CN111013501B - Slurry bed continuous hydrogenation reaction device and method - Google Patents
Slurry bed continuous hydrogenation reaction device and method Download PDFInfo
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- CN111013501B CN111013501B CN201911026339.8A CN201911026339A CN111013501B CN 111013501 B CN111013501 B CN 111013501B CN 201911026339 A CN201911026339 A CN 201911026339A CN 111013501 B CN111013501 B CN 111013501B
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- 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
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/20—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium
- B01J8/22—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid
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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
- B01J8/005—Separating solid material from the gas/liquid stream
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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
- B01J8/005—Separating solid material from the gas/liquid stream
- B01J8/006—Separating solid material from the gas/liquid stream by filtration
Abstract
The invention belongs to the technical field of chemical industry, and relates to a slurry bed continuous hydrogenation reaction device and a method thereof. The device and the method provided by the invention can realize continuous operation of gas-liquid-solid three-phase reaction and separation; the solid catalyst particles can be uniformly distributed in the tubular reactor; the segmented temperature control of the reaction can be realized, and the probability of side reaction caused by high temperature is greatly reduced; the sectional supplement of gas can be realized, and the full reaction of gas phase can be realized.
Description
Technical Field
The invention belongs to the technical field of chemical processes and equipment, and relates to a slurry bed continuous hydrogenation reaction device and a method.
Background
The hydrogenation reaction is an important chemical reaction, and the products of the hydrogenation reaction have various types and wide application. The reaction generally adopts liquid raw materials to react with hydrogen, and uses metal particles as catalysts, so the mass transfer problem of gas, liquid and solid phases in a reaction system is the key point of the reaction. The industrial stirring kettle type intermittent hydrogenation process is usually adopted, the reaction temperature is 100-180 ℃, the pressure is high, when catalyst particles are small, the catalyst cannot be uniformly distributed in a reactor depending on stirring, the mass transfer effect of gas, liquid and solid phases is poor, the reaction time is long, and side reactions often occur; after the reaction is finished, the reaction liquid and the solid catalyst need to be separated, and the operation is complex. The hydrogenation reaction device of the magnetic stabilization bed reported at present depends on the external magnetic force of the reactor to uniformly distribute magnetic catalyst particles in the reactor, so that gas, liquid and solid phases are in good contact with each other, and continuous operation is realized. The reaction device often needs to dissolve hydrogen in raw material liquid firstly, then the hydrogen is fed into the reactor to react under the action of the catalyst, the hydrogen dissolving link is added, the flowing of the gas is prevented from interfering the distribution of the catalyst, the gas-liquid flow rate is limited greatly, and the cost is higher due to the arrangement of a high-power electromagnetic coil.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a slurry bed continuous hydrogenation reaction device and a slurry bed continuous hydrogenation reaction method. The system and the method can realize continuous operation of hydrogenation reaction and separation; the probability of side reactions occurring is reduced.
The invention adopts the following technical scheme:
a slurry bed continuous hydrogenation reaction device comprises a low-pressure hydrogen storage tank, a hydrogen compressor, a high-pressure hydrogen storage tank, a catalyst feeding tank A, a catalyst feeding tank B, a raw material liquid storage tank, a raw material liquid pressure pump, a raw material liquid preheater, a gas preheater, a reactor group, a gas-liquid separator, a membrane separator, a catalyst recovery and replenishing tank and a catalyst feeding pump;
the side surface of the low-pressure hydrogen storage tank is connected with a hydrogen pipeline, and an outlet pipe of the low-pressure hydrogen storage tank at the top is connected with an inlet of the hydrogen compressor; the outlet of the hydrogen compressor is connected with a high-pressure hydrogen storage tank inlet pipe at the top of the high-pressure hydrogen storage tank; an outlet pipe of the high-pressure hydrogen storage tank at the top of the high-pressure hydrogen storage tank is connected with hydrogen inlet pipes of catalyst feeding tanks at the tops of the catalyst feeding tank A and the catalyst feeding tank B; an outlet pipe of the high-pressure hydrogen storage tank at the top of the high-pressure hydrogen storage tank is connected with an inlet of the gas preheater through a hydrogen inlet pipe of the reactor; the outlet of the gas preheater is connected with a hydrogen inlet pipe; the hydrogen pressure relief pipes of the catalyst feeding tanks at the tops of the catalyst feeding tank A and the catalyst feeding tank B are connected with a hydrogen pipeline on the side surface of the low-pressure hydrogen storage tank; outlets at the bottoms of the catalyst feeding tank A and the catalyst feeding tank B are connected with a raw material slurry inlet pipe through a catalyst slurry feeding pipe;
the side surface of the raw material liquid storage tank is connected with a raw material liquid feeding pipe, and an outlet at the bottom of the raw material liquid storage tank is connected with an inlet of a raw material liquid pressurizing pump through a raw material liquid storage tank discharging pipe; the outlet of the raw material liquid booster pump is connected with the inlet of the raw material liquid preheater, and the outlet of the raw material liquid preheater is connected with the bottom of the first tubular reactor in the reactor group through a raw material slurry inlet pipe; the outlet of the last tubular reactor of the reactor group is connected with the side surface of the gas-liquid separator through a gas-liquid-solid reaction material outlet pipe; the top outlet of the gas-liquid separator is connected with a hydrogen pipeline on the side surface of the low-pressure hydrogen storage tank through an unreacted hydrogen return pipe, and the bottom outlet of the gas-liquid separator is connected with the lower inlet on the side surface of the membrane separator through a reaction slurry pipe; the outlet at the top of the membrane separator is connected with a reaction liquid delivery pipe, and the outlet at the bottom of the membrane separator is connected with the top of the catalyst recovery and replenishment tank through a catalyst thick slurry pipe;
the top of the catalyst recovery and replenishment tank is connected with a fresh catalyst slurry feeding pipe, and the bottom outlet of the catalyst recovery and replenishment tank is connected with the inlet of a catalyst feeding pump through an inlet pipe of the catalyst feeding pump; the outlet of the catalyst feeding pump is connected with the feed inlets at the top of the catalyst feeding tank A and the catalyst feeding tank B through a catalyst slurry return pipe;
the reactor group consists of a plurality of tubular reactors, and each tubular reactor consists of a reaction tube, a heat exchange jacket, an inner member and a solid-liquid separator; the heat exchange jacket is welded outside the reaction tube, and the upper part and the lower part of the side surface of the heat exchange jacket are respectively provided with a heat exchange medium inlet tube and a heat exchange medium outlet tube; an inner member is arranged in the reaction tube; an outlet at the upper end of the top of the reaction tube is connected with a gas-phase inlet of the solid-liquid separator through a gas-phase tube, and an outlet at the side surface of the top of the reaction tube is connected with a slurry inlet of the solid-liquid separator through a liquid-phase tube; the lower part of the side surface of the solid-liquid separator is connected with a gas-liquid-solid slurry inlet pipe of the next tubular reactor through a gas-liquid material outlet pipe; a catalyst slurry outlet pipe at the bottom of the solid-liquid separator is connected with a catalyst slurry inlet pipe on the side surface of the reaction pipe through a catalyst return pipe; the bottom of the reaction tube is provided with a hydrogen inlet tube;
the solid-liquid separator consists of an inner cylinder, an outer cylinder, a settling bell jar and an electromagnetic coil; the sedimentation bell jar is arranged in the inner cylinder and is connected with a slurry inlet at the top of the outer cylinder through a pipeline; the top of the outer cylinder is provided with a gas phase inlet, and the side surface of the bottom of the outer cylinder is provided with a gas-liquid material outlet pipe; the bottom of the inner cylinder is provided with a catalyst slurry outlet pipe; the electromagnetic coil is positioned outside the outer cylinder;
the inner member is in the form of a sieve plate, a tower or a ridge;
the membrane separator is a tubular membrane filter.
