WO2016110268A1 - Green and environmentally friendly sulfuric acid process titanium dioxide powder production equipment and technique - Google Patents

Green and environmentally friendly sulfuric acid process titanium dioxide powder production equipment and technique Download PDF

Info

Publication number
WO2016110268A1
WO2016110268A1 PCT/CN2016/070464 CN2016070464W WO2016110268A1 WO 2016110268 A1 WO2016110268 A1 WO 2016110268A1 CN 2016070464 W CN2016070464 W CN 2016070464W WO 2016110268 A1 WO2016110268 A1 WO 2016110268A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
washing
sulfuric acid
membrane
water
Prior art date
Application number
PCT/CN2016/070464
Other languages
French (fr)
Chinese (zh)
Inventor
杨积志
李海波
张俊
邵宋邵
吴科
Original Assignee
上海安赐环保科技股份有限公司
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 上海安赐环保科技股份有限公司 filed Critical 上海安赐环保科技股份有限公司
Publication of WO2016110268A1 publication Critical patent/WO2016110268A1/en

Links

Images

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

Definitions

  • the invention relates to the technical field of environmental protection, in particular to a titanium dioxide powder industry suitable for sulfuric acid method, and at the same time realizes low equipment investment, low energy consumption and low oil removal for improving the recovery rate of titanium dioxide, improving the utilization rate of sulfuric acid circulation, and improving the utilization rate of water washing water circulation.
  • a green environmentally friendly sulfuric acid titanium dioxide production device and process with high sulfur removal efficiency is provided.
  • the yield of titanium dioxide in the titanium dioxide industry of sulfuric acid method is 87-88%.
  • the main loss comes from the hydrolysis section, the washing section, the calcination section and the packaging section.
  • the loss is 4-5%, 2-3%, 1- 2%, 1-2%.
  • the loss of the washing section is mainly due to the titanium oxysulfate dissolved in the washing wastewater, which is partly due to the inability of the CN filter to trap dissolved titanium.
  • the loss of the calcination section is mainly due to the fact that the dust collector in the back section of the rotary kiln cannot completely capture the titanium dioxide dust in the flue gas, causing the titanium dioxide particles to be discharged with the flue gas; in addition, the titanium dioxide particles in the sprayed spent acid are not completely recovered and sent to the acid solution.
  • the titanium dioxide particles sent to the wastewater treatment section are also wasted.
  • the method adopted by each manufacturer for the waste acid is that a part is returned to the acid hydrolysis section as an initiator, and a part is sent to the wastewater treatment.
  • waste acid concentration device Although many manufacturers have built waste acid concentrating devices to treat this part of the waste acid, the waste acid concentration device is basically idle because of the limited strength of the waste acid concentration technology and the complexity of the waste acid component. It is obvious that this part of the waste acid sent to the wastewater treatment will eventually become a waste of solid waste.
  • the demand for water in the sulfuric acid process titanium dioxide process is quite large. At present, the two wash waters and the three wash waters are reused to one wash, one wash water is discharged, and one wash water is lost water.
  • the main object of the present invention is to provide a titanium dioxide powder industry suitable for the sulfuric acid process, and at the same time, to realize a low investment in equipment for improving the recovery rate of titanium dioxide, increasing the utilization rate of sulfuric acid circulation, and improving the utilization rate of the water washing water, and low energy consumption.
  • the degreasing and desulfurization can be carried out at the same time, and the green and environmentally friendly sulfuric acid titanium dioxide production device and process with high blowing efficiency are high.
  • a green environmentally friendly sulfuric acid method titanium dioxide production device which comprises, in order from the most upstream to the most downstream of the production process, a grinding device, an acid hydrolysis device, Clarification device, vacuum crystallization device, disk filter device, fine filter device, vacuum concentrating device, titanium liquid preheating device, hydrolysis device, washing and sizing device, beating device, washing device, bleaching device, washing device, plate Frame filter device, salt treatment vacuum drum dewatering device, calcining device, Raymond mill device, beating and dispersing device, sanding device, coating device, three washing device, drying device, airflow pulverizing device and packaging device.
  • a washing acid film processing device is connected to the washing device; a washing wastewater film processing device is connected to the washing device; a washing liquid film treating device is connected to the second washing device; and a three washing wastewater film treating device is connected to the three washing device.
  • the invention discloses a green environmentally-friendly sulfuric acid method for producing titanium dioxide, wherein the production process includes, from the most upstream to the most downstream, grinding, acid hydrolysis, clarification, vacuum crystallization, disk filtration, fine filtration, vacuum concentration, and titanium liquid preheating. Hydrolysis, one wash, one beat, one wash, one bleach, two washes, plate and frame press filtration, salt treatment, vacuum drum dehydration, calcination, Raymond mill, beating dispersion, sanding, coating, three washing, drying, airflow Smash and pack.
  • the waste acid produced by washing the sheet is subjected to a membrane treatment to recover metatitanic acid particles in the spent acid and a concentrated solution containing ferrous sulfate and titanyl sulfate, and to produce clean dilute sulfuric acid.
  • the waste acid needs to be subjected to membrane treatment, including the microfiltration membrane treatment in the front stage and the acid-resistant membrane treatment in the latter stage, and the concentrated solution containing metatitanic acid produced by the microfiltration membrane is returned to the washing tank, and the clear liquid enters the acid-resistant membrane; the acid-resistant membrane
  • the produced concentrated solution containing ferrous sulfate and titanyl sulfate is returned to the acid hydrolysis section, and the clean dilute sulfuric acid produced is used as the calcining kiln exhaust gas. Spray solution.
  • the microfiltration membrane functions to intercept the metatitanic acid solid in the waste acid, and the precision of the microfiltration membrane used is 50-500 nm, and the transmembrane pressure difference is 0.05-0.8 MPa; the effect of the acid-resistant membrane
  • the sulfuric acid is allowed to permeate.
  • the acid-resistant membrane used has a rejection of ferrous ions of 85-98%, and the retention rate of titanyl sulfate is 80-95%.
  • the concentration is 0-30%, and the operating pressure is 1.5-4.5 MPa.
  • the weak acid white water produced by a washing is subjected to a membrane treatment to recover metatitanic acid particles in white water and a concentrated liquid containing ferrous sulfate and titanyl sulfate, and to produce clean dilute acid water.
  • the white water film treatment includes the microfiltration membrane treatment in the front stage and the acid-resistant membrane treatment in the latter stage, and the concentrated solution containing the metatitanic acid produced by the microfiltration membrane is returned to the washing tank, and the clear liquid enters the acid-resistant membrane; the sulfuric acid-containing subgas produced by the acid-resistant membrane treatment The concentrated solution of iron and titanyl sulfate is returned to the acid hydrolysis section, and the clean dilute acid water produced is used as a wash water cycle.
  • the function of the microfiltration membrane is to intercept the metatitanic acid solid in the waste acid.
  • the precision of the microfiltration membrane is 50-500 nm, and the transmembrane pressure difference is 0.05-0.8 MPa.
  • the role of the acid-resistant membrane is to intercept the ferrous sulfate in the spent acid. And titanium oxysulfate, allowing sulfuric acid to pass through, the acid-resistant membrane used has a rejection of ferrous ions of 85-98%, a retention rate of titanium oxysulfate of 80-95%, a sulfuric acid concentration of 0-30%, and operating pressure. It is 1.5-4.5 MPa.
  • the second washing wastewater generated by the second washing is subjected to a membrane treatment to recover the metatitanic acid particles in the wastewater and the concentrated liquid containing ferrous sulfate and titanyl sulfate, and produce clean dilute acid water. .
  • the second washing wastewater membrane treatment includes the microfiltration membrane treatment in the front stage and the acid-resistant membrane treatment in the latter stage, and the concentrated solution containing the metatitanic acid produced by the microfiltration membrane is returned to the second washing tank, and the clear liquid enters the acid-resistant membrane;
  • the concentrated solution of ferrous sulfate and titanyl sulfate is returned to the acid hydrolysis section, and the clean dilute acid water produced is used for the second wash water cycle.
  • the function of the microfiltration membrane is to intercept the metatitanic acid solid in the waste acid.
  • the precision of the microfiltration membrane is 50-500 nm, and the transmembrane pressure difference is 0.05-0.8 MPa.
  • the role of the acid-resistant membrane is to intercept the ferrous sulfate in the spent acid.
  • sulfuric acid Oxygen titanium allowing sulfuric acid to pass through, the acid-resistant membrane used has a rejection of ferrous ions of 85-98%, a retention rate of titanium oxysulfate of 80-95%, a sulfuric acid resistant concentration of 0-30%, and an operating pressure of 1.5. -4.5 MPa.
  • the second wash needs to be supplemented with deionized water, and the amount of water added is 0-30% of the amount of the second wash water.
  • the dilute sulfuric acid generated from the waste acid of a washed sheet is treated as a tail gas spray liquid of the calcining kiln, and the waste liquid generated after the spraying is subjected to a membrane treatment to Recovering the titanium dioxide particles in the waste liquid, and producing clean dilute sulfuric acid, and the dilute sulfuric acid enters the sulfuric acid concentration device;
  • the function of the microfiltration membrane is to intercept the titanium dioxide solids in the spray waste liquid, and the intercepted titanium dioxide solids are returned to the calcining kiln, and the condensed dilute acid water produced by the sulfuric acid concentrating device is returned to a washing tank for use as a washing water, and the sulfuric acid concentrating device is produced.
  • the concentrated sulfuric acid is returned to the acid hydrolysis section.
  • the microfiltration membrane used has an accuracy of 50-500 nm and a transmembrane pressure difference of 0.05-0.8 MPa.
  • the concentration of concentrated sulfuric acid produced by the sulfuric acid concentration unit is 50-96%.
  • a wash needs to be supplemented with deionized water, and the amount of water added is 0-30% of a wash.
  • the three washing wastewater produced by the three washings is subjected to a membrane treatment to recover titanium dioxide particles in the wastewater and a concentrated solution containing sodium sulfate, and to produce a clean desalinated water.
  • the three-washing wastewater membrane treatment includes the microfiltration membrane treatment in the front stage and the reverse osmosis membrane treatment in the latter stage.
  • the concentrated solution containing titanium dioxide produced by the microfiltration membrane is returned to the three washing tank, and the clear liquid enters the reverse osmosis membrane; the reverse osmosis membrane treatment produces
  • the sodium sulfate-containing concentrate is sent to the post-treatment section, and the resulting demineralized water is used as a three-wash water cycle.
  • the function of the microfiltration membrane is to intercept the metatitanic acid solid in the waste acid.
  • the precision of the microfiltration membrane is 50-500 nm, and the transmembrane pressure difference is 0.05-0.8 MPa.
  • the reverse osmosis membrane acts to intercept the sodium sulfate in the wastewater. Only water permeation is allowed, and the desalination rate of the reverse osmosis membrane is 95-99%.
  • the three washes need to be supplemented with deionized water, and the amount of water added is 0-30% of the three wash water.
  • the post-treatment section of sodium sulphate is partially recovered for discharge, recovery or partial discharge.
  • the weak acid white water produced by one washing and the second washing wastewater generated by the second washing are combined or processed by a membrane treatment, and the metatitanic acid particles in the wastewater and the ferrous sulfate and sulfuric acid are recovered.
  • the combined wastewater membrane treatment includes the microfiltration membrane treatment in the front stage and the acid-resistant membrane treatment in the latter stage.
  • the concentrated solution containing metatitanic acid produced by the microfiltration membrane is returned to a washing tank, and the clear liquid enters the acid-resistant membrane; the sulfuric acid produced by the acid-resistant membrane treatment
  • the concentrated solution of ferrous iron and titanium oxysulfate is returned to the acid hydrolysis section, and the cleaned dilute acid water produced is used as a wash water and a second wash water cycle.
  • the function of the microfiltration membrane is to intercept the metatitanic acid solid in the waste acid.
  • the precision of the microfiltration membrane is 50-500 nm, and the transmembrane pressure difference is 0.05-0.8 MPa.
  • the role of the acid-resistant membrane is to intercept the ferrous sulfate in the spent acid. And titanium oxysulfate, allowing sulfuric acid to permeate, the acid-resistant membrane used has a rejection of ferrous ions of 85-98%, the rejection of titanyl sulfate is greater than 80-95%, the sulfuric acid concentration is 0-30%, operating pressure It is 1.5-4.5 MPa.
  • the positive progress of the invention is that the green environmentally friendly sulfuric acid method titanium dioxide production device and the process provided by the invention have the following advantages: the invention can not only improve the recovery rate of titanium dioxide, but also create economic benefits for the sulfuric acid method titanium dioxide enterprise, and reduce waste. The discharge of acid and waste water has reduced environmental pressure and created environmental benefits for the society. It is a new green environmental protection process.
  • Figure 1 is a flow chart of the overall process of the present invention.
  • Figure 2 is a process flow diagram of the return to the acid hydrolysis section of the present invention.
  • Figure 3 is a flow chart showing the process of waste acid treatment in the present invention.
  • Fig. 4 is a flow chart showing the process of treating weak acid white water in the present invention.
  • Figure 5 is a process flow diagram of the treatment of the second washing wastewater in the present invention.
  • Figure 6 is a process flow diagram of the treatment of calcined tail gas wastewater in the present invention.
  • Fig. 7 is a flow chart showing the process of the three washing wastewater treatment in the present invention.
  • Figure 1 is a flow chart of the overall process of the present invention.
  • the device used in the present invention is produced.
  • the most upstream to the most downstream of the process includes: a grinding device, an acid hydrolysis device, a clarification device, a vacuum crystallization device, a disk filtration device, a fine filtration device, a vacuum concentrating device, a titanium liquid preheating device, a hydrolysis device, and a washing Sheet device, beating device, washing device, bleaching device, second washing device, plate and frame filter press device, salt treatment vacuum drum dewatering device, calcining device, Raymond mill device, beating and dispersing device, sanding device, coating device , three washing devices, drying devices, jet milling devices and packaging devices.
