CN114835543B - Long-chain olefin synthesis system and synthesis process for synthesizing long-chain olefin by using same - Google Patents
Long-chain olefin synthesis system and synthesis process for synthesizing long-chain olefin by using same Download PDFInfo
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- CN114835543B CN114835543B CN202210335661.4A CN202210335661A CN114835543B CN 114835543 B CN114835543 B CN 114835543B CN 202210335661 A CN202210335661 A CN 202210335661A CN 114835543 B CN114835543 B CN 114835543B
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- 150000001336 alkenes Chemical class 0.000 title claims abstract description 78
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 51
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 51
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 40
- 230000008569 process Effects 0.000 title claims abstract description 31
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 27
- 230000003197 catalytic effect Effects 0.000 claims abstract description 74
- 239000002994 raw material Substances 0.000 claims abstract description 67
- 239000000463 material Substances 0.000 claims abstract description 52
- 239000003054 catalyst Substances 0.000 claims abstract description 47
- 238000010438 heat treatment Methods 0.000 claims abstract description 29
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000007036 catalytic synthesis reaction Methods 0.000 claims description 16
- 230000009471 action Effects 0.000 claims description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 10
- 238000005070 sampling Methods 0.000 claims description 10
- 239000000945 filler Substances 0.000 claims description 9
- 238000011049 filling Methods 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 239000011787 zinc oxide Substances 0.000 claims description 5
- 239000006004 Quartz sand Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 238000012856 packing Methods 0.000 claims description 3
- 230000000149 penetrating effect Effects 0.000 claims description 2
- 230000007547 defect Effects 0.000 abstract description 8
- 238000004064 recycling Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 97
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 16
- 239000007788 liquid Substances 0.000 description 13
- 239000007789 gas Substances 0.000 description 11
- 150000003138 primary alcohols Chemical class 0.000 description 9
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 8
- 230000006837 decompression Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 238000009835 boiling Methods 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 238000007086 side reaction Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000011344 liquid material Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 238000006266 etherification reaction Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000009827 uniform distribution Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000009489 vacuum treatment Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 208000005156 Dehydration Diseases 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- C07C2521/08—Silica
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of zinc, cadmium or mercury
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The application relates to the field of olefin synthesis, and particularly discloses a long-chain olefin synthesis system and a synthesis process for synthesizing long-chain olefin by using the same. The long-chain olefin synthesis system comprises a catalytic device, wherein a catalytic cavity communicated along the axial direction of the catalytic device is arranged in the catalytic device, and a catalyst layer is arranged in the catalytic cavity; the material collecting device is provided with condensing equipment for condensing and recycling a product synthesized by the catalysis of the catalyst layer; and one end of the vacuum equipment is communicated with the other end of the condensing equipment, and a vacuum pump is arranged in the vacuum equipment and is used for moving the gaseous raw material from the other end of the catalytic device to the other end of the material device. The synthesis process comprises the following steps: s1, preparing raw materials; s2, preheating treatment; s3, heating, catalyzing and synthesizing; s4, separating and purifying; s5, collecting materials. The method optimizes the scheme of synthesizing long-chain olefin, and overcomes the defect that the fixed bed process reduces the utilization rate of raw materials.
Description
Technical Field
The application relates to the field of olefin synthesis, in particular to a long-chain olefin synthesis system and a synthesis process for synthesizing long-chain olefin by using the same.
Background
In recent years, with the development of petrochemical industry, the use and development of higher alcohols such as C6 to C20 has become more important. The low-cost high-carbon alcohol is mainly used in the aspects of detergents, assistants and the like at present, and the low-cost high-carbon alcohol is converted into olefin, so that the further increase of the added value of the olefin has stronger practical significance. In particular, the olefin has wide application in high molecular materials, so the synthetic process for converting primary alcohol into terminal olefin with high selectivity, high yield, low investment and quick effect is necessary.
