CN117403055A - Method for recycling rare metals in waste residues - Google Patents
Method for recycling rare metals in waste residues Download PDFInfo
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- CN117403055A CN117403055A CN202311341888.0A CN202311341888A CN117403055A CN 117403055 A CN117403055 A CN 117403055A CN 202311341888 A CN202311341888 A CN 202311341888A CN 117403055 A CN117403055 A CN 117403055A
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- 238000000034 method Methods 0.000 title claims abstract description 73
- 239000002699 waste material Substances 0.000 title claims abstract description 69
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 27
- 239000002184 metal Substances 0.000 title claims abstract description 27
- 150000002739 metals Chemical class 0.000 title claims abstract description 25
- 238000004064 recycling Methods 0.000 title claims description 22
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 74
- 239000010937 tungsten Substances 0.000 claims abstract description 73
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000010936 titanium Substances 0.000 claims abstract description 56
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 55
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 230000008569 process Effects 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 238000000227 grinding Methods 0.000 claims description 131
- 238000011282 treatment Methods 0.000 claims description 108
- 238000002386 leaching Methods 0.000 claims description 98
- 239000003513 alkali Substances 0.000 claims description 90
- 239000007788 liquid Substances 0.000 claims description 87
- 238000005342 ion exchange Methods 0.000 claims description 55
- 150000002500 ions Chemical class 0.000 claims description 53
- 238000003825 pressing Methods 0.000 claims description 51
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 50
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 44
- 238000001035 drying Methods 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 239000000706 filtrate Substances 0.000 claims description 32
- 238000006073 displacement reaction Methods 0.000 claims description 31
- 238000010438 heat treatment Methods 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 28
- 230000007246 mechanism Effects 0.000 claims description 28
- -1 tungstic acid ion Chemical class 0.000 claims description 28
- 238000001914 filtration Methods 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 20
- 238000000926 separation method Methods 0.000 claims description 20
- 238000005507 spraying Methods 0.000 claims description 20
- 230000005291 magnetic effect Effects 0.000 claims description 19
- 230000005294 ferromagnetic effect Effects 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 18
- 238000002425 crystallisation Methods 0.000 claims description 16
- 230000008025 crystallization Effects 0.000 claims description 16
- 239000012452 mother liquor Substances 0.000 claims description 16
- 230000001276 controlling effect Effects 0.000 claims description 14
- 239000006148 magnetic separator Substances 0.000 claims description 13
- 230000001105 regulatory effect Effects 0.000 claims description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 12
- 238000012216 screening Methods 0.000 claims description 12
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 11
- 239000001110 calcium chloride Substances 0.000 claims description 11
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 11
- 229910001415 sodium ion Inorganic materials 0.000 claims description 11
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 10
- 238000011010 flushing procedure Methods 0.000 claims description 9
- 239000003456 ion exchange resin Substances 0.000 claims description 8
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 8
- 238000010979 pH adjustment Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 8
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 238000007885 magnetic separation Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims description 6
- 238000000354 decomposition reaction Methods 0.000 claims description 6
- CBXWGGFGZDVPNV-UHFFFAOYSA-N so4-so4 Chemical compound OS(O)(=O)=O.OS(O)(=O)=O CBXWGGFGZDVPNV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 24
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000005457 optimization Methods 0.000 abstract description 4
- 238000004458 analytical method Methods 0.000 abstract description 3
- 230000035484 reaction time Effects 0.000 abstract description 3
- 238000003672 processing method Methods 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 17
- 239000003054 catalyst Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- 239000002893 slag Substances 0.000 description 13
- 238000003795 desorption Methods 0.000 description 9
- 239000002253 acid Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000011684 sodium molybdate Substances 0.000 description 2
- 235000015393 sodium molybdate Nutrition 0.000 description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 2
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000006061 abrasive grain Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- WKXHZKXPFJNBIY-UHFFFAOYSA-N titanium tungsten vanadium Chemical compound [Ti][W][V] WKXHZKXPFJNBIY-UHFFFAOYSA-N 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/005—Preliminary treatment of scrap
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1236—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching
- C22B34/1254—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching using basic solutions or liquors
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/36—Obtaining tungsten
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/008—Wet processes by an alkaline or ammoniacal leaching
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to the technical field of rare metal recovery, and particularly discloses a method for recovering and treating rare metals in waste residues; according to the invention, corresponding data acquisition is carried out on a plurality of processing nodes in the processing method for recovering rare metals such as titanium and tungsten from tungsten-titanium waste residues, so that analysis decision can be carried out on acquired data, and relevant decision is carried out on the acquired data in a dynamic optimization mode so as to optimize the reaction time, the reaction parameter consumption, the environmental parameter and the like of each processing node, thereby forming closed-loop control or multi-loop control, further realizing more refined control and management on the recovery processing process, and finally greatly improving the processing efficiency and the recovery rate of rare metals such as titanium and tungsten.
Description
Technical Field
The invention belongs to the technical field of rare metal recovery, and particularly relates to a method for recovering and treating rare metals in waste residues.
Background
The waste slag containing tungsten and titanium is mainly waste SCR denitration catalyst, smelting waste slag, chimney waste slag and the like, the SCR denitration technology is a necessary means for achieving ultra-clean emission of a power plant, and the catalyst is used as a core part of the SCR denitration technology and can lose activity due to abrasion or blockage and the like in the operation process. Some regenerated catalysts can be used continuously after regeneration, while non-regenerated catalysts are in the place of reasonable utilization and disposal (even if the regenerated catalysts are regenerated for 2-3 times, the regenerated catalysts cannot be regenerated and need to be reasonably utilized and disposed). At present, the mode of treating the waste denitration catalyst abroad is landfill, but the number of the waste denitration catalyst produced each year is quite considerable because of more thermal power plants in China. According to incomplete statistics, the yield of the waste denitration catalyst in China is 5 ten thousand tons each year, and more titanium-containing compounds and tungsten-containing compounds can be recovered from the waste denitration catalyst, so that rare metals such as titanium (Ti) and tungsten (W) can be finally recovered, and therefore, the recycling of the waste denitration catalyst is necessary from the economic point of view and the environmental protection point of view.
Patent publication No. CN103484678A discloses a method for recovering vanadium, tungsten and titanium from waste vanadium-tungsten-titanium-based denitration catalyst, which comprises mixing crushed waste catalyst with concentrated alkali liquor, heating to react to generate slightly soluble titanate and water soluble vanadate and tungstate, separating solid from liquid, and extracting the water soluble vanadate and tungstate by adding ammonium metavanadate and concentrated acid to generate ammonium metavanadate and tungstic acid respectively. Wherein the recovery rate of vanadium is more than 90%, the recovery rate of tungsten is more than 80%, and the recovery rate of titanium is more than 80%. The method has complex operation, the pH value of the solution needs to be strictly controlled in the chemical reaction process, the yield is lower, the reaction temperature is higher and is required to reach 120-350 ℃, and the energy consumption is higher.
