CN102671520B - Titanium factory tail gas treatment method, produced titanium dioxide from tail gas and production method - Google Patents
Titanium factory tail gas treatment method, produced titanium dioxide from tail gas and production method Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 239000010936 titanium Substances 0.000 title claims abstract description 95
- 238000000034 method Methods 0.000 title claims abstract description 74
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 64
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 238000010521 absorption reaction Methods 0.000 claims abstract description 120
- 239000007788 liquid Substances 0.000 claims abstract description 96
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000010438 heat treatment Methods 0.000 claims abstract description 35
- 238000000926 separation method Methods 0.000 claims abstract description 34
- 229910001868 water Inorganic materials 0.000 claims abstract description 31
- 238000001816 cooling Methods 0.000 claims abstract description 27
- 238000001354 calcination Methods 0.000 claims abstract description 24
- 239000013078 crystal Substances 0.000 claims abstract description 24
- 239000002002 slurry Substances 0.000 claims abstract description 22
- 239000007787 solid Substances 0.000 claims abstract description 22
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 32
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 29
- 238000006460 hydrolysis reaction Methods 0.000 claims description 19
- 229910010252 TiO3 Inorganic materials 0.000 claims description 18
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 18
- 229910001626 barium chloride Inorganic materials 0.000 claims description 18
- 229910003074 TiCl4 Inorganic materials 0.000 claims description 17
- 230000007062 hydrolysis Effects 0.000 claims description 13
- 230000032683 aging Effects 0.000 claims description 10
- 238000007599 discharging Methods 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 229910003890 H2TiO3 Inorganic materials 0.000 abstract description 11
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 4
- 239000007789 gas Substances 0.000 description 93
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 40
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 29
- 239000008367 deionised water Substances 0.000 description 28
- 229910021641 deionized water Inorganic materials 0.000 description 28
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 28
- 239000000047 product Substances 0.000 description 24
- 239000012535 impurity Substances 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 13
- 239000012065 filter cake Substances 0.000 description 10
- 239000000706 filtrate Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 239000007921 spray Substances 0.000 description 10
- 238000009826 distribution Methods 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000428 dust Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 229910052909 inorganic silicate Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000012544 monitoring process Methods 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- 238000005086 pumping Methods 0.000 description 5
- 229910021654 trace metal Inorganic materials 0.000 description 5
- 229910003910 SiCl4 Inorganic materials 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000005660 chlorination reaction Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000004064 recycling Methods 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- -1 hydrogen ions Chemical class 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 206010065042 Immune reconstitution inflammatory syndrome Diseases 0.000 description 1
- FSRVIBYHRQFLJQ-UHFFFAOYSA-N [S-2].[Ba+2].Cl Chemical compound [S-2].[Ba+2].Cl FSRVIBYHRQFLJQ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000001636 atomic emission spectroscopy Methods 0.000 description 1
- CJDPJFRMHVXWPT-UHFFFAOYSA-N barium sulfide Chemical compound [S-2].[Ba+2] CJDPJFRMHVXWPT-UHFFFAOYSA-N 0.000 description 1
- LKOGCJXBXLUJIB-UHFFFAOYSA-L barium(2+);hydrogen carbonate;chloride Chemical compound [Cl-].[Ba+2].OC([O-])=O LKOGCJXBXLUJIB-UHFFFAOYSA-L 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000010902 jet-milling Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- QCAWEPFNJXQPAN-UHFFFAOYSA-N methoxyfenozide Chemical compound COC1=CC=CC(C(=O)NN(C(=O)C=2C=C(C)C=C(C)C=2)C(C)(C)C)=C1C QCAWEPFNJXQPAN-UHFFFAOYSA-N 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001932 seasonal effect Effects 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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Abstract
The invention relates to a method for preparing rutile titanium dioxide from tail gas of a titanium factory, which comprises the following steps of: (1) absorbing the tail gas of the titanium factory: absorbing the tail gas of the titanium factory by water to form a solution, stopping absorbing the tail gas by the solution when the concentration of H<+> in the solution is more than or equal to 8.0mol/L to obtain an absorption liquid, and continuously absorbing the tail gas by water; (2) filtering and purifying: carrying out solid-liquid separation on the absorption liquid of the step (1) to obtain solid and solution; (3) hydrolyzing: adding H2TiO3 crystal seed into the solution of the step (2) according to the proportion of 120-170L/m<3>, heating to 72-76DEG C to react, and heating to 90-95DEG C to react, to obtain slurry; (4) carrying out solid-liquid separation: cooling the slurry obtained in the step (3) to be less than 40DEG C, and carrying out the solid-liquid separation to obtain the solid; and (5) calcining the smashed rutile titanium dioxide product. The invention further relates to the rutile titanium dioxide prepared by the method, wherein the content of the titanium dioxide is larger than 99.90%, the content of Fe is less than 10.0ppm, and the D50 is less than 0.350 micrometers. The invention further relates to the titanium factory tail gas treatment method.
Description
Technical Field
The invention relates to the field of comprehensive treatment of pollutants, in particular to a product for preparing rutile titanium dioxide by recovering tail gas of a titanium factory and a preparation method thereof.
Background
Titanium metal is widely used in the fields of aviation, aerospace and various industries, and sponge titanium is prepared by chloridizing rutile or high titanium slag to prepare titanium tetrachloride and then reducing the titanium tetrachloride. The chlorination process generates a relatively large amount of chlorine-containing off-gas, in which TiCl is present4The content of the impurities is 60-80%, NaOH absorption treatment is generally adopted abroad, multistage water countercurrent absorption is generally adopted at home to prepare byproduct hydrochloric acid for environment protection treatment, and the environmental protection device cannot keep stable operation throughout the year due to higher content of impurities such as titanium and the like and obvious market seasonal demand of the byproduct hydrochloric acid, so that the common problem of the titanium sponge industry at home is solved.
