CN105624721B - One kind prepares copper amine（Ammonia）The method of complex compound - Google Patents
One kind prepares copper amine（Ammonia）The method of complex compound Download PDFInfo
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- CN105624721B CN105624721B CN201511031835.4A CN201511031835A CN105624721B CN 105624721 B CN105624721 B CN 105624721B CN 201511031835 A CN201511031835 A CN 201511031835A CN 105624721 B CN105624721 B CN 105624721B
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- ammonia
- hydrogen carbonate
- ammonium hydrogen
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
Abstract
One kind of the present invention prepares copper amine（Ammonia）The method of complex compound, using an electrolytic cell, anode chamber and cathode chamber are provided with electrolytic cell, split between anode chamber and cathode chamber by anion membrane, anode is used as using metallic copper in anode chamber, in cathode chamber negative electrode is used as using stainless steel substrates, monoethanolamine is used in anode chamber, the mixed aqueous solution or ammonia spirit of ammonium hydrogen carbonate, the mixed aqueous solution or monoethanolamine of ammonium hydrogen carbonate, ammoniacal liquor, the mixed aqueous solution of ammonium hydrogen carbonate is used as electrolyte, sodium hydroxide solution is used in cathode chamber for conduction liquid, electrically connected between anode and negative electrode, voltage is 4 ~ 10V, electric current is 0.8 ~ 1.5A, electrolysis 4 ~ 10 hours.The present invention uses metallic copper, in amine（Ammonia）In property solution, it is electrolysed with amberplex, copper amine can be directly made（Ammonia）Complex compound, simple and reliable process saves raw material, energy-conserving and environment-protective are that one kind is worthy to be popularized new technology again.
Description
Technical field
The invention belongs to chemical field, more particularly to a kind of copper amine (ammonia) complex compound, specifically one kind prepares copper amine
The method of (ammonia) complex compound.
Background technology
Copper amine (ammonia) complex compound is one of main component of current Wood in Common Use preservative, and it generally uses the compound of copper
(basic copper carbonate, Kocide SD) is made with organic amine (monoethanolamine) or inorganic ammonia reaction, but the compound for preparing copper will
The a large amount of acid of consumption, alkali industrial chemicals.
The content of the invention
For defect present in above-mentioned prior art, the technical problems to be solved by the invention are to provide one kind and prepare copper
The method of amine (ammonia) complex compound, the described this method for preparing copper amine (ammonia) complex compound will solve to prepare copper amine in the prior art
The compound of copper is used during (ammonia) complex compound, and prepares the compound of copper needs to consume the chemical industry such as a large amount of bronsted lowry acids and bases bronsted lowries original
The technical problem of material.
In order to solve the above-mentioned technical problem, the method that one kind provided by the present invention prepares copper amine (ammonia) complex compound, is used
Anode chamber and cathode chamber are provided with one electrolytic cell, described electrolytic cell, the moon is passed through between described anode chamber and cathode chamber
Ion diaphragm is split, it is characterised in that：Using metallic copper as anode in described anode chamber, using not in described cathode chamber
Steel disc become rusty as negative electrode, using monoethanolamine, the mixed aqueous solution of ammonium hydrogen carbonate or ammonia spirit, bicarbonate in described anode chamber
The mixed aqueous solution or monoethanolamine of ammonium, ammoniacal liquor, the mixed aqueous solution of ammonium hydrogen carbonate are adopted in described cathode chamber as electrolyte
It is conduction liquid with sodium hydroxide or potassium hydroxide solution, is electrically connected between described anode and negative electrode, voltage is 4~10V, electric current
For 0.8~1.5A, it is electrolysed 4~10 hours.
Further, the concentration of described sodium hydroxide or potassium hydroxide solution is 0.5~1mol/L.
Further, described anion membrane is polystyrene quaternary amine type.
Further, a circulating pump is provided with described anode chamber and cathode chamber.
Further, when using monoethanolamine, the mixed aqueous solution of ammonium hydrogen carbonate as electrolyte in described anode chamber,
The concentration of monoethanolamine is 3~4mol/L, and the concentration of described ammonium hydrogen carbonate is 0.2~1mol/L.
Further, when using ammonia spirit, the mixed aqueous solution of ammonium hydrogen carbonate as electrolyte in described anode chamber,
The concentration of ammonia spirit is 0.4~1mol/L, and the concentration of described ammonium hydrogen carbonate is 0.5~1mol/L.
