CN1569644A - Method for preparing barium stannate trihydrate using stannum in waste tin stripper - Google Patents
Method for preparing barium stannate trihydrate using stannum in waste tin stripper Download PDFInfo
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- CN1569644A CN1569644A CN 200410027139 CN200410027139A CN1569644A CN 1569644 A CN1569644 A CN 1569644A CN 200410027139 CN200410027139 CN 200410027139 CN 200410027139 A CN200410027139 A CN 200410027139A CN 1569644 A CN1569644 A CN 1569644A
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- tin
- stannate
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Abstract
The hydration barium stannate preparing process disclosed by the invention comprising the steps of, (1) separating tin from the solution, (2) conversion of metastannic acid, (3) preparation of hydrated barium stannate, charging BaCl2 solvent into the obtained filtrate, heating and filtering, washing with hot-water several times, and drying.
Description
Technical field
The present invention relates to a kind of method of utilizing tin in the waste tin stripper to prepare barium stannate trihydrate.
Background technology
Waste tin stripper is a kind of very a large amount of waste water that printed circuit board industry produces, and according to the difference of the tin stripper kind that is adopted, the stanniferous amount of waste water grams per liter more than tens grams per liters to 150 does not wait, so waste tin stripper is a kind of precious resources of worth utilization.In the research that traditional waste tin stripper is handled, the general method and the simple polymer coacervation method that add heat sink tin of adopting makes the tin precipitation.The method that adds heat sink tin uses face narrow, the heavy tin rate of indivedual kinds can reach 95%, even but also precipitate not exclusively for the heavy tin method of the additional oxidation of other kind, can only reach 75% heavy tin rate, lower for the unconspicuous then separation rate of micelle, even less than 50%.Simple flocculating polymer method is also relatively poor for the sedimentation effect of no obvious size distribution.Centrifugation is big for colloidal solid, the tangible waste water of micelle has certain effect, but then very poor for the waste water effect of other colloidal state distribution uniform.
In waste tin stripper, tin mainly is with the undissolved metastannic acid colloid of water (β-H
2SnO
3) be the form existence of insoluble tin dioxide hydrate, insoluble metastannic acid is transformed into the stannate of solubility, in the documents and materials and actual industrial production substantially all be under sodium hydroxide or potassium hydroxide fused condition, to carry out, that have even will add necessary oxygenant such as SODIUMNITRATE, condition harshness, cost are also high.
Barium stannate trihydrate (BaSnO
3.3H
2O) as a kind of particularly raw material of lamination electrical condenser of high dielectric electronic ceramics element of producing, aspect its low-temperature sintering, small-sized thin layerization, reliability, the effect highly significant.Can be used as the decoration tinting material of high-grade ceramic, the modification of gas sensing electrodes etc. in addition.
The now external disclosed method for preparing barium stannate trihydrate substantially all is that the single water soluble barium salt of component and water-soluble tin such as hydration tindioxide or resolvability stannate react in strong alkali solution, is sintered into the barium stannate trihydrate powder at last.These technologies are had relatively high expectations to starting material bar none, thereby cost is also higher; Product impurity control indexes aspect, according to selected raw-material difference and control emphasis is different, as the requirement to sulphur, what have does not do requirement, and the requirement that has is less than 0.15%, thereby causes the difference of product total quality.
Still lose report and utilize tin in the waste tin stripper to prepare barium stannate trihydrate.
Summary of the invention
The object of the present invention is to provide that a kind of cost is low, the separation rate of tin is high and barium stannate preparation is superior in quality utilizes tin in the waste tin stripper to prepare the method for barium stannate trihydrate.
The object of the present invention is achieved like this: method of the present invention comprises the step of following order:
(1) separation of tin in the tin stripper: in waste tin stripper, add anion surfactant and polymeric flocculant, form stable coagulation immediately, the ratio of solid surfactant usage quantity and waste tin stripper volume is the 10-60 grams per liter, concentration is that the consumption of 0.2% flocculating polymer agent solution is the 1-6% (volume) of waste tin stripper total amount, filters then and makes solid-liquid separation;
(2) conversion of metastannic acid: the step gained precipitates and adds entry before getting, generally with just flood be precipitated as suitable, add sodium hydroxide or potassium hydroxide again, the mol ratio of tin and sodium hydroxide or potassium hydroxide is 1: 4-12, heating gentle boil 20-60 minute, make insoluble metastannic acid change the sodium stannate or the potassium stannate of solubility into, the water extraction sodium stannate or the potassium stannate that add capacity again filter, with the less water washing precipitation, merging filtrate discards precipitation;
(3) preparation of barium stannate trihydrate: add BaCl forward while go on foot to stir in the filtrate of gained
2Solution, treat that stannate radicle precipitation (leaves standstill, adds not regeneration precipitation of bariumchloride) fully after, be heated to 75-85 ℃, filtered while hot, the reusable heat water washing for several times, oven dry promptly obtains the barium stannate trihydrate product.