Rutile titanium dichloride is mainly applied to the industries of electronics, printing ink, fibers, coatings and the like, is generally produced by a chlorination process or a sulfuric acid process, and has no report on the aspect of flue gas recovery and preparation at present.
At present, the hydrochloric acid as a byproduct is generally prepared by multistage water absorption and treated, and the application of the hydrochloric acid as the byproduct is limited due to the high content of impurities such as Ti4+, and precious titanium resources are not utilized.
Barium chloride is a bulk material and is mainly applied to the electrolytic preparation industry, and the conventional production methods include a barium sulfide-hydrochloric acid method, a barium carbonate-hydrochloric acid method and the like, and BaCl is prepared by using flue gas HCl2·2H2O has the advantage of low energy consumption. (the barium sulfide method and the barium carbonate method both need to evaporate a large amount of water brought in HCl after adding hydrochloric acid, and have high energy consumption)
Disclosure of Invention
The invention solves the technical problem of treating the tail gas of a titanium factory and simultaneously adopts the tail gas of the titanium factory to produce rutile titanium dioxide.
The invention produces rutile titanium dioxide product by absorbing and treating the tail gas of titanium factory. The method adopts purified water to absorb chlorine-containing tail gas in the chlorination process of the titanium factory, adds crystal seeds for hydrolysis to prepare rutile titanium dioxide after washing and purification, and recycles HCl gas generated in the hydrolysis process, for example, barium carbonate can be used for absorption to prepare industrial barium chloride products, thereby solving the environmental protection problem of the chlorine-containing tail gas of the titanium factory and simultaneously recycling precious titanium resources.
Specifically, the present invention solves the above technical problems by the following technical solutions:
the invention provides a method for preparing rutile titanium dioxide by using tail gas of a titanium factory, which comprises the following steps:
(1) titanium factory tail gas absorption: absorbing the tail gas of titanium factory with water to form solution, and using the solution as [ H ]+]Stopping absorbing tail gas with the solution to obtain absorption solution at a concentration of 8.0mol/L or more, preferably [ H ] in the solution+]Stopping absorbing tail with the solution at 8.0-10.0mol/LGas is used to obtain absorption liquid; then continuously absorbing tail gas by using water; preferably, the temperature of the absorption liquid is kept to be less than 40 ℃ in the absorption process, and the temperature is preferably kept to be 35-40 ℃;
(2) filtering and purifying; carrying out solid-liquid separation on the absorption liquid obtained in the step (1) to obtain a solid and a solution, and controlling and measuring Ti in the solution4+The concentration of (A) is 1.000-2.000 mol/L; preferably, activated carbon is added into the absorption liquid obtained in the step (1) and then solid-liquid separation is carried out to obtain a solid and a solution;
(3) hydrolysis: adding the solution obtained in the step (2) according to the proportion of 120-170L/m3Adding H with the concentration of 0.126-0.198mol/L2TiO3Seed crystal, heating to 72-76 ℃ for reaction, and heating to 90-95 ℃ for reaction to obtain slurry;
(4) solid-liquid separation: cooling the slurry obtained in the step (3) to below 40 ℃, preferably to 30-40 ℃, and then carrying out solid-liquid separation to obtain a solid and a solution; and
(5) calcining and crushing: and (4) calcining and crushing the solid obtained in the step (4) to obtain a rutile titanium dioxide product.
Wherein, H in the step (3)2TiO3The seed crystal is prepared by the following method: mixing TiCl4To produce Ti4+Adding a solution with the concentration of 1.80-2.20mol/L into water with the temperature of 90-95 ℃ according to the proportion of 70-90ml/L, and stirring and aging; preferably, the aging time is 55 to 65 minutes.
And (3) heating to 72-76 ℃, stirring for reaction for 60-80 minutes, heating to 90-95 ℃, stirring for reaction for 120-150 minutes, and preferably absorbing HCl gas generated in the heating reaction process in the step (3) by barium carbonate to prepare barium chloride.
Wherein, the amount of the solvent is 2-3 kg/m in the step (2)3Proportionally adding activated carbon into the absorption liquid; preferably, the reaction time is stirred for 30 to 60 minutes.
Wherein,in the tail gas absorption process in the step (1), the gas-liquid ratio is 10-12L/m3。
Wherein, the HCl gas generated in the step (3) and the step (5) is absorbed by barium carbonate for preparing barium chloride.
Wherein, the solution in the step (4) is treated by adding alkali or alkaline oxide until the pH value of the solution is 7.0-7.5, and preferably CaO is added until the pH value of the solution is 7.0-7.5; then settling and discharging are carried out.
The invention also provides rutile titanium dioxide prepared by the method for preparing the rutile titanium dioxide by using the tail gas of the titanium factory.
Wherein the content of titanium dioxide is more than 99.90%, the content of Fe is less than 10.0ppm, D50Less than 0.350 micron, D10Are all greater than 0.170 micrometer, D90All below 0.870 micron.
