CN1765764A - Copper-containing waste acid water treatment method - Google Patents
Copper-containing waste acid water treatment method Download PDFInfo
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- CN1765764A CN1765764A CN 200410086303 CN200410086303A CN1765764A CN 1765764 A CN1765764 A CN 1765764A CN 200410086303 CN200410086303 CN 200410086303 CN 200410086303 A CN200410086303 A CN 200410086303A CN 1765764 A CN1765764 A CN 1765764A
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- 239000002253 acid Substances 0.000 title claims abstract description 72
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 47
- 239000010949 copper Substances 0.000 title claims abstract description 47
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000002699 waste material Substances 0.000 title claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 37
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 42
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 claims abstract description 17
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 14
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims abstract description 8
- YAECNLICDQSIKA-UHFFFAOYSA-L calcium;sulfanide Chemical compound [SH-].[SH-].[Ca+2] YAECNLICDQSIKA-UHFFFAOYSA-L 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 239000007789 gas Substances 0.000 claims description 22
- 239000000047 product Substances 0.000 claims description 22
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 21
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 21
- 238000002386 leaching Methods 0.000 claims description 19
- 239000002244 precipitate Substances 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000010521 absorption reaction Methods 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 6
- 230000002745 absorbent Effects 0.000 claims description 5
- 239000002250 absorbent Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims 1
- 238000007599 discharging Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 7
- 229910052979 sodium sulfide Inorganic materials 0.000 abstract description 4
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 abstract description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- -1 at the same time Substances 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- IELPSGPHQCRVQW-UHFFFAOYSA-L barium(2+);sulfanide Chemical compound [SH-].[SH-].[Ba+2] IELPSGPHQCRVQW-UHFFFAOYSA-L 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000005649 metathesis reaction Methods 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000003403 water pollutant Substances 0.000 description 2
- 239000005749 Copper compound Substances 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- LBVNUQQORDPZCR-UHFFFAOYSA-N calcium;sulfane Chemical compound S.[Ca] LBVNUQQORDPZCR-UHFFFAOYSA-N 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000035617 depilation Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 210000003097 mucus Anatomy 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000988 sulfur dye Substances 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- Manufacture And Refinement Of Metals (AREA)
Abstract
一种含铜废酸水处理方法，它以硫化钡或硫化钠为原料，处理工业含铜废酸水，可制得硫酸钡、硫化铜和硫氢化钠或硫氢化钙等多种化工产品，同时，还可以回收H+含量＞16％的酸液，做为除铁锈剂，不产生公害，对环境无污染，可有效地保护环境，造福于人类，产生了显著的社会效益，并且经济效益显著。
A copper-containing waste acid water treatment method, which uses barium sulfide or sodium sulfide as raw materials to treat industrial copper-containing waste acid water, and can produce barium sulfate, copper sulfide, sodium hydrosulfide or calcium hydrosulfide and other chemical products, At the same time, the acid solution with H + content > 16% can also be recovered as a rust remover, which does not produce public nuisance, has no pollution to the environment, can effectively protect the environment, benefit mankind, and has produced significant social and economic benefits. significantly.
Description
技术领域Technical field
本发明涉及一种液体废物处理方法，特别是含铜废酸水的处理方法。它适用于在化工生产过程中产生含铜废酸水污染物的化工行业。The invention relates to a liquid waste treatment method, in particular to a treatment method for copper-containing waste acid water. It is suitable for the chemical industry that produces copper-containing waste acid water pollutants in the chemical production process.
