WO2019127305A1 - Processing method for producing sodium sulfite product by so2 flue gas absorption and arsenic-removal purification using leaching solution of arsenic-containing industrial alkaline residue - Google Patents
Processing method for producing sodium sulfite product by so2 flue gas absorption and arsenic-removal purification using leaching solution of arsenic-containing industrial alkaline residue Download PDFInfo
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- WO2019127305A1 WO2019127305A1 PCT/CN2017/119647 CN2017119647W WO2019127305A1 WO 2019127305 A1 WO2019127305 A1 WO 2019127305A1 CN 2017119647 W CN2017119647 W CN 2017119647W WO 2019127305 A1 WO2019127305 A1 WO 2019127305A1
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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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- the present invention relates to non-ferrous smelting industry, particularly to a technique of flue gas desulfurization inorganic chemicals, particularly relates to a method Flue Gas SO 2 removal arsenic purification, the production of products utilizing sodium sulfite Containing Industrial Alkali alkali flooding, absorption.
- the annual output of arsenic-containing industrial alkali slag is about 10,000 to 20,000 tons. Because it contains 1 to 8% of arsenic, it is a toxic solid waste strictly controlled by the environmental protection department. The secondary resources of value.
- smelting furnaces such as blast furnaces and smelting furnaces produce a large amount of smelting flue gas containing SO 2 concentration of 500-15000 mg/m 3 . Due to the low concentration of SO 2 , it is difficult to directly use it for acid production. Desulfurization is generally carried out using a spray desulfurization tower. The commonly used method is to use limestone powder as the absorption medium, produce calcium sulfite, further oxidize to calcium sulfate with air, and press the filtrate to separate and obtain a large amount of gypsum slag. Because the grade is not high, there is no consumer market, so the slag yard pile is built. It is easy to cause secondary pollution.
- Chinese public patent application CN101899574A proposes a method for comprehensively recovering arsenic alkali slag and sulfur dioxide flue gas in fire refining.
- the idea of using arsenic alkali slag to absorb flue gas SO 2 and produce sodium sulfite is proposed. It shows good prospects for the environmental protection industry that has been abolished, but its methods have many obvious technical defects. According to the method in the manual, it is impossible to produce a stable quality sodium sulfite product, and the industrially produced stable sodium sulfite product is the key to measuring whether the patented technology is mature and has practical value.
- arsenic alkali slag in the leaching step of arsenic alkali slag, it is immersed for 30 to 60 minutes with 2 times of mass of water, 90-100 ° C, re-dip once, and filtered, which is feasible under laboratory conditions, but industrial In scale production, arsenic slag often has large blocks that can block the mixer, sometimes causing mechanical accidents; and because arsenic slag usually contains 20-30% soluble Na 2 O, and contains 0.5 to 1% sulfuric acid.
- liquid-solid ratio 2:1 to dissolve the arsenic alkali slag, it is feasible at high temperature, but under industrial production conditions, especially in winter production, after the ambient temperature is lower than 10 °C, in the high concentration lye A small amount of Na 2 SO 4 will precipitate hydrate crystals, which will block pipes and valves seriously. Such liquid-solid ratio parameters are not appropriate.
- sulfur dioxide neutralization step sulfur dioxide waste gas is introduced into the leachate, and the reaction is neutralized at 20-50 °C. 10 to 20 hours, high-priced strontium and high-priced arsenic are reduced. When the pH of the solution reaches 3 to 6, the ventilation is stopped, and such an end point pH selection has serious problems.
- the lye absorbs SO 2 and produces Na 2 SO 3 .
- the pH value of the system is lower, the more easily the sodium sulfite is oxidized to Na 2 SO 4 , the Na 2 SO 3 content in the product is lowered;
- an aqueous solution of a vulcanizing agent having a mass of 1.0 to 2.0 times is added dropwise at a temperature of 20 to 40 ° C, and the reaction is carried out for 1 to 2 hours, and the pH is adjusted to 6.0 to 7.0 with sulfuric acid, and the mixture is allowed to stand for 2 to 6 hours, and the arsenic sulfide and the low arsenic are separated by filtration.
- the sodium sulfite solution, the hydrogen sulfide gas generated is absorbed by the waste arsenic alkali water and returned to the arsenic removal.
- the disadvantage of this step is that a large amount of sulfuric acid is introduced to adjust the pH, and the sulfurous acid solution is mixed with sodium sulfate, thereby reducing the content of the sodium sulfite product again.
- the generation of toxic gas of hydrogen sulfide has potential safety hazard; in the deep arsenic removal step, slowly add the iron sulfate of As content in the solution of low arsenic sodium sulfite solution, react for 1 hour, to pH 6-9, and stand still for 4 hours.
- CN101899574A proposes the idea of waste treatment and the technical process parameters under laboratory conditions, but it has not been in-depth in terms of industrial scale production, especially how to stably produce high-content sodium sulfite products. Not done enough, no practical value.
- the object of the present invention is to solve the above-mentioned technical problems, in particular, the technical disadvantage of CN101899574A, and propose a process for purifying arsenic by using arsenic industrial alkali slag immersion lye to absorb SO 2 flue gas to remove arsenic.
- the technical solution of the present invention is used: Alkali flooding Containing Industrial utilizing alkali flue gas SO 2 absorbent, the production process for purifying arsenic removal of sodium sulfite, the method steps:
- the leaching slag is smelted to replenish the ingredients and recover valuable metal elements.
- the leachate usually contains about 6-10% NaOH and As 1-15g/L, and is stored for use;
- p-phenylenediamine is added to the leachate, and the final concentration of p-phenylenediamine in the leachate is 0.01-0.1 g/L, which is used for preventing oxidation and is advantageous for increasing the percentage of sodium sulfite product;
- a concentrated aqueous solution of ferric sulfate having a mass concentration of 50 to 200 g/L is added to carry out arsenic deposition, and the amount of addition is controlled according to the molar ratio of Fe:As in the absorbing liquid system to 3-6; newly introduced As, thereby arsenic precipitation process The precipitate is removed together.
- the aqueous solution of the ferric sulfate is first hydrolyzed to ferric iron hydroxide, and then the iron hydroxide reacts with Na 3 AsO 4 in the solution to form a precipitate of FeAsO 4 .
- the chemical reaction equation is as follows (at normal temperature):
- arsenic in arsenic industrial alkali slag accounts for more than 85% of all arsenic, and a small amount is trivalent arsenic. Therefore, arsenic includes two reaction formulas of pentavalent arsenic and trivalent arsenic.
- the iron arsenate is precipitated by flocculation of inorganic macromolecules in excess of trivalent iron hydroxide in the solution, and adsorbed and rapidly settled, so that the As in the system can be purified to the level of 1 PPM, meeting the requirements of national environmental protection standards;
- the filter residue obtained after pressure filtration is mainly FeAsO 4 ⁇ 4Fe(OH) 3 ⁇ n ⁇ MeS, containing up to 40% iron, which can be returned to the smelting production ingredients as iron raw materials, and the arsenic can be further enriched into smelting. In the dust, it is further treated in a harmless manner.
- the precipitated crystals are separated by a centrifuge to separate the mother liquor; the wet crystals after separating the mother liquor are dried to obtain a sodium sulfite product having a mass concentration of ⁇ 96%.