The invention also provides a treatment method of the tail gas of the titanium factory, which comprises the following steps:
(1) titanium factory tail gas absorption: absorbing the tail gas of titanium factory with water to form solution, and using the solution as [ H ]+]Stopping absorbing tail gas with the solution to obtain absorption solution at a concentration of 8.0mol/L or more, preferably [ H ] in the solution+]Stopping absorbing the tail gas by using the solution when the concentration is 8.0-10.0mol/L to obtain absorption liquid; then continuously absorbing tail gas by using water; preferably, the temperature of the absorption liquid is kept to be less than 40 ℃ in the absorption process, and the temperature is preferably kept to be 35-40 ℃;
(2) filtering and purifying; carrying out solid-liquid separation on the absorption liquid obtained in the step (1) to obtain a solid and a solution, and measuring Ti in the solution4+The concentration of (A) is 1.000-2.000 mol/L; preferably, activated carbon is added into the absorption liquid obtained in the step (1) and then solid-liquid separation is carried out to obtain a solid and a solution;
(3) hydrolysis: adding the solution obtained in the step (2) according to the proportion of 120-170L/m3Adding H with the concentration of 0.126-0.198mol/L2TiO3Seed crystal solution, heating to 72-76 deg.c for reaction, and heating toReacting at 90-95 ℃ to obtain slurry;
(4) solid-liquid separation: cooling the slurry obtained in the step (3) to below 40 ℃, preferably to 30-40 ℃, and then carrying out solid-liquid separation to obtain a solid and a solution; and
(5) calcining and crushing: and (4) calcining and crushing the solid obtained in the step (4) to obtain a rutile titanium dioxide product.
Wherein, in the tail gas absorption process of the tail gas treatment method in the step (1), the gas-liquid ratio is 10-12L/m3。
Wherein, the HCl gas generated in the step (3) and the step (5) is absorbed by barium carbonate for preparing barium chloride.
The invention has the following beneficial effects:
the invention avoids the mature process of preparing TiO by using a chlorination method and a sulfuric acid method2. The invention utilizes chlorine-containing tail gas of a titanium factory to prepare rutile titanium dioxide, recovers titanium resources, solves the problem of tail gas treatment of the titanium factory, and obtains the high-purity submicron spherical TiO by the seed crystal induced hydrolysis method2And (5) producing the product. The obtained titanium dioxide has high content and low content of impurity elements.
The invention prepares the rutile titanium dioxide by using the chlorine-containing tail gas of a titanium factory, the prepared rutile titanium dioxide has higher purity, the particle size reaches submicron, and the obtained titanium dioxide is nearly spherical.
Description of the drawings:
FIG. 1: a reaction process flow diagram of one embodiment of the invention;
FIG. 2: a reaction process flow diagram of a preferred embodiment of the present invention;
Detailed Description
A method for preparing rutile titanium dioxide by using tail gas of a titanium factory comprises the following steps:
(1) titanium factory tail gas absorption: absorbing the tail gas of titanium factory with water to form solution, and using the solution as [ H ]+]Stopping absorption when the concentration is more than or equal to 8.0mol/L to obtain absorption liquid, and then continuously absorbing tail gas by using water; preferably, the temperature of the absorption liquid is kept to be less than 40 ℃ in the absorption process; preferably, the temperature is kept between 35 and 40 ℃; in the preferable tail gas absorption process, the gas-liquid ratio is 10-12L/m3。
The purpose of the step is to absorb the tail gas of the titanium factory by water to obtain absorption liquid containing titanium, wherein H in the absorption process is controlled+The absorption is stopped under the control of the concentration of the raw material, then new water is used for absorbing tail gas of a titanium factory, and absorption liquid is obtained by circulating in sequence and is used for preparing rutile titanium dioxide. Wherein the temperature of the absorption liquid is controlled below 40 deg.C (such as cooling by heat exchanger), and is mainly used for preventing H from being directly generated2TiO3So as to generate H with the required properties such as purity and the like in the subsequent step through the control of the conditions2TiO3. In the step, the gas-liquid ratio is controlled to be 10-12L/m3And the tail gas of the titanium factory can be completely absorbed by water.
The reaction equation for this step occurs as follows:
（TiCl4、SiCl4、HCl）+H2O→Ti4++H4SiO4+H++Cl-
(2) filtering and purifying; adding an adsorbent into the absorption liquid obtained in the step (1), stirring for reaction, performing solid-liquid separation to obtain a solid and a solution, and controlling Ti in the solution4+The concentration of (A) is 1.000-2.000 mol/L; preferably, activated carbon is added into the absorption liquid obtained in the step (1) and then solid-liquid separation is carried out to obtain a solid and a solution; preferably 2 to 3kg/m3Proportionally adding activated carbon into the absorption liquid; preferably, the stirring time is 30 to 60 minutes.
The step is to add an adsorbent such as activated carbon and fiber filter material for adsorbing H in the absorption liquid4SiO4And tar, dust and other impurities, so that the impurities in the absorption liquid are reduced, and the product with higher purity is obtained. Wherein, in the step, Ti in the solution is added4+When the concentration of Ti in the solution is controlled4+When the concentration of (A) is less than 1.000mol/L, Ti in the solution obtained by the other sub-absorption is mixed with Ti4+Mixing the solution with relatively high concentration, and similarly, when Ti is contained in the solution4+When the concentration of (A) is higher than 2.000mol/L, Ti in the solution obtained by other times of absorption4+Mixing the solution with relatively low concentration, or adding deionized water to make Ti4+Is less than 2.000 mol/L. Finally Ti is added by the above-mentioned various means4+The concentration is controlled within the range.
(3) Hydrolysis: adding the solution obtained in the step (2) according to the proportion of 120-170L/m3Adding H with the concentration of 0.126-0.198mol/L2TiO3And heating the seed crystal solution to 72-76 ℃ for reaction, and heating to 90-95 ℃ for reaction to obtain the slurry.