Anion surfactant can be for one of following among the present invention: sodium laurylsulfonate, sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, hexadecyl disulfonate acid, calcium dodecylbenzene sulphonate, sodium laurate etc., specifically can select, be preferably sodium laurylsulfonate from cost aspect and operation convenience.
Polymeric flocculant can be for one of following among the present invention: polyacrylic acid, and polyacrylic ester, polyacrylamide is preferably polyacrylamide.
In (1) step, if do not carry out successive production, then will precipitate drying in the present invention after filtration, and get the dried slag of metastannic acid, if carry out successive production, then this step drying process can omit.
The present invention is in the leaching process of (2) step, and the leaching factor that influences tin has the consumption of temperature, time and alkali, during low temperature the leaching yield increase of tin very slow, maximum leaching yield is not high yet; Use suitable alkali number, the leaching yield of tin can reach more than 96% under boiling temperature (102-105 ℃), cooperates higher basicity leaching yield can reach 99%.
The all right partially recycled tensio-active agent of the present invention: in the present invention's (2) step, behind the water extraction sodium stannate, be heated to 80 ℃, filtered while hot is removed impurity such as de-iron, copper, cooling, treat that tensio-active agent is separated out after, filter, reclaiming tensio-active agent can utilize again, and filtrate enters next step and prepares barium stannate trihydrate.
The impurity of the barium stannate trihydrate product needed control of the present invention's preparation is mainly Al.Fe.Si.Ca.Na etc.According to the raw-material characteristics of the inventive method, the index of actual needs control also has Cu, S, because the same with iron, copper also is one of relatively large impurity in the waste tin stripper recovery component, and sulphur impurity to be recovering means cause (containing sulphur in the tensio-active agent).As for other impurity project, aluminium, silicon, calcium are that the tin stripper starting material are introduced basically, and sodium then is to introduce in the treating processes of back, and amount is bigger.But through after the method for the present invention, impurity can be controlled effectively:
(1) moves back the dried slag process sodium hydroxide conversion that useless Xi Shui obtains, except that aluminium, silicon exist with the acid salt form, other has all become insoluble oxyhydroxide basically, so after adding relatively large flooding sodium stannate, filtration procedure subsequently can be removed insoluble oxyhydroxide.The gluey characteristics of ironic hydroxide can be removed part aluminium, silicate impurity and tensio-active agent by active adsorption, and the absorption of tensio-active agent has also improved the strainability of ferric hydroxide colloid effectively;
(2) though remaining sila matter also can generate precipitation with barium, and barium silicate is decomposed by heat energy, can adsorb during heating above the small part barium stannate trihydrate floats over the foam shape, skim this layer liquid foam, dioxide-containing silica is further reduced;
(3) the hot wash product can be removed residual a small amount of other soluble impurity.
The analysis indexes of barium stannate trihydrate product of the present invention sees Table one;
| Project | BaO.SnO 2(weight %) | Al 2O 3(％) | CaO(％) | Fe 2O 3(％) | ??SiO 2(weight %) | SO 3(％) | Na 2O(％) |
| Index | ＞99.2 | ＜0.01 | ＜0.05 | ＜0.02 | ??＜0.05 | ＜0.1 | ＜0.05 |
Table one
Technique effect of the present invention is: the present invention utilizes tin in the waste tin stripper as basic starting material, belongs to the regeneration of refuse, can reduce the barium stannate trihydrate production cost of products greatly like this; Adopt method of the present invention, the separation rate of tin can reach more than 99% in the waste tin stripper; The present invention adopts sodium hydroxide or potassium hydroxide strong solution boiling process that the insoluble metastannic acid is converted into the resolvability stannate, avoided common high-temperature fusion operation, can reduce cost and to the requirement of equipment material, after suitable removal of impurities processing, can obtain the outstanding electronic-grade barium stannate trihydrate of quality.So the present invention is from economic benefit or the social benefit aspect all has significant value.
Embodiment
Embodiment one to embodiment six:
(1) separation of tin in the tin stripper: in waste tin stripper, add anion surfactant and polymeric flocculant, filter, make solid-liquid separation, will precipitate drying, get the dried slag of metastannic acid.