- the arsenic-containing industrial alkali residue according to the present invention generally has As 1 to 8%, Na 2 O 20 to 35%, Pb 1 to 3%, Sb 2 to 8%, Sn 0.5 to 3%, and S 1 to 3% is a toxic solid waste strictly controlled by the national environmental protection department. This method carries forward the spirit of waste treatment and waste. Based on the Chinese patent application CN101899574A, starting from industrialized stable production, increasing the content of sodium sulfite as much as possible, optimizing the technical process and parameter selection, and achieving obvious technological progress, making use of arsenic The industrial alkali slag water immersion lye absorbs SO 2 in flue gas to produce arsenite.
- the process of producing sodium sulfite has become a practical and mature technology for industrial production. According to the national output of 20,000 tons of alkali slag per year, the economic benefit can be increased by about 35 million yuan.
- FIG. 1 is a flow chart showing the preparation process of sodium sulfite of the present invention
- the present invention is a process for producing sodium sulfite by using arsenic industrial alkali residue immersion lye to absorb SO 2 flue gas to remove arsenic and purify arsenic.
- the method steps are as follows:
- the specific gravity is 1.25-1.4; the leaching residue and the leachate are separated by pressure filtration; the leaching slag is returned to the smelting method to replenish the supplementary ingredients, and the valuable metal elements are recovered.
- the leachate usually contains about 6-10% NaOH and As 1-15g/L, and is stored for use;
- p-phenylenediamine is added to the leachate, and the final concentration of p-phenylenediamine in the leachate is 0.01-0.1 g/L, which is used for preventing oxidation and is advantageous for increasing the percentage of sodium sulfite product;
- a concentrated aqueous solution of ferric sulfate having a mass concentration of 50 to 200 g/L is added to carry out arsenic deposition, and the amount of addition is controlled according to the molar ratio of Fe:As in the absorbing liquid system to 3-6; newly introduced As, thereby arsenic precipitation process The precipitate is removed together.
- the aqueous solution of the ferric sulfate is first hydrolyzed to ferric iron hydroxide, and then the iron hydroxide reacts with Na 3 AsO 4 in the solution to form a precipitate of FeAsO 4 .
- the chemical reaction equation is as follows (at normal temperature):
- the precipitated crystals are separated by a centrifuge to separate the mother liquor; the wet crystals after separating the mother liquor are dried to obtain a sodium sulfite product having a mass concentration of ⁇ 96%.
- Argon-containing industrial alkali slag crushing water immersing circulating beating system using B250 ⁇ L400 hammer crusher with circulating pump to spray water to eliminate dust coarse crushing, combined ⁇ 1.8 ⁇ L3.6m ball mill and spiral classifier combined with 15m 3 ⁇ 2 stirring tank Form a cyclic beating leaching system.
- the pressure filter is extracted (two sets of 60 m 2 box filter presses are alternately pressure-filtered) to obtain a leaching solution having a specific gravity of about 1.12, which contains about 9% of NaOH.
- a 15m 3 agitation tank to take the leachate from the filter press and use it as a mass concentration of Na 2 S (with a mass concentration of 0.5 g/L of Na 2 S in the leachate after addition) and p-phenylenediamine (The final concentration of the mass volume in the leachate after the addition was 0.08 g/L) was treated with a treating agent.
- a 40m 2 box filter press was set up, and the leaching solution containing arsenic leaching solution obtained by fine pressure filtration of the leaching solution treated with Na 2 S and p-phenylenediamine was sent to a 120 m 3 high storage tank for use.
- the absorption liquid containing NaHSO 3 was 3.5%, Na 2 SO 3 was 10.5%, Na 2 SO 4 was 0.4%, As +5 to 6.8g / L, As +3 to 1.2g / L, in Add the arsenic leaching lye solution to the arsenic agitation tank, completely neutralize NaHSO 3 and convert it to Na 2 SO 3 , then slowly replenish it until the pH reaches 11 and then add 200g/ to the arsenic tank. An aqueous solution of Fe 2 (SO 4 ) 3 having a concentration of L was immersed in 1.4 m 3 of arsenic. The liquid-solid separation of the 60m 2 filter press was set up.
- the sodium sulfite solution was 13.3m 3 , and the pump was sent to the 30m 3 high-level liquid storage tank for sampling and testing.
- the residual arsenic was 1.1PPm and Fe +3 ⁇ 100PPm.
- the sulphur-depleted sodium sulfite solution was continuously pumped from a 30 m 3 liquid storage tank to a 2 ton boiler, and concentrated and dehydrated by evaporation and concentration.
- the boiler was intermittently discharged to a volume of 2 m 3 vacuum-stirred crystallizer to deliver a concentrated concentrated hot liquid of a sodium sulfite solution having a concentration of 24%. The crystals are continuously accumulated and precipitated.
- the batch is discharged, and the mother liquid is separated by a ⁇ 600mm horizontal stainless steel automatic discharge centrifuge, and the wet crystal heat-flowing air dryer is dried to obtain a sodium sulfite content of more than 96%.
- Fe +3 ⁇ 0.001% qualified sodium sulfite product As ⁇ 1PPm, Fe +3 ⁇ 0.001% qualified sodium sulfite product.
- the specific yield varies with the amount of blast furnace flue gas and the concentration of SO 2 contained. In general, when the average flue gas volume is 50000 m 3 /h and the SO 2 5000 mg/m 3 is contained, 96% of the sodium sulfite product can be produced per day, which is about 12.3 tons/day.
- Example 2 The same equipment and process parameters as in Example 1 were used, but the leachate was pretreated without adding Na 2 S, ie, trace amounts of Pb(OH) 2 , Sb(OH) 3 and Zn(OH) 2 in the leachate were not performed. Precipitation; as a comparison, due to the change of an important process, the sodium sulfite produced in this example is catalytically oxidized to form Na 2 SO 4 , which reduces the Na 2 SO 3 content to 82.4%, and does not reach the industrial standard of 96%. At the content level, the product content decreased significantly.
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Abstract
Disclosed is a processing method for producing a sodium sulfite product by SO2 flue gas absorption and arsenic-removal purification using a leaching solution of an arsenic-containing industrial alkaline residue. The method comprises: crushing an arsenic-containing industrial alkaline residue, adding water, pulping, and filter pressing to obtain a leaching solution; adding sodium sulfide aqueous solution and p-phenylenediamine into the leaching solution, followed by filter pressing to obtain a clear arsenic-containing alkaline leaching solution for standby; pumping the clear solution into a spray desulfurization tower to absorb SO2, so as to reduce pH value of a resulting absorption solution to about 6.2-6.4, followed by adding the clear arsenic-containing alkaline leaching solution to adjust the pH value to about 10.5~11.5; adding a poly-ferric sulfate aqueous solution for arsenic precipitation and filter pressing so as to perform liquid-solid separation, followed by concentration and evaporation of the clear solution, and then crystallization to separate the mother solution, and finally drying, thereby obtaining a sodium sulfite product having a mass concentration greater than or equal to 96%.