Wherein, in one embodiment, said H2TiO3The seed crystal is prepared by the following steps: mixing TiCl4To produce Ti4+Adding a solution with the concentration of 1.80-2.20mol/L into water with the temperature of 90-95 ℃ according to the proportion of 70-90ml/L, and stirring and aging; preferably the aging time is 55-65 minutes; preferably, the temperature is increased to 72-76 ℃, the stirring reaction is carried out for 60-80 minutes, then the temperature is increased to 90-95 ℃, the stirring reaction is carried out for 120-150 minutes, and preferably, HCl gas generated in the temperature increasing reaction process is absorbed by barium carbonate for preparing barium chloride.
(4) Solid-liquid separation: cooling the slurry obtained in the step (3) to below 40 ℃, and then carrying out solid-liquid separation to obtain a solid and a solution; preferably, the solution is treated by adding alkali or alkaline oxide until the pH value of the solution is 7.0-7.5, and more preferably, CaO is added until the pH value of the solution is 7.0-7.5; then settling and discharging are carried out.
The two steps are mainly to carry out heating hydrolysis reaction on the absorption liquid in the presence of seed crystals to prepare H2TiO3In which addition of H is employed2TiO3The seed crystals being predominantly H formed2TiO3The purity and other properties of the product meet the requirements, and the H is easier to generate2TiO3. The above steps also treat the waste gas and the like generated in the steps, recover the hydrogen chloride gas generated in the step (3), treat the solution in the step (4) and discharge the solution, so that the by-products of the process can be reasonably utilized, wherein the alkali can be NaOH, Ca (OH)2The alkaline oxide can also be CaO, and the solution does not pollute the environment after the treatment.
The reaction equation occurring in the above-mentioned tail gas recovery step is as follows:
（TiCl4、SiCl4、HCl）+H2O→Ti4++H4SiO4+H++Cl-
specifically, the tail gas TiCl of the titanium plant4The reaction principle of deionized water absorption is as follows:
TiCl4+H2O+HCl→Ti4++H++5Cl-+H2O
titanium factory tail gas SiCl4The reaction principle of deionized water absorption is as follows:
SiCl4+4H2O+HCl→H4SiO4+5H++5Cl-
the TiCl is hydrolyzed after the seed crystal is added4The reaction equation of (a) is as follows:
Ti4++H2TiO3+H++4Cl-+3H2O→2H2TiO3+4HCl↑
(5) calcining and crushing: calcining and crushing the solid obtained in the step (4) to obtain a rutile type titanium dioxide product; preferably, the calcination process comprises the steps of firstly raising the temperature to 850 ℃ at the speed of 250 ℃/h, keeping the temperature for 0.5 to 1 hour, and then lowering the temperature to room temperature at the speed of 300 ℃/h; the preferred mode of comminution is jet milling.
This step is carried out by subjecting the obtained H2TiO3The titanium oxide is decomposed into titanium dioxide by heating and calcining. During the calcination and evaporation, hydrogen chloride gas is released, and the gas can be recycled by preparing barium chloride after being absorbed by barium carbonate, and the treatment method is the same as that of the HCl generated in the step (3).
The reaction equation generated in the above step is as follows:
H2TiO3+H++Cl-→TiO2+H2O+HCl↑
in the process of the invention for preparing rutile titanium dioxide by using tail gas of a titanium factory, one embodiment is to recycle HCl generated in the step (3) and the step (5) in the preparation process, such as preparing hydrochloric acid, and the like, and in another embodiment, the HCl generated in the step (3) and the step (5) is absorbed by barium carbonate to prepare barium chloride. Regarding the method for producing barium chloride by using HCl gas generated from tail gas of titanium factory, the applicant has already disclosed in the patent application No. 201210090320.1, which is previously filed, and the entire content of which is incorporated herein by reference. In the prior application, a method for producing barium chloride by using tail gas of a titanium factory is disclosed, wherein HCl in the tail gas is absorbed by barium carbonate slurry with the mass content of 20-25%, and [ H ] in absorption liquid is used as+]When the concentration reaches more than 2.0mol/l, barium chloride is obtained by separation.
Examples
First, the following examples will explain the method of producing rutile titanium dioxide using titanium factory tail gas and the measuring apparatus and measuring method used for analyzing the product, as follows:
the flow of the titanium factory chlorinated tail gas is 7000-10000 m3H (% by volume)
The tail gas of the titanium factory comprises the following components:
the determination of the content of various elements in the analysis of the rutile titanium dioxide product was made by Inductively Coupled Plasma (ICP) atomic emission spectrometry by the elemental analysis method.
An elemental analysis device: IRIS Intrepid II XSP inductively coupled plasma atomic emission spectrometer, manufactured by U.S. thermal electric corporation.
The content of the titanium dioxide is determined according to the content determination method in GB/T1706-2006.
The pH value was measured by a PHS-3C precision acidimeter manufactured by Shanghai precision instruments and meters.
The concentration of hydrogen ions and hydroxide ions is determined by a conventional titration method.
Ti4+The concentration was measured by a conventional redox method.
Industrial grade TiCl4：TiCl4The content was 99.97%.
And (3) determining the appearance of the titanium dioxide product: JSM-6490LV scanning electron microscope, manufactured by Nippon electronic division.
The particle size analysis method comprises the following steps: volume-based particle size as measured by wet laser method;
particle size distribution testing device: model 2000MU particle sizer, manufactured by malvern, uk.
Example 1
Referring to fig. 1, a method for preparing rutile titanium dioxide by using tail gas of a titanium factory comprises the following steps:
(1) seed preparation
Taking industrial grade TiCl470 kg of Ti is prepared by deionized water on a cold water bath4+Heating deionized water to 93 deg.C while the solution concentration is 2.00mol/L, and stirring to obtain 2.00mol/L TiCl4Adding the solution into the spare deionized water, stirring, and aging for 60 minutes to obtain H2TiO3And (5) seed crystals are ready for use.
