CN106365197A - Recycling method of titanium dioxide waste acid - Google Patents
Recycling method of titanium dioxide waste acid Download PDFInfo
- Publication number
- CN106365197A CN106365197A CN201610789379.8A CN201610789379A CN106365197A CN 106365197 A CN106365197 A CN 106365197A CN 201610789379 A CN201610789379 A CN 201610789379A CN 106365197 A CN106365197 A CN 106365197A
- Authority
- CN
- China
- Prior art keywords
- washing
- filtrate
- bleaching
- titanium dioxide
- titanium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
- C01G23/0532—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing sulfate-containing salts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/08—Drying; Calcining ; After treatment of titanium oxide
Abstract
The invention discloses a recycling method of a titanium dioxide waste acid. The titanium dioxide waste acid comprises a second washing filtrate which is unwashed after the bleaching and a filter pressing filtrate before a calcining kiln, wherein the second washing filtrate which is unwashed after the bleaching is used for first washing pulping in the titanium dioxide producing process, and the filter pressing filtrate before the calcining kiln is used for second washing pulping. Using the second washing filtrate which is unwashed after the bleaching to conduct the first washing pulping achieves recycling of vitriol and trivalent titanium added in the bleaching process at the same time. Metatitanic acid second washing pulping water is provided by filter pressing filtrate before the calcining kiln, which can save salt treatment dose. Due to the fact that the temperature of the second washing filtrate is about 50 DEG C, which is higher than that of sand filter water, using the second washing filtrate to conduct the first washing pulping can also increase the temperature of the slurry before the bleaching so as to save steam.
Description
Technical field
The present invention relates in a kind of Rutile type titanium dioxide production process spent acid recycling method, particularly to one kind
The recycling method of filtrate in Rutile type titanium dioxide production process.
Background technology
Titanium dioxide is white inorganic pigment, and it is considered as most important Chinese white in the world, is widely used in coating, moulds
The fields such as material, papermaking, printing-ink, chemical fibre, rubber.The main composition of titanium dioxide is titanium dioxide, and TiO 2 pigment is producing
Most important effect in industry, is the opacity being dispersed in medium using it, thus reaching the effect of covering.
The industry production method of titanium dioxide has sulfuric acid process and two kinds of chloridising.Domestic at present it is most commonly that Production By Sulfuric Acid Process
Titanium dioxide, its step generally comprises titanium dioxide and carries out acidolysis reaction generation titanyl sulfate with concentrated sulphuric acid, through sedimentation, crystallization, hydrolysis
Produce metatitanic acid, metatitanic acid is washed, bleaches through one, two wash, salt treatment, calcining obtain Rutile type titanium dioxide titanium dioxide first product,
Titanium dioxide first product obtains titanium dioxide finished product through wet grinding, sand milling, the gentle powder of peplos.
During above-mentioned Titanium White Production By Sulfuric Acid Process, in order to improve the pigment performance of product, generally gained need to will be hydrolyzed
Metatitanic acid carries out washing, bleaches, two wash, and its purpose is to reduce to greatest extent iron content, improves product brightness and whiteness.Mesh
Front Sichuan Lomon Titanium Industry Co., Ltd. acidity wash water loop condition is as described in patent cn103274462a: acid wash water includes
Metatitanic acid one wash after produce acid wash water and metatitanic acid two wash after produce acid wash water, described metatitanic acid two wash after generation
An acid wash water part is for a washed journey of metatitanic acid；And the leading portion water of wash water needed for the washed journey of described metatitanic acid two is by inclined titanium
Acid two produces filtrate after washing the neutralized process of total acidic waste water washing generation with metatitanic acid one and provides.
And one washes and washes making beating water with two and all use sand filter water, company's hydrolysis terminates unwashed filtrate (washing filtrate) as special
It is used for company's sulfur-phosphorus-titanium Recycling Economy System titanium white waste acid pre-treating phosphorite technology, two washing filtrates described in sharp cn102674278a
Through thickener, cn filter, therebetween plus insoluble titanium is recycled to one and washes by flocculant, sulphuric acid, titanous spent acidic is contained in upper strata
Water discharges after going to sewage plant neutralisation treatment.
