CN115228383A - Device and method for preparing tetrahydrofuran through cyclization of 1, 4-butanediol - Google Patents
Device and method for preparing tetrahydrofuran through cyclization of 1, 4-butanediol Download PDFInfo
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- CN115228383A CN115228383A CN202210965194.3A CN202210965194A CN115228383A CN 115228383 A CN115228383 A CN 115228383A CN 202210965194 A CN202210965194 A CN 202210965194A CN 115228383 A CN115228383 A CN 115228383A
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 title claims abstract description 116
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 title claims abstract description 84
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000007363 ring formation reaction Methods 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 18
- 230000007246 mechanism Effects 0.000 claims abstract description 72
- 239000003054 catalyst Substances 0.000 claims abstract description 66
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- 239000007788 liquid Substances 0.000 claims abstract description 47
- 239000002994 raw material Substances 0.000 claims abstract description 40
- 238000007599 discharging Methods 0.000 claims abstract description 7
- 238000002347 injection Methods 0.000 claims description 39
- 239000007924 injection Substances 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000009826 distribution Methods 0.000 claims description 13
- 238000011084 recovery Methods 0.000 claims description 11
- 230000008859 change Effects 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 6
- 238000007872 degassing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000009833 condensation Methods 0.000 abstract description 9
- 230000005494 condensation Effects 0.000 abstract description 9
- 238000003756 stirring Methods 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 4
- 239000007791 liquid phase Substances 0.000 description 17
- 239000012071 phase Substances 0.000 description 16
- 239000000725 suspension Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 7
- 238000006297 dehydration reaction Methods 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000009827 uniform distribution Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/06—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
- C07D307/08—Preparation of tetrahydrofuran
-
- 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
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a device for preparing tetrahydrofuran by cyclization of 1, 4-butanediol and a method for preparing tetrahydrofuran by cyclization by using the device. Wherein, the device includes: a hollow reactor; the reactor is provided with a rectifying device, a catalyst feeding mechanism, a raw material feeding mechanism and a gas feeding mechanism at the top part in a communicating way, and the reactor is provided with a heat exchanger. The rectifying device, the catalyst feeding mechanism, the raw material feeding mechanism and the gas feeding mechanism are all communicated with the inner cavity of the reactor; wherein, the raw material feeding mechanism is communicated with the liquid distributor, and the gas feeding mechanism is communicated with the gas distributor. The rectification device is internally provided with a condensation section, and a gas phase discharging mechanism communicated with an external collecting device is arranged at a preset temperature section. The invention increases the contact probability of 1, 4-butanediol and the catalyst by stirring and mixing the gas and the liquid, effectively improves the reaction space velocity and obviously reduces the investment of the whole equipment.
Description
Technical Field
The disclosure relates to the technical field of tetrahydrofuran preparation, and in particular relates to a device and a method for preparing tetrahydrofuran through cyclization of 1, 4-butanediol.
Background
In the prior art, the processes for industrially producing Tetrahydrofuran (THF) mainly comprise: furfural hydrogenation, maleic anhydride direct hydrogenation, 1, 4-Butanediol (BDO) dehydration. Wherein: 1. the furfural method has complex process and serious pollution which is gradually eliminated. 2. The direct maleic anhydride hydrogenation process uses maleic anhydride water solution as raw material and makes hydrogenation reaction under the condition of very high pressure. In addition, the maleic anhydride aqueous solution shows strong acidity, so the requirement on equipment materials is high. The fixed investment and the operation cost of the process are high. The 3.1, 4-butanediol dehydration method is to make 1, 4-butanediol undergo the dehydration reaction under the condition of acid catalysis to obtain tetrahydrofuran, and has the characteristics of low reaction temperature, low operation pressure and high product yield.
The 1, 4-butanediol dehydration method is a main process method for preparing tetrahydrofuran by cyclizing 1, 4-butanediol due to the excellent characteristics of the tetrahydrofuran prepared by the 1, 4-butanediol dehydration method. The common 1, 4-butanediol dehydration method continuous preparation equipment in the prior art comprises: a fixed reaction bed type technical system and a reaction rectification device technical system. Wherein:
the fixed reaction bed type technical system adopts a fixed reaction bed as a reactor, the reactor is filled with a solid catalyst, and a liquid phase reactant flow is subjected to catalytic reaction under the action of the solid catalyst, but the preparation method is limited by chemical equilibrium, so that the reaction conversion degree is low (the conversion rate is usually 35 to 45 percent), the product yield is influenced, a large amount of unreacted 1, 4-butanediol needs to be recovered, and the overall preparation process cost is increased.
The reaction and separation process is coupled into a chemical device, unreacted raw materials are discharged from the bottom of a reaction kettle, and the raw materials are reused after impurity removal treatment, so that the conversion rate of the raw materials 1, 4-butanediol is increased to about 90% by continuously removing reaction products. But are also present; 1. the discharged unreacted raw materials must be subjected to impurity removal treatment, so that the process difficulty and the cost are increased. 2. The operation mode, the amount of the catalyst and the generated byproduct water have great influence on the conversion rate of the raw material 1, 4-butanediol. If the operation ratio is not proper or the weight hourly space velocity is not matched, higher conversion rate can not be achieved by a single reaction rectification device, and even the risk of equipment shutdown caused by abnormal operation state of the equipment is further caused.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a device for preparing tetrahydrofuran by cyclization of 1, 4-butanediol, which comprises: a hollow reactor; the top of the reactor is communicated with a rectifying device, the top or the side wall of the reactor is provided with a catalyst feeding mechanism, the part of the side wall close to the bottom is provided with a raw material feeding mechanism, and the bottom of the reactor is provided with a gas feeding mechanism; the reactor is provided with a heat exchanger. The rectifying device, the catalyst feeding mechanism, the raw material feeding mechanism and the gas feeding mechanism are all communicated with the inner cavity of the reactor; wherein, the part of the raw material feeding mechanism in the reactor is communicated with the liquid distributor, and the part of the gas feeding mechanism in the reactor is communicated with the gas distributor. The gas distributor comprises: an air inlet pipe; one end of the gas inlet pipe is communicated with the gas feeding mechanism, and the other end of the gas inlet pipe is communicated with each annular pipe in the annular pipe group through a gas primary distribution pipe; and the bottom of the annular pipe is provided with an air injection pipe.
