CN111170339A - System and method for preparing sodium sulfite by recycling active coke desulfurization rich gas - Google Patents
System and method for preparing sodium sulfite by recycling active coke desulfurization rich gas Download PDFInfo
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- CN111170339A CN111170339A CN202010072611.2A CN202010072611A CN111170339A CN 111170339 A CN111170339 A CN 111170339A CN 202010072611 A CN202010072611 A CN 202010072611A CN 111170339 A CN111170339 A CN 111170339A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/14—Preparation of sulfites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
- B01D53/502—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract
The invention provides a system and a method for preparing sodium sulfite by recycling active coke desulfurization rich gas, wherein the system comprises the following steps: the pretreatment system is used for purifying and cooling the regeneration gas and separating gas and solid; the reaction recovery system comprises a reaction unit and a recovery unit, wherein the reaction unit of the reaction recovery system is connected with a gas outlet of the pretreatment system and is used for reacting, synthesizing and recovering sodium sulfite; the evaporation concentration system is used for circularly evaporating and concentrating the sodium sulfite slurry generated by the reaction unit, and the evaporated and concentrated sodium sulfite slurry enters from the inlet of the recovery unit to be recovered; and the tail gas treatment system is used for absorbing sulfur dioxide and dust in the tail gas. Method of producing a composite materialThe method comprises the following steps: pretreating the regeneration gas; synthesizing, evaporating, concentrating and recovering a product; and (4) tail gas treatment. The system of the invention has low energy consumption, high purity, good absorption and purification effect, low water consumption and SO adaptability to continuous production requirements2The loss rate is low, and the system independence is strong.
Description
Technical Field
The invention belongs to the technical field of dry-process active coke desulfurization and denitrification rich gas recycling in the environmental protection industry, and particularly relates to a system and a method for preparing sodium sulfite by recycling active coke desulfurization rich gas.
Background
At present, the atmospheric pollutant treatment measures of steel enterprises in China can be roughly summarized into three categories: 1. basic conditions of raw material control and flue gas emission reduction; 2. an effective means of controlling the sintering process and reducing the emission of flue gas; 3. the final means and the final guarantee of the flue gas treatment. Among the three treatment measures, people often pay more attention to the tail end treatment of the flue gas. At present, the tail end treatment of sintering flue gas mainly comprises active coke desulfurization and denitration integration, flue gas desulfurization (wet method, dry method and semi-dry method), medium-low temperature SCR denitration integration and other technologies.
The integration of flue gas desulfurization (wet method, dry method and semi-dry method) and medium-low temperature SCR denitration is to treat the flue gas at the tail end of the sintering flue gas through a flue gas treatment system and remove harmful substances SO in the flue gas through absorption2And NOx, substances after tail gas absorption treatment can not be recycled; the dry active coke desulfurization and denitrification technology utilizes the active coke to remove SO in the flue gas2And NOx, and resolving the active coke at 450 ℃ to obtain gases with higher concentration, wherein the gases with higher concentration are collectively called active coke regeneration gases, the regeneration gases are desulfurization rich gases of the active coke, and the main components of the regeneration gases are shown in the following table:
the regeneration gas generated by the dry method active coke desulfurization and denitrification technology contains moreSO of (A)2Gas, absorbing and resolving the active coke to obtain high-concentration SO2Gas, if capable of converting SO in high concentration2The gas is reasonably utilized and used as an industrial preparation raw material to prepare industrial sodium sulfite, the sintering flue gas is recycled, the environmental pollution is reduced, and the method has important significance for improving the industrial production process.
Therefore, there is a need to provide an improved solution to the above-mentioned deficiencies of the prior art.
Disclosure of Invention
The invention aims to provide a system and a method for preparing sodium sulfite by recycling active coke desulfurization rich gas, which aim to solve the problems that the utilization rate of sintering flue gas is low, the pollution flue gas cannot be recycled and the resource is wasted in the current steel production process.
In order to achieve the above purpose, the invention provides the following technical scheme:
a system for preparing sodium sulfite by recycling active coke desulfurization rich gas, which comprises:
the pretreatment system is used for purifying, cooling and carrying out gas-solid separation on the regeneration gas to obtain a pretreated gas with the purity of sulfur dioxide being increased;
the reaction recovery system comprises a reaction unit and a recovery unit, wherein the reaction unit of the reaction recovery system is connected with a gas outlet of the pretreatment system and is used for reacting, synthesizing and recovering sodium sulfite;
the evaporation concentration system is connected with the outlet of the reaction unit and is used for circularly evaporating and concentrating the sodium sulfite slurry generated by the reaction unit, and the evaporated and concentrated sodium sulfite slurry enters from the inlet of the recovery unit of the reaction recovery system to be recovered;
and the tail gas treatment system is connected with a tail gas outlet of the reaction recovery system and is used for purifying and treating the tail gas generated in the reaction recovery system so as to further absorb sulfur dioxide and dust in the tail gas.
