CN1171777C - Process for recovering waste acid in producing titanium white powder by sulfuric acid method - Google Patents
Process for recovering waste acid in producing titanium white powder by sulfuric acid method Download PDFInfo
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- CN1171777C CN1171777C CNB02109098XA CN02109098A CN1171777C CN 1171777 C CN1171777 C CN 1171777C CN B02109098X A CNB02109098X A CN B02109098XA CN 02109098 A CN02109098 A CN 02109098A CN 1171777 C CN1171777 C CN 1171777C
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Abstract
The present invention relates to a method for recovering waste acid in titanium white powder production by a sulfuric acid method. A gas-liquid separation type non-volatile solution concentrating device is used for concentration. The method orderly comprises following steps: firstly, precipitation pretreatment is carried out on waste acid, and solid titanium is separated and recovered; the waste acid treated by precipitation is preconcentrated, the temperature is controlled at 50 to 60 DEG C, when the concentration of the preconcentrated waste acid is from 40 to 50%, the preconcentration is stopped; the preconcentrated waste acid is filtered; filter liquor is transferred into the concentrating device and is concentrated at the temperature of 65 to 75 DEGC, and the concentrated acid is obtained. The present invention removes the bulk of solid titanium and inorganic salts in the waste acid by the treating and preconcentrating process and solves the problem of the titanium white powder production that the concentrating device can be seriously blocked by the impurities of the solid titanium, the inorganic salts, etc.; thereby, the concentrated acid of a high concentration (more than 70%) can be obtained in the concentration process, and the concentrated acid can be completely recovered and used.
Description
Technical field
The present invention relates to recovering waste acid method in a kind of sulfuric acid method titanium pigment production.
Background technology
The method of producing titanium dioxide at present has sulfuric acid process and chlorination process, sulfuric acid process has advantages such as sufficient raw, production cost be low, but produce a large amount of sulfur waste acid in its production process, if not treated direct discharging, can pollute environment, if it is improper that treatment process is selected, can increase considerably production cost.
A kind of common useless vitriolic treatment process is that this method is not only wasted resource, produced a large amount of waste residues, spends huge processing costs, and causes secondary pollution with the discharging of in the lime and back.Another kind method is to concentrate the back with useless dilute sulphuric acid to make phosphate fertilizer, but complex process, cost height react slow and insufficient, and the phosphate fertilizer quality is low, though the improved method (CN1101637A) that adds catalyzer is arranged at present, the application on spent acid is handled in sulfuric acid method titanium pigment production is restricted.
Nittetsu Mining Co., Ltd. discloses a kind of method (CN1113081A) that reclaims containing metal vitriol spent acid.This method is removed titanium in the spent acid with the solvent extraction facture, and the solution that extraction is obtained carries out diffusion dialysis and handles then.This method complex technical process, and when removing impurity, introduced new impurity---organic solvent, although can be removed by the method for activated carbon adsorption, increased processing cost on the one hand, caused new difficulty for the reuse of spent acid on the other hand.
Patent CN87211261U discloses the non-volatile solution condensing device of a kind of gas-liquid separation type, is applicable to the processing of food, pharmacy, chemical industry, particularly electroplating effluent.But when this device is applied to the recovering waste acid of generation in the sulfuric acid method titanium pigment production, but run into very big obstacle.This be because this spent acid solution in except that the sulfuric acid that contains about 20%, also contain a large amount of solid shape titaniums, inorganic salt plurality of impurities such as (vitriol of iron, calcium, magnesium and silicate).If these impurity are not removed, when just being difficult to satisfy the gelled acid reuse to the requirement of foreign matter content.Even more serious is, if carrying out spent acid, this device of simple application concentrates, then can in concentration process, produce a large amount of inorganic salt, when solids reaches certain ratio (as more than 1/3～1/2) in acid solution after, parts such as shower nozzle, leafy ball or Bao Erhuan, separation guide plate group and separate mesh in the device all can block, and concentrating unit promptly can't continue operation.Simultaneously,, then in concentration process, can produce a large amount of gluey hydrolyzates, cause salt originally can't effectively separate, in fact can not get gelled acid let alone reuse with acid group as the content of solid shape titanium in the spent acid not being controlled.
