An environmentally friendly binary carbonate cyclic reaction system

Abstract

The present application discloses an environmentally friendly binary carbonate circulation reaction system, including a reaction system, a spray system, a delivery pump, a filter and a membrane separator, wherein the reaction system includes a reactor. The reactor is filled with molten salt, and the upper part of the reactor is provided with a biomass feed port, a molten salt inlet, a gasification agent inlet and a pyrolysis gas outlet, and the upper part of the reactor side wall is provided with an overflow port, and the molten salt liquid level in the reactor is slightly higher than the overflow port; the overflow port of the reactor is connected to the spray system through an overflow pipe, and the activated carbon produced by the reaction in the reactor can overflow into the spray system together with the molten salt, and the spray system sprays clean water for washing treatment, filtering, and drying the wet activated carbon filter residue to obtain an activated carbon product, and the filtrate is desalinated by the membrane separator, and the obtained concentrated salt solution is reused in the reactor. The present invention realizes the recycling of water vapor and molten salt in the reaction system, strengthens the reaction, simplifies the process, and has the advantages of environmental protection, energy saving and no consumption.

Description

Technical Field

[0001] The present application belongs to the field of biomass gasification and cracking, and specifically relates to an environmentally friendly binary carbonate circulation reaction system. Background Art

[0002] In the process of biomass gasification to produce activated carbon, since the activated carbon is evenly distributed in the molten salt, the general mechanical separation method is to scrape the crude activated carbon product on the surface of the salt cake after the molten salt is cooled into a salt cake to separate the activated carbon and the molten salt body, which is a cumbersome process. In addition, the activated carbon pickling solution cannot be reused, and the molten salt cannot be directly recycled in the system, which has the disadvantage of high energy consumption. Therefore, an environmentally friendly binary carbonate circulation reaction system is urgently needed. Summary of the invention

[0003] In view of the above problems, the purpose of the present application is to provide an environmentally friendly binary carbonate circulation reaction system, which realizes that the water vapor generated in the reaction system and the separated binary carbonate can be recycled, and the pneumatic system simultaneously produces a stirring effect, and can activate and produce activated carbon below the molten salt liquid level, and utilize the temperature change of the molten salt to make the activated carbon overflow, which has the advantages of being environmentally friendly and zero consumption.

[0004] The environmentally friendly binary carbonate circulation reaction system is characterized by comprising a reaction system, a spray system, a delivery pump, a filter and a membrane separator, wherein the reaction system comprises a reactor; the reactor contains molten salt, and the upper part of the reactor is provided with a biomass feed port, a molten salt inlet, a gasification agent inlet and a pyrolysis gas outlet, and the upper part of the side wall of the reactor is provided with an overflow port, and the molten salt liquid level in the reactor is slightly higher than the overflow port on the upper part of the side wall; the overflow port of the reactor is connected to the spray system through an overflow pipe, and the liquid outlet of the spray system is connected to the filter through a pipeline through a delivery pump, and the filtrate outlet of the filter is connected to the membrane separator through a pipeline, and control valves are provided on the corresponding pipelines;

[0005] The biomass and the gasifying agent react catalytically in the molten salt in the reactor to generate activated carbon and pyrolysis gas. The activated carbon can float to the surface of the molten salt and be sent to the spray system through the overflow port through the pipeline together with a small amount of molten salt; the spray system sprays clean water on the activated carbon-molten salt mixture entering, and the water vapor generated during the washing process is reused in the reactor for catalytic reaction, and a mixed solution of brine solution and activated carbon is formed at the same time, which is then transported to the filter by a delivery pump for filtration. The wet activated carbon filter residue is dried to obtain an activated carbon product, and the filtrate is sent to a membrane separator for desalination treatment to obtain fresh water and concentrated salt solution. The fresh water can be reused in the spray system, and the concentrated salt solution can be reused in the reactor for catalytic reaction.

[0006] The environmentally friendly binary carbonate cyclic reaction system is characterized in that the spray system includes a spray chamber, a spray head and a clean water inlet pipe arranged inside the upper end of the spray chamber, the clean water inlet pipe penetrates into the spray chamber and is connected to the spray head, so as to spray clean water into the spray chamber to wash the molten salt, and form a mixed solution of salt water solution and activated carbon in the spray chamber;

[0007] The fresh water side outlet of the membrane separator is connected to the side of the clean water inlet pipe by a pipeline, so that the fresh water obtained by the desalination treatment of the membrane separator can be sprayed into the spray chamber through the spray head; the concentrated water side outlet of the membrane separator is connected to the molten salt inlet side of the reactor by a pipeline, so that the concentrated salt solution obtained by the desalination treatment of the membrane separator can be reused in the reactor for catalytic reaction.