In embodiment one to embodiment six, selected six kinds of each 100ml of different waste tin strippers to carry out top lock out operation, the Chemical Composition of waste tin stripper composition sees Table among the embodiment one to six
Table two
The main component analysis in table three of the dried slag of gained metastannic acid:
Table three
(2) preparation of the conversion of metastannic acid and barium stannate trihydrate:
Take by weighing 100g and go up the dried slag of metastannic acid that the step separation obtains, add the 200ml deionized water, 100g sodium hydroxide heats little 30min that boils, and cooling a little adds 1.5L water, stirs 10min, and filtration discards filter cake; Under fully stirring, in filtrate, add 110g bariumchloride (BaCL gradually
2.2H
2O) 20% aqueous solution that is made into is heated to 80 ℃, skims upper foam, filters, and uses 60 ℃ of hot wash filter cakes three times again, drains, and at 120 ℃ of dry 2h, promptly can obtain the barium stannate trihydrate finished product at last.
The tensio-active agent and the feeding quantity of polymeric flocculant and the separation rate of tin saw Table four during the every 100ml of above-mentioned each waste water handled:
Table four
Sodium laurylsulfonate is an anion surfactant in the table four, during use its solid is dissolved in the water, and working concentration is 2%; Polyacrylamide is a polymeric flocculant, and use-pattern is to be mixed with 0.2% the aqueous solution, and the consumption in the form is the volume ratio of its aqueous solution and waste water.
Embodiment seven to 12:
Get 10g respectively and from the foregoing description, separate the dried slag of the metastannic acid that obtains, each adds 20ml water, add 8g, 9g, 10g, 12g, 14g, 20gNaOH more respectively, heat little 30min that boils, add the 100ml flooding, filter, with the less water washing precipitation, merging filtrate discards precipitation, measure the leaching yield of tin, the results are shown in Table five.
| Numbering | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Embodiment 11 | Embodiment 12 |
| NaOH(g) | ????8 | ????9 | ????10 | ????12 | ????14 | ????20 |
| The leaching yield of tin (%) | ????59.9 | ????74.1 | ????85.6 | ????89.6 | ????96.5 | ????99.5 |
Table five
The filtrate that previous step is obtained adds 6.6g respectively, 8.2g, 9.5g, 9.9g, 10.7g, 11.1g bariumchloride (BaCL
2.2H
2O) concentration that is made into is 20% solution, and reaction generates the barium stannate precipitation, is heated to 80 ℃ of filtrations, and with 50 ℃ hot washes for several times, drying obtains the barium stannate trihydrate product.
Embodiment 13,14:
Get two parts of dried slags of each 10g embodiment one resulting metastannic acid, add 20ml water respectively, respectively add 10.2g and 30.5g KOH under stirring, respectively ebuillition of heated 60min, 20min, use flooding, filter, with the less water washing precipitation, merging filtrate, discard precipitation, measure the leaching yield of tin, the results are shown in Table six.
| Heat-up time (min) | ????20min | ????60min |
| KOH add-on (g) | ????30.5 | ????10.2 |
| Tin leaching yield (%) | ????99.1 | ????96.3 |
Table six
The filtrate that previous step is obtained adds 10.9g respectively, 10.6g bariumchloride (BaCL
2.2H
2O) solution that is made into, reaction generate the barium stannate precipitation, are heated to 80 ℃ of filtrations, and with 55 ℃ hot washes for several times, drying obtains the barium stannate trihydrate product.
Claims (7)
1. method of utilizing tin in the waste tin stripper to prepare barium stannate trihydrate is characterized in that comprising the step of following order:
(1) separation of tin in the tin stripper: in waste tin stripper, add anion surfactant and polymeric flocculant, form stable coagulation immediately, the ratio of solid surfactant usage quantity and waste tin stripper volume is the 10-60 grams per liter, concentration is that the consumption of 0.2% flocculating polymer agent solution is the 1-6% (volume) of waste tin stripper total amount, filters then and makes solid-liquid separation;
(2) conversion of metastannic acid: the step gained precipitates and adds entry before getting, add sodium hydroxide or potassium hydroxide again, the mol ratio of tin and sodium hydroxide or potassium hydroxide is 1: 4-12, heating gentle boil 20-60 minute makes insoluble metastannic acid change the sodium stannate or the potassium stannate of solubility into, adds the water extraction sodium stannate or the potassium stannate of capacity again, filter, with the less water washing precipitation, merging filtrate discards precipitation;
(3) preparation of barium stannate: add BaCl forward while go on foot to stir in the filtrate of gained
2Solution, treat that stannate radicle precipitation fully after, be heated to 75-85 ℃, filtered while hot, again the hot wash of usefulness for several times, oven dry promptly obtains the barium stannate product.
