CN102423608A - Desulfurizer prepared by causticized white mud and method thereof for flue gas desulphurization - Google Patents
Desulfurizer prepared by causticized white mud and method thereof for flue gas desulphurization Download PDFInfo
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Abstract
The invention discloses a desulfurizer prepared by causticized white mud and a method of the desulfurizer for flue gas desulphurization. The desulfurizer is prepared by the following steps: when alkali furnace smelt is dissolved into a green liquid, adding 2-3 % of the smelt amount of lime and 0.5-1 % of the smelt amount of flocculating agent in the green liquid, mixing lime with the green liquid after clarification according to theoretical amount ratio of calcium hydrate in the lime to sodium carbonate in the green liquid being 1.05-1.1, then carrying out causticization at a temperature of 90-102 DEG C to obtain a causticized solution, clarifying the causticized solution to obtain a white liquid and white mud, washing the white mud with 50-70 DEG C water, and then filtering and dehydrating the white mud to let the dryness of the white mud be more than 60 %. A saturated or oversaturated absorption liquid comprsing the desulfurizer and water is used for flue gas desulphurization, and a scale and corrosion inhibitor having a concentration of 5-30 mg/L is added in the saturated or oversaturated absorption liquid. According to the invention, the purity of the desulfurizer prepared by causticized white mud is raised, the problems of easy scale formation, blocking, corrosion and the like in the process of desulphurization are solved, and the desulfurizer can be applied for desulphurization inside the furnace.
Description
Technical field
The present invention relates to a kind of desulfurizing agent, especially relate to the desulfurizing agent that a kind of causticization white clay is processed; The invention still further relates to desulfurizing agent that the causticization white clay processes and be used for the method for flue gas desulfurization.
Background technology
The Energy Mix of China is main with coal, and its consumption figure accounts for about 70% of primary energy aggregate consumption, and this situation can not change in the long from now on time.The sulfur dioxide that discharges in the coal-fired process is the key factor of atmosphere pollution; Coal desulfurization can be divided into desulfurization and flue gas desulfurization three major types method in the preceding desulfurization of burning, the burning at present; The coal-burning boiler desulfurization is the Air Pollution Control measure of China's mandatory requirement, and coal-fired boiler smoke devulcanization can be divided into dry method, wet method and semidry method three major types.For different sulfur methods, its desulfuration efficiency is different with the scope of application, and the wet desulphurization technology is because desulfuration efficiency is high; Obtained extensive use, lime stone is present the most frequently used desulfurizing agent, and its exploitation can destroy ecological; Need carry out fragmentation; Production cost is higher, and under-supply situation possibly occur, thereby the desulfurizing agent of searching replace lime stone just seems very important.
Paper white sludge is that alkali reclaims the accessory substance that produces in the causticization process, and its main component is CaCO
3, the white clay quantity of discharging in the paper industry process is more, for the disposal of paper white sludge; General paper mill is all adopted to buy and is stacked the place; White clay is transported to the appointed place stacks, be prone to cause environmental pollution, its improvement becomes the difficult problem that many enterprises press for solution.The content sum of calcium carbonate and the efficient oxidation calcium is not less than 90% in the white clay, if can utilize the causticization white clay will be a kind of very desirable selection as the coal-burning boiler desulfurization, can reach the treatment of wastes with processes of wastes against one another, the purpose that changing waste into resources utilizes.
CN101993756A discloses a kind of energy saving desulfurizer for bunker coal, is made up of mixture, magnesium sulfate and the magnesian mixture of waste sludge from paper mill white clay, sodium phosphate, aluminium polychloride, sodium carbonate, sodium acetate and potassium acetate.
CN101301566A discloses the method and apparatus that a kind of white clay removes sulfur dioxide in flue gas: adopt the white clay slurries to do doctor solution; Utilize desulfurizing tower that sulfur dioxide in flue gas is absorbed; Demist afterwards; Discharging is carried out the phase I desulfurization in the desulfurizing tower bottom to flue gas, on desulfurizing tower top flue gas is carried out the second stage desulfurization; Collect the doctor solution after the phase I absorbs at low level, store the back recycle, form the low level circulation, collect the doctor solution after second stage absorbs, store the back recycle, form high-order circulation in a high position; Doctor solution overflow to the low level that high-order circulation stores circulates, and the desulfurated plaster slurries that the low level circulation produces pump cyclonic separation, and the rare gypsum slurries after the cyclonic separation is back to high-order circulation, and thick gypsum slurries deslagging is handled.
CN102051834A discloses the method that a kind of causticization clay-slag is used to remove sulfur in smoke: make causticization white clay slurries constantly contact with flue gas through desulphurization plant, to remove sulfur dioxide in flue gas and to generate gypsum slurries; Gypsum slurries makes gypsum through dehydration.
