CN102115058A - A method for producing manganese phosphate and co-producing lithium sulfate and ammonium phosphate with manganese-containing waste liquid produced by hydroquinone - Google Patents
A method for producing manganese phosphate and co-producing lithium sulfate and ammonium phosphate with manganese-containing waste liquid produced by hydroquinone Download PDFInfo
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- CN102115058A CN102115058A CN2010106158468A CN201010615846A CN102115058A CN 102115058 A CN102115058 A CN 102115058A CN 2010106158468 A CN2010106158468 A CN 2010106158468A CN 201010615846 A CN201010615846 A CN 201010615846A CN 102115058 A CN102115058 A CN 102115058A
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- Prior art keywords
- phosphate
- manganese
- waste liquid
- ammonium phosphate
- lithium sulfate
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- 239000007788 liquid Substances 0.000 title claims abstract description 18
- 239000002699 waste material Substances 0.000 title claims abstract description 18
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 239000011572 manganese Substances 0.000 title claims abstract description 16
- 239000004254 Ammonium phosphate Substances 0.000 title claims abstract description 15
- 229910000148 ammonium phosphate Inorganic materials 0.000 title claims abstract description 15
- 235000019289 ammonium phosphates Nutrition 0.000 title claims abstract description 15
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 title claims abstract 12
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 title claims abstract 9
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 title claims abstract 9
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 title claims abstract 7
- 239000000047 product Substances 0.000 claims abstract description 10
- 239000000706 filtrate Substances 0.000 claims abstract 6
- 239000012065 filter cake Substances 0.000 claims abstract 3
- 238000001914 filtration Methods 0.000 claims abstract 3
- 238000000967 suction filtration Methods 0.000 claims abstract 3
- 239000013078 crystal Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 3
- 229910001386 lithium phosphate Inorganic materials 0.000 claims 2
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims 2
- 238000001816 cooling Methods 0.000 claims 1
- 238000002425 crystallisation Methods 0.000 claims 1
- 230000008025 crystallization Effects 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 238000004806 packaging method and process Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 238000005292 vacuum distillation Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 14
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000004821 distillation Methods 0.000 abstract 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 22
- 229910019142 PO4 Inorganic materials 0.000 description 6
- LFIWDPYJFLBDMX-UHFFFAOYSA-N lithium;sulfuric acid Chemical compound [Li].OS(O)(=O)=O LFIWDPYJFLBDMX-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- CCQLOTNQWSBPLX-UHFFFAOYSA-N manganese phosphoric acid Chemical compound [Mn].OP(O)(O)=O CCQLOTNQWSBPLX-UHFFFAOYSA-N 0.000 description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Substances OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- PYLLWONICXJARP-UHFFFAOYSA-N manganese silicon Chemical compound [Si].[Mn] PYLLWONICXJARP-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
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- Removal Of Specific Substances (AREA)
Abstract
The invention relates to the technical field of utilization of manganese-containing waste liquid generated in hydroquinone production, in particular to a method for preparing manganese phosphate and co-producing lithium sulfate and ammonium phosphate by using the manganese-containing waste liquid generated in hydroquinone production; the method mainly comprises the steps of carrying out suction filtration on waste liquid generated by hydroquinone by using a suction filter to obtain filtrate, distilling and filtering the filtrate, and deeply processing filter cakes to obtain manganese phosphate products; carrying out reduced pressure distillation on the filtrate, and then respectively carrying out further deep processing to obtain lithium sulfate and ammonium phosphate products; the invention can not only completely swallow the waste liquid, but also reduce the pollution of the waste liquid to the environment; and valuable manganese phosphate, lithium sulfate and ammonium phosphate products can be prepared, the method has remarkable social and economic benefits, and the process and production equipment are simple, so that the method is a relatively practical treatment and utilization method.
Description
Technical field
The present invention relates to produce the technical field that contains the manganese waste water utilization that Resorcinol produces, particularly a kind of with producing the method that the manganese waste liquid is made manganous phosphate co-producing sulfuric acid lithium and ammonium phosphate that contains that Resorcinol produced.
