CN116251540A - Bubbling bed reactor and method for continuous dehydration and esterification - Google Patents
Bubbling bed reactor and method for continuous dehydration and esterification Download PDFInfo
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- 238000005886 esterification reaction Methods 0.000 title claims abstract description 44
- 230000032050 esterification Effects 0.000 title claims abstract description 34
- 230000005587 bubbling Effects 0.000 title claims abstract description 29
- 230000018044 dehydration Effects 0.000 title claims abstract description 26
- 238000006297 dehydration reaction Methods 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 116
- 239000007788 liquid Substances 0.000 claims abstract description 113
- 239000007789 gas Substances 0.000 claims abstract description 81
- 239000002994 raw material Substances 0.000 claims abstract description 64
- 230000003197 catalytic effect Effects 0.000 claims abstract description 48
- 238000007789 sealing Methods 0.000 claims abstract description 39
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000002148 esters Chemical class 0.000 claims abstract description 13
- 239000012495 reaction gas Substances 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 19
- 239000012295 chemical reaction liquid Substances 0.000 claims description 16
- 150000008064 anhydrides Chemical class 0.000 claims description 15
- 239000007791 liquid phase Substances 0.000 claims description 14
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 4
- 230000008016 vaporization Effects 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- 239000012071 phase Substances 0.000 description 11
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 6
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 6
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 6
- 235000011037 adipic acid Nutrition 0.000 description 5
- 239000001361 adipic acid Substances 0.000 description 5
- UOBSVARXACCLLH-UHFFFAOYSA-N monomethyl adipate Chemical compound COC(=O)CCCCC(O)=O UOBSVARXACCLLH-UHFFFAOYSA-N 0.000 description 5
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 238000000066 reactive distillation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- CPKISUMKCULUNR-UHFFFAOYSA-N 2-methoxy-2-oxoacetic acid Chemical compound COC(=O)C(O)=O CPKISUMKCULUNR-UHFFFAOYSA-N 0.000 description 1
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
- B01J8/0446—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical
- B01J8/0461—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical annular shaped beds
- B01J8/0469—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical annular shaped beds the beds being superimposed one above the other
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/0005—Catalytic processes under superatmospheric pressure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
- B01J8/0492—Feeding reactive fluids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
Abstract
The invention discloses a bubbling bed reactor for continuous dehydration and esterification, which relates to the technical field of chemical reactors and comprises the following components: an outer cylinder arranged vertically; a plurality of reaction units which are distributed in the outer cylinder body from top to bottom at intervals; the reaction unit comprises a catalytic bed layer, a gas distributor, a liquid distributor, an inner sealing head, a liquid inlet pipe, a drain pipe, an air inlet pipe and a liquid outlet, wherein the catalytic bed layer, the gas distributor, the liquid distributor and the inner sealing head are sequentially distributed from top to bottom; in the two adjacent reaction units, a liquid outlet in the reaction unit positioned above is communicated with the other end of a liquid inlet pipe in the reaction unit positioned below through a liquid through pipe. The method comprises the following steps: liquid raw materials are introduced through the uppermost liquid inlet pipe, and reaction gas is introduced through the lowermost gas inlet pipe, so that the liquid raw materials and the gas raw materials react under the action of a catalyst to generate corresponding ester and water. The invention continuously dewaters during the esterification reaction, the conversion rate of raw materials is high, and the selectivity of the esterified product is good.
Description
Technical Field
The invention relates to the technical field of chemical industry reactors, in particular to a bubbling bed reactor and a bubbling bed method for continuous dehydration and esterification.
Background
At present, the esterification reactor is divided into a reactive distillation tower reactor and a fixed bed reactor according to the type of the reactor. For example CN103347602B employs a reactive distillation column reactor comprising a column reactor of a plurality of trays mounted in a stack, each tray being adapted to hold thereon a predetermined liquid volume and charge of solid catalyst particles, the gas phase being operated from bottom to top to strip water generated by the liquid phase reaction, the liquid phase entering the next tray through an externally hung liquid pack, the catalyst being packed in an on-line packing system. Because the catalyst is piled up on the tray and is not fixed, the catalyst is easily carried to the tray on the upper layer by the gas phase clamp from the tray on the lower layer, and the catalyst on the tray is easily lost when the gas phase flow is large, thus the reaction effect is poor. In US5510089, a similar column reactor is used. However, these esterification column reactors all require equipment for the on-line separation and installation of the corresponding catalyst. The production energy consumption is increased, the process is complicated, and the reaction effect is not ideal.
