1. A technology for preparing biomass activated carbon and coproducing synthesis gas by physical and chemical coupling activation is characterized by comprising the following steps:

1) crushing, washing and impurity removing and drying the biomass raw material, uniformly mixing the treated biomass raw material with an activating agent, putting the mixture into a carbonization-activation integrated reactor, heating the carbonization-activation integrated reactor to a carbonization temperature under the condition of introducing nitrogen into the reactor, and performing carbonization treatment;

2) step 1), after carbonization treatment is finished, keeping the temperature in the carbonization-activation integrated reactor at an activation temperature, and then switching gas introduced into the reactor into activated gas to carry out physical-chemical coupling activation treatment;

3) step 2), cooling to room temperature after the activation treatment is finished, taking out a product from an activating agent, washing the product with deionized water and 0.5-1.5 mol/L hydrochloric acid solution in sequence, washing the product with deionized water to be neutral, drying the product to obtain an activated carbon finished product, condensing and washing the synthesis gas generated in the carbon preparation process, and collecting the synthesis gas to a gas collecting tank;

wherein the chemical activating agent used in step 1) is an alkali metal salt to which a catalyst is added.

2. The process for preparing synthesis gas by co-production of biomass activated carbon through physical and chemical coupling activation as claimed in claim 1, wherein the biomass raw material is any one or a combination of agricultural waste and forestry waste; the agricultural waste is at least one of crop straws, bagasse and rice husks, the forestry waste is at least one of wood chips, bamboos, walnut shells and coconut shells, and the activated gas is one or two mixed gases of water vapor and carbon dioxide.

3. The process for preparing the co-production synthesis gas of the biomass activated carbon by the physical and chemical coupling activation as claimed in claim 1, wherein the alkali metal salt is a ternary mixed salt composed of lithium carbonate, sodium carbonate and potassium carbonate, the mass ratio is 28-35: 30-38, and the alkali metal salt is in a molten state at the carbonization temperature in the step 1) and the activation temperature in the step 2); the catalyst is Fe₂O₃、Fe₃O₄、FeCl₃、TiO₂、Co₂O₃、CoCl₂、Cr₂O₃、MgO、ZnCl₂The mass ratio of the catalyst to the alkali metal salt is 0.02-0.1: 1, preferably 0.02-0.06: 1.

4. The process for preparing biomass activated carbon through coproduction of synthesis gas by physical and chemical coupling activation as claimed in claim 1, wherein in the step 1), the mass ratio of the biomass raw material to the chemical activating agent is 0.5-2: 20, preferably 1: 20.

5. The process for preparing biomass activated carbon coproduced synthesis gas according to claim 1, wherein in the step 1), the carbonization treatment process comprises the following steps: and (3) raising the temperature of the carbonization-activation integrated reactor from room temperature to 500-600 ℃ at a temperature raising rate of 10-20 ℃/min, and then keeping the constant temperature for 1-2 h.

6. The process for preparing biomass activated carbon coproduced synthesis gas by physical and chemical coupling activation as claimed in claim 1, wherein in the step 2), the activation reaction temperature is 500-900 ℃, preferably 650-850 ℃; the mass ratio of the introduced activated gas to the biomass raw material is 0.5-2: 1, preferably 0.8-1.2: 1; the physical and chemical coupling activation time is 0.5-5 h, preferably 1-1.5 h.

7. A device for preparing biomass activated carbon coproduction synthesis gas by physical and chemical coupling activation is characterized by comprising a nitrogen storage tank (1), a carbon dioxide storage tank (2), a water vapor generating device, a carbonization-activation integrated reaction device and a gas-liquid product collecting device; the carbonization-activation integrated reaction device comprises an electric heating furnace (10), a carbonization-activation integrated reactor (11) and a thermocouple (13), a mixture of a biomass raw material and a chemical activating agent is contained in the carbonization-activation integrated reactor (11), a gas inlet (1101), a thermocouple jack (1102) and a gas product gas outlet (1103) are arranged at the top of the carbonization-activation integrated reactor (11), the temperature measuring end of the thermocouple (13) penetrates through the thermocouple jack (1102) to stretch into the reaction product of the carbonization-activation integrated reactor (11) for measuring the temperature, a gas distributor (12) is arranged in the carbonization-activation integrated reactor (11), the gas outlet of the gas distributor (12) is immersed into the mixture of the biomass raw material and the activating agent, and activated gas enters the gas distributor (12) from the gas inlet (1101) at the top of the carbonization-activation integrated reactor (11), the gas product outlet (1103) is connected with the gas product collecting device through a pipeline;