System for preparing sodium sulfite by recycling active coke desulfurization rich gasPreferably, the pretreatment system comprises: scrubber for cleaning gas to remove SO from regeneration gas3HCl, HF and dust, and simultaneously realize gas cooling and gas-liquid separation;
preferably, the scrubber comprises two stages of scrubbers connected in sequence, wherein the one stage of scrubber is used for purifying the activated coke regeneration gas to remove SO in the activated coke regeneration gas in a preliminary step3HCl, HF and dust and primarily realize gas cooling; the secondary scrubber is used for purifying the gas from the primary scrubber again to further remove SO therein3HCl, HF and dust, further cooling the gas, and removing fog drops in the gas after secondary purification;
more preferably, a vortex generating device is arranged at the upper part inside the primary scrubber, a washing circulating pump is arranged outside the primary scrubber, and washing liquid at the bottom of the primary scrubber enters the vortex generating device through the washing circulating pump to generate a transient vortex liquid suspension layer and then form a downward-running rotating liquid flow to perform an impact reaction with upward-running regeneration gas;
preferably, the vortex generating device is provided with an upper layer and a lower layer which are respectively a first vortex generating device and a second vortex generating device;
preferably, the secondary scrubber comprises a washing section, a filling section and an electric defogging section from bottom to top;
further preferably, a washing circulating pump and a cooler are arranged outside the washing section and are respectively used for circulating the washing liquid of the washing section and cooling the gas;
still more preferably, the gas dust and total salt content passing through the secondary scrubber is less than 5mg/m3。
In the system for preparing sodium sulfite by recycling the active coke desulfurization rich gas, preferably, the reaction unit of the reaction recovery system comprises:
the reaction device is connected with a gas outlet of the pretreatment system and is used for synthesizing sodium sulfite through reaction;
the recovery unit includes: the centrifugal device is connected with a concentrated slurry outlet of the evaporation concentration system and is used for recovering a solid material containing the sodium sulfite; the drying device is connected with the solid outlet of the centrifugal device and is used for drying the solid material containing the sodium sulfite;
the reaction device comprises a primary reactor and a secondary reactor, the pretreated gas enters the primary reactor, and an upper gas outlet of the primary reactor is connected to an upper gas inlet of the secondary reactor through a first gas transmission pipeline; the first gas transmission pipeline is used for transmitting gas containing sulfur dioxide; the bottom slurry outlet of the primary reactor is connected to the evaporation concentration system through a pipeline; the lower slurry outlet of the secondary reactor is connected to the upper slurry inlet of the primary reactor through a first liquid conveying pipeline, and the first liquid conveying pipeline is used for conveying slurry;
preferably, the secondary reactor is connected with an alkali liquor tank, and alkali liquor in the alkali liquor tank is periodically conveyed into the secondary reactor for supplement;
still preferably, the secondary reactor is provided with a circulation pump for self-circulation of the slurry.
In the system for preparing sodium sulfite by recycling the active coke desulfurization rich gas as described above, preferably, the evaporation concentration system includes:
the heater comprises a tube side and a shell side, the tube side is used for storing slurry, the shell side is used for storing hot steam, and the heater is connected with a bottom slurry outlet of the primary reactor and is used for heating, evaporating and concentrating the sodium sulfite slurry;
the inlet of the separator is connected with the tube pass outlet of the heater, the separator is used for carrying out gas-liquid separation on the sodium sulfite slurry, and the bottom circulating slurry outlet of the separator conveys the slurry to the tube pass bottom inlet of the heater through an evaporation circulating pump so as to continuously circulate and evaporate the slurry; the bottom concentrated slurry outlet of the separator is connected with the centrifugal device;
the condenser is used for cooling the steam from the separator and the heater;
the vacuum pump is connected with the condenser and enables negative pressure to be formed in the condenser; preferably also creating a negative pressure within the separator;
preferably, the vacuum pump is connected to the vacuum tank, and both a top outlet and a bottom outlet of the condenser are connected to the vacuum tank.
In the system for preparing sodium sulfite by recycling the active coke desulfurization rich gas, preferably, the reaction unit further comprises a mother liquor tank, the liquid generated by the centrifugal device and the tail gas treatment system is conveyed into the mother liquor tank, and the liquid in the mother liquor tank is conveyed into the alkali liquor tank through a pipeline.
In the system for preparing sodium sulfite by recycling the active coke desulfurization rich gas, preferably, the drying device comprises an air dryer and a cyclone collector, and the material dried by the air dryer enters the cyclone collector for particle collection;
preferably, the cyclone collector is a two-stage cyclone collector.
In the system for preparing sodium sulfite by recycling the active coke desulfurization rich gas, preferably, a drying feeder is further arranged in front of the air dryer, and the material enters the drying space inside the drying feeder and is then transported to the air dryer.
In the system for preparing sodium sulfite by recycling the active coke desulfurization rich gas, preferably, the tail gas treatment system comprises a tail gas absorption tower, a circulating pump is arranged outside the tail gas absorption tower, and the alkali liquor at the bottom of the tail gas absorption tower is conveyed to the top and continuously circulated.