Existing company workshop bleaching sulphuric acid cost about 14,000,000 is annual, replaces one to wash making beating if a kind of sulfur-bearing acid solution can be found
Water, such as one wash water, 25% acid, 55% acid, two wash waters, two washing filtrates etc., both can be able to be dropped with saving water resource again
Sulfuric acid consumption during low bleaching, if this temperature of liquid is higher than sand filter water, can be with steam saving consumption.
Content of the invention
For the problems referred to above, provide a kind of recycling method of titanium white waste acid.
The technical solution used in the present invention is as follows:
A kind of recycling method of titanium white waste acid, described titanium white waste acid includes bleaching and terminates unwashed two washing filtrates
With filter pressing filtrate before calcining kiln, described bleaching terminates unwashed two washing filtrates and washes making beating in production process of titanium pigment one,
Before calcining kiln, filter pressing filtrate washes making beating for two.
As preferred: described bleaching terminates unwashed two washing filtrates and is completely used in production process of titanium pigment one and washes beating
Slurry.
Heretofore described bleaching terminates to contain substantial amounts of ferrous irons, sulphuric acid, titanous in unwashed two washing filtrates,
And ferrum is the impact topmost factor of production process of titanium pigment, because ferrum destroys titanium dioxide crystalline substance in metatitanic acid calcination process
Lattice, increase lattice defect, iron ion is coloring matter again simultaneously, and ferrum makes titanium dioxide finished product brightness and whiteness be greatly lowered,
Therefore inventor has carried out ferrum impact feasibility analysis to this technology.
Before taking company's workshop bleaching, slip is in laboratory sucking filtration, experimental data (as table 1).
Table 1
Draw from above-mentioned data analysiss: before drift slip after sucking filtration, in filtrate ferrum be filter before total ferrum 49% (average
Value), it is up to 69%, in filtrate, 75% calculating before filtering pressed by ferrum, and before the workshop drift of current company, average content of iron is 396ppm,
Be computed washing making beating with two washing filtrates one, final float before ferrum can increase to 2226ppm, increase this part ferrum to producing no shadow
Ring.
Formula proving is as follows:
Illustrate that n is ppm for iron content unit before bleaching, n subscript letter represents two washing filtrate cycle-indexes, and 3/4 represents drift
White slip after filter pressing, iron content proportion in filtrate.396 represent current company workshop average content of iron.
N1=396+396*3/4
N2=396+n1*3/4=396+ (396+396*3/4) * 3/4
N3=396+n2*3/4=396+ (396+ (396+396*3/4) * 3/4) * 3/4
Nx=[1+3/4* (1-3/4)(x-1)/(1-3/4)]*396+396*(3/4)(x-1)
If being pulled an oar with two washing filtrates, ferrum before bleaching is affected than two larger data: one washes cake iron content, and ferrum
Turnover rate, whole cyclic process, finally washed away through a wash water by the ferrum that two washing filtrate making beating are brought into.
Two washing filtrate detection sulphuric acid, titanous, and iron content between pick-up, data such as table 2:
Table 2:
Can be seen that two washing filtrate sulphuric acid meansigma methodss are 4.91% from above-mentioned data, if washing making beating with two washing filtrates one, 1 ton
tio2Need 1.1 tons of making beating water, titanium white powder yield presses 190,000 tons of calculating, and the annual sulphuric acid reclaiming is 190,000 tons of * 4.91%=9329
Ton, retrieval of sulfuric acid rate is about bleaches the 1/4 of sulphuric acid, is converted to ten thousand yuan of 98% acid value 9329/0.98*0.0428=407,
Sewage plant neutralizes 10832 tons of 470,000 yuan of carbide slags of this part of sulfuric acid value on demand simultaneously, simultaneously the average ferrum of filtrate in above-mentioned data
Content is less than iron content 415ppm before control form drift in workshop for 400ppm, and therefore this programme is feasible.
In sum, the invention has the beneficial effects as follows:
Terminate unwashed two washing filtrates to carry out washing making beating and also achieving in sulphuric acid and bleaching process adding with bleaching
Titanous recovery, avoid current company two washing filtrate through thickener simultaneously, cn filter, period adds flocculant by thick paste
It is recycled to one to wash, the traditional approach that upper strata acid waste water is directly arranged outward after going to sewage plant neutralisation treatment, saved cn filter
And flocculant, reduce sand filter water consumption, saved ton Producing Titanium Dioxide cost, alleviated company's environmental protection pressure.