Currently, schemes for synthesizing olefins from higher alcohols generally have two main directions: the first solution is catalytic synthesis by means of strong protonic acids. However, this scheme requires a large amount of acid for catalysis, is easy to pollute the environment, and the terminal alkene is easy to polymerize under the strong acid condition, so that the yield of the alkene is low.
The second scheme is to perform catalytic synthesis through a fixed bed process. According to the scheme, a solid catalyst is used as a fixed catalytic phase, and terminal alkene is prepared under the catalytic dehydration treatment of a catalyst bed layer through continuous feeding of raw materials. However, in the actual operation and production process, due to the continuous feeding of raw materials, the catalyst is easy to carbonize and coke or end alkene polymerization and coking, and needs to be cleaned regularly so as to generate a large amount of solid wastes; in addition, the generated product terminal alkene and the primary alcohol which is not completely converted are easy to react to generate ether when passing through a catalyst bed layer, and the yield is influenced.
In view of the above related art, the inventors believe that the conventional catalytic schemes for synthesizing olefins from higher alcohols have the disadvantage of low yields.
Disclosure of Invention
In order to overcome the defect of low yield of the traditional scheme for synthesizing olefin by using high-carbon alcohol, the application provides a long-chain olefin synthesis system and a synthesis process for synthesizing long-chain olefin by using the same.
In a first aspect, the present application provides a long-chain olefin synthesis system, which adopts the following technical scheme:
a long chain olefin synthesis system comprising:
the catalytic device is formed into a column body, a catalytic cavity penetrating along the axial direction of the catalytic device is arranged in the catalytic device, and a catalyst layer is arranged in the catalytic cavity;
the material collecting device is provided with condensing equipment to condense and recycle the product synthesized by the catalysis of the catalyst layer;
and one end of the vacuum equipment is communicated with the other end of the condensing equipment, and the vacuum equipment is used for decompressing the raw material from liquid to gas and moving from the other end of the catalytic device to the other end of the material device.
Through adopting above-mentioned technical scheme, this application has optimized long-chain olefin synthesis's scheme and device, has simplified traditional long-chain olefin synthesis's scheme, and this application combines vacuum equipment through catalytic unit, under vacuum equipment's effect, and the raw materials is through vacuum treatment, and after the decompression gasification, directly carry to material collection device after catalyzing in catalytic unit, has improved traditional fixed bed technology and has needed a large amount of carrier gas to carry the defect of material. Meanwhile, the product after catalytic synthesis has lower boiling point due to the decompression treatment of the vacuum device, and can be well separated from unreacted raw materials under the condition of vacuum decompression, so that the defect that etherification impurities are formed due to side reaction generated by mixing raw materials and products in the scheme of synthesizing and producing long-chain olefins by the traditional fixed bed process, and the utilization rate of the raw materials is reduced is overcome.
Meanwhile, the system for synthesizing the long-chain olefin has a simple structure, can conveniently clean equipment, has strong applicability, can finish synthesis treatment by simply adjusting the temperature and the vacuum degree of a catalyst for different terminal olefin products produced by catalysis, and thus improves the applicability of various synthesis of the terminal olefin products.
Preferably, the catalytic device further comprises:
the rectification separation tower is arranged between the material collecting device and the catalytic device, one end of the rectification separation tower is connected with one end of the catalytic device, the other end of the rectification separation tower is connected with one end of the material collecting device, raw material components heated and catalyzed by the catalyst layer are separated into qualified components and unqualified components through rectification, the qualified components are conveyed to the material collecting device, the unqualified components flow back to the catalytic device, and the unqualified components are conveyed to the material collecting device after repeated catalytic conversion is completed.
Through adopting above-mentioned technical scheme, this application has further optimized catalytic unit's structure, through set up the rectifying separation tower structure in catalytic unit at catalytic unit's raw materials catalysis and the in-process of generating the product, realizes the separation purification of obtained product simultaneously, once only obtains qualified product, does not need rectifying purification again to not only improve synthetic efficiency, the purity of purification is higher simultaneously, has improved the quality of product.
