CN102602980B - Industrial preparation method of alkali copper sulfate - Google Patents
Industrial preparation method of alkali copper sulfate Download PDFInfo
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- CN102602980B CN102602980B CN201210123599.9A CN201210123599A CN102602980B CN 102602980 B CN102602980 B CN 102602980B CN 201210123599 A CN201210123599 A CN 201210123599A CN 102602980 B CN102602980 B CN 102602980B
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Abstract
The invention discloses an industrial preparation method of alkali copper sulfate. The used materials are non-toxic and harmless and can be obtained at low cost, which is good for industrial production; in the production process, citric acid root ion is used as a complexing agent so that the product grain size is increased, which is beneficial to cleaning; usually, washing just needs to be carried out twice and the production efficiency is improved; after reaction, the citric acid root ion is remained in the waste water, is non-toxic, pollution-free and degradable, and can be complex with heavy metal ions (such as arsenic and lead) possibly existing in the production system so that the heavy metal ions can be discharged out of the production system together with the waste water, thereby effectively preventing the heavy metal ions from entering the target output and further improving the purity of the product. In addition, ammonia nitrogen is not involved in the production process, thereby solving the problem of recycling of ammonia nitrogen in the traditional method. Therefore, the invention has favorable social and economical benefits.
Description
Technical field
The present invention relates to a kind of preparation method of compound of copper, be specifically related to a kind of industrial production process of Basic Chrome Sulphate.
Background technology
Basic Chrome Sulphate is the main component of Inorganic Copper fungicide Bordeaux mixture, can be used as the additive application of trace copper in feed, can also be widely used in public nuisance-free agricultural chemicals as sterilant, sterilant, but lack on market always, a kind of production efficiency is high, the preparation method of good product quality.Such as, application number is that 201010117119.9 patent has proposed to utilize electronics waste liquid to add the method for alkali ammonia excretion legal system for Basic Chrome Sulphate, can prepare Basic Chrome Sulphate, but there is following main drawback: 1, Schweitzeros reagent easily forms copper hydroxide under alkaline condition, affect purity and the quality of product; 2, in preparation system, there is ammonia nitrogen, can be very not thorough and reclaim ammonia nitrogen by heating ammonia excretion method, thoroughly reclaim ammonia nitrogen cost very high, reclaim and thoroughly do not pollute the environment.The patent that and for example application number is 200810107597.4 has proposed to pass into carbonic acid gas in ammonium copper sulfate solution and has prepared Basic Chrome Sulphate, and its main drawback is: 1, part copper can form ventilation breather with carbonic acid gas, affects purity and the quality of product; 2, carbonic acid gas is gas phase, and solution is liquid phase, and reacting between gas phase and liquid phase can cause production efficiency low; And in reaction system, exist equally ammonia nitrogen to be difficult to the problem reclaiming.
Summary of the invention
For solving the deficiencies in the prior art, the object of the present invention is to provide a kind of industrial production process of Basic Chrome Sulphate, adopt cheap and easy to get, nontoxic raw materials for production, technological process is simple, in guaranteeing quality product, can enhance productivity, and then reduce production cost.Also solve the ammonia nitrogen problem in restriction and the factory effluent that output in existing preparation method is subject to raw material.
In order to realize above-mentioned target, the present invention adopts following technical scheme:
A kind of industrial production process of Basic Chrome Sulphate, is characterized in that, comprises the steps:
The A solution that a, preparation contain sulfate ion and cupric ion, stand-by;
The B solution that b, preparation contain hydroxide ion, stand-by;
C, introduce complexing agent: at least one in above-mentioned A solution and B solution, add complexing agent C, after dissolving, above-mentioned complexing agent C forms the solution that comprises citrate ion, carry out after this step, above-mentioned A solution and B solution are denoted as respectively A1 solution and B1 solution again;
D, by A1 solution and B1 solution simultaneously, flow in reactor lentamente, there is chemical reaction in both, and in reaction process, regulating the flow of A1 solution and B1 solution to make the pH value of reaction kettle for reaction liquid is 3 ~ 9, produces intermediate product;
E, intermediate product is transferred in suction filter, washs to washings and be neutral, and carry out suction filtration tentatively to dewater, produce primary product;
F, primary product is carried out to drying and processing, prepare target product Basic Chrome Sulphate.