  • a washing acid film processing device is connected to the washing device, a washing waste water film processing device is connected to the washing device, a second washing wastewater film processing device is connected to the second washing device, and a three washing wastewater film processing device is connected to the three washing device.
  • the invention adopts wet iron-titanium to produce rutile type titanium dioxide, and the working sections thereof are: grinding, acid hydrolysis, clarification, vacuum crystallization, disk filtration, fine filtration, vacuum concentration, titanium liquid preheating, hydrolysis, and washing. Topping, beating, washing, bleaching, second washing, plate and frame pressure filtration, salt treatment, vacuum drum dehydration, calcination, Raymond grinding, beating dispersion, sanding, coating, three washing, drying, airflow crushing, packaging.
  • washing-up sections increased the waste acid membrane treatment process, a washing wastewater treatment process was added to the washing section, and the second washing wastewater treatment process was added to the second washing section.
  • the calcining section increased the membrane treatment process of the calcined tail gas wastewater and sulfuric acid. In the concentration process, the three washing sections have added three washing wastewater membrane treatment processes.
  • the waste acid produced by washing the sheet is subjected to a membrane treatment to recover the metatitanic acid particles in the spent acid and the concentrated solution containing ferrous sulfate and titanyl sulfate, and to produce clean dilute sulfuric acid, which is required for waste acid.
  • the membrane treatment includes the microfiltration membrane treatment in the front stage and the acid-resistant membrane treatment in the latter stage, and the concentrated solution containing the metatitanic acid produced by the microfiltration membrane is returned to the washing tank, and the clear liquid enters the acid-resistant membrane;
  • the concentrated solution of ferrous sulfate and titanyl sulfate is returned to the acid hydrolysis section, and the clean dilute sulfuric acid produced is used as a spray liquid for calcining the kiln exhaust gas.
  • the microfiltration membrane functions to intercept the metatitanic acid solid in the spent acid
  • the precision of the microfiltration membrane used is 50-500 nm
  • the transmembrane pressure difference is 0.05-0.8 MPa
  • the role of the acid-resistant membrane is to trap the spent acid.
  • the ferrous sulfate and titanium oxysulfate allow sulfuric acid to permeate.
  • the acid-resistant membrane used has a rejection of ferrous ions of 85-98%, a retention rate of titanyl sulfate of 80-95%, and a sulfuric acid resistant concentration of 0- 30%, operating pressure is 1.5-4.5 MPa.
  • the weak acid white water produced by one washing is subjected to a membrane treatment to recover metatitanic acid particles in white water and a concentrated liquid containing ferrous sulfate and titanyl sulfate, and to produce clean dilute acid water.
  • the white water film treatment includes the microfiltration membrane treatment in the front stage and the acid-resistant membrane treatment in the latter stage, and the concentrated solution containing the metatitanic acid produced by the microfiltration membrane is returned to the washing tank, and the clear liquid enters the acid-resistant membrane; the sulfuric acid-containing subgas produced by the acid-resistant membrane treatment The concentrated solution of iron and titanyl sulfate is returned to the acid hydrolysis section, and the clean dilute acid water produced is used as a wash water cycle.
  • the function of the microfiltration membrane is to intercept the metatitanic acid solid in the waste acid.
  • the precision of the microfiltration membrane is 50-500 nm, and the transmembrane pressure difference is 0.05-0.8 MPa.
  • the role of the acid-resistant membrane is to intercept the ferrous sulfate in the spent acid. And titanium oxysulfate, allowing sulfuric acid to pass through, the acid-resistant membrane used has a rejection of ferrous ions of 85-98%, a retention rate of titanium oxysulfate of 80-95%, a sulfuric acid concentration of 0-30%, and operating pressure. It is 1.5-4.5 MPa.
  • the second washing wastewater produced by the second washing is subjected to a membrane treatment to recover the metatitanic acid particles in the wastewater and the concentrated liquid containing ferrous sulfate and titanyl sulfate, and to produce clean dilute acid water.
  • the second washing wastewater membrane treatment includes the microfiltration membrane treatment in the front stage and the acid-resistant membrane treatment in the latter stage, and the concentrated solution containing the metatitanic acid produced by the microfiltration membrane is returned to the second washing tank, and the clear liquid enters the acid-resistant membrane;
  • the concentrated solution of ferrous sulfate and titanyl sulfate is returned to the acid hydrolysis section, and the clean dilute acid water produced is used for the second wash water cycle.
  • the function of the microfiltration membrane is to intercept the metatitanic acid solid in the waste acid.
  • the precision of the microfiltration membrane is 50-500 nm, and the transmembrane pressure difference is 0.05-0.8 MPa.
  • the role of the acid-resistant membrane is to intercept the ferrous sulfate in the spent acid. And titanium oxysulfate, allowing sulfuric acid to pass through, the acid-resistant membrane used has a rejection of ferrous ions of 85-98%, a retention rate of titanium oxysulfate of 80-95%, a sulfuric acid concentration of 0-30%, and operating pressure. It is 1.5-4.5 MPa.
  • the second wash needs to be supplemented with deionized water, and the amount of water added is 0-30% of the amount of the second wash water.
  • the dilute sulfuric acid generated from the waste acid of a washed sheet after being treated by the microfiltration membrane is used as the tail gas spray liquid of the calcining kiln, and the waste liquid generated after the spraying is subjected to membrane treatment to recover the waste liquid.
  • the titanium dioxide particles produce clean dilute sulfuric acid and dilute sulfuric acid into the sulfuric acid concentrating unit.
  • the function of the microfiltration membrane is to intercept the titanium dioxide solids in the spray waste liquid, and the intercepted titanium dioxide solids are returned to the calcining kiln, and the condensed dilute acid water produced by the sulfuric acid concentrating device is returned to a washing tank for washing.
  • the concentrated sulfuric acid produced by the sulfuric acid concentrating device is returned to the acid hydrolysis section.
  • the microfiltration membrane used has an accuracy of 50-500 nm and a transmembrane pressure difference of 0.05-0.8 MPa.
  • the concentration of concentrated sulfuric acid produced by the sulfuric acid concentration unit is 50-96%.
  • a wash needs to be supplemented with deionized water, and the amount of water added is 0-30% of a wash.
  • the three washing waste water produced by the three washings is subjected to a membrane treatment to recover the titanium dioxide particles in the wastewater and the concentrated solution containing sodium sulfate, and to produce a clean desalinated water.
  • the three-washing wastewater membrane treatment includes the microfiltration membrane treatment in the front stage and the reverse osmosis membrane treatment in the latter stage.
  • the concentrated solution containing titanium dioxide produced by the microfiltration membrane is returned to the three washing tank, and the clear liquid enters the reverse osmosis membrane; the reverse osmosis membrane treatment produces
  • the sodium sulfate-containing concentrate is sent to the post-treatment section, and the resulting demineralized water is used as a three-wash water cycle.
  • the function of the microfiltration membrane is to intercept the metatitanic acid solid in the waste acid.
  • the precision of the microfiltration membrane is 50-500 nm, and the transmembrane pressure difference is 0.05-0.8 MPa.
  • the reverse osmosis membrane acts to intercept the sodium sulfate in the wastewater. Only water permeation is allowed, and the desalination rate of the reverse osmosis membrane is 95-99%.
  • the three washes need to be supplemented with deionized water, and the amount of water added is 0-30% of the three wash water.
  • the post-treatment section of sodium sulphate is partially recovered for discharge, recovery or partial discharge.
  • the weak acid white water produced by one washing and the second washing waste water produced by the second washing may be treated separately as described above, or may be combined or subjected to membrane treatment after the process is applied, and the metatitanic acid particles in the waste water are recovered and contained.
  • a concentrated solution of ferrous sulfate and titanyl sulfate and produces a clean dilute acid water.
  • the combined wastewater membrane treatment includes the microfiltration membrane treatment in the front stage and the acid-resistant membrane treatment in the latter stage.
  • the concentrated solution containing metatitanic acid produced by the microfiltration membrane is returned to a washing tank, and the clear liquid enters the acid-resistant membrane; the sulfuric acid produced by the acid-resistant membrane treatment
  • the concentrated solution of ferrous iron and titanium oxysulfate is returned to the acid hydrolysis section, and the cleaned dilute acid water produced is used as a wash water and a second wash water cycle.
  • the function of the microfiltration membrane is to intercept the metatitanic acid solid in the waste acid.
  • the precision of the microfiltration membrane is 50-500 nm, and the transmembrane pressure difference is 0.05-0.8 MPa.
  • the role of the acid-resistant membrane is to intercept the ferrous sulfate in the spent acid. And titanium oxysulfate, allowing sulfuric acid to permeate, the acid-resistant membrane used has a rejection of ferrous ions of 85-98%, the rejection of titanyl sulfate is greater than 80-95%, the sulfuric acid concentration is 0-30%, operating pressure It is 1.5-4.5 MPa.
  • FIG. 2 is a process flow diagram of the return to the acid hydrolysis section of the present invention. As shown in Figure 2: concentrated sulfuric acid from the waste acid concentrating device, and ferrous sulfate and titanyl sulfate from a washed acid film treatment, a washing wastewater membrane treatment and a second washing wastewater membrane treatment. The concentrated solution is returned to the acid hydrolysis section.
  • FIG. 3 is a flow chart showing the process of waste acid treatment in the present invention.
  • the waste acid film treatment process produced by washing the upper sheet includes the microfiltration membrane treatment in the front stage and the acid-resistant membrane treatment in the latter stage, and the concentrated solution containing the metatitanic acid produced by the microfiltration membrane is returned to the wash sheet.
  • the trough and the clear liquid enter the acid-resistant membrane; the concentrated liquid containing ferrous sulfate and titanyl sulfate produced by the acid-resistant membrane treatment is returned to the acid hydrolysis section, and the clean dilute sulfuric acid is produced as the spray liquid of the calcining kiln exhaust gas.
  • the treatment of the weak acid white water film produced by one washing comprises the treatment of the microfiltration membrane in the front stage and the acid treatment treatment in the latter stage, and the treatment by the microfiltration membrane treatment.
  • the concentrated solution of metatitanic acid is returned to a washing tank, and the clear liquid enters the acid-resistant membrane; the concentrated liquid containing ferrous sulfate and titanyl sulfate produced by the acid-resistant membrane treatment is returned to the acid hydrolysis section, and the clean diluted acid water is used as a washing water cycle.
  • FIG. 5 is a process flow diagram of the treatment of the second washing wastewater in the present invention.
  • the second washing wastewater membrane treatment includes the microfiltration membrane treatment in the front stage and the acid-resistant membrane treatment in the latter stage, and the concentrated solution containing the metatitanic acid produced by the microfiltration membrane is returned to the second washing tank, and the clear liquid enters the acid-resistant membrane;
  • the concentrated solution containing ferrous sulfate and titanyl sulfate produced by the acid-resistant membrane treatment is returned to the acid hydrolysis section, and the clean dilute acid water produced is used for the second wash water cycle.
  • FIG. 6 is a process flow diagram of the treatment of calcined tail gas wastewater in the present invention, as shown in FIG. 6 : the dilute sulfuric acid spray calcined tail gas after treatment with a waste acid film treatment to produce calcined tail gas wastewater.
  • the wastewater is subjected to membrane treatment to intercept the titanium dioxide solids in the spray waste liquid, and the intercepted titanium dioxide solids are returned to the calcining kiln, and the clear liquid produced by the membrane treatment is dilute sulfuric acid, and the dilute sulfuric acid enters the sulfuric acid concentration device.
  • the condensed dilute acid water produced by the sulfuric acid concentrating device is returned to a washing tank for use as a washing water, and the concentrated sulfuric acid produced by the sulfuric acid concentrating device is returned to the acid hydrolysis section.
  • FIG 7 is a process flow diagram of the three-washing wastewater treatment in the present invention, as shown in Figure 7: the three-wash wastewater membrane treatment includes the microfiltration membrane treatment in the front stage and the reverse osmosis membrane treatment in the latter stage, and the titanium dioxide-containing treatment by the microfiltration membrane treatment.
  • the concentrated liquid returns to the three washing tank, and the clear liquid enters the reverse osmosis membrane.
  • Sodium sulfate-containing concentrate produced by reverse osmosis membrane treatment It is sent to the post-treatment section, and the resulting demineralized water is used for three wash water cycles.
  • the concentration of titanium in the waste acid was 9.22 g/L, the ferrous ion concentration was 45 g/L, and the sulfuric acid content was 20%.
  • the spent acid was first treated by a microfiltration membrane with a precision of 200 nm and a transmembrane pressure difference of 0.2 MPa. After the membrane treatment, the concentrated solution containing metatitanic acid was returned to the washing tank, and the concentration of titanium in the supernatant after the membrane treatment was 2 g/L. The supernatant after the microfiltration membrane treatment was continuously treated with an acid-resistant membrane at an operating pressure of 3.8 MPa.
  • the concentrated solution containing ferrous sulfate and titanyl sulfate is returned to the acid hydrolysis pot, and the concentration of titanium in the supernatant after treatment with the single-stage acid-resistant membrane is 140 mg/L, the concentration of ferrous ions is 2.25 g/L, and the content of sulfuric acid is It is 20%; the concentration of titanium in the supernatant after the two-stage acid-resistant treatment is 9.8 mg/L, the ferrous ion concentration is 112 mg/L, and the sulfuric acid content is 20%.
  • the supernatant is sent to a calcining kiln as a calcined tail gas spray.
  • the interception efficiency of the microfiltration membrane for metatitanic acid is 99% or more, and the remaining titanium is soluble titanium (titanium sulfate sulfate).
  • the single-stage acid-resistant membrane has a rejection of ferrous ions of 95% and a retention of 93% for titanyl sulfate.

