CN109908918A - Photocatalyst material - Google Patents

Abstract

A kind of photocatalyst material, including titanium dioxide, aluminium salt, nitrogen source, molysite, silver salt, tungsten salt, rare earth metal, wherein titanium, aluminium, nitrogen, iron, silver, tungsten, thulium molar ratio be 5: (0.05~0.3): (2~3): (0.2~0.3): (0.4~0.6): (0.1~0.2): (0.3~0.4).

Description

Photocatalyst material

Technical field

The present invention relates to the production fields of the preparation field of catalyst, especially photocatalyst material.

Background technique

Photocatalysis technology is as a kind of environmentally friendly depollution of environment technology efficiently, safe, to indoor air quality Improvement has obtained the approval of international academic community.Photocatalysis purifying technology has secondary pollution small, and operating cost is low and is expected to utilize Sunlight be reaction light source the advantages that, so in the special suitable chamber of photocatalysis volatile organic compounds purification, in terms of deep purifying Show huge application potential.Common photochemical catalyst is mostly metal oxide and sulfide, such as TiO₂, ZnO, CdS, WO₃ Deng wherein TiO₂Comprehensive performance it is best, it is most widely used.TiO₂With good anti-light corrosivity and catalytic activity, and performance Stablize, it is cheap and easy to get, it is nontoxic, it is best photochemical catalyst generally acknowledged at present.

It is very high to the quality of raw material, the requirement of preparation condition but in photochemical catalyst preparation process, it is better in order to reach Catalytic effect needs titanium dioxide to reach nano-scale.But titanium dioxide, the photocatalyst material produced in the prior art exists It is extremely difficult to apply the demand in photochemical catalyst in the factors such as granularity, degree of purity, it is difficult to be mass produced, rest on laboratory level Not.In view of the problems of the existing technology the purpose of the present invention, improves the prior art, improve the industrialization of photochemical catalyst The yield rate of preparation.

Summary of the invention

In view of the deficiencies of the prior art, it is an object of the invention to provide a kind of photocatalyst materials, including titanium dioxide, aluminium Salt, nitrogen source, molysite, silver salt, tungsten salt, rare earth metal, wherein titanium, aluminium, nitrogen, iron, silver, tungsten, thulium molar ratio be 5 : (0.05~0.3): (2~3): (0.2~0.3): (0.4~0.6): (0.1~0.2): (0.3~0.4).

The preparation step of its photocatalyst material are as follows: step 1 crushes；Step 2, acidolysis；Step 3, sedimentation；Step 4, knot It is brilliant；Step 5, hydrolysis；Step 6, primary washing；Step 7, bleaching；Step 8, secondary washing；The preparation of step 9, crystal seed；Step 10, salt treatment；Step 11, calcining；Step 12 crushes；The synthesis of step 13, photocatalyst material；Step 14 is washed three times； Step 15 press dry；Step 16, expansion drying；Step 17, micrometer crusher；Step 18 selects powder to be classified；Step 19, pulse dust removal.

Wherein step 5: processed crystal seed is injected in hydrolytic tank and is hydrolyzed, the titanyl sulfate in titanium liquid is in heating Under the conditions of, it is hydrolyzed by the induction of active seed, the hydrated titanium dioxide with certain partial size is made.

5.1, the titanium liquid prepared is measured and squeezes into hydrolysis foreheater and crystal seed titanium liquid bath respectively, when liquid level reaches agitating paddle When, i.e. unlatching foreheater stirring measures the liquid alkaline for preparing concentration that throw crystal seed lye tank (vat) into spare.

5.2, after having broken material, foreheater steam inlet valve to be opened, is heated up to titanium liquid, heating outlet temperature is controlled at 96 DEG C, Etc. crystal seed to be added.When foreheater titanium liquid temperature is raised to 75 DEG C, crystal seed titanium liquid bath steam inlet valve is opened, gives crystal seed titanium liquid liter Temperature；Then it opens liquid alkaline slot steam inlet valve and is warming up to 85 DEG C to liquid alkaline, and keep this temperature；85 DEG C are warming up to crystal seed titanium liquid When, starting crystal seed production slot stirring opens liquid alkaline slot baiting valve and liquid alkaline is quickly put into crystal seed production slot, then opens crystal seed titanium Liquid bath baiting valve make crystal seed titanium liquid and liquid alkaline make in slot in crystal seed and, discharge and continue to heat crystal seed production slot after crystal seed titanium liquid In material to 96 DEG C when stop heating, quickly detect its stability, crystal seed production slot quickly opened when stability is in 130ml Outlet valve quickly puts the crystal seed made into and is preheating to 96 DEG C of foreheater titanium liquid.The titanium liquid of foreheater is allowed to be warming up to 96 Equal crystal seeds are carried out DEG C again, the equal titaniums liquid heating that cannot allow that crystal seed makes, and otherwise crystal seed stability can sharply decline, and influence whole pot matter Amount.

5.3, it is stirred 10 minutes after adding crystal seed, opens hydrolyzer inlet valve, foreheater baiting valve is opened, foreheater Titanium liquid is put into hydrolyzer, while starting hydrolyzer stirring.

5.4, after foreheater titanium liquid is put into hydrolyzer, hydrolyzer direct steam inlet valve is opened, starts hydrolysis heating.

5.5, it (from time requirement≤28 minute for being warming up to boiling) after Hydrolysis of Titanium liquid once boils, turns steam down, prevents Transition boiling；When hydrolysis, which reaches 1: 1, whitens, stops steam, stops stirring heat preservation 30 minutes.

5.6, heat preservation terminates, then opens stirring and steam progress secondary temperature elevation, and Hydrolysis of Titanium liquid is allowed to reach two in 20 minutes Secondary boiling.

5.7, the foreheater of titanium liquid and crystal seed production pot are rinsed well, flushing liquor is discharged into hydrolyzer when dilution water use, punching It washes to finish and closes valve.

5.8, turning down direct steam valve keeps slight boiling condition (to keep pot inner pressure in 90~120mmH₂O) 150 minutes.

5.9, pressure maintaining terminates, and opens the exhaust-valve of hydrolyzer, and quantitative dilution water is added, concentration is reduced to 140~ (add volume 13.5m after water between 155g/l³), it is continuously heating to boil, be kept for slightly boiled 50 minutes.

5.10, hydrolysis terminates, steam off valve.

5.11, quantitative lignocellulosic is added toward the metatitanic acid after hydrolysis, and stirring 10 minutes can blowing.

5.12, it opens the bottom of a pan baiting valve and metatitanic acid after hydrolysis is sent to cooling system.

5.13, it after blowing, rinses hydrolyzer inner wall to no plain boiled water well and flows out.Flushing finishes, and closes hydrolyzer and puts Expect valve, waits use next time.

Wherein step 6: it after hydrolysis, by graphite heat exchanger, is once washed.

Wherein step 7: it after primary washing, is bleached.