背景技术 Background technique
通常，糖精钠的生产过程中，在重氮液置换反应、氯化反应生成磺酰氯时，会产生大量的含铜废酸水污染物，该废酸水中主要含：CL-，SO4 2-，Na+，H+含量＞16％以及一些有机物质。目前，对于这种废酸水的处理，曾采用一种铁置换的方法，将铁粉置于该废酸水中进行置换反应，生成海绵铜，从而达到回收铜的目的。但是，置换反应后的酸性废水无利用价值全部被排放掉，这不仅使废酸性水中所含的有用物质白白的浪费掉，得不到充分的利用，而且，还会造成严重的环境污染，给社会及人们的生活带来危害。Usually, during the production process of sodium saccharin, when diazo solution replacement reaction and chlorination reaction generate sulfuryl chloride, a large amount of copper-containing waste acid water pollutants will be produced. The waste acid water mainly contains: CL - , SO 4 2- , Na + , H + content > 16% and some organic matter. At present, for the treatment of this waste acid water, a method of iron replacement has been adopted, in which iron powder is placed in the waste acid water for a replacement reaction to generate sponge copper, thereby achieving the purpose of copper recovery. However, the acid waste water after the replacement reaction has no use value and is all discharged, which not only wastes the useful substances contained in the waste acid water and cannot be fully utilized, but also causes serious environmental pollution. Harm to society and people's lives.
发明内容Contents of Invention
本发明的目的在于提供一种含铜废酸水处理方法，它能够克服现有技术的不足，使含铜废酸水处理过程中，避免产生废酸污水，并且能生产出沉淀硫酸钡、硫化铜及硫氢化钠或硫氢化钙等多种化工产品，还能同时回收H+含量＞16％的酸液。这样，不仅能从根本上消除含铜废酸水的污染，而且使废物得到充分的综合利用，在回收铜的同时，又能生产出有用的化工产品，经济效益显著。The object of the present invention is to provide a kind of copper-containing waste acid water treatment method, it can overcome the deficiencies in the prior art, make copper-containing waste acid water treatment process, avoid producing waste acid sewage, and can produce precipitated barium sulfate, sulfide Copper, sodium hydrosulfide or calcium hydrosulfide and other chemical products can also recover acid solution with H + content > 16% at the same time. In this way, not only can the pollution of copper-containing waste acid water be fundamentally eliminated, but also the waste can be fully and comprehensively utilized. While recovering copper, useful chemical products can be produced at the same time, and the economic benefits are remarkable.
含铜废酸水中主要含CL-，SO4 2-，Na+，H+含量＞16％及一些有机物质，在对该废酸水的处理过程中，以硫化钡或硫化钠为原料，综合利用含铜废酸水，通过浸取、化合、除铜、吸收、烘干、粉碎筛分等工序，生产硫酸钡，硫化铜和硫氢化钠或硫氢化钙等多种化工产品，同时，还可以回收富余的酸液其中H+含量＞16％。由于硫化钠的价格较贵，最好选用价廉的工业硫化钡作为原料。Copper-containing waste acid water mainly contains CL - , SO 4 2- , Na + , H + content > 16% and some organic substances. During the treatment of the waste acid water, barium sulfide or sodium sulfide is used as raw material, comprehensive Utilize copper-containing waste acid water to produce various chemical products such as barium sulfate, copper sulfide, sodium hydrogen sulfide or calcium hydrogen sulfide through leaching, compounding, copper removal, absorption, drying, crushing and screening, etc. Excess acid liquid can be recovered in which the H + content is >16%. Since the price of sodium sulfide is relatively expensive, it is best to use cheap industrial barium sulfide as a raw material.
本发明包括如下的处理工艺步骤：The present invention comprises following processing steps:
1、利用热水浸取工业硫化钡生成硫氢化钡和氢氧化钡溶液，与酸液反应，在产生硫酸钡沉淀的同时产生硫化氢气体。1. Use hot water to leach industrial barium sulfide to generate barium hydrosulfide and barium hydroxide solution, react with acid solution, and produce hydrogen sulfide gas while producing barium sulfate precipitation.