Abstract

The present invention relates to green and environmentally friendly sulfuric acid process titanium dioxide powder production equipment and technique. Production processes from the most upstream to the most downstream comprise sequentially: pulverization, acidolysis, precipitation, vacuum crystallization, disk filtration, fine filtration, vacuum concentration, titanium solution preheating, hydrolysis, first wash plate mounting, beating, first wash, bleaching, second wash, frame filter press, salt-treatment vacuum drum dehydration, calcination, Raymond mill, beating dispersion, sanding, coating, third wash, drying, jet milling, and packaging. The present invention not only allows increased titanium dioxide recovery rate, thus creating economic benefits for sulfuric acid process titanium dioxide powder enterprises, but also reduces discharging of waste acid and of wastewater, thus reducing environmental impact and creating environmental benefits for society, and is a green and environmentally friendly novel technique.

Description

一种绿色环保硫酸法钛白粉生产装置以及工艺Green environmentally friendly sulfuric acid method titanium dioxide production device and process 技术领域Technical field
本发明涉及环保技术领域，具体涉及一种适用于硫酸法钛白粉行业，同时实现了提高钛白粉回收率，提高硫酸循环利用率，提高水洗水循环利用率的设备投资少，能耗低，除油除硫能同时进行，吹脱效率高的绿色环保硫酸法钛白粉生产装置以及工艺。The invention relates to the technical field of environmental protection, in particular to a titanium dioxide powder industry suitable for sulfuric acid method, and at the same time realizes low equipment investment, low energy consumption and low oil removal for improving the recovery rate of titanium dioxide, improving the utilization rate of sulfuric acid circulation, and improving the utilization rate of water washing water circulation. A green environmentally friendly sulfuric acid titanium dioxide production device and process with high sulfur removal efficiency.
背景技术Background technique
目前硫酸法钛白粉行业内钛白粉收率为87-88％，主要损失来源于水解工段，水洗工段，煅烧工段，包装工段，损失量分别为：4-5％，2-3％，1-2％，1-2％。水洗工段的损失主要来源于溶解于水洗废水中的硫酸氧钛，这部分损失是因为CN过滤器无法截留溶解态的钛。煅烧工段的损失主要是回转窑后段的除尘器无法完全捕集烟气中的二氧化钛粉尘，导致二氧化钛颗粒随烟气排放；另外喷淋废酸中的二氧化钛颗粒没有被完全回收即送往酸解工段和废水处理工段，送往废水处理工段的二氧化钛颗粒也被浪费掉。各厂家对废酸采用的方式是一部分返回至酸解工段作为引发剂，一部分送至废水处理。虽然有很多厂家建有废酸浓缩装置来处理这部分废酸，但因为废酸浓缩技术实力有限，以及废酸成份复杂容易造成浓缩装置堵塞，使得废酸浓缩装置基本闲置。很显然送往废水处理的这部分废酸最终就变成固废浪费掉。硫酸法钛白粉工艺对水的需求相当大，目前常用的是二洗水、三洗水回用至一洗，一洗水排放，一洗水即为流失水。At present, the yield of titanium dioxide in the titanium dioxide industry of sulfuric acid method is 87-88%. The main loss comes from the hydrolysis section, the washing section, the calcination section and the packaging section. The loss is 4-5%, 2-3%, 1- 2%, 1-2%. The loss of the washing section is mainly due to the titanium oxysulfate dissolved in the washing wastewater, which is partly due to the inability of the CN filter to trap dissolved titanium. The loss of the calcination section is mainly due to the fact that the dust collector in the back section of the rotary kiln cannot completely capture the titanium dioxide dust in the flue gas, causing the titanium dioxide particles to be discharged with the flue gas; in addition, the titanium dioxide particles in the sprayed spent acid are not completely recovered and sent to the acid solution. In the section and wastewater treatment section, the titanium dioxide particles sent to the wastewater treatment section are also wasted. The method adopted by each manufacturer for the waste acid is that a part is returned to the acid hydrolysis section as an initiator, and a part is sent to the wastewater treatment. Although many manufacturers have built waste acid concentrating devices to treat this part of the waste acid, the waste acid concentration device is basically idle because of the limited strength of the waste acid concentration technology and the complexity of the waste acid component. It is obvious that this part of the waste acid sent to the wastewater treatment will eventually become a waste of solid waste. The demand for water in the sulfuric acid process titanium dioxide process is quite large. At present, the two wash waters and the three wash waters are reused to one wash, one wash water is discharged, and one wash water is lost water.
很多厂家对工艺进行技术改造，减少钛白粉的流失，减少废酸的损失，减少水的使用，虽然成效显著，但没有从源头上解决损失问题，所以工艺的改进依然有潜力可挖。 Many manufacturers have technically modified the process to reduce the loss of titanium dioxide, reduce the loss of waste acid, and reduce the use of water. Although the results have been remarkable, but the loss problem has not been solved from the source, the improvement of the process still has potential to be tapped.
发明内容Summary of the invention
针对上述问题，本发明的主要目的在于提供一种适用于硫酸法钛白粉行业，同时实现了提高钛白粉回收率，提高硫酸循环利用率，提高水洗水循环利用率的设备投资少，能耗低，除油除硫能同时进行，吹脱效率高的绿色环保硫酸法钛白粉生产装置以及工艺。In view of the above problems, the main object of the present invention is to provide a titanium dioxide powder industry suitable for the sulfuric acid process, and at the same time, to realize a low investment in equipment for improving the recovery rate of titanium dioxide, increasing the utilization rate of sulfuric acid circulation, and improving the utilization rate of the water washing water, and low energy consumption. The degreasing and desulfurization can be carried out at the same time, and the green and environmentally friendly sulfuric acid titanium dioxide production device and process with high blowing efficiency are high.
本发明是通过下述技术方案来解决上述技术问题的：一种绿色环保硫酸法钛白粉生产装置，所述生产装置从生产工序的最上游到最下游依次包括：粉磨装置、酸解装置、澄清装置、真空结晶装置、圆盘过滤装置、精细过滤装置、真空浓缩装置、钛液预热装置、水解装置、一洗上片装置、打浆装置、一洗装置、漂白装置、二洗装置、板框压滤装置、盐处理真空转鼓脱水装置、煅烧装置、雷蒙磨装置、打浆分散装置、砂磨装置、包膜装置、三洗装置、干燥装置、气流粉碎装置和包装装置。The present invention solves the above technical problems by the following technical solutions: a green environmentally friendly sulfuric acid method titanium dioxide production device, which comprises, in order from the most upstream to the most downstream of the production process, a grinding device, an acid hydrolysis device, Clarification device, vacuum crystallization device, disk filter device, fine filter device, vacuum concentrating device, titanium liquid preheating device, hydrolysis device, washing and sizing device, beating device, washing device, bleaching device, washing device, plate Frame filter device, salt treatment vacuum drum dewatering device, calcining device, Raymond mill device, beating and dispersing device, sanding device, coating device, three washing device, drying device, airflow pulverizing device and packaging device.
一洗上片装置上连接有废酸膜处理装置；一洗装置上连接有一洗废水膜处理装置；二洗装置上连接有二洗废水膜处理装置；三洗装置上连接有三洗废水膜处理装置。A washing acid film processing device is connected to the washing device; a washing wastewater film processing device is connected to the washing device; a washing liquid film treating device is connected to the second washing device; and a three washing wastewater film treating device is connected to the three washing device. .
一种绿色环保硫酸法钛白粉生产工艺，所述生产工艺从最上游到最下游依次包括：粉磨、酸解、澄清、真空结晶、圆盘过滤、精细过滤、真空浓缩、钛液预热、水解、一洗上片、打浆、一洗、漂白、二洗、板框压滤、盐处理真空转鼓脱水、煅烧、雷蒙磨、打浆分散、砂磨、包膜、三洗、干燥、气流粉碎和包装。The invention discloses a green environmentally-friendly sulfuric acid method for producing titanium dioxide, wherein the production process includes, from the most upstream to the most downstream, grinding, acid hydrolysis, clarification, vacuum crystallization, disk filtration, fine filtration, vacuum concentration, and titanium liquid preheating. Hydrolysis, one wash, one beat, one wash, one bleach, two washes, plate and frame press filtration, salt treatment, vacuum drum dehydration, calcination, Raymond mill, beating dispersion, sanding, coating, three washing, drying, airflow Smash and pack.
在本发明的具体实施例子中，一洗上片产生的废酸需经过膜处理，回收废酸中的偏钛酸颗粒以及含硫酸亚铁和硫酸氧钛的浓液，并产生清洁的稀硫酸，废酸需经过膜处理包括前段的微滤膜处理和后段的耐酸膜处理，微滤膜处理产生的含偏钛酸的浓液返回一洗上片槽，清液进入耐酸膜；耐酸膜处理产生的含硫酸亚铁和硫酸氧钛的浓液返回酸解工段，而产生的清洁稀硫酸作煅烧窑尾气 的喷淋液。In a specific embodiment of the present invention, the waste acid produced by washing the sheet is subjected to a membrane treatment to recover metatitanic acid particles in the spent acid and a concentrated solution containing ferrous sulfate and titanyl sulfate, and to produce clean dilute sulfuric acid. The waste acid needs to be subjected to membrane treatment, including the microfiltration membrane treatment in the front stage and the acid-resistant membrane treatment in the latter stage, and the concentrated solution containing metatitanic acid produced by the microfiltration membrane is returned to the washing tank, and the clear liquid enters the acid-resistant membrane; the acid-resistant membrane The produced concentrated solution containing ferrous sulfate and titanyl sulfate is returned to the acid hydrolysis section, and the clean dilute sulfuric acid produced is used as the calcining kiln exhaust gas. Spray solution.
在本发明的具体实施例子中，微滤膜的作用为拦截废酸中的偏钛酸固体，所用微滤膜精度为50-500纳米，跨膜压差为0.05-0.8MPa；耐酸膜的作用为截留废酸中的硫酸亚铁和硫酸氧钛，允许硫酸透过，所用耐酸膜对亚铁离子的截留率为85-98％，对硫酸氧钛的截留率为80-95％，耐硫酸浓度为0-30％，操作压力为1.5-4.5MPa。In a specific embodiment of the present invention, the microfiltration membrane functions to intercept the metatitanic acid solid in the waste acid, and the precision of the microfiltration membrane used is 50-500 nm, and the transmembrane pressure difference is 0.05-0.8 MPa; the effect of the acid-resistant membrane In order to intercept the ferrous sulfate and titanyl sulfate in the waste acid, the sulfuric acid is allowed to permeate. The acid-resistant membrane used has a rejection of ferrous ions of 85-98%, and the retention rate of titanyl sulfate is 80-95%. The concentration is 0-30%, and the operating pressure is 1.5-4.5 MPa.
在本发明的具体实施例子中，一洗产生的弱酸白水需经过膜处理，以回收白水中的偏钛酸颗粒以及含硫酸亚铁和硫酸氧钛的浓液，并产生清洁的稀酸水。In a specific embodiment of the present invention, the weak acid white water produced by a washing is subjected to a membrane treatment to recover metatitanic acid particles in white water and a concentrated liquid containing ferrous sulfate and titanyl sulfate, and to produce clean dilute acid water.
白水膜处理包括前段的微滤膜处理和后段的耐酸膜处理，微滤膜处理产生的含偏钛酸的浓液返回一洗槽，清液进入耐酸膜；耐酸膜处理产生的含硫酸亚铁和硫酸氧钛的浓液返回酸解工段，而产生的清洁稀酸水作一洗水循环使用。The white water film treatment includes the microfiltration membrane treatment in the front stage and the acid-resistant membrane treatment in the latter stage, and the concentrated solution containing the metatitanic acid produced by the microfiltration membrane is returned to the washing tank, and the clear liquid enters the acid-resistant membrane; the sulfuric acid-containing subgas produced by the acid-resistant membrane treatment The concentrated solution of iron and titanyl sulfate is returned to the acid hydrolysis section, and the clean dilute acid water produced is used as a wash water cycle.
