CN1069008A - Method for treating heavy metals in waste water with dithiamine-based chelating agent - Google Patents
Method for treating heavy metals in waste water with dithiamine-based chelating agent Download PDFInfo
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- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 38
- 239000002738 chelating agent Substances 0.000 title claims abstract description 37
- 239000002351 wastewater Substances 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000002244 precipitate Substances 0.000 claims abstract description 8
- 239000013522 chelant Substances 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 14
- 238000001556 precipitation Methods 0.000 claims description 10
- 238000012545 processing Methods 0.000 claims description 5
- 150000001768 cations Chemical class 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229920000083 poly(allylamine) Polymers 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 claims 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- 235000011114 ammonium hydroxide Nutrition 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 7
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 abstract description 7
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052802 copper Inorganic materials 0.000 abstract description 7
- 239000010949 copper Substances 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 7
- 239000011133 lead Substances 0.000 abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052793 cadmium Inorganic materials 0.000 abstract description 6
- 229910052759 nickel Inorganic materials 0.000 abstract description 6
- 229910017052 cobalt Inorganic materials 0.000 abstract description 4
- 239000010941 cobalt Substances 0.000 abstract description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract description 4
- 239000011701 zinc Substances 0.000 abstract description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052742 iron Inorganic materials 0.000 abstract description 3
- 229910052725 zinc Inorganic materials 0.000 abstract description 3
- 239000013049 sediment Substances 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 24
- 239000007788 liquid Substances 0.000 description 18
- 239000002699 waste material Substances 0.000 description 16
- 239000011734 sodium Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910000570 Cupronickel Inorganic materials 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910001430 chromium ion Inorganic materials 0.000 description 3
- 239000000701 coagulant Substances 0.000 description 3
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000007429 general method Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000010814 metallic waste Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- JZRWCGZRTZMZEH-UHFFFAOYSA-N Thiamine Natural products CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N JZRWCGZRTZMZEH-UHFFFAOYSA-N 0.000 description 1
- XKMAKWPZGDBONG-UHFFFAOYSA-N [Co].[Cd] Chemical compound [Co].[Cd] XKMAKWPZGDBONG-UHFFFAOYSA-N 0.000 description 1
- LIABKAQKQSUQJX-UHFFFAOYSA-N [Mn].[Pb] Chemical compound [Mn].[Pb] LIABKAQKQSUQJX-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- BESJRHHIPGWPTC-UHFFFAOYSA-N azane;copper Chemical class N.[Cu] BESJRHHIPGWPTC-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 230000003902 lesion Effects 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000008450 motivation Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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- 230000002250 progressing effect Effects 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- KYMBYSLLVAOCFI-UHFFFAOYSA-N thiamine Chemical compound CC1=C(CCO)SCN1CC1=CN=C(C)N=C1N KYMBYSLLVAOCFI-UHFFFAOYSA-N 0.000 description 1
- 229960003495 thiamine Drugs 0.000 description 1
- 235000019157 thiamine Nutrition 0.000 description 1
- 239000011721 thiamine Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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Abstract
Description
本发明是有关一种利用二硫胺基类螯合剂处理废水中重金属的方法，尤指一种利用二硫胺基化合物去除一般工矿业工厂排放的流水中的重金属的方法，以避免目前河川溪流沿海及土壤再受重金属的污染。The present invention relates to a method for treating heavy metals in waste water with dithiamine-based chelating agents, especially a method for using dithiamine-based compounds to remove heavy metals in running water discharged from general industrial and mining factories, so as to avoid the current pollution of rivers and streams. The coast and soil are again polluted by heavy metals.
环境保护是现代化国家当前首重的热门话题，因为，随著工业进步，虽然提高人类生活水平，但其所带来的重工业污染，将波及全人类未来的生存空间，这也正是为何世界性环保组织不断扩大的主因。Environmental protection is currently the most important hot topic in modern countries, because, with the advancement of industry, although the standard of living of human beings is improved, the heavy industrial pollution it brings will affect the living space of all human beings in the future, which is why the worldwide The main reason for the continuous expansion of environmental organizations.
