CN1994890A - High purity water-soluble cupric salt reagent production method and precipitating reagent used therefor - Google Patents
High purity water-soluble cupric salt reagent production method and precipitating reagent used therefor Download PDFInfo
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Abstract
The invention discloses a manufacturing method of high-purity soluble copper salt agent and sediment agent (copper polyphosphate), which comprises the following steps: dissolving polyphosphate in the water; stirring; adding agent-grade basic copper carbonate powder until the bubble doesn't appear; filtering; washing; drying to obtain the solid product as sediment agent; adding more than 5ppm copper polyphosphate into copper salt solution; stirring; filtering to obtain purified copper salt solution with Fe, Pb, Zn, Tn, Ni, Ba less than 10ppm; displaying the same impurity removing effect in the low-density copper salt solution.
Description
Technical field
The present invention relates to a kind of production high purity water-soluble cupric salt compositions and methods and employed precipitation agent thereof, specifically is to remove foreign metal ionic method in the water-soluble mantoquita, and precipitates these foreign metal ionic precipitation agents.
Background technology
High purity water-soluble cupric salt reagent such as cupric chloride, cupric fluoborate are the heavy copper of electronic industry and industry of printed circuit boards with indispensable important reagent.The high-purity Cupric Chloride Solution of also a large amount of uses carries out acid etching, carries out alkali etching and make ammonia copper mother liquor with Cupric Chloride Solution and ammonia react.
The preparation method of high-purity cupric chloride can be varied, mainly contains:
1. use recrystallization purifying, but purity is difficult to reach requirement;
2. prepare Cupric Chloride Solution with high-purity copper oxide and hydrochloric acid reaction, but high-purity copper oxide costs an arm and a leg, can't satisfy demand of market competition;
3. prepare Cupric Chloride Solution with electrolysis red copper and hydrochloric acid, nitric acid reaction, because the existence and the nitric acid of nitric acid are difficult for Ex-all, thereby be not suitable for printed circuit board industry use, preparation process is complicated simultaneously;
4. prepare Cupric Chloride Solution or copper chloride etching waste liquid with industrial cupric oxide and hydrochloric acid reaction, prepare high-purity Cupric Chloride Solution by purification technique.This method not only has the advantage of cost, also is the recycle of printed circuit board industry resource, reduces production costs and to subtract useless consumption reduction institute necessary.
For the purifying of copper chloride solution, mainly also be that what to remove least easily is the impurity iron ion that wherein contains, in the process of deironing, often also other heavy metal can be removed in the lump.The method of deironing in the Cupric Chloride Solution, modal is with hydrogen peroxide ferrous ion to be oxidized to ferric ion, by adjust pH impurity cationics such as iron ion is removed with the form precipitation of oxyhydroxide.But this method is in high density chlorination copper solutions, and the ability of stablizing deironing can only reach between iron-holder 70～100ppm, and it is then beyond one's ability to reach 10ppm or following requirement.
1993, JP5179465 disclosed the Cupric Chloride Solution (about concentration 2mol/L) that makes after the etch processes anionite-exchange resin of flowing through earlier, and the hydrochloric acid with 7～10mol/L concentration reclaims cupric chloride with the cupric chloride wash-out again.Its shortcoming is that the exchange capacity of resin is limited, can't carry out production-scale application, and concentration of hydrochloric acid is excessive in the Cupric Chloride Solution that obtains, and can't reach the requirement of use.
1996, the Cupric Chloride Solution that Japanese Patent JP8081719 discloses with 50 liters of 9mol/L hydrochloric acid, 15 liter of 30% hydrogen peroxide and 1 kilogram of copper powder production flows through anionite-exchange resin, copper is adsorbed on the resin, cross anionite-exchange resin with the hydrochloric acid stream of 9mol/L again, make nickel, chromium wash-out, cross with the 4.8mol/L hydrochloric acid stream again and wash out copper.This method is except that the shortcoming that has JP5179465, and the concentration of the copper of its processing is 0.23mol/L only, does not have ability to handle the cupric chloride of high density.