The method for producing dimethyl maleate disclosed in CN103360253B adopts a fixed bed reactor to carry out double esterification reaction, but the simple double esterification reaction is a reversible equilibrium reaction, and if water generated by the reaction cannot be timely removed, the conversion rate of the monomethyl maleate is only 80-90%.
CN217341282U discloses a fixed bed catalytic reactor for continuous esterification, which adopts a method of combining reaction and flash evaporation, and has the disadvantage that flash evaporation can remove a part of water in the product after the reaction, but can not dehydrate while carrying out the esterification reaction, and has no great promotion effect on the esterification reaction.
Disclosure of Invention
The invention aims to provide a bubbling bed reactor and a bubbling bed method for continuous dehydration and esterification, which are used for solving the problems in the prior art and improving the reaction effect of esterification.
In order to achieve the above object, the present invention provides the following solutions:
the invention provides a bubbling bed reactor for continuous dehydration and esterification, which is characterized by comprising the following components:
an outer cylinder arranged vertically;
a plurality of reaction units which are distributed in the outer cylinder body from top to bottom at intervals; the reaction unit comprises a catalytic bed layer, a gas distributor, a liquid distributor and an inner seal head which are sequentially distributed from top to bottom, wherein the catalytic bed layer, the gas distributor and the inner seal head are respectively and fixedly connected with the inner wall of the outer cylinder, the liquid distributor is fixedly connected with the inner seal head, the reaction unit further comprises a liquid inlet pipe, a row of pipes, an air inlet pipe and a liquid outlet, one end of the liquid inlet pipe is communicated with the liquid distributor, one end of the air inlet pipe is communicated with the gas distributor, the other end of the air inlet pipe penetrates through the inner seal head and is positioned below the inner seal head, and the liquid outlet is arranged on the outer cylinder and is positioned above the catalytic bed layer; in the two adjacent reaction units, the liquid outlet in the upper reaction unit is communicated with the other end of the liquid inlet pipe in the lower reaction unit through a liquid passing pipe; the top of the outer cylinder body is provided with an upper sealing head, and the upper sealing head is provided with an exhaust port.
Preferably, a manhole is disposed on the wall of the outer cylinder corresponding to each reaction unit, and the manhole is located above the catalytic bed layer in the corresponding reaction unit.
Preferably, the liquid inlet pipe penetrates through the inner sealing head, the liquid inlet pipe and the air inlet pipe are in sealing connection with the inner sealing head, the edge of the inner sealing head is in sealing connection with the inner wall of the outer cylinder body, and the inner sealing head is used for lifting liquid entering through the liquid distributor and preventing the liquid entering through the liquid distributor from directly flowing to the lower part of the outer cylinder body.
Preferably, the inner seal head adopts a spherical cap seal head; the catalytic bed comprises an upper Johnson mesh, a catalyst and a lower Johnson mesh, the catalyst is arranged between the upper Johnson mesh and the lower Johnson mesh, and the mesh diameters of the upper Johnson mesh and the lower Johnson mesh are smaller than the size of the particles of the catalyst.
Preferably, the device further comprises a row of pipes, one end of each row of pipes is communicated with the inner sealing head, and the other end of each row of pipes extends out of the outer cylinder.
Preferably, a lower seal head is arranged at the bottom end of the outer cylinder body, and the lower seal head is used as an inner seal head in the reaction unit at the lowest part.
Preferably, the air inlet pipe comprises an inner pipe and an outer pipe, the outer pipe is sleeved on the inner pipe, the top end of the outer pipe is closed, two ends of the inner pipe are opened, the inner pipe penetrates through the inner sealing head, and the gas distributor is communicated with the annular space between the outer pipe and the inner pipe.
The invention also provides a continuous dehydration and esterification method, which is based on the bubbling bed reactor for continuous dehydration and esterification, wherein liquid raw materials are introduced through a liquid inlet pipe in the uppermost reaction unit, uniformly distributed in the uppermost reaction unit through a liquid distributor and upwards pass through a catalytic bed layer; simultaneously, introducing reaction gas through the gas inlet pipe in the reaction unit at the lowest part, enabling the gas raw material to flow out through a gas distributor, enabling the gas raw material to upwards pass through a catalytic bed layer, and enabling the gas raw material to enter the reaction unit at the upper layer through the gas inlet pipe of the reaction unit at the upper layer until the gas raw material passes through all the reaction units;
in the catalytic bed layer of each reaction unit, the liquid raw material and the gas raw material react under the action of a catalyst in the catalytic bed layer to generate corresponding ester and water, and the reaction liquid flows into the next reaction unit through a liquid phase liquid outlet; the reaction liquid discharged through a liquid outlet in the lowest reaction unit is used as a liquid-phase product; and part of the gas raw material is dissolved in the reaction liquid to be used as the reaction raw material, and the other part of undissolved gas is used for vaporizing water generated by the reaction and enters the reaction unit at the upper layer until the water passes through the reaction unit at the uppermost layer and is discharged through the gas outlet.
