CN110092396A - A kind of method and system of graphene Waste Sulfuric Acid recycling - Google Patents
A kind of method and system of graphene Waste Sulfuric Acid recycling Download PDFInfo
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- CN110092396A CN110092396A CN201910477238.6A CN201910477238A CN110092396A CN 110092396 A CN110092396 A CN 110092396A CN 201910477238 A CN201910477238 A CN 201910477238A CN 110092396 A CN110092396 A CN 110092396A
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- Prior art keywords
- liquid
- sulfuric acid
- mother liquor
- potassium
- reaction
- Prior art date
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 238000000034 method Methods 0.000 title claims abstract description 57
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 55
- 239000002699 waste material Substances 0.000 title claims abstract description 51
- 238000004064 recycling Methods 0.000 title claims abstract description 33
- 239000007788 liquid Substances 0.000 claims abstract description 108
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims abstract description 52
- 239000012452 mother liquor Substances 0.000 claims abstract description 46
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 46
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 42
- 238000000926 separation method Methods 0.000 claims abstract description 39
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000007787 solid Substances 0.000 claims abstract description 34
- 238000002288 cocrystallisation Methods 0.000 claims abstract description 32
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims abstract description 30
- 229910052939 potassium sulfate Inorganic materials 0.000 claims abstract description 30
- 235000011151 potassium sulphates Nutrition 0.000 claims abstract description 27
- 239000000706 filtrate Substances 0.000 claims abstract description 26
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims abstract description 26
- 235000019341 magnesium sulphate Nutrition 0.000 claims abstract description 26
- 238000002425 crystallisation Methods 0.000 claims abstract description 25
- 230000001590 oxidative effect Effects 0.000 claims abstract description 24
- 230000008025 crystallization Effects 0.000 claims abstract description 23
- 239000013049 sediment Substances 0.000 claims abstract description 23
- WZISDKTXHMETKG-UHFFFAOYSA-H dimagnesium;dipotassium;trisulfate Chemical compound [Mg+2].[Mg+2].[K+].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O WZISDKTXHMETKG-UHFFFAOYSA-H 0.000 claims abstract description 19
- 238000005189 flocculation Methods 0.000 claims abstract description 19
- 230000016615 flocculation Effects 0.000 claims abstract description 19
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 19
- 239000007800 oxidant agent Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims description 47
- 239000007789 gas Substances 0.000 claims description 38
- 239000012295 chemical reaction liquid Substances 0.000 claims description 27
- 230000003647 oxidation Effects 0.000 claims description 27
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims 1
- 238000010025 steaming Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 21
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 abstract description 11
- 239000002253 acid Substances 0.000 abstract description 10
- 229910001437 manganese ion Inorganic materials 0.000 abstract description 9
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 abstract description 7
- 229910001414 potassium ion Inorganic materials 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 16
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 11
- 239000003337 fertilizer Substances 0.000 description 11
- 239000011572 manganese Substances 0.000 description 11
- 229910052748 manganese Inorganic materials 0.000 description 11
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 239000005864 Sulphur Substances 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZGBSOTLWHZQNLH-UHFFFAOYSA-N [Mg].S(O)(O)(=O)=O Chemical compound [Mg].S(O)(O)(=O)=O ZGBSOTLWHZQNLH-UHFFFAOYSA-N 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 229940072033 potash Drugs 0.000 description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
- 235000015320 potassium carbonate Nutrition 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FCLAUNCUBAQVMB-UHFFFAOYSA-N [K].[Mg].S(O)(O)(=O)=O Chemical compound [K].[Mg].S(O)(O)(=O)=O FCLAUNCUBAQVMB-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 230000003196 chaotropic effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000008394 flocculating agent Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- ILRLTAZWFOQHRT-UHFFFAOYSA-N potassium;sulfuric acid Chemical compound [K].OS(O)(=O)=O ILRLTAZWFOQHRT-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 1
- 208000008167 Magnesium Deficiency Diseases 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 240000003768 Solanum lycopersicum Species 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229930002875 chlorophyll Natural products 0.000 description 1
- 235000019804 chlorophyll Nutrition 0.000 description 1
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000008141 laxative Substances 0.000 description 1
- 239000010871 livestock manure Substances 0.000 description 1
- 235000004764 magnesium deficiency Nutrition 0.000 description 1
- OJXVUEMVNWMNCR-UHFFFAOYSA-L magnesium;potassium;sulfate Chemical compound [Mg+2].[K+].[O-]S([O-])(=O)=O OJXVUEMVNWMNCR-UHFFFAOYSA-L 0.000 description 1