Furthermore, a condensation section is arranged in the rectifying device, and a gas phase discharging mechanism communicated with an external collecting device is arranged at a preset temperature section.
Further, the annular tube group is divided into an inner annular tube region and an outer annular tube region; the average distance between adjacent pipes of the inner annular pipe group in the inner annular pipe area is L1, and the average distance between adjacent pipes of the outer annular pipe group in the outer annular pipe area is L2; wherein L2 > L1.
Further, the distance between adjacent pipes of the inner annular pipe group in the inner annular pipe area is L1-n, and n is a positive integer. Wherein L1-1 is the pipe spacing between the two innermost inner annular pipes, L1-2 is the pipe spacing between the second inner annular pipe and the third inner annular pipe from the inner side, L1-m is the pipe spacing between the two outermost inner annular pipes, and the L1-L1-m satisfies the increasing change relationship.
For example, K1-1= (L1-2) - (L1-1), K1-2= (L1-3) - (L1-2).. K1-s = (L1-m) - (L1-m-1) is satisfied between L1-1 and L1-m, where K1-1, K1-2.. K1-s is greater than 0.
Further, the distance between adjacent tubes of the outer annular tube group in the outer annular tube area is L2-q, and q is a positive integer. Wherein L2-1 is the pipe spacing between two outer annular pipes at the innermost side, L2-2 is the pipe spacing between the second outer annular pipe and the third outer annular pipe from the inner side, L2-w is the pipe spacing between two outer annular pipes at the outermost side, and L2-1 to L2-w satisfy the increasing change relationship.
For example, K2-1= (L2-2) - (L2-1), K2-2= (L2-3) - (L2-2).. K2-d = (L2-w) - (L2-w-1) is satisfied between L2-1 and L2-w, where K2-1, K2-2.. K2-d is greater than 0.
Further, the average distance between the gas injection pipes arranged on the annular pipes of the inner annular pipe group is M1, and the average distance between the gas injection pipes arranged on the annular pipes of the outer annular pipe group is M2; wherein M2 > M1.
Furthermore, the distance between the gas injection pipes arranged on each annular pipe of the inner annular pipe group is M1-e, and e is a positive integer. Wherein M1-1 is the average distance between adjacent gas nozzles on the innermost inner annular tube, M1-2 is the average distance between adjacent gas nozzles on the second inner annular tube from the inner side, M1-3 is the average distance between adjacent gas nozzles on the third inner annular tube from the inner side.
For example, G1-1= (M1-2) - (M1-1), G1-2= (M1-3) - (M1-2) ·.
Furthermore, the distance between the gas injection pipes arranged on the annular pipes of the outer annular pipe group is M2-r, and r is a positive integer. Wherein M2-1 is the average distance between adjacent gas injection pipes on the innermost outer ring pipe, M2-2 is the average distance between adjacent gas injection pipes on the second outer ring pipe from the inner side, M2-3 is the average distance between adjacent gas injection pipes on the third outer ring pipe from the inner side.
For example, G2-1= (M2-2) - (M2-1), G2-2= (M2-3) - (M2-2) · G2-t = (M2-v) - (M2-v-1) is satisfied between M2-1 and M2-v, where G2-1, G2-2.. G2-t is greater than 0.
Further, the liquid dispenser includes: a liquid inlet pipe; one end of the liquid inlet pipe is communicated with the raw material feeding mechanism, and the other end of the liquid inlet pipe is communicated with the liquid uniform distribution pipe; and a plurality of liquid injection pipes are arranged on the liquid uniform distribution pipe.
Furthermore, the liquid uniform distribution pipe is of an annular structure, and the plurality of liquid injection pipes are parallel to each other and arranged along the same direction, and form an included angle of 20-60 degrees with the radius of the liquid uniform distribution pipe.
Further, the heat exchanger includes: at least one of an inner heat exchanger and an outer heat exchanger.
Further, the internal heat exchanger includes: the first heat exchange tube array is arranged in the inner cavity of the reactor; the medium inlet of the first heat exchange tube array is communicated with a first heat medium supply device outside the reactor through a first pipeline, and the medium outlet of the first heat exchange tube array is communicated with a first medium recovery device outside the reactor through a second pipeline.
Further, the external heat exchanger includes: a first circulation pipe and a second circulation pipe communicated with the inner cavity of the reactor; the parts of the first circulating pipe and the second circulating pipe, which are positioned outside the reactor, are communicated through a third circulating pipe; an external heat exchanger and an external circulating pump are arranged on the third circulating pipe; after entering the third circulating pipe from the first circulating pipe and being heated at the external heat exchanger, the circulating medium is blown into the inner cavity of the reactor by the external circulating pump through the second circulating pipe; and a degassing baffle is arranged at the outlet of the second circulating pipe in the cavity inside the reactor.
Furthermore, temperature and pressure measuring ports are arranged on the reactor.
Further, a cooler is arranged inside the rectifying device; the cooler includes: the second heat exchange tube array is positioned in the rectifying device; and a medium inlet of the second heat exchange tube array is communicated with second medium supply equipment outside the rectifying device through a third pipeline, and a medium outlet of the second heat exchange tube array is communicated with second medium recovery equipment outside the rectifying device through a fourth pipeline.
Furthermore, a constant pressure valve is arranged at the top of the rectifying device and controls the reaction pressure of the inner cavity of the reactor communicated with the rectifying device by controlling the air pressure in the rectifying device. Meanwhile, the gas pressure of the gas-phase component output outwards by the rectifying device can be controlled.
