CN109160536A - The method for reducing titanium slag acid hydrolysis tail gas sulphur emissions - Google Patents
The method for reducing titanium slag acid hydrolysis tail gas sulphur emissions Download PDFInfo
- Publication number
- CN109160536A CN109160536A CN201811157089.7A CN201811157089A CN109160536A CN 109160536 A CN109160536 A CN 109160536A CN 201811157089 A CN201811157089 A CN 201811157089A CN 109160536 A CN109160536 A CN 109160536A
- Authority
- CN
- China
- Prior art keywords
- tail gas
- titanium slag
- acidolysis
- premix
- acid hydrolysis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
Abstract
The present invention relates to the methods for reducing titanium slag acid hydrolysis tail gas sulphur emissions, belong to Titanium White Production By Sulfuric Acid Process field.Present invention solves the technical problem that being that sulfur content is high in the tail gas of titanium slag acid hemolysis process generation, vent gas treatment is at high cost.The present invention provides the method for reducing titanium slag acid hydrolysis tail gas sulphur emissions, step includes first premixing titanium slag and 98% concentrated sulfuric acid to obtain premix, then reactor is added portionwise in premix, be passed through water or steam initiation reaction and carry out acidolysis, acidolysis main reaction terminate after through curing, leach, acidolysis titanium liquid be obtained by filtration.Tail gas sulfur content when the present invention can effectively reduce titanium slag acidolysis, acidolysis rate is suitable with the prior art, easy to operate, easy to implement, has a good application prospect.
Description
Technical field
The invention belongs to Titanium White Production By Sulfuric Acid Process fields, and in particular to the method for reducing titanium slag acid hydrolysis tail gas sulphur emissions.
Background technique
The production method of titanium dioxide is mainly two kinds i.e. sulfuric acid process and chloridising, 90% or more titanium white production of the current country
Method is sulfuric acid process.Sulfate process titanium dioxide deadly defect is environmental issue, such as spent acid, ferrous sulfate and sulfur-containing tail gas.If with titanium
Iron ore produces titanium dioxide, and average titanium white per ton wants ferrous sulfate by-product 2.5t~4.0t, spent acid 5t~8t that concentration is about 20%,
Acid sulphur-containing exhaust gas 15000m3~2000m3.In fact, disposal of waste gas, water and industrial residue just becomes the work from being born from sulfate process titanium dioxide
Skill stubborn problem, each sulfate process titanium dioxide manufacturing enterprise is all utilizing some fruitful techniques and technology in the world at present
With reduction " three wastes ", wherein being typically represented as titanium slag instead of ilmenite concentrate.
Titanium slag replaces ilmenite concentrate to be the fundamental way for reducing or eliminating by-product green vitriol, it, which at least has the advantage that, subtracts
Few sulphur consumption 20%~30%；Greatly reduce and even is eliminated by-product green vitriol；Improve unit equipment production capacity about 30%；Reduce fixed throw
Money 7%.With constantly improve with strictly for national environmental protection policy, it is the general trend of events that it is raw material that domestic sulfuric acid method titanium pigment factory, which uses titanium slag instead,
Become.But the process of titanium slag acidolysis has the characteristics that acid is expected than high, reaction temperature is high etc. compared to ilmenite concentrate acidolysis, thus gives off
A large amount of sulfur-containing tail gas, the quick-fried table of sulfur content in chimney breast tail gas (more than 2000ppm, the several hundred a 200ppm of environmental requirement with
Under), seriously constrain the popularization and application of titanium slag.
It is mainly concentrated in the optimization of exhaust gas processing device for the super calibration method of sulfur content in titanium slag acid hydrolysis tail gas at present, it should
Though method can solve the exceeded problem of tail gas sulfur content to a certain extent, cost of investment and operating cost (alkaline consumption, water are caused
Consumption and maintenance) increase.
Summary of the invention
Present invention solves the technical problem that be that sulfur content is high in the tail gas of titanium slag acid hemolysis process generation, vent gas treatment cost
It is high.