Japanese Patent JP2004299974 disclosed muriate and the copper powder that adds basic metal or alkaline-earth metal in copper chloride etching waste liquid in 2004, generated the cuprous chloride precipitation, generated cupric chloride with the chlorine oxidation cuprous chloride again.This method complex process, the processing cost height, waste water is many, and will use the very big chlorine of toxicity, is not a kind of good purification technique.2006 JP2006283102 (being equal to CN1840738) studied the purification process of copper chloride etching waste liquid in great detail, it is weakly alkaline or strongly basic anion exchange resin absorption foreign metal (mainly being iron, zinc) the ionic anionic property coordination ion that adopts equally, reaches the purpose of purifying, refining Cupric Chloride Solution.In the Cupric Chloride Solution of the described processing of JP2006283102, copper ion concentration is 1.1～1.7mol/L, and concentration of hydrochloric acid is 0.4～2.2mol/L.When concentration of hydrochloric acid during less than 0.25mol/L, the effect of absorption iron, zinc obviously descends, thereby is unsuitable for the purification refine of low free hydrochloric acid Cupric Chloride Solution.This method does not relate to the purification process that copper content is higher than the 1.7mol/L Cupric Chloride Solution yet simultaneously, finds almost not have the effect of deironing, zinc when the purification experiment of the Cupric Chloride Solution that carries out the 3.2-3.3mol/L high density.
Being used for heavy copper and etched Cupric Chloride Solution in the printed wiring board industry all has higher requirement or qualification to positive and negative ion such as iron and free hydrochloric acid, and its leading indicator comprises:
1, copper content: 3.20～3.30mol/L
2, iron :≤15ppm
3, lead :≤10ppm
4, zinc :≤10ppm
5, tin :≤10ppm
6, nickel :≤10ppm
7, barium :≤10ppm
8, sodium :≤30ppm
9, vitriol is (with SO
4 2-) :≤10ppm
10, phosphoric acid salt (PO
4 3-) :≤40ppm
11, total organic carbon (TOC) :≤70ppm
By the requirement of above impurity index, even if the pure level of operational analysis cupric chloride is a raw material, also being difficult to directly, preparation impurity requires qualified high-purity Cupric Chloride Solution.Therefore, be that the simple high-purity Cupric Chloride Solution that closes the above-mentioned specification of quality of symbol of producing on a large scale of raw material just seems necessary as how industrial cupric oxide or cupric chloride etching are useless, but adsorbing rule, the resin anion(R.A) of the existing document of reference is difficult to deal with problems.
Summary of the invention
The object of the present invention is to provide a kind of high-purity cupric chloride compositions and methods of industrialized production that is easy to, this method also is fit to produce other high purity water-soluble cupric salt reagent.
Another object of the present invention provide a kind of can be with the precipitation agent of foreign metal ion precipitation in the copper salt solution.
For achieving the above object, precipitation agent of the present invention is a polyphosphoric acid copper, be by polyphosphoric acid water-soluble after, stir and progressively to add SILVER REAGENT basic carbonate copper powder down up to there not being bubble to produce, filter, washing the solids that drying obtains.
In the above-mentioned polyphosphoric acid with P
2O
5The weight content that calculates is 76～88%, preferably 80～86%, more preferably 80～85%.
A kind of semi-solid state polyphosphoric acid that the polyphosphoric acid that the present invention uses can be obtained through high temperature dehydration by phosphorylating reagent, the polyphosphoric acid copper that polyphosphoric acid and copper carbonate reaction make is blue powder shape solid.The a kind of of its reaction may situation be:
Wherein n is a positive integer.
The production method of the high-purity mantoquita reagent of the present invention is the above-mentioned polyphosphoric acid copper more than copper salt solution adding copper salt solution gross weight 5ppm, stirs the copper salt solution that after-filtration obtains.
The consumption of above-mentioned polyphosphoric acid copper can not have the upper limit, but consumption too much can cause the waste of polyphosphoric acid copper, and preferred consumption is 10ppm～0.5%, is more preferably 10～100ppm.
Under 20～90 ℃ of the copper salt solution temperature, be preferably 40～80 ℃ among the present invention, be more preferably 40～60 ℃.
