CN101618864A - Method for recycling waste product and by-product in sulfuric acid method titanium dioxide production - Google Patents
Method for recycling waste product and by-product in sulfuric acid method titanium dioxide production Download PDFInfo
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- CN101618864A CN101618864A CN200810132926A CN200810132926A CN101618864A CN 101618864 A CN101618864 A CN 101618864A CN 200810132926 A CN200810132926 A CN 200810132926A CN 200810132926 A CN200810132926 A CN 200810132926A CN 101618864 A CN101618864 A CN 101618864A
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Abstract
The invention relates to a method for recycling the waste product and by-product in sulfuric acid method titanium dioxide production which adopts a forced circulation system which contains a sulfuric acid circulating pump, a cooler and recycle acid pipelines to cool and mix sulfuric acid, and combines the processes of refrigeration, purification and preparation of concentrated sulfuric acid in the sulfuric acid method titanium dioxide production to only one process through filtration, thus greatly simplifying the production process and reducing the production cost and investment. Because the invention adopts big flow forced circulation technology, the temperature of circulating sulfuric acid and the temperature difference are lower so that the demand to the material of the sulfuric acid circulating pump is reduced and the service life is prolonged; besides, the flow velocity on the sulfuric acid side of the cooler in the forced circulation technology is higher so that the scaling forming speed on the sulfuric acid side of the cooler is slower and the operation rate is higher. The invention solves the problems of the sulfuric acid method titanium dioxide production that the flows of refrigeration, purification and preparation of concentrated sulfuric acid are long, the investment is large, the operation rate is low, the production cost and the maintenance cost are high and the like, and the obtained economic benefit is remarkable.
Description
Affiliated technical field
The present invention relates to the method that the useless byproduct of sulfuric acid method titanium pigment production is recycled, specifically, the invention provides method cooling, removal of impurities and the preparation of the concentrated vitriol liquid of association in the Titanium White Production By Sulfuric Acid Process.
Background technology
At present, the sustainable growth demand of the white pigment of global performance excellence---titanium dioxide is mainly provided by sulfuric acid process and two kinds of products of chlorination process, chloride process titanium dioxide powder production technology is praised highly and is monopolized with " cleaning procedure " by western developed country, and sulfuric acid process has advantages such as sufficient raw and production cost be low, therefore, at present and even in one quite long in the future period, Titanium White Production By Sulfuric Acid Process technology in China's titanium white powder industry all with dominate.
Must consume a large amount of industrial sulphuric acids in the Titanium White Production By Sulfuric Acid Process and produce, when consuming a large amount of industrial sulphuric acids, self produce a large amount of rare sulfur waste acid again, the concentration of this spent acid solution is about the H2SO4 of 15～25% (weight).At present, people are just by reclaiming spent acid and being converted into useful material or product changes environmental protection condition, make great efforts to make Production By Sulfuric Acid Process technology that the influence of environment is made no distinction of rank with chlorination process gradually, therefore, how the rare sulfur waste acid that self produces is carried and be reused for acidolysis process or export trade after dense other consumes sour enterprise, reduce titanium white production consumption and cost, reduce three waste discharge simultaneously, realize scientific development, become the problem that China's titanium white powder industry is competitively studied at present.
Rare useless vitriolic reclaims and must realize by various concentration method.At present, rare sulfur waste acid of domestic titanium white production enterprise concentrates adopts mostly that segmentation concentrates, the technology of segmentation removal of impurities, to solve problems such as equipment corrosion, fouling obstruction, energy consumption height.According to requirement difference with sour quality, concentrate also differently with the hop count of removal of impurities, the rarest one section, there are three sections at most.
Sulfuric acid after concentrating is general also to need processing through three steps just can be reused for the hydrolysis procedure of sulfuric acid method titanium pigment production process or other consumes sour enterprise.These three steps are: slaking is cooled off with concentrated vitriol by the first step, elder generation, filters with pressure filter then, removes the solid crystal thing based on ferrous sulfate monohydrate wherein; Second goes on foot, concentrated vitriol is mixed with industrial sulphuric acid, makes the sulfuric acid that meets processing requirement concentration; After mixing, the 3rd step, two kinds of acid can further separate out the solid crystal thing of a part based on ferrous sulfate monohydrate, meanwhile produce a large amount of mixture heat, the sulfuric acid temperature is raise, therefore also need mixing sulfuric acid is cooled off slaking again, and then, remove solid crystal thing wherein based on ferrous sulfate monohydrate with the pressure filter filtration.
Be not difficult to find out, the cooling of existing concentrated vitriol, removal of impurities and preparation process are long, invest bigger, driving rate is low, the cost of producing maintenance and organization and administration is also inevitable higher, this is at Global Competition aggravation and environmental requirement height and under the more and more lower pressure of titanium dioxide price, enterprise makes product lose the advantage of self in competition often owing to bearing more and more higher working cost.
