products at the upper part of the spraying kettle through a gas circulating pipe 107 besides sucking the synthesis gas 110, a vapor-liquid two-phase full contact is formed in the sprayer, and the liquid phase carries a large amount of micro bubbles to enter a sprayer diffusion section. Most of the reaction is completed in a bottom-spraying self-sucking sprayer.
Example 15
A test was conducted using propylene as an olefin raw material in the reaction system shown in FIG. 2, and the catalyst rhodium concentration was 80ppm, and the ligand was a composition of tris (o-methylphenyl) phosphorus L0 and L5, wherein the molar ratio of Rh: L0: L5 was 1:10:4, the temperature of the spray tank was maintained at 90 ℃, the reaction pressure was 1.6MPa, the effective reaction liquid volume of the spray tank 100 was 10L, the height of the spray tank was 900mm, the lower spray self-priming ejector 104 provided at the top of the spray tank had a nozzle orifice diameter of 2.5mm, an ejection angle of 30 degrees, an ejection extension tube diameter of 20mm, and an ejection tube extension length of 850 mm.
The circulating liquid is taken from the bottom of the spraying kettle through a pipeline 113, mixed with propylene feeding 111 and a subsequent circulating catalyst 122 after passing through a circulating pump 102 and a circulating heat exchanger 103, and then enters a lower spraying self-suction type sprayer 104, the liquid phase can also greatly suck a mixed gas phase consisting of unreacted propylene, synthesis gas and partial products at the upper part of the spraying kettle through a gas circulating pipe 107 besides sucking the synthesis gas 110, a vapor-liquid two-phase full contact is formed in the sprayer, and the liquid phase carries a large amount of micro bubbles to enter a sprayer diffusion section. Most of the reaction is completed in a bottom-spraying self-sucking sprayer.
Example 16
A test was conducted using propylene as an olefin raw material using the reaction system shown in FIG. 2, and the catalyst rhodium concentration was 60ppm, the ligand was a composition of tris (o-methylphenyl) phosphorus L0 and monophosphite L7, wherein Rh: L0: L7 was in a molar ratio of 1:10:4, the temperature of the spray tank was maintained at 90 ℃, the reaction pressure was 1.6MPa, the effective reaction liquid volume of the spray tank 100 was 10L, the height of the spray tank was 900mm, the lower spray self-priming sprayer 104 provided at the top of the spray tank had a nozzle orifice diameter of 2.5mm, a spray angle of 30 °, a spray extension pipe diameter of 20mm, and a spray extension pipe length of 850 mm.
The circulating liquid is taken from the bottom of the spraying kettle through a pipeline 113, mixed with propylene feeding 111 and a subsequent circulating catalyst 122 after passing through a circulating pump 102 and a circulating heat exchanger 103, and then enters a lower spraying self-suction type sprayer 104, the liquid phase can also greatly suck a mixed gas phase consisting of unreacted propylene, synthesis gas and partial products at the upper part of the spraying kettle through a gas circulating pipe 107 besides sucking the synthesis gas 110, a vapor-liquid two-phase full contact is formed in the sprayer, and the liquid phase carries a large amount of micro bubbles to enter a sprayer diffusion section. Most of the reaction is completed in a bottom-spraying self-sucking sprayer.
Comparative example 3
A test was conducted using propylene as an olefin raw material in the reaction system shown in FIG. 2, and the catalyst rhodium concentration was 80ppm, and the ligand was a composition of tris (o-methylphenyl) phosphorus L0 and L5, wherein the molar ratio of Rh: L0: L5 was 1:10:4, the temperature of the spray tank was maintained at 90 ℃, the reaction pressure was 1.6MPa, the effective reaction liquid volume of the spray tank 100 was 10L, the height of the spray tank was 900mm, the lower spray self-priming ejector 104 provided at the top of the spray tank had a nozzle orifice diameter of 2.5mm, an ejection angle of 30 degrees, an ejection extension tube diameter of 20mm, and an ejection tube extension length of 850 mm.