wherein, gas distributor (12) include intake pipe (1201), gaseous surge chamber (1202) and a plurality of square branch pipe (1203), intake pipe (1201) set up at the top of gaseous surge chamber (1202), a plurality of square branch pipe (1203) evenly set up the bottom at gaseous surge chamber (1202), the upper end and the carbomorphism of intake pipe (1201) activate gas inlet (1101) at integrative reactor (11) top and be connected, the lower extreme of square branch pipe (1203) evenly sets up a plurality of tongue shape water conservancy diversion holes (1204), the opening upper end outside of tongue shape water conservancy diversion hole (1204) is provided with the tongue piece of downward sloping, the contained angle on tongue piece and square branch pipe (1203) surface is 15~ 25.

8. The device for preparing the synthesis gas by the co-production of the biomass activated carbon through the physical and chemical coupling activation as claimed in claim 7, wherein the water vapor generation device comprises a water storage tank (5), a water pump (6), a gasification chamber (7), a gasification chamber heating furnace (8) and a heating belt (9), the gasification chamber heating furnace (8) is used for heating the gasification chamber (7) to raise the temperature, the gasification chamber (7) is provided with a liquid inlet, a gas inlet and a gas outlet, the gas outlets of the nitrogen storage tank (1) and the carbon dioxide storage tank (2) are connected with the gas inlet of the gasification chamber (7) through pipelines, the water pump (6) is used for conveying the water in the water storage tank (5) into the gasification chamber (7), and the gas outlet of the gasification chamber (7) is connected with a gas inlet (1101) at the top of the carbonization and activation integrated reactor (11) through a pipeline; wherein, the pipeline between the gas outlet of the gasification chamber (7) and the gas inlet (1101) is coated with the heating belt (9).

9. The device for preparing the synthesis gas by the co-production of the biomass activated carbon through the physical and chemical coupling activation as claimed in claim 7, wherein the gas-liquid product collecting device comprises a condenser (14), a liquid storage tank (15), a low-temperature cooling circulating pump (16), a scrubber tank (17) and a gas collecting tank (18); a gas product gas outlet (1103) at the top of the carbonization-activation integrated reactor (11) is connected with a gas inlet at the bottom of a condenser (14) through a pipeline, gas discharged from a gas outlet at the top of the condenser (14) is introduced into a gas washing tank (17) through a pipeline, and a gas outlet of the gas washing tank (17) is connected with a gas collecting tank (18) through a pipeline; a condensing jacket is arranged on the outer side of the condenser (14), and an inlet and an outlet of the condensing jacket are respectively connected with an outlet and an inlet of a low-temperature cooling circulating pump (16) through pipelines to form a condensed fluid loop; the liquid formed by condensation in the condenser (14) is collected in a liquid storage tank (15).

Background

The biomass energy is used as the fourth most energy in the world, and has important significance for maintaining the energy structure and safety of human society. Currently, the average biomass energy utilization rate is less than 40%, and most biomass energy is released in a combustion mode, so that how to realize high-efficiency and high-value utilization of biomass energy becomes one of important topics of current research. The preparation of biomass activated carbon and synthesis gas is an important way for realizing high-value utilization of biomass resources.

The activated carbon has the characteristics of developed pore structure, larger specific surface area, abundant surface chemical groups, stronger specific adsorption capacity and the like, and is widely applied to the fields of petrochemical industry, food, medicine, metallurgy, environmental management, energy storage and the like. The common preparation method of the activated carbon comprises the following steps: physical activation, chemical activation, and physical-chemical coupling activation. The commonly used activated gas of the physical activation method is water vapor, carbon dioxide, air, flue gas and the like, the activation process is simple, the environmental pollution is small, but the activation time is long, the temperature is high, and the energy consumption is large. The activating agents commonly used in the chemical activation method comprise potassium hydroxide, phosphoric acid, zinc chloride, potassium carbonate and the like, the activation temperature is low, the activation time is short, the yield of the activated carbon is high, the specific surface area is large, but most of chemical activating agents have corrosion behavior on equipment and are not friendly to the environment. The biomass synthesis gas can be used as chemical raw material or fuel, and the main component of the biomass synthesis gas is H₂And CO, typically to produce synthesis gas by pyrolysis of the gasified biomass. Pyrolysis is the decomposition reaction of organic matter in biomass under the action of heat to produce gas. The gasification takes air, water vapor and the like as gasifying agents and is carried out under the high-temperature conditionThe biomass is then converted to syngas by thermochemical reaction. The preparation technology of the synthesis gas has the difficulties of low grade of gas products, tar removal and the like.