Preferably, the outer diameter of the inner cylinder is 0.4-1.0 m, and the height is 1.0-2.0 m; the ratio of the outer diameter of the settling bell jar to the inner diameter of the inner cylinder is 0.4-0.8, the ratio of the height of the settling bell jar to the height of the inner cylinder is 0.5-0.8, and the distance between the bottom edge of the settling bell jar and the upper edge of the conical part of the inner cylinder is 0.2-0.5 m; the distance between the top surface of the outer cylinder and the top edge of the inner cylinder is 0.2-0.4 m.
Preferably, the distance between the catalyst slurry inlet pipe and the bottom of the reaction pipe is 0.5-3.0 m; the ratio of the inner diameter of the heat exchange jacket to the inner diameter of the reaction tube is 1.2-2.0; the inner diameter of the reaction tube is 100 mm-800 mm, and the height is 3.0 m-20.0 m.
A slurry bed continuous hydrogenation reaction method using the device comprises the following process steps:
a. starting a catalyst feeding pump to add the catalyst in the catalyst recovery and replenishing tank into a catalyst feeding tank A and a catalyst feeding tank B, simultaneously starting a raw material liquid pressure pump, preheating the raw material liquid by a raw material liquid preheater, mixing the raw material liquid with the catalyst from the catalyst feeding tank A and the catalyst feeding tank B, and then feeding the mixture into a tubular reactor in a reactor group from the bottom through a raw material slurry inlet pipe; heating the tubular reactor to a set temperature of 80-200 ℃;
the preheating temperature of the raw material liquid is 30-100 ℃;
b. opening a hydrogen pipeline valve, enabling hydrogen to enter a low-pressure hydrogen storage tank, starting a hydrogen compressor, pressurizing the low-pressure hydrogen and then conveying the pressurized low-pressure hydrogen to the high-pressure hydrogen storage tank, enabling one part of the high-pressure hydrogen to enter a catalyst feeding tank A and a catalyst feeding tank B through a hydrogen inlet pipe of a catalyst feeding tank to maintain the pressure of the catalyst feeding tank, and enabling the other part of the high-pressure hydrogen to enter a tubular reactor through a hydrogen inlet pipe of the reactor after being preheated by a gas preheater;
c. the raw material liquid, the catalyst slurry and the hydrogen are fully contacted in the tubular reactor, unreacted hydrogen enters the solid-liquid separator through a gas-phase inlet through a gas-phase pipe at the top of the tubular reactor, and the reaction liquid and the solid catalyst slurry enter the solid-liquid separator through a slurry inlet through a liquid-phase pipe at the top of the reactor; part of the catalyst is separated and then returns to the tubular reactor through a catalyst slurry feeding hole by a catalyst return pipe, and part of the catalyst enters the next tubular reactor along with reaction liquid and hydrogen through a gas-liquid discharging hole and a gas-liquid-solid slurry inlet pipe to realize continuous operation; reaction slurry enters a gas-liquid separator from the last tubular reactor in the reactor group through a gas-liquid-solid reaction material outlet pipe;
d. the gas phase enters a low-pressure hydrogen storage tank for recycling through a hydrogen pipeline from an unreacted hydrogen return pipe, the reaction liquid and the catalyst slurry enter a membrane separator through a reaction slurry pipe, the separated liquid-phase product is sent out of a pipe through the reaction liquid, and the separated catalyst thick slurry enters a catalyst recovery and replenishing tank through a catalyst thick slurry pipe for recycling.
Preferably, the pressure of the low-pressure hydrogen storage tank in the step b is 1-3 MPa, the pressure of the high-pressure hydrogen storage tank is 6-15 MPa, and the preheating temperature of hydrogen is 30-100 ℃.
Preferably, the molar ratio of the raw material liquid to the hydrogen in the step c is 0.5-2.0: 1; the catalyst is magnetic particles or nonmagnetic particles, and the mass concentration is 5-40%.
Preferably, the pressure in the tubular reactor in the step c is 5-15 Mpa, and the temperature is 80-200 ℃.
Preferably, the residence time of the gas phase, the liquid phase and the solid phase in the reactor group in the step c is 10-500 min.
Preferably, the solid-liquid separator in step c is externally provided with an electromagnetic coil, the electromagnetic coil can fix magnetic catalyst particles in slurry from the slurry inlet on the inner cylinder of the solid-liquid separator after being opened, so that the catalyst particles are separated from liquid, and the catalyst particles enter the reactor through the catalyst slurry outlet pipe and the catalyst return pipe after the electromagnetic coil is closed; when catalyst particles in the slurry from the slurry inlet are not magnetic, the flow rate of the slurry entering the sedimentation bell jar from the slurry inlet is reduced, the catalyst particles in the slurry are continuously sedimentated, the liquid overflows into the outer cylinder from the upper edge of the inner wall of the inner cylinder, is mixed with the gas from the gas phase inlet, and then enters the next tubular reactor through the gas-liquid-solid slurry inlet pipe through the gas-liquid material outlet pipe.
Preferably, unreacted hydrogen and slurry after the raw material liquid, the catalyst slurry and the hydrogen react in the tubular reactor in the step c can directly enter the next tubular reactor through a gas-liquid-solid slurry inlet pipe.
Compared with the prior art, the invention has the following remarkable advantages:
1. the tubular reactor is adopted to replace a kettle type reactor, so that the continuous operation of hydrogenation reaction and separation is realized.
2. The solid catalyst is uniformly distributed in the tubular reactor, the gas-liquid-solid three-phase contact is good, the reaction is sufficient, and the reaction pressure can be reduced.
3. The reactor group consists of a plurality of tubular reactors, can realize the sectional temperature control of the reaction, greatly reduces the probability of side reaction caused by high temperature, and improves the product quality.
4. The solid-liquid separator adopted by the invention is externally provided with the electromagnetic coil, and the catalyst particles with magnetism can be fixed on the inner cylinder of the separator by magnetic force, so that the catalyst and the reaction liquid can be well separated.
5. The production efficiency is improved, the equipment investment is reduced, and the cost is reduced.
Drawings
FIG. 1 is a schematic diagram of a slurry-bed continuous hydrogenation reactor.
In the figure: 1. a low pressure hydrogen storage tank; 2. a hydrogen compressor; 3. a high pressure hydrogen storage tank; 4. a catalyst feeding tank A; 5. a catalyst feeding tank B; 6. a raw material liquid storage tank: 7. a raw material liquid pressure pump; 8. a raw material liquid preheater; 9. a gas preheater; 10. a reactor group; 11. a gas-liquid separator; 12. a membrane separator; 13. a catalyst recovery and replenishment tank; 14. a catalyst charge pump; 15. a hydrogen gas conduit; 16. a low pressure hydrogen storage tank outlet pipe; 17. an inlet pipe of a high-pressure hydrogen storage tank; 18. an outlet pipe of the high-pressure hydrogen storage tank; 19. a hydrogen inlet pipe of the catalyst feeding tank; 20. a reactor hydrogen inlet pipe; 21. a hydrogen pressure relief pipe of the catalyst feeding tank; 22. a catalyst slurry addition tube; 23. a raw material liquid feeding pipe; 24. a discharge pipe of the raw material liquid storage tank; 25. raw material slurry enters the pipe; 26. a gas-liquid-solid reaction material outlet pipe; 27. a reaction slurry pipe; 28. an unreacted hydrogen return pipe; 29. a reaction liquid outlet pipe; 30. a catalyst thick slurry pipe; 31. a fresh catalyst slurry addition tube; 32. an inlet pipe of a catalyst feeding pump; 33. a catalyst slurry return pipe; 34. a tubular reactor.