Further, electrolyte is used as using monoethanolamine, ammoniacal liquor, the mixed aqueous solution of ammonium hydrogen carbonate in described anode chamber
When, the concentration of monoethanolamine is 2~4mol/L, and the concentration of ammonia spirit is 0.1~0.5mol/L, the concentration of described ammonium hydrogen carbonate
For 0.2~0.6mol/L.
The principle of the present invention is described below：
Electrolytic cell is separated into anode chamber and cathode chamber by anion membrane, makees anode in the anode compartment with metallic copper, uses second
Hydramine (or ammoniacal liquor), the aqueous solution of ammonium hydrogen carbonate make electrolyte.Make negative electrode in cathode chamber with stainless steel substrates, it is molten with sodium hydroxide
Liquid makees conduction liquid.Two extremely lead on dc source when, two extremely on there may be following reaction：
Anode (1) Cu (NH3)4 2++ 2e=Cu+4NH3 E0 1=-0.041V
(2)Cu(ent)4 2++ 2e=Cu+4ent E0 2=-0.001V
(3)Cu2++ 2e=Cu E0 3=0.345V
(4)O2+2H2O+4e=4OH-E0 4=0.404V
Negative electrode (5) 2H2O+2e=H2↑+2OH-E0 5=-0.828V
(6)Na++ e=Na E0 6=-0.2.69V
Wherein ent represents monoethanolamine abbreviation.By the principle of electrochemistry, on anode carrying out reaction first is：Electrode potential
Most negative reduced form material, i.e. metallic copper lose electronics, generation Cu (ent) in amine (ammonia) property solution first4 2+Or Cu
(NH3)4 2+, that is, react (1) or (2) and carry out first, it is electrode potential most positive oxidized form material that reaction is carried out on negative electrode, i.e.,
By water power separate out Lai H+Electronics is obtained first, generates H2Separated out in negative electrode, that is, react (5) and carry out first.At the same time, generate
OH-Ion is shifted to anode in the presence of anode, by cavity block and combined with copper amine (ammonia) complex ion, generation Cu (ent)4(OH)2
Or Cu (NH3)4(OH)2Complex compound.Summary, overall reaction is during electrolysis：
Cu+4ent+2H2O=Cu (ent)4(OH)2+H2↑ or
Cu+4NH3+2H2O=Cu (NH3)4(OH)2+H2↑
Selective absorption of the ionic membrane in electrolyte solution to ion and under electric field action in film Ion transfer, reach
To separation purpose.
Ionic membrane is the film that a kind of polymer-function material is made, and tradable active group is connected on macromolecular chain
Group, is broadly divided into two classes, a class is according to the type of active group：Tradable group is cation, such as sulphonic acids base
Group (R-SO3H), referred to as anode membrane.It is another kind of to be：Tradable group is anion, such as quaternary ammonium group (R-CH2-N-
(CH3)3), OH referred to as cavity block.Because these groups can be ionized in aqueous, therefore, when ionic membrane is molten in electrolyte
When in liquid, anode membrane can be with Liquidity limit, and cavity block can be with adsorpting anion, simultaneously because existing inside this kind of macromolecule membrane big
Micro-crack is measured, under the effect of electric field boundary, cation can shift to negative electrode by anode membrane, equally, and anion can be shifted to by cavity block
Anode, conversely, because identical charges repel each other, cation can not can not separate electrolysis by anode membrane by cavity block, anion so as to reach
Matter purpose.
The present invention is compared with prior art, and its technological progress is significant.Present invention use metallic copper (or it is recyclable
Metal copper scrap), in amine (ammonia) property solution, it is electrolysed with amberplex (hereinafter referred to as ionic membrane), copper amine can be directly made
(ammonia) complex compound, simple and reliable process saves raw material, energy-conserving and environment-protective again, while production can also be reduced using paddy electricity production
Cost, is that one kind is worthy to be popularized new technology.
Brief description of the drawings
Fig. 1 is that one kind of the present invention prepares the structural representation of the electrolytic cell used in the method for copper amine (ammonia) complex compound,
Wherein, 1 it is anion membrane, 2 be pure copper anode, 3 stainless steel cathodes, 4 be anode chamber, 5 is cathode chamber.
