CN113634200B - Fixed bed hydrothermal gasification reactor and application - Google Patents

Fixed bed hydrothermal gasification reactor and application Download PDF

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Publication number
CN113634200B
CN113634200B CN202110942711.0A CN202110942711A CN113634200B CN 113634200 B CN113634200 B CN 113634200B CN 202110942711 A CN202110942711 A CN 202110942711A CN 113634200 B CN113634200 B CN 113634200B
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fixed bed
water inlet
gasification reactor
inlet pipe
water
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CN113634200A (en
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吕路
王林平
黄前霖
张炜铭
潘丙才
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Enire Jiangsu Environmental Development Co ltd
Nanjing University
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Enire Jiangsu Environmental Development Co ltd
Nanjing University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
    • B01J8/0446—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical
    • B01J8/0449—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
    • B01J8/0496—Heating or cooling the reactor
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Abstract

The invention discloses a fixed bed hydrothermal gasification reactor and application, belonging to the technical field of chemical hazardous waste resource treatment, comprising an upper plug, a lower plug, a large flange plate, a reaction kettle barrel, a catalyst filling tube array, a fixed bed device and a water distribution device, wherein the upper plug and the lower plug are respectively fixed with the upper end and the lower end of the reaction kettle barrel through the large flange plate, and a water inlet pipe interface is fixedly connected above the upper plug. Has good application prospect.

Description

Fixed bed hydrothermal gasification reactor and application
Technical Field
The invention relates to the technical field of chemical hazardous waste recycling treatment, in particular to a fixed bed hydrothermal gasification reactor and application thereof.
Background
In recent years, the chemical industry in China is developed vigorously, and great economic benefits are brought to the society, and meanwhile, series of environmental problems are brought. Particularly, the method is more prominent in the expression of a large amount of solid, semisolid or slurry chemical hazardous wastes generated in the industrial production process, and the hazardous wastes have complex components, contain high-concentration nondegradable macromolecular organic matters and have various toxicities such as physical, chemical and biological properties. Therefore, how to effectively treat the high-COD chemical hazardous wastes becomes a problem of green sustainable development of the chemical industry.
Among the various treatment methods, the hydrothermal gasification method is a technology for rapidly and selectively decomposing organic matters into gaseous clean energy or harmless gas by utilizing the special properties of water under the high-temperature and high-pressure state, has the advantages of high efficiency, energy conservation, resource utilization and the like, has the advantages of treating chemical hazardous wastes containing high-concentration nondegradable COD, and is gradually concerned by domestic and foreign scholars and enterprises. However, the hydrothermal gasification reaction conditions are special, and the high-salt and high-COD chemical hazardous wastes are mainly slurry substances with complex components, and have the characteristics of high viscosity, easy adhesion and the like, so that the following significant problems exist when the existing fixed bed reactor is applied to the hydrothermal gasification technology-based treatment of the high-salt and high-COD chemical hazardous wastes: (1) the high-salt high-COD chemical hazardous waste has high viscosity, is easy to remain in a reactor, and causes the problems of pipeline blockage, catalyst inactivation and the like due to long-term accumulation; (2) the poor heat transfer performance of the reactor makes the reactor unable to reach a subcritical or supercritical state, thereby hindering the hydrothermal gasification reaction and producing a series of byproducts.
Disclosure of Invention
In order to solve the technical problems, the invention provides a fixed bed hydrothermal gasification reactor and application thereof.
The technical scheme of the invention is as follows: a fixed bed hydrothermal gasification reactor comprises an upper plug, a lower plug, a large flange disc, a reaction kettle barrel, a catalyst filling tube array, a fixed bed device and a water distribution device, wherein the upper plug and the lower plug are respectively fixed with the upper end and the lower end of the reaction kettle barrel through the large flange disc, a water inlet pipe interface is fixedly connected above the upper plug, a thermometer interface for inserting a thermometer is arranged on the left side of the water inlet pipe interface, a pressure meter for monitoring the internal air pressure of the reaction kettle and a safety valve interface for discharging hot water and gas are arranged on the right side of the water inlet pipe interface, a bottom end enclosure clapboard is transversely arranged in the lower plug, the catalyst filling tube array is vertically fixed above the bottom end enclosure clapboard, the fixed bed device is fixedly arranged in the catalyst filling tube array, a heat source outlet is arranged on one side above the fixed bed device, a heat source inlet is arranged on one side below the fixed bed device, the outer end of the heat source outlet and the outer end of the heat source inlet both penetrate through the outer wall of the reaction kettle barrel, the upper end of the water distribution device is communicated with a water inlet pipe connector, the lower end of the water distribution device is communicated with the fixed bed device, and the outer heat-insulating layer wraps the outer wall of the upper plug, the outer wall of the lower plug and the outer wall of the reaction kettle barrel;
the fixed bed device comprises a plurality of vertical pipes and cross rods, and the side walls of the plurality of vertical pipes are communicated with each other through the cross rods;
the water distribution device comprises a water inlet pipe, a plurality of water inlet branch pipes, water distribution ports and inclined pipes, wherein the upper part of the water inlet pipe is communicated with the water inlet pipe connector, the lower end of the water inlet pipe is connected with the inclined pipes, the water inlet branch pipes are arranged in a plurality of V-shaped symmetrical mode and are arranged on two sides of the inclined pipes and communicated with the inclined pipes, the water distribution ports are arranged in a plurality of mode, the upper parts of the water distribution ports are communicated with the water inlet branch pipes, and the lower parts of the water distribution ports are communicated with the top parts of the vertical pipes in a one-to-one correspondence mode.
