CN108372185A - A kind of titanium chloride slag resource utilization method and its device - Google Patents
A kind of titanium chloride slag resource utilization method and its device Download PDFInfo
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- CN108372185A CN108372185A CN201810369603.7A CN201810369603A CN108372185A CN 108372185 A CN108372185 A CN 108372185A CN 201810369603 A CN201810369603 A CN 201810369603A CN 108372185 A CN108372185 A CN 108372185A
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- filtrate
- ceramic membrane
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- 238000000034 method Methods 0.000 title claims abstract description 98
- 239000002893 slag Substances 0.000 title claims abstract description 97
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 title claims abstract description 57
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 147
- 239000012528 membrane Substances 0.000 claims abstract description 90
- 239000007788 liquid Substances 0.000 claims abstract description 81
- 239000000706 filtrate Substances 0.000 claims abstract description 71
- 239000000919 ceramic Substances 0.000 claims abstract description 65
- 239000003513 alkali Substances 0.000 claims abstract description 58
- 238000001556 precipitation Methods 0.000 claims abstract description 52
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 46
- 238000005406 washing Methods 0.000 claims abstract description 45
- 238000000926 separation method Methods 0.000 claims abstract description 38
- 239000002002 slurry Substances 0.000 claims abstract description 36
- 239000007787 solid Substances 0.000 claims abstract description 31
- 150000003839 salts Chemical class 0.000 claims abstract description 26
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 25
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 18
- 150000002500 ions Chemical class 0.000 claims abstract description 17
- 239000012267 brine Substances 0.000 claims abstract description 16
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 16
- 230000008859 change Effects 0.000 claims abstract description 6
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000007654 immersion Methods 0.000 claims description 19
- 241000370738 Chlorion Species 0.000 claims description 18
- 238000012545 processing Methods 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 15
- 239000012535 impurity Substances 0.000 claims description 15
- 238000006386 neutralization reaction Methods 0.000 claims description 15
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 13
- 239000000460 chlorine Substances 0.000 claims description 13
- 229910052801 chlorine Inorganic materials 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 12
- 238000005516 engineering process Methods 0.000 claims description 11
- 230000003472 neutralizing effect Effects 0.000 claims description 11
- 238000000746 purification Methods 0.000 claims description 11
- 238000004064 recycling Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 238000001223 reverse osmosis Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 238000005660 chlorination reaction Methods 0.000 claims description 9
- 238000002386 leaching Methods 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 239000012141 concentrate Substances 0.000 claims description 7
- 230000014759 maintenance of location Effects 0.000 claims description 7
- 239000004035 construction material Substances 0.000 claims description 6
- 239000012466 permeate Substances 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000012530 fluid Substances 0.000 claims description 3
- 238000005984 hydrogenation reaction Methods 0.000 claims description 3
- 238000001764 infiltration Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 230000000149 penetrating effect Effects 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 3
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 3
- 238000004458 analytical method Methods 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 31
- 239000004408 titanium dioxide Substances 0.000 abstract description 14
- 238000003843 chloralkali process Methods 0.000 abstract description 11
- 230000008901 benefit Effects 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 239000004566 building material Substances 0.000 abstract description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 22
- 230000008569 process Effects 0.000 description 18
- 235000010215 titanium dioxide Nutrition 0.000 description 15
- 239000000047 product Substances 0.000 description 13
- 239000011780 sodium chloride Substances 0.000 description 11
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000001110 calcium chloride Substances 0.000 description 6
- 229910001628 calcium chloride Inorganic materials 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000004411 aluminium Substances 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 235000019270 ammonium chloride Nutrition 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 239000011449 brick Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 238000001728 nano-filtration Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002006 petroleum coke Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- -1 5.809mg/L Substances 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000003818 cinder Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Processing Of Solid Wastes (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention relates to a kind of titanium chloride slag resource utilization method and its devices, belong to titanium dioxide chemical field.This approach includes the following steps：Step 1：Alkali soaks, and forms slurry；Step 2：Slurry is separated by solid-liquid separation；Step 3：The solid isolated in step 2 is washed again；Step 5：Secondary precipitation：PH=9~10, precipitation are adjusted to remove heavy metal ion therein, form secondary slurry jointly in the filtrate sodium carbonate and sodium hydroxide that are separated by solid-liquid separation out in step 2.Step 6：Ceramic membrane filter, dope is used to be separated by solid-liquid separation with plate and frame filter press or centrifuge together with washing slurry secondary slurry；Clear liquid then uses membrane separation technique to carry out depths reason, and chloralkali process salt dissolving light salt brine is made.Harmless building material and chloralkali process light salt brine are become to the harmful titanium chloride slag of environmental protection by the method for the invention, change is given up as " treasured ", has apparent economy and environmental benefit.
Description
Technical field
The present invention relates to a kind of new methods and its device of titanium chloride slag recycling, relate in particular to a kind of use
Alkali leaching, washing and UF membrane depth treatment process recycle the new of chlorion and the solid slag containing heavy metal ion in titanium chloride slag
Method belongs to titanium dioxide chemical field.
