CN109650412B - Method for producing sodium sulfite by removing sulfur in sulfur-containing flue gas by arsenic-containing industrial alkaline residue - Google Patents
Method for producing sodium sulfite by removing sulfur in sulfur-containing flue gas by arsenic-containing industrial alkaline residue Download PDFInfo
- Publication number
- CN109650412B CN109650412B CN201811624379.8A CN201811624379A CN109650412B CN 109650412 B CN109650412 B CN 109650412B CN 201811624379 A CN201811624379 A CN 201811624379A CN 109650412 B CN109650412 B CN 109650412B
- Authority
- CN
- China
- Prior art keywords
- arsenic
- sulfur
- sodium
- sodium sulfite
- flue gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B13/00—Obtaining lead
- C22B13/02—Obtaining lead by dry processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/04—Obtaining arsenic
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
- C01P2006/82—Compositional purity water content
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
A method for producing sodium sulfite by using arsenic-containing industrial caustic sludge to remove sulfur in sulfur-containing flue gas comprises the steps of adding water into arsenic-containing industrial caustic sludge, circularly pulping, performing filter pressing, adding excessive lime into filtrate to precipitate arsenic, adding sodium sulfide solution to purify, performing filter pressing, feeding alkali liquor into a desulfurization absorption tower to perform absorption desulfurization reaction on sulfur-containing flue gas, and performing filter pressing to obtain clear liquid containing sodium sulfite and sodium sulfate; adding appropriate amount of SO into the clear liquid2And excessive lime is added, sodium sulfate in the clear liquid is reduced and converted into sodium bisulfite, and the pH value of the filtrate obtained after filter pressing is adjusted by adding sodium hydroxide solution to convert the sodium bisulfite into sodium sulfite; and finally, evaporating to oversaturate and crystallize, centrifugally dewatering, and drying crystals to obtain a sodium sulfite product with the mass concentration of more than or equal to 90%. The method can realize harmless and resource treatment of large-scale industrialized arsenic-containing industrial alkaline residue, the sodium sulfite product has high production quality and stable content, really realizes the desire of treating wastes with wastes, and realizes the full-value recovery of sulfur in the arsenic-containing industrial alkaline residue and sulfur-containing flue gas.
Description
Technical Field
The invention relates to the environmental protection field of sulfur-containing flue gas desulfurization technology, caustic sludge treatment and the like in nonferrous smelting industry, in particular to a method for producing sodium sulfite by removing sulfur in sulfur-containing flue gas by using arsenic-containing industrial caustic sludge.
Background
In the nonferrous smelting industry, a blast furnace, a fuming furnace and a reverberatory furnace generate a large amount of sulfurThe sulfur-containing flue gas has a common point that the sulfur content is low, and the typical value is 1000-8000 mg/m3It is very difficult to produce sulfuric acid, and only other media can be used for absorbing and removing sulfur. There are well established related techniques and equipment such as limestone method, alkaline method, etc.; wherein, the limestone method has lower operating cost, but is easy to scale and block pipelines and nozzles; the alkaline process has high efficiency, no scale and resistance, relatively small investment, high running cost and high supplementary consumption of expensive alkaline resource.
The primary arsenic-containing alkaline residue for producing refined antimony and the secondary arsenic-containing alkaline residue for producing a large amount of smelting smoke in the antimony industry of nonferrous smelting generally contain 2-6 wt% of arsenic, 30-40 wt% of soluble alkali, 1-4 wt% of sulfate, 8-35 wt% of insoluble valuable metals of lead, antimony, tin, indium, tellurium and the like, and the balance is other slagging components such as silicon, iron, calcium and the like. The arsenic-containing industrial alkaline residue (including the primary arsenic-containing alkaline residue and the secondary arsenic-containing alkaline residue) has a historical storage amount of nearly million tons in China, and the annual increment is more than 2-3 million tons. Because the caustic sludge is soluble, if the caustic sludge is leaked to the surrounding environment, the caustic sludge is very dangerous and is dangerous solid waste which is strictly environment-friendly. However, the arsenic-containing industrial alkaline residue has high utilization value in the aspect of resource utilization.