Furthermore, the outer ends of the water inlet pipe interface, the heat source outlet and the heat source inlet are fixedly connected with small flange plates, the connection mode of the flange plates is more reliable, and the flange plates are not easy to collapse under high pressure.
Furthermore, the pipe diameter of the water inlet pipe is 15mm-25mm, the pipe diameter of the water inlet branch pipe is 10mm, the aperture of the water distribution hole is 3mm-5mm, and the selection of the pipe diameter is favorable for uniform flow of water and reduces impact force of water flow on the pipeline.
Furthermore, the bottom end enclosure partition plate is densely distributed with small holes of 1mm-2mm, the bottom end enclosure partition plate is connected with the inner wall of the lower end enclosure through spot welding, and the welding mode is reliable and is not easy to fall off.
Furthermore, the bottom fixedly connected with of end cap is used for the holistic base of stabilising arrangement down, and the base is favorable to increasing the steadiness of this device.
Furthermore, the vertical pipe, the cross rod, the water inlet pipe, the water inlet branch pipe and the inclined pipe are all made of copper-chromium alloy materials, the mass percentage of copper elements and chromium elements in the copper-chromium alloy materials is 9:1, and the copper-chromium alloy has good heat conductivity.
Further, the outside of the reaction kettle barrel is wound with a high-frequency heating wire pipe for heating the catalyst filling array pipe, so that the heating mode is rapid, and the heat is concentrated.
Furthermore, the outer side of the high-frequency heating wire pipe is wrapped with a heat insulation layer, so that heat loss in the reaction kettle is prevented, and energy loss is further reduced.
Further, the fixed bed hydrothermal gasification reactor is applied to treatment of high-salt high-COD chemical hazardous waste.
Further, the fixed bed hydrothermal gasification reactor is applied to the treatment of wastewater containing phenolic resin, when the wastewater containing phenolic resin is treated, the COD content of the wastewater containing phenolic resin is 8-9%, the catalyst adopts ruthenium-based catalyst, the temperature of molten salt is 450 ℃, the temperature of a catalyst filling tube array is 330-360 ℃, the reaction time is 30-50min, the COD content in water gas discharged from a safety valve interface is less than 100mg/L, the methane content in the generated gas is 50-80%, and the COD can be rapidly decomposed into methane and CO in the reactor2Thus achieving the purpose of resource utilization.
Further, the fixed bed hydrothermal gasification reactor is applied to pesticide wastewater treatment, when the pesticide wastewater is treated, the appearance color of the pesticide wastewater is brownish red, the COD content in the pesticide wastewater is 30%, the catalyst adopts a ruthenium-based catalyst, the temperature of molten salt is 400 ℃, the temperature of a catalyst filling tube array is 250-330 ℃, the reaction time is 30-50min, the color of water gas discharged from a safety valve interface is transparent and clear, the content of methane in the generated gas is more than 50-80%, and the COD can be rapidly decomposed into methane and CO in the reactor2The purpose of recycling is achieved, the removal rate of COD is high, and the removal effect is good.
The invention relates to a fixed bed hydrothermal gasification reactor working principle:
the reactor is mainly used for treating high COD wastewater by a hydrothermal gasification method, and after the wastewater flows through a catalyst bed layer reaching a set temperature, COD can be rapidly decomposed into methane in the reactorAnd CO2Thus achieving the purpose of resource utilization.
The invention has the beneficial effects that:
(1) aiming at the problem that the existing fixed bed reactor is difficult to meet the requirement of treating high-salt high-COD chemical hazardous waste by a hydrothermal gasification method, the designed fixed bed hydrothermal gasification reactor can quickly and selectively convert COD-containing substances in the hazardous waste into methane after contacting with a catalyst based on the application requirement of a hydrothermal gasification technology and the physicochemical characteristics of the high-salt high-COD chemical hazardous waste, solves the problems of heat transfer and mass transfer of the traditional fixed bed reactor, and has good application prospect.