CN1709554A discloses a kind of technology of utilizing paper white sludge to remove sulfur dioxide in flue gas; Join in the pond of sizing mixing with white clay with from the recirculated water in the depositing reservoir; Slurries after the stirring get into the slurries pond, are pumped in the desulfurizing tower by force (forcing) pump to contact with flue gas, and reacted solution is flowed out by the desulfurizing tower bottom; In the entering sedimentation basin, the recirculated water of removing post precipitation gets into participates in the depositing reservoir recycling.
In the above technology, the causticization white clay is used for the coal-burning boiler desulfurization, has one of following defective at least:
The white clay purity that obtains in the tradition causticization production process is not high, and especially the white clay silicone content of straw fiber raw material slurrying causticization generation is high, in the desulfurization use, is prone to operation problems such as fouling, obstruction, corrosion, and the stable operation difficulty is higher;
The wet white clay pH value of causticization is higher, and the long-term corrosiveness that desulphurization plant is produced of using is bigger, therefore, needs to strengthen anti-corrosion treatment.
Summary of the invention
In order to solve the problem that prior art exists, the method that the object of the present invention is to provide desulfurizing agent that a kind of causticization white clay processes and this desulfurizing agent to be used for flue gas desulfurization.This desulfurizing agent has higher purity, and desulfurization effect, use cost are lower; And can solve and be prone to operation problems such as fouling, obstruction, corrosion in the desulfurizing agent use.
In order to solve the problems of the technologies described above, on the one hand, the desulfurizing agent that the present invention provides a kind of causticization white clay to process makes through traditional causticization process having been carried out improve, and may further comprise the steps in the manufacturing process:
S1: green liquor purification processes: when alkali stove fused mass is dissolved into green liquor in the fusion groove; Add the lime of fused mass amount 2%～3% and the flocculant of fused mass amount 0.5%～1% in the lysate; Green liquor is delivered in the green liquor clarification groove and clarifies, and obtains upper strata clarification green liquor, and lower floor's precipitum green mud after filtering; Filter residue green mud otherwise processed, filtrating is returned in the green liquor clarification groove and is clarified;
S2: causticization is handled: lime and clarification green liquor by the ratio of the theoretical amount of sodium carbonate complete reaction in calcium oxide in the lime and the green liquor be 1.05～1.1 mix after; Carry out causticizing reaction at 90～102 ℃; Obtain the causticization emulsion; The causticization emulsion is sent in the white liquid defecator and is clarified, and obtains the upper strata and clarifies white liquid and lower floor's precipitum white clay, and white clay is through filtering device separates; The gained white clay send subsequent step to handle, and gained filters white liquid and merges to the upper strata and clarify and send pulping and digesting to use in the white liquid or send in the white liquid defecator and clarify;
The white clay that S3: lime mud treatment: step S2 obtains is with 50～70 ℃ hot wash, and washing obtains the desulfurizing agent that said causticization white clay is processed after pre-hung formula vacuum filter or pressure disc type filter filtering means dehydration reach more than 60% the mass dryness fraction of white clay.
Filter residue green mud otherwise processed in step S1 is for the processing method of green mud in the prior art, such as landfill.
The flocculant that in step S1, adds can be selected polyacrylic acid, Sodium Polyacrylate, calcium polyacrylate (CPA) or water soluble starch etc. for use, adds flocculant and can remove the colloid material to greatest extent, reduces the viscosity of system, improves the purity of desulfurizing agent.Preferably; The said flocculant of step S1 is calcium polyacrylate (CPA) or water soluble starch; Optimization polypropylene acid calcium or water soluble starch flocculant have overcome because of green liquor temperature degree, high, the relatively poor technical problem of the high common flocculant result of use of calcium content of salt content effectively, have flocculating effect preferably.
Preferably, when the said green liquor of step S1 is the green liquor that produces in the straw fiber raw material slurrying alkali recovery process, in said green liquor clarification groove, feed CO
2Gas, regulating green liquor pH is 9.5～10, makes part element silicon in the green liquor form the silicide deposition and removes.Thereby the content of silicon in the reduction desulfurizing agent in the desulfurizing agent use, reduces the fouling of desulphurization system, and said optimal technical scheme can adapt to the white clay production desulfurizing agent that straw fiber raw material slurrying alkali reclaims better.
Preferably, the said filter plant of step S2 is pre-hung formula vacuum filter, lime mud folter or white hydraulic coupling disk filter, and gained filters white liquid and send in the white liquid defecator and clarify.