7.1, clay kettle bottom baiting valve is closed, pot mouth inlet valve is opened, one is added in clay kettle and washes rear metatitanic acid 45m³, Starting stirring；

7.2, concentrated sulfuric acid volume should be added by accurately measuring toward concentrated sulfuric acid measuring tank；

7.3, titanous volume should be added by accurately measuring toward titanous measuring tank；

7.4, after ten minutes, the concentrated sulfuric acid measured is first added in stirring in clay kettle；

7.5, the trivalent titanium solution measured is added in clay kettle again；

7.6, slurry is heated to 90 DEG C by the steam admission valve for opening clay kettle, and constant temperature keeps the temperature 2 hours；

7.7, heat preservation terminates, steam off admission valve, inspection by sampling trivalent Ti content and effective acid content, if meeting work What skill required, then bleaching work terminates.

If 7.8, Ti³⁺≤ 0.30g/l will then add titanous depending on departure, and continue reduction 30 minutes, it is ensured that after bleaching Slurry Ti³⁺Between 0.30~0.4g/l；

7.9, after inspection by sampling bleaching after slurry qualified, slowly plus water is cooled to slurry≤75 DEG C.

Wherein step 8: secondary washing is carried out after bleaching.

Open metatitanic acid storage tank baiting valve after floating, conveying metatitanic acid to 400m²Filter press.It is washed with qualified water, most Whole metatitanic acid iron-content≤30ppm after the mashing of inclined titanium scraping blade hollander tub.Qualified metatitanic acid is delivered to two and washes qualified inclined titanium Sour storage tank.

Wherein step 9: the preparation of crystal seed；

9.1, alkali fusion: qualified (its iron content the is lower than 50PPm) TiO of Jing Erxi filter press filtration washing²Hydrate, with first Crystal seed preparation is pumped into metatitanic acid heating measuring tank, NaOH is heated separately to 60 DEG C and 90 DEG C after alkali heating measuring tank metering Afterwards, by TiO²Hydrate NaOH and being put into alkali fusion tank carries out reaction and 50%NaOH solution reaction, generates positive sodium titanate.Through cold But afterwards with the second crystal seed preparation pump squeeze into filter press by upper piece, washing, discharging, filter cake be beaten, positive sodium titanate from containing greatly It measures and is separated in the filtrate of free NaOH solution, the NaOH filtrate of content 15% flows into lye collecting tank, then with third crystal seed Preparation is pumped into external system and is used as tail gas spray.Special filter press, which is prepared, with crystal seed washs NaOH in positive sodium titanate filter cake, when Measure after filtrate NaOH content is less than 1500PPm, discharging enters hollander tub, then again with 10% hydrochloric acid be neutralized to pH value to 3.5~ 4.0 range, with the 4th crystal seed preparation pump squeeze into crystal seed prepare Special filter press using upper piece, washing, until washing filtrate When pH value is greater than 7, TiO is made in discharging, filter cake mashing²Concentration is controlled in 200-220g/l, is prepared into positive metatitanic acid intermediate products.

9.2, prepared by crystal seed: positive sodium titanate generates titanium chloride peptization with 30% hydrochloric acid reaction, makes for salt treatment post With.Peptization reaction carries out in the molten tank of crystal seed preparation vessel acid, and the crystal seed pump made is squeezed into storage tank.

Wherein, the chemical equation of rutile titanium dioxide crystal seed is as follows:

a、TiO₂·nH₂O+4NaOH=Na₄TiO₄+(n+1)H₂O

b、Na₄TiO₄+4H₂O=4NaOH+H₄TiO₄

c、Na₄TiO₄+ 4HCl=H₄TiO₄+4NaCl

d、H₄TiO₄+ 2HCl=TiOCl₂+3H₂O

The technic index of crystal seed preparation is as follows:

1. the TiO in metatitanic acid measuring tank₂Concentration: 270-290g/l；Its volume 6.5-7m³；Iron≤50ppm

2. the TiO in metatitanic acid measuring tank₂Concentration: 270-290g/l；Heating temperature: 60 DEG C

3. the alkali in alkali measuring tank: 50%NaOH；Its volume: 4.2m³；Heating temperature: 90 DEG C

4. the reaction temperature in alkali soluble tank: (108-120) DEG C: boiling temperature: (97-103) DEG C

5. cold water solution meta-titanium perborate temperature: (50-55) DEG C

6. temperature of washing water: (40-55) DEG C

7. washing rear TiO₂Content: 220-240g/l

8. the pH value after neutralizing: 3.5-4.0

9. the pH value after peptization :≤1.0

10. nucleus reaction temperature: about 101 DEG C

11. crystal seed partial size: 0.25-0.5 μm.

Wherein step 10: after secondary washing terminates, crystal seed prepares, salt treatment is carried out.

10.1,45m is beaten³Metatitanic acid after washing is qualified is stirred evenly into salt treatment slot, notifies laboratory sampling analysis Its iron content and concentration.Slurry concentration is controlled between 280-320g/l；

10.2, according to slurry concentration and volume in salt treatment slot, the slot slurry titanium dioxide quality W (kg) is calculated:

W (kg)=C (kg/m³)×V(m³)；

10.3, titanium dioxide quality is pressed, the amount that all kinds of salt treatment agents should be added is calculated:

(NH₄)₂HPO₄Answer additional amount (kg)=W × 0.30%

K₂CO₃Answer additional amount (kg)=W × 0.64%；

(NH₄)₂CO₃Answer additional amount (kg)=W × 1.30%

10.4, all kinds of salt treatment agent dry powder weight (kg) should be added by accurately weighing on electronic scale, be first added claim in order The diammonium hydrogen phosphate of amount stirs 20 minutes after adding；It is added followed by the potassium carbonate of weighing, is stirred 20 minutes after adding；Finally Ammonium hydrogen carbonate is added, is stirred one hour after adding, salt treatment terminates；

10.5, it stops stirring；

10.6, slurry conveying valve is regulated, slurry is sent to calcination plant slurry storage tank with pump；

10.7, after slurry conveying, stop delivery pump, shut each valve, used to next time.

Wherein after step 11, salt treatment, squeezing is pressed dry, and injection rotary kiln is calcined,

11.3, kiln operation is dried:

(1) small firepower baking rotary kiln is kept to be not less than 12 hours.

(2) " small firepower, the slow-speed of revolution " should be kept in the process by drying kiln, to prevent kiln brick impaired and the generation of a large amount of raw material.Specifically It is controlled at 400 DEG C for preceding 4 hours high-temperature areas hereinafter, 8 hours temperature are controlled at 600 DEG C hereinafter, temperature control in 10 hours exists 800 DEG C, 12 hours high-temperature region temperature rise to 900~950 DEG C, and kiln end temperature rises to 250~300 DEG C.

It (3), should be according to the practical feelings of material calcining in temperature of kiln head, high-temperature region temperature, kiln end temperature, kiln during drying kiln Condition is appropriate to adjust rotary kiln revolving speed or gas supply amount.

(4) during drying kiln, in the case where guaranteeing that kiln atmosphere is good, kiln tail negative pressure is maintained at 2000Pa or so tail gas wind Machine opening degree is small as far as possible, to reduce heat losses in kiln.

