CN105660615A - Method for preparing copper abietate colloidal suspension agent by utilizing printed circuit board copper etching waste liquid - Google Patents
Method for preparing copper abietate colloidal suspension agent by utilizing printed circuit board copper etching waste liquid Download PDFInfo
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- CN105660615A CN105660615A CN201610125572.1A CN201610125572A CN105660615A CN 105660615 A CN105660615 A CN 105660615A CN 201610125572 A CN201610125572 A CN 201610125572A CN 105660615 A CN105660615 A CN 105660615A
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- copper
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- stone powder
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- colloidal suspension
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/06—Aluminium; Calcium; Magnesium; Compounds thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
- A01N59/20—Copper
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The invention discloses a method for preparing a copper abietate colloidal suspension agent by utilizing a printed circuit board copper etching waste liquid, and belongs to the field of pesticide preparation. A water-containing copper compound and food grade mountain flour are in the ratio of 1:1.2; the pH of a reaction solution is controlled between 7.5 and 8; a reaction is performed in a 2-5 m<3> container or a reaction kettle at the normal temperature of 20 to 35 DEG C; the mountain flour (CaCO3) is added while stirring until the mountain flour material is added; air bubbles of a reaction material are gradually reduced in about 2 hours; the reaction is completed to obtain the copper abietate colloidal suspension agent. According to the method, two copper abietate colloidal suspension agents, namely copper sulfate hydrate and copper chloride dehydrate, can be obtained; the reaction of the product is performed at the normal temperature; the reaction process is simple and can be completed by one step; only carbon dioxide gas can be produced in the reaction process; any other industrial pollutants are not produced or emitted; the production process is green and environmentally friendly.
Description
Technical field
The invention belongs to field of pesticide preparation, particularly relate to a kind of method utilizing circuit version copper waste etching solution to prepare green breast copper colloidal suspending agent.
Background technology
Copper agent antibacterial is a kind of protection type antibacterial; from the history developing existing more than 200 year till now; owing to it without Drug resistance and to people, animal, the plant feature such as safely, is currently still the principal item of disinfectant use in agriculture by its broad-spectrum, high-efficiency environment friendly, pathogenic bacteria. Tradition basic copper sulfate production: for Bordeaux mixture, is by manually quick lime (CaO) being added water furnishing lime cream Ca (OH)2By copper sulfate CuSO4After dissolving, under agitation pour the basic copper sulfate made in lime cream into. This technique to consume a large amount of expensive industrial cupric sulfates, and quick lime (CaO) adds water furnishing lime cream Ca (OH)2Producing substantial amounts of heat, product not easily stores simultaneously. The problem that the complicated technologies such as filtration, precipitation, crystallization just solve storage need to be passed through.
In recent years basic copper sulfate production: for green breast copper, green breast copper is again copper rosinate, is the upgrading products of Bordeaux mixture, adds in the lime cream of the furnishing that added water by a certain proportion of Colophonium input Calx man-hour, then, after copper sulfate being dissolved, pour under stirring in lime cream to boil and form. Green breast copper is notable with conventional insecticidal bactericide synergism, can replace Bordeaux mixture, but the drug effect phase is slightly shorter than Bordeaux mixture. To many planting fruit-trees fungus and bacteriosises such as alternaria leaf spot of apple, ring spot, anthrax and downys mildew of garpe, there is good preventive and therapeutic effect. Not only to consume substantial amounts of Colophonium during this production, and to adopt the reaction conditions such as high temperature.
At present, circuitboard etching waste liquid is utilized to prepare the technique of copper oxychloride, basic carbonate process for copper and prepare the method for other copper agent and all have relevant patent, but, the technological process of these copper agents is all more complicated: through neutralization, precipitation, leaching, negative pressure heating ammonia still process just can obtain copper oxychloride, basic copper carbonate precipitation. Therefore this type of product cost still high enterprise is produced. " a kind of carve the method that copper sulfate prepares copper oxide that reclaims waste liquid from micro-decorations " publication number: CN104016401B disclosed in 13 days January in 2016 of Patent Office of the People's Republic of China, its processing step is: concentrates micro-decorations and carves waste liquid, prepare copper sulfate and sodium sulfate mixture, prepare copper oxide.Although the method decreases the treating capacity to acid waste liquid, reduce the consumption of alkali, but equally exist complex process, the defect that cost is high. Prepared copper oxide product is very big with the green breast copper colloidal suspending agent difference described in present patent application.
The method also not finding at present to utilize circuit version copper waste etching solution to prepare green breast copper colloidal suspending agent.
Summary of the invention
It is an object of the invention to for there is no this situation of method adopting circuit version copper waste etching solution to prepare green breast copper colloidal suspending agent at present, it is proposed to a kind of circuit version copper waste etching solution prepares the method for green breast copper colloidal suspending agent.
