CN108913209B - Method and system for supercritical water multi-pass resource treatment of recalcitrant organic hazardous waste - Google Patents
Method and system for supercritical water multi-pass resource treatment of recalcitrant organic hazardous waste Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000002920 hazardous waste Substances 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000007787 solid Substances 0.000 claims abstract description 90
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 238000000926 separation method Methods 0.000 claims abstract description 41
- 239000002893 slag Substances 0.000 claims abstract description 37
- 238000005496 tempering Methods 0.000 claims abstract description 35
- 150000003839 salts Chemical class 0.000 claims abstract description 29
- 238000002309 gasification Methods 0.000 claims abstract description 23
- 238000004064 recycling Methods 0.000 claims abstract description 22
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 18
- 238000001816 cooling Methods 0.000 claims abstract description 17
- 230000003197 catalytic effect Effects 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 10
- 230000003647 oxidation Effects 0.000 claims abstract description 6
- 238000004537 pulping Methods 0.000 claims abstract description 6
- 230000003750 conditioning effect Effects 0.000 claims abstract description 4
- 239000002699 waste material Substances 0.000 claims description 35
- 238000007599 discharging Methods 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 30
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 28
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 27
- 239000001301 oxygen Substances 0.000 claims description 27
- 229910052760 oxygen Inorganic materials 0.000 claims description 27
- 239000007789 gas Substances 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 17
- 239000010815 organic waste Substances 0.000 claims description 14
- 239000000498 cooling water Substances 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 230000001502 supplementing effect Effects 0.000 claims description 8
- 239000008399 tap water Substances 0.000 claims description 8
- 235000020679 tap water Nutrition 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 239000000446 fuel Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 238000010791 quenching Methods 0.000 claims description 4
- 230000000171 quenching effect Effects 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000005416 organic matter Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims 2
- 238000005516 engineering process Methods 0.000 abstract description 21
- 238000005260 corrosion Methods 0.000 abstract description 12
- 230000007797 corrosion Effects 0.000 abstract description 12
- 238000009284 supercritical water oxidation Methods 0.000 description 9
- 239000000571 coke Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000036284 oxygen consumption Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0953—Gasifying agents
- C10J2300/0973—Water
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0983—Additives
- C10J2300/0986—Catalysts
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses a method and a system for treating organic hazardous waste difficult to decompose by supercritical water multi-pass recycling, which mainly adopt supercritical water multi-pass technology, rapid mixing heating and rapid mixing cooling technology and W-shaped flow field control technology, treat the organic hazardous waste difficult to decompose by tempering pretreatment, direct mixing heating and partial oxidation in a reaction stage I and catalytic gasification in a reaction stage II so as to realize complete decomposition and recycling, and finally obtain combustible gas which can be recycled, water meeting emission standards and solid slag through separation. According to the invention, on one hand, the complete decomposition and recycling of the organic hazardous waste are realized, meanwhile, the salt is removed, the corrosion of system equipment is weakened, on the other hand, the partially separated high-pressure water is heated by the heat regenerator and then enters the reaction stage I to be rapidly mixed with the organic hazardous waste and heat the organic hazardous waste, and meanwhile, the partially separated water is decompressed and then is used for conditioning and pulping, so that the consumption and the discharge of the water are reduced.
Description
Technical Field
The invention belongs to the field of hazardous waste treatment, and particularly relates to a method and a system for supercritical water multi-pass resource treatment of refractory organic hazardous waste.
Background
Along with the increasing of the yield of the hazardous waste, the environmental protection index is stricter, the prior art is difficult to meet the requirement, and the development and application of new technology for treating the organic hazardous waste which is difficult to decompose are urgent, especially the organic hazardous waste with the concentration of 1-20wt%. When organic hazardous waste in the concentration range of the organic matters is treated, the supercritical water treatment technology of the organic hazardous waste can compete with the traditional technologies such as incineration and the like, but has better treatment effect and less pollution emission compared with the traditional technologies such as incineration and the like.
