CN102633290A - Preparation method for basic copper nitrate - Google Patents
Preparation method for basic copper nitrate Download PDFInfo
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- CN102633290A CN102633290A CN2012100819432A CN201210081943A CN102633290A CN 102633290 A CN102633290 A CN 102633290A CN 2012100819432 A CN2012100819432 A CN 2012100819432A CN 201210081943 A CN201210081943 A CN 201210081943A CN 102633290 A CN102633290 A CN 102633290A
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Abstract
The invention discloses a preparation method for basic copper nitrate, and the method comprises the following steps of: preparing a solution A containing Cu<2+> and NO3<->; preparing a solution B containing OH<->; introducing a citrate ion catalyst; preparing an intermediate product; transferring the intermediate product; and preparing a target product, namely basic copper nitrate. The preparation method for basic copper nitrate has the following advantages that: the raw materials which are low in price and easy to get are used, and the catalyst is introduced during the reaction process, thus increasing the production efficiency; simultaneously, production equipment is simplified, and technological processes are reduced, thus being more beneficial to industrial production and operation, and then lowering the production cost of the basic copper nitrate. Besides, the basic copper nitrate product prepared by the method disclosed by the invention is good and stable in quality.
Description
Technical field
The present invention relates to a kind of preparation method of chemical products, be specifically related to a kind of preparation method of basic copper nitrate.
Background technology
Basic copper nitrate can be widely used in the various fields such as oxygenant of pyrotechnics, propelling agent, brass work midbody and preparation air bag propellant; Especially along with rapid development of automobile industry and requirements at the higher level that the security of air bag propellant and stability are proposed, the market requirement breach of basic copper nitrate is very big always.Basic copper nitrate in the market all is the simple mixtures of cupric nitrate and verditer a lot, and quality is very unstable.In fact also there is not a kind of method for preparing basic copper nitrate; Can produce the basic copper nitrate of stay in grade; Take into account production cost and production efficiency; So, develop a kind of be convenient to suitability for industrialized production, cost of material rationally, the basic copper nitrate preparation method that effectively enhances productivity, reduce production costs is extremely urgent.
Summary of the invention
For solving the deficiency of prior art; The object of the present invention is to provide a kind of preparation method of basic copper nitrate, adopt raw material comparatively cheap and easy to get, simplify production unit; Be convenient to suitability for industrialized production and operation; The reduction technical process is introduced catalyzer and has effectively been improved production efficiency, and then reduced the production cost of basic copper nitrate.In addition, basic copper nitrate good product quality and the stay in grade prepared of method of the present invention.
In order to realize above-mentioned target, the present invention adopts following technical scheme:
A kind of preparation method of basic copper nitrate is characterized in that, comprises the steps:
(1) preparing A solution: preparation comprises Cu in first reactor drum
2+And NO
3 -A solution;
(2) preparation B solution: preparation comprises OH in second reactor drum
-B solution;
(3) introduce catalyzer: add C at least one in A solution or B solution, the water-soluble or aqueous solution of above-mentioned C forms the solution that comprises citrate ion; After carrying out this step, A solution in step (1) and the step (2) and B solution are remembered respectively and are made A ' solution and B ' solution;
(4) preparation intermediate product: A ' solution and B ' solution are flowed in the 3rd reactor drum simultaneously, react at aqueous phase, the pH value of controlling reaction solution in the 3rd reactor drum is 3～10, makes intermediate product;
(5) shift intermediate product: intermediate product is transferred in the 4th reactor drum, and washs to washings and be neutral, carry out tentatively removing water treatment then, make primary product;
(6) preparation title product: in the 5th reactor drum, primary product is carried out processed, again it is transferred in the drying treatment device, under 30 ℃～180 ℃, carry out drying treatment, make the title product basic copper nitrate.
The preparation method of aforesaid a kind of basic copper nitrate is characterized in that, in the above-mentioned steps (4), through the pH value of reaction solution in flow control the 3rd reactor drum of regulating A ' solution and B ' solution.
The preparation method of aforesaid a kind of basic copper nitrate is characterized in that, above-mentioned A solution directly makes by cupric nitrate is water-soluble, is perhaps made by copper, verditer, ventilation breather, cupric oxide and nitric acid reaction.
The preparation method of aforesaid a kind of basic copper nitrate is characterized in that, above-mentioned B solution is solubility oxyhydroxide water-soluble formation.
The preparation method of aforesaid a kind of basic copper nitrate is characterized in that, above-mentioned C is Hydrocerol A or solubility Citrate trianion.