The circulating liquid is taken from the bottom of the spraying kettle through a pipeline 113, mixed with propylene feeding 111 and a subsequent circulating catalyst 122 after passing through a circulating pump 102 and a circulating heat exchanger 103, and then enters a lower spraying self-suction type sprayer 104, the liquid phase can also greatly suck a mixed gas phase consisting of unreacted propylene, synthesis gas and partial products at the upper part of the spraying kettle through a gas circulating pipe 107 besides sucking the synthesis gas 110, a vapor-liquid two-phase full contact is formed in the sprayer, and the liquid phase carries a large amount of micro bubbles to enter a sprayer diffusion section. Most of the reaction is completed in a bottom-spraying self-sucking sprayer.
Comparative example 4
A traditional kettle type stirring reaction kettle is selected, a double-kettle series process is selected, the effective reaction liquid volume of each kettle is 10L, propylene is selected as an olefin raw material for testing, the concentration of rhodium in a catalyst is 80ppm, a ligand is a composition of tri (o-methylphenyl) phosphorus L0 and L5, the molar ratio of Rh to L0 to L5 is 1:10:4, the feeding amount of synthesis gas is 2140NL/H, the molar ratio of CO to H2 is 1:1, the distribution molar ratio of the synthesis gas fed into the first stirring reaction kettle to the synthesis gas fed into the second stirring reaction kettle is 3:1, and the feeding amount of propylene is 2.0 kg/h. The butyraldehyde yield is 3.15kg/h, and the conversion rate of converting propylene into butyraldehyde is 92.0 percent. The butyraldehyde space-time yield STY was found to be 2.19mol/(l h) with a product positive-to-iso ratio of 20.
From the above examples and comparative examples, it can be seen that the efficiency of the reaction is unexpectedly and greatly improved when the injection reactor provided with the vapor-phase circulation circuit and the liquid-phase circulation circuit is compared with the injection reactor provided with only the liquid-phase circulation circuit in the rhodium-catalyzed hydroformylation of propylene. Compared with a stirring kettle, the efficiency of only 1 jet reaction kettle can be realized and exceeds that of two stirring reaction kettles. Because the reaction strength is enhanced, the volume of the reaction kettle is reduced, the one-time investment cost of the catalyst is reduced by at least half, and the ligand consumption is lower.
Example 17：
A reaction system shown in FIG. 2 is used for a test with ethylene as an olefin raw material, the concentration of rhodium as a catalyst is 150ppm, a ligand is triphenylphosphine, the molar ratio of Rh to TPP is 1:200, the temperature of a spray kettle is maintained at 90 ℃, the reaction pressure is 1.6MPa, the effective reaction liquid volume of the spray kettle 100 is 10L, the height of the spray kettle is 900mm, a lower spray self-suction type sprayer 104 is arranged at the top of the spray kettle, the diameter of a nozzle spray opening of the sprayer is 2.5mm, the spray angle is 30 degrees, the diameter of a spray expanding pipe is 20mm, and the length of the spray expanding pipe is 850 mm.
The circulating liquid is taken from the bottom of the spraying kettle through a pipeline 113, mixed with a subsequent circulating catalyst 122 after passing through a circulating pump 102 and a circulating heat exchanger 103, and then enters a lower spraying self-suction type sprayer 104, the liquid phase can also greatly suck a mixed gas phase consisting of unreacted ethylene, synthesis gas and partial products at the upper part of the spraying kettle through a gas circulating pipe 107 besides sucking the synthesis gas 110 and the ethylene feeding material 111, a vapor-liquid two-phase full contact is formed in the sprayer, and the liquid phase carries a large amount of micro bubbles to enter a diffusion section of the sprayer. Most of the reaction is completed in a bottom-spraying self-sucking sprayer.
The syngas 110 was 2100NL/H with a CO: H2 molar ratio of 1:1, 1.3kg/h of alkene feed 111, a circulating liquid volume flow of 300L/h and a gas circulation volume indicated at (350L/h). The yield of propionaldehyde is 2.67kg/h, and the conversion rate of conversion of ethylene into propionaldehyde is 99.2 percent. The propanal space time yield STY was found to be 4.60mol/(l × h).