Summary of the invention
For solving the problems referred to above of prior art, the present invention proposes the method for the spent acid that produces in a kind of efficient recovery sulfuric acid method titanium pigment production.
The present invention adopts the non-volatile solution condensing device of gas-liquid separation type to concentrate, and this method may further comprise the steps successively:
A. spent acid is precipitated pre-treatment earlier, separate and the solid shape titanium of recovery;
B. carry out pre-concentration through precipitating pretreated spent acid, temperature is controlled at 50-60 ℃, when acid-spending strength behind the pre-concentration is 40-50%, stops pre-concentration;
C. filter through the spent acid behind the pre-concentration;
D. above-mentioned filtrate is sent in the concentrating unit and under 65-75 ℃, concentrated, obtain gelled acid.
Spent acid also can first crystallization and filtration behind the pre-concentration of mentioning in the above-mentioned recovery method.
Mention in the above-mentioned recovery method gelled acid also can filter.
The preferred 70-75 of the thickening temperature of mentioning in the above-mentioned recovery method ℃.
Realize that concrete steps of the present invention are as follows successively:
A, precipitation pre-treatment: from spent acid (the major impurity content: iron 30～45g/l in the sulfuric acid method titanium pigment production; Calcium, each 2～8g/l of magnesium; Gu shape titanium 0.3～2.5g/l also has a spot of aluminium, vanadium etc.) through post precipitation, most of solid shape titanium is assembled recovery by sedimentation, obtains the spent acid of solid shape titanium content 0.2～0.5g/l.
B, pre-concentration: will send into the non-volatile solution condensing device of gas-liquid separation type and carry out pre-concentration through precipitating pretreated spent acid, control pre-concentration temperature be at 50 ℃～60 ℃, preferred 55-60 ℃.(preferred 44-50%) stops to concentrate when acid concentration reaches 40-50%.
C, filtration: will filter (can first crystallization and filtration) through the spent acid of pre-concentration, remove wherein a large amount of inorganic salt (vitriol and silicate, the aluminate etc. that comprise iron, calcium, magnesium) and a spot of solid shape titanium hydrolyzate, obtain filtrate.
D, concentrated: above-mentioned filtrate further adopts the non-volatile solution condensing device of gas-liquid separation type to concentrate.Temperature is controlled at 65-75 ℃, and preferred 70 ℃～75 ℃, obtain gelled acid concentration greater than 70% o'clock, stop to concentrate.Or can further gelled acid be sent into strainer, and leach small amounts of inorganic salt (major ingredient is the ferrous sulfate monohydrate) wherein, obtain the higher gelled acid of purity.Gained gelled acid and 98% industrial sulphuric acid are mixed, the hydrolyzing process reuse in producing to sulfuric acid method titanium pigment.The inorganic salt that reclaim carry out the health heap and bury.
The inorganic salt content that produces during sulfuric acid method titanium pigment is produced in the spent acid adopts aas determination, Gu the shape titanium content adopts titration measuring.
Improvement of the present invention is, produce the characteristics that contain a large amount of shape titaniums admittedly and inorganic salt in the spent acid at sulfuric acid method titanium pigment, earlier through precipitating and isolating most of solid shape titanium, carry out pre-concentration and filtration (or first crystallization and filtration) again, remove most of inorganic salt and a spot of solid shape titanium hydrolyzate, at last spent acid is carried densely, the gelled acid that obtains is back to the hydrolyzing process of titanium white production.Simultaneously, because the concentration of red-tape operati temperature and pre-concentration acid has suppressed the generation of hydrolyzate, make the inorganic salt strainability that generates in the preprocessing process good, be easy to from spent acid, separate, make spent acid through carrying the gelled acid that obtains high density after dense, can realize fully recovering.The present invention improves and also is: compare with the extraction desalination, the present invention need not to introduce organic solvent, has simplified technology, has reduced the reuse cost; Overcome the problem that prior art (CN 87211261U) exists in addition, the present invention is directed to the characteristics of the spent acid that is produced in the sulfuric acid method titanium pigment production, proposed to separate solid shape titanium, removed the method for inorganic salt and the generation of control condition inhibition hydrolyzate, realize that smoothly inorganic salt separate with spent acid, thereby the spent acid in the sulfuric acid method titanium pigment production can be concentrated to more than 70%, realize fully recovering.