The preparation method of aforesaid a kind of basic copper nitrate is characterized in that, above-mentioned Cu
2+With the mol ratio of citrate ion be 1: 0.01～0.8.
The preparation method of aforesaid a kind of basic copper nitrate is characterized in that, the degree Beaume of above-mentioned A solution is 5～55.
The preparation method of aforesaid a kind of basic copper nitrate is characterized in that, the temperature of reaction in the above-mentioned steps (4) is: 10 ℃～95 ℃.
The preparation method of aforesaid a kind of basic copper nitrate is characterized in that, the mass concentration of OH-is 1%～30% in the above-mentioned B solution.
The preparation method of aforesaid a kind of basic copper nitrate is characterized in that, the pH value in the above-mentioned steps (4) is 6～8.
Usefulness of the present invention is: utilize raw material cheap and easy to get, thereby and in reaction process, introduced catalyzer and enhanced productivity; Simplify production unit simultaneously, the reduction technical process helps suitability for industrialized production and operation more, and then has lowered the production cost of basic copper nitrate.In addition, basic copper nitrate good product quality and the stay in grade prepared of method of the present invention.
Description of drawings
Fig. 1 is preparing method's synoptic diagram of a kind of basic copper nitrate of the present invention.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment the present invention is done concrete introduction.
Referring to Fig. 1, the preparation method of a kind of basic copper nitrate of the present invention comprises following step:
(1), preparing A solution: preparation comprises Cu in first reactor drum
2+And NO
3 -A solution;
Specifically, A solution can be directly water-soluble formulated by cupric nitrate, also can be made with nitric acid reaction by copper, verditer, ventilation breather, cupric oxide etc.Concentration to A solution does not have special requirement here, and as a kind of preferred, the degree Beaume of A solution is 5～55.
(2) preparation B solution: preparation comprises OH in second reactor drum
-B solution;
Generally speaking, B solution is by solubility oxyhydroxide, and is water-soluble formulated like Pottasium Hydroxide, sodium hydroxide.As a kind of preferred, OH in the B solution
-Mass concentration be 1%-30%.Preferred as further, OH
-Mass concentration be 10%-20%.
(3) introduce catalyzer:
Add C in A solution or B solution at least one, the water-soluble or aqueous solution of C forms and comprises citrate ion (C
6H
5O
7 3-) solution; After carrying out this step, remember respectively and make A ' solution and B ' solution for the ease of describing A solution and B solution in step (1) and the step (2).
We can find out from top description, and that in reaction, play catalyst action is citrate ion (C
6H
5O
7 3-), can add in A solution or the B solution, also can add simultaneously in A solution and the B solution.In view of forming citrate ion behind the water-soluble or aqueous solution of C, so C is Hydrocerol A or solubility Citrate trianion, like Trisodium Citrate, Tripotassium Citrate etc.
As a kind of preferred version, Cu
2+With the mol ratio of citrate ion be 1: 0.01～0.8.
(4) preparation intermediate product:
A ' solution and B ' solution are flowed in the 3rd reactor drum simultaneously, react at aqueous phase, the pH value of controlling reaction solution in the 3rd reactor drum is 3～10, makes intermediate product.
The indication water is meant the solution that water or soluble substance and water form among the present invention.
We said the front, and citrate ion plays catalyst action, and actual production shows, under the identical situation of other conditions, can the reaction times be shortened more than 1/3rd behind the use catalyzer.Concrete reaction process is: C
6H
5O
7 3-At first generate inner complex [Cu with the cupric ion reaction
3(C
6H
5O
7H
3)
4]
2+, then at OH
-Effect generates verditer down, and the verditer of generation is at C
6H
5O
7 3-Effect down with solution in the cupric nitrate reaction generate basic copper nitrate and precipitate.
Concrete reaction principle is:
Therefore, in fact said intermediate product is meant the solidliquid mixture of being made up of basic copper nitrate deposition and reaction solution (being the aqueous solution of other soluble substances) among the present invention.
This step is the committed step of preparation basic copper nitrate, and the control of reaction conditions has remarkable influence to quality, quality and the stability of product.Temperature of reaction does not have strict requirement in this step, preferably is controlled at 10 ℃～95 ℃.
Preferred as further, in the reaction process, the pH value of reaction solution is 6～8 in the 3rd reactor drum.
Control to the pH value among the present invention is very easy, only needs promptly can control through the flow of adjustment A ' solution and B ' solution the pH value of reaction solution in the 3rd reactor drum.Specifically, comprise OH in the B ' solution
-If the pH value that we will control reaction solution is 6～8, in case the pH value that monitors reaction solution less than 6, we just through reducing A ' solution or increasing the flow of B ' solution, make the increase of pH value so; Otherwise, then increase A ' solution or reduce the flow of B ' solution, the pH value is reduced.