A method for preparing sodium sulfite by recycling active coke desulfurization rich gas comprises the following steps:
step one, pretreatment of regeneration gas, comprising:
purifying the regenerated gas subjected to desulfurization, denitrification and desorption of the active coke by using a pretreatment system to obtain a pretreated gas with high sulfur dioxide purity;
step two, the synthesis, the evaporation concentration and the recovery of the product comprise:
the pretreated gas enters a reaction unit of a reaction recovery system, absorption liquid is adopted to pass through a two-stage reaction device to prepare sodium sulfite slurry, and the sodium sulfite slurry is subjected to evaporation concentration and then is subjected to centrifugal separation and drying by a recovery unit to obtain sodium sulfite powder particles;
step three, tail gas treatment, comprising:
and tail gas generated by the reaction unit and the recovery unit enters the tail gas treatment system, the absorption liquid is adopted for secondary washing and purification, and the treated gas is discharged.
In the method for preparing sodium sulfite by recycling the active coke desulfurization rich gas, preferably, the pretreated gas enters the reaction unit of the reaction recovery system after being pressurized by the tail gas fan;
preferably, the absorption liquid is an alkali solution, more preferably a sodium carbonate solution;
still preferably, the method is performed using the system.
Compared with the closest prior art, the technical scheme provided by the invention has the following excellent effects:
the system and the method for preparing sodium sulfite by recycling the active coke desulfurization rich gas have the following excellent effects:
the primary reactor and the secondary reactor are communicated and shared, SO that the reaction time of the primary reactor can be stabilized, the influence on the discharge of the primary reactor due to the failure of the reactor is reduced, the continuous and stable operation of a downstream evaporation concentration system, a centrifugal separation system and a drying system is facilitated, and the SO absorbed by the primary reactor is increased2The concentration of the alkali liquor reduces the consumption of the alkali liquor, and is beneficial to reducing the energy consumption of a system and improving the product quality.
But continuous output sodium sulfite powder product, more adapt to the continuity production requirement, and the sodium sulfite powder product purity that obtains is greater than 90%, satisfies industry service standard.
The flue gas is continuously washed by adopting a circulating rotating liquid flow generated by a two-stage vortex generating deviceSO as to achieve better absorption and purification effects, less water consumption and SO2The loss rate is lower.
By adopting a two-stage absorption method, the absolute circulation amount of the circulating absorption liquid is effectively reduced, and the SO in the waste gas is improved2Absorption efficiency, SO Using the method and System of the invention2The absorption rate is more than 98 percent, the alkali liquor consumption is less, and the treated gas can be directly discharged into the atmosphere and meets the discharge standard.
The pretreatment system is relatively independent and has no related interlocking relation with a later reaction recovery system, and when the pretreatment system fails, the pretreatment system can be directly replaced by a standby device, so that the influence on a downstream sodium sulfite powder product preparation system is reduced.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. Wherein:
FIG. 1 is a flow chart of a system for preparing sodium sulfite by recycling the active coke desulfurization rich gas in the embodiment of the invention.
In the figure: 1. a pre-treatment system; 11. a first-stage scrubber; 111. a first vortex generating device; 112. a second vortex generating device; 12. a secondary scrubber; 121. a washing section; 122. a filler section; 123. an electric demisting section; 13. a washing circulating pump; 14. a cooler; 15. a wastewater tank; 2. a reaction recovery system; 21. a first stage reactor; 22. a secondary reactor; 23. an alkali liquor tank; 24. a mother liquor tank; 25. a centrifugal separator; 26. drying the feeder; 27. an air dryer; 28. a cyclone collector; 29. a tail gas fan; 210. an induced draft fan; 211. a first gas transmission pipeline; 212. a first infusion line; 3. an evaporative concentration system; 31. a heater; 32. a separator; 33. an evaporation circulating pump; 34. a condenser; 35. a vacuum pump; 36. a vacuum tank; 4. a tail gas treatment system; 41. a tail gas absorption tower; 5. and a circulating pump.
Detailed Description
The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
In the description of the present invention, the terms "longitudinal", "lateral", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", and the like indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, which are for convenience of description of the present invention only and do not require that the present invention must be constructed and operated in a specific orientation, and thus, should not be construed as limiting the present invention. The terms "connected" and "connected" used herein should be interpreted broadly, and may include, for example, a fixed connection or a detachable connection; they may be directly connected or indirectly connected through intermediate members, and specific meanings of the above terms will be understood by those skilled in the art as appropriate.
As shown in fig. 1, according to an embodiment of the present invention, there is provided a system for preparing sodium sulfite by recycling active coke desulfurization rich gas, the system for preparing sodium sulfite comprising:
a pretreatment system 1, the pretreatment system is used for purifying, cooling and gas-solid separation of the active coke regeneration gas, in the embodiment of the invention, the pretreatment system 1 comprises a scrubber for purifying the gas to remove SO in the active coke regeneration gas3HCl, HF and dust, and simultaneously realize gas cooling and gas-solid separation to remove the dust in the flue gas; preferably, the scrubber comprises a primary scrubber 11 and a secondary scrubber 12 connected in sequence, wherein the primary scrubber 11 is used for purifying the activated coke regeneration gas to primarily remove SO therein3HCl, HF and dust and primarily realize gas cooling; the secondary scrubber 12 is used to purify the gas from the primary scrubber 11 again to further remove SO therefrom3HCl, HF and dust, further cooling the gas, and removing fog drops in the gas after secondary purification; the primary scrubber 11 and the secondary scrubber 12 work together to purify, cool and separate gas and solid from the regenerated gas to obtain a pretreated gas with high purity of sulfur dioxide.