(2) Tail gas absorption
Firstly placing deionized water into a spray absorption tower, then starting a circulating pump, introducing tail gas of a titanium factory into the spray absorption tower for absorption, wherein the tail gas flow is 8000m3H, controlling the ratio of absorbed gas to liquid at 11L/m3Controlling the temperature of the absorption liquid to be less than 40 ℃, cooling the absorption liquid by a heat exchanger when the temperature of the absorption liquid is more than 40 ℃, and monitoring the absorption liquid during the absorption process [ H ]+]Concentration of [ H ]+]Stopping absorption when the concentration is more than or equal to 8.11mol/L, then switching the tail gas to be absorbed by fresh deionized water, and enabling the absorption liquid to enter the next operation.
(3) Filtering to remove impurities
The powdered activated carbon was weighed to 2.5kg/m3Proportionally adding the mixture into absorption liquid, stirring for reaction for 45 minutes, and then performing filter pressing and separation by a filter press to remove H4SiO4And mechanical impurities such as tar and dust, and measuring [ Ti ] by redox method4+]At 1.318mol/L, filter residue is discarded, and the clear filtrate enters the next operation.
(4) Hydrolysis reaction
Pumping the clear solution in the last step into a glass lining reactor, and adding 130L of H prepared in the step (1) into the glass lining reactor according to the proportion of per cubic meter2TiO3Seed crystal, starting jacket, stirring, heating to 74 deg.C, hydrolyzing for 70 min, heating to 93 deg.C, stirring, and reacting for 135 min to obtain the final productAnd (5) recycling the HCl gas.
(5) Separation of
Cooling the slurry to below 35 ℃ by a jacket after the hydrolysis is finished, separating by a filter press, carrying out the next operation on a filter cake, treating CaO in the filtrate until the pH value of the solution is 7.2, settling, discharging clear liquid, and discarding residues.
(6) Calcining and pulverizing
Raising the temperature of the filter cake obtained in the step (5) to 850 ℃ according to a heating rate of 250 ℃/h, keeping the temperature for 1 hour, and then cooling to room temperature according to a cooling rate of 300 ℃/h; and (3) recycling HCl gas generated in the calcining process, and carrying out airflow crushing on the calcined material to obtain a rutile titanium dioxide product. The content of titanium dioxide, the content of various trace metal elements and the particle size distribution of the obtained titanium dioxide product are measured, and the measurement results are shown in table 1.
Example 2
Referring to fig. 2, the method for preparing rutile titanium dioxide by using tail gas of a titanium factory comprises the following steps:
(1) seed preparation
Taking industrial grade TiCl470 kg of Ti is prepared by deionized water on a cold water bath4+Heating deionized water to 93 deg.C while the solution concentration is 2.00mol/L, and stirring to obtain 2.00mol/L TiCl4Adding the solution into the spare deionized water, stirring, and aging for 60 minutes to obtain H2TiO3And (5) seed crystals are ready for use.
(2) Tail gas absorption
Firstly placing deionized water into a spray absorption tower, then starting a circulating pump, introducing tail gas of a titanium factory into the spray absorption tower for absorption, wherein the tail gas flow is 8000m3H, controlling the ratio of absorbed gas to liquid at 11L/m3Controlling the temperature of the absorption liquid to be less than 40 ℃, and when the temperature of the absorption liquid is more than 40 ℃, dredgingCooling with a heat exchanger, monitoring the absorption liquid [ H ] during the absorption process+]Concentration of [ H ]+]Stopping absorption when the concentration is more than or equal to 9.48mol/L, then switching the tail gas absorption by fresh deionized water, and making the absorption liquid enter the next operation.
(3) Filtering to remove impurities
The powdered activated carbon was weighed to 2.5kg/m3Proportionally adding the mixture into absorption liquid, stirring for reaction for 45 minutes, and then performing filter pressing and separation by a filter press to remove H4SiO4And mechanical impurities such as tar and dust, and measuring [ Ti ] by redox method4+]The concentration is 1.659mol/L, filter residue is discarded, and clear filtrate enters the next operation.
(4) Hydrolysis reaction
Pumping the clear solution in the previous step into a glass lining reactor, and adding the H prepared in the step (1) according to the proportion of 163L per cubic meter2TiO3And (3) seed crystal, starting a jacket, stirring, heating to 74 ℃, hydrolyzing for 70 minutes, heating to 93 ℃, stirring, reacting for 135 minutes, and absorbing the generated HCl gas with barium carbonate to prepare barium chloride.
(5) Separation of
Cooling the slurry to below 35 ℃ by a jacket after the hydrolysis is finished, separating by a filter press, carrying out the next operation on a filter cake, treating CaO in the filtrate until the pH value of the solution is 7.2, settling, discharging clear liquid, and discarding residues.
(6) Calcining and pulverizing
Raising the temperature of the filter cake obtained in the step (5) to 850 ℃ according to a heating rate of 250 ℃/h, keeping the temperature for 1 hour, and then cooling to room temperature according to a cooling rate of 300 ℃/h; BaCO for HCl gas generated during calcination3Preparation of BaCl by absorbing slurry2·2H2And O, carrying out air flow crushing on the calcined material to obtain a rutile titanium dioxide product. The content of titanium dioxide, the content of various trace metal elements and the particle size distribution of the obtained titanium dioxide product are measured, and the measurement results are shown in table 1.
