CN106987263A - A kind of continous way catalysis upgrading reaction system of microalgae liquefaction oil - Google Patents
A kind of continous way catalysis upgrading reaction system of microalgae liquefaction oil Download PDFInfo
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- CN106987263A CN106987263A CN201710167127.6A CN201710167127A CN106987263A CN 106987263 A CN106987263 A CN 106987263A CN 201710167127 A CN201710167127 A CN 201710167127A CN 106987263 A CN106987263 A CN 106987263A
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 151
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 58
- 239000012071 phase Substances 0.000 claims abstract description 27
- 239000007791 liquid phase Substances 0.000 claims abstract description 8
- 230000003197 catalytic effect Effects 0.000 claims description 119
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 57
- 229910052739 hydrogen Inorganic materials 0.000 claims description 53
- 239000001257 hydrogen Substances 0.000 claims description 52
- 238000000926 separation method Methods 0.000 claims description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 239000002002 slurry Substances 0.000 claims description 38
- 241000195493 Cryptophyta Species 0.000 claims description 37
- 239000007789 gas Substances 0.000 claims description 35
- 239000012528 membrane Substances 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 23
- 239000003054 catalyst Substances 0.000 claims description 21
- 238000011084 recovery Methods 0.000 claims description 11
- 239000012295 chemical reaction liquid Substances 0.000 claims description 10
- 238000004062 sedimentation Methods 0.000 claims description 10
- 239000002638 heterogeneous catalyst Substances 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 239000002912 waste gas Substances 0.000 claims description 4
- 239000002699 waste material Substances 0.000 claims description 4
- 238000007599 discharging Methods 0.000 abstract 2
- 239000003921 oil Substances 0.000 description 98
- 238000005516 engineering process Methods 0.000 description 7
- 238000005265 energy consumption Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000012075 bio-oil Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229920005597 polymer membrane Polymers 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002918 waste heat Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
- C10G2300/1014—Biomass of vegetal origin
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention provides a kind of continous way catalysis upgrading reaction system of microalgae liquefaction oil, including hydrothermal liquefaction reaction member, hydrothermal liquefaction separative element, catalysis upgrading reaction member, catalysis upgrading separative element and oil storage tank;Hydrothermal liquefaction reaction member is connected with hydrothermal liquefaction separative element;Hydrothermal liquefaction separative element is connected with catalysis upgrading reaction member;Catalysis upgrading reaction member is connected with catalysis upgrading separative element;Catalysis upgrading separative element is connected with oil storage tank;The catalysis upgrading separative element includes gas-liquid separator and upgrading centrifuge;The charging aperture of gas-liquid separator is connected with catalysis upgrading reaction member, and the liquid phase discharging opening of gas-liquid separator is connected with the charging aperture of upgrading centrifuge;The oil phase discharging opening of upgrading centrifuge is connected with oil storage tank;Hydrothermal liquefaction separative element includes liquefaction centrifuge.The continous way catalysis upgrading reaction system for the microalgae liquefaction oil that the present invention is provided, can enable the catalysis upgrading system of microalgae liquefaction oil to realize efficient and continuity run.
Description
Technical Field
The invention belongs to the field of biomass energy, and particularly relates to a continuous catalytic upgrading reaction system for microalgae liquefied oil.
Background
The microalgae hydrothermal liquefaction technology refers to a process of converting microalgae raw materials into bio-oil by a thermochemical method under a liquid-phase hydrothermal condition. Hydrothermal liquefaction is a microalgae oil production technology with great development prospect, and a biomass liquid fuel production technology using microalgae as a raw material has higher economic and technical feasibility; it has important significance for relieving environmental pollution and improving energy safety. However, microalgae liquefied oil generally has higher N, S and O content, and poor physical and chemical properties. The bio-oil cannot be directly applied and must be subjected to upgrading treatment, and a very effective upgrading method is hydrothermal catalytic upgrading. In the general hydrothermal catalytic upgrading, under the hydrothermal condition of 350-400 ℃, a heterogeneous catalyst with excellent performance is selected to carry out upgrading modification treatment on the liquefied oil so as to reduce the content of heteroatoms, viscosity, total acid value and the like in the bio-oil and improve the content of C, H, heat value and the like.
Research on catalytic upgrading of microalgae liquefied oil is increasing, and a common catalytic upgrading reaction is carried out in a batch high-pressure reaction kettle which generally has the defects of low production efficiency, high energy consumption, unsuitability for large-scale industrial application and the like. In order to realize the continuous operation of the catalytic upgrading system of the microalgae liquefied oil, the following problems need to be solved: firstly, the continuous and efficient separation of oil phase and gas phase from the reaction solvent after the upgrading reaction is realized. Secondly, the waste heat after the upgrading reaction needs to be fully utilized to preheat the materials before the reaction, so that the operation cost of the continuous reaction system is reduced, and the energy efficiency is improved. In addition, reasonable catalyst arrangement is very important, and the catalyst is convenient to replace while the heterogeneous catalyst is ensured to be fully contacted with the microalgae liquefied oil in the catalytic upgrading reaction.