Chinese patent (publication No. CN102417179A) discloses that peanut shells are used as biomass raw materials, potassium hydroxide and sodium hydroxide are used as activating agents to prepare a biomass with a specific surface area of 990-1277 m²Per gram of activated carbon. Chinese patent (CN201711481483.1) discloses a preparation method of supercapacitor activated carbon with controllable specific surface area, raw materials are carbonized for 23-25 hours at 700 ℃, and then are activated for 11-13 hours at 1180-1250 ℃ by taking water vapor as an activating agent to prepare the supercapacitor activated carbon with the specific surface area of 2000-2200 m²Per g of super activated carbon. Chinese patent (CN201811203217.7) discloses a 'downdraft straw carbonized carbon gas co-production device and a production method thereof', wherein the feeding amount of chip straw raw materials is 1.1t/h, the carbon yield is 308kg/h, and the biomass gas yield is 1764Nm³H is used as the reference value. Chinese patent (CN201410571477.5) discloses a carbon and gas co-production treatment method of garbage and production line equipment thereof, combustible gas generated in the production process is used for tail gas treatment, and the generated garbage carbon is used as power generation fuel.

Disclosure of Invention

Aiming at the problems of low multi-stage utilization rate of biomass, environmental-friendliness in the production process and the like in the existing biomass utilization technology, the invention aims to provide a process and a device for preparing biomass activated carbon through physical and chemical coupling activation. The addition of the related catalyst can reduce the generation of tar so as to improve the quality of the activated carbon and the synthesis gas.

The process for preparing the biomass activated carbon through the physical and chemical coupling activation to coproduce the synthesis gas is characterized by comprising the following steps of:

1) crushing, washing and impurity removing and drying the biomass raw material, uniformly mixing the treated biomass raw material with an activating agent, putting the mixture into a carbonization-activation integrated reactor, heating the carbonization-activation integrated reactor to a carbonization temperature under the condition of introducing nitrogen into the carbonization-activation integrated reactor, and performing carbonization treatment;

2) step 1), after carbonization treatment is finished, keeping the temperature in the carbonization-activation integrated reactor at an activation reaction temperature, and then switching gas introduced into the reactor into activated gas to carry out physical-chemical coupling activation treatment;

3) step 2), cooling to room temperature after the activation treatment is finished, taking the product out of the activating agent, washing the product with deionized water and 0.5-1.5 mol/L hydrochloric acid solution in sequence, washing the product with deionized water to be neutral, and drying the product to obtain an activated carbon finished product;

wherein the activator used in step 1) is an alkali metal salt to which a catalyst is added.

The process for preparing the biomass activated carbon coproduced synthesis gas by physical and chemical coupling activation is characterized in that the biomass raw material is any one or the combination of two of agricultural wastes and forestry wastes; the agricultural waste is at least one of crop straws, bagasse and rice husks, and the forestry waste is at least one of wood chips, bamboos, walnut shells and coconut shells; the activating gas is one or two mixed gases of water vapor and carbon dioxide.

The process for preparing the biomass activated carbon coproduction synthesis gas by physical and chemical coupling activation is characterized in that the alkali metal salt is a ternary mixed salt composed of lithium carbonate, sodium carbonate and potassium carbonate, and the mass ratio of the ternary mixed salt to the alkali metal salt is 28-35: 30-38, the alkali metal salt is in a molten state at the carbonization temperature in the step 1) and the activation temperature in the step 2), namely the alkali metal salt is in a molten state in the process of preparing the synthesis gas by co-production of the activated carbon. The catalyst is Fe₂O₃、Fe₃O₄、FeCl₃、TiO₂、Co₂O₃、CoCl₂、Cr₂O₃、MgO、ZnCl₂One or more than two of catalyst, catalyst and alkali metal saltThe mass ratio is 0.02-0.1: 1, preferably 0.02-0.06: 1.

