CN102730743A - Method for producing tribasic copper chloride - Google Patents
Method for producing tribasic copper chloride Download PDFInfo
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- CN102730743A CN102730743A CN2012102292895A CN201210229289A CN102730743A CN 102730743 A CN102730743 A CN 102730743A CN 2012102292895 A CN2012102292895 A CN 2012102292895A CN 201210229289 A CN201210229289 A CN 201210229289A CN 102730743 A CN102730743 A CN 102730743A
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- copper chloride
- basic copper
- sodium hydroxide
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- etching waste
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- ORTQZVOHEJQUHG-UHFFFAOYSA-L Copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 title claims abstract description 13
- 239000004135 Bone phosphate Substances 0.000 title abstract 8
- LWIHDJKSTIGBAC-UHFFFAOYSA-K Tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 title abstract 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 122
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 238000005530 etching Methods 0.000 claims abstract description 37
- 239000002699 waste material Substances 0.000 claims abstract description 37
- 239000007788 liquid Substances 0.000 claims abstract description 34
- 230000002378 acidificating Effects 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000243 solution Substances 0.000 claims abstract description 26
- CVTZKFWZDBJAHE-UHFFFAOYSA-N [N].N Chemical compound [N].N CVTZKFWZDBJAHE-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000012535 impurity Substances 0.000 claims abstract description 23
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000000967 suction filtration Methods 0.000 claims abstract description 6
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 5
- 230000002194 synthesizing Effects 0.000 claims abstract description 5
- CPOSXJRGXIJOHG-UHFFFAOYSA-I dicopper;dichloride;trihydroxide Chemical compound [OH-].[OH-].[OH-].[Cl-].[Cl-].[Cu+2].[Cu+2] CPOSXJRGXIJOHG-UHFFFAOYSA-I 0.000 claims description 53
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 40
- 239000010949 copper Substances 0.000 claims description 21
- 229910052802 copper Inorganic materials 0.000 claims description 20
- 239000012452 mother liquor Substances 0.000 claims description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 16
- 239000003513 alkali Substances 0.000 claims description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- UIIMBOGNXHQVGW-UHFFFAOYSA-M NaHCO3 Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- JPVYNHNXODAKFH-UHFFFAOYSA-N cu2+ Chemical group [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 8
- 238000005342 ion exchange Methods 0.000 claims description 8
- -1 ammonium radical ion Chemical class 0.000 claims description 7
- 238000005660 chlorination reaction Methods 0.000 claims description 7
- 229910001431 copper ion Inorganic materials 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 235000019270 ammonium chloride Nutrition 0.000 claims description 6
- QDHHCQZDFGDHMP-UHFFFAOYSA-N monochloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 5
- 235000017550 sodium carbonate Nutrition 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 239000007921 spray Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 235000010755 mineral Nutrition 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 150000002978 peroxides Chemical class 0.000 claims description 4
- 239000002351 wastewater Substances 0.000 claims description 4
- YZHUMGUJCQRKBT-UHFFFAOYSA-M Sodium chlorate Chemical compound [Na+].[O-]Cl(=O)=O YZHUMGUJCQRKBT-UHFFFAOYSA-M 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- VKJKEPKFPUWCAS-UHFFFAOYSA-M Potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000007664 blowing Methods 0.000 claims description 2
- 229960003280 cupric chloride Drugs 0.000 claims description 2
- 230000002045 lasting Effects 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 abstract description 7
- 239000002245 particle Substances 0.000 abstract description 6
- 238000001035 drying Methods 0.000 abstract description 4
- 238000005406 washing Methods 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000010924 continuous production Methods 0.000 abstract description 2
- 238000007599 discharging Methods 0.000 abstract description 2
- 238000005119 centrifugation Methods 0.000 abstract 1
- 239000010413 mother solution Substances 0.000 abstract 1
- 230000035484 reaction time Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- ARUVKPQLZAKDPS-UHFFFAOYSA-L Copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 6
- 229910000365 copper sulfate Inorganic materials 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000010802 sludge Substances 0.000 description 5
- 238000005755 formation reaction Methods 0.000 description 4
- 238000005273 aeration Methods 0.000 description 3
- 230000003042 antagnostic Effects 0.000 description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 3
- 229910052785 arsenic Inorganic materials 0.000 description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 3
- 229910052793 cadmium Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 229940029983 VITAMINS Drugs 0.000 description 2
- 229940021016 Vitamin IV solution additives Drugs 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive Effects 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium monoxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000013343 vitamin Nutrition 0.000 description 2
- 239000011782 vitamin Substances 0.000 description 2