复以国内观之，随著经济改革的加速，吸引外商或台商的投资，使得各式工厂林立，此一方兴未艾现象，除证明祖国不断进步且跃向进步国家之林外，却也旋踵带来了重工业污染问题。由于工厂源源不断快速繁生，各式工厂废水排放造成的污染，将大量破坏环境生态，进而影响未来生活空间。但目前仍未为有关当局的重视。From a domestic point of view, with the acceleration of economic reforms, foreign or Taiwanese investment has been attracted, resulting in the establishment of various factories. This booming phenomenon not only proves that the motherland is constantly progressing and leaping into the forest of progressive countries, but it also brings with it Here comes the problem of heavy industrial pollution. Due to the continuous and rapid growth of factories, the pollution caused by the discharge of various factory wastewater will greatly damage the environment and ecology, and then affect the future living space. However, it has not yet been paid attention to by the relevant authorities.
根据研究，一般工厂排放的废水皆含有高量的重金属，例如铜、镍、镉、铅、锰、钴、铁、锌及六价铬等重金属离子、此类重金属离子即为污染的来源。当此类含有重金属的废水流入水源后，将使农产品或饮水波及污染，食用后在人体中会发生可怕的病变，此类案例，于世界多处地方曾经发生，影响极巨，不可不防。为防范于未然，是否能提供一种高效率处理废水中的重金属的方法，以保障国人健康，为本发明所要探究的主要范畴。According to research, the wastewater discharged from general factories contains high amounts of heavy metals, such as copper, nickel, cadmium, lead, manganese, cobalt, iron, zinc, and hexavalent chromium. Such heavy metal ions are the source of pollution. When such waste water containing heavy metals flows into water sources, it will pollute agricultural products or drinking water, and cause terrible lesions in the human body after consumption. Such cases have occurred in many places in the world, and the impact is huge. It must be prevented. In order to take precautions, whether a method for efficiently treating heavy metals in wastewater can be provided to protect the health of Chinese people is the main category to be explored by the present invention.
目前一般处理重金属废液的方法为利用化学沉降法，即在pH值为10左右的情况下，加入三氯化铁（FeCl3）当作凝聚剂，并加入高分子助凝 剂以加速除去废液中的重金属。At present, the general method of treating heavy metal waste liquid is to use chemical sedimentation method, that is, at a pH value of about 10, add ferric chloride (FeCl 3 ) as a coagulant, and add a polymer coagulant to accelerate the removal of waste. heavy metals in the liquid.
利用上述处理方法虽能有效去除某些金属离子，但无法完全将废液中的重金属除去。因此，这种效果并不理想，且处理时所需的空间、时间及经费成本皆很大，故并不适用于目前小型工厂使用，更何况一些形成螯合物的金属离子的废水至今仍无法解决（参阅以下实施例Ⅱ的说明）。Although some metal ions can be effectively removed by the above-mentioned treatment method, the heavy metals in the waste liquid cannot be completely removed. Therefore, this effect is unsatisfactory, and the required space, time and cost of funds are all very large during treatment, so it is not suitable for the use of small factories at present, not to mention the wastewater of some metal ions forming chelates is still not available. Solution (see description of Example II below).
上述所述的方法须有很大的空间与环境，在成本及经费上所耗不赀，不符合经济效益。The above-mentioned method requires a lot of space and environment, and consumes a lot of cost and funds, and does not meet economic benefits.
因此，找寻一种既方便迅速且处理时所需空间小，经费成本廉宜的处理技术是本发明的创作动机及所欲达求之目的。Therefore, it is the motivation and the goal of the present invention to find a processing technology that is convenient and fast, requires little space for processing, and is cheap in cost.