Patent document CN105152216a discloses a method and apparatus for recovering Ti and W from waste flue gas denitration catalyst, which comprises pulverizing catalyst, adding concentrated sulfuric acid for acidolysis, adding water for acidolysis to obtain titanyl sulfate solution, heating, concentrating and hydrolyzing the obtained solution, separating to obtain metatitanic acid precipitate and filtrate, performing salt treatment on the metatitanic acid precipitate, drying, and calcining to obtain TiO 2 Adding excessive ammonia water into acidolysis filter residue, reacting, filtering, heating filtrate to obtain ammonium paratungstate crystal, drying and calcining to obtain the final product Obtaining pure WO 3 . Wherein TiO is 2 And WO 3 The recovery rates were 95% and 93%, respectively. The acid solution is 85% -92% concentrated sulfuric acid, the reaction process is also heated to 150-180 ℃, the operation is dangerous, and the energy consumption is high; in addition to obtaining TiO 2 And WO 3 The product also needs complex treatment, drying, calcining and other steps, thus not only having high equipment requirements, but also having large investment and high cost.
In the prior art, the treatment method for recovering titanium and tungsten from tungsten-titanium-containing waste residues has the defects of low treatment efficiency, large material input amount, high energy consumption, large exhaust gas and waste water discharge amount and the like in the intermediate reaction process because all links of the treatment process are rough control and lack of fine control management. Therefore, it is necessary to provide a new solution to improve the efficiency of the treatment for recovering titanium and tungsten.
Disclosure of Invention
The invention aims to provide a method for recycling rare metals in waste residues, and aims to solve the technical problem of low recycling efficiency caused by lack of fine control management in recycling rare metals such as titanium, tungsten and the like in the prior art.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a method for recycling rare metals in waste residues is used for recycling tungsten-containing compounds and titanium-containing compounds from tungsten-titanium waste residues, and comprises the following steps:
S100, grinding and screening the tungsten-titanium waste residues through a grinding magnetic separator so as to separate ferromagnetic substances in the tungsten-titanium waste residues;
s200, performing alkali liquor leaching treatment on the tungsten titanium waste residues subjected to grinding and screening treatment by an alkali liquor leaching machine so as to realize tungsten titanium decomposition;
s300, performing filter pressing type solid-liquid separation treatment on the solid-liquid mixture obtained through alkali liquor leaching treatment by utilizing a solid-liquid filtration leaching machine so as to realize tungsten-titanium separation; the titanium-containing filter residue and the tungsten-containing filter liquid are obtained after the filter pressing type solid-liquid separation treatment;
s400, drying and grinding the titanium-containing filter pressing residues by using a drying and grinding tail gas processor, and finally preparing a titanium-containing compound, wherein the titanium-containing compound comprises titanium dioxide;
s500, adjusting the concentration and the pH value of the tungsten-containing filter pressing liquid by using a concentration and pH value adjusting treatment device, and performing ion exchange treatment on the tungsten-containing filter pressing liquid with the concentration and the pH value adjusted by an ion exchange machine after the concentration and the pH value are adjusted to a preset standard concentration and a standard pH value;
s600, crystallizing peak liquid after ion exchange treatment, performing solid-liquid separation treatment to obtain a crystal and a crystallization mother liquor, leaching and drying the crystal to finally obtain a tungsten-containing compound, wherein the tungsten-containing compound comprises sodium tungstate and ammonium paratungstate;
Inputting the crystallization mother liquor into a displacement reaction device, adding calcium chloride into the displacement reaction device according to the requirement to carry out displacement reaction, and then carrying out filter pressing separation treatment to obtain calcium tungstate;
in the step S100, after the tungsten-titanium waste residue is ground to a preset target size and reaches a preset ferromagnetic substance removal rate, the process proceeds to a step S200;
in the step S200, adding NaOH and water into an alkali liquor leaching machine to carry out alkali liquor leaching treatment on tungsten-titanium waste residues subjected to grinding and screening treatment; the alkali liquor leaching machine is controlled by a main controller, the alkali liquor leaching machine is provided with a PH value sensor and a temperature sensor which are electrically connected with the main controller,
the pH value sensor is used for detecting the pH value of the alkali liquor in the alkali liquor leaching tank of the alkali liquor leaching machine, and when the detected pH value is lower than a preset pH value, the NaOH feeding mechanism in the alkali liquor leaching machine is controlled to feed NaOH into the alkali liquor leaching tank so that the alkali liquor reaches the preset pH value range; when the detected pH value is higher than a preset pH value, controlling a water adding mechanism in the alkali liquor leaching machine to add water into an alkali liquor leaching tank so that the alkali liquor reaches the preset pH value range;
the temperature sensor is used for detecting the temperature of the alkali liquor in the alkali liquor leaching tank of the alkali liquor leaching machine, when the detected temperature of the alkali liquor leaching tank is lower than a preset temperature value, the heating power of the heating mechanism in the alkali liquor leaching machine is controlled to enable the heating mechanism to be in a full heating power state, when the detected temperature of the alkali liquor leaching tank is higher than the preset temperature value, the heating mechanism is enabled to stop heating, and when the detected temperature of the alkali liquor leaching tank is within the preset temperature value range, the heating mechanism is enabled to be in a constant-temperature heating state.
In one of the preferred embodiments, in the step S100, it is checked and judged whether the tungsten titanium slag is ground to a preset target size and ferromagnetic substance removal rate by:
the grinding magnetic separator is provided with a speed sensor for detecting the grinding speed of the grinding magnetic separator, a force sensor for detecting the grinding force of the grinding magnetic separator and a magnetic force for detecting tungsten-titanium waste residues after grinding treatment;
detecting and judging whether the grinding force of the grinding motor is stable at a preset grinding force value by using the force sensor, and judging that the tungsten-titanium waste residues are ground to a target size;
and dynamically detecting magnetic force parameters of the tungsten-titanium waste residues which are ground into particles by using the magnetic force sensor, ensuring that the magnetic force parameters reach a target magnetic separation rate, and finally confirming the ferromagnetic substance removal rate by the ferromagnetic substance adsorption time.
In one preferred embodiment, in the step S300, the titanium-containing filter residues obtained after the solid-liquid separation treatment are cleaned by pure water, the solid-liquid filtration leaching machine is controlled by a main controller, the solid-liquid filtration leaching machine is provided with a first ion sensor electrically connected with the main controller, the first ion sensor is used for detecting the ion residual quantity on the surface of the titanium-containing filter residues in real time, and the main controller controls the spraying times of a flushing water leaching valve in the solid-liquid filtration leaching machine according to the detected ion residual quantity; and when the residual ion quantity detected by the first ion sensor reaches a preset value, controlling a flushing shower valve in the solid-liquid filtration leaching machine to stop spraying, and entering step S400.
Preferably, the first ion sensor is a tungstic acid ion sensor or a sodium ion sensor.