In the specific embodiment of the invention, the desulfurized rich gas after desulfurization, denitrification and desorption of the activated coke enters the lower part of the primary scrubber 11, and the air inlet position is positioned above the washing liquid arranged at the bottom of the primary scrubber 11; upper portion is provided with vortex generating device in one-level scrubber 11, vortex generating device is used for producing rotatory vortex to the washing liquid that gets into inside, preferably, be provided with first vortex generating device 111 and second vortex generating device 112 (prior art, see application number 200720195551.3's utility model patent) inside from the top down in one-level scrubber 11, one-level scrubber 11 outside is provided with washing circulating pump 13, the washing liquid that is in one-level scrubber 11 bottom gets into first vortex generating device 111 and second vortex generating device 112 respectively through washing circulating pump 13, two-layer spray set up can be to the ascending regeneration gas cooling that one-level scrubber 11 lower part got into simultaneously, remove impurity and dust. Under the action of the vortex generating device, the washing liquid generates a transient vortex liquid suspension layer, then a downward rotating liquid flow with a certain speed is formed, the gas forms an upward rotating air flow with a certain speed, the rotating liquid flow and the rotating air flow are collided and mixed, the liquid phase and the gas phase are mixed violently, the mixing strength and the retention time of the washing liquid are increased, impurities are further absorbed under the effect of rotary cutting collision, and the removal rate of the impurities is improved. The arrangement of the vortex generating device greatly increases the gas-liquid contact area and the contact time, and improves the washing efficiency.
A washing circulating pump 13 arranged in the first-stage scrubber 11 fully absorbs and removes SO in the regeneration gas by circulating flow of the washing liquid3HCl, HF, dust, etc., to convert SO2The gas is kept in the gas treated by the primary scrubber 11, most of fluoride, chloride, dust, ammonia and salt substances in the regenerated gas are absorbed by the washing liquid in the process, and the temperature of the gas is reduced from 350-420 ℃ to 60-85 ℃. The washing liquid is process water, mainly removes acid gases such as sulfur trioxide, and the sulfur dioxide gas can not be absorbed by the washing liquid.
The gas unabsorbed after passing through the primary scrubber 11 enters from the lower part of the secondary scrubber 12, and the secondary scrubber 12 includes, from bottom to top, a scrubbing section 121 (also called a lower scrubbing section), a packing section 122, and a scrubbing section 121(also called upper washing section) and an electric demisting section 123 for further purifying the gas and separating the gas from the liquid, removing the impurity components, dust and SO in the flue gas3Increase SO2The degree of purity of (d); the gas discharged from the primary scrubber 11 enters a secondary scrubber, and an inlet on the secondary scrubber for receiving the gas discharged from the primary scrubber 11 is arranged above the lower-layer washing section 121 and below the packing section 122; the washing liquid in the secondary washer 12 circulates from the lower washing section to the upper washing section to be sprayed, namely the lower washing section is filled with the washing liquid; the purpose of the packing section 122 is to make the washing liquid in the washing section 121 fully contact with the ascending rich gas, and the impurities in the rich gas are continuously removed by the mutual collision with the packing; the filler of the filler section 122 is an inclined suspension type porous suspended filler (MBBR) made of polytetrafluoroethylene; the rich gas passing through the packing section 122 enters the washing section 121 above the packing section again, and the residence time of the rich gas is prolonged through the reverse contact with the washing liquid, so that the washing effect is ensured; the rich gas passing through the upper washing section 121 enters the electric demisting section 123, and fine particles in the rich gas are removed through the electric demisting section 123, namely, the water content in the rich gas is reduced, so that the quality of the rich gas is further ensured. Preferably, a washing circulation pump 13 and a cooler 14 are further provided outside the lower washing stage 121, for circulating the washing liquid of the lower washing stage 121 and cooling the gas, respectively; the wash liquid in the secondary scrubber 12 is process water as is the wash liquid in the primary scrubber 11. The operating principle of the cooler 14 is: cooling water is introduced into the cooler 14 from the outside, and when the circulating washing liquid passes through the cooler 14, the circulating washing liquid is cooled, and the temperature of the flue gas is reduced through indirect heat exchange with the flue gas. The gas passes through the packing section 122, the scrubbing section 121 (i.e. the upper scrubbing section) and the electric demisting section 123 in the secondary scrubber 12 in sequence, the dust and total salt content of the clean gas leaving the secondary scrubber 12 being less than 5mg/m3And then the gas enters the reaction recovery system 2. Preferably, the gas is pressurized by a tail gas blower 29 and then sent to the reaction recovery system 2. In the bottom of the secondary scrubber 12After the concentration of ammonium salt in the washing liquid reaches a set value, the washing liquid is periodically discharged to a wastewater pool 15 through a sewage discharge pump.
The reaction recovery system 2 comprises a reaction unit and a recovery unit, wherein the reaction unit of the reaction recovery system 2 is connected with a gas outlet of the pretreatment system 1 and is used for reacting, synthesizing and recovering sodium sulfite; the reaction unit of the reaction recovery system 2 includes a reaction device; the recovery unit comprises a centrifugal device and a drying device, and the reaction device is connected with a gas outlet of the pretreatment system 1 and used for synthesizing sodium sulfite slurry through reaction.