The water-soluble mantoquita of metal ion comprises copper sulfate, cupric nitrate, cupric chloride, cupric fluoborate or copper methanesulfonate in the available aforesaid method purification mantoquita, and in addition, the also available the inventive method of other water-soluble mantoquitas such as venus crystals is purified.
The free acid that contains in the copper salt solution that the inventive method is handled is low more, and treatment effect is good more, and the equivalent concentration of free acid is more preferably less than 0.03N preferably less than 0.10N.Adopt cupric oxide slightly in excessive mode, the equivalent concentration of free acid is everlasting below the 0.03N.If will prepare the copper salt solution that free acid concentration is higher than 0.03N, available reagent hydrochloric acid is directly allocated.
The method for preparing at present cupric oxide mainly contains two kinds, and a kind of is copper powder high-temperature air burning oxidation style, and high temperature resistant material of the oxidized still of this method and copper powder raw material are the main sources of introducing impurity.Second method is to utilize to reclaim mantoquita (as the electroplating effluent of cupric chloride, copper sulfate, cupric fluoborate, copper methanesulfonate etc.) through sodium hydroxide conversion preparation, and its impurity mainly comes from quality and the treatment process technology that reclaims mantoquita.Second method is the main method that present domestic cupric oxide is produced.Main rank, technical indicator and the reference price of commercial various cupric oxide sees the following form on the domestic market:
| Rank | Technical indicator | |||||
| Cupric oxide (CuO) | Hydrochloric acid insoluble substance | Muriate (C1 -) | Vitriol (SO 4 2-) | Iron (Fe 3+) | Zinc (Zn 2+) | |
| Technical grade | ≥98.0 | ≤0.20 | ≤0.20 | ≤0.20 | - | - |
| Electroplate level | ≥98.5 | ≤0.10 | ≤0.01 | - | ≤0.20 | ≤0.20 |
| Reagent C P | ≥98.0 | ≤0.05 | ≤0.005 | ≤0.05 | ≤0.04 | - |
| Reagent A R | ≥99.0 | ≤0.02 | ≤0.003 | ≤0.01 | ≤0.01 | - |
As can be seen from the above table, be raw material even adopt reagent A R grade copper oxide, production such as the iron level of copper salt solutions such as cupric chloride also more than 20ppm, do not reach the requirement of producing the high purity copper salts solution, simultaneously to other positively charged ion yet not control.And the iron level of industrial cupric oxide is usually between 0.025～0.04%, also promptly between 250～400ppm.
Deironing and heavy metal for the copper salt solution of iron level more than 60～70ppm can adopt traditional adjust pH method to carry out, adopt the adjust pH method then beyond one's ability to iron level at 60～70ppm or following copper salt solution, add foreign metal ions such as to make iron by polyphosphoric acid copper of the present invention and drop between 5～15ppm.In addition, precipitation agent polyphosphoric acid copper of the present invention also can be applicable to produce in the printed wiring board industry purifying regeneration of copper waste etching solution.
Present method adopts the Cupric Chloride Solution of industrial cupric oxide and hydrochloric acid reaction preparation, removes part metals impurity through the adjust pH method, after to handle back acquisition quality product situation through precipitation agent of the present invention as follows:
1, copper content (Cu
2+): 3.20～3.30mol/L;
2, iron (Fe
3+): 5.0～10.0ppm;
3, plumbous (pb
2+): 1.0～8.0ppm;
4, zinc (Zn
2+): 1.0～8.0ppm;
5, tin (Sn
4+): 1.0～8.0ppm;
6, nickel (Ni
3+): 1.0～8.0ppm;
7, barium (Ba
2+): 1.0～8.0ppm;
8, sodium (Na
+): 1.0～8.0ppm;
9, vitriol (SO
4 2-): 3.0～8.0ppm;
10, phosphoric acid salt (PO
4 3-): 10～30ppm;
11, total organic carbon (TOC): 30～50ppm.