A kind of industrial production process of aforesaid Basic Chrome Sulphate, it is characterized in that, above-mentioned A solution is directly acid wiring board bluestone waste, or is copper-bath, or is made by one or more and sulfuric acid reaction in copper hydroxide, ventilation breather, cupric oxide.
A kind of industrial production process of aforesaid Basic Chrome Sulphate, is characterized in that, above-mentioned B solution is sodium hydroxide and/or potassium hydroxide solution.
A kind of industrial production process of aforesaid Basic Chrome Sulphate, is characterized in that, above-mentioned complexing agent C is citric acid or solubility Citrate trianion.
A kind of industrial production process of aforesaid Basic Chrome Sulphate, is characterized in that, in above-mentioned A solution, the mass concentration of cupric ion is 2% ~ 12%.
A kind of industrial production process of aforesaid Basic Chrome Sulphate, is characterized in that, in above-mentioned B solution, the mass concentration of hydroxide ion is 5% ~ 15%.
A kind of industrial production process of aforesaid Basic Chrome Sulphate, is characterized in that, the mol ratio of above-mentioned cupric ion and citrate ion is 1:0.01 ~ 0.8.
A kind of industrial production process of aforesaid Basic Chrome Sulphate, is characterized in that, the temperature of reaction in above-mentioned steps d is 35 ~ 75 ℃.
A kind of industrial production process of aforesaid Basic Chrome Sulphate, is characterized in that, adopts pH electrode to monitor the pH value of reaction kettle for reaction liquid in above-mentioned steps d.
A kind of industrial production process of aforesaid Basic Chrome Sulphate, is characterized in that, in above-mentioned steps d, the pH value of reaction solution is 4 ~ 7.
Usefulness of the present invention is: a kind of industrial production process of Basic Chrome Sulphate of the present invention, and the advantages of nontoxic raw materials of employing is harmless and cheap and easy to get, is conducive to industrialization volume production; In production process, adopt citrate ion as complexing agent, product granularity is grown, be conducive to clean, generally carry out twice washing, can enhance productivity, having reacted rear citrate ion remains in waste water, nontoxic, pollution-free and easily degraded, make heavy metal ion discharge production system with waste water but also can carry out complexing with the heavy metal ion (as arsenic, lead) that may exist in production system, effectively avoid heavy metal ion to enter into target product, further improve the purity of product; In addition, in production process, do not relate to ammonia nitrogen, solved the problem of the ammonia nitrogen of puzzlement recovery always in traditional method.Therefore the present invention has good society and economic benefit.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the preferred embodiment of a kind of industrial production process of Basic Chrome Sulphate of the present invention.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is done to concrete introduction.
With reference to Fig. 1, the industrial production process of Basic Chrome Sulphate of the present invention, comprises following step:
A, preparation contain sulfate ion (SO
4 2-) and cupric ion (Cu
2+) A solution, stand-by;
Specifically, A solution can be directly acid wiring board bluestone waste, can directly utilize industrial effluent like this, reduces production costs; Also can be copper-bath, or be made by one or more and sulfuric acid reaction in copper hydroxide, ventilation breather, cupric oxide.In the present invention, the concentration of A solution is not had to special requirement, preferred as one, in order to take into account production cost, production efficiency and productive rate, Cu in A solution
2+mass concentration be 2% ~ 12%.
B, preparation contain hydroxide ion (OH
-) B solution, stand-by;
B solution is solubility hydroxide solution, as industrial lye, sodium hydroxide and/or potassium hydroxide solution.Preferred as one, OH in B solution
-mass concentration be 5% ~ 15%, can take into account like this production cost, efficiency and productive rate.
It should be noted that, the order of step a and step b is unrestricted, that is to say, can first carry out step b and carry out step a again, and this is clearly, does not repeat herein.
C, at least one in A solution and B solution, introduce complexing agent C, complexing agent C should form and comprise citrate ion (C after dissolving
6h
5o
7 3-) solution, for convenience of description and be unlikely to cause and obscure, carrying out after this step, A solution and B solution are denoted as respectively A1 solution and B1 solution again.
That is to say, no matter A solution and B solution are only to have wherein one to add complexing agent C or all added complexing agent C in step c, after having carried out step c, A solution and B solution are all denoted as respectively A1 and B1 solution again, to show difference.
In view of C is water-soluble or the aqueous solution in form and comprise C
6h
5o
7 3-the aqueous solution, so C is citric acid or solubility Citrate trianion, as Trisodium Citrate, Tripotassium Citrate etc.