- 229930003231 vitamins Natural products 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 210000004767 Rumen Anatomy 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 235000015450 Tilia cordata Nutrition 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 230000000844 anti-bacterial Effects 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- XGZRAKBCYZIBKP-UHFFFAOYSA-L disodium;dihydroxide Chemical compound [OH-].[OH-].[Na+].[Na+] XGZRAKBCYZIBKP-UHFFFAOYSA-L 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxyl anion Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000000411 inducer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 230000000050 nutritive Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory Effects 0.000 description 1
- 239000001187 sodium carbonate Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Abstract
The invention discloses a method for producing tribasic copper chloride. The method for producing the tribasic copper chloride includes the following steps of: (1) removing impurities from an acidic etching waste solution; (2) adding clean water or a tirbasic copper chloride production mother solution to a synthesis reactor, performing preheating, and then, preheating the acidic etching waste solution whose impurities have been removed and an alkaline solution of sodium hydroxide and mixing the two solutions for a reaction with the pH value and temperature of the reaction being controlled so as to gradually form the tribasic copper chloride, and discharging partial materials after a certain amount of reaction time; (3) filtering the materials discharged from the reaction system, and performing washing, suction filtration, centrifugation and drying on the filtrated residues to obtain the tribasic copper chloride; and (4) performing ammonia nitrogen removal treatment on filtrated liquid. By adopting the method for producing the tribasic copper chloride in the invention, continuous production can be achieved and the tribasic copper chloride with large particle size and high purity can be produced; further, production cost can be reduced and overall process can be integrated; and the method for producing the tribasic copper chloride is advantaged in simple ultimate steps of ammonia nitrogen removal, easiness in operation as well as reduced difficulty and cost of ammonia nitrogen treatment.
Description
Technical field
The invention belongs to the etching waste liquor process field, be specifically related to a kind of working method of basic copper chloride.
Background technology
At present; The domestic copper sulfate that in feed, mostly uses is as trace mineral supplement, but copper sulfate in use exist be prone to moisture absorption caking, bad dispersibility, oxidisability is strong and destroy nutritive substances such as VITAMINs and fat in the feed, zinc and iron are had antagonistic action and influences shortcoming such as its absorption.Therefore be necessary to develop a kind of new and effective copper source additive and replace copper sulfate.
Basic copper chloride is at U.S.'s applicating history of existing more than ten years.Research shows that basic copper chloride has following advantage compared with copper sulfate: 1. nonhygroscopicly do not lump, be evenly distributed, ruminating animal was had function of rumen, help the antagonistic action that wherein copper is avoided sulphur in the cud, molybdenum; 2. water insoluble, in aquatic feed, have higher biology utilization ratio than copper sulfate; 3. oxidisability is low, has reduced the destruction to feed nutrient such as VITAMINs, fat; 4. copper content is high, and the biology utilization ratio is high, and zinc and iron are not had antagonistic action; 5. reduced feedstuff-meat ratio, improved the weightening finish of feed efficiency and animal, antibacterial effect is better than copper sulfate simultaneously, can effectively improve the disease resistance of animal; 6. consumption is few, and efficient is high, helps protecting environment, meets the sustainable development of animal husbandry policy.Therefore, national Ministry of Agriculture approval basic copper chloride in 2003 is as novel fodder additive.
At present, domestic comparatively advanced etching waste liquor treatment process is: utilize acidic and alkaline waste etching solution generation neutralization reaction, produce basic copper chloride.Factory effluent is handled the back discharging through operations such as IX, mechanical vapor recompressions again.But along with the upgrading of circuit board plant technology, alkaline etching waste liquid generation reduces gradually, generally adopts ammoniacal liquor to substitute alkaline etching waste liquid for producing.The shortcoming that this operational path is produced basic copper chloride is an adding ammonia nitrogen artificial when producing; Increase the intractability and the cost of subsequent waste water, simultaneously this operational path production cost is high, operation sequence increases, labour intensity is big, the waste gas environmental pollution is bigger.And the main evaporation recovery system (MVR) of ammonium chloride is ripe not enough in the mother liquor, and the etching problem of compressor head does not also have fine solution, and reclaims the ammonium chloride inferior quality.
Therefore, the processing to etching waste liquor at present finishes, and exists the problem that the ammonia-nitrogen content intractability is big, processing cost is high to have to be solved.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, a kind of working method of basic copper chloride is provided.Described basic copper chloride is produced mother liquor and can be back to and produce basic copper chloride or can be up to standard after simple process.