(2) The invention adopts a mode of combining molten salt heating and electric heating, can fully ensure that the reactor quickly reaches a subcritical or supercritical state, thereby ensuring that the hydrothermal gasification reaction is normally carried out, and simultaneously, the two heating modes have high automation degree and improve the safety factor of equipment operation.
Drawings
Fig. 1 is a schematic structural view of the present invention.
Figure 2 is a cross-sectional view of a catalyst packing array tube of the present invention.
FIG. 3 is a cross-sectional view of the water distribution device of the present invention.
Wherein, 1-an upper plug, 2-a lower plug, 3-a large flange disc, 4-a reaction kettle barrel, 5-a catalyst filling array pipe, 6-a fixed bed device, 7-a water distribution device, 11-a water inlet pipe interface, 12-a thermometer interface, 13-a pressure gauge, 14-a safety valve interface, 15-a bottom end socket clapboard, 16-a heat source outlet, 17-a heat source inlet, 18-a small flange disc, 61-a vertical pipe, 62-a cross bar, 71-a water inlet pipe, 72-a water inlet branch pipe, 73-a water distribution port, 74-an inclined pipe, 21-a base, 41-a high-frequency heating line pipe and 42-a heat insulation layer.
Detailed Description
Example 1
As shown in figure 1, a fixed bed hydrothermal gasification reactor comprises an upper plug 1, a lower plug 2, a large flange plate 3, a reaction kettle barrel 4, a catalyst filling tubular array 5, a fixed bed device 6 and a water distribution device 7, wherein the upper plug 1 and the lower plug 2 are respectively fixed with the upper end and the lower end of the reaction kettle barrel 4 through the large flange plate 3, a water inlet pipe connector 11 is fixedly connected above the upper plug 1, a thermometer connector 12 for inserting a thermometer is arranged at the left side of the water inlet pipe connector 11, a pressure gauge 13 for monitoring the internal pressure of the reaction kettle and a safety valve connector 14 for discharging hot and water gas are arranged at the right side of the water inlet pipe connector 11, a bottom end enclosure clapboard 15 is transversely arranged in the lower plug 2, the catalyst filling tubular array 5 is vertically fixed above the bottom end enclosure clapboard 15, the fixed bed device 6 is fixedly arranged in the catalyst filling tubular array 5, a heat source outlet 16 is arranged at one side above the fixed bed device 6, a heat source inlet 17 is arranged on one side below the fixed bed device 6, the outer end of the heat source outlet 16 and the outer end of the heat source inlet 17 both penetrate through the outer wall of the reaction kettle barrel 4, the upper end of the water distribution device 7 is communicated with the water inlet pipe connector 11, the lower end of the water distribution device 7 is communicated with the fixed bed device 6, and an external heat insulation layer 42 is wrapped on the outer wall of the upper plug 1, the outer wall of the lower plug 2 and the outer wall of the reaction kettle barrel 4;
as shown in fig. 2, the fixed bed unit 6 comprises a plurality of vertical tubes 61 and cross rods 62, wherein the plurality of vertical tubes 61 are provided, and the side walls of the plurality of vertical tubes 61 are communicated with each other through the cross rods 62;
as shown in fig. 3, the water distribution device 7 includes a water inlet pipe 71, water inlet branch pipes 72, a plurality of water distribution ports 73, and inclined pipes 74, wherein the upper portion of the water inlet pipe 71 is communicated with the water inlet pipe joint 11, the lower end of the water inlet pipe 71 is connected with the inclined pipes 74, the number of the water inlet branch pipes 72 is multiple, the plurality of water inlet branch pipes 72 are symmetrically arranged on two sides of the inclined pipes 74 in a V shape and are communicated with the inclined pipes 74, the number of the water distribution ports 73 is multiple, the upper portions of the plurality of water distribution ports 73 are communicated with the water inlet branch pipes 72, and the lower portions thereof are communicated with the top portions of the vertical pipes 61 in a one-to-one correspondence manner.
The pipe diameter of the water inlet pipe 71 is 15mm, the pipe diameter of the water inlet branch pipe 72 is 10mm, and the aperture of the water distribution hole is 3 mm.
The bottom head baffle 15 is densely covered with 1mm small holes, the bottom head baffle 15 is connected with the inner wall of the lower head by spot welding, and the welding mode is reliable and is not easy to fall off.
