CN113249595A - Method for recovering tungsten from waste alkali liquor generated by regenerating waste SCR catalyst and application of method - Google Patents
Method for recovering tungsten from waste alkali liquor generated by regenerating waste SCR catalyst and application of method Download PDFInfo
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- 239000002699 waste material Substances 0.000 title claims abstract description 92
- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 90
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000010937 tungsten Substances 0.000 title claims abstract description 89
- 238000000034 method Methods 0.000 title claims abstract description 57
- 239000003513 alkali Substances 0.000 title claims abstract description 55
- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- 230000001172 regenerating effect Effects 0.000 title claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 57
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 48
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000011282 treatment Methods 0.000 claims abstract description 47
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims abstract description 46
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 35
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 35
- 239000011574 phosphorus Substances 0.000 claims abstract description 35
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 35
- 239000010703 silicon Substances 0.000 claims abstract description 35
- 239000012141 concentrate Substances 0.000 claims abstract description 27
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims abstract description 23
- 235000019341 magnesium sulphate Nutrition 0.000 claims abstract description 23
- 238000001556 precipitation Methods 0.000 claims abstract description 21
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000292 calcium oxide Substances 0.000 claims abstract description 19
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 19
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 135
- 239000000706 filtrate Substances 0.000 claims description 38
- 238000001914 filtration Methods 0.000 claims description 36
- 239000002244 precipitate Substances 0.000 claims description 35
- 239000013078 crystal Substances 0.000 claims description 32
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000011221 initial treatment Methods 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 14
- 238000001704 evaporation Methods 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 7
- 230000008929 regeneration Effects 0.000 claims description 5
- 238000011069 regeneration method Methods 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 abstract description 39
- 239000012535 impurity Substances 0.000 abstract description 10
- 239000000126 substance Substances 0.000 description 20
- 238000011084 recovery Methods 0.000 description 15
- 238000002386 leaching Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 7
- 230000001105 regulatory effect Effects 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- 238000005070 sampling Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 4
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 4
- 239000004137 magnesium phosphate Substances 0.000 description 4
- 229960002261 magnesium phosphate Drugs 0.000 description 4
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 4
- 235000010994 magnesium phosphates Nutrition 0.000 description 4
- 239000000391 magnesium silicate Substances 0.000 description 4
- 229910052919 magnesium silicate Inorganic materials 0.000 description 4
- 235000019792 magnesium silicate Nutrition 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- TUNFSRHWOTWDNC-UHFFFAOYSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 4
- -1 tungstate radical ions Chemical class 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910001425 magnesium ion Inorganic materials 0.000 description 3
- 229960002366 magnesium silicate Drugs 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229940000489 arsenate Drugs 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical group [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
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
- C22B34/00—Obtaining refractory metals
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/36—Obtaining tungsten
- C22B34/365—Obtaining tungsten from spent catalysts
-
- 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
-
- 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
Abstract
The application discloses a method for recovering tungsten from waste alkali liquor generated by regenerating a waste SCR catalyst and application thereof. Then acid is added to remove carbonate ions, and the processes of adding magnesium sulfate to remove impurities and adding calcium oxide to separate tungsten elements are adopted to obtain the scheelite concentrate. The mode of firstly adding acid to remove carbonate ions is adopted, so that the carbonate ions can be prevented from consuming magnesium sulfate in the next procedure; and (3) counting the contents of the arsenic element, the silicon element and the phosphorus element, and then adding sufficient magnesium sulfate into the secondary treatment liquid to avoid the condition that the arsenic element cannot be fully precipitated due to the existence of the silicon element and the phosphorus element. According to the method for recovering tungsten, the precipitation rate of tungsten element in waste alkali liquor can be more than 91%, arsenic element in recovered white tungsten concentrate is not detected, and the content of tungsten trioxide is more than 65%.
Description
Technical Field
The application relates to the technical field of secondary resource utilization, in particular to a method for recovering tungsten from waste alkali liquor generated by regenerating a waste SCR catalyst and application thereof.