FIG. 2 is a schematic view of a tubular reactor.
In the figure: 34. a tubular reactor; 35. a gas-liquid-solid slurry inlet pipe; 36. a heat exchange jacket; 37. an inner member; 38. a heat exchange medium inlet pipe; 39. a reaction tube; 40. a gas phase pipe; 41. a liquid phase pipe; 42. a solid-liquid separator; 43. a gas-liquid material outlet pipe; 44. a catalyst return pipe; 45. a catalyst slurry inlet pipe; 46. a heat exchange medium outlet pipe; 47. a hydrogen inlet pipe.
FIG. 3 is a schematic view of a solid-liquid separator.
In the figure: 43. a gas-liquid material outlet pipe; 48. an inner barrel; 49. a settling bell jar; 50. an electromagnetic coil; 51. an outer cylinder; 52. a slurry inlet; 53. a gas phase inlet; 54. and a catalyst slurry outlet pipe.
Detailed Description
The following detailed description of the embodiments of the present invention refers to the accompanying drawings 1-3.
A slurry bed continuous hydrogenation reaction device comprises a low-pressure hydrogen storage tank 1, a hydrogen compressor 2, a high-pressure hydrogen storage tank 3, a catalyst feeding tank A4, a catalyst feeding tank B5, a raw material liquid storage tank 6, a raw material liquid pressure pump 7, a raw material liquid preheater 8, a gas preheater 9, a reactor group 10, a gas-liquid separator 11, a membrane separator 12, a catalyst recovery and replenishment tank 13 and a catalyst feeding pump 14;
the side surface of the low-pressure hydrogen storage tank 1 is connected with a hydrogen pipeline 15, and an outlet pipe 16 of the low-pressure hydrogen storage tank at the top is connected with an inlet of the hydrogen compressor 2; the outlet of the hydrogen compressor 2 is connected with a high-pressure hydrogen storage tank inlet pipe 17 at the top of the high-pressure hydrogen storage tank 3; an outlet pipe 18 of the high-pressure hydrogen storage tank at the top of the high-pressure hydrogen storage tank 3 is connected with a hydrogen inlet pipe 19 of the catalyst feeding tank A4 and the catalyst feeding tank at the top of the catalyst feeding tank B5; an outlet pipe 18 of the high-pressure hydrogen storage tank at the top of the high-pressure hydrogen storage tank 3 is connected with an inlet of the gas preheater 9 through a reactor hydrogen inlet pipe 20; the outlet of the gas preheater 9 is connected with a hydrogen inlet pipe 47; the hydrogen pressure relief pipes 21 of the catalyst feeding tanks A4 and B5 at the top of the catalyst feeding tank are connected with the hydrogen pipeline 15 at the side of the low-pressure hydrogen storage tank 1; the outlets at the bottoms of the catalyst addition tank a4 and the catalyst addition tank B5 are connected to the raw material slurry inlet pipe 25 through a catalyst slurry inlet pipe 22;
the side surface of the raw material liquid storage tank 6 is connected with a raw material liquid feeding pipe 23, and an outlet at the bottom of the raw material liquid storage tank 6 is connected with an inlet of a raw material liquid pressure pump 7 through a raw material liquid storage tank discharging pipe 24; the outlet of the raw material liquid pressure pump 7 is connected with the inlet of the raw material liquid preheater 8, and the outlet of the raw material liquid preheater 8 is connected with the bottom of the first tubular reactor 34 in the reactor group 10 through a raw material slurry inlet pipe 25; the outlet of the last tubular reactor 34 of the reactor group 10 is connected with the side surface of the gas-liquid separator 11 through a gas-liquid-solid reaction material outlet pipe 26; an outlet at the top of the gas-liquid separator 11 is connected with a hydrogen pipeline 15 at the side surface of the low-pressure hydrogen storage tank 1 through an unreacted hydrogen return pipe 28, and an outlet at the bottom of the gas-liquid separator 11 is connected with an inlet at the lower part of the side surface of the membrane separator 12 through a reaction slurry pipe 27; the outlet at the top of the membrane separator 12 is connected with a reaction liquid outlet pipe 29, and the outlet at the bottom of the membrane separator 12 is connected with the top of the catalyst recovery and replenishment tank 13 through a catalyst thick slurry pipe 30;
the top of the catalyst recovery and replenishment tank 13 is connected with a fresh catalyst slurry feeding pipe 31, and the outlet at the bottom of the catalyst recovery and replenishment tank 13 is connected with the inlet of a catalyst feeding pump 14 through an inlet pipe 32 of the catalyst feeding pump; the outlet of the catalyst addition pump 14 is connected to the feed inlets at the top of the catalyst addition tank A4 and the catalyst addition tank B5 through a catalyst slurry return pipe 33;
the reactor group 10 consists of a plurality of tubular reactors 34, wherein each tubular reactor 34 consists of a reaction tube 39, a heat exchange jacket 36, an inner member 37 and a solid-liquid separator 42; the heat exchange jacket 36 is welded outside the reaction tube 39, and the upper part and the lower part of the side surface of the heat exchange jacket 36 are respectively provided with a heat exchange medium inlet pipe 38 and a heat exchange medium outlet pipe 46; the reaction tube 39 is provided with an inner member 37; an outlet at the upper end of the top of the reaction tube 39 is connected with a gas-phase inlet 53 of the solid-liquid separator 42 through a gas-phase tube 40, and an outlet at the side surface of the top of the reaction tube 39 is connected with a slurry inlet 52 of the solid-liquid separator 42 through a liquid-phase tube 41; the lower part of the side surface of the solid-liquid separator 42 is connected with a gas-liquid-solid slurry inlet pipe 35 of the next tubular reactor through a gas-liquid material outlet pipe 43; a catalyst slurry outlet pipe 54 at the bottom of the solid-liquid separator 42 is connected to a catalyst slurry inlet pipe 45 at the side of the reaction tube through a catalyst return pipe 44; the bottom of the reaction tube 39 is provided with a hydrogen inlet pipe 47;
the solid-liquid separator 42 is composed of an inner cylinder 48, an outer cylinder 51, a settling bell jar 49 and an electromagnetic coil 50; the settling bell jar 49 is arranged in the inner barrel 48 and is connected with a slurry inlet 52 at the top of the outer barrel 51 through a pipeline; the top of the outer cylinder 51 is provided with a gas phase inlet 53, and the side surface of the bottom is provided with a gas-liquid material outlet pipe 43; the bottom of the inner cylinder 48 is provided with a catalyst slurry outlet pipe 54; the electromagnetic coil 50 is positioned outside the outer cylinder 51;
the inner member 37 is in the form of a sieve plate, tower or ridge;
the membrane separator 12 is a tubular membrane filter.
Preferably, the outer diameter of the inner cylinder 48 is 0.4m to 1.0m, and the height is 1.0m to 2.0 m; the ratio of the outer diameter of the settling bell jar 49 to the inner diameter of the inner cylinder 48 is 0.4-0.8, the ratio of the height of the settling bell jar to the height of the inner cylinder 48 is 0.5-0.8, and the distance between the bottom edge of the settling bell jar and the upper edge of the conical part of the inner cylinder 48 is 0.2-0.5 m; the distance between the top surface of the outer cylinder 51 and the top edge of the inner cylinder 48 is 0.2 m-0.4 m.
Preferably, the catalyst slurry inlet pipe 45 is 0.5m to 3.0m away from the bottom of the reaction pipe 39; the ratio of the inner diameter of the heat exchange jacket 36 to the inner diameter of the reaction tube 39 is 1.2-2.0; the inner diameter of the reaction tube 39 is 100 mm-800 mm, and the height is 3.0 m-20.0 m.