The vertical pipe 61, the cross rod 62, the water inlet pipe 71, the water inlet branch pipe 72 and the inclined pipe 74 are all made of copper-chromium alloy, the mass percentage of copper elements and chromium elements in the copper-chromium alloy is 9:1, and the copper-chromium alloy has good thermal conductivity.
The fixed bed hydrothermal gasification reactor is applied to the treatment of high-salt high-COD chemical hazardous waste.
When the fixed bed hydrothermal gasification reactor is applied to the treatment of wastewater containing phenolic resin, the COD content of the wastewater containing the phenolic resin is 8 percent, the catalyst adopts ruthenium-based catalyst, the temperature of molten salt is 450 ℃, the temperature of a catalyst filling tube 5 is 330 ℃, the reaction time is 30min, the COD content in water gas discharged by a safety valve interface 14 is less than 100mg/L, the methane content in the generated gas is 50 percent, and the COD can be rapidly decomposed into methane and CO in the reactor2Thus achieving the purpose of resource utilization.
When the fixed bed hydrothermal gasification reactor is applied to pesticide wastewater treatment, the appearance color of the pesticide wastewater is brownish red, the COD content in the pesticide wastewater is 30%, the catalyst is ruthenium-based catalyst, the temperature of molten salt is 400 ℃, the temperature of a catalyst filling tube 5 is 250 ℃, the reaction time is 30min, the color of water gas discharged by a safety valve interface 14 is transparent and clear, the methane content in the generated gas is more than 50%, and COD can be rapidly decomposed into methane and CO in the reactor2The purpose of recycling is achieved, the removal rate of COD is high, and the removal effect is good.
Example 2
As shown in figure 1, a fixed bed hydrothermal gasification reactor comprises an upper plug 1, a lower plug 2, a large flange plate 3, a reaction kettle barrel 4, a catalyst filling tubular array 5, a fixed bed device 6 and a water distribution device 7, wherein the upper plug 1 and the lower plug 2 are respectively fixed with the upper end and the lower end of the reaction kettle barrel 4 through the large flange plate 3, a water inlet pipe connector 11 is fixedly connected above the upper plug 1, a thermometer connector 12 for inserting a thermometer is arranged at the left side of the water inlet pipe connector 11, a pressure gauge 13 for monitoring the internal pressure of the reaction kettle and a safety valve connector 14 for discharging hot and water gas are arranged at the right side of the water inlet pipe connector 11, a bottom end enclosure clapboard 15 is transversely arranged in the lower plug 2, the catalyst filling tubular array 5 is vertically fixed above the bottom end enclosure clapboard 15, the fixed bed device 6 is fixedly arranged in the catalyst filling tubular array 5, a heat source outlet 16 is arranged at one side above the fixed bed device 6, a heat source inlet 17 is arranged on one side below the fixed bed device 6, the outer end of the heat source outlet 16 and the outer end of the heat source inlet 17 both penetrate through the outer wall of the reaction kettle barrel 4, the upper end of the water distribution device 7 is communicated with the water inlet pipe connector 11, the lower end of the water distribution device 7 is communicated with the fixed bed device 6, and an external insulating layer 42 wraps the outer wall of the upper plug 1, the outer wall of the lower plug 2 and the outer wall of the reaction kettle barrel 4;
as shown in fig. 2, the fixed bed unit 6 comprises a plurality of vertical tubes 61 and cross rods 62, wherein the plurality of vertical tubes 61 are provided, and the side walls of the plurality of vertical tubes 61 are communicated with each other through the cross rods 62;
as shown in fig. 3, the water distribution device 7 includes a water inlet pipe 71, water inlet branch pipes 72, a plurality of water distribution ports 73, and inclined pipes 74, wherein the upper portion of the water inlet pipe 71 is communicated with the water inlet pipe joint 11, the lower end of the water inlet pipe 71 is connected with the inclined pipes 74, the number of the water inlet branch pipes 72 is multiple, the plurality of water inlet branch pipes 72 are symmetrically arranged on two sides of the inclined pipes 74 in a V shape and are communicated with the inclined pipes 74, the number of the water distribution ports 73 is multiple, the upper portions of the plurality of water distribution ports 73 are communicated with the water inlet branch pipes 72, and the lower portions thereof are communicated with the top portions of the vertical pipes 61 in a one-to-one correspondence manner.
The outer ends of the water inlet pipe connector 11, the heat source outlet 16 and the heat source inlet 17 are fixedly connected with small flange plates 18, the connection mode of the flange plates is more reliable, and the flange plates are not prone to being broken under high pressure.
The pipe diameter of the water inlet pipe 71 is 20mm, the pipe diameter of the water inlet branch pipe 72 is 10mm, and the aperture of the water distribution hole is 4 mm.