Example 18:
a test is carried out by using a reaction system shown in FIG. 2 and taking vinyl as an olefin raw material, wherein the concentration of rhodium in the catalyst is 60ppm, a ligand is a composition of tris (o-methylphenyl) phosphorus L0 and L8, the molar ratio of Rh to L0 to L8 is 1:10:10, the temperature of a spray kettle is maintained at 90 ℃, the reaction pressure is 1.6MPa, the volume of an effective reaction liquid of the spray kettle 100 is 10L, the height of the spray kettle is 900mm, a lower spray self-suction type sprayer 104 is arranged at the top of the spray kettle, the nozzle orifice diameter is 2.5mm, the spray angle is 30 degrees, the spray expansion pipe diameter is 20mm, and the spray expansion pipe length is 850 mm.
The circulating liquid is taken from the bottom of the spraying kettle through a pipeline 113, mixed with a subsequent circulating catalyst 122 after passing through a circulating pump 102 and a circulating heat exchanger 103, and then enters a lower spraying self-suction type sprayer 104, the liquid phase can also greatly suck a mixed gas phase consisting of unreacted ethylene, synthesis gas and partial products at the upper part of the spraying kettle through a gas circulating pipe 107 besides sucking the synthesis gas 110 and the ethylene feeding material 111, a vapor-liquid two-phase full contact is formed in the sprayer, and the liquid phase carries a large amount of micro bubbles to enter a diffusion section of the sprayer. Most of the reaction is completed in a bottom-spraying self-sucking sprayer.
The syngas 110 was 2570NL/H with a molar ratio of CO: H2 of 1:1, ethylene feed 111 was 1.6kg/h, the circulating liquid volume flow was 300L/h, and the gas circulation amount was shown at (350L/h). The yield of propionaldehyde is 3.28kg/h, and the conversion rate of conversion of ethylene into propionaldehyde is 99.56%. The propanal space time yield STY was found to be 5.66mol/(l × h).
Example 19：
The reaction system shown in FIG. 4 is used for an experiment with ethylene as an olefin raw material, the concentration of rhodium as a catalyst is 150ppm, the ligand is triphenylphosphine, the molar ratio of Rh to TPP is 1:200, the temperature of a spray kettle is maintained at 90 ℃, the reaction pressure is 1.6MPa, the effective reaction liquid volume of a new spray kettle 100 is 10L, the height of the spray kettle is 900mm, two downward-spraying self- suction type sprayers 104A and 104B are arranged at the top of the spray kettle, the nozzle diameters of the sprayers are both 2.5mm, the spraying angle is 30 degrees, the diameter of a spraying expanding pipe is 20mm, and the length of the spraying pipe is 850 mm.
The circulating liquid 113 is taken from the bottom of the spraying kettle, mixed with the subsequent circulating catalyst 120 after passing through the circulating pump 103, and then respectively enters the lower spraying self- suction type sprayers 104A and 104B in two paths, the liquid phase can also greatly suck the mixed gas phase consisting of unreacted ethylene, synthesis gas and part of products in the gas phase of the spraying kettle through the gas circulating pipe 107 besides the entrainment of the synthesis gas 110 and the ethylene feeding material 111, so that the gas phase and the liquid phase are fully contacted with each other in a gas-liquid two-phase manner in the sprayers, and the liquid phase carries a large amount of micro bubbles to enter the diffusion section of the lower spraying self. Most of the reaction is completed in a bottom-spraying self-sucking sprayer.
In this example the synthesis gas 110 was 2100NL/h, the ethylene feed 111 was 1.3kg/h and the recycle liquor ratio reactor volume was 20. The yield of propionaldehyde is 2.67kg/h, and the conversion rate of conversion of ethylene into propionaldehyde is 99.2 percent. The propanal space time yield STY was found to be 4.6mol/(l × h).