Background technology
Currently, the method for production titanium dioxide mainly has sulfuric acid process and chloridising.Due to the long flow path of sulfuric acid process, pollution is tight
Weight, poor product quality and be gradually chlorinated method substitution.
In current Titanium Dioxide Produced by Chloride Procedure production, main flow is：
A, (such as by titanium material：High titanium slag) and reducing agent is (such as：Petroleum coke) it is sent into chlorination furnace after evenly mixing, it is passed through chlorine
Gas carries out fluidizing chlorination at a temperature of 800 DEG C~1000 DEG C；
B, separating-purifying is carried out to the crude titanium tetrachloride obtained after chlorination and removes the impurity such as magnesium, iron, silicon and vanadium, obtain essence
Titanium tetrachloride processed；
C, refining titanic chloride liquid obtained carries out pre- thermal evaporation and is converted into gas phase, and is preheated to 300 DEG C~500 DEG C；
And a small amount of compound modifying agent simultaneously is added (such as in gas phase titanium tetrachloride：Alchlor) be mixed into oxidation furnace with it is pre-
Heat to 1300 DEG C or more of oxygen mixes rapidly in oxidation furnace, at a temperature of 1300 DEG C~1800 DEG C, less than 0.1 second in carry out oxygen
Change reaction and generates solid phase titanium dioxide；
D, and then titanium dioxide solids powder is removed into reaction zone rapidly and reaction heat is made to remove rapidly；
E, chlorine obtained by the reaction in oxidation furnace is separated into return chlorination furnace through filter, synchronization is collected through filter
Titanium dioxide granule powder and be beaten into liquid, send postprocessing working procedures that rutile type titanium white finished product is made.
In Titanium Dioxide Produced by Chloride Procedure production process, a large amount of dust-slag collection is generated in chlorination workshop section cyclone separator bottom.According to report
Road, 0.2 ton or so solid slag will be generated by often producing 1t titanium tetrachlorides.These solid slags are mainly the metal produced by chlorination reaction
Chloride, and the high titanium slag and petroleum coke that the reaction was complete form, and main component not only contains KCl, NaCl, MgCl2、
CaCl2Deng being also enriched the salt of various metals impurity (aluminium, iron, titanium, cobalt, chromium, manganese, arsenic, vanadium), these salts are most of to exist
Exist in a chloride-form under high temperature, aluminium and silicon are outer with oxide presence, and unreacted carbon exists with simple substance form.If waste residue
It is directly deposited in without processing outdoor, wherein a large amount of chloride will be caused to meet water dissolution, environment is caused seriously to pollute.
Processing for titanium chloride slag still has no better method in foreign data other than using deep-well landfill.It is domestic
After enterprise mostly uses greatly water flushing, in lime and formation lime slag solidification send cinder field to stack or fill, and there is presently no to this slag
Carry out the effective ways of harmless treatment or recycling.
Number of patent application is that CN103447283A discloses a kind of security processing of titanium tetrachloride slag, is mainly used
After water rinses, after the toxicity that the reducing agents such as iron filings reduce heavy metal ion therein is first added in filtrate, then being neutralized with lime will
A large amount of chlorions therein are transformed into calcium chloride.Number of patent application is that CN104874590 discloses another titanium chloride slag resource
Change processing method, after mainly carrying out stiff classification to titanium chloride slag, solid phase obtains petroleum coke and iron oxide product, and liquid phase is then led to
It crosses addition ammonium hydroxide and converts chlorion to ammonium chloride, both methods is all the extension of water developing technique in fact, and being all will be in slag
A large amount of chlorion is converted into the ion in liquid phase, is finally precipitated again with solid calcium chloride and ammonium chloride product.Both techniques
It is directed to the evaporation or crystallization of a chlorination product salt, consumes a large amount of energy, and both products are very cheap, in technique
It is uneconomical.Li Dongmei converts heavy metal chlorate in slag to oxide using high-temperature roasting technique, and chlorion is converted into hydrochloric acid,
And the concentrated sulfuric acid being added generates sulfur dioxide reuse again with the pattern roasting of sulfate.This technique thinking is fine, but there are two
Big disadvantage：First, roasting needs to consume a large amount of energy, and the corrosivity of hydrochloric acid is very strong, and equipment investment is larger；Second is that chlorination
The conversion ratio of salt is not high, and the heavy metal conversion ratio in slag cannot be handled 80% or more, also 20%.CN106044799 is disclosed
A kind of titanium chloride slag and its processing method of filtrate exactly with alkali neutralization titanium chloride slag and wash, heavy metal ion are neutralized
After precipitation, chlorion is recycled in a manner of sodium chloride in chlorine industry salt dissolving water.The technique is by Titanium Dioxide Produced by Chloride Procedure
Technique and chloralkali process are combined, and have not only recycled a large amount of chlorion, but also processing has precipitated heavy metal ion, technics comparing
It is advanced.But there are three problems：First, produce a large amount of slag after acid is molten, in pressure-filtering process due to adhesiveness is too strong, fine and close mistake
It is bad to filter effect, or even occurs pressing the problem of not being discharged；Second is that the pH of first-time filtrate is directly neutralized to 12 or more mistakes using alkali
Filter, under the conditions of such high alkalinity, the amphiprotic substances such as aluminium, silicon can be dissolved in lye, and with the retention of NF membrane, concentration can be got over
Hydrolytic precipitation occurs come higher on film surface, influences being smoothed out for membrane process, and aluminium, silicon concentration are high in nanofiltration charging
As a result aluminium, silicone content in nanofiltration clear liquid will be caused high, the requirement of the salt dissolving light salt brine of chloralkali process is not achieved；Third, by
Enter ultrafiltration system with after filtrate and the mixing of wash water filtrate.This method not only reduces the concentration of salt in filtrate, and substantially
Degree increases the treating capacity of membranous system, increases investment and operating cost.