Background
In a coal-fired power plant, the SCR catalyst for denitration is poisoned and aged by active components along with the increase of the running timeAnd the denitration activity is gradually reduced due to other reasons, and when the activity is lower than the designed inactivation threshold, the denitration activity must be replaced layer by layer in sequence. At present, the commercial SCR denitration catalyst is a vanadium-titanium catalyst, and the main component of the commercial SCR denitration catalyst comprises 80-85 wt% of TiO2、0.5%~1wt%V2O5、4~10wt%WO3And SiO2、Al2O3And the like. V, W contained in the waste SCR denitration catalyst and heavy metals such As Fe, As, Pb and the like adsorbed in the using process cause serious harm to the environment. Meanwhile, the V, W and Ti valuable metal resources in the catalyst cannot be effectively utilized, which causes huge waste of resources.
Aiming at WO in waste SCR denitration catalyst3、V2O5And TiO2The leaching extraction and recovery mainly comprises a reduction leaching method, an acid leaching method, an alkaline leaching method and the like. In the leaching process, part of valuable metals in the waste SCR denitration catalyst can be dissolved in a leaching solution, and if the part of the leaching solution is directly discharged, the resource waste is caused. Meanwhile, part of impurities are mixed into the leaching liquor, and the part of impurities can influence the recovery of valuable metals in the leaching liquor, for example, when tungsten is recovered, arsenic mixed into the leaching liquor can increase the difficulty of the tungsten recovery process and influence the recovery efficiency of the tungsten. Therefore, how to reduce the interference of impurities in the leaching liquor and improve the recovery efficiency of valuable metals has very important significance for recovering the valuable metals in the waste SCR denitration catalyst.
Disclosure of Invention
The application provides a method for recovering tungsten from waste lye generated by regenerating a waste SCR catalyst and application thereof, which can efficiently recover tungsten from the waste lye.
In a first aspect, an embodiment of the present application provides a method for recovering tungsten from a waste lye generated from regenerating a waste SCR catalyst, where the waste lye is obtained by disposing the waste SCR catalyst in a sodium hydroxide solution, and the method for recovering tungsten includes the following steps:
evaporating and concentrating the waste alkali liquor until the mass concentration of the sodium hydroxide is 20%, and cooling, crystallizing and filtering to obtain pretreated crystals. Wherein, the existence form of the tungsten element in the waste alkali liquor can be tungsten trioxide and tungstate radical ions.
And fully dissolving the pretreatment crystals to obtain a pretreatment solution.
And adding an acid solution into the pretreatment solution, adjusting the pretreatment solution to a first preset pH value, and performing a carbonate ion removal reaction to obtain a primary treatment solution.
And adding sodium hydroxide into the primary treatment liquid, and adjusting the primary treatment liquid to a second preset pH value to obtain a secondary treatment liquid, wherein the second preset pH value is greater than 7.
And adding magnesium sulfate into the secondary treatment liquid for precipitation reaction at least according to the contents of arsenic element, silicon element and phosphorus element in the secondary treatment liquid, filtering to obtain primary filtrate, and obtaining primary precipitate.
Wherein, arsenic element, silicon element and phosphorus element can respectively exist in the waste alkali liquor in the form of arsenate ion, silicate ion and phosphate ion. In alkaline environment, arsenate ions, silicate ions and phosphate ions can all react with magnesium ions to correspondingly generate magnesium arsenate, magnesium silicate and magnesium phosphate, and the magnesium arsenate, the magnesium silicate and the magnesium phosphate are precipitated in the primary precipitate, so that the removal of arsenic, silicon and phosphorus is realized.
Adding calcium oxide into the primary filtrate according to the content of the tungsten element for precipitation reaction again, filtering to obtain a secondary precipitate containing the tungsten element, cleaning the secondary precipitate, and filtering to obtain a recovered product, namely the scheelite concentrate. Wherein, tungsten element existing under alkaline condition can react with calcium oxide to generate calcium tungstate precipitate, the calcium tungstate precipitate is separated out to secondary precipitate, and the secondary precipitate is cleaned to remove impurities to obtain a recovered product, namely scheelite concentrate.