Technical background
Resorcinol is important organic intermediate, and China has also dropped into suitability for industrialized production in the development seventies in 20th century.Advantages such as at present domestic mainly taking used aniline-Manganse Dioxide explained hereafter Resorcinol, and this technology is compared with external phenol-hydrogen peroxide process, has the product purity height, and impurity is few.But its shortcoming is that the quantity discharged of waste liquid is big.Under the common state, one ton of Resorcinol of every production has 40 tons of Mn-bearing waste waters approximately.The chemical composition that contains manganese waste liquid the inside of Resorcinol is the content 11～12% of manganous sulfate, and ammonium sulfate content is 1.4～1.6%, and sulfuric acid content is 1.8～2.2%, simple substance element residue 5～6%.At present domestic factories' utilizations contain the manganese waste liquid and produce crystal manganous sulfate or common phosphoric acid salt, and high-purity phosphoric acid manganese etc.High-purity phosphoric acid manganese is ideal high performance strong magneticsubstance, is the main raw material of the manganese-silicon that developed rapidly modern age, mangal, high-performance manganese dioxide product.High-purity phosphoric acid manganese mainly is as soft magnet oxygen magneticsubstance at present, is that raw material is produced with electrolytic manganese or manganous sulfate, ammonium hydrogen phosphate etc. generally.But do not have a kind of at present with producing the relevant report that the manganese waste liquid is made the method for manganous phosphate co-producing sulfuric acid lithium and ammonium phosphate that contains that Resorcinol produced yet.
Summary of the invention
The invention provides that a kind of this method not only technology is simple with producing the method that the manganese waste liquid is made manganous phosphate co-producing sulfuric acid lithium and ammonium phosphate that contains that Resorcinol produced, and can also make multiple value product when can effectively dispose waste liquid.
To achieve the above object, technical scheme of the present invention is:
A kind of with producing the method that the manganese waste liquid is made manganous phosphate co-producing sulfuric acid lithium and ammonium phosphate that contains that Resorcinol produced, comprise being prepared as follows step:
Steps A, will produce the waste liquid that Resorcinol produces and carry out suction filtration with the suction filtration machine;
Step B, suction filtration gained simple substance residual filter cake in the steps A is used to develop other products;
Step C, suction filtration gained filtrate in the steps A is transferred in the reactor, drops into Trilithium phosphate solution simultaneously and react, the mass ratio between filtrate and the Trilithium phosphate solution is 1: 0.31～0.71; Reaction generates the mixture I of manganous phosphate and Lithium Sulphate and ammonium phosphate;
Step D, the mixture I of gained among the step C is filtered with strainer;
Step e, with filter among the step D gained filter cake through wash drying, crushing packing becomes the manganous phosphate product;
Step F, with the clarifying filtrate of sulphur of gained among the step D through underpressure distillation, gradient cooling, crystallization, obtain Lithium Sulphate crystal and ammonium phosphate crystal respectively;
Step G, with step F gained Lithium Sulphate crystal through wash drying, crushing packing becomes the Lithium Sulphate product;
Step H, with step F gained ammonium phosphate crystal through wash drying, crushing packing becomes the ammonium phosphate product.
The present invention carries out suction filtration with the waste liquid that Resorcinol produced with the suction filtration machine earlier, obtains filtrate and carries out distillating filtering, and the filter cake deep processing obtains the manganous phosphate product; Further respectively deep processing obtained Lithium Sulphate and ammonium phosphate product respectively after filtrate was carried out underpressure distillation again; The present invention can as clean as a pennyly gulp down waste liquid, alleviates the pollution of waste liquid to environment; Can make valuable manganous phosphate, Lithium Sulphate and ammonium phosphate product again, not only have remarkable social benefit and economic benefit, and technology and production unit are simple, be a kind of relatively actual processing and utilize method.
Its chemical equation is:
3MnSO
4+2Li
3PO
4＝＝＝＝＝Mn
3(PO
4)
2+3Li
2SO
4
3(NH
4)
2SO
4+2Li
3PO
4＝＝＝＝＝2(NH
4)
3PO
4+3Li
2SO
4
3H
2SO
4+2Li
3PO
4＝＝＝＝＝3Li
2SO
4+H
3PO
4
Concrete embodiment
Embodiment 1
A kind of with producing the method that the manganese waste liquid is made manganous phosphate co-producing sulfuric acid lithium and ammonium phosphate that contains that Resorcinol produced, comprise being prepared as follows step:
Steps A, will produce the 1000kg waste liquid (wherein, comprising the 120kg manganous sulfate, 15kg ammonium sulfate and 20kg sulfuric acid) that Resorcinol produces and carry out suction filtration with the suction filtration machine;
Step B, suction filtration gained simple substance residual filter cake in the steps A is used to develop other products;
Step C, suction filtration gained filtrate in the steps A is transferred in the reactor, drops into Trilithium phosphate solution simultaneously and react, the mass ratio between filtrate and the Trilithium phosphate solution is 1: 0.31; Reaction generates the mixture I of manganous phosphate and Lithium Sulphate and ammonium phosphate;
Step D, the mixture I of gained among the step C is filtered with strainer;
Step e, with filter among the step D gained filter cake through wash drying, crushing packing becomes 56.90kg manganous phosphate product;
Step F, with the clarifying filtrate of sulphur of gained among the step D through underpressure distillation, gradient cooling, crystallization, obtain Lithium Sulphate crystal and ammonium phosphate crystal respectively;
Step G, with step F gained Lithium Sulphate crystal through wash drying, crushing packing becomes 68.37kg Lithium Sulphate product;
Step H, with step F gained ammonium phosphate crystal through wash drying, crushing packing becomes 5.25kg ammonium phosphate product.