Embodiment
Embodiments of the invention are described in further detail below in conjunction with brief description of the drawings, but the present embodiment is not used to limit
The system present invention, every similar structure using the present invention and its similar change, all should be included in protection scope of the present invention.
Embodiment 1
The concrete structure for the electrolytic cell that following embodiments are used is described below：
(1) electrolytic cell is homemade with lucite, and size is 160 × 100 × 100mm, and centre cavity block 1 is separated.
(2) anode 2 is that fine copper chip size is 80 × 40 × 2mm, and negative electrode 3 is stainless steel substrates, and size is identical with anode 2.
(3) cavity block 1 using Hefei Ke Jia Technology Co., Ltd. provide, cj-cda-200 quaternary amine type cavity blocks, area be 80 ×
80mm。
(4) electrolyte：Negative electrode is 1mol/L NaOH.Anode is monoethanolamine, the mixed aqueous solution of ammonium hydrogen carbonate；Or ammoniacal liquor
The mixed aqueous solution of solution, ammonium hydrogen carbonate；Or the mixed aqueous solution of monoethanolamine, ammoniacal liquor, ammonium hydrogen carbonate.
(5) dc source is PS-3050 High-accuracy direct current voltage-stabilized power supplies, the production of Hong Kong dragon impressive and dignified manner table Co., Ltd.
(6) respectively there is a set of independent loops pump in anode chamber 4 and cathode chamber 5, electrolyte is circulated, reduce concentration polarization
Change.
Embodiment 2
20 grams of solid NaOH is taken, water is dissolved in, is diluted to 500ml, be placed in cathode chamber.Take 110 grams of monoethanolamines, 10 grams of carbon
Sour hydrogen ammonium is soluble in water to be diluted to 500ml, is placed in anode chamber, and two poles connect dc source, and tank voltage is 4.5 volts, and electric current is
1.05 peaces times, are electrolysed 4 hours, copper string bag concentration (in terms of CuO) can reach 8% in anode chamber.
Embodiment 3
20 grams of solid NaOH is taken, water is dissolved in and is diluted to 500ml, be placed in cathode chamber.Take 40 grams of 25% ammoniacal liquor, 30 grams of carbon
Sour hydrogen ammonium is soluble in water to be diluted to 500ml, is placed in anode chamber, and it is 6.5 volts that two poles, which connect dc source tank voltage, and electric current is
1.05 peaces times, are electrolysed 6 hours, copper string bag concentration (in terms of CuO) can reach 10% in anode chamber.
Embodiment 4
20 grams of solid NaOH is taken, water is dissolved in and is diluted to 500ml, be placed in cathode chamber, 87 grams of monoethanolamines, 25% ammoniacal liquor are taken
12 grams, 17 grams of ammonium hydrogen carbonate is soluble in water, is diluted to 500ml, is placed in anode chamber, and two poles connect dc source tank voltage and are
4.5 volt.Electric current is 1.05 peaces times, is electrolysed 5 hours, copper string bag concentration (in terms of CuO) can reach 10% in anode chamber.
Claims (3)
1. one kind prepares copper amine（Ammonia）The method of complex compound, using an electrolytic cell, anode chamber is provided with described electrolytic cell
And cathode chamber, split between described anode chamber and cathode chamber by anion membrane, it is characterised in that：In described anode chamber
Using metallic copper as anode, using stainless steel substrates as negative electrode in described cathode chamber, ethanol is used in described anode chamber
Amine, the mixed aqueous solution of ammonium hydrogen carbonate or ammonia spirit, the mixed aqueous solution of ammonium hydrogen carbonate or monoethanolamine, ammoniacal liquor, bicarbonate
The mixed aqueous solution of ammonium is used as electricity as electrolyte in described anode chamber using monoethanolamine, the mixed aqueous solution of ammonium hydrogen carbonate
When solving matter, the concentration of monoethanolamine is 3 ~ 4mol/L, and the concentration of described ammonium hydrogen carbonate is 0.2 ~ 1mol/L；
In described anode chamber using ammonia spirit, the mixed aqueous solution of ammonium hydrogen carbonate as electrolyte when, ammonia spirit it is dense
Spend for 0.4 ~ 1mol/L, the concentration of described ammonium hydrogen carbonate is 0.5 ~ 1mol/L；
In described anode chamber using monoethanolamine, ammoniacal liquor, the mixed aqueous solution of ammonium hydrogen carbonate as electrolyte when, monoethanolamine it is dense
Spend for 2 ~ 4mol/L, the concentration of ammonia spirit is 0.1 ~ 0.5mol/L, the concentration of described ammonium hydrogen carbonate is 0.2 ~ 0.6mol/L；
Sodium hydroxide or potassium hydroxide solution are used in described cathode chamber for conduction liquid, described sodium hydroxide or potassium hydroxide
The concentration of solution is 0.5 ~ 1mol/L, is electrically connected between described anode and negative electrode, and voltage is 4 ~ 10V, and electric current is 0.8 ~ 1.5A,
Electrolysis 4 ~ 10 hours.