The problem that the present invention program to solve: (1) can find a kind of cheap moisture copper compound? can (2) salt of weak acid reacted with this cheap moisture copper compound and mantoquita be found? (3) can reaction carry out under normal temperature condition, can put in place by single step reaction, drop end cost and produce copper agent? (4) selection of stone powder kind, not only select containing calcium carbonate but also the material containing certain proportion calcium oxide, extremely various in the kind of nature and chemicals, and content complicated component, select suitable to generate to meet green breast copper colloidal suspending agent and require the key factor of success or not by being containing stone powder reactant.
Find through long-term substantial amounts of test and analysis:
1. the complex copper that this cheap moisture copper compound just originates from the wiring board course of processing in copper-containing etching waste solution, the copper ion of copper-containing etching waste solution is with Hydrated copper chloride CuCL2.2H2The CuSO of O or hydrated copper sulfate4.5H2O form exists.
2. can with Hydrated copper chloride CuCL2.2H2O or hydrated copper sulfate CuSO4.5H2The compound that O all reacts is food stage stone powder, and its main component is calcium carbonate CaCO and the mixture of small amounts calcium CaO.
The technical scheme is that the method utilizing circuit version copper waste etching solution to prepare green breast copper colloidal suspending agent, its processing step is: one, selects and prepares green breast copper colloidal suspending agent primary raw material:
1. one of raw material is from copper-containing etching waste solution in the wiring board course of processing. There are two kinds of copper waste etching solutions, namely with hydrochloric acid for copper ion in copper etching its dilute hydrochloric acid lean solution of primary raw material with Hydrated copper chloride CuCL2.2H2O form exists; With sulphuric acid for copper ion in copper etching its dilute sulfuric acid lean solution of primary raw material with hydrated copper sulfate CuSO4.5H2O form exists.
2. the two of raw material are food stage stone powders, main composition-calcium carbonate (CaCO).
Two, copper waste etching solution and stone powder is utilized to prepare the preparation technology of green breast copper colloidal suspending agent
1. the concentration of the content of copper ion in detection copper waste etching solution, acid solution:
Emit the content of copper ion in copper waste etching solution, be typically in 7-8g/L, but the sulphuric acid emitted and concentration of hydrochloric acid change greatly. In order to make whole course of reaction thoroughly to carry out during production, the quality making product is identical with standard, therefore to design production technology according to testing result, to regulate the extension rate of acid solution, calculate cupric liquid and reaction mass proportioning. The content of stabilizer ammonia (NH) in detection solution, the amount of exceeding to increase ammonia-removal process.
2. calculate copper waste etching solution and reactant ratio:
Copper sulfate cupric liquid and reactant ratio: V (CuSO4):V(CaCO?)=1:1.2。
Copper chloride cupric liquid and reactant ratio: V (CuCL4)2:V(CaCO?)=1:1.2。
3. reaction condition controls: reaction solution pH controls between 7.5～8, react at 2-5m3 container or reactor under 20-35 DEG C of normal temperature condition, add stone powder material (CaCO) while stirring until stone powder material adds, reaction mass bubble reduces gradually, this process is about 2h, reaction terminates, it is thus achieved that green breast copper colloidal suspending agent.
Now reacting rear material becomes emerald green green breast copper glue suspension emulsion. Aborning inside etching waste liquor reactant in fact with CuCL2.2H2O、CuSO4.5H2Four and water of O copper ion or six and aquo complex exist. Green breast copper glue suspension is 800-1000 times for the diluted concentration of the green breast copper colloidal suspending agent of controlling plant diseases, and copper content is 10mg/L.
The present invention has following remarkable result:
1. the main composition-calcium carbonate of reaction mass stone powder can in dilute hydrochloric acid solution with Hydrated copper chloride CuCL2.2H2O reacts, again can in dilution heat of sulfuric acid with hydrated copper sulfate CuSO4.5H2O reacts, copper chloride hydroxide after reaction, basic copper sulfate copper ion be all present in calcium sulfate 2Ca with the form of complex2SO4, calcium chloride 2Ca2In the newborn suspension of these precipitated calciums of CL, in emerald green thickness emulsion state body. Therefore, according to the difference of copper compound, i.e. hydrated copper sulfate and Hydrated copper chloride in copper-containing etching waste solution, 2 kinds of green breast copper colloidal suspending agents can be produced.
2. the reaction of this product carries out at normal temperatures, and course of reaction is simple, can settle at one go.
3. course of reaction only produces carbon dioxide, without other any industrial pollutants output or discharge, production process environmental protection.
4. reaction mass copper-containing etching waste solution selective collection, therefore the content of beary metal outside industrial pollutants such as copper is low.