The process for preparing the biomass activated carbon coproduced synthesis gas through physical and chemical coupling activation is characterized in that in the step 1), the mass ratio of the biomass raw material to the chemical activating agent is 0.5-2: 20, and preferably 1: 20.

The process for preparing the biomass activated carbon through the physical-chemical coupling activation and coproducing the synthesis gas is characterized in that in the step 1), the carbonization treatment process comprises the following steps: and (3) heating the temperature of the reactor from room temperature to a carbonization temperature of 500-600 ℃ at a heating rate of 10-20 ℃/min, and then keeping the temperature constant for 1-2 hours.

The production process for preparing the biomass activated carbon is characterized in that in the step 2), the activation reaction temperature is 500-900 ℃, preferably 650-850 ℃; the mass ratio of the introduced activated gas to the biomass raw material is 0.5-2: 1, preferably 0.8-1.2: 1; the physical and chemical coupling activation time is 0.5-5 h, preferably 1-1.5 h.

The device for preparing the biomass activated carbon coproduction synthesis gas by physical and chemical coupling activation is characterized by comprising a nitrogen storage tank, a carbon dioxide storage tank, a water vapor generating device, a carbonization-activation integrated device and a gas-liquid product collecting device; the carbonization-activation integrated reaction device comprises an electric heating furnace, a carbonization-activation integrated reactor and a thermocouple, a biomass raw material and activator mixture is contained in the carbonization-activation integrated reactor, a gas inlet, a thermocouple jack and a gas product outlet are arranged at the top of the carbonization-activation integrated reactor, the temperature measuring end of the thermocouple penetrates through the thermocouple jack and extends into the carbonization-activation integrated reactor to measure the temperature, a gas distributor is arranged in the carbonization-activation integrated reactor, a gas outlet of the gas distributor is immersed in the biomass raw material and activator mixture, activated gas enters the gas distributor from the gas inlet at the top of the carbonization-activation integrated reactor, and the gas product outlet is connected with a gas-liquid product collecting device through a pipeline;

wherein, gas distributor includes intake pipe, gaseous surge chamber and a plurality of square branch pipe, the intake pipe sets up the top at gaseous surge chamber, and a plurality of square branch pipes evenly set up in the bottom of gaseous surge chamber, and the upper end of intake pipe is connected with the gaseous air inlet at the integrative reactor top of carbomorphism activation, and the lower extreme of square branch pipe evenly sets up a plurality of gaseous tongue shape water conservancy diversion holes, and the opening upper end outside in tongue shape water conservancy diversion hole is provided with the tongue piece of downward sloping, and the tongue piece is 15~25 with the contained angle on square branch pipe surface.

The device for preparing the biomass activated carbon coproduction synthesis gas through physical and chemical coupling activation is characterized in that the water vapor generating device comprises a water storage tank, a water pump, a gasification chamber heating furnace and a heating belt, wherein the gasification chamber heating furnace is used for heating and warming the gasification chamber, the gasification chamber is provided with a liquid inlet, a gas inlet and a gas outlet, gas outlets of the nitrogen storage tank and the carbon dioxide storage tank are connected with the gas inlet of the gasification chamber through pipelines, the water pump is used for conveying water in the water storage tank into the gasification chamber, and the gas outlet of the gasification chamber is connected with a gas inlet at the top of the carbonization and activation integrated reactor through a pipeline; wherein, the heating belt is coated on the pipeline between the gas outlet of the gasification chamber and the gas inlet of the carbonization-activation integrated reactor.

The device for preparing the biomass activated carbon coproduction synthesis gas by virtue of carbonization-activation coupling is characterized in that the gas-liquid product collecting device comprises a condenser, a liquid storage tank, a low-temperature circulating cooling pump, a gas washing tank and a gas collecting tank; a gas product gas outlet at the top of the carbonization-activation integrated reactor is connected with a gas inlet at the bottom of the condenser through a pipeline, gas discharged from the gas outlet at the top of the condenser is introduced into a gas washing tank through the pipeline, and a gas outlet of the gas washing tank is connected with a gas collecting groove through the pipeline; a condensing jacket is arranged outside the condenser, and an inlet and an outlet of the condensing jacket are respectively connected with an outlet and an inlet of the low-temperature cooling circulating pump through pipelines to form a condensed fluid loop; the liquid formed by condensation in the condenser is collected in a liquid storage tank.