2. one kind according to claim 1 prepares copper amine（Ammonia）The method of complex compound, it is characterised in that：Described anion
Barrier film is polystyrene quaternary amine type.
3. one kind according to claim 1 prepares copper amine（Ammonia）The method of complex compound, it is characterised in that：In described anode
A circulating pump is provided with room and cathode chamber.
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| CN105624721B true CN105624721B (en) | 2017-10-27 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107675202A (en) * | 2017-09-27 | 2018-02-09 | 广西七色珠光材料股份有限公司 | Pigment hydrolyzes coating reactor |
| JP6912845B2 (en) * | 2018-08-28 | 2021-08-04 | 学校法人 工学院大学 | A method for producing a composition for forming a metal film, a method for producing a metal film, a metal film, a metal film laminate, and an apparatus for producing a composition for forming a metal film. |
| CN111592024B (en) * | 2020-04-24 | 2022-09-06 | 广西科学院 | Method for preparing submicron solid spherical calcium carbonate from calcium chloride |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003328198A (en) * | 2002-05-10 | 2003-11-19 | Mitsubishi Materials Corp | Method of generating copper ion and apparatus therefor, method of producing copper sulfate and apparatus therefor, method of generating metallic ion and apparatus therefor, and method of producing acid water and apparatus therefor |
| CN1500605A (en) * | 2002-11-15 | 2004-06-02 | 东莞市天保木材防护科技有限公司 | Process for producing D- copper-amine quaternary ammonium salt wood repellent |
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| CN101748425B (en) * | 2008-12-05 | 2014-07-09 | 宜兴方晶科技有限公司 | Preparation method of stannous methanesulfonate |
| CN101880888B (en) * | 2009-05-06 | 2013-07-24 | 宜兴方晶科技有限公司 | Preparation method of nickel aminosulfonate |
| CN102050480B (en) * | 2009-11-06 | 2012-10-03 | 长沙铂鲨环保设备有限公司 | Method for preparing cuprous compound |
| CN101928827A (en) * | 2010-08-31 | 2010-12-29 | 湖南子廷有色金属有限公司 | Method for removing impurities and refining zinc from zinc ammine complex |
| CN103778992B (en) * | 2014-01-10 | 2016-08-17 | 浙江大学 | A kind of copper slurry based on cupric ammine complex and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003328198A (en) * | 2002-05-10 | 2003-11-19 | Mitsubishi Materials Corp | Method of generating copper ion and apparatus therefor, method of producing copper sulfate and apparatus therefor, method of generating metallic ion and apparatus therefor, and method of producing acid water and apparatus therefor |
| CN1500605A (en) * | 2002-11-15 | 2004-06-02 | 东莞市天保木材防护科技有限公司 | Process for producing D- copper-amine quaternary ammonium salt wood repellent |
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Effective date of registration: 20191219 Address after: 214500 No.19 Fukang Road, Xieqiao Town, Jingjiang City, Taizhou City, Jiangsu Province Patentee after: Jingjiang Guolin Wood Co. Ltd. Address before: 201709 Shanghai city Qingpu District Baihe Town Teng Road No. 9 Patentee before: Shanghai Dabutong Wood Technology Co., Ltd. |
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Effective date of registration: 20200618 Address after: 200030 room 03, equipment floor, No. 2025, Zhongshan West Road, Xuhui District, Shanghai Patentee after: Shanghai Mingang New Material Technology Co., Ltd Address before: 214500 No.19 Fukang Road, Xieqiao Town, Jingjiang City, Taizhou City, Jiangsu Province Patentee before: JINGJIANG GUOLIN FOREST Co.,Ltd. |
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