At present, few researches on a continuous catalytic upgrading reaction system of microalgae liquefied oil relate to, and no continuous catalytic upgrading reaction device of microalgae liquefied oil can effectively solve the problems.
Disclosure of Invention
The invention aims to provide a continuous catalytic upgrading reaction system for microalgae liquefied oil, so that the catalytic upgrading system for microalgae liquefied oil can realize high-efficiency and continuous operation.
The invention is realized by the following technical scheme:
a continuous catalytic upgrading reaction system for microalgae liquefied oil comprises a hydrothermal liquefaction reaction unit, a hydrothermal liquefaction separation unit, a catalytic upgrading reaction unit, a catalytic upgrading separation unit and an oil storage tank;
wherein the hydrothermal liquefaction reaction unit is connected with the hydrothermal liquefaction separation unit; the hydrothermal liquefaction separation unit is connected with the catalytic upgrading reaction unit; the catalytic upgrading reaction unit is connected with the catalytic upgrading separation unit; the catalytic upgrading separation unit is connected with the oil storage tank;
wherein the catalytic upgrading separation unit comprises a gas-liquid separator and an upgrading centrifuge; a feed inlet of the gas-liquid separator is connected with the catalytic upgrading reaction unit, and a liquid-phase discharge outlet of the gas-liquid separator is connected with a feed inlet of the upgrading centrifugal machine; an oil phase discharge port of the quality-improving centrifuge is connected with the oil storage tank;
the hydrothermal liquefaction separation unit comprises a liquefaction centrifugal machine, a feed inlet of the liquefaction centrifugal machine is connected with the hydrothermal liquefaction reaction unit, and an oil phase discharge outlet of the liquefaction centrifugal machine is connected with the catalysis quality-improvement reaction unit.
Preferably, the hydrothermal liquefaction separation unit further comprises a liquefaction sedimentation tank, and the liquefaction sedimentation tank is connected with a waste material discharge port of the liquefaction centrifugal machine;
preferably, the gas-liquid separator has a temperature control device and a pressure gauge, and the internal temperature of the gas-liquid separator is lower than the saturation temperature of water corresponding to the working pressure.
Preferably, the catalytic upgrading separation unit further comprises an upgrading liquid storage bottle, and the upgrading liquid storage bottle is connected with a water phase discharge port of the upgrading centrifuge.
Preferably, the catalytic upgrading reaction unit comprises a hydrogen gas storage cylinder, a water storage tank, a liquefied oil high-pressure pump and a catalytic upgrading reactor; wherein,
a feed inlet of the liquefied oil high-pressure pump is connected with an oil phase discharge outlet of the liquefied centrifugal machine;
a discharge hole of the liquefied oil high-pressure pump is connected with a feed hole of the catalytic upgrading reactor through a pipeline;
the hydrogen gas storage cylinder is connected with the first supercharger through a pipeline; the first booster is connected to a pipeline between the liquefied oil high-pressure pump and the catalytic upgrading reactor;
the water storage tank is connected with a water tank high-pressure pump; the water tank high-pressure pump is connected to a pipeline between the liquefied oil high-pressure pump and the catalytic upgrading reactor;
the discharge port of the catalytic upgrading reactor is connected with the feed port of the gas-liquid separator through a pipeline, and an upgrading back pressure valve is arranged on the pipeline.
Further preferably, a catalyst wall is arranged in the catalytic upgrading reactor, and the catalyst wall is of an annular structure formed by metal micro-grids wrapped with heterogeneous catalysts; the reaction material enters from the wall surface of the reactor and is discharged from the axial side.
Further preferably, the catalytic upgrading reaction unit further comprises an upgrading preheater having a microalgae liquefied oil side and an upgrading liquid side;
a discharge port of the liquefied oil high-pressure pump and a feed port of the catalytic upgrading reactor are respectively connected with an inlet and an outlet of a microalgae liquefied oil side of the upgrading preheater;
the discharge port of the catalytic upgrading reactor and the feed port of the upgrading back pressure valve are respectively connected with the inlet and the outlet of the upgrading liquid side of the upgrading preheater;
the first booster and the water tank high-pressure pump are connected to a pipeline between the liquefied oil high-pressure pump and the upgrading preheater.
Preferably, the hydrothermal liquefaction reaction unit comprises an algae slurry high-pressure pump and a hydrothermal liquefaction reactor,
the discharge hole of the algae slurry high-pressure pump is connected with the feed inlet of the hydrothermal liquefaction reactor;
the discharge port of the hydrothermal liquefaction reactor is connected with the feed port of the liquefaction centrifugal machine through a pipeline, and a liquefaction back pressure valve is arranged on the pipeline.
Further preferably, the hydrothermal liquefaction reaction unit further comprises a liquefaction preheater having an algal slurry side and a hydrothermal liquefaction reaction liquid side;
a discharge port of the algae slurry high-pressure pump and a feed port of the hydrothermal liquefaction reactor are respectively connected with an inlet and an outlet of an algae slurry side of the liquefaction preheater;
the discharge port of the hydrothermal liquefaction reactor and the feed port of the liquefaction back pressure valve are respectively connected with the inlet and the outlet of the hydrothermal liquefaction reaction liquid side of the liquefaction preheater.