Comparative example 5：
A reaction system shown in FIG. 2 is used for a test with ethylene as an olefin raw material, the concentration of rhodium as a catalyst is 150ppm, a ligand is triphenylphosphine, the molar ratio of Rh to TPP is 1:200, the temperature of a spray kettle is maintained at 90 ℃, the reaction pressure is 1.6MPa, the effective reaction liquid volume of the spray kettle 100 is 10L, the height of the spray kettle is 900mm, a lower spray self-suction type sprayer 104 is arranged at the top of the spray kettle, the diameter of a nozzle spray opening of the sprayer is 2.5mm, the spray angle is 30 degrees, the diameter of a spray expanding pipe is 20mm, and the length of the spray expanding pipe is 850 mm.
The circulating liquid is taken from the bottom of the spraying kettle through a pipeline 113, mixed with a subsequent circulating catalyst 122 after passing through a circulating pump 102 and a circulating heat exchanger 103, and then enters a lower spraying self-suction type sprayer 104, the liquid phase can also greatly suck a mixed gas phase consisting of unreacted ethylene, synthesis gas and partial products at the upper part of the spraying kettle through a gas circulating pipe 107 besides sucking the synthesis gas 110 and the ethylene feeding material 111, a vapor-liquid two-phase full contact is formed in the sprayer, and the liquid phase carries a large amount of micro bubbles to enter a diffusion section of the sprayer. Most of the reaction is completed in a bottom-spraying self-sucking sprayer.
The syngas 110 was 2100NL/H with a CO: H2 molar ratio of 1:1, olefin feed 111 was 1.3kg/h, the circulating liquid volume flow was 300L/h, and the gas circulation amount was adjusted by closing a valve so as to show 0L/h. The yield of propionaldehyde is 2.21kg/h, and the conversion rate of conversion of ethylene into propionaldehyde is 82 percent. The propanal space time yield STY was found to be 3.81mol/(l × h).
Example 20：
The reaction system shown in FIG. 5 is used for carrying out a test by taking ethylene and propylene as olefin raw materials, the ethylene and the propylene enter in a certain mass ratio, the distribution ratio of synthesis gas entering a first reaction kettle and a second reaction kettle is 80: 20%, the concentration of rhodium of a catalyst is 60ppm, a ligand is a composition of tris (o-methylphenyl) phosphorus L0 and L5, the molar ratio of Rh to L0 to L5 is 1:10:4, the temperature of each injection kettle is maintained at 90 ℃, the reaction pressure is 1.6MPa, two injection kettles 100A/100B are connected through a pipeline 114, the effective reaction liquid volume of each injection kettle is 10L, the height of the injection kettle is 900mm, the top of each injection kettle is provided with a lower self-suction type injector 104A/104B, the nozzle diameter of each injection kettle is 2.5mm, the injection angle is 30 degrees, the diameter of an injection expanding pipe is 20mm, and the length of the injection pipe is 850 mm.
The circulating liquid 112A is taken from the bottom of the injection kettle 100A, and is divided into two parts after passing through a circulating pump 102A, one part passes through a circulating heat exchanger 103A, and is mixed with ethylene-propylene mixed olefin feeding material 111 and a subsequent circulating catalyst 122, and then enters a lower injection self-priming injector 104A of the injection kettle 100A, the liquid phase not only entrains the synthesis gas 110, but also largely entrains the mixed gas phase consisting of unreacted ethylene, propylene, synthesis gas and part of products through a gas circulating pipe 107, so that the vapor phase and the liquid phase are fully contacted in the injector, and the liquid phase carries a large amount of micro bubbles to enter an expansion section of the injector. Most of the reaction is completed in the injection tube.