In one preferred embodiment, in the step S400, the drying and grinding tail gas processor is controlled by a main controller, and the drying and grinding tail gas processor is provided with a temperature sensor, a grinding speed sensor and a grinding force sensor which are electrically connected with the main controller;
the temperature sensor, the grinding speed sensor and the grinding force sensor are respectively used for detecting the temperature, the grinding speed and the grinding force of the drying and grinding tail gas processor in the process of drying and grinding the titanium-containing filter pressing residues, and feeding the detected temperature, grinding speed and grinding force data back to the main controller, and the main controller controls the working state of the drying and grinding tail gas processor according to the detected data.
In one preferred embodiment, in the step S500, the concentration and ph adjustment processing device is controlled by a main controller, and the concentration and ph adjustment processing device is provided with an ion tungstic acid concentration sensor, a temperature sensor and a ph sensor electrically connected with the main controller;
When the concentration of the tungsten-containing filter pressing liquid is detected to be regulated to a preset target concentration by a tungstic acid ion concentration sensor, sulfuric acid is added to regulate the pH value, in the process of regulating the pH value, the pH value of the tungsten-containing filter pressing liquid is regulated by controlling the mass concentration of the sulfuric acid, a mixed solution consisting of the tungsten-containing filter pressing liquid and the sulfuric acid is heated to a preset target temperature, the temperature and the pH value of the mixed solution are detected by a temperature sensor and a pH value sensor respectively, and the detected temperature and pH value data are fed back to a main controller;
and after the pH value sensor detects that the mixed solution is regulated to a preset target pH value, introducing the mixed solution into an ion exchanger for ion exchange treatment.
In one preferred embodiment, the following formula is used before the mixed solution is passed to the ion exchange unit for ion exchange treatment:
adjusting the concentration Q of the filtrate of the mixed solution Filtrate from the filtration Mass concentration Q of sulfuric acid Sulfuric acid And reaction temperature P of ion exchange Exchange of To increase the generation rate W of ion exchange treatment Exchange of Wherein Q is Standard filtrate Is the standard concentration of filtrate, Q Standard sulfuric acid Is of standard concentration of sulfuric acid, P Standard exchange For reaction standard temperature, CH is the exchange capacity of ion exchange resin in ion exchanger, CH Standard exchange Standard exchange capacity, Q, of ion exchange resins in ion exchangers Standard filtrate 、Q Standard sulfuric acid 、P Standard exchange 、CH Standard exchange All are preset values; δ1 is the standard deviation of the concentration of the filtrate, δ2 is the standard deviation of the pH value balance, δ3 is the standard deviation of the ion exchange stage, δ4 is the standard deviation of the resin exchange capacity, and δ1, δ2, δ3 and δ4 are constants.
In one preferred embodiment, in the step S600, the displacement reaction device is controlled by a master controller, and the displacement reaction device is provided with a tungstic acid ion concentration sensor electrically connected with the master controller and a liquid flow rate, wherein the liquid flow rate sensor is used for detecting the inflow amount of crystallization mother liquor entering the displacement reaction device, and the tungstic acid ion concentration sensor is used for detecting the concentration of tungstic acid ions in a reaction treatment tank in the displacement reaction device;
let the inflow of the crystallization mother liquor detected by the liquid flow sensor be P1m 3 And/h, detecting the concentration of the obtained tungstic acid ions by a tungstic acid ion concentration sensor to be Q1 m 3 And (3) adding calcium chloride to the displacement reaction device to perform displacement reaction, wherein the required quantity of the calcium chloride to be added to the displacement reaction device is W1=P1×Q1 (1+A%), and A is 1-3.
In one embodiment, the method further comprises:
s700, returning the lean peak liquid after ion exchange treatment to a concentration and pH value adjusting treatment device to enable the lean peak liquid to participate in the adjustment of the concentration and pH value of the tungsten-containing press filtrate;
and conveying the three-stage liquid after the ion exchange treatment to a desorber tank for desorber circulation treatment, and returning the desorbed liquid to the ion exchanger to participate in the ion exchange treatment.
In one preferred embodiment, the desorbent tank is provided with an ammonium ion concentration sensor, a chloride ion concentration sensor, a sodium ion concentration sensor and a hydroxide ion concentration sensor for detecting the ammonium ion concentration, the chloride ion concentration, the sodium ion concentration and the hydroxide ion concentration, respectively.
According to the invention, corresponding data acquisition is carried out on a plurality of processing nodes in the processing method for recovering rare metals such as titanium and tungsten from tungsten-titanium waste residues, so that analysis decision can be carried out on acquired data, and relevant decision is carried out on the acquired data in a dynamic optimization mode so as to optimize the reaction time, the reaction parameter consumption, the environmental parameter and the like of each processing node, thereby forming closed-loop control or multi-loop control, further realizing more refined control and management on the recovery processing process, and finally greatly improving the processing efficiency and the recovery rate of rare metals such as titanium and tungsten.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The technical scheme provided by the embodiment of the invention is as follows:
a method for recycling rare metals in waste residues is used for recycling tungsten-containing compounds and titanium-containing compounds from tungsten-titanium waste residues, and comprises the following steps:
s100, grinding and screening the tungsten-titanium waste residues through a grinding magnetic separator so as to separate ferromagnetic substances in the tungsten-titanium waste residues;
s200, performing alkali liquor leaching treatment on the tungsten titanium waste residues subjected to grinding and screening treatment by an alkali liquor leaching machine so as to realize tungsten titanium decomposition;
s300, performing filter pressing type solid-liquid separation treatment on the solid-liquid mixture obtained through alkali liquor leaching treatment by utilizing a solid-liquid filtration leaching machine so as to realize tungsten-titanium separation; the titanium-containing filter residue and the tungsten-containing filter liquid are obtained after the filter pressing type solid-liquid separation treatment;
S400, drying and grinding the titanium-containing filter pressing residues by using a drying and grinding tail gas processor, and finally preparing a titanium-containing compound, wherein the titanium-containing compound comprises titanium dioxide;
s500, adjusting the concentration and the pH value of the tungsten-containing filter pressing liquid by using a concentration and pH value adjusting treatment device, and performing ion exchange treatment on the tungsten-containing filter pressing liquid with the concentration and the pH value adjusted by an ion exchange machine after the concentration and the pH value are adjusted to a preset standard concentration and a standard pH value;
s600, crystallizing peak liquid after ion exchange treatment, performing solid-liquid separation treatment to obtain a crystal and a crystallization mother liquor, leaching and drying the crystal to finally obtain a tungsten-containing compound, wherein the tungsten-containing compound comprises sodium tungstate and ammonium paratungstate; wherein sodium molybdate is also generated during the process of leaching and drying the crystal;
and (3) inputting the crystallization mother liquor into a displacement reaction device, adding calcium chloride into the displacement reaction device according to the requirement to carry out displacement reaction, and then carrying out filter pressing separation treatment to obtain the calcium tungstate.