Invention content
In order to solve problem above, this patent technique is especially ground in CN106044799 on the basis of the above result of study
Study carefully and be improved on the basis of result, passes through the improvement of the use and the two step precipitation method of alkali soaking technology so that the mistake of titanium chloride slag
Filter performance is greatly improved, while also reducing the content for neutralizing the amphoteric metal ion in filtrate, is more advantageous to film mistake
The progress of journey, the while but also brine after film process can reach the ingredient requirement of chlorine industry, in addition will neutralize filtrate and
Washing filtrate separates treatment for reuse, so that two kinds of water quality reuses is had a role to play, and had not interfere with each other, and has not been exhausted directly to make in environment
At pollution, it is often more important that reduce the treating capacity of lower road technique, brine strength in improving into the raw material of chlorine industry, to
It has been truly realized the combination of chlor-alkali and titanium white technique.
A kind of titanium chloride slag resource utilization method, includes the following steps：
1st step, alkali leaching：Titanium chloride slag is impregnated with sodium hydroxide lye, pH is adjusted 5.5~6.5, keeps chlorion immersed
Go out, and precipitation of heavy metals ion, forms slurry；
2nd step is separated by solid-liquid separation：The slurry of 1st step is separated by solid-liquid separation, obtain neutralizing slag and neutralizes filtrate；
3rd step, washing：The neutralization slag obtained to the 2nd step is washed, and removing chloride is further removed, then carries out solid-liquid point
From, obtain washing slag and washing filtrate；
4th step, secondary precipitation：Sodium carbonate and sodium hydroxide is added in neutralization filtrate in step 2, adjusts pH=9~11,
Further precipitation of heavy metals ion, forms secondary slurry；
5th step, ceramic membrane filter：Secondary slurry is used into ceramic membrane filter, filtrate after purification is obtained, as chlor-alkali work
Industry brine.
In 1st step, titanium chloride slag is generation during chloridising production titanium tetrachloride.
In 1st step, alkali soaking technology parameter：Solid-to-liquid ratio is 1：10~20 (weight ratios), preferably 1：15 (weight
Than)；Alkali soaks the time for 5~12h, and preferably 10h, with stirring technique when alkali soaks, pH when alkali soaks terminal is 5.5~6.5, excellent
It is selected as 6.
In 1st step, alkali used is the NaOH generated in chlorine industry, and lye mass percent concentration is
30wt%.
In 2nd step, be separated by solid-liquid separation using in ceramic membrane separation, plate-frame filtering, centrifugation one kind or
Several combinations.
Further, in the 2nd step, separation of solid and liquid is integrated using ceramic membrane and plate and frame filter press or centrifuge, i.e.,
First ceramic membrane is used to be filtered concentration in alkali phase analysis slurry, the underflow that ceramic membrane generates after concentrating then using plate and frame filter press or from
Scheming further removes moisture and recycles in solid and slag, and ceramic membrane clear liquid then enters secondary precipitation technique, and plate and frame filter press
Or the filtrate of centrifuge then returns to ceramic membrane and neutralization filtrate is recovered by filtration again again.
In 3rd step, washing slag recycles in the production of construction material.
In 3rd step, washing filtrate is back to again during alkali leaching.
In 3rd step, washing process parameter is：Solid-to-liquid ratio is 1：10~20 (weight ratios), preferably 1：15 (weight
Than)；Washing time is 5~12h, preferably 10h.
In 4th step, secondary precipitation is to carry out the tune of alkali to neutralizing filtrate together using sodium carbonate and sodium hydroxide
Section, it is 9~11, preferably 10 to adjust pH, and addition sequence is first plus sodium carbonate back end hydrogenation sodium oxide molybdena, the addition of sodium carbonate according to
It neutralizes in filtrate depending on the impurity contents such as barium, calcium, magnesium, precipitation reaction time 30min~1.5h, preferably 1h, in reaction process
There is stirring technique.
