CN111234888A - System and method for recycling supercritical water reaction product and wet biomass - Google Patents
System and method for recycling supercritical water reaction product and wet biomass Download PDFInfo
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Abstract
A system for recycling supercritical water reaction products in conjunction with wet biomass, comprising: the supercritical water reaction product separation system is used for carrying out gas-liquid separation on the supercritical water reaction product; a wet biomass separation and recovery system for performing solid-oil-water three-phase separation of wet biomass; microalgae cultivation and concentration system, water phase obtained by supercritical water reaction product separation system and wet biomass separation and recovery system, and CO obtained by supercritical water reaction product separation system2Performing microalgae photobiological reaction to culture microalgae, and concentrating the microalgae slurry outlet by a concentration device; the hydrothermal liquefaction oil production system is used for producing oil by performing hydrothermal liquefaction on concentrated algae slurry of a concentration device and an oil phase obtained by a wet biomass separation and recovery system. The invention also provides a corresponding comprehensive microalgae culture and bio-oil preparation method, and realizes the environment-friendly comprehensive resource utilization of wastewater, grease and gas in the process.
Description
Technical Field
The invention belongs to the technical field of waste recycling and waste heat utilization, relates to environment-friendly comprehensive recycling of heat, wastewater, grease and gas in the process of processing wet biomass and supercritical water, and particularly relates to a system and a method for recycling supercritical water reaction products in cooperation with wet biomass.
Background
Supercritical water treatment is a high-efficiency harmless treatment and resource utilization technology of high-concentration organic waste liquid, and is a process of rapidly converting organic macromolecules into water and hydrogen-rich fuel gas in an anaerobic or anoxic state or rapidly converting the organic macromolecules into pollution-free micromolecular compounds and inorganic salts in an peroxy condition by utilizing the characteristics of high diffusion coefficient, low viscosity, low dielectric constant and the like of supercritical water in water with temperature and pressure higher than the critical state.
The wet biomass refers to biomass with high water content, and comprises organic waste liquid, animal manure, water bloom blue algae, kitchen waste and the like. Taking kitchen waste as an example, the kitchen waste usually comprises grease, leftovers, vegetable leaves, fruit peels, egg shells and the like, kitchen waste is not less than 6000 million tons generated in China cities every year, and the kitchen waste yield in large and medium cities is staggering.
One of the major problems affecting the industrialization of supercritical water reactions is the economics of the treatment process. Mainly in the aspects of effective recovery and utilization of system energy and substances. The fluid after reaction is generally maintained at a high temperature (> 500 ℃), and then the energy needs to be fully utilized to ensure the economical efficiency of the treatment system. Meanwhile, in the treatment process, the organic matter is fully reacted to generate a large amount of carbon dioxide. If not utilized, direct discharge can cause greenhouse effect. Meanwhile, the conventional wet biomass treatment method such as kitchen waste and the like is mainly used for mixing and stacking with household waste in the prior art by traditional incineration and landfill. The recycling of resources such as grease and the like can not be realized, and the environment is greatly damaged.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a system and a method for recycling supercritical water reaction products and wet biomass, which can efficiently utilize resources in the supercritical water reaction products to cooperate with wet biomass recycling, realize the environment-friendly comprehensive recycling of wastewater, grease and gas in the process, solve the problems in the supercritical water reaction and common wet biomass treatment and disposal processes, and have important engineering application value.
In order to achieve the purpose, the invention adopts the technical scheme that:
a system for recycling supercritical water reaction products in conjunction with wet biomass, comprising:
the supercritical water reaction product separation system is used for carrying out gas-liquid separation on the supercritical water reaction product;
a wet biomass separation and recovery system for performing solid-oil-water three-phase separation of wet biomass;
microalgae cultivation and concentration system, water phase obtained by supercritical water reaction product separation system and wet biomass separation and recovery system, and CO obtained by supercritical water reaction product separation system2Performing microalgae photobiological reaction to culture microalgae, and concentrating the microalgae slurry outlet by a concentration device;
the hydrothermal liquefaction oil production system is used for producing oil by performing hydrothermal liquefaction on concentrated algae slurry of a concentration device and an oil phase obtained by a wet biomass separation and recovery system.