Some directly put the block-shaped arsenic-containing industrial alkaline slag into a blast furnace according to a preferred proportion to be reduced and smelted together with sintered blocks, and valuable metals such as antimony and the like in the alkaline slag are recovered, but the arsenic content in the blast furnace smoke dust is greatly increased, and a large amount of alkali enters the ferrosilicon calcium slag, so that the circulating slag flushing water of the water quenching slag is sticky and blackened.
Some have boiled the caustic sludge with water to dissolve out soluble arsenic alkali and sulfate. The insoluble slag enriches all valuable metals and returns to the smelting system for recycling. After the soluble part is purified, the soluble part is concentrated and crystallized to produce composite alkali and salt, which is specially used for the clarifier for glass production, but the composite alkali salt gradually loses the application market along with the environmental protection and strict control of arsenic in the glass industry.
And the caustic sludge is boiled by water and leached, and the filtered slag is returned to a smelting system for recycling. The alkali liquor is used for desulfurizing sulfur-containing flue gas of smelting enterprises, and the alkali liquor after absorbing sulfur dioxide is converted into arsenic-containing mixed liquor mainly containing sodium sulfite. Adding sodium sulfide to deposit arsenic, adding iron salt to deeply remove arsenic, pressing filtrate to perform solid-liquid separation to obtain a purified solution, evaporating to oversaturate and crystallize, centrifugally removing mother liquor, and then sending hot air to dry to produce an anhydrous sodium sulfite product. In China, people explore for two or thirty years under the idea of treating wastes with wastes, so far, the design target cannot be reached, the quality of the produced sulfurous acid product is unstable, the effective mass content fluctuates between 50 and 75 percent, and the relevant standard of a sodium sulfite product cannot be reached.
The inventor finds out in the research that:
firstly, in a sulfur-containing flue gas desulfurization mode, arsenic-containing alkali liquor absorbs sulfur dioxide to generate sodium sulfite, and simultaneously carries out oxidation mass transfer reaction with oxygen in flue gas by a very large interface, namely the generated sodium sulfite is easily oxidized into sodium sulfate.
Secondly, smelting flue gas is generally subjected to cloth bag dust collection and then enters a desulfurization process, but in actual operation, the cloth bag is always damaged and loses efficacy, so that trace nonferrous metal oxide dust is mixed in the flue gas, the trace nonferrous metal oxide dust is a high-efficiency catalyst for the oxidation reaction, and the effect of the trace nonferrous metal oxide dust is far greater than that of an antioxidant which is added in a solution in advance.
Thirdly, sulfate SO is introduced in the arsenic precipitation process4 2－。
Fourthly, the caustic sludge contains 1-2 wt% of sulfur which exists in the form of sulfate.
The above four reasons can be understood, and the good desire to treat waste with waste has not been realized for decades.