[0008] The environmentally friendly binary carbonate circulation reaction system is characterized in that a steam outlet is also provided at the top of the spray chamber. When clean water is sprayed in the spray chamber to cool the molten salt, part of the water vaporizes at the high temperature of the molten salt to form water vapor; the water vapor discharged from the steam outlet at the top of the spray chamber is reused in the reactor through a pipeline as a gasifying agent.

[0009] The environmentally friendly binary carbonate circulation reaction system is characterized in that it also includes a rotary kiln. The wet activated carbon filtered out by the filter is sent to the rotary kiln. The pyrolysis gas formed by the reaction in the reactor is discharged from the pyrolysis gas outlet at the top of the reactor, ignited in the heating sleeve to be converted into flue gas, and then sent to the rotary kiln as a heat source for heating the rotary kiln. The moisture in the wet activated carbon is vaporized by heat to form water vapor, and the water vapor can be reused in the reactor as a gasifying agent.

[0010] The environmentally friendly binary carbonate circulation reaction system is characterized in that the reaction system also includes a sleeve assembly, which consists of a sleeve and a turntable vertically fixedly installed on the outer side of the lower end of the sleeve, the sleeve is rotatably arranged on the top of the reactor, and the turntable is arranged in the reactor; a notch is provided on the turntable so that when biomass is fed through the biomass feed port on the upper part of the reactor, the biomass can enter the molten salt through the notch on the turntable; when the biomass and the gasification agent are catalytically reacted in the molten salt in the reactor, the turntable is slightly immersed below the surface of the molten salt, and the rotation of the sleeve drives the turntable to rotate together to prevent the biomass in the molten salt from floating to the surface.

[0011] The environmentally friendly binary carbonate circulation reaction system is characterized in that the reaction system further comprises a coil assembly, the coil assembly comprises a hollow connecting rod sleeved inside the casing and a mosquito coil arranged at the lower end of the hollow connecting rod, the upper end of the hollow connecting rod passes through the casing, and the mosquito coil is provided with a plurality of air outlets; wherein the hollow connecting rod and the casing are rotatably sealed and connected;

[0012] When the biomass and the gasifier undergo a catalytic reaction in the molten salt in the reactor, the mosquito-repellent coil is immersed in the molten salt, and the hollow connecting rod rotates to drive the mosquito-repellent coil to rotate together. At the same time, the gasifier is introduced into the upper end of the hollow connecting rod, and the gasifier is discharged through a number of air outlets on the mosquito-repellent coil and is evenly distributed in the molten salt to contact and react with the biomass.

[0013] The environmentally friendly binary carbonate circulation reaction system is characterized in that a heating jacket is arranged on the outside of the reactor, and the heating jacket is an electric heating jacket or a sandwich casing. The electric heating jacket heats the reactor by energizing, and the sandwich casing heats the reactor by passing high-temperature flue gas. A flue gas inlet and a flue gas outlet are arranged on the sandwich casing; wherein the heating jacket includes a side wall heating jacket arranged on the outside of the side of the reactor and a bottom heating jacket arranged on the outside of the bottom of the reactor.

[0014] The environmentally friendly binary carbonate circulation reaction system is characterized in that when the catalytic reaction of biomass and gasification agent is carried out in the molten salt of the reactor, it includes the following steps:

[0015] 1) Start the side wall heating jacket on the outside of the side of the reactor and the bottom heating jacket on the outside of the bottom of the reactor to heat the reactor to 700-1000°C, add the biomass into the molten salt in the reactor through the notch on the turntable, the turntable of the sleeve assembly is slightly immersed below the surface of the molten salt, and the sleeve assembly rotates to make the biomass and the molten salt fully contact, the mosquito coil of the coil assembly is immersed in the molten salt, and the gasifier is introduced. The gasifier is discharged through a number of air outlets on the mosquito coil, and a stirring effect is generated while pneumatically moving, so that the gasifier and the biomass are fully contacted and reacted in the molten salt;

[0016] 2) After the biomass is gasified and cracked, the casing assembly and the coil assembly are lifted above the molten salt liquid level, and the bottom heating jacket on the outside of the bottom of the reactor is closed to slowly cool the molten salt to 400-500°C. The density of the bottom molten salt changes, and the activated carbon generated by the reaction slowly floats to the surface of the molten salt and is sent to the spray system through the overflow port along with a small amount of molten salt;

[0017] 3) The spray system sprays clean water on the activated carbon-molten salt mixture entering for washing. Part of the clean water is gasified by the high temperature of the molten salt and circulated to the reactor after preheating for reuse as a gasification agent. The sprayed mixture is filtered through a filter to obtain wet activated carbon, which is then heat exchanged with pyrolysis gas in a rotary kiln to obtain dry activated carbon. The water vapor generated during the heat exchange process is preheated and circulated to the reactor for reuse as a gasification agent. The brine solution obtained by the sprayed mixture through the filter is then desalinated by a membrane separator to obtain fresh water and concentrated salt solution. The fresh water can be reused in the spray system, and the concentrated salt solution can be reused in the reactor for catalytic reaction.