The supercritical water reaction product separation system comprises a first heat exchanger, a hot fluid inlet of the first heat exchanger is connected with an outlet of the supercritical water reactor, a hot fluid outlet of the first heat exchanger is connected with an inlet of a first back pressure device,the outlet of the first back pressure device is connected with the inlet of the gas-liquid separator, the liquid outlet of the gas-liquid separator is connected with the water phase storage tank, and CO2The gas outlet is connected with the gas phase inlet of the microalgae culturing and concentrating system, and the outlet of the water phase storage tank is connected with the water phase inlet of the microalgae culturing and concentrating system.
The wet biomass separation and recovery system comprises a crusher, wherein an inlet of the crusher is connected with a wet biomass material outlet, an outlet of the crusher is connected with an inlet of a solid-oil-water separator, a solid-phase outlet of the solid-oil-water separator is connected with an inlet of the dry distillation equipment, and a water-phase outlet is connected with an inlet of the water-phase storage tank.
The microalgae culturing and concentrating system comprises a microalgae photobioreactor, the water phase inlet of the microalgae photobioreactor is connected with the outlet of the water phase storage tank, and the gas phase inlet is connected with the CO2And the gas outlet and the outlet are connected with the inlet of the concentration device, and the water phase outlet of the concentration device is connected with the inlet of the water phase storage tank.
The hydrothermal liquefaction oil production system comprises a second heat exchanger, a hot fluid inlet of the second heat exchanger is connected with a concentrated algae slurry outlet of the concentration device and an oil phase outlet of the solid-oil-water separator through a high-pressure pump, a hot fluid outlet of the second heat exchanger is connected with an inlet of the hydrothermal liquefaction reactor, an outlet of the hydrothermal liquefaction reactor is connected with a hot fluid inlet of the third heat exchanger, a hot fluid outlet of the third heat exchanger is connected with an inlet of a second backpressure device, an outlet of the second backpressure device is connected with an inlet of an oil-water-gas-solid separator, an oil phase outlet of the oil-water-gas-solid separator outputs biological crude oil, a gas phase outlet is connected with a gas phase inlet of the microalgae photobioreactor, a water phase outlet is connected back to an inlet of the water phase storage tank, and.
And a cooling water inlet of the first heat exchanger is connected with a cooling water outlet of the second heat exchanger, and a cooling water outlet of the first heat exchanger is connected with a cooling water inlet of the second heat exchanger.
And a cooling water inlet of the heat exchanger III is connected with a cooling water outlet of the dry distillation equipment, and a cooling water outlet of the heat exchanger III is connected with a cooling water inlet of the dry distillation equipment.
According to the invention, through arranging the first heat exchanger and the second heat exchanger, the cooling water is adopted to recover the surplus heat of the high-temperature fluid at the outlet of the supercritical water reactor through heat exchange, and the surplus heat is used for the preheating process of the hydrothermal liquefaction reaction of the concentrated algae slurry. And the surplus heat after the hydrothermal reaction is recovered by arranging a heat exchanger III and is used for the dry distillation process of the solid residues in the system.
H generated by supercritical water reaction of the invention2The combustible gas can be recovered by a high-pressure gas separator. CO separated after supercritical water fluid decompression through gas-liquid separation and hydrothermal liquefaction reaction2The recovered product is utilized in a microalgae photobioreactor.
The water after the supercritical water reaction, the microalgae concentrated leachate and the water separated from the product after the microalgae hydrothermal reaction are recycled and used as a water source in the microalgae photobioreactor for recycling.
The oil separated by the oil-water-solid separator after the wet biomass is crushed is recovered and then is mixed with the concentrated algae slurry for improving the oil yield of the hydrothermal oil-making reaction.