Description
本发明涉及有色冶炼行业，特别涉及烟气脱硫及无机化工技术，具体涉及一种利用含砷工业碱渣水浸碱液，吸收冶炼烟气中SO
2脱砷净化，生产亚硫酸钠产品的方法。
The present invention relates to non-ferrous smelting industry, particularly to a technique of flue gas desulfurization inorganic chemicals, particularly relates to a method Flue Gas SO 2 removal arsenic purification, the production of products utilizing sodium sulfite Containing Industrial Alkali alkali flooding, absorption.
在有色冶炼行业，常有大量的烟气尘产生，被布袋收尘回收，因其含铅、锑等较高，同时含一定量的砷，一般用反射炉还原冶炼回收有价金属，为顺利造渣，加入较大量的纯碱，造高碱稀渣，烟尘中的砷大部分进入高碱稀渣中，放出炉外，铸模冷却后，俗称含砷工业碱渣。据不完全统计，目前全国含砷工业碱渣每年的产出量约有1～2万吨，因其含有1～8％的砷，是被环保部门严控的有毒固废物，但同时也是有价值的二次资源。In the non-ferrous smelting industry, there is often a large amount of smoke and dust generated, which is collected and collected by cloth bags. Because of its high content of lead and antimony, it also contains a certain amount of arsenic. It is generally used in the reverberatory furnace to reduce and smelt and recover valuable metals. The slag is formed, a relatively large amount of soda ash is added, and a high alkali slag is formed. Most of the arsenic in the soot enters the high alkali slag and is released outside the furnace. After the mold is cooled, it is commonly called arsenic industrial alkali slag. According to incomplete statistics, the annual output of arsenic-containing industrial alkali slag is about 10,000 to 20,000 tons. Because it contains 1 to 8% of arsenic, it is a toxic solid waste strictly controlled by the environmental protection department. The secondary resources of value.
在有色冶炼行业，鼓风炉、烟化炉等冶炼炉产出大量含SO
2浓度在500～15000mg/m
3的冶炼烟气。因含SO
2浓度较低，用其直接制酸困难。一般用喷淋脱硫塔脱硫。常用的方法是用石灰石粉作吸收介质，产出亚硫酸钙，用空气进一步氧化成硫酸钙，压滤液固分离后，得到大量石膏渣，因品位不高，没有消费市场，只好建渣场堆存，容易造成二次污染。
In the non-ferrous smelting industry, smelting furnaces such as blast furnaces and smelting furnaces produce a large amount of smelting flue gas containing SO 2 concentration of 500-15000 mg/m 3 . Due to the low concentration of SO 2 , it is difficult to directly use it for acid production. Desulfurization is generally carried out using a spray desulfurization tower. The commonly used method is to use limestone powder as the absorption medium, produce calcium sulfite, further oxidize to calcium sulfate with air, and press the filtrate to separate and obtain a large amount of gypsum slag. Because the grade is not high, there is no consumer market, so the slag yard pile is built. It is easy to cause secondary pollution.
中国公开专利申请CN101899574A提出了一种火法炼锑中综合回收砷碱渣和二氧化硫烟气的方法。提出了利用砷碱渣吸收烟气SO
2，并产出亚硫酸钠的思路。为以废治废的环保产业展现了良好的前景，但其方法有许多明显的技术缺陷。若按其说明书中的方法，根本无法产出质量稳定的亚硫酸钠产品，而工业化产出质量稳定的亚硫酸钠产品是衡量这一专利技术是否成熟、有无实用价值的关键所在。
Chinese public patent application CN101899574A proposes a method for comprehensively recovering arsenic alkali slag and sulfur dioxide flue gas in fire refining. The idea of using arsenic alkali slag to absorb flue gas SO 2 and produce sodium sulfite is proposed. It shows good prospects for the environmental protection industry that has been abolished, but its methods have many obvious technical defects. According to the method in the manual, it is impossible to produce a stable quality sodium sulfite product, and the industrially produced stable sodium sulfite product is the key to measuring whether the patented technology is mature and has practical value.
具体地看，CN101899574A中，于砷碱渣的浸出步骤，用2倍质量的水， 90～100℃搅拌浸出30～60分钟，复浸一次，过滤，在实验室条件下是可行的，但工业规模生产时，砷碱渣常有大块的料块会卡阻搅拌机，有时会造成机械事故；又因砷碱渣通常含有20～30％的可溶性Na
2O，同时含有0.5～1％的硫酸盐，若按液固比2：1来水溶砷碱渣，高温下是可行的，但在工业生产条件下，特别是在冬天生产时，环境温度低于10℃后，高浓度碱液中的少量Na
2SO
4会析出水合物结晶，严重堵塞管道及阀门，这样的液固比参数选择是不妥当的；于二氧化硫中和步骤，在浸出液中通入二氧化硫废气，20～50℃中和反应10～20小时，还原高价锑和高价砷，当溶液的pH值达到3～6时，停止通气，这样的终点pH选择存在严重问题。由实践知道，碱液吸收SO
2，产出Na
2SO
3，当体系pH值愈低时，则亚硫酸钠愈容易被氧化成Na
2SO
4，使产品中Na
2SO
3含量降低；于硫化脱砷步骤，在温度20～40℃滴加质量1.0～2.0倍的硫化剂水溶液，反应1～2小时，用硫酸调节pH6.0～7.0，静止2～6小时，过滤分离硫化砷渣和低砷亚硫酸钠溶液，产生的硫化氢气体用废砷碱水吸收后返回脱砷，这一步骤的缺点是引入较大量的硫酸调pH，使亚硫酸液中混入了硫酸钠，再次降低了亚硫酸钠产品的含量，同时硫化氢有毒气体的产生，有安全隐患；于深度除砷步骤，在低砷亚硫酸钠溶液中慢慢加入溶液中As含量摩尔比的硫酸铁，反应1小时，至pH6～9，静止4小时，过滤出含砷铁渣，再重复一次。此步骤沉砷终点pH选择有问题。因为由实践知道，硫酸铁沉砷的正确pH应大于10.5，这样溶于液体的硫酸铁才会水解，生成Fe(OH)
3，而水解生成的三价氢氧化铁才会与溶液中的Na
2AsO
4进行化学反应而生成砷酸铁沉淀，达到深度脱砷的目的。综前所述，CN101899574A提出以废治废的思路，在实验室条件下提出了技术工艺条件参数，但未从工业规模生产方面深入，特别是怎样稳定产出高含量的亚硫酸钠产品的研究，工作做得不够，无实用价值。
Specifically, in CN101899574A, in the leaching step of arsenic alkali slag, it is immersed for 30 to 60 minutes with 2 times of mass of water, 90-100 ° C, re-dip once, and filtered, which is feasible under laboratory conditions, but industrial In scale production, arsenic slag often has large blocks that can block the mixer, sometimes causing mechanical accidents; and because arsenic slag usually contains 20-30% soluble Na 2 O, and contains 0.5 to 1% sulfuric acid. Salt, if the liquid-solid ratio is 2:1 to dissolve the arsenic alkali slag, it is feasible at high temperature, but under industrial production conditions, especially in winter production, after the ambient temperature is lower than 10 °C, in the high concentration lye A small amount of Na 2 SO 4 will precipitate hydrate crystals, which will block pipes and valves seriously. Such liquid-solid ratio parameters are not appropriate. In the sulfur dioxide neutralization step, sulfur dioxide waste gas is introduced into the leachate, and the reaction is neutralized at 20-50 °C. 10 to 20 hours, high-priced strontium and high-priced arsenic are reduced. When the pH of the solution reaches 3 to 6, the ventilation is stopped, and such an end point pH selection has serious