Example 3
The method for preparing rutile titanium dioxide by using the tail gas of the titanium factory comprises the following steps:
(1) seed preparation
Taking industrial grade TiCl470 kg of Ti is prepared by deionized water on a cold water bath4+Heating deionized water to 93 deg.C while the solution concentration is 2.00mol/L, and stirring to obtain 2.00mol/L TiCl4Adding the solution into the spare deionized water, stirring, and aging for 60 minutes to obtain H2TiO3And (5) seed crystals are ready for use.
(2) Tail gas absorption
Firstly placing deionized water into a spray absorption tower, then starting a circulating pump, introducing tail gas of a titanium factory into the spray absorption tower for absorption, wherein the tail gas flow is 8000m3H, controlling the ratio of absorbed gas to liquid at 11L/m3Controlling the temperature of the absorption liquid to be less than 40 ℃, cooling the absorption liquid by a heat exchanger when the temperature of the absorption liquid is more than 40 ℃, and monitoring the absorption liquid during the absorption process [ H ]+]Concentration of [ H ]+]Stopping absorption when the concentration is more than or equal to 8.61mol/L, then switching the tail gas to absorb by fresh deionized water, and enabling the absorption liquid to enter the next operation.
(3) Filtering to remove impurities
The powdered activated carbon was weighed to 2.5kg/m3Proportionally adding the mixture into absorption liquid, stirring for reaction for 45 minutes, and then performing filter pressing and separation by a filter press to remove H4SiO4And mechanical impurities such as tar and dust, and measuring [ Ti ] by redox method4+]At 1.507mol/L, filter residue is discarded, and clear filtrate enters the next operation.
(4) Hydrolysis reaction
Pumping the clear solution in the previous step into a glass lining reactor, and adding the H prepared in the step (1) according to the proportion of 163L per cubic meter2TiO3Seed crystal, stirring and raising by opening jacketHydrolyzing at 74 ℃ for 70 minutes, heating to 93 ℃, stirring and reacting for 135 minutes, and absorbing the generated HCl gas with barium carbonate to prepare barium chloride.
(5) Separation of
Cooling the slurry to below 35 ℃ by a jacket after the hydrolysis is finished, separating by a filter press, carrying out the next operation on a filter cake, treating CaO in the filtrate until the pH value of the solution is 7.2, settling, discharging clear liquid, and discarding residues.
(6) Calcining and pulverizing
Raising the temperature of the filter cake obtained in the step (5) to 850 ℃ according to a heating rate of 250 ℃/h, keeping the temperature for 1 hour, and then cooling to room temperature according to a cooling rate of 300 ℃/h; BaCO for HCl gas generated during calcination3Preparation of BaCl by absorbing slurry2·2H2And O, carrying out air flow crushing on the calcined material to obtain a rutile titanium dioxide product. The content of titanium dioxide, the content of various trace metal elements and the particle size distribution of the obtained titanium dioxide product are measured, and the measurement results are shown in table 1.
Example 4
The method for preparing rutile titanium dioxide by using the tail gas of the titanium factory comprises the following steps:
(1) seed preparation
Taking industrial grade TiCl480 kg of Ti is prepared by deionized water on a cold water bath4+1.80mol/L solution is added, deionized water is heated to 90 ℃ for standby, and the prepared 1.80mol/L TiCl is stirred according to the proportion of 70ml/L4Adding the solution into the spare deionized water, stirring, and aging for 40 minutes to obtain H2TiO3And (5) seed crystals are ready for use.
(2) Tail gas absorption
Firstly placing deionized water into a spray absorption tower, then starting a circulating pump, introducing tail gas of a titanium factory into the spray absorption tower for absorption, wherein the tail gas flow is 7000m3H, controlling the ratio of absorbed gas to liquid at 10L/m3Controlling the temperature of the absorption liquid to be less than 35 ℃, and monitoring the absorption liquid during the absorption process [ H+]Concentration of [ H ]+]Stopping absorption when the concentration is more than or equal to 8.00mol/L, then switching the tail gas to be absorbed by fresh deionized water, and enabling the absorption liquid to enter the next operation.
(3) Filtering to remove impurities
2kg/m of powdered activated carbon3Proportionally adding the mixture into absorption liquid, stirring for reaction for 30 minutes, and then performing filter pressing separation by a filter press to remove H4SiO4And mechanical impurities such as tar and dust, and measuring [ Ti ] by redox method4+]The concentration is 1.000mol/L, filter residue is discarded, and the clear filtrate enters the next operation.
(4) Hydrolysis reaction
Pumping the clear solution in the last step into a glass lining reactor, and adding the H prepared in the step (1) according to the proportion of 120L per cubic meter2TiO3And (3) seed crystal, starting a jacket, stirring, heating to 72 ℃, hydrolyzing for 60 minutes, heating to 90 ℃, stirring, reacting for 120 minutes, and absorbing the generated HCl gas with barium carbonate to prepare barium chloride.
(5) Separation of
Cooling the slurry to below 30 ℃ by a jacket after the hydrolysis is finished, separating by a filter press, carrying out the next operation on a filter cake, treating CaO in the filtrate until the pH value of the solution is 7.0, settling, discharging clear liquid, and discarding residues.
(6) Calcining and pulverizing
Raising the temperature of the filter cake obtained in the step (5) to 850 ℃ according to a heating rate of 250 ℃/h, keeping the temperature for 1 hour, and then cooling to room temperature according to a cooling rate of 300 ℃/h; BaCO for HCl gas generated during calcination3Preparation of BaCl by absorbing slurry2·2H2And O, carrying out air flow crushing on the calcined material to obtain a rutile titanium dioxide product. The obtained titanium dioxide product has the titanium dioxide content, the content of various trace metal elements and particlesThe diameter distribution was measured, and the results are shown in Table 1.