A slurry bed continuous hydrogenation reaction method using the device comprises the following process steps:
a. starting a catalyst feeding pump 14 to add the catalyst in the catalyst recovery and replenishment tank 13 into a catalyst feeding tank A4 and a catalyst feeding tank B5, simultaneously starting a raw material liquid pressure pump 7, preheating the raw material liquid by a raw material liquid preheater 8, mixing the raw material liquid with the catalyst from a catalyst feeding tank A4 and a catalyst feeding tank B5, and then entering a tubular reactor 34 in the reactor group 10 from the bottom through a raw material slurry inlet pipe 25; heating the tubular reactor 34 to a set temperature of 80-200 ℃;
the preheating temperature of the raw material liquid is 30-100 ℃;
b. opening a valve of a hydrogen pipeline 15, enabling hydrogen to enter a low-pressure hydrogen storage tank 1, starting a hydrogen compressor 2, pressurizing the low-pressure hydrogen and then conveying the pressurized low-pressure hydrogen to a high-pressure hydrogen storage tank 3, enabling one part of the high-pressure hydrogen to enter a catalyst feeding tank A4 and a catalyst feeding tank B5 through a hydrogen inlet pipe 19 of the catalyst feeding tank to maintain the pressure of the catalyst feeding tank, and enabling the other part of the high-pressure hydrogen to enter a tubular reactor 34 through a hydrogen inlet pipe 47 after being preheated by a gas preheater 9 through a hydrogen inlet pipe 20 of the reactor;
c. the raw material liquid, the catalyst slurry and the hydrogen are fully contacted in the tubular reactor 34, unreacted hydrogen enters the solid-liquid separator 42 through a gas phase inlet 53 via a gas phase pipe 40 at the top of the tubular reactor 34, and the reaction liquid and the solid catalyst slurry enter the solid-liquid separator 42 through a slurry inlet 52 via a reactor top liquid phase pipe 41; part of the catalyst is separated and then returns to the tubular reactor 34 through the catalyst slurry feeding hole by the catalyst return pipe 44, and part of the catalyst enters the next tubular reactor 34 through the gas-liquid-solid slurry inlet pipe 34 by the gas-liquid discharging hole 43 along with the reaction liquid and the hydrogen to realize continuous operation; the reaction slurry enters the gas-liquid separator 11 from the last tubular reactor 34 in the reactor group 10 through the gas-liquid-solid reaction material outlet pipe 26;
d. the gas phase enters the low-pressure hydrogen storage tank 1 for recycling through a hydrogen pipeline from an unreacted hydrogen return pipe 28, the reaction liquid and the catalyst slurry enter the membrane separator 12 through a reaction slurry pipe 27, the separated liquid-phase product is sent out through a reaction liquid outlet pipe 29, and the separated catalyst thick slurry enters the catalyst recovery and replenishment tank 13 through a catalyst thick slurry pipe 30 for recycling.
Preferably, in the step b, the pressure of the low-pressure hydrogen storage tank 1 is 1-3 MPa, the pressure of the high-pressure hydrogen storage tank 2 is 6-15 MPa, and the preheating temperature of hydrogen is 30-100 ℃.
Preferably, the molar ratio of the raw material liquid to the hydrogen in the step c is 0.5-2.0: 1; the catalyst is magnetic particles or nonmagnetic particles, and the mass concentration is 5-40%.
Preferably, the pressure in the tubular reactor 34 in the step c is 5-15 Mpa, and the temperature is 80-200 ℃.
Preferably, the residence time of the gas phase, the liquid phase and the solid phase in the reactor group 10 in the step c is 10-500 min.
Preferably, the solid-liquid separator 42 described in step c is externally provided with an electromagnetic coil 50, the electromagnetic coil 50 is turned on to fix the catalyst particles with magnetism in the slurry from the slurry inlet 52 onto the inner cylinder 48 of the solid-liquid separator 42, so as to separate the catalyst particles from the liquid, and after the electromagnetic coil 50 is turned off, the catalyst particles enter the reactor 34 through the catalyst slurry outlet pipe 54 and the catalyst return pipe 44; when the catalyst particles in the slurry from the slurry inlet 52 are not magnetic, the flow rate of the slurry entering the settling bell 49 from the slurry inlet 52 is reduced, the catalyst particles in the slurry are continuously settled, the liquid overflows into the outer cylinder 51 through the upper edge of the inner wall of the inner cylinder 48, is mixed with the gas from the gas phase inlet 53, and then enters the next tubular reactor through the gas-liquid-solid slurry inlet pipe 34 through the gas-liquid-solid slurry outlet pipe 43.
Preferably, the unreacted hydrogen and slurry after the reaction of the raw material liquid, the catalyst slurry and the hydrogen in the tubular reactor 34 in the step c can directly enter the next tubular reactor through a gas-liquid-solid slurry inlet pipe 35.
Example 1
The inner diameter of the tubular reactor 34 is 400mm, the height is 6.0m, and the number of the tubular reactors is 5; the reaction tube 39 is internally provided with an inner member 37 which is in a sieve plate shape; the catalyst slurry inlet pipe 45 is 0.6m away from the bottom of the reaction pipe 39; the ratio of the inner diameter of the heat exchange jacket 36 to the reaction tube 39 was 1.5. The outer diameter of the inner cylinder 48 of the solid-liquid separator 42 is 0.8m, and the height thereof is 1.5 m; the ratio of the outer diameter of the settling bell 49 to the inner diameter of the inner cylinder 48 is 0.5, the ratio of the height of the settling bell 49 to the height of the inner cylinder 48 is 0.6, and the distance between the bottom edge of the settling bell and the upper edge of the conical part of the inner cylinder 48 is 0.4 m; the distance between the top surface of the outer cylinder 51 and the top edge of the inner cylinder 48 is 0.3 m. The membrane separator 12 is a tubular silicon carbide membrane filter having a pore size of 4 μm.
Starting a catalyst feeding pump 14 to add the catalyst in the catalyst recovery and replenishment tank 13 into a catalyst feeding tank A4 and a catalyst feeding tank B5, wherein the pressure reaches 6.2MPa, simultaneously starting a raw material liquid pressure pump 7 to control the mass concentration of the glucose solution to be 40% and the flow rate to be 2884.62kg/h, preheating the raw material liquid to 60 ℃ by a raw material liquid preheater 8, mixing the raw material liquid with the catalyst from a catalyst feeding tank A4 and a catalyst feeding tank B5, and then feeding the mixed raw material liquid into a tubular reactor 34 in the reactor group 10 from the bottom by a raw material slurry inlet pipe 25, wherein the mass concentration of the catalyst is controlled to be 30%; the reactor 34 is heated to 100 ℃; opening a valve of a hydrogen pipeline 15, enabling hydrogen to enter a low-pressure hydrogen storage tank 1, controlling the pressure to be 3.0MPa, starting a hydrogen compressor 2, pressurizing the low-pressure hydrogen and then conveying the pressurized hydrogen to a high-pressure hydrogen storage tank 3, controlling the pressure to be 6.3MPa, enabling part of the high-pressure hydrogen to enter a catalyst feeding tank A4 and a catalyst feeding tank B5 through a hydrogen inlet pipe 19 of the catalyst feeding tank to maintain the pressure of the catalyst feeding tank, enabling the other part of the high-pressure hydrogen to enter a tubular reactor 34 through a hydrogen inlet pipe 20 of the reactor, preheating the other part of the high-pressure hydrogen to 60 ℃ through a gas preheater 9, and entering a hydrogen inlet pipe 47, wherein the molar ratio of hydrogen to glucose is controlled to be 1.3:1, the pressure of the reactor is controlled to be 6.0MPa, and the liquid holdup is controlled to be 60%; the raw material liquid, the catalyst slurry and the hydrogen are fully contacted in the tubular reactor 34, unreacted hydrogen enters the solid-liquid separator 42 through a gas phase inlet 53 through a gas phase pipe 40 at the top of the reactor, and the reaction liquid and the solid catalyst slurry enter the solid-liquid separator 42 through a slurry inlet 52 through a liquid phase pipe 41 at the top of the reactor; part of the catalyst is separated and then returns to the reactor through a catalyst slurry feeding hole by a catalyst return pipe 44, and part of the catalyst enters the next tubular reactor through a gas-liquid-solid slurry inlet pipe 34 by a gas-liquid discharging hole 43 along with reaction liquid and hydrogen so as to realize continuous operation; the total residence time of the reaction slurry in the reactor group 10 is 60min, and the reaction slurry enters the gas-liquid separator 11 through the gas-liquid-solid reaction material outlet pipe 26 by the last reactor; the gas phase enters the low-pressure hydrogen storage tank 1 for recycling through a hydrogen pipeline from an unreacted hydrogen return pipe 28, the reaction liquid and the catalyst slurry enter the membrane separator 12 through a reaction slurry pipe 27, the separated liquid-phase product is sent out through a reaction liquid outlet pipe 29, the concentration is 60%, and the separated catalyst thick slurry enters the catalyst recovery and replenishment tank 13 through a catalyst thick slurry pipe 30 for recycling.
