CN110371933A - A kind of method of purification of spent acid - Google Patents
A kind of method of purification of spent acid Download PDFInfo
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- CN110371933A CN110371933A CN201910685247.4A CN201910685247A CN110371933A CN 110371933 A CN110371933 A CN 110371933A CN 201910685247 A CN201910685247 A CN 201910685247A CN 110371933 A CN110371933 A CN 110371933A
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- 239000002253 acid Substances 0.000 title claims abstract description 36
- 238000000746 purification Methods 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000002699 waste material Substances 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 9
- 238000004042 decolorization Methods 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 239000003712 decolorant Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 238000005265 energy consumption Methods 0.000 description 3
- 239000012286 potassium permanganate Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 150000003109 potassium Chemical class 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/90—Separation; Purification
- C01B17/92—Recovery from acid tar or the like, e.g. alkylation acids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种废酸的提纯方法，它包括：1）脱色：在15~150℃下，向废酸中缓慢加入脱色剂，所述的废酸和脱色剂质量比为4~5:1，脱色剂添加的速度为4~6g/min，直到废酸变成无色或接近无色，得到溶液A，同时回收反应产生的气体；2）硫酸提纯：溶液A在300~400℃下精馏，气体馏分经冷凝得到稀硫酸溶液，同时得到釜底的液体；将液体过滤，除去固体残渣，得到浓硫酸；优点在于：用本发明的方法简单易操作，成本低廉；提纯得到的浓硫酸，浓度为97.95%，纯度高；适于工业生产。The invention discloses a purification method of waste acid, which includes: 1) decolorization: at 15-150°C, slowly add a decolorant to the waste acid, the mass ratio of the waste acid to the decolorant is 4-5: 1. Add the decolorizing agent at a rate of 4~6g/min until the waste acid becomes colorless or nearly colorless to obtain solution A, and at the same time recover the gas generated by the reaction; 2) Sulfuric acid purification: Solution A is at 300~400°C Rectification, the gas fraction is condensed to obtain dilute sulfuric acid solution and the liquid at the bottom of the kettle; the liquid is filtered to remove solid residues to obtain concentrated sulfuric acid; the advantages are: the method of the present invention is simple and easy to operate, and the cost is low; the concentrated sulfuric acid obtained by purification Sulfuric acid, the concentration is 97.95%, high purity; suitable for industrial production.
Description
技术领域technical field
本发明属于废酸处理技术领域，具体涉及一种废酸的提纯方法。The invention belongs to the technical field of waste acid treatment, and in particular relates to a method for purifying waste acid.
背景技术Background technique
石油磺酸盐是以石油及其馏份为原料，用SO3作为磺化剂进行磺化，再用碱中和而制成的产品。它是一种高品质的表面活性剂，与表面活性剂助剂复配，其作用是降低油水界面张力，更好地提高洗油效率，主要用于油田三采期的驱油。Petroleum sulfonate is a product made from petroleum and its fractions, sulfonated with SO 3 as a sulfonating agent, and then neutralized with alkali. It is a high-quality surfactant, compounded with surfactant additives, its function is to reduce the interfacial tension of oil and water, better improve the efficiency of oil washing, and is mainly used for oil displacement in the tertiary recovery period of oil fields.
在磺化过程中，一般用浓硫酸吸收多余的SO3，产生深棕色的废酸。废酸是一种液体，偷排偷放比固体废物和废气来得方便和隐蔽，因此，从环境保护的角度讲，废酸的治理极为迫切。从化学角度来讲，所谓的废物是指没被利用的物质，如果将这些物质加以利用，不但可以减少污染，同时也可节省资源，具有重大的经济效益和环境效益。目前大多废酸处理技术采用的方法是高温焙烧，产生的气体经处理得到SO2，再氧化为SO3，制备硫酸。该方法过程复杂，能耗高，不符合当今的要求。In the sulfonation process, concentrated sulfuric acid is generally used to absorb excess SO 3 , resulting in dark brown spent acid. Waste acid is a kind of liquid, which is more convenient and concealed than solid waste and waste gas. Therefore, from the perspective of environmental protection, the treatment of waste acid is extremely urgent. From a chemical point of view, the so-called waste refers to unused substances. If these substances are used, not only can reduce pollution, but also save resources, which has significant economic and environmental benefits. At present, most waste acid treatment technologies adopt high-temperature roasting, and the generated gas is processed to obtain SO 2 , which is then oxidized to SO 3 to prepare sulfuric acid. This method is complex in process, high in energy consumption, and does not meet today's requirements.