Supercritical water treatment organic hazardous waste technologies can be divided into two main categories, namely supercritical water gasification technologies and supercritical water oxidation technologies. The supercritical water gasification technology has the advantages of treating organic hazardous waste: the method can generate combustible gas such as hydrogen, methane and the like, and can realize the recycling of waste; compared with supercritical water oxidation technology, the corrosion of system equipment is weaker. Its disadvantages are: the organic dangerous waste has complex components, changeable forms and properties, the degradation effect is difficult to ensure by the supercritical water gasification technology, and the treated water is difficult to reach the discharge standard; external heat supply is needed, and the energy consumption is high; the reaction is not complete, and the reaction temperature needs to be increased or a catalyst needs to be used. The supercritical water oxidation technology releases a large amount of heat in the oxidation reaction process, so that self-heating of a reaction system can be realized, the decomposition rate of organic hazardous wastes is high, and complete decomposition of the organic hazardous wastes can be realized, but the supercritical water oxidation technology generally needs to use excessive oxygen, the corrosion of system equipment can be aggravated due to the excessive oxygen in the system, the service life of the system equipment is shortened, and the waste cannot be recycled.
Although some researchers have combined supercritical water gasification technology and supercritical water oxidation technology to treat organic hazardous waste, the general method is to gasify the organic hazardous waste by supercritical water, realize the decomposition of the organic hazardous waste, realize the recycling of combustible gas, and then carry out supercritical water oxidation reaction on unreacted substances to further decompose the organic hazardous waste. However, this method has problems in that: if the combustible gas is required to be recycled, a cooling system, a gas phase separation system and a heat recovery system are required to be added between the supercritical water gasification technology and the supercritical water oxidation technology, the system is relatively complex, the cooling and heat recovery processes are carried out through a temperature window with serious system corrosion, namely 250-300 ℃, the corrosion of system equipment is serious, and the reliability of the system equipment is reduced; if the combustible gas is not utilized in a recycling way, the oxygen consumption of the system cannot be reduced, meanwhile, compared with the supercritical water oxidation technology, the system is more complex, the reliability of the system is poorer, and two major problems of corrosion and salt blockage existing in the supercritical water oxidation treatment dangerous waste are not solved.
Salt blockage has been one of the important factors limiting the supercritical water treatment of organic hazardous waste. The salt separator and the reactor are designed in series, but the system is relatively complex, the salt separation temperature cannot be determined, incomplete salt separation is easy to cause, and meanwhile, the cost of a salt separation device is additionally increased, so that the salt separator and the reactor can be integrally designed, the system is simplified, and the investment is reduced.
The rapid heating can reduce the generation of tar coke and control the decomposition of macromolecular organic matters into micromolecular matters; the serious temperature window of system equipment corrosion of supercritical water treatment organic hazardous waste technology is 250-300 ℃, so that the temperature window can be avoided by means of direct mixed heating and direct mixed cooling, further corrosion of the system equipment is controlled, the W-shaped flow field design is adopted to reduce salt transportation and adhere to the wall surface of a reactor, and meanwhile, salt separation is enhanced by multiple factors such as inertial collision and gravity separation.
Disclosure of Invention
In view of the above, one of the purposes of the present invention is to provide a method for treating refractory organic hazardous waste by supercritical water multi-pass resource, and the other purpose of the present invention is to provide a system for treating refractory organic hazardous waste by supercritical water multi-pass resource.
In order to achieve the above purpose, the present invention provides the following technical solutions:
1. a method for treating refractory organic dangerous waste by supercritical water multi-pass resource comprises the following steps:
1) Pretreatment: the method comprises the steps of performing slurry mixing and tempering pretreatment on raw materials of organic hazardous wastes, including auxiliary fuel mixing, pH value adjustment, solid particle size control and organic matter concentration control;
2) Reaction stage I: the pretreated organic hazardous waste in the step 1) is conveyed into a preheater through a high-pressure pump, the material outlet temperature of the preheater is 200-250 ℃, then the preheater is directly mixed with recycled hot water, a small amount of oxygen is introduced to perform partial oxidation reaction, heat is released at the same time, rapid temperature rise is performed to induce rapid crystallization and precipitation of salt, and the salt is intermittently discharged through a solid slag discharge device;
3) Reaction stage II: and 2) enabling the organic matters subjected to partial oxidation reaction in the step 2) to enter a secondary reactor for catalytic gasification reaction, wherein the reaction product is a mixture containing combustible gas.