Object of the Invention
The purpose of the invention is: aiming at the defects of the prior art, the method for producing sodium sulfite by removing sulfur in sulfur-containing flue gas by using arsenic-containing industrial alkaline residue is provided, and the problems that the sulfur in sulfur-containing flue gas is removed by using the arsenic-containing industrial alkaline residue, and the produced sodium sulfite product has unstable quality and low content can be solved.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a method for producing sodium sulfite by using arsenic-containing industrial caustic sludge to remove sulfur in sulfur-containing flue gas comprises the following steps, which are combined and refer to a figure 1:
the method comprises the following steps: taking arsenic-containing industrial alkaline residue, and adding water which is 2-6 times of the weight of the arsenic-containing industrial alkaline residue into the arsenic-containing industrial alkaline residue for cyclic pulping;
step two: performing filter pressing to perform liquid-solid separation to obtain filtrate;
step three: adding lime into the filtrate according to the ratio of Ca/As of 2-3, stirring at normal temperature to sink arsenic, wherein the chemical reaction formula is As follows: 2Na3AsO4+3Ca(OH)2＝Ca3(AsO4)2↓ +6 NaOH; adding 8-20% of sodium sulfide solution by mass concentration, wherein the addition amount of the sodium sulfide solution is 1-5L of the sodium sulfide solution in the alkali liquor obtained after arsenic precipitation reaction per cubic meter, so As to convert trace lead, antimony, zinc, tin and the like dissolved in the alkali liquor due to high alkalinity into insoluble sulfides to precipitate out, and thus, residual As in the treated alkali liquor5+Reduced to 0.4-1.7 mg/L and Pb2+、Sb3+、Sn4+And Zn2+Grade less than 0.5mg/L, and the chemical reaction formula is as follows:
Pb2++Na2S→PbS↓+2Na+，
2Sb3++3Na2S→Sb2S3↓+6Na+，
Zn2++Na2S→ZnS↓+2Na+，
Sn4++2Na2S→SnS2↓+4Na+；
filter pressing and liquid-solid separation are carried out to obtain the alkali liquor after arsenic removal and purification. The key significance of the step is that in one process operation, the purposes of removing arsenic and heavy metal impurities are achieved, and the process flow is simplified;
step four: inputting the alkali liquor after dearsenification and purification as absorption liquid into a desulfurization absorption tower to carry out absorption desulfurization reaction on sulfur-containing flue gas generated by smelting enterprises until the pH value of the absorption liquid is reduced to 5.5-7.5 (a final value), wherein the chemical reaction formula is as follows: 2NaOH + SO2＝Na2SO3+H2O, because sodium sulfite is easily oxidized into sodium sulfate, part of the sodium sulfite is oxidized into sodium sulfate in the reaction, so that the content of the sodium sulfite is reduced; carrying out liquid-solid separation on the absorption hydraulic filter to obtain clear liquid containing sodium sulfite and sodium sulfate;
the flue gas generated by the volatilization and fuming of the filter residue in the second step and the flue gas generated by the lead smelting of the filter residue in the third step in the blast furnace can be applied to the fourth step because the sulfur is also the sulfur-containing flue gas.
Step five: adding appropriate amount of SO into the clear liquid2And excess lime, and reducing sodium sulfate in the clear solution to convert into sodium bisulfite, wherein the reaction formula is as follows: na (Na)2SO4+Ca(OH)2+2SO2+2H2O＝2NaHSO3+CaSO4·2H2And O, performing filter pressing to perform liquid-solid separation to obtain filtrate. The key point of setting this step is that since the oxidation phenomena in the aforementioned process of sodium sulfite production are inevitable, only to a different extent, anyway to suppress and prevent, this directly leads to unstable fluctuations in the sodium sulfite product content. Compared with passive strict defense, the method is not as good as active reduction and conversion, so that the product content is increased and stabilized. Adding SO2When the concentration of the sodium sulfate is higher than the concentration of the sodium sulfate, the concentration of the sodium sulfate cannot be excessive, and the concentration can be judged only by reducing the sodium sulfate in the clear liquid to be converted into sodium bisulfite, and the pH value of the solution can reach 5.5-7.5 at the end point;
step six: adding a sodium hydroxide solution into the filtrate to adjust the pH value to 10.5-12, so that sodium bisulfite generated by the reduction conversion in the fifth step is converted into sodium sulfite; the chemical reaction formula is as follows: NaHSO3+NaOH＝Na2SO3+H2O；
Step seven: and (3) evaporating to oversaturate and crystallize, centrifugally removing crystal slurry mother liquor, and drying crystals by hot air flow to obtain a sodium sulfite product with the mass concentration of more than or equal to 90%.
Mixing the filter residues obtained after filter pressing in the second step according to a self-fluxing slag type ingredient, and then sending the mixture to a fuming furnace for fuming and volatilizing, wherein slagging components of silicon, iron and calcium in the filter residues generate calcium ferrosilicon slag for opening a circuit; and cooling the flue gas generated by volatilization, collecting dust by using a cloth bag to obtain enriched high-grade valuable metal (Pb, Sb, Sn and the like) smoke dust, and conveying the smoke dust to subsequent smelting and recycling.