Summary of the invention
Therefore, to be that exploitation is a kind of significantly reduce cost and save the treatment of investment method task of the present invention, by adopting big forces traffic circulation technology, realization is to the economic recovery of the spent acid solution of association when the Titanium White Production By Sulfuric Acid Process, again be used in hydrolysis procedure, or sending the absorption operation work of sulfuric acid production plant to absorb acid, other consumes sour enterprise also to can be used as the finished acid export trade.
According to the present invention, the above-mentioned task technical scheme of step embodiment by the following method solves.
The method that the useless byproduct of sulfuric acid method titanium pigment production of the present invention is recycled, at first, will from the spent acid concentrating unit without cooling, the concentrated vitriol of removal of impurities is directly delivered to water cooler circulation cooling, add industrial sulphuric acid simultaneously at refrigerative, employing is by the sulfuric acid recycle pump, the big forces traffic recycle system that water cooler and recycle acid pipeline are formed is cooled off in cooling circuit these two kinds of sulfuric acid and is mixed, heat of being brought into by concentrated vitriol and industrial sulphuric acid mix the heat that the produces water that is cooled and remove in the lump, then, the sulfuric acid that is cooled that will contain the solid crystal thing is under the pressure effect of recycle acid pipeline, automatically discharge a part and be pumped to the pressure filter filtering and impurity removing, the filter-press residues that finally filters out send ferrous retrieving arrangement; The sulfuric acid that filters out carries pumping with sour device or export trade by sulfuric acid.
Above-mentioned cooling, removal of impurities and three operations of press filtration configuration are combined into an operation by described forced circulation system.Wherein said sulfuric acid recycle pump adopts the propeller pump or the mixed of big flow, low lift.
Described from the spent acid concentrating unit without the concentration of concentrated vitriol of cooling, removal of impurities in 24%～75% scope.Described in the scope of concentration 92%～98.5% of the industrial sulphuric acid that refrigerative adds simultaneously.Described mixed low temperature sulfuric acid concentration is controlled at 45%～92% according to the difference with sour quality, and mixed sulfuric acid is removed heat through the water cooler water that is cooled, and the temperature maintenance that makes recycle acid is at 55～65 ℃.
Method of the present invention mainly has following advantage:
1, the present invention is combined into an operation with cooling, removal of impurities and three operations of preparation of concentrated vitriol in the sulfuric acid method titanium pigment production, has simplified Production Flow Chart greatly, has reduced investment and production run cost.
2, the present invention adopts big forces traffic circulation technology, because the pressure filter use temperature requires to be controlled at about 60 ℃, makes that the temperature of recycle sulfuric acid is lower, its temperature difference is less, significantly reduced material requirement, prolonged its work-ing life, and the production maintenance cost significantly reduces the sulfuric acid recycle pump.
3, owing to adopt big forces traffic circulation technology, the flow velocity of water cooler sulfuric acid one side is higher, make the speed of water cooler sulfuric acid one side fouling significantly reduce, so driving rate is than the obvious raising of prior art.
4, the present invention adopts the sulfuric acid recycle pump of big flow, low lift, and its lift only need overcome resistance loss of pipeline and get final product, and therefore, motor power consumption significantly reduces, and the sulfuric acid recycle pump can directly be selected propeller pump or mixed for use.
Method of the present invention well solved sulfuric acid method titanium pigment produce in concentrated vitriol cooling, removal of impurities and preparation process is tediously long, the investment big, problems such as driving rate is low, production maintenance cost height, the qualified sulfuric acid that makes by the inventive method is good quality not only, and environmental friendliness, can be reused for the hydrolysis procedure of sulfuric acid method titanium pigment production equipment, or sending the absorption operation work of sulfuric acid production plant to absorb acid, other consumes sour enterprise also to can be used as the finished acid export trade.Through evidence, economic benefit of the present invention is very remarkable.Sulfate process titanium dioxide device with 60,000 tons/year of industrial scales of cover is an example, and can save production cost more than 1,080,000 yuan every year, saves production cost and expense specifically sees table.
| Sequence number | Project | The amount of money | Unit | Remarks |
| ??1 | The electricity charge | ??403,200.00 | Unit/year | 0.5 unit/kwh |
| ??2 | Manually | ??180,000.00 | Unit/year | 1.5 ten thousand yuan/people. year |
| ??3 | Asset depreciation | ??300,000.00 | Unit/year | Depreciation in 10 years |
| ??4 | Maintenance of equipment | ??200,000.00 | Unit/year | |
| Add up to | ??1,083,200.00 | Unit/year |
Description of drawings
Fig. 1 is the workflow diagram of cooling, removal of impurities and the compound method embodiment of concentrated vitriol of the present invention.