4) Separation and utilization: the mixture treated in the step 3) enters a regenerator from the outlet of a secondary reactor to exchange heat with recycled hot water to recover heat, the temperature of the mixture outlet of the regenerator is not lower than 320 ℃, then enters a gas-liquid-solid three-phase separator, the temperature of the mixture cooled by cooling water is lower than 80 ℃, and the mixture of combustible gas and liquid-solid two-phase is separated to obtain the mixture of the combustible gas and the liquid-solid two-phase which can be recycled; the liquid-solid two-phase mixture enters a liquid-solid separation device to realize further separation, part of separated high-pressure water is heated by a heat regenerator and then enters a first-stage reactor to be rapidly mixed with raw materials and heat the raw materials, and meanwhile, part of separated water is depressurized and then used for conditioning and pulping.
Preferably, in step 1), the auxiliary fuel is isopropanol; the pH value is 8-13; the solid particle size is not greater than 100 μm; the concentration of the organic matters is 1-20wt% in percentage by mass.
Preferably, the partial oxidation reaction temperature in the step 2) is 520-550 ℃, the pressure is 23-28Mpa, and the ratio of the oxidation coefficient of the partial oxidation reaction, namely the addition amount of oxygen to the theoretical chemical oxygen demand of the organic hazardous waste is 0.2-0.4.
Preferably, in the step 2), an oxygen inlet, a quenched and tempered organic waste inlet and a recycled hot water inlet are arranged in the primary reactor, and the primary reactor realizes W-shaped flow field control in a layout mode of the oxygen inlet, the quenched and tempered organic waste inlet and the recycled hot water inlet, so that rapid material mixing is realized, and rapid temperature rise and rapid salt crystallization separation of the organic hazardous waste are realized.
Preferably, the catalytic gasification reaction temperature in the step 3) is 600-630 ℃, the pressure is 23-28MPa, and the reaction residence time is 1-2min. The catalytic gasification reaction is added with a proper amount of alkali to regulate the reaction environment and catalyze the decomposition of organic hazardous wastes, wherein the alkali is any one or more of sodium carbonate, sodium hydroxide, potassium hydroxide or potassium carbonate, the catalytic gasification reaction is added with a catalyst to enhance the gasification reaction, and the catalyst is one or more of nickel, ruthenium, copper, platinum or active carbon.
Preferably, the temperature of the mixture before the mixture enters the gas-liquid-solid three-phase separator from the heat regenerator in the step 4) is not lower than 320 ℃, cooling water is introduced into the separator to be quickly mixed with the mixture, the temperature of the cooled mixture is lower than 80 ℃, part of high-pressure water separated by the liquid-solid separation device is recycled to the first-stage reactor through the heat regenerator, and part of water separated by the liquid-solid separation device is subjected to tempering and pulping after being depressurized, so that the consumption and the discharge of the water are reduced.
2. The system is used for realizing a method for carrying out multi-pass recycling treatment on refractory organic hazardous waste by supercritical water, and comprises a primary reactor 4, a secondary reactor 11, a regenerator 12, a gas-liquid-solid three-phase separator 14, a liquid-solid separation device 16, a liquid oxygen storage tank 19, a liquid oxygen high-pressure pump 20, a waste pretreatment tempering device 21, a waste high-pressure pump 22, a tap water supplementing device 23, an organic hazardous waste preheater 24 to be treated and a liquid oxygen preheater 25; the primary reactor 4 is provided with an oxygen inlet 1, an organic waste inlet 2 to be treated after tempering and a recycling hot water inlet 3, the liquid oxygen storage tank 19, the liquid oxygen high-pressure pump 20 and the liquid oxygen preheater 25 are sequentially connected, the liquid oxygen preheater 25 is connected with the primary reactor 4 through the oxygen inlet 1, the tap water supplementing device 23, the waste pretreatment tempering device 21, the waste high-pressure pump 22 and the organic hazardous waste preheater 24 to be treated are sequentially connected, and the organic hazardous waste preheater 24 to be treated is connected with the primary reactor 4 through the organic waste inlet 2 to be treated after tempering; the top of the primary reactor 4, the secondary reactor 11, the heat regenerator 12, the gas-liquid-solid three-phase separator 14 and the liquid-solid separation device 16 are connected in sequence.