By the method, titanium dioxide, sodium tungstate, ammonium paratungstate and calcium tungstate can be prepared, and finally rare metals such as titanium, tungsten and the like can be recovered.
In order to improve the recovery rate of rare metals such as titanium, tungsten and the like, the recovery processing process is controlled and managed more finely, corresponding data acquisition is carried out on each processing node in the processing process, analysis decision is carried out on acquired data, and relevant decision is carried out on the acquired data in a dynamic optimization mode so as to optimize the reaction time, the reaction parameter consumption, the environmental parameter and the like of each node, thereby forming closed-loop control or multi-loop control, and further greatly improving the processing efficiency and the recovery rate.
In order to achieve the above object, the present invention is specifically realized by the following means:
in order to make the lye leaching process in step S200 more efficient, in step S100, after the tungsten titanium slag is ground to a preset target size and reaches a preset ferromagnetic substance removal rate, step S200 is performed again.
For the step S100, since the content of the active substance in the tungsten-titanium waste residue is greatly different and the granularity is not uniform, the tungsten-titanium waste residue needs to be ground into particles with a certain size and then subjected to magnetic screening treatment. In order to improve the efficiency and quality of the tungsten-titanium decomposition, the tungsten-titanium waste residues are ground into particles with a certain size and reach a certain ferromagnetic substance removal rate, and then the step S200 is carried out for alkali liquor leaching treatment.
In this embodiment, the grinding magnetic separator is provided with a speed sensor for detecting the grinding speed of the grinding magnetic separator, a force sensor for detecting the grinding force of the grinding magnetic separator, and a magnetic force for detecting tungsten-titanium waste residues after grinding treatment.
For how to detect and judge whether to grind tungsten-titanium waste residues to a preset target size, the embodiment is realized by the following ways:
in the grinding process, detecting and judging whether the grinding force of the grinding motor is stable at a preset grinding force value by using a force sensor, and judging that the tungsten-titanium waste residues are ground to a target size;
specifically, the approximate size of the abrasive grains can be determined by converting the torque of the grinding motor of the grinding separator to the grinding speed. In the grinding process, as the grinding disc has a certain size adjusting function, the grinding disc in the grinding process is adjusted from large to small, the larger the distance of the grinding disc is, the larger the grinding particles are, and when the distance is unchanged and the grinding speed is fixed, the torque change is consistent along with the grinding of the particles of the ground materials, and the torque change tends to be the stable maximum value. After the grinding disc is set to a certain distance, the torque is stabilized, the distance between the grinding disc is reduced, the grinding disc is in a stable state, the distance between the grinding disc and the target is finally reached, and the torque is stabilized, namely the target granularity is reached. Therefore, in actual application, the strength sensor is used for detecting and judging whether the grinding strength of the grinding motor is stable at a preset grinding strength value, so that whether the grinding mechanism in the grinding magnetic separator grinds tungsten-titanium waste residues to a preset target size can be judged.
For how to detect and judge whether to grind tungsten titanium waste residues to a preset ferromagnetic substance removal rate, the embodiment is realized by the following modes:
and dynamically detecting magnetic force parameters of the tungsten-titanium waste residues which are ground into particles by using the magnetic force sensor, ensuring that the magnetic force parameters reach a target magnetic separation rate, and finally confirming the ferromagnetic substance removal rate by the ferromagnetic substance adsorption time.
Specifically, the method is classified into 1-level or multi-level magnetic screening according to the accuracy requirement of grinding screening, for example, the magnetic force of 1-level magnetic separation is 3000-6000 gauss, and the magnetic force of multi-level magnetic separation is classified into: 3000-6000 gauss, 10000-12000 gauss, 15000-20000 gauss and the like, in the magnetic separation process, the magnetic force sensor dynamically detects magnetic force parameters of tungsten-titanium waste residues after being ground into particles, forms a control closed loop, ensures that the magnetic force parameters reach a target magnetic separation rate, and finally confirms the ferromagnetic removal rate through the ferromagnetic adsorption time.
Example 2
On the basis of the embodiment 1, the embodiment 2 further optimizes and improves the step S200.
The step S200 specifically includes: adding NaOH and water into an alkali liquor leaching machine to carry out alkali liquor leaching treatment on tungsten-titanium waste residues subjected to grinding and screening treatment; the alkali liquor leaching machine is controlled by a main controller, the alkali liquor leaching machine is provided with a PH value sensor and a temperature sensor which are electrically connected with the main controller,
The pH value sensor is used for detecting the pH value of the alkali liquor in the alkali liquor leaching tank of the alkali liquor leaching machine, and feeding back the detected pH value to the main controller, and when the detected pH value is lower than a preset pH value, the main controller controls a NaOH feeding mechanism in the alkali liquor leaching machine to feed NaOH into the alkali liquor leaching tank so that the alkali liquor reaches the preset pH value range; when the detected PH value is higher than a preset PH value, the main controller controls the water adding mechanism in the alkali liquor leaching machine to add water to the alkali liquor leaching tank so that the alkali liquor reaches the preset PH value range, and in the process of adding water to the alkali liquor leaching tank to adjust the PH value, the PH value of the alkali liquor is too low in order to avoid excessive water addition, so that the water adding mechanism detects and controls the water adding amount through the water flow sensor. In a specific embodiment, when the detected PH value is lower than the lower limit 11.3, controlling a NaOH feeding mechanism to feed NaOH into the alkali liquor leaching tank to enable the PH value of alkali liquor to be within the preset PH value range, otherwise, when the detected PH value is higher than the upper limit 13.5, controlling a water adding mechanism in the alkali liquor leaching machine to add water into the alkali liquor leaching tank to dilute so that the PH value of alkali liquor is within the preset PH value range; the pH value is controlled to be 11.5-13.5 because of the fluctuation of the alkaline leaching process, because a certain degree of alkaline supersaturation is needed, and when the PHC value is in the above range, the reaction efficiency of NaOH is higher.
The temperature sensor is used for detecting the temperature of the alkali liquor in the alkali liquor leaching tank of the alkali liquor leaching machine, feeding back the detected temperature value to the main controller, and controlling the heating power of a heating mechanism in the alkali liquor leaching machine by the main controller when the detected temperature of the alkali liquor leaching tank is lower than a preset temperature value, so that the heating mechanism is in a full heating power state and reaches a preset temperature value range as soon as possible; when the detected temperature of the alkali liquor leaching tank is higher than a preset temperature value, the heating mechanism is stopped to heat, the temperature value of the alkali liquor leaching tank is reduced to be within a preset temperature value range as soon as possible, and when the detected temperature of the alkali liquor leaching tank is within the preset temperature value range, the heating mechanism is in a constant-temperature heating state, so that the temperature of the alkali liquor leaching tank is maintained within the preset temperature range value; in a specific embodiment, the preset temperature range is 85-95 ℃, specifically, the temperature is controlled to be 85-95 ℃, so that the liquid flow is active, the reaction speed is high, and the temperature is lower than 95 ℃, so that the boiling of the reaction liquid can be avoided.