[0018] The environmentally friendly binary carbonate cyclic reaction system is characterized in that the molten salt is a binary eutectic of sodium carbonate and potassium carbonate, the mass ratio of sodium carbonate to potassium carbonate is 60:40-40:60, preferably 55.5:44.5; the reaction temperature is 700-1000°C, and the gasifying agent is water vapor; the biomass is coconut shell, walnut shell, chestnut shell, bamboo powder or cellulose monomer, and the cellulose monomer is glucose or cellobiose.

[0019] The environmentally friendly binary carbonate circulation reaction system is characterized in that the reaction system can be applied to molten salt catalytic decoking to produce hydrogen, biomass gasification to produce hydrogen, biomass gasification to produce activated carbon or biomass gasification to produce supercapacitors.

[0020] Compared with the prior art, the beneficial effects achieved by this application are:

[0021] 1) The application provides an environmentally friendly binary carbonate circulation reaction system, which simplifies the mechanical separation process, is low-cost, has a rapid reaction, is safe and environmentally friendly, and enables the water vapor generated in the reaction system and the separated binary carbonate to be recycled. The movement of the gasifying agent also produces a stirring effect, and can activate the activated carbon below the molten salt liquid level. The activated carbon overflows by utilizing the temperature change of the molten salt, which has the advantages of being environmentally friendly and non-consumption.

[0022] 2) In the present application, while the spray system cools the molten salt, part of the water is vaporized by the high temperature of the molten salt and circulated to the reaction system after preheating; the wet activated carbon obtained by filtration is heat exchanged with the pyrolysis gas in a heat exchanger to obtain the finished dry activated carbon, and the water vapor obtained in the heat exchange process is preheated and circulated back to the reaction system, so that the heat can be recycled, thereby better solving the energy consumption problem of the entire process.

[0023] 3) In the present application, a mixture of sodium carbonate and potassium carbonate (i.e., binary molten carbonate) with a mass ratio of 60:40-40:60 is used as a heat medium and catalyst, and the mass ratio is preferably 55.5:44.5 (melting point is 710.3°C), which is suitable for a reaction temperature of 700-1000°C, has the advantages of extremely low corrosion to equipment, stable chemical properties, low viscosity, large specific heat capacity, good catalytic activation effect and recyclability.

[0024] The binary carbonate circulation reaction system provided in the present application utilizes molten salt as a heat transfer medium and catalyst. The water vapor generated in the process and the separated binary carbonate can be recycled, which has the advantages of being environmentally friendly and zero consumption. It can also be coupled with a gasification agent to produce biomass activated carbon in one step, thereby reducing tar production. At the same time, the product activated carbon can be separated by temperature change of molten salt, so that the system provides technical support for the industrial production of activated carbon and the decoking process of hydrogen production. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 This is a schematic diagram of the process flow of the binary carbonate circulation reaction system of the present application;

[0026] Figure 2 This is a schematic diagram of the structure of the electrically heated binary carbonate circulation reaction system of the present application;

[0027] Figure 3 This is a schematic structural diagram of the flue gas heated binary carbonate circulation reaction system of the present application;

[0028] Figure 4 is a schematic diagram of the structure of a gas distributor;

[0029] In the figure: 1-reaction system, 1-1 side wall heating jacket, 1-2 bottom heating jacket, 1-3 ceramic lining, 1-4 reactor, 1-5 hollow connecting rod, 1-6 casing, 1-7 turntable, 1-8 mosquito coil, 1-9 overflow pipe, 2-spraying system, 2-1 spray head, 2-2 spray chamber, 3-delivery pump, 4-filter, 5-membrane separator, 6-rotary kiln, 7-heating casing, 8-heat exchanger. DETAILED DESCRIPTION

[0030] The present invention will be further described below in conjunction with specific embodiments, but the protection scope of the present invention is not limited thereto.

[0031] Example: Control Figure 1-4

[0032] An environmentally friendly binary carbonate circulation reaction system comprises a reaction system, a spray system, a delivery pump 3, a filter 4 and a membrane separator 5, wherein the reaction system comprises a reactor 1-4. The reactor 1-4 contains molten salt, and the upper part of the reactor 1-4 is provided with a biomass feed port, a molten salt inlet, a gasification agent inlet and a pyrolysis gas outlet, and the upper part of the side wall of the reactor 1-4 is provided with an overflow port, and the molten salt liquid level in the reactor 1-4 is slightly higher than the overflow port on the upper part of the side wall; the overflow port of the reactor 1-4 is connected to the spray system through an overflow pipe 1-9, and the liquid outlet of the spray system is connected to the filter 4 through a pipeline through the delivery pump 3, and the filtrate outlet of the filter 4 is connected to the membrane separator 5 through a pipeline, and control valves are provided on the corresponding pipelines.