本发明的方法是利用二硫胺基类螯合剂与排出废液中的各种重金属离子形成螯合物沉淀而去除废水中的重金属;其中所使用的二硫胺基类螯合剂的结构式大致可分为两种：The method of the present invention is to utilize dithiamine-based chelating agent to form chelate precipitation with various heavy metal ions in the waste liquid to remove heavy metals in waste water; wherein the structural formula of dithiamine-based chelating agent used can be Divided into two types:
其中R，R′为H，CnH2n+1，CnH2n-1或CnH2n，而X+为Na+，K+，NH+ 4等阳离子;或为Where R, R' is H, C n H 2n+1 , C n H 2n-1 or C n H 2n , and X + is Na + , K + , NH + 4 and other cations; or is
其中，R，R′为H，CnH2n+1，CnH2n-1或芳基，而n＝2-6或聚烯丙胺（Polyallylamine，M.W.在60000以内皆可），而X+为Na+，K+，NH+ 4等阳离子。Among them, R, R' is H, C n H 2n+1 , C n H 2n-1 or aryl, and n=2-6 or polyallylamine (Polyallylamine, MW within 60000 is acceptable), and X + For Na + , K + , NH + 4 and other cations.
上述两大类螯合剂中的X+是由制备螯合剂过程中所加入的不同的碱，如NaOH，NH4OH或KOH衍生的，其目的乃在使所说螯合剂能溶于水中。 X in above-mentioned two big classes of chelating agents is derived from the different bases added in the preparation of chelating agents, such as NaOH, NH 4 OH or KOH, and its purpose is to make said chelating agents soluble in water.
另外，本发明所采用的二硫胺基类螯合剂与废水中重金属形成沉淀的螯合物的结构如下：In addition, the structure of the chelate formed by the dithiamine-based chelating agent used in the present invention and the heavy metal in the waste water is as follows:
其中，R和R′以及n的定义同上，M为过渡金属元素。Wherein, the definitions of R, R' and n are the same as above, and M is a transition metal element.
此一形成的螯合物，是不溶或仅微溶于水中的化合物，因此可顺利将废水中的重金属元素完全沉淀滤出。The formed chelate is insoluble or only slightly soluble in water, so it can successfully precipitate and filter out the heavy metal elements in the wastewater.
若采用上述的方法，可方便且快速处理废液中的重金属，使其形成螯合物沉淀，而完成对废液的有效处理。所以使用本发明的方法可防止水源污染，缩小所需的处理空间环境及时间，以及降低成本。If the above method is adopted, the heavy metals in the waste liquid can be conveniently and quickly processed to form chelate precipitates, thereby completing the effective treatment of the waste liquid. Therefore, using the method of the present invention can prevent water source pollution, reduce the required treatment space environment and time, and reduce costs.
本发明的处理步骤包括将重金属废液置于一拌槽中，加入二硫胺基化合物搅拌约20分钟后，将沉淀物用过滤器或自然放置方式使其自然沉淀。The treatment steps of the present invention include placing the heavy metal waste liquid in a mixing tank, adding the dithiamine-based compound and stirring for about 20 minutes, and then using a filter or placing the precipitate naturally to allow it to settle naturally.
处理过程试剂的使用量，可视待处理废液的浓度至何种程度及废液中所含重金属总浓度多少而定。在正常状况下，如废液中只含单一离子的铜，其浓度约10mg/l，若欲除至3mg/l标准（环保单位所定的标准）时，则1000公升的废液中约须用2.5公升的试剂处理。The amount of reagent used in the treatment process depends on the concentration of the waste liquid to be treated and the total concentration of heavy metals contained in the waste liquid. Under normal conditions, if the waste liquid contains only a single ion of copper, its concentration is about 10mg/l. If it is to be removed to the standard of 3mg/l (the standard set by the environmental protection unit), about 1,000 liters of waste liquid must be used 2.5 liters of reagents to handle.
若待处理的废液浓度为1.0mg/l的铅或镉时，其所用的试剂量仍相同，唯其所形成的颗粒较小，所以如加入5mg/l的高分子助凝剂或放置过夜，再过滤时将可除去重金属而达到环保单位所定的标准范围之内。If the concentration of the waste liquid to be treated is 1.0 mg/l of lead or cadmium, the amount of reagent used is still the same, but the particles formed are smaller, so if adding 5 mg/l of polymer coagulant or leaving it overnight , and re-filtering will remove heavy metals and reach the standard range set by the environmental protection unit.