Preferably, the main component of the liquid raw material comprises monoester of dicarboxylic acid containing two carbon atoms to six carbon atoms, dicarboxylic acid containing two carbon atoms to six carbon atoms or anhydride thereof, and monohydric alcohol containing one to four carbon atoms; the main component of the gas raw material is monohydric alcohol with one carbon to four carbon.
Preferably, the molar ratio of alcohol to acid ester in the mixed material consisting of the liquid raw material and the gas raw material entering the bubbling bed reactor is 2-15, and the acid ester comprises acid, anhydride and monoester; the feeding temperature of the liquid raw material is 100-120 ℃, the feeding temperature of the gas raw material is 100-120 ℃, and the reaction temperature of each catalytic bed layer is 100-130 ℃.
Compared with the prior art, the invention has the following technical effects:
the bubbling bed reactor and the method for continuous dehydration and esterification integrate the reaction and the separation, continuously dehydrate while the esterification reaction is carried out, promote the esterification reaction to be carried out, have high raw material conversion rate and good selectivity of esterified products.
Furthermore, the number of the reaction units in the bubbling bed reactor for continuous dehydration and esterification can be adaptively set according to the needs, the yield is easy to expand, the method can be used for the production scale of esterification devices of 1-10 ten thousand tons/year, and the industrialized application prospect is good.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions of the prior art, the drawings that are needed in the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of a bubbling bed reactor for continuous dehydration esterification according to the present invention;
wherein, 1, upper end socket; 2. a manhole; 3. an outer cylinder; 4. a catalytic bed layer; 5. a gas distributor; 6. a liquid distributor; 7. an inner seal head; 8. a liquid inlet pipe; 9. an inner tube; 10. an outer tube; 11. although it is arranged; 12. a liquid outlet; 13. a liquid pipe; 14. an air inlet; 15. an exhaust port; 16. and a lower sealing head.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention aims to provide a bubbling bed reactor and a bubbling bed method for continuous dehydration and esterification, which are used for solving the problems in the prior art and improving the reaction effect of esterification.
In order that the above-recited objects, features and advantages of the present invention will become more readily apparent, a more particular description of the invention will be rendered by reference to the appended drawings and appended detailed description.
Example 1
As shown in fig. 1, the present embodiment provides a bubbling bed reactor for continuous dehydration and esterification, which is characterized by comprising an outer cylinder 3 arranged vertically and a plurality of reaction units distributed in the outer cylinder 3 from top to bottom at intervals.
The reaction unit comprises a catalytic bed layer 4, a gas distributor 5, a liquid distributor 6 and an inner sealing head 7 which are sequentially distributed from top to bottom, wherein the catalytic bed layer 4, the gas distributor 5 and the inner sealing head 7 are respectively and fixedly connected with the inner wall of the outer cylinder body 3, a supporting connecting piece is arranged on the inner sealing head 7 corresponding to the liquid distributor 6, and the liquid distributor 6 is fixedly connected with the inner sealing head 7 through the supporting connecting piece; the reaction unit further comprises a liquid inlet pipe 8, a drain pipe 11, an air inlet pipe and a liquid outlet 12, one end of the liquid inlet pipe 8 is communicated with the liquid distributor 6, one end of the air inlet pipe is communicated with the gas distributor 5, the other end of the air inlet pipe penetrates through the inner sealing head 7 and is located below the inner sealing head 7, and the liquid outlet 12 is arranged on the outer cylinder body 3 and is located above the catalytic bed layer 4.
The catalytic bed layer 4 comprises an upper Johnson mesh, a catalyst and a lower Johnson mesh, the catalyst is arranged between the upper Johnson mesh and the lower Johnson mesh, and the mesh diameters of the upper Johnson mesh and the lower Johnson mesh are smaller than the particle size of the catalyst; clamping the catalyst between an upper Johnson mesh and a lower Johnson mesh to avoid loss of the catalyst; the upper Johnson net and the lower Johnson net are respectively fixedly connected with the inner wall of the outer cylinder body 3; to increase the structural stability, the upper and lower johnson nets may also be connected by a plurality of connecting bars.