Precipitation agent of the present invention is not only applicable to the copper salt solution of copper content 3.20～3.30mol/L, in saturated copper sulfate, cupric nitrate, cupric chloride, cupric fluoborate or methylsulphonic acid copper solutions, and in the copper salt solution of lower concentration, all there is same precipitation to remove foreign metal ionic effect.
Embodiment
Embodiment 1: the SILVER REAGENT phosphoric acid of weight content 85% is contained on the quartz evaporating dish, and thermal dehydration to weight reduces 28%, obtains a kind of by P
2O
5The semi-solid state article of weight content about 85% of meter, these article are polyphosphoric acid, water-soluble after, stir and add SILVER REAGENT basic carbonate copper powder down up to not having the bubble generation, filtration, washing, drying, make blue powder shape solid, this solid is a polyphosphoric acid copper precipitation agent of the present invention.
Embodiment 2: the SILVER REAGENT phosphoric acid of weight content 85% is contained on the quartz evaporating dish, and thermal dehydration to weight reduces 23%, obtains a kind of by P
2O
5The meter content about 80% the semi-solid state article, these article are polyphosphoric acid, with these article water-soluble after, stir and add SILVER REAGENT basic carbonate copper powder down up to not having the bubble generation, filtration, washing, drying, make blue powder shape solid, this solid is a polyphosphoric acid copper precipitation agent of the present invention.
Embodiment 3: in the reaction flask of the 2000mL that stirring, thermometer and reflux condensing tube are housed, adds 440 gram pure water, starts stirring and add the 280 industrial cupric oxide of gram down in batches and drip 710 grams, 36% reagent hydrochloric acid, and exothermic heat of reaction, it is too fierce that control is reacted.After adding hydrochloric acid, when temperature is reduced to 90 ℃, from liquid level, slowly add an amount of aqueous hydrogen peroxide solution while hot, the speed that adds aqueous hydrogen peroxide solution is as the criterion with the fierceness within reason that foams, add the back stirring reaction after 1 hour, about 55 ℃ reaction product is divided into two parts, a copy of it adds the activated carbon of gross weight 0.2%, and another part adds embodiment 1 precipitation agent and 0.2% activated carbon of gross weight 0.002%.Two parts are continued respectively to stir about 3 hours, be cooled to room temperature, use the micro-pore-film filtration of 0.2 μ m after the coarse filtration again, filtrate is carried out the detection of every index respectively, the results are shown in following table, adding the reacted filtrate of precipitation agent is the high-purity copper chloride solution reagent of the present invention product.
| Test item | Do not add precipitation agent filtrate | Add precipitation agent filtrate |
| Copper (Cu 2+，mol/L) | 3.27 | 3.27 |
| Iron (Fe 3+，ppm) | 48.1 | 8.5 |
| Plumbous (pb 2+，ppm) | 22.6 | 2.6 |
| Zinc (Zn 2+，ppm) | 58.8 | 7.8 |
| Tin (Sn 4+，ppm) | 23.4 | 6.3 |
| Nickel (Ni 3+，ppm) | 16.8 | 6.6 |
| Barium (Ba 2+，ppm) | 5.6 | 5.2 |
| Sodium (Na +，ppm) | 7.7 | 7.8 |
| Vitriol (SO 4 2-) | 3.8 | 3.9 |
| Phosphoric acid salt (PO 4 3-) | 22.0 | 23.0 |
| Total organic carbon (TOC) | 39.0 | 35.0 |
Embodiment 4: add 440 gram pure water in the reaction flask of the 2000mL that stirring, thermometer and reflux condensing tube are housed, start to stir and add the 280 industrial cupric oxide of gram down in batches and drip 710 grams, 36% reagent hydrochloric acid, because exothermic heat of reaction, control reaction are too not fierce.After adding hydrochloric acid, when temperature is reduced to 90 ℃, from liquid level, slowly add an amount of aqueous hydrogen peroxide solution while hot, the speed that adds aqueous hydrogen peroxide solution is as the criterion with the fierceness within reason that foams, and adds the back stirring reaction after 1 hour, adds 0.001% embodiment 2 precipitation agents and 0.2% activated carbon about 55 ℃, continue to stir about 3 hours, be cooled to room temperature, again with the mocromembrane filtration of 0.2 μ m, filtrate is carried out the detection of every index after the coarse filtration.The foreign ion analytical results is listed in down:
1, iron (Fe
3+): 8.6ppm;
2, plumbous (pb
2+): 2.8ppm;
3, zinc (Zn
2+): 7.9ppm;
4, tin (Sn
4+): 6.6ppm;
5, nickel (Ni
3+): 6.8ppm;
6, barium (Ba
2+): 5.1ppm;
7, sodium (Na
+): 7.6ppm;
8, vitriol (SO
4 2-): 3.9ppm
9, phosphoric acid salt (PO
4 3-): 21.0ppm;
10, total organic carbon (TOC): 36.0ppm.