In 5th step, obtained filtrate after purification can carry out deep purifying processing again：It is cleaned using NF membrane
It is combined technique with reverse osmosis concentration and deep purifying processing is carried out to filtrate after purification, NF membrane clear liquid is as reverse osmosis charging
Liquid, NF membrane dope then return to the further removing impurity by means of precipitation of secondary precipitation technique；The filtrate of reverse osmosis concentration is used as washing water,
Counter-infiltration dope is then used as the salt dissolving water of chlorine industry.
Ceramic membrane concentrate returns to the 3rd step and carries out solid-liquid separation treatment in 5th step.
A kind of device of titanium chloride slag recycling, including：
Alkali immersion trough 1, for being impregnated with sodium hydroxide lye to titanium chloride slag；
NaOH lye adds tank 2, is connected to alkali immersion trough 1, for adding NaOH lye to immersion trough；
First ceramic membrane 3, is connected to alkali immersion trough 1, for being filtered to the slurry in alkali immersion trough；
Plate filter 4 is connected to the first ceramic membrane concentrate side, and solid-liquid is carried out for the concentrate to the first ceramic membrane
Separation；The permeate side of plate filter is connected to the liquor inlet of the first ceramic membrane；
Rinsing bowl 5 is connected to the retention side of plate filter, for the neutralization slag being obtained by filtration to plate filter into
Row washing；
Equipment for separating liquid from solid 6 is connected to rinsing bowl 5, for being separated by solid-liquid separation to the washing material obtained in rinsing bowl,
Obtain washing slag；The penetrating fluid side of equipment for separating liquid from solid is connected to alkali immersion trough 1；
Secondary precipitation slot 7 is connected to the per-meate side of the first ceramic membrane, for the neutralization to being obtained after the first ceramic membrane filter
Sodium carbonate is added in filtrate and sodium hydroxide carries out precipitation reaction；
NaOH adds tank 9, Na2CO3Tank 10 is added, secondary precipitation slot 7 is connected to, is respectively used to throw into secondary precipitation slot
Add NaOH and Na2CO3；
Second ceramic membrane 8, is connected to secondary precipitation slot 7, for being filtered to the material after precipitation reaction, is filtered
The retention side of liquid, the second ceramic membrane 8 is connected to equipment for separating liquid from solid.
Advantageous effect
In this patent technique for the purpose of handling the heavy metal ion impurities in titanium chloride slag and recycling chlorion, by solid
Waste residue is converted into harmless solid and is back to construction material brick and tile, cement etc., then is by barrier separation integral process thickening-purification technology
Chlorine industry is used with light salt brine, by the implementation of this technique, has not only recycled the valuable resource in titanium chloride slag, heavier
What is wanted has been handled for a full due to the serious titanium chloride slag of environmental pollution, and the intractable bottle of chloridising solid slag is breached
Neck so that chloridising production titanium dioxide technique has strided forward essential step towards more environmentally friendly direction, has apparent advance, with
It is external it is buried, be converted into calcium chloride, ammonium chloride is compared with similar sodium chloride Product Process and with roasting method, have as follows
Superiority：
1, the present invention provides a kind of new methods of the recycling of titanium chloride slag, by the harmful titanium chloride of environmental protection
Slag becomes the processing of harmless building material and chloralkali process light salt brine, and change is given up as " treasured ", has apparent economy and ring
Border benefit, it is natural more than buried method progress.
2, compared with being converted into calcium chloride and ammonium chloride product, which has the advantages that apparent energy-saving, and produces
Product above the value ratio of product sodium chloride is much bigger, is either converted into calcium chloride or ammonium chloride product technique, final to produce
Product occur with solid, be required for evaporation or process for freezing and crystallizing, consume a large amount of energy, and this technique need not then evaporate or
Refrigerating process is directly gone to the pattern of liquid in the raw material of chloralkali process, eliminates a large amount of energy.
3, the roasting method technique of Li Dongmei, it is implicit that, be under the high temperature conditions with sulfuric acid reaction, by heavy metal chloride
It is converted into sulfate, and chlorion is recycled with hydrochloric acid pattern, this technique, roasting will consume a large amount of energy, and reaction will be in height
It is carried out under the conditions of temperature, peracidity, it is big to the corrosivity of equipment, it is high to the material requirements of equipment.And this technique is without in height
It is carried out under the conditions of warm peracidity, it is not high to the material requirements of equipment, and also energy consumption is also little, has effect energy-saving well
Fruit.