In this embodiment, the air inlet pipe specifically includes an inner pipe 9 and an outer pipe 10, the outer pipe 10 is sleeved on the inner pipe 9, the top end of the outer pipe 10 is closed, two ends of the inner pipe 9 are opened, the inner pipe 9 passes through the inner seal head 7 and is in sealing connection with the inner seal head 7, and the gas distributor 5 is communicated with an annulus between the outer pipe 10 and the inner pipe 9; after entering the inner tube 9, the gas will enter the annulus between the inner tube 9 and the outer tube 10 through the gap between the top end of the inner tube 9 and the top end of the outer tube 10 and then pass into the gas distributor 5.
The liquid inlet pipe 8 passes through the inner sealing head 7, the liquid inlet pipe 8 is in sealing connection with the inner sealing head 7, the edge of the inner sealing head 7 is in sealing connection with the inner wall of the outer cylinder 3, the inner sealing head 7 is used for lifting liquid entering through the liquid distributor 6 and preventing the liquid entering through the liquid distributor 6 from directly flowing to the lower part of the outer cylinder 3.
In the two adjacent reaction units, a liquid outlet 12 in the upper reaction unit is communicated with the other end of a liquid inlet pipe 8 in the lower reaction unit through a liquid through pipe 13; in this way, the reaction liquid in the reaction unit of the upper layer can be introduced into the reaction unit of the lower layer through the liquid outlet 12, the liquid inlet pipe 13 and the liquid inlet pipe 8, so that the liquid raw materials can sequentially pass through each reaction unit.
A drain pipe 11 is arranged in each reaction unit, one end of the drain pipe 11 is communicated with the inner sealing head 7, and the other end of the drain pipe 11 extends out of the outer cylinder 3. The drain 11 is used to drain the reaction liquid remaining in the reactor after the completion of the operation of the reactor. The wall of the outer cylinder body 3 is provided with a manhole 2 corresponding to each reaction unit, the manhole 2 is positioned above the catalytic bed layer 4 in the corresponding reaction unit, and maintenance personnel can enter the reactor through the manhole 2 to carry out relevant maintenance work.
The top of the outer cylinder body 3 is provided with an upper sealing head 1, and the upper sealing head 1 is provided with an exhaust port 15. The bottom end of the outer cylinder 3 is provided with a lower seal head 16, and the lower seal head 16 is used as an inner seal head 7 in the lowermost reaction unit.
In this embodiment, the upper seal head 1 and the lower seal head 16 are both elliptical seal heads, the inner seal head 7 is a spherical crown seal head, and the seal heads are selected according to the seal head standard GB/T25198-2010.
Example two
The present embodiment provides a continuous dehydration and esterification method, which is based on the bubbling bed reactor for continuous dehydration and esterification in the first embodiment, and specifically includes:
liquid raw materials are introduced through a liquid inlet pipe 8 in the uppermost reaction unit, uniformly distributed in the uppermost reaction unit through a liquid distributor 6 and upwards pass through the catalytic bed layer 4; simultaneously, the reaction gas is introduced through the gas inlet pipe in the reaction unit at the lowest position, then the gas raw material flows out through the gas distributor 5 and upwards passes through the catalytic bed layer 4, and then enters the reaction unit at the upper layer through the gas inlet pipe of the reaction unit at the upper layer until passing through all the reaction units;
in the catalytic bed layer 4 of each reaction unit, the liquid raw material and the gas raw material react under the action of the catalyst in the catalytic bed layer 4 to generate corresponding ester and water, and the reaction liquid flows into the next reaction unit through the liquid phase liquid outlet 12; the reaction liquid discharged through the liquid outlet 12 in the lowermost reaction unit is used as a liquid phase product; and a part of the gas raw material is dissolved in the reaction liquid, and as the reaction raw material, the other part of the undissolved gas vaporizes the water generated by the reaction and enters the reaction unit of the upper layer until passing through the reaction unit of the uppermost layer and then is discharged through the gas outlet 15.
In this embodiment, the main components of the liquid raw material include monoester of dicarboxylic acid having two to six carbon atoms, dicarboxylic acid having two to six carbon atoms or anhydride thereof, and monohydric alcohol having one to four carbon atoms; the main component of the gas raw material is monohydric alcohol with one carbon to four carbon.
The monoester of the dicarboxylic acid containing two carbon atoms to six carbon atoms is one of monomethyl oxalate, monomethyl maleate and monomethyl adipate; the dicarboxylic acid containing two carbon atoms to six carbon atoms is one of maleic acid, oxalic acid and adipic acid; the acid anhydride of the dicarboxylic acid having two to six carbon atoms is maleic anhydride; the monohydric alcohol with one to four carbon atoms is one of methanol, ethanol and n-butanol.