(5) when kiln end temperature rises to 250~300 DEG C, the charging of notice kiln tail post.

(6) waste water is in time beaten away according to hot-tub water level conditions in vent gas treatment post.

(7) at the end of drying kiln, gas supply amount should tend towards stability, and rotary kiln reaches regulation kiln speed, each calcining zone temperature, wind Amount, kiln hood burner gas valve opening degree, inlet amount, offgas outlet valve opening degree should all reach normal condition.Meanwhile Kiln material performance is fallen to touch the mark in range.

11.4, it operates normally:

In a normal course of operation, the calcining situation of material in rotary kiln is kept a close eye on, adjusts gas supply accurately and in time Amount or kiln speed, it is ensured that material calcining is all right.Ordinary circumstance not adjust rotary kiln speed.

B timing sampling, on-site test fall apparent whiteness, hardness, the pH value of kiln material.Kiln hood, kiln tail, high-temperature region are grasped at any time Temperature examines the actual size of firepower, the calcining situation of high-temperature region material, it is ensured that Calcine Strength appropriate.

It is stringent to observe high-temperature region calcined material particle situation in c normal course of operation.Guarantee falls kiln material whiteness, reducing power reaches Mark.

D supervises kiln tail inlet amount in time, makes every effort to feed uniform and stable, and (kiln speed is too low, coal gas is insufficient in case of exceptional circumstances Deng) timely adjustment input material is answered, it avoids kiln tail batch turning, bed of material disconnection, fall the half-cooked phenomenon generation of kiln product.

E keeps a close eye on the ventilation condition in rotary kiln.Offgas outlet valve and exhaust fan are adjusted in time according to calcining situation Absorbing quantity, it is ensured that kiln atmosphere is good, and kiln end temperature is relatively stable, and kiln tail negative pressure is maintained at 2000Pa or so.

11.5, stop kiln operation

(1) when needing to stop kiln, first stop charging.

(2) after the completion of stopping fill process, kiln speed is turned down, coal is stopped.

(3) stop working.

A is not when material can turn in kiln, knock down the flame.Stop kiln hood blower fan, closes gas valve；Opening accident chimney valve, Venturi imported valve is closed, termination of pumping stops exhaust fan, while circular gas furnace opens exhaust-valve, stops gas fan, into supporting Heater stage.

B reduces kiln speed, and rotary kiln keeps the state slowly rotated.40 DEG C are down to hereinafter, shutting down to temperature of kiln head.In case of The emergency cases such as power failure, it is necessary to artificial disc kiln is taken, in case kiln body deforms.Open venturi accident emergency water source dress rapidly simultaneously It sets.

C, which stops the raw material gone out during kiln, to be stored by workshop section's requirement, and makes record.

Wherein step 12: calcining and with blower it is cooling after, crushed using Raymond mill machine,

A, anatase titanium dioxide powder fineness (325um screen over-size)≤0.10%, enamel type titanium white powder fineness≤0.50%

B, titanium dioxide net content: (25 ± 0.1) kg

C, motor temperature is no more than 70 DEG C.

Wherein step 13: the synthesis of photocatalyst material

Titanium dioxide, aluminium salt, nitrogen source, molysite, silver salt, tungsten salt, rare earth metal are mixed, titanium dioxide is beaten first, , aluminium salt, nitrogen source, molysite, silver salt, tungsten salt, rare earth metal dissolution, by titanium dioxide, aluminium salt, nitrogen source, molysite, silver salt, tungsten salt, It is mixed in rare earth metal investment dispersing agent；And it is dried in vacuo and obtains presoma；Wherein titanium, aluminium, nitrogen, iron, silver, tungsten, rare earth metal The molar ratio of element is 5: (0.05~0.3): (2~3): and (0.2~0.3): (0.4~0.6): (0.1~0.2): (0.3~ 0.4) presoma, is put into the calcining of inert gas heating furnace high temperature, 800-1000 DEG C of temperature, the time is more than 8 hours, then will Calcined product drops to room temperature and obtains photocatalyst compound material；Nickel salt can also be added, the molar ratio of nickel and titanium is 5: (0.01~0.1) further proposes the magnetic conductivity of photochemical catalyst；It, can also be at calcining in order to further propose light-catalysed effect Graphene is added when reason；Nitrogen source uses urea；Molysite uses one of iron hydroxide, ferric carbonate, ferric nitrate, ferric sulfate Or it is several；Aluminium salt is using aluminium hydroxide, aluminium carbonate, aluminum nitrate, alumina silicate etc.；Silver salt is using a or several, the tungsten in silver carbonate Salt is selected from one or more of scandium, yttrium, lanthanum, cerium etc. using silicic acid tungsten etc., rare earth metal；Inert gas using argon gas, nitrogen, One or more of helium, neon；Dispersing agent uses dehydrated alcohol.

Wherein step 14: it washes three times

Three wash through centrifugal pump a (1403), b (1404), and pass through on-off valve a (1405), b (1406), will using pipeline Photocatalyst material is transported to three and washes filter press (1407) in agitator tank a (1401), b (1402)；Three wash on filter press (1407) It is arranged central feeding mouth (1408), photocatalyst material is washed in filter press (1407) by central feeding mouth (1408) injection three, Rinse three hours；On central feeding mouth (1408) periphery, four liquid outlet a (1409), b (1410), c (1411), d are set (1412), four liquid outlet a (1409), b (1410), c (1411), d (1412) are separately connected liquid outlet pipe a, b, c, d, out liquid Solenoid valve a (1413), b (1414), c (1415), d (1416) are set on pipeline a, b, c, d；Water inlet line passes through solenoid valve a (1413), b (1414) is connected with liquid outlet pipe a, b, fills the water for Xiang Sanxi filter press；Pass through connecting tube a (1420) outlet tube Road a is directly connected with liquid outlet pipe c, is directly connected with liquid outlet pipe d by connecting tube b (1421) liquid outlet pipe b；Liquid outlet pipe C, the liquid of discharge is transported to wastewater trough by solenoid valve c (1415), d (1416) by d.At the bottom that three wash filter press (1407) Portion's setting connects liquid bucket (1417), further evacuation of liquid to wastewater trough；It is arranged again side by side in the bottom that three wash filter press (1407) Chute (1418), by treated, photocatalyst material is transported to mashing stirred tank (1419), preferably by photocatalyst material Dispersion.Three wash the application method of filter press (1407) are as follows: open solenoid valve a (1413), close solenoid valve b, c, d, clear water passes through Liquid outlet a (1413), c (1411) injection three in left side is washed in filter press (1407), after cleaning, closes solenoid valve a (1413), b (1414), (1415) c open solenoid valve d (1416), waste water are discharged；It opens solenoid valve b (1414), closes solenoid valve a (1413), c (1415), d (1416), clear water are washed in filter press by liquid outlet b (1414), d (1416) injection three on right side, clearly After washing, solenoid valve a (1413), b (1414), d (1416) are closed, opens solenoid valve c (1415), waste water is discharged；It repeats above-mentioned The step of flushing, flushing three times can reach cleaning effect, and effectively prevent blocking.