The beneficial effects obtained by the invention are as follows:

1. the biomass activated carbon is prepared by a physical-chemical coupling activation method, so that the activation temperature is reduced, the activation time is shortened, and the production cost is reduced. The specific surface area, the pore volume and the pore size distribution of the activated carbon are regulated and controlled by changing the type of the activated gas, the type and the proportion of the catalyst and the alkali metal salt.

2. The alkali metal salt added with the catalyst is used as a heat medium and a chemical activating agent, and metal ions in the molten alkali metal salt permeate into biomass particles in the activation process, so that the heat and mass transfer rate in the biomass is increased, the activation time is obviously shortened, and the activation temperature is reduced. The catalyst can change the pyrolysis gasification process of the biomass raw material, can effectively reduce the generation of byproduct tar, and is beneficial to improving the quality of the activated carbon and the synthesis gas.

3. The arrangement of the gas distributor improves the contact state of the activating agent and the biomass raw material in the reactor and increases the contact probability of the activating agent and the carbonized material. The activated gas escapes from the mixture of the carbonized material and the molten alkali metal salt in a bubbling mode through the tongue-shaped diversion holes which are arranged downwards, so that the stirring effect is achieved, and the contact between the activated gas and the carbonized material and the heat transfer and mass transfer effects are enhanced.

4. The biomass activated carbon and the synthesis gas are co-produced through preparation, so that the multi-stage utilization of biomass resources and the diversification and high-valued of biomass products are realized, and the method has important significance for assisting in realizing the aims of carbon peak reaching and carbon neutralization.

Drawings

FIG. 1 is a schematic structural diagram of a production apparatus for preparing biomass activated carbon according to the present invention;

FIG. 2 is a cross-sectional view of a carbonization-activation integrated reactor of the present invention;

FIG. 3 is a front view of the gas distributor of the present invention;

FIG. 4 is a top view of a gas distributor of the present invention;

in fig. 1: 1-a nitrogen storage tank; 2-a carbon dioxide storage tank; 3-a pressure reducing valve; 4-a flow meter; 5-a water storage tank; 6, a water pump; 7-a gasification chamber; 8-a gasification chamber furnace; 9-heating a belt; 10-an electric heating furnace; 11-carbonization-activation integrated reactor; 12-a gas distributor; 13-a thermocouple; 14-a condenser; 15-a liquid storage tank; 16-cryogenic cooling circulation pump; 17-a scrubber tank; 18-a gas collecting tank;

in fig. 2: 1101-gas inlet; 1102-thermocouple insertion holes; 1103-gas product outlet.

In fig. 3 and 4: 1201-intake pipe; 1202-gas buffer chamber; 1203-square manifold; 1204-tongue deflector hole.

Detailed Description

The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.

Example (b): compare FIGS. 1 to 4

A process for preparing biomass activated carbon and coproducing synthesis gas by physical and chemical coupling activation comprises the following steps:

and washing the crushed biomass raw material with water to remove impurities, and drying for later use. Uniformly mixing the treated biomass raw material with a chemical activating agent, putting the mixture into a carbonization and activation integrated reactor, and carbonizing the material in a nitrogen atmosphere. And after carbonization, keeping the temperature in the carbonization-activation integrated reactor at the activation temperature, and introducing activated gas to activate the raw material. And after activation, cooling to room temperature, taking out a product from the chemical activator to obtain crude activated carbon, washing the crude activated carbon with water, dissolving most of the activator on the surface of the crude activated carbon in water, washing with 1mol/L hydrochloric acid solution to remove redundant activator and ash, washing with deionized water to be neutral, and drying to obtain a finished product. The biomass raw material is any one or the combination of two of agricultural wastes and forestry wastes; the agricultural waste is at least one of crop straws, bagasse and rice husks, and the forestry waste is at least one of wood chips, bamboos, walnut shells and coconut shells; the activating gas is one or two mixed gases of water vapor and carbon dioxide.

The alkali metal salt is prepared from the following components in a mass ratio of 30-35: 30-35: and 32-38 of ternary mixed salt of lithium carbonate, sodium carbonate and potassium carbonate, wherein the ternary mixed salt is in a molten state in the process of preparing the activated carbon coproduction synthesis gas. The catalyst is Fe₂O₃、Fe₃O₄、FeCl₃、TiO₂、Co₂O₃、CoCl₂、Cr₂O₃、MgO、ZnCl₂The mass ratio of the catalyst to the alkali metal salt is 0.02-0.1: 1, preferably 0.02-0.06: 1.