Above-mentioned purpose of the present invention is achieved through following technical scheme:
A kind of working method of basic copper chloride comprises the steps:
(1) removal of impurities: in acidic etching waste liquid, add oxygenant, add mineral alkali then the pH value of acidic etching waste liquid is adjusted between 0.1 ~ 3, remove impurity;
(2) in synthesis reactor, add clear water or basic copper chloride production mother liquor, be preheated to 30 ~ 100 ℃; With the acidic etching waste liquid after step (1) removal of impurities and sodium hydroxide mass content is after 5 ~ 50% alkaline solution is preheated to 40 ~ 80 ℃ respectively; Be that the volume flow ratio of 5 ~ 50% alkaline solution is that 1:0.5 ~ 4 are added in the synthesis reactor according to acidic etching waste liquid after the removal of impurities and sodium hydroxide mass content then; And the control reaction pH value is 3 ~ 7; The temperature of reaction system forms basic copper chloride gradually at 50 ~ 100 ℃; Reaction continues to emit the material that accounts for reaction system TV 20 ~ 80% after 0.6 ~ 6 hour, and in blowing, acidic etching waste liquid after the lasting adding removal of impurities and sodium hydroxide mass content are 5 ~ 50% alkaline solution, make and produce continuously; In reaction process, in reaction kettle, add ammonium chloride or ammoniacal liquor, the ammonia-nitrogen content in the reaction solution is remained in 0.1 ~ 40g/L scope;
(3) material of from reaction system, releasing is filtered, gained filtrating is produced mother liquor for basic copper chloride; Filter residue washs, suction filtration, centrifugal, dry, promptly obtains the basic copper chloride product;
(4) step (3) gained basic copper chloride production mother liquor carries out press filtration with pressure filter, again the mother liquor after the press filtration is squeezed into Copper Ion Exchange post copper removal; At normal temperatures the mother liquor after the IX is added in pH=8 ~ 13 scopes of alkali lye regulation system then, make the ammonium radical ion change into amino molecule, with the ammonia molecule of pressurized air blow-off method removal mother liquor, ammonia absorbs the preparation ammoniacal liquor with three grades of sprays and is back to production; In the waste water surplus ammonium radical ion, adopt break point chlorination, add drift ice and remove middle water reuse of processing or qualified discharge after simple process;
As a kind of preferred version, in the step (2), to be 5 ~ 50% alkaline solution be the sodium hydroxide mass content mixed alkali liquor that to be 5 ~ 50% sodium hydroxide solution or sodium hydroxide form with yellow soda ash and/or sodium hydrogencarbonate to said sodium hydroxide mass content.
After the absorption of Copper Ion Exchange post is saturated, carry out wash-out with hydrochloric acid, the elutriant of gained cupric and ammonium chloride is produced the mother liquor reuse as basic copper chloride.
As a kind of preferred version, in the step (1), said oxygenant is preferably ydrogen peroxide 50, VAL-DROP or Potcrate.
As a kind of preferred version, in the step (1), said mineral alkali is sodium hydroxide, yellow soda ash, sodium bicarbonate solid or its aqueous solution.
In the step (2), the temperature of said reaction system is chosen as 50 ~ 100 ℃, in this TR, can generate crystal formation basic copper chloride crystal preferably.
As a kind of preferred version; In the step (2), the pH value of said reaction system is preferably 4 ~ 7, crosses to hang down then can produce the basic copper chloride copper sludge; Too highly then can generate the verditer copper sludge, only in this pH scope, can synthesize crystal formation basic copper chloride crystal preferably.
In the step (2); The volume flow ratio of acidic etching waste liquid after the said removal of impurities and sodium hydroxide mixed ammonium/alkali solutions is chosen as 1:0.5 ~ 4, can guarantee better that in this scope the hydroxide ion in cupric ion, cl ions and the sodium hydroxide in the acidic etching waste liquid synthesizes crystal formation basic copper chloride crystal preferably in the ratio of 2:1:3.Be higher than this throughput ratio, the sodium hydroxide instantaneous delivery is excessive relatively, and directly generates verditer, influences the quality and the purity of product; Be lower than this throughput ratio, the instantaneous delivery of acidic etching waste liquid is excessive relatively, causes the crystal grain of basic copper chloride less than normal, and the reaction of the copper in the acidic etching waste liquid not exclusively, increased the burden of subsequent wastewater treatment.