5. the present invention selects reaction mass to be food stage stone powder, and control or reduction objectionable impurities content that can be artificial produce, and meet the requirement of green agricultural product and environmental protection.
6. green breast copper glue suspension controlling plant diseases--high-quality, efficient green breast copper glue suspension 800-1000 times of copper content of dilution are 10mg/L. Showing for plant disease Preliminary experiment results such as Rhizoma Solani tuber osi morning, late blight, vegetable tikka, prevention effect more than 80%, in practice it has proved that Rhizoma Solani tuber osi is more sensitive to copper agent, this product is still safer to Rhizoma Solani tuber osi.
7. the pH value of two kinds of copper compounds is between 7-8, and stable performance is beneficial to storage, does not corrode packaging and aerosol apparatus is guarded against.
8. the product that this method produces has good economic benefit. Prepare green breast copper glue suspension with copper-containing etching waste solution, stone powder for raw material, in annual production 1000 tons, year integrated cost 10,000,000 yuan, 1000 tons of annual value of production about 20,000,000 yuan, annual return 10000000 yuan. Therefore, utilize this explained hereafter green breast copper colloidal suspending agent to have good economic benefit.
Detailed description of the invention
The specific embodiment of the present invention is as follows:
Utilize the method that circuit version copper waste etching solution prepares green breast copper colloidal suspending agent, adopt moisture copper compound and food stage stone powder, the ratio of the two is: 1:1.2, reaction solution pH controls between 7.5～8, reacts at 2-5m3 container or reactor under 20-35 DEG C of normal temperature condition, adds stone powder material (CaCO) while stirring until stone powder material adds, reaction mass bubble reduces gradually, this process is about 2h, and reaction terminates, it is thus achieved that green breast copper colloidal suspending agent.
Described moisture copper compound is from the complex copper in copper-containing etching waste solution in the wiring board course of processing.
Described moisture copper compound is with Hydrated copper chloride CuCL2.2H2The CuSO of O or hydrated copper sulfate4.5H2Bis-kinds of forms of O exist.
Described food stage stone powder, it is mainly composed of calcium carbonate (CaCO).
The described content of copper ion in copper waste etching solution, is typically in 7-8g/L.
Green breast copper colloidal suspending agent is 800-1000 times for the diluted concentration of controlling plant diseases, and copper content is 10mg/L.
Prepare chemical reaction process and the principle of green breast copper colloidal suspending agent:
The cupric dilute hydrochloric acid waste liquid produced after adopting HCL etching and stone powder course of reaction;
In the cupric dilute hydrochloric acid waste liquid produced after adopting HCL etching, copper ion is mainly Hydrated copper chloride (CuCL2.2H2O) adding stone powder (CaCO) reaction of formation is:
CuCL2.2H2O+CaCO3+HCL=Cu2(OH)2CO3+CO2↑+2Ca2CL↓+H2O
Its product is basic copper carbonate, carbon dioxide and calcium chloride precipitation thing.
This reaction only could occur when solution contains stabilizer ammonia (NH).
Or two: CuCL of reaction of formation2.2H2O+CaCO3+HCL=3Cu(OH)2·CuCL2+CO2↑+2Ca2CL↓+H2O
Generate copper chloride hydroxide and be again copper oxychloride, carbon dioxide and calcium chloride precipitation.
Adopt H2SO4The cupric dilute sulfuric acid waste liquid produced after etching and stone powder course of reaction:
Adopt H2SO4In the cupric dilute sulfuric acid waste liquid produced after etching, copper ion is mainly hydrated copper sulfate (CuSO4.5H2O) stone powder (CaCO) is added.
One of reaction of formation: CuSO4.5H2O+CaCO3+HSO4=Cu2(OH)2CO?+CO2↑+2Ca2SO4↓+H2O
Its product is basic copper carbonate, carbon dioxide and calcium sulfate precipitation.
This reaction only contains stabilizer ammonia (NH at solution3) when could occur.
Or two: CuSO of reaction of formation4.5H2O+CaCO3+HSO4=CuSO4.3Cu(OH)2+CO2↑+2Ca2SO4↓+H2O
Generate basic copper sulfate and be again Bordeaux mixture, carbon dioxide and calcium sulfate precipitation.
Above-mentioned Hydrated copper chloride CuCL2.2H2O, hydrated copper sulfate CuSO4.5H2O solution and calcium carbonate (CaCO3) occur the color of material after chemical reaction all to become emerald green coloring agent suspension emulsion.
The ionic equation principle of two kinds of courses of reaction:
Contained waste liquid after etching with HCL for raw material reacts:
Ionic equation: CaCO3+2H+=Ca2+H2O.CO2
With H2SO4After etching for raw material, contained waste liquid reacts
Ionic equation: CaCO3+2H=Ca2+.H2O.SO4-CO2.