Wherein step 15, press dry:

Scattered photocatalyst material is transported to storage tank a (1501), b (1502) by pipeline；By storage tank a (1501), the titanium dioxide in b (1502) is transported to diaphragm filter press (1505) and is pressed dry by centrifugal pump c (1503), d (1504) (there is no water-washing process), the time one and a half hours；Belt conveyor (1506) are set in diaphragm filter press (1505) lower part, belt Conveyer (1506) connects spiral transferring pipeline, is transported to flash dryer (1601) by helical feed pipeline.

Wherein step 16, expansion drying:

Photocatalyst material is dried in flash dryer (1601).

Wherein step 17, micrometer crusher:

Photocatalyst material after drying is transported to dry bag hose (1701) by vacuum pipe, by photochemical catalyst material Material and air separation, then the material bin for micron disintegrator (1704) top being transported to the photocatalyst material after air separation (1702), photocatalyst material enters micron disintegrator (1704) by planet discharge valve (1703) from material bin (1702)；Through Micron disintegrator (1704) treated photocatalyst material is transported to by vacuum pipe a (1705) and selects powder grader (1801)；Vacuum tube is set on the drying bag hose (1701) on material bin (1702) top on micron disintegrator (1704) top Road connects negative pressure air exhauster (1702), and the air that dry bag hose is isolated is emptied by negative pressure air exhauster (1707).In micron Material bin (1702) top on pulverizer (1704) top is also set up vacuum pipe b (1705), and vacuum pipe b's (1705) is another End setting discharge valve (1706), selects the lower end of powder grader (1801) to be also connected with vacuum pipe b (1705).

Wherein step 18, select powder to be classified:

Photocatalyst material is further screened in selecting powder grader (1801), and by the photochemical catalyst of garbled mistake Material is transported to pulse dust collector (1901).

Wherein step 19, pulse dust removal:

Centrifugal blower (1902) are arranged in pulse dust collector (1901) side, and in the lower part of pulse dust collector (1901), setting is defeated Finished product photocatalyst material is transported to finished product bin (2001), finished product bin by square auger (1903), conveyor screw (1903) 11 (2001) lower part setting planet discharge valve (2002)；Finished product titanium dioxide is transported to finished product packing by planet discharge valve (2002) Machine, is weighed, is packed, and storehouse storage is finally put into.

The present invention has following technical effect compared with prior art: the present invention is used the preparation of photocatalyst material and titanium White powder production is fused together；The particle surface of the photocatalyst material of preparation is smooth, shape is uniform, size tunable；In waste water Purified treatment, air cleaning etc. have broad application prospects；Simple process is feasible, at low cost, can industrialize big rule Mould production.

Detailed description of the invention

Fig. 1 is the total technological process figure in preparation system.

Fig. 2 is step 14 process flow chart in preparation system.

Fig. 3 is the process flow chart of the step 15-19 in preparation system.

Fig. 4 is properties of product test effect figure.

Specific embodiment

With reference to embodiments, more detailed description is done to above-mentioned technical characteristic of the invention and advantage.

A kind of photocatalyst material, including titanium dioxide, aluminium salt, nitrogen source, molysite, silver salt, tungsten salt, rare earth metal, wherein Titanium, aluminium, nitrogen, iron, silver, tungsten, thulium molar ratio be 5: (0.05~0.3): (2~3): (0.2~0.3): (0.4 ~0.6): (0.1~0.2): (0.3~0.4).

The preparation step of its photocatalyst material are as follows: step 1 crushes；Step 2, acidolysis；Step 3, sedimentation；Step 4, knot It is brilliant；Step 5, hydrolysis；Step 6, primary washing；Step 7, bleaching；Step 8, secondary washing；The preparation of step 9, crystal seed；Step 10, salt treatment；Step 11, calcining；Step 12 crushes；The synthesis of step 13, photocatalyst material；Step 14, three wash；Step 15, it press dry；Step 16, expansion drying；Step 17, micrometer crusher；Step 18 selects powder to be classified；Step 19, pulse dust removal.

Wherein step 5: processed crystal seed is injected in hydrolytic tank and is hydrolyzed, the titanyl sulfate in titanium liquid is in heating Under the conditions of, it is hydrolyzed by the induction of active seed, the hydrated titanium dioxide with certain partial size is made.

5.1, the titanium liquid prepared is measured and squeezes into hydrolysis foreheater and crystal seed titanium liquid bath respectively, when liquid level reaches agitating paddle When, i.e. unlatching foreheater stirring measures the liquid alkaline for preparing concentration that throw crystal seed lye tank (vat) into spare.

5.2, after having broken material, foreheater steam inlet valve to be opened, is heated up to titanium liquid, heating outlet temperature is controlled at 96 DEG C, Etc. crystal seed to be added.When foreheater titanium liquid temperature is raised to 75 DEG C, crystal seed titanium liquid bath steam inlet valve is opened, gives crystal seed titanium liquid liter Temperature；Then it opens liquid alkaline slot steam inlet valve and is warming up to 85 DEG C to liquid alkaline, and keep this temperature；85 DEG C are warming up to crystal seed titanium liquid When, starting crystal seed production slot stirring opens liquid alkaline slot baiting valve and liquid alkaline is quickly put into crystal seed production slot, then opens crystal seed titanium Liquid bath baiting valve make crystal seed titanium liquid and liquid alkaline make in slot in crystal seed and, discharge and continue to heat crystal seed production slot after crystal seed titanium liquid In material to 96 DEG C when stop heating, quickly detect its stability, crystal seed production slot quickly opened when stability is in 130ml Outlet valve quickly puts the crystal seed made into and is preheating to 96 DEG C of foreheater titanium liquid.The titanium liquid of foreheater is allowed to be warming up to 96 Equal crystal seeds are carried out DEG C again, the equal titaniums liquid heating that cannot allow that crystal seed makes, and otherwise crystal seed stability can sharply decline, and influence whole pot matter Amount.

5.3, it is stirred 10 minutes after adding crystal seed, opens hydrolyzer inlet valve, foreheater baiting valve is opened, foreheater Titanium liquid is put into hydrolyzer, while starting hydrolyzer stirring.

5.4, after foreheater titanium liquid is put into hydrolyzer, hydrolyzer direct steam inlet valve is opened, starts hydrolysis heating.

5.5, it (from time requirement≤28 minute for being warming up to boiling) after Hydrolysis of Titanium liquid once boils, turns steam down, prevents Transition boiling；When hydrolysis, which reaches 1: 1, whitens, stops steam, stops stirring heat preservation 30 minutes.

5.6, heat preservation terminates, then opens stirring and steam progress secondary temperature elevation, and Hydrolysis of Titanium liquid is allowed to reach two in 20 minutes Secondary boiling.

5.7, the foreheater of titanium liquid and crystal seed production pot are rinsed well, flushing liquor is discharged into hydrolyzer when dilution water use, punching It washes to finish and closes valve.