该处理过程包括如下的步骤：The process includes the following steps:
(1)将清水置于浸取釜中，加热至90℃-100℃之间，缓慢加入工业硫化钡，继续加热至沸，保温搅拌，在浸取反应过程中，生成硫氢化钡和氢氧化钡溶液，使浸取液浓度不低于15Be`，浸取反应完毕后，经过滤除残渣、分离出浸取液，备化合用。(1) Put clear water in the leaching kettle, heat it to between 90°C and 100°C, slowly add industrial barium sulfide, continue heating to boiling, keep stirring, and during the leaching reaction process, barium hydrosulfide and hydroxide will be generated Barium solution, so that the concentration of the leaching solution is not lower than 15Be`, after the leaching reaction is completed, the residue is removed by filtration, the leaching solution is separated, and it is prepared for chemical combination.
(2)将酸液置于耐酸反应釜中，该酸液可是硫酸、盐酸、硝酸，最好选用硫酸，或是本工艺生产的除铜酸液，开引风或真空、搅拌，徐徐加入硫化钡浸取液，进行复分解反应，待接近反应终点时，必须控制合成液的PH值为微酸性。反应产生的硫化氢气体直接为含铜废酸水的除铜工序使用；反应产生的沉淀过滤分离获得硫酸钡沉淀，滤液进行中性排放。(2) Put the acid solution in an acid-resistant reaction kettle. The acid solution can be sulfuric acid, hydrochloric acid, or nitric acid. It is best to use sulfuric acid or the acid solution for removing copper produced by this process. The barium leaching solution is subjected to a metathesis reaction. When the end of the reaction is approaching, the pH of the synthetic solution must be controlled to be slightly acidic. The hydrogen sulfide gas generated by the reaction is directly used in the copper removal process of copper-containing waste acid water; the precipitate generated by the reaction is filtered and separated to obtain barium sulfate precipitate, and the filtrate is discharged neutrally.
反应原理：Reaction principle:
①
②
2、将分离的硫酸钡沉淀经洗涤、过滤、烘干、粉碎筛分，制得沉淀硫酸钡成品。2. The separated barium sulfate precipitate is washed, filtered, dried, pulverized and sieved to obtain the finished product of precipitated barium sulfate.
3、将前工序1、(2)反应产生的硫化氢气体引入精制含铜废酸水中进行化学反应，生成硫化铜沉淀物，同时可除去废酸水中的一些有机杂质。3. Introduce the hydrogen sulfide gas produced by the reaction of the previous process 1 and (2) into the refined copper-containing waste acid water for chemical reaction to form copper sulfide precipitates, and at the same time remove some organic impurities in the waste acid water.
该除铜过程包括如下步骤：This copper removal process comprises the steps:
(1)将工业含铜废酸水，经过滤，除去杂质，制得精制含铜废酸水。(1) Filter industrial copper-containing waste acid water to remove impurities to obtain refined copper-containing waste acid water.
(2)将精制含铜废酸水置于耐酸反应釜中，开引风或真空、搅拌，通入前工序1、(2)产生的硫化氢气体，进行离子反应，直至含铜废酸水由绿色变成白色，产生硫化铜等沉淀；反应完毕后，充分排净未参加反应的硫化氢气体，多余硫化氢气体引入下道工序的吸收反应；而后过滤分离反应物制得硫化铜沉淀物，该硫化铜沉淀物经焚烧可制取氧化铜、进而可酸溶浓缩、结晶、制取硫酸铜。滤液为除铜酸液(H+含量＞16％)，引入酸储槽，一部分供前工序1、(2)的化学反应继续使用，多余部分可直接作为产品出售。(2) Put the refined copper-containing waste acid water in an acid-resistant reaction kettle, turn on the induced wind or vacuum, stir, and feed the hydrogen sulfide gas produced in the previous process 1 and (2), and carry out ion reaction until the copper-containing waste acid water From green to white, copper sulfide and other precipitates are produced; after the reaction is completed, the hydrogen sulfide gas that has not participated in the reaction is fully discharged, and the excess hydrogen sulfide gas is introduced into the absorption reaction of the next process; then the reactants are filtered and separated to obtain copper sulfide precipitates , the copper sulfide precipitate can be incinerated to produce copper oxide, and then can be acid-soluble, concentrated, crystallized, and copper sulfate can be produced. The filtrate is copper-removing acid solution (H + content > 16%), which is introduced into the acid storage tank, and a part is used for the chemical reaction of the previous process 1 and (2), and the excess part can be directly sold as a product.