Example 2
The inner diameter of the tubular reactor 34 is 500mm, the height is 6.0m, and the number of the tubular reactors is 5; the reaction tube 39 is internally provided with an inner member 37 in the form of a ridge; the catalyst slurry inlet pipe 45 is 0.5m away from the bottom of the reaction pipe 39; the ratio of the inner diameter of the heat exchange jacket 36 to the reaction tube 39 was 1.5. The outer diameter of the inner cylinder 48 of the solid-liquid separator 42 is 0.8m, and the height thereof is 1.5 m; the ratio of the outer diameter of the settling bell 49 to the inner diameter of the inner cylinder 48 is 0.5, the ratio of the height of the settling bell 49 to the height of the inner cylinder 48 is 0.6, and the distance between the bottom edge of the settling bell and the upper edge of the conical part of the inner cylinder 48 is 0.4 m; the distance between the top surface of the outer cylinder 51 and the top edge of the inner cylinder 48 is 0.3 m. The membrane separator 12 is a tubular sintered metal membrane filter having a pore size of 3 μm.
Starting a catalyst feeding pump 14 to add the catalyst in the catalyst recovery and replenishment tank 13 into a catalyst feeding tank A4 and a catalyst feeding tank B5, wherein the pressure reaches 6.2MPa, simultaneously starting a raw material liquid pressure pump 7 to control the mass concentration of the glucose solution to be 30% and the flow rate to be 3205.13kg/h, preheating the raw material liquid to 60 ℃ by a raw material liquid preheater 8, mixing the raw material liquid with the catalyst from a catalyst feeding tank A4 and a catalyst feeding tank B5, and then feeding the mixed raw material liquid into a tubular reactor 34 in the reactor group 10 from the bottom by a raw material slurry inlet pipe 25, wherein the mass concentration of the catalyst is controlled to be 25%; the reactor 34 was heated to 130 ℃; opening a valve of a hydrogen pipeline 15, enabling hydrogen to enter a low-pressure hydrogen storage tank 1, controlling the pressure to be 3.0MPa, starting a hydrogen compressor 2, pressurizing the low-pressure hydrogen and then conveying the pressurized hydrogen to the high-pressure hydrogen storage tank 3, controlling the pressure to be 6.3MPa, enabling part of the high-pressure hydrogen to enter a catalyst feeding tank A4 and a catalyst feeding tank B5 through a hydrogen inlet pipe 19 of the catalyst feeding tank to maintain the pressure of the catalyst feeding tank, enabling the other part of the high-pressure hydrogen to enter a tubular reactor 34 through a hydrogen inlet pipe 47 of the reactor, preheating the other part of the high-pressure hydrogen to 60 ℃ through a gas preheater 9 through a hydrogen inlet pipe 20 of the reactor, controlling the molar ratio of hydrogen to glucose to be 1.2:1, controlling the pressure of the reactor to be 6.0MPa, and controlling the liquid holding capacity to be 50%; the raw material liquid, the catalyst slurry and the hydrogen are fully contacted in the tubular reactor 34, unreacted hydrogen enters the solid-liquid separator 42 through a gas phase inlet 53 through a gas phase pipe 40 at the top of the reactor, and the reaction liquid and the solid catalyst slurry enter the solid-liquid separator 42 through a slurry inlet 52 through a liquid phase pipe 41 at the top of the reactor; part of the catalyst is separated and then returns to the reactor through a catalyst slurry feeding hole by a catalyst return pipe 44, and part of the catalyst enters the next tubular reactor through a gas-liquid-solid slurry inlet pipe 34 by a gas-liquid discharging hole 43 along with reaction liquid and hydrogen so as to realize continuous operation; the total residence time of the reaction slurry in the reactor group 10 is 60min, and the reaction slurry enters the gas-liquid separator 11 through the gas-liquid-solid reaction material outlet pipe 26 by the last reactor; the gas phase enters the low-pressure hydrogen storage tank 1 for recycling through a hydrogen pipeline from an unreacted hydrogen return pipe 28, the reaction liquid and the catalyst slurry enter the membrane separator 12 through a reaction slurry pipe 27, the separated liquid-phase product is sent out through a reaction liquid outlet pipe 29, the concentration is 55%, and the separated catalyst thick slurry enters the catalyst recovery and replenishment tank 13 through a catalyst thick slurry pipe 30 for recycling.
Example 3
The inner diameter of the tubular reactor 34 is 450mm, the height is 6.0m, and the number of the tubular reactors is 5; the reaction tube 39 is provided with an inner member 37 in the form of a tower; the catalyst slurry inlet pipe 45 is 0.5m away from the bottom of the reaction pipe 39; the ratio of the inner diameter of the heat exchange jacket 36 to the reaction tube 39 was 1.5. The outer diameter of the inner cylinder 48 of the solid-liquid separator 42 is 0.8m, and the height thereof is 1.5 m; the ratio of the outer diameter of the settling bell 49 to the inner diameter of the inner cylinder 48 is 0.5, the ratio of the height of the settling bell 49 to the height of the inner cylinder 48 is 0.6, and the distance between the bottom edge of the settling bell and the upper edge of the conical part of the inner cylinder 48 is 0.4 m; the distance between the top surface of the outer cylinder 51 and the top edge of the inner cylinder 48 is 0.3 m. The membrane separator 12 is a tubular sintered metal membrane filter having a pore size of 3 μm.