As a kind of preferred version, Cu in production system
2+with C
6h
5o
7 3-mol ratio be 1:0.01 ~ 0.8, as further preferably, both mol ratios are 1:0.05 ~ 0.4.
D, produce intermediate product: by A1 solution and B1 solution simultaneously, flow in reactor lentamente, making both that chemical reaction occur, is 3 ~ 9 by regulating the flow of A1 solution and B1 solution to make the pH value of reaction kettle for reaction liquid in reaction process, produces intermediate product;
In step c, the C of introducing is called complexing agent by we, briefly sets forth herein: in reaction process, and C
6h
5o
7 3-the role who serves as complexing agent, detailed process is as follows: C
6h
5o
7 3-first with Cu
2+there is complex reaction, generate inner complex [Cu
3(C
6h
5o
7h
3)
4]
2+, then at OH
-lower copper hydroxide (the Cu (OH) that generates of effect
2), the Cu (OH) of generation
2at C
6h
5o
7 3-effect lower with solution in copper sulfate (CuSO
4) reaction generation Basic Chrome Sulphate precipitation (CuSO
43Cu (OH)
2); After having reacted, C
6h
5o
7 3-be left in reaction solution with ionic species, if there is heavy metal ion (as arsenic, lead) in reaction solution, will be with complex to avoid in heavy metal ion target approach product.
Generally speaking, reaction principle of the present invention can be expressed as follows:
Therefore, in the present invention, in fact said intermediate product refers to by CuSO
43Cu (OH)
2solidliquid mixture with reaction solution (solution that other soluble substances or ion form) composition.
Steps d is to prepare the core procedure of Basic Chrome Sulphate, and the selection of reaction conditions and quality, quality and the stability controlled product have significant impact.In fact, this step does not have strict requirement to temperature of reaction, preferably 35 ~ 75 ℃.But the control to pH value and select most important, and adopted one extremely easily method pH value is regulated, that is: regulate the pH value of reaction kettle for reaction liquid by adjusting the flow of A1 solution and B1 solution.Specifically, we know, in B1 solution, contain OH
-if the pH value that we will control reaction solution is 3 ~ 9, be less than or will be less than 3 once monitor the pH value of reaction solution, we,, just by reducing the flow of A1 solution or increase B1 solution, increase pH value so; Once and the pH value that monitors reaction solution is greater than or will be greater than 9, increase A1 solution or reduce the flow of B1 solution, pH value is reduced.
Preferred as one, the pH value of reaction solution is 4 ~ 7.
For convenient, effectively monitor pH value, can monitor the pH value of reaction solution by pH test paper, certain, in order to be more convenient to suitability for industrialized production, preferably adopt pH electrode to carry out continuous real-time automatic monitoring to the reaction solution in reactor.
E, the intermediate product that steps d is produced are transferred in suction filter, wash to washings and are neutral, then carry out suction filtration tentatively to dewater, and produce primary product;
F, the primary product that step e is produced carry out drying and processing, prepare target product Basic Chrome Sulphate.
Certainly, before drying, can also increase a dehydrating step, thereby can dry quickly product, enhance productivity.Bake out temperature and drying time do not have strict restriction, determine in conjunction with concrete process condition, and bake out temperature is selected between 30 ~ 180 ℃ conventionally.
embodiment 1:
Copper sulfate is dissolved in a reactor and forms Cu
2+mass concentration is 2% A solution, stand-by; Sodium hydroxide is dissolved in No. two reactors and forms OH
-mass concentration is 5% B solution, stand-by; In A solution, add citric acid, make Cu
2+with C
6h
5o
7 3-mol ratio be 1:0.01, after this, A solution and B solution are denoted as respectively A1 solution and B1 solution again; In the reactor of 2L, add 500mL water, water temperature is 35 ℃, by A1 solution and B1 solution simultaneously, flow in reactor lentamente, the pH value that adopts pH electrode to monitor in real time reaction kettle for reaction liquid in reaction process also determines whether to adjust the flow of two kinds of solution according to the pH value situation monitoring, make the pH value of reaction solution be controlled at 3 left and right and be greater than 3, after successive reaction for some time, close A1 solution and B1 solution, produce intermediate product; Intermediate product is transferred in suction filter, washes with water and record washings for twice and be neutral, carry out suction filtration and produce primary product tentatively to dewater; Primary product is transferred in drying processor and carries out drying and processing, make target product Basic Chrome Sulphate.The mass content that records Basic Chrome Sulphate is 99.24%, and median size is 35 microns.