In this embodiment, the molar ratio of alcohol to acid ester in the mixture of the liquid raw material and the gas raw material entering the bubbling bed reactor is 2-15, wherein the acid ester comprises acid, anhydride and monoester, and the amount of the acid ester is the sum of the amounts of the acid, the anhydride and the monoester; the feeding temperature of the liquid raw material is 100-120 ℃, the feeding temperature of the gas raw material is 100-120 ℃, and the reaction temperature of each catalytic bed layer 4 is 100-130 ℃. The reaction temperature rise is controlled by the catalyst loading of each catalyst bed layer 4, and the total mass airspeed of the reaction liquid passing through the esterification reactor is 1-3 h -1 . The operating pressure of the reactor is 0.1-0.5 MPa; the product of the esterification reaction of the liquid raw material and the gas raw material is dicarboxylic acid dialkyl ester, such as one of dimethyl oxalate, dimethyl maleate and dimethyl adipate. In this example, the total conversion of the acid, anhydride and monoester was 97.5% or more, and the selectivity of the dialkyl dicarboxylate was 99% or more.
The term "total mass space velocity" is defined as follows: the ratio of the sum of the mass flow rates of acid, anhydride and monoester in the liquid raw material to the total mass of the catalyst in the reactor;
the definition of "total conversion of acid, anhydride and monoester" is as follows: (sum of acid, anhydride, monoester mass flow rate into the reactor-sum of acid, anhydride, monoester mass flow rate out of the reactor)/sum of acid, anhydride, monoester mass flow rate into the reactor;
the definition of "selectivity of dialkyl dicarboxylate" is as follows: the molar flow rate of dicarboxylic acid dialkyl ester/(sum of the molar flow rates of acid, anhydride, monoester entering the reactor) -sum of the molar flow rates of acid, anhydride, monoester exiting the reactor.
Example 1
Taking a double esterification reactor of 1 ten thousand tons/year 1, 6-hexanediol device as an example, the structure schematic diagram of the bubbling bed reactor adopting the invention is shown in figure 1, and 8 sections of catalytic beds 4 are provided.
The temperature of the pre-esterification reaction is 110 ℃, the flow rate of 2369kg/h of mixed liquid phase raw materials of adipic acid, monomethyl adipate and methanol is introduced through a liquid inlet pipe 8 of the uppermost reaction unit, the mixed liquid phase raw materials are uniformly distributed in the uppermost reaction unit through a liquid distributor 6, the mixed liquid phase raw materials pass through a catalytic bed layer 4 upwards, the reaction products generate corresponding dimethyl adipate and water, the reaction liquid at 112 ℃ passes through a liquid outlet 12 to be discharged from the reactor, then passes through a liquid inlet pipe 13, enters the next reaction unit, enters a catalytic bed layer 4 in the next reaction unit for reaction, and finally liquid phase products reacted through a plurality of catalytic bed layers 4 flow out of the reactor through a final section of liquid outlet 12.
Simultaneously, methanol gas phase raw material with the temperature of 110 ℃ and the flow rate of 2940kg/h enters the reactor from the gas inlet 14, upwards enters the gas distributor 5 through the gas inlet pipe, upwards passes through the catalytic bed layer 4, one part of the methanol gas phase raw material is dissolved in reaction liquid to serve as reaction raw material, the other part of undissolved gas is used for vaporizing water generated by the reaction, and the gas phase upwards passes through the catalytic bed layers 4 and then flows out of the reactor through the gas outlet 15.
The operating pressure of the reactor is 190 kPa-260 kPa, the temperature rise of the reaction of each section of catalytic bed layer 4 is not more than 5 ℃, the total temperature rise of the reaction is not more than 10 ℃, and the liquid hourly mass space velocity of adipic acid and adipic acid monomethyl ester is 2h -1 . The molar ratio of methanol (sum of methanol in liquid and gas phase) and adipic acid/monomethyl adipate in the reaction feed was 13.7.
The raw materials and the results of the product analysis of this example are shown in Table 1.
TABLE 1
As is clear from Table 1, the total conversion of adipic acid and monomethyl adipate was 98.67% and the dimethyl adipate selectivity was 99% or more under the conditions of this example.
Example 2
Taking a double-esterification reactor of a device for preparing 1, 4-butanediol by esterifying and hydrogenating 5.5 ten thousand tons/year maleic anhydride as an example, the structure schematic diagram of a bubbling bed reactor adopting the invention is shown in figure 1, and 8 sections of catalytic beds 4 are provided.