本发明配制的二硫胺基类螯合剂是利用等量的二胺类有机物和二硫化碳在低温（0～20℃）下搅拌与反应数小时后，慢慢加入等量的碱性溶液使之中和，再使温度回升至室温状态，然后再分离未反应的二硫化碳，并稀释至最佳使用量浓度。此试剂如要使形成固状的试剂时，可将反应后的溶液倒入酒精或丙酮溶液中而产生白色固体，过滤后所得的固体部分即为二硫胺基类螯合剂。The dithioamine-based chelating agent prepared in the present invention is to use the same amount of diamine organic matter and carbon disulfide to stir and react at low temperature (0-20°C) for several hours, and then slowly add the same amount of alkaline solution to make it And, the temperature is returned to room temperature, and then the unreacted carbon disulfide is separated and diluted to the optimum concentration. If the reagent is to form a solid reagent, the reacted solution can be poured into alcohol or acetone solution to produce a white solid, and the solid part obtained after filtration is dithiamine-based chelating agent.
以下，是依据本发明所提供的方法而分别对含不同成分的重金属的废水所做的测试检验，其中实施例Ⅰ～Ⅳ所使用的二硫胺基类的螯合剂，是前述结构式（A）螯合剂，其分子式可为C5H10NS2Na，使用浓度为10%（重量/重量）的试剂，而其他不同分子式的结构式（A）螯合剂的效果的测试显示：当该试剂加到含有重金属的废液中时，亦迅速产生螯合物之沉淀。可见分子式虽不同，但它如同实施例所用的试剂一样，对废水中重金属的去除效果非常好。另实施例Ⅴ及Ⅵ中所使用的螯合剂是前述结构式（B）类螯合剂，其分子式可为C4H6N2S4Na2，而浓度亦为10%（重量/重量）的试剂，而其他不同分子式的结构式（B）的螯合剂效果的测试亦显示：当该试剂加到含有重金属的废液中，结果速迅产生螯合物沉淀。可见分子式虽不同，但其去除重金属的能力与实施例中所用的试剂一样非常好。Below, according to the method provided by the present invention, the test inspections were done on the waste water containing heavy metals of different components, wherein the dithiamine-based chelating agent used in Examples Ⅰ～Ⅳ is the aforementioned structural formula (A) A chelating agent, whose molecular formula may be C 5 H 10 NS 2 Na, was used at a concentration of 10% (w/w) of the reagent, while tests of the effect of other chelating agents of structural formula (A) of different molecular formulas showed that: when the reagent was added to When it is in the waste liquid containing heavy metals, the precipitation of chelates will also occur rapidly. Although it can be seen that the molecular formula is different, it is the same as the reagent used in the embodiment, and it has a very good effect on the removal of heavy metals in waste water. In addition, the chelating agent used in Examples V and VI is the aforementioned structural formula (B) class chelating agent, its molecular formula can be C 4 H 6 N 2 S 4 Na 2 , and the concentration is also a reagent of 10% (weight/weight) , and the test of the effect of the chelating agent of the structural formula (B) of other different molecular formulas also shows that: when the agent is added to the waste liquid containing heavy metals, the result is a rapid precipitation of the chelating compound. It can be seen that although the molecular formula is different, its ability to remove heavy metals is as good as the reagents used in the examples.
实施例ⅠExample I
在电镀工厂所排放的废水中含有铜约10mg/l，镍约15mg/l，经取200ml废液加入浓度10%（W/W），分子式为C5H10NS2Na的二硫胺基类螯合剂，则迅速有沉淀产生，经搅拌20分钟使沉淀完全后，让沉淀物沉积、过滤，并取上层水溶液，利用原子吸收光谱仪测试上层水溶液中重金属的含量，以下结果是加入不同体积的试剂时的处理结果。The wastewater discharged from the electroplating factory contains about 10mg/l of copper and about 15mg/l of nickel. After taking 200ml of waste liquid, add a dithiamine group with a concentration of 10% (W/W) and a molecular formula of C 5 H 10 NS 2 Na For chelating agents, precipitation occurs quickly. After stirring for 20 minutes to complete the precipitation, the sediment is deposited, filtered, and the upper aqueous solution is taken, and the content of heavy metals in the upper aqueous solution is tested by atomic absorption spectrometer. The following results are obtained by adding different volumes of Reagent processing results.