In the invention, the process of performing alkali liquor leaching treatment on tungsten and titanium waste residues by using an alkali liquor leaching machine in the step S200 is called an alkali liquor leaching treatment process, wherein in the alkali liquor leaching treatment process, the tungsten and titanium waste residues and NaOH are subjected to alkali hydrolysis reaction in an alkali liquor leaching tank, after the alkali hydrolysis reaction, tungsten-containing components form sodium tungstate, other impurities such as sodium silicate, sodium aluminate and the like are water-soluble substances, and titanium-containing substances mainly exist in a meta-titanic acid form and are separated out in an alkaline environment to form solids, so that tungsten and titanium decomposition can be realized. In the alkaline leaching treatment process, parameters such as the temperature, the PH value and the like of the alkaline hydrolysis reaction are dynamically changed, so that the temperature value and the PH value are monitored in real time through a PH value sensor and a temperature sensor, and the temperature value and the PH value of the alkaline hydrolysis reaction are dynamically adjusted through controlling corresponding components (such as a NaOH feeding mechanism, a heating mechanism, a water adding mechanism and the like) through a main controller, so that the alkaline hydrolysis reaction can be more efficient and rapid.
In the embodiment, the reaction parameters in the alkali liquor leaching treatment process are monitored and collected by utilizing the pH value sensor, the temperature sensor, the water flow sensor and other sensors, so that the main controller can accurately control the components such as the NaOH feeding mechanism, the heating mechanism, the water addition mechanism and the like, the PH value, the reaction temperature, the water addition amount and other parameters of the alkali liquor leaching treatment process can be accurately controlled, the completion efficiency of the alkali liquor leaching treatment process is higher, and tungsten and titanium decomposition can be better and faster realized.
Example 3
On the basis of example 1 or example 2, this example 3 makes a further optimization modification to the step S300.
The method comprises the following steps: in the step S300, pure water is used to clean the titaniferous filter residues after the filter-pressing type solid-liquid separation treatment, the solid-liquid filtration leaching machine is controlled by a main controller, the solid-liquid filtration leaching machine is provided with a first ion sensor which is electrically connected with the main controller and is used for detecting the ion residual quantity on the surface of the titaniferous filter-pressing residues in real time, and the main controller controls the spraying times of a flushing shower valve in the solid-liquid filtration leaching machine according to the detected ion residual quantity; and when the ion residual quantity detected by the ion sensor reaches a preset value, controlling a flushing shower valve in the solid-liquid filtration leaching machine to stop spraying, and entering step S400. The first ion sensor may be a tungstic acid ion sensor or a sodium ion sensor. In particular, according to practical needs, in this embodiment, the first ion sensor is preferably a sodium ion sensor, because the cost of the sodium ion sensor is relatively lower.
Specifically, titanium-containing filter residues and tungsten-containing filter liquor are obtained after filter pressing type solid-liquid separation treatment; the surface of the titanium-containing filter pressing residues is remained with the tungsten-containing filter pressing liquid, so that pure water can be utilized to repeatedly wash the titanium-containing filter pressing residues, and the washed solution is mixed with the tungsten-containing filter pressing liquid after solid-liquid separation treatment so as to improve the recovery of tungsten-containing compounds. According to the ion sensor, the ion residue on the surface of the titanium-containing filter pressing slag is detected, and the spraying times of the flushing shower valve are correspondingly controlled, so that the recovery rate of tungsten-containing compounds can be effectively improved, and water conservation can be realized. If the ion sensor detects that the ion residue on the surface of the titanium-containing filter pressing slag is more, the spraying times are correspondingly increased, otherwise, the ion sensor detects that the ion residue on the surface of the titanium-containing filter pressing slag is less, and the spraying times are correspondingly reduced.
For example, according to engineering experience values, the removal rate of one spraying is 85 percent, then the residual amount of spraying 3 times is 0.15 x 0.15=0.3375%, the residual amount of spraying 4 times is 0.15 x 0.15= 0.050625%, the residual quantity of spraying 5 times is 0.15 x 0.15= 0.0000759375 percent, if the target residual rate of the surface residual tungsten-containing press filtrate of the titanium-containing press filter residue reaches 0.15 percent, the spraying is required to be carried out for at least 4 times to meet the requirement, therefore, after the main controller controls the spraying times of the flushing water spraying valve in the solid-liquid filtration leaching machine to be 4 times, the ion sensor detects whether the ion residual quantity reaches the standard again, if so, the main controller controls the flushing water spraying valve in the solid-liquid filtration leaching machine to stop spraying, and the step S400 is entered, so that the water can be effectively saved and the spraying time can be reduced.
In this embodiment, by setting the first ion sensor to detect the ion residual amount on the surface of the titanium-containing filter pressing slag and controlling the spraying times, more accurate control can be achieved, so that the tungsten-containing filter pressing liquid remained on the surface of the titanium-containing filter pressing slag enters the steps S500-S600 as much as possible, and the recovery rate of the tungsten-containing compound can be effectively improved.
Example 4
On the basis of examples 1-3, this example 4 provides a preferred embodiment, specifically:
in the step S400, the drying and grinding tail gas processor is controlled by a main controller, and the drying and grinding tail gas processor is provided with a temperature sensor, a grinding speed sensor and a grinding force sensor which are electrically connected with the main controller;
the temperature sensor, the grinding speed sensor and the grinding force sensor are respectively used for detecting the temperature, the grinding speed and the grinding force of the drying and grinding tail gas processor in the process of drying and grinding the titanium-containing filter pressing residues, and feeding the detected temperature, grinding speed and grinding force data back to the main controller, and the main controller controls the working state of the drying and grinding tail gas processor according to the detected data.
During specific application, the drying and grinding tail gas processor firstly carries out drying treatment on titanium-containing filter pressing slag, can utilize natural gas combustion to supply heat to dry the titanium-containing filter pressing slag, then carries out grinding treatment, adopts cyclone to continuously lift up powder after drying and grinding in the grinding process, then uses a cloth bag to collect the powder, can obtain titanium dioxide (powder), simultaneously discharges tail gases such as particulate matters, sulfur dioxide, nitrogen oxides and the like, can monitor whether the tail gases reach the standard when discharging the tail gases, and otherwise carries out corresponding treatment on the tail gases without overlapping and then carries out compliance discharge. In the process of drying titanium-containing filter pressing slag by utilizing natural gas combustion to supply heat, a temperature sensor can be utilized to detect the temperature of heating and drying in real time and feed back the detected temperature value to a main controller, and the controller controls the temperature of heating and drying according to the detected temperature data, so that the drying efficiency and the drying quality can be effectively improved; in the grinding process, the grinding speed sensor and the grinding force sensor can detect the grinding speed and the grinding force in the grinding treatment process in real time, the grinding speed data and the grinding force data obtained by detection are fed back to the main controller, and the controller controls the working state of the grinding processor according to the grinding speed data and the grinding force data obtained by detection, so that the grinding efficiency and the grinding quality can be effectively improved.