微滤膜的作用为拦截废酸中的偏钛酸固体，所用微滤膜精度为50-500纳米，跨膜压差为0.05-0.8MPa；耐酸膜的作用为截留废酸中的硫酸亚铁和硫酸氧钛，允许硫酸透过，所用耐酸膜对亚铁离子的截留率为85-98％，对硫酸氧钛的截留率为80-95％，耐硫酸浓度为0-30％，操作压力为1.5-4.5MPa。The function of the microfiltration membrane is to intercept the metatitanic acid solid in the waste acid. The precision of the microfiltration membrane is 50-500 nm, and the transmembrane pressure difference is 0.05-0.8 MPa. The role of the acid-resistant membrane is to intercept the ferrous sulfate in the spent acid. And titanium oxysulfate, allowing sulfuric acid to pass through, the acid-resistant membrane used has a rejection of ferrous ions of 85-98%, a retention rate of titanium oxysulfate of 80-95%, a sulfuric acid concentration of 0-30%, and operating pressure. It is 1.5-4.5 MPa.
在本发明的具体实施例子中，二洗产生的二洗废水需经过膜处理，以回收废水中的偏钛酸颗粒以及含硫酸亚铁和硫酸氧钛的浓液，并产生清洁的稀酸水。In a specific embodiment of the present invention, the second washing wastewater generated by the second washing is subjected to a membrane treatment to recover the metatitanic acid particles in the wastewater and the concentrated liquid containing ferrous sulfate and titanyl sulfate, and produce clean dilute acid water. .
二洗废水膜处理包括前段的微滤膜处理和后段的耐酸膜处理，微滤膜处理产生的含偏钛酸的浓液返回二洗槽，清液进入耐酸膜；耐酸膜处理产生的含硫酸亚铁和硫酸氧钛的浓液返回酸解工段，而产生的清洁稀酸水作二洗水循环使用。The second washing wastewater membrane treatment includes the microfiltration membrane treatment in the front stage and the acid-resistant membrane treatment in the latter stage, and the concentrated solution containing the metatitanic acid produced by the microfiltration membrane is returned to the second washing tank, and the clear liquid enters the acid-resistant membrane; The concentrated solution of ferrous sulfate and titanyl sulfate is returned to the acid hydrolysis section, and the clean dilute acid water produced is used for the second wash water cycle.
微滤膜的作用为拦截废酸中的偏钛酸固体，所用微滤膜精度为50-500纳米，跨膜压差为0.05-0.8MPa；耐酸膜的作用为截留废酸中的硫酸亚铁和硫酸 氧钛，允许硫酸透过，所用耐酸膜对亚铁离子的截留率为85-98％，对硫酸氧钛的截留率为80-95％，耐硫酸浓度为0-30％，操作压力为1.5-4.5MPa。The function of the microfiltration membrane is to intercept the metatitanic acid solid in the waste acid. The precision of the microfiltration membrane is 50-500 nm, and the transmembrane pressure difference is 0.05-0.8 MPa. The role of the acid-resistant membrane is to intercept the ferrous sulfate in the spent acid. And sulfuric acid Oxygen titanium, allowing sulfuric acid to pass through, the acid-resistant membrane used has a rejection of ferrous ions of 85-98%, a retention rate of titanium oxysulfate of 80-95%, a sulfuric acid resistant concentration of 0-30%, and an operating pressure of 1.5. -4.5 MPa.
二洗需要补充去离子水，补充水量为二洗水量的0-30％。The second wash needs to be supplemented with deionized water, and the amount of water added is 0-30% of the amount of the second wash water.
在本发明的具体实施例子中，来自于一洗上片的废酸经微滤膜处理后产生的稀硫酸作为煅烧窑的尾气喷淋液，喷淋后产生的废液需经过膜处理，以回收废液中的二氧化钛颗粒，并产生清洁的稀硫酸，稀硫酸进入硫酸浓缩装置；In a specific embodiment of the present invention, the dilute sulfuric acid generated from the waste acid of a washed sheet is treated as a tail gas spray liquid of the calcining kiln, and the waste liquid generated after the spraying is subjected to a membrane treatment to Recovering the titanium dioxide particles in the waste liquid, and producing clean dilute sulfuric acid, and the dilute sulfuric acid enters the sulfuric acid concentration device;
微滤膜的作用为拦截喷淋废液中的二氧化钛固体，被拦截的二氧化钛固体返回至煅烧窑，硫酸浓缩装置产生的冷凝稀酸水返回至一洗水槽作一洗水使用，硫酸浓缩装置产生的浓硫酸返回至酸解工段。The function of the microfiltration membrane is to intercept the titanium dioxide solids in the spray waste liquid, and the intercepted titanium dioxide solids are returned to the calcining kiln, and the condensed dilute acid water produced by the sulfuric acid concentrating device is returned to a washing tank for use as a washing water, and the sulfuric acid concentrating device is produced. The concentrated sulfuric acid is returned to the acid hydrolysis section.
所用微滤膜精度为50-500纳米，跨膜压差为0.05-0.8MPa。硫酸浓缩装置产生的浓硫酸的浓度为50-96％。The microfiltration membrane used has an accuracy of 50-500 nm and a transmembrane pressure difference of 0.05-0.8 MPa. The concentration of concentrated sulfuric acid produced by the sulfuric acid concentration unit is 50-96%.
一洗需要补充去离子水，补充水量为一洗水量的0-30％。A wash needs to be supplemented with deionized water, and the amount of water added is 0-30% of a wash.
在本发明的具体实施例子中，三洗产生的三洗废水需经过膜处理，回收废水中的二氧化钛颗粒以及含硫酸钠的浓液，并产生清洁的脱盐水。In a specific embodiment of the present invention, the three washing wastewater produced by the three washings is subjected to a membrane treatment to recover titanium dioxide particles in the wastewater and a concentrated solution containing sodium sulfate, and to produce a clean desalinated water.
三洗废水膜处理包括前段的微滤膜处理和后段的反渗透膜处理，微滤膜处理产生的含二氧化钛的浓液返回三洗槽，清液进入反渗透膜；反渗透膜处理产生的含硫酸钠浓液送至后处理工段，而产生的脱盐水作三洗水循环使用。The three-washing wastewater membrane treatment includes the microfiltration membrane treatment in the front stage and the reverse osmosis membrane treatment in the latter stage. The concentrated solution containing titanium dioxide produced by the microfiltration membrane is returned to the three washing tank, and the clear liquid enters the reverse osmosis membrane; the reverse osmosis membrane treatment produces The sodium sulfate-containing concentrate is sent to the post-treatment section, and the resulting demineralized water is used as a three-wash water cycle.
微滤膜的作用为拦截废酸中的偏钛酸固体，所用微滤膜精度为50-500纳米，跨膜压差为0.05-0.8MPa；反渗透膜的作用为截留废水中的硫酸钠，仅允许水透过，反渗透膜的脱盐率为95-99％。The function of the microfiltration membrane is to intercept the metatitanic acid solid in the waste acid. The precision of the microfiltration membrane is 50-500 nm, and the transmembrane pressure difference is 0.05-0.8 MPa. The reverse osmosis membrane acts to intercept the sodium sulfate in the wastewater. Only water permeation is allowed, and the desalination rate of the reverse osmosis membrane is 95-99%.
三洗需要补充去离子水，补充水量为三洗水量的0-30％。The three washes need to be supplemented with deionized water, and the amount of water added is 0-30% of the three wash water.
硫酸钠的后处理工段为排放、回收或部分排放部分回收。The post-treatment section of sodium sulphate is partially recovered for discharge, recovery or partial discharge.
在本发明的另外的具体实施例子中，一洗产生的弱酸白水和二洗产生的二洗废水合并或工艺套用后采用膜处理，回收废水中的偏钛酸颗粒以及含硫酸亚铁和硫酸氧钛的浓液，并产生清洁的稀酸水。 In another embodiment of the present invention, the weak acid white water produced by one washing and the second washing wastewater generated by the second washing are combined or processed by a membrane treatment, and the metatitanic acid particles in the wastewater and the ferrous sulfate and sulfuric acid are recovered. A concentrated solution of titanium and produces clean dilute acid water.
合并废水膜处理包括前段的微滤膜处理和后段的耐酸膜处理，微滤膜处理产生的含偏钛酸的浓液返回一洗槽，清液进入耐酸膜；耐酸膜处理产生的含硫酸亚铁和硫酸氧钛的浓液返回酸解工段，而产生的清洁稀酸水作一洗水和二洗水循环使用。The combined wastewater membrane treatment includes the microfiltration membrane treatment in the front stage and the acid-resistant membrane treatment in the latter stage. The concentrated solution containing metatitanic acid produced by the microfiltration membrane is returned to a washing tank, and the clear liquid enters the acid-resistant membrane; the sulfuric acid produced by the acid-resistant membrane treatment The concentrated solution of ferrous iron and titanium oxysulfate is returned to the acid hydrolysis section, and the cleaned dilute acid water produced is used as a wash water and a second wash water cycle.
微滤膜的作用为拦截废酸中的偏钛酸固体，所用微滤膜精度为50-500纳米，跨膜压差为0.05-0.8MPa；耐酸膜的作用为截留废酸中的硫酸亚铁和硫酸氧钛，允许硫酸透过，所用耐酸膜对亚铁离子的截留率为85-98％，对硫酸氧钛的截留率大于80-95％，耐硫酸浓度为0-30％，操作压力为1.5-4.5MPa。The function of the microfiltration membrane is to intercept the metatitanic acid solid in the waste acid. The precision of the microfiltration membrane is 50-500 nm, and the transmembrane pressure difference is 0.05-0.8 MPa. The role of the acid-resistant membrane is to intercept the ferrous sulfate in the spent acid. And titanium oxysulfate, allowing sulfuric acid to permeate, the acid-resistant membrane used has a rejection of ferrous ions of 85-98%, the rejection of titanyl sulfate is greater than 80-95%, the sulfuric acid concentration is 0-30%, operating pressure It is 1.5-4.5 MPa.
本发明的积极进步效果在于：本发明提供的绿色环保硫酸法钛白粉生产装置以及工艺具有以下优点：本发明不仅能提高钛白回收率，为硫酸法钛白粉企业创造经济效益，而且减少了废酸和废水的排放，减轻了环境压力，为社会创造了环境效益，是一种绿色环保新工艺。The positive progress of the invention is that the green environmentally friendly sulfuric acid method titanium dioxide production device and the process provided by the invention have the following advantages: the invention can not only improve the recovery rate of titanium dioxide, but also create economic benefits for the sulfuric acid method titanium dioxide enterprise, and reduce waste. The discharge of acid and waste water has reduced environmental pressure and created environmental benefits for the society. It is a new green environmental protection process.
附图说明DRAWINGS
图1为本发明的整体工艺流程图。Figure 1 is a flow chart of the overall process of the present invention.
图2是本发明中返回至酸解工段的工艺流程图。Figure 2 is a process flow diagram of the return to the acid hydrolysis section of the present invention.
图3是本发明中废酸处理的工艺流程图。Figure 3 is a flow chart showing the process of waste acid treatment in the present invention.
图4是本发明中弱酸白水处理的工艺流程图。Fig. 4 is a flow chart showing the process of treating weak acid white water in the present invention.
图5是本发明中二洗废水处理的工艺流程图。Figure 5 is a process flow diagram of the treatment of the second washing wastewater in the present invention.
图6是本发明中煅烧尾气废水处理的工艺流程图。Figure 6 is a process flow diagram of the treatment of calcined tail gas wastewater in the present invention.
图7是本发明中三洗废水处理的工艺流程图。Fig. 7 is a flow chart showing the process of the three washing wastewater treatment in the present invention.
具体实施方式detailed description
下面结合附图给出本发明较佳实施例，以详细说明本发明的技术方案。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.
图1为本发明的整体工艺流程图。如图1所示，本发明中采用的装置生产 工序的最上游到最下游依次包括：粉磨装置、酸解装置、澄清装置、真空结晶装置、圆盘过滤装置、精细过滤装置、真空浓缩装置、钛液预热装置、水解装置、一洗上片装置、打浆装置、一洗装置、漂白装置、二洗装置、板框压滤装置、盐处理真空转鼓脱水装置、煅烧装置、雷蒙磨装置、打浆分散装置、砂磨装置、包膜装置、三洗装置、干燥装置、气流粉碎装置和包装装置。Figure 1 is a flow chart of the overall process of the present invention. As shown in Figure 1, the device used in the present invention is produced. The most upstream to the most downstream of the process includes: a grinding device, an acid hydrolysis device, a clarification device, a vacuum crystallization device, a disk filtration device, a fine filtration device, a vacuum concentrating device, a titanium liquid preheating device, a hydrolysis device, and a washing Sheet device, beating device, washing device, bleaching device, second washing device, plate and frame filter press device, salt treatment vacuum drum dewatering device, calcining device, Raymond mill device, beating and dispersing device, sanding device, coating device , three washing devices, drying devices, jet milling devices and packaging devices.