The liquid phase raw materials of maleic anhydride, maleic acid, monomethyl maleate and methanol with the temperature of 112 ℃ and the flow rate of 12084kg/h are introduced through a liquid inlet pipe 8 of the uppermost reaction unit and uniformly distributed in the uppermost reaction unit through a liquid distributor 6, pass through a catalytic bed layer 4 upwards to react to generate corresponding dimethyl adipate and water, the reaction liquid with the temperature of 121 ℃ is discharged out of the reactor through a liquid outlet 12, then enters a next-layer reaction unit through a liquid inlet pipe 13, enters a catalytic bed layer 4 in the next-layer reaction unit to react, and finally, the liquid phase product reacted through a plurality of catalytic bed layers 4 flows out of the reactor through a last-stage liquid outlet 12.
Simultaneously, methanol gas phase raw material with the temperature of 109 ℃ and the flow of 12730kg/h enters the reactor from the gas inlet 14, upwards enters the gas distributor 5 through the gas inlet pipe, upwards passes through the catalytic bed layer 4, one part of the methanol gas phase raw material is dissolved in reaction liquid to be used as reaction raw material, the other part of undissolved gas is used for vaporizing water generated by the reaction, and the gas phase upwards passes through the catalytic bed layers 4 and then flows out of the reactor through the gas outlet 15.
The operating pressure of the reactor is 190 kPa-325 kPa, the temperature rise of the reaction of each section of the catalytic bed layer 4 is not more than 15 ℃, the total temperature rise of the reaction is not more than 20 ℃, and the liquid hourly mass space velocity of maleic anhydride and monomethyl maleate is 2h -1 . The molar ratio of methanol (sum of methanol in liquid and gas phase) to maleic anhydride/monomethyl maleate in the reaction feed was 4.8.
The raw materials and the results of the product analysis of this example are shown in Table 2.
TABLE 2
As is clear from Table 2, under the conditions of example 2, the total conversion of maleic anhydride and monomethyl maleate was 97.6%, and the selectivity for dimethyl maleate was 99% or more.
The principles and embodiments of the present invention have been described in detail with reference to specific examples, which are provided to facilitate understanding of the method and core ideas of the present invention; also, it is within the scope of the present invention to be modified by those of ordinary skill in the art in light of the present teachings. In view of the foregoing, this description should not be construed as limiting the invention.
Claims (10)
1. A bubbling bed reactor for continuous dehydration esterification, comprising:
an outer cylinder arranged vertically;
a plurality of reaction units which are distributed in the outer cylinder body from top to bottom at intervals; the reaction unit comprises a catalytic bed layer, a gas distributor, a liquid distributor and an inner seal head which are sequentially distributed from top to bottom, wherein the catalytic bed layer, the gas distributor and the inner seal head are respectively and fixedly connected with the inner wall of the outer cylinder, the liquid distributor is fixedly connected with the inner seal head, the reaction unit further comprises a liquid inlet pipe, a row of pipes, an air inlet pipe and a liquid outlet, one end of the liquid inlet pipe is communicated with the liquid distributor, one end of the air inlet pipe is communicated with the gas distributor, the other end of the air inlet pipe penetrates through the inner seal head and is positioned below the inner seal head, and the liquid outlet is arranged on the outer cylinder and is positioned above the catalytic bed layer; in the two adjacent reaction units, the liquid outlet in the upper reaction unit is communicated with the other end of the liquid inlet pipe in the lower reaction unit through a liquid passing pipe; the top of the outer cylinder body is provided with an upper sealing head, and the upper sealing head is provided with an exhaust port.
2. The bubbling bed reactor for continuous dehydration esterification according to claim 1, characterized in that: and a manhole is arranged on the wall of the outer cylinder body corresponding to each reaction unit, and the manhole is positioned above the catalytic bed layer in the corresponding reaction unit.
3. The bubbling bed reactor for continuous dehydration esterification according to claim 1, characterized in that: the liquid inlet pipe penetrates through the inner sealing head, the liquid inlet pipe and the air inlet pipe are in sealing connection with the inner sealing head, the edge of the inner sealing head is in sealing connection with the inner wall of the outer cylinder body, and the inner sealing head is used for lifting liquid entering through the liquid distributor and preventing the liquid entering through the liquid distributor from directly flowing to the lower side of the outer cylinder body.
4. The bubbling bed reactor for continuous dehydration esterification according to claim 1, characterized in that: the inner seal head adopts a spherical cap seal head; the catalytic bed comprises an upper Johnson mesh, a catalyst and a lower Johnson mesh, the catalyst is arranged between the upper Johnson mesh and the lower Johnson mesh, and the mesh diameters of the upper Johnson mesh and the lower Johnson mesh are smaller than the size of the particles of the catalyst.