Starting a catalyst feeding pump 14 to add the catalyst in the catalyst recovery and replenishment tank 13 into a catalyst feeding tank A4 and a catalyst feeding tank B5, wherein the pressure reaches 7.3MPa, simultaneously starting a raw material liquid pressure pump 7 to control the mass concentration of the glucose solution to be 30% and the flow rate to be 2163.46kg/h, preheating the raw material liquid to 60 ℃ by a raw material liquid preheater 8, mixing the raw material liquid with the catalyst from a catalyst feeding tank A4 and a catalyst feeding tank B5, and then feeding the mixed raw material liquid into a tubular reactor 34 in the reactor group 10 from the bottom by a raw material slurry inlet pipe 25, wherein the mass concentration of the catalyst is controlled to be 30%; the reactor 34 is heated to 120 ℃; opening a valve of a hydrogen pipeline 15, enabling hydrogen to enter a low-pressure hydrogen storage tank 1, controlling the pressure to be 3.0MPa, starting a hydrogen compressor 2, pressurizing the low-pressure hydrogen and then conveying the pressurized hydrogen to the high-pressure hydrogen storage tank 3, controlling the pressure to be 7.3MPa, enabling part of the high-pressure hydrogen to enter a catalyst feeding tank A4 and a catalyst feeding tank B5 through a hydrogen inlet pipe 19 of the catalyst feeding tank to maintain the pressure of the catalyst feeding tank, enabling the other part of the high-pressure hydrogen to enter a tubular reactor 34 through a hydrogen inlet pipe 47 of the reactor, preheating the other part of the high-pressure hydrogen to 60 ℃ through a gas preheater 9 through a hydrogen inlet pipe 20 of the reactor, controlling the molar ratio of hydrogen to glucose to be 1.2:1, controlling the pressure of; the raw material liquid, the catalyst slurry and the hydrogen are fully contacted in the tubular reactor 34, unreacted hydrogen enters the solid-liquid separator 42 through a gas phase inlet 53 through a gas phase pipe 40 at the top of the reactor, and the reaction liquid and the solid catalyst slurry enter the solid-liquid separator 42 through a slurry inlet 52 through a liquid phase pipe 41 at the top of the reactor; part of the catalyst is separated and then returns to the reactor through a catalyst slurry feeding hole by a catalyst return pipe 44, and part of the catalyst enters the next tubular reactor through a gas-liquid-solid slurry inlet pipe 34 by a gas-liquid discharging hole 43 along with reaction liquid and hydrogen so as to realize continuous operation; the total residence time of the reaction slurry in the reactor group 10 is 90min, and the reaction slurry enters the gas-liquid separator 11 through the gas-liquid-solid reaction material outlet pipe 26 by the last reactor; the gas phase enters the low-pressure hydrogen storage tank 1 for recycling through a hydrogen pipeline from an unreacted hydrogen return pipe 28, the reaction liquid and the catalyst slurry enter the membrane separator 12 through a reaction slurry pipe 27, the separated liquid-phase product is sent out through a reaction liquid outlet pipe 29, the concentration is 75%, and the separated catalyst thick slurry enters the catalyst recovery and replenishment tank 13 through a catalyst thick slurry pipe 30 for recycling.
Example 4
The inner diameter of the tubular reactor 34 is 600mm, the height is 6.0m, and the number of the tubular reactors is 4; the reaction tube 39 is provided with an inner member 37 in the form of a tower; the catalyst slurry inlet pipe 45 is 1.0m away from the bottom of the reaction pipe 39; the ratio of the inner diameter of the heat exchange jacket 36 to the reaction tube 39 was 1.6. The outer diameter of the inner cylinder 48 of the solid-liquid separator 42 is 0.6m, and the height thereof is 1.6 m; the ratio of the outer diameter of the settling bell 49 to the inner diameter of the inner cylinder 48 is 0.6, the ratio of the height of the settling bell 49 to the height of the inner cylinder 48 is 0.7, and the distance between the bottom edge of the settling bell 49 and the upper edge of the conical part of the inner cylinder 48 is 0.3 m; the distance between the top surface of the outer cylinder 51 and the top edge of the inner cylinder 48 is 0.4 m. The membrane separator 12 is a tubular sintered metal membrane filter having a pore size of 4 μm.
Starting a catalyst feeding pump 14 to add the catalyst in the catalyst recovery and replenishment tank 13 into a catalyst feeding tank A4 and a catalyst feeding tank B5, wherein the pressure reaches 8.2MPa, simultaneously starting a raw material liquid pressure pump 7 to control the mass concentration of the glucose solution to be 30% and the flow rate to be 2884.61kg/h, preheating the raw material liquid to 60 ℃ by a raw material liquid preheater 8, mixing the raw material liquid with the catalyst from a catalyst feeding tank A4 and a catalyst feeding tank B5, and then feeding the mixed raw material liquid into a tubular reactor 34 in the reactor group 10 from the bottom by a raw material slurry inlet pipe 25, wherein the mass concentration of the catalyst is controlled to be 10%; the reactor 34 is heated to 100 ℃; opening a valve of a hydrogen pipeline 15, enabling hydrogen to enter a low-pressure hydrogen storage tank 1, controlling the pressure to be 3.0MPa, starting a hydrogen compressor 2, pressurizing the low-pressure hydrogen and then conveying the pressurized hydrogen to a high-pressure hydrogen storage tank 3, controlling the pressure to be 7.3MPa, enabling part of the high-pressure hydrogen to enter a catalyst feeding tank A4 and a catalyst feeding tank B5 through a hydrogen inlet pipe 19 of the catalyst feeding tank to maintain the pressure of the catalyst feeding tank, enabling the other part of the high-pressure hydrogen to enter a tubular reactor 34 through a hydrogen inlet pipe 20 of the reactor, preheating the other part of the high-pressure hydrogen to 60 ℃ through a gas preheater 9, and entering a hydrogen inlet pipe 47, controlling the molar ratio of hydrogen to glucose to be 1.3:1, controlling the pressure of the reactor to be 7.0MPa, and controlling the liquid holdup to be 70%; the raw material liquid, the catalyst slurry and the hydrogen are fully contacted in the tubular reactor 34, unreacted hydrogen enters the solid-liquid separator 42 through a gas phase inlet 53 through a gas phase pipe 40 at the top of the reactor, and the reaction liquid and the solid catalyst slurry enter the solid-liquid separator 42 through a slurry inlet 52 through a liquid phase pipe 41 at the top of the reactor; part of the catalyst is separated and then returns to the reactor through a catalyst slurry feeding hole by a catalyst return pipe 44, and part of the catalyst enters the next tubular reactor through a gas-liquid-solid slurry inlet pipe 34 by a gas-liquid discharging hole 43 along with reaction liquid and hydrogen so as to realize continuous operation; the total residence time of the reaction slurry in the reactor group 10 is 120min, and the reaction slurry enters the gas-liquid separator 11 through the gas-liquid-solid reaction material outlet pipe 26 by the last reactor; the gas phase enters the low-pressure hydrogen storage tank 1 for recycling through a hydrogen pipeline from an unreacted hydrogen return pipe 28, the reaction liquid and the catalyst slurry enter the membrane separator 12 through a reaction slurry pipe 27, the separated liquid-phase product is sent out through a reaction liquid outlet pipe 29, the concentration is 70%, and the separated catalyst thick slurry enters the catalyst recovery and replenishment tank 13 through a catalyst thick slurry pipe 30 for recycling.
Example 5
The inner diameter of the tubular reactor 34 is 600mm, the height is 6.0m, and the number of the tubular reactors is 4; the reaction tube 39 is internally provided with an inner member 37 in the form of a ridge; the catalyst slurry inlet pipe 45 is 1.2m away from the bottom of the reaction pipe 39; the ratio of the inner diameter of the heat exchange jacket 36 to the reaction tube 39 was 1.6. The outer diameter of the inner cylinder 48 of the solid-liquid separator 42 is 0.6m, and the height thereof is 1.5 m; the ratio of the outer diameter of the settling bell 49 to the inner diameter of the inner cylinder 48 is 0.6, the ratio of the height of the settling bell 49 to the height of the inner cylinder 48 is 0.7, and the distance between the bottom edge of the settling bell 49 and the upper edge of the conical part of the inner cylinder 48 is 0.3 m; the distance between the top surface of the outer cylinder 51 and the top edge of the inner cylinder 48 is 0.4 m. The membrane separator 12 is a tubular sintered metal membrane filter having a pore size of 5 μm.
