CN112142073A - Method for resource utilization of chromium-containing sodium bisulfate - Google Patents
Method for resource utilization of chromium-containing sodium bisulfate Download PDFInfo
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- CN112142073A CN112142073A CN201910580516.0A CN201910580516A CN112142073A CN 112142073 A CN112142073 A CN 112142073A CN 201910580516 A CN201910580516 A CN 201910580516A CN 112142073 A CN112142073 A CN 112142073A
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 138
- 239000011651 chromium Substances 0.000 title claims abstract description 138
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 title claims abstract description 127
- 229910000342 sodium bisulfate Inorganic materials 0.000 title claims abstract description 127
- 238000000034 method Methods 0.000 title claims abstract description 47
- 239000003463 adsorbent Substances 0.000 claims abstract description 53
- 238000000926 separation method Methods 0.000 claims abstract description 29
- 238000001704 evaporation Methods 0.000 claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 24
- JXAZAUKOWVKTLO-UHFFFAOYSA-L sodium pyrosulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OS([O-])(=O)=O JXAZAUKOWVKTLO-UHFFFAOYSA-L 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 16
- 239000007791 liquid phase Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 4
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims description 33
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 23
- 229910001430 chromium ion Inorganic materials 0.000 claims description 20
- 229920000642 polymer Polymers 0.000 claims description 20
- 238000002425 crystallisation Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 16
- 230000008020 evaporation Effects 0.000 claims description 15
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 14
- 238000001179 sorption measurement Methods 0.000 claims description 14
- 239000006227 byproduct Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 238000004064 recycling Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 11
- 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 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 9
- 238000003795 desorption Methods 0.000 claims description 9
- 239000003456 ion exchange resin Substances 0.000 claims description 9
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 9
- 235000010265 sodium sulphite Nutrition 0.000 claims description 7
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 6
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 6
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 6
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 6
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 5
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 4
- MILMJAFFMWCPLL-UHFFFAOYSA-J sodium;chromium(3+);disulfate Chemical compound [Na+].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MILMJAFFMWCPLL-UHFFFAOYSA-J 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 2
- 230000003068 static effect Effects 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 2
- 239000002952 polymeric resin Substances 0.000 claims 1
- 229920003002 synthetic resin Polymers 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 11
- 230000008901 benefit Effects 0.000 abstract description 8
- 239000000243 solution Substances 0.000 description 72
- 239000000047 product Substances 0.000 description 39
- 239000000706 filtrate Substances 0.000 description 30
- 238000001914 filtration Methods 0.000 description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 16
- 239000012065 filter cake Substances 0.000 description 12
- KIEOKOFEPABQKJ-UHFFFAOYSA-N sodium dichromate Chemical compound [Na+].[Na+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KIEOKOFEPABQKJ-UHFFFAOYSA-N 0.000 description 7
- 150000001845 chromium compounds Chemical class 0.000 description 6
- 239000002699 waste material Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 229910000423 chromium oxide Inorganic materials 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- PXLIDIMHPNPGMH-UHFFFAOYSA-N sodium chromate Chemical compound [Na+].[Na+].[O-][Cr]([O-])(=O)=O PXLIDIMHPNPGMH-UHFFFAOYSA-N 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001844 chromium Chemical class 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002535 acidifier Substances 0.000 description 1
- 229940095602 acidifiers Drugs 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/16—Purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a method for resource utilization of chromium-containing sodium bisulfate, which comprises the following steps: dissolving chromium-containing sodium bisulfate, performing solid-liquid separation, and adding a reducing agent into the obtained liquid phase for reaction; and mixing the reacted solution with an adsorbent, adsorbing, carrying out solid-liquid separation, and evaporating, cooling and crystallizing the obtained liquid phase to obtain anhydrous sodium bisulfate. According to the invention, the chromium in the chromium-containing sodium bisulfate is reduced and selectively adsorbed, so that the separation of components in the chromium-containing sodium bisulfate is realized, the chromium is harmless, the sodium bisulfate is purified, the purity of an anhydrous sodium bisulfate product can reach more than 98%, the further prepared sodium pyrosulfate has the purity of more than 95%, and the added value of the product is high; the method has the advantages of simple process, renewable and recyclable adsorbent, low operation and raw material cost, and good economic benefit and application prospect.
Description
Technical Field
The invention belongs to the technical field of solid waste utilization, and relates to a resource utilization method of chromium-containing sodium bisulfate.
Background
The chromium-containing sodium bisulfate is one of solid wastes generated in the traditional chromium salt industry, about 1.3 tons of chromium-containing sodium bisulfate can be generated when 1 ton of chromic anhydride is produced, wherein chromium mainly exists in a hexavalent chromium form, and has strong toxicity, high acid value and strong corrosivity; the sodium bisulfate can be used as dyeing assistants, cleaning agents, preservatives, acidifiers and the like, has wide application and higher added value, and can easily cause serious environmental pollution and resource waste if directly discharged. Based on the above-mentioned characteristics of chromium-containing sodium hydrogensulfate, it is necessary to perform a harmless treatment and a resource utilization.