反应原理：Reaction principle:
4、将除铜工序产生的多余硫化氢气体引入吸收液循环槽内的吸收剂中，该吸收剂为氢氧化钠溶液或氢氧化钙溶液，进行完全化学吸收，生成硫氢化钠或硫氢化钙产品。4. Introduce the excess hydrogen sulfide gas generated in the copper removal process into the absorbent in the absorption liquid circulation tank. The absorbent is sodium hydroxide solution or calcium hydroxide solution for complete chemical absorption to generate sodium hydrosulfide or calcium hydrosulfide product.
反应原理：Reaction principle:
或者
本发明主要以糖精钠生产过程中产生的大量含铜废酸水和含量60％的工业硫化钡为原料，进行浸取、化合、除铜及吸收化学反应工序，制得硫酸钡、硫化铜和硫氢化钠或硫氢化钙等多种化工产品，同时，还能回收H+含量＞16％的酸液，此酸液可作为化工原料，无废物，不产生公害、无污染。该处理方法不仅使污染严重的含铜废酸水得到充分的综合利用，解决了铁置换回收铜工艺废水无利用价值直接排放造成的长期污染问题，而且所制得化工产品，具有广泛的用途。硫酸钡可用作制钡盐的原料和美术印刷纸的涂布剂；用于制造明亮的着色化合物；在造纸、橡胶、油墨、颜料等行业中可用作填充剂。硫氢化钠可作为染料及各种有机产品的中间体，用于皮革的脱毛，黏液丝的脱硫，硫化染料的助剂，也可用于肥料及农药等行业。硫化铜可用于提炼铜和制备铜化合物。本发明使废物资源化，提高了物料的利用率，符合循环经济、清洁生产、可持续发展的现代理念。可保护环境，造福人类，并产生显著的经济效益和社会效益。The present invention mainly uses a large amount of copper-containing waste acid water produced in the production process of sodium saccharin and industrial barium sulfide with a content of 60% as raw materials to carry out leaching, compounding, copper removal and absorption chemical reaction processes to obtain barium sulfate, copper sulfide and Sodium hydrosulfide or calcium hydrosulfide and other chemical products, at the same time, acid liquid with H + content > 16% can also be recovered. This acid liquid can be used as chemical raw materials without waste, pollution and pollution. The treatment method not only fully utilizes the heavily polluted copper-containing waste acid water, but also solves the problem of long-term pollution caused by the direct discharge of waste water from the process of iron replacement and recovery of copper with no use value, and the chemical products produced have a wide range of uses. Barium sulfate can be used as a raw material for making barium salt and a coating agent for art printing paper; it can be used to make bright coloring compounds; it can be used as a filler in papermaking, rubber, ink, pigment and other industries. Sodium hydrosulfide can be used as an intermediate of dyes and various organic products, used for depilation of leather, desulfurization of mucus silk, auxiliaries of sulfur dyes, and can also be used in industries such as fertilizers and pesticides. Copper sulfide can be used to extract copper and prepare copper compounds. The invention turns waste into resources, improves the utilization rate of materials, and conforms to the modern concepts of circular economy, clean production and sustainable development. It can protect the environment, benefit mankind, and produce significant economic and social benefits.