Technical proposal that the invention solves the above-mentioned problems is to provide the method for reducing titanium slag acid hydrolysis tail gas sulphur emissions, step packet
It includes and first premixes titanium slag and 98% concentrated sulfuric acid to obtain premix, reactor then is added portionwise in premix, be passed through water or steam
Initiation reaction carries out acidolysis, acidolysis main reaction terminate after through curing, leach, acidolysis titanium liquid be obtained by filtration.
Wherein, the control of acid hemolysis process reaction system acid concentration is 92% or more.
Wherein, premix is all added temperature of reaction system when finishing and controls at 150~180 DEG C, and reaction system is in equal
Even slurry form.
Wherein, the control of acid hemolysis process maximum temperature is at 200~210 DEG C.
Wherein, the mode being added portionwise is the 30%~40% of first addition premix, and second batch is added remaining pre-
Mixing.
Wherein, the opportunity of premix is added as when temperature of reaction system reaches 180~190 DEG C in second batch.
Wherein, second batch is added premix and adds in 2~4min.
Wherein, the mass ratio of 98% concentrated sulfuric acid and titanium slag is 1.7~1.8.
Beneficial effects of the present invention:
The present invention controls reaction temperature and reaction acid concentration, tail when effectively reducing titanium slag acidolysis by batch charging
Gas sulfur content mitigates the pressure of tail gas absorption, reduces the consumption of tail gas absorption agent；The present invention does not increase in prior art basis
Device, easy to operate, easy to implement, the method for taking optimization acidolysis process, acidolysis rate is suitable with the prior art, reduces in tail gas
Sulfur content, to reduce production cost.
Specific embodiment
The present invention provides the method for reducing titanium slag acid hydrolysis tail gas sulphur emissions, and step includes first that titanium slag and 98% concentrated sulfuric acid is pre-
It is mixed to obtain premix, reactor then is added portionwise in premix, water is passed through or steam initiation reaction carries out acidolysis, acidolysis master is anti-
After should terminating through curing, leach, acidolysis titanium liquid be obtained by filtration.
Multistep feeding method mainly passes through reduction temperature of reaction system, the time of reaction is appropriately extended, to guarantee acidolysis
Rate and the volatilization for reducing sulfuric acid in reaction system reduce sulfur content in tail gas.
Wherein, the control of acid hemolysis process reaction system acid concentration is 92% or more.Reaction acid concentration is controlled higher as far as possible
Level, the boiling point of sulfuric acid is improved, to reduce the volatilization of sulfuric acid.After premix is added, enter acidolysis main reaction therewith
Stage can reach 200 DEG C~210 DEG C, the moisture inside reaction system will be a large amount of since temperature is higher when acidolysis main reaction
Evaporation, acid concentration can change always, be gradually increased until that reaction reaches balance.
Wherein, premix is all added temperature of reaction system when finishing and controls at 150~180 DEG C, and reaction system is in equal
Even slurry form, it is ensured that do not occur solidification phenomenon.
Wherein, the control of acid hemolysis process maximum temperature is at 200~210 DEG C.Maximum temperature is controlled in suitable model
It encloses, one side acidolysis rate needs certain temperature to guarantee, while high temperature will lead to sulfuric acid decomposition and volatile quantity increases.
Wherein, the mode being added portionwise is the 30%~40% of first addition premix, and second batch is added remaining pre-
Mixing.After first premix is added, it is passed through suitable water or steam initiation reaction.
Wherein, the addition opportunity of second batch is when temperature of reaction system reaches 180~190 DEG C.First premix exists
Start to react under the initiation of water or steam, temperature can gradually rise, and add when temperature of reaction system reaches 180~190 DEG C
Second batch premix, then it is passed through suitable water or steam initiation reaction continues.Steam or water mesh are passed through after second batch charging
Be give reaction system increase heat so that reaction maximum temperature reach 200~210 DEG C, so that it is guaranteed that acidolysis rate is higher
It is horizontal.
Wherein, second step is added premix and adds in 2~4min.
Wherein, the mass ratio of 98% concentrated sulfuric acid and titanium slag is 1.7~1.8:1.
Wherein, the mode of filtering is sheet frame expression separation.
