CN103663536A - Process for preparing precipitated barium sulfate by pretreatment of waste acid of sulfuric acid process titanium dioxide - Google Patents
Process for preparing precipitated barium sulfate by pretreatment of waste acid of sulfuric acid process titanium dioxide Download PDFInfo
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- CN103663536A CN103663536A CN201310448564.7A CN201310448564A CN103663536A CN 103663536 A CN103663536 A CN 103663536A CN 201310448564 A CN201310448564 A CN 201310448564A CN 103663536 A CN103663536 A CN 103663536A
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- sulfuric acid
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- barium carbonate
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Abstract
The invention discloses a process for preparing precipitated barium sulfate by pretreatment of waste acid of sulfuric acid process titanium dioxide. The process comprises the following steps: step 1) adding soluble barium salt power into pure water for beating and stirring in an environment at normal temperature (about 25 DEG C) to obtain a uniform barium carbonate solution; step 2) introducing the waste acid produced in the production process of the sulfuric acid process titanium dioxide into a reaction tank of a precipitated barium carbonate production device for later use; step 3) gradually adding the barium carbonate solution in the step 1) into the waste acid solution in the reaction tank of the step 2), stirring, and simultaneously continuously measuring the pH value for adjustment till the measured pH value range of the solution is stabilized at 1-1.5; step 4) keeping the temperature unchanged, and rapidly beating and filtering the solution in the step 2) to obtain filtrate and filter residues; step 5) drying the filter residues obtained in the step 4) to obtain precipitated barium sulfate powder; step 6) further filtering and purifying the filtrate obtained in the step 4) to obtain a ferrous sulfate solution. The method disclosed by the invention has the characteristics of lowering production cost, reducing emission of wastewater, reducing overall investment of equipment, realizing low energy consumption, simple process and excellent and stable product properties and the like.
Description
Technical field
The present invention relates to the technique that a kind of process white is manufactured, refer more particularly to a kind of spent acid producing in pre-treatment sulfuric acid method titanium pigment production process of recycling, prepare the environment-protective process of process white.
Background technology
Along with the progressively development of domestic titanium dioxide industry, no matter sulfuric acid method titanium pigment is accomplished the wall scroll production line of 50,000 tons/year at present, be in the upper or equipment of design, technique, domesticly can meet it and build production requirement.So far the total annual capacity of domestic titanium dioxide approximately reaches 1,750,000 tons and also in the enlarging of expanding production of constantly rising.Domestic titanium white production technique is mainly to adopt sulfuric acid process, and sulfuric acid process principal pollutant are exactly the spent acid that washing produces, and produce the dense spent acid 8m3 that every 1 ton of titanium dioxide produces 20-24% simultaneously, and wherein ferrous sulfate content is 10-8%.Dense spent acid mainly adopts concentration systems to concentrate aftertreatment, ferrous sulfate crystallization occluding device in concentration process, dilute sulphuric acid is large to equipment corrosion simultaneously, the facility investment of high temperature concentration systems is very large, current such spent acid is mainly with lime white or calcite neutralization, aeration oxidation, filters rear processing mode of discharging, it is large that this processing mode exists wastewater treatment difficulty, and produce a large amount of GYPSUM RUBRUM slag waste materials, the problem that these GYPSUM RUBRUM slag waste materials are difficult to process simultaneously.
Process white (BaSO
4) be a kind of broad-spectrum industrial chemicals, although be a kind of simple inorganic raw material, its purposes is comparatively special, existing market demand is increasing, is widely used in plastics, coating, ink etc. in industry, can replace part titanium white powder pigment simultaneously.The traditional processing technology of process white is to adopt process white method: will after barium carbonate and sulfuric acid reaction, after washing-dry-art breading such as pulverizing, make.Because its added value of precipitation is low, production cost is high, and high-concentration sulfuric acid is participated in reaction directly and had higher danger.The technique of barium sulfate material produce is completely independent at present, and same existence requires the feature that material purity is high, factory effluent quantity discharged is large, wastewater treatment is difficult, and the cost of desired raw material is also higher.
Summary of the invention
In order to overcome existing shortcoming, the spent acid that the raw material barium carbonate of producing process white is produced with Titanium White Production By Sulfuric Acid Process reacts, and realizes the pre-processing of sulfuric acid method titanium pigment spent acid when producing process white.
The technical solution adopted for the present invention to solve the technical problems is:
Production principle of the present invention is as follows: utilize the solubleness of ferrous sulfate in sulfuric acid to reduce along with the raising of sulfuric acid concentration.
Sulfuric acid concentration 20-24% in sulfuric acid method titanium pigment spent acid, wherein ferrous sulfate content is 10-8%.Under temperature 25 degree, in pure water, the solubleness of ferrous sulfate reaches 13.2%, and under temperature 50 degree, in pure water, the solubleness of ferrous sulfate reaches 18%.