Preferably, the rectifying separation column includes:
the rectification column packing is axially arranged in the internal cavity of the rectification separation tower along the rectification separation tower so as to separate the heated and catalyzed raw materials;
the distributor is arranged at one end of the rectifying column filler, which is close to the material collecting device, so as to uniformly distribute the heated and catalyzed raw materials.
Through adopting above-mentioned technical scheme, this application has further optimized the structure of rectifying separation tower, through setting up the rectifying column filler in the rectifying column, realizes good separation to the product. The distributor is further arranged to ensure that the liquid is uniformly distributed on the cross section of the tower, thereby ensuring that the original uniform distribution state of the synthesized product is maintained in the flowing process without affecting the contact of gas phase and liquid phase, and improving the mass transfer efficiency of the product.
Preferably, the material collecting device further comprises:
and one end of the sampling part is connected with the rectification separation tower through a return pipe so as to sample the product separated by the rectification separation tower.
Through adopting above-mentioned technical scheme, this application still further sets up sampling portion on material collection device, not only can conveniently carry out further accuse to product quality, can also effectively detect simultaneously to long-chain olefin's synthetic condition and set for different product synthetic temperature and vacuum.
Preferably, the long-chain olefin synthesis system further comprises:
the feeding part is provided with a containing cavity for storing and transferring raw materials;
the preheating device is communicated with the feeding part through a feeding pipe and is provided with a heating device for heating and treating raw materials.
Through adopting above-mentioned technical scheme, this application has further optimized long-chain olefin synthesis system's structure, through the feed portion that sets up, makes solid high molecular weight raw materials store, material conversion etc. in the feed portion, has effectively optimized synthetic efficiency and step, further improves the synthetic efficiency of conversion of raw materials.
Meanwhile, through the arrangement of the preheating part, the vacuum equipment can be conveniently depressurized to enable the vacuum equipment to be formed into a gas structure, the catalytic synthesis efficiency of the following raw materials is improved, the side reaction between the raw materials and the products is reduced, the impurity rate is reduced, and the product yield is improved.
Preferably, the catalytic device further comprises:
and a heating catalyst part, at least a part of which is connected with the catalyst layer to heat the catalyst layer.
Through adopting above-mentioned technical scheme, this application technical scheme has further optimized catalytic unit's structure, through the heating catalytic unit that sets up, can improve the synthetic environment of catalysis, through the effect of high temperature environment, the motion and the activity of raw materials are accelerated to catalytic unit's efficiency in actual catalytic reaction in-process improves.
Preferably, the vacuum apparatus further comprises:
the two low-temperature cooling and collecting devices are respectively arranged at two ends of the vacuum pump to recycle qualified gaseous products.
By adopting the technical scheme, in the actual production process of the product, when the target product is the low-boiling-point terminal alkene, the boiling point of the target product is lower, and meanwhile, the boiling point of the target product is further reduced in a vacuum environment, so that the front end and the rear section of a vacuum pump in a vacuum equipment device are required to be added with low-temperature cooling collecting devices so as to recover the qualified low-boiling-point terminal alkene product and prevent loss of the low-boiling-point terminal alkene product.
In a second aspect, the present application provides a process for synthesizing long-chain olefins using the long-chain olefin synthesis system described above, comprising the following synthesis steps:
s1, preparing raw materials: the raw materials are converted into materials and then are transferred and stored in the feeding part;
s2, preheating: conveying the raw materials stored in the transit to preheating equipment for preheating treatment;
s3, heating, catalyzing and synthesizing: the preheated raw materials are conveyed into a catalytic device, and are heated through a catalyst layer to be catalyzed and synthesized, so that a catalytic synthesis product is obtained;
s4, separating and purifying: delivering the catalytic synthesis product to a rectifying separation tower, separating qualified products under the separation action of a rectifying column filler, delivering the qualified products to a material collecting device, delivering unqualified products to a catalytic device again, and repeatedly heating and catalyzing to synthesize until the qualified products are qualified under the catalysis action of a catalyst layer;
s5, collecting materials: condensing and refluxing the qualified product by a material collecting device, and then filling and collecting the product to synthesize long-chain olefin.