Comparative example 1
Under agitation, after taking 98% concentrated sulfuric acid 173.5g, titanium slag 100g to premix, according to titanium slag acidolysis process: reaction
Acid concentration 92%, 130 DEG C of initiation temperature, curing time 1.5h, 170 DEG C of curing temperature, 68 DEG C of extraction temperature, extraction time 1.5h
Acidolysis is carried out, calculates sulfur content in acidolysis rate and tail gas after obtaining acidolysis titanium liquid by sheet frame expression separation.
Embodiment 2
Under agitation, after taking 98% concentrated sulfuric acid 173.5g, titanium slag 100g to premix, acid is carried out according to two-step method of the present invention
Solution calculates sulfuric acid content in acidolysis rate and tail gas after obtaining acidolysis titanium liquid by sheet frame expression separation, wherein reaction acid concentration
92%, 130 DEG C of initiation temperature, second step adding proportion 60%, for when system temperature is 180 DEG C at the time of addition, when addition
Between control in 1.5min, curing time 1.5h, 170 DEG C of curing temperature, 68 DEG C of extraction temperature, extraction time 1.5h.
Embodiment 3
Under agitation, after taking 98% concentrated sulfuric acid 173.5g, titanium slag 100g to premix, acid is carried out according to two-step method of the present invention
Solution calculates sulfuric acid content in acidolysis rate and tail gas after obtaining acidolysis titanium liquid by sheet frame expression separation, wherein reaction acid concentration
92%, 130 DEG C of initiation temperature, second step adding proportion 65%, for when system temperature is 180 DEG C at the time of addition, when addition
Between control in 1.5min, curing time 1.5h, 170 DEG C of curing temperature, 68 DEG C of extraction temperature, extraction time 1.5h.
Embodiment 4
Under agitation, after taking 98% concentrated sulfuric acid 173.5g, titanium slag 100g to premix, acid is carried out according to two-step method of the present invention
Solution calculates sulfuric acid content in acidolysis rate and tail gas after obtaining acidolysis titanium liquid by sheet frame expression separation, wherein reaction acid concentration
92%, 130 DEG C of initiation temperature, second step adding proportion 70%, for when system temperature is 180 DEG C at the time of addition, when addition
Between control in 1.5min, curing time 1.5h, 170 DEG C of curing temperature, 68 DEG C of extraction temperature, extraction time 1.5h.
Embodiment 5
Under agitation, after taking 98% concentrated sulfuric acid 173.5g, titanium slag 100g to premix, acid is carried out according to two-step method of the present invention
Solution calculates sulfuric acid content in acidolysis rate and tail gas after obtaining acidolysis titanium liquid by sheet frame expression separation, wherein reaction acid concentration
92%, 130 DEG C of initiation temperature, second step adding proportion 65%, for when system temperature is 180 DEG C at the time of addition, when addition
Between control in 3min, curing time 1.5h, 170 DEG C of curing temperature, 68 DEG C of extraction temperature, extraction time 1.5h.
Comparative example 6
Under agitation, after taking 98% concentrated sulfuric acid 173.5g, titanium slag 100g to premix, acid is carried out according to two-step method of the present invention
Solution calculates sulfuric acid content in acidolysis rate and tail gas after obtaining acidolysis titanium liquid by sheet frame expression separation, wherein reaction acid concentration
85%, 130 DEG C of initiation temperature, second step adding proportion 65%, for when system temperature is 180 DEG C at the time of addition, when addition
Between control in 1.5min, curing time 1.5h, 170 DEG C of curing temperature, 68 DEG C of extraction temperature, extraction time 1.5h.
Embodiment 7
Under agitation, after taking 98% concentrated sulfuric acid 173.5g, titanium slag 100g to premix, acid is carried out according to two-step method of the present invention
Solution calculates sulfuric acid content in acidolysis rate and tail gas after obtaining acidolysis titanium liquid by sheet frame expression separation, wherein reaction acid concentration
92%, 130 DEG C of initiation temperature, second step adding proportion 65%, for when system temperature is 180 DEG C at the time of addition, when addition
Between control in 1.5min, curing time 1.5h, 170 DEG C of curing temperature, 68 DEG C of extraction temperature, extraction time 1.5h.
The relevant parameter index of above-described embodiment and comparative example is summarized as shown in table 1.