In addition, the invention also provides a method for preparing tetrahydrofuran by cyclization of 1, 4-butanediol, which adopts the device for preparing tetrahydrofuran by cyclization of 1, 4-butanediol as a reaction device, controls the reaction temperature of BDO to be 100-130 ℃, controls the reaction pressure to be 0.25-0.4 MPaG and controls the temperature of THF flowing out of the reaction device to be more than 66 ℃.
Further, a mixture of THF and water with the temperature of 40-90 ℃ is introduced into the inner cavity of the reactor from the top of the rectifying device.
After the technical scheme is adopted, the invention has at least one of the following beneficial effects:
(1) According to the invention, through stirring and mixing of gas and liquid, the contact probability of BDO and the catalyst is increased, the reaction space velocity is effectively improved, and the investment of the whole equipment is obviously reduced.
(2) The invention can provide heat for reaction and product evaporation through the mixed gas of external THF and water and the heat exchange element, and has good heat supply effect, controllable reaction environment temperature intensity and stable temperature control. Meanwhile, the pressure of the reaction process can be controlled.
(3) According to the invention, the flow of the mixed gas and BDO is adopted to push the mixing of the materials and the catalyst in the reactor, so that the suspension of the catalyst is realized, the contact probability of the catalyst and the raw materials is increased, and the catalyst crushing problem and the stirring shaft sealing problem caused by mechanical stirring are avoided.
(4) The invention realizes that the catalyst is suspended in the whole liquid phase space of the reactor, and the volume ratio of the reaction space to the reactor is far higher than that of other prior art. The amount of conversion per unit reactor space is therefore also higher than in other prior art.
(5) The condensation section at the top of the reactor can realize that BDO entrained in a gas phase and gasified BDO are condensed and flow back to the reaction space of the reactor, thereby increasing the overall conversion rate of the BDO.
(6) The catalyst adopted by the invention has longer service life and does not need an on-line catalyst regeneration device. The problem of matching the production cycle of the reactor with that of the catalyst regeneration unit is also avoided. The operation difficulty of the reaction device is reduced.
(7) The invention adopts a common kettle type reactor, and the reaction zone does not need to be divided into a high-temperature reaction zone and a low-temperature reaction zone. And the heat insulation problem of the middle baffle plate in the high-temperature area and the low-temperature area is also avoided.
Drawings
FIG. 1 is a schematic view showing the structure of a THF preparation apparatus by cyclization of BDO according to an embodiment of the present invention;
FIG. 2 is a schematic structural view of a THF preparation apparatus by cyclization of BDO according to another embodiment of the present invention;
FIG. 3 is a schematic view of the structure of a THF preparation apparatus using BDO cyclization in accordance with still another embodiment of the present invention;
FIG. 4 is a schematic structural view of a gas distributor according to an embodiment of the present invention;
FIG. 5 is a schematic structural view of a ring tube and a gas lance according to an embodiment of the present invention;
fig. 6 is a schematic configuration diagram of a liquid dispenser according to an embodiment of the present invention.
Description of reference numerals:
1. a reactor; 101. a gas feed mechanism; 102. a catalyst feed mechanism; 103. temperature and pressure measuring ports; 2. an internal heat exchanger; 201. a first array of heat exchange tubes; 202. a first conduit; 203. a second conduit; 3. a raw material feeding mechanism; 4. a gas distributor; 401. an air inlet pipe; 402. an inner annular tube set; 403. a primary gas distribution pipe; 404. an outer annular tube set; 405. an inner annular tube region; 406. an outer annular tube region; 407. a gas ejector tube; 5. a rectification device; 501. a condensing section; 502. a gas phase discharging mechanism; 503. a mixture feeding mechanism; 6. a cooler; 601. a second heat exchange tube array; 602. a third pipeline; 603. a fourth conduit; 7. an external heat exchanger; 701. a first circulation pipe; 702. a second circulation pipe; 703. a third circulation pipe; 704. an external circulating pump; 705. circulating the medium; 706. an external heat exchanger; 8. liquid is uniformly distributed on the pipe; 801. a liquid inlet pipe; 802. liquid is uniformly distributed on the pipe; 803. a liquid injection tube.
Detailed Description
The present disclosure will be described in further detail with reference to the following embodiments. It is to be understood that the specific embodiments described herein are for purposes of illustration only and are not to be construed as limitations of the present disclosure.
It should be noted that the embodiments and features of the embodiments in the present disclosure may be combined with each other without conflict. The present disclosure will be described in detail with reference to embodiments.
Example 1
A device for preparing tetrahydrofuran by cyclization of 1, 4-butanediol is shown in figure 1 and comprises: a hollow reactor 1; the top of the reactor 1 is communicated with a rectifying device 5, the top or the side wall of the reactor is provided with a catalyst feeding mechanism 102, the part of the side wall close to the bottom is provided with a raw material feeding mechanism 3, and the bottom is provided with a gas feeding mechanism 101; the reactor 1 is provided with a heat exchanger.
As shown in fig. 4 and 5, the gas distributor 4 includes: an intake pipe 401; one end of the gas inlet pipe 401 is communicated with the gas feeding mechanism 101, and the other end of the gas inlet pipe is communicated with each annular pipe in the annular pipe group through a gas primary distribution pipe 403; the bottom of the annular pipe is provided with an air injection pipe 407.
The rectifying device 5, the catalyst feeding mechanism 102, the raw material feeding mechanism 3 and the gas feeding mechanism 101 are all communicated with the cavity inside the reactor 1; wherein, the part of the raw material feeding mechanism 3 located inside the reactor 1 is communicated with the liquid distributor 8, and the part of the gas feeding mechanism 101 located inside the reactor 1 is communicated with the gas distributor 4.
The rectifying device 5 is internally provided with a condensing section 501, and a gas phase discharging mechanism 502 communicated with an external collecting device is arranged at a preset temperature section. And a constant pressure valve (not shown in the figure) is arranged at the top of the rectifying device and controls the reaction pressure of the inner cavity of the reactor communicated with the rectifying device by controlling the air pressure in the rectifying device. Meanwhile, the gas pressure of the gas-phase component output outwards by the rectifying device can be controlled.