In order effectively to monitor the pH value, can monitor the pH value of reaction solution through the pH test paper, certainly,, preferably adopt pH meter that reaction solution is carried out the successive real-time automatic monitoring in order to be convenient to suitability for industrialized production more.
(5) shift intermediate product:
Intermediate product is transferred in the 4th reactor drum, and washs to washings and be neutral, carry out tentatively removing water treatment then, make primary product.
This step is actually the process that the last intermediate product prepared of step is carried out roughing, and said here primary product is to have carried out washing and through the preliminary basic copper nitrate that removes water treatment.So as a kind of preferred, the 4th reactor drum is a suction filter; Not only can in suction filter, wash middle product, whether washing reaches requirement is then judged with the situation of washings, generally speaking; When washings was neutral or is neutrality basically, expression had been washed up to standard.Then carry out next operation---suction filtration, middle product is carried out tentatively removing water treatment, make primary product.
(6) preparation title product:
In the 5th reactor drum, primary product is carried out processed, again it is transferred in the drying treatment device, under 30 ℃～180 ℃, carry out drying treatment, make the title product basic copper nitrate.This step is for primary product is further handled, to prepare the title product basic copper nitrate of good stability.As for concrete dehydration and the not strict requirement of drying treatment time, decide according to concrete process condition.
Through above-mentioned steps, we have made basic copper nitrate.But different industrial circles often has different requirement to basic copper nitrate, Given this, can also pulverize or sub-sieve basic copper nitrate, makes the industrial basic copper nitrate that is applicable to different industrial production.Certainly, for different industrial requirements, the concrete technological process of pulverizing or sub-sieve also is not quite similar, and does not give unnecessary details here.
Embodiment one:
(1) preparing A solution: a certain amount of degree Beaume of preparation is 5 copper nitrate solution in first reactor drum, and is for use;
(2) preparation B solution: a certain amount of OH of preparation in second reactor drum
-Mass concentration is 1% hydroxide solution, and is for use;
(3) introduce catalyzer: in A solution, add Hydrocerol A, make mol ratio Cu
2+: C
6H
5O
7 3-=1: 0.01; A solution and B solution are remembered respectively and are made A ' solution and B ' solution;
(4) in the 3rd reactor drum of 2000L, add 500L water, water temperature is 10 ℃, makes A ' solution and B ' the solution while then, flows in the 3rd reactor drum lentamente, carries out reaction process.The pH value that adopts pH meter to monitor solution in the 3rd reactor drum in real time in the reaction process also according to circumstances determines whether to adjust the flow of two kinds of solution, and the pH value in the reactor drum is controlled at about 3.Successive reaction is closed two kinds of solution after for some time, makes intermediate product;
(5) shift intermediate product: intermediate product is transferred in the 4th reactor drum, and washs to washings and be neutral, carry out tentatively removing water treatment then, make primary product;
(6) preparation title product: in the 5th reactor drum, primary product is carried out processed, again it is transferred in the drying treatment device, carry out drying treatment, make the title product basic copper nitrate at 30 ℃.
Embodiment two:
(1) preparing A solution: a certain amount of degree Beaume of preparation is 10 copper nitrate solution in first reactor drum, and is for use;
(2) preparation B solution: a certain amount of OH of preparation in second reactor drum
-Mass concentration is 10% hydroxide solution, and is for use;
(3) introduce catalyzer: in A solution, add Trisodium Citrate, make mol ratio Cu
2+: C
6H
5O
7 3-=1: 0.3; A solution and B solution are remembered respectively and are made A ' solution and B ' solution;
(4) in the 3rd reactor drum of 2000L, add 500L water, water temperature is 40 ℃, makes A ' solution and B ' the solution while then, flows in the 3rd reactor drum lentamente, carries out reaction process.The pH value that adopts pH meter to monitor solution in the 3rd reactor drum in real time in the reaction process also according to circumstances determines whether to adjust the flow of two kinds of solution, and the pH value in the reactor drum is controlled at about 6.Successive reaction is closed two kinds of solution after for some time, makes intermediate product;
(5) shift intermediate product: intermediate product is transferred in the 4th reactor drum, and washs to washings and be neutral, carry out tentatively removing water treatment then, make primary product;
(6) preparation title product: in the 5th reactor drum, primary product is carried out processed, again it is transferred in the drying treatment device, under 80 ℃, carry out drying treatment, make the title product basic copper nitrate.