In the embodiment of the present invention, the reaction apparatus includes a primary reactor 21 and a secondary reactor 22, the pretreated gas enters the primary reactor 21, and the upper gas outlet of the primary reactor 21 is connected to the upper gas inlet of the secondary reactor 22 through a first gas transmission pipeline 211; a first gas conveying pipe 211 for conveying the sulfur dioxide-containing gas from the primary reactor 21 to the secondary reactor 22; the bottom slurry outlet of the primary reactor 21 is connected to the evaporation concentration system 3 through a pipeline; the lower slurry outlet of the secondary reactor 22 is connected to the upper slurry inlet of the primary reactor 21 through a first transfer line 212, and the first transfer line 212 is used for transferring the reacted slurry from the secondary reactor 22 to the primary reactor 21. Preferably, the reaction unit further comprises an alkali liquor tank 23, the secondary reactor 22 is connected with the alkali liquor tank 23, and alkali liquor in the alkali liquor tank 23 is periodically conveyed into the secondary reactor 22 for supplement; preferably, the lye in the lye tank 23 is a soda lye, i.e. a sodium carbonate solution, preferably a sodium carbonate solution with a mass concentration of 20-30% (e.g. 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%) is used. Preferably, the secondary reactor 22 is provided with a circulating pump 5 for self-circulation of the slurry in the reactor, and the secondary reactor 22 is circularly absorbed by the circulating pump 5, SO that the gas and the liquid can be fully contacted and SO can be fully absorbed2. In the invention, the first-stage reactor 21 produces finished liquid (sodium sulfite slurry), the concentration of sulfur dioxide in the flue gas in the first-stage reactor 21 is highest, the sulfur dioxide is easy to absorb and does not need to be absorbed repeatedly, so that the first-stage reactor 21 does not need to be provided with the circulating pump 5, the sulfur dioxide in the flue gas in the second-stage reactor 22 is reduced, and the solution circulation is needed to be carried outThe absorption rate is improved.
The purified gas passing through the secondary scrubber 12 enters the primary reactor 21 for synthetic reaction, the residual gas out of the primary reactor 21 enters the secondary reactor 22 for further reaction, and SO2The gas is further absorbed; the liquid level of the primary reactor 21 is periodically replenished from the secondary reactor 22, the liquid level of the secondary reactor 22 is periodically replenished from the lye tank 23, and the SO in the solution is gradually increased2Concentration of SO absorbed in solution2The concentration of (c) is maximized; finally, the gas not absorbed in the secondary reactor 22 is sent to the tail gas treatment system 4. Preferably, the first-stage reactor 21 and the second-stage reactor 22 are provided with a gas outlet communicated with the tail gas treatment system 4, a sodium sulfite slurry outlet communicated with the evaporation concentration system 3 and a gas inlet communicated with the gas outlet of the pretreatment system 1, so that gas and liquid can directly enter and exit from the first-stage reactor 21 and the second-stage reactor 22, and once one reactor fails, the discharging of the other reactor is not influenced.
The evaporation concentration system 3, the evaporation concentration system 3 comprises a heater 31, a separator 32, a condenser 34 and a vacuum pump 35. Sodium sulfite thick liquid generates the high temperature that the temperature needs 150-160 ℃, and the reaction temperature through reaction unit alone does not reach the generation temperature, and sodium sulfite output is few, and is inefficient, can improve the yield of sodium sulfite through setting up evaporative concentration system to sodium sulfite thick liquid heating evaporative concentration, improves output, reduce cost. The heater 31 comprises a tube side and a shell side, the tube side is used for storing slurry, the shell side is used for storing hot steam, the heater 31 is connected with a slurry outlet at the bottom of the primary reactor 21, the slurry enters the tube side (the slurry in the primary reactor 21 has the pH value of 7.7-8.2 and enters the tube side when the discharging temperature reaches 65-75 ℃), and the sodium sulfite slurry is heated, evaporated and concentrated through steam heat exchange of the tube side and the shell side. The separator 32 is connected to a condenser 34, the condenser 34 is connected to a vacuum pump 35, and the inside of the condenser 34 is maintained at a negative pressure by the suction action of the vacuum pump 35, and the inside of the separator 32 is maintained at a slight negative pressure. The concentrated slurry enters a separator 32 under the action of pressure difference, an inlet of the separator 32 is connected with a tube pass outlet of a heater 31, the sodium sulfite slurry enters the separator 32 and then is subjected to gas-liquid separation through flash evaporation, a bottom slurry circulating outlet of the separator 32 conveys the slurry to the tube pass bottom inlet of the heater 31 through an evaporation circulating pump 33, and the slurry is continuously subjected to circulating evaporation concentration between the heater 31 and the separator 32; the outlet of the concentrated slurry at the bottom of the separator 32 is connected to a centrifugal device, and the concentrated slurry which has been concentrated by multiple times of evaporation to a certain concentration enters the centrifugal device. An upper steam outlet of the separator 32 and an upper steam outlet of the shell pass of the heater 31 are both connected with a condenser 34, and the condenser 34 is used for cooling steam; the condenser 34 also includes a tube side through which condensation takes place and a shell side to which circulating cooling water is connected. Saturated steam is used as a heat source, enters the shell pass of the heater 31 for heat exchange and condensation, and enters the condenser 34 together with secondary steam generated by the separator 32 for condensation, and is pumped away by the vacuum pump 35.