The reactor 1 is provided with a temperature and pressure measuring port 103.
The heat exchanger includes: an internal heat exchanger 2.
The inner heat exchanger 2 includes: a first heat exchange tube array 201 disposed inside the inner cavity of the reactor 1; the medium inlet of the first heat exchange tube array 201 is communicated with a first heat medium supply device outside the reactor 1 through a first pipe 202, and the medium outlet of the first heat exchange tube array 201 is communicated with a first medium recovery device outside the reactor 1 through a second pipe 203.
Example 2
An apparatus for preparing tetrahydrofuran by cyclization of 1, 4-butanediol is shown in fig. 2, and comprises: a hollow reactor 1; the top of the reactor 1 is communicated with a rectifying device 5, the top or the side wall of the reactor is provided with a catalyst feeding mechanism 102, the part of the side wall close to the bottom is provided with a raw material feeding mechanism 3, and the bottom is provided with a gas feeding mechanism 101; the reactor 1 is provided with a heat exchanger.
As shown in fig. 4 and 5, the gas distributor 4 includes: an intake pipe 401; one end of the gas inlet pipe 401 is communicated with the gas feeding mechanism 101, and the other end of the gas inlet pipe is communicated with each annular pipe in the annular pipe group through a gas primary distribution pipe 403; the bottom of the annular pipe is provided with an air injection pipe 407.
The rectifying device 5, the catalyst feeding mechanism 102, the raw material feeding mechanism 3 and the gas feeding mechanism 101 are all communicated with the cavity inside the reactor 1; wherein, the part of the raw material feeding mechanism 3 located inside the reactor 1 is communicated with the liquid distributor 8, and the part of the gas feeding mechanism 101 located inside the reactor 1 is communicated with the gas distributor 4.
The rectifying device 5 is internally provided with a condensing section 501, and a gas phase discharging mechanism 502 communicated with an external collecting device is arranged at a preset temperature section. And a constant pressure valve (not shown in the figure) is arranged at the top of the rectifying device and controls the reaction pressure of the inner cavity of the reactor communicated with the rectifying device by controlling the air pressure in the rectifying device. Meanwhile, the gas pressure of the gas-phase component output outwards by the rectifying device can be controlled. The reactor 1 is provided with a temperature and pressure measuring port 103.
The heat exchanger includes: an external heat exchanger 7.
The external heat exchanger 7 includes: a first circulation pipe 701 and a second circulation pipe 702 communicating with the inner cavity of the reactor 1; the portions of the first circulation pipe 701 and the second circulation pipe 702 located outside the reactor 1 are communicated through a third circulation pipe 703; an external heat exchanger 706 and an external circulating pump 704 are arranged on the third circulating pipe 703; the circulating medium 705 enters the third circulating pipe 703 from the first circulating pipe 701, is heated by the external circulating pump 704, and is blown into the internal cavity of the reactor 1 through the second circulating pipe 702; in the internal cavity of the reactor 1, a degassing baffle is arranged at the outlet of the second circulation pipe 702.
Example 3
A device for preparing tetrahydrofuran by cyclization of 1, 4-butanediol is shown in figure 3 and comprises: a hollow reactor 1; the top of the reactor 1 is communicated with a rectifying device 5, the top or the side wall of the reactor is provided with a catalyst feeding mechanism 102, the part of the side wall close to the bottom is provided with a raw material feeding mechanism 3, and the bottom is provided with a gas feeding mechanism 101; the reactor 1 is provided with a heat exchanger.
As shown in fig. 4 and 5, the gas distributor 4 includes: an intake pipe 401; one end of the air inlet pipe 401 is communicated with the air feeding mechanism 101, and the other end of the air inlet pipe is respectively communicated with each annular pipe in the annular pipe group through an air primary distribution pipe 403; and the bottom of the annular pipe is provided with an air injection pipe 407.
The rectifying device 5, the catalyst feeding mechanism 102, the raw material feeding mechanism 3 and the gas feeding mechanism 101 are all communicated with the cavity inside the reactor 1; wherein, the part of the raw material feeding mechanism 3 located inside the reactor 1 is communicated with the liquid distributor 8, and the part of the gas feeding mechanism 101 located inside the reactor 1 is communicated with the gas distributor 4.
The rectifying device 5 is internally provided with a condensing section 501, and a gas phase discharging mechanism 502 communicated with an external collecting device is arranged at a preset temperature section. And a constant pressure valve (not shown in the figure) is arranged at the top of the rectifying device and controls the reaction pressure of the inner cavity of the reactor communicated with the rectifying device by controlling the air pressure in the rectifying device. Meanwhile, the gas pressure of the gas-phase component output outwards by the rectifying device can be controlled.
The reactor 1 is provided with a temperature and pressure measuring port 103.
The heat exchanger includes: an inner heat exchanger 2 and an outer heat exchanger 7.
The inner heat exchanger 2 includes: a first heat exchange tube array 201 disposed inside the inner cavity of the reactor 1; the medium inlet of the first heat exchange tube array 201 is communicated with a first heat medium supply device outside the reactor 1 through a first pipeline 202, and the medium outlet of the first heat exchange tube array 201 is communicated with a first medium recovery device outside the reactor 1 through a second pipeline 203;
the external heat exchanger 7 in fig. 3 employs the external heat exchanger 7 shown in fig. 2, and a part of the structure is not shown in fig. 3. The external heat exchanger 7 includes: a first circulation pipe 701 and a second circulation pipe 702 communicating with the inner cavity of the reactor 1; the portions of the first circulation pipe 701 and the second circulation pipe 702 located outside the reactor 1 are communicated through a third circulation pipe 703; an external heat exchanger 706 and an external circulating pump 704 are arranged on the third circulating pipe 703; after entering the third circulation pipe 703 from the first circulation pipe 701, the circulation medium 705 is heated at the external heat exchanger 706 and then blown into the internal cavity of the reactor 1 through the second circulation pipe 702 by the external circulation pump 704; in the internal cavity of the reactor 1, a degassing baffle is arranged at the outlet of the second circulation pipe 702.