[0033] Comparison Figure 2 and Figure 3The spray system includes a spray chamber 2-2, a spray head 2-1 and a clean water inlet pipe arranged at the upper end of the spray chamber 2-2. The clean water inlet pipe penetrates into the spray chamber 2-2 and is connected to the spray head 2-1, so as to spray clean water into the spray chamber 2-2 to cool the molten salt, and form a mixed solution of salt water solution and activated carbon in the spray chamber 2-2; the fresh water outlet of the membrane separator 5 is connected to the side of the clean water inlet pipe by a pipeline, so as to pass the fresh water obtained by the desalination treatment of the membrane separator 5 through the spraying The head 2-1 sprays into the spray chamber 2-2; the concentrated water side outlet of the membrane separator 5 is connected to the molten salt inlet side of the reactor 1-4 by a pipeline, so that the concentrated salt solution obtained by the desalination treatment of the membrane separator 5 can be reused in the reactor 1-4 for catalytic reaction; wherein, the concentrated salt solution obtained by the concentration of the membrane separator 5 mainly includes binary carbonate components and water, the binary carbonate components are introduced into the reactor 1-4 and reused as molten salt, and the water is introduced into the reactor 1-4 and used as a gasifying agent.

[0034] Furthermore, a steam outlet is provided at the top of the spray chamber 2-2. When clean water is sprayed in the spray chamber 2-2 to cool the molten salt, part of the water vaporizes when encountering the high temperature of the molten salt to form water vapor; the water vapor discharged from the steam outlet at the top of the spray chamber 2-2 is reused in the reaction system through the pipeline as a gasifying agent.

[0035] Furthermore, the device of the present application also includes a rotary kiln 6, and the wet activated carbon filtered out by the filter 4 is sent to the rotary kiln 6. The pyrolysis gas formed by the reaction in the reactor 1-4 is discharged from the pyrolysis gas outlet at the upper part of the reactor 1-4, ignited in the heating sleeve 7, and converted into flue gas, and then sent to the rotary kiln 6 as a heat source for heating the rotary kiln 6. The moisture in the wet activated carbon is vaporized by heat to form water vapor, and the water vapor can be reused in the reactor 1-4 as a gasification agent.

[0036] Comparison Figure 2-4The reaction system of the present application also includes a sleeve assembly, which consists of a sleeve 1-6 and a turntable 1-7 vertically fixedly installed on the outer side of the lower end of the sleeve 1-6. The sleeve 1-6 is rotatably arranged on the top of the reactor 1-4, and the turntable 1-7 is arranged in the reactor 1-4; a notch is provided on the turntable 1-7 so that when biomass is fed through the biomass feed port at the top of the reactor 1-4, the biomass can enter the molten salt through the notch on the turntable 1-7; when the biomass and the gasification agent are catalytically reacted in the molten salt in the reactor 1-4, the turntable 1-7 is slightly immersed below the surface of the molten salt, and the rotation of the sleeve 1-6 drives the turntable 1-7 to rotate together. The rotating turntable 1-7 can play a certain blocking role to prevent the biomass in the molten salt from floating to the surface. Among them, the rotation method of the sleeve 1-6 belongs to the existing conventional technology, for example: a motor and a belt can be used, a pulley is fixedly set on the side of the sleeve 1-6, the motor is connected to the pulley on the side of the sleeve 1-6 through the belt, and the sleeve 1-6 is rotated under the transmission action of the belt.

[0037] Furthermore, the reaction system of the present application also includes a coil assembly, which includes a hollow connecting rod 1-5 sleeved inside the sleeve 1-6 and a mosquito-repellent coil 1-8 arranged at the lower end of the hollow connecting rod 1-5, the upper end of the hollow connecting rod 1-5 passes through the sleeve 1-6, and the mosquito-repellent coil 1-8 is provided with a plurality of air outlets, and the upper end of the hollow connecting rod 1-5 can be provided with an air inlet pipe for introducing a gasifying agent, and the upper end of the hollow connecting rod 1-5 is provided with the air inlet pipe in a sealed rotation connection. Among them, the hollow connecting rod 1-5 and the sleeve 1-6 are provided with a rotational sealing connection.

[0038] When the biomass and the gasifier are catalytically reacted in the molten salt in the reactor 1-4, the mosquito coil 1-8 is immersed in the molten salt, and the gasifier is introduced into the upper port of the hollow connecting rod 1-5, and the gasifier is discharged through a number of air outlets on the mosquito coil 1-8. The pneumatic system also produces a stirring effect, and the gasifier is evenly distributed in the molten salt to contact and react with the biomass. Among them, the rotation method of the hollow connecting rod 1-5 belongs to the existing conventional technology, for example: a motor and a belt can be used, a pulley is fixedly set on the side of the hollow connecting rod 1-5, and the motor is connected to the pulley on the side of the hollow connecting rod 1-5 through a belt. Under the transmission action of the belt, the hollow connecting rod 1-5 rotates.