Preferably, the said filter plant of step S2 is white hydraulic coupling filter, and gained filters white liquid and merges to the upper strata and clarify and send pulping and digesting to use in the white liquid.
On the other hand; The present invention also provides a kind of method of flue gas desulfurization; Include a desulfuration absorbing tower, this desulfuration absorbing tower is disposed with from bottom to top: the exhanst gas outlet after the saturated or supersaturation absorption liquid that desulfurizing agent and water are formed, the absorption liquid effuser on the sidewall of absorption tower and liquid supplementation pipe, smoke inlet, absorption liquid spray district, demister and the desulfurization, and absorption liquid pumps into the spray district and is vaporific ejection through circulating pump; This moment with get into desulfuration absorbing tower via smoke inlet and contain sulfur dioxide flue gas and carry out countercurrent washing; After sulfur in smoke absorbed, this flue gas was discharged via the exhanst gas outlet at demister and desulfuration absorbing tower top, again by smoke stack emission in atmosphere; Desulfurizing agent absorbs sulfur in smoke and reaction generates calcium sulfite; Introduce force air oxidation calcium sulfite and generate gypsum, from absorption liquid, separate gypsum, desulfurizing agent described in the present technique scheme is the desulfurizing agent of aforementioned arbitrary technical scheme gained in the summary of the invention; Add in said absorption liquid that anti-incrustation corrosion inhibitor, the addition of anti-incrustation corrosion inhibitor are arranged is 5～30mg/L.
Anti-incrustation corrosion inhibitor can be selected ATMP (ATMP), PAPE (PAPE) etc. for use; Preferably; Said anti-incrustation corrosion inhibitor is polyamino polyether methylene phosphonic acids or poly-aspartate type anti-incrustation corrosion inhibitor, adds the effect that polyamino polyether methylene phosphonic acids or poly-aspartate type anti-incrustation corrosion inhibitor have scale inhibition, dispersion, inhibition concurrently.As antisludging agent, help suppressing the formation of calcium carbonate scale, calcium sulfate dirt and calcium phosphate scale in the production process; As dispersant, can improve the concentration of desulfurizing agent in the absorption liquid, have better dispersion effect, improve desulfuration efficiency; Can effectively prevent the corrosion of hardware as corrosion inhibiter.
Preferably; Said saturated or supersaturation absorption liquid is that desulfurizing agent and the washings and the lime in the lignosulfonate production process of aforementioned arbitrary technical scheme gained in the summary of the invention is formulated; In the process for preparation, earlier, make its pH value greater than 6 with in the lime and the washings in the lignosulfonate production process; In after deposition is removed sediment, obtaining and washings, in be mixed with saturated with said desulfurizing agent again or the supersaturation absorption liquid with washings; Said lime is also replaceable to be white lime or milk of lime.The production of lignosulfonate, comprise black liquid and sulfuric acid mixing and stirring after, leave standstill, filter, wash, process such as drying, in the lignosulfonate washings, contain Na
2SO
4With excessive sulfuric acid etc., with in lime, white lime and/or the milk of lime and after, in washings in contain Na
2SO
4, Na
2CO
3And lignosulfonate.Na
2SO
4And Na
2CO
3Calcium carbonate in the ability activation desulfurizing agent, the utilization rate of increase desulfurizing agent; Lignosulfonate can improve the dispersed homogeneous degree of desulfurizing agent as dispersant, thereby improves the concentration of desulfurizing agent in the absorption liquid, improves desulfuration efficiency.Use the washings preparation absorption liquid in the lignosulfonate production process, not only reached the treatment of wastes with processes of wastes against one another, the purpose of protection environment also helps the effect that improves desulfurization.
In addition, the present invention also provides a kind of method of circulating fluidized bed combustion coal boiler desulfurization, comprises desulfuration in furnace and/or flue gas desulfurization, and said desulfuration in furnace adds the desulfurizing agent of aforementioned arbitrary technical scheme gained in the summary of the invention in fire coal, and making calcium sulfur ratio is 1.5～3.0; Said flue gas desulfurization is for adopting the method for the said flue gas desulfurization of aforementioned arbitrary technical scheme in the summary of the invention.
Beneficial effect: add lime and flocculant when in the fusion groove, being dissolved into green liquor, green liquor is carried out purification processes, improved the purity of desulfurizing agent because of fused mass; In addition, can also make the part element silicon in the green liquor form precipitated calcium silicate and be removed the content of silicon in the reduction desulfurizing agent; In the desulfurizing agent use; Reduce the fouling of desulphurization system, can adapt to wood pulp or straw pulp alkali recovery causticization white clay and produce desulfurizing agent, enlarged the source of raw material; Use higher excessive ash during causticization, make and contain a certain amount of calcium oxide in the white clay, improved the desulfurized effect of desulfurizing agent.The desulfurizing agent that the causticization white clay is processed in use adds anti-incrustation corrosion inhibitor, helps suppressing the formation of calcium carbonate scale, calcium sulfate dirt and calcium phosphate scale in the production process; Prevent the corrosion of desulfurizing agent to hardware.The desulfurizing agent mass dryness fraction is reached more than 60%, can be powdery under the general state, easy to use in process of production, be prone to when carrying out desulfuration in furnace mix with fire coal.