Embodiment three:
(1) preparing A solution: a certain amount of degree Beaume of preparation is 20 copper nitrate solution in first reactor drum, and is for use;
(2) preparation B solution: a certain amount of OH of preparation in second reactor drum
-Mass concentration is 20% hydroxide solution, and is for use;
(3) introduce catalyzer: in B solution, add Hydrocerol A, make mol ratio Cu
2+: C
6H
5O
7 3-=1: 0.6; A solution and B solution are remembered respectively and are made A ' solution and B ' solution;
(4) in the 3rd reactor drum of 2000L, add 500L water, water temperature is 70 ℃, makes A ' solution and B ' the solution while then, flows in the 3rd reactor drum lentamente, carries out reaction process.The pH value that adopts pH meter to monitor solution in the 3rd reactor drum in real time in the reaction process also according to circumstances determines whether to adjust the flow of two kinds of solution, and the pH value in the reactor drum is controlled at about 8.Successive reaction is closed two kinds of solution after for some time, makes intermediate product;
(5) shift intermediate product: intermediate product is transferred in the 4th reactor drum, and washs to washings and be neutral, carry out tentatively removing water treatment then, make primary product;
(6) preparation title product: in the 5th reactor drum, primary product is carried out processed, again it is transferred in the drying treatment device, under 100 ℃, carry out drying treatment, make the title product basic copper nitrate.
Embodiment four:
(1) preparing A solution: a certain amount of degree Beaume of preparation is 55 copper nitrate solution in first reactor drum, and is for use;
(2) preparation B solution: a certain amount of OH of preparation in second reactor drum
-Mass concentration is 30% hydroxide solution, and is for use;
(3) introduce catalyzer: in A solution, add Tripotassium Citrate, make mol ratio Cu
2+: C
6H
5O
7 3-=1: 0.8; A solution and B solution are remembered respectively and are made A ' solution and B ' solution;
(4) in the 3rd reactor drum of 2000L, add 500L water, water temperature is 95 ℃, makes A ' solution and B ' the solution while then, flows in the 3rd reactor drum lentamente, carries out reaction process.The pH value that adopts pH meter to monitor solution in the 3rd reactor drum in real time in the reaction process also according to circumstances determines whether to adjust the flow of two kinds of solution, and the pH value in the reactor drum is controlled at about 10.Successive reaction is closed two kinds of solution after for some time, makes intermediate product;
(5) shift intermediate product: intermediate product is transferred in the 4th reactor drum, and washs to washings and be neutral, carry out tentatively removing water treatment then, make primary product;
(6) preparation title product: in the 5th reactor drum, primary product is carried out processed, again it is transferred in the drying treatment device, carry out drying treatment, make the title product basic copper nitrate at 180 ℃.
We have carried out hot analysis (TGA) to the sample that above four embodiment prepare, and write down the temperature that its thermolysis begins and finishes, and concrete numerical value is referring to table 1:
| Sample | Thermolysis begin temperature (℃) | The thermolysis end temp (℃) |
| Embodiment 1 | 218.24 | 240.58 |
| Embodiment 2 | 220.61 | 245.32 |
| Embodiment 3 | 223.27 | 249.51 |
| Embodiment 4 | 221.09 | 238.69 |
Table 1
In thermal decomposition process, generated the material of black, i.e. cupric oxide (CuO), this meets the chemical equation that basic copper nitrate decomposes:
Cu(NO
3)
2·3Cu(OH)
2→4CuO+3H
2O+2NO
2+0.5O
2
Simultaneously; We know; The decomposition temperature of verditer is 60 ℃～80 ℃, and the decomposition temperature of cupric nitrate is about 170 ℃, so; Product of the present invention never is the simple mixtures of verditer and cupric nitrate, and further having proved the product that this method prepares is that decomposition temperature is high, the basic copper nitrate of good stability.
The foregoing description does not limit the present invention in any form, and all employings are equal to the technical scheme that mode obtained of replacement or equivalent transformation, all drop in protection scope of the present invention.
Claims (10)
1. the preparation method of a basic copper nitrate is characterized in that, comprises the steps:
(1) preparing A solution: preparation comprises Cu in first reactor drum
2+And NO
3 -A solution;
(2) preparation B solution: preparation comprises OH in second reactor drum
-B solution;
(3) introduce catalyzer: add C at least one in A solution or B solution, the water-soluble or aqueous solution of above-mentioned C forms the solution that comprises citrate ion; After carrying out this step, A solution in step (1) and the step (2) and B solution are remembered respectively and are made A ' solution and B ' solution;
(4) preparation intermediate product: A ' solution and B ' solution are flowed in the 3rd reactor drum simultaneously, react at aqueous phase, the pH value of controlling reaction solution in the 3rd reactor drum is 3 ~ 10, makes intermediate product;
(5) shift intermediate product: intermediate product is transferred in the 4th reactor drum, and washs to washings and be neutral, carry out tentatively removing water treatment then, make primary product;
(6) preparation title product: in the 5th reactor drum, primary product is carried out processed, again it is transferred in the drying treatment device, under 30 ℃ ~ 180 ℃, carry out drying treatment, make the title product basic copper nitrate.