[0039] The outside of the reactor 1-4 is equipped with a heating jacket, which is an electric heating jacket or a sandwich casing. The electric heating jacket heats the reactor 1-4 by energizing. Figure 2 The sandwich casing heats the reactor 1-4 by introducing high-temperature flue gas. The sandwich casing is provided with a flue gas inlet and a flue gas outlet. Figure 3 It is a structural diagram of the flue gas heating type.

[0040] Comparison Figure 2-3 The outer side of the reaction kettle 1-4 is provided with a ceramic lining 1-3, and the ceramic lining 1-3 is provided with a heating jacket.

[0041] Furthermore, the heating jacket includes a side wall heating jacket 1-1 arranged on the outside of the side of the reactor 1-4 and a bottom heating jacket 1-2 arranged on the outside of the bottom of the reactor 1-4. The heating of the molten salt in the reactor to a molten state is controlled by the side wall and the bottom heating jacket, that is, when the reactor is heated and heated, the side wall heating jacket 1-1 and the bottom heating jacket 1-2 are opened at the same time; when the reactor is cooled after the reaction is completed, the bottom heating jacket 1-2 is closed, and the side wall heating jacket 1-1 is kept open, the molten salt at the bottom of the reactor is slowly cooled, and the density of the bottom molten salt changes (due to the slow cooling of the bottom molten salt, the density of the bottom molten salt will slowly increase; due to the higher temperature of the upper molten salt, the density will be smaller than that of the bottom molten salt), and the activated carbon generated by the reaction in the molten salt will slowly float to the surface of the molten salt by utilizing the upper and lower density difference of the molten salt.

[0042] Comparison Figure 2-3 The device of the present application also includes a heat exchanger 8. The water vapor generated by washing in the spray chamber 2-2 and the water vapor formed by drying the wet activated carbon in the rotary kiln 6 can be introduced into the cold channel of the heat exchanger 8. The flue gas generated by the reaction in the reactor 1-4 can be introduced into the hot channel of the heat exchanger 8. The water vapor and the flue gas are heat exchanged through the heat exchanger 8. For example, the pyrolysis gas formed by the reaction in the reactor 1-4 is discharged from the pyrolysis gas outlet at the top of the reactor 1-4 and ignited in the heating sleeve 7 to be converted into flue gas. It can be discharged in two ways, one as a heat source for heating the rotary kiln 6, and the other is introduced into the hot channel of the heat exchanger 8 as a heat source for heating the heat exchanger 8.

[0043] When the device of this application is working:

[0044] The biomass and the gasifier react catalytically in the molten salt in the reactor 1-4 to generate activated carbon and pyrolysis gas. The activated carbon can float to the surface of the molten salt and be sent to the spray system through the overflow port along with a small amount of molten salt (when overflowing, the control valve on the overflow pipe 1-9 needs to be opened); the spray system sprays the activated carbon-molten salt mixture entering with clean water, and part of the water is vaporized at high temperature in the molten salt to form water vapor, which can be re-introduced into the reactor as a gasifier. The mixed solution of the salt solution and activated carbon formed after spraying is then transported to the filter 4 by the delivery pump 3 for filtration, and the filter residue (i.e., wet activated carbon) is dried to obtain an activated carbon product. The filtrate (i.e., the salt solution) is sent to the membrane separator 5 for desalination treatment to obtain fresh water and concentrated salt solution. The fresh water can be reused in the spray system, and the concentrated salt solution can be reused in the reactor 1-4 for catalytic reaction. It can be seen from the above working process that the reaction system of the present application does not produce any waste liquid at all during operation, and all substances can be recycled.

[0045] The reaction system of the present application, when carrying out the catalytic reaction between biomass and gasification agent in the molten salt of the reactor, comprises the following steps (refer to Figure 1 ):

[0046] 1) Start the side wall heating jacket on the outside of the side of the reactor and the bottom heating jacket on the outside of the bottom of the reactor to heat the reactor to 700-1000°C, add the biomass into the molten salt in the reactor through the notch on the turntable, the turntable of the sleeve assembly is slightly immersed below the surface of the molten salt, and the sleeve assembly rotates to make the biomass and the molten salt fully contact, the mosquito coil of the coil assembly is immersed in the molten salt, and the gasifier is introduced. The gasifier is discharged through a number of air outlets on the mosquito coil, and a stirring effect is generated while pneumatically moving, so that the gasifier and the biomass are fully contacted and reacted in the molten salt;