4, compared with applying for a patent CN106044799 techniques, this technique has following advantage：First, straight to acid titanium slag
The technique for connecing alkali leaching, not only so that primary sedimentation slag loosely improves strainability so that precipitation slag is easy press filtration, and
Water logging technique is eliminated, water logging and alkali neutralization two-step process are combined into one so that technique becomes simple and practicable；Second is that using
The technique of the two step precipitation method is exactly that pH is first adjusted to 5.5~6.5 with alkali, after ceramic membrane filter, then to filtrate sodium carbonate and
Sodium hydroxide adjusts pH to 9~11, greatly reduces the content of amphoteric oxide in filtrate, is conducive to the progress of membrane process, together
When also ensure in chloralkali process and met the requirements of the standard as the foreign ion in raw material light salt brine；Third, filtrate and water will be neutralized
Washing filtrate separately utilizes, and neutralizes filtrate and directly uses membrane separation process thickening-purification technology, and washes filtrate and then return to alkali soaking technology and return again
With in this way, the filtrate water resource neither after waste washing, can obtain reasonable reuse；It does not reduce again and neutralizes salt in filtrate
Concentration, reduce the treating capacity and processing cost of membrane process.
Description of the drawings
Fig. 1 is the flow chart of titanium chloride slag resource utilization method of the present invention；
Fig. 2 is the installation drawing of titanium chloride slag recycling of the present invention；
Wherein reference numeral in figure：1, alkali immersion trough；2, NaOH lye adds tank；3, the first ceramic membrane；4, plate filter；
5, rinsing bowl；6, equipment for separating liquid from solid；7, secondary precipitation slot；8, the second ceramic membrane；9, NaOH adds tank；10、Na2CO3It adds
Tank.
Specific implementation mode
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention
It is described in further detail.It should be appreciated that described herein, specific examples are only used to explain the present invention, does not limit
In the present invention.
The purpose of the present invention is be soaked respectively chlorion in titanium chloride slag and heavy metal ion using alkali leaching and washing process
Go out and precipitate, recycles membrane separation technique to carry out the high concentration brine in thickening-purification technology recycling leachate, wash heat will be precipitated
It is the raw material in construction material to wash reuse, to reach thorough complete-reclaiming titanium chloride slag waste, solves Titanium Dioxide Produced by Chloride Procedure
The fixed-end forces problem of production.
Titanium Dioxide Produced by Chloride Procedure production technology has an advantage small, that production is continuous, product quality is high that pollutes, but its consolidating of generating
The processing of body titanium chloride slag is but always a global problem, and main cause is exactly heavy metal noxious material therein and contains
Acid chlorion exists, and puts and is easily absorbing moisture in air and changes into acid waste water.This acid waste water does not contain only weight
Metal ion, and the presence of a large amount of chlorion makes its generate very strong corrosivity, untreated or simple process just stack or
It is buried, long-range harm is will produce to environment.This patent technique is harmful to environment therein these from the angle of the utilization of resources
Substance carry out integrated treatment and recycling so that it is had a role to play after processing, becomes evil as useful resources.Greatly protect ring
Border.
A kind of titanium chloride slag resource utilization method, includes the following steps：
Step 1：Alkali soaks：Titanium chloride slag sodium hydroxide lye is leached into wherein chlorion, and precipitates heavy metal therein
Ion, while pH is adjusted 5.5~6.5, form slurry；
Step 2：It is separated by solid-liquid separation, the slurry using ceramic membrane and plate and frame filter press or the pairs of step 1 of centrifuge collection is consolidated
Liquid detaches, and obtains neutralizing slag and neutralizes filtrate；
Step 3：Washing：The neutralization slag isolated in step 2 is washed again, slurry is again with sheet frame pressure after washing
Filter or centrifuge are separated by solid-liquid separation, and washing slag and washing filtrate are obtained；The washing slag separated in step 3 can be used as making
Make the raw material reuse of construction material brick and tile, and separating filtrate can be back to again during alkali leaching；
Step 4：Secondary precipitation：PH is adjusted jointly with sodium carbonate and sodium hydroxide to the filtrate for being separated by solid-liquid separation out in step 3
=9~10, further precipitation removal heavy metal ion therein, forms secondary slurry；
Step 5：Ceramic membrane filter：Ceramic membrane filter, dope is used to be washed with step 3 the secondary slurry in step 4
Slurry is separated by solid-liquid separation with plate and frame filter press or centrifuge together；Clear liquid then uses membrane separation technique to carry out depths reason, is made
Chloralkali process salt dissolving light salt brine.
The present invention is using recycling Titanium Dioxide Produced by Chloride Procedure titanium chloride slag as guiding theory, by by the chlorine in titanium chloride slag
The technique that ion is soaked and washed with alkali removes, and is able to recycle titanium chloride slag on solid, is then washed out to recycling on filtrate
Brine rich in chlorion takes membrane separation process to be converted to chloralkali process salt dissolving light salt brine, has recycled titanium chloride slag
In a large amount of chlorions realize process solids waste residue to thoroughly having carried out innoxious processing to chloridising titanium chloride slag
The zero-emission of processing.Not only there is significantly Environmental Role to Titanium Dioxide Produced by Chloride Procedure production, but also the resource in waste residue is obtained
To make full use of, there is significantly society and environmental benefit.
In the above-mentioned technique, the pending titanium chloride slag in step 1 be chloridising production titanium tetrachloride during
It generates, not only contained heavy metal ion but also contains a large amount of chlorion.