2. the preparation method of a kind of basic copper nitrate according to claim 1 is characterized in that, in the above-mentioned steps (4), through the pH value of reaction solution in flow control the 3rd reactor drum of regulating A ' solution and B ' solution.
3. the preparation method of a kind of basic copper nitrate according to claim 1 is characterized in that, above-mentioned A solution directly makes by cupric nitrate is water-soluble, is perhaps made by copper, verditer, ventilation breather, cupric oxide and nitric acid reaction.
4. the preparation method of a kind of basic copper nitrate according to claim 1 is characterized in that, above-mentioned B solution is the solution of the water-soluble formation of solubility oxyhydroxide.
5. the preparation method of a kind of basic copper nitrate according to claim 1 is characterized in that, above-mentioned C is Hydrocerol A or solubility Citrate trianion.
6. the preparation method of a kind of basic copper nitrate according to claim 1 is characterized in that, above-mentioned Cu
2+With the mol ratio of citrate ion be 1:0.01 ~ 0.8.
7. the preparation method of a kind of basic copper nitrate according to claim 3 is characterized in that, the degree Beaume of above-mentioned A solution is 5 ~ 55.
8. the preparation method of a kind of basic copper nitrate according to claim 3 is characterized in that, the temperature of reaction in the above-mentioned steps (4) is: 10 ℃ ~ 95 ℃.
9. the preparation method of a kind of basic copper nitrate according to claim 1 is characterized in that, OH in the above-mentioned B solution
-Mass concentration be 1% ~ 30%.
10. according to the preparation method of each described a kind of basic copper nitrate of claim 1 ~ 9, it is characterized in that the pH value in the above-mentioned steps (4) is 6 ~ 8.
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103193260A (en) * | 2013-03-22 | 2013-07-10 | 三明科飞技术开发有限公司 | Method for producing nano basic copper nitrate |
| CN103833066A (en) * | 2014-02-24 | 2014-06-04 | 青岛科技大学 | Preparation method for plate-type copper nitrate basic |
| CN105502474A (en) * | 2016-01-12 | 2016-04-20 | 大连大学 | Preparation method of atmospheric pressure plasma of basic copper nitrate |
| CN109621714A (en) * | 2018-12-29 | 2019-04-16 | 盐城工学院 | A kind of flue-gas denitration process method generating precipitating |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040131529A1 (en) * | 2001-03-29 | 2004-07-08 | Shogo Tomiyama | Method for producing basic metal nitrate |
| CN101195497A (en) * | 2006-12-04 | 2008-06-11 | 沈祖达 | Process for producing cupric hydroxide or cupric oxide |
-
2012
- 2012-03-26 CN CN2012100819432A patent/CN102633290A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040131529A1 (en) * | 2001-03-29 | 2004-07-08 | Shogo Tomiyama | Method for producing basic metal nitrate |
| CN101195497A (en) * | 2006-12-04 | 2008-06-11 | 沈祖达 | Process for producing cupric hydroxide or cupric oxide |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103193260A (en) * | 2013-03-22 | 2013-07-10 | 三明科飞技术开发有限公司 | Method for producing nano basic copper nitrate |
| CN103193260B (en) * | 2013-03-22 | 2014-09-24 | 三明科飞技术开发有限公司 | Method for producing nano basic copper nitrate |
| CN103833066A (en) * | 2014-02-24 | 2014-06-04 | 青岛科技大学 | Preparation method for plate-type copper nitrate basic |
| CN103833066B (en) * | 2014-02-24 | 2015-04-01 | 青岛科技大学 | Preparation method for plate-type copper nitrate basic |
| CN105502474A (en) * | 2016-01-12 | 2016-04-20 | 大连大学 | Preparation method of atmospheric pressure plasma of basic copper nitrate |
| CN109621714A (en) * | 2018-12-29 | 2019-04-16 | 盐城工学院 | A kind of flue-gas denitration process method generating precipitating |
| CN109621714B (en) * | 2018-12-29 | 2022-01-18 | 盐城工学院 | Flue gas denitration process method for generating precipitate |
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Application publication date: 20120815 |