[0047] 2) After the biomass is gasified and cracked, the casing assembly and the coil assembly are lifted above the molten salt liquid level, and the bottom heating jacket on the outside of the bottom of the reactor is closed to slowly cool the molten salt to 400-500°C. The density of the bottom molten salt changes, and the activated carbon generated by the reaction slowly floats to the surface of the molten salt and is sent to the spray system through the overflow port along with a small amount of molten salt;

[0048] 3) The spray system sprays clean water to cool the incoming activated carbon-molten salt mixture. Part of the clean water is gasified by the high temperature of the molten salt and circulated to the reactor after preheating for reuse as a gasification agent. The sprayed mixture is filtered through a filter to obtain wet activated carbon, which is then heat-exchanged with pyrolysis gas in a heat exchanger to obtain dry activated carbon. The water vapor generated during the heat exchange process is preheated and circulated to the reactor for reuse as a gasification agent. The brine solution obtained by the sprayed mixture is filtered through a filter and then desalinated by a membrane separator to obtain fresh water and concentrated salt solution. The fresh water can be reused in the spray system, and the concentrated salt solution can be reused in the reactor for catalytic reaction.

[0049] The molten salt is a binary eutectic of sodium carbonate and potassium carbonate, and the mass ratio of sodium carbonate to potassium carbonate is 55.5:44.5; the reaction temperature is 700-1000°C, and the gasifying agent is water vapor; the biomass is coconut shell, walnut shell, chestnut shell, bamboo powder or cellulose monomer, and the cellulose monomer is glucose or cellobiose.

[0050] After the reaction is completed, air or oxygen can be introduced into the molten salt in the reactor to remove the tar carbon generated in the molten salt in the reactor.

[0051] The reaction system of the present application can be used for molten salt decoking to produce hydrogen, biomass gasification to produce hydrogen, biomass gasification to produce activated carbon, or biomass gasification to produce supercapacitors.

[0052] When the reaction system of the present application is used for molten salt decoking to produce hydrogen and biomass gasification to produce hydrogen, it is also necessary to introduce CO2 through the coil assembly to remove the carbon in the molten salt in the reactor.

[0053] When the reaction system of the present application is used for biomass gasification to produce activated carbon and biomass gasification to produce supercapacitors, after the reaction is completed, air or oxygen needs to be introduced into the molten salt in the reactor to remove the tar carbon generated in the molten salt in the reactor.

[0054] Embodiment 1:

[0055] 200g of a mixture of sodium carbonate and potassium carbonate (i.e., molten salt) with a mass ratio of 55.5:44.5 was used as a heat medium and catalyst (melting point of 710.3℃), and was added to the reactor through the notch of the turntable, and the side wall heating jacket and the bottom heating jacket were started to heat the reactor to 750℃. Maintaining an oxygen-free atmosphere, the coil was extended into the molten salt to pass water vapor with a flow rate of 10 g / h, and 10g of crushed and dried fir sawdust raw materials were added to the reactor. The fir sawdust was carbonized / activated in the reactor at 750℃ for 15min, and the pyrolysis gas generated by the reaction was continuously discharged from the pyrolysis gas outlet at the top of the reactor. The gasification rate of fir sawdust was between 78.6% and 81.3% (mass percentage%), the volume percentage of synthesis gas (H2 and CO) in the pyrolysis gas generated by the reaction was between 79.2% and 84.7%, and the volume ratio of H2 and CO in the synthesis gas was between 3.9 and 4.2:1.

[0056] After the reaction is completed, the bottom heating jacket is closed to cool the molten salt to about 450°C. The density of the bottom molten salt changes, and the activated carbon slowly floats up and enters the spray system through the overflow port. The molten salt is cooled by spraying with clean water. The mixture after spraying is filtered through a filter to obtain wet activated carbon, which is then heat-exchanged with pyrolysis gas in a heat exchanger to obtain dry activated carbon. According to BET characterization, the specific surface area of ​​the finished activated carbon prepared in this example is 855.945 m 2 / g, the pore volume is 0.4416 mL / g, and the average pore diameter is 1.1065 nm.

[0057] Embodiment 2:

[0058] 200g of a mixture of sodium carbonate and potassium carbonate (molten salt) with a mass ratio of 55.5:44.5 was used as a heat medium and catalyst (melting point of 710.3℃), and was added to the reactor through the notch of the turntable to start the side wall and bottom heating jacket to raise the temperature to 750℃. The oxygen-free atmosphere was maintained, and the coil was extended below the molten salt liquid surface to pass water vapor with a flow rate of 10 g / h. 10g of warp knitted waste leather cut into uniform small pieces was added to the reactor. The decoking reaction was continued for 20 hours, and the decoking efficiency remained stable. The test results showed that the tar yield was reduced by more than 95%, and the gas yield was increased by more than 15%.