Further preferably, the hydrothermal liquefaction reaction unit further comprises a storage tank, and the storage tank is connected with a feed inlet of the algae slurry high-pressure pump.
Preferably, the continuous catalytic upgrading reaction system for the microalgae liquefied oil further comprises a hydrogen recovery unit, wherein the hydrogen recovery unit comprises a hydrogen membrane separator;
the feed inlet of the hydrogen membrane separator is connected with the gas phase discharge outlet of the gas-liquid separator through a pipeline, and a second supercharger is arranged on the pipeline;
the hydrogen discharge port of the hydrogen membrane separator is connected with the first booster compressor through a pipeline.
Further preferably, the hydrogen recovery unit further comprises a gas storage cylinder, and the gas storage cylinder is connected with the waste gas outlet of the hydrogen membrane separator.
Preferably, the algae slurry high-pressure pump, the liquefied oil high-pressure pump, the water tank high-pressure pump and the first supercharger are respectively provided with a frequency converter controller.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention provides a continuous catalytic upgrading reaction system for microalgae liquefied oil, which comprises a hydrothermal liquefaction reaction unit, a hydrothermal liquefaction separation unit, a catalytic upgrading reaction unit, a catalytic upgrading separation unit and an oil storage tank, wherein the hydrothermal liquefaction reaction unit is connected with the hydrothermal liquefaction separation unit; the algae slurry as a reaction raw material enters a hydrothermal liquefaction reaction unit to generate a hydrothermal liquefaction reaction to generate microalgae liquefied oil; the hydrothermal liquefaction reaction liquid enters a liquefaction centrifugal machine, and the generated microalgae liquefaction oil is separated; the microalgae liquefied oil enters a catalytic upgrading reaction unit for reaction and then enters a catalytic upgrading separation unit; the catalytic upgrading separation unit is provided with a gas-liquid separator and an upgrading centrifuge, reaction gas can be quickly separated out from a reaction system, the residual liquid phase is separated by the upgrading centrifuge to obtain upgraded oil, and the upgraded oil enters an oil storage tank for storage. The arrangement of the liquefaction centrifugal machine, the gas-liquid separator and the quality improvement centrifugal machine can efficiently and continuously realize hydrothermal liquefaction and separation of catalytic quality improvement products, so that the whole continuous catalytic quality improvement reaction system for the microalgae liquefied oil can continuously and efficiently carry out continuous reaction, and the whole system is stable and reliable in operation and high in reaction efficiency.
Furthermore, the heterogeneous catalyst is wrapped in the metal microgrid, so that the catalyst can be ensured to be fully contacted with reaction materials, and the replacement of the catalyst is facilitated; the catalyst wall is of an annular structure, and the reaction materials enter from the wall surface of the reactor and are discharged from the axial side, so that all the reaction materials are ensured to necessarily pass through the catalyst wall and be fully contacted with the catalyst.
Furthermore, the arrangement of the hydrogen membrane separator can separate and utilize the residual hydrogen which does not participate in the reaction in the catalytic upgrading reaction again, thereby realizing the recycling of the reducing gas and saving the operation cost of the system; moreover, the hydrogen membrane separation technology can effectively separate hydrogen, and has the advantages of low investment and operation cost compared with the common low-temperature pressurized liquefied gas separation technology.
Furthermore, the arrangement of the liquefaction preheater and the quality improvement preheater enables the system to fully utilize the high-temperature fluid after the hydrothermal liquefaction reaction and the quality improvement reaction to preheat the material to be reacted, thereby effectively reducing the overall energy consumption and the operating cost of the reaction system.
Furthermore, frequency converter controllers are arranged on the algae slurry high-pressure pump, the liquefied oil high-pressure pump, the water tank high-pressure pump and the first supercharger; the control of the feeding amount and the material flow in the system is realized through the algae slurry high-pressure pump, the liquefied oil high-pressure pump, the first supercharger, the water tank high-pressure pump and the like, the residence time of reaction materials in the reactor can be adjusted, the whole reaction process is continuous, and the reaction of each step can be fully reacted.
Drawings
FIG. 1 is a schematic diagram of a continuous catalytic upgrading reaction system for microalgae liquefied oil provided by the invention.
The symbols used in the drawings of the specification are explained below:
1 is a material storage box; 2 is a high-pressure pump of algae pulp; a liquefaction preheater is arranged at the position 3; 4 is a hydrothermal liquefaction reactor; 5 is a hydrogen gas storage cylinder; 6 is a first supercharger; 7 is an upgrading preheater; 8 is a catalytic upgrading reactor; 9 is a hydrogen membrane separator; 10 is a gas storage cylinder; 11 is an oil storage tank; 12 is a quality-improved liquid storage bottle; 13 is a quality-improving centrifuge; 14 is a second supercharger; 15 is a gas-liquid separator; 16 is a quality-improving back pressure valve; 17 is a catalyst wall; 18 is a water storage tank; 19 is a water tank high-pressure pump; 20 is a liquefied oil high-pressure pump; 21 is a liquefaction sedimentation tank; 22 is a liquefaction centrifuge; 23 is a liquefaction back pressure valve.