Embodiment
Embodiment 1
1 ton in spent acid during sulfuric acid method titanium pigment produced (assay determination: sulfuric acid 20.70%, iron: 41.2g/l, calcium: 3.20g/l, magnesium: 6.51g/l, Gu the shape titanium: 1.42g/l) following operation:
The precipitation pre-treatment: above-mentioned spent acid enters and carries out the preliminary precipitation processing in the inclined-plate clarifying basin, reclaims Gu the shape titanium is assembled in the settling tank bottom by settlement action, and the spent acid that settling tank top obtains enters storage tank.Consolidating the shape titanium content in the spent acid after the precipitation pre-treatment is 0.50g/l after measured.
Pre-concentration: the spent acid in the storage tank through be pumped into heat exchanger heats to 55-60 ℃ after, enter injector by liquid-inlet pipe, make mist by shower nozzle, the droplet that proportion is heavier is fallen in the leafy ball or Bao Erhuan of filling in the solution vaporizer, pre-concentration acid basin is delivered in moisture gasification, the acid solution behind pre-concentration; The mist pearl that proportion is lighter enters gas-liquid separator, the separate mesh that is formed by stacking through the multilayer gauze and separate the absorption of guide plate group, and nationality gravity and compiling gas-liquid separator bottom is delivered to the sour basin of pre-concentration by pipeline.When conventional assay determination acid-spending strength is 49.3%, stop pre-concentration.There are a large amount of inorganic salt to separate out in the spent acid of pre-concentration acid this moment basin, and contain the hydrolyzate of the solid shape titanium of minute quantity.
Filter: the spent acid in the pre-concentration acid basin enters crystallizer, carries out vacuum filtration after the crystallization, obtains filtrate, and reclaims inorganic salt 200kg.
Concentrate: above-mentioned filtrate through be pumped to heat exchanger heats to 70-75 ℃ after, enter concentrating unit and carry dense (the same pre-concentration of step), when when conventional assay determination acid concentration is 70.7%, stop to concentrate.The gelled acid that obtains is carried out obtaining final gelled acid 203kg after the vacuum filtration, reclaim inorganic salt 60kg.This gelled acid and 98% industrial sulphuric acid are mixed, and enter into the hydrolyzing process reuse that sulfuric acid method titanium pigment is produced.
Product result: measure by analysis that inorganic salt content is 2.64% (wherein ferrous sulfate 2.17%) in the product gelled acid.It is dense that 1 ton of spent acid is carried through above-mentioned technological process, can obtain 70.7% gelled acid 203kg, and common property is given birth to the 260kg inorganic salt, and the sulfuric acid yield can reach 69%.
Embodiment 2
1 ton of (assay determination: sulfuric acid 19.80% of spent acid during sulfuric acid method titanium pigment is produced, iron: 38.19g/l, calcium: 5.40g/l, magnesium: 7.17g/l, Gu shape titanium: 1.94g/l) enter and carry out pre-treatment in the vertical sedimentation tank, after the precipitation pre-treatment in the spent acid solid shape titanium content be determined as 0.50g/l by analysis.
Pre-concentration, filtration, enrichment step are with embodiment 1.But its processing condition are as follows:
The pre-concentration temperature is controlled at 50-55 ℃, measures acid-spending strength and is at 48.2% o'clock and stop pre-concentration; Thickening temperature is controlled at 70-75 ℃, measures acid concentration and is at 69.7% o'clock and stop to concentrate.
Product result: measure by analysis that inorganic salt content is 2.72% (ferrous sulfate 2.24%) in the product gelled acid.Acquisition concentration is 69.7% gelled acid 204kg, reclaims inorganic salt 265kg, and the sulfuric acid yield can reach 71%.