5. The bubbling bed reactor for continuous dehydration esterification according to claim 1, characterized in that: the device also comprises a row of pipes, one end of each row of pipes is communicated with the inner sealing head, and the other end of each row of pipes extends out of the outer cylinder.
6. The bubbling bed reactor for continuous dehydration esterification according to claim 1, characterized in that: the bottom of the outer cylinder body is provided with a lower seal head which is used as an inner seal head in the reaction unit at the lowest part.
7. The bubbling bed reactor for continuous dehydration esterification according to claim 1, characterized in that: the gas inlet pipe comprises an inner pipe and an outer pipe, the outer pipe is sleeved on the inner pipe, the top end of the outer pipe is closed, two ends of the inner pipe are opened, the inner pipe penetrates through the inner sealing head, and the gas distributor is communicated with the annular space between the outer pipe and the inner pipe.
8. A process for continuous dehydration esterification based on the bubbling bed reactor for continuous dehydration esterification according to any one of claims 1-7, characterized in that: introducing liquid raw materials through a liquid inlet pipe in the uppermost reaction unit, uniformly distributing the liquid raw materials in the uppermost reaction unit through a liquid distributor, and passing upwards through a catalytic bed layer; simultaneously, introducing reaction gas through the gas inlet pipe in the reaction unit at the lowest part, enabling the gas raw material to flow out through a gas distributor, enabling the gas raw material to upwards pass through a catalytic bed layer, and enabling the gas raw material to enter the reaction unit at the upper layer through the gas inlet pipe of the reaction unit at the upper layer until the gas raw material passes through all the reaction units;
in the catalytic bed layer of each reaction unit, the liquid raw material and the gas raw material react under the action of a catalyst in the catalytic bed layer to generate corresponding ester and water, and the reaction liquid flows into the next reaction unit through a liquid phase liquid outlet; the reaction liquid discharged through a liquid outlet in the lowest reaction unit is used as a liquid-phase product; and part of the gas raw material is dissolved in the reaction liquid to be used as the reaction raw material, and the other part of undissolved gas is used for vaporizing water generated by the reaction and enters the reaction unit at the upper layer until the water passes through the reaction unit at the uppermost layer and is discharged through the gas outlet.
9. The continuous dehydration esterification method according to claim 8, characterized in that: the main components of the liquid raw material comprise monoester of dicarboxylic acid containing two carbon atoms to six carbon atoms, dicarboxylic acid containing two carbon atoms to six carbon atoms or anhydride thereof and monohydric alcohol containing one carbon to four carbon atoms; the main component of the gas raw material is monohydric alcohol with one carbon to four carbon.
10. The continuous dehydration esterification method according to claim 9, characterized in that: the molar ratio of alcohol to acid ester in the mixed material consisting of the liquid raw material and the gas raw material entering the bubbling bed reactor is 2-15, and the acid ester comprises acid, anhydride and monoester; the feeding temperature of the liquid raw material is 100-120 ℃, the feeding temperature of the gas raw material is 100-120 ℃, and the reaction temperature of each catalytic bed layer is 100-130 ℃.
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Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5510089A (en) * | 1991-07-22 | 1996-04-23 | Chemical Research & Licensing Company | Method for operating a distillation column reactor |
| CN1123270A (en) * | 1994-11-21 | 1996-05-29 | 株式会社乐喜 | Improved process for preparing unsaturated carboxylic acid esters and novel apparatus for preparing the same |
| US5536856A (en) * | 1989-01-17 | 1996-07-16 | Davy Process Technology Limited | Production of carboxylic acid ester by esterification and apparatus thereof |