Detailed Description
The present invention will be described in further detail with reference to specific examples and fig. 1, which are provided for illustration and not for limitation.
Example 1
A continuous catalytic upgrading reaction system for microalgae liquefied oil comprises a hydrothermal liquefaction reaction unit, a hydrothermal liquefaction separation unit, a catalytic upgrading reaction unit, a catalytic upgrading separation unit and an oil storage tank 11;
wherein the hydrothermal liquefaction reaction unit is connected with the hydrothermal liquefaction separation unit; the hydrothermal liquefaction separation unit is connected with the catalytic upgrading reaction unit; the catalytic upgrading reaction unit is connected with the catalytic upgrading separation unit; the catalytic upgrading separation unit is connected with the oil storage tank 11;
wherein the catalytic upgrading separation unit comprises a gas-liquid separator 15 and an upgrading centrifuge 13; a feed inlet of the gas-liquid separator 15 is connected with the catalytic upgrading reaction unit, and a liquid-phase discharge outlet of the gas-liquid separator 15 is connected with a feed inlet of the upgrading centrifugal machine 13; an oil phase discharge port of the quality-improving centrifuge 13 is connected with the oil storage tank 11;
the hydrothermal liquefaction separation unit comprises a liquefaction centrifugal machine 22, a feed inlet of the liquefaction centrifugal machine 22 is connected with the hydrothermal liquefaction reaction unit, and an oil phase discharge outlet of the liquefaction centrifugal machine 22 is connected with the catalysis quality-improvement reaction unit.
In a possible implementation manner, the gas-liquid separator 15 has a temperature control device and a pressure gauge, and the internal temperature of the gas-liquid separator 15 is lower than the saturation temperature of water corresponding to the working pressure. Thus, it is ensured that water is not mixed into the gas phase in the form of steam, and the working efficiency of the hydrogen membrane separator 9 is improved.
The invention provides a continuous catalytic upgrading reaction system for microalgae liquefied oil, which comprises a hydrothermal liquefaction reaction unit, a hydrothermal liquefaction separation unit, a catalytic upgrading reaction unit, a catalytic upgrading separation unit and an oil storage tank 11; the algae slurry as a reaction raw material enters a hydrothermal liquefaction reaction unit to generate a hydrothermal liquefaction reaction to generate microalgae liquefied oil; the hydrothermal liquefaction reaction liquid enters a liquefaction centrifugal machine 22 through a liquefaction back pressure valve 23, and the generated microalgae liquefaction oil is separated; the microalgae liquefied oil enters a catalytic upgrading reaction unit for reaction and then enters a catalytic upgrading separation unit; the catalytic upgrading separation unit is provided with a gas-liquid separator 15 and an upgrading centrifuge 13, reaction gas can be rapidly separated from a reaction system, and the residual liquid phase is separated by the upgrading centrifuge 13 to obtain upgraded oil which enters an oil storage tank 11 for storage.
The arrangement of the liquefaction centrifugal machine 22, the gas-liquid separator 15 and the quality-improving centrifugal machine 13 can efficiently and continuously realize hydrothermal liquefaction and separation of catalytic quality-improving products, so that the whole continuous catalytic quality-improving reaction system for the microalgae liquefied oil can continuously and efficiently carry out continuous reaction, and the whole system is stable and reliable in operation and high in reaction efficiency.
In a feasible implementation manner, the hydrothermal liquefaction separation unit further includes a liquefaction sedimentation tank 21, and the liquefaction sedimentation tank 21 is connected with a waste material discharge port of a liquefaction centrifuge 22; in this way, the residual liquid and the residue after the microalgae liquefied oil is separated by the liquefaction centrifuge 22 are discharged into the liquefaction sedimentation tank 21.
In a feasible implementation manner, the catalytic upgrading separation unit further comprises an upgrading liquid storage bottle 12, and the upgrading liquid storage bottle 12 is connected with a water phase discharge port of an upgrading centrifuge 13. Thus, the residual liquid separated by the quality-improving centrifuge 13 is sent to the quality-improving liquid storage bottle 12.
Example 2
A continuous catalytic upgrading reaction system of microalgae liquefied oil based on embodiment 1 is provided, wherein the catalytic upgrading reaction unit comprises a hydrogen gas storage bottle 5, a water storage tank 18, a liquefied oil high-pressure pump 20 and a catalytic upgrading reactor 8; wherein,
the feed inlet of the liquefied oil high-pressure pump 20 is connected with the oil phase discharge outlet of the liquefied centrifuge 22;
a discharge hole of the liquefied oil high-pressure pump 20 is connected with a feed hole of the catalytic upgrading reactor 8 through a pipeline;
the hydrogen gas storage bottle 5 is connected with a first booster 6 through a pipeline; the first booster 6 is connected to a pipeline between the liquefied oil high-pressure pump 20 and the catalytic upgrading reactor 8;
the water storage tank 18 is connected with a water tank high-pressure pump 19; the water tank high-pressure pump 19 is connected to a pipeline between the liquefied oil high-pressure pump 20 and the catalytic upgrading reactor 8; in some applications, deionized water is stored in the tank.