Table 1
It can see from upper table, the use one-step method progress acidolysis of comparative example 1, acidolysis rate 90.3%, sulfur content in tail gas
For 1.09g；Comparative example 6 uses two-step method of the invention and carries out acidolysis, but it is lower to react acid concentration, and control is 85%, tail
Sulfur content is not dropped and is improved instead in gas；Remaining embodiment carries out acidolysis, reaction acid concentration control using two-step method of the invention
>=92%, less, tail gas sulfur content is substantially reduced, and shows that the present invention can effectively reduce acid hemolysis process tail gas sulphur for acidolysis rate variation
Content, while keeping acidolysis rate suitable with the prior art.
Claims (8)
1. the method for reducing titanium slag acid hydrolysis tail gas sulphur emissions, it is characterised in that include the following steps: titanium slag and 98% dense sulphur first
Acid premix obtains premix, and reactor then is added portionwise in premix, is passed through water or steam initiation reaction carries out acidolysis, acidolysis
Main reaction terminate after through curing, leach, acidolysis titanium liquid be obtained by filtration.
2. the method according to claim 1 for reducing titanium slag acid hydrolysis tail gas sulphur emissions, it is characterised in that: the acid hemolysis process
Reaction system acid concentration is controlled 92% or more.
3. the method according to claim 1 or 2 for reducing titanium slag acid hydrolysis tail gas sulphur emissions, it is characterised in that: the premix
Temperature of reaction system control when finishing all is added in material, and, at 150~180 DEG C, reaction system is in uniform slurry form.
4. described in any item methods for reducing titanium slag acid hydrolysis tail gas sulphur emissions according to claim 1~3, it is characterised in that: institute
The control of acid hemolysis process maximum temperature is stated at 200~210 DEG C.
5. the method according to any one of claims 1 to 4 for reducing titanium slag acid hydrolysis tail gas sulphur emissions, it is characterised in that: institute
30%~40% that the mode being added portionwise is first addition premix is stated, remaining premix is added in second batch.
6. the method according to claim 5 for reducing titanium slag acid hydrolysis tail gas sulphur emissions, it is characterised in that: the second batch adds
The opportunity for entering premix is when temperature of reaction system reaches 180~190 DEG C.
7. the method according to claim 5 or 6 for reducing titanium slag acid hydrolysis tail gas sulphur emissions, it is characterised in that: described second
Addition premix is criticized to add in 2~4min.
8. described in any item methods for reducing titanium slag acid hydrolysis tail gas sulphur emissions according to claim 1~7, it is characterised in that: institute
The mass ratio for stating 98% concentrated sulfuric acid and titanium slag is 1.7~1.8:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811157089.7A CN109160536B (en) | 2018-09-30 | 2018-09-30 | Method for reducing sulfur emission of titanium slag acidolysis tail gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811157089.7A CN109160536B (en) | 2018-09-30 | 2018-09-30 | Method for reducing sulfur emission of titanium slag acidolysis tail gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109160536A true CN109160536A (en) | 2019-01-08 |
| CN109160536B CN109160536B (en) | 2021-04-06 |
Family
ID=64877349
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811157089.7A Active CN109160536B (en) | 2018-09-30 | 2018-09-30 | Method for reducing sulfur emission of titanium slag acidolysis tail gas |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109160536B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110980804A (en) * | 2019-12-31 | 2020-04-10 | 安徽迪诺环保新材料科技有限公司 | Method for inhibiting hydrogen sulfide generation by acidolysis tail gas |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101323465A (en) * | 2008-07-25 | 2008-12-17 | 攀钢集团研究院有限公司 | Method for acid hydrolysis of acid soluble titanium slag |
| CN102277489A (en) * | 2011-08-05 | 2011-12-14 | 攀钢集团有限公司 | Acidolysis method of titanium-containing slag |
| CN104843784A (en) * | 2015-05-21 | 2015-08-19 | 贵州东华工程股份有限公司 | Method and equipment for carrying out acidolysis in titanium white production by sulfuric acid process |
