CN115072762B - Preparation method of basic copper chloride crystal - Google Patents
Preparation method of basic copper chloride crystal Download PDFInfo
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- CN115072762B CN115072762B CN202210775038.0A CN202210775038A CN115072762B CN 115072762 B CN115072762 B CN 115072762B CN 202210775038 A CN202210775038 A CN 202210775038A CN 115072762 B CN115072762 B CN 115072762B
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- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 title claims abstract description 72
- 239000013078 crystal Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 177
- 239000010949 copper Substances 0.000 claims abstract description 177
- 229910052802 copper Inorganic materials 0.000 claims abstract description 177
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 78
- 238000002386 leaching Methods 0.000 claims abstract description 58
- 235000019270 ammonium chloride Nutrition 0.000 claims abstract description 39
- 238000005530 etching Methods 0.000 claims abstract description 23
- 239000002699 waste material Substances 0.000 claims abstract description 23
- 239000010871 livestock manure Substances 0.000 claims abstract description 20
- 244000025254 Cannabis sativa Species 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 131
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 210000003608 fece Anatomy 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 27
- 239000002994 raw material Substances 0.000 claims description 27
- 241001465754 Metazoa Species 0.000 claims description 24
- 238000001914 filtration Methods 0.000 claims description 24
- 239000003864 humus Substances 0.000 claims description 17
- 229960003280 cupric chloride Drugs 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000012535 impurity Substances 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 241000287828 Gallus gallus Species 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000000502 dialysis Methods 0.000 claims description 5
- 238000000909 electrodialysis Methods 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229920000298 Cellophane Polymers 0.000 claims 1
- 239000002244 precipitate Substances 0.000 claims 1
- 239000000047 product Substances 0.000 claims 1
- 238000002791 soaking Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 4
- 239000005749 Copper compound Substances 0.000 abstract description 2
- 150000001880 copper compounds Chemical class 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 1
- 235000015763 Artemisia ludoviciana Nutrition 0.000 description 6
- 241000608847 Gnaphalium Species 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 4
- 239000013049 sediment Substances 0.000 description 4
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011573 trace mineral Substances 0.000 description 2
- 235000013619 trace mineral Nutrition 0.000 description 2
- 239000005752 Copper oxychloride Substances 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- HKMOPYJWSFRURD-UHFFFAOYSA-N chloro hypochlorite;copper Chemical compound [Cu].ClOCl HKMOPYJWSFRURD-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 210000003743 erythrocyte Anatomy 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000003278 haem Chemical class 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000011164 ossification Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/04—Halides
- C01G3/05—Chlorides
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention relates to the technical field of copper compound preparation, and discloses a preparation method of basic copper chloride crystals, which comprises the steps of preparing copper-containing leaching liquor, copper-containing ammonium chloride balance liquor, treating acid etching waste liquor and alkali etching waste liquor, reacting and treating. The invention is more environment-friendly, can utilize copper in the livestock manure and copper in the copper grass, and can utilize agriculture and forestry waste; meanwhile, certain substances in the copper grass can promote the generation of target products, improve the yield and the quality of use, and the granularity and the color of the generated target products are stable and uniform compared with the prior art, and the recovery rate of the target products is high.
Description
Technical Field
The invention relates to the technical field of copper compound preparation, in particular to a preparation method of basic copper chloride crystals.
Background
Copper is one of the trace elements essential for animals, and it is involved in synthesis of heme, maturation of red blood cells, osteogenesis, etc. in animals, and acts as a component of several important enzymes in animals. Copper sulfate with high dosage is added into domestic feed, but the copper sulfate has a plurality of defects in the use process, such as: high water solubility, strong oxidation, low absorption and utilization rate, high content of soluble copper in the feces, and large dosage of additive pollutes the environment. Based on the defects of the copper sulfate, the development of a safe and efficient new copper source for the development of the modern animal husbandry becomes important. The basic copper chloride is a novel copper source which is developed by a neutralization and crystallization method, has the advantages of no moisture absorption and caking, good fluidity, no oxidation damage to fat and vitamins in feed, high bioavailability, little environmental pollution and the like, is increasingly concerned by the industry, and is a novel copper source which is ideal at present.
The basic copper chloride is also called cupric oxychloride or copper oxychloride, can be used as an additive of trace element copper in feed and can be widely used as a bactericide in nuisanceless pesticides, so that the market demand is great. The raw materials for preparing the basic copper chloride at present mainly come from acidic and alkaline circuit board etching waste liquid containing copper, and the preparation method is mostly synthesized by acidic circuit board copper chloride etching liquid and alkaline circuit board copper etching liquid. The synthesis method has the advantages that the yield of the target product is low, the utilization rate of the copper raw material is still not ideal, the granularity and the color of the same batch of the synthesized target product are not stable enough, and the quality of the product is difficult to control.