The mass ratio of the biomass raw material to the chemical activating agent is 0.5-2: 20, preferably 1: 20.

The nitrogen flow rate is 0.1 to 1L/min, preferably 0.3 to 0.5L/min.

The temperature is 500-900 deg.C, and the activated gas is preferably 650-850 deg.C.

The time for the physicochemical coupling activation is 0.5 to 5 hours, preferably 1 to 1.5 hours.

The mass ratio of the introduced activated gas to the biomass raw material is 0.5-2: 1, preferably 0.8-1.2: 1.

A device for preparing biomass activated carbon coproduction synthesis gas by physical and chemical coupling activation comprises a nitrogen storage tank 1, a carbon dioxide storage tank 2, a water vapor generation device, a carbonization and activation integrated device and a gas-liquid product collection device; the integrated carbonization-activation device comprises an electric heating furnace 10, an integrated carbonization-activation reactor 11 and a thermocouple 13, a biomass raw material and an activating agent mixture are contained inside the integrated carbonization-activation reactor 11, a gas inlet 1101, a thermocouple jack 1102 and a gas product gas outlet 1103 are arranged at the top of the integrated carbonization-activation reactor 11, the temperature measuring end of the thermocouple 13 penetrates through the thermocouple jack 1201 to extend into the integrated carbonization-activation reactor 11 for measuring the temperature, a gas distributor 12 is arranged inside the integrated carbonization-activation reactor 11, the gas outlet of the gas distributor 12 is immersed into the biomass raw material and the activating agent mixture, the activated gas enters the gas distributor 12 from the gas inlet 1101 at the top of the integrated carbonization-activation reactor, and the gas product gas outlet 1103 is connected with a gas product collecting device through a pipeline.

The gas distributor 12 comprises a gas inlet pipe 1201, a gas buffer chamber 1202 and a plurality of square branch pipes 1203, the gas inlet pipe 1201 is arranged at the top of the gas buffer chamber 1202, the square branch pipes 1203 are uniformly arranged at the bottom of the gas buffer chamber 1202, the upper end of the gas inlet pipe 1201 is connected with a gas inlet 1101 at the top of the carbonization-activation integrated reactor 11, a plurality of uniform tongue-shaped guide holes 1204 are formed in the lower end of the square branch pipe 1203, a tongue piece which is inclined downwards is arranged on the outer side of the upper end of an opening of the tongue-shaped guide hole 1204, and the included angle between the tongue piece and the surface of the square branch pipe 1203 is 15-25 degrees.

Further, the gas buffer chamber 1202 comprises a cylindrical chamber and an annular chamber arranged outside the cylindrical chamber, the cylindrical chamber is communicated with the annular chamber through at least 3 pipeline chambers, the gas inlet pipe 1201 is arranged at the top of the cylindrical chamber of the gas buffer chamber 1202, and a plurality of square branch pipes 1203 are uniformly arranged at the bottom of the cylindrical chamber and the bottom of the annular chamber. In the comparison of fig. 4, the bottom of the cylindrical chamber is provided with 4 square pipe branches 1203, and the bottom of the annular chamber is provided with 6 square pipe branches 1203.

The water vapor generating device comprises a water storage tank 5, a water pump 6, a gasification chamber 7, a gasification chamber heating furnace 8 and a heating belt 9, wherein the gasification chamber heating furnace 8 is used for heating the gasification chamber 7, the gasification chamber 7 is provided with a liquid inlet, a gas inlet and a gas outlet, gas outlets of the nitrogen storage tank 1 and the carbon dioxide storage tank 2 are connected with the gas inlet of the gasification chamber 7 through pipelines, the water pump 6 is used for conveying water in the water storage tank 5 into the gasification chamber 7, and the gas outlet of the gasification chamber 7 is connected with a gas inlet 1101 at the top of the carbonization and activation integrated reactor 11 through a pipeline; wherein, the heating band 9 is coated on the pipeline between the gas outlet of the gasification chamber 7 and the gas inlet 1101. Wherein the temperature of the gasification chamber is 200-400 ℃, preferably 200-250 ℃.