Embodiment
Referring to Fig. 1, the sulfuric acid forced circulation system that the inventive method adopts specifically comprises big forces traffic circulation loop and control, the display instrument etc. that water cooler, sulfuric acid recycle pump, recycle acid pipeline constitute.Because the present invention adopts the sulfuric acid recycle pump of big flow, low lift, its lift only need overcome resistance loss of pipeline and get final product, and therefore, motor power consumption significantly reduces, and the sulfuric acid recycle pump can directly be selected propeller pump or mixed for use.Control, display instrument comprise vitriolic acid flux meter, sulfuric acid thermometer, cooling water temperation gauge etc.Method of the present invention both can directly have been carried out detailed improvement project design and construction on existing sulfuric acid method titanium pigment Production Flow Chart basis, also can directly include detailed engineering design and construction on the newly-built titanium dioxide device of planning and design and design from now on.
Below in conjunction with the schema of embodiment shown in the drawings, illustrate the technical process and the significant parameter of cooling, removal of impurities and the compound method of concentrated vitriol of the present invention.
Embodiment 1
At first, will sending in the lump in the pipeline of forced circulation system from the spent acid concentrating unit without 30% concentrated vitriol of cooling, removal of impurities and 98% industrial sulphuric acid, mix with big flow, low temperature sulfuric acid in the circulation line, mixed sulfuric acid concentration is controlled at 55%, mixed sulfuric acid is removed heat through the water cooler water that is cooled, make the recycle acid temperature maintenance at 60 ℃, separate out the solid crystal thing of a part simultaneously again based on ferrous sulfate monohydrate at the mixing refrigerative.The sulfuric acid that is cooled is discharged a part of sulfuric acid in sulfuric acid storage tank A automatically under the pressure effect of circulation line.
Then, the cooling sulfuric acid that sulfuric acid transferpump A will contain the solid crystal thing is exported and is sent into pressure filter and filters from sulfuric acid storage tank A, and the filter-press residues that filters out send ferrous retrieving arrangement; The sulfuric acid that filters out drops down the storage to sulfuric acid storage tank B, send with sour device or export trade by sulfuric acid transferpump B at last.
Test shows, adopts method of the present invention can reach the technical indicator shown in the following table.
| Sequence number | The index project | Index |
| ??1 | Concentrated vitriol concentration | ??30％ |
| ??2 | Industrial sulphuric acid concentration | ??98％ |
| ??3 | The sulfuric acid melting concn | ??55％ |
| ??4 | The concentrated vitriol flow, kg/h | ??6324 |
| ??5 | The industrial sulphuric acid flow, kg/h | ??3676 |
| ??6 | The mixing acid total flux, kg/h | ??10000 |
| ??7 | The recycle acid flow, m3/h | ??650 |
| ??8 | The recycle acid temperature, ℃ | ??60 |
Embodiment 2
At first, will sending in the lump in the pipeline in pump circulation loop from the spent acid concentrating unit without 55% concentrated vitriol of cooling, removal of impurities and 98% industrial sulphuric acid, mix with big flow, low temperature sulfuric acid in the circulation line, mixed sulfuric acid concentration is controlled at 91%, mixed sulfuric acid is removed heat through the water cooler water that is cooled, make the recycle acid temperature maintenance at 55 ℃, separate out the solid crystal thing of a part simultaneously again based on ferrous sulfate monohydrate at the mixing refrigerative.The sulfuric acid that is cooled is discharged a part of sulfuric acid in sulfuric acid storage tank A automatically under the pressure effect of circulation line.
Then, the cooling sulfuric acid that sulfuric acid transferpump A will contain the solid crystal thing is exported and is sent into pressure filter and filters from sulfuric acid storage tank A, and the filter-press residues that filters out send ferrous retrieving arrangement; The sulfuric acid that filters out drops down the storage to sulfuric acid storage tank B, send with sour device or export trade by sulfuric acid transferpump B at last.
Test shows, adopts method of the present invention can reach the technical indicator shown in the following table.
| Sequence number | The index project | Index |
| ??1 | Concentrated vitriol concentration | ??55％ |
| ??2 | Industrial sulphuric acid concentration | ??98％ |
| ??3 | The sulfuric acid melting concn | ??91％ |
| ??4 | The concentrated vitriol flow, kg/h | ??1628 |
| ??5 | The industrial sulphuric acid flow, kg/h | ??8372 |
| ??6 | The mixing acid total flux, kg/h | ??10000 |
| ??7 | The recycle acid flow, m3/h | ??650 |
| ??8 | The recycle acid temperature, ℃ | ??55 |
Embodiment 3
At first, will sending in the lump in the pipeline of forced circulation system from the spent acid concentrating unit without 70% concentrated vitriol of cooling, removal of impurities and 93% industrial sulphuric acid, mix with big flow, low temperature sulfuric acid in the circulation line, mixed sulfuric acid concentration is controlled at 80%, mixed sulfuric acid is removed heat through the water cooler water that is cooled, make the recycle acid temperature maintenance at 65 ℃, separate out the solid crystal thing of a part simultaneously again based on ferrous sulfate monohydrate at the mixing refrigerative.The sulfuric acid that is cooled is discharged a part of sulfuric acid in sulfuric acid storage tank A automatically under the pressure effect of circulation line.