发明内容Contents of the invention
本发明目的是为解决现有废酸提纯的工艺复杂、能耗高的问题，而提供一种简单易行、能耗低的废酸的提纯方法。The purpose of the present invention is to provide a simple and easy purification method of waste acid with low energy consumption in order to solve the problems of complex process and high energy consumption in the existing waste acid purification process.
一种废酸的提纯方法，它包括：A kind of purification method of waste acid, it comprises:
1）脱色：在15~150℃下，向废酸中缓慢加入脱色剂，所述的废酸和脱色剂质量比为4~5:1，脱色剂添加的速度为4~6g/min，直到废酸变成无色或接近无色，得到溶液A，同时回收反应产生的气体；1) Decolorization: at 15~150°C, slowly add a decolorizer to the waste acid, the mass ratio of the waste acid to the decolorizer is 4~5:1, and the speed of adding the decolorizer is 4~6g/min until The spent acid becomes colorless or nearly colorless, and solution A is obtained, and the gas produced by the reaction is recovered simultaneously;
2）硫酸提纯：溶液A在300~400℃下精馏，气体馏分经冷凝得到稀硫酸溶液，同时得到釜底的液体；除去液体中固体残渣，得到浓硫酸；2) Sulfuric acid purification: solution A is rectified at 300~400°C, and the gas fraction is condensed to obtain a dilute sulfuric acid solution, and at the same time obtain the liquid at the bottom of the kettle; remove the solid residue in the liquid to obtain concentrated sulfuric acid;
步骤1）所述的脱色剂为强氧化剂；The decolorizing agent described in step 1) is a strong oxidizing agent;
步骤2）所述的除去液体中固体残渣，是过滤或蒸馏除去；In step 2), the solid residue in the liquid is removed by filtration or distillation;
步骤2）所述的精馏，温度为300~350℃。For the rectification described in step 2), the temperature is 300~350°C.
本发明提供了一种废酸的提纯方法，它包括：1）脱色：在15~150℃下，向废酸中缓慢加入脱色剂，所述的废酸和脱色剂质量比为4~5:1，脱色剂添加的速度为4~6g/min，直到废酸变成无色或接近无色，得到溶液A，同时回收反应产生的气体；2）硫酸提纯：溶液A在300~400℃下精馏，气体馏分经冷凝得到稀硫酸溶液，同时得到釜底的液体；将液体过滤，除去固体残渣，得到浓硫酸；优点在于：用本发明的方法简单易操作，成本低廉；提纯得到的浓硫酸，浓度为97.95%，纯度高；适于工业生产。The invention provides a method for purifying waste acid, which includes: 1) decolorization: at 15-150°C, slowly add a decolorizer to the waste acid, and the mass ratio of the waste acid to the decolorant is 4-5: 1. Add the decolorizing agent at a rate of 4~6g/min until the waste acid becomes colorless or nearly colorless to obtain solution A, and at the same time recover the gas generated by the reaction; 2) Sulfuric acid purification: Solution A is at 300~400°C Rectification, the gas fraction is condensed to obtain dilute sulfuric acid solution and the liquid at the bottom of the kettle; the liquid is filtered to remove solid residues to obtain concentrated sulfuric acid; the advantages are: the method of the present invention is simple and easy to operate, and the cost is low; the concentrated sulfuric acid obtained by purification Sulfuric acid, the concentration is 97.95%, high purity; suitable for industrial production.
附图说明Description of drawings
图1 脱色时产生气体的质谱图；The mass spectrogram of gas produced during Fig. 1 decolorization;
图2 废酸及提纯后的硫酸对比结果；Fig. 2 Comparison results of spent acid and purified sulfuric acid;
图3 提纯后分离出的固体残渣。Figure 3. Solid residue isolated after purification.