Embodiment 2
A kind of with producing the method that the manganese waste liquid is made manganous phosphate co-producing sulfuric acid lithium and ammonium phosphate that contains that Resorcinol produced, comprise being prepared as follows step:
Steps A, will produce the 1000kg waste liquid (wherein, comprising the 120kg manganous sulfate, 15kg ammonium sulfate and 20kg sulfuric acid) that Resorcinol produces and carry out suction filtration with the suction filtration machine;
Step B, suction filtration gained simple substance residual filter cake in the steps A is used to develop other products;
Step C, suction filtration gained filtrate in the steps A is transferred in the reactor, drops into Trilithium phosphate solution simultaneously and react, the mass ratio between filtrate and the Trilithium phosphate solution is 1: 0.51; Reaction generates the mixture I of manganous phosphate and Lithium Sulphate and ammonium phosphate;
Step D, the mixture I of gained among the step C is filtered with strainer;
Step e, with filter among the step D gained filter cake through wash drying, crushing packing becomes 93.61kg manganous phosphate product;
Step F, with the clarifying filtrate of sulphur of gained among the step D through underpressure distillation, gradient cooling, crystallization, obtain Lithium Sulphate crystal and ammonium phosphate crystal respectively;
Step G, with step F gained Lithium Sulphate crystal through wash drying, crushing packing becomes 112.46kg Lithium Sulphate product;
Step H, with step F gained ammonium phosphate crystal through wash drying, crushing packing becomes 8.64kg ammonium phosphate product.
Embodiment 3
A kind of with producing the method that the manganese waste liquid is made manganous phosphate co-producing sulfuric acid lithium and ammonium phosphate that contains that Resorcinol produced, comprise being prepared as follows step:
Steps A, will produce the 1000kg waste liquid (wherein, comprising the 120kg manganous sulfate, 15kg ammonium sulfate and 20kg sulfuric acid) that Resorcinol produces and carry out suction filtration with the suction filtration machine;
Step B, suction filtration gained simple substance residual filter cake in the steps A is used to develop other products;
Step C, suction filtration gained filtrate in the steps A is transferred in the reactor, drops into Trilithium phosphate solution simultaneously and react, the mass ratio between filtrate and the Trilithium phosphate solution is 1: 0.71; Reaction generates the mixture I of manganous phosphate and Lithium Sulphate and ammonium phosphate;
Step D, the mixture I of gained among the step C is filtered with strainer;
Step e, with filter among the step D gained filter cake through wash drying, crushing packing becomes 130.32kg manganous phosphate product;
Step F, with the clarifying filtrate of sulphur of gained among the step D through underpressure distillation, gradient cooling, crystallization, obtain Lithium Sulphate crystal and ammonium phosphate crystal respectively;
Step G, with step F gained Lithium Sulphate crystal through wash drying, crushing packing becomes 156.57kg Lithium Sulphate product;
Step H, with step F gained ammonium phosphate crystal through wash drying, crushing packing becomes 12.03kg ammonium phosphate product.
The foregoing description is preferred embodiment of the present invention, is not to be used for limiting the scope of the present invention, so all equivalences of being done with described feature of claim of the present invention and principle change or modify, all should be included within the claim scope of the present invention.
Claims (1)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010106158468A CN102115058A (en) | 2010-12-30 | 2010-12-30 | A method for producing manganese phosphate and co-producing lithium sulfate and ammonium phosphate with manganese-containing waste liquid produced by hydroquinone |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010106158468A CN102115058A (en) | 2010-12-30 | 2010-12-30 | A method for producing manganese phosphate and co-producing lithium sulfate and ammonium phosphate with manganese-containing waste liquid produced by hydroquinone |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102115058A true CN102115058A (en) | 2011-07-06 |
Family
ID=44214003
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010106158468A Pending CN102115058A (en) | 2010-12-30 | 2010-12-30 | A method for producing manganese phosphate and co-producing lithium sulfate and ammonium phosphate with manganese-containing waste liquid produced by hydroquinone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102115058A (en) |
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2010
- 2010-12-30 CN CN2010106158468A patent/CN102115058A/en active Pending
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Application publication date: 20110706 |