According to the invention, the solid-phase residue after the wet biomass separation and the solid-phase residue after the microalgae hydrothermal reaction fluid separation are collected and subjected to dry distillation to prepare the biochar, so that the resource utilization of the biochar is realized.
The invention also provides a method for realizing the recycling of supercritical water reaction products and wet biomass, which comprises the following steps:
1) the supercritical water reaction product is high-temperature fluid with the temperature of more than or equal to 500 ℃, the high-temperature fluid is separated into hydrogen-rich gas in a high-pressure gas separator and then enters a gas-liquid separator to separate CO2This part of CO is introduced2Recovering and using the recovered carbon source as a carbon source required in the growth of the microalgae in the microalgae cultivation process; the content of organic matters in the water phase product is greatly reduced, COD is less than or equal to 1000mg/L, and the water phase product has no biotoxicity, and can be recycled as a culture water body in the microalgae culture process after being recycled;
2) crushing wet biomass, and separating solid, oil and water in a solid-oil-water three-phase separator; wherein the water phase is rich in protein and organic matters, is recycled and utilized in the microalgae cultivation process, and the solid phase residue is dehydrated, dried and dry distilled to prepare biochar;
3) in the microalgae photobiological reactionCarrying out a microalgae cultivation process in a reactor, collecting after ripening, concentrating in a concentration device, leaching out liquid containing N, P elements, recycling in a microalgae photobioreactor after blending, mixing and preheating grease obtained by separating concentrated algae slurry and wet biomass to 250-370 ℃, then entering an hydrothermal liquefaction reactor, obtaining bio-oil after separating, preparing biochar after carrying out dry distillation on solid phase products, and enabling gas products to be rich in CO2And the recovered carbon source is used as a microalgae growth carbon source and returned to the photobioreactor for recycling, and the water phase is returned to the photobioreactor for recycling.
And recovering surplus heat of the fluid through a first heat exchanger, utilizing the surplus heat in the preheating process of the microalgae hydrothermal liquefaction oil preparation process, and preheating grease obtained by separating concentrated algae slurry from wet biomass to 250-370 ℃ through a second heat exchanger.
The cooling water is circulated in the process, and an additional cooling water source is not needed to be supplemented.
Compared with the prior art, the invention has the beneficial effects that:
by combining supercritical water reaction, hydrothermal liquefaction and wet biomass high-value utilization technologies, system heat and generated CO are recovered to the maximum extent2Grease, water resources and nutrient elements in wet biomass such as solid-phase residue, kitchen waste and the like are subjected to microalgae hydrothermal liquefaction to prepare bio-oil, so that high-value utilization of resources is achieved. The process has no secondary pollution and has remarkable social and economic benefits.
Drawings
FIG. 1 is a schematic diagram of the system architecture of the present invention.
Detailed Description
The invention is further described below with reference to the drawings and the specific examples. The examples are intended to be illustrative of the invention only and are not intended to limit the scope of the disclosure.
The invention is mainly based on the following principle:
in the supercritical water reaction, because water is used as a reaction medium, if a large amount of water can be effectively recycled and utilized in the process, water resources can be greatly saved.
The wet biomass, particularly the kitchen waste, basically does not contain heavy metals, is rich in organic matters and has high content of biochar. The collected kitchen waste can be subjected to preliminary impurity removal, and then organic matter dry residue and an oil-water mixture can be obtained by means of centrifugation, separation and the like. The organic dry slag can be used for preparing biochar. After the oil-water mixture is separated again, the oil can be used for producing biodiesel, and the finally remained water contains rich organic matters, substances such as nitrogen, phosphorus and the like besides high-concentration salt, and can be used for microalgae culture, carbon dioxide fixation and preparation of biological crude oil.