The discharge port of the catalytic upgrading reactor 8 is connected with the feed port of the gas-liquid separator 15 through a pipeline, and an upgrading back pressure valve 16 is arranged on the pipeline.
Thus, under the control of the liquefied oil high-pressure pump 20, the first booster 6 and the water tank high-pressure pump 19, the microalgae liquefied oil, hydrogen and water simultaneously enter the catalytic upgrading reactor 8 at a certain speed according to a preset ratio, and an upgrading reaction occurs. Upgrading backpressure valve 16 may maintain pressure in catalytic upgrading reactor 8 so that the catalytic upgrading reaction continues.
In a feasible implementation manner, a catalyst wall 17 is arranged in the catalytic upgrading reactor 8, and the catalyst wall 17 is an annular structure formed by metal microgrids wrapped with heterogeneous catalysts; the reaction material enters from the wall surface of the reactor and is discharged from the axial side. The heterogeneous catalyst is wrapped in the metal micro-grid, so that the catalyst can be ensured to be fully contacted with reaction materials, and the catalyst is convenient to replace; the annular structure of the catalyst wall 17 allows the reaction mass to enter through the wall of the reactor and exit axially, which further ensures that all the reaction mass must necessarily pass through the catalyst wall 17 and come into full contact with the catalyst.
Wherein, in one possible implementation, the catalytic upgrading reaction unit further comprises an upgrading preheater 7, the upgrading preheater 7 having a microalgae liquefied oil side and an upgrading liquid side;
a discharge port of the liquefied oil high-pressure pump 20 and a feed port of the catalytic upgrading reactor 8 are respectively connected with an inlet and an outlet of a microalgae liquefied oil side of the upgrading preheater 7;
a discharge port of the catalytic upgrading reactor 8 and a feed port of the upgrading back pressure valve 16 are respectively connected with an inlet and an outlet of the upgrading liquid side of the upgrading preheater 7;
the first booster 6 and the water tank high-pressure pump 19 are connected to a pipeline between the liquefied oil high-pressure pump 20 and the upgrading preheater 7.
The quality-improving preheater 7 is arranged, so that the system can fully utilize the high-temperature fluid after quality-improving reaction to preheat the material to be reacted, and the overall energy consumption and the operating cost of the reaction system are effectively reduced.
Example 3
A continuous catalytic upgrading reaction system of microalgae liquefied oil based on embodiment 1 or 2, wherein the hydrothermal liquefaction reaction unit comprises a microalgae slurry high-pressure pump 2 and a hydrothermal liquefaction reactor 4,
the discharge hole of the algae slurry high-pressure pump 2 is connected with the feed inlet of the hydrothermal liquefaction reactor 4;
the discharge port of the hydrothermal liquefaction reactor 4 is connected to the feed port of the liquefaction centrifuge 22 via a pipe, and a liquefaction back pressure valve 23 is provided in the pipe.
The liquefaction back-pressure valve 23 may maintain the pressure in the hydrothermal liquefaction reactor 4 so that the hydrothermal liquefaction reaction may be continuously performed.
Wherein, in a possible implementation manner, the hydrothermal liquefaction reaction unit further comprises a liquefaction preheater 3, and the liquefaction preheater 3 has an algae slurry side and a hydrothermal liquefaction reaction liquid side;
a discharge port of the algae slurry high-pressure pump 2 and a feed port of the hydrothermal liquefaction reactor 4 are respectively connected with an inlet and an outlet of an algae slurry side of the liquefaction preheater 3;
the discharge port of the hydrothermal liquefaction reactor 4 and the feed port of the liquefaction back pressure valve 23 are respectively connected with the inlet and the outlet of the hydrothermal liquefaction reaction liquid side of the liquefaction preheater 3.
The arrangement of the liquefaction preheater 3 enables the system to fully utilize the high-temperature fluid of the hydrothermal liquefaction reaction to preheat the materials to be reacted, thereby effectively reducing the overall energy consumption and the operating cost of the reaction system.
In a feasible implementation manner, the hydrothermal liquefaction reaction unit further comprises a storage tank 1, and the storage tank 1 is connected with a feed inlet of the algae slurry high-pressure pump 2. Therefore, the algae slurry with proper concentration can be placed in the storage box 1 in advance to meet the use requirement of the algae slurry high-pressure pump 2. In application, the algae slurry can be added into the storage tank 1 at one time, and the algae slurry can be continuously or intermittently fed into the storage tank 1 during the reaction process.
Example 4
A continuous catalytic upgrading reaction system of microalgae liquefied oil based on embodiment 2 or 3, wherein the system further comprises a hydrogen recovery unit, and the hydrogen recovery unit comprises a hydrogen membrane separator 9;
the feed inlet of the hydrogen membrane separator 9 is connected with the gas phase discharge outlet of the gas-liquid separator 15 through a pipeline, and the pipeline is provided with a second supercharger 14;
the hydrogen outlet of the hydrogen membrane separator 9 is connected with the first supercharger 6 through a pipeline.