The specific embodiment
Embodiment 1:
When alkali stove fused mass is dissolved into green liquor in the fusion groove; Add the lime of fused mass amount 2% and the calcium polyacrylate (CPA) flocculant of fused mass amount 0.5% in the lysate; Green liquor is delivered in the green liquor clarification groove and clarifies, and obtains upper strata clarification green liquor, and lower floor's precipitum green mud after filtering; Filter residue green mud otherwise processed, filtrating is returned in the green liquor clarification groove and is clarified; Lime and clarification green liquor by the ratio of the theoretical amount of the sodium carbonate complete reaction in the calcium oxide in the lime and the green liquor be 1.05 mix after; Carry out causticizing reaction at 102 ℃, obtain the causticization emulsion, the causticization emulsion is sent in the white liquid defecator and is clarified; Obtain the upper strata and clarify white liquid and lower floor's white clay precipitum; The white clay precipitum is through pre-hung formula vacuum filter isolated by filtration, and the gained white clay send subsequent step to handle, and gained filters white liquid and send in the white liquid defecator and clarify; The gained white clay is with 50 ℃ hot wash, and washing obtains the desulfurizing agent that said causticization white clay is processed after pre-hung formula vacuum filter filtering means dehydration reaches more than 60% the mass dryness fraction of white clay.
Gained desulfurizing agent and water are mixed with saturated or the supersaturation absorption liquid; And in saturated or supersaturation absorption liquid, add the polyamino polyether methylene phosphonic acids anti-incrustation corrosion inhibitor of 5mg/L; Send into and carry out flue gas desulfurization in the desulfuration absorbing tower; This desulfuration absorbing tower is disposed with from bottom to top: the exhanst gas outlet after the saturated or supersaturation absorption liquid that desulfurizing agent and water are formed, the absorption liquid effuser on the sidewall of absorption tower and liquid supplementation pipe, smoke inlet, absorption liquid spray district, demister and the desulfurization; Saturated or supersaturation absorption liquid pumps into the spray district and is vaporific ejection through circulating pump, and carry out countercurrent washing with the flue gas that contains sulfur dioxide via smoke inlet entering desulfuration absorbing tower this moment, after sulfur in smoke is absorbed; This flue gas is discharged via the exhanst gas outlet at demister and desulfuration absorbing tower top; Again by smoke stack emission in atmosphere, desulfurizing agent absorbs sulfur in smoke and reaction generates calcium sulfite, introduces force air oxidation calcium sulfite and generates gypsum; From absorption liquid, separate gypsum, reach 90% through the desulfuration efficiency of testing flue gas.
Embodiment 2:
When alkali stove fused mass is dissolved into green liquor in the fusion groove; Add the lime of fused mass amount 3% and the calcium polyacrylate (CPA) flocculant of fused mass amount 1% in the lysate; Green liquor is delivered in the green liquor clarification groove and clarifies, and obtains upper strata clarification green liquor, and lower floor's precipitum green mud after filtering; Filter residue green mud otherwise processed, filtrating is returned in the green liquor clarification groove and is clarified; Lime and clarification green liquor by the ratio of the theoretical amount of the sodium carbonate complete reaction in the calcium oxide in the lime and the green liquor be 1.1 mix after; Carry out causticizing reaction at 90 ℃, obtain the causticization emulsion, the causticization emulsion is sent in the white liquid defecator and is clarified; Obtain the upper strata and clarify white liquid and lower floor's white clay precipitum; The white clay precipitum is through the lime mud folter isolated by filtration, and the gained white clay send subsequent step to handle, and gained filters white liquid and send in the white liquid defecator and clarify; The gained white clay is with 70 ℃ hot wash, and washing obtains the desulfurizing agent that said causticization white clay is processed after pre-hung formula vacuum filter filtering means dehydration reaches more than 60% the mass dryness fraction of white clay.