In this embodiment, parameters such as temperature, grinding speed and grinding force in the drying and grinding process are detected and collected by using a temperature sensor, a grinding speed sensor and a grinding force sensor, so that the main controller controls the working state of the drying and grinding tail gas processor according to the detected data, thereby realizing accurate control and management of the drying and grinding process of the titanium-containing filter residues, effectively improving the efficiency and quality of the drying and grinding process, and further effectively improving the recovery rate of titanium dioxide.
In a preferred embodiment, in the step S500, the concentration and ph adjustment processing device is controlled by a main controller, and the concentration and ph adjustment processing device is provided with a tungstic acid ion concentration sensor and a temperature sensor and a ph sensor electrically connected to the main controller; wherein, the tungstic acid ion concentration sensor can adopt a sodium tungstate concentration meter or an MSDR-S series online liquid concentration sensor;
when the concentration of the tungsten-containing filter pressing liquid is detected to be regulated to a preset target concentration by a tungstic acid ion concentration sensor, sulfuric acid is added to regulate the pH value, in the process of regulating the pH value, the pH value of the tungsten-containing filter pressing liquid is regulated by controlling the mass concentration of the sulfuric acid, a mixed solution consisting of the tungsten-containing filter pressing liquid and the sulfuric acid is heated to a preset target temperature, the temperature and the pH value of the mixed solution are detected by a temperature sensor and a pH value sensor respectively, and the detected temperature and pH value data are fed back to a main controller;
And after the pH value sensor detects that the mixed solution is regulated to a preset target pH value, introducing the mixed solution into an ion exchanger for ion exchange treatment.
In this embodiment, by setting the concentration sensor, the temperature sensor, the ph sensor, and other component sensors in the concentration and ph adjustment processing device, the information such as the concentration, the temperature, and the ph of the tungsten-containing pressed filtrate can be obtained more accurately, so that the concentration and ph adjustment process is more efficient, thereby improving the generation rate of the ion exchange processing and performing precise control and management on the adjustment process.
In order to further increase the rate of formation of the ion exchange treatment to recover more tungsten-containing compounds in the tungsten-containing press filtrate, i.e., to increase the recovery rate of tungsten-containing compounds, the following formula is used before introducing the mixed solution into the ion exchange exchanger for ion exchange treatment:
adjusting the concentration Q of the filtrate of the mixed solution Filtrate from the filtration Mass concentration Q of sulfuric acid Sulfuric acid And reaction temperature P of ion exchange Exchange of Then ion exchange treatment is carried out to improve the generation rate W of the ion exchange treatment Exchange of Wherein Q is Standard sulfuric acid Is of standard concentration of sulfuric acid, P Standard exchange For the standard reaction temperature, CH Exchange of For the exchange capacity, CH, of ion exchange resins in ion exchangers Standard exchange Standard exchange capacity, Q, of ion exchange resins in ion exchangers Standard filtrate 、Q Standard sulfuric acid 、P Standard exchange 、CH Standard exchange All are preset values; δ1 is the standard deviation of the concentration of the filtrate, δ2 is the standard deviation of the pH value balance, δ03 is the standard deviation of the ion exchange stage, δ14 is the standard deviation of the resin exchange capacity, and δ1, δ2, δ3 and δ4 are constants; in this embodiment, δ1=0.2, δ2=0.3, δ3=40, δ4=8; and said Q Standard filtrate 、Q Standard sulfuric acid 、P Standard exchange 、CH Standard exchange The specific numerical values of (2) are obtained from engineering experience values, and are specifically: q (Q) Standard filtrate ＝13％，Q Standard sulfuric acid ＝17％，P Standard exchange ＝98℃，CH Standard exchange =2h (hours).
In specific application, a root can be arranged in the main controllerThe above formula is used to calculate the generation rate W of ion exchange treatment Exchange of The master controller can conveniently and rapidly calculate the filtrate concentration Q according to the formula Filtrate from the filtration Mass concentration Q of sulfuric acid Sulfuric acid And reaction temperature P of ion exchange Exchange of These parameters, and the filtrate concentration Q calculated by the above formula Filtrate from the filtration Reaction temperature P of ion exchange Exchange of Respectively using the temperature as the preset target concentration and the preset target temperature; and the calculated mass concentration Q of sulfuric acid Sulfuric acid The sulfuric acid with the mass concentration of the numerical value is used for regulating the pH value of the mixed solution to reach the target pH value, and the exchange capacity CH of the ion exchange resin in the ion exchange machine is realized Exchange of Selecting CH as much as possible Standard exchange (2 hours) equal or close ion exchange resins to increase the reaction efficiency.
In practical application, since each value in the reaction process is dynamically changed, the concentration Q of filtrate is controlled Filtrate from the filtration Mass concentration Q of sulfuric acid Sulfuric acid And reaction temperature P of ion exchange Exchange of The yield of the ion exchange treatment can be effectively improved by matching the standard value as much as possible or controlling the standard value to be close to the standard value as much as possible and changing the standard value, and further the recovery rate of the tungsten-containing compound can be effectively improved.
Example 5
On the basis of examples 1-4, this example 5 provides a preferred embodiment, specifically:
in the step S600, in the process of rinsing and drying the crystal, pure water is used to rinse the crystal repeatedly, the rinsing waste liquid generated by rinsing flows into a wastewater treatment station for treatment, and the crystal after rinsing is dried to obtain a tungsten-containing compound and sodium molybdate, wherein the tungsten-containing compound comprises sodium tungstate and ammonium paratungstate. During the drying process, steam is generated, the generated steam can be subjected to heat recovery through a heat exchange device, and meanwhile, the prepared condensed water can be used for leaching the crystal by pure water.
In the step S600, the main component of the crystallization mother liquor is sodium tungstate, and because the combination of tungstate ions and calcium can produce precipitation, the crystallization mother liquor is input into the displacement reaction device, and calcium chloride is added into the displacement reaction device according to the requirement for carrying out displacement reaction, so that calcium tungstate can be obtained, and the recovery of tungsten element can be realized. Wherein the substitution reaction equation is Na 2 WO 4 +CaCl 2 →CaWO 4 +2NaCI。
In a preferred embodiment, the added calcium chloride is maintained in a certain excess of calcium ions during the displacement reaction to achieve more efficient tungsten element displacement. The specific scheme of the embodiment is as follows: the displacement reaction device is controlled by a main controller, and is provided with a tungstic acid ion concentration sensor and a liquid flow rate which are electrically connected with the main controller, wherein the liquid flow rate sensor is used for detecting the inflow of crystallization mother liquor entering the displacement reaction device, and the tungstic acid ion concentration sensor is used for detecting the concentration of tungstic acid ions in a reaction treatment tank in the displacement reaction device;
let the inflow of the crystallization mother liquor detected by the liquid flow sensor be P1m 3 And/h, detecting the concentration of the obtained tungstic acid ions by a tungstic acid ion concentration sensor to be Q1 m 3 In the embodiment, a is 1 to 3, and may be actually set according to specific needs; that is, the amount of calcium ions in the added calcium chloride is 1% -3% more than that of tungsten ions in the crystallization mother liquor, so that the tungsten element replacement can be realized efficiently.