Preferably, the vacuum pump 35 is connected to the vacuum tank 36, the vacuum tank 36 plays a role of buffering, the vacuum tank 36 is pumped into a vacuum state through the action of the vacuum pump 35, both a top outlet and a bottom outlet of the condenser 34 are connected to the vacuum tank 36, the top outlet of the condenser 34 is communicated with the vacuum tank 36, so that the interior of the condenser 34 is in a negative pressure environment, and water condensed in the condenser 34 is conveyed into the vacuum tank 36 through the bottom outlet, so that the cooling and recovery process of steam is completed.
The concentrated sodium sulfite slurry after the heating separation and concentration enters a centrifugal device from the separator 32 for solid-liquid separation, and the filter cake enters a drying device, and then solid sodium sulfite powder is obtained.
In the embodiment of the present invention, the reaction recovery system 2 further comprises a mother liquor tank 24, the liquid generated by the centrifugal device and the tail gas treatment system 4 is conveyed into the mother liquor tank 24, and the mother liquor tank 24 can convey the liquid into the lye tank 23 through a mother liquor transfer pump. The liquid in the mother liquor tank 24 is the absorbed part of SO2The gas slurry can be conveyed to the lye tank 23 for further utilization, thereby realizing the maximum utilization of resources.
More preferably, the mother liquor after centrifugation is sent to a mother liquor tank 24, and the filter cake is fed to a drying device through a chute.
In the embodiment of the present invention, the drying device includes an air dryer 27 and a cyclone collector 28, and the material dried by the air dryer 27 enters the cyclone collector 28 for particle collection; preferably, the cyclone collector 28 is a two-stage cyclone collector 28. Further preferably, a drying feeder 26 is further arranged before the air dryer 27, the drying feeder 26 is an internal drying sealed space, and the filter cake enters the drying space inside the drying feeder 26 and is transported to the air dryer 27.
And the tail gas treatment system 4 is used for purifying and treating tail gas generated after the tail gas passes through the reaction device, the centrifugal device and the drying device so as to further absorb sulfur dioxide and dust in the tail gas. In the embodiment of the present invention, the residual gas in the secondary reactor 22 and the residual gas in the cover body where the centrifugal separator 25 is located are both delivered to the tail gas treatment system 4; preferably, the residual gas generated by the second-stage cyclone collector 28 is conveyed to the tail gas treatment system 4 through the induced draft fan 210; preferably, the residual gas generated inside the soda ash tank (i.e., the soda ash tank 23) also enters the off-gas treatment system 4 to be purified.
In the embodiment of the present invention, the tail gas treatment system 4 includes a tail gas absorption tower 41, an alkali solution pool is disposed at the bottom of the tail gas absorption tower 41, the residual gas enters from the lower portion of the tail gas absorption tower 41, an inlet of the residual gas is disposed above the alkali solution at the bottom of the tail gas absorption tower, a circulation pump 5 is disposed outside the tail gas absorption tower 41, the alkali solution at the bottom of the tail gas absorption tower 41 is conveyed to the top for spraying, and is continuously circulated, and the sprayed alkali solution moves downward to contact with the upward tail gas. When the pH value or the concentration of the continuously circulated alkali liquor reaches a certain value, the continuously circulated alkali liquor is periodically conveyed to a mother liquor tank 24; the gas purified and treated by the tail gas absorption tower 41 is discharged to the air at high altitude, so as to reach the atmospheric emission standard. The alkali liquor in the alkali liquor pool at the bottom of the tail gas absorption tower 41 is pure alkali liquor, i.e. sodium carbonate solution, and sodium carbonate solution with mass concentration of 20-30% (such as 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%) is preferably adopted.
In order to further understand the system for preparing sodium sulfite by recycling the active coke desulfurization rich gas, the invention also provides a method for preparing sodium sulfite by recycling the active coke desulfurization rich gas, which comprises the following steps:
step one, pretreatment of regeneration gas, comprising:
the regenerated gas after desulfurization, denitrification and desorption of the active coke is subjected to washing, temperature reduction and gas-solid separation by a primary scrubber 11 and a secondary scrubber 12 of the pretreatment system 1, and SO is removed3And impurities such as HCl, HF, dust and the like to obtain the pretreated gas with high purity of sulfur dioxide.
Step two, the synthesis, the evaporation concentration and the recovery of the product comprise:
after being pressurized by a tail gas fan 29, the pretreated gas enters a primary reactor 21, residual gas in the primary reactor 21 enters a secondary reactor 22, slurry after absorbing sulfur dioxide in the secondary reactor 22 periodically supplements liquid to the primary reactor 21, and soda liquid in a soda liquid tank 23 periodically supplements to the secondary reactor 22; the secondary reactor 22 continuously absorbs sulfur dioxide gas in a circulating manner through a circulating pump 5; when the reaction of the first-stage reactor 21 reaches the end point (when the pH of the solution in the first-stage reactor 21 is 7.7-8.2 and the temperature of the discharged material reaches 65-75 ℃), the system closes the raw material inlet valve, opens the liquid discharge valve, discharges the slurry into the tube side of the heater 31, and evaporates and concentrates the slurry through heat exchange of steam of the shell side; and (3) opening the vacuum pump 35, vacuumizing to enable the condenser 34 and the separator 32 to be in a negative pressure state, enabling the concentrated slurry to enter the separator 32, further concentrating through gas-liquid separation, continuously circulating and concentrating the slurry between the heater 31 and the separator 32 under the action of the evaporation circulating pump 33, and cooling, condensing and recycling steam through the condenser 34.