现以年产5000吨的糖精钠生产厂为例，每天要排放含铜废酸水50吨，采用本方法，除每年可生产硫酸钡、硫化铜、硫氢化钠等化工产品外。仅废酸一项每年就可以回收能应用于工业生产的H+含量＞16％酸液15000吨以上，相当于节约30％盐酸8000吨以上。可少向环境排放强酸水废水15000吨以上。由此，可以看出采用本方法的先进性以及所产生经济效益和社会效益的显著性。Take the sodium saccharin production plant with an annual output of 5,000 tons as an example, and 50 tons of copper-containing waste acid water will be discharged every day. With this method, chemical products such as barium sulfate, copper sulfide, and sodium hydrosulfide can be produced every year. The waste acid alone can recover more than 15,000 tons of acid solution with H + content > 16% that can be used in industrial production every year, which is equivalent to saving more than 8,000 tons of 30% hydrochloric acid. It can save more than 15,000 tons of strong acid water wastewater to the environment. From this, it can be seen that the advancement of the method and the significance of the resulting economic and social benefits can be seen.
附图说明Description of drawings
附图为含铜废酸水处理方法的工艺流程图。The accompanying drawing is a process flow chart of the copper-containing waste acid water treatment method.
具体实施方式 Detailed ways
下面结合实施例详细描述本发明的具体实施方式。The specific implementation of the present invention will be described in detail below in conjunction with the examples.
实施例1Example 1
在浸取釜中加入3.5T清水，加热至100℃，开排风或真空、搅拌，缓慢加入含量为60％的粉状硫化钡1.2T；继续加热至100℃，保温搅拌30分钟，使浸取液浓度不低于15Be`；打开釜底阀门，用泵打入板框压滤机进行过滤，固相杂质滤渣清除至废料场集中处理；经处理后的滤渣可作为生产水泥或生产墙砖的原料；滤液引入储槽备用。在过滤浸取硫化钡溶液时，如出现硫化钡析出现象，将滤渣用100℃水再浸取。Add 3.5T of clear water into the leaching kettle, heat to 100°C, turn on the exhaust or vacuum, stir, and slowly add 1.2T of powdered barium sulfide with a content of 60%; continue to heat to 100°C, keep stirring for 30 minutes, and make the The concentration of the liquid taken is not lower than 15Be`; open the valve at the bottom of the kettle, pump it into the plate and frame filter press for filtration, remove the solid phase impurities and filter residue to the waste yard for centralized treatment; the treated filter residue can be used to produce cement or produce wall tiles Raw materials; the filtrate is introduced into the storage tank for standby. When filtering and leaching the barium sulfide solution, if barium sulfide is precipitated, the filter residue should be leached again with 100°C water.
取预处理后的除铜酸液5T置于耐酸反应釜中，开引风或真空、搅拌，徐徐加入备用的硫化钡浸取液，进行复分解反应，在接近反应终点时，使硫化钡浸取液所加入量达到合成液呈中性或微酸性为止，控制PH值为5-6，可通过用4-10(PH)试纸试之，或取硫酸钡混浊液10-15ml，加入5滴1％的酚酞，以试液不显红色为止。反应完全，产生硫酸钡沉淀，并同时产生硫化氢气体，供除铜工序使用，在反应完毕后，充分排净硫化氢气体，并打开釜底阀门，排放釜内合成液至板框压滤机进行过滤分离，滤液为中性或微酸性排放，不产生公害污染，滤饼为硫酸钡沉淀，经酸洗、水洗、过滤、烘干、粉碎筛分获得沉淀硫酸钡产品。烘干是在130℃的温度下进行的。所述的预处理除铜酸液是指将直接从生产中获得含铜废酸水经过滤除去杂质后，再进行除铜反应后而制得的。将所制得的沉淀硫酸钡产品，按照GB2899-82规定的方法进行分析测定，其结果符号GB2899-82所规定的各项标准，其中硫酸钡(干基)＞98％。Take the pretreated copper removal acid solution 5T and place it in an acid-resistant reaction kettle, turn on the induced wind or vacuum, stir, and slowly add the spare barium sulfide leaching solution to carry out the metathesis reaction. When the end of the reaction is approaching, the barium sulfide leaching The added amount of the solution is until the synthetic solution is neutral or slightly acidic, and the pH value of the control is 5-6, which can be tested with 4-10 (PH) test paper, or take 10-15ml of barium sulfate cloudy solution, add 5 drops of 1 % of phenolphthalein until the test solution does not appear red. The reaction is complete, barium sulfate precipitates, and hydrogen sulfide gas is produced at