The gas-liquid product collecting device comprises a condenser 14, a liquid storage tank 15, a condensation circulating pump 16, a gas washing tank 17 and a gas collecting tank 18; a gas product gas outlet 1103 at the top of the carbonization-activation integrated reactor 11 is connected with a gas inlet at the bottom of the condenser 14 through a pipeline, gas discharged from a gas outlet at the top of the condenser 14 is introduced into a gas washing tank 17 through a pipeline, and a gas outlet of the gas washing tank 17 is connected with a gas collecting tank 18 through a pipeline; a condensing jacket is arranged on the outer side of the condenser 14, and an inlet and an outlet of the condensing jacket are respectively connected with an outlet and an inlet of a condensing circulating pump 16 through pipelines to form a condensed fluid loop; the liquid formed by condensation in the condenser 14 is collected in a liquid storage tank 15.

In the comparison graph 1, a nitrogen storage tank 1 and a carbon dioxide storage tank 2 are both provided with a pressure reducing valve 3, the gas outlets of the nitrogen storage tank 1 and the carbon dioxide storage tank 2 are respectively connected to a main gas inlet pipe through branch pipes, a flow meter 4 is arranged on the main gas inlet pipe, and the outlet of the main gas inlet pipe is connected with the gas inlet of a gasification chamber 7.

Example 1:

a process for preparing biomass activated carbon and coproducing synthesis gas by physical and chemical coupling activation comprises the following steps:

1) screening 10 g of cedar chips by using a screen of 80-100 meshes as a raw material, washing with water, drying, uniformly mixing with a chemical activating agent, putting into a reactor with the nitrogen flow of 0.3L/min, heating to carbonize, raising the temperature of the reactor from room temperature to 600 ℃ at the heating rate of 10 ℃/min, and keeping the constant temperature for 1.5 h.

2) After the carbonization treatment is finished, the temperature of the carbonization-activation integrated reactor is raised to 650 ℃ at the heating rate of 10 ℃/min, the introduction of nitrogen is stopped, water vapor with the mass flow of 10 g/h is introduced into the reactor, and the physical-chemical coupling activation treatment is carried out for 1.5 h. Wherein the total amount of the chemical activating agent is 200 g, and the chemical activating agent is formed by mixing a catalyst and an alkali metal salt according to the mass ratio of 0.02: 1. The alkali metal salt is a mixed salt of lithium carbonate, sodium carbonate and potassium carbonate in a mass ratio of 3:3:4, and the catalyst is Fe in a mass ratio of 2:1₂O₃And Co₂O₃And (3) mixing the catalyst.

3) And after the reaction in the step 2), washing the activated crude activated carbon by using deionized water and 1mol/L hydrochloric acid solution in sequence to remove salt and ash in the activated crude activated carbon, washing the activated crude activated carbon by using deionized water to be neutral, and drying to obtain an activated carbon finished product, wherein the yield of the activated carbon is 11.4%. The BET specific surface area of the activated carbon product is 575.99 m by characterization²The pore volume is 0.3839 mL/g, the average pore diameter is 2.44 nm, and the micropore volume accounts for 74.77%.

Example 2:

a process for preparing biomass activated carbon and coproducing synthesis gas by physical and chemical coupling activation comprises the following steps:

1) screening 10 g of cedar chips by using a 80-100-mesh screen as a raw material, washing with water, drying, uniformly mixing with an activating agent, putting into a carbonization-activation integrated reactor, heating the temperature of the reactor from room temperature to 600 ℃ at a heating rate of 10 ℃/min, and keeping for 1.5 h.

2) After the carbonization treatment in the step 1), heating at a heating rate of 10 ℃/minAnd (3) raising the temperature of the carbonization and activation integrated reactor to 650 ℃, stopping introducing nitrogen, introducing water vapor with the mass flow of 10 g/h into the reactor, and performing physical-chemical coupling activation treatment for 0.5 h. Wherein the total amount of the activating agent is 200 g, and the activating agent is formed by mixing a catalyst and an alkali metal salt according to the mass ratio of 0.02: 1. The alkali metal salt is a mixed salt of lithium carbonate, sodium carbonate and potassium carbonate in a mass ratio of 3:3:4, and the catalyst is Fe in a mass ratio of 2:1₂O₃And Co₂O₃And (3) mixing the catalyst.