The slurry in the separator 32 is periodically discharged into a centrifugal device, then the mother liquor is conveyed to a mother liquor tank 24 after centrifugal separation of the centrifugal device, the filter cake enters a drying feeder 26, the filter cake is conveyed to an air dryer 27 by the drying feeder 26 to be dried, and then the filter cake enters a two-stage cyclone collector 28 to collect sodium sulfite powder particles.
Step three, tail gas treatment, comprising:
tail gas generated in the secondary reactor 22, the centrifugal device, the secondary cyclone collector 28 and the lye tank 23 enters the tail gas treatment system 4 and is washed and purified by lye sodium carbonate solution, lye in the washing tower is continuously and circularly sprayed from bottom to top, the circulating lye is periodically conveyed to the mother liquor tank 24 after the concentration reaches a certain value, liquid in the mother liquor tank 24 is conveyed into the lye tank 23, and the resource utilization is maximized; and (5) emptying the air at high altitude after the air is purified.
In summary, the system and the method for preparing sodium sulfite by recycling the active coke desulfurization rich gas have the following excellent effects: the primary reactor and the secondary reactor are communicated and shared, SO that the reaction time of the primary reactor can be stabilized, the influence on the discharge of the primary reactor due to the failure of the reactor is reduced, the continuous and stable operation of a downstream evaporation concentration system, a centrifugal separation system and a drying system is facilitated, and the SO absorbed by the primary reactor is increased2The concentration of the alkali liquor reduces the consumption of the alkali liquor, and is beneficial to reducing the energy consumption of a system and improving the product quality.
But continuous output sodium sulfite powder product, more adapt to the continuity production requirement, and the sodium sulfite powder product purity that obtains is greater than 90%, satisfies the industrial operation standard.
The flue gas is continuously washed by adopting the circulating rotating liquid flow generated by the two-stage vortex generating device, SO that better absorption and purification effects and SO (sulfur oxide) can be achieved2The loss rate is lower.
By adopting a two-stage absorption method, the absolute circulation amount of the circulating absorption liquid is effectively reduced, and the SO in the waste gas is improved2Absorption efficiency, SO Using the method and System of the invention2The absorption rate is more than 98 percent, the consumption of the alkali liquor is lower, and the treated gas can be directly discharged into the atmosphere and meets the discharge standard.
The pretreatment system is relatively independent and has no related interlocking relation with a later reaction recovery system, and when the pretreatment system fails, the pretreatment system can be directly replaced by a standby device, so that the influence on a downstream sodium sulfite powder product preparation system is reduced.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The utility model provides a system for sodium sulfite is prepared in rich gas resource of active coke desulfurization which characterized in that, the system includes:
the pretreatment system is used for purifying, cooling and carrying out gas-solid separation on the regeneration gas to obtain a pretreated gas with the purity of sulfur dioxide being increased;
the reaction recovery system comprises a reaction unit and a recovery unit, wherein the reaction unit of the reaction recovery system is connected with a gas outlet of the pretreatment system and is used for reacting, synthesizing and recovering sodium sulfite;
the evaporation concentration system is connected with the outlet of the reaction unit and is used for circularly evaporating and concentrating the sodium sulfite slurry generated by the reaction unit, and the evaporated and concentrated sodium sulfite slurry enters from the inlet of the recovery unit of the reaction recovery system to be recovered;
and the tail gas treatment system is connected with a tail gas outlet of the reaction recovery system and is used for purifying and treating the tail gas generated in the reaction recovery system so as to further absorb sulfur dioxide and dust in the tail gas.