Further, the first-stage reactor 4 realizes W-shaped flow field control through an oxygen inlet 1, an organic waste inlet 2 to be treated after tempering and a recycling hot water inlet 3, a salt discharging port is arranged at the bottom of the first-stage reactor 4, and the salt discharging port at the bottom of the first-stage reactor 4 is sequentially connected with a solid slag cooling device 8 and a solid slag discharging device 6.
Further, a stop valve 5 is arranged between the solid slag discharging device 6 and the solid slag cooling device 8, and the solid slag discharging device 6 is provided with a pressure charging and discharging device 7.
Further, the secondary reactor 11 is connected to a catalyst device 9 and a neutralizer device 10, respectively.
Further, the regenerator 12 is connected to the primary reactor 4 through a recycled hot water inlet 3.
Further, the gas-liquid-solid three-phase separator 14 is connected with the cooling water charging device 13, and the combustible gas discharging device 15 is connected with the small amount of solid slag discharging device 17 respectively.
Further, the circulating pump 18, the liquid-solid separation device 16, the circulating pump 18 and the regenerator 12 are sequentially connected.
Further, the liquid-solid separation device 16 is connected to the waste pretreatment conditioning device 21 after passing through the depressurization device.
Further, the liquid-solid separation device 16 is connected to a small amount of solid slag discharging device 17.
The invention has the beneficial effects that:
1) According to the invention, the rapid heating of the organic hazardous waste is realized by directly mixing the quenched and tempered raw material and the recycled hot water and introducing a small amount of oxygen to generate partial oxidation exothermic reaction, so that the temperature window 250-300 ℃ with serious corrosion of system equipment is avoided, the corrosion of the system equipment is reduced, and the generation of tar coke is reduced by rapid heating.
2) According to the invention, the W-shaped flow field arrangement is realized in the primary reactor, the precipitated salt transportation is reduced and adhered to the wall surface of the reactor by controlling the flow field, and meanwhile, the separation of the salt from the primary reactor is enhanced by utilizing multiple factors such as inertial collision, gravity separation and the like, so that the integrated design of reactant decomposition and salt separation is realized.
3) The invention carries out partial oxidation reaction in the first-stage reactor to degrade the refractory organic matters into micromolecular organic matters, and the oxidation coefficient is only 0.2-0.4, so that the reaction temperature is easy to control, and meanwhile, the catalytic gasification reaction is carried out in the second-stage reactor to generate combustible gas, thereby realizing the complete decomposition and recycling of hazardous wastes of the refractory organic matters, reducing the oxygen consumption and lowering the use cost.
4) The invention controls the corrosion of system equipment by controlling the pH value and the outlet temperature (not lower than 320 ℃) of the mixture after reaction in the heat regenerator, and then directly introduces cooling water into the gas-liquid-solid three-phase separator to realize the direct mixed cooling (cooling to below 80 ℃), meanwhile, as oxygen is not introduced in the reaction stage II, the heat regenerator does not contain oxygen, and the corrosion of the system equipment in the heat regeneration and cooling process is weakened under the action of various factors.
5) According to the invention, part of the separated high-pressure water is boosted by the circulating pump and is recycled to the first-stage reactor after being warmed by the heat regenerator, and part of the separated water is subjected to tempering and pulping after being decompressed, so that the consumption and the discharge of the water are reduced.
6) The invention realizes degradation of the hard-to-decompose organic matters into organic matter micromolecules by means of direct mixing and partial oxidation, reduces tar coke generation, controls reactant components of the catalytic gasification reaction in the reaction stage II, and prolongs the service life of the catalyst in the catalytic gasification reaction process.