3) And 2) after the reaction in the step 2), washing the activated crude activated carbon by using deionized water and 1mol/L hydrochloric acid solution in sequence to remove salt and ash in the activated crude activated carbon, washing the activated crude activated carbon by using deionized water to be neutral, and drying the activated crude activated carbon to obtain an activated carbon finished product, wherein the yield of the activated carbon is 13.1%. The BET specific surface area of the comparative product is 555.16 m by characterization²The pore volume was 0.3024 mL/g, the average pore diameter was 2.56 nm, and the micropore volume was 70.23%.

Example 3:

a process for preparing biomass activated carbon and coproducing synthesis gas by physical and chemical coupling activation comprises the following steps:

1) screening 10 g of China fir sawdust by using a 80-100-mesh screen as a raw material, washing with water, drying, uniformly mixing with an activating agent, and putting into a carbonization-activation integrated reactor with the nitrogen flow of 0.3L/min for heating and carbonization. The reactor temperature was raised from room temperature to 600 ℃ at a ramp rate of 10 ℃/min and then held at constant temperature for 1.5 h.

2) After the carbonization treatment is finished, the temperature of the carbonization-activation integrated reactor is raised to 700 ℃ at the heating rate of 10 ℃/min, the introduction of nitrogen is stopped, water vapor with the mass flow of 10 g/h is introduced into the reactor, and the physical-chemical coupling activation treatment is carried out for 1.5 h. Wherein the total amount of the activating agent is 200 g, and the activating agent is formed by mixing a catalyst and an alkali metal salt according to the mass ratio of 0.1: 1. The alkali metal salt is a mixed salt of lithium carbonate, sodium carbonate and potassium carbonate in a mass ratio of 3:3:4, and the catalyst is Fe in a mass ratio of 2:1₂O₃And Co₂O₃And (3) mixing the catalyst.

3) Inverse directionAnd after the reaction is finished, washing the crude activated carbon obtained by activation by using ionized water and 1mol/L hydrochloric acid solution in sequence to remove salt and ash in the crude activated carbon, washing the crude activated carbon to be neutral by using the ionized water, and drying to obtain an activated carbon finished product, wherein the yield of the activated carbon is 9.3%. The BET specific surface area of the activated carbon product is 1049.40 m by characterization²The pore volume was 0.7535 mL/g, the average pore diameter was 2.83 nm, and the micropore volume was 69.38%.

Example 4:

a process for preparing biomass activated carbon and coproducing synthesis gas by physical and chemical coupling activation comprises the following steps:

1) screening 10 g of China fir sawdust by using a 80-100-mesh screen as a raw material, washing with water, drying, uniformly mixing with an activating agent, and putting into a carbonization-activation integrated reactor with the nitrogen flow of 0.3L/min for heating and carbonization. The temperature of the carbonization-activation integrated reactor is raised from room temperature to 600 ℃ at the temperature raising rate of 10 ℃/min, and then the temperature is kept constant for 1.5 h.

2) After the carbonization treatment is finished, the temperature of the carbonization-activation integrated reactor is raised to 700 ℃ at the heating rate of 10 ℃/min, the introduction of nitrogen is stopped, water vapor with the mass flow of 10 g/h is introduced into the carbonization-activation integrated reactor, and the physical-chemical coupling activation treatment is carried out for 1.5 h. Wherein the total amount of the activating agent is 200 g, and the activating agent is formed by mixing a catalyst and an alkali metal salt according to the mass ratio of 0.05: 1. The alkali metal salt is a mixed salt of lithium carbonate, sodium carbonate and potassium carbonate in a mass ratio of 3:3:4, and the catalyst is Fe in a mass ratio of 2:1₂O₃And Co₂O₃And (3) mixing the catalyst.

3) After the reaction is finished, washing the activated crude activated carbon by using ionized water and 1mol/L hydrochloric acid solution in sequence to remove salt and ash in the activated crude activated carbon, washing the activated crude activated carbon by using the ionized water to be neutral, and drying the activated crude activated carbon to obtain an activated carbon finished product, wherein the yield of the activated carbon is 10.1%. The BET specific surface area of the comparative product is 821.08 m by characterization²The pore volume is 0.5222 mL/g, the average pore diameter is 3.03nm, and the micropore volume accounts for 68.31%.

The main components of the synthesis gas collected in examples 1 to 4 are shown in Table 1, and the main component of the synthesis gas isH₂、CO、CH₄、CO₂Four gases, the balance being impurity gases.

The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.