Claims (4)
1. recovering waste acid method during sulfuric acid method titanium pigment is produced, spent acid concentrates in the non-volatile solution condensing device of gas-liquid separation type, it is characterized in that this method may further comprise the steps successively:
A. spent acid is precipitated pre-treatment earlier, separate and the solid shape titanium of recovery;
B. carry out pre-concentration through precipitating pretreated spent acid, temperature is controlled at 50-60 ℃, when acid-spending strength behind the pre-concentration is 40-50%, stops pre-concentration;
C. filter through the spent acid behind the pre-concentration;
D. above-mentioned filtrate is sent in the concentrating unit and under 65-75 ℃, concentrated, obtain gelled acid.
2. method according to claim 1 is characterized in that the spent acid elder generation crystallization and filtration behind the pre-concentration.
3. method according to claim 1 is characterized in that the gelled acid that obtains is filtered.
4. method according to claim 1 is characterized in that thickening temperature wherein is 70-75 ℃.
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| CNB02109098XA CN1171777C (en) | 2002-01-25 | 2002-01-25 | Process for recovering waste acid in producing titanium white powder by sulfuric acid method |
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| CN1171777C true CN1171777C (en) | 2004-10-20 |
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Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1330562C (en) * | 2005-06-30 | 2007-08-08 | 武汉方圆钛白粉有限责任公司 | Process of industrialize for waste acid concentrition recovering used in titanium white production by sulfuric acid method |
| CN100581994C (en) * | 2008-01-09 | 2010-01-20 | 龚家竹 | Concentrating and impurity removing method for dilute sulfuric acid in titanium dioxide powder production process by employing sulfuric acid process |
| CN101538021B (en) * | 2008-03-20 | 2011-10-26 | 四川龙蟒钛业股份有限公司 | Method and device for producing concentrated sulfuric acid by recycling waste acid from sulfate process titanium dioxide production |
| CN101618864B (en) * | 2008-07-02 | 2011-06-29 | 四川龙蟒钛业股份有限公司 | Method for recycling waste product and by-product in sulfuric acid method titanium dioxide production |
| CN101759166B (en) * | 2009-12-31 | 2011-06-29 | 四川龙蟒钛业股份有限公司 | Method for pre-treating phosphorite by using acidic waste water in the production process of titanium pigment |
| CN101857203A (en) * | 2010-05-24 | 2010-10-13 | 东营方圆有色金属有限公司 | Process for comprehensively recycling heavy metal-polluted acid |
| CN101973530A (en) * | 2010-10-19 | 2011-02-16 | 河南佰利联化学股份有限公司 | Method for treating waste titanium dioxide acid |
| CN102424366B (en) * | 2011-09-05 | 2013-04-03 | 南通三圣石墨设备科技股份有限公司 | Titanium white waste sulfuric acid concentration method solving scaling and blocking of single-effect heat exchanger |
| CN102515114B (en) * | 2011-11-13 | 2016-08-31 | 山东鲁北企业集团总公司 | A kind of method that titanium white waste acid high level efficiently utilizes |
| CN103663547B (en) * | 2012-09-24 | 2015-09-23 | 上海凯鑫分离技术有限公司 | The process of acid waste water and recovery process in production process of titanium pigment |
| CN103172032A (en) * | 2013-03-27 | 2013-06-26 | 刘立文 | Method for decoloring sulfuric acid by using ultramicropore plastic plate |
| CN103351029B (en) * | 2013-05-31 | 2014-11-19 | 句容亿格纳米材料厂 | Method for processing waste liquid of titanium dioxide factory |
| CN104555948B (en) * | 2014-12-28 | 2017-07-14 | 贵州兰鑫石墨机电设备制造有限公司 | A kind of waste acid concentration technique |
| CN104773713B (en) * | 2015-04-09 | 2017-11-03 | 漳州市华威电源科技有限公司 | The acid-restoring plant and recovery method of a kind of lead-acid accumulator |
| CN107416776B (en) * | 2016-12-30 | 2020-04-24 | 新洋丰农业科技股份有限公司 | Waste acid treatment method for sulfur concentrate acid production |
| CN109368604A (en) * | 2018-10-24 | 2019-02-22 | 四川大学 | A kind of technique carrying out titanium white waste acid concentration by generating crystalline hydrate using principle is balanced each other |
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