By adopting the technical scheme, the product and the raw materials are instantaneously separated by optimizing the synthesis process and adopting the process steps of reaction and separation, and products of etherified impurities are reduced or avoided, so that the yield of the products is improved. The method has the advantages that the required product is directly obtained through rectification separation, and simultaneously, unconverted raw materials are conveyed to the catalyst layer again under the action of the rectification separation tower and gravity, so that 100% conversion rate of the raw materials is realized, and the yield of the product is improved.
Preferably, the catalyst in the catalyst layer in step S3 includes one or more of zinc oxide, aluminum oxide, and quartz sand.
Through adopting above-mentioned technical scheme, this application has optimized the kind of catalyst, according to the difference of raw materials, can selectively select the raw materials that the reactivity is different, and conditions such as rethread catalyst layer temperature and system vacuum are adjusted to the yield of further improvement product.
In summary, the present application has the following beneficial effects:
first, this application has optimized long-chain olefin synthesis's scheme and device, has simplified traditional long-chain olefin synthesis's scheme, and this application combines vacuum equipment through catalytic unit, and under vacuum equipment's effect, the raw materials is through vacuum treatment, and after the decompression gasification, in catalytic unit catalysis back, directly carry to material collection device in, has improved traditional fixed bed technology and has needed a large amount of carrier gas to carry the defect of material. Meanwhile, the product after catalytic synthesis has lower boiling point due to the decompression treatment of the vacuum device, and can be well separated from unreacted raw materials under the condition of vacuum decompression, so that the defect that etherification impurities are formed due to side reaction generated by mixing raw materials and products in the scheme of synthesizing and producing long-chain olefins by the traditional fixed bed process, and the utilization rate of the raw materials is reduced is overcome.
Meanwhile, the system for synthesizing the long-chain olefin has a simple structure, can conveniently clean equipment, has strong applicability, and can complete synthesis treatment by adjusting the temperature and the vacuum degree of a catalyst for different terminal olefin products, thereby improving the efficiency of synthesizing various kinds of terminal olefin products.
Secondly, this application has further optimized catalytic unit's structure, through set up the rectifying separation tower structure in catalytic unit at catalytic unit's raw materials catalysis and the in-process of generating the product, realizes the separation purification of obtained product simultaneously, once only obtains qualified product, need not rectify the purification again to not only improve synthetic efficiency, the purity of purification is higher simultaneously, has improved the quality of product. Meanwhile, good separation of products is realized by arranging a rectifying column filler in the rectifying column. Meanwhile, the distributor is arranged, so that the liquid can be uniformly distributed transversely and upwards in the tower, the original uniform distribution state is kept in the flowing process of the synthesized product, the contact of gas phase and liquid phase is not influenced, and the mass transfer efficiency is improved.
Thirdly, the method adopts the process steps of reaction and separation, instantly separates the product and the raw material, reduces or avoids etherified impurities, improves the yield, directly obtains the required product, and simultaneously, under the action of a rectification separation tower and gravity, retransmits the unconverted raw material to the catalyst layer, thereby realizing 100% conversion rate of the raw material and improving the yield of the product.
Drawings
FIG. 1 is a schematic structural diagram of a long chain olefin synthesis system according to an embodiment of the present application;
FIG. 2 is a partial cross-sectional view of a long chain olefin synthesis system of an embodiment of the present application;
fig. 3 is a schematic view of a partial structure of a cryogenically cooled collection device in a vacuum apparatus according to an embodiment of the present application.
Reference numerals illustrate: 1. a catalytic device; 11. heating the catalytic part; 12. a catalyst layer; 13. a rectifying and separating tower; 132. a distributor; 2. a material collection device; 21. a condensing device; 22. a sampling unit; 3. a vacuum device; 31. a vacuum pump; 32. a cryogenically cooled collection device; 321. a first cryogenically cooled device; 322. a first collection tank; 323. a second cryogenically cooled device; 324. a second collection tank; 4. a feed section; 5. a preheating device; 51. a stirring device.