The microalgae has the advantages of high photosynthesis efficiency, strong carbon fixation capacity, short cultivation period, small occupied area, no land competition with grains and the like, and is considered as a third-generation biofuel raw material with great potential, the unit oil yield of the microalgae is hundreds of times of that of the corn, and 1.5-8 ten thousand liters of biodiesel can be produced per hectare. The microalgae is used for preparing the bio-oil, so that excessive dependence on petroleum and coal can be reduced, absorption and fixation of carbon dioxide can be realized, greenhouse effect is reduced, and obvious environmental benefit is achieved. The bio-oil preparation is carried out on the microalgae by adopting a hydrothermal liquefaction technology, and compared with the traditional technology, the bio-oil preparation method has the characteristics of high oil yield, good oil product quality and the like. Meanwhile, after the oil-water mixture after hydrothermal liquefaction is separated, the water-phase product is rich in necessary nutrient elements in the growth process of microalgae, can be recycled, and has remarkable economical efficiency.
Based on the above, as shown in FIG. 1, the invention combines the supercritical water reaction process, wet biomass separation and recovery, microalgae culture and hydrothermal liquefaction oil production process, fully utilizes the technical advantages, and realizes water and CO2And recycling the nutrient substances, the oil and the solid-phase residue. Taking kitchen waste as an example, the kitchen waste is mainly embodied in the following aspects:
1) after supercritical water reaction, the temperature of the fluid is up to 500-600 ℃, waste heat is recovered through a heat exchanger, the temperature of the fluid is reduced to below 50 ℃, and then hydrogen-rich combustible gas is separated through a high-pressure gas separator. Then the water phase and the carbon dioxide are separated after the pressure is reduced to normal pressure through a backpressure device. Separated CO2And the carbon source enters the microalgae culture photobioreactor through a gas distribution system to provide a carbon source for the growth of the microalgae. The liquid phase is mainly water and some organic compounds, soluble nitrates, phosphates and the like which are not completely reacted, and is mixed with insoluble inorganic salt solid particles such as coke, silicates and the like, and the COD of the liquid phase is<1000mg/L, can be used as a microalgae culture water body and enters a water phase storage tank.
2) The main components of the wet biomass kitchen waste can comprise lignocellulose, organic compounds, grain residues, grease, fruit peels, bones, shells, food packages and the like. The wet biomass firstly passes through a crusher, the solid is crushed into particles with the particle size of less than 1cm, the particles enter a solid-oil-water three-phase separator after deodorization, the water phase is rich in water-soluble protein and amino acid and can provide nutrient elements necessary for the growth of the microalgae, and the water phase enters a water phase storage tank after dilution. And preparing the solid-phase residue into biochar through dry distillation. The heat in the dry distillation process is obtained from surplus heat recovered from fluid after hydrothermal reaction. The main component of the grease is triglyceride, and the grease is recycled and mixed with the concentrated algae slurry to improve the yield of the biological oil.
3) Adding the water and algae seeds recovered from the water phase storage tank into a photobioreactor, and adding CO2Uniformly enters the photoreactor through a gas supply system to control CO2The air supply concentration is 10 percent, and the air flow rate is controlled to be 0.25 to 1L/min. Adjusting the pH value of the water body to 6-8, adjusting the nitrogen concentration to 80-165 mg/L and the nitrogen-phosphorus ratio to 6-9, and controlling sulfate ions<0.35mmol/L, phenol concentration<100mg/L, 25-30 g/L of salinity, 0.8-1.2 g/L of potassium ion concentration, calcium and magnesium ion concentration>30mg/L, the iron/phosphorus ratio was adjusted to 0.7. Adjusting the water temperature to 20-30 DEG C
4) After microalgae is cultured, concentrated algae slurry is formed through enrichment and dehydration, and filtrate contains necessary nutrient elements and is recycled in the photobioreactor after returning to the water phase storage tank. After the algae slurry and the recovered grease are fully and uniformly mixed, the materials are pressurized to 15-25 MPa through a high-pressure pump.