Gained desulfurizing agent and water are mixed with saturated or the supersaturation absorption liquid; And in saturated or supersaturation absorption liquid, add the poly-aspartate type anti-incrustation corrosion inhibitor of 30mg/L; Send into and carry out flue gas desulfurization in the desulfuration absorbing tower; This desulfuration absorbing tower is disposed with from bottom to top: the exhanst gas outlet after the saturated or supersaturation absorption liquid that desulfurizing agent and water are formed, the absorption liquid effuser on the sidewall of absorption tower and liquid supplementation pipe, smoke inlet, absorption liquid spray district, demister and the desulfurization; Saturated or supersaturation absorption liquid pumps into the spray district and is vaporific ejection through circulating pump, and carry out countercurrent washing with the flue gas that contains sulfur dioxide via smoke inlet entering desulfuration absorbing tower this moment, after sulfur in smoke is absorbed; This flue gas is discharged via the exhanst gas outlet at demister and desulfuration absorbing tower top; Again by smoke stack emission in atmosphere, desulfurizing agent absorbs sulfur in smoke and reaction generates calcium sulfite, introduces force air oxidation calcium sulfite and generates gypsum; From absorption liquid, separate gypsum, reach 90.5% through the desulfuration efficiency of testing flue gas.
Embodiment 3:
In bamboo sulfate pulping alkali recovery process; When alkali stove fused mass is dissolved into green liquor in the fusion groove; Add the lime of fused mass amount 2.5% and the calcium polyacrylate (CPA) flocculant of fused mass amount 0.8% in the lysate, green liquor is delivered in the green liquor clarification groove and clarifies, and in said green liquor clarification groove, feeds CO
2Gas, regulating green liquor pH is 9.5～10, makes in the green liquor part element silicon form the silicide deposition and is filtered and removes, and obtains upper strata clarification green liquor, lower floor's precipitum green mud after filtering, filter residue green mud otherwise processed, filtrating is returned in the green liquor clarification groove and is clarified; Lime and clarification green liquor by the ratio of the theoretical amount of the sodium carbonate complete reaction in the calcium oxide in the lime and the green liquor be 1.08 mix after; Carry out causticizing reaction at 97 ℃, obtain the causticization emulsion, the causticization emulsion is sent in the white liquid defecator and is clarified; Obtain the upper strata and clarify white liquid and lower floor's white clay precipitum; The white clay precipitum is through white hydraulic coupling disk filter isolated by filtration, and the gained white clay send subsequent step to handle, and gained filters white liquid and send in the white liquid defecator and clarify; The gained white clay is with 60 ℃ hot wash, and washing obtains the desulfurizing agent that said causticization white clay is processed after pre-hung formula vacuum filter filtering means dehydration reaches more than 60% the mass dryness fraction of white clay.
The gained desulfurizing agent is used for the circulating fluidized bed combustion coal boiler desulfurization, comprises desulfuration in furnace and flue gas desulfurization, the desulfurizing agent of said desulfuration in furnace gained in fire coal, and making calcium sulfur ratio is 1.5; Flue gas desulfurization comprises: gained desulfurizing agent and water are mixed with saturated or the supersaturation absorption liquid; And in saturated or supersaturation absorption liquid, add the polyamino polyether methylene phosphonic acids anti-incrustation corrosion inhibitor of 20mg/L; Send into and carry out flue gas desulfurization in the desulfuration absorbing tower; This desulfuration absorbing tower is disposed with from bottom to top: the exhanst gas outlet after the saturated or supersaturation absorption liquid that desulfurizing agent and water are formed, the absorption liquid effuser on the sidewall of absorption tower and liquid supplementation pipe, smoke inlet, absorption liquid spray district, demister and the desulfurization; Saturated or supersaturation absorption liquid pumps into the spray district and is vaporific ejection through circulating pump, and carry out countercurrent washing with the flue gas that contains sulfur dioxide via smoke inlet entering desulfuration absorbing tower this moment, after sulfur in smoke is absorbed; This flue gas is discharged via the exhanst gas outlet at demister and desulfuration absorbing tower top; Again by smoke stack emission in atmosphere, desulfurizing agent absorbs sulfur in smoke and reaction generates calcium sulfite, introduces force air oxidation calcium sulfite and generates gypsum; From absorption liquid, separate gypsum, reach 91.5% through the test desulfuration efficiency.