Detailed Description
The present application is described in further detail below in conjunction with figures 1-3.
The embodiment of the application discloses a long-chain olefin synthesis system. Referring to fig. 1 to 2, a long-chain olefin synthesis system is provided with a feeding part 4, and a containing cavity for storing raw materials is arranged in the feeding part 4, and can be used for preserving heat and storing solid raw materials after material conversion, so that the solid raw materials are prevented from being solidified again, the synthesis efficiency and steps are optimized, and the raw material synthesis conversion efficiency is improved. One end of the feeding part 4 is communicated with the preheating device 5 through a pipeline, a vacuum device 3 is further arranged between the preheating device 5 and the feeding part 4, a vacuum pump 31 is arranged in the vacuum device 3, the vacuum device 3 is used for decompressing the inside of the feeding part 4, and after the high-molecular-weight alcohol is converted into liquid in advance, the high-molecular-weight alcohol is sucked into the feeding part 4 by the vacuum pump 31 in the vacuum device 3. The liquid material in the feeding part 4 is conveyed to the preheating device 5, the liquid material is vaporized into gas by adjusting the vacuum degree of the vacuum device 3 and the preheating temperature of the preheating device 5 according to the actual technological property of the liquid material, and the liquid material is sucked into the catalytic device 1 under the suction effect of the vacuum device 3 to heat and catalyze the treatment. Meanwhile, the preheating device 5 is also provided with a stirring device 51, and the stirring device 51 can uniformly heat the raw materials and improve the preheating effect in the process of preheating the raw materials.
Referring to fig. 1 to 2, a catalyst device 1 is provided above a preheating device 5, the catalyst device 1 is formed in a columnar structure, and a catalyst layer 12 is further provided in a chamber provided inside the catalyst device 1. The raw materials are catalyzed by the catalyst in the catalyst layer 12 and can be synthesized into products. The catalytic device 1 improves the heating uniformity of the catalyst layer 12 in the process of heating and catalyzing the raw materials by arranging the heating catalytic part 11 on the periphery of the catalyst layer 12 along the circumferential direction, and simultaneously can accelerate the catalytic activity and efficiency and improve the synthesis efficiency of long-chain olefins by heating the raw materials through the heating catalytic part 11.
Referring to fig. 1-2, a rectification separation tower 13 is further arranged above the catalytic device 1 and is communicated with the catalytic device, and by arranging the rectification separation tower 13 above the catalytic device 1, products in gas form can enter the rectification separation tower 13 from bottom to top due to the decompression treatment of a vacuum device, and under the condition of vacuum decompression, the catalytic separation effect of catalytic synthesized products and unreacted raw materials is realized by the rectification column filler, so that the defect that etherification impurities are formed by side reaction generated by mixing the raw materials and the products in the scheme of producing long-chain olefins by using the traditional fixed bed technology is overcome, and the utilization rate of the raw materials is reduced.
The distributor 132 is arranged at the outlet of the upper end part of the rectifying and separating tower 13, and the arrangement of the distributor 132 ensures that the original uniform distribution transformation state of the catalytic synthesis product is maintained in the flowing process, the contact of gas phase and liquid phase is not influenced, and the mass transfer efficiency is improved.
Referring to fig. 1 to 2, a material collecting device 2 is connected to an outlet of a rectifying and separating tower 13, and products separated by the rectifying and separating tower 13 are condensed and conveyed to the collecting device by condensing and recovering the products by a condensing device 21 in the material collecting device 2, so that the catalytic products are collected. A vacuum tube is arranged between the vacuum equipment 3 and the material collecting device 2 to carry out balance vacuum, so that the defect that the condensing equipment 2 is not smooth in condensing and collecting materials due to the fact that liquid seal is formed after the condensing equipment 2 is filled with liquid is overcome.