一洗上片装置上连接有废酸膜处理装置，一洗装置上连接有一洗废水膜处理装置，二洗装置上连接有二洗废水膜处理装置，三洗装置上连接有三洗废水膜处理装置。A washing acid film processing device is connected to the washing device, a washing waste water film processing device is connected to the washing device, a second washing wastewater film processing device is connected to the second washing device, and a three washing wastewater film processing device is connected to the three washing device. .
本发明中采用的是湿铁钛矿生产金红石型二氧化钛，其工段依次为：粉磨、酸解、澄清、真空结晶、圆盘过滤、精细过滤、真空浓缩、钛液预热、水解、一洗上片、打浆、一洗、漂白、二洗、板框压滤、盐处理真空转鼓脱水、煅烧、雷蒙磨、打浆分散、砂磨、包膜、三洗、干燥、气流粉碎、包装。The invention adopts wet iron-titanium to produce rutile type titanium dioxide, and the working sections thereof are: grinding, acid hydrolysis, clarification, vacuum crystallization, disk filtration, fine filtration, vacuum concentration, titanium liquid preheating, hydrolysis, and washing. Topping, beating, washing, bleaching, second washing, plate and frame pressure filtration, salt treatment, vacuum drum dehydration, calcination, Raymond grinding, beating dispersion, sanding, coating, three washing, drying, airflow crushing, packaging.
其中一洗上片工段增加了废酸膜处理工艺，一洗工段增加了一洗废水膜处理工艺，二洗工段增加了二洗废水膜处理工艺，煅烧工段增加了煅烧尾气废水膜处理工艺和硫酸浓缩工艺，三洗工段增加了三洗废水膜处理工艺。One of the washing-up sections increased the waste acid membrane treatment process, a washing wastewater treatment process was added to the washing section, and the second washing wastewater treatment process was added to the second washing section. The calcining section increased the membrane treatment process of the calcined tail gas wastewater and sulfuric acid. In the concentration process, the three washing sections have added three washing wastewater membrane treatment processes.
在本发明中，一洗上片产生的废酸需经过膜处理，回收废酸中的偏钛酸颗粒以及含硫酸亚铁和硫酸氧钛的浓液，并产生清洁的稀硫酸，废酸需经过膜处理包括前段的微滤膜处理和后段的耐酸膜处理，微滤膜处理产生的含偏钛酸的浓液返回一洗上片槽，清液进入耐酸膜；耐酸膜处理产生的含硫酸亚铁和硫酸氧钛的浓液返回酸解工段，而产生的清洁稀硫酸作煅烧窑尾气的喷淋液。In the present invention, the waste acid produced by washing the sheet is subjected to a membrane treatment to recover the metatitanic acid particles in the spent acid and the concentrated solution containing ferrous sulfate and titanyl sulfate, and to produce clean dilute sulfuric acid, which is required for waste acid. The membrane treatment includes the microfiltration membrane treatment in the front stage and the acid-resistant membrane treatment in the latter stage, and the concentrated solution containing the metatitanic acid produced by the microfiltration membrane is returned to the washing tank, and the clear liquid enters the acid-resistant membrane; The concentrated solution of ferrous sulfate and titanyl sulfate is returned to the acid hydrolysis section, and the clean dilute sulfuric acid produced is used as a spray liquid for calcining the kiln exhaust gas.
在本发明中，微滤膜的作用为拦截废酸中的偏钛酸固体，所用微滤膜精度为50-500纳米，跨膜压差为0.05-0.8MPa；耐酸膜的作用为截留废酸中的硫酸亚铁和硫酸氧钛，允许硫酸透过，所用耐酸膜对亚铁离子的截留率为85-98％，对硫酸氧钛的截留率为80-95％，耐硫酸浓度为0-30％，操作压力为1.5-4.5MPa。 In the present invention, the microfiltration membrane functions to intercept the metatitanic acid solid in the spent acid, the precision of the microfiltration membrane used is 50-500 nm, and the transmembrane pressure difference is 0.05-0.8 MPa; the role of the acid-resistant membrane is to trap the spent acid. The ferrous sulfate and titanium oxysulfate allow sulfuric acid to permeate. The acid-resistant membrane used has a rejection of ferrous ions of 85-98%, a retention rate of titanyl sulfate of 80-95%, and a sulfuric acid resistant concentration of 0- 30%, operating pressure is 1.5-4.5 MPa.
在本发明中，一洗产生的弱酸白水需经过膜处理，以回收白水中的偏钛酸颗粒以及含硫酸亚铁和硫酸氧钛的浓液，并产生清洁的稀酸水。In the present invention, the weak acid white water produced by one washing is subjected to a membrane treatment to recover metatitanic acid particles in white water and a concentrated liquid containing ferrous sulfate and titanyl sulfate, and to produce clean dilute acid water.
白水膜处理包括前段的微滤膜处理和后段的耐酸膜处理，微滤膜处理产生的含偏钛酸的浓液返回一洗槽，清液进入耐酸膜；耐酸膜处理产生的含硫酸亚铁和硫酸氧钛的浓液返回酸解工段，而产生的清洁稀酸水作一洗水循环使用。The white water film treatment includes the microfiltration membrane treatment in the front stage and the acid-resistant membrane treatment in the latter stage, and the concentrated solution containing the metatitanic acid produced by the microfiltration membrane is returned to the washing tank, and the clear liquid enters the acid-resistant membrane; the sulfuric acid-containing subgas produced by the acid-resistant membrane treatment The concentrated solution of iron and titanyl sulfate is returned to the acid hydrolysis section, and the clean dilute acid water produced is used as a wash water cycle.
微滤膜的作用为拦截废酸中的偏钛酸固体，所用微滤膜精度为50-500纳米，跨膜压差为0.05-0.8MPa；耐酸膜的作用为截留废酸中的硫酸亚铁和硫酸氧钛，允许硫酸透过，所用耐酸膜对亚铁离子的截留率为85-98％，对硫酸氧钛的截留率为80-95％，耐硫酸浓度为0-30％，操作压力为1.5-4.5MPa。The function of the microfiltration membrane is to intercept the metatitanic acid solid in the waste acid. The precision of the microfiltration membrane is 50-500 nm, and the transmembrane pressure difference is 0.05-0.8 MPa. The role of the acid-resistant membrane is to intercept the ferrous sulfate in the spent acid. And titanium oxysulfate, allowing sulfuric acid to pass through, the acid-resistant membrane used has a rejection of ferrous ions of 85-98%, a retention rate of titanium oxysulfate of 80-95%, a sulfuric acid concentration of 0-30%, and operating pressure. It is 1.5-4.5 MPa.
在本发明中，二洗产生的二洗废水需经过膜处理，以回收废水中的偏钛酸颗粒以及含硫酸亚铁和硫酸氧钛的浓液，并产生清洁的稀酸水。In the present invention, the second washing wastewater produced by the second washing is subjected to a membrane treatment to recover the metatitanic acid particles in the wastewater and the concentrated liquid containing ferrous sulfate and titanyl sulfate, and to produce clean dilute acid water.
二洗废水膜处理包括前段的微滤膜处理和后段的耐酸膜处理，微滤膜处理产生的含偏钛酸的浓液返回二洗槽，清液进入耐酸膜；耐酸膜处理产生的含硫酸亚铁和硫酸氧钛的浓液返回酸解工段，而产生的清洁稀酸水作二洗水循环使用。The second washing wastewater membrane treatment includes the microfiltration membrane treatment in the front stage and the acid-resistant membrane treatment in the latter stage, and the concentrated solution containing the metatitanic acid produced by the microfiltration membrane is returned to the second washing tank, and the clear liquid enters the acid-resistant membrane; The concentrated solution of ferrous sulfate and titanyl sulfate is returned to the acid hydrolysis section, and the clean dilute acid water produced is used for the second wash water cycle.
微滤膜的作用为拦截废酸中的偏钛酸固体，所用微滤膜精度为50-500纳米，跨膜压差为0.05-0.8MPa；耐酸膜的作用为截留废酸中的硫酸亚铁和硫酸氧钛，允许硫酸透过，所用耐酸膜对亚铁离子的截留率为85-98％，对硫酸氧钛的截留率为80-95％，耐硫酸浓度为0-30％，操作压力为1.5-4.5MPa。The function of the microfiltration membrane is to intercept the metatitanic acid solid in the waste acid. The precision of the microfiltration membrane is 50-500 nm, and the transmembrane pressure difference is 0.05-0.8 MPa. The role of the acid-resistant membrane is to intercept the ferrous sulfate in the spent acid. And titanium oxysulfate, allowing sulfuric acid to pass through, the acid-resistant membrane used has a rejection of ferrous ions of 85-98%, a retention rate of titanium oxysulfate of 80-95%, a sulfuric acid concentration of 0-30%, and operating pressure. It is 1.5-4.5 MPa.
二洗需要补充去离子水，补充水量为二洗水量的0-30％。The second wash needs to be supplemented with deionized water, and the amount of water added is 0-30% of the amount of the second wash water.
在本发明中，来自于一洗上片的废酸经微滤膜处理后产生的稀硫酸作为煅烧窑的尾气喷淋液，喷淋后产生的废液需经过膜处理，以回收废液中的二氧化钛颗粒，并产生清洁的稀硫酸，稀硫酸进入硫酸浓缩装置。In the present invention, the dilute sulfuric acid generated from the waste acid of a washed sheet after being treated by the microfiltration membrane is used as the tail gas spray liquid of the calcining kiln, and the waste liquid generated after the spraying is subjected to membrane treatment to recover the waste liquid. The titanium dioxide particles produce clean dilute sulfuric acid and dilute sulfuric acid into the sulfuric acid concentrating unit.
微滤膜的作用为拦截喷淋废液中的二氧化钛固体，被拦截的二氧化钛固体返回至煅烧窑，硫酸浓缩装置产生的冷凝稀酸水返回至一洗水槽作一洗水使 用，硫酸浓缩装置产生的浓硫酸返回至酸解工段。The function of the microfiltration membrane is to intercept the titanium dioxide solids in the spray waste liquid, and the intercepted titanium dioxide solids are returned to the calcining kiln, and the condensed dilute acid water produced by the sulfuric acid concentrating device is returned to a washing tank for washing. The concentrated sulfuric acid produced by the sulfuric acid concentrating device is returned to the acid hydrolysis section.
所用微滤膜精度为50-500纳米，跨膜压差为0.05-0.8MPa。硫酸浓缩装置产生的浓硫酸的浓度为50-96％。The microfiltration membrane used has an accuracy of 50-500 nm and a transmembrane pressure difference of 0.05-0.8 MPa. The concentration of concentrated sulfuric acid produced by the sulfuric acid concentration unit is 50-96%.
一洗需要补充去离子水，补充水量为一洗水量的0-30％。A wash needs to be supplemented with deionized water, and the amount of water added is 0-30% of a wash.
在本发明中，三洗产生的三洗废水需经过膜处理，回收废水中的二氧化钛颗粒以及含硫酸钠的浓液，并产生清洁的脱盐水。In the present invention, the three washing waste water produced by the three washings is subjected to a membrane treatment to recover the titanium dioxide particles in the wastewater and the concentrated solution containing sodium sulfate, and to produce a clean desalinated water.
三洗废水膜处理包括前段的微滤膜处理和后段的反渗透膜处理，微滤膜处理产生的含二氧化钛的浓液返回三洗槽，清液进入反渗透膜；反渗透膜处理产生的含硫酸钠浓液送至后处理工段，而产生的脱盐水作三洗水循环使用。The three-washing wastewater membrane treatment includes the microfiltration membrane treatment in the front stage and the reverse osmosis membrane treatment in the latter stage. The concentrated solution containing titanium dioxide produced by the microfiltration membrane is returned to the three washing tank, and the clear liquid enters the reverse osmosis membrane; the reverse osmosis membrane treatment produces The sodium sulfate-containing concentrate is sent to the post-treatment section, and the resulting demineralized water is used as a three-wash water cycle.
微滤膜的作用为拦截废酸中的偏钛酸固体，所用微滤膜精度为50-500纳米，跨膜压差为0.05-0.8MPa；反渗透膜的作用为截留废水中的硫酸钠，仅允许水透过，反渗透膜的脱盐率为95-99％。The function of the microfiltration membrane is to intercept the metatitanic acid solid in the waste acid. The precision of the microfiltration membrane is 50-500 nm, and the transmembrane pressure difference is 0.05-0.8 MPa. The reverse osmosis membrane acts to intercept the sodium sulfate in the wastewater. Only water permeation is allowed, and the desalination rate of the reverse osmosis membrane is 95-99%.