Disclosure of Invention
Based on the problems, the invention provides the preparation method of the basic copper chloride crystal, which can utilize copper in livestock manure and copper in copper grass, and simultaneously utilize certain substances in the copper grass to promote the generation of target products, and the granularity and the color of the generated target products are stable and uniform compared with the prior art, and the recovery rate of the target products is high.
In order to solve the technical problems, the invention provides a preparation method of basic copper chloride crystals, which comprises the following steps:
s1: extracting copper in animal humic excrement to obtain copper-containing leaching liquor; extracting and treating copper in the copper grass to obtain copper-containing ammonium chloride balance liquid; placing a copper-containing leaching solution into a first reactor, and placing a copper-containing ammonium chloride balance solution into a second reactor for later use;
s2: the acid etching waste liquid is subjected to impurity removal treatment, and copper content and pH value are regulated to obtain copper chloride raw material solution: removing impurities from the alkaline etching waste liquid, and adjusting the copper content and the pH value to obtain an alkaline copper-containing solution; preheating a copper chloride raw material solution and an alkaline copper-containing solution to 40 ℃, and then adding the copper chloride raw material solution and the alkaline copper-containing solution into a third reactor;
s3: then, the copper-containing leaching solution in the first reactor and the copper-containing ammonium chloride balance solution in the second reactor simultaneously and slowly flow into a third reactor, wherein the flow ratio of the copper-containing leaching solution to the copper-containing ammonium chloride balance solution is (0.5-0.8): 1, maintaining the pH value in the third reactor to be 4-4.5, and stopping the copper-containing leaching solution and the copper-containing ammonium chloride balance solution from entering the third reactor when basic copper chloride crystals appear at the bottom of the third reactor; filtering the basic cupric chloride crystal, and washing, dewatering and drying to obtain the target product basic cupric chloride.
Furthermore, the animal humus manure is chicken manure and pig manure, and the animal humus manure is humus of more than sixty days.
Further, the method for extracting copper from animal humus feces comprises the following steps: respectively using water, 0.1mol/L NaOH and 0.1mol/L Na 4 P 2 O 7 Extracting with mixed solution of NaOH with pH of 9 continuously, wherein the weight ratio of leaching solution to feces is 15:1, oscillating for 24 hours, filtering by adopting a 0.45 mu m filter membrane to obtain leaching liquor, repeatedly leaching for three times, combining all leaching liquor, and obtaining copper-containing leaching liquor after glass paper dialysis and electrodialysis.
Further, the method for extracting and treating copper in the copper grass comprises the following steps: the harvested copper grass is dried and crushed into powder, the powder copper grass is soaked in 0.02mol/L acetic acid solution for 3-5 hours, sediment is removed by filtration, the filtration solution is filtered, ammonia water with the volume equal to that of the 0.02mol/L acetic acid solution is added into the filtration solution, and after stirring for half an hour, 20-35g/L ammonium chloride solution is added.
Further, the copper content of the copper chloride raw material solution is 25-35g/L, and the pH value is 1.6-1.8.
Further, the alkaline copper-containing solution has a copper content of 20-25g/L and a pH value of 8-8.5.
Further, the copper-containing leach liquor in the first reactor and the copper-containing ammonium chloride balance liquor in the second reactor need to be preheated to 60 ℃ before entering the third reactor.
Further, the volume ratio of the copper chloride raw material solution and the alkaline copper-containing solution is (1:1.5) - (1:1).
Compared with the prior art, the invention has the beneficial effects that: the invention is more environment-friendly, can utilize copper in the livestock manure and copper in the copper grass, and can utilize agriculture and forestry waste; meanwhile, certain substances in the copper grass can promote the generation of target products, improve the yield and the quality of use, and the granularity and the color of the generated target products are stable and uniform compared with the prior art, and the recovery rate of the target products is high.
Detailed Description
The present invention will be described in further detail with reference to the following examples, for the purpose of making the objects, technical solutions and advantages of the present invention more apparent, and the description thereof is merely illustrative of the present invention and not intended to be limiting.