The arrangement of the hydrogen membrane separator 9 can separate and utilize the residual hydrogen which does not participate in the reaction in the catalytic upgrading reaction again, thereby realizing the recycling of the reducing gas and saving the operation cost of the system; moreover, the hydrogen membrane separation technology can effectively separate hydrogen, and has the advantages of low investment and operation cost compared with the common low-temperature pressurized liquefied gas separation technology. The pressure of the hydrogen membrane separator 9 is controlled at an optimal working pressure point, so that the hydrogen in the gas phase can be quickly and efficiently separated; the polymer membrane used in the hydrogen membrane separator 9 has selectivity to the permeation rates of different gases, hydrogen with high permeation rate is rapidly separated when high-pressure gas flows through the polymer membrane in the separator, and other gases are discharged together with the high-pressure gas flow.
Wherein, in a feasible realization mode, the hydrogen recovery unit further comprises a gas storage cylinder 10, and the gas storage cylinder 10 is connected with the waste gas outlet of the hydrogen membrane separator 9.
Therefore, after the gas after the upgrading reaction enters the hydrogen membrane separator 9, hydrogen is separated and reused, and the rest gas is stored in the gas storage cylinder 10, so that the environmental pollution possibly caused by the emission of tail gas and the potential safety hazard caused by the residual combustible gas are avoided, and meanwhile, the available components in the tail gas have the opportunity to be separated and utilized.
In a feasible implementation manner, frequency converter controllers are arranged on the algae slurry high-pressure pump 2, the liquefied oil high-pressure pump 20, the water tank high-pressure pump 19 and the first supercharger 6; the control of the feeding amount and the material flow in the system is realized through the algae slurry high-pressure pump 2, the liquefied oil high-pressure pump 20, the first supercharger 6, the water tank high-pressure pump 19 and the like, the residence time of reaction materials in a reactor can be adjusted, the whole reaction process is continuous, and the reaction of each step can be fully reacted.
Example 5
A continuous catalytic upgrading reaction system of microalgae liquefied oil comprises a hydrothermal liquefaction reaction unit, a hydrothermal liquefaction separation unit, a catalytic upgrading reaction unit, a catalytic upgrading separation unit, a hydrogen recovery unit and an oil storage tank 11, wherein,
the hydrothermal liquefaction reaction unit comprises a storage tank 1, an algae slurry high-pressure pump 2, a liquefaction preheater 3, a hydrothermal liquefaction reactor 4 and a liquefaction back pressure valve 23, wherein the liquefaction preheater 3 is provided with an algae slurry side and a hydrothermal liquefaction reaction liquid side. The storage box 1 is connected with the feed inlet of the algae slurry high-pressure pump 2, the discharge outlet of the algae slurry high-pressure pump 2 and the feed inlet of the hydrothermal liquefaction reactor 4 are respectively connected with the inlet and the outlet of the algae slurry side of the liquefaction preheater 3, and the discharge outlet of the hydrothermal liquefaction reactor 4 and the feed inlet of the liquefaction back pressure valve 23 are respectively connected with the inlet and the outlet of the hydrothermal liquefaction reaction liquid side of the liquefaction preheater 3.
The hydrothermal liquefaction separation unit comprises a liquefaction centrifugal machine 22 and a liquefaction sedimentation tank 21, a feed inlet of the liquefaction centrifugal machine 22 is connected with a discharge outlet of a liquefaction back pressure valve 23, and an oil phase discharge outlet of the liquefaction centrifugal machine 22 is connected with a feed inlet of a liquefied oil high-pressure pump 20; the liquefaction sedimentation tank 21 is connected with a waste discharge port of the liquefaction centrifuge 22.
The catalytic upgrading reaction unit comprises a hydrogen gas storage bottle 5, a water storage tank 18, a liquefied oil high-pressure pump 20, an upgrading preheater 7, a catalytic upgrading reactor 8 and an upgrading back pressure valve 16, wherein the upgrading preheater 7 is provided with a microalgae liquefied oil side and an upgrading liquid side; a discharge port of the liquefied oil high-pressure pump 20 and a feed port of the catalytic upgrading reactor 8 are respectively connected with an inlet and an outlet of a microalgae liquefied oil side of the upgrading preheater 7; a discharge port of the catalytic upgrading reactor 8 and a feed port of the upgrading back pressure valve 16 are respectively connected with an inlet and an outlet of the upgrading liquid side of the upgrading preheater 7; the hydrogen gas storage bottle 5 is connected with a first booster 6 through a pipeline, the water storage tank 18 is connected with a water tank high-pressure pump 19, and the first booster 6 and the water tank high-pressure pump 19 are connected to a pipeline between a liquefied oil high-pressure pump 20 and the upgrading preheater 7. A catalyst wall 17 is arranged in the catalytic upgrading reactor 8, and the catalyst wall 17 is of an annular structure formed by metal micro-grids wrapped with heterogeneous catalysts; the reaction material enters from the wall surface of the reactor and is discharged from the axial side.