（浓度：mg/l）(concentration: mg/l)
ND：含量小于仪器可测的值ND: The content is less than the measurable value of the instrument
实施例ⅡExample II
在一般工厂废水中，其废水的pH值约10，该废水中含有铜27.5mg/l及镍7.5mg/l，此废液因含有过量的氨，而形成铜氨配合物，而无法再以一般方式去除废液中的重金属，但如加入浓度为10%（W/W），分子式为C5H10NS2Na的二硫胺基螯合剂时，则沉淀迅速产生，经搅拌20分钟让沉淀完全后再过滤，水溶液以原子吸收光谱仪测试，其结果如下：In general factory wastewater, the pH value of the wastewater is about 10, and the wastewater contains 27.5 mg/l copper and 7.5 mg/l nickel. This waste liquid forms copper-ammonia complexes due to excessive ammonia, and cannot be used as The general method is to remove heavy metals in waste liquid, but if a dithiamine-based chelating agent with a concentration of 10% (W/W) and a molecular formula of C 5 H 10 NS 2 Na is added, the precipitation will occur rapidly. After stirring for 20 minutes, let it Filter after the precipitation is complete, and the aqueous solution is tested with an atomic absorption spectrometer, and the results are as follows:
实施例ⅢExample III
为进一步了解此类试剂对各类重金属的处理效果，本发明人配制各含10mg/l的铜、铅、镍、锰、钴、镉等六种元素，加入不同体积而浓度为10%（W/W），分子式为C5H10NS2Na的二硫胺基螯合剂而使其产生沉淀，同样浓度的样品也利用习用方式处理，操作方式为慢慢入浓度为45%，体积为25ml的氢氧化纳，使其产生沉淀，过滤沉淀后，利用原子吸收光谱仪测试上层水溶液所余的各种重金属的含量，其结果如下（其中所处理样品的体积为200ml）：For further understanding of the treatment effect of this type of reagent on various heavy metals, the inventor prepared six elements such as copper, lead, nickel, manganese, cobalt, cadmium each containing 10mg/l, added different volumes and the concentration was 10% (W /W), the molecular formula is C 5 H 10 NS 2 Na dithiamine-based chelating agent to cause precipitation, and the same concentration of samples are also processed by the usual method, the operation method is to slowly add the concentration of 45%, and the volume is 25ml Sodium hydroxide to make it precipitate, after filtering the precipitate, use the atomic absorption spectrometer to test the content of various heavy metals remaining in the upper aqueous solution, the results are as follows (the volume of the processed sample is 200ml):
ND：含量小于仪器可测的值ND: The content is less than the measurable value of the instrument
实施例ⅣExample IV
为测试本发明的试剂对较难处理且浓度不很高的重金属处理效果，本发明人配制10mg/l的镉与铅溶液，分别取200ml的样品，加入1ml浓度为10%（W/W），分子式为C5H10NS2Na的二硫胺基类螯合剂，加入时则产生白色很细颗粒的沉淀，经搅拌20分钟后，为方便过滤，将此样品放置过夜再过滤，取水溶液测试其所残余的重金属含量，其结果如下：In order to test the treatment effect of the reagent of the present invention on heavy metals that are difficult to handle and not very high in concentration, the inventors prepared 10 mg/l of cadmium and lead solutions, took 200 ml of samples respectively, and added 1 ml of them at a concentration of 10% (W/W) , the dithiamine-based chelating agent with the molecular formula of C 5 H 10 NS 2 Na, when added, white very fine particle precipitates are produced. After stirring for 20 minutes, for the convenience of filtration, the sample is placed overnight and then filtered, and the aqueous solution is taken Test its residual heavy metal content, the results are as follows:
废水中六价铬离子（Cr+6），是一种相当难处理且具有剧毒的离子，在目前一般传统废水处理上，还没有一种简便且迅速的处理方法加以排除，而利用本发明以二硫胺基螯合剂处理的方法，将废水的pH值控制在1.6～2.5之间加入二硫胺基螯合剂，使处理后的废水pH值在7.2以内时，则能沉淀废水中的六价铬离子，效果将会相当良好;如果废液内有其他离子共同存在时，将使处理效果更为良好。Hexavalent chromium ion (Cr +6 ) in wastewater is a very difficult and highly toxic ion. In the current general traditional wastewater treatment, there is no simple and rapid treatment method to eliminate it. However, using the present invention With the method of dithiamine-based chelating agent treatment, the pH value of the wastewater is controlled between 1.6 and 2.5, and the dithiamine-based chelating agent is added so that the pH value of the treated wastewater is within 7.2, and the hexaphosphate in the wastewater can be precipitated. If the chromium ion is used, the effect will be quite good; if there are other ions in the waste liquid, the treatment effect will be better.