Example 1:
the embodiment provides a preparation method of basic copper chloride crystal, which comprises the following steps:
s1: extracting copper in animal humic excrement to obtain copper-containing leaching liquor; extracting and treating copper in the copper grass to obtain copper-containing ammonium chloride balance liquid; placing a copper-containing leaching solution into a first reactor, and placing a copper-containing ammonium chloride balance solution into a second reactor for later use;
s2: the acid etching waste liquid is subjected to impurity removal treatment, and copper content and pH value are regulated to obtain copper chloride raw material solution: removing impurities from the alkaline etching waste liquid, and adjusting the copper content and the pH value to obtain an alkaline copper-containing solution; preheating a copper chloride raw material solution and an alkaline copper-containing solution to 40 ℃, and then adding the copper chloride raw material solution and the alkaline copper-containing solution into a third reactor, wherein the volume ratio of the copper chloride raw material solution to the alkaline copper-containing solution is 1:1.5; copper content of the copper chloride raw material solution is 28g/L, and pH value is 1.6; the copper content of the alkaline copper-containing solution is 23g/L, and the pH value is 8;
s3: and then the copper-containing leaching solution in the first reactor and the copper-containing ammonium chloride balance solution in the second reactor simultaneously and slowly flow into a third reactor, and before the copper-containing leaching solution in the first reactor and the copper-containing ammonium chloride balance solution in the second reactor enter the third reactor, the copper-containing leaching solution and the copper-containing ammonium chloride balance solution need to be preheated to 60 ℃, and the flow ratio of the copper-containing leaching solution to the copper-containing ammonium chloride balance solution is 0.5:1, maintaining the pH value in the third reactor to be 4.3, and stopping the copper-containing leaching solution and the copper-containing ammonium chloride balance solution from entering the third reactor when basic copper chloride crystals appear at the bottom of the third reactor; filtering the basic cupric chloride crystal, and washing, dewatering and drying to obtain the target product basic cupric chloride.
The animal humus manure of the embodiment is chicken manure and pig manure, the animal humus manure is humus of more than sixty days in humus, and the method for extracting copper in the animal humus manure is as follows: respectively using water, 0.1mol/L NaOH and 0.1mol/L Na 4 P 2 O 7 Extracting with mixed solution of NaOH with pH of 9 continuously, wherein the weight ratio of leaching solution to feces is 15:1, oscillating for 24 hours, filtering by adopting a 0.45 mu m filter membrane to obtain leaching liquor, repeatedly leaching for three times, combining all leaching liquor, and obtaining copper-containing leaching liquor after glass paper dialysis and electrodialysis. The method for extracting and treating copper in the copper grass comprises the following steps: the harvested cudweed is dried and crushed into powder, the powder cudweed is soaked in 0.02mol/L acetic acid solution for 3 hours, sediment is removed by filtration, the filtration solution is filtered, ammonia water with the volume equal to that of the 0.02mol/L acetic acid solution is added into the filtration solution, and after stirring for half an hour, 26g/L ammonium chloride solution is added.
Example 2:
the embodiment provides a preparation method of basic copper chloride crystal, which comprises the following steps:
s1: extracting copper in animal humic excrement to obtain copper-containing leaching liquor; extracting and treating copper in the copper grass to obtain copper-containing ammonium chloride balance liquid; placing a copper-containing leaching solution into a first reactor, and placing a copper-containing ammonium chloride balance solution into a second reactor for later use;
s2: the acid etching waste liquid is subjected to impurity removal treatment, and copper content and pH value are regulated to obtain copper chloride raw material solution: removing impurities from the alkaline etching waste liquid, and adjusting the copper content and the pH value to obtain an alkaline copper-containing solution; preheating a copper chloride raw material solution and an alkaline copper-containing solution to 40 ℃, and then adding the copper chloride raw material solution and the alkaline copper-containing solution into a third reactor, wherein the volume ratio of the copper chloride raw material solution to the alkaline copper-containing solution is 1:1, a step of; copper content of the copper chloride raw material solution is 32g/L, and pH value is 1.8; the copper content of the alkaline copper-containing solution is 25g/L, and the pH value is 8;
s3: and then the copper-containing leaching solution in the first reactor and the copper-containing ammonium chloride balance solution in the second reactor simultaneously and slowly flow into a third reactor, and before the copper-containing leaching solution in the first reactor and the copper-containing ammonium chloride balance solution in the second reactor enter the third reactor, the copper-containing leaching solution and the copper-containing ammonium chloride balance solution need to be preheated to 60 ℃, and the flow ratio of the copper-containing leaching solution to the copper-containing ammonium chloride balance solution is 0.6:1, maintaining the pH value in the third reactor to be 4.5, and stopping the copper-containing leaching solution and the copper-containing ammonium chloride balance solution from entering the third reactor when basic copper chloride crystals appear at the bottom of the third reactor; filtering the basic cupric chloride crystal, and washing, dewatering and drying to obtain the target product basic cupric chloride.