embodiment 2:
In a reactor, put into a certain amount of acid wiring board bluestone waste, form Cu
2+mass concentration is 7.6% A solution, stand-by; Potassium hydroxide is dissolved in No. two reactors and forms OH
-mass concentration is 8% B solution, stand-by; In A solution, add Trisodium Citrate, make Cu
2+with C
6h
5o
7 3-mol ratio be 1:0.3, after this, A solution and B solution are denoted as respectively A1 solution and B1 solution again; In the reactor of 2L, add 500mL water, water temperature is 50 ℃, by A1 solution and B1 solution simultaneously, flow in reactor lentamente, the pH value that adopts pH electrode to monitor in real time reaction kettle for reaction liquid in reaction process also determines whether to adjust the flow of two kinds of solution according to the pH value situation monitoring, make the pH value of reaction solution be controlled at 5 left and right, after successive reaction for some time, close A1 solution and B1 solution, produce intermediate product; Intermediate product is transferred in suction filter, washes with water and record washings for twice and be neutral, carry out suction filtration and produce primary product tentatively to dewater; After primary product is dewatered, be transferred in drying processor and carry out drying and processing, make target product Basic Chrome Sulphate.Heavy metal content in target product is analyzed, and lead ion mass concentration is 7.6ppm, and arsonium ion mass concentration is 5.4ppm, can not form impact to the purity of Basic Chrome Sulphate.The mass content that records Basic Chrome Sulphate is 99.08%, and median size is 42 microns.
embodiment 3:
Copper sulfate is dissolved in a reactor and forms Cu
2+mass concentration is 10% A solution, stand-by; Sodium hydroxide is dissolved in No. two reactors and forms OH
-mass concentration is 12% B solution, stand-by; In B solution, add citric acid, make Cu
2+with C
6h
5o
7 3-mol ratio be 1:0.6, after this, A solution and B solution are denoted as respectively A1 solution and B1 solution again; In the reactor of 2L, add 500mL water, water temperature is 60 ℃, by A1 solution and B1 solution simultaneously, flow in reactor lentamente, the pH value that adopts pH electrode to monitor in real time reaction kettle for reaction liquid in reaction process also determines whether to adjust the flow of two kinds of solution according to the pH value situation monitoring, make the pH value of reaction solution be controlled at 7 left and right, after successive reaction for some time, close A1 solution and B1 solution, produce intermediate product; Intermediate product is transferred in suction filter, washes with water and record washings for twice and be neutral, carry out suction filtration and produce primary product tentatively to dewater; Primary product is transferred in drying processor and carries out drying and processing, make target product Basic Chrome Sulphate.The mass content that records Basic Chrome Sulphate is 99.31%, and median size is 28 microns.
embodiment 4:
In a reactor, put into a certain amount of acid wiring board bluestone waste, form Cu
2+mass concentration is 12% A solution, stand-by; Potassium hydroxide is dissolved in No. two reactors and forms OH
-mass concentration is 15% B solution, stand-by; In A solution and B solution, all add Trisodium Citrate, make Cu
2+with C
6h
5o
7 3-total mol ratio be 1:0.8, after this, A solution and B solution are denoted as respectively A1 solution and B1 solution again; In the reactor of 2L, add 500mL water, water temperature is 75 ℃, by A1 solution and B1 solution simultaneously, flow in reactor lentamente, the pH value that adopts pH electrode to monitor in real time reaction kettle for reaction liquid in reaction process also determines whether to adjust the flow of two kinds of solution according to the pH value situation monitoring, make the pH value of reaction solution be controlled at 9 left and right and be less than 9, after successive reaction for some time, close A1 solution and B1 solution, produce intermediate product; Intermediate product is transferred in suction filter, washes with water and record washings for twice and be neutral, carry out suction filtration and produce primary product tentatively to dewater; After primary product is dewatered, be transferred in drying processor and carry out drying and processing, make target product Basic Chrome Sulphate.Heavy metal content in target product is analyzed, and lead ion mass concentration is 6.4ppm, and the mass concentration of arsonium ion is 3.5ppm, can not form impact to the purity of Basic Chrome Sulphate.The mass content that records Basic Chrome Sulphate is 99.01%, and median size is 36 microns.
More than show and described ultimate principle of the present invention, principal character and advantage.The technician of the industry should understand, and above-described embodiment does not limit the present invention in any form, and all employings are equal to replaces or technical scheme that the mode of equivalent transformation obtains, all drops in protection scope of the present invention.