5.8, turning down direct steam valve keeps slight boiling condition (to keep pot inner pressure in 90~120mmH₂O) 150 minutes.

5.9, pressure maintaining terminates, and opens the exhaust-valve of hydrolyzer, and quantitative dilution water is added, concentration is reduced to 140~ (add volume 13.5m after water between 155g/l³), it is continuously heating to boil, be kept for slightly boiled 50 minutes.

5.10, hydrolysis terminates, steam off valve.

5.11, quantitative lignocellulosic is added toward the metatitanic acid after hydrolysis, and stirring 10 minutes can blowing.

5.12, it opens the bottom of a pan baiting valve and metatitanic acid after hydrolysis is sent to cooling system.

5.13, it after blowing, rinses hydrolyzer inner wall to no plain boiled water well and flows out.Flushing finishes, and closes hydrolyzer and puts Expect valve, waits use next time.

Wherein step 6: it after hydrolysis, by graphite heat exchanger, is once washed.

Wherein step 7: it after primary washing, is bleached.

7.1, clay kettle bottom baiting valve is closed, pot mouth inlet valve is opened, one is added in clay kettle and washes rear metatitanic acid 45m³, Starting stirring；

7.2, concentrated sulfuric acid volume should be added by accurately measuring toward concentrated sulfuric acid measuring tank；

7.3, titanous volume should be added by accurately measuring toward titanous measuring tank；

7.4, after ten minutes, the concentrated sulfuric acid measured is first added in stirring in clay kettle；

7.5, the trivalent titanium solution measured is added in clay kettle again；

7.6, slurry is heated to 90 DEG C by the steam admission valve for opening clay kettle, and constant temperature keeps the temperature 2 hours；

7.7, heat preservation terminates, steam off admission valve, inspection by sampling trivalent Ti content and effective acid content, if meeting work What skill required, then bleaching work terminates.

If 7.8, Ti³⁺≤ 0.30g/l will then add titanous depending on departure, and continue reduction 30 minutes, it is ensured that after bleaching Slurry Ti³⁺Between 0.30~0.4g/l；

7.9, after inspection by sampling bleaching after slurry qualified, slowly plus water is cooled to slurry≤75 DEG C.

Wherein step 8: secondary washing is carried out after bleaching.

Open metatitanic acid storage tank baiting valve after floating, conveying metatitanic acid to 400m²Filter press.It is washed with qualified water, most Whole metatitanic acid iron-content≤30ppm after the mashing of inclined titanium scraping blade hollander tub.Qualified metatitanic acid is delivered to two and washes qualified inclined titanium Sour storage tank.

Wherein step 9: the preparation of crystal seed；

1. driving to prepare

(1), check whether the public works conditions such as compressed air, process water, steam have.

(2), check whether the equipment such as post storage tank, reactor are intact, and whether sundries is cleaned out in all devices, single machine The problem is that no rectification finishes, it is unimpeded whether all process pipes have for equipment operation, and either with or without leak point, equipment is pumped and stirred Whether have oiling, run either with or without abnormal voice if mixing.

(3), the drain valve into this post steam valve and jet chimney is opened.It is closed after the drained water of drain valve

(4), whether the stock situation for checking NaOH, HCl, analyze its quality index in Con trolling index range.

2. alkali fusion (the producing reaction of positive sodium titanate)

(1), TiO is checked²Whether metatitanic acid measuring tank drains, and closes outlet valve, starts the blender in the slot.

(2), hollander tub two is washed to qualified TiO²Slurries (wherein containing Fe≤50mg/l) are pumped into metatitanic acid measuring tank to rule Determine liquid level and (realizes 270~290g/l of concentration, volume 7m³)。

(3), the first steam valve is opened, the slurries in metatitanic acid slot are heated to 60 DEG C of first steam valves of closing.

(4), it checks whether NaOH measuring tank material drains, closes slot outlet valve.

(5), open pump exits and entrances valve to alkali measuring tank inlet valve and start pump and blender.It is pumped into liquid alkaline 4.6m³。

(6), the second steam valve is opened, the NaOH in NaOH measuring tank closes the second steam valve after being heated to 90 DEG C.

(7), that closes alkali soluble tank drains valve, and starts blender.

(6), the outlet valve for opening NaOH measuring tank, is put into alkali fusion tank for NaOH.

(9), the outlet valve for opening metatitanic acid measuring tank, by TiO²Suspension is put into alkali fusion flow container, and (flow is by diameter The orifice plate of 16mm controls), discharging time 30 minutes.

(10), opening third steam valve simultaneously makes temperature be kept for 100~105 DEG C, and insulated and stirred is boiled 2 hours.

(11), third steam valve is closed, water valve is opened, adds water 5m³After turn off water valve and make its liquor capacity 15m³, after Continuous stirring 10 minutes.

(12), before positive metatitanic acid suspension is put into cooling bath, it must check whether cooling bath has enough vacancy, and in blowing It is preceding that 10m is first added³Cold water opens cooling bath stirring.

(13), alkali fusion tank outlet valve is opened, Cold water tap is opened simultaneously.By material and cold water (material and water ratio be 1: 2) Cocurrent is put into cooling bath.

(14), after discharging positive sodium titanate, alkali fusion tank is rinsed, closes soda fusion pot bottom valve.

(15), it discharges material and continues stirring 30 minutes, so that positive sodium titanate is cooled to 50~55 DEG C, if stirring intensity is not It is enough, which is configured circulating cooling.

(16), alkali fusion Special filter press is sent to after cooling qualification to be washed.◆ filtration washing step: a, check alkali The hydraulic pump of molten Special filter press and its filter cloth situation, starting alkali fusion Special filter press compresses filter plate.B, the dedicated filters pressing of alkali fusion is played The feed pump of the inlet valve of machine, starting alkali fusion Special filter press is fed.When feed pressure reaches setting value, stops its pump and close Its inlet valve.C, the washing valve of alkali fusion Special filter press is opened, the wash water pump of starting alkali fusion Special filter press is washed.90 points Clock takes filtrate analysis NaOH, if content is lower than 1500ppm, washing is finished.Analysis method is as follows: taper is added in 50ml filtrate Bottle (200ml) and instill 3 drop methyl oranges use again 0.1mol/l HCl titration until solution from yellow to red until.If the titration used Agent HCl dosage is lower than 25ml.Then Washing of Filter Cake is qualified, otherwise continues to wash.D, washing water detection is qualified.Stop wash water pump, starting Blowpit stirring, carries out discharging.TiO in hollander tub²Concentration controls (200~220) g/l.

(17), it the positive metatitanic acid in hollander tub with being pumped into neutralization reaction slot (being also titanic acid buffering slot), and opens Dashpot stirring, controls titanic acid concentration in (180~200) g/l, volume 18-20m³。

(18), neutralization reaction；After hydrochloric acid is squeezed into hydrochloric acid measuring tank with pump, exits and entrances valve is closed in termination of pumping, opens hydrochloric acid Measuring tank bottom valve is neutralized, and 30% hydrochloric acid 1.1m is taken around³, hydrochloric acid flow is controlled, guarantees that neutralizing the time controls 30 points Clock, neutralization terminal are pH value (3.5~4.0), and about hydrochloric acid, which is put into, starts to detect pH value for 20 minutes, survey one within every 3 minutes later It is secondary, when neutralization terminal reaches pH value (3.5~4.0), neutralizes and complete.Stirring 15 minutes send two to wash filter press material with pump.