problems. It is known by practice that the lye absorbs SO 2 and produces Na 2 SO 3 . When the pH value of the system is lower, the more easily the sodium sulfite is oxidized to Na 2 SO 4 , the Na 2 SO 3 content in the product is lowered; In the arsenic step, an aqueous solution of a vulcanizing agent having a mass of 1.0 to 2.0 times is added dropwise at a temperature of 20 to 40 ° C, and the reaction is carried out for 1 to 2 hours, and the pH is adjusted to 6.0 to 7.0 with sulfuric acid, and the mixture is allowed to stand for 2 to 6 hours, and the arsenic sulfide and the low arsenic are separated by filtration. The sodium sulfite solution, the hydrogen sulfide gas generated is absorbed by the waste arsenic alkali water and returned to the arsenic removal. The disadvantage of this step is that a large amount of sulfuric acid is introduced to adjust the pH, and the sulfurous acid solution is mixed with sodium sulfate, thereby reducing the content of the sodium sulfite product again. At the same time, the generation of toxic gas of hydrogen sulfide has potential safety hazard; in the deep arsenic removal step, slowly add the iron sulfate of As content in the solution of low arsenic sodium sulfite solution, react for 1 hour, to pH 6-9, and stand still for 4 hours. Filter out the arsenic-containing iron slag and repeat it again. There is a problem with the pH selection of the arsenic end point in this step. Because it is known by practice that the correct pH of iron sulphate arsenic should be greater than 10.5, so that the iron sulphate dissolved in liquid will be hydrolyzed to form Fe(OH) 3 , and the ferric trivalent iron hydroxide formed by hydrolysis will react with Na in solution. 2 AsO 4 chemically reacts to form iron arsenate precipitate, which achieves the purpose of deep arsenic removal. As mentioned above, CN101899574A proposes the idea of waste treatment and the technical process parameters under laboratory conditions, but it has not been in-depth in terms of industrial scale production, especially how to stably produce high-content sodium sulfite products. Not done enough, no practical value.
发明内容Summary of the invention
本发明的目的是，针对上述技术问题的不足，特别是CN101899574A的技术缺点，提出一种利用含砷工业碱渣水浸碱液吸收SO
2烟气脱砷净化生产亚硫酸钠的工艺方法。
The object of the present invention is to solve the above-mentioned technical problems, in particular, the technical disadvantage of CN101899574A, and propose a process for purifying arsenic by using arsenic industrial alkali slag immersion lye to absorb SO 2 flue gas to remove arsenic.
为达上述目的，本发明所采用的技术方案是：一种利用含砷工业碱渣水浸碱液吸收SO
2烟气、脱砷净化生产亚硫酸钠的工艺方法，该方法步骤如下：
To achieve the above object, the technical solution of the present invention is used: Alkali flooding Containing Industrial utilizing alkali flue gas SO 2 absorbent, the production process for purifying arsenic removal of sodium sulfite, the method steps:
(1)将含砷工业碱渣破碎后加入为含砷工业碱渣重量3-5倍的水，混匀，常温循环打浆，以浸出可溶性的碱和砷酸盐，至打浆水含悬浮渣总比重为1.25-1.4；压滤分离浸出渣和浸出液；(1) After crushing the arsenic-containing industrial alkali slag, adding 3-5 times of the weight of the arsenic-containing industrial alkali slag, mixing, and pulverizing at room temperature to leach the soluble alkali and arsenate, to the beating water containing the suspended slag total The specific gravity is 1.25-1.4; the leaching residue and the leachate are separated by pressure filtration;
浸出渣返火法冶炼补充配料，回收有价值金属元素。浸出液通常含NaOH约6～10％、As 1～15g/L，储存备用；The leaching slag is smelted to replenish the ingredients and recover valuable metal elements. The leachate usually contains about 6-10% NaOH and As 1-15g/L, and is stored for use;
(2)于浸出液中加入质量体积浓度为50～100g/L的硫化钠水溶液，使浸出液中的Na
2S的质量体积浓度为0.05～2g/L，以将浸出液中溶解的微量Pb(OH)
2、Sb
2(OH)
3、Zn(OH)
2硫化沉淀，化学反应方程式为：
(2) adding a sodium sulfide aqueous solution having a mass volume concentration of 50 to 100 g/L to the leachate, so that the mass concentration of Na 2 S in the leachate is 0.05 to 2 g/L to dissolve the trace amount of Pb(OH) in the leachate. 2 , Sb 2 (OH) 3 , Zn (OH) 2 sulfide precipitation, the chemical reaction equation is:
Pb(OH)
2+Na
2S＝PbS↓+2NaOH
Pb(OH) 2 +Na 2 S=PbS↓+2NaOH
2Sb(OH)
3+3Na
2S＝Sb
2S
3↓+6NaOH
2Sb(OH) 3 +3Na 2 S=Sb 2 S 3 ↓+6NaOH
Zn(OH)
2+Na
2S＝ZnS↓+2NaOH
Zn(OH) 2 +Na 2 S=ZnS↓+2NaOH
因为本发明人从实践中发现：脱硫吸收液中，既使有微量的有色金属氢氧化物存在也会对生成的Na
2SO
3氧化成Na
2SO
4有强烈的催化生成作用，故此步骤对提高亚硫酸钠产品质量有重大影响；
Because the inventors have found from practice that in the desulfurization absorption liquid, even if a trace amount of non-ferrous metal hydroxide is present, it will have a strong catalytic formation effect on the oxidation of Na 2 SO 3 to Na 2 SO 4 , so this step is There is a significant impact on improving the quality of sodium sulfite products;
同时，于浸出液中加入对苯二胺，至浸出液中对苯二胺的质量体积终浓度为0.01～0.1g/L，用于阻止氧化作用，利于提高亚硫酸钠产品的含量百分比；At the same time, p-phenylenediamine is added to the leachate, and the final concentration of p-phenylenediamine in the leachate is 0.01-0.1 g/L, which is used for preventing oxidation and is advantageous for increasing the percentage of sodium sulfite product;
(3)将上述经硫化钠水溶液和对苯二胺处理的浸出液搅拌后压滤，含砷浸出碱液清液备用，微量滤渣返回配料；(3) stirring the above-mentioned sodium sulphate aqueous solution and p-phenylenediamine-treated leachate, and then press-filtering, arsenic-containing leaching solution of the alkali solution, and returning the micro-filter residue to the ingredients;
(4)将含砷浸出碱液清液泵入喷淋脱硫塔，吸收冶炼烟气中的SO
2， 控制吸收液温度小于55℃，当吸收液pH值降至6.2～6.4时，将吸收液泵出储存，备用；同时向喷淋脱硫塔补充新的备用含砷浸出碱液清液，使喷淋脱硫塔系统继续运行；