the same time for the copper removal process. After the reaction is completed, the hydrogen sulfide gas is fully exhausted, and the valve at the bottom of the kettle is opened to discharge the synthetic liquid in the kettle to the plate and frame filter press. Filtration and separation, the filtrate is neutral or slightly acidic discharge, no pollution pollution, the filter cake is barium sulfate precipitation, after pickling, water washing, filtration, drying, crushing and screening to obtain the precipitated barium sulfate product. Drying is carried out at a temperature of 130°C. The pretreatment copper-removing acid solution refers to the preparation of copper-containing waste acid water directly obtained from production after filtering to remove impurities, and then performing a copper-removing reaction. The prepared precipitated barium sulfate product is analyzed and measured according to the method specified in GB2899-82, and the result symbol is the various standards stipulated in GB2899-82, wherein barium sulfate (dry basis) > 98%.
将过滤除杂后的精制含铜废酸水，置于耐酸反应釜中，开引风或真空、搅拌，通入前工序产生的硫化氢气体，直至含铜废酸水由绿色变成白色，停加硫化氢气体，使反应釜中的硫化氢与含铜废酸水内的铜离子进行化学反应，生成黑色硫化铜沉淀；多余硫化氢气体，供下道工序吸收；反应完毕后，充分排净釜中的硫化氢气体，并打开釜底阀门，排放出釜内的合成液至板框压滤机进行过滤，滤液为除铜酸液(H+含量＞16％)引入酸储槽，其中一部分为前面的制硫酸钡沉淀工序继续使用，而多余部分的除铜酸液存储，可直接作为产品出售；滤饼为硫化铜沉淀，可直接做为产品出售，还可经焚烧制取氧化铜、进而酸溶、浓缩、结晶、制得硫酸铜成品。Put the refined copper-containing waste acid water after filtering and removing impurities into an acid-resistant reaction kettle, turn on the induced wind or vacuum, stir, and let in the hydrogen sulfide gas generated in the previous process until the copper-containing waste acid water turns from green to white. Stop adding hydrogen sulfide gas to make the hydrogen sulfide in the reaction kettle chemically react with the copper ions in the copper-containing waste acid water to form black copper sulfide precipitates; the excess hydrogen sulfide gas is absorbed by the next process; after the reaction is completed, it is fully discharged Clean the hydrogen sulfide gas in the still, and open the valve at the bottom of the still, discharge the synthetic liquid in the still to a plate and frame filter press for filtration, and the filtrate is copper-removing acid solution (H + content > 16%) and is introduced into the acid storage tank, wherein Part of it is used in the previous barium sulfate precipitation process, and the excess copper removal acid solution is stored and can be sold directly as a product; the filter cake is copper sulfide precipitate, which can be directly sold as a product, and can also be incinerated to produce copper oxide , and then acid-dissolved, concentrated, crystallized, and made copper sulfate finished product.
在吸收液循环槽内加入3T含量15％液碱，将除铜工序中多余的硫化氢气体尾气通入吸收液循环槽内的液碱中，进行循环吸收化学反应，直至反应完全，制得硫氢化钠成品；将所制得的硫氢化钠产品按H G/T 3687-2000规定方法进行分析测定，其结果符合HG/T3687-2000规定的各项指标。Add 3T liquid caustic soda with a content of 15% in the absorption liquid circulation tank, pass the excess hydrogen sulfide gas tail gas in the absorption liquid circulation tank into the liquid caustic soda in the absorption liquid circulation tank, and carry out the circulation absorption chemical reaction until the reaction is complete, and obtain sulfur Sodium hydride finished product; the prepared sodium sulfide product is analyzed and measured according to the method stipulated in HG/T 3687-2000, and the results meet the various indicators stipulated in HG/T3687-2000.