At present, the most common utilization method of chromium-containing sodium bisulfate is a comprehensive recycling method, the chromium-containing sodium bisulfate is recycled to a chromium salt production system to replace sulfuric acid for neutralizing a sodium chromate alkaline solution and an acidification process of a sodium chromate solution, but a large amount of impurity elements such as iron, aluminum, vanadium and the like are enriched in the chromium-containing sodium bisulfate, so that the product quality is greatly influenced, and the recycling of the chromium-containing sodium bisulfate is limited. Therefore, the relevant practitioners have also been conducting new research on recycling chromium-containing sodium bisulfate.
CN 106395904A discloses a method for producing chromium oxide green by using chromium-containing sodium bisulfate, which comprises the steps of directly reducing the chromium-containing sodium bisulfate by using a reducing agent, adjusting the pH value of a feed liquid to be neutral, filtering to obtain a chromium hydroxide filter cake, and roasting at high temperature to obtain a chromium oxide green product; CN 102351247A discloses a method for producing chromium oxide black by using a chromic anhydride by-product sodium bisulfate, which comprises the steps of reducing the chromic anhydride by-product solid sodium bisulfate, adding waste scrap iron, heating and dissolving, adjusting the pH value, introducing air, and roasting the obtained precipitate at high temperature to obtain the chromium oxide black pigment. The method has the advantages of high roasting temperature, relatively high energy consumption, complex chromium-containing sodium bisulfate component and limited purity of the obtained product.
CN 104445284A discloses a method for separating and recovering anhydrous sodium sulfate, concentrated sulfuric acid and chromium from chromium-containing sodium bisulfate, wherein chromium-containing sodium bisulfate is subjected to heat preservation treatment, then is placed in alcohol for countercurrent extraction and is filtered to form a mixed solution of the alcohol and the sulfuric acid and solid chromium-containing sodium sulfate, the mixed solution of the alcohol and the sulfuric acid is evaporated, the sulfuric acid and the alcohol are separated, and the solid chromium-containing sodium sulfate is leached and filtered to obtain a sodium sulfate solution and a chromium-containing filter cake.
In conclusion, for recycling chromium-containing sodium bisulfate, a new utilization way needs to be found, which can realize the sufficient separation of components and obtain products with high added value.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a resource utilization method of chromium-containing sodium bisulfate, which is characterized in that hexavalent chromium is reduced after the chromium-containing sodium bisulfate is dissolved, then the chromium is selectively adsorbed, and then products with high added values are recovered from the rest solution, so that the separation, recovery and utilization of valuable components in the chromium-containing sodium bisulfate waste are realized, and the application value is high.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for resource utilization of chromium-containing sodium bisulfate, which comprises the following steps:
(1) dissolving chromium-containing sodium bisulfate, performing solid-liquid separation, and adding a reducing agent into the obtained liquid phase for reaction;
(2) and (2) mixing the solution reacted in the step (1) with an adsorbent, adsorbing, then carrying out solid-liquid separation, and evaporating, cooling and crystallizing the obtained liquid phase to obtain anhydrous sodium bisulfate.
In the invention, after the chromium-containing sodium bisulfate waste is dissolved, water insoluble substances, mainly sodium chromium sulfate, are separated, a reducing agent is added into the obtained liquid phase, hexavalent chromium is reduced into trivalent chromium, new impurity ions are not introduced at the same time, the trivalent chromium is absorbed by selecting a proper adsorbent, the adsorbent is regenerated after solid-liquid separation, and the anhydrous sodium bisulfate product is prepared by liquid-phase evaporation; the method realizes the separation of components in the chromium-containing sodium bisulfate and performs resource utilization, thereby not only solving the problem of toxic hazard of wastes, but also obtaining high-valued products; simple process, low cost, and good economic benefit and application prospect.
The following technical solutions are preferred technical solutions of the present invention, but not limited to the technical solutions provided by the present invention, and technical objects and advantageous effects of the present invention can be better achieved and achieved by the following technical solutions.
As a preferable technical scheme of the invention, the chromium-containing sodium bisulfate in the step (1) is a byproduct generated in the chromic anhydride production process.
In the invention, chromium-containing sodium bisulfate is a byproduct generated in a chromic anhydride production process, wherein the chromic anhydride production process comprises two processes, one process is to prepare the chromic anhydride by using sodium bichromate and concentrated sulfuric acid as raw materials and adopting a melt crystallization method; secondly, sodium chromate/sodium dichromate and sulfuric acid are used as raw materials and prepared by a solution crystallization method; generally, chromium in the chromium-containing sodium bisulfate by-product obtained by a melt crystallization method exists in the forms of hexavalent chromium, soluble trivalent chromium and water-insoluble substances, while chromium in the chromium-containing sodium bisulfate by-product obtained by a solution crystallization method mainly exists in the form of hexavalent chromium and basically does not contain trivalent chromium and water-insoluble substances.
Preferably, the hexavalent chromium content of the chromium-containing sodium bisulfate of step (1) is 2 to 3 wt%, such as 2 wt%, 2.2 wt%, 2.4 wt%, 2.6 wt%, 2.8 wt%, or 3 wt%, but not limited to the recited values, and other unrecited values within the range of the recited values are also applicable, wherein the hexavalent chromium content is Na2Cr2O7·2H2And (4) measuring O.
Preferably, the chromium-containing sodium bisulfate of step (1) is dissolved with water.
Preferably, the temperature for the dissolution in step (1) is 20 to 100 ℃, for example 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 80 ℃ or 100 ℃, but not limited to the recited values, and other values not recited within the range of the values are also applicable, preferably 20 to 80 ℃, and more preferably 25 to 60 ℃.
Preferably, the dissolving time in step (1) is 0.1 to 48 hours, such as 0.1 hour, 0.5 hour, 1 hour, 2 hours, 4 hours, 8 hours, 16 hours, 24 hours, 36 hours or 48 hours, but not limited to the recited values, and other values not recited in the range of the values are also applicable, preferably 0.1 to 24 hours, and more preferably 0.5 to 4 hours.
Preferably, the mass ratio of the volume of water used for dissolution in step (1) to chromium-containing sodium hydrogensulfate is not less than 3mL:1g, for example, 3mL:1g, 4mL:1g, 5mL:1g, 6mL:1g, 8mL:1g, 10mL:1g, 12mL:1g, or 15mL:1g, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned numerical range are also applicable, and preferably (3-10) mL:1g, and more preferably (3-5) mL:1 g.
As a preferable technical scheme of the invention, the liquid phase obtained by the solid-liquid separation in the step (1) is a sodium hydrogen sulfate solution containing hexavalent chromium, and the obtained solid phase comprises sodium chromium sulfate.
Preferably, the reducing agent in step (1) comprises any one of sodium sulfite, sodium bisulfite, sodium metabisulfite or sodium thiosulfate, or a combination of at least two of them, typical but non-limiting examples being: combinations of sodium sulfite and sodium bisulfite, sodium metabisulfite and sodium thiosulfate, sodium sulfite, sodium bisulfite and sodium metabisulfite, sodium sulfite, sodium metabisulfite and sodium thiosulfate, and the like.
Preferably, the reducing agent of step (1) is added in an amount at least sufficient to completely reduce the hexavalent chromium in the solution.
In the invention, the addition of the reducing agent is required to meet the requirement that no new impurity ions are introduced into the solution, and the products after the reaction of the selected reducing agent are original sodium ions and sulfate ions in the solution. In order to ensure complete reduction of hexavalent chromium, the addition amount of the reducing agent is slightly more than the theoretical amount, but is not too much, generally the addition amount is not more than 1.1 times of the theoretical amount, otherwise the purity of a crystallized product is influenced; the reduction end point is confirmed by detecting whether hexavalent chromium ions exist in the solution.
In a preferred embodiment of the present invention, the temperature of the reaction in the step (1) is 20 to 100 ℃, for example, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 80 ℃ or 100 ℃, but not limited to the above-mentioned values, and other values not shown in the above-mentioned value range are also applicable, preferably 20 to 80 ℃, and more preferably 30 to 60 ℃.
Preferably, the reaction mode of the step (1) is static reduction or dynamic reduction, and preferably dynamic reduction.
Preferably, the dynamic reduction comprises dynamic agitation reduction.
Preferably, the reaction time in step (1) is not less than 0.2h, such as 0.2h, 0.5h, 1h, 2h, 3h, 4h, 8h, 16h, 24h or 36h, but not limited to the recited values, and other values not recited in the range of the values are also applicable, preferably 0.5 to 24h, and more preferably 0.5 to 3 h.
Preferably, after the reaction described in step (1), the solution is controlled to a pH of less than 2, for example 1.9, 1.6, 1.4, 1.2, 1.0 or 0.8, but not limited to the values recited, and other values not recited within this range are equally applicable, preferably less than 1.5.
In the invention, the chromium-containing sodium bisulfate contains free sulfuric acid, the acid value of the solution after dissolution is very low, the precipitation condition of the sodium bisulfate can be basically met, and if the pH value does not meet the condition, the pH value can be adjusted by adding sulfuric acid to ensure the precipitation of the sodium bisulfate.
As a preferred technical solution of the present invention, the adsorbent in step (2) is an adsorbent capable of selectively adsorbing trivalent chromium, preferably any one of or a combination of at least two of a chromium ion imprinted polymer, a chromium ion non-imprinted polymer or an ion exchange resin, and typical but non-limiting examples of the combination are: a combination of a chromium ion imprinted polymer and a chromium ion non-imprinted polymer, a combination of a chromium ion imprinted polymer and an ion exchange resin, a combination of a chromium ion imprinted polymer, a chromium ion non-imprinted polymer and an ion exchange resin, and the like.
Preferably, the chromium ion imprinted polymer, the chromium ion non-imprinted polymer or the ion exchange resin independently contains any one of a phosphonic acid group, a sulfonic acid group or a carboxylic acid group.
In the invention, the imprinted polymer has a vacancy for identifying special molecular imprinting, can only adsorb special ions and has good selectivity, and the non-imprinted polymer and the ion exchange resin can adsorb by depending on the selectivity of functional groups.
Preferably, the adsorbent in step (2) is used in an amount at least sufficient to completely adsorb trivalent chromium.
In the invention, the adsorption capacities of different adsorbents are different, wherein the adsorption capacity of the chromium ion imprinted polymer is about 15-30 mg/g, the adsorption capacity of the chromium ion non-imprinted polymer is about 10-20 mg/g, and the adsorption capacity of the ion exchange resin is about 100-200 mg/g.
Preferably, the adsorbent is added to the solution after the reaction in step (1) in step (2).
In a preferred embodiment of the present invention, the temperature of adsorption in step (2) is 20 to 100 ℃, for example, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 80 ℃ or 100 ℃, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range of values are also applicable, and preferably 20 to 50 ℃.
Preferably, the adsorption time in step (2) is not less than 0.1h, such as 0.1h, 0.5h, 1h, 2h, 4h, 8h, 16h, 24h or 36h, but not limited to the recited values, and other values not recited in the range of the values are also applicable, preferably 0.5 to 24h, and more preferably 0.5 to 4 h.
In a preferred embodiment of the present invention, the temperature of the evaporation in the step (2) is 80 to 200 ℃, for example, 80 ℃, 100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃, or 200 ℃, but not limited to the above-mentioned values, and other values not shown in the above-mentioned value range are also applicable, preferably 80 to 150 ℃, and more preferably 80 to 120 ℃.
Preferably, the absolute pressure of the evaporation in step (2) is 0.02 to 0.1MPa, such as 0.02MPa, 0.04MPa, 0.06MPa, 0.08MPa, 0.09MPa or 0.1MPa, but not limited to the values listed, and other values not listed in the numerical range are also applicable, i.e., the evaporation can be carried out under normal pressure or reduced pressure.
Preferably, the evaporation end point of the step (2) is that the solution is saturated and crystals are precipitated.
Preferably, the cooling crystallization in step (2) is carried out to a temperature of 30 to 80 ℃, for example 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃ or 80 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable, preferably 60 to 70 ℃.
Preferably, the solid-liquid separation temperature after the cooling crystallization in the step (2) is 30 to 80 ℃, for example, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃ or 80 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable, preferably 60 to 70 ℃.
In the invention, the evaporation operation is carried out until the solution is saturated, crystals are separated out, then the heating is stopped, a large amount of crystals are continuously separated out in the cooling process, and then the solid-liquid separation is carried out by keeping the temperature. The purity of the anhydrous sodium bisulfate product obtained after evaporation crystallization treatment reaches more than 98 percent, and the product quality meets the requirements of HG/T4516-2013.
As a preferable technical scheme of the invention, the solid phase obtained by the solid-liquid separation in the step (2) is desorbed to obtain the regenerated adsorbent.
Preferably, the desorbent used for desorption is a lye, preferably any one or a combination of at least two of NaOH solution, KOH solution or ammonia, as typical but non-limiting examples: a combination of a NaOH solution and a KOH solution, a combination of a KOH solution and ammonia water, a combination of a NaOH solution, a KOH solution and ammonia water, and the like.
Preferably, the concentration of the alkali liquor is not less than 0.01mol L-1For example 0.01mol L-1、0.1mol L-1、0.5mol L-1、1mol L-1、2mol L-1、3mol L-1、4mol L-1、5mol L-1Or 6mol L-1And the like, but not limited to the recited values, and other values not recited within the numerical range are also applicable, and 1 to 5mol L is preferable-1。
Preferably, the desorption time is not less than 0.1 hour, for example, 0.1 hour, 0.5 hour, 1 hour, 2 hours, 4 hours, 8 hours, 16 hours, 24 hours or 36 hours, but is not limited to the recited values, and other values not recited in the range of the values are also applicable, preferably 0.5 to 24 hours, and more preferably 1 to 4 hours.
Preferably, the regenerated adsorbent obtained after desorption is recycled.
In the present invention, the adsorbent is regenerated to obtain a solution containing trivalent chromium, which can be used as a raw material for producing chromium compounds in the chromium chemical industry.
As a preferable technical scheme of the invention, the anhydrous sodium bisulfate obtained in the step (2) is heated to prepare the sodium pyrosulfate.
Preferably, the heating temperature is 315 to 460 ℃, such as 315 ℃, 320 ℃, 340 ℃, 360 ℃, 380 ℃, 400 ℃, 420 ℃, 440 ℃ or 460 ℃, but not limited to the recited values, and other values not recited within the range of values are also applicable, preferably 320 to 450 ℃.
Preferably, the heating time is not less than 0.1h, for example, 0.1h, 0.5h, 1h, 2h, 3h, 4h, 6h, 8h or 10h, but is not limited to the recited values, and other values not recited in the range of the values are also applicable, preferably 0.5 to 10h, and more preferably 1 to 3 h.
In the invention, anhydrous sodium bisulfate can be heated to prepare sodium pyrosulfate, the heating mode can be conventional heating or microwave heating, the added value of the product is further improved, the purity of the obtained sodium pyrosulfate product is more than 95%, and the quality meets the standard requirement of Q/HXSJ 6312016.
As a preferred technical scheme of the invention, the method comprises the following steps:
(1) dissolving chromium-containing sodium bisulfate in water at the dissolving temperature of 20-100 ℃ for 0.1-48 h, wherein the liquid-solid ratio in dissolving is not less than 3mL:1g, and then carrying out solid-liquid separation to obtain a sodium bisulfate solution containing hexavalent chromium;
(2) adding a reducing agent into the solution obtained in the step (1) for reaction, wherein the adding amount of the reducing agent at least meets the requirement of completely reducing hexavalent chromium in the solution, the reaction temperature is 20-100 ℃, and the reaction time is not less than 0.2h, so as to obtain a sodium bisulfate solution containing trivalent chromium;
(3) adding an adsorbent into the solution obtained in the step (2) for adsorption, wherein the adsorption temperature is 20-100 ℃, the adsorption time is not less than 0.1h, the dosage of the adsorbent at least meets the requirement of completely adsorbing trivalent chromium, and then carrying out solid-liquid separation to obtain a chromium-containing adsorbent and a chromium-free sodium bisulfate solution;
(4) evaporating the solution obtained in the step (3) at the evaporation temperature of 80-200 ℃ and the absolute evaporation pressure of 0.02-0.1 MPa until the solution is saturated, separating out crystals, cooling for crystallization, and then carrying out solid-liquid separation at the temperature of 30-80 ℃ to obtain anhydrous sodium bisulfate;
(5) desorbing the chromium-containing adsorbent obtained in the step (3), wherein the desorbent is alkali liquor, the desorption time is not less than 0.1h, and the obtained regenerated adsorbent is returned to the step (3) for recycling.
(6) And (4) heating the anhydrous sodium bisulfate obtained in the step (4) at 315-460 ℃ for not less than 0.1h to obtain sodium pyrosulfate.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the chromium in the chromium-containing sodium bisulfate is reduced and selectively adsorbed, so that the separation of components in the chromium-containing sodium bisulfate is realized, the chromium is harmless, the sodium bisulfate is purified, and the purity of an anhydrous sodium bisulfate product can reach more than 98%;
(2) the adsorbent used in the invention can be recycled after regeneration, and the anhydrous sodium bisulfate product can be used for further preparing sodium pyrosulfate, the purity reaches more than 95%, and the added value of the product is high;
(3) the method has the advantages of simple process, low operation and raw material cost, and good economic benefit and application prospect.
Drawings
FIG. 1 is a process flow chart of a method for recycling chromium-containing sodium bisulfate provided in embodiment 1 of the present invention.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the following embodiments are only simple examples of the present invention and do not represent or limit the scope of the present invention, which is defined by the claims.
The specific embodiment of the invention provides a method for resource utilization of chromium-containing sodium bisulfate, which comprises the following steps:
(1) dissolving chromium-containing sodium bisulfate, performing solid-liquid separation, and adding a reducing agent into the obtained liquid phase for reaction;
(2) and (2) mixing the solution reacted in the step (1) with an adsorbent, adsorbing, then carrying out solid-liquid separation, and evaporating, cooling and crystallizing the obtained liquid phase to obtain anhydrous sodium bisulfate.
The following are typical but non-limiting examples of the invention:
example 1:
the embodiment provides a method for resource utilization of chromium-containing sodium bisulfate, and a process flow chart of the method is shown in figure 1, and the method comprises the following steps:
(1) dissolving 1000g of chromium-containing sodium hydrogen sulfate which is a byproduct of chromic anhydride production by a melt crystallization method in 4L of water at 30 ℃ for 4h, wherein hexavalent chromium is Na2Cr2O7·2H2The content of O is 3 wt%, and the soluble trivalent chromium is Cr2O3The calculated content is 0.5 wt%, filtering to obtain hexavalent chromium-containing filtrate and a chromium-containing filter cake, adding 32g of sodium bisulfite into the hexavalent chromium-containing filtrate, and reacting for 2 hours at 40 ℃ to obtain a trivalent chromium-containing sodium bisulfate solution;
(2) adding 540g of chromium ion imprinted polymer into the solution obtained in the step (1), adsorbing for 1h at 40 ℃, and filtering to obtain a chromium-containing adsorbent and a chromium-free sodium bisulfate solution;
(3) 0.05mol L of the chromium-containing adsorbent obtained in the step (2)-1Desorbing the NaOH solution for 4 hours, filtering to obtain a regenerated adsorbent and chromium-containing filtrate, and returning the regenerated adsorbent to the step (2) for recycling;
(4) and (3) evaporating the solution obtained in the step (2) at 100 ℃ under normal pressure until crystals are separated out from the solution, cooling and crystallizing, filtering at 70 ℃ to obtain an anhydrous sodium bisulfate product and a filtrate, returning the filtrate to be evaporated and crystallized again, and heating the anhydrous sodium bisulfate at 320 ℃ for 4 hours to obtain a sodium pyrosulfate product.
In the embodiment, the chromium-containing sodium bisulfate is treated, and the chromium-containing filter cake in the step (1) and the chromium-containing filtrate in the step (3) can be used as raw materials for producing chromium compounds; the purity of the anhydrous sodium bisulfate product in the step (4) can reach 98.5 percent, and the purity of the sodium pyrosulfate product reaches 95.0 percent.
Example 2:
the embodiment provides a method for resource utilization of chromium-containing sodium bisulfate, which comprises the following steps:
(1) dissolving 1000g of chromium-containing sodium bisulfate in 5L of water at 50 ℃ for 3h, wherein the chromium-containing sodium bisulfate is a byproduct in chromic anhydride production by a solution crystallization method, and hexavalent chromium is Na2Cr2O7·2H2The content of O is 2.5 wt%, filtering to obtain hexavalent chromium-containing filtrate and chromium-containing filter cake, adding 35g of sodium sulfite into the hexavalent chromium-containing filtrate, and reacting at 60 ℃ for 1.2h to obtain trivalent chromium-containing sodium bisulfate solution;
(2) adding 460g of chromium ion non-imprinted polymer into the solution obtained in the step (1), adsorbing for 0.8h at the temperature of 60 ℃, and filtering to obtain a chromium-containing adsorbent and a chromium-free sodium bisulfate solution;
(3) adopting 1mol L of the chromium-containing adsorbent obtained in the step (2)-1Desorbing the KOH solution for 1 hour, filtering to obtain a regenerated adsorbent and chromium-containing filtrate, and returning the regenerated adsorbent to the step (2) for recycling;
(4) evaporating the solution obtained in the step (2) at 120 ℃ and under the absolute pressure of 0.06MPa until crystals are separated out from the solution, cooling and crystallizing, filtering at 60 ℃ to obtain an anhydrous sodium bisulfate product and a filtrate, returning the filtrate to be evaporated and crystallized again, and heating the anhydrous sodium bisulfate at 350 ℃ for 3 hours to obtain a sodium pyrosulfate product.
In the embodiment, the chromium-containing sodium bisulfate is treated, and the chromium-containing filter cake in the step (1) and the chromium-containing filtrate in the step (3) can be used as raw materials for producing chromium compounds; the purity of the anhydrous sodium bisulfate product in the step (4) can reach 98.7 percent, and the purity of the sodium pyrosulfate product reaches 95.5 percent.
Example 3:
the embodiment provides a method for resource utilization of chromium-containing sodium bisulfate, which comprises the following steps:
(1) dissolving 1000g of chromium-containing sodium hydrogen sulfate which is a byproduct of chromic anhydride production by a melt crystallization method in 3L of water at 60 ℃ for 2.5h, wherein hexavalent chromium is Na2Cr2O7·2H2The content of O is 2wt percent, and the soluble trivalent chromium is Cr2O3The calculated content is 1 wt%, filtering to obtain hexavalent chromium-containing filtrate and a chromium-containing filter cake, adding 25g of sodium sulfite and sodium bisulfite into the hexavalent chromium-containing filtrate, and reacting for 1h at 80 ℃ to obtain trivalent chromium-containing sodium bisulfate solution;
(2) adding 100g of ion exchange resin into the solution obtained in the step (1), adsorbing for 0.5h at the temperature of 80 ℃, and filtering to obtain a chromium-containing adsorbent and a chromium-free sodium bisulfate solution;
(3) adopting 0.5mol L of the chromium-containing adsorbent obtained in the step (2)-1Desorbing the ammonia water solution for 2 hours, filtering to obtain a regenerated adsorbent and a chromium-containing filtrate, and returning the regenerated adsorbent to the step (2) for recycling;
(4) evaporating the solution obtained in the step (2) at 80 ℃ and under the absolute pressure of 0.02MPa until crystals are separated out from the solution, cooling and crystallizing, filtering at 40 ℃ to obtain an anhydrous sodium bisulfate product and a filtrate, returning the filtrate to the evaporation and crystallization again, and heating the anhydrous sodium bisulfate at 400 ℃ for 1h to obtain a sodium pyrosulfate product.
In the embodiment, the chromium-containing sodium bisulfate is treated, and the chromium-containing filter cake in the step (1) and the chromium-containing filtrate in the step (3) can be used as raw materials for producing chromium compounds; the purity of the anhydrous sodium bisulfate product in the step (4) can reach 98.4 percent, and the purity of the sodium pyrosulfate product reaches 95.8 percent.
Example 4:
the embodiment provides a method for resource utilization of chromium-containing sodium bisulfate, which comprises the following steps:
(1) dissolving 1000g of chromium-containing sodium bisulfate in 10L of water at 20 ℃ for 12h, wherein the chromium-containing sodium bisulfate is a byproduct in chromic anhydride production by a solution crystallization method, and hexavalent chromium is Na2Cr2O7·2H2The content of O is 2.7 wt%, filtering is carried out to obtain hexavalent chromium-containing filtrate and chromium-containing filter cake, 10.8g of sodium thiosulfate is added into the hexavalent chromium-containing filtrate, and reaction is carried out for 8 hours at the temperature of 30 ℃ to obtain trivalent chromium-containing sodium bisulfate solution;
(2) adding 405g of chromium ion imprinted polymer into the solution obtained in the step (1), adsorbing for 10h at the temperature of 30 ℃, and filtering to obtain a chromium-containing adsorbent and a chromium-free sodium bisulfate solution;
(3) 2mol L of the chromium-containing adsorbent obtained in the step (2)-1Desorbing NaOH solution for 0.6h, filtering to obtain a regenerated adsorbent and chromium-containing filtrate, and returning the regenerated adsorbent to the step (2) for recycling;
(4) evaporating the solution obtained in the step (2) at 150 ℃ under normal pressure until crystals are separated out from the solution, cooling and crystallizing, filtering at 65 ℃ to obtain an anhydrous sodium bisulfate product and a filtrate, returning the filtrate to be evaporated and crystallized again, and heating the anhydrous sodium bisulfate at 450 ℃ for 0.2h to obtain a sodium pyrosulfate product.
In the embodiment, the chromium-containing sodium bisulfate is treated, and the chromium-containing filter cake in the step (1) and the chromium-containing filtrate in the step (3) can be used as raw materials for producing chromium compounds; the purity of the anhydrous sodium bisulfate product in the step (4) can reach 98.1 percent, and the purity of the sodium pyrosulfate product reaches 96.0 percent.
Example 5:
the embodiment provides a method for resource utilization of chromium-containing sodium bisulfate, which comprises the following steps:
(1) dissolving 1000g of chromium-containing sodium bisulfate in 6L of water at 90 ℃ for 0.1h, wherein the chromium-containing sodium bisulfate is a byproduct in chromic anhydride production by a solution crystallization method, and hexavalent chromium is Na2Cr2O7·2H2The content of O is 3 weight percent, filtering is carried out to obtain hexavalent chromium-containing filtrate and a chromium-containing filter cake, 30g of sodium metabisulfite is added into the hexavalent chromium-containing filtrate, and the mixture reacts for 0.2h at the temperature of 90 ℃ to obtain trivalent chromium-containing sodium bisulfate solution;
(2) adding 580g of chromium ion non-imprinted polymer into the solution obtained in the step (1), adsorbing for 0.4h at the temperature of 80 ℃, and filtering to obtain a chromium-containing adsorbent and a chromium-free sodium bisulfate solution;
(3) 4mol L of the chromium-containing adsorbent obtained in the step (2)-1Desorbing NaOH solution for 0.2h, filtering to obtain a regenerated adsorbent and chromium-containing filtrate, and returning the regenerated adsorbent to the step (2) for recycling;
(4) evaporating the solution obtained in the step (2) at 200 ℃ under normal pressure until crystals are separated out from the solution, cooling and crystallizing, filtering at 80 ℃ to obtain an anhydrous sodium bisulfate product and a filtrate, returning the filtrate to be evaporated and crystallized again, and heating the anhydrous sodium bisulfate at 360 ℃ for 2.5 hours to obtain a sodium pyrosulfate product.
In the embodiment, the chromium-containing sodium bisulfate is treated, and the chromium-containing filter cake in the step (1) and the chromium-containing filtrate in the step (3) can be used as raw materials for producing chromium compounds; the purity of the anhydrous sodium bisulfate product in the step (4) can reach 98.2 percent, and the purity of the sodium pyrosulfate product reaches 95.2 percent.
The synthesis of the above embodiments shows that the separation of components in the chromium-containing sodium bisulfate is realized by reducing and selectively adsorbing chromium in the chromium-containing sodium bisulfate, the chromium is harmless, and the anhydrous sodium bisulfate product is obtained by crystallization, the purity of the anhydrous sodium bisulfate product can reach more than 98%, and the further prepared sodium pyrosulfate product has higher added value; the method has the advantages of simple process, renewable and recyclable adsorbent, low operation and raw material cost, and good economic benefit and application prospect.
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 does not mean that the present invention must rely on the above methods for its implementation. It will be apparent to those skilled in the art that any modifications to the invention, equivalents of the materials used, additions of auxiliary materials, and operations, and selection of particular means, are within the scope and disclosure of the invention.
Claims (10)
1. A method for resource utilization of chromium-containing sodium bisulfate is characterized by comprising the following steps:
(1) dissolving chromium-containing sodium bisulfate, performing solid-liquid separation, and adding a reducing agent into the obtained liquid phase for reaction;
(2) and (2) mixing the solution reacted in the step (1) with an adsorbent, adsorbing, then carrying out solid-liquid separation, and evaporating, cooling and crystallizing the obtained liquid phase to obtain anhydrous sodium bisulfate.
2. The method of claim 1, wherein the chromium-containing sodium bisulfate of step (1) is a byproduct generated in a chromic anhydride production process;
preferably, the content of hexavalent chromium in the chromium-containing sodium hydrogen sulfate in the step (1) is 2-3 wt%;
preferably, the chromium-containing sodium bisulfate in the step (1) is dissolved by water;
preferably, the dissolving temperature in the step (1) is 20-100 ℃, preferably 20-80 ℃, and further preferably 25-60 ℃;
preferably, the dissolving time in the step (1) is 0.1-48 h, preferably 0.1-24 h, and further preferably 0.5-4 h;
preferably, the mass ratio of the volume of the water for dissolving in the step (1) to the chromium-containing sodium bisulfate is not less than 3mL to 1g, preferably (3-10) mL to 1g, and more preferably (3-5) mL to 1 g.
3. The process according to claim 1 or 2, wherein the liquid phase obtained by the solid-liquid separation in step (1) is a sodium hydrogen sulfate solution containing hexavalent chromium, and the obtained solid phase comprises sodium chromium sulfate;
preferably, the reducing agent in step (1) comprises any one or a combination of at least two of sodium sulfite, sodium bisulfite, sodium metabisulfite or sodium thiosulfate;
preferably, the reducing agent of step (1) is added in an amount at least sufficient to completely reduce the hexavalent chromium in the solution.
4. The process according to any one of claims 1 to 3, wherein the temperature of the reaction in step (1) is 20 to 100 ℃, preferably 20 to 80 ℃, and more preferably 30 to 60 ℃;
preferably, the reaction mode of the step (1) is static reduction or dynamic reduction, preferably dynamic reduction;
preferably, the dynamic reduction comprises dynamic agitation reduction;
preferably, the reaction time in the step (1) is not less than 0.2h, preferably 0.5-24 h, and further preferably 0.5-3 h;
preferably, after the reaction described in step (1), the solution needs to be controlled to a pH of less than 2, preferably less than 1.5.
5. The method according to any one of claims 1 to 4, wherein the adsorbent in step (2) is an adsorbent capable of selectively adsorbing trivalent chromium, preferably any one of or a combination of at least two of chromium ion imprinted polymer, chromium ion non-imprinted polymer or ion exchange resin;
preferably, the chromium ion imprinted polymer, the chromium ion non-imprinted polymer or the ion exchange resin independently contain any one or a combination of at least two of phosphonic acid groups, sulfonic acid groups or carboxylic acid groups;
preferably, the adsorbent in the step (2) is used at least in an amount that the trivalent chromium is completely adsorbed;
preferably, the adsorbent is added to the solution after the reaction in step (1) in step (2).
6. The method according to any one of claims 1 to 5, wherein the temperature of the adsorption in step (2) is 20 to 100 ℃, preferably 20 to 50 ℃;
preferably, the adsorption time in the step (2) is not less than 0.1h, preferably 0.5-24 h, and further preferably 0.5-4 h.
7. The method according to any one of claims 1 to 6, wherein the temperature of the evaporation in step (2) is 80 to 200 ℃, preferably 80 to 150 ℃, and more preferably 80 to 120 ℃;
preferably, the absolute pressure of the evaporation in the step (2) is 0.02-0.1 MPa;
preferably, the evaporation end point of the step (2) is that the solution is saturated and crystals are separated out;
preferably, the cooling crystallization in the step (2) is carried out to the temperature of 30-80 ℃, preferably 60-70 ℃;
preferably, the solid-liquid separation is carried out after the cooling crystallization in the step (2), and the temperature of the solid-liquid separation is 30-80 ℃, preferably 60-70 ℃.
8. The method according to any one of claims 1 to 7, wherein the solid phase obtained by the solid-liquid separation in the step (2) is subjected to desorption to obtain a regenerated adsorbent;
preferably, the desorbent used for desorption is an alkali solution, preferably one or a combination of at least two of a NaOH solution, a KOH solution or ammonia water;
preferably, the concentration of the alkali liquor is not less than 0.01mol L-1Preferably 1 to 5mol L-1；
Preferably, the desorption time is not less than 0.1h, preferably 0.5-24 h, and further preferably 1-4 h;
preferably, the regenerated adsorbent obtained after desorption is recycled.
9. The process according to any one of claims 1 to 8, wherein the anhydrous sodium bisulfate obtained in step (2) is heated to produce sodium pyrosulfate;
preferably, the heating temperature is 315-460 ℃, and preferably 320-450 ℃;
preferably, the heating time is not less than 0.1h, preferably 0.5-10 h, and more preferably 1-3 h.
10. Method according to any of claims 1-9, characterized in that the method comprises the steps of:
(1) dissolving chromium-containing sodium bisulfate in water at the dissolving temperature of 20-100 ℃ for 0.1-48 h, wherein the liquid-solid ratio in dissolving is not less than 3mL:1g, and then carrying out solid-liquid separation to obtain a sodium bisulfate solution containing hexavalent chromium;
(2) adding a reducing agent into the solution obtained in the step (1) for reaction, wherein the adding amount of the reducing agent at least meets the requirement of completely reducing hexavalent chromium in the solution, the reaction temperature is 20-100 ℃, and the reaction time is not less than 0.2h, so as to obtain a sodium bisulfate solution containing trivalent chromium;
(3) adding an adsorbent into the solution obtained in the step (2) for adsorption, wherein the adsorption temperature is 20-100 ℃, the adsorption time is not less than 0.1h, the dosage of the adsorbent at least meets the requirement of completely adsorbing trivalent chromium, and then carrying out solid-liquid separation to obtain a chromium-containing adsorbent and a chromium-free sodium bisulfate solution;
(4) evaporating the solution obtained in the step (3) at the evaporation temperature of 80-200 ℃ and the absolute evaporation pressure of 0.02-0.1 MPa until the solution is saturated, separating out crystals, cooling for crystallization, and then carrying out solid-liquid separation at the temperature of 30-80 ℃ to obtain anhydrous sodium bisulfate;
(5) desorbing the chromium-containing adsorbent obtained in the step (3), wherein the desorbent is alkali liquor, the desorption time is not less than 0.1h, and the obtained regenerated adsorbent is returned to the step (3) for recycling.
(6) And (4) heating the anhydrous sodium bisulfate obtained in the step (4) at 315-460 ℃ for not less than 0.1h to obtain sodium pyrosulfate.
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| CN116947269A (en) * | 2023-09-20 | 2023-10-27 | 成都铬科高化工技术有限责任公司 | Method for recycling chromium and sodium salt from chromium-containing sodium bisulfate wastewater |
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Application publication date: 20201229 |