2. The system for preparing sodium sulfite by recycling active coke desulfurization rich gas as claimed in claim 1, wherein the pretreatment system comprises: scrubber for cleaning gas to remove SO from regeneration gas3HCl, HF and dust, and simultaneously realize gas cooling and gas-liquid separation;
preferably, the scrubber comprises two stages of scrubbers connected in sequence, wherein the one stage of scrubber is used for purifying the activated coke regeneration gas to remove SO in the activated coke regeneration gas in a preliminary step3HCl, HF and dust and primarily realize gas cooling; the secondary scrubber is used for purifying the gas from the primary scrubber again to further remove SO therein3HCl, HF and dust, further cooling the gas, and removing fog drops in the gas after secondary purification;
more preferably, a vortex generating device is arranged at the upper part inside the primary scrubber, a washing circulating pump is arranged outside the primary scrubber, and washing liquid at the bottom of the primary scrubber enters the vortex generating device through the washing circulating pump to generate a transient vortex liquid suspension layer and then form a downward-running rotating liquid flow to perform an impact reaction with upward-running regeneration gas;
preferably, the vortex generating device is provided with an upper layer and a lower layer which are respectively a first vortex generating device and a second vortex generating device;
preferably, the secondary scrubber comprises a washing section, a filling section and an electric defogging section from bottom to top;
further preferably, a washing circulating pump and a cooler are arranged outside the washing section and are respectively used for circulating the washing liquid of the washing section and cooling the gas;
still more preferably, the gas dust and total salt content passing through the secondary scrubber is less than 5mg/m3。
3. The system for preparing sodium sulfite by recycling active coke desulfurization rich gas as claimed in claim 1 or 2, wherein the reaction unit of the reaction recovery system comprises:
the reaction device is connected with a gas outlet of the pretreatment system and is used for synthesizing sodium sulfite through reaction;
the recovery unit includes: the centrifugal device is connected with a concentrated slurry outlet of the evaporation concentration system and is used for recovering a solid material containing the sodium sulfite; the drying device is connected with the solid outlet of the centrifugal device and is used for drying the solid material containing the sodium sulfite;
the reaction device comprises a primary reactor and a secondary reactor, the pretreated gas enters the primary reactor, and an upper gas outlet of the primary reactor is connected to an upper gas inlet of the secondary reactor through a first gas transmission pipeline; the first gas transmission pipeline is used for transmitting gas containing sulfur dioxide; the bottom slurry outlet of the primary reactor is connected to the evaporation concentration system through a pipeline; the lower slurry outlet of the secondary reactor is connected to the upper slurry inlet of the primary reactor through a first liquid conveying pipeline, and the first liquid conveying pipeline is used for conveying slurry;
preferably, the secondary reactor is connected with an alkali liquor tank, and alkali liquor in the alkali liquor tank is periodically conveyed into the secondary reactor for supplement;
still preferably, the secondary reactor is provided with a circulation pump for self-circulation of the slurry.
4. The system for preparing sodium sulfite by recycling the active coke desulfurization rich gas as claimed in claim 3, wherein the evaporation concentration system comprises:
the heater comprises a tube side and a shell side, the tube side is used for storing slurry, the shell side is used for storing hot steam, and the heater is connected with a bottom slurry outlet of the primary reactor and is used for heating, evaporating and concentrating the sodium sulfite slurry;
the inlet of the separator is connected with the tube pass outlet of the heater, the separator is used for carrying out gas-liquid separation on the sodium sulfite slurry, and the bottom circulating slurry outlet of the separator conveys the slurry to the tube pass bottom inlet of the heater through an evaporation circulating pump so as to continuously circulate and evaporate the slurry; the bottom concentrated slurry outlet of the separator is connected with the centrifugal device;
the condenser is used for cooling the steam from the separator and the heater;
the vacuum pump is connected with the condenser and enables negative pressure to be formed in the condenser; preferably also creating a negative pressure within the separator;
preferably, the vacuum pump is connected to the vacuum tank, and both a top outlet and a bottom outlet of the condenser are connected to the vacuum tank.
5. The system for preparing sodium sulfite by recycling active coke desulfurization rich gas as recited in claim 3 or 4, wherein said reaction unit further comprises a mother liquor tank, the liquid generated by said centrifugal device and said tail gas treatment system is transported into said mother liquor tank, and the liquid in said mother liquor tank is transported into said alkali liquor tank through a pipeline.
6. The system for preparing sodium sulfite by recycling active coke desulfurization rich gas as recited in claim 3, wherein said drying device comprises an air dryer and a cyclone collector, and the material dried by said air dryer enters said cyclone collector for particle collection;
preferably, the cyclone collector is a two-stage cyclone collector.
7. The system for preparing sodium sulfite by recycling active coke desulfurization rich gas as recited in claim 6, characterized in that a dry feeder is further arranged before the air dryer, and the material enters into the drying space inside the dry feeder and is transported to the air dryer.
8. The system for preparing sodium sulfite by recycling active coke desulfurization rich gas as recited in claim 1, wherein the tail gas treatment system comprises a tail gas absorption tower, a circulating pump is arranged outside the tail gas absorption tower, and lye at the bottom of the tail gas absorption tower is conveyed to the top and continuously circulated.
9. A method for preparing sodium sulfite by recycling active coke desulfurization rich gas is characterized by comprising the following steps:
step one, pretreatment of regeneration gas, comprising:
purifying the regenerated gas subjected to desulfurization, denitrification and desorption of the active coke by using a pretreatment system to obtain a pretreated gas with high sulfur dioxide purity;
step two, the synthesis, the evaporation concentration and the recovery of the product comprise:
the pretreated gas enters a reaction unit of a reaction recovery system, absorption liquid is adopted to pass through a two-stage reaction device to prepare sodium sulfite slurry, and the sodium sulfite slurry is subjected to evaporation concentration and then is subjected to centrifugal separation and drying by a recovery unit to obtain sodium sulfite powder particles;
step three, tail gas treatment, comprising:
and tail gas generated by the reaction unit and the recovery unit enters the tail gas treatment system, the absorption liquid is adopted for secondary washing and purification, and the treated gas is discharged.
10. The method for preparing sodium sulfite by recycling the active coke desulfurization rich gas as claimed in claim 9, wherein the pretreated gas enters the reaction unit of the reaction recovery system after being pressurized by a tail gas fan;
preferably, the absorption liquid is an alkali solution, more preferably a sodium carbonate solution;
still preferably, the method is performed using the system of any one of claims 1-8.
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