The catalytic upgrading separation unit comprises a gas-liquid separator 15, an upgrading liquid storage bottle 12 and an upgrading centrifuge 13; a feed inlet of the gas-liquid separator 15 is connected with the catalytic upgrading reaction unit, and a liquid-phase discharge outlet of the gas-liquid separator 15 is connected with a feed inlet of the upgrading centrifugal machine 13; an oil phase discharge port of the quality-improving centrifuge 13 is connected with the oil storage tank 11, and a quality-improving liquid storage bottle 12 is connected with a water phase discharge port of the quality-improving centrifuge 13.
The hydrogen recovery unit comprises a hydrogen membrane separator 9 and a gas storage cylinder 10. The feed inlet of the hydrogen membrane separator 9 is connected with the gas phase discharge outlet of the gas-liquid separator 15 through a pipeline, and the pipeline is provided with a second supercharger 14; the hydrogen discharge port of the hydrogen membrane separator 9 is connected with the first supercharger 6 through a pipeline, and the gas storage cylinder 10 is connected with the waste gas discharge port of the hydrogen membrane separator 9.
The algae slurry high-pressure pump 2, the liquefied oil high-pressure pump 20, the water tank high-pressure pump 19 and the first supercharger 6 are all provided with frequency converter controllers; the control of the feeding amount and the material flow in the system is realized through the algae slurry high-pressure pump 2, the liquefied oil high-pressure pump 20, the first supercharger 6, the water tank high-pressure pump 19 and the like, the residence time of reaction materials in a reactor can be adjusted, the whole reaction process is continuous, and the reaction of each step can be fully reacted.
The continuous catalytic upgrading reaction system for the microalgae liquefied oil provided by the embodiment has the working mode as follows: the algae slurry in the storage tank 1 is pumped into a hydrothermal liquefaction reaction system by an algae slurry storage high-pressure pump 2, and the reaction material enters a hydrothermal liquefaction reactor 4 to be heated to a specified temperature after being preheated by a liquefaction preheater 3 and to have hydrothermal liquefaction reaction. High-temperature fluid at the outlet of the hydrothermal liquefaction reactor 4 firstly enters the liquefaction preheater 3 to exchange heat with reaction materials, the outlet end of the liquefaction preheater 3 is connected with a liquefaction centrifugal machine 22 through a liquefaction back pressure valve 23, and the liquefaction centrifugal machine 22 is used for separating microalgae liquefied oil generated by hydrothermal liquefaction; the separated microalgae liquefied oil is pumped into an upgrading reaction system by a liquefied oil high-pressure pump 20, and the separated residual liquid and residue are discharged into a liquefied settling tank 21. The hydrogen in the hydrogen gas storage cylinder and the clean water in the water storage tank 18 are pumped into the quality-improving reaction system through a first booster 6 and a water tank high-pressure pump 19 respectively.
The inlet end of the catalytic upgrading reactor 8 is connected with an upgrading preheater 7, and the upgrading preheater 7 preheats materials before upgrading reaction by using the waste heat after catalytic upgrading reaction; the preheated material enters a catalytic upgrading reactor 8 to be continuously heated to a set reaction temperature and is used for the catalytic upgrading reaction of the microalgae liquefied oil. The reaction product cooled by the upgrading preheater 7 is decompressed by the upgrading back pressure valve 16 and then enters the gas-liquid separator 15 for separation of gas-phase products, and the separated gas phase is directly conveyed to the hydrogen membrane separator 9 through the second supercharger 14. The high-pressure gas flows through the high-molecular membrane in the hydrogen membrane separator 9, the hydrogen with high membrane permeation rate is separated out and recycled, and other gases are discharged along with the high-pressure gas flow and finally conveyed into the gas storage bottle 10. The outlet of the gas-liquid separator 15 is connected with the inlet of the quality-improving centrifuge 13, the quality-improving centrifuge 13 is used for separating quality-improved oil, the separated oil phase is stored in the oil storage tank 11, and the residual liquid is discharged into the quality-improving liquid storage bottle 12.
Claims (10)
1. A continuous catalytic upgrading reaction system for microalgae liquefied oil is characterized by comprising a hydrothermal liquefaction reaction unit, a hydrothermal liquefaction separation unit, a catalytic upgrading reaction unit, a catalytic upgrading separation unit and an oil storage tank (11) which are sequentially connected through a pipeline;
wherein the catalytic upgrading separation unit comprises a gas-liquid separator (15) and an upgrading centrifuge (13); a feed inlet of the gas-liquid separator (15) is connected with the catalytic upgrading reaction unit, and a liquid-phase discharge outlet of the gas-liquid separator (15) is connected with a feed inlet of the upgrading centrifugal machine (13); an oil phase discharge port of the quality-improving centrifugal machine (13) is connected with the oil storage tank (11);
the hydrothermal liquefaction separation unit comprises a liquefaction centrifugal machine (22), a feed inlet of the liquefaction centrifugal machine (22) is connected with the hydrothermal liquefaction reaction unit, and an oil phase discharge outlet of the liquefaction centrifugal machine (22) is connected with the catalysis quality-improvement reaction unit.
2. The continuous catalytic upgrading reaction system of microalgae liquefied oil according to claim 1, wherein the gas-liquid separator (15) has a temperature control device and a pressure gauge.