As shown in examples 1 to 3, when the apparatus for producing tetrahydrofuran by cyclization of 1, 4-butanediol of the present invention is used, the raw material BDO is first fed into the internal cavity of the reactor 1 from the raw material feeding mechanism 3 through the liquid distributor 8, and the raw material BDO is made to form a rotational flow in the internal cavity of the reactor 1 by the liquid distributor 8. The catalyst is added into the inner cavity of the reactor 1 from the catalyst feeding mechanism 102 and is mixed with the BDO raw material in a rotational flow mode. Then, the mixed gas of THF and water is fed from the gas feed mechanism 101 through the gas distributor 4 into the internal cavity of the reactor 1, and the gas flow direction is toward the catalyst accumulation-prone region, such as the bottom of the internal cavity of the reactor 1. Under the stirring action of the gas flow, the catalyst and the raw material BDO can be further promoted to be fully mixed, on the one hand, the raw material BDO can be promoted to be cyclized to THF more quickly, and thus the reaction space velocity is increased. On the other hand, continuous mechanical stirring is not needed, so that dynamic sealing treatment is not needed at the stirring shaft, the equipment investment is reduced, and the maintenance frequency of the equipment is reduced. On the other hand, the catalytic activity of the catalyst is fully utilized, and the yield is improved.
Specifically, a mixed gas of THF and water from the gas feed mechanism 101 is introduced into each of the annular tubes of the annular tube group through the gas inlet pipe 401 by the gas primary distribution pipe 403, and is ejected from the gas ejection pipe 407 of the annular tube. The ejected gas flow can disturb the liquid phase part in the reactor 1 from different directions and different positions, so that the material and the catalyst are pushed by the gas flow to be disturbed and mixed continuously, and meanwhile, the continuous gas flow can ensure that the catalyst is not accumulated at a fixed position and is continuously and fully mixed with the liquid phase part in the reactor 1. On one hand, the suspension of the catalyst is realized, the contact probability of the catalyst and the liquid phase reaction raw material BDO is increased, and on the other hand, the problems of catalyst breakage and stirring shaft sealing caused by mechanical stirring are avoided. Meanwhile, the invention realizes that the catalyst is suspended in the whole liquid phase space of the reactor, not only realizes the utilization of the traditional reaction space, but also realizes the conversion of the end enclosure space at the bottom of the reactor into the reaction space by fully stirring and mixing the reactant at the bottom of the reactor and the catalyst, so the volume ratio of the reaction space to the reactor is far higher than that of other prior art. The amount of conversion per unit reactor space is therefore also higher than in other prior art. The significance of this advantage increases significantly, in particular, with increasing reactor diameter.
The THF and water formed in the reaction then leave the liquid-phase space of the reactor 1 in the gas phase under the reaction conditions and are passed together with unreacted BDO into the rectification apparatus 5 in the upper part of the reactor. The gas-liquid two phases transfer heat and mass on the surface of the condensation section 501, re-condense BDO evaporated and entrained in the reactor 106, and flow back to the liquid phase space of the reactor 106 for further reaction. The gas phase product of THF and water exits the reactor from gas phase take-off 502 to a downstream separation device. After a part of the THF and water separated by the downstream separation device is split, they are fed from the gas feed mechanism 101 through the gas distributor 4 into the internal cavity of the reactor 1.
At this time, the BDO reaction temperature is controlled to be 100-130 ℃, the reaction pressure is controlled to be 0.25-0.4 MPaG, and the THF temperature flowing out of the reaction device is controlled to be more than 66 ℃.
The condensation section 501 can be a condensation sheet, a filler and the like according to requirements. The condensation section at the top of the reactor can realize that BDO entrained in a gas phase and gasified BDO are condensed and flow back to the reaction space of the reactor, thereby increasing the overall conversion rate of the BDO.
The present invention may select either the inner heat exchanger 2 or the outer heat exchanger 7 or a combination of both, as desired. The heating mode of the internal heat exchanger 2 is as follows: the first heat medium supplying device is a circulation pump device having a heating function. The first heat medium supplying device heats a medium, which is a medium for general heating, such as steam, heat transfer oil, and the like. Then, the heat medium heated to the target temperature is blown into the first heat exchange tube array 201 through the first pipe 202, and the first heat exchange tube array 201 completes heat exchange with the liquid phase part inside the reactor 1, thereby heating the liquid phase part inside the reactor 1. The medium which completes heat exchange in the first heat exchange tube array 201 flows from the second tube 203 to the first medium recovery device, which may be a liquid storage tank or other device with certain medium storage capacity. And the first medium recovery means communicates with the inlet end of the first heat medium supplying means to supply the first heat medium supplying means with the circulating medium.
The heating mode of the external heat exchanger 7 of the invention is as follows: the external circulation pump 704 draws out a liquid phase portion inside the reactor 1 from the first circulation pipe 701, and after the third circulation pipe 703 is heated to a target temperature by the external heat exchanger 706, it is sent to the inside of the reactor 1 through the second circulation pipe 702. Wherein, the setting of degasification baffle can prevent the liquid containing bubbles from entering the circulating medium pump.
The heat exchanger can provide necessary heat energy for reaction and evaporation for the liquid phase part in the reactor 1, and has good heat supply effect, controllable temperature intensity of the reaction environment and stable temperature control, thereby effectively improving the utilization rate of equipment and stabilizing the yield.
In addition, the invention adopts a common kettle type reactor, and the reaction zone does not need to be divided into a high-temperature reaction zone and a low-temperature reaction zone. And the heat insulation problem of the middle baffle plate in the high-temperature area and the low-temperature area is also avoided.
Example 4
An apparatus for the cyclization of 1, 4-butanediol to tetrahydrofuran in accordance with any of examples 1-3, wherein the annular tube set is divided into an inner annular tube region 405 and an outer annular tube region 406; the average spacing between adjacent tubes of the inner annular tube set 402 in the inner annular tube region 405 is L1, and the average spacing between adjacent tubes of the outer annular tube set 404 in the outer annular tube region 406 is L2; wherein L2 > L1.