Referring to fig. 1 to 2, a sampling unit 22 is further provided between the condensing unit 21 and the collecting device, one end of the sampling unit 22 is connected to the distributor 132, the other end is connected to the outlet section of the condensing unit 21, a U-shaped pipe is provided in a pipe connecting the sampling unit 22 to the distributor 132, and a liquid seal formed by the U-shaped pipe prevents the generated gas product from directly entering the sampling unit through the pipe. The other end of the sampling part 22 and the outlet section of the condensing equipment 21 are controlled to be closed or opened by a valve. Meanwhile, the sampling part 22 is provided with two valves, so that the product quality can be conveniently further controlled, and meanwhile, the synthesis condition of long-chain olefin can be effectively detected.
Referring to fig. 3: in the scheme that the target product is low-boiling-point alkene, the boiling point of the target product is lower, and meanwhile, the boiling point of the target product is further reduced in a vacuum environment, so that a low-temperature cooling collecting device 32 is required to be added at the front end and the rear end of a vacuum pump 31 in a vacuum device 3, condensation treatment is carried out on the low-boiling-point alkene product through a first low-temperature cooling device 321 arranged at the front end of the vacuum pump 31 and a second low-temperature cooling device 323 arranged at the rear end of the vacuum pump 31, and then the condensation treatment is carried out on the low-boiling-point alkene product through a first collecting tank 322 connected with the first low-temperature cooling device 321 and a second collecting tank 324 connected with the second low-temperature cooling device 323, so that loss of dissipation of the condensed low-boiling-point alkene product is prevented.
Examples
Example 1
A synthetic process for synthesizing terminal alkene by primary alcohol comprises the following synthetic steps:
s1, preparing raw materials: firstly, placing n-hexanol in a feeding part for storage;
s2, preheating: conveying the stored liquid n-hexanol to a preheating device through a vacuum device, decompressing to 10kPa, adjusting the temperature of the preheating device to 90 ℃, and converting the n-hexanol from liquid to gas;
s3, heating, catalyzing and synthesizing: conveying the preheated gaseous n-hexanol into a catalytic device, and heating and catalyzing the mixture at 300 ℃ through zinc oxide to synthesize a catalytic synthesis product;
s4, separating and purifying: delivering the catalytic synthesis product to a rectifying separation tower, separating qualified products under the separation action of a rectifying column filler, delivering the qualified products to a material collecting device, delivering unqualified products to a catalytic device again, and repeatedly heating and catalyzing to synthesize until the qualified products are qualified under the catalysis action of a catalyst layer;
s5: and (3) collecting materials: condensing and refluxing the qualified product by a material collecting device, and then filling and collecting the product to synthesize the 1-hexene.
Example 2
A synthetic process for synthesizing terminal alkene by primary alcohol comprises the following synthetic steps:
s1, preparing raw materials: firstly, placing n-hexanol in a feeding part for storage;
s2, preheating: conveying the stored liquid n-hexanol to a preheating device through a vacuum device, decompressing to 20kPa, adjusting the temperature of the preheating device to 109 ℃, and converting the n-hexanol from liquid to gas;
s3, heating, catalyzing and synthesizing: conveying the preheated gaseous n-hexanol into a catalytic device, and heating and catalyzing the mixture at 325 ℃ through zinc oxide to obtain a catalytic synthesis product;
s4, separating and purifying: delivering the catalytic synthesis product to a rectifying separation tower, separating qualified products under the separation action of a rectifying column filler, delivering the qualified products to a material collecting device, delivering unqualified products to a catalytic device again, and repeatedly heating and catalyzing to synthesize until the qualified products are qualified under the catalysis action of a catalyst layer;
s5: and (3) collecting materials: condensing and refluxing the qualified product by a material collecting device, and then filling and collecting the product to synthesize the 1-hexene.