(19) it filters secondary washing step: a, checking alkali fusion Special filter press and its filter cloth situation, start the dedicated pressure of alkali fusion The hydraulic pump of filter compresses filter plate.B, the inlet valve of alkali fusion Special filter press is opened, the feed pump of alkali fusion Special filter press is started It is fed.When feed pressure reaches setting value, stops its pump and close its inlet valve.C, the washing of alkali fusion Special filter press is opened The wash water pump of valve, starting alkali fusion Special filter press is washed.Washing takes filtrate to detect pH for 40 minutes, until washing filtrate pH value It is qualification when greater than 7 (adjusting according to the actual situation) production, otherwise continues to wash.D, washing water detection is qualified.Stop wash water pump, opens The blowpit stirring of dynamic alkali fusion Special filter press, carries out discharging.TiO in hollander tub²Concentration controls (220~240) g/l, grade Prepare to be pumped into the molten tank of acid after testing testing result qualification.

3. crystal seed prepares (reaction of titanium chloride peptization)

(1), it checks whether the molten tank of crystal seed preparation vessel acid drains, closes outlet valve.

(2), two baiting valves for washing hollander tub are opened, it will about 7~8m³Positive metatitanic acid with pump be added crystal seed preparation vessel acid it is molten In tank.

(3), start blender, the liquid bulk being rinsed with water in two outlet lines for washing hollander tub, then the molten tank of measuring flume acid Product stirs 15 minutes, and sampling 150ml send laboratory to measure TiO²Concentration.

(4), the terminal valve of hydrochloric acid pump and the inlet valve of HCL measuring tank, starting pump are opened.

(5), after the charging of hydrochloric acid measuring tank, exits and entrances valve is closed in termination of pumping.

(6), TiO is obtained²Slurry dilution to TiO in the molten tank of crystal seed preparation vessel acid after measured value²Content is 200g/l.

(7), the hydrochloric acid that the concentration of metering is about 30% is added in crystal seed preparation vessel and is obtained in slurries；Two steps are divided to be added； The first step；According to hydrochloric acid and TiO²Ratio is 0.15 addition, and about 30% hydrochloric acid is incorporated as 0.75~0.85m³, time control is added 15 minutes, continue stirring after ten minutes constant-speed heating to 60 DEG C (1 DEG C per minute)；Second step is according to hydrochloric acid and TiO²Ratio is 0.25 is added；It is about 1.25~1.35m that 30% hydrochloric acid, which is added,³, time control 15 minutes is added, pH value is less than 1.

(8), it stirs 10 minutes, opens steam valve, constant-speed heating then adjusts steam flow to boiling (1 DEG C per minute) Slurries are kept to boil 101 DEG C, 90 minutes, steam off valve.

(9), by slurry dilution to TiO²Content is about 100g/l.Last volume about 17m³, about plus water 7m³, open water Valve after reaching last volume, closes water valve, 100ml sample is taken to send laboratory.It adds water and stirs 20 minutes and is put into crystal seed storage tank.

(10), check whether crystal seed storage tank has the material of the molten tank of enough vacancy dress crystal seed preparation vessel acid.

(11), the molten tank bottom terminal valve of the molten tank crystal seed preparation vessel acid of acid is opened, after discharging, stops blender, closes outlet valve. Laboratory is delivered in sampling from crystal seed storage tank.

3. post is stopped

1) before 1. orderly shutdown is stopped should by measuring tank metatitanic acid and NaOH put back in respective storage tank, it is all empty Slot.2. metatitanic acid slot storage tank must not stop stirring after parking, prevent metatitanic acid from precipitating fouling.3. empty before the parking of positive sodium titanate storage tank Slot has the stirring in material trough to answer continuous work.4. crystal seed should have certain reserves.

2) it stops in emergency: A, having a power failure: having a power failure when 1. measuring tank feeds, close storage tank inlet valve.After incoming call, either on or off valve Door, then starting stirring and progress continuous processing operation.2. cannot be discharged from metatitanic acid measuring tank after NaOH is added in alkali fusion tank TiO²Hydrolysate.Deng opening reactor agitator after incoming call, then alkali soluble operation is carried out.3. when material reaction, alkali fusion tank is stirred out Existing failure, then have the danger of crystallization (solidification).Alkali fusion tank drain valve is opened, compressed air valve is then opened and mixes material, Opening water valve dilutes mixture, cleans alkali soluble tank.4. alkali fusion jar agitator breaks down, then should dilute in material curing Mixture simultaneously mixes according to the above method, and mixture is put into cooler, and then sampling is sent to analysis room.5. power failure alkali soluble tank stirs Device can not work, and it is necessary to stop process operation, stop hydrochloric acid storage tank is added.It cannot mix therefore not be adjustable pH value, Close sump valve and reaction pot valve.After debugging, pump is opened, closes valve, starts blender, then starts to operate.B, without work Skill water: 1. stopping dilution, closes water valve.2. termination of pumping.3. after troubleshooting, restarting is stopped operation.C, without steam: 1. Stop heating storage tank, closes valve.2. stopping heating response device, 3. closing valve after troubleshooting, is opened original closing valve, is then opened Beginning technological operation.

3) scram 1. alkali fusion jar agitator failure is carried out by operating when no electricity.2. other slot blender failures stop Technological operation, device to be mixed continue to operate after repairing.

Wherein step 10: after secondary washing terminates, crystal seed prepares, salt treatment is carried out.

10.1,45m is beaten³Metatitanic acid after washing is qualified is stirred evenly into salt treatment slot, notifies laboratory sampling analysis Its iron content and concentration.Slurry concentration is controlled between 280~320g/l；

10.2, according to slurry concentration and volume in salt treatment slot, the slot slurry titanium dioxide quality W (kg) is calculated:

W (kg)=C (kg/m³)×V(m³)；

10.3, titanium dioxide quality is pressed, the amount that all kinds of salt treatment agents should be added is calculated:

(NH₄)₂HPO₄Answer additional amount (kg)=W × 0.30%

K₂CO₃Answer additional amount (kg)=W × 0.64%；

(NH₄)₂CO₃Answer additional amount (kg)=W × 1.30%

10.4, all kinds of salt treatment agent dry powder weight (kg) should be added by accurately weighing on electronic scale, be first added claim in order The diammonium hydrogen phosphate of amount stirs 20 minutes after adding；It is added followed by the potassium carbonate of weighing, is stirred 20 minutes after adding；Finally Ammonium hydrogen carbonate is added, is stirred one hour after adding, salt treatment terminates；

10.5, it stops stirring；

10.6, slurry conveying valve is regulated, slurry is sent to calcination plant slurry storage tank with pump；

10.7, after slurry conveying, stop delivery pump, shut each valve, used to next time.