The bottom head baffle 15 is densely covered with small holes of 2mm, the bottom head baffle 15 is connected with the inner wall of the lower head by spot welding, and the welding mode is reliable and is not easy to fall off.
The vertical pipe 61, the cross rod 62, the water inlet pipe 71, the water inlet branch pipe 72 and the inclined pipe 74 are all made of copper-chromium alloy, the mass percentage of copper elements and chromium elements in the copper-chromium alloy is 9:1, and the copper-chromium alloy has good thermal conductivity.
The fixed bed hydrothermal gasification reactor is applied to the treatment of high-salt high-COD chemical hazardous waste.
The fixed bed hydrothermal gasification reactor is applied to the treatment of wastewater containing phenolic resin, and the COD content of the wastewater containing phenolic resin is9 percent, the catalyst adopts ruthenium-based catalyst, the temperature of the molten salt is 450 ℃, the temperature of the catalyst filling tube 5 is 350 ℃, the reaction time is 40min, the COD content in the water gas discharged from the safety valve interface 14 is less than 100mg/L, the methane content in the generated gas is 60 percent, and the COD can be rapidly decomposed into methane and CO in the reactor2Thus achieving the purpose of resource utilization.
When the fixed bed hydrothermal gasification reactor is applied to pesticide wastewater treatment, the appearance color of the pesticide wastewater is brownish red, the COD content in the pesticide wastewater is 30%, the catalyst is ruthenium-based catalyst, the temperature of molten salt is 400 ℃, the temperature of a catalyst filling tube array 5 is 300 ℃, the reaction time is 40min, the water gas discharged by a safety valve interface 14 is transparent and clear, the methane content in the generated gas is more than 70%, and the COD can be rapidly decomposed into methane and CO in the reactor2The purpose of recycling is achieved, the removal rate of COD is high, and the removal effect is good.
Compared with the embodiment 1, the embodiment 2 has the advantages that the small flanges 18 are fixedly connected to the outer ends of the water inlet pipe connector 11, the heat source outlet 16 and the heat source inlet 17 of the embodiment 2, the connection mode of the flanges is more reliable, and the flanges are not prone to being broken under high pressure.
Example 3
A fixed bed hydrothermal gasification reactor comprises an upper plug 1, a lower plug 2, a large flange plate 3, a reaction kettle barrel 4, a catalyst filling tube array 5, a fixed bed device 6 and a water distribution device 7, wherein the upper plug 1 and the lower plug 2 are respectively fixed with the upper end and the lower end of the reaction kettle barrel 4 through the large flange plate 3, a water inlet pipe connector 11 is fixedly connected above the upper plug 1, a thermometer connector 12 for inserting a thermometer is arranged on the left side of the water inlet pipe connector 11, a pressure gauge 13 for monitoring the internal air pressure of a reaction kettle and a safety valve connector 14 for discharging hot water and hot gas are arranged on the right side of the water inlet pipe connector 11, a bottom end enclosure clapboard 15 is transversely arranged in the lower plug 2, the catalyst filling tube array 5 is vertically fixed above the bottom end enclosure clapboard 15, the fixed bed device 6 is fixedly arranged in the catalyst filling tube array 5, a heat source outlet 16 is arranged on one side above the fixed bed device 6, a heat source inlet 17 is arranged on one side below the fixed bed device 6, the outer end of the heat source outlet 16 and the outer end of the heat source inlet 17 both penetrate through the outer wall of the reaction kettle barrel 4, the upper end of the water distribution device 7 is communicated with the water inlet pipe connector 11, the lower end of the water distribution device 7 is communicated with the fixed bed device 6, and an external heat insulation layer 42 is wrapped on the outer wall of the upper plug 1, the outer wall of the lower plug 2 and the outer wall of the reaction kettle barrel 4;
as shown in fig. 2, the fixed bed unit 6 comprises a plurality of vertical tubes 61 and cross rods 62, wherein the plurality of vertical tubes 61 are provided, and the side walls of the plurality of vertical tubes 61 are communicated with each other through the cross rods 62;
as shown in fig. 3, the water distribution device 7 includes a water inlet pipe 71, water inlet branch pipes 72, a plurality of water distribution ports 73, and inclined pipes 74, wherein the upper portion of the water inlet pipe 71 is communicated with the water inlet pipe joint 11, the lower end of the water inlet pipe 71 is connected with the inclined pipes 74, the number of the water inlet branch pipes 72 is plural, the plurality of water inlet branch pipes 72 are symmetrically arranged on both sides of the inclined pipes 74 in a V shape and are communicated with the inclined pipes 74, the number of the water distribution ports 73 is plural, the upper portions of the plurality of water distribution ports 73 are communicated with the water inlet branch pipes 72, and the lower portions thereof are communicated with the top portions of the vertical pipes 61 in a one-to-one correspondence.