Drawings
In order to make the objects, technical solutions and advantageous effects of the present invention clearer, the present invention provides the following drawings:
the system structure diagram of the supercritical water multi-pass resource treatment system for the organic refractory dangerous waste adopted by the invention is shown in the figure 1, wherein the system structure diagram is 1 an oxygen inlet, 2 an organic waste inlet to be treated after tempering, 3 a hot water recycling inlet, 4 a primary reactor, 5 a stop valve, 6 a solid slag discharging device, 7 a pressure filling and releasing device, 8 a solid slag cooling device, 9 a catalyst device, 10 a neutralizer device, 11 a secondary reactor, 12 a regenerator, 13 a cooling water filling device, 14 a gas-liquid-solid three-phase separator, 15 a combustible gas discharging device, 16 a liquid-solid separating device, 17 a small amount of solid slag discharging device, 18 a circulating pump, 19 a liquid oxygen storage tank, 20 a liquid-oxygen high-pressure pump, 21 a waste pretreatment tempering device, 22 a waste high-pressure pump, 23 a tap water supplementing device, 24 a to be treated organic dangerous waste preheater and 25 a liquid oxygen preheater.
Detailed Description
Preferred embodiments of the present invention will be described in detail below. The experimental methods for which specific conditions are not specified in the examples are generally conducted under conventional conditions or under conditions recommended by the manufacturer.
As shown in figure 1, the supercritical water multi-pass recycling treatment system for refractory organic hazardous waste comprises an oxygen inlet 1, a post-tempering organic waste inlet 2 to be treated, a recycling hot water inlet 3, a primary reactor 4, a stop valve 5, a solid slag discharge device 6, a pressure charging and discharging device 7, a solid slag cooling device 8, a catalyst device 9, a neutralizer device 10, a secondary reactor 11, a heat regenerator 12, a cooling water charging device 13, a gas-liquid-solid three-phase separator 14, a combustible gas discharge device 15, a liquid-solid separation device 16, a small amount of solid slag discharge device 17, a circulating pump 18, a liquid oxygen storage tank 19, a liquid oxygen high-pressure pump 20, a waste pretreatment tempering device 21, a waste high-pressure pump 22, a tap water supplementing device 23, a pre-heater 24 for organic hazardous waste to be treated and a liquid oxygen pre-heater 25;
the top of the primary reactor 4, the secondary reactor 11, the heat regenerator 12, the gas-liquid-solid three-phase separator 14 and the liquid-solid separation device 16 are sequentially connected in the system.
The primary reactor 4 is provided with an oxygen inlet 1, a quenched and tempered organic waste inlet 2 and a recycled hot water inlet 3, wherein a liquid oxygen storage tank 19, a liquid oxygen high-pressure pump 20 and a liquid oxygen preheater 25 are sequentially connected, the liquid oxygen preheater 25 is connected with the primary reactor 4 through the oxygen inlet 1, oxygen with the pressure of 23-28MPa and the temperature of 200-250 ℃ is provided for partial oxidation reaction in the primary reactor 4, a tap water supplementing device 23, a waste pretreatment quenching and tempering device 21, a waste high-pressure pump 22 and a to-be-treated organic hazardous waste preheater 24 are sequentially connected, and the to-be-treated organic hazardous waste preheater 24 is connected with the primary reactor 4 through the quenched and tempered organic waste inlet 2, so that to-be-treated refractory organic hazardous waste enters the primary reactor 4 after quenching and tempering pretreatment, heating to 200-250 ℃ and boosting to 23-28MPa;
the top of the primary reactor 4 is controlled by an oxygen inlet 1, an organic waste inlet 2 to be treated after tempering and a recycling hot water inlet 3 in a W-shaped flow field, rapid mixing and heating of materials are realized, a salt discharging port is arranged at the bottom of the primary reactor, the primary reactor 4 is sequentially connected with a solid slag cooling device 8 and a solid slag discharging device 6 through the bottom salt discharging port, a stop valve 5 is arranged between the solid slag discharging device 6 and the solid slag cooling device 8, and the solid slag discharging device 6 is provided with a pressure filling and releasing device 7, so that generated and separated salt is intermittently discharged.
The secondary reactor 11 is connected to the catalyst device 9 and the neutralizer device 10, and the catalyst device 9 provides a catalyst for the catalytic gasification reaction of the secondary reactor 11, and the neutralizer device 10 provides a neutralizer for neutralizing the acid or acidic substances generated in the secondary reactor 11.