The waste alkali liquor in the embodiment of the application can be obtained by treating a waste SCR catalyst in a sodium hydroxide solution, and the waste alkali liquor obtained by treating the waste SCR denitration catalyst can contain tungsten, arsenic, silicon, phosphorus and the like. Before the evaporation concentration of the waste alkali liquor, sampling and detecting the waste alkali liquor to obtain the concentration of each substance in the waste alkali liquor, wherein the detected substances include but are not limited to tungsten, arsenic, silicon and phosphorus. And the concentration of each substance in the concentrated solution after concentration is regulated and controlled according to the concentration of each substance in the waste alkali liquor so as to improve the precipitation rate of the substances to be separated from the pretreated crystals.
According to the method for recovering tungsten from waste alkali liquor generated by regeneration of the waste SCR catalyst, provided by the embodiment of the application, the mass concentration of sodium hydroxide in concentrated solution after evaporation and concentration is controlled to be 20wt.%, and the concentrated solution is cooled and crystallized to obtain the pretreatment crystals and the recovery solution, so that the precipitation rate of substances such as tungsten elements, arsenic elements, silicon elements and phosphorus elements precipitated in the pretreatment crystals can be effectively improved. And the temperature of the cooling crystallization can be regulated and controlled to reduce the precipitation rate of the sodium hydroxide precipitated into the pretreatment crystallization, so that the sodium hydroxide still remains in the obtained recovery liquid, and the recovery liquid can be continuously recycled in the regeneration treatment process of the waste SCR catalyst.
In some exemplary embodiments, the concentrated solution is cooled and crystallized after evaporation concentration, and the temperature of crystallization is in the range of 45 ℃ to 50 ℃.
In some exemplary embodiments, the pretreatment crystals are dissolved with deionized water to obtain the pretreatment solution.
In some exemplary embodiments, the ratio of the mass of deionized water that dissolves the pretreatment crystals to the mass of the pretreatment crystals ranges from 1: 1-4: 1, for example, may be 1: 1. 2: 1. 3: 1 or 4: 1, etc. Preferably, the ratio of the mass of deionized water dissolving the pretreatment crystals to the mass of the pretreatment crystals ranges from 1.5: 1-2: 1.
the inventor finds that during the process of treating the waste SCR catalyst by using a sodium hydroxide solution, carbonate ions are mixed and remain in the waste alkali liquor, and after evaporation, concentration and crystallization, the carbonate ions can generate sodium carbonate with sodium ions and precipitate into pretreatment crystals. Carbonate ions can be combined with magnesium ions to generate magnesium carbonate precipitates, so that before magnesium sulfate is added to precipitate substances such as arsenic, silicon and phosphorus, acid is added to fully remove the carbonate ions, and the impurity removal efficiency is prevented from being influenced by the reaction of the carbonate ions and the magnesium ions in the process of precipitating the substances such as the arsenic, the silicon and the phosphorus.
In some exemplary embodiments, the pH of the pretreatment solution is adjusted to the first predetermined pH using a sulfuric acid solution.
In some exemplary embodiments, the first predetermined pH is 4.0 to 7.0, and may be, for example, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, or the like.
In some exemplary embodiments, the second predetermined pH is 10.0 to 12.0, and may be, for example, 10.0, 10.5, 11.0, 11.5, 12.0, or the like.
Magnesium arsenate, magnesium silicate and magnesium phosphate can be precipitated under alkaline conditions, and based on the above embodiment, the secondary treatment liquid is alkaline, so as to improve the precipitation rate of magnesium arsenate, magnesium silicate and magnesium phosphate, and to make tungsten element more fully dissolved in the liquid phase to enter the next process.
In some exemplary embodiments, magnesium sulfate is added to the secondary treatment solution in a molar amount of 1.0 to 1.5 times, for example, 1.0, 1.1, 1.2, 1.3, 1.4, or 1.5 times, of the sum of molar amounts of arsenic, silicon, and phosphorus in the secondary treatment solution.