Metatitanic acid two washes making beating water to be provided by calcining filter pressing filtrate before front kiln, is primarily present a small amount of two in filter pressing filtrate before kiln
The soluble-salt adding during valency ferrum (about 20ppm) and salt treatment, its ph is about 7.0, can during follow-up salt treatment
To save salt treatment agent dosage, save two simultaneously and washed making beating desalination water consumption.
This invention achieves the recycling of filter pressing filtrate before two washing filtrates and kiln in sulfuric acid method titanium pigment production process, presses
Calculate according to producing 190000 tons of titanium dioxides per year, annual about 4,070,000 yuan of sulfate value of recovery, annual carbide slag of saving is worth 470,000 yuan, section
About pull an oar about 110,000 yuan of water, save about 60,000 yuan of flocculant, annual reclaim about 70,000 yuan of titanous, steam saving every year about 300,000
Unit.
Brief description
Fig. 1 is the recycling schematic diagram of titanium white waste acid of the present invention.
Specific embodiment
Below the present invention is elaborated.
In order that the objects, technical solutions and advantages of the present invention become more apparent, below in conjunction with drawings and Examples, right
The present invention is further elaborated.It should be appreciated that specific embodiment described herein, only in order to explain the present invention,
It is not intended to limit the present invention.
Embodiment 1
Wash making beating and two using company existing to wash making beating mode and prepare Rutile type titanium dioxide.
Bleaching in production process of titanium pigment is terminated unwashed filtrate a1Add wadding through thickener, cn filter, period
Thick paste is recycled to one and washes by solidifying agent, and upper strata acid waste water goes to the discharge of sewage plant neutralisation treatment；Filter pressing filtrate b before kiln1Directly turn
To sewage plant neutralisation treatment discharge, one wash making beating and two wash making beating all use desalted water, titanium dioxide one per ton wash making beating need to sand
Drainage a21.1 tons, two wash making beating need to use desalted water b21 ton, two wash qualified metatitanic acid obtains rutile-type through salt treatment, calcining
Titanium dioxide first product, then obtain titanium dioxide product c through operations such as wet grinding, sand milling, the gentle powder of peplos1, related data is shown in Table 1.
Embodiment 2
As shown in figure 1, bleaching is terminated unwashed filtrate a1It is stored in two washing filtrate dashpots, be used for carrying out washing
Making beating, by filter pressing filtrate b before kiln1It is stored in filtrate dashpot before kiln, be used for carrying out two washing making beating.
The slurry that bleaching is terminated carries out filter pressing, secondary washing, obtains filter pressing filtrate a13 tons are stored in two washing filtrate bufferings
In groove, wash making beating for next group metatitanic acid one and process.Washing cake is discharged into two and washes hollander tub addition desalted water a23 tons carry out two
Wash making beating, then carry out salt treatment, behind place, slip carries out filter pressing with pressure filter, obtain filter pressing filtrate b14 tons are stored in filtrate before kiln
Dashpot, washes making beating for next group metatitanic acid two and processes.Then carry out calcining, wet grinding, sand milling, peplos, obtain titanium after gas powder
White lead product c2, related data is shown in Table 1.
Embodiment 3
A by gained in embodiment 213 tons carry out washing making beating, then making beating material is put into bleaching tank addition sulphuric acid, trivalent
Titanium carries out bleaching, bleaching is terminated sample pressure filter and carries out filter pressing, secondary washing, and gained filtrate is stored in two washing filtrates and delays
Jet-bedding, the b of gained in embodiment 2 of the filter cake after secondary washing14 tons carry out two and wash making beating, then carry out salt treatment, expect behind place
Slurry carries out filter pressing before kiln, and filtrate is stored directly in filtrate dashpot before kiln, and filter cake enters calcined by rotary kiln, then through wet grinding, sand
Mill, peplos, gas powder obtain titanium dioxide finished product c3, and related data is shown in Table 1.
Embodiment 4
According to this patent process route: 3 tons of the unwashed filtrate of bleaching end washes making beating for one, filter pressing filtrate 4 before kiln
Ton washes making beating for two, circulates with reference to embodiment 3, circulates 100 times in strict accordance with process route, obtains titanium dioxide product c4, phase
Close data and be shown in Table 3.