After step 11, salt treatment, squeezing is pressed dry, and injection rotary kiln is calcined,

11.3, kiln operation is dried:

(1) small firepower baking rotary kiln is kept to be not less than 12 hours.

(2) " small firepower, the slow-speed of revolution " should be kept in the process by drying kiln, to prevent kiln brick impaired and the generation of a large amount of raw material.Specifically It is controlled at 400 DEG C for preceding 4 hours high-temperature areas hereinafter, 8 hours temperature are controlled at 600 DEG C hereinafter, temperature control in 10 hours exists 800 DEG C, 12 hours high-temperature region temperature rise to 900~950 DEG C, and kiln end temperature rises to 250~300 DEG C.

It (3), should be according to the practical feelings of material calcining in temperature of kiln head, high-temperature region temperature, kiln end temperature, kiln during drying kiln Condition is appropriate to adjust rotary kiln revolving speed or gas supply amount.

(4) during drying kiln, in the case where guaranteeing that kiln atmosphere is good, kiln tail negative pressure is maintained at 2000Pa or so tail gas wind Machine opening degree is small as far as possible, to reduce heat losses in kiln.

(5) when kiln end temperature rises to 250~300 DEG C, the charging of notice kiln tail post.

(6) waste water is in time beaten away according to hot-tub water level conditions in vent gas treatment post.

(7) at the end of drying kiln, gas supply amount should tend towards stability, and rotary kiln reaches regulation kiln speed, each calcining zone temperature, wind Amount, kiln hood burner gas valve opening degree, inlet amount, offgas outlet valve opening degree should all reach normal condition.Meanwhile Kiln material performance is fallen to touch the mark in range.

11.4, it operates normally:

In a normal course of operation, the calcining situation of material in rotary kiln is kept a close eye on, adjusts gas supply accurately and in time Amount or kiln speed, it is ensured that material calcining is all right.Ordinary circumstance not adjust rotary kiln speed.

B timing sampling, on-site test fall apparent whiteness, hardness, the pH value of kiln material.Kiln hood, kiln tail, high-temperature region are grasped at any time Temperature examines the actual size of firepower, the calcining situation of high-temperature region material, it is ensured that Calcine Strength appropriate.

It is stringent to observe high-temperature region calcined material particle situation in c normal course of operation.Guarantee falls kiln material whiteness, reducing power reaches Mark.

D supervises kiln tail inlet amount in time, makes every effort to feed uniform and stable, and (kiln speed is too low, coal gas is insufficient in case of exceptional circumstances Deng) timely adjustment input material is answered, it avoids kiln tail batch turning, bed of material disconnection, fall the half-cooked phenomenon generation of kiln product.

E keeps a close eye on the ventilation condition in rotary kiln.Offgas outlet valve and exhaust fan are adjusted in time according to calcining situation Absorbing quantity, it is ensured that kiln atmosphere is good, and kiln end temperature is relatively stable, and kiln tail negative pressure is maintained at 2000Pa or so.

11.5, stop kiln operation

(1) when needing to stop kiln, first stop charging.

(2) after the completion of stopping fill process, kiln speed is turned down, coal is stopped.

(3) stop working.

A is not when material can turn in kiln, knock down the flame.Stop kiln hood blower fan, closes gas valve；Opening accident chimney valve, Venturi imported valve is closed, termination of pumping stops exhaust fan, while circular gas furnace opens exhaust-valve, stops gas fan, into supporting Heater stage.

B reduces kiln speed, and rotary kiln keeps the state slowly rotated.40 DEG C are down to hereinafter, shutting down to temperature of kiln head.In case of The emergency cases such as power failure, it is necessary to artificial disc kiln is taken, in case kiln body deforms.Open venturi accident emergency water source dress rapidly simultaneously It sets.

C, which stops the raw material gone out during kiln, to be stored by workshop section's requirement, and makes record.

Wherein step 12: calcining and with blower it is cooling after, crushed using Raymond mill machine,

12.1, the preparation before driving

Check whether elevator, storage bin(hopper), Raymond machine work normally, if any bad equipment, could work after should repairing.

12.2, normal to drive and operate

(1) suction and conveying: first opening compressed air, in activation system, then opens vacuum pump, feeds into feed bin, wherein 1# vacuum It pumps and is fed to 1# feed bin, corresponding grinding machine is 1#, 2# Raymond machine, and 3# vacuum pump is fed to 2# feed bin, and corresponding grinding machine is 3#, 4# Raymond machine.2# vacuum pump is spare.Old line crushes enamel grade titanium dioxide now with omnipotent grinding machine, and suction and conveying principle is similar.

(2) Raymond machine milling is opened:

For a when material is enough in feed bin, airport logistic park starts Raymond machine, drives in order: it is (complete to close to open the analysis machine → machine that blows in Close starting, open air door after operating) → host → (" starting " skips to " operating ") → booting charging is opened, it is started to armamentarium normal Feeding afterwards.

After b drives, fan inlet butterfly valve, lingering remnants of past customs pipe butterfly valve should should will be opened to the optimum position for meeting technique requirement, Charger electric current relay and control handle are adjusted to host electric current and mill sound optimum state.Keep a close eye on ammeter, voltage The fluctuation of table and mill sound.

C shutdown, first closes corresponding vacuum pump and closes system button again, if two simultaneously when running, if 1 vacuum pump Suction and conveying only closes corresponding vacuum pump, is not related to system.

D material grinding finishes, the basic idle running Shi Zaiting host of Raymond machine, then blowing-out organ air door.Stopping procedure It should be opposite with driving sequence.

Check whether each motor temperature and controller, nut etc. are intact after e parking.

(3) omnipotent mill milling is opened

A first opens cooling water → opening host → and opens bucket charging when material is enough in feed bin.

B pays attention to host curent change situation (< 105A) during charging.

C is packed after hopper is full, and when packaging pays attention to preventing material from spraying, and reduces inlet amount or shutdown when necessary.

D is shut down: being stopped charging, after material has been ground in grinding machine, is closed host, then close cooling water.

Wherein step 13: the synthesis of photocatalyst material

Titanium dioxide, aluminium salt, nitrogen source, molysite, silver salt, tungsten salt, rare earth metal are mixed, titanium dioxide is beaten first, , aluminium salt, nitrogen source, molysite, silver salt, tungsten salt, rare earth metal dissolution, by titanium dioxide, aluminium salt, nitrogen source, molysite, silver salt, tungsten salt, It is mixed in rare earth metal investment dispersing agent；And it is dried in vacuo and obtains presoma；Wherein titanium, aluminium, nitrogen, iron, silver, tungsten, rare earth metal The molar ratio of element is 5: (0.05~0.3): (2~3): and (0.2~0.3): (0.4~0.6): (0.1~0.2): (0.3~ 0.4) presoma, is put into the calcining of inert gas heating furnace high temperature, 800-1000 DEG C of temperature, the time is more than 8 hours, then will Calcined product drops to room temperature and obtains photocatalyst compound material；Nickel salt can also be added, the molar ratio of nickel and titanium is 5: (0.01~0.1) further proposes the magnetic conductivity of photochemical catalyst；It, can also be at calcining in order to further propose light-catalysed effect Graphene is added when reason；Nitrogen source uses urea；Molysite uses one of iron hydroxide, ferric carbonate, ferric nitrate, ferric sulfate Or it is several；Aluminium salt is using aluminium hydroxide, aluminium carbonate, aluminum nitrate, alumina silicate etc.；Silver salt uses one or more of silver carbonate, Tungsten salt is selected from one or more of scandium, yttrium, lanthanum, cerium etc. using silicic acid tungsten etc., rare earth metal；Inert gas uses argon gas, nitrogen One or more of gas, helium, neon；Dispersing agent uses dehydrated alcohol.