2. the method for utilizing tin in the waste tin stripper to prepare barium stannate trihydrate according to claim 1, it is characterized in that: described anion surfactant is selected from one of following, sodium laurylsulfonate, sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, hexadecyl disulfonate acid, calcium dodecylbenzene sulphonate, sodium laurate.
3. the method for utilizing tin in the waste tin stripper to prepare barium stannate trihydrate according to claim 2, it is characterized in that: described anion surfactant is a sodium laurylsulfonate.
4. the method for utilizing tin in the waste tin stripper to prepare barium stannate trihydrate according to claim 1 is characterized in that: described polymeric flocculant is one of following, polyacrylic acid, polyacrylic ester, polyacrylamide.
5. the method for utilizing tin in the waste tin stripper to prepare barium stannate trihydrate according to claim 4, it is characterized in that: described polymeric flocculant is a polyacrylamide.
6. the method for utilizing tin in the waste tin stripper to prepare barium stannate trihydrate according to claim 1 is characterized in that: in described (1) step, after filtration, will precipitate dry, the dried slag of metastannic acid.
7. the method for utilizing tin in the waste tin stripper to prepare barium stannate trihydrate according to claim 1, it is characterized in that: in described (2) step, with water extraction sodium stannate post-heating to 80 ℃, filtered while hot, cooling, after treating that tensio-active agent is separated out, refilter, filtrate enters the operation of next step.
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| CN1569644A true CN1569644A (en) | 2005-01-26 |
| CN1241835C CN1241835C (en) | 2006-02-15 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101497458B (en) * | 2008-01-30 | 2010-10-06 | 深圳市东江环保股份有限公司 | Method for preparing sodium stannate using circuit board tin-stripping wastewater |
| CN101948133A (en) * | 2010-10-28 | 2011-01-19 | 四川理工学院 | Method for co-producing sodium stannate and stannic oxide by solder removing liquid |
| CN102492860A (en) * | 2011-12-31 | 2012-06-13 | 东莞市东元新能源科技有限公司 | Method for recovering simple substance tin by nitric acid type tin-stripping waste liquid |
| CN102515259A (en) * | 2011-12-31 | 2012-06-27 | 东莞市东元新能源科技有限公司 | Method utilizing nitric acid type solder stripping waste water to synthetize zinc hexahydroxystannate |
| CN110182840A (en) * | 2019-06-24 | 2019-08-30 | 深圳市海文环保技术有限公司 | Move back tin waste treatment processes |
| CN113663708A (en) * | 2021-08-16 | 2021-11-19 | 中化学朗正环保科技有限公司 | High-efficiency photocatalytic material and preparation method and application thereof |
-
2004
- 2004-04-30 CN CN 200410027139 patent/CN1241835C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101497458B (en) * | 2008-01-30 | 2010-10-06 | 深圳市东江环保股份有限公司 | Method for preparing sodium stannate using circuit board tin-stripping wastewater |
| CN101948133A (en) * | 2010-10-28 | 2011-01-19 | 四川理工学院 | Method for co-producing sodium stannate and stannic oxide by solder removing liquid |
| CN101948133B (en) * | 2010-10-28 | 2014-08-06 | 四川理工学院 | Method for co-producing sodium stannate and stannic oxide by solder removing liquid |
| CN102492860A (en) * | 2011-12-31 | 2012-06-13 | 东莞市东元新能源科技有限公司 | Method for recovering simple substance tin by nitric acid type tin-stripping waste liquid |
| CN102515259A (en) * | 2011-12-31 | 2012-06-27 | 东莞市东元新能源科技有限公司 | Method utilizing nitric acid type solder stripping waste water to synthetize zinc hexahydroxystannate |
| CN102515259B (en) * | 2011-12-31 | 2014-03-26 | 东莞市东元新能源科技有限公司 | Method for utilizing nitric acid type solder stripping waste water to synthetize zinc hexahydroxystannate |
| CN102492860B (en) * | 2011-12-31 | 2014-07-09 | 东莞市东元新能源科技有限公司 | Method for recovering simple substance tin by nitric acid type tin-stripping waste liquid |
| CN110182840A (en) * | 2019-06-24 | 2019-08-30 | 深圳市海文环保技术有限公司 | Move back tin waste treatment processes |
| CN113663708A (en) * | 2021-08-16 | 2021-11-19 | 中化学朗正环保科技有限公司 | High-efficiency photocatalytic material and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1241835C (en) | 2006-02-15 |
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