As a kind of preferred version, in the reaction process of step (2), add ammonia chloride crystal or ammoniacal liquor with respect to reaction system massfraction 0.001 ~ 0.1%.The ammonium radical ion is the inducer that brings out the basic copper chloride building-up reactions, only needs a small amount of the existence that reaction is carried out continuously, and synthetic crystal formation is the basic copper chloride crystal preferably.
As a kind of preferred version, to remove in the ammonia nitrogen process at the pressurized air blow-off method of step (4), the pH value of system is preferably 11 ~ 12, and the ammonium radical ion can more fully be converted into amino molecule under this pH value, and ammonia nitrogen removal frank reaches 95% ~ 97%; And under this pH condition, better for the effect that the waste water behind the stripping is removed remaining ammonia nitrogen with break point chlorination, ammonia nitrogen is dropped to below the 10ppm, reach Guangdong Province's first discharge standard.
As a kind of preferred version, in step (2), possibly produce overflowing liquid in the reaction process, can collect this overflowing liquid, mix the treating method reuse of (4) set by step then with the mother liquor that step (3) obtains.
The basic copper chloride product particle that employing the method for the invention prepares is between 30～300 μ m, and copper content is more than 59.1%.
Molecular formula Cu from basic copper chloride
2(OH)
3Cl, its theoretical copper content is 59.48%; Can find out that product gas purity of the present invention is more than 99%.
Compared with prior art, the present invention has following beneficial effect: the novel method that the invention discloses a kind of continuous production basic copper chloride.Adopt sodium hydroxide or sodium hydroxide mixed alkali liquor to substitute the ammoniacal etchant waste liquid or the ammoniacal liquor of existing technology; Through in reaction soln, adding a spot of ammonium radical ion; And the ratio of regulating suitable reaction temperature, pH value and acidic etching waste liquid and alkali lye, can produce the basic copper chloride of larger particles; Mother liquor behind the production basic copper chloride; Ammonia-nitrogen content is in 0.1～40g/L scope, and the allotment through suitable can be used as in the preparation of raw material reuse to basic copper chloride; Also can combine to handle, get final product qualified discharge through simple ion exchange method, blow-off method and break point chlorination.
Embodiment
Below in conjunction with specific embodiment the present invention is further specified, but specific embodiment is not done any qualification to the present invention.
Embodiment 1
(1) with 5m
3The cupric massfraction is that the acidic etching waste liquid of 9 % is squeezed into the removal of impurities reaction kettle; Add the 10L ydrogen peroxide 50, reacted 10 minutes, add sodium hydroxide again its pH is transferred to 1.3; React press filtration after 20 minutes, remove impurity rear filtrates such as delead, arsenic, cadmium, mercury, iron and get into the acidic etching waste liquid medial launder.
(2) toward 5.4 m
3Add 600kg solid sodium hydroxide and 68.5kg solid sodium carbonate in the water, be made into the sodium hydroxide mass concentration and be about 10% sodium hydroxide mixed alkali liquor.
The basic copper chloride mother liquor that (3) will contain 600mg/L copper and 15g/L ammonia nitrogen is preheating to 70 ℃; According to the volumetric flow rate ratio is acidic etching waste liquid and sodium hydroxide mixing solutions after 1:1.5 adds removal of impurities respectively; PH is between 6.0 ~ 6.5 in control; React after 4 hours, consume acidic etching waste liquid 5.41t altogether, 10% sodium hydroxide mixed alkali liquor 6.1t.Emit the material that accounts for reaction system TV 20%, obtain cupric 59.19% after filtration, washing, suction filtration, centrifugal, the drying, particle size is the blackish green basic copper chloride crystal 810kg about 189 μ m.
(4) step (3) is filtered the filtrating obtain through detecting, and it contains the ammonia nitrogen of 7560mg/L, after the pressure filter press filtration, then filtrating is squeezed into the Copper Ion Exchange post, makes water outlet copper content<0.5mg/>L, again 0.21 m is used in water outlet
3Massfraction is that 50 % sodium hydroxide solutions adjusting pH is 11.5, then it is squeezed in the stripping tower, and normal temperature stripping, water outlet ammonia nitrogen concentration are 267.8mg/L, and pH is about 11, and ammonia absorbs preparation ammoniacal liquor products with three grades of sprays.Adopt break point chlorination; In the water outlet of stripping tower, add the 133.9kg drift ice, aeration is handled, and last water outlet contains ammonia nitrogen < 10mgL; PH is between 8 ~ 9, reaches behind Guangdong Province's first discharge standard qualified discharge or is back in the production process to replenish water, cleaning product, cleaning equipment.