And for calcium tungstate subjected to filter pressing treatment, a weight sensor can be used for weighing and confirming, and if the weight exceeds a theoretical calculation precipitation value, the water content exceeds the standard in filter pressing; if the weight is lower than the theoretical calculation value, the solid loss is possibly caused by the breakage of the filter pressing screen, or the abnormal precipitation amount is caused by the unreasonable proportioning of the front-end replacement reaction, and whether the replacement proportioning of the crystallization mother liquor and the calcium chloride is reasonable or not can be detected and is in a reasonable range through careful calculation, so that the efficient utilization of the replacement raw materials is realized, and the recovery rate of tungsten element is effectively improved.
Example 6
On the basis of examples 1-5, this example 6 provides a preferred embodiment, specifically:
to improve recovery, the method further comprises:
s700, returning the lean peak liquid after ion exchange treatment to a concentration and pH value adjusting treatment device to enable the lean peak liquid to participate in the adjustment of the concentration and pH value of the tungsten-containing press filtrate;
and conveying the three-stage liquid after the ion exchange treatment to a desorber tank for desorber circulation treatment, and returning the desorbed liquid to the ion exchanger to participate in the ion exchange treatment.
In the step, the concentration and the pH value of the lean peak liquid are returned to the treatment device, so that the residual tungsten-containing filter pressing liquid in the lean peak liquid can participate in the regulation of the concentration and the pH value again, and the recovery rate is further effectively improved; the adjusted mixed solution enters an ion exchanger to carry out ion exchange treatment; after the ion exchange treatment is completed, the ion exchange electrode in the ion exchange machine adsorbs tungsten-containing ions; after the adsorption is finished, other waste water is discharged; then returning the desorption liquid to the ion exchanger to participate in the desorption of tungsten-containing element ions; the residual desorption solution after ion exchange polar desorption is returned to the ion exchanger to participate in the desorption of tungsten-containing ions, so that the recycling of the desorbing agent can be realized.
In a specific embodiment, in step S700, three-stage solution is generated during the ion exchange treatment, and the three-stage solution after the ion exchange treatment is conveyed to a desorber tank for desorber circulation treatment, wherein condensed water, liquid ammonia water, ammonia chloride and the like flow together to the desorber tank and are combined with a desorber (the desorber is added with NH) 4 CL and NH 3 The solvent with a certain concentration is prepared) to participate in the desorbing agent circulation treatment, and the desorption solution generated by the desorbing agent circulation treatment is returned to the ion exchanger to participate in the ion exchange treatment, and the heat circulation and the element circulation of the desorption solution are continuously carried out in the ion exchange treatment process. In this embodiment, to achieve better desorption, corresponding ion concentration sensors, such as ammonium ion concentration sensors, are disposed in the desorber tankThe sensor, the chloride ion concentration sensor, the sodium ion concentration sensor and the hydroxide ion concentration sensor are respectively used for detecting the concentration of ammonium ions, the concentration of chloride ions, the concentration of sodium ions and the concentration of hydroxide ions, and by detecting the concentrations of the ions, the optimal allocation of desorbing agent, liquid ammonia water, ammonia chloride and sodium hydroxide in the desorbing agent tank can be calculated, so that the desorbing solution keeps good desorption effect, and finally the effect of ion exchange treatment can be effectively improved.
Finally, it should be noted that: the above is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that the present invention is described in detail with reference to the foregoing embodiments, and modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for recycling rare metals in waste residues is used for recycling tungsten-containing compounds and titanium-containing compounds from tungsten-titanium waste residues, and is characterized by comprising the following steps:
s100, grinding and screening the tungsten-titanium waste residues through a grinding magnetic separator so as to separate ferromagnetic substances in the tungsten-titanium waste residues;
s200, performing alkali liquor leaching treatment on the tungsten titanium waste residues subjected to grinding and screening treatment by an alkali liquor leaching machine so as to realize tungsten titanium decomposition;
s300, performing filter pressing type solid-liquid separation treatment on the solid-liquid mixture obtained through alkali liquor leaching treatment by utilizing a solid-liquid filtration leaching machine so as to realize tungsten-titanium separation; the titanium-containing filter residue and the tungsten-containing filter liquid are obtained after the filter pressing type solid-liquid separation treatment;
S400, drying and grinding the titanium-containing filter pressing residues by using a drying and grinding tail gas processor, and finally preparing a titanium-containing compound, wherein the titanium-containing compound comprises titanium dioxide;
s500, adjusting the concentration and the pH value of the tungsten-containing filter pressing liquid by using a concentration and pH value adjusting treatment device, and performing ion exchange treatment on the tungsten-containing filter pressing liquid with the concentration and the pH value adjusted by an ion exchange machine after the concentration and the pH value are adjusted to a preset target concentration and a target pH value;
s600, crystallizing peak liquid after ion exchange treatment, performing solid-liquid separation treatment to obtain a crystal and a crystallization mother liquor, leaching and drying the crystal to finally obtain a tungsten-containing compound, wherein the tungsten-containing compound comprises sodium tungstate and ammonium paratungstate;
inputting the crystallization mother liquor into a displacement reaction device, adding calcium chloride into the displacement reaction device according to the requirement to carry out displacement reaction, and then carrying out filter pressing separation treatment to obtain calcium tungstate;
in the step S100, after the tungsten-titanium waste residue is ground to a preset target size and reaches a preset ferromagnetic substance removal rate, the process proceeds to a step S200;
in the step S200, adding NaOH and water into an alkali liquor leaching machine to carry out alkali liquor leaching treatment on tungsten-titanium waste residues subjected to grinding and screening treatment; the alkali liquor leaching machine is controlled by a main controller, the alkali liquor leaching machine is provided with a PH value sensor and a temperature sensor which are electrically connected with the main controller,
The pH value sensor is used for detecting the pH value of the alkali liquor in the alkali liquor leaching tank of the alkali liquor leaching machine, and when the detected pH value is lower than a preset pH value, the NaOH feeding mechanism in the alkali liquor leaching machine is controlled to feed NaOH into the alkali liquor leaching tank so that the alkali liquor reaches the preset pH value range; when the detected pH value is higher than a preset pH value, controlling a water adding mechanism in the alkali liquor leaching machine to add water into an alkali liquor leaching tank so that the alkali liquor reaches the preset pH value range;
the temperature sensor is used for detecting the temperature of the alkali liquor in the alkali liquor leaching tank of the alkali liquor leaching machine, when the detected temperature of the alkali liquor leaching tank is lower than a preset temperature value, the heating power of the heating mechanism in the alkali liquor leaching machine is controlled to enable the heating mechanism to be in a full heating power state, when the detected temperature of the alkali liquor leaching tank is higher than the preset temperature value, the heating mechanism is enabled to stop heating, and when the detected temperature of the alkali liquor leaching tank is within the preset temperature value range, the heating mechanism is enabled to be in a constant-temperature heating state.