[0059] The contents described in this specification are merely an enumeration of implementation forms of the inventive concept, and the protection scope of the present invention should not be regarded as being limited to the specific forms described in the embodiments.

Claims

1. An environmentally friendly binary carbonate cycle reaction system, characterized in that The invention comprises a reaction system, a spray system, a delivery pump (3), a filter (4) and a membrane separator (5), wherein the reaction system comprises a reactor (1-4); the reactor (1-4) contains molten salt, the upper part of the reactor (1-4) is provided with a biomass feed port, a molten salt inlet, a gasification agent inlet and a pyrolysis gas outlet, the upper part of the side wall of the reactor (1-4) is provided with an overflow port, and the molten salt liquid level in the reactor (1-4) is slightly higher than the overflow port on the upper part of the side wall; the overflow port of the reactor (1-4) is connected to the spray system (2) through an overflow pipe (1-9), the liquid outlet of the spray system is connected to the filter (4) through a pipeline through a delivery pump (3), and the filtrate outlet of the filter (4) is connected to the membrane separator (5) through a pipeline, and control valves are provided on the corresponding pipelines; The biomass and the gasifying agent react catalytically in the molten salt in the reactor (1-4) to generate activated carbon and pyrolysis gas. The activated carbon floats to the surface of the molten salt and is sent to the spray system through the overflow port along with a small amount of molten salt. The spray system sprays clean water on the activated carbon-molten salt mixture entering the reactor (1-4) for washing. The water vapor generated during the washing process is reused in the reactor (1-4) for catalytic reaction. At the same time, a mixed solution of salt water solution and activated carbon is formed. The mixed solution is then transported to the filter (4) by the delivery pump (3) for filtration. The wet activated carbon residue is dried to obtain an activated carbon product. The filtrate is sent to the membrane separator (5) for desalination treatment to obtain fresh water and concentrated salt solution. The fresh water is reused in the spray system, and the concentrated salt solution is reused in the reactor (1-4) for catalytic reaction. The reaction system further comprises a sleeve assembly, which comprises a sleeve (1-6) and a turntable (1-7) vertically fixedly mounted on the outer side of the lower end of the sleeve (1-6); the sleeve (1-6) is rotatably arranged on the top of the reactor (1-4), and the turntable (1-7) is arranged in the reactor (1-4); a notch is arranged on the turntable (1-7), so that when biomass is fed through the biomass feed port at the top of the reactor (1-4), the biomass can enter the molten salt through the notch on the turntable (1-7); when the biomass and the gasifying agent are catalytically reacted in the molten salt in the reactor (1-4), the turntable (1-7) is slightly immersed below the surface of the molten salt, and the sleeve (1-6) rotates to drive the turntable (1-7) to rotate together, so as to prevent the biomass in the molten salt from floating to the surface; The reaction system further comprises a coil assembly, the coil assembly comprising a hollow connecting rod (1-5) sleeved inside the sleeve (1-6) and a mosquito coil (1-8) arranged at the lower end of the hollow connecting rod (1-5), the upper end of the hollow connecting rod (1-5) passing through the sleeve (1-6), and a plurality of air outlet holes being arranged on the mosquito coil (1-8); wherein the hollow connecting rod (1-5) and the sleeve (1-6) are connected in a rotating sealed manner; When the biomass and the gasifying agent undergo a catalytic reaction in the molten salt in the reactor (1-4), the mosquito coil (1-8) is immersed in the molten salt, and the hollow connecting rod (1-5) rotates to drive the mosquito coil (1-8) to rotate together. At the same time, the gasifying agent is introduced into the upper end of the hollow connecting rod (1-5), and the gasifying agent is discharged through a plurality of gas outlets on the mosquito coil (1-8) and is evenly distributed in the molten salt to contact and react with the biomass.

2. An environmentally friendly binary carbonate circulation reaction system as claimed in claim 1, characterized in that The spray system comprises a spray chamber (2-2), a spray head (2-1) and a clean water inlet pipe arranged inside the upper end of the spray chamber (2-2); the clean water inlet pipe penetrates into the spray chamber (2-2) and is connected to the spray head (2-1) so as to spray clean water into the spray chamber (2-2) to wash the molten salt, thereby forming a mixed solution of a salt water solution and activated carbon in the spray chamber (2-2); The fresh water side outlet of the membrane separator (5) is connected to the side of the clean water inlet pipe by a pipeline, so that the fresh water obtained by the desalination treatment of the membrane separator (5) can be sprayed into the spray chamber (2-2) through the spray head (2-1); the concentrated water side outlet of the membrane separator (5) is connected to the molten salt inlet side of the reactor (1-4) by a pipeline, so that the concentrated salt solution obtained by the desalination treatment of the membrane separator (5) can be reused in the reactor (1-4) for catalytic reaction.