In the third step, the filter residue separated by filter pressing after arsenic precipitation and sulfuration purification is matched with element iron powder (the weight ratio of the filter residue to the iron powder is 1: 1.85), and then the filter residue and the traditional lead smelting raw material are put into a lead blast furnace of a lead smelting enterprise together for lead smelting, so that the lead smelting method can be used for producing the crude lead alloy and the ferro-silicon calcium slag, and the produced ferro-arsenic alloy accounts for 2-8% of the total weight of the raw material put into the furnace. The arsenic-iron alloy contains 18-25 wt% of As, 60-65 wt% of Fe and 7.2 of specific gravity, is very stable, and is detected by a method of GB 5805.3-2007 standard to obtain water
As content in the effluent meets the standard requirement and is judged to be non-toxic. The produced arsenic-iron alloy is stable, nontoxic and similar to steel materials in large specific gravity, and is used as a counter weight material for sale and open circuit, so that harmless, recycling, safe and environment-friendly treatment of arsenic-containing hazardous wastes is realized.
According to the method, the arsenic-containing industrial alkaline residue is used for removing sulfur in the sulfur-containing flue gas to produce the sodium sulfite product, so that the harmless and resource treatment of the large-scale industrial arsenic-containing industrial alkaline residue can be realized, the byproduct sodium sulfite with high quality and stable content (the mass concentration is more than or equal to 90%) can be produced, the desire of treating wastes with wastes is really realized, the full-value recovery of sulfur in the arsenic-containing industrial alkaline residue and the sulfur-containing flue gas is realized, and the environmental protection benefit and the economic benefit are obvious.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
Example 1
Taking a certain middle-sized comprehensive recovery nonferrous smelting enterprise in Leishui Yang as an example to carry out experiments, the enterprise has equipment systems such as alkali slag circulating pulping, filter pressing, blast furnace lead smelting, fuming furnace, dust collection and desulfurization, and the like, and according to the method, the enterprise equipment systems are utilized to carry out specific implementation tests:
the method comprises the following steps: circularly pulping the obtained arsenic-containing industrial alkaline residue, and soaking 20 tons of alkaline residue in water at a liquid-solid ratio of 3: 1 (by weight);
step two: filter pressing to obtain filtrate. The specific gravity of the filtrate is 1.11, and the filtrate averagely contains 10 weight percent of NaOH and 16/L of As16 g; 18.9 tons of filter residue (containing silicon, iron, calcium and the like) contains 26 weight percent of water; adding the obtained filter residue into the mixture according to a self-dissolving residue type2Fuming and volatilizing in a fuming furnace to generate calcium ferrosilicon slag;
step three: adding completely digested lime powder into the filtrate at a Ca/As ratio of more than or equal to 2.8, adding 15m3Stirring in a stirring tank with the diameter of 3.8 multiplied by the diameter of H1.5m for 90 minutes at normal temperature, and adding 2 liters of Na with the mass concentration of 15 percent into each cubic meter of the obtained alkali liquor2S solution, sulfurizing and precipitating trace Pb, Sb, Zn, Sn, etc. dissolved in alkali liquor, continuously stirring for 30 min to dye white calcium arsenate into brown black with black sulfide, and filter pressing the mixed liquor with 800X 800 type 60 square meter diaphragm filter press to obtain dearsenized and purified alkali liquor containing NaOH 10 wt% and As5+1.6mg/L，Pb2+、Sb3+、Zn2+、Sn4+Less than 0.5mg/L, and conveying the alkali liquor to a storage tank for storage for later use; performing filter pressing to obtain calcium arsenate slag and sulfide slag, wherein the slag rate is 129.5kg per cubic meter of alkali liquor, the water content is 40%, and the arsenic content is As20.6% by weight;