以下以实施例说明：Illustrate with embodiment below:
实施例ⅤExample V
取50毫升pH值为1.8、浓度为100mg/l的六价铬离子的废水，加入不同体积，但浓度为10%（W/W），分子式为C4H6N2S4Na2的二硫胺基类螯合剂时，则迅速产生沉淀，经搅拌20分钟并放置过夜且过滤后，用上层水溶液测试六价铬的残存量，结果发现其残存六价铬的含量除了和试剂量有关外，也和处理后水样的酸碱值有关，其结果如下：Take 50 ml of waste water with a pH value of 1.8 and a concentration of 100 mg/l of hexavalent chromium ions , add di When the thiamine-based chelating agent is used, precipitation will occur rapidly. After stirring for 20 minutes and standing overnight and filtering, the remaining amount of hexavalent chromium is tested with the upper aqueous solution. It is found that the remaining hexavalent chromium content is related to the amount of reagents. , is also related to the pH value of the treated water sample, and the results are as follows:
实施例ⅥExample VI
取50毫升pH值为2.0的废水，其内含有铜、铁、锌、镍、镉、钴、锰、铅各10mg/l，及六价铬5mg/l，加入不同体积但浓度为10%（W/W），分子式为C2H6N2S4Na2的二硫胺基类螯合剂，其处理步骤如前所述，其处理结果及处理后水样的酸碱值如下：Take 50 ml of wastewater with a pH value of 2.0, which contains 10 mg/l each of copper, iron, zinc, nickel, cadmium, cobalt, manganese, and lead, and 5 mg/l of hexavalent chromium. Add different volumes but the concentration is 10% ( W/W), dithiamine-based chelating agent with molecular formula C 2 H 6 N 2 S 4 Na 2 , the treatment steps are as described above, the treatment results and the pH value of the treated water samples are as follows:
ND：含量小于仪器可测的值ND: The content is less than the measurable value of the instrument
对于螯合剂，上述各实施例以结构式（A）或（B）中的一种化合物为例说明，对其他各种不同分子式的结构式（A）和（B）的二硫胺基类螯合剂，发明人也以与实施例Ⅰ-Ⅵ的方法进行同样实验，证明都具有同样的去除废水中重金属的效果。另外，对于所采用的螯合剂浓度，于实施中虽以10%为准，但在采用本发明的处理方法时，该试剂的浓度并无严格要求，如处理相同样品时，使用试剂的浓度较稀，则其试剂使用量相对增多，特此指明。For chelating agent, above-mentioned each embodiment is illustrated with a kind of compound in structural formula (A) or (B), for the dithiamine-based chelating agent of structural formula (A) and (B) of other various molecular formulas, The inventor also carried out the same experiment with the method of Examples I-VI, and proved that both have the same effect of removing heavy metals in wastewater. In addition, for the concentration of the chelating agent adopted, though it is based on 10% in the implementation, when adopting the processing method of the present invention, the concentration of the reagent is not strictly required, as when processing the same sample, the concentration of the reagent used is higher than that of the reagent. If it is dilute, the amount of reagent used will be relatively increased, which is hereby specified.
从上述中我们可以明显地看出，若是依据本发明方法，则能在工矿业工厂中，以较小的空间环境与较短的时间及较少的经费，利用二硫胺基化合物可有效去除废水中的重金属，具有产业上利用价值。From the above, we can clearly see that if according to the method of the present invention, the dithiamine-based compound can be used to effectively remove the Heavy metals in wastewater have industrial value.
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- 1991-07-30 CN CN 91105361 patent/CN1025670C/en not_active Expired - Fee Related
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