In some exemplary embodiments, the molar amount of calcium oxide added to the primary filtrate is 1.0 to 1.5 times, for example, 1.0 time, 1.1 times, 1.2 times, 1.3 times, 1.4 times, 1.5 times, or the like, the molar amount of tungsten element in the primary filtrate. Under alkaline conditions, substances containing tungsten elements can react with calcium oxide to generate calcium tungstate which is precipitated into secondary precipitates. Meanwhile, the calcium oxide is selected to avoid introducing other impurities into the reaction system.
In some exemplary embodiments, the secondary precipitate is washed with deionized water, filtered, and dried to obtain a recovered scheelite concentrate.
In a second aspect, the present application also provides an application of the method for recovering tungsten from waste lye generated by regenerating the waste SCR catalyst, as described above, in a treatment process for recovering the waste SCR catalyst. And (3) treating the waste SCR catalyst by using a sodium hydroxide solution, and filtering to obtain the waste alkali liquor.
Before the waste lye is obtained by filtration, the method also comprises the following steps: the method comprises the following steps of (1) after ash removal and grinding of the waste SCR catalyst into powder, putting the powder into a sodium hydroxide solution with a preset content for alkali leaching heat treatment, cooling and filtering to obtain a waste alkali liquor of the treated waste SCR catalyst; and treating the waste lye of the treated waste SCR catalyst by adopting the separation method.
Preferably, the conditions of the alkali soaking heat treatment are as follows:
the mass concentration range of the sodium hydroxide solution is 2-5%;
the mass ratio of the sodium hydroxide solution to the waste SCR denitration catalyst is 2-8;
the temperature range of the alkali leaching heat treatment is 200-300 ℃;
the time range of the alkali leaching heat treatment is 0.5h-8 h.
The application provides a method for recovering tungsten from waste alkali liquor generated by regeneration of a waste SCR catalyst, which separates substances such as tungsten elements from an alkali solution by adopting an evaporation concentration crystallization method, effectively improves the separation efficiency of the substances such as the tungsten elements by controlling the concentration of sodium hydroxide in the evaporation concentration process, and reduces the crystallization amount of the sodium hydroxide precipitated into pretreatment crystals. Then acid is added to remove carbonate ions, and the processes of adding magnesium sulfate to remove impurities and adding calcium oxide to separate tungsten elements are combined, so that impurities in the waste alkali liquor are fully removed, and the separation efficiency of the tungsten elements is effectively improved. The method of adding acid to remove carbonate ions firstly is adopted, so that the carbonate ions can be prevented from competing with arsenic elements to consume magnesium sulfate in the next procedure, and the consumption of the magnesium sulfate is reduced; in the process of removing impurities by adopting magnesium sulfate, the contents of arsenic element, silicon element and phosphorus element are counted to add sufficient magnesium sulfate into the secondary treatment liquid, so that the phenomenon that the arsenic element is not fully precipitated due to the existence of the silicon element and the phosphorus element is avoided. According to the method for recovering tungsten, the precipitation rate of tungsten element in waste alkali liquor can be more than 91%, arsenic element in recovered white tungsten concentrate is not detected, and the content of tungsten trioxide is more than 65%. The treatment method of the embodiment of the application can improve the recovery rate of tungsten in the waste SCR catalyst, and is energy-saving and environment-friendly.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a flow chart of a method for recovering tungsten from spent caustic solution from regeneration of a spent SCR catalyst in an embodiment of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the present application is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
Referring to FIG. 1, a flow chart of a method for recovering tungsten from spent caustic solution generated by regenerating a spent SCR catalyst according to an embodiment of the present application is shown, and the method for recovering tungsten in the present application is described below with reference to a specific embodiment.
Example 1
The embodiment provides a method for recovering tungsten from waste lye generated by regenerating a waste SCR catalyst, which comprises the following steps:
and sampling and detecting the waste alkali liquor to respectively obtain the concentrations of sodium hydroxide, tungsten element, arsenic element, silicon element and phosphorus element in the waste alkali liquor.