The implementation step of embodiment 5-8: embodiment 5,6,7,8 is identical with embodiment 3, and difference only is the consumption of precipitation agent.Each embodiment precipitation agent consumption is:
Embodiment 5: 0.01% of gross weight;
Embodiment 6: 0.005% of gross weight;
Embodiment 7: 0.05% of gross weight;
Embodiment 8: 0.1% of gross weight.
The detection case of foreign ion is as follows in the experimental result:
| Project | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 |
| Iron (Fe 3+，ppm) | 8.9 | 12.6 | 8.3 | 8.1 |
| Plumbous (pb 2+，ppm) | 3.8 | 5.8 | 2.3 | 2.4 |
| Zinc (Zn 2+，ppm) | 8.9 | 9.8 | 7.3 | 7.1 |
| Tin (Sn 4+，ppm) | 7.8 | 8.5 | 6.0 | 6.1 |
| Nickel (Ni 3+，ppm) | 7.7 | 9.9 | 6.1 | 6.2 |
| Barium (Ba 2+，ppm) | 6.4 | 5.9 | 5.0 | 5.3 |
| Sodium (Na +，ppm) | 7.9 | 7.7 | 7.8 | 7.2 |
| Vitriol (SO 4 2-，ppm) | 4.9 | 3.8 | 4.6 | 4.8 |
| Phosphoric acid salt (PO 4 3-，ppm) | 20.0 | 13.0 | 41.0 | 46.0 |
| Total organic carbon (TOC, ppm) | 39.0 | 37.0 | 32.0 | 38.0 |
Embodiment 9: add 0.1mol/L copper sulfate 800mL in the reaction flask of the 1000mL that stirring, thermometer and reflux condensing tube are housed, in this copper-bath iron, lead, zinc, tin, nickel content be respectively 70,20,40,16,22ppm, total organic carbon 140ppm.When stirring intensification degree to 80 ℃, drip an amount of superoxol while hot, the speed that adds hydrogen peroxide is as the criterion with the fierceness within reason that foams, add the back stirring reaction after 1 hour, embodiment 1 precipitation agent and 0.2% activated carbon that add gross weight 0.003% about 55 ℃ continue to stir about 3 hours, are cooled to room temperature, mocromembrane with 0.2 μ m after the coarse filtration filters, and filtrate is carried out the detection of every index.Analytical results is listed in down:
1, iron (Fe
3+): 8.1ppm;
2, plumbous (pb
2+): 2.3ppm;
3, zinc (Zn
2+): 7.2ppm;
4, tin (Sn
4+): 6.0ppm;
5, nickel (Ni
3+): 6.7ppm;
6, total organic carbon (TOC): 33.0ppm.