Alkali soaking technology in step 1 is：Solid-to-liquid ratio is 1：10~20 (weight ratios), preferably 1：15 (weight ratios)；Alkali soaks
Time is 5~12h, preferably 10h, and with stirring technique when alkali soaks, alkali soaks pH=5.5~6.5 when terminal, preferably 6.Institute
It is the alkali generated in chlorine industry, mass percent concentration 30% with alkali.
In 2nd step, be separated by solid-liquid separation using in ceramic membrane separation, plate-frame filtering, centrifugation one kind or
Several combinations.
Further, the separation of solid and liquid in step 2 is integrated using ceramic membrane and plate and frame filter press or centrifuge, i.e., is soaked to alkali
Slurry is first filtered concentration using ceramic membrane, the underflow generated after ceramic membrane concentration then use plate and frame filter press or centrifuge into
One-step removal moisture and recycle in solid and slag, ceramic membrane clear liquid then enters secondary precipitation technique, and plate and frame filter press or centrifugation
The filtrate of machine then returns to ceramic membrane and neutralization filtrate is recovered by filtration again again.
Washing process parameter in step 3 is：Solid-to-liquid ratio is 1：10~20 (weight ratios), preferably 1：15 (weight ratios)；
Washing time is 5~12h, and preferably 10h, when washing also will be with stirring technique.
The secondary precipitation of step 5 is to carry out two alkali to the neutralization filtrate in step 3 together using sodium carbonate and sodium hydroxide
Adjusting, adjust pH=9~11, preferably 10, order of addition of ingredients is first plus sodium carbonate back end hydrogenation sodium oxide molybdena, the addition of sodium carbonate
According to neutralizing in filtrate depending on the impurity contents such as barium, calcium, magnesium, precipitation reaction time 30min~1.5h, preferably 1h reacted
There is stirring technique in journey.
In 5th step, obtained filtrate after purification can carry out deep purifying processing again：It is cleaned using NF membrane
It is combined technique with reverse osmosis concentration and deep purifying processing is carried out to filtrate after purification, NF membrane clear liquid is as reverse osmosis charging
Liquid, NF membrane dope then return to the further removing impurity by means of precipitation of above-mentioned 4th step secondary precipitation technique；The filtrate conduct of reverse osmosis concentration
Washing water is used, and counter-infiltration dope is then used as the salt dissolving water of chlorine industry.
According to above technique, the device that the present invention uses is as shown in Figure 2：
A kind of titanium chloride slag resource utilization device, including：
Alkali immersion trough 1, for being impregnated with sodium hydroxide lye to titanium chloride slag；
NaOH lye adds tank 2, is connected to alkali immersion trough 1, for adding NaOH lye to immersion trough 1；
First ceramic membrane 3, is connected to alkali immersion trough 1, for being filtered to the slurry in alkali immersion trough 1；
Plate filter 4 is connected to 3 concentrate side of the first ceramic membrane, consolidates for the concentrate to the first ceramic membrane 3
Liquid detaches；The permeate side of plate filter 4 is connected to the liquor inlet of the first ceramic membrane 3；
Rinsing bowl 5 is connected to the retention side of plate filter 4, for the neutralization slag being obtained by filtration to plate filter 4
It is washed；
Equipment for separating liquid from solid 6 is connected to rinsing bowl 5, for carrying out solid-liquid point to the washing material obtained in rinsing bowl 5
From obtaining washing slag；The penetrating fluid side of equipment for separating liquid from solid 6 is connected to alkali immersion trough 1；
Secondary precipitation slot 7 is connected to the per-meate side of the first ceramic membrane 3, used in being obtained after being filtered to the first ceramic membrane 3
Sodium carbonate is added with filtrate and sodium hydroxide carries out precipitation reaction；
NaOH adds tank 9, Na2CO3Tank 10 is added, secondary precipitation slot 7 is connected to, is respectively used to throw into secondary precipitation slot 7
Add NaOH and Na2CO3；
Second ceramic membrane 8, is connected to secondary precipitation slot 7, for being filtered to the material after precipitation reaction, is filtered
The retention side of liquid, the second ceramic membrane 8 is connected to equipment for separating liquid from solid 6.
Embodiment 1
It is operated according to process flow chart as shown in Figure 1.