3. The continuous catalytic upgrading reaction system of microalgae liquefied oil as claimed in claim 1, wherein the catalytic upgrading reaction unit comprises a hydrogen gas storage cylinder (5), a water storage tank (18), a liquefied oil high-pressure pump (20) and a catalytic upgrading reactor (8);
wherein, a feed inlet of the liquefied oil high-pressure pump (20) is connected with an oil phase discharge outlet of a liquefied centrifugal machine (22); a discharge hole of the liquefied oil high-pressure pump (20) is connected with a feed inlet of the catalytic upgrading reactor (8) through a pipeline; the hydrogen gas storage bottle (5) is connected with a first booster (6) through a pipeline; the first booster (6) is connected to a pipeline between the liquefied oil high-pressure pump (20) and the catalytic upgrading reactor (8); the water storage tank (18) is connected with a water tank high-pressure pump (19); a water tank high-pressure pump (19) is arranged on a pipeline between the liquefied oil high-pressure pump (20) and the catalytic upgrading reactor (8); the discharge hole of the catalytic upgrading reactor (8) is connected with the feed hole of the gas-liquid separator (15) through a pipeline, and an upgrading back pressure valve (16) is arranged on the pipeline.
4. The continuous catalytic upgrading reaction system for microalgae liquefied oil according to claim 3, wherein a catalyst wall (17) is arranged in the catalytic upgrading reactor (8), and the catalyst wall (17) is an annular structure formed by metal microgrids wrapped with heterogeneous catalysts; the reaction material enters from the wall surface of the reactor and is discharged from the axial side.
5. The continuous catalytic upgrading reaction system of microalgae liquefied oil according to claim 3, wherein the catalytic upgrading reaction unit further comprises an upgrading preheater (7), the upgrading preheater (7) is provided with a microalgae liquefied oil side and an upgrading liquid side; a discharge port of the liquefied oil high-pressure pump (20) and a feed port of the catalytic upgrading reactor (8) are respectively connected with an inlet and an outlet of a microalgae liquefied oil side of the upgrading preheater (7); a discharge port of the catalytic upgrading reactor (8) and a feed port of the upgrading back pressure valve (16) are respectively connected with an inlet and an outlet of the upgrading liquid side of the upgrading preheater (7); a first booster (6) and a water tank high-pressure pump (19) are connected to a pipeline between a liquefied oil high-pressure pump (20) and the upgrading preheater (7).
6. The continuous catalytic upgrading reaction system of microalgae liquefied oil according to claim 1, wherein the hydrothermal liquefaction reaction unit comprises a algae slurry high-pressure pump (2) and a hydrothermal liquefaction reactor (4), and a discharge port of the algae slurry high-pressure pump (2) is connected with a feed port of the hydrothermal liquefaction reactor (4); the discharge port of the hydrothermal liquefaction reactor (4) is connected with the feed port of the liquefaction centrifugal machine (22) through a pipeline, and a liquefaction back pressure valve (23) is arranged on the pipeline.
7. The continuous catalytic upgrading reaction system of microalgae liquefied oil according to claim 6, wherein the hydrothermal liquefaction reaction unit further comprises a liquefaction preheater (3), the liquefaction preheater (3) having an algae slurry side and a hydrothermal liquefaction reaction liquid side; a discharge port of the algae slurry high-pressure pump (2) and a feed port of the hydrothermal liquefaction reactor (4) are respectively connected with an inlet and an outlet of the algae slurry side of the liquefaction preheater (3); the discharge hole of the hydrothermal liquefaction reactor (4) and the feed hole of the liquefaction back pressure valve (23) are respectively connected with the inlet and the outlet of the hydrothermal liquefaction reaction liquid side of the liquefaction preheater (3).
8. The continuous catalytic upgrading reaction system for microalgae liquefied oil according to claim 6, wherein the hydrothermal liquefaction reaction unit further comprises a storage tank (1), and the storage tank (1) is connected with a feeding port of the algae slurry high-pressure pump (2).
9. The continuous catalytic upgrading reaction system for microalgae liquefied oil as claimed in any one of claims 3 to 7, further comprising a hydrogen recovery unit, wherein the hydrogen recovery unit comprises a hydrogen membrane separator (9); the feed inlet of the hydrogen membrane separator (9) is connected with the gas phase discharge outlet of the gas-liquid separator (15) through a pipeline, and a second booster (14) is arranged on the pipeline; the hydrogen discharge port of the hydrogen membrane separator (9) is connected with the first booster (6) through a pipeline.
10. The continuous catalytic upgrading reaction system for microalgae liquefied oil as claimed in claim 9, wherein the hydrogen recovery unit further comprises a gas cylinder (10), and the gas cylinder (10) is connected with a waste gas outlet of the hydrogen membrane separator (9); the hydrothermal liquefaction separation unit also comprises a liquefaction sedimentation tank (21), and the liquefaction sedimentation tank (21) is connected with a waste material discharge hole of a liquefaction centrifugal machine (22); the catalytic upgrading separation unit further comprises an upgrading liquid storage bottle (12), and the upgrading liquid storage bottle (12) is connected with a water phase discharge port of an upgrading centrifugal machine (13).
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