The average distance between the gas injection pipes 407 arranged on the annular pipes of the inner annular pipe group 402 is M1, and the average distance between the gas injection pipes 407 arranged on the annular pipes of the outer annular pipe group 404 is M2; wherein M2 > M1.
Because the liquid is easy to form a vortex in the middle part during the rotational flow, solid-phase materials such as a catalyst are accumulated in the middle part, and the annular pipe group and the air injection pipe 407 are arranged at intervals, on one hand, more jet flow disturbance can be performed on mixed gas of THF and water in the middle part, so that the problem that the catalyst gathers to the center of a rotational flow liquid phase is effectively avoided, and the catalyst can be more uniformly distributed in a liquid phase component. On the other hand, the catalyst is fully suspended and uniformly dispersed in reactants, so that the operation stability of the reactor can be enhanced, the mechanical wear rate of catalyst particles is reduced, and the service life of the catalyst is prolonged.
Example 5
Based on the device for preparing tetrahydrofuran by cyclization of 1, 4-butanediol described in example 4, the distance between adjacent tubes of the inner annular tube group in the inner annular tube area is L1-n, and n is a positive integer. Wherein L1-1 is the pipe spacing between the two innermost inner annular pipes, L1-2 is the pipe spacing between the second inner annular pipe and the third inner annular pipe from the inner side, L1-m is the pipe spacing between the two outermost inner annular pipes, and the L1-L1-m satisfies the increasing change relationship.
For example, K1-1= (L1-2) - (L1-1), K1-2= (L1-3) - (L1-2).. K1-s = (L1-m) - (L1-m-1) is satisfied between L1-1 and L1-m, where K1-1, K1-2.. K1-s is greater than 0.
And the distance between adjacent pipes of the outer annular pipe group in the outer annular pipe area is L2-q, and q is a positive integer. Wherein L2-1 is the pipe spacing between the two innermost outer annular pipes, L2-2 is the pipe spacing between the second outer annular pipe and the third outer annular pipe from the inner side, L2-w is the pipe spacing between the two outermost outer annular pipes, and L2-1 to L2-w satisfy the increasing change relationship.
For example, between L2-1 and L2-w, K2-1= (L2-2) - (L2-1), K2-2= (L2-3) - (L2-2).. K2-d = (L2-w) - (L2-w-1), wherein K2-1, K2-2.. K2-d is greater than 0.
Example 6
Based on the device for preparing tetrahydrofuran by cyclization of 1, 4-butanediol as described in example 4, the distances between adjacent tubes of the inner annular tube group 402 in the inner annular tube region 405 are all L1, and the distances between adjacent tubes of the outer annular tube group 404 in the outer annular tube region 406 are all L2; wherein L2 > L1.
The main difference between example 5 and example 6 is that the spacing between adjacent tubes of example 5 is gradually varied, whereas the spacing between adjacent tubes of example 6 is constant. Compared with the prior art, the embodiment 5 and the embodiment 6 can both obviously increase the contact probability of BDO and the catalyst, effectively improve the reaction space velocity and effectively realize the suspension and uniform dispersion of the catalyst. Wherein, the catalytic efficiency of the catalyst represents the contact probability of BDO and the catalyst, the wear rate of the catalyst represents the suspension and uniform dispersion degree of the catalyst, and the suspension and dispersion of the catalyst and the improvement effect of the contact probability of BDO and the catalyst are stronger in example 5 than in example 6.
Example 7
Based on the device for preparing tetrahydrofuran by cyclization of 1, 4-butanediol described in example 4, the distances between the gas injection pipes arranged on each annular pipe of the inner annular pipe group are M1-e, and e is a positive integer. Wherein M1-1 is the average distance between adjacent gas nozzles on the innermost inner annular tube, M1-2 is the average distance between adjacent gas nozzles on the second inner annular tube from the inner side, M1-3 is the average distance between adjacent gas nozzles on the third inner annular tube from the inner side.
For example, G1-1= (M1-2) - (M1-1), G1-2= (M1-3) - (M1-2) ·.
The distance between the gas injection pipes arranged on the annular pipe of the outer annular pipe group is M2-r, and r is a positive integer. Wherein M2-1 is the average distance between adjacent gas injection pipes on the innermost outer ring pipe, M2-2 is the average distance between adjacent gas injection pipes on the second outer ring pipe from the inner side, M2-3 is the average distance between adjacent gas injection pipes on the third outer ring pipe from the inner side.
For example, G2-1= (M2-2) - (M2-1), G2-2= (M2-3) - (M2-2) · G2-t = (M2-v) - (M2-v-1) is satisfied between M2-1 and M2-v, where G2-1, G2-2.. G2-t is greater than 0.
Example 8
Based on the apparatus for preparing tetrahydrofuran by cyclization of 1, 4-butanediol described in embodiment 4, the distances between the gas injection pipes 407 arranged on the annular pipes of the inner annular pipe group 402 are M1, and the distances between the gas injection pipes 407 arranged on the annular pipes of the outer annular pipe group 404 are M2; wherein M2 > M1.
The main difference between example 7 and example 8 is that the gas lance spacing provided on the ring tube of example 7 is varied gradually, whereas the gas lance spacing provided on the ring tube of example 8 is constant. Compared with the prior art, the embodiment 7 and the embodiment 8 can obviously increase the contact probability of BDO and the catalyst, effectively improve the reaction space velocity and effectively realize the suspension and uniform dispersion of the catalyst. Wherein, the catalytic efficiency of the catalyst represents the contact probability of BDO and the catalyst, the wear rate of the catalyst represents the suspension and uniform dispersion degree of the catalyst, and the suspension and dispersion of the catalyst and the improvement effect of the contact probability of BDO and the catalyst are stronger in example 7 than in example 8.