Claims (9)
1. a kind of industrial production process of Basic Chrome Sulphate, is characterized in that, comprises the steps:
A, prepare acid wiring board bluestone waste, be denoted as A solution, stand-by;
The B solution that b, preparation contain hydroxide ion, stand-by;
C, introduce complexing agent: at least one in above-mentioned A solution and B solution, add complexing agent C, after dissolving, above-mentioned complexing agent C forms the solution that comprises citrate ion, carry out after this step, above-mentioned A solution and B solution are denoted as respectively A1 solution and B1 solution again, and the mol ratio of cupric ion and citrate ion is 1:0.01 ~ 0.8;
D, by A1 solution and B1 solution simultaneously, flow in reactor lentamente, there is chemical reaction in both, and in reaction process, regulating the flow of A1 solution and B1 solution to make the pH value of reaction kettle for reaction liquid is 3 ~ 9, produces intermediate product;
E, intermediate product is transferred in suction filter, washs to washings and be neutral, and carry out suction filtration tentatively to dewater, produce primary product;
F, primary product is carried out to drying and processing, prepare target product Basic Chrome Sulphate.
2. a kind of industrial production process of Basic Chrome Sulphate according to claim 1, is characterized in that, above-mentioned A solution is replaced by copper-bath, or is made by one or more and sulfuric acid reaction in copper hydroxide, ventilation breather, cupric oxide.
3. a kind of industrial production process of Basic Chrome Sulphate according to claim 1, is characterized in that, above-mentioned B solution is sodium hydroxide and/or potassium hydroxide solution.
4. a kind of industrial production process of Basic Chrome Sulphate according to claim 1, is characterized in that, above-mentioned complexing agent C is citric acid or solubility Citrate trianion.
5. a kind of industrial production process of Basic Chrome Sulphate according to claim 1, is characterized in that, in above-mentioned A solution, the mass concentration of cupric ion is 2% ~ 12%.
6. a kind of industrial production process of Basic Chrome Sulphate according to claim 1, is characterized in that, in above-mentioned B solution, the mass concentration of hydroxide ion is 5% ~ 15%.
7. a kind of industrial production process of Basic Chrome Sulphate according to claim 1, is characterized in that, in above-mentioned steps d, temperature of reaction is 35 ~ 75 ℃.
8. a kind of industrial production process of Basic Chrome Sulphate according to claim 1, is characterized in that, adopts pH electrode to monitor the pH value of reaction kettle for reaction liquid in above-mentioned steps d.
9. according to a kind of industrial production process of the Basic Chrome Sulphate described in claim 1 ~ 8 any one, it is characterized in that, in above-mentioned steps d, the pH value of reaction solution is 4 ~ 7.
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| CN103043769A (en) * | 2012-12-07 | 2013-04-17 | 常州大学 | Compound agent for removing lead from waste water |
| CN103145172B (en) * | 2013-04-03 | 2014-06-18 | 北京科技大学 | Method for preparing yolk/shell structured basic copper sulfate |
| CN106430282B (en) * | 2016-11-28 | 2018-05-25 | 青岛科技大学 | A kind of preparation method of basic copper sulfate |
| CN107151028A (en) * | 2017-06-07 | 2017-09-12 | 江门市东江环保技术有限公司 | A kind of method that utilization alkaline etching liquid produces basic copper sulfate |
| CN107324373B (en) * | 2017-07-18 | 2019-05-28 | 清华大学 | The method of purification of malachite pigment |
| FR3092727B1 (en) * | 2019-02-19 | 2023-05-12 | Upl Ltd | Process for the preparation of copper compounds |
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| US7411080B2 (en) * | 2006-05-19 | 2008-08-12 | Phibro-Tech, Inc. | Direct synthesis of copper carbonate |
| CN101423241B (en) * | 2008-11-21 | 2010-07-21 | 沈阳大学 | Method for preparing alkali copper sulfate powder inhibiting activity of sulphate reducing bacteria |
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Effective date of registration: 20160427 Address after: 01, room 5, building 369, 215129 deer Road, hi tech Zone, Jiangsu, Suzhou Patentee after: Suzhou Long Lake nano science and Technology Co Ltd Address before: 215129 Jiangsu province Suzhou city road high tech Zone deer No. 369 Industrial Park No. 21 501-505 Patentee before: Liao Yongzhi |