三洗需要补充去离子水，补充水量为三洗水量的0-30％。The three washes need to be supplemented with deionized water, and the amount of water added is 0-30% of the three wash water.
硫酸钠的后处理工段为排放、回收或部分排放部分回收。The post-treatment section of sodium sulphate is partially recovered for discharge, recovery or partial discharge.
在本发明中，一洗产生的弱酸白水和二洗产生的二洗废水既可如上面所述的单独处理，也可合并或工艺套用后采用膜处理，回收废水中的偏钛酸颗粒以及含硫酸亚铁和硫酸氧钛的浓液，并产生清洁的稀酸水。In the present invention, the weak acid white water produced by one washing and the second washing waste water produced by the second washing may be treated separately as described above, or may be combined or subjected to membrane treatment after the process is applied, and the metatitanic acid particles in the waste water are recovered and contained. A concentrated solution of ferrous sulfate and titanyl sulfate, and produces a clean dilute acid water.
合并废水膜处理包括前段的微滤膜处理和后段的耐酸膜处理，微滤膜处理产生的含偏钛酸的浓液返回一洗槽，清液进入耐酸膜；耐酸膜处理产生的含硫酸亚铁和硫酸氧钛的浓液返回酸解工段，而产生的清洁稀酸水作一洗水和二洗水循环使用。The combined wastewater membrane treatment includes the microfiltration membrane treatment in the front stage and the acid-resistant membrane treatment in the latter stage. The concentrated solution containing metatitanic acid produced by the microfiltration membrane is returned to a washing tank, and the clear liquid enters the acid-resistant membrane; the sulfuric acid produced by the acid-resistant membrane treatment The concentrated solution of ferrous iron and titanium oxysulfate is returned to the acid hydrolysis section, and the cleaned dilute acid water produced is used as a wash water and a second wash water cycle.
微滤膜的作用为拦截废酸中的偏钛酸固体，所用微滤膜精度为50-500纳米，跨膜压差为0.05-0.8MPa；耐酸膜的作用为截留废酸中的硫酸亚铁和硫酸氧钛，允许硫酸透过，所用耐酸膜对亚铁离子的截留率为85-98％，对硫酸氧钛的截留率大于80-95％，耐硫酸浓度为0-30％，操作压力为1.5-4.5MPa。 The function of the microfiltration membrane is to intercept the metatitanic acid solid in the waste acid. The precision of the microfiltration membrane is 50-500 nm, and the transmembrane pressure difference is 0.05-0.8 MPa. The role of the acid-resistant membrane is to intercept the ferrous sulfate in the spent acid. And titanium oxysulfate, allowing sulfuric acid to permeate, the acid-resistant membrane used has a rejection of ferrous ions of 85-98%, the rejection of titanyl sulfate is greater than 80-95%, the sulfuric acid concentration is 0-30%, operating pressure It is 1.5-4.5 MPa.
图2是本发明中返回至酸解工段的工艺流程图。如图2所示：来自于废酸浓缩装置产生的浓硫酸，和来自于一洗上片废酸膜处理、一洗废水膜处理和二洗废水膜处理后的含硫酸亚铁、硫酸氧钛的浓液，均返回至酸解工段。Figure 2 is a process flow diagram of the return to the acid hydrolysis section of the present invention. As shown in Figure 2: concentrated sulfuric acid from the waste acid concentrating device, and ferrous sulfate and titanyl sulfate from a washed acid film treatment, a washing wastewater membrane treatment and a second washing wastewater membrane treatment. The concentrated solution is returned to the acid hydrolysis section.
图3是本发明中废酸处理的工艺流程图。如图3所示：一洗上片产生的废酸膜处理工艺包括前段的微滤膜处理和后段的耐酸膜处理，微滤膜处理产生的含偏钛酸的浓液返回一洗上片槽，清液进入耐酸膜；耐酸膜处理产生的含硫酸亚铁和硫酸氧钛的浓液返回酸解工段，而产生的清洁稀硫酸作煅烧窑尾气的喷淋液。Figure 3 is a flow chart showing the process of waste acid treatment in the present invention. As shown in Fig. 3, the waste acid film treatment process produced by washing the upper sheet includes the microfiltration membrane treatment in the front stage and the acid-resistant membrane treatment in the latter stage, and the concentrated solution containing the metatitanic acid produced by the microfiltration membrane is returned to the wash sheet. The trough and the clear liquid enter the acid-resistant membrane; the concentrated liquid containing ferrous sulfate and titanyl sulfate produced by the acid-resistant membrane treatment is returned to the acid hydrolysis section, and the clean dilute sulfuric acid is produced as the spray liquid of the calcining kiln exhaust gas.
图4是本发明中弱酸白水处理的工艺流程图，如图4所示：一洗产生的弱酸白水膜处理包括前段的微滤膜处理和后段的耐酸膜处理，微滤膜处理产生的含偏钛酸的浓液返回一洗槽，清液进入耐酸膜；耐酸膜处理产生的含硫酸亚铁和硫酸氧钛的浓液返回酸解工段，而产生的清洁稀酸水作一洗水循环使用。4 is a process flow diagram of the treatment of weak acid white water in the present invention, as shown in FIG. 4: the treatment of the weak acid white water film produced by one washing comprises the treatment of the microfiltration membrane in the front stage and the acid treatment treatment in the latter stage, and the treatment by the microfiltration membrane treatment. The concentrated solution of metatitanic acid is returned to a washing tank, and the clear liquid enters the acid-resistant membrane; the concentrated liquid containing ferrous sulfate and titanyl sulfate produced by the acid-resistant membrane treatment is returned to the acid hydrolysis section, and the clean diluted acid water is used as a washing water cycle. .
图5是本发明中二洗废水处理的工艺流程图。如图5所示：二洗废水膜处理包括前段的微滤膜处理和后段的耐酸膜处理，微滤膜处理产生的含偏钛酸的浓液返回二洗槽，清液进入耐酸膜；耐酸膜处理产生的含硫酸亚铁和硫酸氧钛的浓液返回酸解工段，而产生的清洁稀酸水作二洗水循环使用。Figure 5 is a process flow diagram of the treatment of the second washing wastewater in the present invention. As shown in Figure 5: the second washing wastewater membrane treatment includes the microfiltration membrane treatment in the front stage and the acid-resistant membrane treatment in the latter stage, and the concentrated solution containing the metatitanic acid produced by the microfiltration membrane is returned to the second washing tank, and the clear liquid enters the acid-resistant membrane; The concentrated solution containing ferrous sulfate and titanyl sulfate produced by the acid-resistant membrane treatment is returned to the acid hydrolysis section, and the clean dilute acid water produced is used for the second wash water cycle.
图6是本发明中煅烧尾气废水处理的工艺流程图，如图6所示：来自于一洗上片废酸膜处理后的稀硫酸喷淋煅烧尾气，产生煅烧尾气废水。废水经过膜处理拦截喷淋废液中的二氧化钛固体，被拦截的二氧化钛固体返回至煅烧窑，膜处理产生的清液为稀硫酸，稀硫酸进入硫酸浓缩装置。硫酸浓缩装置产生的冷凝稀酸水返回至一洗水槽作一洗水使用，硫酸浓缩装置产生的浓硫酸返回至酸解工段。6 is a process flow diagram of the treatment of calcined tail gas wastewater in the present invention, as shown in FIG. 6 : the dilute sulfuric acid spray calcined tail gas after treatment with a waste acid film treatment to produce calcined tail gas wastewater. The wastewater is subjected to membrane treatment to intercept the titanium dioxide solids in the spray waste liquid, and the intercepted titanium dioxide solids are returned to the calcining kiln, and the clear liquid produced by the membrane treatment is dilute sulfuric acid, and the dilute sulfuric acid enters the sulfuric acid concentration device. The condensed dilute acid water produced by the sulfuric acid concentrating device is returned to a washing tank for use as a washing water, and the concentrated sulfuric acid produced by the sulfuric acid concentrating device is returned to the acid hydrolysis section.
图7是本发明中三洗废水处理的工艺流程图，如图7所示：三洗废水膜处理包括前段的微滤膜处理和后段的反渗透膜处理，微滤膜处理产生的含二氧化钛的浓液返回三洗槽，清液进入反渗透膜。反渗透膜处理产生的含硫酸钠浓液 送至后处理工段，而产生的脱盐水作三洗水循环使用。Figure 7 is a process flow diagram of the three-washing wastewater treatment in the present invention, as shown in Figure 7: the three-wash wastewater membrane treatment includes the microfiltration membrane treatment in the front stage and the reverse osmosis membrane treatment in the latter stage, and the titanium dioxide-containing treatment by the microfiltration membrane treatment. The concentrated liquid returns to the three washing tank, and the clear liquid enters the reverse osmosis membrane. Sodium sulfate-containing concentrate produced by reverse osmosis membrane treatment It is sent to the post-treatment section, and the resulting demineralized water is used for three wash water cycles.
实施例一Embodiment 1
一洗上片废酸中钛浓度为9.22g/L，亚铁离子浓度为45g/L，硫酸含量为20％。该废酸首先经过微滤膜处理，微滤膜精度为200nm，跨膜压差为0.2MPa。膜处理后含偏钛酸的浓液返回一洗上片槽，膜处理后清液中钛浓度为2g/L。微滤膜处理后的清液继续采用耐酸膜处理，操作压力为3.8MPa。耐酸膜处理后含硫酸亚铁和硫酸氧钛的浓液返回至酸解锅，单级耐酸膜处理后的清液中钛浓度为140mg/L，亚铁离子浓度为2.25g/L，硫酸含量为20％；两级耐酸膜处理后的清液中钛浓度为9.8mg/L，亚铁离子浓度为112mg/L，硫酸含量为20％。该清液送往煅烧窑作为煅烧尾气喷淋液。The concentration of titanium in the waste acid was 9.22 g/L, the ferrous ion concentration was 45 g/L, and the sulfuric acid content was 20%. The spent acid was first treated by a microfiltration membrane with a precision of 200 nm and a transmembrane pressure difference of 0.2 MPa. After the membrane treatment, the concentrated solution containing metatitanic acid was returned to the washing tank, and the concentration of titanium in the supernatant after the membrane treatment was 2 g/L. The supernatant after the microfiltration membrane treatment was continuously treated with an acid-resistant membrane at an operating pressure of 3.8 MPa. After the acid-resistant membrane treatment, the concentrated solution containing ferrous sulfate and titanyl sulfate is returned to the acid hydrolysis pot, and the concentration of titanium in the supernatant after treatment with the single-stage acid-resistant membrane is 140 mg/L, the concentration of ferrous ions is 2.25 g/L, and the content of sulfuric acid is It is 20%; the concentration of titanium in the supernatant after the two-stage acid-resistant treatment is 9.8 mg/L, the ferrous ion concentration is 112 mg/L, and the sulfuric acid content is 20%. The supernatant is sent to a calcining kiln as a calcined tail gas spray.
从膜处理效率来看，微滤膜对偏钛酸的拦截效率为99％以上，剩余的钛则是溶解性的钛(硫酸氧钛)。单级耐酸膜对亚铁离子的截留率为95％，对硫酸氧钛的截留率为93％。From the viewpoint of membrane treatment efficiency, the interception efficiency of the microfiltration membrane for metatitanic acid is 99% or more, and the remaining titanium is soluble titanium (titanium sulfate sulfate). The single-stage acid-resistant membrane has a rejection of ferrous ions of 95% and a retention of 93% for titanyl sulfate.
以上显示和描述了本发明的基本原理和主要特征和本发明的优点。本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明精神和范围的前提下，本发明还会有各种变化和改进，这些变化和改进都落入要求保护的本发明范围内，本发明要求保护范围由所附的权利要求书及其等效物界定。 The basic principles and main features of the present invention and the advantages of the present invention are shown and described above. It should be understood by those skilled in the art that the present invention is not limited by the foregoing embodiments, and that the present invention is only described in the foregoing description and the description of the present invention, without departing from the spirit and scope of the invention. Various changes and modifications are intended to be included within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and their equivalents.