3. An environmentally friendly binary carbonate circulation reaction system as claimed in claim 2, characterized in that The top of the spray chamber (2-2) is also provided with a steam outlet. When clean water is sprayed in the spray chamber (2-2) to cool the molten salt, part of the water vaporizes at the high temperature of the molten salt to form water vapor. The water vapor discharged from the steam outlet at the top of the spray chamber (2-2) is reused in the reaction kettle (1-4) through a pipeline as a gasifying agent.

4. An environmentally friendly binary carbonate circulation reaction system as claimed in claim 1, characterized in that The invention also comprises a rotary kiln (6). The wet activated carbon filtered out by the filter (4) is sent to the rotary kiln (6). The pyrolysis gas formed by the reaction in the reactor (1-4) is discharged from the pyrolysis gas outlet at the upper part of the reactor (1-4), ignited in the heating sleeve, converted into flue gas, and then sent to the rotary kiln (6) as a heat source for heating the rotary kiln (6). The moisture in the wet activated carbon is vaporized by the heat to form water vapor, and the water vapor is reused in the reactor (1-4) as a gasifying agent.

5. An environmentally friendly binary carbonate circulation reaction system as claimed in claim 1, characterized in that The outside of the reactor (1-4) is provided with a heating jacket, the heating jacket being an electric heating jacket or a sandwich jacket, the electric heating jacket heats the reactor (1-4) by supplying electricity, the sandwich jacket heats the reactor (1-4) by passing high-temperature flue gas, and the sandwich jacket is provided with a flue gas inlet and a flue gas outlet; wherein the heating jacket comprises a side wall heating jacket (1-1) provided on the outside of the side of the reactor (1-4) and a bottom heating jacket (1-2) provided on the outside of the bottom of the reactor (1-4).

6. A process using the environmentally friendly binary carbonate cycle reaction system as claimed in claim 1, characterized in that The process method is to carry out a catalytic reaction between biomass and a gasifying agent in a molten salt in a reactor, and comprises the following steps: 1) Start the side wall heating jacket on the outside of the side of the reactor and the bottom heating jacket on the outside of the bottom of the reactor to heat the reactor to 700-1000°C, add the biomass into the molten salt in the reactor through the notch on the turntable, the turntable of the sleeve assembly is slightly immersed below the surface of the molten salt, and the sleeve assembly rotates to make the biomass and the molten salt fully contact, the mosquito coil of the coil assembly is immersed in the molten salt, and the gasifier is introduced. The gasifier is discharged through a number of air outlets on the mosquito coil, and a stirring effect is generated while pneumatically moving, so that the gasifier and the biomass are fully contacted and reacted in the molten salt; 2) After the biomass is gasified and cracked, the casing assembly and the coil assembly are lifted above the molten salt liquid level, and the bottom heating jacket on the outside of the bottom of the reactor is closed to slowly cool the molten salt to 400-500°C. The density of the bottom molten salt changes, and the activated carbon generated by the reaction slowly floats to the surface of the molten salt and is sent to the spray system through the overflow port along with a small amount of molten salt; 3) The spray system sprays clean water on the activated carbon-molten salt mixture entering for washing. Part of the clean water is gasified by the high temperature of the molten salt and circulated to the reactor after preheating for reuse as a gasification agent. The sprayed mixture is filtered through a filter to obtain wet activated carbon, which is then heat exchanged with pyrolysis gas in a rotary kiln to obtain dry activated carbon. The water vapor generated during the heat exchange process is preheated and circulated to the reactor for reuse as a gasification agent. The brine solution obtained by the sprayed mixture is filtered through a filter and then desalinated by a membrane separator to obtain fresh water and concentrated salt solution. The fresh water is reused in the spray system, and the concentrated salt solution is reused in the reactor for catalytic reaction.

7. The process according to claim 6, characterized in that The molten salt is a binary eutectic of sodium carbonate and potassium carbonate, and the mass ratio of sodium carbonate to potassium carbonate is 60:40-40:60; the reaction temperature is 700-1000° C., and the gasifying agent is water vapor; the biomass is coconut shell, walnut shell, chestnut shell, bamboo powder or cellulose monomer, and the cellulose monomer is glucose or cellobiose.

8. The process according to claim 7, characterized in that The molten salt is a binary eutectic of sodium carbonate and potassium carbonate, and the mass ratio of sodium carbonate to potassium carbonate is 55.5:44.

5.

9. A use of the environmentally friendly binary carbonate circulation reaction system as claimed in claim 1, characterized in that The reaction system can be applied to molten salt catalytic decoking to produce hydrogen, biomass gasification to produce hydrogen, biomass gasification to produce activated carbon or biomass gasification to produce supercapacitors.

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