Example 3
A synthetic process for synthesizing terminal alkene by primary alcohol comprises the following synthetic steps:
s1, preparing raw materials: firstly, placing n-hexanol in a feeding part for storage;
s2, preheating: conveying the stored liquid n-hexanol to a preheating device through a vacuum device, decompressing to 30kPa, adjusting the temperature of the preheating device to 120 ℃, and converting the n-hexanol from liquid to gas;
s3, heating, catalyzing and synthesizing: conveying the preheated gaseous n-hexanol into a catalytic device, and heating and catalyzing the mixture at 350 ℃ through zinc oxide to obtain a catalytic synthesis product;
s4, separating and purifying: delivering the catalytic synthesis product to a rectifying separation tower, separating qualified products under the separation action of a rectifying column filler, delivering the qualified products to a material collecting device, delivering unqualified products to a catalytic device again, and repeatedly heating and catalyzing to synthesize until the qualified products are qualified under the catalysis action of a catalyst layer;
s5: and (3) collecting materials: condensing and refluxing the qualified product by a material collecting device, and then filling and collecting the product to synthesize the 1-hexene.
Example 4: in contrast to example 1, the catalyst used in this example is alumina.
Example 5: in contrast to example 1, the catalyst used in this example is quartz sand.
It should be noted that the raw materials used in the present application include, but are not limited to, n-hexanol, which may be primary alcohols having a carbon number within 6-20, and the synthesized products include, but are not limited to, 1-hexene.
Further, the solid alcohol with high molecular weight is transferred into the feeding part 4 for heat preservation pre-storage after the advanced material conversion treatment, and the heat preservation temperature is 3-5 ℃ higher than that of the solid alcohol with high molecular weight.
Comparative example
Comparative example 1
The synthesis process of synthesizing terminal alkene from primary alcohol is different from the embodiment 1 in that a traditional fixed bed reaction process is adopted in the comparative example 1, and the specific steps are as follows:
placing aluminum oxide serving as a catalyst sample in a constant temperature area in the middle of a fixed bed reactor, and heating to 300 ℃ in nitrogen atmosphere; introducing n-hexanol into a fixed bed reactor for thermal insulation catalytic reaction, wherein the reaction pressure is normal pressure, and the reaction space velocity is 1.0-3.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the And collecting the catalytic product, condensing and collecting the catalytic product to prepare a reaction product.
Comparative example 2
A synthesis process for synthesizing terminal alkene from primary alcohol is different from example 1 in that no preheating treatment is performed in comparative example 2.
Performance test
The products of examples 1 to 5 and comparative example 1 were tested for conversion, and the test results are shown in Table 1 below:
table 1 performance test table
In combination with examples 1 to 5, comparative examples 1 to 2 and the performance test tables of Table 1, comparison can be found that:
examples 1 to 3, examples 4 to 5 and comparative examples 1 to 2 were now compared as comparative groups, and the following are specific:
(1) Firstly, by comparing the performances of examples 1 to 3 with those of comparative example 1, it can be seen from the data in table 1 that the data of examples 1 to 3 are significantly better than the data of comparative example 1, and as the technical scheme of comparative example 1 adopts the traditional fixed bed process, the conversion rate and the yield of the primary alcohol synthetic terminal alkene in the technical scheme of the application are effectively improved, and a large amount of carrier gas is not needed for synthesis.
(2) Comparing examples 1-3 with comparative example 2, it can be found that the data of examples 1-3 are better than those of comparative example 2, which indicates that the synthesis system after the technical scheme is optimized can effectively avoid side reactions between raw materials and products, thereby reducing the generation of etherified impurities and improving the conversion rate and yield.