具体实施方式Detailed ways
实施例1 一种废酸的提纯方法Embodiment 1 A kind of purification method of waste acid
以过氧化氢为脱色剂进行废酸的提纯，具体的步骤如下：Carry out the purification of spent acid with hydrogen peroxide as decolorizing agent, concrete steps are as follows:
（1）脱色：取废酸510g，放在烧杯中，在室温下缓慢滴加过氧化氢，由于浓硫酸吸水或发生氧化反应使废酸温度逐渐升高，当达到100℃时，反应激烈，放出大量的气体（约16克，含有水蒸气、氧气、二氧化碳等，见图1）；在20 min内滴加过氧化氢110g后，废酸的温度升到170℃，此时达到淡绿色溶液A；(1) Decolorization: Take 510g of waste acid, put it in a beaker, slowly add hydrogen peroxide dropwise at room temperature, the temperature of waste acid will gradually rise due to the absorption of concentrated sulfuric acid or oxidation reaction, when it reaches 100°C, the reaction will be intense, Release a large amount of gas (about 16 grams, containing water vapor, oxygen, carbon dioxide, etc., see Figure 1); after adding 110g of hydrogen peroxide dropwise within 20 minutes, the temperature of the waste acid rises to 170°C, and at this time it reaches a light green solution A;
（2）硫酸提纯：将溶液A转移到石英圆底烧瓶中，350℃精馏，气体馏分经冷凝得到稀硫酸（无色透明，99.6克，密度1.106 g/ml）；釜底的液体中含有一些杂质，经过过滤，得到的液体即为浓硫酸（无色透明，约500克，密度1.848 g/ml），同时过滤得到淡绿色固体残渣1.1克（图3）。(2) Purification of sulfuric acid: transfer solution A to a quartz round bottom flask, rectify at 350°C, and condense the gas fraction to obtain dilute sulfuric acid (colorless and transparent, 99.6 grams, density 1.106 g/ml); the liquid at the bottom of the kettle contains Some impurities, after filtration, the liquid obtained is concentrated sulfuric acid (colorless and transparent, about 500 grams, density 1.848 g/ml), and filtered at the same time to obtain 1.1 grams of light green solid residue (Figure 3).
测定处理后得到的硫酸指标，结果如表1所示。The sulfuric acid index obtained after the treatment was measured, and the results are shown in Table 1.
实施例2 一种废酸的提纯方法Embodiment 2 A kind of purification method of waste acid
以高锰酸钾为脱色剂进行废酸的提纯，具体的步骤如下：Carry out the purification of spent acid with potassium permanganate as decolorizer, concrete steps are as follows:
（1）脱色：取废酸78.8g，放在烧杯中，加热至100℃停止加热，缓慢滴加饱和高锰酸钾溶液，由于浓硫酸吸水或发生氧化反应使废酸温度逐渐升高，控制温度在200℃左右；在20min内滴加饱和高锰酸钾溶液25 ml后，得到淡黄色溶液A；(1) Decolorization: Take 78.8g of waste acid, put it in a beaker, heat to 100°C to stop heating, slowly add saturated potassium permanganate solution dropwise, the temperature of waste acid will gradually increase due to the absorption of concentrated sulfuric acid or oxidation reaction, control The temperature is around 200°C; after adding 25 ml of saturated potassium permanganate solution dropwise within 20 minutes, a light yellow solution A is obtained;
（2）硫酸提纯：将溶液A转移到石英圆底烧瓶中，350℃蒸馏，气体馏分经冷凝得到稀硫酸（无色透明，28.3克，密度1.03 g/ml）；釜底的液体加热到400℃蒸馏，馏分冷却后得到浓硫酸（淡黄色，约73.1克，密度1.821 g/ml），烧瓶中棕色固体残渣（5.5克）。(2) Purification of sulfuric acid: transfer solution A to a quartz round bottom flask, distill at 350°C, and condense the gas fraction to obtain dilute sulfuric acid (colorless and transparent, 28.3 grams, density 1.03 g/ml); the liquid at the bottom of the kettle is heated to 400 Distill at °C, and the distillate was cooled to obtain concentrated sulfuric acid (light yellow, about 73.1 g, density 1.821 g/ml), and a brown solid residue (5.5 g) in the flask.
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| CN113336198A (en) * | 2021-08-05 | 2021-09-03 | 清大国华环境集团股份有限公司 | Method and system for recycling waste sulfuric acid in integrated circuit industry |
| CN116161621A (en) * | 2023-04-23 | 2023-05-26 | 联仕(昆山)化学材料有限公司 | Purification device and purification process of electronic grade hydrochloric acid |
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