Table 3
Table 1 data illustrates: terminates unwashed filtrate using bleaching in this patent and washes in production process of titanium pigment one
Making beating is processed, and before kiln before calcining, filter pressing filtrate is washed making beating in production process of titanium pigment two and processed, and one or two wash the inclined titanium obtaining
Sour quality is all uninfluenced, and before two washing filtrates and kiln, filtrate recycles many times and all do not produce impact to titanium dioxide quality.
Claims (2)
1. a kind of recycling method of titanium white waste acid, described titanium white waste acid include bleaching terminate unwashed two washing filtrates and
Filter pressing filtrate before calcining kiln it is characterised in that: described bleaching terminate unwashed two washing filtrates be used for production process of titanium pigment in
One washes making beating, and before calcining kiln, filter pressing filtrate washes making beating for two.
2. a kind of titanium white waste acid according to claim 1 recycling method it is characterised in that: described bleaching terminate not
Two washing filtrates of washing are completely used in production process of titanium pigment one and wash making beating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610789379.8A CN106365197A (en) | 2016-08-31 | 2016-08-31 | Recycling method of titanium dioxide waste acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610789379.8A CN106365197A (en) | 2016-08-31 | 2016-08-31 | Recycling method of titanium dioxide waste acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106365197A true CN106365197A (en) | 2017-02-01 |
Family
ID=57898797
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610789379.8A Pending CN106365197A (en) | 2016-08-31 | 2016-08-31 | Recycling method of titanium dioxide waste acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106365197A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107128971A (en) * | 2017-06-19 | 2017-09-05 | 四川龙蟒钛业股份有限公司 | The circulation utilization method of metatitanic acid bleaching liquor |
| CN107324385A (en) * | 2017-08-03 | 2017-11-07 | 四川龙蟒钛业股份有限公司 | One kind reduces washing method in production process of titanium pigment |
| CN111135615A (en) * | 2019-12-30 | 2020-05-12 | 宜宾天原海丰和泰有限公司 | Method for recovering post-treatment filtrate of titanium dioxide |
| CN111874945A (en) * | 2020-08-03 | 2020-11-03 | 上海安赐环保科技股份有限公司 | Sulfuric acid process titanium dioxide washing system, purification system and process |
| CN114470896A (en) * | 2021-12-31 | 2022-05-13 | 龙佰襄阳钛业有限公司 | Titanium dioxide powder membrane washing and filtering system and method |
| CN115650284A (en) * | 2022-09-09 | 2023-01-31 | 攀钢集团攀枝花钢铁研究院有限公司 | Recycling method of titanium dioxide kiln tail leaked materials |
| CN115924966A (en) * | 2022-12-12 | 2023-04-07 | 龙佰四川钛业有限公司 | Titanium white powder salt treating agent recovery process and titanium white powder production process |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103224297A (en) * | 2013-04-28 | 2013-07-31 | 山东玉鑫环保科技有限公司 | Titanium dioxide production wastewater reuse process |
| CN103274462B (en) * | 2013-03-15 | 2015-03-11 | 四川龙蟒钛业股份有限公司 | Method for recycling acidic washing water in rutile titanium dioxide production process |
| CN104692456A (en) * | 2015-01-09 | 2015-06-10 | 上海安赐机械设备有限公司 | Green and environment-friendly sulfuric acid method titanium dioxide production device and process |
| CN105271397A (en) * | 2015-10-29 | 2016-01-27 | 济南裕兴化工有限责任公司 | Production method of titanium dioxide capable of reducing water consumption |
-
2016
- 2016-08-31 CN CN201610789379.8A patent/CN106365197A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103274462B (en) * | 2013-03-15 | 2015-03-11 | 四川龙蟒钛业股份有限公司 | Method for recycling acidic washing water in rutile titanium dioxide production process |
| CN103224297A (en) * | 2013-04-28 | 2013-07-31 | 山东玉鑫环保科技有限公司 | Titanium dioxide production wastewater reuse process |
| CN104692456A (en) * | 2015-01-09 | 2015-06-10 | 上海安赐机械设备有限公司 | Green and environment-friendly sulfuric acid method titanium dioxide production device and process |