Example 5
(1) Seed preparation
Taking industrial grade TiCl4100 kg of Ti is prepared by deionized water on a cold water bath4+Heating deionized water to 95 deg.C while the solution concentration is 2.20mol/L, and stirring to obtain 2.20mol/L TiCl4Adding the solution into the spare deionized water, stirring, and aging for 80 minutes to obtain H2TiO3And (5) seed crystals are ready for use.
(2) Tail gas absorption
Firstly placing deionized water into a spray absorption tower, then starting a circulating pump, introducing tail gas of a titanium factory into the spray absorption tower for absorption, wherein the tail gas flow is 10000m3H, controlling the ratio of absorbed gas to liquid at 12L/m3Controlling the temperature of the absorption liquid to be less than 38 ℃, cooling the absorption liquid by a heat exchanger when the temperature of the absorption liquid is more than 40 ℃, and monitoring the absorption liquid during the absorption process [ H ]+]Concentration of [ H ]+]Stopping absorption when the concentration is more than or equal to 10.00mol/L, then switching the tail gas to absorb by fresh deionized water, and enabling the absorption liquid to enter the next operation.
(3) Filtering to remove impurities
The powdered activated carbon was charged in an amount of 3kg/m3Adding the mixture into absorption liquid in proportion, stirring for reaction for 60 minutes, and then removing H by filter pressing and separation of a filter press4SiO4And mechanical impurities such as tar and dust, and measuring [ Ti ] by redox method4+]The concentration is 2.000mol/L, filter residue is discarded, and the clear filtrate enters the next operation.
(4) Hydrolysis reaction
Pumping the clear solution in the previous step into a glass lining reactor, and adding the H prepared in the step (1) according to the proportion of 170L per cubic meter2TiO3Seed crystal, starting jacket, stirring, heating to 76 deg.C for 80 min, heating to 95 deg.C, stirring, and reacting for 150 minAnd the generated HCl gas is absorbed by barium carbonate to prepare barium chloride.
(5) Separation of
Cooling the slurry to below 35 ℃ by a jacket after the hydrolysis is finished, separating by a filter press, carrying out the next operation on a filter cake, treating CaO in the filtrate until the pH value of the solution is 7.5, settling, discharging clear liquid, and discarding residues.
(6) Calcining and pulverizing
Raising the temperature of the filter cake obtained in the step (5) to 850 ℃ according to a heating rate of 250 ℃/h, keeping the temperature for 1 hour, and then cooling to room temperature according to a cooling rate of 300 ℃/h; BaCO for HCl gas generated during calcination3Preparation of BaCl by absorbing slurry2·2H2And O, carrying out air flow crushing on the calcined material to obtain a rutile titanium dioxide product. The content of titanium dioxide, the content of various trace metal elements and the particle size distribution of the obtained titanium dioxide product are measured, and the measurement results are shown in table 1.
TABLE 1 determination of the Properties of the rutile titanium dioxide product prepared in the example of the invention
| Item | 1# | 2# | 3# | 4# | 5# |
| TiO2% | 99.92 | 99.96 | 99.95 | 99.92 | 99.93 |
| K ppm | ＜5.0 | ＜5.0 | ＜5.0 | ＜5.0 | ＜5.0 |
| Na ppm | ＜5.0 | ＜5.0 | ＜5.0 | ＜5.0 | ＜5.0 |
| Ca ppm | ＜2.0 | ＜2.0 | ＜2.0 | ＜2.0 | ＜2.0 |
| Mg ppm | ＜2.0 | ＜2.0 | ＜2.0 | ＜2.0 | ＜2.0 |
| Fe ppm | ＜10.0 | ＜10.0 | ＜10.0 | ＜10.0 | ＜10.0 |
| Si ppm | ＜2.0 | ＜2.0 | ＜2.0 | ＜2.0 | ＜2.0 |
| Al ppm | ＜2.0 | ＜2.0 | ＜2.0 | ＜2.0 | ＜2.0 |
| D10μm | 0.172 | 0.177 | 0.174 | 0.175 | 0.176 |
| D50μm | 0.331 | 0.341 | 0.337 | 0.331 | 0.340 |
| D90μm | 0.872 | 0.864 | 0.866 | 0.860 | 0.870 |
| Morphology of | Near spherical shape | Near spherical shape | Near spherical shape | Near spherical shape | Near spherical shape |
The results in Table 1 above show that the rutile titanium dioxide produced in the examples of the present invention has a content of greater than 99.2%, the products produced in examples 2 and 3 have a content of greater than 99.5%, and the rutile titanium dioxide produced in examples 1-5 has Na and K contents of less than 5.0ppm, Ca and Mg contents of less than 2.0ppm, Fe contents of less than 10.0ppm, and Si and Al contents of less than 2.0 ppm; examples 1-5 the rutile titanium dioxide produced had a better particle size distribution, D50Below 0.350 micron. D10Are all greater than 0.170 micrometer, D90All below 0.870 micron, some of which are shown as D50And may be between 0.330 and 0.340 microns. The data show that the titanium dioxide prepared by the method has high purity, low impurity content and narrow particle size distribution.