Concrete technology flow process of the present invention is as follows:
Step 1: under normal temperature (25 ° of C left and right) environment, add pure water to pull an oar and stir barium carbonate powder and obtain uniform barium carbonate solution;
Step 2: the spent acid producing in sulfuric acid method titanium pigment production process is imported in the reactive tank of production of precipitated barium carbonate equipment standby;
Step 3: the barium carbonate solution of step 1 joined gradually in the waste acid liquor in the reactive tank of step 2 and stir, constantly pH value determination is adjusted simultaneously, until the pH scope of surveying is stabilized between 1-1.5;
Step 4: keep temperature-resistant, the solution of step 2 is pulled an oar fast, filtered, obtain filtrate and filter residue;
Step 5: the filter residue that step 4 is obtained is dried, is precipitated barium sulfate powder;
Step 6: the filtrate that step 4 obtains is further filtered and purified, and obtains copperas solution.
In above-mentioned step 3, barium carbonate reacts with the sulfuric acid in spent acid, until sulfuric acid concentration is reduced to pH value between 1-1.5 in solution, because this reaction is thermopositive reaction, temperature at least 30 degree (55 ° about C) that can rise after reaction, therefore the solubleness of the ferrous sulfate in spent acid can improve, and ferrous sulfate can crystallization, but dissolves completely.
The filter residue that the present invention produces is process white, and after filtration washing, sampling filter residue is dried and then detects whiteness.For improving whiteness, the filtration washing of filter residue repeatedly can being pulled an oar, till reaching required whiteness product.
The filtration washing of repeatedly pulling an oar in above-mentioned step 4 is again to filter and use a certain amount of water washing filter residue simultaneously after adding certain water gaging to stir filter residue, and this process can repeatable operation.
The solution that contains ferrous sulfate that the molar content that the filtrate of above-mentioned step 6 gained is sulfate ion is 1-2%, this solution ferrous sulfate purity is high, can concentrate that to prepare high-purity sulfuric acid ferrous or for the preparation of other molysite material, as red iron oxide, iron oxide yellow etc.
Barium carbonate in step 1 can be used other barium salt bag, such as hydrated barta, barium bicarbonate etc.
Process white grain size intervals prepared by the present invention is narrow, fine size, whiteness are high, because barium ion is by a large amount of soluble ion precipitations in raw material, titanium ion in spent acid is also precipitated as titanium dioxide, further improved the whiteness of process white, there is optimized production process, reduce production costs, reduce the feature of wastewater discharge, minimizing overall investment.
Accompanying drawing explanation
Fig. 1 is the particle size distribution figure of the synthetic process white of the present invention.
Embodiment
By following examples, can further set forth the present invention, but the present invention is not only confined to following examples.
By certain titanium powder plant spent acid sulfuric acid content 21%, ferrous sulfate content 8.3%.Under agitation add in the slurry of 100g barium carbonate, detect its pH value, pH stops acid adding at 1 o'clock.Filter, use 100ml water washing, after sampling is dry, detect dry powder whiteness and reach 94.3.With 200ml water, will after filter residue making beating, filter and use 100ml water washing, after sampling is dry, detecting dry powder whiteness and reach 98.2.Detecting granularity D (50) is that 0.325um, D (100) are 4.60um,, BaSO4 content reaches 98.7%, reaches process white premium grads level.
Filtrate is detected sulfuric acid content 1.4%, and spent acid intractability reduces much relatively before, and has reduced processing cost and reduced a large amount of waste residue amounts.
By certain titanium powder plant spent acid sulfuric acid content 21%, ferrous sulfate content 8.3%.Under agitation add in the slurry of 100g barium carbonate, detect its pH value, pH stops acid adding at 4 o'clock.Filter, use 100ml water washing, after sampling is dry, detect dry powder whiteness and reach 86.4.With 200ml water, will after filter residue making beating, filter and use 100ml water washing, after sampling is dry, detecting dry powder whiteness and reach 91.5.BaSO
4content reaches 95%, does not reach process white premium grads level.
Reason is acidity too low (pH is 4) after reaction, and ferrous ion is hydrolyzed into ferrous hydroxide crystallization and is deposited in BaSO4 product, affects product whiteness.
Claims (5)
1. the spent acid of pre-treatment sulfuric acid method titanium pigment is prepared a technique for process white, and its step is as follows:
Step 1: under normal temperature (25 ° of C left and right) environment, add pure water to pull an oar and stir in soluble barium salt's powder and obtain uniform barium carbonate solution;
Step 2: the spent acid producing in sulfuric acid method titanium pigment production process is imported in the reactive tank of production of precipitated barium carbonate equipment standby;
Step 3: the barium carbonate solution of step 1 joined gradually in the waste acid liquor in the reactive tank of step 2 and stir, constantly pH value determination is adjusted simultaneously, until the pH scope of surveying is stabilized between 1-1.5;
Step 4: keep temperature-resistant, the solution of step 2 is pulled an oar fast, filtered, obtain filtrate and filter residue;
Step 5: the filter residue that step 4 is obtained is dried, is precipitated barium sulfate powder;
Step 6: the filtrate that step 4 obtains is further filtered and purified, and obtains copperas solution.