Embodiment 10-12: according to the identical step of embodiment 9, copper sulfate is replaced to cupric nitrate, cupric fluoborate and methylsulphonic acid copper solutions handle respectively, result is as follows:
| Test item | Embodiment 10 copper nitrate solutions | Embodiment 11 cupric fluoborate solution | Embodiment 12 copper methanesulfonate | |||
| Before the processing | After the processing | Before the processing | After the processing | Before the processing | After the processing | |
| Copper (Cu 2+，mol/L) | 0.13 | 0.13 | 0.26 | 0.26 | 0.18 | 0.18 |
| Iron (Fe 3+，ppm) | 73 | 8.8 | 72 | 8.7 | 67 | 8.2 |
| Plumbous (pb 2+，ppm) | 25 | 2.9 | 28 | 2.8 | 23 | 2.1 |
| Zinc (Zn 2+，ppm) | 41 | 7.6 | 30 | 7.5 | 41 | 7.4 |
| Tin (Sn 4+，ppm) | 18 | 6.1 | 26 | 6.4 | 19 | 6.7 |
| Nickel (Ni 3+，ppm) | 28 | 6.6 | 32 | 6.1 | 27 | 6.5 |
| Total organic carbon (TOC, ppm) | 130 | 39.0 | 120 | 36.0 | - | - |
Claims (10)
1. a precipitation agent that is used to produce high purity water-soluble cupric salt reagent is characterized in that, this precipitation agent is a polyphosphoric acid copper, be by polyphosphoric acid water-soluble after, stir and progressively add SILVER REAGENT basic carbonate copper powder down up to not having the bubble generation, filtration, washing, the solids that drying obtains.
2. according to the described precipitation agent of claim 1, it is characterized in that, in the described polyphosphoric acid with P
2O
5The weight content that calculates is 76～88%.
3. according to the described precipitation agent of claim 2, it is characterized in that, in the described polyphosphoric acid with P
2O
5The weight content that calculates is 80～85%.
4. the production method of a high purity water-soluble cupric salt reagent is characterized in that, adds the described polyphosphoric acid copper of claim 1 more than the copper salt solution gross weight 5ppm in copper salt solution, stirs the copper salt solution that after-filtration obtains.
5. according to the production method of the described high purity water-soluble cupric salt reagent of claim 4, it is characterized in that the consumption of described polyphosphoric acid copper is 10ppm～0.5%.
6. according to the production method of the described high purity water-soluble cupric salt reagent of claim 5, it is characterized in that the consumption of described polyphosphoric acid copper is 10～100ppm.
7. according to the production method of the described high purity water-soluble cupric salt reagent of claim 4, it is characterized in that described copper salt solution temperature is 20～90 ℃.
8. according to the production method of the described high purity water-soluble cupric salt reagent of claim 7, it is characterized in that described copper salt solution temperature is 40～60 ℃.
9. according to the production method of the described high purity water-soluble cupric salt reagent of claim 4, it is characterized in that the equivalent concentration that contains free acid in the described copper salt solution is less than 0.1N.
10. according to the production method of the described high purity water-soluble cupric salt reagent of claim 4, it is characterized in that described mantoquita is cupric chloride, copper sulfate, cupric nitrate, cupric fluoborate or copper methanesulfonate.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108562576A (en) * | 2018-03-07 | 2018-09-21 | 苏州市宇驰检测技术有限公司 | A kind of method of copper in detection water body |
| CN112607762A (en) * | 2020-12-29 | 2021-04-06 | 东江环保股份有限公司 | Preparation method of electronic-grade copper chloride dihydrate |
| WO2022141045A1 (en) * | 2020-12-29 | 2022-07-07 | 东江环保股份有限公司 | Preparation method for electronic-grade copper chloride dihydrate |
-
2006
- 2006-12-25 CN CNB2006101243896A patent/CN100513314C/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108562576A (en) * | 2018-03-07 | 2018-09-21 | 苏州市宇驰检测技术有限公司 | A kind of method of copper in detection water body |
| CN112607762A (en) * | 2020-12-29 | 2021-04-06 | 东江环保股份有限公司 | Preparation method of electronic-grade copper chloride dihydrate |
| WO2022141045A1 (en) * | 2020-12-29 | 2022-07-07 | 东江环保股份有限公司 | Preparation method for electronic-grade copper chloride dihydrate |
| CN112607762B (en) * | 2020-12-29 | 2022-09-27 | 东江环保股份有限公司 | Preparation method of electronic-grade copper chloride dihydrate |
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Address after: 515064 Guangdong city of Shantou province Chaoshan Road West Long Street No. 1-3 Patentee after: XILONG SCIENTIFIC CO., LTD. Address before: 515064 Guangdong city of Shantou province Chaoshan Road West Long Street No. 1-3 Patentee before: Xilong Chemical Co., Ltd. |