| US20060052619A1 (en) * | 2002-12-10 | 2006-03-09 | Bernhard Gutsche | Method for producing linear or branched fatty acid esters by means of heterogeneously catalysed reactive rectification with an upstream reactor |
| CN101618304A (en) * | 2008-07-04 | 2010-01-06 | 中国石油化工股份有限公司 | Esterification reactor |
| CN101940848A (en) * | 2010-09-27 | 2011-01-12 | 大庆油田飞马有限公司 | Catalytic rectification column member |
| CN103347602A (en) * | 2011-09-22 | 2013-10-09 | 戴维加工技术有限公司 | Apparatus and method |
| CN103360253A (en) * | 2012-04-01 | 2013-10-23 | 中国石油化工股份有限公司 | Method for producing dimethyl maleate |
| CN206204188U (en) * | 2016-10-21 | 2017-05-31 | 山东泰和水处理科技股份有限公司 | A kind of dimethyl maleate synthesizer |
| CN207576354U (en) * | 2017-10-20 | 2018-07-06 | 合盛硅业股份有限公司 | Can fixed catalyst fixed bed |
| CN109395672A (en) * | 2018-12-06 | 2019-03-01 | 浙江工业大学 | A kind of fixed bed reactors for production of sugar polyol |
| CN110947341A (en) * | 2019-12-30 | 2020-04-03 | 安庆精益精化工有限公司 | Continuous catalytic esterification dehydration fixed bed reactor |
| CN111234932A (en) * | 2020-02-12 | 2020-06-05 | 常州市金坛区维格生物科技有限公司 | Method for preparing biodiesel by continuous countercurrent esterification reaction |
| CN213049457U (en) * | 2020-07-17 | 2021-04-27 | 福建福大双众化工科技有限公司 | Loose-packed catalytic filler fixing structure of looped netowrk frame |
| WO2022056913A1 (en) * | 2020-09-21 | 2022-03-24 | 安徽金禾实业股份有限公司 | Preparation method for sucrose-6-carboxylate |
| CN217341282U (en) * | 2022-05-05 | 2022-09-02 | 南京长江江宇环保科技有限公司 | Fixed bed catalytic reactor of esterifying in succession |
| CN115582076A (en) * | 2022-10-19 | 2023-01-10 | 浙江工业大学 | Device and method for continuously producing dimethyl sebacate by solid acid catalytic esterification |
-
2023
- 2023-02-15 CN CN202310119577.3A patent/CN116251540A/en active Pending
Patent Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5536856A (en) * | 1989-01-17 | 1996-07-16 | Davy Process Technology Limited | Production of carboxylic acid ester by esterification and apparatus thereof |
| US5510089A (en) * | 1991-07-22 | 1996-04-23 | Chemical Research & Licensing Company | Method for operating a distillation column reactor |
| CN1123270A (en) * | 1994-11-21 | 1996-05-29 | 株式会社乐喜 | Improved process for preparing unsaturated carboxylic acid esters and novel apparatus for preparing the same |
| US20060052619A1 (en) * | 2002-12-10 | 2006-03-09 | Bernhard Gutsche | Method for producing linear or branched fatty acid esters by means of heterogeneously catalysed reactive rectification with an upstream reactor |
| CN101618304A (en) * | 2008-07-04 | 2010-01-06 | 中国石油化工股份有限公司 | Esterification reactor |
| CN101940848A (en) * | 2010-09-27 | 2011-01-12 | 大庆油田飞马有限公司 | Catalytic rectification column member |
| CN103347602A (en) * | 2011-09-22 | 2013-10-09 | 戴维加工技术有限公司 | Apparatus and method |
| CN103360253A (en) * | 2012-04-01 | 2013-10-23 | 中国石油化工股份有限公司 | Method for producing dimethyl maleate |
| CN206204188U (en) * | 2016-10-21 | 2017-05-31 | 山东泰和水处理科技股份有限公司 | A kind of dimethyl maleate synthesizer |
| CN207576354U (en) * | 2017-10-20 | 2018-07-06 | 合盛硅业股份有限公司 | Can fixed catalyst fixed bed |
| CN109395672A (en) * | 2018-12-06 | 2019-03-01 | 浙江工业大学 | A kind of fixed bed reactors for production of sugar polyol |
| CN110947341A (en) * | 2019-12-30 | 2020-04-03 | 安庆精益精化工有限公司 | Continuous catalytic esterification dehydration fixed bed reactor |
| CN111234932A (en) * | 2020-02-12 | 2020-06-05 | 常州市金坛区维格生物科技有限公司 | Method for preparing biodiesel by continuous countercurrent esterification reaction |
| CN213049457U (en) * | 2020-07-17 | 2021-04-27 | 福建福大双众化工科技有限公司 | Loose-packed catalytic filler fixing structure of looped netowrk frame |
| WO2022056913A1 (en) * | 2020-09-21 | 2022-03-24 | 安徽金禾实业股份有限公司 | Preparation method for sucrose-6-carboxylate |
| CN217341282U (en) * | 2022-05-05 | 2022-09-02 | 南京长江江宇环保科技有限公司 | Fixed bed catalytic reactor of esterifying in succession |
| CN115582076A (en) * | 2022-10-19 | 2023-01-10 | 浙江工业大学 | Device and method for continuously producing dimethyl sebacate by solid acid catalytic esterification |
Non-Patent Citations (1)
| Title |
|---|
| 卞克建等: "《工业化学反应及应用》", 28 February 1999, 中国科学技术大学出版社, pages: 4 - 5 * |
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