Wherein step 14: it washes three times

By centrifugal pump a (1403), b (1404), and pass through on-off valve a (1405), b (1406), will be stirred using pipeline Photocatalyst material is transported to three and washes filter press (1407) in tank a (1401), b (1402)；Three wash on filter press (1407) and are arranged Central feeding mouth (1408), photocatalyst material are washed in filter press (1407) by central feeding mouth (1408) injection three, are rinsed Three hours；On central feeding mouth (1408) periphery, four liquid outlet a (1409), b (1410), c (1411), d are set (1412), four liquid outlet a (1409), b (1410), c (1411), d (1412) are separately connected liquid outlet pipe a, b, c, d, out liquid Solenoid valve a (1413), b (1414), c (1415), d (1416) are set on pipeline a, b, c, d；Water inlet line passes through solenoid valve a (1413), b (1414) is connected with liquid outlet pipe a, b, fills the water for Xiang Sanxi filter press；Pass through connecting tube a (1420) outlet tube Road a is directly connected with liquid outlet pipe c, is directly connected with liquid outlet pipe d by connecting tube b (1421) liquid outlet pipe b；Liquid outlet pipe C, the liquid of discharge is transported to wastewater trough by solenoid valve c (1415), d (1416) by d.At the bottom that three wash filter press (1407) Portion's setting connects liquid bucket (1417), further evacuation of liquid to wastewater trough；It is arranged again side by side in the bottom that three wash filter press (1407) Chute (1418), by treated, photocatalyst material is transported to mashing stirred tank (1419), preferably by photocatalyst material Dispersion.Three wash the application method of filter press (1407) are as follows: open solenoid valve a (1413), close solenoid valve b, c, d, clear water passes through Liquid outlet a (1413), c (1411) injection three in left side is washed in filter press (1407), after cleaning, closes solenoid valve a (1413), b (1414), (1415) c open solenoid valve d (1416), waste water are discharged；It opens solenoid valve b (1414), closes solenoid valve a (1413), c (1415), d (1416), clear water are washed in filter press by liquid outlet b (1414), d (1416) injection three on right side, clearly After washing, solenoid valve a (1413), b (1414), d (1416) are closed, opens solenoid valve c (1415), waste water is discharged；It repeats above-mentioned The step of flushing, flushing three times can reach cleaning effect, and effectively prevent blocking.

Wherein step 15, press dry:

Scattered photocatalyst material is transported to storage tank a (1501), b (1502) by pipeline；By storage tank a (1501), the titanium dioxide in b (1502) is transported to diaphragm filter press (1505) and is pressed dry by centrifugal pump c (1503), d (1504) (there is no water-washing process), the time one and a half hours；Belt conveyor (1506) are set in diaphragm filter press (1505) lower part, belt Conveyer (1506) connects spiral transferring pipeline, is transported to flash dryer (1601) by helical feed pipeline.

Wherein step 16, expansion drying:

Photocatalyst material is dried in flash dryer (1601).

Wherein step 17, micrometer crusher:

Photocatalyst material after drying is transported to dry bag hose (1701) by vacuum pipe, by photochemical catalyst material Material and air separation, then the material bin for micron disintegrator (1704) top being transported to the photocatalyst material after air separation (1702), photocatalyst material enters micron disintegrator (1704) by planet discharge valve (1703) from material bin (1702)；Through Micron disintegrator (1704) treated photocatalyst material is transported to by vacuum pipe a (1705) and selects powder grader (1801)；Vacuum tube is set on the drying bag hose (1701) on material bin (1702) top on micron disintegrator (1704) top Road connects negative pressure air exhauster (1702), and the air that dry bag hose is isolated is emptied by negative pressure air exhauster (1707).In micron Material bin (1702) top on pulverizer (1704) top is also set up vacuum pipe b (1705), and vacuum pipe b's (1705) is another End setting discharge valve (1706), selects the lower end of powder grader (1801) to be also connected with vacuum pipe b (1705).

Wherein step 18, select powder to be classified:

Photocatalyst material is further screened in selecting powder grader (1801), and by the photochemical catalyst of garbled mistake Material is transported to pulse dust collector (1901).

Wherein step 19, pulse dust removal:

Centrifugal blower (1902) are arranged in pulse dust collector (1901) side, and in the lower part of pulse dust collector (1901), setting is defeated Finished product photocatalyst material is transported to finished product bin (2001), finished product bin by square auger (1903), conveyor screw (1903) 11 (2001) lower part setting planet discharge valve (2002)；Finished product titanium dioxide is transported to finished product packing by planet discharge valve (2002) Machine, is weighed, is packed, and storehouse storage is finally put into.

Properties of product test: referring to properties of product test effect figure, the high catalytic efficiency of the photocatalyst material of this product In the photocatalyst material of traditional product, expected raising catalyst material performance is achieved the effect that.

Embodiment described above only describe the preferred embodiments of the invention, not to model of the invention It encloses and is defined, without departing from the spirit of the design of the present invention, those skilled in the art are to technical solution of the invention The various changes and improvements made should all be included in the protection scope that claims of the present invention determines.

Claims (6)

1. a kind of photocatalyst material, including titanium dioxide, aluminium salt, nitrogen source, molysite, silver salt, tungsten salt, rare earth metal, wherein titanium, Aluminium, nitrogen, iron, silver, tungsten, thulium molar ratio be 5: (0.05~0.3): (2~3): (0.2~0.3): (0.4~ 0.6): (0.1~0.2): (0.3~0.4).

2. photocatalyst material according to claim 1, which is characterized in that the molar ratio of addition nickel salt, nickel and titanium is 5: (0.01~0.1).

3. photocatalyst material according to claim 1, which is characterized in that nitrogen source uses urea.

4. photocatalyst material according to claim 1, which is characterized in that molysite uses iron hydroxide, ferric carbonate, nitric acid One or more of iron, ferric sulfate.

5. photocatalyst material according to claim 1, which is characterized in that aluminium salt uses aluminium hydroxide, aluminium carbonate, nitric acid One or more of aluminium, alumina silicate.

6. photocatalyst material according to claim 1, which is characterized in that rare earth metal is in scandium, yttrium, lanthanum, cerium It is one or more of.