Taking waste alkali liquor with a preset volume, evaporating and concentrating the waste alkali liquor until the mass concentration of sodium hydroxide is 20wt.%, obtaining concentrated solution, cooling, crystallizing and filtering the concentrated solution, and obtaining pretreated crystal and recovery solution. Wherein the temperature range for cooling, crystallizing and filtering the concentrated solution is 45-50 ℃.
Fully dissolving the pretreatment crystals by using deionized water to obtain a pretreatment solution. Wherein the mass of the added deionized water is 1.5 times of the mass of the pretreated crystals.
And adding a sulfuric acid solution into the pretreatment solution, regulating the pH value of the pretreatment solution to 5.5 by using the sulfuric acid solution, and performing removal reaction of carbonate ions to obtain a primary treatment solution.
And adding sodium hydroxide into the primary treatment liquid, and adjusting the pH value of the primary treatment liquid to 11.0 by adopting the sodium hydroxide to obtain a secondary treatment liquid.
Adding magnesium sulfate into the secondary treatment liquid according to the contents of the arsenic element, the silicon element and the phosphorus element in the secondary treatment liquid, stirring the secondary treatment liquid to fully precipitate the arsenic element, the silicon element and the phosphorus element, and filtering to obtain primary filtrate and primary precipitate. Wherein the molar weight of the magnesium sulfate added into the secondary treatment liquid is 1.1 times of the sum of the molar weights of the arsenic element, the silicon element and the phosphorus element in the secondary treatment liquid.
Adding calcium oxide into the primary filtrate according to the content of the tungsten element in the primary filtrate to perform precipitation reaction again, and filtering to obtain secondary filtrate and secondary precipitate. Wherein the molar weight of calcium oxide added into the primary filtrate is 1.1 times of the molar weight of tungsten element in the primary filtrate.
And washing the secondary precipitate by using deionized water, filtering and drying to obtain the scheelite concentrate.
And detecting the white tungsten concentrate, wherein the arsenic element in the white tungsten concentrate is not detected, and the content of tungsten trioxide in the white tungsten concentrate is 66.0%. And calculating to obtain the tungsten element precipitation efficiency of 92.0 percent according to the content of tungsten trioxide in the scheelite concentrate and the content of tungsten trioxide in the waste alkali liquor.
Example 2
The embodiment provides a method for recovering tungsten from waste lye generated by regenerating a waste SCR catalyst, which comprises the following steps:
and sampling and detecting the waste alkali liquor to respectively obtain the concentrations of sodium hydroxide, tungsten element, arsenic element, silicon element and phosphorus element in the waste alkali liquor.
Taking waste alkali liquor with a preset volume, evaporating and concentrating the waste alkali liquor until the mass concentration of sodium hydroxide is 20wt.%, obtaining concentrated solution, cooling, crystallizing and filtering the concentrated solution, and obtaining pretreated crystal and recovery solution. Wherein the temperature range for cooling, crystallizing and filtering the concentrated solution is 45-50 ℃.
Fully dissolving the pretreatment crystals by using deionized water to obtain a pretreatment solution. Wherein the mass of the added deionized water is 3.0 times of the mass of the pretreated crystals.
And adding a sulfuric acid solution into the pretreatment solution, regulating the pH value of the pretreatment solution to 6.0 by using the sulfuric acid solution, and performing removal reaction of carbonate ions to obtain a primary treatment solution.
And adding sodium hydroxide into the primary treatment liquid, and adjusting the pH value of the primary treatment liquid to 11.0 by adopting the sodium hydroxide to obtain a secondary treatment liquid.
Adding magnesium sulfate into the secondary treatment liquid according to the contents of the arsenic element, the silicon element and the phosphorus element in the secondary treatment liquid, stirring the secondary treatment liquid to fully precipitate the arsenic element, the silicon element and the phosphorus element, and filtering to obtain primary filtrate and primary precipitate. Wherein the molar weight of the magnesium sulfate added into the secondary treatment liquid is 1.1 times of the sum of the molar weights of the arsenic element, the silicon element and the phosphorus element in the secondary treatment liquid.