2. The method for recycling rare metals in waste residue according to claim 1, wherein in said step S100, it is detected and judged whether or not to grind the tungsten titanium waste residue to a preset target size and ferromagnetic substance removal rate by:
The grinding magnetic separator is provided with a speed sensor for detecting the grinding speed of the grinding magnetic separator, a force sensor for detecting the grinding force of the grinding magnetic separator and a magnetic force for detecting tungsten-titanium waste residues after grinding treatment;
detecting and judging whether the grinding force of the grinding motor is stable at a preset grinding force value by using the force sensor, and judging that the tungsten-titanium waste residues are ground to a target size;
and dynamically detecting magnetic force parameters of the tungsten-titanium waste residues which are ground into particles by using the magnetic force sensor, ensuring that the magnetic force parameters reach a target magnetic separation rate, and finally confirming the ferromagnetic substance removal rate by the ferromagnetic substance adsorption time.
3. The method for recycling rare metals in waste residues according to claim 1, wherein the method comprises the following steps:
in the step S300, pure water is used to clean the titanium-containing filter residues obtained after the filter-pressing type solid-liquid separation treatment, the solid-liquid filtration leaching machine is controlled by a main controller, the solid-liquid filtration leaching machine is provided with a first ion sensor which is electrically connected with the main controller and is used for detecting the ion residual quantity on the surface of the titanium-containing filter residues in real time, and the main controller controls the spraying times of a flushing shower valve in the solid-liquid filtration leaching machine according to the detected ion residual quantity; and when the residual ion quantity detected by the first ion sensor reaches a preset value, controlling a flushing shower valve in the solid-liquid filtration leaching machine to stop spraying, and entering step S400.
4. The method for recycling rare metals in waste residues according to claim 1, wherein the method comprises the following steps: the first ion sensor is a tungstic acid ion sensor or a sodium ion sensor.
5. The method for recycling rare metals in waste residues according to claim 1, wherein the method comprises the following steps: in the step S400, the drying and grinding tail gas processor is controlled by a main controller, and the drying and grinding tail gas processor is provided with a temperature sensor, a grinding speed sensor and a grinding force sensor which are electrically connected with the main controller;
the temperature sensor, the grinding speed sensor and the grinding force sensor are respectively used for detecting the temperature, the grinding speed and the grinding force of the drying and grinding tail gas processor in the process of drying and grinding the titanium-containing filter pressing residues, and feeding the detected temperature, grinding speed and grinding force data back to the main controller, and the main controller controls the working state of the drying and grinding tail gas processor according to the detected data.
6. The method for recycling rare metals in waste residues according to claim 1, wherein the method comprises the following steps: in the step S500, the concentration and ph adjustment processing device is controlled by a main controller, and the concentration and ph adjustment processing device is provided with a tungstic acid ion concentration sensor, a temperature sensor and a ph sensor electrically connected with the main controller;
When the concentration of the tungsten-containing filter pressing liquid is detected to be regulated to a preset target concentration by a tungstic acid ion concentration sensor, sulfuric acid is added to regulate the pH value, in the process of regulating the pH value, the pH value of the tungsten-containing filter pressing liquid is regulated by controlling the mass concentration of the sulfuric acid, a mixed solution consisting of the tungsten-containing filter pressing liquid and the sulfuric acid is heated to a preset target temperature, the temperature and the pH value of the mixed solution are detected by a temperature sensor and a pH value sensor respectively, and the detected temperature and pH value data are fed back to a main controller;
and after the pH value sensor detects that the mixed solution is regulated to a preset target pH value, introducing the mixed solution into an ion exchanger for ion exchange treatment.
7. The method for recycling rare metals in waste residue according to claim 6, wherein: before the mixed solution is introduced into the ion exchanger for ion exchange treatment, the following formula is adopted:
adjusting the concentration Q of the filtrate of the mixed solution Filtrate from the filtration Mass concentration Q of sulfuric acid Sulfuric acid And reaction temperature P of ion exchange Exchange of Then ion exchange treatment is carried out to improve the generation rate W of the ion exchange treatment Exchange of Wherein Q is Standard filtrate Is the standard concentration of filtrate, Q Standard sulfuric acid Is of standard concentration of sulfuric acid, P Standard exchange For the standard reaction temperature, CH Exchange of For the exchange capacity, CH, of ion exchange resins in ion exchangers Standard exchange Standard exchange capacity, Q, of ion exchange resins in ion exchangers Standard filtrate 、Q Standard sulfuric acid 、P Standard exchange 、CH Standard exchange All are preset values; δ1 is the standard deviation of the concentration of the filtrate, δ2 is the standard deviation of the pH value balance, δ3 is the standard deviation of the ion exchange stage, δ4 is the standard deviation of the resin exchange capacity, and δ1, δ2, δ3 and δ4 are constants.
8. The method for recycling rare metals in waste residues according to claim 1, wherein the method comprises the following steps: in the step S600, the displacement reaction device is controlled by a main controller, and the displacement reaction device is provided with a tungstic acid ion concentration sensor and a liquid flow sensor weighing sensor, which are electrically connected with the main controller, wherein the liquid flow sensor is used for detecting the inflow of crystallization mother liquor entering the displacement reaction device, and the tungstic acid ion concentration sensor is used for detecting the concentration of tungstic acid ions in a reaction treatment tank in the displacement reaction device;
Let the inflow of the crystallization mother liquor detected by the liquid flow sensor be P1m 3 And/h, detecting the concentration of the obtained tungstic acid ions by a tungstic acid ion concentration sensor to be Q1 m 3 And (3) adding calcium chloride to the displacement reaction device to perform displacement reaction, wherein the required quantity of the calcium chloride to be added to the displacement reaction device is W1=P1×Q1 (1+A%), and A is 1-3.
9. The method for recycling rare metals in waste residues according to claim 1, wherein the method comprises the following steps: the method further comprises the steps of:
s700, returning the lean peak liquid after ion exchange treatment to a concentration and pH value adjusting treatment device to enable the lean peak liquid to participate in the adjustment of the concentration and pH value of the tungsten-containing press filtrate;
and conveying the three-stage liquid after the ion exchange treatment to a desorber tank for desorber circulation treatment, and returning the desorbed liquid to the ion exchanger to participate in the ion exchange treatment.
10. The method for recycling rare metals in waste residue according to claim 9, which is characterized in that: and the desorbing agent tank is provided with an ammonium ion concentration sensor, a chloride ion concentration sensor, a sodium ion concentration sensor and a hydroxide ion concentration sensor which are respectively used for detecting the ammonium ion concentration, the chloride ion concentration, the sodium ion concentration and the hydroxide ion concentration.
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