| CN105271397A (en) * | 2015-10-29 | 2016-01-27 | 济南裕兴化工有限责任公司 | Production method of titanium dioxide capable of reducing water consumption |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107128971A (en) * | 2017-06-19 | 2017-09-05 | 四川龙蟒钛业股份有限公司 | The circulation utilization method of metatitanic acid bleaching liquor |
| CN107324385A (en) * | 2017-08-03 | 2017-11-07 | 四川龙蟒钛业股份有限公司 | One kind reduces washing method in production process of titanium pigment |
| CN111135615A (en) * | 2019-12-30 | 2020-05-12 | 宜宾天原海丰和泰有限公司 | Method for recovering post-treatment filtrate of titanium dioxide |
| CN111135615B (en) * | 2019-12-30 | 2022-04-26 | 宜宾天原海丰和泰有限公司 | Method for recovering post-treatment filtrate of titanium dioxide |
| CN111874945A (en) * | 2020-08-03 | 2020-11-03 | 上海安赐环保科技股份有限公司 | Sulfuric acid process titanium dioxide washing system, purification system and process |
| CN111874945B (en) * | 2020-08-03 | 2022-08-16 | 上海安赐环保科技股份有限公司 | Sulfuric acid process titanium dioxide washing system, purification system and process |
| CN114470896A (en) * | 2021-12-31 | 2022-05-13 | 龙佰襄阳钛业有限公司 | Titanium dioxide powder membrane washing and filtering system and method |
| CN115650284A (en) * | 2022-09-09 | 2023-01-31 | 攀钢集团攀枝花钢铁研究院有限公司 | Recycling method of titanium dioxide kiln tail leaked materials |
| CN115924966A (en) * | 2022-12-12 | 2023-04-07 | 龙佰四川钛业有限公司 | Titanium white powder salt treating agent recovery process and titanium white powder production process |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106365197A (en) | Recycling method of titanium dioxide waste acid | |
| CN103274462B (en) | Method for recycling acidic washing water in rutile titanium dioxide production process | |
| CN104086027B (en) | Method for treating titanium dioxide wastewater through sulfuric acid process | |
| CN104692456A (en) | Green and environment-friendly sulfuric acid method titanium dioxide production device and process | |
| CN107720801A (en) | A kind of method that blanc fixe is prepared using titanium white waste acid | |
| CN107674975B (en) | The separation and recovery method of cobalt and manganese in a kind of cobalt manganese waste material | |
| CN103058253A (en) | Method for preparing gypsum by free sulfuric acid in titanium dioxide wastewater | |
| CN104480314A (en) | Method for recycling waste residue in manganese industry production | |
| CN106892453A (en) | The method that washing filtrate is used for acidolysis leaching | |
| CN104108814B (en) | A kind of method processing Rutile type Titanium Dioxide waste water | |
| CN101863512B (en) | Acid method recycling process of chromium-containing aluminum mud | |
| CN109987637A (en) | A method of iron oxide yellow is prepared using red soil | |
| CN110467218A (en) | The method for bleaching of metatitanic acid in a kind of Titanium White Production By Sulfuric Acid Process | |
| CN105293574B (en) | A kind of method of spent acid amount in reduction titanium white production | |
| CN103936064B (en) | A kind of method adopting titanium ore to produce titanium dioxide | |
| CN108101105A (en) | The method of preparation and use of calcining seeds in sulfuric acid method titanium pigment production | |
| CN107413521A (en) | The industrial method of magnetic separation ilmenite concentrate in acidolysis tailings is produced from sulfuric acid method titanium pigment | |
| CN106699919B (en) | A kind of double calcium calcification extractions of seaweed chemical alginic glue and waste water circulation reusing technology | |
| CN109160537A (en) | A kind of production technology improving anatase thpe white powder performance | |
| CN107055600A (en) | Two washing lotion recoverying and utilizing method in a kind of method for producing gtitanium dioxide with sulphuric acid | |
| CN106800314A (en) | Lateritic nickel ore pickle liquor is except iron while the method for wet production ferric oxide red colorant | |
| CN104556183A (en) | Improved technology for preparing lime mud calcium carbonate filler through causticization of straw pulp green liquor | |
| CN207361808U (en) | A kind of titanium white waste acid utilization system | |
| CN107128971A (en) | The circulation utilization method of metatitanic acid bleaching liquor | |
| CN107021466B (en) | Sulfuric acid method titanium pigment acid waste water is used for the pretreated closed circulation process of phosphorus ore |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170201 |