The regenerator 12 enables part of separated high-pressure water to enter the primary reactor 4 for recycling after being regenerated and warmed by the regenerator 12 through the hot water recycling inlet 3 and the primary reactor 4.
The gas-liquid-solid three-phase separator 14 is respectively connected with the cooling water charging device 13, the combustible gas discharging device 15 and the small amount of solid slag discharging device 17; the circulating pump 18, the liquid-solid separation device 16 and the circulating pump 18 are sequentially connected with the heat regenerator 12; the liquid-solid separation device 16 is connected with the waste pretreatment tempering device 21 after passing through the depressurization device; the liquid-solid separation device 16 is connected with a small amount of solid slag discharging device 17.
A method for treating refractory organic dangerous waste by supercritical water multi-pass resource comprises the following steps:
1) Quenching and tempering pretreatment: firstly, grinding and screening organic dangerous waste raw materials, wherein the granularity of the particles is not more than 100 mu m, then conveying the organic dangerous waste raw materials into a waste pretreatment tempering device 21 for tempering, adding auxiliary fuels such as isopropanol and the like to regulate and control the heat value during the tempering, controlling the concentration of the tempered organic matters to be 1-20wt% and the pH value to be 8-13, wherein tempering water is supplemented by a tap water supplementing device 23;
2) Reaction stage I: the organic hazardous waste raw material after tempering pretreatment is preheated to 200-250 ℃ by a waste high-pressure pump 22 after being boosted (the pressure is controlled to be 23-28 MPa), and then enters a primary reactor 4 through a waste inlet 2 to be treated after tempering and is directly mixed with recycled hot water entering through a recycled hot water inlet 3, so that rapid temperature rise is realized; wherein the recycled hot water flows out of the liquid-solid separation device 16, is boosted by the circulating pump 18 and is heated by the heat regenerator 12, and then enters through the recycled hot water inlet 3; after the liquid oxygen in the liquid oxygen storage tank 19 is boosted to 23-28MPa by the liquid oxygen high-pressure pump 20, and is heated to 200-250 ℃ by the liquid oxygen preheater 25, then enters the primary reactor 4 from the oxygen inlet 1, and is subjected to partial oxidation reaction with the organic hazardous waste after rapid temperature rise to degrade the organic hazardous waste, wherein the reaction temperature of the primary reactor 4 is set to 520-550 ℃ and the pressure is set to 23-28MPa; the W-shaped flow field is formed in the primary reactor 4 through the arrangement of the oxygen inlet 1, the organic waste inlet 2 to be treated after tempering and the recycling hot water inlet 3, so that the materials are quickly mixed, the temperature of the organic hazardous waste is quickly raised to be above the critical temperature, the quick crystallization precipitation of salt is realized in the primary reaction 4, and the separation of the salt from the primary reactor 4 is enhanced under multiple factors such as inertial collision, gravity sedimentation and the like. The separated salt is discharged from a salt discharge port at the bottom of the primary reactor 4, mixed with cooling water entering from a solid slag cooling device 8, enters a solid slag discharge device 6 through a stop valve 5 after being cooled, and is intermittently discharged (the pressure of the solid slag discharge device 6 is controlled through a pressure charging and releasing device 7);
3) Reaction stage II: the supercritical water mixture generated in the reaction stage I is discharged from the top of the first-stage reactor 4 and enters the second-stage reactor 11, and is subjected to catalytic gasification reaction under the combined action of a neutralizer and a catalyst, wherein the catalytic gasification reaction temperature is set to be 600-630 ℃, the pressure is set to be 23-28MPa, the reaction residence time is set to be 1-2min, and the mixture containing combustible gas is generated; wherein the catalyst is added through a catalyst device 9, the catalyst is one or more of nickel, ruthenium, copper, platinum or active carbon, the neutralizer is added through a neutralizer device 10, and the neutralizer is one or more of sodium carbonate, sodium hydroxide, potassium carbonate or potassium hydroxide;
4) Separation and utilization: the mixture after catalytic gasification reaction in the reaction stage II flows out from the secondary reactor 11 and enters the regenerator 12 to exchange heat with reuse water (the temperature of the mixture before entering the gas-liquid-solid three-phase separator from the regenerator is not lower than 320 ℃), then enters the gas-liquid-solid three-phase separator 14 to be directly mixed with cooling water entering from the cooling water charging device 13 for cooling (the temperature of the cooled mixture is not higher than 80 ℃), separated combustible gas is discharged from the combustible gas discharging device 15, separated part of solid slag is intermittently discharged from a small amount of solid slag discharging device 17, the liquid-solid two-phase mixture enters the liquid-solid separating device 16 for further separation, part of the separated high-pressure water is pressurized by the circulating pump 18 and enters the regenerator 12 for heating, then enters the first-stage reactor 4 from the reuse hot water inlet 3 for rapid mixing and heating organic dangerous waste, part of the separated water is depressurized and then is reused to the waste pretreatment tempering device 21, and other separated water is directly discharged after being depressurized after being inspected to be qualified; the solid slag separated in the liquid-solid separation device 16 is intermittently discharged through the small amount of solid slag discharging device 17.