5) After the materials are pressurized, the materials are preheated to 250-370 ℃ through a second heat exchanger and enter a hydrothermal liquefaction reactor. And (3) after 2-5min of reaction time, the reaction fluid flows out of the reactor, the temperature of the reaction fluid is reduced to below 50 ℃ through a third heat exchanger, and the surplus heat of the fluid is used in the dry distillation process of the solid residues in the system. And reducing the temperature of the reaction fluid to normal pressure through a back pressure device II. The reaction fluid is in a solid, oil and water three-phase state (containing a small amount of gas products) at normal temperature and normal pressure, and the biological oil is obtained after separation. And (3) recovering the water phase product, then feeding the water phase product into a water phase storage tank, recycling the water phase product in the microalgae culture process, collecting the solid phase product, then separating the solid phase product from the wet biomass, mixing the solid phase product with the solid phase residue, and preparing the biochar through the dry distillation process.
6) All cooling water in the system circularly enters the system after heat exchange, and no additional cooling water source is introduced.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical solution according to the technical idea of the present invention is within the protection scope of the claims of the present invention.
Claims (10)
1. A system for recycling supercritical water reaction products in cooperation with wet biomass, comprising:
the supercritical water reaction product separation system is used for carrying out gas-liquid separation on the supercritical water reaction product;
a wet biomass separation and recovery system for performing solid-oil-water three-phase separation of wet biomass;
microalgae cultivation and concentration system, water phase obtained by supercritical water reaction product separation system and wet biomass separation and recovery system, and CO obtained by supercritical water reaction product separation system2Performing microalgae photobiological reaction to culture microalgae, and concentrating the microalgae slurry outlet by a concentration device;
the hydrothermal liquefaction oil production system is used for producing oil by performing hydrothermal liquefaction on concentrated algae slurry of a concentration device and an oil phase obtained by a wet biomass separation and recovery system.
2. The system for recycling supercritical water reaction products as claimed in claim 1, wherein the supercritical water reaction product separation system comprises a first heat exchanger, a hot fluid inlet of the first heat exchanger is connected with an outlet of the supercritical water reactor, and a hot fluid outlet of the first heat exchanger is connected with a backpressure deviceAn inlet of the first backpressure device, an outlet of the first backpressure device is connected with an inlet of the gas-liquid separator, a liquid outlet of the gas-liquid separator is connected with the water phase storage tank, and CO2The gas outlet is connected with the gas phase inlet of the microalgae culturing and concentrating system, and the outlet of the water phase storage tank is connected with the water phase inlet of the microalgae culturing and concentrating system.
3. The system for recycling supercritical water reaction products and wet biomass together as claimed in claim 2, wherein the wet biomass separation and recovery system comprises a crusher, an inlet of the crusher is connected with a wet biomass material outlet, an outlet of the crusher is connected with an inlet of a solid-oil-water separator, a solid phase outlet of the solid-oil-water separator is connected with an inlet of the dry distillation equipment, and a water phase outlet is connected with an inlet of the water phase storage tank.
4. The system of claim 3, wherein the system for culturing and concentrating microalgae comprises a microalgae photobioreactor, the water phase inlet of the microalgae photobioreactor is connected to the outlet of the water phase storage tank, and the gas phase inlet is connected to the CO2And the gas outlet and the outlet are connected with the inlet of the concentration device, and the water phase outlet of the concentration device is connected with the inlet of the water phase storage tank.
5. The system for recycling supercritical water reaction products together with wet biomass as claimed in claim 4, wherein the hydrothermal liquefaction oil production system comprises a second heat exchanger, a hot fluid inlet of the second heat exchanger is connected with a concentrated algae slurry outlet of the concentrating device and an oil phase outlet of the solid-oil-water separator through a high pressure pump, a hot fluid outlet of the second heat exchanger is connected with an inlet of the hydrothermal liquefaction reactor, an outlet of the hydrothermal liquefaction reactor is connected with a hot fluid inlet of the third heat exchanger, a hot fluid outlet of the third heat exchanger is connected with an inlet of the second backpressure device, an outlet of the second backpressure device is connected with an inlet of the oil-water-gas-solid separator, an oil phase outlet of the oil-water-gas-solid separator outputs the bio-crude oil, a gas phase outlet is connected with a gas phase inlet of the microalgae photobioreactor, a water phase outlet is connected back to an inlet of the water phase storage tank, and.