-
2018
- 2018-09-30 CN CN201811157089.7A patent/CN109160536B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101323465A (en) * | 2008-07-25 | 2008-12-17 | 攀钢集团研究院有限公司 | Method for acid hydrolysis of acid soluble titanium slag |
| CN102277489A (en) * | 2011-08-05 | 2011-12-14 | 攀钢集团有限公司 | Acidolysis method of titanium-containing slag |
| CN104843784A (en) * | 2015-05-21 | 2015-08-19 | 贵州东华工程股份有限公司 | Method and equipment for carrying out acidolysis in titanium white production by sulfuric acid process |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110980804A (en) * | 2019-12-31 | 2020-04-10 | 安徽迪诺环保新材料科技有限公司 | Method for inhibiting hydrogen sulfide generation by acidolysis tail gas |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109160536B (en) | 2021-04-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109775678B (en) | Method for preparing battery-grade iron phosphate and industrial-grade lithium phosphate from waste lithium iron phosphate batteries | |
| CN101643852B (en) | Heap-leaching method for separating copper and tin from tin-plated copper wires | |
| CN109207740A (en) | The extraction vanadium method of vanadium-bearing slag of high calcium and high phosphor | |
| CN107447113A (en) | A kind of method that iron and aluminium are separated from red mud and/or iron content solid waste | |
| CN108946802A (en) | The method for improving titanium slag acidolysis rate | |
| US11196107B2 (en) | Method for recycling lead paste in spent lead-acid battery | |
| CN108103321A (en) | A kind of regeneration method of last aluminium ash | |
| CN103993173B (en) | Method for the dechlorination of hydroxide nickel cobalt | |
| CN104178632A (en) | Method for comprehensively utilizing titanium white waste acid | |
| CN107699714A (en) | A kind of method that manganese sulfate electrolyte is prepared suitable for leaching pyrolusite by sulfur dioxide | |
| CN104261473B (en) | A kind of preparation method of Vanadium Pentoxide in FLAKES | |
| CN112323097B (en) | Method and system for removing sulfur dioxide in flue gas by zinc ammonia complexation coupling persulfate advanced oxidation technology | |
| CN109536700A (en) | A method of comprehensive utilization steel-making dust enriched iron | |
| CN108557901A (en) | A kind of production technology of steel mill's spent acid production bodied ferric sulfate | |
| CN106587122B (en) | A method of producing ice crystal using cell cathode carbon block alkaline leaching liquid | |
| CN109160536A (en) | The method for reducing titanium slag acid hydrolysis tail gas sulphur emissions | |
| CN110106353A (en) | A kind of short route leaching method of zinc abstraction | |
| CN106636615B (en) | The mica treatment process of lithium carbonate is prepared using lepidolite | |
| CN105400960A (en) | Method for pressurizing cobalt-rich copper matte to leach out nickel and cobalt and remove iron | |
| CN107840357A (en) | A kind of method that ice crystal is produced using cell cathode carbon block alkaline leaching liquid | |
| CN104386737A (en) | Method for preparing cadmium oxide by using cadmium-containing smoke dust generated by zinc smelting | |
| CN103922294A (en) | Methods for recovering arsenic sulfide and metallic arsenic from arsenic sulfide waste residues | |
| CN101871045A (en) | Method for producing zinc by utilizing sulphate process titanium dioxide waste acid | |
| CN103979755A (en) | Comprehensive treatment method of electro-plating sludge and sludge containing low amount of copper | |
| CN104789784B (en) | A kind of pyrometallurgy of zinc fume recovery handling process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 610306 Chengdu City, Chengdu, Sichuan, China (Sichuan) free trade test zone, Chengdu City, Qingbaijiang District, xiangdao Boulevard, Chengxiang Town, No. 1509 (room 13, A District, railway port mansion), room 1319 Patentee after: Chengdu advanced metal material industry technology Research Institute Co.,Ltd. Address before: 610306 Chengdu City, Chengdu, Sichuan, China (Sichuan) free trade test zone, Chengdu City, Qingbaijiang District, xiangdao Boulevard, Chengxiang Town, No. 1509 (room 13, A District, railway port mansion), room 1319 Patentee before: CHENGDU ADVANCED METAL MATERIAL INDUSTRIAL TECHNOLOGY RESEARCH INSTITUTE Co.,Ltd. |
|
| CP01 | Change in the name or title of a patent holder |