The syngas 110A in this example is 3800NL/H, 110B is 920NL/H, with a CO: H2 molar ratio of 1:1, the ethylene propylene feed 111 was 3.6kg/h, wherein propylene was 2.0kg/h, ethylene was 1.6kg/h, the first reactor circulating liquid volume flow was 115A at 300L/h, and the gas circulation amount was shown at (350L/h). The volume flow of the circulating liquid in the first reaction tank was 115B and 300L/h, and the gas circulation amount was shown at (350L/h). The propionaldehyde yield was 3.29kg/h, the conversion of ethylene to propionaldehyde was 99.2%, and the measured propionaldehyde space-time yield STY was 2.84mol/(l × h); the butyraldehyde yield is 3.41kg/h, and the conversion rate of converting propylene into butyraldehyde is 99.2 percent. The measured butyraldehyde space-time yield STY was 2.37mol/(l × h);
as can be seen from the above examples and comparative examples, when the spray reactor provided with the vapor-phase circulation circuit and the liquid-phase circulation circuit is compared with the spray reactor provided with only the liquid-phase circulation circuit, the efficiency of the reaction is unexpectedly and greatly improved in the case of catalyzing the propylene carbonyl reaction with rhodium. Compared with a stirring kettle, the efficiency of only 2 jet reaction kettles can be realized and exceed that of three stirring reaction kettles. Because the reaction strength is enhanced, the volume of the reaction kettle is reduced, the one-time investment cost of the catalyst is reduced, and the ligand consumption is lower.
Claims (10)
1. An oxo process spray tank comprising one or more under-spray self-priming sprayers disposed at the top of the spray tank, each of the under-spray self-priming sprayers comprising a nozzle and a suction section, a mixing section and a diffuser section in fluid communication, the nozzle being located within the suction section, the suction section being in fluid communication with a feed gas source;
each air suction section is also in fluid communication with the part above the liquid phase line of the spraying kettle through a pipeline.
2. The spray tank of claim 1 wherein the suction sections of the lower spray self-priming spray each have two separate gas inlets, one fluidly connected to a gas source via a conduit and the other fluidly connected to the gas phase portion of the spray tank via a conduit.
3. The spray tank of claim 1 or 2 wherein said suction section, mixing section and diffuser section of said lower spray self-priming spray comprise a venturi.
4. A reaction system for an oxo reaction, comprising an oxo reactor, the reactor comprising:
one or more lower spray self-suction injectors arranged at the top of the injection kettle, wherein each injector sequentially comprises a nozzle, a suction section, a mixing section and a diffusion section which are communicated with each other in fluid, the nozzle is positioned in the suction section, and the suction section is communicated with a raw material gas source in fluid;
a reaction kettle outlet arranged at the lower part of the injection kettle and used for discharging a reaction mixture; and
the distribution plate is arranged in the jetting kettle and positioned between the lower jetting self-suction type sprayer and the outlet of the jetting kettle;
the outlet of the spraying kettle is in fluid communication with the nozzle of each lower spraying self-suction type sprayer through a pipeline outside the spraying kettle;
the device is characterized in that the air suction section of each lower-spraying self-suction type ejector is communicated with the gas phase part of the spraying kettle through a pipeline.
5. The reaction system of claim 4 comprising two oxo reactors in fluid communication in the vapor phase.
6. The reaction system of claim 4 or 5 wherein each of said oxo-reactors comprises 1-2 bottom-spray self-priming sprayers.
7. The reaction system of claim 4 or 5 wherein the suction sections of the lower spray self-priming ejector each have two separate gas inlets, one fluidly connected to a gas source via a conduit and the other fluidly connected to the gas phase portion of the injection kettle via a conduit.
8. The reaction system of claim 4 or 5 wherein said suction, mixing and diffusion sections of said lower spray self-priming injector form a venturi.
9. A bottom spray self-priming sprayer comprises a nozzle, and a suction section, a mixing section and a diffusion section which are communicated with each other, and is characterized in that the nozzle is positioned in the suction section, and the suction section is provided with two independent gas inlets.
10. The bottom-spray self-priming injector according to claim 9, wherein the suction, mixing and diverging sections of the bottom-spray self-priming injector form a venturi.
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| CN110156580B (en) * | 2019-06-24 | 2024-03-15 | 上海华谊（集团）公司 | Method and apparatus for producing aldehyde from olefin |
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