2. the spent acid of pre-treatment sulfuric acid method titanium pigment according to claim 1 is prepared the technique of process white, it is characterized in that: described filter residue is for filtering and washing through repeatedly pulling an oar.
3. the spent acid of pre-treatment sulfuric acid method titanium pigment according to claim 1 is prepared the technique of process white, it is characterized in that: the soluble barium salt in described step 1 is barium carbonate.
4. the spent acid of pre-treatment sulfuric acid method titanium pigment according to claim 1 is prepared the technique of process white, it is characterized in that: the soluble barium salt in described step 1 is hydrated barta.
5. the spent acid of pre-treatment sulfuric acid method titanium pigment according to claim 1 is prepared the technique of process white, it is characterized in that: the soluble barium salt in described step 1 is barium bicarbonate.
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| CN201310448564.7A CN103663536A (en) | 2013-09-28 | 2013-09-28 | Process for preparing precipitated barium sulfate by pretreatment of waste acid of sulfuric acid process titanium dioxide |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113462198A (en) * | 2021-08-12 | 2021-10-01 | 佛山集美精化科技有限公司 | Method for preparing composite titanium dioxide by barium sulfate coprecipitation method |
| CN115806745A (en) * | 2022-11-22 | 2023-03-17 | 云浮鸿志新材料有限公司 | Composite nano transparent iron oxide red and preparation method thereof |
| CN118307023A (en) * | 2024-04-08 | 2024-07-09 | 广东尚宸环境科技有限公司 | Method and treatment system for recycling titanium dioxide waste acid by sulfuric acid process |
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| CN1381406A (en) * | 2001-04-18 | 2002-11-27 | 宋康尧 | Process for using barium carbonate to treat high-content slfuric acid radicals in saline |
| CN1473760A (en) * | 2003-07-01 | 2004-02-11 | 沈阳化工股份有限公司 | Method for removing sulfuric radical from brine with barium carbonate |
| CN1765764A (en) * | 2004-10-25 | 2006-05-03 | 郭胜 | Method for treating copper-containing waste acid water |
| CN102115209A (en) * | 2010-12-31 | 2011-07-06 | 谢善情 | Method for producing ferrous nitrate and barium sulfate by using waste acid obtained by producing titanium white by sulfuric acid method |
| CN102795701A (en) * | 2012-08-16 | 2012-11-28 | 胡治邠 | Method for treating acidic waste water from titanium dioxide preparation by sulfuric acid method |
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2013
- 2013-09-28 CN CN201310448564.7A patent/CN103663536A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1381406A (en) * | 2001-04-18 | 2002-11-27 | 宋康尧 | Process for using barium carbonate to treat high-content slfuric acid radicals in saline |
| CN1473760A (en) * | 2003-07-01 | 2004-02-11 | 沈阳化工股份有限公司 | Method for removing sulfuric radical from brine with barium carbonate |
| CN1765764A (en) * | 2004-10-25 | 2006-05-03 | 郭胜 | Method for treating copper-containing waste acid water |
| CN102115209A (en) * | 2010-12-31 | 2011-07-06 | 谢善情 | Method for producing ferrous nitrate and barium sulfate by using waste acid obtained by producing titanium white by sulfuric acid method |
| CN102795701A (en) * | 2012-08-16 | 2012-11-28 | 胡治邠 | Method for treating acidic waste water from titanium dioxide preparation by sulfuric acid method |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113462198A (en) * | 2021-08-12 | 2021-10-01 | 佛山集美精化科技有限公司 | Method for preparing composite titanium dioxide by barium sulfate coprecipitation method |
| CN115806745A (en) * | 2022-11-22 | 2023-03-17 | 云浮鸿志新材料有限公司 | Composite nano transparent iron oxide red and preparation method thereof |
| CN115806745B (en) * | 2022-11-22 | 2023-09-29 | 云浮鸿志新材料有限公司 | Composite nano transparent iron oxide red and preparation method thereof |
| CN118307023A (en) * | 2024-04-08 | 2024-07-09 | 广东尚宸环境科技有限公司 | Method and treatment system for recycling titanium dioxide waste acid by sulfuric acid process |
| CN118307023B (en) * | 2024-04-08 | 2024-10-18 | 广东尚宸环境科技有限公司 | Method and treatment system for recycling titanium dioxide waste acid by sulfuric acid process |
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Application publication date: 20140326 |