实施例2Example 2
在耐酸反应釜中放置30％的硫酸溶液，再缓慢加入硫化钡浸取液，而在吸收液循环槽内加放石灰水作吸收剂，其他均同实施例1，制得硫氢化钙成品。所得成品经相关规定的方法分析测定，符合相关规定的方法标准的规定。Place 30% sulfuric acid solution in the acid-resistant reactor, then slowly add the barium sulfide leaching solution, and add lime water to make the absorbent in the absorption liquid circulation tank, and the others are the same as in Example 1 to obtain the calcium hydrosulfide finished product. The resulting finished product is analyzed and measured by the method specified in the relevant regulations, and meets the requirements of the method standards specified in the relevant regulations.
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| CN103663536A (en) * | 2013-09-28 | 2014-03-26 | 赵同甫 | Process for preparing precipitated barium sulfate by pretreatment of waste acid of sulfuric acid process titanium dioxide |
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| CN104962949A (en) * | 2015-06-09 | 2015-10-07 | 中国科学院兰州化学物理研究所 | Method for removing copper in nickel electrolysis anode solution for purification |
| CN105481096A (en) * | 2015-12-18 | 2016-04-13 | 刘高志 | Method for biological remediation of copper-containing sewage |
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| US5035807A (en) * | 1989-03-15 | 1991-07-30 | Csir | Water treatment for sulfate ion removal |
| CN1158320A (en) * | 1996-02-29 | 1997-09-03 | 本溪市环境科学研究所 | Method for reclaiming waste keto-acid liquid in prodn. of soluble gluside |
| CN1063407C (en) * | 1996-04-11 | 2001-03-21 | 刘立华 | Method for treatment of waste acid liquid containing copper production of gluside and sodium saccharin |
| JP4126415B2 (en) * | 1998-03-31 | 2008-07-30 | Ｄｏｗａホールディングス株式会社 | Method for removing and fixing arsenic present in iron sulfate solution |
| JP3945216B2 (en) * | 2001-10-25 | 2007-07-18 | 住友金属鉱山株式会社 | Waste acid gypsum manufacturing method |
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| CN103663536A (en) * | 2013-09-28 | 2014-03-26 | 赵同甫 | Process for preparing precipitated barium sulfate by pretreatment of waste acid of sulfuric acid process titanium dioxide |
| CN104370301A (en) * | 2014-10-29 | 2015-02-25 | 云南北方驰宏光电有限公司 | Method for treating H2S tail gas in CVD-ZnS preparation process |
| CN104962949A (en) * | 2015-06-09 | 2015-10-07 | 中国科学院兰州化学物理研究所 | Method for removing copper in nickel electrolysis anode solution for purification |
| CN105481096A (en) * | 2015-12-18 | 2016-04-13 | 刘高志 | Method for biological remediation of copper-containing sewage |
| CN105540853A (en) * | 2015-12-18 | 2016-05-04 | 刘高志 | Bioremediation method for copper-bearing sewage |
| RU2650991C1 (en) * | 2017-05-10 | 2018-04-18 | Общество с ограниченной ответственностью "ХАММЕЛЬ" | Method for removing copper from wastewater of acrylic acid production |
| CN108946889A (en) * | 2017-06-01 | 2018-12-07 | 株洲三特环保节能股份有限公司 | A kind of processing method and processing equipment of the spent acid containing heavy metal |
| CN113136579A (en) * | 2021-04-26 | 2021-07-20 | 王水平 | Method and device for recovering copper from waste circuit board etching solution and regenerating etching solution |
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