Embodiment 4:
In reed sulfate pulping alkali recovery process; When alkali stove fused mass is dissolved into green liquor in the fusion groove; Add the lime of fused mass amount 2.6% and the water soluble starch flocculant of fused mass amount 0.5% in the lysate; Green liquor is delivered in the green liquor clarification groove and clarifies, and in said green liquor clarification groove, feeds CO
2Gas, regulating green liquor pH is 9.5～10, makes in the green liquor part element silicon form the silicide deposition and is filtered and removes, and obtains upper strata clarification green liquor, lower floor's precipitum green mud after filtering, filter residue green mud otherwise processed, filtrating is returned in the green liquor clarification groove and is clarified; Lime and clarification green liquor by the ratio of the theoretical amount of the sodium carbonate complete reaction in the calcium oxide in the lime and the green liquor be 1.05 mix after; Carry out causticizing reaction 95 ℃ of temperature, make the causticization emulsion, the causticization emulsion is sent in the white liquid defecator and is clarified; Obtain the upper strata and clarify white liquid and lower floor's white clay precipitum; The white clay precipitum is through white hydraulic coupling filter isolated by filtration, and the gained white clay send subsequent step to handle, and gained filters white liquid and merges to the upper strata and clarify and send pulping and digesting to use in the white liquid; The gained white clay is with the hot wash of 70 ℃ of temperature, and washing obtains the desulfurizing agent that said causticization white clay is processed after the pressure disc type filter filtering means dehydration reaches more than 65% the mass dryness fraction of white clay.
The gained desulfurizing agent is used for the circulating fluidized bed combustion coal boiler desulfurization, comprises desulfuration in furnace and flue gas desulfurization, and said desulfuration in furnace adds the desulfurizing agent of gained in fire coal, and making calcium sulfur ratio is 3.0; Flue gas desulfurization comprises: earlier with in the quick lime and the washings in the lignosulfonate production process; Make its pH value greater than 6; In after deposition is removed sediment, obtaining and washings, in be mixed with saturated with said desulfurizing agent again or the supersaturation absorption liquid with washings, and in saturated or supersaturation absorption liquid, add the polyamino polyether methylene phosphonic acids anti-incrustation corrosion inhibitor of 30mg/L; Send into and carry out flue gas desulfurization in the desulfuration absorbing tower; This desulfuration absorbing tower is disposed with from bottom to top: the exhanst gas outlet after the saturated or supersaturation absorption liquid that desulfurizing agent and water are formed, the absorption liquid effuser on the sidewall of absorption tower and liquid supplementation pipe, smoke inlet, absorption liquid spray district, demister and the desulfurization, saturated or supersaturation absorption liquid pumps into the spray district and is vaporific ejection through circulating pump, this moment with get into desulfuration absorbing tower via smoke inlet and contain sulfur dioxide flue gas and carry out countercurrent washing; After the sulfur in smoke absorption; This flue gas is discharged via the exhanst gas outlet at demister and desulfuration absorbing tower top, again by smoke stack emission in atmosphere, desulfurizing agent absorbs sulfur in smoke and reaction generates calcium sulfite; Introduce force air oxidation calcium sulfite and generate gypsum; From absorption liquid, separate gypsum, desulfuration efficiency reaches 63% in test furnace, and smoke desulfurization efficiency reaches 93.5%.
Embodiment 5:
In bagasse sulfate pulping alkali recovery process; When alkali stove fused mass is dissolved into green liquor in the fusion groove; Add the lime of fused mass amount 2.9% and the water soluble starch flocculant of fused mass amount 1% in the lysate, green liquor is delivered in the green liquor clarification groove and clarifies, and in said green liquor clarification groove, feeds CO
2Gas, regulating green liquor pH is 9.5～10, makes in the green liquor part element silicon form the silicide deposition and is filtered and removes, and obtains upper strata clarification green liquor, lower floor's precipitum green mud after filtering, filter residue green mud otherwise processed, filtrating is returned in the green liquor clarification groove and is clarified; Lime and clarification green liquor by the ratio of the theoretical amount of the sodium carbonate complete reaction in the calcium oxide in the lime and the green liquor be 1.07 mix after; Carry out causticizing reaction at 96 ℃, obtain the causticization emulsion, the causticization emulsion is sent in the white liquid defecator and is clarified; Obtain the upper strata and clarify white liquid and lower floor's white clay precipitum; The white clay precipitum is through pre-hung formula vacuum filter isolated by filtration, and the gained white clay send subsequent step to handle, and gained filters white liquid and send in the white liquid defecator and clarify; The gained white clay is with 62 ℃ hot wash, and washing obtains the desulfurizing agent that said causticization white clay is processed after pre-hung formula vacuum filter filtering means dehydration reaches more than 60% the mass dryness fraction of white clay.