Embodiment 2
(1) with 5.5m
3The cupric massfraction is that the acidic etching waste liquid of 9.5 % is squeezed into the removal of impurities reaction kettle; Under well-beaten situation; Add 15L VAL-DROP, reacted 10 minutes, add sodium hydroxide again its pH is transferred to 1.5; React press filtration after 20 minutes, remove impurity rear filtrates such as delead, arsenic, cadmium, mercury, iron and get into the acidic etching waste liquid medial launder.
(2) toward 5.5 m
3Add the 786kg solid sodium hydroxide in the water, be made into the sodium hydroxide mass concentration and be 12.5% sodium hydroxide solution.
The basic copper chloride mother liquor that (3) will contain 743mg/L copper and 11g/L ammonia nitrogen is preheating to 75 ℃; According to the volumetric flow rate ratio is acidic etching waste liquid and sodium hydroxide solution after 1:2 adds removal of impurities respectively; PH is between 6.5 ~ 7.0 in control; React after 4 hours, consume acidic etching waste liquid 5.5t altogether, 12.5% sodium hydroxide solution 5.6t.Emit the material that accounts for reaction system TV 25%, obtain cupric 59.21% after filtration, washing, suction filtration, centrifugal, the drying, particle size is the blackish green basic copper chloride crystal 875kg about 208 μ m.
(4) step (3) is filtered the filtrating obtain through detecting, and it contains the ammonia nitrogen of 6250mg/L, after the pressure filter press filtration; Then filtrating is squeezed into efficient Copper Ion Exchange post, make water outlet copper content 0.5mg/L, using the 107.29kg quicklime to regulate pH water outlet again is 11.8; Then it is squeezed in the stripping tower, normal temperature stripping, water outlet ammonia nitrogen concentration are 187.5mg/L; PH is about 11, and ammonia absorbs preparation ammoniacal liquor product with three grades of sprays.Adopt break point chlorination; In the stripping tower water outlet, add the 93.75kg drift ice, aeration is handled, and last water outlet contains ammonia nitrogen < 10mg/>L; PH is between 8 ~ 9, reaches behind Guangdong Province's first discharge standard qualified discharge or is back in the production process to replenish water, cleaning product, cleaning equipment.
Embodiment 3
(1) with 4.5m
3The cupric massfraction is that the acidic etching waste liquid of 8.5 % is squeezed into the removal of impurities reaction kettle; Add the 8L ydrogen peroxide 50, reacted 10 minutes, add sodium hydroxide again its pH is transferred to 1.0; React press filtration after 20 minutes, remove impurity rear filtrates such as delead, arsenic, cadmium, mercury, iron and get into the acidic etching waste liquid medial launder.
(2) toward 4.5 m
3Add 500kg solid sodium hydroxide and 55.6kg solid sodium bicarbonate in the water, be made into mass concentration and be about 10% sodium hydroxide mixed alkali liquor.
The basic copper chloride mother liquor that (3) will contain 652mg/L copper and 8g/L ammonia nitrogen is preheating to 70 ℃; According to the volumetric flow rate ratio is acidic etching waste liquid and sodium hydroxide mixing solutions after 1:1 adds removal of impurities respectively; PH is between 4.0 ~ 4.5 in control; React after 4 hours, consume acidic etching waste liquid 4.98t altogether, 10% sodium hydroxide mixed alkali liquor 5.01t.Emit the material that accounts for reaction system TV 30%, obtain cupric 59.17% after filtration, washing, suction filtration, centrifugal, the drying, particle size is the deep green basic copper chloride crystal 755kg about 222 μ m.
(4) step (3) is filtered the filtrating obtain through detecting, and it contains the ammonia nitrogen of 7133mg/L, after the pressure filter press filtration; Then filtrating is squeezed into the Copper Ion Exchange post, make water outlet copper content 0.5mg/L, using 122.48kg lime to regulate pH water outlet again is 11.8; Then it is squeezed in the stripping tower, normal temperature stripping, water outlet ammonia nitrogen concentration are 228.32mg/L; PH is about 11, and ammonia absorbs preparation ammoniacal liquor product with three grades of sprays.Adopt break point chlorination; In the water outlet of stripping tower, add the 114.16kg drift ice, aeration is handled, and last water outlet contains ammonia nitrogen < 10mg/>L; PH is between 8 ~ 9, reaches behind Guangdong Province's first discharge standard qualified discharge or is back in the production process to replenish water, cleaning product, cleaning equipment.