Finally, it is noted that the above-mentioned preferred embodiments are only intended to illustrate rather than limit the invention, and that, although the invention has been described in detail by means of the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the invention as defined by the appended claims.
Claims (10)
1. The method for treating the recalcitrant organic hazardous waste by supercritical water multi-pass resource is characterized by comprising the following steps of:
1) Quenching and tempering pretreatment: the method comprises the steps of performing slurry mixing and tempering pretreatment on raw materials of organic hazardous wastes, including auxiliary fuel mixing, pH value adjustment, solid particle size control and organic matter concentration control;
2) Reaction stage I: the pretreated organic hazardous waste in the step 1) is conveyed into a preheater through a high-pressure pump, the material outlet temperature of the preheater is 200-250 ℃, then the organic hazardous waste enters a primary reactor and recycled hot water to be directly mixed and heated, a small amount of oxygen is introduced to perform partial oxidation reaction, heat is released at the same time, the rapid heating initiates rapid crystallization precipitation of salt, and the salt is discharged through a solid slag discharge device;
3) Reaction stage II: the mixture after the partial oxidation reaction in the step 2) enters a secondary reactor for catalytic gasification reaction, and the reaction product is a mixture containing combustible gas;
4) Separation and utilization: the mixture treated in the step 3) enters a regenerator from the outlet of a secondary reactor to exchange heat with recycled hot water to recover heat, the temperature of the mixture outlet of the regenerator is not lower than 320 ℃, then enters a gas-liquid-solid three-phase separator, the temperature of the mixture cooled by cooling water is lower than 80 ℃, and the separation of the combustible gas and the liquid-solid two-phase mixture is carried out to obtain the combustible gas and the liquid-solid two-phase mixture which can be recycled; the liquid-solid two-phase mixture enters a liquid-solid separation device to realize further separation, part of separated high-pressure water is heated by a heat regenerator and then enters a first-stage reactor to be rapidly mixed with raw materials and heat the raw materials, and meanwhile, part of separated water is depressurized and then used for conditioning and pulping.
2. The method for the supercritical water multi-pass recycling treatment of recalcitrant organic hazardous waste according to claim 1, wherein the auxiliary fuel in step 1) is isopropanol; the pH value is 8-13; the solid particle size is less than 100 μm; the concentration of the organic matters is 1-20wt% in percentage by mass.
3. The method for treating organic hazardous waste refractory to supercritical water multi-pass resource recovery according to claim 1, wherein in the step 2), the partial oxidation reaction temperature is 520-550 ℃, the pressure is 23-28Mpa, and the ratio of the oxidation coefficient of the partial oxidation reaction, namely the oxygen addition amount, to the theoretical chemical oxygen demand of the organic hazardous waste is 0.2-0.4.