Claims (9)

  1. 一种绿色环保硫酸法钛白粉生产装置，其特征在于：所述生产装置从生产工序的最上游到最下游依次包括：粉磨装置、酸解装置、澄清装置、真空结晶装置、圆盘过滤装置、精细过滤装置、真空浓缩装置、钛液预热装置、水解装置、一洗上片装置、打浆装置、一洗装置、漂白装置、二洗装置、板框压滤装置、盐处理真空转鼓脱水装置、煅烧装置、雷蒙磨装置、打浆分散装置、砂磨装置、包膜装置、三洗装置、干燥装置、气流粉碎装置和包装装置。A green environmentally friendly sulfuric acid method titanium dioxide production device, characterized in that: the production device comprises, in order from the most upstream to the most downstream of the production process, a grinding device, an acid hydrolysis device, a clarification device, a vacuum crystallization device, and a disk filter device. , fine filter device, vacuum concentrating device, titanium liquid preheating device, hydrolysis device, washing device, beating device, washing device, bleaching device, washing device, plate and frame filter press, salt treatment vacuum drum dehydration Device, calcining device, Raymond mill device, beating and dispersing device, sanding device, coating device, three-washing device, drying device, airflow pulverizing device and packaging device.
    一洗上片装置上连接有废酸膜处理装置；一洗装置上连接有一洗废水膜处理装置；二洗装置上连接有二洗废水膜处理装置；三洗装置上连接有三洗废水膜处理装置。A washing acid film processing device is connected to the washing device; a washing wastewater film processing device is connected to the washing device; a washing liquid film treating device is connected to the second washing device; and a three washing wastewater film treating device is connected to the three washing device. .
  2. 一种绿色环保硫酸法钛白粉生产工艺，其特征在于：所述生产工艺从最上游到最下游依次包括：粉磨、酸解、澄清、真空结晶、圆盘过滤、精细过滤、真空浓缩、钛液预热、水解、一洗上片、打浆、一洗、漂白、二洗、板框压滤、盐处理真空转鼓脱水、煅烧、雷蒙磨、打浆分散、砂磨、包膜、三洗、干燥、气流粉碎和包装。The invention relates to a green environmentally friendly sulfuric acid method titanium dioxide production process, which is characterized in that: the production process from the most upstream to the most downstream includes: grinding, acid hydrolysis, clarification, vacuum crystallization, disk filtration, fine filtration, vacuum concentration, titanium Preheating, hydrolysis, washing, washing, washing, bleaching, washing, plate and frame filtration, salt treatment, vacuum drum dehydration, calcination, Raymond grinding, beating dispersion, sanding, coating, three washing , drying, jet milling and packaging.
  3. 根据权利要求2所述的绿色环保硫酸法钛白粉生产工艺，其特征在于：一洗上片产生的废酸需经过膜处理，回收废酸中的偏钛酸颗粒以及含硫酸亚铁和硫酸氧钛的浓液，并产生清洁的稀硫酸，废酸需经过膜处理包括前段的微滤膜处理和后段的耐酸膜处理，微滤膜处理产生的含偏钛酸的浓液返回一洗上片槽，清液进入耐酸膜；耐酸膜处理产生的含硫酸亚铁和硫酸氧钛的浓液返回酸解工段，而产生的清洁稀硫酸作煅烧窑尾气的喷淋液。The green environmentally-friendly sulfuric acid method for producing titanium dioxide according to claim 2, wherein the waste acid produced by washing the sheet is subjected to membrane treatment to recover metatitanic acid particles in the spent acid and ferrous sulfate and sulfuric acid. Titanium concentrate, and produce clean dilute sulfuric acid. The waste acid needs to be subjected to membrane treatment, including the microfiltration membrane treatment in the front stage and the acid-resistant membrane treatment in the latter stage. The concentrated solution containing metatitanic acid produced by the microfiltration membrane is returned to a wash. The trough, the clear liquid enters the acid-resistant membrane; the concentrated liquid containing ferrous sulfate and titanyl sulfate produced by the acid-resistant membrane treatment is returned to the acid hydrolysis section, and the clean dilute sulfuric acid produced is used as the spray liquid of the calcining kiln exhaust gas.
  4. 根据权利要求3所述的绿色环保硫酸法钛白粉生产工艺，其特征在于：微滤膜的作用为拦截废酸中的偏钛酸固体，所用微滤膜精度为50-500纳米，跨膜压差为0.05-0.8MPa；耐酸膜的作用为截留废酸中的硫酸亚铁和硫酸氧 钛，允许硫酸透过，所用耐酸膜对亚铁离子的截留率为85-98％，对硫酸氧钛的截留率为80-95％，耐硫酸浓度为0-30％，操作压力为1.5-4.5MPa。The green environmentally-friendly sulfuric acid titanium dioxide production process according to claim 3, wherein the microfiltration membrane functions to intercept the metatitanic acid solid in the waste acid, and the precision of the microfiltration membrane used is 50-500 nm, transmembrane pressure. The difference is 0.05-0.8 MPa; the role of the acid-resistant membrane is to trap ferrous sulfate and sulfuric acid in the spent acid. Titanium, allowing sulfuric acid to pass through, the acid-resistant membrane used has a rejection of ferrous ions of 85-98%, a retention rate of titanium oxysulfate of 80-95%, a sulfuric acid concentration of 0-30%, and an operating pressure of 1.5- 4.5 MPa.
  5. 根据权利要求2所述的绿色环保硫酸法钛白粉生产工艺，其特征在于：The green environmentally friendly sulfuric acid method titanium dioxide production process according to claim 2, characterized in that:
    一洗产生的弱酸白水需经过膜处理，以回收白水中的偏钛酸颗粒以及含硫酸亚铁和硫酸氧钛的浓液，并产生清洁的稀酸水；The weak acid white water produced by one washing needs to be subjected to membrane treatment to recover the metatitanic acid particles in white water and the concentrated liquid containing ferrous sulfate and titanyl sulfate, and produce clean dilute acid water;
    白水膜处理包括前段的微滤膜处理和后段的耐酸膜处理，微滤膜处理产生的含偏钛酸的浓液返回一洗槽，清液进入耐酸膜；耐酸膜处理产生的含硫酸亚铁和硫酸氧钛的浓液返回酸解工段，而产生的清洁稀酸水作一洗水循环使用；The white water film treatment includes the microfiltration membrane treatment in the front stage and the acid-resistant membrane treatment in the latter stage, and the concentrated solution containing the metatitanic acid produced by the microfiltration membrane is returned to the washing tank, and the clear liquid enters the acid-resistant membrane; the sulfuric acid-containing subgas produced by the acid-resistant membrane treatment The concentrated solution of iron and titanyl sulfate is returned to the acid hydrolysis section, and the cleaned dilute acid water produced is used as a washing water cycle;
    微滤膜的作用为拦截废酸中的偏钛酸固体，所用微滤膜精度为50-500纳米，跨膜压差为0.05-0.8MPa；耐酸膜的作用为截留废酸中的硫酸亚铁和硫酸氧钛，允许硫酸透过，所用耐酸膜对亚铁离子的截留率为85-98％，对硫酸氧钛的截留率为80-95％，耐硫酸浓度为0-30％，操作压力为1.5-4.5MPa。The function of the microfiltration membrane is to intercept the metatitanic acid solid in the waste acid. The precision of the microfiltration membrane is 50-500 nm, and the transmembrane pressure difference is 0.05-0.8 MPa. The role of the acid-resistant membrane is to intercept the ferrous sulfate in the spent acid. And titanium oxysulfate, allowing sulfuric acid to pass through, the acid-resistant membrane used has a rejection of ferrous ions of 85-98%, a retention rate of titanium oxysulfate of 80-95%, a sulfuric acid concentration of 0-30%, and operating pressure. It is 1.5-4.5 MPa.
  6. 根据权利要求2所述的绿色环保硫酸法钛白粉生产工艺，其特征在于：The green environmentally friendly sulfuric acid method titanium dioxide production process according to claim 2, characterized in that:
    二洗产生的二洗废水需经过膜处理，以回收废水中的偏钛酸颗粒以及含硫酸亚铁和硫酸氧钛的浓液，并产生清洁的稀酸水；The second washing wastewater generated by the second washing is subjected to membrane treatment to recover the metatitanic acid particles in the wastewater and the concentrated liquid containing ferrous sulfate and titanyl sulfate, and to produce clean dilute acid water;
    二洗废水膜处理包括前段的微滤膜处理和后段的耐酸膜处理，微滤膜处理产生的含偏钛酸的浓液返回二洗槽，清液进入耐酸膜；耐酸膜处理产生的含硫酸亚铁和硫酸氧钛的浓液返回酸解工段，而产生的清洁稀酸水作二洗水循环使用；The second washing wastewater membrane treatment includes the microfiltration membrane treatment in the front stage and the acid-resistant membrane treatment in the latter stage, and the concentrated solution containing the metatitanic acid produced by the microfiltration membrane is returned to the second washing tank, and the clear liquid enters the acid-resistant membrane; The concentrated solution of ferrous sulfate and titanyl sulfate is returned to the acid hydrolysis section, and the clean dilute acid water produced is used for the second wash water cycle;
    微滤膜的作用为拦截废酸中的偏钛酸固体，所用微滤膜精度为50-500纳米，跨膜压差为0.05-0.8MPa；耐酸膜的作用为截留废酸中的硫酸亚铁和硫酸氧钛，允许硫酸透过，所用耐酸膜对亚铁离子的截留率为85-98％，对硫酸氧钛的截留率为80-95％，耐硫酸浓度为0-30％，操作压力为1.5-4.5MPa；The function of the microfiltration membrane is to intercept the metatitanic acid solid in the waste acid. The precision of the microfiltration membrane is 50-500 nm, and the transmembrane pressure difference is 0.05-0.8 MPa. The role of the acid-resistant membrane is to intercept the ferrous sulfate in the spent acid. And titanium oxysulfate, allowing sulfuric acid to pass through, the acid-resistant membrane used has a rejection of ferrous ions of 85-98%, a retention rate of titanium oxysulfate of 80-95%, a sulfuric acid concentration of 0-30%, and operating pressure. Is 1.5-4.5MPa;
    二洗需要补充去离子水，补充水量为二洗水量的0-30％。The second wash needs to be supplemented with deionized water, and the amount of water added is 0-30% of the amount of the second wash water.
  7. 根据权利要求2所述的绿色环保硫酸法钛白粉生产工艺，其特征在于： The green environmentally friendly sulfuric acid method titanium dioxide production process according to claim 2, characterized in that:
    来自于一洗上片的废酸经微滤膜处理后产生的稀硫酸作为煅烧窑的尾气喷淋液，喷淋后产生的废液需经过膜处理，以回收废液中的二氧化钛颗粒，并产生清洁的稀硫酸，稀硫酸进入硫酸浓缩装置；The dilute sulfuric acid produced from the waste acid of a washed sheet is treated as a tail gas spray liquid of the calcining kiln, and the waste liquid generated after the spraying is subjected to a membrane treatment to recover the titanium dioxide particles in the waste liquid, and Producing clean dilute sulfuric acid, dilute sulfuric acid into the sulfuric acid concentration device;
    微滤膜的作用为拦截喷淋废液中的二氧化钛固体，被拦截的二氧化钛固体返回至煅烧窑，硫酸浓缩装置产生的冷凝稀酸水返回至一洗水槽作一洗水使用，硫酸浓缩装置产生的浓硫酸返回至酸解工段；The function of the microfiltration membrane is to intercept the titanium dioxide solids in the spray waste liquid, and the intercepted titanium dioxide solids are returned to the calcining kiln, and the condensed dilute acid water produced by the sulfuric acid concentrating device is returned to a washing tank for use as a washing water, and the sulfuric acid concentrating device is produced. The concentrated sulfuric acid is returned to the acid hydrolysis section;
    所用微滤膜精度为50-500纳米，跨膜压差为0.05-0.8MPa。硫酸浓缩装置产生的浓硫酸的浓度为50-96％；The microfiltration membrane used has an accuracy of 50-500 nm and a transmembrane pressure difference of 0.05-0.8 MPa. The concentration of concentrated sulfuric acid produced by the sulfuric acid concentrating device is 50-96%;
    一洗需要补充去离子水，补充水量为一洗水量的0-30％。A wash needs to be supplemented with deionized water, and the amount of water added is 0-30% of a wash.
  8. 根据权利要求2所述的绿色环保硫酸法钛白粉生产工艺，其特征在于：三洗产生的三洗废水需经过膜处理，回收废水中的二氧化钛颗粒以及含硫酸钠的浓液，并产生清洁的脱盐水；The green environmentally-friendly sulfuric acid titanium dioxide production process according to claim 2, characterized in that: the three washing waste water generated by the three washings is subjected to membrane treatment, and the titanium dioxide particles in the wastewater and the concentrated liquid containing sodium sulfate are recovered, and the cleaning is produced. Desalting water;
    三洗废水膜处理包括前段的微滤膜处理和后段的反渗透膜处理，微滤膜处理产生的含二氧化钛的浓液返回三洗槽，清液进入反渗透膜；反渗透膜处理产生的含硫酸钠浓液送至后处理工段，而产生的脱盐水作三洗水循环使用；The three-washing wastewater membrane treatment includes the microfiltration membrane treatment in the front stage and the reverse osmosis membrane treatment in the latter stage. The concentrated solution containing titanium dioxide produced by the microfiltration membrane is returned to the three washing tank, and the clear liquid enters the reverse osmosis membrane; the reverse osmosis membrane treatment produces The sodium sulfate-containing concentrate is sent to the post-treatment section, and the resulting demineralized water is used for three wash water cycles;
    微滤膜的作用为拦截废酸中的偏钛酸固体，所用微滤膜精度为50-500纳米，跨膜压差为0.05-0.8MPa；反渗透膜的作用为截留废水中的硫酸钠，仅允许水透过，反渗透膜的脱盐率为95-99％；The function of the microfiltration membrane is to intercept the metatitanic acid solid in the waste acid. The precision of the microfiltration membrane is 50-500 nm, and the transmembrane pressure difference is 0.05-0.8 MPa. The reverse osmosis membrane acts to intercept the sodium sulfate in the wastewater. Only water permeation is allowed, and the desalination rate of the reverse osmosis membrane is 95-99%;
    三洗需要补充去离子水，补充水量为三洗水量的0-30％；The three washes need to be supplemented with deionized water, and the amount of water added is 0-30% of the amount of three washes;
    硫酸钠的后处理工段为排放、回收或部分排放部分回收。The post-treatment section of sodium sulphate is partially recovered for discharge, recovery or partial discharge.
  9. 根据权利要求2所述的绿色环保硫酸法钛白粉生产工艺，其特征在于：The green environmentally friendly sulfuric acid method titanium dioxide production process according to claim 2, characterized in that:
    一洗产生的弱酸白水和二洗产生的二洗废水合并或工艺套用后采用膜处理，回收废水中的偏钛酸颗粒以及含硫酸亚铁和硫酸氧钛的浓液，并产生清洁的稀酸水；The weak acid white water produced by one washing is combined with the second washing wastewater generated by the second washing or the membrane is treated after the process is applied, and the metatitanic acid particles in the wastewater and the concentrated liquid containing ferrous sulfate and titanyl sulfate are recovered, and a clean dilute acid is produced. water;
    合并废水膜处理包括前段的微滤膜处理和后段的耐酸膜处理，微滤膜处理 产生的含偏钛酸的浓液返回一洗槽，清液进入耐酸膜；耐酸膜处理产生的含硫酸亚铁和硫酸氧钛的浓液返回酸解工段，而产生的清洁稀酸水作一洗水和二洗水循环使用；Combined wastewater membrane treatment includes microfiltration membrane treatment in the front stage and acid-resistant membrane treatment in the latter stage, microfiltration membrane treatment The produced concentrated solution containing metatitanic acid is returned to a washing tank, and the clear liquid enters the acid-resistant membrane; the concentrated liquid containing ferrous sulfate and titanyl sulfate produced by the acid-resistant membrane treatment is returned to the acid hydrolysis section, and the cleaned dilute acid water is produced as one. Washing water and washing water are recycled;
    微滤膜的作用为拦截废酸中的偏钛酸固体，所用微滤膜精度为50-500纳米，跨膜压差为0.05-0.8MPa；耐酸膜的作用为截留废酸中的硫酸亚铁和硫酸氧钛，允许硫酸透过，所用耐酸膜对亚铁离子的截留率为85-98％，对硫酸氧钛的截留率大于80-95％，耐硫酸浓度为0-30％，操作压力为1.5-4.5MPa。 The function of the microfiltration membrane is to intercept the metatitanic acid solid in the waste acid. The precision of the microfiltration membrane is 50-500 nm, and the transmembrane pressure difference is 0.05-0.8 MPa. The role of the acid-resistant membrane is to intercept the ferrous sulfate in the spent acid. And titanium oxysulfate, allowing sulfuric acid to permeate, the acid-resistant membrane used has a rejection of ferrous ions of 85-98%, the rejection of titanyl sulfate is greater than 80-95%, the sulfuric acid concentration is 0-30%, operating pressure It is 1.5-4.5 MPa.
PCT/CN2016/070464 2015-01-09 2016-01-08 Green and environmentally friendly sulfuric acid process titanium dioxide powder production equipment and technique WO2016110268A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201510011659.1A CN104692456A (en) 2015-01-09 2015-01-09 Green and environment-friendly sulfuric acid method titanium dioxide production device and process
CN201510011659.1 2015-01-09