The outer ends of the water inlet pipe connector 11, the heat source outlet 16 and the heat source inlet 17 are fixedly connected with small flange plates 18, the connection mode of the flange plates is more reliable, and the flange plates are not prone to being broken under high pressure.
The pipe diameter of the water inlet pipe 71 is 25mm, the pipe diameter of the water inlet branch pipe 72 is 10mm, and the aperture of the water distribution hole is 5 mm.
The bottom head baffle 15 is densely covered with small holes of 2mm, the bottom head baffle 15 is connected with the inner wall of the lower head by spot welding, and the welding mode is reliable and is not easy to fall off.
The bottom fixedly connected with of lower end cap 2 is used for the holistic base 21 of stabilising arrangement, and base 21 is favorable to increasing the steadiness of this device.
The vertical pipe 61, the cross rod 62, the water inlet pipe 71, the water inlet branch pipe 72 and the inclined pipe 74 are all made of copper-chromium alloy, the mass percentage of copper elements and chromium elements in the copper-chromium alloy is 9:1, and the copper-chromium alloy has good thermal conductivity.
The fixed bed hydrothermal gasification reactor is applied to the treatment of high-salt high-COD chemical hazardous waste.
The fixed bed hydrothermal gasification reactor is appliedWhen the wastewater containing the phenolic resin is treated, the COD content of the wastewater containing the phenolic resin is 9 percent, the catalyst adopts a ruthenium-based catalyst, the temperature of molten salt is 450 ℃, the temperature of a catalyst filling tube 5 is 360 ℃, the reaction time is 50min, the COD content in the water gas discharged by a safety valve interface 14 is less than 100mg/L, the methane content in the generated gas is 80 percent, and the COD can be rapidly decomposed into methane and CO in the reactor2Thus achieving the purpose of resource utilization.
When the fixed bed hydrothermal gasification reactor is applied to pesticide wastewater treatment, the appearance color of the pesticide wastewater is brownish red, the COD content in the pesticide wastewater is 30%, the catalyst is ruthenium-based catalyst, the temperature of molten salt is 400 ℃, the temperature of a catalyst filling tube array 5 is 330 ℃, the reaction time is 50min, the color of water gas discharged by a safety valve interface 14 is transparent and clear, the methane content in the generated gas is more than 80%, and COD can be rapidly decomposed into methane and CO in the reactor2The purpose of recycling is achieved, the removal rate of COD is high, and the removal effect is good.
Embodiment 3 compares with embodiment 2, and the bottom fixedly connected with of the lower end cap 2 of embodiment 3 is used for the holistic base 21 of stabilising arrangement, and base 21 is favorable to increasing the steadiness of this device.
Example 4
A fixed bed hydrothermal gasification reactor comprises an upper plug 1, a lower plug 2, a large flange plate 3, a reaction kettle barrel 4, a catalyst filling tube array 5, a fixed bed device 6 and a water distribution device 7, wherein the upper plug 1 and the lower plug 2 are respectively fixed with the upper end and the lower end of the reaction kettle barrel 4 through the large flange plate 3, a water inlet pipe connector 11 is fixedly connected above the upper plug 1, a thermometer connector 12 for inserting a thermometer is arranged on the left side of the water inlet pipe connector 11, a pressure gauge 13 for monitoring the internal air pressure of a reaction kettle and a safety valve connector 14 for discharging hot water and hot gas are arranged on the right side of the water inlet pipe connector 11, a bottom end enclosure clapboard 15 is transversely arranged in the lower plug 2, the catalyst filling tube array 5 is vertically fixed above the bottom end enclosure clapboard 15, the fixed bed device 6 is fixedly arranged in the catalyst filling tube array 5, a heat source outlet 16 is arranged on one side above the fixed bed device 6, a heat source inlet 17 is arranged on one side below the fixed bed device 6, the outer end of the heat source outlet 16 and the outer end of the heat source inlet 17 both penetrate through the outer wall of the reaction kettle barrel 4, the upper end of the water distribution device 7 is communicated with the water inlet pipe connector 11, the lower end of the water distribution device 7 is communicated with the fixed bed device 6, and an external heat insulation layer 42 is wrapped on the outer wall of the upper plug 1, the outer wall of the lower plug 2 and the outer wall of the reaction kettle barrel 4;
as shown in fig. 2, the fixed bed unit 6 comprises a plurality of vertical tubes 61 and cross rods 62, wherein the plurality of vertical tubes 61 are provided, and the side walls of the plurality of vertical tubes 61 are communicated with each other through the cross rods 62;
as shown in fig. 3, the water distribution device 7 includes a water inlet pipe 71, water inlet branch pipes 72, a plurality of water distribution ports 73, and inclined pipes 74, wherein the upper portion of the water inlet pipe 71 is communicated with the water inlet pipe joint 11, the lower end of the water inlet pipe 71 is connected with the inclined pipes 74, the number of the water inlet branch pipes 72 is plural, the plurality of water inlet branch pipes 72 are symmetrically arranged on both sides of the inclined pipes 74 in a V shape and are communicated with the inclined pipes 74, the number of the water distribution ports 73 is plural, the upper portions of the plurality of water distribution ports 73 are communicated with the water inlet branch pipes 72, and the lower portions thereof are communicated with the top portions of the vertical pipes 61 in a one-to-one correspondence.