Comparative Examples 1
Adopt the technology identical with embodiment 1, difference is in the step (2), pH value control 2 ~ 2.5, the gained basic copper chloride is the basic copper chloride copper sludge, granularity 10 μ m, need process heightening pH value to 5.5 to react 3h after, obtain the product of copper content 58.77%.
Comparative Examples 2
Adopt the technology identical with embodiment 1, distinguish and be that in the step (2), the temperature of reaction system is controlled at 30 ℃, what obtain is the basic copper chloride copper sludge basically.
Comparative Examples 3
Adopt the technology identical with embodiment 1, distinguish and be that in the step (2), the acidic etching waste liquid after the said removal of impurities and the volume flow ratio of sodium hydroxide solution are 1:5, what obtain is the basic copper chloride copper sludge basically.
Claims (7)
1. the working method of a basic copper chloride is characterized in that, comprises the steps:
(1) removal of impurities: in acidic etching waste liquid, add oxygenant, add mineral alkali then the pH value of acidic etching waste liquid is adjusted between 0.1 ~ 3, remove impurity;
(2) in synthesis reactor, add clear water or basic copper chloride production mother liquor, be preheated to 30 ~ 100 ℃; With the acidic etching waste liquid after step (1) removal of impurities and sodium hydroxide mass content is after 5 ~ 50% alkaline solution is preheated to 40 ~ 80 ℃ respectively; Be that the volume flow ratio of 5 ~ 50% alkaline solution is that 1:0.5 ~ 4 are added in the synthesis reactor according to acidic etching waste liquid after the removal of impurities and sodium hydroxide mass content then; And the control reaction pH value is 3 ~ 7; The temperature of reaction system forms basic copper chloride gradually at 50 ~ 100 ℃; Reaction continues to emit the material that accounts for reaction system TV 20 ~ 80% after 0.6 ~ 6 hour, and in blowing, acidic etching waste liquid after the lasting adding removal of impurities and sodium hydroxide mass content are 5 ~ 50% alkaline solution, make and produce continuously; In reaction process, in reaction kettle, add ammonium chloride or ammoniacal liquor, the ammonia-nitrogen content in the reaction solution is remained in 0.1 ~ 40g/L scope;
(3) material of from reaction system, releasing is filtered; Gained filtrating is produced mother liquor for basic copper chloride; Filter residue washs, suction filtration, centrifugal, dry, promptly obtains the basic copper chloride product;
(4) step (3) gained basic copper chloride production mother liquor carries out press filtration with pressure filter, again the mother liquor after the press filtration is squeezed into Copper Ion Exchange post copper removal; PH=8 ~ 13 that add the alkali lye regulation system then at normal temperatures make the ammonium radical ion change into amino molecule, and with the ammonia molecule of pressurized air blow-off method removal mother liquor, ammonia absorbs the preparation ammoniacal liquor with three grades of sprays and is back to production; In the waste water surplus ammonium radical ion, adopt break point chlorination, add drift ice and remove middle water reuse of processing or qualified discharge after simple process;
After the absorption of Copper Ion Exchange post is saturated, carry out wash-out with hydrochloric acid, the elutriant of gained cupric and ammonium chloride is produced the mother liquor reuse as basic copper chloride.
2. the working method of basic copper chloride according to claim 1 is characterized in that in the step (1), said oxygenant is ydrogen peroxide 50, VAL-DROP or Potcrate.
3. the working method of basic copper chloride according to claim 1 is characterized in that in the step (1), said mineral alkali is sodium hydroxide, yellow soda ash, sodium bicarbonate solid or its aqueous solution.
4. the working method of basic copper chloride according to claim 1; It is characterized in that; In the step (2), to be 5 ~ 50% alkaline solution be the sodium hydroxide mass content mixed alkali liquor that to be 5 ~ 50% sodium hydroxide solution or sodium hydroxide form with yellow soda ash and/or sodium hydrogencarbonate to said sodium hydroxide mass content.
5. the working method of basic copper chloride according to claim 1 is characterized in that in the step (2), the pH value of said reaction system is 4 ~ 7.
6. the working method of basic copper chloride according to claim 1 is characterized in that, in the reaction process of step (2), adds ammonia chloride crystal or ammoniacal liquor with respect to reaction system massfraction 0.001 ~ 0.1%.
7. the working method of basic copper chloride according to claim 1 is characterized in that, in the step (4), the pressurized air blow-off method removes in the ammonia nitrogen process, and the pH value of system is 11 ~ 12.
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