Claims (17)
1. A method for preparing rutile titanium dioxide by using tail gas of a titanium factory comprises the following steps:
(1) titanium factory tail gas absorption: absorbing the tail gas of titanium factory with water to form solution, and using the solution as [ H ]+]Stopping absorbing the tail gas by using the solution to obtain an absorption solution when the concentration is more than or equal to 8.0 mol/L; then continuously absorbing tail gas by using water;
(2) filtering and purifying; carrying out solid-liquid separation on the absorption liquid obtained in the step (1) to obtain a solid and a solution, and controlling Ti in the solution4+The concentration of (A) is 1.000-2.000 mol/L; adding the absorption liquid obtained in the step (1)Adding activated carbon, and performing solid-liquid separation to obtain a solid and a solution;
(3) hydrolysis: adding the solution obtained in the step (2) according to the proportion of 120-170L/m3Adding H with the concentration of 0.126-0.198mol/L2TiO3Heating the seed crystal solution to 72-76 ℃ for reaction, and heating to 90-95 ℃ for reaction to obtain slurry;
(4) solid-liquid separation: cooling the slurry obtained in the step (3) to below 40 ℃, and then carrying out solid-liquid separation to obtain a solid and a solution; and
(5) calcining and crushing: and (4) calcining and crushing the solid obtained in the step (4) to obtain a rutile titanium dioxide product.
2. The method of producing rutile titanium dioxide according to claim 1, wherein the H in step (3)2TiO3The seed crystal is prepared by the following method: mixing TiCl4To produce Ti4+Adding the solution with the concentration of 1.80-2.20mol/L into water with the temperature of 90-95 ℃ according to the proportion of 70-90ml/L, stirring and aging for 55-65 minutes.
3. The method of producing rutile titanium dioxide of claim 1, wherein the step (1) is performed while [ H ] is in solution+]Stopping absorbing the tail gas by using the solution when the concentration is 8.0-10.0mol/L to obtain the absorption solution.
4. The process for producing rutile titanium dioxide of claim 1, wherein the temperature of the absorption liquid is maintained at less than 40 ℃ during absorption of the tail gas in step (1).
5. The method for preparing rutile titanium dioxide according to claim 1, wherein the temperature of step (3) is raised to 72-76 ℃ and stirred for reaction for 60-80 minutes, and then raised to 90-95 ℃ and stirred for reaction for 120-150 minutes.
6. The rutile titanium dioxide production process according to any one of claims 1 to 5, wherein the amount of the rutile titanium dioxide is 2 to 3kg/m in the step (2)3Proportionally adding activated carbon into the absorption liquid; adding active carbon, and stirring for reaction for 30-60 min.
7. The rutile titanium dioxide production method of any one of claims 1-5, wherein the ratio of gas to liquid in the tail gas absorption process of step (1) is 10-12L/m3。
8. The rutile titanium dioxide production method of any one of claims 1 to 5, wherein the HCl gas produced in step (3) and step (5) is absorbed with barium carbonate for production of barium chloride.
9. The rutile titanium dioxide production method of claim 6, wherein the HCl gas generated in the steps (3) and (5) is absorbed with barium carbonate for production of barium chloride.
10. The rutile titanium dioxide production method of any one of claims 1 to 5, wherein the solution in step (4) is treated by adding an alkali or an alkali oxide to the solution to a pH of 7.0 to 7.5; then settling and discharging are carried out; the cooling to below 40 ℃ is to 30-40 ℃.
11. The rutile titanium dioxide production method of claim 9, wherein the solution in step (4) is treated by adding alkali or alkaline oxide until the solution has a pH of 7.0-7.5, and then settling and discharging; the cooling to below 40 ℃ is to 30-40 ℃.
12. The method for producing rutile titanium dioxide according to claim 10, wherein the solution in step (4) is treated by adding CaO to a pH of the solution of 7.0 to 7.5.
13. A rutile titanium dioxide produced by the process of any one of claims 1-12 using titanium mill tail gas to produce rutile titanium dioxide, wherein the titanium dioxide content is greater than 99.90%, the Fe content is less than 10.0ppm, and D50Less than 0.350 micron, D10Are all greater than 0.170 micrometer, D90All below 0.870 micron.
14. A method for treating tail gas of a titanium factory comprises the following steps:
(1) titanium factory tail gas absorption: absorbing the tail gas of titanium factory with water to form solution, and using the solution as [ H ]+]Stopping absorbing the tail gas by using the solution to obtain an absorption solution when the concentration is more than or equal to 8.0 mol/L; then continuously absorbing tail gas by using water; keeping the temperature of the absorption liquid to be less than 40 ℃ in the absorption process;
(2) filtering and purifying; carrying out solid-liquid separation on the absorption liquid obtained in the step (1) to obtain a solid and a solution, and measuring Ti in the solution4+The concentration of (A) is 1.000-2.000 mol/L; adding activated carbon into the absorption liquid obtained in the step (1), and then carrying out solid-liquid separation to obtain a solid and a solution;
(3) hydrolysis: adding the solution obtained in the step (2) according to the proportion of 120-170L/m3Adding H with the concentration of 0.126-0.198mol/L2TiO3Heating the seed crystal solution to 72-76 ℃ for reaction, and heating to 90-95 ℃ for reaction to obtain slurry;
(4) solid-liquid separation: cooling the slurry obtained in the step (3) to below 40 ℃, and then carrying out solid-liquid separation to obtain a solid and a solution; and
(5) calcining and crushing: and (4) calcining and crushing the solid obtained in the step (4) to obtain a rutile titanium dioxide product.
15. The method for treating tail gas of titanium factory according to claim 14, wherein the ratio of gas to liquid in the tail gas absorption process of step (1)For example, 10 to 12L/m3。
16. The method for treating tail gas of a titanium plant according to claim 14 or 15, wherein the HCl gas generated in step (3) and step (5) is absorbed by barium carbonate for preparing barium chloride.
17. The method for treating tail gas of titanium factory according to claim 16, wherein [ H ] in the solution in step (1)+]Stopping absorbing the tail gas by using the solution when the concentration is 8.0-10.0mol/L to obtain the absorption solution.
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