Economic and Efficiency Analysis: prepare green breast copper glue suspension for raw material with copper-containing etching waste solution, stone powder, in annual production 1000 tons, year integrated cost 10,000,000 yuan, 1000 tons of annual value of production about 20,000,000 yuan, annual return 10000000 yuan. Therefore, utilize this explained hereafter green breast copper colloidal suspending agent to have good economic benefit.
Social benefit is analyzed: green breast copper colloidal suspending agent dilutes 800-1000 times, and its copper content is 10mg/L, just can effectively suppress phytopathogen in such a concentration range. With plant growth intermediate plant amount bigger period, every mu with 100 kilograms of calculating of medicinal liquid, one bottle 500 milliliters green breast copper colloidal suspending agents can join 400-500 kilogram of dilute liquid medicine, can prevent and treat the area of 3-5 mu, and every mu only with 150 milliliters of green newborn copper colloidal suspending agents. With one bottle 500 milliliters green breast copper colloidal suspending agents with 10 yuans of calculating, the agricultural chemicals expense only 3-5 unit of peasant every mu expenditure. The agricultural chemicals expense of the existing close pesticide species peasant in market every mu expenditure is with about 10 yuans, even higher. The expense that peasant saves, the income namely increased.
Environmental Effect Analysis: compared with traditional basic copper sulfate, copper chloride hydroxide production technology, this technology utilization is advantage selectively, without additionally adding other medicaments for remove impurity, thus while economizing on resources, also reduce the production cost of green breast copper glue suspension. Due to every mu only with 150 milliliters of green breast copper colloidal suspending agents, being greatly reduced of dosage, consequently reduce the pesticide pollution to environment.
Utilize copper-containing etching waste solution to produce green breast copper glue suspension not only to eliminate the pollution to environment, obtain good environmental benefit, also can obtain good Social benefit and economic benefit.
Claims (6)
1. utilize the method that circuit version copper waste etching solution prepares green breast copper colloidal suspending agent, it is characterized in that: adopt moisture copper compound and food stage stone powder, the ratio of the two is: 1:1.2, reaction solution pH controls between 7.5～8, reacts at 2-5m3 container or reactor under 20-35 DEG C of normal temperature condition, adds stone powder material (CaCO) while stirring until stone powder material adds, reaction mass bubble reduces gradually, this process is about 2h, and reaction terminates, it is thus achieved that green breast copper colloidal suspending agent.
2. method according to claim 1, it is characterised in that: described moisture copper compound is from the complex copper in copper-containing etching waste solution in the wiring board course of processing.
3. method according to claim 1 and 2, it is characterised in that: described moisture copper compound is with Hydrated copper chloride CuCL2.2H2The CuSO of O or hydrated copper sulfate4.5H2Bis-kinds of forms of O exist.
4. method according to claim 1, it is characterised in that: described food stage stone powder, it is mainly composed of calcium carbonate (CaCO).
5. method according to claim 1, it is characterised in that: the described content of copper ion in copper waste etching solution, it is typically in 7-8g/L.
6. method according to claim 1, it is characterised in that: green breast copper colloidal suspending agent is 800-1000 times for the diluted concentration of controlling plant diseases, and copper content is 10mg/L.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610125572.1A CN105660615A (en) | 2016-03-07 | 2016-03-07 | Method for preparing copper abietate colloidal suspension agent by utilizing printed circuit board copper etching waste liquid |
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| CN201610125572.1A CN105660615A (en) | 2016-03-07 | 2016-03-07 | Method for preparing copper abietate colloidal suspension agent by utilizing printed circuit board copper etching waste liquid |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1093868A (en) * | 1994-01-26 | 1994-10-26 | 宋波 | The preparation method of amonia-copper composite bacteriacide |
| CN1792860A (en) * | 2005-11-17 | 2006-06-28 | 常州市裕和金属材料有限公司 | High-efficient environment treating method for acidic etching waste liquid |
| CN1840739A (en) * | 2005-03-04 | 2006-10-04 | 法布罗技术有限公司 | Regeneration of cupric etchants and recovery of copper sulfate |
-
2016
- 2016-03-07 CN CN201610125572.1A patent/CN105660615A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1093868A (en) * | 1994-01-26 | 1994-10-26 | 宋波 | The preparation method of amonia-copper composite bacteriacide |
| CN1840739A (en) * | 2005-03-04 | 2006-10-04 | 法布罗技术有限公司 | Regeneration of cupric etchants and recovery of copper sulfate |
| CN1792860A (en) * | 2005-11-17 | 2006-06-28 | 常州市裕和金属材料有限公司 | High-efficient environment treating method for acidic etching waste liquid |
Non-Patent Citations (1)
| Title |
|---|
| 陈昌铭等: "利用含铜蚀刻废液生产碱式碳酸铜", 《化工环保》 * |
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