Starting a catalyst feeding pump 14 to add the catalyst in the catalyst recovery and replenishment tank 13 into a catalyst feeding tank A4 and a catalyst feeding tank B5, wherein the pressure reaches 6.2MPa, simultaneously starting a raw material liquid pressure pump 7 to control the mass concentration of the glucose solution to be 30% and the flow rate to be 2564.10kg/h, preheating the raw material liquid to 60 ℃ by a raw material liquid preheater 8, mixing the raw material liquid with the catalyst from a catalyst feeding tank A4 and a catalyst feeding tank B5, and then feeding the mixed raw material liquid into a tubular reactor 34 in the reactor group 10 from the bottom by a raw material slurry inlet pipe 25, wherein the mass concentration of the catalyst is controlled to be 20%; the reactor 34 is heated to 100 ℃; opening a valve of a hydrogen pipeline 15, enabling hydrogen to enter a low-pressure hydrogen storage tank 1, controlling the pressure to be 3.0MPa, starting a hydrogen compressor 2, pressurizing the low-pressure hydrogen and then conveying the pressurized hydrogen to the high-pressure hydrogen storage tank 3, controlling the pressure to be 6.3MPa, enabling part of the high-pressure hydrogen to enter a catalyst feeding tank A4 and a catalyst feeding tank B5 through a hydrogen inlet pipe 19 of the catalyst feeding tank to maintain the pressure of the catalyst feeding tank, enabling the other part of the high-pressure hydrogen to enter a tubular reactor 34 through a hydrogen inlet pipe 20 of the reactor, preheating the other part of the high-pressure hydrogen to 60 ℃ through a gas preheater 9, and entering a hydrogen inlet pipe 47, controlling the molar ratio of hydrogen to glucose to be 1.2:1, controlling the pressure of the reactor to be 6.0MPa, and controlling the liquid holdup to be 65%; the raw material liquid, the catalyst slurry and the hydrogen are fully contacted in the tubular reactor 34, unreacted hydrogen enters the solid-liquid separator 42 through a gas phase inlet 53 through a gas phase pipe 40 at the top of the reactor, and the reaction liquid and the solid catalyst slurry enter the solid-liquid separator 42 through a slurry inlet 52 through a liquid phase pipe 41 at the top of the reactor; part of the catalyst is separated and then returns to the reactor through a catalyst slurry feeding hole by a catalyst return pipe 44, and part of the catalyst enters the next tubular reactor through a gas-liquid-solid slurry inlet pipe 34 by a gas-liquid discharging hole 43 along with reaction liquid and hydrogen so as to realize continuous operation; the total residence time of the reaction slurry in the reactor group 10 is 60min, and the reaction slurry enters the gas-liquid separator 11 through the gas-liquid-solid reaction material outlet pipe 26 by the last reactor; the gas phase enters the low-pressure hydrogen storage tank 1 for recycling through a hydrogen pipeline from an unreacted hydrogen return pipe 28, the reaction liquid and the catalyst slurry enter the membrane separator 12 through a reaction slurry pipe 27, the separated liquid-phase product is sent out through a reaction liquid outlet pipe 29, the concentration is 68%, and the separated catalyst thick slurry enters the catalyst recovery and replenishment tank 13 through a catalyst thick slurry pipe 30 for recycling.
Claims (10)
1. A slurry bed continuous hydrogenation reaction device is characterized by comprising a low-pressure hydrogen storage tank (1), a hydrogen compressor (2), a high-pressure hydrogen storage tank (3), a catalyst feeding tank A (4), a catalyst feeding tank B (5), a raw material liquid storage tank (6), a raw material liquid pressure pump (7), a raw material liquid preheater (8), a gas preheater (9), a reactor group (10), a gas-liquid separator (11), a membrane separator (12), a catalyst recovery and replenishment tank (13) and a catalyst feeding pump (14);
the side surface of the low-pressure hydrogen storage tank (1) is connected with a hydrogen pipeline (15), and an outlet pipe (16) of the low-pressure hydrogen storage tank at the top is connected with an inlet of the hydrogen compressor (2); the outlet of the hydrogen compressor (2) is connected with a high-pressure hydrogen storage tank inlet pipe (17) at the top of the high-pressure hydrogen storage tank (3); an outlet pipe (18) of the high-pressure hydrogen storage tank at the top of the high-pressure hydrogen storage tank (3) is connected with a hydrogen inlet pipe (19) of the catalyst feeding tank at the top of the catalyst feeding tank A (4) and the catalyst feeding tank B (5); an outlet pipe (18) of the high-pressure hydrogen storage tank at the top of the high-pressure hydrogen storage tank (3) is connected with an inlet of the gas preheater (9) through a reactor hydrogen inlet pipe (20); the outlet of the gas preheater (9) is connected with a hydrogen inlet pipe (47); the catalyst feeding tank A (4) and the catalyst feeding tank B (5) are connected with the hydrogen pipeline (15) on the side of the low-pressure hydrogen storage tank (1) through the hydrogen pressure relief pipe (21); the outlets at the bottoms of the catalyst feeding tank A (4) and the catalyst feeding tank B (5) are connected with a raw material slurry inlet pipe (25) through a catalyst slurry feeding pipe (22);
the side surface of the raw material liquid storage tank (6) is connected with a raw material liquid feeding pipe (23), and an outlet at the bottom of the raw material liquid storage tank (6) is connected with an inlet of a raw material liquid pressure pump (7) through a raw material liquid storage tank discharging pipe (24); the outlet of the raw material liquid pressure pump (7) is connected with the inlet of the raw material liquid preheater (8), and the outlet of the raw material liquid preheater (8) is connected with the bottom of a first tubular reactor (34) in the reactor group (10) through a raw material slurry inlet pipe (25); the outlet of the last tubular reactor (34) of the reactor group (10) is connected with the side surface of the gas-liquid separator (11) through a gas-liquid-solid reaction material outlet pipe (26); an outlet at the top of the gas-liquid separator (11) is connected with a hydrogen pipeline (15) at the side surface of the low-pressure hydrogen storage tank (1) through an unreacted hydrogen return pipe (28), and an outlet at the bottom of the gas-liquid separator (11) is connected with an inlet at the lower part of the side surface of the membrane separator (12) through a reaction slurry pipe (27); the outlet at the top of the membrane separator (12) is connected with a reaction liquid outlet pipe (29), and the outlet at the bottom of the membrane separator (12) is connected with the top of the catalyst recovery and replenishment tank (13) through a catalyst thick slurry pipe (30);
the top of the catalyst recovery and replenishment tank (13) is connected with a fresh catalyst slurry feeding pipe (31), and the outlet at the bottom of the catalyst recovery and replenishment tank (13) is connected with the inlet of a catalyst charging pump (14) through an inlet pipe (32) of the catalyst charging pump; the outlet of the catalyst feeding pump (14) is connected with the feed inlets at the top of the catalyst feeding tank A (4) and the catalyst feeding tank B (5) through a catalyst slurry return pipe (33);
the reactor group (10) consists of a plurality of tubular reactors (34), wherein each tubular reactor (34) consists of a reaction tube (39), a heat exchange jacket (36), an inner member (37) and a solid-liquid separator (42); the heat exchange jacket (36) is welded outside the reaction tube (39), and the upper part and the lower part of the side surface of the heat exchange jacket (36) are respectively provided with a heat exchange medium inlet pipe (38) and a heat exchange medium outlet pipe (46); an inner member (37) is installed in the reaction tube (39); an outlet at the upper end of the top of the reaction tube (39) is connected with a gas-phase inlet (53) of the solid-liquid separator (42) through a gas-phase tube (40), and an outlet at the side surface of the top of the reaction tube (39) is connected with a slurry inlet (52) of the solid-liquid separator (42) through a liquid-phase tube (41); the lower part of the side surface of the solid-liquid separator (42) is connected with a gas-liquid-solid slurry inlet pipe (35) of the next tubular reactor through a gas-liquid material outlet pipe (43); a catalyst slurry outlet pipe (54) at the bottom of the solid-liquid separator (42) is connected with a catalyst slurry inlet pipe (45) at the side of the reaction pipe through a catalyst return pipe (44); the bottom of the reaction tube (39) is provided with a hydrogen inlet tube (47);
the solid-liquid separator (42) consists of an inner cylinder (48), an outer cylinder (51), a settling bell jar (49) and an electromagnetic coil (50); the settling bell jar (49) is arranged in the inner cylinder (48) and is connected with a slurry inlet (52) at the top of the outer cylinder (51) through a pipeline; the top of the outer cylinder (51) is provided with a gas phase inlet (53), and the side surface of the bottom is provided with a gas-liquid material outlet pipe (43); the bottom of the inner cylinder (48) is provided with a catalyst slurry outlet pipe (54); the electromagnetic coil (50) is positioned outside the outer cylinder (51);
the inner member (37) is in the form of a sieve plate, tower or ridge;
the membrane separator (12) is a tubular membrane filter.