Then, the cooling sulfuric acid that sulfuric acid transferpump A will contain the solid crystal thing is exported and is sent into pressure filter and filters from sulfuric acid storage tank A, and the filter-press residues that filters out send ferrous retrieving arrangement; The sulfuric acid that filters out drops down the storage to sulfuric acid storage tank B, send with sour device or export trade by sulfuric acid transferpump B at last.
Test shows, adopts method of the present invention can reach the technical indicator shown in the following table.
Claims (6)
1, the method for the useless byproduct recycling of a kind of sulfuric acid method titanium pigment production comprises:
A) will directly deliver to water cooler circulation cooling from the concentrated vitriol without cooling, removal of impurities of spent acid concentrating unit,
B) add industrial sulphuric acid simultaneously at refrigerative, the forced circulation system that employing is made up of sulfuric acid recycle pump, water cooler and recycle acid pipeline is cooled off in cooling circuit these two kinds of sulfuric acid and is mixed,
C) the recycle acid pipeline of the sulfuric acid that is cooled under the pressure effect that will contain the solid crystal thing discharged a part automatically and pumped into the pressure filter filtering and impurity removing,
D) filter-press residues that filters out send ferrous retrieving arrangement; The sulfuric acid that filters out carries pumping with sour device or export trade by sulfuric acid.
2, according to step a), the b that the process of claim 1 wherein), c) described cooling, removal of impurities and three operations of press filtration configuration are combined into an operation by described forced circulation system.
3, method according to claim 1 and 2, wherein step a) described from the spent acid concentrating unit without the concentration of concentrated vitriol of cooling, removal of impurities in the scope of 24%-75%.
4, method according to claim 1 and 2, wherein the concentration of the described industrial sulphuric acid of step b) is in the scope of 92%-98.5%.
5, method according to claim 1 and 2, wherein the described mixed low temperature sulfuric acid concentration of step b) is controlled at 45%-92% according to the difference with sour quality, mixed sulfuric acid is removed heat through the water cooler water that is cooled, and the temperature maintenance that makes recycle acid is at 55%-65 ℃.
6, method according to claim 1 and 2, wherein the described sulfuric acid recycle pump of step a) adopts the propeller pump or the mixed of big flow, low lift.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102557128A (en) * | 2010-12-07 | 2012-07-11 | 河南佰利联化学股份有限公司 | Novel production process of titanium dioxide powder |
| CN113479853A (en) * | 2021-08-17 | 2021-10-08 | 浙江旗创科技集团有限公司 | Printing plate oxidation process sulfuric acid recycling equipment |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1171777C (en) * | 2002-01-25 | 2004-10-20 | 吉林市吉研高新技术开发公司 | Process for recovering waste acid in producing titanium white powder by sulfuric acid method |
| CN100369804C (en) * | 2006-05-29 | 2008-02-20 | 冶金部建筑研究总院上海分院 | Regenerating acid method by sulfuric acid substitution |
| CN101157447B (en) * | 2007-09-12 | 2010-09-01 | 合肥泰诺化工科技有限公司 | Method for removing ferrous and other metal salt from titanium white waste acid |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102557128A (en) * | 2010-12-07 | 2012-07-11 | 河南佰利联化学股份有限公司 | Novel production process of titanium dioxide powder |
| CN102557128B (en) * | 2010-12-07 | 2014-05-07 | 河南佰利联化学股份有限公司 | Novel production process of titanium dioxide powder |
| CN113479853A (en) * | 2021-08-17 | 2021-10-08 | 浙江旗创科技集团有限公司 | Printing plate oxidation process sulfuric acid recycling equipment |
| CN113479853B (en) * | 2021-08-17 | 2024-04-19 | 浙江旗创科技集团有限公司 | Sulfuric acid recycling equipment for oxidation process of printing plate |
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Owner name: XIANGYANG LONGMANG TITANIUM INDUSTRY CO., LTD. Free format text: FORMER OWNER: SICHUAN LOMON TITANIUM INDUSTRY CO., LTD. Effective date: 20130226 |
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Effective date of registration: 20130226 Address after: 441500, Hubei County, Nanzhang Province Chengguan Town Road No. 1 Patentee after: XIANGYANG LOMON TITANIUM INDUSTRY CO., LTD. Address before: 618200 industrial concentration area of Sichuan, Mianzhu Patentee before: Sichuan Lomon Titanium Industry Co., Ltd. |