4. The method for treating refractory organic hazardous waste by supercritical water multi-pass resource treatment according to claim 1, wherein the catalytic gasification reaction temperature in the step 3) is 600-630 ℃, the pressure is 23-28MPa, and the reaction residence time is 1-2min; and a proper amount of alkali is added during the catalytic gasification reaction to regulate the reaction environment and catalyze the decomposition of organic hazardous wastes, wherein the alkali is any one or more of sodium carbonate, sodium hydroxide, potassium hydroxide or potassium carbonate, a catalyst is added during the catalytic gasification reaction to enhance the gasification reaction, and the catalyst is one or more of nickel, ruthenium, copper, platinum or active carbon.
5. The method for the supercritical water multi-pass recycling treatment of the organic hazardous waste difficult to decompose as claimed in claim 1, wherein the temperature of the mixture before the mixture enters the gas-liquid-solid three-phase separator from the heat regenerator in the step 4) is not lower than 320 ℃, cooling water is introduced into the separator to be rapidly mixed with the mixture, the temperature of the cooled mixture is lower than 80 ℃, part of high-pressure water separated by the liquid-solid separation device is recycled to the first-stage reactor through the heat regenerator, and part of water separated by the liquid-solid separation device is subjected to tempering and pulping after being depressurized, so that the consumption and the discharge of the water are reduced.
6. A supercritical water multi-pass resource treatment system for refractory organic hazardous waste, which is characterized by comprising a primary reactor (4), a secondary reactor (11), a regenerator (12), a gas-liquid-solid three-phase separator (14), a liquid-solid separation device (16), a liquid oxygen storage tank (19), a liquid oxygen high-pressure pump (20), a waste pretreatment tempering device (21), a waste high-pressure pump (22), a tap water supplementing device (23), an organic hazardous waste to be treated preheater (24) and a liquid oxygen preheater (25), wherein the system is used for realizing the method of any one of claims 1-5; the system is characterized in that the primary reactor (4) is provided with an oxygen inlet (1), a post-tempering organic waste inlet (2) and a recycling hot water inlet (3), the liquid oxygen storage tank (19), the liquid oxygen high-pressure pump (20) and the liquid oxygen preheater (25) are sequentially connected, the liquid oxygen preheater (25) is connected with the primary reactor (4) through the oxygen inlet (1), the tap water supplementing device (23), the waste pretreatment tempering device (21), the waste high-pressure pump (22) and the pre-treatment organic hazardous waste preheater (24) are sequentially connected, and the pre-treatment organic hazardous waste preheater (24) is connected with the primary reactor (4) through the post-tempering organic waste inlet (2); the top of the primary reactor (4), the secondary reactor (11), the heat regenerator (12), the gas-liquid-solid three-phase separator (14) and the liquid-solid separation device (16) are connected in sequence.
7. The supercritical water multi-pass resource treatment organic refractory dangerous waste system according to claim 6, wherein the first-stage reactor (4) realizes W-shaped flow field control through an oxygen inlet (1), an organic waste inlet (2) to be treated after tempering and a recycling hot water inlet (3), a salt discharging port is arranged at the bottom of the first-stage reactor (4), and a solid slag cooling device (8) and a solid slag discharging device (6) are sequentially connected with the bottom salt discharging port of the first-stage reactor (4); a stop valve (5) is arranged between the solid slag discharging device (6) and the solid slag cooling device (8), and the solid slag discharging device (6) is connected with a pressure charging and discharging device (7); the heat regenerator (12) is connected with the primary reactor (4) through a recycling hot water inlet (3).
8. The supercritical water multi-pass resource system for treating organic refractory hazardous waste according to claim 6, wherein the secondary reactor (11) is further connected with a catalyst device (9) and a neutralizer device (10).
9. The supercritical water multi-pass resource treatment system for organic refractory dangerous waste according to claim 6, wherein the gas-liquid-solid three-phase separator (14) is further connected with a cooling water charging device (13), a combustible gas discharging device (15) and a small amount of solid slag discharging device (17).
10. The supercritical water multi-pass resource treatment system for organic refractory dangerous waste according to claim 6, wherein the system is provided with a circulating pump (18), and the liquid-solid separation device (16), the circulating pump (18) and the heat regenerator (12) are sequentially connected; the liquid-solid separation device (16) is connected with the waste pretreatment tempering device (21) after passing through the depressurization device; the liquid-solid separation device (16) is connected with a small amount of solid slag discharge device (17).
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