The effects of examples 5 and 7 are superior to those of examples 6 and 8, and the possible reasons for this are: for the fluid which rotates directionally, the central part of the fluid is easy to silt, namely a large amount of catalyst particles can gather to the central part of the fluid, the situation that the catalyst gathers to the center can be effectively broken through arranging the dense gas injection pipe 407 array in the center of the fluid, and meanwhile, compared with the fixed pipe spacing and the gas injection pipe 407 spacing, the gradually increased pipe spacing and the gas injection pipe 407 spacing can better match the flow change of different areas of the fluid, so that the catalyst forms a suspension or suspension-like state in different flow areas, the contact area of the catalyst and a reactant (fluid BDO) is increased, the catalytic efficiency is increased, the possibility of mutual collision between the catalysts is reduced, the mechanical wear rate of the catalyst is reduced, and the service life of the catalyst is prolonged.
Example 9
In an apparatus for producing tetrahydrofuran by cyclization of 1, 4-butanediol according to any one of embodiments 1 to 3, as shown in fig. 6, the liquid distributor 8 includes: a liquid inlet pipe 801; one end of the liquid inlet pipe 801 is communicated with the raw material feeding mechanism 3, and the other end of the liquid inlet pipe is communicated with the liquid uniform distribution pipe 802; the liquid distribution pipe 802 is provided with a plurality of liquid injection pipes 803.
The liquid distribution pipe 802 is an annular structure, and the plurality of liquid injection pipes 803 are parallel to each other and arranged along the same direction, and form an included angle of 20-60 degrees with the radius of the liquid distribution pipe 802.
At this time, the BDO raw material enters the liquid distribution pipe 802 through the liquid inlet pipe 801 and enters the inner cavity of the reactor 1 through the liquid injection pipe 803. Because the liquid distribution pipe 802 is of an annular structure, and the plurality of liquid injection pipes 803 are parallel to each other and arranged along the same direction, and form an included angle of 20-60 degrees with the radius of the liquid distribution pipe 802, the raw material BDO entering the cavity inside the reactor 1 can flow in from a plurality of positions at a certain speed and direction, so that the liquid phase part inside the reactor 1 is promoted to form liquid rotational flow, and the liquid phase component can be disturbed by matching with the gas distributor 4, so that the catalyst is fully and uniformly dispersed in the raw material BDO, and the generated gas phase THF and water vapor can be quickly evaporated and leave the liquid phase part, so that the raw material BDO is promoted to continuously react, and the conversion rate of the raw material BDO can be increased to more than 90 percent.
Example 10
Based on the device for preparing tetrahydrofuran by cyclizing 1, 4-butanediol as described in any one of examples 1-3, as shown in FIG. 2, a cooler 6 is arranged in the rectifying device 5; the cooler 6 includes: a second heat exchange tube array 601 located inside the rectifying device 5; the medium inlet of the second heat exchange tube array 601 is communicated with a second medium supply device outside the rectifying device 5 through a third pipeline 602, and the medium outlet of the second heat exchange tube array 601 is communicated with a second medium recovery device outside the rectifying device 5 through a fourth pipeline 603.
At this time, the low-temperature medium is blown into the second heat exchange tube array 601 from the second medium supply device through the third pipe 602, and sufficiently exchanges heat with the THF, water, BDO mixed gas flowing through, and the temperature of the THF, water, BDO mixed gas is reduced, so that BDO is condensed again and flows back to the inner cavity of the reactor 1. The low-temperature medium after heat exchange flows into a second medium recovery device from the fourth pipeline 603, for example, a liquid storage tank or other devices having a storage function and a standing and cooling function, such as a standing and settling tank. The second medium recovery device is communicated with the second medium supply device and supplies the circulating low-temperature medium to the second medium supply device. The low temperature medium may be room temperature water as required. The second medium supplying device may be a circulation pump.
The arrangement can further promote the condensation and reflux of BDO entrained in the mixed gas of THF, water and BDO and gasified BDO to the reaction space of the reactor, and increase the overall conversion rate of BDO.
Example 11
Based on the device for preparing tetrahydrofuran by cyclizing 1, 4-butanediol as described in any one of examples 1-3, as shown in FIG. 1, a mixture of THF and water at 40-90 deg.C is introduced into the inner cavity of the reactor 1 from the top of the rectifying device 5, so that the condensation of BDO is more sufficient. At this time, a mixture feeding mechanism 503 is installed at the top of the rectifying apparatus 5.
In the description herein, reference to the description of the terms "one embodiment/mode," "some embodiments/modes," "example," "specific example," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment/mode or example is included in at least one embodiment/mode or example of the application. In this specification, the schematic representations of the terms used above are not necessarily intended to be the same embodiment/mode or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments/modes or examples. Furthermore, the various embodiments/aspects or examples and features of the various embodiments/aspects or examples described in this specification can be combined and combined by one skilled in the art without conflicting therewith.
It will be understood by those skilled in the art that the foregoing embodiments are merely for clarity of illustration of the disclosure and are not intended to limit the scope of the disclosure. Other variations or modifications may be made to those skilled in the art, based on the above disclosure, and still be within the scope of the present disclosure.
Claims (10)
1. A device for preparing tetrahydrofuran through cyclization of 1, 4-butanediol is characterized by comprising: a hollow reactor (1); the top of the reactor (1) is communicated with a rectifying device (5), the top or the side wall is provided with a catalyst feeding mechanism (102), the part of the side wall close to the bottom is provided with a raw material feeding mechanism (3), and the bottom is provided with a gas feeding mechanism (101); the reactor (1) is provided with a heat exchanger; the heat exchanger includes: at least one of an inner heat exchanger (2) and an outer heat exchanger (7);
the rectifying device (5), the catalyst feeding mechanism (102), the raw material feeding mechanism (3) and the gas feeding mechanism (101) are communicated with the inner cavity of the reactor (1); wherein, the part of the raw material feeding mechanism (3) positioned in the reactor (1) is communicated with the liquid distributor (8), and the part of the gas feeding mechanism (101) positioned in the reactor (1) is communicated with the gas distributor (4);
the gas distributor (4) comprises: an intake pipe (401); one end of the air inlet pipe (401) is communicated with the air feeding mechanism (101), and the other end of the air inlet pipe is respectively communicated with each annular pipe in the annular pipe group through an air primary distribution pipe (403); and the bottom of the annular pipe is provided with an air injection pipe (407).