2. The slurry bed continuous hydrogenation reaction device according to claim 1, wherein the outer diameter of the inner cylinder (48) is 0.4m to 1.0m, and the height is 1.0m to 2.0 m; the ratio of the outer diameter of the settling bell jar (49) to the inner diameter of the inner cylinder (48) is 0.4-0.8, the ratio of the height of the settling bell jar to the height of the inner cylinder (48) is 0.5-0.8, and the distance between the bottom edge of the settling bell jar and the upper edge of the conical part of the inner cylinder (48) is 0.2-0.5 m; the distance between the top surface of the outer cylinder (51) and the top edge of the inner cylinder (48) is 0.2-0.4 m.
3. The slurry bed continuous hydrogenation reaction device as claimed in claim 2, wherein the catalyst slurry inlet pipe (45) is 0.5-3.0 m from the bottom of the reaction pipe (39); the ratio of the inner diameter of the heat exchange jacket (36) to the inner diameter of the reaction tube (39) is 1.2-2.0; the inner diameter of the reaction tube (39) is 100 mm-800 mm, and the height is 3.0 m-20.0 m.
4. A slurry bed continuous hydrogenation reaction method using the slurry bed continuous hydrogenation reaction device of claim 1, which is characterized by comprising the following process steps:
a. starting a catalyst feeding pump (14) to add the catalyst in the catalyst recovery and replenishment tank (13) into a catalyst feeding tank A (4) and a catalyst feeding tank B (5), and simultaneously starting a raw material liquid pressure pump (7), wherein the raw material liquid is preheated by a raw material liquid preheater (8), mixed with the catalyst from the catalyst feeding tank A (4) and the catalyst feeding tank B (5), and then enters a tubular reactor (34) in the reactor group (10) from the bottom through a raw material slurry inlet pipe (25); heating the tubular reactor (34) to a set temperature of 80-200 ℃;
the preheating temperature of the raw material liquid is 30-100 ℃;
b. opening a valve of a hydrogen pipeline (15), enabling hydrogen to enter a low-pressure hydrogen storage tank (1), starting a hydrogen compressor (2), pressurizing the low-pressure hydrogen and then conveying the pressurized low-pressure hydrogen to a high-pressure hydrogen storage tank (3), enabling one part of the high-pressure hydrogen to enter a catalyst feeding tank A (4) and a catalyst feeding tank B (5) through a hydrogen inlet pipe (19) of a catalyst feeding tank so as to maintain the pressure of the catalyst feeding tank, and enabling the other part of the high-pressure hydrogen to enter a tubular reactor (34) through a hydrogen inlet pipe (47) after being preheated by a gas preheater (9) through a hydrogen inlet pipe (20) of the reactor;
c. the raw material liquid, the catalyst slurry and the hydrogen are fully contacted in the tubular reactor (34), unreacted hydrogen enters the solid-liquid separator (42) through a gas phase inlet (53) through a gas phase pipe (40) at the top of the tubular reactor (34), and the reaction liquid and the solid catalyst slurry enter the solid-liquid separator (42) through a slurry inlet (52) through a liquid phase pipe (41) at the top of the reactor; part of the catalyst is separated and then returns to the tubular reactor (34) through a catalyst slurry feeding hole by a catalyst return pipe (44), and part of the catalyst enters the next tubular reactor (34) along with reaction liquid and hydrogen from a gas-liquid discharging hole through a gas-liquid-solid slurry inlet pipe (35) so as to realize continuous operation; reaction slurry enters a gas-liquid separator (11) from the last tubular reactor (34) in the reactor group (10) through a gas-liquid-solid reaction material outlet pipe (26);
d. the gas phase enters a low-pressure hydrogen storage tank (1) for recycling through a hydrogen pipeline from an unreacted hydrogen return pipe (28), reaction liquid and catalyst slurry enter a membrane separator (12) through a reaction slurry pipe (27), a liquid-phase product after separation is sent out through a reaction liquid outlet pipe (29), and the separated catalyst thick slurry enters a catalyst recovery and replenishment tank (13) through a catalyst thick slurry pipe (30) for recycling.
5. The slurry bed continuous hydrogenation reaction method according to claim 4, wherein the pressure of the low-pressure hydrogen storage tank (1) in the step b is 1-3 MPa, the pressure of the high-pressure hydrogen storage tank (3) is 6-15 MPa, and the preheating temperature of hydrogen is 30-100 ℃.
6. The slurry bed continuous hydrogenation reaction method according to claim 4, wherein the molar ratio of the feed liquid to the hydrogen in step c is 0.5-2.0: 1; the catalyst is magnetic particles or nonmagnetic particles, and the mass concentration is 5-40%.
7. The slurry bed continuous hydrogenation reaction method according to claim 4, wherein the pressure in the tubular reactor (34) in the step c is 5-15 MPa, and the temperature is 80-200 ℃.
8. The slurry bed continuous hydrogenation reaction method according to claim 4, wherein the residence time of the gas phase, the liquid phase and the solid phase in the reactor group (10) in the step c is 10-500 min.
9. The slurry bed continuous hydrogenation reaction method according to claim 4, characterized in that the solid-liquid separator (42) in step c is externally provided with a solenoid (50), the solenoid (50) is opened to fix the catalyst particles with magnetism in the slurry from the slurry inlet (52) on the inner cylinder (48) of the solid-liquid separator (42) to separate the catalyst particles from the liquid, and after the solenoid (50) is closed, the catalyst particles enter the reactor (34) through the catalyst return pipe (44) via the catalyst slurry outlet pipe (54); when catalyst particles in the slurry from the slurry inlet (52) are not magnetic, the flow rate of the slurry enters the settling bell jar (49) from the slurry inlet (52) is reduced, the catalyst particles in the slurry are continuously settled, the liquid overflows into the outer cylinder (51) along the upper edge of the inner wall of the inner cylinder (48), is mixed with the gas from the gas-phase inlet (53), and then enters the next tubular reactor through the gas-liquid-solid slurry inlet pipe (35) through the gas-liquid outlet pipe (43).
10. The slurry-bed continuous hydrogenation reaction method according to claim 4, wherein the unreacted hydrogen and slurry in step c after the reaction of the feed liquid, the catalyst slurry and the hydrogen in the tubular reactor (34) can directly enter the next tubular reactor through the gas-liquid-solid slurry inlet pipe (35).
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