60kg titanium chloride slags are leached with sodium hydroxide lye, while adjusting pH=6, control solid-to-liquid ratio is 1：15 (weight
Than), it is stirred to react 10h, is formed and neutralizes slurry；Ceramic membrane filter supernatant is first used to neutralizing slurry, is waited in ceramic membrane dope
Solid content when reaching 3%, by dope discharge and and neutralize slurry bottom liquid and be separated by solid-liquid separation with plate and frame filter press or centrifuge,
It obtains in solid and slag, ceramic membrane clear liquid is to neutralize filtrate to enter secondary precipitation technique, sheet frame filtrate then returns to ceramic membrane again
It is secondary to be filtered.The content for neutralizing sodium chloride in filtrate at this time is 5361mg/L, volume 850l, impurity A l, Si content difference
For 0.146mg/L, 0.404mg/L；
To being washed again with slag in solid, control washing solid-to-liquid ratio is 1：15 (weight ratios), and agitator treating 10h,
Washing slurry is formed, slurry is separated by solid-liquid separation with plate and frame filter press or centrifuge again after washing, obtains washing slag and washing
Filtrate；And separating filtrate can be back to again during alkali leaching；
Secondary precipitation：PH is adjusted jointly with sodium carbonate and sodium hydroxide to neutralizing the clear liquid that slurry ceramic membrane is separated by solid-liquid separation out
=10, form secondary slurry after being stirred to react 1h.With the secondary slurry of ceramic membrane filter, it is 3% to control the solid content in dope, row
It can be used as making construction material brick and tile after being separated by solid-liquid separation with plate and frame filter press or centrifuge together with empty dope and washing slurry
The raw material reuse of cement；Plate and frame filter press or centrifuge clear liquid then return to alkali soaking technology and do process water, and ceramic membrane clear liquid is then adopted
Depths reason is carried out with membrane separation technique.The content for neutralizing sodium chloride in filtrate at this time is 5361mg/L, impurity A l, Si content difference
For 0.294mg/L, 0.495mg/L, volume 750L；
Ceramic membrane clear liquid is introduced into after secondary precipitation carries out purification and impurity removal with NF membrane, and the sodium chloride content after removal of impurities is
4825mg/L is concentrated subsequently into reverse osmosis membrane, and dope cleans through NF membrane again after concentration, and last sodium chloride concentration is 79g/L,
Al, Si content are respectively 0.1mg/L and 0.138mg/L.It can reach the charging standard that salt dissolving water is less than 0.1mg/L.(chloralkali process
The feed impurities requirement of salt dissolving light salt brine is Al<0.1mg/L, Si<2.3mg/L.)
Reference examples 1
Reference examples 1 (CN106044799 patents)
60kg titanium chloride slag water loggings are gone out, while adjusting pH=1, control solid-to-liquid ratio is 1:15 (weight ratios), stirring are anti-
10h is answered, acidleach slurry is formed；Acidleach slurry is separated by solid-liquid separation using plate and frame filter press or centrifuge, obtains solid acidleach
Slag and first-time filtrate, first-time filtrate sodium hydroxide tune pH=7 continue with sodium hydroxide tune pH after complete reaction>12, it stirs
Reaction 1h is mixed, after being separated by solid-liquid separation with plate and frame filter press or centrifuge, secondary filtrate and secondary slag is formed, water is used again for secondary slag
It is 1 in proportion:10h is followed by stirring and washing in 15 (weight ratios), is formed after being separated by solid-liquid separation with plate and frame filter press or centrifuge and is filtered three times
Liquid and slag, by secondary filtrate and three times filtrate mix after, volume 1.8m3, mix filtrate and be filtered with ceramic membrane.It filters
It is to neutralize filtrate 1.75m3 to ceramic membrane clear liquid, the content of ingredient sodium chloride is 5666mg/L, and impurity A l, Si content is respectively
30.62mg/L 31.85mg/L；
To the above ceramic membrane clear liquid using after NF membrane desalination, it is found that when filtrate is concentrated to 10 times, have in dope muddy existing
As generating, dope ingredient is analyzed, Al, Si content therein has reached 189mg/l, 29.18mg/L, and sodium chloride content is
17845mg/L, and Al, Si content have reached 0.49mg/l in clear liquid, 5.809mg/L, sodium chloride content 3133.5mg/L.
Obviously be only on the one hand difficult that salinity is concentrated to 70~80g/L levels with NF membrane, on the other hand Al therein,
Si contents severely exceed, can not be as the light salt brine of chloralkali process.Turbidity and precipitation phenomenon is especially produced in nanofiltration process, is allowed and is received
Filtration Cheng Wufa is normally carried out.
Claims (10)
1. a kind of titanium chloride slag resource utilization method, which is characterized in that include the following steps：
1st step, alkali leaching：Titanium chloride slag is impregnated with sodium hydroxide lye, pH is adjusted 5.5~6.5, and chlorion is made to be leached,
And precipitation of heavy metals ion, form slurry；
2nd step is separated by solid-liquid separation：The slurry of 1st step is separated by solid-liquid separation, obtain neutralizing slag and neutralizes filtrate；
3rd step, washing：The neutralization slag obtained to the 2nd step is washed, and is further removed removing chloride, then be separated by solid-liquid separation, is obtained
To washing slag and washing filtrate；
4th step, secondary precipitation：Sodium carbonate and sodium hydroxide is added in neutralization filtrate in step 2, pH=9~11 is adjusted, into one
Precipitation of heavy metals ion is walked, secondary slurry is formed；
5th step, ceramic membrane filter：Secondary slurry is used into ceramic membrane filter, obtains filtrate after purification, is used as chlorine industry
Brine.