the produced calcium arsenate black slag is mixed with iron powder, and the process specification comprises the following ingredients in parts by weight: calcium arsenate slag, iron powder as element and river sand in the weight ratio of 1 to 1.85 to 0.6, pressing into cylinder of phi 120 XH 120, air drying, and smelting together with lead containing furnace material in blast furnace in traditional lead smelting process. The weight ratio of the calcium arsenate slag to the total raw materials is 9 percent, namely about 18 tons of calcium arsenate slag are charged into the furnace every day to produce the arsenic-iron alloy. Because the arsenic-iron alloy is produced together with other furnace materials of the blast furnace, the data are not easy to be counted independently. When the arsenic-iron alloy is manufactured, the solid arsenic rate of iron is higher than 90%, the secondary smoke dust rate of arsenic is less than 10%, and the manufactured arsenic-iron alloy contains 22 wt% of As and 63 wt% of Fe, the specific gravity of the arsenic-iron alloy is 7.2, and the melting point of the arsenic-iron alloy is 680 ℃. According to the detection of GB 5805.3-2007 standard, the water extract contains As0.5mg/L which is less than the standard 1mg/L requirement, the arsenic-iron alloy is judged to be nonhazardous, and the arsenic-iron alloy is sold to professional weighting enterprises to be used as a weighting material, and the selling price reaches 2400 yuan/T;
step four, supplementing the alkali liquor which is stored in the step three and is subjected to arsenic removal purification to 80000m3And in a bottom circulating pool of the/h multistage pneumatic mixing desulfurization absorption tower, performing secondary circulating absorption reaction desulfurization on sulfur-containing flue gas generated by smelting enterprises. When the pH value of the tail stage circulating pool liquid is reduced to 6.5, 15m of the tail stage circulating pool liquid is pumped out each time3And after filter pressing purification, the lead powder is put into a storage tank for temporary storage for later use, and a small amount of filter pressing residues are accumulated and then returned to a lead system for proportioning. The clear liquid obtained by filter pressing contains Na2SO310% by weight of Na2SO44.7 wt%;
step five: SO is sucked by three-stage countercurrent and Venturi pump injection2Mixing, adding lime, mechanical stirring, reducing and converting in reactor, and water cooling to regulate reaction temperature below 35 deg.c and 15m per stage3The absorption liquid consumes 265.2kg of sulfur and lime (Ca (OH)2More than 80%) 306.1kg, reducing and converting sodium sulfate in clear liquid obtained after filter pressing in the fourth step, and converting Na in solution after reduction2SO4The amount of (B) was reduced from 4.7 wt% to 1.0 wt%. And filtering the mixed liquid after the reaction to obtain filtrate, and sending the filtrate to a storage tank for later use. Washing and filter-pressing the filter-pressing residue gypsum, and piling or selling the filter-pressing residue gypsum for a cement plant to serve as ingredients;
step six: pumping the filtrate obtained after reduction and conversion to 30m3PP stirring tank, adding sodium hydroxide to adjust pH value for conversion reaction to obtain NaHSO converted in step five3Conversion to Na2SO3Controlling the amount of alkali to be added, and selecting the end point pH value to be 11.0;
step seven: the solution obtained in the sixth step is evaporated to obtain Na-containing solution through a multi-effect evaporation crystallization system2SO3The crystal slurry of (1); sending the crystal mush into a centrifuge, and removing mother liquor to obtain sodium sulfite wet dispersion crystals with the water content of less than 4%; feeding the wet bulk crystal into a hot air flow dryer, drying until the water content is less than 0.5%, to obtain anhydrous sodium sulfite product, Na2SO3The content of the sodium sulfite is more than or equal to 90 percent, the content of Fe is less than 0.03 percent, the content of As is less than 0.003 percent and the whiteness is 80 percent, and the product quality reaches the standard requirements of qualified products in the national chemical industry standard HG/T2967-2010 of anhydrous sodium sulfite products.