The animal humic excrement is chicken manure and pig manure, and the animal humic excrement is humus with a period of more than sixty days. The method for extracting copper from animal humus feces comprises the following steps: respectively using water, 0.1mol/L NaOH and 0.1mol/L Na 4 P 2 O 7 Extracting with mixed solution of NaOH with pH of 9 continuously, wherein the weight ratio of leaching solution to feces is 15:1, oscillating for 24 hours, filtering by adopting a 0.45 mu m filter membrane to obtain leaching liquor, repeatedly leaching for three times, combining all leaching liquor, and obtaining copper-containing leaching liquor after glass paper dialysis and electrodialysis. The method for extracting and treating copper in the copper grass comprises the following steps: the harvested cudweed is dried and crushed into powder, the powder cudweed is soaked in 0.02mol/L acetic acid solution for 5 hours, sediment is removed by filtration, the filtration solution is filtered, ammonia water with the volume equal to that of the 0.02mol/L acetic acid solution is added into the filtration solution, and after stirring for half an hour, 35g/L ammonium chloride solution is added.
Example 3:
the acid etching waste liquid and the alkaline etching waste liquid are respectively preheated to 48, mixed in the presence of basic copper chloride seed crystal, reacted at 70 and the rotating speed of 70r/min to obtain mixed liquid containing basic copper chloride, filtered and solid is collected to obtain the basic copper chloride. Wherein the pH of the acidic etching waste liquid and the alkaline etching waste liquid is 4.3 when the acidic etching waste liquid and the alkaline etching waste liquid react. The acidic etching waste liquid and the alkaline etching waste liquid are subjected to impurity removal treatment before the reaction, and the obtained target product basic copper chloride is subjected to the same washing, dewatering and drying processes as in example 1 and example 2.
Comparing the products of the basic cupric chloride obtained in each of the examples 1 to 3, the comparison results are shown in Table 1. It can be seen that the products of the examples 1 and 2 are better than the product of the example 3 in terms of copper content of the target product, caking and discoloration, and mass content of 60-250 μm particles in the sample, which shows that the strength and color of the target product produced by the method of the invention are more stable, the recovery rate is high, and the copper content reaches the national standard.
TABLE 1 quality comparison of product basic cupric chloride
Six batches of production experiments were also performed for each example, and the batch differences for example 1 and example 2 were found to be 0.023% and 0.034%, respectively.
Example 4:
the embodiment provides a preparation method of basic copper chloride crystal, which comprises the following steps:
s1: extracting copper in animal humic excrement to obtain copper-containing leaching liquor; placing a copper-containing leaching solution into a first reactor, and placing a copper-containing ammonium chloride solution into a second reactor for later use;
s2: the acid etching waste liquid is subjected to impurity removal treatment, and copper content and pH value are regulated to obtain copper chloride raw material solution: removing impurities from the alkaline etching waste liquid, and adjusting the copper content and the pH value to obtain an alkaline copper-containing solution; preheating a copper chloride raw material solution and an alkaline copper-containing solution to 40 ℃, and then adding the copper chloride raw material solution and the alkaline copper-containing solution into a third reactor, wherein the volume ratio of the copper chloride raw material solution to the alkaline copper-containing solution is 1:1, a step of; copper content of the copper chloride raw material solution is 32g/L, and pH value is 1.8; the copper content of the alkaline copper-containing solution is 25g/L, and the pH value is 8;
s3: and then the copper-containing leaching solution in the first reactor and the copper-containing ammonium chloride solution in the second reactor simultaneously and slowly flow into a third reactor, and before the copper-containing leaching solution in the first reactor and the copper-containing ammonium chloride solution in the second reactor enter the third reactor, the copper-containing leaching solution and the copper-containing ammonium chloride solution need to be preheated to 60 ℃, and the flow ratio of the copper-containing leaching solution to the copper-containing ammonium chloride solution is 0.6:1, maintaining the pH value in the third reactor to be 4.5, and stopping the copper-containing leaching solution and the copper-containing ammonium chloride solution from entering the third reactor when basic copper chloride crystals appear at the bottom of the third reactor; filtering the basic cupric chloride crystal, and washing, dewatering and drying to obtain the target product basic cupric chloride.