2. titanium chloride slag resource utilization method according to claim 1, it is characterised in that：In 1st step, chlorination
Titanium slag is generation during chloridising production titanium tetrachloride.
3. titanium chloride slag resource utilization method according to claim 1, it is characterised in that：Alkali soaks in 1st step
Technological parameter：Solid-to-liquid ratio is 1：10~20, preferably 1：15；It is 5~12h, preferably 10h that alkali, which soaks the time, with stirring when alkali soaks
Mix technique, alkali soaks pH=5.5~6.5 when terminal, and preferably 6.
4. titanium chloride slag resource utilization method according to claim 1, it is characterised in that：Hydrogen-oxygen in 1st step
It is the NaOH generated in chlorine industry to change soda lye, and lye mass percent concentration is 30wt%.
5. the method for titanium chloride slag recycling according to claim 1, which is characterized in that in the 2nd step, Gu
Liquid detaches the combination using one or more of ceramic membrane separation, plate-frame filtering, centrifugation.
6. titanium chloride slag resource utilization method according to claim 5, which is characterized in that in the 2nd step, solid-liquid
Separation is integrated using ceramic membrane and plate and frame filter press or centrifuge, i.e., is first filtered using ceramic membrane to alkali phase analysis slurry dense
Contracting, the underflow generated after ceramic membrane concentration then further remove moisture using plate and frame filter press or centrifuge and recycle solid and neutralize
Slag, ceramic membrane clear liquid then enters secondary precipitation technique, and the filtrate of plate and frame filter press or centrifuge then returns to ceramic membrane again
It is recovered by filtration again and neutralizes filtrate.
7. titanium chloride slag resource utilization method according to claim 1, which is characterized in that in the 3rd step, washing
Slag recycles in the production of construction material；Washing filtrate is back to again during alkali leaching；Washing process parameter is：Solid-to-liquid ratio
It is 1：10~20, preferably 1：15；Washing time is 5~12h, preferably 10h.
8. titanium chloride slag resource utilization method according to claim 1, which is characterized in that secondary in the 4th step
Precipitation is to carry out the adjusting of alkali to neutralizing filtrate together using sodium carbonate and sodium hydroxide, tune pH=9~11, preferably 10, add
It is first to add sodium carbonate to enter sequence, back end hydrogenation sodium oxide molybdena, and the addition of sodium carbonate is according to barium, calcium, magnesium addition content in neutralization filtrate
Depending on, precipitation reaction time 30min~1.5h, preferably 1h have stirring technique in reaction process.
9. titanium chloride slag resource utilization method according to claim 1, which is characterized in that in the 5th step, obtain
Filtrate after purification can carry out deep purifying processing again：Technique is combined to pure using NF membrane removal of impurities and reverse osmosis concentration
Filtrate after change carries out deep purifying processing, and NF membrane clear liquid then returns to secondary as reverse osmosis feeding liquid, NF membrane dope
The further removing impurity by means of precipitation of depositing technology；The filtrate of reverse osmosis concentration is used as washing water, and counter-infiltration dope is then used as chlorine industry
Salt dissolving water use.
10. a kind of titanium chloride slag resource utilization device, which is characterized in that including：
Alkali immersion trough (1), for being impregnated with sodium hydroxide lye to titanium chloride slag；
NaOH lye adds tank (2), is connected to alkali immersion trough (1), for adding NaOH lye to immersion trough (1)；
First ceramic membrane (3) is connected to alkali immersion trough (1), for being filtered to the slurry in alkali immersion trough (1)；
Plate filter (4) is connected to the first ceramic membrane (3) concentrate side, is carried out for the concentrate to the first ceramic membrane (3)
It is separated by solid-liquid separation；The permeate side of plate filter (4) is connected to the liquor inlet of the first ceramic membrane (3)；
Rinsing bowl (5) is connected to the retention side of plate filter (4), for the neutralization being obtained by filtration to plate filter (4)
Slag is washed；
Equipment for separating liquid from solid (6) is connected to rinsing bowl (5), for carrying out solid-liquid point to the washing material obtained in rinsing bowl (5)
From obtaining washing slag；The penetrating fluid side of equipment for separating liquid from solid (6) is connected to alkali immersion trough (1)；
Secondary precipitation slot (7), is connected to the per-meate side of the first ceramic membrane (3), for what is obtained after being filtered to the first ceramic membrane (3)
It neutralizes filtrate and sodium carbonate and sodium hydroxide progress precipitation reaction is added；
NaOH adds tank (9), Na2CO3Tank (10) is added, secondary precipitation slot (7) is connected to, is respectively used to secondary precipitation slot (7)
In add NaOH and Na2CO3；
Second ceramic membrane (8) is connected to secondary precipitation slot (7), for being filtered to the material after precipitation reaction, is filtered
The retention side of liquid, the second ceramic membrane (8) is connected to equipment for separating liquid from solid (6).
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