Claims (2)
1. A method for producing sodium sulfite by removing sulfur in sulfur-containing flue gas by arsenic-containing industrial alkaline residue is characterized by comprising the following steps:
the method comprises the following steps: taking arsenic-containing industrial alkaline residue, and adding water which is 2-6 times of the weight of the arsenic-containing industrial alkaline residue into the arsenic-containing industrial alkaline residue for cyclic pulping;
step two: performing filter pressing to perform liquid-solid separation to obtain filtrate;
step three: adding lime into the filtrate according to the mass ratio of Ca to As of 2-3, stirring at normal temperature to sink arsenic, wherein the reaction formula is As follows: 2Na3AsO4+3Ca(OH)2＝Ca3(AsO4)2↓ +6 NaOH; adding 8-20% of sodium sulfide solution by mass, wherein the addition amount of the sodium sulfide solution is 1-5L of the sodium sulfide solution in the alkali liquor obtained after arsenic precipitation reaction per cubic meter, and converting trace lead, antimony, zinc and tin dissolved in the alkali liquor into sulfides for precipitation, so that residual As in the treated alkali liquor5+Reduced to 0.4-1.7 mg/L and Pb2+、Sb3+、Sn4+And Zn2+Are all less than 0.5 mg/L; filter pressing and liquid-solid separation are carried out to obtain alkali liquor after arsenic removal and purification;
step four: inputting the alkali liquor after dearsenification and purification as absorption liquid into a desulfurization absorption tower to carry out absorption desulfurization reaction on sulfur-containing flue gas generated by smelting enterprises to generate sodium sulfite and sodium sulfate, reducing the pH value of the absorption liquid to 5.5-7.5, and carrying out liquid-solid separation on absorption liquid to obtain clear liquid containing sodium sulfite and sodium sulfate;
step five: adding appropriate amount of SO into the clear liquid2And excess lime, and reducing sodium sulfate in the clear solution to convert into sodium bisulfite, wherein the reaction formula is as follows: na (Na)2SO4+Ca(OH)2+2SO2+2H2O＝2NaHSO3+CaSO4·2H2O, until the end point pH value of the solution is 5.5-7.5, performing filter pressing for liquid-solid separation to obtain a filtrate;
step six: adding a sodium hydroxide solution into the filtrate to adjust the pH value to 10.5-12, so that sodium bisulfite generated by the reduction conversion in the fifth step is converted into sodium sulfite;
step seven: and (3) evaporating to oversaturate and crystallize, centrifugally removing crystal slurry mother liquor, and drying crystals by hot air flow to obtain a sodium sulfite product with the mass concentration of more than or equal to 90%.
2. The method for producing sodium sulfite by using arsenic-containing industrial caustic sludge to remove sulfur in sulfur-containing flue gas according to claim 1, wherein the filter residue obtained after filter pressing in the third step is mixed with element iron powder and then is put into a lead blast furnace of a lead smelting enterprise together with the traditional lead smelting raw materials to smelt lead, so that arsenic-iron alloy can be smelted.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811624379.8A CN109650412B (en) | 2018-12-28 | 2018-12-28 | Method for producing sodium sulfite by removing sulfur in sulfur-containing flue gas by arsenic-containing industrial alkaline residue |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811624379.8A CN109650412B (en) | 2018-12-28 | 2018-12-28 | Method for producing sodium sulfite by removing sulfur in sulfur-containing flue gas by arsenic-containing industrial alkaline residue |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109650412A CN109650412A (en) | 2019-04-19 |
| CN109650412B true CN109650412B (en) | 2021-09-21 |
Family
ID=66118104
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811624379.8A Active CN109650412B (en) | 2018-12-28 | 2018-12-28 | Method for producing sodium sulfite by removing sulfur in sulfur-containing flue gas by arsenic-containing industrial alkaline residue |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109650412B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111068486B (en) * | 2019-12-31 | 2020-11-27 | 焱鑫环保科技有限公司 | SO of smelting flue gas is removed by using soda ash2Method for producing sodium sulfite product |