The animal humic excrement is chicken manure and pig manure, and the animal humic excrement is humus with a period of more than sixty days. The method for extracting copper from animal humus feces comprises the following steps: respectively using water, 0.1mol/L NaOH and 0.1mol/L Na 4 P 2 O 7 Extracting with mixed solution of NaOH with pH of 9 continuously, wherein the weight ratio of leaching solution to feces is 15:1, oscillating for 24 hours, filtering by adopting a 0.45 mu m filter membrane to obtain leaching liquor, repeatedly leaching for three times, combining all leaching liquor, and obtaining copper-containing leaching liquor after glass paper dialysis and electrodialysis. The method for extracting and treating copper in the copper grass comprises the following steps: the harvested cudweed is dried and crushed into powder, the powder cudweed is soaked in 0.02mol/L acetic acid solution for 5 hours, sediment is removed by filtration, the filtration solution is filtered, ammonia water with the volume equal to that of the 0.02mol/L acetic acid solution is added into the filtration solution, and after stirring for half an hour, 35g/L ammonium chloride solution is added.
Comparing example 4 with example 2, the copper content of the target product was compared, and it was found that the copper content of the target product of example 4 was 55.89%, the copper content of the target product of example 2 was 58.29%, and the average particle size of the target product of example 4 was smaller than that of example 2, probably because the copper-containing ammonium chloride equilibrium liquid of example 2 contained a substance that promoted the carrying amount of copper in the target product and adhered the target product, specifically what substance caused, further investigation was required.
The above is an embodiment of the present invention. The foregoing embodiments and the specific parameters of the embodiments are only for clarity of description of the invention and are not intended to limit the scope of the invention, which is defined by the appended claims, and all equivalent structural changes made in the content of the description of the invention are intended to be included in the scope of the invention.
Claims (1)
1. The preparation method of the basic copper chloride crystal is characterized by comprising the following steps:
s1: extracting copper in animal humic excrement to obtain copper-containing leaching liquor; extracting and treating copper in the copper grass to obtain copper-containing ammonium chloride balance liquid; placing a copper-containing leaching solution into a first reactor, and placing a copper-containing ammonium chloride balance solution into a second reactor for later use; wherein the animal humus manure is chicken manure and pig manure, and the animal humus manure is humus of more than sixty days;
the method for extracting copper from animal humus feces comprises the following steps: respectively using water, 0.1mol/L NaOH and 0.1mol/LNa 4 P 2 O 7 Extracting with mixed solution of NaOH with pH of 9 continuously, wherein the weight ratio of leaching solution to feces is 15:1, oscillating for 24 hours, filtering by adopting a 0.45 mu m filter membrane to obtain leaching liquor, repeatedly leaching for three times, combining all leaching liquor, and obtaining copper-containing leaching liquor after cellophane dialysis and electrodialysis;
the method for extracting and treating copper in the copper grass comprises the following steps: drying and crushing the harvested copper grass into powder, soaking the powder copper grass in 0.02mol/L acetic acid solution for 3-5 hours, filtering to remove precipitate, filtering the solution, adding ammonia water with the same volume as that of the 0.02mol/L acetic acid solution into the filtered solution, stirring for half an hour, and adding 20-35g/L ammonium chloride solution;
s2: carrying out impurity removal treatment on the acid etching waste liquid, and regulating copper content and pH value to obtain a copper chloride raw material solution, wherein the copper content of the copper chloride raw material solution is 25-35g/L, and the pH value is 1.6-1.8; removing impurities from the alkaline etching waste liquid, and regulating copper content and pH value to obtain an alkaline copper-containing solution, wherein the copper content of the alkaline copper-containing solution is 20-25g/L, and the pH value is 8-8.5; preheating a copper chloride raw material solution and an alkaline copper-containing solution to 40 ℃, and then adding the copper chloride raw material solution and the alkaline copper-containing solution into a third reactor, wherein the volume ratio of the copper chloride raw material solution to the alkaline copper-containing solution is (1:1.5) - (1:1);
s3: then, the copper-containing leaching liquor in the first reactor and the copper-containing ammonium chloride balance liquor in the second reactor simultaneously and slowly flow into a third reactor, and the copper-containing leaching liquor in the first reactor and the copper-containing ammonium chloride balance liquor in the second reactor need to be preheated to 60 ℃ before entering the third reactor; the flow ratio of the copper-containing leaching solution to the copper-containing ammonium chloride balance solution is (0.5-0.8): 1, maintaining the pH value in the third reactor to be 4-4.5, and stopping the copper-containing leaching solution and the copper-containing ammonium chloride balance solution from entering the third reactor when basic copper chloride crystals appear at the bottom of the third reactor; filtering the basic cupric chloride crystal, and washing, dewatering and drying to obtain the target product basic cupric chloride.
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