Publications (1)

Publication Number Publication Date
WO2016110268A1 true WO2016110268A1 (en) 2016-07-14

Family

ID=53340075

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2016/070464 WO2016110268A1 (en) 2015-01-09 2016-01-08 Green and environmentally friendly sulfuric acid process titanium dioxide powder production equipment and technique

Country Status (2)

Country Link
CN (1) CN104692456A (en)
WO (1) WO2016110268A1 (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108083326A (en) * 2017-12-18 2018-05-29 广西雅照钛白有限公司 The method and apparatus of the energy saving Joint Production titanium dioxide of titanium powder plant, sulfuric acid and iron ore concentrate
CN112624189A (en) * 2021-01-14 2021-04-09 上海安赐环保科技股份有限公司 Method and system for recycling waste acid and white water of titanium dioxide produced by sulfuric acid process
CN112897782A (en) * 2021-01-14 2021-06-04 上海安赐环保科技股份有限公司 Method and system for recycling waste acid and white water of titanium dioxide produced by sulfuric acid process
CN114149025A (en) * 2021-12-30 2022-03-08 龙佰集团股份有限公司 Comprehensive utilization method of sulfate process titanium dioxide wastewater
CN114380328A (en) * 2021-12-28 2022-04-22 龙佰襄阳钛业有限公司 Titanium dioxide three-washing process
CN114408966A (en) * 2021-12-28 2022-04-29 龙佰襄阳钛业有限公司 Acidolysis process for filtering concentrated water by using membrane
CN115308079A (en) * 2022-08-26 2022-11-08 攀钢集团重庆钒钛科技有限公司 Characterization method for acidolysis rate of titanium concentrate in laboratory
CN116216773A (en) * 2023-03-02 2023-06-06 武汉工程大学 Method for preparing high-purity meta-titanic acid from solution containing hetero titanyl sulfate

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN105152207B (en) * 2015-07-31 2017-07-25 上海安赐环保科技股份有限公司 A kind of efficient sulfuric acid method titanium pigment water wash system and its washing process
CN105948291A (en) * 2016-06-03 2016-09-21 南京蓝色天空环保科技有限公司 Titanium-dioxide low-salt-waste-water recycling device and recycling method for low-salt waste water
CN106365197A (en) * 2016-08-31 2017-02-01 四川龙蟒钛业股份有限公司 Recycling method of titanium dioxide waste acid
CN106587121A (en) * 2016-12-21 2017-04-26 上海安赐环保科技股份有限公司 Water washing device and water washing method applied to washing process of aluminum hydroxide powder
CN109110939A (en) * 2018-08-07 2019-01-01 南京怡丰月明环保科技有限公司 A kind of three wash water recovery method of titanium dioxide and recyclable device
CN109133163A (en) * 2018-10-25 2019-01-04 上海安赐环保科技股份有限公司 A kind of novel sulfuric acid method titanium pigment washing process and system
CN113354179A (en) * 2021-07-13 2021-09-07 北京水木方科技有限公司 Recycling treatment method for titanium dioxide waste acid and primary washing waste acid water by sulfuric acid process
CN115872444A (en) * 2022-12-26 2023-03-31 攀枝花市海峰鑫化工有限公司 Method for improving recovery rate of titanium dioxide waste acid by sulfuric acid process

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103663547A (en) * 2012-09-24 2014-03-26 上海凯鑫分离技术有限公司 Treatment and recovery process of acid wastewater in 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

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FI89901C (en) * 1990-10-23 1993-12-10 Kemira Oy purification method
CN203269598U (en) * 2012-12-31 2013-11-06 上海安赐机械设备有限公司 Tubular membrane device applied to washing of titanium dioxide

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103663547A (en) * 2012-09-24 2014-03-26 上海凯鑫分离技术有限公司 Treatment and recovery process of acid wastewater in 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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
GONG, JIAZHU: "Application of Solid-liquid Separation in Titanium Dioxide Manufacture with Sulphate Route", CHEMICAL EQUIPMENT TECHNOLOGY, vol. 32, no. 1, 28 February 2011 (2011-02-28), pages 5 - 7 *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108083326A (en) * 2017-12-18 2018-05-29 广西雅照钛白有限公司 The method and apparatus of the energy saving Joint Production titanium dioxide of titanium powder plant, sulfuric acid and iron ore concentrate
CN112624189A (en) * 2021-01-14 2021-04-09 上海安赐环保科技股份有限公司 Method and system for recycling waste acid and white water of titanium dioxide produced by sulfuric acid process
CN112897782A (en) * 2021-01-14 2021-06-04 上海安赐环保科技股份有限公司 Method and system for recycling waste acid and white water of titanium dioxide produced by sulfuric acid process
CN112897782B (en) * 2021-01-14 2024-01-23 上海安赐环保科技股份有限公司 Method and system for recycling waste acid and white water of titanium dioxide by sulfuric acid method
CN114380328A (en) * 2021-12-28 2022-04-22 龙佰襄阳钛业有限公司 Titanium dioxide three-washing process
CN114408966A (en) * 2021-12-28 2022-04-29 龙佰襄阳钛业有限公司 Acidolysis process for filtering concentrated water by using membrane
CN114149025A (en) * 2021-12-30 2022-03-08 龙佰集团股份有限公司 Comprehensive utilization method of sulfate process titanium dioxide wastewater
CN114149025B (en) * 2021-12-30 2023-10-13 龙佰集团股份有限公司 Comprehensive utilization method of sulfuric acid process titanium dioxide wastewater
CN115308079A (en) * 2022-08-26 2022-11-08 攀钢集团重庆钒钛科技有限公司 Characterization method for acidolysis rate of titanium concentrate in laboratory
CN115308079B (en) * 2022-08-26 2024-03-29 攀钢集团重庆钒钛科技有限公司 Characterization method of acidolysis rate of titanium concentrate in laboratory
CN116216773A (en) * 2023-03-02 2023-06-06 武汉工程大学 Method for preparing high-purity meta-titanic acid from solution containing hetero titanyl sulfate

Also Published As

Publication number Publication date
CN104692456A (en) 2015-06-10

Similar Documents

Publication Publication Date Title
WO2016110268A1 (en) Green and environmentally friendly sulfuric acid process titanium dioxide powder production equipment and technique
CN105502790B (en) A kind of desulfurization wastewater treatment system
CN103030175B (en) Device and method applied to metatitanic acid washing room
CN106521160B (en) A kind of vanadium extraction from discarded SCR catalyst and the method for preparing activation titanium silicon tungsten powder
CN106044951A (en) Recycling method and device of industrial acidic wastewater
WO2013143236A1 (en) Method for recycling acidolysis residue from production of titanium white by sulphuric acid process
CN105152271A (en) Titanium dioxide white water reuse process and system thereof
CN104445720A (en) Pickling waste liquid treatment process of steel industry
CN103771631A (en) Process for treating and recycling alkaline wastewater containing zinc and chromium ions
CN204873875U (en) Green sulfate process titanium dioxide powder apparatus for producing
CN104805303A (en) Method for synchronously recovering vanadium and chromium from vanadium-chromium slag by acid process
CN105621478A (en) Washing impurity removal method for metatitanic acid in production of titanium dioxide by sulfuric acid method
CN105217582A (en) The method of a kind of titanium white waste acid film process
CN104275178A (en) Method for recycling waste SCR denitration catalyst and regenerated SCR catalyst carrier
CN108910955A (en) A method of titanium tungsten powder is manufactured using discarded SCR denitration
CN108793568A (en) A kind of stainless steel cleaning containing acid wastewater zero discharge waste water unit equipment
CN112624189B (en) Method and system for recycling waste acid and white water of titanium dioxide produced by sulfuric acid process
CN112897782B (en) Method and system for recycling waste acid and white water of titanium dioxide by sulfuric acid method
CN104086011A (en) Zero discharge process suitable for waste water of viscose fiber industrial acid station
CN203079706U (en) Device applied to metatitanic acid washing working section
CN110835120A (en) Efficient acidolysis process for titanium concentrate
CN108314081A (en) A kind of comprehensive utilization of resources of inorganic coating and salt treatment
WO2022142363A1 (en) Filtration and separation system and method for recovering fe3o4 nanoparticles
CN109437181B (en) Comprehensive treatment system for graphene oxide slurry
CN110921915A (en) Titanium dioxide production-based sewage treatment process

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16734928

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16734928

Country of ref document: EP

Kind code of ref document: A1