| CN112607751B (en) * | 2020-12-31 | 2021-11-12 | 耒阳市焱鑫有色金属有限公司 | Method for re-dissolving, freezing and purifying mixed salt containing arsenic, sodium sulfite and sodium sulfate |
| CN113599761B (en) * | 2021-07-14 | 2022-02-25 | 钢铁研究总院 | Petrochemical alkaline residue treatment system and treatment method |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1375565A (en) * | 2002-01-14 | 2002-10-23 | 史汉祥 | Dearsenifying method for Cu-Zn-Co material |
| CN1436737A (en) * | 2003-03-13 | 2003-08-20 | 广西壮族自治区职业病防治研究所 | Tackling method of river or region with high-concentration white arsenic pollution |
| CN1762809A (en) * | 2005-09-02 | 2006-04-26 | 吕国锋 | Method for preparing anhydrous sodium sulfite using industrial by-product anhydrous sodium sulfate |
| CN1864811A (en) * | 2006-04-10 | 2006-11-22 | 广州市天赐三和环保工程有限公司 | Fume desulfurizing process employing multiple circulation and stable double alkali method and apparatus |
| CN101899574A (en) * | 2010-08-04 | 2010-12-01 | 锡矿山闪星锑业有限责任公司 | Method for comprehensively reclaiming arsenic caustic dross and sulfur dioxide flue gas in antimony pyrometallurgical smelting |
| CN201762195U (en) * | 2010-09-10 | 2011-03-16 | 长沙维力固德科技发展有限公司 | Device for treating waste acid and water containing arsenic and recovering arsenic therefrom |
| CN102351360A (en) * | 2011-07-04 | 2012-02-15 | 锡矿山闪星锑业有限责任公司 | Method for comprehensive recovery of arsenic-containing alkaline liquid and waste gas of sulfur dioxide |
| CN102851707A (en) * | 2012-08-29 | 2013-01-02 | 江西自立资源再生有限公司 | Technology for recovering production of electrolytic zinc powder and lead powder from smelting ash through alkali leaching method |
| CN104192871A (en) * | 2014-09-03 | 2014-12-10 | 吉林化工学院 | Method for producing sodium sulfite through two-stage ejection absorption |
| CN107963642A (en) * | 2017-12-29 | 2018-04-27 | 焱鑫环保科技有限公司 | SO is absorbed using the water logging of industrial caustic containing arsenic lye2The process of flue gas, dearsenification purification production sodium sulfite product |
| CN108441642A (en) * | 2018-04-08 | 2018-08-24 | 郴州钖涛环保科技有限公司 | The wet method recycling and harmless treatment process of antimony smelting arsenic alkali slag |
| CN108998677A (en) * | 2018-08-28 | 2018-12-14 | 郴州丰越环保科技有限公司 | A kind of method of wet-treating high arsenic smoke dust containing indium |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4241041A (en) * | 1979-01-22 | 1980-12-23 | Mei Systems Inc. | Methods for the recovery of sulfur components from flue gas and recycle sodium sulfite by reduction-smelting and carbonating to strip hydrogen sulfide |
-
2018
- 2018-12-28 CN CN201811624379.8A patent/CN109650412B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1375565A (en) * | 2002-01-14 | 2002-10-23 | 史汉祥 | Dearsenifying method for Cu-Zn-Co material |
| CN1436737A (en) * | 2003-03-13 | 2003-08-20 | 广西壮族自治区职业病防治研究所 | Tackling method of river or region with high-concentration white arsenic pollution |
| CN1762809A (en) * | 2005-09-02 | 2006-04-26 | 吕国锋 | Method for preparing anhydrous sodium sulfite using industrial by-product anhydrous sodium sulfate |
| CN1864811A (en) * | 2006-04-10 | 2006-11-22 | 广州市天赐三和环保工程有限公司 | Fume desulfurizing process employing multiple circulation and stable double alkali method and apparatus |
| CN101899574A (en) * | 2010-08-04 | 2010-12-01 | 锡矿山闪星锑业有限责任公司 | Method for comprehensively reclaiming arsenic caustic dross and sulfur dioxide flue gas in antimony pyrometallurgical smelting |
| CN201762195U (en) * | 2010-09-10 | 2011-03-16 | 长沙维力固德科技发展有限公司 | Device for treating waste acid and water containing arsenic and recovering arsenic therefrom |
| CN102351360A (en) * | 2011-07-04 | 2012-02-15 | 锡矿山闪星锑业有限责任公司 | Method for comprehensive recovery of arsenic-containing alkaline liquid and waste gas of sulfur dioxide |