6. The system for recycling supercritical water reaction products in coordination with wet biomass as claimed in claim 5, wherein a cooling water inlet of the first heat exchanger is connected to a cooling water outlet of the second heat exchanger, a cooling water outlet of the first heat exchanger is connected to a cooling water inlet of the second heat exchanger, a cooling water inlet of the third heat exchanger is connected to a cooling water outlet of the dry distillation equipment, and a cooling water outlet of the third heat exchanger is connected to a cooling water inlet of the dry distillation equipment.
7. The system for recycling supercritical water reaction products in cooperation with wet biomass as claimed in claim 5 or 6, wherein the wet biomass is kitchen waste.
8. A method for realizing the recycling of supercritical water reaction products and wet biomass is characterized by comprising the following steps:
1) the supercritical water reaction product is high-temperature fluid with the temperature of more than or equal to 500 ℃, and the high-temperature fluid is separated into hydrogen-rich combustible gas and CO in a high-pressure gas separator and a gas-liquid separator respectively2This part of CO is introduced2Recovering and using the recovered carbon source as a carbon source required in the growth of the microalgae in the microalgae cultivation process; the content of organic matters in the water phase product is greatly reduced, COD is less than or equal to 1000mg/L, and the water phase product has no biotoxicity, and can be recycled as a culture water body in the microalgae culture process after being recycled;
2) crushing wet biomass, and separating solid, oil and water in a solid-oil-water three-phase separator; wherein the water phase is rich in protein and organic matters, is recycled and utilized in the microalgae cultivation process, and the solid phase residue is dehydrated, dried and dry distilled to prepare biochar;
3) carrying out microalgae cultivation process in a microalgae photobioreactor, collecting after ripening, concentrating in a concentration device, leaching out liquid containing N, P elements, recycling in the microalgae photobioreactor after blending, mixing and preheating grease obtained by separating concentrated algae slurry and wet biomass to 250-370 ℃, and then entering an aqueous hydrothermal liquefaction reactor, wherein the product fluid is oil, water, a solid phase and a small amount of gasSeparating the mixed product to obtain bio-oil, dry distilling the solid product to prepare biochar, and enriching CO in the gas product2And the recovered carbon source is used as a microalgae growth carbon source and returned to the photobioreactor for recycling, and the water phase is returned to the photobioreactor for recycling.
9. The method for realizing the recycling of supercritical water reaction products and wet biomass as claimed in claim 8, wherein the surplus heat of the fluid is recovered by the first heat exchanger and utilized in the preheating process of the oil preparation process by microalgae hydrothermal liquefaction, and the grease obtained by separating the concentrated algae slurry from the wet biomass is preheated to 250-370 ℃ by the second heat exchanger.
10. The method for recycling supercritical water reaction products and wet biomass as claimed in claim 8, wherein the cooling water is circulated during the process without supplementing additional cooling water source.
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| CN113322110A (en) * | 2021-04-07 | 2021-08-31 | 西安交通大学 | Device and method for preparing fuel and humic acid liquid by treating waste vegetable leaves with hydrothermal method |
| CN114308981A (en) * | 2021-12-27 | 2022-04-12 | 上海工程技术大学 | Multi-generation comprehensive utilization system and treatment process for treating wet garbage by supercritical water |
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| CN110527558A (en) * | 2019-07-26 | 2019-12-03 | 西安交通大学 | A kind of wet biomass produces the continuous reaction system of flammable biogas |
| CN211896835U (en) * | 2020-03-11 | 2020-11-10 | 西安交通大学 | System for supercritical water reaction product is wet biomass resource in coordination |
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| CN113322110A (en) * | 2021-04-07 | 2021-08-31 | 西安交通大学 | Device and method for preparing fuel and humic acid liquid by treating waste vegetable leaves with hydrothermal method |
| CN114308981A (en) * | 2021-12-27 | 2022-04-12 | 上海工程技术大学 | Multi-generation comprehensive utilization system and treatment process for treating wet garbage by supercritical water |
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