Adding calcium oxide into the primary filtrate according to the content of the tungsten element in the primary filtrate to perform precipitation reaction again, and filtering to obtain secondary filtrate and secondary precipitate. Wherein the molar weight of calcium oxide added into the primary filtrate is 1.3 times of the molar weight of tungsten element in the primary filtrate.
And washing the secondary precipitate by using deionized water, filtering and drying to obtain the scheelite concentrate.
And detecting the white tungsten concentrate, wherein the arsenic element in the white tungsten concentrate is not detected, and the content of tungsten trioxide in the white tungsten concentrate is 67.2%. According to the content of tungsten trioxide in the scheelite concentrate and the content of tungsten trioxide in the waste alkali liquor, the tungsten element precipitation efficiency is calculated to be 93.5%.
Example 3
The embodiment provides a method for recovering tungsten from waste lye generated by regenerating a waste SCR catalyst, which comprises the following steps:
and sampling and detecting the waste alkali liquor to respectively obtain the concentrations of sodium hydroxide, tungsten element, arsenic element, silicon element and phosphorus element in the waste alkali liquor.
Taking waste alkali liquor with a preset volume, evaporating and concentrating the waste alkali liquor until the mass concentration of sodium hydroxide is 20wt.%, obtaining concentrated solution, cooling, crystallizing and filtering the concentrated solution, and obtaining pretreated crystal and recovery solution. Wherein the temperature range for cooling, crystallizing and filtering the concentrated solution is 45-50 ℃.
Fully dissolving the pretreatment crystals by using deionized water to obtain a pretreatment solution. Wherein the mass of the added deionized water is 3.0 times of the mass of the pretreated crystals.
And adding a sulfuric acid solution into the pretreatment solution, regulating the pH value of the pretreatment solution to 6.5 by using the sulfuric acid solution, and performing removal reaction of carbonate ions to obtain a primary treatment solution.
And adding sodium hydroxide into the primary treatment liquid, and adjusting the pH value of the primary treatment liquid to 11.0 by adopting the sodium hydroxide to obtain a secondary treatment liquid.
Adding magnesium sulfate into the secondary treatment liquid according to the contents of the arsenic element, the silicon element and the phosphorus element in the secondary treatment liquid, stirring the secondary treatment liquid to fully precipitate the arsenic element, the silicon element and the phosphorus element, and filtering to obtain primary filtrate and primary precipitate. Wherein the molar weight of the magnesium sulfate added into the secondary treatment liquid is 1.5 times of the sum of the molar weights of the arsenic element, the silicon element and the phosphorus element in the secondary treatment liquid.
Adding calcium oxide into the primary filtrate according to the content of the tungsten element in the primary filtrate to perform precipitation reaction again, and filtering to obtain secondary filtrate and secondary precipitate. Wherein the molar weight of calcium oxide added into the primary filtrate is 1.0 time of the molar weight of tungsten element in the primary filtrate.
And washing the secondary precipitate by using deionized water, filtering and drying to obtain the scheelite concentrate.
And detecting the white tungsten concentrate, wherein the arsenic element in the white tungsten concentrate is not detected, and the content of tungsten trioxide in the white tungsten concentrate is 68.0%. According to the content of tungsten trioxide in the scheelite concentrate and the content of tungsten trioxide in the waste alkali liquor, the tungsten element precipitation efficiency is calculated to be 93.0%.
Comparative example 1
The technical scheme in the application is not adopted in the comparative example, and the scheelite concentrate is prepared by recovering from the waste alkali liquorWO in the substance obtained by the method of this comparative example3The content is low, and meanwhile, arsenic element exists in the obtained substance.
And sampling and detecting the waste alkali liquor to respectively obtain the concentrations of sodium hydroxide, tungsten element, arsenic element, silicon element and phosphorus element in the waste alkali liquor.
Taking waste alkali liquor with a preset volume, evaporating and concentrating the waste alkali liquor until the mass concentration of sodium hydroxide is 20wt.%, obtaining concentrated solution, cooling, crystallizing and filtering the concentrated solution, and obtaining pretreated crystal and recovery solution. Wherein the temperature range for cooling, crystallizing and filtering the concentrated solution is 45-50 ℃.
Fully dissolving the pretreatment crystals by using deionized water to obtain a pretreatment solution. Wherein the mass of the added deionized water is 8.0 times of the mass of the pretreated crystals.
And adding a sulfuric acid solution into the pretreatment solution, regulating the pH value of the pretreatment solution to 4.0 by using the sulfuric acid solution, and performing removal reaction of carbonate ions to obtain a primary treatment solution.
And adding sodium hydroxide into the primary treatment liquid, and adjusting the pH value of the primary treatment liquid to 12.0 by adopting the sodium hydroxide to obtain a secondary treatment liquid.
Adding magnesium sulfate into the secondary treatment liquid according to the contents of the arsenic element, the silicon element and the phosphorus element in the secondary treatment liquid, stirring the secondary treatment liquid to fully precipitate the arsenic element, the silicon element and the phosphorus element, and filtering to obtain primary filtrate and primary precipitate. Wherein the molar weight of the magnesium sulfate added into the secondary treatment liquid is 2.0 times of the sum of the molar weights of the arsenic element, the silicon element and the phosphorus element in the secondary treatment liquid.
Adding calcium oxide into the primary filtrate according to the content of the tungsten element in the primary filtrate to perform precipitation reaction again, and filtering to obtain secondary filtrate and secondary precipitate. Wherein the molar weight of calcium oxide added into the primary filtrate is 1.0 time of the molar weight of tungsten element in the primary filtrate.
And washing the secondary precipitate by using deionized water, filtering and drying to obtain a recovered substance.
Detecting the recovered substance to obtain arsenic (As)2O3Meter) ofThe content was 0.5%, and the content of tungsten trioxide in the recovered product was 61.0%. According to the content of the tungsten trioxide in the recovered substances and the content of the tungsten trioxide in the waste alkali liquor, the tungsten element precipitation efficiency is calculated to be 82.0%.
Comparative example 2
This comparative example, without the technical solution in the present application for the recovery of scheelite concentrate from sodium hydroxide lye, is intended to demonstrate the WO content in the material obtained by the method of this comparative example3The content is low, and meanwhile, arsenic element exists in the obtained substance.
And sampling and detecting the waste alkali liquor to respectively obtain the concentrations of sodium hydroxide, tungsten element, arsenic element, silicon element and phosphorus element in the waste alkali liquor.
Taking waste alkali liquor with a preset volume, evaporating and concentrating the waste alkali liquor until the mass concentration of sodium hydroxide is 20wt.%, obtaining concentrated solution, cooling, crystallizing and filtering the concentrated solution, and obtaining pretreated crystal and recovery solution. Wherein the temperature range for cooling, crystallizing and filtering the concentrated solution is 45-50 ℃.
Fully dissolving the pretreatment crystals by using deionized water to obtain a pretreatment solution. Wherein the mass of the added deionized water is 3.0 times of the mass of the pretreated crystals.
And adding a sulfuric acid solution into the pretreatment solution, regulating the pH value of the pretreatment solution to 4.5 by using the sulfuric acid solution, and performing removal reaction of carbonate ions to obtain a primary treatment solution.
And adding sodium hydroxide into the primary treatment liquid, and adjusting the pH value of the primary treatment liquid to 13.0 by adopting the sodium hydroxide to obtain a secondary treatment liquid.
Adding magnesium sulfate into the secondary treatment liquid according to the contents of the arsenic element, the silicon element and the phosphorus element in the secondary treatment liquid, stirring the secondary treatment liquid to fully precipitate the arsenic element, the silicon element and the phosphorus element, and filtering to obtain primary filtrate and primary precipitate. Wherein the molar weight of the magnesium sulfate added into the secondary treatment liquid is 2.5 times of the sum of the molar weights of arsenic, silicon and phosphorus in the secondary treatment liquid.
Adding calcium oxide into the primary filtrate according to the content of the tungsten element in the primary filtrate to perform precipitation reaction again, and filtering to obtain secondary filtrate and secondary precipitate. Wherein the molar weight of calcium oxide added into the primary filtrate is 2.0 times of the molar weight of tungsten element in the primary filtrate.
And washing the secondary precipitate by using deionized water, filtering and drying to obtain a recovered substance.
Detecting the recovered substance to obtain arsenic (As)2O3Calculated by mass) was 1.8%, and the content of tungsten trioxide in the recovered product was 56.0%. According to the content of the tungsten trioxide in the recovered substances and the content of the tungsten trioxide in the waste alkali liquor, the tungsten element precipitation efficiency is calculated to be 87.8%.
It can be seen from the above examples and comparative examples that the method in the example of the present application can effectively separate the tungsten element from the waste alkali solution, and can achieve a precipitation rate of the tungsten element in the waste alkali solution of more than 91%, the arsenic element in the recovered white tungsten concentrate is not detected, and the content of the tungsten trioxide in the white tungsten concentrate is more than 65%.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A method for recovering tungsten from waste lye generated by regenerating a waste SCR catalyst is characterized in that the method for recovering tungsten comprises the following steps:
evaporating and concentrating the waste alkali liquor until the mass concentration of sodium hydroxide is 20wt.%, cooling, crystallizing and filtering to obtain pretreated crystals;
dissolving the pretreatment crystals to obtain a pretreatment solution;
adding an acid solution into the pretreatment solution, adjusting the pretreatment solution to a first preset pH value, and performing a removal reaction of carbonate ions to obtain a primary treatment solution;
adding sodium hydroxide into the primary treatment liquid, and adjusting the primary treatment liquid to a second preset pH value to obtain a secondary treatment liquid, wherein the second preset pH value is greater than 7;
adding magnesium sulfate into the secondary treatment liquid for precipitation reaction at least according to the contents of arsenic element, silicon element and phosphorus element in the secondary treatment liquid, and filtering to obtain primary filtrate;
adding calcium oxide into the primary filtrate according to the content of the tungsten element to perform precipitation reaction again, and filtering to obtain a secondary precipitate containing the tungsten element;
and cleaning the secondary precipitate, and filtering to obtain a recovered product, namely the scheelite concentrate.
2. The method for recovering tungsten according to claim 1, wherein the pretreatment crystals are dissolved with deionized water to obtain the pretreatment solution.
3. The method for recovering tungsten according to claim 2, wherein the mass ratio of the deionized water for dissolving the pretreatment crystals to the pretreatment crystals is in the range of 1: 1-4: 1.
4. the method for recovering tungsten according to claim 1, wherein the pH value of the pretreatment solution is adjusted to the first preset pH value by using a sulfuric acid solution.
5. The method for recovering tungsten according to claim 1, wherein the first predetermined pH value is 4.0 to 7.0.
6. The method for recovering tungsten according to claim 1, wherein the second predetermined pH value is 10.0 to 12.0.
7. The method for recovering tungsten according to claim 1, wherein the molar amount of magnesium sulfate added to the secondary treatment liquid is 1.0 to 1.5 times the sum of the molar amounts of arsenic, silicon and phosphorus in the secondary treatment liquid.
8. The method for recovering tungsten according to claim 1, wherein the molar amount of calcium oxide added to the primary filtrate is 1.0 to 1.5 times the molar amount of the tungsten element in the primary filtrate.
9. The method for recovering tungsten according to claim 1, wherein the secondary precipitate is washed with deionized water, filtered and dried to obtain a recovered product, namely scheelite concentrate.
10. Use of the method for recovering tungsten from spent wash from regeneration of spent SCR catalyst according to any one of claims 1 to 9 in a treatment process for recovering spent SCR catalyst.
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