| CN102851707A (en) * | 2012-08-29 | 2013-01-02 | 江西自立资源再生有限公司 | Technology for recovering production of electrolytic zinc powder and lead powder from smelting ash through alkali leaching method |
| CN104192871A (en) * | 2014-09-03 | 2014-12-10 | 吉林化工学院 | Method for producing sodium sulfite through two-stage ejection absorption |
| CN107963642A (en) * | 2017-12-29 | 2018-04-27 | 焱鑫环保科技有限公司 | SO is absorbed using the water logging of industrial caustic containing arsenic lye2The process of flue gas, dearsenification purification production sodium sulfite product |
| CN108441642A (en) * | 2018-04-08 | 2018-08-24 | 郴州钖涛环保科技有限公司 | The wet method recycling and harmless treatment process of antimony smelting arsenic alkali slag |
| CN108998677A (en) * | 2018-08-28 | 2018-12-14 | 郴州丰越环保科技有限公司 | A kind of method of wet-treating high arsenic smoke dust containing indium |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109650412A (en) | 2019-04-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109650412B (en) | Method for producing sodium sulfite by removing sulfur in sulfur-containing flue gas by arsenic-containing industrial alkaline residue | |
| CN107012340B (en) | A kind of technique that Whote-wet method extracts arsenic from arsenones waste residue | |
| CN102534187B (en) | Method for treating pyrite cinder by combining acidic leaching with alkaline dissolving | |
| CN103526017A (en) | Extraction method of valuable elements from acid mud produced in sulfuric acid production by copper smelting flue gas | |
| CN102390868B (en) | Method for producing manganese sulfate from smelting furnace gas | |
| CN103588240B (en) | A kind of green utilization method of dirty acid | |
| CN107963642A (en) | SO is absorbed using the water logging of industrial caustic containing arsenic lye2The process of flue gas, dearsenification purification production sodium sulfite product | |
| CN102101699A (en) | Method for extracting pyrolusite and producing manganese sulfate by utilizing by-product in production of titanium white | |
| CN108396158A (en) | A kind of processing method of the complex salt crystal object of electrolytic manganese process | |
| CN112941312B (en) | Comprehensive recovery process for antimony and arsenic smelting alkaline residue | |
| CN111647754A (en) | Comprehensive utilization method of zinc-containing dust and sludge in steel plant | |
| CN111118301B (en) | Method for recycling arsenic slag resources by arsenic and alkali in freezing separation alkali slag water leaching solution | |
| CN106756056A (en) | A kind of method of Copper making white cigarette dirt dearsenification | |
| CN109534387A (en) | A kind of method that zinc sulfite is oxidized to zinc sulfate | |
| CN102828034B (en) | Method for producing high-purity zinc oxide through decarbonization on low-grade zinc oxide ore by adopting ammonia process | |
| CN104445425B (en) | A kind of preparation method of high purity manganese sulfate | |
| CN104232889A (en) | Technology for producing electrolytic metal manganese from low-grade manganese mine | |
| CN113816399A (en) | Method for recycling NaCl and recycling Fe, Mn and Mg resources in titanium slag | |
| CN109876630A (en) | A method of sulfur dioxide flue gas is administered with alkaline scrap material and recycles tin antimony metal and sodium sulfite crystal | |
| CN1321200C (en) | Method for separating copper, arsenic and zinc from copper-smelting high-arsenic flue dust sulphuric acid leach liquor | |
| CN102849782B (en) | Method for producing high-purity zinc oxide by steel mill smoke dust ash ammonia method decarburization | |
| WO2020133210A1 (en) | Method for producing sodium sulfite by removing sulfur from sulfur-containing flue gas using industrial alkali residue containing arsenic | |
| CN111979421A (en) | Method for comprehensively utilizing copper-containing arsenic-containing soot produced in copper smelting process | |
| CN102828033A (en) | Method for recycling electrolytic zinc acid leaching slag | |
| CN110923440A (en) | Method for removing arsenic and recovering heavy metal from copper smelting wastewater |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |