WO2014194790A1 - Method for extracting two secondary salts from desulfurized salt-containing waste liquid of coke oven gas - Google Patents

Method for extracting two secondary salts from desulfurized salt-containing waste liquid of coke oven gas Download PDF

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WO2014194790A1
WO2014194790A1 PCT/CN2014/078860 CN2014078860W WO2014194790A1 WO 2014194790 A1 WO2014194790 A1 WO 2014194790A1 CN 2014078860 W CN2014078860 W CN 2014078860W WO 2014194790 A1 WO2014194790 A1 WO 2014194790A1
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filtrate
ammonium
concentration
salt
ethanol
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PCT/CN2014/078860
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Chinese (zh)
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陈宏�
闫鹏
籍文武
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枣庄德信环保技术有限公司
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01CAMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00Ammonia; Compounds thereof
    • C01C1/24Sulfates of ammonium
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00Sulfur; Compounds thereof
    • C01B17/64Thiosulfates; Dithionites; Polythionates
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01CAMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C3/00Cyanogen; Compounds thereof
    • C01C3/20Thiocyanic acid; Salts thereof

Abstract

A method for extracting two secondary salts from desulfurized salt-containing waste liquid of coke oven gas. Waste liquid treatment and secondary salt extraction techniques comprise decoloring and decontaminating, decompressing and concentrating the salt-containing filtrate, separating ammonium thiocyanate, concentrating and crystallizing the ammonium thiocyanate ethanol filtrate, drying the ammonium thiocyanate product, separating ammonium sulfate, concentrating and crystallizing the ammonium thiosulfate filtrate, and drying the ammonium thiosulfate product. The invention completely treats desulfurized waste liquid, has high product recycling rate, and produces no mixed salt. The waste water discharge contains no secondary pollution. The technique is clean and environmentally friendly. The invention also has substantial advantages such as high adaptability, scalability, and resource utility rate.

Description

说 明 书  Description
一种从焦炉煤气脱硫含盐废液中提取两种副盐的方法 技术领域  Method for extracting two kinds of secondary salts from coke oven gas desulfurization and salty waste liquid
本发明属于焦化行业废物处理技术领域。 涉及一种焦炉煤气脱硫废液的处理方法, 同时 还涉及一种从焦化厂 HPF法或 PDS法脱硫生产过程中产生的脱硫废液中分别提取硫代硫酸铵 和硫氰酸铵的方法。  The invention belongs to the technical field of waste treatment in the coking industry. The invention relates to a method for treating a coke oven gas desulfurization waste liquid, and relates to a method for separately extracting ammonium thiosulfate and ammonium thiocyanate from a desulfurization waste liquid produced in a coking plant HPF process or a PDS process.
背景技术 Background technique
在煤焦化过程产生的焦炉煤气中含有 5〜8g/m3的硫化氢 (H2S)和 1〜1. 5g/m3氰化氢 (HCN), 其燃烧后生成的硫氧化物及氮氧化物严重的污染环境, 并且上述两种气体属于有毒物质。 因 此目前国内焦化企业均装备焦炉煤气脱硫脱氰设备, 对应该设备使用的脱硫脱氰工艺可分为 氧化法和吸收法两大类。 其中, HPF法是以焦炉煤气中所含氨为碱源, HPF (对苯二酚、 PDS— 酞菁钴磺酸盐、 FeSO^I成的复合型催化剂)为催化剂的湿式液相催化氧化脱硫脱氰工艺。 HPF 法具有利用焦炉煤气自身的氨为碱源, 运行成本比较经济, 并且设备投资低, 工艺简单等优 点而成为目前我国焦化企业中应用最广泛的脱硫脱氰工艺。 The coke oven gas produced in the coal coking process contains 5 to 8 g/m 3 of hydrogen sulfide (H 2 S) and 1 to 1.5 g/m 3 of hydrogen cyanide (HCN), and the sulfur oxides formed after combustion and Nitrogen oxides seriously pollute the environment, and the above two gases are toxic substances. Therefore, domestic coking enterprises are equipped with coke oven gas desulfurization and de-cyanide equipment, and the desulfurization and de-cyanide process for equipment should be divided into oxidation and absorption methods. Among them, the HPF method is based on the ammonia contained in the coke oven gas as the alkali source, and the wet phase liquid phase catalytic oxidation of HPF (hydroquinone, PDS-phthalocyanine sulfonate, FeSO^I composite catalyst) as a catalyst. Desulfurization and de-cyanide process. The HPF method has the advantages of using coke oven gas's own ammonia as an alkali source, relatively economical operation cost, low equipment investment, simple process, etc., and has become the most widely used desulfurization and de-cyanide process in coking enterprises in China.
但是, 随着目前以氨为碱源的 HFP法脱硫脱氰工艺在煤焦化行业的大规模运行, 其脱硫 脱氰工艺生产所产生的脱硫脱氰废液 (为避免催化剂中毒, 当硫盐达到一定浓度时需部分排 放的脱硫液) 因带有特殊的臭味及高盐含量导致无法生化处理。 因此脱硫废液的处理已日益 成为亟待有效解决的难题。 脱硫废液中硫氰酸铵、 硫代硫酸铵的提取成为解决上述难题的突 破口, 因此大量文献及专利对此给予了各种不同解决方案的报道。 目前, 对于脱硫废液的处 理分为两类: (一)作为配煤用水喷洒在煤堆上继续随煤送入炼焦(CN201010122403. 5); (二) 从 HPF脱硫废水中回收硫铵盐。 目前, 脱硫废液的第一种处理方式虽然从表面看解决了脱硫 废液的排放, 但是废液中盐进入炼焦后会再次分解排放, 重复进入脱硫脱氰系统, 产生恶性 循环, 而鉴于第二种处理工艺的不完善, 目前焦化厂普遍采用喷洒至炼焦煤中的方式解决废 液排放的问题。  However, with the current large-scale operation of the HFP desulfurization and de-cyanation process with ammonia as the alkali source in the coal coking industry, the desulfurization and de-cyanide waste produced by the desulfurization and de-cyanation process is produced (to avoid catalyst poisoning, when the sulfur salt reaches Desulfurization solution that needs to be partially discharged at a certain concentration) cannot be biochemically treated due to its special odor and high salt content. Therefore, the treatment of desulfurization waste liquid has become an increasingly difficult problem to be solved effectively. The extraction of ammonium thiocyanate and ammonium thiosulfate in the desulfurization waste liquid has become a breakthrough in solving the above problems, and thus a large number of documents and patents have reported various solutions. At present, the treatment of desulfurization waste liquid is divided into two categories: (1) spraying as coal blending water on coal piles and continuing to feed coking with coal (CN201010122403. 5); (2) recovering ammonium sulfate from HPF desulfurization wastewater. At present, although the first treatment method of desulfurization waste liquid solves the discharge of desulfurization waste liquid from the surface, the salt in the waste liquid will be decomposed and discharged again after entering the coking, and repeatedly enters the desulfurization and de-cyanation system to generate a vicious circle. The two treatment processes are not perfect. At present, coking plants generally use the method of spraying to coking coal to solve the problem of waste liquid discharge.
从 HPF脱硫废水中回收硫铵盐, 目前主要的处理方法有三种: 第一种是利用共饱和的多 元体系相图的原理多次浓缩, 分步结晶的方式将硫氰酸铵和硫代硫酸铵分离提纯 ( CN201110180361. 5, CN200810128357. 2), 由于硫氰酸铵与硫代硫酸铵的溶解度差异不大, 因此该方法工艺繁琐, 结晶浓度及温度控制要求高, 得到的盐纯度低, 经济效益差, 并且不 适用于硫酸铵含量高的废水溶液; 第二种是通过催化剂将脱硫液中的硫代硫酸铵氧化成硫酸 铵后分步结晶提纯硫氰酸铵和硫酸铵(CN201210147582. 7, CN2007101395747, 日本专利特公 昭 55-126531 ), 这种方法的缺点在于使用铜盐提纯硫氰酸铵时需要高温再生铜盐, 无法提纯 经济价值高的硫代硫酸铵, 经济效益差, 其提纯过程中损失的铜盐成为新的污染源, 而且有 更多的工业废水排放; 第三种是高温高压下并在催化剂作用下将废水中的铵盐全部转化成硫 酸铵回收 (日本专利特公昭 57-7852), 该方法对于设备条件要求高, 运行成本大, 并且氧化 得到的硫酸铵经济价值低, 一般企业无法使用该方法。 The recovery of ammonium sulphate from HPF desulfurization wastewater has three main treatment methods: The first one is to use multiple principles of co-saturated multiphase system phase diagram to concentrate ammonium thiocyanate and thiosulfuric acid in a stepwise crystallization manner. Ammonium separation and purification (CN201110180361. 5, CN200810128357. 2), because the solubility difference between ammonium thiocyanate and ammonium thiosulfate is not large, the method is cumbersome, the crystallization concentration and temperature control requirements are high, and the obtained salt has low purity and economy. The utility model has the advantages of poor efficiency and is not suitable for the wastewater solution with high ammonium sulfate content; the second method is to purify ammonium thiocyanate and ammonium sulfate by stepwise crystallization by oxidation of ammonium thiosulfate in the desulfurization solution into ammonium sulfate by a catalyst (CN201210147582. 7) , CN2007101395747, Japanese Patent Publication No. Sho 55-126531, the disadvantage of this method is that the use of copper salt to purify ammonium thiocyanate requires high temperature regeneration of copper salt, which cannot be purified. The high economic value of ammonium thiosulfate has poor economic benefits. The copper salt lost during the purification process becomes a new source of pollution, and more industrial wastewater is discharged. The third is high temperature and high pressure and the catalyst is used in the wastewater. The ammonium salt is completely converted into ammonium sulfate recovery (Japanese Patent Publication No. Sho 57-7852), which has high requirements on equipment conditions, high operating cost, and low economic value of ammonium sulfate obtained by oxidation, which is not available to general companies.
基于上述情况, 本发明采用一种新型的环保技术工艺路线, 解决上述脱硫废液的环保处 理和回收利用问题。  Based on the above situation, the present invention adopts a novel environmental protection technology process route to solve the environmental protection treatment and recycling problem of the above-mentioned desulfurization waste liquid.
发明内容 Summary of the invention
本发明的目的是针对现有技术的不足, 提供一种处理 HPF法脱氰脱硫工艺所产生的脱硫 废液的方法, 同时提供脱硫废液中提取两种副盐的方法。 该方法通过较简单、 易于控制的工 艺路线和工艺条件, 对脱硫废液进行彻底的处理, 不但避免了废液排放所对环境造成的污染, 而且同时提取回收了重要的化工原料硫氰酸铵和硫代硫酸铵,在确保生产过程无污染的同时, 带来可观的经济效益。  SUMMARY OF THE INVENTION The object of the present invention is to provide a method for treating a desulfurization waste liquid produced by a desulfurization desulfurization process of the HPF method, and a method for extracting two sub-salts in a desulfurization waste liquid, in view of the deficiencies of the prior art. The method thoroughly treats the desulfurization waste liquid through a relatively simple and easy-to-control process route and process conditions, thereby avoiding environmental pollution caused by waste liquid discharge, and simultaneously extracting and recovering an important chemical raw material ammonium thiocyanate. And ammonium thiosulfate, while ensuring no pollution in the production process, bring considerable economic benefits.
本发明的目的是这样实现的: 一种处理焦炉煤气脱硫含盐废液的方法, 其特征在于: 步骤 1 : 脱色除杂: 脱硫废液中加入 0. l〜l% (w/w)活性炭于 80〜100°C下保温 30〜60分 钟, 然后进行过滤操作得脱色后含盐滤液和活性炭滤饼, 活性炭滤饼送专业回收 企业再生处理;  L〜l% (w/w) The purpose of the present invention is as follows: a method of treating a coke oven gas desulfurization salty waste liquid, wherein: The activated carbon is kept at 80 to 100 ° C for 30 to 60 minutes, and then subjected to a filtration operation to obtain a salt-containing filtrate and an activated carbon filter cake after decolorization, and the activated carbon filter cake is sent to a professional recycling enterprise for regeneration treatment;
步骤 2: 含盐滤液减压浓缩: 将步骤 1含盐滤液于 60〜80°C, 真空度 70〜90mmHg下减压 浓缩至比重为 1. 18〜1. 26 (g/ml)时停止浓缩, 获得含水量为 10〜30% (w/w) 的 浓缩含盐滤液, 将浓缩含盐滤液保温状态下转至析晶釜, 浓缩过程蒸出的含氨水 溶液留待后续步骤使用和补充至焦炉煤气脱硫系统中;  Step 2: Stop the concentration of the salt-containing filtrate at a concentration of 1.18~1. 26 (g/ml) when the concentration of the salt-containing filtrate is concentrated at 60-80 ° C under a vacuum of 70-90 mmHg. Obtaining a concentrated salty filtrate having a water content of 10 to 30% (w/w), transferring the concentrated salt-containing filtrate to a crystallizing kettle under the state of being kept warm, and discharging the ammoniated aqueous solution in the concentration process for use in subsequent steps and replenishing to the coke Furnace gas desulfurization system;
步骤 3: 硫氰酸铵分离: 按照 4〜10L/kg比例, 将 95%乙醇与浓缩含盐滤液加入析晶釜中 混合搅拌后冷却至 10〜30°C, 然后进行离心操作, 得含硫氰酸铵乙醇滤液和含硫 代硫酸铵与硫酸铵混合盐的滤饼;  Step 3: Ammonium thiocyanate separation: According to the ratio of 4~10L/kg, add 95% ethanol and concentrated salty filtrate to the crystallizing kettle, mix and stir, cool to 10~30 °C, and then centrifuge to obtain sulfur. An ammonium cyanate ethanol filtrate and a filter cake containing a mixed salt of ammonium thiosulfate and ammonium sulfate;
步骤 4: 硫氰酸铵乙醇滤液浓缩析晶: 将步骤 3硫氰酸铵乙醇滤液于常压下蒸出含水乙醇 至比重为 1. 2〜1. 25 (g/ml)时停止浓缩, 降至 10〜30°C后进行离心操作, 得硫氰 酸铵晶体和硫氰酸铵乙醇饱和滤液,硫氰酸铵乙醇饱和滤液返回至步骤 3 中循环 利用, 蒸出含水乙醇经精熘装置分离出乙醇后返回步骤 3中循环使用; 步骤 5: 硫氰酸铵产品干燥: 将步骤 4所得硫氰酸铵晶体热风干燥, 温度 80〜100°C, 时 间 l〜2h, 得纯度 > 99%的硫氰酸铵产品;  Step 2: The ammonium thiocyanate ethanol filtrate is concentrated and crystallized: Step 3: The ammonium thiocyanate ethanol filtrate is distilled off under normal pressure to remove the aqueous ethanol to a specific gravity of 1. 2~1. 25 (g/ml), the concentration is stopped, and the concentration is lowered. After centrifugation at 10~30 °C, the ammonium thiocyanate crystal and ammonium thiocyanate ethanol saturated filtrate are obtained, and the ammonium thiocyanate ethanol saturated filtrate is returned to the step 3 for recycling, and the distilled ethanol is separated by the fine sputum device. After the ethanol is returned, it is returned to the step 3 for recycling; Step 5: The ammonium thiocyanate product is dried: The ammonium thiocyanate crystal obtained in the step 4 is dried by hot air, the temperature is 80-100 ° C, and the time is l~2 h, and the purity is >99%. Ammonium thiocyanate product;
步骤 6: 硫酸铵分离: 按照 3〜5L/kg的比例, 将步骤 2中蒸出的含氨水溶液与步骤 3含 硫代硫酸铵与硫酸铵混合盐的滤饼加入反应釜中混合, 然后按照氢氧化钙 /硫酸 铵的摩尔比为 1 : 1〜1. 2: 1 的比例加入氢氧化钙粉末; 继续搅拌 30〜60分钟, 离心过滤, 得含硫代硫酸铵滤液和硫酸钙滤饼; 硫酸钙滤饼在 100〜12(TC下干燥 1〜2小时后得纯度 > 98%的硫酸钙产品; Step 6: Separation of ammonium sulfate: According to the ratio of 3 to 5 L/kg, the aqueous solution containing ammonia distilled in step 2 is contained in step 3 The filter cake of the mixed salt of ammonium thiosulfate and ammonium sulfate is added to the reaction vessel for mixing, and then the calcium hydroxide powder is added in a ratio of 1:1 to 1. 2:1 in a molar ratio of calcium hydroxide to ammonium sulfate; stirring is continued 30 ~60 minutes, centrifugal filtration, to obtain ammonium thiosulfate filtrate and calcium sulfate filter cake; calcium sulfate filter cake in 100~12 (dried under TC for 1~2 hours to obtain purity > 98% calcium sulfate product;
步骤 7: 硫代硫酸铵滤液浓缩析晶: 将步骤 6硫代硫酸铵滤液于 60〜80°C, 真空度 70〜 90mmHg下减压浓缩至比重为 1. 2〜1. 24 (g/ml)时停止浓缩, 保温转移至析晶釜, 冷却至 10〜30°C后进行离心操作,得含硫代硫酸铵的滤饼和含硫代硫酸铵的饱和 滤液; 浓缩过程蒸出的含氨水溶液补充至焦炉煤气脱硫系统中; 含硫代硫酸铵的 饱和滤液返回步骤 6滤液中继续浓缩析晶;  Step 2: The thiosulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate When the concentration is stopped, the heat transfer is transferred to the crystallizer, and after cooling to 10 to 30 ° C, centrifugation is performed to obtain a filter cake containing ammonium thiosulfate and a saturated filtrate containing ammonium thiosulfate; ammonia contained in the concentration process The aqueous solution is replenished into the coke oven gas desulfurization system; the saturated filtrate containing ammonium thiosulfate is returned to the filtrate in step 6 to continue to concentrate and devitrify;
步骤 8: 硫代硫酸铵产品干燥: 将步骤 7硫代硫酸铵滤饼于常压 50〜80°C下热风干燥 1〜 Step 8: Drying of the ammonium thiosulfate product: Step 7 The ammonium thiosulfate filter cake is dried by hot air at a normal pressure of 50 to 80 ° C. 1~
2小时得纯度 > 98%的硫代硫酸酸铵产品。 2 hours purity > 98% ammonium thiosulfate product.
本发明从焦炉煤气脱硫含盐废液中提取两种副盐的方法是: The method for extracting two kinds of secondary salts from the coke oven gas desulfurization and salty waste liquid is:
步骤 1 : 脱色除杂: 脱硫废液中加入 0. l〜l% (w/w)活性炭于 80〜100°C下保温 30〜60分 钟, 然后进行过滤操作得脱色后含盐滤液和活性炭滤饼, 活性炭滤饼送专业回收 企业再生处理;  Step 1: Decolorization and decontamination: 0. l~l% (w/w) activated carbon is kept at 80~100 °C for 30~60 minutes, and then filtered to obtain demineralized salt filtrate and activated carbon filter. Cake, activated carbon filter cake for professional recycling enterprise recycling;
步骤 2: 含盐滤液减压浓缩: 将步骤 1含盐滤液于 60〜80°C, 真空度 70〜90mmHg下减压 浓缩至比重为 1. 18〜1. 26 (g/ml)时停止浓缩, 获得含水量为 10〜30% (w/w) 的 浓缩含盐滤液, 将浓缩含盐滤液保温状态下转至析晶釜, 浓缩过程蒸出的含氨水 溶液留待后续步骤使用和补充至焦炉煤气脱硫系统中;  Step 2: Stop the concentration of the salt-containing filtrate at a concentration of 1.18~1. 26 (g/ml) when the concentration of the salt-containing filtrate is concentrated at 60-80 ° C under a vacuum of 70-90 mmHg. Obtaining a concentrated salty filtrate having a water content of 10 to 30% (w/w), transferring the concentrated salt-containing filtrate to a crystallizing kettle under the state of being kept warm, and discharging the ammoniated aqueous solution in the concentration process for use in subsequent steps and replenishing to the coke Furnace gas desulfurization system;
步骤 3: 硫氰酸铵分离: 按照 4〜10L/kg比例, 将 95%乙醇与浓缩含盐滤液加入析晶釜中 混合搅拌后冷却至 10〜30°C, 然后进行离心操作, 得含硫氰酸铵乙醇滤液和含硫 代硫酸铵与硫酸铵混合盐的滤饼;  Step 3: Ammonium thiocyanate separation: According to the ratio of 4~10L/kg, add 95% ethanol and concentrated salty filtrate to the crystallizing kettle, mix and stir, cool to 10~30 °C, and then centrifuge to obtain sulfur. An ammonium cyanate ethanol filtrate and a filter cake containing a mixed salt of ammonium thiosulfate and ammonium sulfate;
步骤 4: 硫氰酸铵乙醇滤液浓缩析晶: 将步骤 3硫氰酸铵乙醇滤液于常压下蒸出含水乙醇 至比重为 1. 2〜1. 25 (g/ml)时停止浓缩, 降至 10〜30°C后进行离心操作, 得硫氰 酸铵晶体和硫氰酸铵乙醇饱和滤液,硫氰酸铵乙醇饱和滤液返回至步骤 3 中循环 利用, 蒸出含水乙醇经精熘装置分离出乙醇后返回步骤 3中循环使用; 步骤 5: 硫氰酸铵产品干燥: 将步骤 4所得硫氰酸铵晶体热风干燥, 温度 80〜100°C, 时 间 l〜2h, 得纯度 > 99%的硫氰酸铵产品;  Step 2: The ammonium thiocyanate ethanol filtrate is concentrated and crystallized: Step 3: The ammonium thiocyanate ethanol filtrate is distilled off under normal pressure to remove the aqueous ethanol to a specific gravity of 1. 2~1. 25 (g/ml), the concentration is stopped, and the concentration is lowered. After centrifugation at 10~30 °C, the ammonium thiocyanate crystal and ammonium thiocyanate ethanol saturated filtrate are obtained, and the ammonium thiocyanate ethanol saturated filtrate is returned to the step 3 for recycling, and the distilled ethanol is separated by the fine sputum device. After the ethanol is returned, it is returned to the step 3 for recycling; Step 5: The ammonium thiocyanate product is dried: The ammonium thiocyanate crystal obtained in the step 4 is dried by hot air, the temperature is 80-100 ° C, and the time is l~2 h, and the purity is >99%. Ammonium thiocyanate product;
步骤 6: 硫酸铵分离: 按照 3〜5L/kg的比例, 将步骤 2中蒸出的含氨水溶液与步骤 3含 硫代硫酸铵与硫酸铵混合盐的滤饼加入反应釜中混合, 然后按照氢氧化钙 /硫酸 铵的摩尔比为 1 : 1〜1. 2: 1 的比例加入氢氧化钙粉末; 继续搅拌 30〜60分钟, 离心过滤, 得含硫代硫酸铵滤液和硫酸钙滤饼; 硫酸钙滤饼在 100〜12(TC下干燥 1〜2小时后得纯度 > 98%的硫酸钙产品; Step 6: Separation of ammonium sulfate: According to the ratio of 3~5L/kg, the aqueous ammonia solution distilled in step 2 and the filter cake containing the mixed salt of ammonium thiosulfate and ammonium sulfate in step 3 are mixed into the reaction kettle, and then Calcium hydroxide / sulfuric acid The molar ratio of ammonium is 1:1~1. The ratio of 2:1 is added to the calcium hydroxide powder; the stirring is continued for 30 to 60 minutes, and the mixture is centrifuged to obtain a filtrate containing ammonium thiosulfate and a calcium sulfate filter cake; 100~12 (purity after drying for 1~2 hours at TC > 98% calcium sulfate product;
步骤 7: 硫代硫酸铵滤液浓缩析晶: 将步骤 6硫代硫酸铵滤液于 60〜80°C, 真空度 70〜 90mmHg下减压浓缩至比重为 1. 2〜1. 24 (g/ml)时停止浓缩, 保温转移至析晶釜, 冷却至 10〜30°C后进行离心操作,得含硫代硫酸铵的滤饼和含硫代硫酸铵的饱和 滤液; 浓缩过程蒸出的含氨水溶液补充至焦炉煤气脱硫系统中; 含硫代硫酸铵的 饱和滤液返回步骤 6滤液中继续浓缩析晶; Step 2: The thiosulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate When the concentration is stopped, the heat transfer is transferred to the crystallizer, and after cooling to 10 to 30 ° C, centrifugation is performed to obtain a filter cake containing ammonium thiosulfate and a saturated filtrate containing ammonium thiosulfate; ammonia contained in the concentration process The aqueous solution is replenished into the coke oven gas desulfurization system; the saturated filtrate containing ammonium thiosulfate is returned to the filtrate in step 6 to continue to concentrate and devitrify;
步骤 8: 硫代硫酸铵产品干燥: 将步骤 7硫代硫酸铵滤饼于常压 50〜80°C下热风干燥 1〜 2小时得纯度 > 98%的硫代硫酸酸铵产品。 Step 8: Drying of the ammonium thiosulfate product: The step 7 ammonium thiosulfate filter cake is dried by hot air at a normal pressure of 50 to 80 ° C for 1 to 2 hours to obtain a purity of 98% of ammonium thiosulfate.
本发明从焦炉煤气脱硫含盐废液中提取硫氰酸铵的方法是: The method for extracting ammonium thiocyanate from the coke oven gas desulfurization salty waste liquid is:
步骤 1 : 脱色除杂: 脱硫废液中加入 0. l〜l% (w/w)活性炭于 80〜100°C下保温 30〜60分 钟, 然后进行过滤操作得脱色后含盐滤液和活性炭滤饼, 活性炭滤饼送专业回收 企业再生处理; Step 1: Decolorization and decontamination: 0. l~l% (w/w) activated carbon is kept at 80~100 °C for 30~60 minutes, and then filtered to obtain demineralized salt filtrate and activated carbon filter. Cake, activated carbon filter cake for professional recycling enterprise recycling;
步骤 2: 含盐滤液减压浓缩: 将步骤 1含盐滤液于 60〜80°C, 真空度 70〜90mmHg下减压 浓缩至比重为 1. 18〜1. 26 (g/ml)时停止浓缩, 获得含水量为 10〜30% (w/w) 的 浓缩含盐滤液, 将浓缩含盐滤液保温状态下转至析晶釜, 浓缩过程蒸出的含氨水 溶液留待后续步骤使用和补充至焦炉煤气脱硫系统中; Step 2: Stop the concentration of the salt-containing filtrate at a concentration of 1.18~1. 26 (g/ml) when the concentration of the salt-containing filtrate is concentrated at 60-80 ° C under a vacuum of 70-90 mmHg. Obtaining a concentrated salty filtrate having a water content of 10 to 30% (w/w), transferring the concentrated salt-containing filtrate to a crystallizing kettle under the state of being kept warm, and discharging the ammoniated aqueous solution in the concentration process for use in subsequent steps and replenishing to the coke Furnace gas desulfurization system;
步骤 3: 硫氰酸铵分离: 按照 4〜10L/kg比例, 将 95%乙醇与浓缩含盐滤液加入析晶釜中 混合搅拌后冷却至 10〜30°C, 然后进行离心操作, 得含硫氰酸铵乙醇滤液和含硫 代硫酸铵与硫酸铵混合盐的滤饼; Step 3: Ammonium thiocyanate separation: According to the ratio of 4~10L/kg, add 95% ethanol and concentrated salty filtrate to the crystallizing kettle, mix and stir, cool to 10~30 °C, and then centrifuge to obtain sulfur. An ammonium cyanate ethanol filtrate and a filter cake containing a mixed salt of ammonium thiosulfate and ammonium sulfate;
步骤 4: 硫氰酸铵乙醇滤液浓缩析晶: 将步骤 3硫氰酸铵乙醇滤液于常压下蒸出含水乙醇 至比重为 1. 2〜1. 25 (g/ml)时停止浓缩, 降至 10〜30°C后进行离心操作, 得硫氰 酸铵晶体和硫氰酸铵乙醇饱和滤液,硫氰酸铵乙醇饱和滤液返回至步骤 3 中循环 利用, 蒸出含水乙醇经精熘装置分离出乙醇后返回步骤 3中循环使用; 步骤 5: 硫氰酸铵产品干燥: 将步骤 4所得硫氰酸铵晶体热风干燥, 温度 80〜100°C, 时 间 l〜2h, 得纯度 > 99%的硫氰酸铵产品; Step 2: The ammonium thiocyanate ethanol filtrate is concentrated and crystallized: Step 3: The ammonium thiocyanate ethanol filtrate is distilled off under normal pressure to remove the aqueous ethanol to a specific gravity of 1. 2~1. 25 (g/ml), the concentration is stopped, and the concentration is lowered. After centrifugation at 10~30 °C, the ammonium thiocyanate crystal and ammonium thiocyanate ethanol saturated filtrate are obtained, and the ammonium thiocyanate ethanol saturated filtrate is returned to the step 3 for recycling, and the distilled ethanol is separated by the fine sputum device. After the ethanol is returned, it is returned to the step 3 for recycling; Step 5: The ammonium thiocyanate product is dried: The ammonium thiocyanate crystal obtained in the step 4 is dried by hot air, the temperature is 80-100 ° C, and the time is l~2 h, and the purity is >99%. Ammonium thiocyanate product;
本发明从焦炉煤气脱硫含盐废液中提取硫代硫酸酸铵的方法是: The method for extracting ammonium thiosulfate from the coke oven gas desulfurization salty waste liquid is:
步骤 1 : 脱色除杂: 脱硫废液中加入 0. l〜l% (w/w)活性炭于 80〜100°C下保温 30〜60分 钟, 然后进行过滤操作得脱色后含盐滤液和活性炭滤饼, 活性炭滤饼送专业回收 企业再生处理; Step 1: Decolorization and decontamination: 0. l~l% (w/w) activated carbon is kept at 80~100 °C for 30~60 minutes, and then filtered to obtain demineralized salt filtrate and activated carbon filter. Cake, activated carbon filter cake for professional recycling Enterprise regeneration processing;
步骤 2: 含盐滤液减压浓缩: 将步骤 1含盐滤液于 60〜80°C, 真空度 70〜90mmHg下减压 浓缩至比重为 1. 18〜1. 26 (g/ml)时停止浓缩, 获得含水量为 10〜30% (w/w) 的 浓缩含盐滤液, 将浓缩含盐滤液保温状态下转至析晶釜, 浓缩过程蒸出的含氨水 溶液留待后续步骤使用和补充至焦炉煤气脱硫系统中; Step 2: Stop the concentration of the salt-containing filtrate at a concentration of 1.18~1. 26 (g/ml) when the concentration of the salt-containing filtrate is concentrated at 60-80 ° C under a vacuum of 70-90 mmHg. Obtaining a concentrated salty filtrate having a water content of 10 to 30% (w/w), transferring the concentrated salt-containing filtrate to a crystallizing kettle under the state of being kept warm, and discharging the ammoniated aqueous solution in the concentration process for use in subsequent steps and replenishing to the coke Furnace gas desulfurization system;
步骤 3: 硫氰酸铵分离: 按照 4〜10L/kg比例, 将 95%乙醇与浓缩含盐滤液加入析晶釜中 混合搅拌后冷却至 10〜30°C, 然后进行离心操作, 得含硫氰酸铵乙醇滤液和含硫 代硫酸铵与硫酸铵混合盐的滤饼; Step 3: Ammonium thiocyanate separation: According to the ratio of 4~10L/kg, add 95% ethanol and concentrated salty filtrate to the crystallizing kettle, mix and stir, cool to 10~30 °C, and then centrifuge to obtain sulfur. An ammonium cyanate ethanol filtrate and a filter cake containing a mixed salt of ammonium thiosulfate and ammonium sulfate;
步骤 4: 硫酸铵分离: 按照 3〜5L/kg的比例, 将步骤 2中蒸出的含氨水溶液与步骤 3含 硫代硫酸铵与硫酸铵混合盐的滤饼加入反应釜中混合, 然后按照氢氧化钙 /硫酸 铵的摩尔比为 1 : 1〜1. 2: 1 的比例加入氢氧化钙粉末; 继续搅拌 30〜60分钟, 离心过滤, 得含硫代硫酸铵滤液和硫酸钙滤饼; 硫酸钙滤饼在 100〜12(TC下干燥 1〜2小时后得纯度 > 98%的硫酸钙产品; Step 4: Ammonium sulfate separation: According to the ratio of 3~5L/kg, the ammonia solution distilled from step 2 and the filter cake containing the mixed salt of ammonium thiosulfate and ammonium sulfate in step 3 are mixed into the reaction kettle, and then The molar ratio of calcium hydroxide/ammonium sulfate is 1:1~1. The ratio of 2:1 is added to the calcium hydroxide powder; stirring is continued for 30 to 60 minutes, and centrifugal filtration is performed to obtain a filtrate containing ammonium thiosulfate and a calcium sulfate filter cake; The calcium sulfate filter cake has a purity of 98% calcium sulfate after drying for 1 to 2 hours at 100 to 12 (TC);
步骤 5: 硫代硫酸铵滤液浓缩析晶: 将步骤 6硫代硫酸铵滤液于 60〜80°C, 真空度 70〜 Step 5: Concentration and crystallization of ammonium thiosulfate filtrate: Step 6 ammonium thiosulfate filtrate at 60~80 ° C, vacuum 70~
90mmHg下减压浓缩至比重为 1. 2〜1. 24 (g/ml)时停止浓缩, 保温转移至析晶釜, 冷却至 10〜30°C后进行离心操作,得含硫代硫酸铵的滤饼和含硫代硫酸铵的饱和 滤液; 浓缩过程蒸出的含氨水溶液补充至焦炉煤气脱硫系统中; 含硫代硫酸铵的 饱和滤液返回步骤 6滤液中继续浓缩析晶;  After concentration under reduced pressure of 90 mmHg to a specific gravity of 1. 2~1. 24 (g/ml), the concentration is stopped, the heat transfer is transferred to the crystallizer, and the mixture is cooled to 10 to 30 ° C, and then centrifuged to obtain ammonium thiosulfate. a filter cake and a saturated filtrate containing ammonium thiosulfate; the aqueous ammonia solution distilled from the concentration process is replenished to the coke oven gas desulfurization system; the saturated filtrate containing ammonium thiosulfate is returned to the filtrate in step 6 to continue concentration and crystallization;
步骤 6: 硫代硫酸铵产品干燥: 将步骤 7硫代硫酸铵滤饼于常压 50〜80°C下热风干燥 1〜 Step 6: Drying of the ammonium thiosulfate product: Step 7 The ammonium thiosulfate filter cake is dried by hot air at a normal pressure of 50 to 80 ° C. 1~
2小时得纯度 > 98%的硫代硫酸酸铵产品。  2 hours purity > 98% ammonium thiosulfate product.
与现有技术相比, 本发明的有益效果是: Compared with the prior art, the beneficial effects of the present invention are:
( 1 ) 处理彻底, 无二次污染, 工艺清洁环保  (1) Complete treatment, no secondary pollution, clean and environmentally friendly
本发明的提纯工艺路线目前尚无公开的报道与之相同, 该废液处理过程无废水废气 废渣的产生,在确保生产设备密封安全无泄漏的条件下,可确保生产环节清洁生产。 传统的废液处理工艺所使用的梯度浓缩结晶法产生混盐量大, 容易造成二次污染。 本发明在处理脱硫废液时, 产品回收利用率高, 无混盐和废水排放, 蒸发冷凝水可 返回至焦化脱硫工序, 相对现有技术处理工艺, 既回收了高纯度硫氰酸铵、硫代硫 酸酸铵和硫酸钙产品, 也无三废排放, 清洁环保。  The purification process of the present invention has no report at the same time. The waste liquid treatment process has no waste water and waste residue, and ensures clean production in the production process under the condition of ensuring that the production equipment is sealed safely and without leakage. The gradient concentration crystallization method used in the conventional waste liquid treatment process produces a large amount of mixed salt, which is liable to cause secondary pollution. When the desulfurization waste liquid is treated, the product recovery rate is high, no mixed salt and waste water are discharged, and the evaporating condensed water can be returned to the coking desulfurization process, and the high-purity ammonium thiocyanate and sulfur are recovered compared with the prior art treatment process. Ammonium sulphate and calcium sulphate products, no three wastes, clean and environmentally friendly.
( 2 ) 适应能力强, 生产弹性大:  (2) Strong adaptability and large production flexibility:
相比现有技术脱硫废液的提盐工艺, 传统的梯度结晶法对废液中 SCN―, SO/—, S203 2— 几种离子的浓度关系依赖性大, 回收产品的品质难以保证, 处理效果不够稳定。 另 一方面, 传统方法在处理大量脱硫废液时, 由于产品质量不高, 附加值有限, 导致 综合经济效益较低, 产品收益难以弥补处理成本。 本发明首次利用不同盐在有机溶 剂 /水中溶解度差异, 将三种主要铵盐完全分开, 避免无使用价值的混盐产生, 避 免了二次污染。 同时可随时根据废水成分变化, 对工艺操作条件进行调整, 处理工 艺弹性大, 适应性强, 综合经济效益高。 Compared with the salt extraction process of the prior art desulfurization waste liquid, the conventional gradient crystallization method is for SCN-, SO/-, S 2 0 3 2 in the waste liquid. The concentration dependence of several ions is large, the quality of the recovered product is difficult to guarantee, and the treatment effect is not stable enough. On the other hand, when the traditional method deals with a large amount of desulfurization waste liquid, the product value is not high and the added value is limited, resulting in low comprehensive economic benefits, and it is difficult to make up for the treatment cost. For the first time, the present invention utilizes the difference in solubility of different salts in an organic solvent/water to completely separate the three main ammonium salts, thereby avoiding the use of mixed salt of no use value and avoiding secondary pollution. At the same time, according to the change of wastewater composition, the process operating conditions can be adjusted, the process flexibility is large, the adaptability is strong, and the comprehensive economic benefit is high.
( 3 ) 资源利用率高:  (3) High resource utilization rate:
本发明采用独创的新工艺实现了将脱硫废液中铵盐全组分的综合利用, 尤其是高 附加值硫代硫酸铵的提取方法。 废液提盐产出产品多, 回收产品纯度高 ( > 98%), 回收的硫氰酸铵、 硫代硫酸酸铵和硫酸钙产品可进一步用于其它精细化工行业, 因此资源利用率高, 回收率高。  The invention adopts a unique new process to realize the comprehensive utilization of the whole component of the ammonium salt in the desulfurization waste liquid, especially the extraction method of the high added value ammonium thiosulfate. There are many products produced by waste liquid extraction, and the purity of the recovered products is high (> 98%). The recovered ammonium thiocyanate, ammonium thiosulfate and calcium sulfate products can be further used in other fine chemical industries, so the resource utilization rate is high. High recovery rate.
附图说明 DRAWINGS
附图 1是本发明脱硫废液处理工艺流程图  Figure 1 is a flow chart of the treatment process of the desulfurization waste liquid of the present invention
具体实施方式 detailed description
以下结合附图 1、 和具体实施例详细介绍本发明工艺的实施过程和技术效果, 以便清楚 地理解本发明的技术内容和发明实质, 但不构成对本发明权利要求保护范围的任何限定。  The implementation of the process of the present invention and the technical effects of the present invention are described in detail below with reference to the accompanying drawings and specific embodiments, in order to clearly understand the technical scope of the invention and the scope of the invention.
实施例 1 : 参照图 1所示的脱硫废液提盐工艺流程  Embodiment 1 : Referring to the desulfurization waste liquid salt extraction process shown in FIG.
来自硫膏中焦炉煤气脱硫脱氰废液 1000kg (约含硫氰酸铵含量 13%, 硫代硫酸铵含量 9%, 硫酸铵含量 8%)  1000kg of desulfurization and de-cyanide waste liquid from coke oven gas in sulfur paste (about 13% ammonium thiocyanate, 9% ammonium thiosulfate, 8% ammonium sulfate)
步骤 1 : 脱色除杂: 脱硫废液中加入 0. l% (w/w)活性炭 1kg于 100°C下保温 30分钟后进行 过滤操作得脱色后滤液及活性炭滤饼 (活性炭滤饼送专业回收企业再生处理)。 步骤 2: 脱色液减压浓缩: 将步骤 1滤液于 70°C (真空度 70mmHg) 下减压浓缩至体系体 系比重为 1. 24时停止浓缩 (含水量为 18% (w/w) ), 将浓缩后体系保温转移至析 晶釜, 蒸出水溶液 (含氨水 0. 4%) 补充至焦炉煤气脱硫系统中。  Step 1: Decolorization and decontamination: Add 0. l% (w/w) activated carbon 1kg at 100 ° C for 30 minutes and then filter to obtain decolorized filtrate and activated carbon filter cake (activated activated carbon filter cake for professional recycling Enterprise regeneration processing). Step 2: Decolorization of the decolorizing solution under reduced pressure: The filtrate of step 1 is concentrated under reduced pressure at 70 ° C (vacuum degree 70 mmHg) until the specific gravity of the system is 1.24, the concentration is stopped (water content is 18% (w/w)), The concentrated system was transferred to a crystallizing kettle, and the distilled aqueous solution (containing ammonia water 0.4%) was added to the coke oven gas desulfurization system.
步骤 3: 硫氰酸铵分离: 将 2900L的 95%乙醇按照 8L/kg (步骤 2中浓缩液) 的比例于析 晶釜中混合搅拌后冷却至 20°C后进行离心操作得含硫氰酸铵的滤液及含硫代硫 酸铵与硫酸铵混合盐的滤饼。  Step 3: Ammonium thiocyanate separation: 2900L of 95% ethanol is mixed and stirred in a crystallizer at a ratio of 8L/kg (concentration in step 2), cooled to 20 ° C, and centrifuged to obtain thiocyanate. An ammonium filtrate and a filter cake containing a mixed salt of ammonium thiosulfate and ammonium sulfate.
步骤 4: 硫氰酸铵乙醇溶液浓缩析晶: 将步骤 3滤液于常压下蒸出含水乙醇至体系比重为  Step 4: Concentration and crystallization of ammonium thiocyanate solution: The filtrate of step 3 is distilled under normal pressure to evaporate aqueous ethanol until the specific gravity of the system is
1. 22 时停止浓缩, 体系降至 20°C后进行离心操作得硫氰酸铵晶体及硫氰酸铵饱 和滤液,硫氰酸铵饱和滤液再次返回至步骤 3 中循环利用, 蒸出含水乙醇经精熘 装置分离出乙醇后再次加入步骤 3中循环使用。 1. At 22 o'clock, the concentration is stopped. The system is cooled to 20 ° C and centrifuged to obtain ammonium thiocyanate crystals and ammonium thiocyanate saturated filtrate. The saturated ammonium thiocyanate filtrate is returned to step 3 for recycling, and the aqueous ethanol is distilled off. Fine After the device separates the ethanol, it is added to the step 3 for recycling.
步骤 5: 硫氰酸铵产品干燥: 将步骤 4所得硫氰酸铵产品于 80°C热风干燥 lh得 105kg纯 度> 99%的硫氰酸铵产品。  Step 5: Drying of the ammonium thiocyanate product: The ammonium thiocyanate product obtained in the step 4 is dried by hot air at 80 ° C for 1 hour to obtain 105 kg of an ammonium thiocyanate product having a purity of > 99%.
步骤 6: 硫酸铵分离: 将步骤 3滤饼与 850kg步骤 2中蒸出的水溶液 (含氨水 0. 4%) 按 照 5L/kg的比例于反应釜中混合后加入 44kg氢氧化钙粉末 (加入比例为氢氧化 钙 /硫酸铵的摩尔比为 1 : 1. 1 ),继续搅拌 30分钟后离心过滤得含硫代硫酸铵滤液 及硫酸钙滤饼。 硫酸钙 100°C下干燥 2小时得 70kg,纯度 > 98%。  Step 6: Ammonium sulfate separation: The step 3 filter cake and 850 kg of the aqueous solution distilled from step 2 (containing ammonia water 0.4%) were mixed in a reaction tank at a ratio of 5 L/kg, and then 44 kg of calcium hydroxide powder was added (addition ratio The molar ratio of calcium hydroxide/ammonium sulfate was 1:1.1), stirring was continued for 30 minutes, and then centrifugal filtration was carried out to obtain a filtrate containing ammonium thiosulfate and a calcium sulfate filter cake. Calcium sulfate was dried at 100 ° C for 2 hours to obtain 70 kg, purity > 98%.
步骤 7: 硫代硫酸铵滤液浓缩析晶: 将步骤 6滤液于 70°C (真空度 70mmHg) 下减压浓缩 至体系至体系比重为 1. 22 时停止浓缩, 将浓缩后体系保温转移至析晶釜, 冷却 至 10°C后进行离心操作得含硫代硫酸铵的滤饼及含硫代硫酸铵的饱和滤液。蒸出 水溶液(含氨水 0. 4%)补充至焦炉煤气脱硫系统中。含硫代硫酸铵的饱和滤液再 次加入至步骤 6滤液中循环利用。  Step 7: Concentration and crystallization of ammonium thiosulfate filtrate: The filtrate of step 6 is concentrated under reduced pressure at 70 ° C (vacuum degree 70 mmHg) until the specific gravity of the system is 1.22, the concentration is stopped, and the concentration of the system is transferred to the precipitate. The crystal kettle was cooled to 10 ° C and centrifuged to obtain a filter cake containing ammonium thiosulfate and a saturated filtrate containing ammonium thiosulfate. The aqueous solution (containing 0.4% of ammonia) was added to the coke oven gas desulfurization system. The saturated filtrate containing ammonium thiosulfate is again added to the filtrate in step 6 for recycling.
步骤 8: 硫代硫酸铵产品干燥: 将步骤 7硫代硫酸铵滤饼于常压 60°C下热风干燥 2小时 得 76kg,纯度 > 98%的硫代硫酸酸铵产品。  Step 8: Drying of the ammonium thiosulfate product: The step 7 ammonium thiosulfate filter cake is dried by hot air at a normal pressure of 60 ° C for 2 hours to obtain 76 kg of ammonium thiosulfate product having a purity of > 98%.
实施例 2: 参照图 1所示的脱硫废液提盐工艺流程  Example 2: Referring to the desulfurization waste liquid salt extraction process shown in FIG.
来自硫膏中焦炉煤气脱硫脱氰废液 1000kg (约含硫氰酸铵含量 15%, 硫代硫酸铵含量 , 硫酸铵含量 9%)  1000kg of desulfurization and de-cyanide waste liquid from coke oven gas in sulfur paste (about 15% ammonium thiocyanate, ammonium thiosulfate content, 9% ammonium sulfate)
步骤 1 : 脱色除杂: 脱硫废液中加入 0. 5% (w/w)活性炭 5kg于 80°C下保温 45分钟后进行 过滤操作得脱色后滤液及活性炭滤饼 (活性炭滤饼送专业回收企业再生处理)。 步骤 2: 脱色液减压浓缩: 将步骤 1滤液于 80°C (真空度 90mmHg) 下减压浓缩至体系体 系比重为 1. 22时停止浓缩 (含水量为 20% (w/w) ), 将浓缩后体系保温转移至析 晶釜, 蒸出水溶液 (含氨水 0. 4%) 补充至焦炉煤气脱硫系统中。  Step 1: Decolorization and decontamination: Add 0.5% (w/w) activated carbon 5kg at 80 ° C for 45 minutes, then filter to obtain decolorized filtrate and activated carbon filter cake (activated activated carbon filter cake for professional recycling) Enterprise regeneration processing). Step 2: The decolorization solution is concentrated under reduced pressure: The filtrate of step 1 is concentrated under reduced pressure at 80 ° C (vacuum degree: 90 mmHg) until the specific gravity of the system is 1.22, and the concentration is stopped (water content is 20% (w/w)). The concentrated system was transferred to a crystallizing kettle, and the distilled aqueous solution (containing ammonia water 0.4%) was added to the coke oven gas desulfurization system.
步骤 3: 硫氰酸铵分离: 将 3750L的 95%乙醇按照 10L/kg (步骤 2中浓缩液) 的比例于析 晶釜中混合搅拌后冷却至 30°C后进行离心操作得含硫氰酸铵的滤液及含硫代硫 酸铵与硫酸铵混合盐的滤饼。  Step 3: Ammonium thiocyanate separation: 3750L of 95% ethanol is mixed with 10L/kg (concentration in step 2) in a crystallizer, cooled to 30 ° C, and then centrifuged to obtain thiocyanate. An ammonium filtrate and a filter cake containing a mixed salt of ammonium thiosulfate and ammonium sulfate.
步骤 4: 硫氰酸铵乙醇溶液浓缩析晶: 将步骤 3滤液于常压下蒸出含水乙醇至体系比重为  Step 4: Concentration and crystallization of ammonium thiocyanate solution: The filtrate of step 3 is distilled under normal pressure to evaporate aqueous ethanol until the specific gravity of the system is
1. 24 时停止浓缩, 体系降至 20°C后进行离心操作得硫氰酸铵晶体及硫氰酸铵饱 和滤液,硫氰酸铵饱和滤液再次返回至步骤 3 中循环利用, 蒸出含水乙醇经精熘 装置分离出乙醇后再次加入步骤 3中循环使用。  1. At 24 o'clock, the concentration is stopped. After the system is cooled to 20 ° C, centrifugation is carried out to obtain ammonium thiocyanate crystals and saturated ammonium thiocyanate filtrate. The saturated ammonium thiocyanate filtrate is returned to step 3 for recycling, and the aqueous ethanol is distilled off. The ethanol is separated by a fine boring device and then added to the step 3 for recycling.
步骤 5: 硫氰酸铵产品干燥: 将步骤 4所得硫氰酸铵产品于 80°C热风干燥 lh得 125kg纯 度> 99%的硫氰酸铵产品。 Step 5: Drying of ammonium thiocyanate product: The ammonium thiocyanate product obtained in step 4 is dried by hot air at 80 ° C for 1 hour to obtain 125 kg of pure Degree > 99% ammonium thiocyanate product.
步骤 6: 硫酸铵分离: 将步骤 3滤饼与 600kg步骤 2中蒸出的水溶液 (含氨水 0. 4%) 按 照 3L/kg的比例于反应釜中混合后加入 49kg氢氧化钙粉末 (加入比例为氢氧化 钙 /硫酸铵的摩尔比为 1 : 1 ),继续搅拌 45分钟后离心过滤得含硫代硫酸铵滤液及 硫酸钙滤饼。 硫酸钙 120°C下干燥 2小时得 75kg,纯度 > 98%。 Step 6: Ammonium sulfate separation: The step 3 filter cake and 600 kg of the aqueous solution distilled from step 2 (containing ammonia water 0.4%) were mixed in the reaction tank at a ratio of 3 L/kg, and 49 kg of calcium hydroxide powder was added (addition ratio) The molar ratio of calcium hydroxide/ammonium sulfate was 1:1), stirring was continued for 45 minutes, and then centrifugal filtration was carried out to obtain a filtrate containing ammonium thiosulfate and a calcium sulfate filter cake. The calcium sulfate was dried at 120 ° C for 2 hours to obtain 75 kg, and the purity was > 98%.
步骤 7: 硫代硫酸铵滤液浓缩析晶: 将步骤 6滤液于 80°C (真空度 90mmHg) 下减压浓缩 至体系至体系比重为 1. 23 时停止浓缩, 将浓缩后体系保温转移至析晶釜, 冷却 至 20°C后进行离心操作得含硫代硫酸铵的滤饼及含硫代硫酸铵的饱和滤液。蒸出 水溶液(含氨水 0. 4%)补充至焦炉煤气脱硫系统中。含硫代硫酸铵的饱和滤液再 次加入至步骤 6滤液中循环利用。 Step 7: Concentration and crystallization of ammonium thiosulfate filtrate: The filtrate of step 6 is concentrated under reduced pressure at 80 ° C (vacuum degree: 90 mmHg) until the specific gravity of the system is 1.23, the concentration is stopped, and the concentration of the system is transferred to the precipitation. The crystal kettle was cooled to 20 ° C and centrifuged to obtain a filter cake containing ammonium thiosulfate and a saturated filtrate containing ammonium thiosulfate. The aqueous solution (containing 0.4% of ammonia) was added to the coke oven gas desulfurization system. The saturated filtrate containing ammonium thiosulfate is again added to the filtrate in step 6 for recycling.
步骤 8: 硫代硫酸铵产品干燥: 将步骤 7硫代硫酸铵滤饼于常压 80°C下热风干燥 2小时 得 48kg,纯度 > 98%的硫代硫酸酸铵产品。 Step 8: Drying of the ammonium thiosulfate product: The step 7 ammonium thiosulfate filter cake is dried by hot air at 80 ° C for 2 hours to obtain 48 kg of ammonium thiosulfate acid product having a purity of > 98%.

Claims

权 利 要 求 书 Claim
1. 一种处理焦炉煤气脱硫含盐废液的方法, 其特征在于:  A method for treating coke oven gas desulfurization salty waste liquid, characterized in that:
步骤 1 : 脱色除杂: 脱硫废液中加入 0. l〜l% (w/w)活性炭于 80〜100°C下保温 30〜60分 钟, 然后进行过滤操作得脱色后含盐滤液和活性炭滤饼, 活性炭滤饼送专业回收 企业再生处理;  Step 1: Decolorization and decontamination: 0. l~l% (w/w) activated carbon is kept at 80~100 °C for 30~60 minutes, and then filtered to obtain demineralized salt filtrate and activated carbon filter. Cake, activated carbon filter cake for professional recycling enterprise recycling;
步骤 2: 含盐滤液减压浓缩: 将步骤 1含盐滤液于 60〜80°C, 真空度 70〜90mmHg下减压 浓缩至比重为 1. 18〜1. 26 (g/ml)时停止浓缩, 获得含水量为 10〜30% (w/w) 的 浓缩含盐滤液, 将浓缩含盐滤液保温状态下转至析晶釜, 浓缩过程蒸出的含氨水 溶液留待后续步骤使用和补充至焦炉煤气脱硫系统中;  Step 2: Stop the concentration of the salt-containing filtrate at a concentration of 1.18~1. 26 (g/ml) when the concentration of the salt-containing filtrate is concentrated at 60-80 ° C under a vacuum of 70-90 mmHg. Obtaining a concentrated salty filtrate having a water content of 10 to 30% (w/w), transferring the concentrated salt-containing filtrate to a crystallizing kettle under the state of being kept warm, and discharging the ammoniated aqueous solution in the concentration process for use in subsequent steps and replenishing to the coke Furnace gas desulfurization system;
步骤 3: 硫氰酸铵分离: 按照 4〜10L/kg比例, 将 95%乙醇与浓缩含盐滤液加入析晶釜中 混合搅拌后冷却至 10〜30°C, 然后进行离心操作, 得含硫氰酸铵乙醇滤液和含硫 代硫酸铵与硫酸铵混合盐的滤饼;  Step 3: Ammonium thiocyanate separation: According to the ratio of 4~10L/kg, add 95% ethanol and concentrated salty filtrate to the crystallizing kettle, mix and stir, cool to 10~30 °C, and then centrifuge to obtain sulfur. An ammonium cyanate ethanol filtrate and a filter cake containing a mixed salt of ammonium thiosulfate and ammonium sulfate;
步骤 4: 硫氰酸铵乙醇滤液浓缩析晶: 将步骤 3硫氰酸铵乙醇滤液于常压下蒸出含水乙醇 至比重为 1. 2〜1. 25 (g/ml)时停止浓缩, 降至 10〜30°C后进行离心操作, 得硫氰 酸铵晶体和硫氰酸铵乙醇饱和滤液,硫氰酸铵乙醇饱和滤液返回至步骤 3 中循环 利用, 蒸出含水乙醇经精熘装置分离出乙醇后返回步骤 3中循环使用; 步骤 5: 硫氰酸铵产品干燥: 将步骤 4所得硫氰酸铵晶体热风干燥, 温度 80〜100°C, 时 间 l〜2h, 得纯度 > 99%的硫氰酸铵产品;  Step 2: The ammonium thiocyanate ethanol filtrate is concentrated and crystallized: Step 3: The ammonium thiocyanate ethanol filtrate is distilled off under normal pressure to remove the aqueous ethanol to a specific gravity of 1. 2~1. 25 (g/ml), the concentration is stopped, and the concentration is lowered. After centrifugation at 10~30 °C, the ammonium thiocyanate crystal and ammonium thiocyanate ethanol saturated filtrate are obtained, and the ammonium thiocyanate ethanol saturated filtrate is returned to the step 3 for recycling, and the distilled ethanol is separated by the fine sputum device. After the ethanol is returned, it is returned to the step 3 for recycling; Step 5: The ammonium thiocyanate product is dried: The ammonium thiocyanate crystal obtained in the step 4 is dried by hot air, the temperature is 80-100 ° C, and the time is l~2 h, and the purity is >99%. Ammonium thiocyanate product;
步骤 6: 硫酸铵分离: 按照 3〜5L/kg的比例, 将步骤 2中蒸出的含氨水溶液与步骤 3含 硫代硫酸铵与硫酸铵混合盐的滤饼加入反应釜中混合, 然后按照氢氧化钙 /硫酸 铵的摩尔比为 1 : 1〜1. 2: 1 的比例加入氢氧化钙粉末; 继续搅拌 30〜60分钟, 离心过滤, 得含硫代硫酸铵滤液和硫酸钙滤饼; 硫酸钙滤饼在 100〜12(TC下干燥 1〜2小时后得纯度 > 98%的硫酸钙产品;  Step 6: Separation of ammonium sulfate: According to the ratio of 3~5L/kg, the aqueous ammonia solution distilled in step 2 and the filter cake containing the mixed salt of ammonium thiosulfate and ammonium sulfate in step 3 are mixed into the reaction kettle, and then The molar ratio of calcium hydroxide/ammonium sulfate is 1:1~1. The ratio of 2:1 is added to the calcium hydroxide powder; stirring is continued for 30 to 60 minutes, and centrifugal filtration is performed to obtain a filtrate containing ammonium thiosulfate and a calcium sulfate filter cake; The calcium sulfate filter cake has a purity of 98% calcium sulfate after drying for 1 to 2 hours at 100 to 12 (TC);
步骤 7: 硫代硫酸铵滤液浓缩析晶: 将步骤 6硫代硫酸铵滤液于 60〜80°C, 真空度 70〜 90mmHg下减压浓缩至比重为 1. 2〜1. 24 (g/ml)时停止浓缩, 保温转移至析晶釜, 冷却至 10〜30°C后进行离心操作,得含硫代硫酸铵的滤饼和含硫代硫酸铵的饱和 滤液; 浓缩过程蒸出的含氨水溶液补充至焦炉煤气脱硫系统中; 含硫代硫酸铵的 饱和滤液返回步骤 6滤液中继续浓缩析晶;  Step 2: The thiosulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate When the concentration is stopped, the heat transfer is transferred to the crystallizer, and after cooling to 10 to 30 ° C, centrifugation is performed to obtain a filter cake containing ammonium thiosulfate and a saturated filtrate containing ammonium thiosulfate; ammonia contained in the concentration process The aqueous solution is replenished into the coke oven gas desulfurization system; the saturated filtrate containing ammonium thiosulfate is returned to the filtrate in step 6 to continue to concentrate and devitrify;
步骤 8: 硫代硫酸铵产品干燥: 将步骤 7硫代硫酸铵滤饼于常压 50〜80°C下热风干燥 1〜 2小时得纯度 > 98%的硫代硫酸酸铵产品。  Step 8: Drying of the ammonium thiosulfate product: The step 7 ammonium thiosulfate filter cake is dried by hot air at a normal pressure of 50 to 80 ° C for 1 to 2 hours to obtain a purity of 98% of ammonium thiosulfate.
2.根据权利要求 1所述的处理焦炉煤气脱硫废液的方法, 其特征在于: 步骤 1 : 脱色除杂: 脱硫废液中加入 0. l% (w/w)活性炭于 100°C下保温 30分钟, 然后进行 过滤操作得脱色后含盐滤液和活性炭滤饼, 活性炭滤饼送专业回收企业再生处 理; 2. The method of treating coke oven gas desulfurization waste liquid according to claim 1, wherein: Step 1: Decolorization and decontamination: Add 0. l% (w/w) of activated carbon to the mixture at 100 ° C for 30 minutes, and then carry out the filtration operation to obtain the salt filtrate and the activated carbon filter cake after decolorization, and the activated carbon filter cake is sent. Professional recycling enterprise recycling treatment;
步骤 2: 含盐滤液减压浓缩: 将步骤 1含盐滤液于 70°C, 真空度 70mmHg下减压浓缩至比 重为 1. 24 (g/ml)时停止浓缩, 获得含水量为 18% (w/w) 的浓缩含盐滤液, 将浓 缩含盐滤液保温状态下转至析晶釜,浓缩过程蒸出的含氨水 0. 4%的水溶液留待后 续步骤使用和补充至焦炉煤气脱硫系统中; Step 2: Concentration of the salt-containing filtrate under reduced pressure: The salt-containing filtrate of step 1 is concentrated under reduced pressure at 70 ° C under a vacuum of 70 mmHg to a specific gravity of 1.24 (g/ml), and the water content is 18% ( w/w) concentrated salt-containing filtrate, the concentrated salt-containing filtrate is transferred to the crystallization tank under heat preservation, and the aqueous solution containing 0.4% of ammonia water distilled from the concentration process is reserved for subsequent steps and is added to the coke oven gas desulfurization system. ;
步骤 3: 硫氰酸铵分离: 按照 8L/kg比例, 将 95%乙醇与浓缩含盐滤液加入析晶釜中混合 搅拌后冷却至 20°C, 然后进行离心操作, 得含硫氰酸铵乙醇滤液和含硫代硫酸铵 与硫酸铵混合盐的滤饼; Step 3: Separation of ammonium thiocyanate: According to the ratio of 8 L/kg, 95% ethanol and concentrated salty filtrate are added to the crystallizing kettle, mixed and stirred, cooled to 20 ° C, and then centrifuged to obtain ammonium thiocyanate. a filtrate and a filter cake comprising a mixed salt of ammonium thiosulfate and ammonium sulfate;
步骤 4: 硫氰酸铵乙醇滤液浓缩析晶: 将步骤 3硫氰酸铵乙醇滤液于常压下蒸出含水乙醇 至比重为 1. 22 (g/ml)时停止浓缩, 降至 20°C后进行离心操作, 得硫氰酸铵晶体 和硫氰酸铵乙醇饱和滤液,硫氰酸铵乙醇饱和滤液返回至步骤 3 中循环利用, 蒸 出含水乙醇经精熘装置分离出乙醇后返回步骤 3中循环使用; Step 4: Concentration and crystallization of ammonium thiocyanate ethanol filtrate: Step 3: The ammonium thiocyanate ethanol filtrate is distilled off under normal pressure to aqueous ethanol until the specific gravity is 1.22 (g/ml), the concentration is stopped, and the concentration is lowered to 20 ° C. After the centrifugation operation, the ammonium thiocyanate crystal and the ammonium thiocyanate ethanol saturated filtrate are obtained, and the ammonium thiocyanate ethanol saturated filtrate is returned to the step 3 for recycling, and the aqueous ethanol is distilled off, and the ethanol is separated by the fine boring device, and then returned to the step 3 Used in circulation;
步骤 5: 硫氰酸铵产品干燥:将步骤 4所得硫氰酸铵晶体热风干燥, 温度 80°C, 时间 lh, 得纯度 > 99%的硫氰酸铵产品; Step 5: drying the ammonium thiocyanate product: drying the ammonium thiocyanate crystal obtained in the step 4 by hot air drying at a temperature of 80 ° C for 1 h to obtain an ammonium thiocyanate product having a purity of >99%;
步骤 6: 硫酸铵分离: 按照 5L/kg的比例, 将步骤 2中蒸出的含氨水 0. 4%的水溶液与步 骤 3含硫代硫酸铵与硫酸铵混合盐的滤饼加入反应釜中混合, 然后按照氢氧化钙 /硫酸铵的摩尔比为 1. 2 : 1的比例加入氢氧化钙粉末; 继续搅拌 30分钟, 离心过 滤, 得含硫代硫酸铵滤液和硫酸钙滤饼; 硫酸钙滤饼在 100°C下干燥 2小时后得 纯度 > 98%的硫酸钙产品; Step 6: Ammonium sulfate separation: According to the ratio of 5 L / kg, the aqueous solution containing 0.4% of ammonia water distilled in step 2 and the filter cake containing the mixed salt of ammonium thiosulfate and ammonium sulfate in step 3 are mixed into the reaction kettle. Then, the calcium hydroxide powder is added in a molar ratio of calcium hydroxide/ammonium sulfate of 1.2:1; stirring is continued for 30 minutes, and centrifugal filtration is carried out to obtain a filtrate containing ammonium thiosulfate and a calcium sulfate filter; calcium sulfate filter The cake was dried at 100 ° C for 2 hours to obtain a calcium sulfate product having a purity of > 98%;
步骤 7: 硫代硫酸铵滤液浓缩析晶: 将步骤 6硫代硫酸铵滤液于 70°C, 真空度 70mmHg下 减压浓缩至比重为 1. 22 (g/ml)时停止浓缩, 保温转移至析晶釜, 冷却至 10°C后 进行离心操作, 得含硫代硫酸铵的滤饼和含硫代硫酸铵的饱和滤液; 浓缩过程蒸 出的含氨水 0. 4% (w/w)的水溶液补充至焦炉煤气脱硫系统中; 含硫代硫酸铵的饱 和滤液返回步骤 6滤液中继续浓缩析晶; Step 7: Concentration and crystallization of the ammonium thiosulfate filtrate: The step 6 ammonium thiosulfate filtrate is concentrated under reduced pressure at 70 ° C under a vacuum of 70 mmHg to a specific gravity of 1.22 (g/ml), the concentration is stopped, and the heat transfer is transferred to 4% (w/w) of the aqueous solution containing ammonium thiosulfate and a saturated filtrate containing ammonium thiosulfate; The aqueous solution is replenished into the coke oven gas desulfurization system; the saturated filtrate containing ammonium thiosulfate is returned to the filtrate in step 6 to continue to concentrate and devitrify;
步骤 8: 硫代硫酸铵产品干燥: 将步骤 7硫代硫酸铵滤饼于常压 60°C下热风干燥 2小时 得纯度 > 98%的硫代硫酸酸铵产品。 Step 8: Drying of the ammonium thiosulfate product: The step 7 ammonium thiosulfate filter cake is dried by hot air at a normal pressure of 60 ° C for 2 hours to obtain a product of ammonium thiosulfate having a purity of > 98%.
3. 根据权利要求 1所述的处理焦炉煤气脱硫废液的方法, 其特征在于:  3. The method of treating coke oven gas desulfurization waste liquid according to claim 1, wherein:
步骤 1 : 脱色除杂: 脱硫废液中加入 0. 5% (w/w)活性炭于 80°C下保温 45分钟, 然后进行 过滤操作得脱色后含盐滤液和活性炭滤饼, 活性炭滤饼送专业回收企业再生处 理; Step 1: Decolorization and decontamination: Add 0.5% (w/w) of activated carbon to the desulfurization waste liquid for 48 minutes at 80 ° C, and then proceed After the decolorization operation, the salt filtrate and the activated carbon filter cake are decolorized, and the activated carbon filter cake is sent to a professional recycling enterprise for regeneration treatment;
步骤 2: 含盐滤液减压浓缩: 将步骤 1含盐滤液于 80°C, 真空度 90mmHg下减压浓缩至比 重为 1. 22 (g/ml)时停止浓缩, 获得含水量为 20% (w/w) 的浓缩含盐滤液, 将浓 缩含盐滤液保温状态下转至析晶釜, 浓缩过程蒸出的含氨水 0. 4% (w/w) 的水溶 液留待后续步骤使用和补充至焦炉煤气脱硫系统中;  Step 2: Concentration of the salt-containing filtrate under reduced pressure: The salt-containing filtrate of step 1 is concentrated at 80 ° C under a vacuum of 90 mmHg to a specific gravity of 1.22 (g/ml) to stop concentration, and the water content is 20% ( w/w) Concentrated salt-containing filtrate, the concentrated salt-containing filtrate is transferred to the crystallization tank under heat preservation, and the aqueous solution containing 0.4% (w/w) of ammonia water distilled from the concentration process is reserved for subsequent steps and replenished to the coke Furnace gas desulfurization system;
步骤 3: 硫氰酸铵分离: 按照 10L/kg比例, 将 95%乙醇与浓缩含盐滤液加入析晶釜中混 合搅拌后冷却至 30°C, 然后进行离心操作, 得含硫氰酸铵乙醇滤液和含硫代硫酸 铵与硫酸铵混合盐的滤饼;  Step 3: Ammonium thiocyanate separation: According to the ratio of 10 L/kg, 95% ethanol and concentrated salty filtrate are added to the crystallizing kettle, mixed and stirred, cooled to 30 ° C, and then centrifuged to obtain ammonium thiocyanate. a filtrate and a filter cake comprising a mixed salt of ammonium thiosulfate and ammonium sulfate;
步骤 4: 硫氰酸铵乙醇滤液浓缩析晶: 将步骤 3硫氰酸铵乙醇滤液于常压下蒸出含水乙醇 至比重为 1. 24 (g/ml)时停止浓缩, 降至 20°C后进行离心操作, 得硫氰酸铵晶体 和硫氰酸铵乙醇饱和滤液,硫氰酸铵乙醇饱和滤液返回至步骤 3 中循环利用, 蒸 出含水乙醇经精熘装置分离出乙醇后返回步骤 3中循环使用;  Step 4: Concentration and crystallization of the ammonium thiocyanate ethanol filtrate: Step 3: The ammonium thiocyanate ethanol filtrate is distilled off under normal pressure to aqueous ethanol until the specific gravity is 1.24 (g/ml), the concentration is stopped, and the concentration is lowered to 20 ° C. After the centrifugation operation, the ammonium thiocyanate crystal and the ammonium thiocyanate ethanol saturated filtrate are obtained, and the ammonium thiocyanate ethanol saturated filtrate is returned to the step 3 for recycling, and the aqueous ethanol is distilled off, and the ethanol is separated by the fine boring device, and then returned to the step 3 Used in circulation;
步骤 5: 硫氰酸铵产品干燥:将步骤 4所得硫氰酸铵晶体热风干燥, 温度 80°C, 时间 lh, 得纯度 > 99%的硫氰酸铵产品;  Step 5: drying the ammonium thiocyanate product: drying the ammonium thiocyanate crystal obtained in the step 4 by hot air drying at a temperature of 80 ° C for 1 h to obtain an ammonium thiocyanate product having a purity of >99%;
步骤 6: 硫酸铵分离: 按照 3L/kg的比例, 将步骤 2中蒸出的含氨水 0. 4% (w/w)的水溶液 与步骤 3含硫代硫酸铵与硫酸铵混合盐的滤饼加入反应釜中混合, 然后按照氢氧 化钙 /硫酸铵的摩尔比为 1 : 1的比例加入氢氧化钙粉末; 继续搅拌 45分钟, 离心 过滤, 得含硫代硫酸铵滤液和硫酸钙滤饼; 硫酸钙滤饼在 120°C下干燥 2小时后 得纯度 > 98%的硫酸钙产品;  Step 6: Separation of ammonium sulfate: According to the ratio of 3 L/kg, the aqueous solution of the aqueous ammonia containing 0.4% (w/w) distilled in step 2 and the filter cake of the mixed salt of ammonium thiosulfate and ammonium sulfate in step 3 Adding to the reaction vessel for mixing, and then adding calcium hydroxide powder according to a molar ratio of calcium hydroxide/ammonium sulfate of 1:1; stirring is continued for 45 minutes, and centrifuging to obtain a filtrate containing ammonium thiosulfate and a calcium sulfate filter cake; The calcium sulfate filter cake is dried at 120 ° C for 2 hours to obtain a calcium sulfate product having a purity of > 98%;
步骤 7: 硫代硫酸铵滤液浓缩析晶: 将步骤 6硫代硫酸铵滤液于 80°C, 真空度 90mmHg下 减压浓缩至比重为 1. 23 (g/ml)时停止浓缩, 保温转移至析晶釜, 冷却至 20°C后 进行离心操作, 得含硫代硫酸铵的滤饼和含硫代硫酸铵的饱和滤液; 浓缩过程蒸 出的含氨水 0. 4% (w/w)的水溶液补充至焦炉煤气脱硫系统中; 含硫代硫酸铵的饱 和滤液返回步骤 6滤液中继续浓缩析晶;  Step 7: Concentration and crystallization of the ammonium thiosulfate filtrate: The step 6 ammonium thiosulfate filtrate is concentrated under reduced pressure at a vacuum of 90 mmHg to a specific gravity of 1.23 (g/ml), and the concentration is stopped. 4% (w/w) of the aqueous solution containing ammonium thiosulfate and a saturated filtrate containing ammonium thiosulfate; The aqueous solution is replenished into the coke oven gas desulfurization system; the saturated filtrate containing ammonium thiosulfate is returned to the filtrate in step 6 to continue to concentrate and devitrify;
步骤 8: 硫代硫酸铵产品干燥: 将步骤 7硫代硫酸铵滤饼于常压 80°C下热风干燥 2小时 得纯度 > 98%的硫代硫酸酸铵产品。  Step 8: Drying of the ammonium thiosulfate product: The step 7 ammonium thiosulfate filter cake is dried by hot air at 80 ° C for 2 hours to obtain a product of ammonium thiosulfate having a purity of > 98%.
4. 一种从焦炉煤气脱硫含盐废液中提取两种副盐的方法, 其特征在于: 4. A method for extracting two sub-salts from a coke oven gas desulfurization salty waste liquid, characterized in that:
步骤 1 : 脱色除杂: 脱硫废液中加入 0. l〜l% (w/w)活性炭于 80〜100°C下保温 30〜60分 钟, 然后进行过滤操作得脱色后含盐滤液和活性炭滤饼, 活性炭滤饼送专业回收 企业再生处理; Step 1: Decolorization and decontamination: 0. l~l% (w/w) activated carbon is kept at 80~100 °C for 30~60 minutes, and then filtered to obtain demineralized salt filtrate and activated carbon filter. Cake, activated carbon filter cake for professional recycling Enterprise regeneration processing;
步骤 2: 含盐滤液减压浓缩: 将步骤 1含盐滤液于 60〜80°C, 真空度 70〜90mmHg下减压 浓缩至比重为 1. 18〜1. 26 (g/ml)时停止浓缩, 获得含水量为 10〜30% (w/w) 的 浓缩含盐滤液, 将浓缩含盐滤液保温状态下转至析晶釜, 浓缩过程蒸出的含氨水 溶液留待后续步骤使用和补充至焦炉煤气脱硫系统中; Step 2: Stop the concentration of the salt-containing filtrate at a concentration of 1.18~1. 26 (g/ml) when the concentration of the salt-containing filtrate is concentrated at 60-80 ° C under a vacuum of 70-90 mmHg. Obtaining a concentrated salty filtrate having a water content of 10 to 30% (w/w), transferring the concentrated salt-containing filtrate to a crystallizing kettle under the state of being kept warm, and discharging the ammoniated aqueous solution in the concentration process for use in subsequent steps and replenishing to the coke Furnace gas desulfurization system;
步骤 3: 硫氰酸铵分离: 按照 4〜10L/kg比例, 将 95%乙醇与浓缩含盐滤液加入析晶釜中 混合搅拌后冷却至 10〜30°C, 然后进行离心操作, 得含硫氰酸铵乙醇滤液和含硫 代硫酸铵与硫酸铵混合盐的滤饼; Step 3: Ammonium thiocyanate separation: According to the ratio of 4~10L/kg, add 95% ethanol and concentrated salty filtrate to the crystallizing kettle, mix and stir, cool to 10~30 °C, and then centrifuge to obtain sulfur. An ammonium cyanate ethanol filtrate and a filter cake containing a mixed salt of ammonium thiosulfate and ammonium sulfate;
步骤 4: 硫氰酸铵乙醇滤液浓缩析晶: 将步骤 3硫氰酸铵乙醇滤液于常压下蒸出含水乙醇 至比重为 1. 2〜1. 25 (g/ml)时停止浓缩, 降至 10〜30°C后进行离心操作, 得硫氰 酸铵晶体和硫氰酸铵乙醇饱和滤液,硫氰酸铵乙醇饱和滤液返回至步骤 3 中循环 利用, 蒸出含水乙醇经精熘装置分离出乙醇后返回步骤 3中循环使用; 步骤 5: 硫氰酸铵产品干燥: 将步骤 4所得硫氰酸铵晶体热风干燥, 温度 80〜100°C, 时 间 l〜2h, 得纯度 > 99%的硫氰酸铵产品; Step 2: The ammonium thiocyanate ethanol filtrate is concentrated and crystallized: Step 3: The ammonium thiocyanate ethanol filtrate is distilled off under normal pressure to remove the aqueous ethanol to a specific gravity of 1. 2~1. 25 (g/ml), the concentration is stopped, and the concentration is lowered. After centrifugation at 10~30 °C, the ammonium thiocyanate crystal and ammonium thiocyanate ethanol saturated filtrate are obtained, and the ammonium thiocyanate ethanol saturated filtrate is returned to the step 3 for recycling, and the distilled ethanol is separated by the fine sputum device. After the ethanol is returned, it is returned to the step 3 for recycling; Step 5: The ammonium thiocyanate product is dried: The ammonium thiocyanate crystal obtained in the step 4 is dried by hot air, the temperature is 80-100 ° C, and the time is l~2 h, and the purity is >99%. Ammonium thiocyanate product;
步骤 6: 硫酸铵分离: 按照 3〜5L/kg的比例, 将步骤 2中蒸出的含氨水溶液与步骤 3含 硫代硫酸铵与硫酸铵混合盐的滤饼加入反应釜中混合, 然后按照氢氧化钙 /硫酸 铵的摩尔比为 1 : 1〜1. 2: 1 的比例加入氢氧化钙粉末; 继续搅拌 30〜60分钟, 离心过滤, 得含硫代硫酸铵滤液和硫酸钙滤饼; 硫酸钙滤饼在 100〜12(TC下干燥 1〜2小时后得纯度 > 98%的硫酸钙产品; Step 6: Separation of ammonium sulfate: According to the ratio of 3~5L/kg, the aqueous ammonia solution distilled in step 2 and the filter cake containing the mixed salt of ammonium thiosulfate and ammonium sulfate in step 3 are mixed into the reaction kettle, and then The molar ratio of calcium hydroxide/ammonium sulfate is 1:1~1. The ratio of 2:1 is added to the calcium hydroxide powder; stirring is continued for 30 to 60 minutes, and centrifugal filtration is performed to obtain a filtrate containing ammonium thiosulfate and a calcium sulfate filter cake; The calcium sulfate filter cake has a purity of 98% calcium sulfate after drying for 1 to 2 hours at 100 to 12 (TC);
步骤 7: 硫代硫酸铵滤液浓缩析晶: 将步骤 6硫代硫酸铵滤液于 60〜80°C, 真空度 70〜 90mmHg下减压浓缩至比重为 1. 2〜1. 24 (g/ml)时停止浓缩, 保温转移至析晶釜, 冷却至 10〜30°C后进行离心操作,得含硫代硫酸铵的滤饼和含硫代硫酸铵的饱和 滤液; 浓缩过程蒸出的含氨水溶液补充至焦炉煤气脱硫系统中; 含硫代硫酸铵的 饱和滤液返回步骤 6滤液中继续浓缩析晶; Step 2: The thiosulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate When the concentration is stopped, the heat transfer is transferred to the crystallizer, and after cooling to 10 to 30 ° C, centrifugation is performed to obtain a filter cake containing ammonium thiosulfate and a saturated filtrate containing ammonium thiosulfate; ammonia contained in the concentration process The aqueous solution is replenished into the coke oven gas desulfurization system; the saturated filtrate containing ammonium thiosulfate is returned to the filtrate in step 6 to continue to concentrate and devitrify;
步骤 8: 硫代硫酸铵产品干燥: 将步骤 7硫代硫酸铵滤饼于常压 50〜80°C下热风干燥 1〜 2小时得纯度 > 98%的硫代硫酸酸铵产品。 Step 8: Drying of the ammonium thiosulfate product: The step 7 ammonium thiosulfate filter cake is dried by hot air at a normal pressure of 50 to 80 ° C for 1 to 2 hours to obtain a purity of 98% of ammonium thiosulfate.
5. 一种从焦炉煤气脱硫含盐废液中提取硫氰酸铵的方法, 其特征在于:  5. A method for extracting ammonium thiocyanate from a coke oven gas desulfurization salty waste liquid, characterized in that:
步骤 1 : 脱色除杂: 脱硫废液中加入 0. l〜l% (w/w)活性炭于 80〜100°C下保温 30〜60分 钟, 然后进行过滤操作得脱色后含盐滤液和活性炭滤饼, 活性炭滤饼送专业回收 企业再生处理; 步骤 2: 含盐滤液减压浓缩: 将步骤 1含盐滤液于 60〜80°C, 真空度 70〜90mmHg下减压 浓缩至比重为 1. 18〜1. 26 (g/ml)时停止浓缩, 获得含水量为 10〜30% (w/w) 的 浓缩含盐滤液, 将浓缩含盐滤液保温状态下转至析晶釜, 浓缩过程蒸出的含氨水 溶液留待后续步骤使用和补充至焦炉煤气脱硫系统中; Step 1: Decolorization and decontamination: 0. l~l% (w/w) activated carbon is kept at 80~100 °C for 30~60 minutes, and then filtered to obtain demineralized salt filtrate and activated carbon filter. Cake, activated carbon filter cake for professional recycling enterprise recycling; Step 2: Stop the concentration of the salt-containing filtrate at a concentration of 1.18~1. 26 (g/ml) when the concentration of the salt-containing filtrate is concentrated at 60-80 ° C under a vacuum of 70-90 mmHg. Obtaining a concentrated salty filtrate having a water content of 10 to 30% (w/w), transferring the concentrated salt-containing filtrate to a crystallizing kettle under the state of being kept warm, and discharging the ammoniated aqueous solution in the concentration process for use in subsequent steps and replenishing to the coke Furnace gas desulfurization system;
步骤 3: 硫氰酸铵分离: 按照 4〜10L/kg比例, 将 95%乙醇与浓缩含盐滤液加入析晶釜中 混合搅拌后冷却至 10〜30°C, 然后进行离心操作, 得含硫氰酸铵乙醇滤液和含硫 代硫酸铵与硫酸铵混合盐的滤饼; Step 3: Ammonium thiocyanate separation: According to the ratio of 4~10L/kg, add 95% ethanol and concentrated salty filtrate to the crystallizing kettle, mix and stir, cool to 10~30 °C, and then centrifuge to obtain sulfur. An ammonium cyanate ethanol filtrate and a filter cake containing a mixed salt of ammonium thiosulfate and ammonium sulfate;
步骤 4: 硫氰酸铵乙醇滤液浓缩析晶: 将步骤 3硫氰酸铵乙醇滤液于常压下蒸出含水乙醇 至比重为 1. 2〜1. 25 (g/ml)时停止浓缩, 降至 10〜30°C后进行离心操作, 得硫氰 酸铵晶体和硫氰酸铵乙醇饱和滤液,硫氰酸铵乙醇饱和滤液返回至步骤 3 中循环 利用, 蒸出含水乙醇经精熘装置分离出乙醇后返回步骤 3中循环使用; 步骤 5: 硫氰酸铵产品干燥: 将步骤 4所得硫氰酸铵晶体热风干燥, 温度 80〜100°C, 时 间 l〜2h, 得纯度 > 99%的硫氰酸铵产品; Step 2: The ammonium thiocyanate ethanol filtrate is concentrated and crystallized: Step 3: The ammonium thiocyanate ethanol filtrate is distilled off under normal pressure to remove the aqueous ethanol to a specific gravity of 1. 2~1. 25 (g/ml), the concentration is stopped, and the concentration is lowered. After centrifugation at 10~30 °C, the ammonium thiocyanate crystal and ammonium thiocyanate ethanol saturated filtrate are obtained, and the ammonium thiocyanate ethanol saturated filtrate is returned to the step 3 for recycling, and the distilled ethanol is separated by the fine sputum device. After the ethanol is returned, it is returned to the step 3 for recycling; Step 5: The ammonium thiocyanate product is dried: The ammonium thiocyanate crystal obtained in the step 4 is dried by hot air, the temperature is 80-100 ° C, and the time is l~2 h, and the purity is >99%. Ammonium thiocyanate product;
6.根据权利要求 4所述的从焦炉煤气脱硫含盐废液中提取硫氰酸铵的方法, 其特征在于: 步骤 1 : 脱色除杂: 脱硫废液中加入 0. l% (w/w)活性炭于 100°C下保温 30分钟, 然后进行 过滤操作得脱色后含盐滤液和活性炭滤饼, 活性炭滤饼送专业回收企业再生处 理;  0% (w/) The desulfurization waste liquid is added to the desulfurization waste liquid. w) The activated carbon is kept at 100 ° C for 30 minutes, and then subjected to a filtration operation to obtain a salt-containing filtrate and an activated carbon filter cake after decolorization, and the activated carbon filter cake is sent to a professional recycling enterprise for regeneration treatment;
步骤 2: 含盐滤液减压浓缩: 将步骤 1含盐滤液于 70°C, 真空度 70mmHg下减压浓缩至比 重为 1. 24 (g/ml)时停止浓缩, 获得含水量为 18% (w/w) 的浓缩含盐滤液, 将浓 缩含盐滤液保温状态下转至析晶釜,浓缩过程蒸出的含氨水 0. 4%的水溶液留待后 续步骤使用和补充至焦炉煤气脱硫系统中; Step 2: Concentration of the salt-containing filtrate under reduced pressure: The salt-containing filtrate of step 1 is concentrated under reduced pressure at 70 ° C under a vacuum of 70 mmHg to a specific gravity of 1.24 (g/ml), and the water content is 18% ( w/w) concentrated salt-containing filtrate, the concentrated salt-containing filtrate is transferred to the crystallization tank under heat preservation, and the aqueous solution containing 0.4% of ammonia water distilled from the concentration process is reserved for subsequent steps and is added to the coke oven gas desulfurization system. ;
步骤 3: 硫氰酸铵分离: 按照 8L/kg比例, 将 95%乙醇与浓缩含盐滤液加入析晶釜中混合 搅拌后冷却至 20°C, 然后进行离心操作, 得含硫氰酸铵乙醇滤液和含硫代硫酸铵 与硫酸铵混合盐的滤饼; Step 3: Separation of ammonium thiocyanate: According to the ratio of 8 L/kg, 95% ethanol and concentrated salty filtrate are added to the crystallizing kettle, mixed and stirred, cooled to 20 ° C, and then centrifuged to obtain ammonium thiocyanate. a filtrate and a filter cake comprising a mixed salt of ammonium thiosulfate and ammonium sulfate;
步骤 4: 硫氰酸铵乙醇滤液浓缩析晶: 将步骤 3硫氰酸铵乙醇滤液于常压下蒸出含水乙醇 至比重为 1. 22 (g/ml)时停止浓缩, 降至 20°C后进行离心操作, 得硫氰酸铵晶体 和硫氰酸铵乙醇饱和滤液,硫氰酸铵乙醇饱和滤液返回至步骤 3 中循环利用, 蒸 出含水乙醇经精熘装置分离出乙醇后返回步骤 3中循环使用; Step 4: Concentration and crystallization of ammonium thiocyanate ethanol filtrate: Step 3: The ammonium thiocyanate ethanol filtrate is distilled off under normal pressure to aqueous ethanol until the specific gravity is 1.22 (g/ml), the concentration is stopped, and the concentration is lowered to 20 ° C. After the centrifugation operation, the ammonium thiocyanate crystal and the ammonium thiocyanate ethanol saturated filtrate are obtained, and the ammonium thiocyanate ethanol saturated filtrate is returned to the step 3 for recycling, and the aqueous ethanol is distilled off, and the ethanol is separated by the fine boring device, and then returned to the step 3 Used in circulation;
步骤 5: 硫氰酸铵产品干燥:将步骤 4所得硫氰酸铵晶体热风干燥, 温度 80°C, 时间 lh, 得纯度 > 99%的硫氰酸铵产品; Step 5: drying the ammonium thiocyanate product: drying the ammonium thiocyanate crystal obtained in the step 4 by hot air drying at a temperature of 80 ° C for 1 h to obtain an ammonium thiocyanate product having a purity of >99%;
7. 根据权利要求 4所述的从焦炉煤气脱硫含盐废液中提取硫氰酸铵的方法,其特征在于: 步骤 1 : 脱色除杂: 脱硫废液中加入 0. 5% (w/w)活性炭于 80°C下保温 45分钟, 然后进行 过滤操作得脱色后含盐滤液和活性炭滤饼, 活性炭滤饼送专业回收企业再生处 理; 5% (w/) The desulfurization waste liquid is added to the desulfurization waste liquid by adding 0.5% (w/). w) The activated carbon is kept at 80 ° C for 45 minutes, and then subjected to a filtration operation to obtain a salt-containing filtrate and an activated carbon filter cake after decolorization, and the activated carbon filter cake is sent to a professional recycling enterprise for regeneration treatment;
步骤 2: 含盐滤液减压浓缩: 将步骤 1含盐滤液于 80°C, 真空度 90mmHg下减压浓缩至比 重为 1. 22 (g/ml)时停止浓缩, 获得含水量为 20% (w/w) 的浓缩含盐滤液, 将浓 缩含盐滤液保温状态下转至析晶釜, 浓缩过程蒸出的含氨水 0. 4% (w/w) 的水溶 液留待后续步骤使用和补充至焦炉煤气脱硫系统中; Step 2: Concentration of the salt-containing filtrate under reduced pressure: The salt-containing filtrate of step 1 is concentrated at 80 ° C under a vacuum of 90 mmHg to a specific gravity of 1.22 (g/ml) to stop concentration, and the water content is 20% ( w/w) Concentrated salt-containing filtrate, the concentrated salt-containing filtrate is transferred to the crystallization tank under heat preservation, and the aqueous solution containing 0.4% (w/w) of ammonia water distilled from the concentration process is reserved for subsequent steps and replenished to the coke Furnace gas desulfurization system;
步骤 3: 硫氰酸铵分离: 按照 10L/kg比例, 将 95%乙醇与浓缩含盐滤液加入析晶釜中混 合搅拌后冷却至 30°C, 然后进行离心操作, 得含硫氰酸铵乙醇滤液和含硫代硫酸 铵与硫酸铵混合盐的滤饼; Step 3: Ammonium thiocyanate separation: According to the ratio of 10 L/kg, 95% ethanol and concentrated salty filtrate are added to the crystallizing kettle, mixed and stirred, cooled to 30 ° C, and then centrifuged to obtain ammonium thiocyanate. a filtrate and a filter cake comprising a mixed salt of ammonium thiosulfate and ammonium sulfate;
步骤 4: 硫氰酸铵乙醇滤液浓缩析晶: 将步骤 3硫氰酸铵乙醇滤液于常压下蒸出含水乙醇 至比重为 1. 24 (g/ml)时停止浓缩, 降至 20°C后进行离心操作, 得硫氰酸铵晶体 和硫氰酸铵乙醇饱和滤液,硫氰酸铵乙醇饱和滤液返回至步骤 3 中循环利用, 蒸 出含水乙醇经精熘装置分离出乙醇后返回步骤 3中循环使用; Step 4: Concentration and crystallization of the ammonium thiocyanate ethanol filtrate: Step 3: The ammonium thiocyanate ethanol filtrate is distilled off under normal pressure to aqueous ethanol until the specific gravity is 1.24 (g/ml), the concentration is stopped, and the concentration is lowered to 20 ° C. After the centrifugation operation, the ammonium thiocyanate crystal and the ammonium thiocyanate ethanol saturated filtrate are obtained, and the ammonium thiocyanate ethanol saturated filtrate is returned to the step 3 for recycling, and the aqueous ethanol is distilled off, and the ethanol is separated by the fine boring device, and then returned to the step 3 Used in circulation;
步骤 5: 硫氰酸铵产品干燥:将步骤 4所得硫氰酸铵晶体热风干燥, 温度 80°C, 时间 lh, 得纯度 > 99%的硫氰酸铵产品; Step 5: drying the ammonium thiocyanate product: drying the ammonium thiocyanate crystal obtained in the step 4 by hot air drying at a temperature of 80 ° C for 1 h to obtain an ammonium thiocyanate product having a purity of >99%;
8. 一种从焦炉煤气脱硫含盐废液中提取硫代硫酸酸铵的方法, 其特征在于:  8. A method for extracting ammonium thiosulfate from a coke oven gas desulfurization salty waste liquid, characterized in that:
步骤 1 : 脱色除杂: 脱硫废液中加入 0. l〜l% (w/w)活性炭于 80〜100°C下保温 30〜60分 钟, 然后进行过滤操作得脱色后含盐滤液和活性炭滤饼, 活性炭滤饼送专业回收 企业再生处理; Step 1: Decolorization and decontamination: 0. l~l% (w/w) activated carbon is kept at 80~100 °C for 30~60 minutes, and then filtered to obtain demineralized salt filtrate and activated carbon filter. Cake, activated carbon filter cake for professional recycling enterprise recycling;
步骤 2: 含盐滤液减压浓缩: 将步骤 1含盐滤液于 60〜80°C, 真空度 70〜90mmHg下减压 浓缩至比重为 1. 18〜1. 26 (g/ml)时停止浓缩, 获得含水量为 10〜30% (w/w) 的 浓缩含盐滤液, 将浓缩含盐滤液保温状态下转至析晶釜, 浓缩过程蒸出的含氨水 溶液留待后续步骤使用和补充至焦炉煤气脱硫系统中; Step 2: Stop the concentration of the salt-containing filtrate at a concentration of 1.18~1. 26 (g/ml) when the concentration of the salt-containing filtrate is concentrated at 60-80 ° C under a vacuum of 70-90 mmHg. Obtaining a concentrated salty filtrate having a water content of 10 to 30% (w/w), transferring the concentrated salt-containing filtrate to a crystallizing kettle under the state of being kept warm, and discharging the ammoniated aqueous solution in the concentration process for use in subsequent steps and replenishing to the coke Furnace gas desulfurization system;
步骤 3: 硫氰酸铵分离: 按照 4〜10L/kg比例, 将 95%乙醇与浓缩含盐滤液加入析晶釜中 混合搅拌后冷却至 10〜30°C, 然后进行离心操作, 得含硫氰酸铵乙醇滤液和含硫 代硫酸铵与硫酸铵混合盐的滤饼; Step 3: Ammonium thiocyanate separation: According to the ratio of 4~10L/kg, add 95% ethanol and concentrated salty filtrate to the crystallizing kettle, mix and stir, cool to 10~30 °C, and then centrifuge to obtain sulfur. An ammonium cyanate ethanol filtrate and a filter cake containing a mixed salt of ammonium thiosulfate and ammonium sulfate;
步骤 4: 硫酸铵分离: 按照 3〜5L/kg的比例, 将步骤 2中蒸出的含氨水溶液与步骤 3含 硫代硫酸铵与硫酸铵混合盐的滤饼加入反应釜中混合, 然后按照氢氧化钙 /硫酸 铵的摩尔比为 1 : 1〜1. 2: 1 的比例加入氢氧化钙粉末; 继续搅拌 30〜60分钟, 离心过滤, 得含硫代硫酸铵滤液和硫酸钙滤饼; 硫酸钙滤饼在 100〜12(TC下干燥 1〜2小时后得纯度 > 98%的硫酸钙产品; Step 4: Ammonium sulfate separation: According to the ratio of 3~5L/kg, the ammonia solution distilled from step 2 and the filter cake containing the mixed salt of ammonium thiosulfate and ammonium sulfate in step 3 are mixed into the reaction kettle, and then Calcium hydroxide / sulfuric acid The molar ratio of ammonium is 1:1~1. The ratio of 2:1 is added to the calcium hydroxide powder; the stirring is continued for 30 to 60 minutes, and the mixture is centrifuged to obtain a filtrate containing ammonium thiosulfate and a calcium sulfate filter cake; 100~12 (purity after drying for 1~2 hours at TC > 98% calcium sulfate product;
步骤 5: 硫代硫酸铵滤液浓缩析晶: 将步骤 4硫代硫酸铵滤液于 60〜80°C, 真空度 70〜 90mmHg下减压浓缩至比重为 1. 2〜1. 24 (g/ml)时停止浓缩, 保温转移至析晶釜, 冷却至 10〜30°C后进行离心操作,得含硫代硫酸铵的滤饼和含硫代硫酸铵的饱和 滤液; 浓缩过程蒸出的含氨水溶液补充至焦炉煤气脱硫系统中; 含硫代硫酸铵的 饱和滤液返回步骤 4滤液中继续浓缩析晶; Step 2: The thiosulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate sulphate When the concentration is stopped, the heat transfer is transferred to the crystallizer, and after cooling to 10 to 30 ° C, centrifugation is performed to obtain a filter cake containing ammonium thiosulfate and a saturated filtrate containing ammonium thiosulfate; ammonia contained in the concentration process The aqueous solution is replenished into the coke oven gas desulfurization system; the saturated filtrate containing ammonium thiosulfate is returned to the filtrate in step 4 to continue to concentrate and devitrify;
步骤 6: 硫代硫酸铵产品干燥: 将步骤 5硫代硫酸铵滤饼于常压 50〜80°C下热风干燥 1〜 2小时得纯度 > 98%的硫代硫酸酸铵产品。 Step 6: Drying of the ammonium thiosulfate product: Step 5: The ammonium thiosulfate filter cake is dried by hot air at a normal pressure of 50 to 80 ° C for 1 to 2 hours to obtain a purity of 98% of ammonium thiosulfate.
9. 根据权利要求 7所述的从焦炉煤气脱硫含盐废液中提取硫代硫酸酸铵的方法, 其特征 在于:  9. The method for extracting ammonium thiosulfate from a coke oven gas desulfurization salty waste liquid according to claim 7, wherein:
步骤 1 : 脱色除杂: 脱硫废液中加入 0. l% (w/w)活性炭于 100°C下保温 30分钟, 然后进行 过滤操作得脱色后含盐滤液和活性炭滤饼, 活性炭滤饼送专业回收企业再生处 理; Step 1: Decolorization and decontamination: Add 0. l% (w/w) of activated carbon to the mixture at 100 ° C for 30 minutes, and then carry out the filtration operation to obtain the salt filtrate and the activated carbon filter cake after decolorization, and the activated carbon filter cake is sent. Professional recycling enterprise recycling treatment;
步骤 2: 含盐滤液减压浓缩: 将步骤 1含盐滤液于 70°C, 真空度 70mmHg下减压浓缩至比 重为 1. 24 (g/ml)时停止浓缩, 获得含水量为 18% (w/w) 的浓缩含盐滤液, 将浓 缩含盐滤液保温状态下转至析晶釜,浓缩过程蒸出的含氨水 0. 4%的水溶液留待后 续步骤使用和补充至焦炉煤气脱硫系统中; Step 2: Concentration of the salt-containing filtrate under reduced pressure: The salt-containing filtrate of step 1 is concentrated under reduced pressure at 70 ° C under a vacuum of 70 mmHg to a specific gravity of 1.24 (g/ml), and the water content is 18% ( w/w) concentrated salt-containing filtrate, the concentrated salt-containing filtrate is transferred to the crystallization tank under heat preservation, and the aqueous solution containing 0.4% of ammonia water distilled from the concentration process is reserved for subsequent steps and is added to the coke oven gas desulfurization system. ;
步骤 3: 硫氰酸铵分离: 按照 8L/kg比例, 将 95%乙醇与浓缩含盐滤液加入析晶釜中混合 搅拌后冷却至 20°C, 然后进行离心操作, 得含硫氰酸铵乙醇滤液和含硫代硫酸铵 与硫酸铵混合盐的滤饼; Step 3: Separation of ammonium thiocyanate: According to the ratio of 8 L/kg, 95% ethanol and concentrated salty filtrate are added to the crystallizing kettle, mixed and stirred, cooled to 20 ° C, and then centrifuged to obtain ammonium thiocyanate. a filtrate and a filter cake comprising a mixed salt of ammonium thiosulfate and ammonium sulfate;
步骤 4: 硫酸铵分离: 按照 5L/kg的比例, 将步骤 2中蒸出的含氨水 0. 4%的水溶液与步 骤 3含硫代硫酸铵与硫酸铵混合盐的滤饼加入反应釜中混合, 然后按照氢氧化钙 /硫酸铵的摩尔比为 1. 2 : 1的比例加入氢氧化钙粉末; 继续搅拌 30分钟, 离心过 滤, 得含硫代硫酸铵滤液和硫酸钙滤饼; 硫酸钙滤饼在 100°C下干燥 2小时后得 纯度 > 98%的硫酸钙产品; Step 4: Separation of ammonium sulfate: According to the ratio of 5 L/kg, the aqueous solution containing 0.5% of the aqueous ammonia in the step 2 and the filter cake containing the mixed salt of ammonium thiosulfate and ammonium sulfate in step 3 are mixed into the reaction kettle. Then, the calcium hydroxide powder is added in a molar ratio of calcium hydroxide/ammonium sulfate of 1.2:1; stirring is continued for 30 minutes, and centrifugal filtration is carried out to obtain a filtrate containing ammonium thiosulfate and a calcium sulfate filter; calcium sulfate filter The cake was dried at 100 ° C for 2 hours to obtain a calcium sulfate product having a purity of > 98%;
步骤 5: 硫代硫酸铵滤液浓缩析晶: 将步骤 4硫代硫酸铵滤液于 70°C, 真空度 70mmHg下 减压浓缩至比重为 1. 22 (g/ml)时停止浓缩, 保温转移至析晶釜, 冷却至 10°C后 进行离心操作, 得含硫代硫酸铵的滤饼和含硫代硫酸铵的饱和滤液; 浓缩过程蒸 出的含氨水 0. 4% (w/w)的水溶液补充至焦炉煤气脱硫系统中; 含硫代硫酸铵的饱 和滤液返回步骤 4滤液中继续浓缩析晶; Step 5: Concentration and crystallization of the ammonium thiosulfate filtrate: The step 4 ammonium thiosulfate filtrate is concentrated under reduced pressure at 70 ° C under a vacuum of 70 mmHg to a specific gravity of 1.22 (g/ml), the concentration is stopped, and the heat transfer is transferred to The crystallizer is cooled to 10 ° C and then centrifuged to obtain a filter cake containing ammonium thiosulfate and a saturated filtrate containing ammonium thiosulfate; The aqueous solution containing 0.4% (w/w) of ammonia water is added to the coke oven gas desulfurization system; the saturated filtrate containing ammonium thiosulfate is returned to the filtrate in step 4 to continue concentration and crystallization;
步骤 6: 硫代硫酸铵产品干燥: 将步骤 5硫代硫酸铵滤饼于常压 60°C下热风干燥 2小时 得纯度 > 98%的硫代硫酸酸铵产品。 Step 6: Drying of the ammonium thiosulfate product: The step 5 ammonium thiosulfate filter cake is dried by hot air at a normal pressure of 60 ° C for 2 hours to obtain a product of ammonium thiosulfate having a purity of > 98%.
10. 根据权利要求 7所述的从焦炉煤气脱硫含盐废液中提取硫代硫酸酸铵的方法, 其特 征在于: 10. The method for extracting ammonium thiosulfate from a coke oven gas desulfurization salty waste liquid according to claim 7, wherein:
步骤 1 : 脱色除杂: 脱硫废液中加入 0. 5% (w/w)活性炭于 80°C下保温 45分钟, 然后进行 过滤操作得脱色后含盐滤液和活性炭滤饼, 活性炭滤饼送专业回收企业再生处 理; Step 1: Decolorization and decontamination: Add 0.5% (w/w) activated carbon to the desulfurization waste liquid for 40 minutes at 80 ° C, and then carry out filtration operation to obtain a salt filtrate and an activated carbon filter cake after decolorization, and the activated carbon filter cake is sent. Professional recycling enterprise recycling treatment;
步骤 2: 含盐滤液减压浓缩: 将步骤 1含盐滤液于 80°C, 真空度 90mmHg下减压浓缩至比 重为 1. 22 (g/ml)时停止浓缩, 获得含水量为 20% (w/w) 的浓缩含盐滤液, 将浓 缩含盐滤液保温状态下转至析晶釜, 浓缩过程蒸出的含氨水 0. 4% (w/w) 的水溶 液留待后续步骤使用和补充至焦炉煤气脱硫系统中; Step 2: Concentration of the salt-containing filtrate under reduced pressure: The salt-containing filtrate of step 1 is concentrated at 80 ° C under a vacuum of 90 mmHg to a specific gravity of 1.22 (g/ml) to stop concentration, and the water content is 20% ( w/w) Concentrated salt-containing filtrate, the concentrated salt-containing filtrate is transferred to the crystallization tank under heat preservation, and the aqueous solution containing 0.4% (w/w) of ammonia water distilled from the concentration process is reserved for subsequent steps and replenished to the coke Furnace gas desulfurization system;
步骤 3: 硫氰酸铵分离: 按照 10L/kg比例, 将 95%乙醇与浓缩含盐滤液加入析晶釜中混 合搅拌后冷却至 30°C, 然后进行离心操作, 得含硫氰酸铵乙醇滤液和含硫代硫酸 铵与硫酸铵混合盐的滤饼; Step 3: Ammonium thiocyanate separation: According to the ratio of 10 L/kg, 95% ethanol and concentrated salty filtrate are added to the crystallizing kettle, mixed and stirred, cooled to 30 ° C, and then centrifuged to obtain ammonium thiocyanate. a filtrate and a filter cake comprising a mixed salt of ammonium thiosulfate and ammonium sulfate;
步骤 4: 硫酸铵分离: 按照 3L/kg的比例, 将步骤 2中蒸出的含氨水 0. 4% (w/w)的水溶液 与步骤 3含硫代硫酸铵与硫酸铵混合盐的滤饼加入反应釜中混合, 然后按照氢氧 化钙 /硫酸铵的摩尔比为 1 : 1的比例加入氢氧化钙粉末; 继续搅拌 45分钟, 离心 过滤, 得含硫代硫酸铵滤液和硫酸钙滤饼; 硫酸钙滤饼在 120°C下干燥 2小时后 得纯度 > 98%的硫酸钙产品; Step 4: Separation of ammonium sulfate: According to the ratio of 3 L/kg, the aqueous solution containing 0.4% (w/w) of ammonia water distilled in step 2 and the filter cake of mixed salt of ammonium thiosulfate and ammonium sulfate in step 3. Adding to the reaction vessel for mixing, and then adding calcium hydroxide powder according to a molar ratio of calcium hydroxide/ammonium sulfate of 1:1; stirring is continued for 45 minutes, and centrifuging to obtain a filtrate containing ammonium thiosulfate and a calcium sulfate filter cake; The calcium sulfate filter cake is dried at 120 ° C for 2 hours to obtain a calcium sulfate product having a purity of > 98%;
步骤 5: 硫代硫酸铵滤液浓缩析晶: 将步骤 4硫代硫酸铵滤液于 80°C, 真空度 90mmHg下 减压浓缩至比重为 1. 23 (g/ml)时停止浓缩, 保温转移至析晶釜, 冷却至 20°C后 进行离心操作, 得含硫代硫酸铵的滤饼和含硫代硫酸铵的饱和滤液; 浓缩过程蒸 出的含氨水 0. 4% (w/w)的水溶液补充至焦炉煤气脱硫系统中; 含硫代硫酸铵的饱 和滤液返回步骤 4滤液中继续浓缩析晶; Step 5: Concentration and crystallization of the ammonium thiosulfate filtrate: The step 4 ammonium thiosulfate filtrate is concentrated under reduced pressure at a vacuum of 90 mmHg to a specific gravity of 1.23 (g/ml), and the concentration is stopped. 4% (w/w) of the aqueous solution containing ammonium thiosulfate and a saturated filtrate containing ammonium thiosulfate; The aqueous solution is replenished into the coke oven gas desulfurization system; the saturated filtrate containing ammonium thiosulfate is returned to the filtrate in step 4 to continue to concentrate and devitrify;
步骤 6: 硫代硫酸铵产品干燥: 将步骤 5硫代硫酸铵滤饼于常压 80°C下热风干燥 2小时 得纯度 > 98%的硫代硫酸酸铵产品。 Step 6: Drying of the ammonium thiosulfate product: The step 5 ammonium thiosulfate filter cake is dried by hot air at 80 ° C for 2 hours to obtain a product of ammonium thiosulfate having a purity of > 98%.
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