The gained desulfurizing agent is used for the circulating fluidized bed combustion coal boiler desulfurization, comprises desulfuration in furnace and flue gas desulfurization, and said desulfuration in furnace adds the desulfurizing agent of gained in fire coal, and making calcium sulfur ratio is 2.0; Flue gas desulfurization comprises: earlier with in the white lime and the washings in the lignosulfonate production process; Make its pH value greater than 6; In after deposition is removed sediment, obtaining and washings, in be mixed with saturated with said desulfurizing agent again or the supersaturation absorption liquid with washings, and in saturated or supersaturation absorption liquid, add the poly-aspartate type anti-incrustation corrosion inhibitor of 5mg/L; Send into and carry out flue gas desulfurization in the desulfuration absorbing tower; This desulfuration absorbing tower is disposed with from bottom to top: the exhanst gas outlet after the saturated or supersaturation absorption liquid of desulfurizing agent and water composition, the absorption liquid effuser on the sidewall of absorption tower and liquid supplementation pipe, smoke inlet, absorption liquid spray district, demister and the desulfurization, and saturated or supersaturation absorption liquid pumps into the spray district and is vaporific ejection through circulating pump, and carry out countercurrent washing with the flue gas that contains sulfur dioxide via smoke inlet entering desulfuration absorbing tower this moment; After the sulfur in smoke absorption; This flue gas is discharged via the exhanst gas outlet at demister and desulfuration absorbing tower top, again by smoke stack emission in atmosphere, desulfurizing agent absorbs sulfur in smoke and reaction generates calcium sulfite; Introduce force air oxidation calcium sulfite and generate gypsum; From absorption liquid, separate gypsum, desulfuration in furnace efficient reaches 65%, and smoke desulfurization efficiency reaches 92.5%.
Embodiment 6:
When alkali stove fused mass is dissolved into green liquor in the fusion groove; Add the lime of fused mass amount 2.4% and the water soluble starch flocculant of fused mass amount 0.7% in the lysate; Green liquor is delivered in the green liquor clarification groove and clarifies, and obtains upper strata clarification green liquor, and lower floor's precipitum green mud after filtering; Filter residue green mud otherwise processed, filtrating is returned in the green liquor clarification groove and is clarified; Lime and clarification green liquor by the ratio of the theoretical amount of the sodium carbonate complete reaction in the calcium oxide in the lime and the green liquor be 1.06 mix after; Carry out causticizing reaction at 100 ℃, obtain the causticization emulsion, the causticization emulsion is sent in the white liquid defecator and is clarified; Obtain the upper strata and clarify white liquid and lower floor's white clay precipitum; The white clay precipitum is through the lime mud folter isolated by filtration, and the gained white clay send subsequent step to handle, and gained filters white liquid and closes to send in the white liquid defecator and clarify; The gained white clay is with 65 ℃ of hot washes, and washing obtains the desulfurizing agent that said causticization white clay is processed after pre-hung formula vacuum filter filtering means dehydration reaches more than 60% the mass dryness fraction of white clay.
Earlier with in the milk of lime and the washings in the lignosulfonate production process; Make its pH value greater than 6; In after deposition is removed sediment, obtaining and washings; In be mixed with saturated with said desulfurizing agent again or the supersaturation absorption liquid with washings, and in saturated or supersaturation absorption liquid, add the poly-aspartate type anti-incrustation corrosion inhibitor of 18mg/L, send into and carry out flue gas desulfurization in the desulfuration absorbing tower; This desulfuration absorbing tower is disposed with from bottom to top: the exhanst gas outlet after the saturated or supersaturation absorption liquid that desulfurizing agent and water are formed, the absorption liquid effuser on the sidewall of absorption tower and liquid supplementation pipe, smoke inlet, absorption liquid spray district, demister and the desulfurization; Saturated or supersaturation absorption liquid pumps into the spray district and is vaporific ejection through circulating pump, and carry out countercurrent washing with the flue gas that contains sulfur dioxide via smoke inlet entering desulfuration absorbing tower this moment, after sulfur in smoke is absorbed; This flue gas is discharged via the exhanst gas outlet at demister and desulfuration absorbing tower top; Again by smoke stack emission in atmosphere, desulfurizing agent absorbs sulfur in smoke and reaction generates calcium sulfite, introduces force air oxidation calcium sulfite and generates gypsum; From absorption liquid, separate gypsum, reach 93% through the test smoke desulfurization efficiency.
The above is merely the preferred embodiments of the present invention, and does not limit the present invention in any way, and for a person skilled in the art, the present invention can have various changes and variation.All within spirit of the present invention and principle, any modification of being done, be equal to replacement, improvement etc., as long as within the spirit that claim limits, also belong to protection scope of the present invention.