The outer ends of the water inlet pipe connector 11, the heat source outlet 16 and the heat source inlet 17 are fixedly connected with small flange plates 18, the connection mode of the flange plates is more reliable, and the flange plates are not prone to being broken under high pressure.
The pipe diameter of the water inlet pipe 71 is 25mm, the pipe diameter of the water inlet branch pipe 72 is 10mm, and the aperture of the water distribution hole is 5 mm.
The bottom head baffle 15 is densely covered with small holes of 2mm, the bottom head baffle 15 is connected with the inner wall of the lower head by spot welding, and the welding mode is reliable and is not easy to fall off.
The bottom fixedly connected with of lower end cap 2 is used for the holistic base 21 of stabilising arrangement, and base 21 is favorable to increasing the steadiness of this device.
The vertical pipe 61, the cross rod 62, the water inlet pipe 71, the water inlet branch pipe 72 and the inclined pipe 74 are all made of copper-chromium alloy, the mass percentage of copper elements and chromium elements in the copper-chromium alloy is 9:1, and the copper-chromium alloy has good thermal conductivity.
The high-frequency heating line pipe 41 for heating the catalyst filling tube array 5 is wound on the outer side of the reaction kettle barrel 4, the heating mode is rapid, and the heat is concentrated.
The outside of the high-frequency heating wire tube 41 is wrapped with the heat-insulating layer 42, so that heat loss in the reaction kettle is prevented, and energy loss is further reduced.
When the fixed bed hydrothermal gasification reactor is applied to the treatment of wastewater containing phenolic resin, the COD content of the wastewater containing the phenolic resin is 9 percent, the catalyst adopts ruthenium-based catalyst, the temperature of molten salt is 450 ℃, the temperature of a catalyst filling tube 5 is 360 ℃, the reaction time is 50min, the COD content in water gas discharged by a safety valve interface 14 is less than 100mg/L, the methane content in the generated gas is 80 percent, and the COD can be rapidly decomposed into methane and CO in the reactor2Thus achieving the purpose of resource utilization.
When the fixed bed hydrothermal gasification reactor is applied to pesticide wastewater treatment, the appearance color of the pesticide wastewater is brownish red, the COD content in the pesticide wastewater is 30%, the catalyst is ruthenium-based catalyst, the temperature of molten salt is 400 ℃, the temperature of a catalyst filling tube array 5 is 330 ℃, the reaction time is 50min, the color of water gas discharged by a safety valve interface 14 is transparent and clear, the methane content in the generated gas is more than 80%, and COD can be rapidly decomposed into methane and CO in the reactor2The purpose of recycling is achieved, the removal rate of COD is high, and the removal effect is good.
Embodiment 4 compares with embodiment 3, and embodiment 4 adopts the high frequency heating spool to fill tubulation 5 to heat to the catalyst, and then keeps the reaction temperature of catalyst, and embodiment 3 is through the catalyst of high temperature, guarantees the reaction temperature in the reation kettle through continuous flow, has still increased the heat preservation in embodiment 4, and the heat loss in the reation kettle can be prevented to the heat preservation, and then reduces energy loss.