2. An apparatus for preparing tetrahydrofuran by cyclization of 1, 4-butanediol according to claim 1, wherein said rectifying apparatus (5) is provided with a condensing section (501) therein, and a gas phase discharging mechanism (502) connected to an external collecting apparatus is provided at a predetermined temperature section.
3. An apparatus for the cyclization of 1, 4-butanediol to tetrahydrofuran according to claim 1 wherein said annular tube set is divided into an inner annular tube region (405) and an outer annular tube region (406); the average spacing of adjacent tubes of the inner annular tube set (402) within the inner annular tube region (405) is L1 and the average spacing of adjacent tubes of the outer annular tube set (404) within the outer annular tube region (406) is L2; wherein L2 > L1.
4. The apparatus for preparing tetrahydrofuran by cyclization of 1, 4-butanediol according to claim 3, wherein the distance between adjacent tubes of the inner annular tube group in the inner annular tube region is L1-n, and n is a positive integer; wherein L1-1 is the pipe spacing between two innermost inner annular pipes, L1-2 is the pipe spacing between a second inner annular pipe and a third inner annular pipe from the inner side, L1-m is the pipe spacing between two outermost inner annular pipes, and L1-1 to L1-m satisfy the increasing change relationship;
the distance between adjacent pipes of the outer annular pipe group in the outer annular pipe area is L2-q, and q is a positive integer; wherein L2-1 is the pipe spacing between the two innermost outer annular pipes, L2-2 is the pipe spacing between the second outer annular pipe and the third outer annular pipe from the inner side, L2-w is the pipe spacing between the two outermost outer annular pipes, and L2-1 to L2-w satisfy the increasing change relationship.
5. An apparatus for producing tetrahydrofuran by cyclization of 1, 4-butanediol according to claim 3, wherein the average pitch of the gas injection pipes (407) arranged on the annular pipes of the inner annular pipe group (402) is M1, and the average pitch of the gas injection pipes (407) arranged on the annular pipes of the outer annular pipe group (404) is M2; wherein M2 > M1.
6. The device for preparing tetrahydrofuran by cyclization of 1, 4-butanediol according to claim 5, wherein the distance between the gas injection pipes arranged on each annular pipe of the inner annular pipe group is M1-e, and e is a positive integer; wherein M1-1 is the average distance between adjacent gas nozzles on the innermost inner annular tube, M1-2 is the average distance between adjacent gas nozzles on the second inner annular tube from the inner side, M1-3 is the average distance between adjacent gas nozzles on the third inner annular tube from the inner side, M1-v is the average distance between adjacent gas nozzles on the outermost inner annular tube, and the M1-1 to M1-v satisfy the increasing change relationship;
the distance between the gas injection pipes arranged on the annular pipes of the outer annular pipe group is M2-r, and r is a positive integer; wherein M2-1 is the average distance between adjacent gas injection pipes on the innermost outer ring pipe, M2-2 is the average distance between adjacent gas injection pipes on the second outer ring pipe from the inner side, M2-3 is the average distance between adjacent gas injection pipes on the third outer ring pipe from the inner side.
7. Device for the cyclisation of 1, 4-butanediol to tetrahydrofuran according to claim 1, characterized in that said internal heat exchanger (2) comprises: a first heat exchange tube array (201) arranged inside the inner cavity of the reactor (1); the medium inlet of the first heat exchange tube array (201) is communicated with a first heat medium supply device outside the reactor (1) through a first pipeline (202), and the medium outlet of the first heat exchange tube array (201) is communicated with a first medium recovery device outside the reactor (1) through a second pipeline (203);
the external heat exchanger (7) comprises: a first circulation pipe (701) and a second circulation pipe (702) communicating with the internal cavity of the reactor (1); the first circulating pipe (701) and the second circulating pipe (702) are communicated with each other through a third circulating pipe (703) at the part outside the reactor (1); an external heat exchanger (706) and an external circulating pump (704) are arranged on the third circulating pipe (703); after entering the third circulating pipe (703) from the first circulating pipe (701), the circulating medium (705) is heated at the external heat exchanger (706) and then is blown into the inner cavity of the reactor (1) by the external circulating pump (704) through the second circulating pipe (702); a degassing baffle is arranged in the inner cavity of the reactor (1) at the outlet of the second circulating pipe (702).
8. An apparatus for preparing tetrahydrofuran by cyclization of 1, 4-butanediol according to claim 1, wherein the rectifying apparatus (5) is internally provided with a cooler (6); the cooler (6) comprises: a second heat exchange tube array (601) positioned inside the rectifying device (5); and a medium inlet of the second heat exchange tube array (601) is communicated with a second medium supply device outside the rectifying device (5) through a third pipeline (602), and a medium outlet of the second heat exchange tube array (601) is communicated with a second medium recovery device outside the rectifying device (5) through a fourth pipeline (603).
9. A process for producing tetrahydrofuran by cyclization of 1, 4-butanediol, characterized by using an apparatus for producing tetrahydrofuran by cyclization of 1, 4-butanediol according to any one of claims 1 to 8 as a reaction apparatus, and controlling the reaction temperature of 1, 4-butanediol to 100 ℃ to 130 ℃, the reaction pressure to 0.25MPaG to 0.4MPaG, and the THF temperature discharged from the reaction apparatus to > 66 ℃.
10. The method for preparing tetrahydrofuran by cyclization of 1, 4-butanediol according to claim 9, wherein the mixture of tetrahydrofuran and water with the temperature of 40-90 ℃ is introduced into the inner cavity of the reactor (1) from the top of the rectifying device.
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