(3) Comparing examples 4-5, example 1 and comparative example 2, the data of examples 4-5 are significantly higher than the data of comparative example 2, and the data is not greatly different from the data of example 1, which indicates that the technical scheme of the application has good conversion rate and yield through the selection of raw material catalysts with different reactivity.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (7)
1. The long-chain olefin synthesis process is characterized by applying a long-chain olefin synthesis system, and comprises the following synthesis steps:
s1, preparing raw materials: the raw materials are converted into materials and then are transferred and stored in a feeding part (4);
s2, preheating: the raw materials which are transferred and stored are conveyed to preheating equipment (5) for preheating treatment;
s3, heating, catalyzing and synthesizing: the preheated raw materials are conveyed into a catalytic device (1), and are heated and catalyzed by a catalyst layer (12) for synthesis to obtain a catalytic synthesis product;
s4, separating and purifying: delivering the catalytic synthesis product into a rectifying separation tower (13), separating qualified products under the separation action of a rectifying column filler, delivering the qualified products into a material collecting device (2), delivering unqualified products into a catalytic device (1) again, and repeatedly heating and catalyzing to synthesize until the qualified products are qualified under the catalysis action of a catalyst layer (12);
s5, collecting materials: condensing and refluxing the qualified product by a material collecting device (2), and then filling and collecting the product to synthesize long-chain olefin;
the long-chain olefin synthesis system comprises:
the catalytic device (1), the catalytic device (1) is formed into a cylinder, a catalytic cavity penetrating along the axial direction of the catalytic device (1) is arranged in the catalytic device, and a catalyst layer (12) is arranged in the catalytic cavity;
the material collecting device (2), one end of the material collecting device (2) is connected with one end of the catalytic device (1), and the material collecting device (2) is provided with condensing equipment (21) to condense and recycle products synthesized by the catalytic layer (12);
the vacuum equipment (3), one end of the vacuum equipment (3) is communicated with the other end of the condensing equipment (21), and a vacuum pump (31) is arranged in the vacuum equipment (3) and is used for moving the gaseous raw material from the other end of the catalytic device (1) to the other end of the material device;
the preheating device (5) is communicated with the feeding part (4) through a feeding pipe, and the preheating device (5) is provided with a heating device for heating and treating raw materials;
the catalytic device (1) further comprises: the rectification separation tower (13), the rectification separation tower (13) is arranged between the material collecting device (2) and the catalytic device (1), one end of the rectification separation tower (13) is connected with one end of the catalytic device (1), the other end of the rectification separation tower (13) is connected with one end of the material collecting device (2) so as to rectify and separate raw material components heated and catalyzed by the catalyst layer (12) into qualified components and unqualified components, the qualified components are conveyed to the material collecting device (2), the unqualified components flow back to the catalytic device (1), and the unqualified components are conveyed to the material collecting device (2) after repeated catalytic conversion is completed;
the rectifying separation column (13) further comprises: the rectification column packing is axially arranged in the internal cavity of the rectification separation tower (13) along the rectification separation tower (13) so as to separate the heated and catalyzed raw materials;
the raw material is C6-C20 primary alcohol, and the long-chain olefin is C6-C20 olefin.
2. The long-chain olefin synthesis process according to claim 1, wherein the rectifying separation column (13) further comprises:
and the distributor (132) is arranged at one end of the rectifying column packing close to the material collecting device (2) so as to uniformly distribute the heated and catalyzed raw materials.
3. The process for the synthesis of long-chain olefins according to claim 1, characterized in that the material collection device (2) further comprises:
and one end of the sampling part (22) is connected with the rectification separation tower (13) through a return pipe so as to sample the product separated by the rectification separation tower (13).
4. The long-chain olefin synthesis process according to claim 1, wherein the long-chain olefin synthesis system further comprises:
and the feeding part (4) is provided with a containing cavity for storing and transferring raw materials.
5. The process for the synthesis of long-chain olefins according to claim 1, characterized in that the catalytic device (1) further comprises:
and a heating catalyst portion (11), wherein at least a part of the heating catalyst portion (11) is connected with the catalyst layer (12) to heat the catalyst layer (12) at a temperature.
6. The process for the synthesis of long-chain olefins according to claim 1, characterized in that the vacuum device (3) further comprises:
and the two cryocooling collecting devices (32) are respectively arranged at two ends of the vacuum pump (31) to recycle qualified gaseous products.
7. The process for synthesizing long-chain olefins according to claim 1, wherein the catalyst in the catalyst layer (12) in step S3 comprises one or more of zinc oxide, aluminum oxide, and quartz sand.
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