Claims (9)

1. A fixed bed hydrothermal gasification reactor is characterized by comprising an upper plug (1), a lower plug (2), a large flange disc (3), a reaction kettle barrel (4), a catalyst filling array pipe (5), a fixed bed device (6) and a water distribution device (7), wherein the upper plug (1) and the lower plug (2) are respectively fixed with the upper end and the lower end of the reaction kettle barrel (4) through the large flange disc (3), a water inlet pipe connector (11) is fixedly connected above the upper plug (1), a thermometer connector (12) for inserting a thermometer is arranged on the left side of the water inlet pipe connector (11), a pressure gauge (13) for monitoring the internal air pressure of the reaction kettle and a safety valve connector (14) for discharging hot and water are arranged on the right side of the water inlet pipe connector (11), a bottom end enclosure partition plate (15) is transversely arranged in the lower plug (2), the catalyst filling tube array (5) is vertically fixed above the bottom end enclosure partition plate (15), the fixed bed device (6) is fixedly installed inside the catalyst filling tube array (5), a heat source outlet (16) is arranged on one side above the fixed bed device (6), a heat source inlet (17) is arranged on one side below the fixed bed device (6), the outer end of the heat source outlet (16) and the outer end of the heat source inlet (17) both penetrate through the outer wall of the reaction kettle barrel (4), the upper end of the water distribution device (7) is communicated with the water inlet pipe connector (11), the lower end of the water distribution device (7) is communicated with the fixed bed device (6), and an external heat insulation layer (42) wraps the outer wall of the upper plug (1), the outer wall of the lower plug (2) and the outer wall of the reaction kettle barrel (4);
a high-frequency heating line pipe (41) for heating the catalyst filling array pipe (5) is wound on the outer side of the reaction kettle barrel body (4);
the fixed bed device (6) comprises a plurality of vertical pipes (61) and cross rods (62), wherein the side walls of the plurality of vertical pipes (61) are communicated with each other through the cross rods (62);
the water distribution device (7) comprises a water inlet pipe (71), water inlet branch pipes (72), water distribution ports (73) and inclined pipes (74), wherein the upper portion of the water inlet pipe (71) is communicated with the water inlet pipe connectors (11), the lower ends of the water inlet pipe (71) are connected with the inclined pipes (74), the water inlet branch pipes (72) are multiple, the water inlet branch pipes (72) are symmetrically arranged on two sides of the inclined pipes (74) in a V shape, the inclined pipes (74) are communicated with each other, the water distribution ports (73) are multiple, the upper portions of the water distribution ports (73) are communicated with the water inlet branch pipes (72), and the lower portions of the water distribution ports are communicated with the vertical pipes (61) in a one-to-one correspondence manner.
2. The fixed bed hydrothermal gasification reactor according to claim 1, wherein the outer ends of the water inlet pipe joint (11), the heat source outlet (16) and the heat source inlet (17) are fixedly connected with small flanges (18).
3. The fixed bed hydrothermal gasification reactor according to claim 1, wherein the pipe diameter of the water inlet pipe (71) is 15mm to 25mm, the pipe diameter of the water inlet branch pipe (72) is 10mm, and the aperture of the water distribution port is 3mm to 5 mm.
4. The fixed bed hydrothermal gasification reactor according to claim 1, wherein the bottom head partition plate (15) is densely distributed with 1mm-2mm small holes, and the bottom head partition plate (15) is connected with the inner wall of the lower plug (2) by spot welding.
5. A fixed bed hydrothermal gasification reactor according to claim 1 characterized in that the bottom of the lower plug (2) is fixedly connected with a base (21) for the stabilization device as a whole.
6. The fixed bed hydrothermal gasification reactor according to claim 1, wherein the vertical tube (61), the cross bar (62), the water inlet tube (71), the water inlet branch tube (72) and the inclined tube (74) are all made of a copper-chromium alloy, and the mass ratio of copper element to chromium element in the copper-chromium alloy is 9: 1.
7. The use of a fixed bed hydrothermal gasification reactor according to any one of claims 1-6, wherein the fixed bed hydrothermal gasification reactor is used for treating high salt and high COD chemical risk waste.
8. The application of the fixed bed hydrothermal gasification reactor as claimed in claim 7, wherein the fixed bed hydrothermal gasification reactor is applied to the treatment of wastewater containing phenolic resin, during the treatment, the COD content in the wastewater containing phenolic resin is 8% -9%, the catalyst adopts ruthenium-based catalyst, the temperature of molten salt is 450 ℃, the temperature of the catalyst filling tube (5) is 330-360 ℃, the reaction time is 30-50min, the COD content in the water gas discharged from the safety valve interface (14) is less than 100mg/L, and the methane content in the generated gas is 50% -80%.
9. The application of the fixed bed hydrothermal gasification reactor as set forth in claim 7, characterized in that the fixed bed hydrothermal gasification reactor is applied to pesticide wastewater treatment, when in treatment, the COD content in the pesticide wastewater is 30%, the ruthenium-based catalyst is adopted as the catalyst, the temperature of the molten salt is 400 ℃, the temperature of the catalyst filling tube (5) is 250-330 ℃, the reaction time is 30-50min, the water gas discharged from the safety valve interface (14) is transparent and clear, and the methane content in the generated gas is more than 80%.
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