Claims (10)
1. desulfurizing agent that the causticization white clay is processed is characterized in that: improve and make through traditional causticization process has been carried out, may further comprise the steps in the manufacturing process:
S1: green liquor purification processes: when alkali stove fused mass is dissolved into green liquor in the fusion groove; Add the lime of fused mass amount 2%～3% and the flocculant of fused mass amount 0.5%～1%; Green liquor is delivered in the green liquor clarification groove and clarifies, and obtains upper strata clarification green liquor, and lower floor's precipitum green mud after filtering; Filter residue green mud otherwise processed, filtrating is returned in the green liquor clarification groove and is clarified;
S2: causticization is handled: lime and clarification green liquor by the ratio of the theoretical amount of the sodium carbonate complete reaction in the calcium oxide in the lime and the green liquor be 1.05～1.1 mix after; Carry out causticizing reaction at 90～102 ℃; Get the causticization emulsion; The causticization emulsion is sent in the white liquid defecator and is clarified, and obtains the upper strata and clarifies white liquid and lower floor's precipitum white clay, and white clay is through filtering the equipment isolated by filtration; The gained white clay send subsequent step to handle, and gained filters white liquid and merges to the upper strata and clarify and send pulping and digesting to use in the white liquid or send in the white liquid defecator and clarify;
The white clay that S3: lime mud treatment: step S2 obtains is with 50～70 ℃ hot wash, and washing obtains the desulfurizing agent that said causticization white clay is processed after pre-hung formula vacuum filter or pressure disc type filter filtering means dehydration reach more than 60% the mass dryness fraction of white clay.
2. desulfurizing agent according to claim 1 is characterized in that: the said green liquor of step S1 is the green liquor that produces in the straw fiber raw material slurrying alkali recovery process, in said green liquor clarification groove, feeds CO
2Gas, regulating green liquor pH is 9.5～10, makes in the green liquor part element silicon form the silicide deposition and is filtered and removes.
3. desulfurizing agent according to claim 1 is characterized in that: the said flocculant of step S1 is calcium polyacrylate (CPA) or water soluble starch.
4. desulfurizing agent according to claim 1 is characterized in that: the said filter plant of step S2 is pre-hung formula vacuum filter, lime mud folter or white hydraulic coupling disk filter, and gained filters white liquid and send in the white liquid defecator and clarify.
5. desulfurizing agent according to claim 1 is characterized in that: the said filter plant of step S2 is white hydraulic coupling filter, and gained filters white liquid and merges to the upper strata and clarify and send pulping and digesting to use in the white liquid.
6. the method for a flue gas desulfurization; Comprise and have a desulfuration absorbing tower; This desulfuration absorbing tower is disposed with from bottom to top: the exhanst gas outlet after the saturated or supersaturation absorption liquid that desulfurizing agent and water are formed, the absorption liquid effuser on the sidewall of absorption tower and liquid supplementation pipe, smoke inlet, absorption liquid spray district, demister and the desulfurization; Absorption liquid pumps into the spray district and is vaporific ejection through circulating pump, and carry out countercurrent washing with the flue gas that contains sulfur dioxide via smoke inlet entering desulfuration absorbing tower this moment, after sulfur in smoke is absorbed; This flue gas is discharged via the exhanst gas outlet at demister and desulfuration absorbing tower top; Again by smoke stack emission in atmosphere, desulfurizing agent absorbs sulfur in smoke and reaction generates calcium sulfite, introduces force air oxidation calcium sulfite and generates gypsum; From absorption liquid, separate gypsum; It is characterized in that: said desulfurizing agent is the described desulfurizing agent of arbitrary claim in the claim 1～5, adds in said saturated or supersaturation absorption liquid that anti-incrustation corrosion inhibitor, the addition of anti-incrustation corrosion inhibitor are arranged is 5～30mg/L.
7. according to the method for the said flue gas desulfurization of claim 6, it is characterized in that: said anti-incrustation corrosion inhibitor is polyamino polyether methylene phosphonic acids or poly-aspartate type anti-incrustation corrosion inhibitor.
8. according to the method for the said flue gas desulfurization of claim 6; It is characterized in that: said saturated or supersaturation absorption liquid is that washings and the lime in the described desulfurizing agent of arbitrary claim and the lignosulfonate production process is formulated in the claim 1～5; In the process for preparation; Earlier with in the lime and the washings in the lignosulfonate production process; Make its pH value greater than 6, in after deposition is removed sediment, obtaining and washings, in be mixed with saturated with said desulfurizing agent again or the supersaturation absorption liquid with washings.
9. the method for a circulating fluidized bed combustion coal boiler desulfurization comprises desulfuration in furnace and/or flue gas desulfurization, it is characterized in that: said desulfuration in furnace adds right power and asks the described desulfurizing agent of arbitrary claim in 1～5 in fire coal, making calcium sulfur ratio is 1.5～3.0.
10. according to the method for the said circulating fluidized bed combustion coal boiler desulfurization of claim 9, it is characterized in that: said flue gas desulfurization is for adopting the method for the described flue gas desulfurization of claim 6.
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