(4) pumping the arsenic-containing leaching alkali liquid into the spray desulfurization tower, absorbing the SO 2 in the smelting flue gas, controlling the temperature of the absorption liquid to be less than 55 ° C, and when the pH value of the absorption liquid falls to 6.2-6.4, the absorption liquid Pumping out the storage and standby; at the same time, adding a new standby arsenic leaching lye solution to the spray desulfurization tower to continue the operation of the spray desulfurization tower system;
(5)于吸收液中先加入步骤(3)所得的含砷浸出碱液清液，搅拌调整pH值为10.5～11.5，以使在喷淋脱硫塔吸收SO
2过程中过量产出的NaHSO
4全部转成Na
2SO
3，其化学反应方程式为：
(5) First adding the arsenic-containing leaching alkali solution obtained in the step (3) to the absorption liquid, stirring and adjusting the pH value of 10.5 to 11.5, so as to excessively produce NaHSO 4 during the process of absorbing SO 2 in the spray desulfurization tower. All converted to Na 2 SO 3 , the chemical reaction equation is:
NaHSO
3+NaOH＝Na
2SO
3+H
2O，
NaHSO 3 + NaOH = Na 2 SO 3 + H 2 O,
利用浸出碱液回调pH值，节省了较贵的片碱，有利于节约生产成本；The use of leaching lye to adjust the pH value saves more expensive caustic soda, which is conducive to saving production costs;
再加入质量体积浓度为50～200g/L的聚合硫酸铁水溶液进行沉砷，加入量按吸收液体系中Fe:As的摩尔比控制为3～6；新带入的As，由此沉砷过程一同沉淀脱去。此时聚合硫酸铁水溶液先水解成三价氢氧化铁，接着氢氧化铁与溶液中的Na
3AsO
4，反应生成FeAsO
4沉淀，其化学反应方程式如下(在常温下进行)：
Further, a concentrated aqueous solution of ferric sulfate having a mass concentration of 50 to 200 g/L is added to carry out arsenic deposition, and the amount of addition is controlled according to the molar ratio of Fe:As in the absorbing liquid system to 3-6; newly introduced As, thereby arsenic precipitation process The precipitate is removed together. At this time, the aqueous solution of the ferric sulfate is first hydrolyzed to ferric iron hydroxide, and then the iron hydroxide reacts with Na 3 AsO 4 in the solution to form a precipitate of FeAsO 4 . The chemical reaction equation is as follows (at normal temperature):
Fe
2(SO
4)
3+6NaOH＝2Fe(OH)
3+3Na
2SO
4
Fe 2 (SO 4 ) 3 +6 NaOH = 2Fe(OH) 3 +3Na 2 SO 4
Fe(OH)
3+Na
3AsO
4＝FeAsO
4↓+3NaOH
Fe(OH) 3 +Na 3 AsO 4 =FeAsO 4 ↓+3NaOH
Fe(OH)
3+Na
3AsO
3＝FeAsO
3↓+3NaOH
Fe(OH) 3 +Na 3 AsO 3 =FeAsO 3 ↓+3NaOH
由实践测知：含砷工业碱渣中的砷，占比超过85％的都是5价砷，少量是3价砷，故沉砷包括5价砷和3价砷的两个反应式，生成的砷酸铁被溶液中过量的三价氢氧化铁呈絮状无机大分子状的沉淀，吸附、快速沉降，可使体系中的As净化到1PPM级别，达到环保国家标准要求；It is known from practice that arsenic in arsenic industrial alkali slag accounts for more than 85% of all arsenic, and a small amount is trivalent arsenic. Therefore, arsenic includes two reaction formulas of pentavalent arsenic and trivalent arsenic. The iron arsenate is precipitated by flocculation of inorganic macromolecules in excess of trivalent iron hydroxide in the solution, and adsorbed and rapidly settled, so that the As in the system can be purified to the level of 1 PPM, meeting the requirements of national environmental protection standards;
(6)将沉砷操作后的溶液压滤进行液固分离，取清液，浓缩蒸发至质量浓度达到23～24％时泵入真空搅拌结晶釜中进一步浓缩析出结晶；(6) The solution after the arsenic operation is subjected to liquid-solid separation by filtration, and the clear liquid is concentrated and evaporated to a mass concentration of 23 to 24%, and pumped into a vacuum stirring crystallizer to further concentrate and precipitate crystals;
压滤后所得滤渣主要是FeAsO
4·4Fe(OH)
3·n·MeS，含铁高达40％以上，可返回冶炼生产配料中的当作配铁原料，而其中的砷可进一步富集进入冶炼烟尘中，进一步无害化处理回收。
The filter residue obtained after pressure filtration is mainly FeAsO 4 ·4Fe(OH) 3 ·n·MeS, containing up to 40% iron, which can be returned to the smelting production ingredients as iron raw materials, and the arsenic can be further enriched into smelting. In the dust, it is further treated in a harmless manner.
(7)将析出的结晶用离心机分离母液；将分离母液后的湿晶烘干，即 得质量浓度≥96％的亚硫酸钠产品。(7) The precipitated crystals are separated by a centrifuge to separate the mother liquor; the wet crystals after separating the mother liquor are dried to obtain a sodium sulfite product having a mass concentration of ≥ 96%.
本发明所述的含砷工业碱渣，一般典型成份是As 1～8％、Na
2O 20～35％、Pb 1～3％、Sb 2～8％、Sn 0.5～3％、S 1～3％，是国家环保部门严控的有毒固体废物。本方法发扬以废治废的精神，在中国专利申请CN101899574A的基础上，从工业化稳定生产，尽可能提高亚硫酸钠产品含量入手，优化技术工艺和参数选择，取得了明显的技术进步，使得用含砷工业碱渣水浸碱液吸收烟气中的SO
2脱砷后生产亚硫酸钠工艺方法真正成为可工业化生产的实用成熟技术。按全国每年2万吨碱渣产出量计，可增创经济效益约3500万元，可脱砷无害化处理总砷量As 6％×20000＝1200吨/年，脱硫4250吨/年，产生巨大的环保效益。
The arsenic-containing industrial alkali residue according to the present invention generally has As 1 to 8%, Na 2 O 20 to 35%, Pb 1 to 3%, Sb 2 to 8%, Sn 0.5 to 3%, and S 1 to 3% is a toxic solid waste strictly controlled by the national environmental protection department. This method carries forward the spirit of waste treatment and waste. Based on the Chinese patent application CN101899574A, starting from industrialized stable production, increasing the content of sodium sulfite as much as possible, optimizing the technical process and parameter selection, and achieving obvious technological progress, making use of arsenic The industrial alkali slag water immersion lye absorbs SO 2 in flue gas to produce arsenite. The process of producing sodium sulfite has become a practical and mature technology for industrial production. According to the national output of 20,000 tons of alkali slag per year, the economic benefit can be increased by about 35 million yuan. The total arsenic content of arsenic detoxification treatment is As 6% × 20000 = 1200 tons / year, and the desulfurization is 4,250 tons / year. Produce huge environmental benefits.
图1是本发明的亚硫酸钠制备工艺流程图。BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a flow chart showing the preparation process of sodium sulfite of the present invention
结合参见图1，本发明为利用含砷工业碱渣水浸碱液吸收SO
2烟气脱砷净化生产亚硫酸钠的工艺方法，该方法步骤如下：
Referring to FIG. 1 , the present invention is a process for producing sodium sulfite by using arsenic industrial alkali residue immersion lye to absorb SO 2 flue gas to remove arsenic and purify arsenic. The method steps are as follows:
(1)将含砷工业碱渣破碎后加入为含砷工业碱渣重量3-5倍的水，混匀，常温循环打浆，以浸出可溶性的碱和砷酸盐，至打浆水含悬浮渣总比重为1.25-1.4；压滤分离浸出渣和浸出液；浸出渣返火法冶炼补充配料，回收有价值金属元素。浸出液通常含NaOH约6～10％、As 1～15g/L，储存备用；(1) After crushing the arsenic-containing industrial alkali slag, adding 3-5 times of the weight of the arsenic-containing industrial alkali slag, mixing, and pulverizing at room temperature to leach the soluble alkali and arsenate, to the beating water containing the suspended slag total The specific gravity is 1.25-1.4; the leaching residue and the leachate are separated by pressure filtration; the leaching slag is returned to the smelting method to replenish the supplementary ingredients, and the valuable metal elements are recovered. The leachate usually contains about 6-10% NaOH and As 1-15g/L, and is stored for use;
(2)于浸出液中加入质量体积浓度为50～100g/L的硫化钠水溶液，使浸出液中的Na
2S的质量体积浓度为0.05～2g/L，以将浸出液中溶解的微量Pb(OH)
2、Sb
2(OH)
3、Zn(OH)
2硫化沉淀，化学反应方程式为：
(2) adding a sodium sulfide aqueous solution having a mass volume concentration of 50 to 100 g/L to the leachate, so that the mass concentration of Na 2 S in the leachate is 0.05 to 2 g/L to dissolve the trace amount of Pb(OH) in the leachate. 2 , Sb 2 (OH) 3 , Zn (OH) 2 sulfide precipitation, the chemical reaction equation is:
Pb(OH)
2+Na
2S＝PbS↓+2NaOH
Pb(OH) 2 +Na 2 S=PbS↓+2NaOH
2Sb(OH)
3+3Na
2S＝Sb
2S
3↓+6NaOH
2Sb(OH) 3 +3Na 2 S=Sb 2 S 3 ↓+6NaOH
Zn(OH)
2+Na
2S＝ZnS↓+2NaOH
Zn(OH) 2 +Na 2 S=ZnS↓+2NaOH
同时，于浸出液中加入对苯二胺，至浸出液中对苯二胺的质量体积终浓度为0.01～0.1g/L，用于阻止氧化作用，利于提高亚硫酸钠产品的含量百分比；At the same time, p-phenylenediamine is added to the leachate, and the final concentration of p-phenylenediamine in the leachate is 0.01-0.1 g/L, which is used for preventing oxidation and is advantageous for increasing the percentage of sodium sulfite product;
(3)将上述经硫化钠水溶液和对苯二胺处理的浸出液搅拌后压滤，微量滤渣返回配料，含砷浸出碱液清液送储槽备用；(3) stirring the above-mentioned sodium sulphate aqueous solution and p-phenylenediamine-treated leachate, and then press-filtering, and the micro-filter residue is returned to the ingredients, and the arsenic-containing leaching solution is sent to the storage tank for use;
(4)将含砷浸出碱液清液泵入喷淋脱硫塔，吸收冶炼烟气中的SO
2，控制吸收液温度小于55℃，当吸收液pH值降至6.2～6.4时，将吸收液泵送至脱硫液储液槽储存，备用；同时向喷淋脱硫塔补充新的备用含砷浸出碱液清液，使喷淋脱硫塔系统继续运行；
(4) pumping the arsenic-containing leaching alkali liquid into the spray desulfurization tower, absorbing the SO 2 in the smelting flue gas, controlling the temperature of the absorbing liquid to be less than 55 ° C, and when the pH value of the absorbing liquid drops to 6.2-6.4, the absorbing liquid Pumping to the desulfurization liquid storage tank for storage and standby; at the same time, adding a new standby arsenic-containing leaching alkali liquid to the spray desulfurization tower to continue the operation of the spray desulfurization tower system;
(5)将吸收液从脱硫液储液槽泵送至沉砷搅拌槽，于吸收液中先加入步骤(3)所得的含砷浸出碱液清液，搅拌调整pH值为10.5～11.5，以使在喷淋脱硫塔吸收SO
2过程中过量产出的NaHSO
4全部转成Na
2SO
3，其化学反应方程式为：NaHSO
3+NaOH＝Na
2SO
3+H
2O，
(5) pumping the absorption liquid from the desulfurization liquid storage tank to the arsenic agitation tank, and first adding the arsenic-containing leaching alkali liquid solution obtained in the step (3) to the absorption liquid, stirring and adjusting the pH value to be 10.5 to 11.5, All of the NaHSO 4 produced in the process of absorbing SO 2 in the spray desulfurization tower is converted into Na 2 SO 3 , and the chemical reaction equation is: NaHSO 3 + NaOH = Na 2 SO 3 + H 2 O,
再加入质量体积浓度为50～200g/L的聚合硫酸铁水溶液进行沉砷，加入量按吸收液体系中Fe:As的摩尔比控制为3～6；新带入的As，由此沉砷过程一同沉淀脱去。此时聚合硫酸铁水溶液先水解成三价氢氧化铁，接着氢氧化铁与溶液中的Na
3AsO
4，反应生成FeAsO
4沉淀，其化学反应方程式如下(在常温下进行)：
Further, a concentrated aqueous solution of ferric sulfate having a mass concentration of 50 to 200 g/L is added to carry out arsenic deposition, and the amount of addition is controlled according to the molar ratio of Fe:As in the absorbing liquid system to 3-6; newly introduced As, thereby arsenic precipitation process The precipitate is removed together. At this time, the aqueous solution of the ferric sulfate is first hydrolyzed to ferric iron hydroxide, and then the iron hydroxide reacts with Na 3 AsO 4 in the solution to form a precipitate of FeAsO 4 . The chemical reaction equation is as follows (at normal temperature):
Fe
2(SO
4)
3+6NaOH＝2Fe(OH)
3+3Na
2SO
4
Fe 2 (SO 4 ) 3 +6 NaOH = 2Fe(OH) 3 +3Na 2 SO 4
Fe(OH)
3+Na
3AsO
4＝FeAsO
4↓+3NaOH
Fe(OH) 3 +Na 3 AsO 4 =FeAsO 4 ↓+3NaOH
Fe(OH)
3+Na
3AsO
3＝FeAsO
3↓+3NaOH
Fe(OH) 3 +Na 3 AsO 3 =FeAsO 3 ↓+3NaOH
(6)将沉砷搅拌槽中沉砷操作后的溶液泵入压滤机进行液固分离，取清液，浓缩蒸发至质量浓度达到23～24％时泵入真空搅拌结晶釜中进一步浓缩析出结晶；压滤后所得滤渣返回冶炼生产配料中的当作配铁原料，而其中的砷可进一步富集进入冶炼烟尘中，进一步无害化处理回收。(6) pumping the solution after the arsenic operation in the arsenic agitation tank into the filter press for liquid-solid separation, taking the clear liquid, and concentrating and evaporating until the mass concentration reaches 23-24%, pumping into the vacuum stirring crystallizer to further concentrate and precipitate. Crystallization; the filter residue obtained after pressure filtration is returned to the smelting production batch as a raw material for iron distribution, and the arsenic therein can be further enriched into the smelting dust and further harmlessly treated and recovered.
(7)将析出的结晶用离心机分离母液；将分离母液后的湿晶烘干，即 得质量浓度≥96％的亚硫酸钠产品。(7) The precipitated crystals are separated by a centrifuge to separate the mother liquor; the wet crystals after separating the mother liquor are dried to obtain a sodium sulfite product having a mass concentration of ≥ 96%.
实施例1Example 1
冶炼鼓风炉炉床面积5.6m
2，烟气排量50000m
3/h，烟气中的SO
2浓度5000mg/m
3，喷淋脱硫塔直径2.5m、单级塔高10m、4层喷淋布置，单级脱硫效率约70％，采用3级单塔组合、总脱硫效率为97.3％，排气含SO
2：5000×2.7％＝135mg/m
3，小于国家二类厂域允许排放200mg/m
3标准。含砷工业碱渣破碎水浸循环打浆系统，选用B250×L400锤式破碎机用循环泵喷水消粉尘粗破碎，组合φ1.8×L3.6m球磨机和螺旋分级机联合15m
3×2搅拌槽，组成循环打浆浸出系统。当打浆水含悬浮渣总比重到1.35时，抽出压滤(选用2台60m
2箱式压滤机交替压滤)，得到比重约为1.12的浸出液，其中含NaOH约9％。设置一个15m
3搅拌槽，承接压滤机来的浸出液并用作加100g/L质量体积浓度的Na
2S(加入后浸出液中的Na
2S质量体积浓度为0.5g/L)和对苯二胺(加入后浸出液中质量体积终浓度为0.08g/L)处理剂处理。设置一台40m
2箱式压滤机，将经Na
2S和对苯二胺处理后的浸出液精细压滤后所得含砷浸出碱液清液泵送入120m
3高位储槽备用。将含砷浸出碱液清液泵入喷淋脱硫塔，当三级喷淋脱硫塔末级循环池的吸收液pH值降至6.2～6.4时，抽出10m
3吸收液泵送至15m
3容积的沉砷搅拌槽。取样化验吸收液，吸收液中含NaHSO
3为3.5％、Na
2SO
3为10.5％、Na
2SO
4为0.4％、As
+5为6.8g/L、As
+3为1.2g/L，于沉砷搅拌槽中加入备用含砷浸出碱液清液，完全中和NaHSO
3转化成Na
2SO
3后，再缓慢补充，至pH值到11时停止，再向沉砷搅拌槽中加入200g/L浓度的Fe
2(SO
4)
3水溶液1.4m
3沉砷。设置60m
2压滤机液固分离，脱砷净化后得稀亚硫酸钠溶液13.3m
3，泵送入30m
3高位储液槽存，取样化验，其中残留砷为1.1PPm，Fe
+3＜100PPm。从30m
3储液槽内向2吨锅炉连续泵入脱砷净化后的稀亚硫酸钠溶液，蒸发浓缩脱水，锅炉间断向容积2m
3真空搅拌结晶釜放送浓度24％的亚硫酸钠溶液的一次浓缩热液，不断积累、析出结晶，当到析晶到半釜容积时， 批次放出，用φ600mm卧式不锈钢自动卸料离心机分离母液，湿晶送热气流烘干机烘干，得到亚硫酸钠含量大于96％的、As＜1PPm，Fe
+3＜0.001％合格亚硫酸钠产品。具体产量随鼓风炉烟气量及含SO
2浓度变化而不同。一般情况下，当平均烟气量50000m
3/h，含SO
2 5000mg/m
3时，每天能产96％的亚硫酸钠产品约12.3吨/天。
Smelting blast furnace hearth area 5.6m 2 , flue gas displacement 50000m 3 /h, SO 2 concentration in flue gas 5000mg/m 3 , spray desulfurization tower diameter 2.5m, single-stage tower height 10m, 4 layer spray arrangement, The single-stage desulfurization efficiency is about 70%. The 3-stage single tower combination is used, the total desulfurization efficiency is 97.3%, and the exhaust gas contains SO 2 : 5000×2.7%=135mg/m 3 , which is less than 200mg/m 3 of the national second-class plant. standard. Argon-containing industrial alkali slag crushing water immersing circulating beating system, using B250×L400 hammer crusher with circulating pump to spray water to eliminate dust coarse crushing, combined φ1.8×L3.6m ball mill and spiral classifier combined with 15m 3 ×2 stirring tank Form a cyclic beating leaching system. When the total weight of the slag containing the slag is 1.35, the pressure filter is extracted (two sets of 60 m 2 box filter presses are alternately pressure-filtered) to obtain a leaching solution having a specific gravity of about 1.12, which contains about 9% of NaOH. Set a 15m 3 agitation tank to take the leachate from the filter press and use it as a mass concentration of Na 2 S (with a mass concentration of 0.5 g/L of Na 2 S in the leachate after addition) and p-phenylenediamine (The final concentration of the mass volume in the leachate after the addition was 0.08 g/L) was treated with a treating agent. A 40m 2 box filter press was set up, and the leaching solution containing arsenic leaching solution obtained by fine pressure filtration of the leaching solution treated with Na 2 S and p-phenylenediamine was sent to a 120 m 3 high storage tank for use. Pumping the arsenic-containing leaching solution to the spray desulfurization tower, when the pH value of the absorption liquid in the final stage of the three-stage spray desulfurization tower is reduced to 6.2-6.4, pumping 10m 3 of the absorption liquid to the volume of 15m 3 Arsenic stirring tank. Absorbing liquid test sample, the absorption liquid containing NaHSO 3 was 3.5%, Na 2 SO 3 was 10.5%, Na 2 SO 4 was 0.4%, As +5 to 6.8g / L, As +3 to 1.2g / L, in Add the arsenic leaching lye solution to the arsenic agitation tank, completely neutralize NaHSO 3 and convert it to Na 2 SO 3 , then slowly replenish it until the pH reaches 11 and then add 200g/ to the arsenic tank. An aqueous solution of Fe 2 (SO 4 ) 3 having a concentration of L was immersed in 1.4 m 3 of arsenic. The liquid-solid separation of the 60m 2 filter press was set up. After removing the arsenic, the sodium sulfite solution was 13.3m 3 , and the pump was sent to the 30m 3 high-level liquid storage tank for sampling and testing. The residual arsenic was 1.1PPm and Fe +3 <100PPm. The sulphur-depleted sodium sulfite solution was continuously pumped from a 30 m 3 liquid storage tank to a 2 ton boiler, and concentrated and dehydrated by evaporation and concentration. The boiler was intermittently discharged to a volume of 2 m 3 vacuum-stirred crystallizer to deliver a concentrated concentrated hot liquid of a sodium sulfite solution having a concentration of 24%. The crystals are continuously accumulated and precipitated. When the crystallization is carried out to the volume of the semi-tank, the batch is discharged, and the mother liquid is separated by a φ600mm horizontal stainless steel automatic discharge centrifuge, and the wet crystal heat-flowing air dryer is dried to obtain a sodium sulfite content of more than 96%. As <1PPm, Fe +3 <0.001% qualified sodium sulfite product. The specific yield varies with the amount of blast furnace flue gas and the concentration of SO 2 contained. In general, when the average flue gas volume is 50000 m 3 /h and the SO 2 5000 mg/m 3 is contained, 96% of the sodium sulfite product can be produced per day, which is about 12.3 tons/day.
对比实施例Comparative example
采用与实施例1全部相同的设备及工艺参数，但未加入Na
2S对浸出液进行预先处理，即未对浸出液中的微量Pb(OH)
2、Sb(OH)
3和Zn(OH)
2进行沉淀；作为对比，由于改变了一个重要工序，使得本实施例产出的亚硫酸钠被其催化氧化生成Na
2SO
4增多，使Na
2SO
3含量降低到82.4％，未达到工业级标准96％的含量级别，产品含量明显下降。
The same equipment and process parameters as in Example 1 were used, but the leachate was pretreated without adding Na 2 S, ie, trace amounts of Pb(OH) 2 , Sb(OH) 3 and Zn(OH) 2 in the leachate were not performed. Precipitation; as a comparison, due to the change of an important process, the sodium sulfite produced in this example is catalytically oxidized to form Na 2 SO 4 , which reduces the Na 2 SO 3 content to 82.4%, and does not reach the industrial standard of 96%. At the content level, the product content decreased significantly.
Claims (3)
- 一种利用含砷工业碱渣水浸碱液吸收SO 2烟气、脱砷净化生产亚硫酸钠产品的工艺方法，其特征在于，该方法步骤如下： The invention relates to a process for absorbing arsenic by using an arsenic industrial alkali slag immersion lye to absorb SO 2 flue gas and arsenic removal to produce sodium sulfite product, wherein the method steps are as follows:(1)将含砷工业碱渣破碎后加入为含砷工业碱渣重量3-5倍的水，混匀，常温循环打浆，以浸出可溶性的碱和砷酸盐，至打浆水含悬浮渣总比重为1.25～1.4；压滤分离浸出渣和浸出液，取浸出液备用；(1) After crushing the arsenic-containing industrial alkali slag, adding 3-5 times of the weight of the arsenic-containing industrial alkali slag, mixing, and pulverizing at room temperature to leach the soluble alkali and arsenate, to the beating water containing the suspended slag total The specific gravity is 1.25 to 1.4; the leaching residue and the leachate are separated by pressure filtration, and the leaching solution is taken up;(2)于浸出液中加入质量体积浓度为50～100g/L的硫化钠水溶液，使浸出液中的Na 2S的质量体积浓度为0.05～2g/L，以将浸出液中溶解的微量Pb(OH) 2、Sb 2(OH) 3、Zn(OH) 2硫化沉淀；同时，于浸出液中加入对苯二胺，至浸出液中对苯二胺的质量体积终浓度为0.01～0.1g/L； (2) adding a sodium sulfide aqueous solution having a mass volume concentration of 50 to 100 g/L to the leachate, so that the mass concentration of Na 2 S in the leachate is 0.05 to 2 g/L to dissolve the trace amount of Pb(OH) in the leachate. 2 , Sb 2 (OH) 3 , Zn (OH) 2 sulfide precipitation; at the same time, adding p-phenylenediamine to the leachate, the final concentration of p-phenylenediamine in the leachate is 0.01 ~ 0.1g / L;(3)将上述经硫化钠水溶液和对苯二胺处理的浸出液搅拌后压滤，取含砷浸出碱液清液，备用；(3) stirring the above-mentioned sodium sulphate aqueous solution and p-phenylenediamine-treated leachate, and then press-filtering, taking arsenic-containing leaching alkali liquid clear solution;(4)将含砷浸出碱液清液泵入喷淋脱硫塔，吸收冶炼烟气中的SO 2，控制吸收液温度小于55℃，当吸收液pH值降至6.2～6.4时，将吸收液泵出储存，备用；同时向喷淋脱硫塔补充新的备用含砷浸出碱液清液，使喷淋脱硫塔系统继续运行； (4) pumping the arsenic-containing leaching alkali liquid into the spray desulfurization tower, absorbing the SO 2 in the smelting flue gas, controlling the temperature of the absorbing liquid to be less than 55 ° C, and when the pH value of the absorbing liquid drops to 6.2-6.4, the absorbing liquid Pumping out the storage and standby; at the same time, adding a new standby arsenic leaching lye solution to the spray desulfurization tower to continue the operation of the spray desulfurization tower system;(5)于吸收液中先加入步骤(3)所得的含砷浸出碱液清液，搅拌调整pH值为10.5～11.5，以使在喷淋脱硫塔吸收SO 2过程中过量产出的NaHSO 4全部转成Na 2SO 3；再加入质量体积浓度为50～200g/L的聚合硫酸铁水溶液进行沉砷，加入量按吸收液体系中Fe:As的摩尔比控制为3～6； (5) First adding the arsenic-containing leaching alkali solution obtained in the step (3) to the absorption liquid, stirring and adjusting the pH value of 10.5 to 11.5, so as to excessively produce NaHSO 4 during the process of absorbing SO 2 in the spray desulfurization tower. All converted to Na 2 SO 3 ; further added a mass volume concentration of 50 ~ 200g / L of aqueous solution of ferric sulfate for arsenic, the amount of addition according to the molar ratio of Fe: As in the absorption system is controlled to 3 ~ 6;(6)将沉砷操作后的溶液压滤进行液固分离，取清液，浓缩蒸发至质量浓度达到23～24％时泵入真空搅拌结晶釜中进一步浓缩析出结晶；(6) The solution after the arsenic operation is subjected to liquid-solid separation by filtration, and the clear liquid is concentrated and evaporated to a mass concentration of 23 to 24%, and pumped into a vacuum stirring crystallizer to further concentrate and precipitate crystals;(7)将析出的结晶用离心机分离母液；将分离母液后的湿晶烘干，即得质量浓度≥96％的亚硫酸钠。(7) Separating the precipitated crystals with a centrifuge to separate the mother liquor; drying the wet crystals after separating the mother liquor to obtain sodium sulfite having a mass concentration of ≥96%.
- 如权利要求1所述的利用含砷工业碱渣水浸碱液吸收SO 2烟气、脱 砷净化生产亚硫酸钠产品的工艺方法，其特征在于，所述步骤(1)中压滤分离出的浸出渣返火法冶炼补充配料，回收有价值金属元素。 The process for producing a sodium sulfite product by using an arsenic-containing industrial alkali residue aqueous immersion alkali solution to absorb SO 2 flue gas and arsenic removal to produce a sodium sulfite product according to claim 1, wherein the leaching is separated by pressure filtration in the step (1) The slag returning method smelts the supplementary ingredients and recovers valuable metal elements.
- 如权利要求1所述的利用含砷工业碱渣水浸碱液吸收SO 2烟气、脱砷净化生产亚硫酸钠产品的工艺方法，其特征在于，所述步骤(6)中压滤分离出的滤渣返回冶炼生产配料中当作配铁原料。 The process for producing a sodium sulfite product by using an arsenic-containing industrial alkali residue aqueous immersion alkali solution to absorb SO 2 flue gas and arsenic removal to produce a sodium sulfite product according to claim 1, wherein the filter residue separated by pressure filtration in the step (6) is prepared. Return to the smelting production ingredients as a raw material for iron.
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