- UBXWAYGQRZFPGU-UHFFFAOYSA-N manganese(2+) oxygen(2-) titanium(4+) Chemical compound [O--].[O--].[Ti+4].[Mn++] UBXWAYGQRZFPGU-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000021049 nutrient content Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000001543 purgative effect Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002881 soil fertilizer Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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
- C01D5/06—Preparation of sulfates by double decomposition
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/40—Magnesium sulfates
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D5/00—Fertilisers containing magnesium
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D9/00—Other inorganic fertilisers
- C05D9/02—Other inorganic fertilisers containing trace elements
Abstract
The present invention provides a kind of method and systems of graphene Waste Sulfuric Acid recycling, are related to technical field of resource environments.Graphene Waste Sulfuric Acid and magnesia are carried out neutralization reaction by the present invention, then carry out oxidation reaction with oxidant, then obtain sediment and filtrate through flocculation treatment；Filtrate is subjected to circulation concentration, crystallization and separation, until potassium sulfate mass concentration >=10% terminates in separating obtained separating liquid, using the separating liquid of potassium sulfate mass concentration >=10% as the first mother liquor, separating obtained solid is magnesium sulfate；First mother liquor is successively subjected to cocrystallization and separation, obtains potassium magnesium sulfate cocrystallization object and the second mother liquor, the second mother liquor returns to the step of recycling condensing crystallizing.The present invention uses in magnesia and graphene Waste Sulfuric Acid, obtains magnesium sulfate and potassium magnesium sulfate, realizes the recycling of sulfuric acid and potassium ion；Using the manganese ion in oxidizing process recycling graphene spent acid.Process of the present invention is simple, and the full element of graphene Waste Sulfuric Acid obtains recycling treatment, and economic and social benefit is significant.
Description
Technical field
The present invention relates to technical field of resource environments, in particular to the method for a kind of graphene Waste Sulfuric Acid recycling and it is
System.
Background technique
Graphene is emerging material, and application prospect is extremely wide；The main production of graphene is that oxidation is gone back at present
Former method, wherein oxidation process mainly uses improved Hummers method, there are two types of the method is common: 1. with potassium permanganate for strong oxygen
Agent, with sulfuric acid intercalation；2. first being pre-oxidized with potassium peroxydisulfate and phosphorus pentoxide to graphite powder, then it is with potassium permanganate
Strong oxidizer, with sulfuric acid intercalation.
Oxidation process can generate a large amount of Waste Sulfuric Acids, wherein sulfuric acid content about 30%~59% (wt%), about containing manganese ion
0.2%~2% (wt%) contains potassium ion about 0.2%~2% (wt%), and there are also the micro heavies that raw material is brought into.Currently, stone
Black alkene Waste Sulfuric Acid mainly uses calcium method to neutralize, still not by abundant resource utilization.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of method and system of graphene Waste Sulfuric Acid recycling.This hair
The method and system of bright offer can realize the full element resource of graphene Waste Sulfuric Acid, reach zero-emission.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of methods of graphene Waste Sulfuric Acid recycling, comprising the following steps:
(1) graphene Waste Sulfuric Acid is mixed with magnesia and carries out neutralization reaction, obtain neutralization reaction liquid；
(2) the neutralization reaction liquid is mixed with oxidant and carries out oxidation reaction, obtain oxidation liquid；
(3) oxidation liquid is mixed with flocculant and carries out flocculation treatment, obtain sediment and filter after separation of solid and liquid
Liquid；
(4) filtrate is subjected to circulation concentration, crystallization and separation, until potassium sulfate quality is dense in separating obtained separating liquid
Degree >=10% terminates, and using the separating liquid of potassium sulfate mass concentration >=10% as the first mother liquor, separating obtained solid is sulfuric acid
Magnesium；
(5) the first mother liquor is successively subjected to cocrystallization and separation, obtains potassium magnesium sulfate cocrystallization object and the second mother liquor；It is described
Second mother liquor return step (4), repeats step (4), (5).
Preferably, the temperature of the neutralization reaction is 40~110 DEG C, and the pH of the neutralization reaction liquid is 4~8.
Preferably, the oxidant is one or more of hydrogen peroxide, sodium hypochlorite and postassium hypochlorite, the oxidant
Quality be the neutralization reaction liquid quality 0.01~2%.
Preferably, the time of the oxidation reaction is 0.1~1h.
Preferably, the flocculant is one in polyacrylamide, bodied ferric sulfate, aluminium polychloride and polyaluminium sulfate
Kind is several, and the quality of the flocculant is the 0.01~0.2% of the oxidation liquid quality.
Preferably, the method for concentration in the circulation condensing crystallizing is negative pressure evaporation and concentration, and temperature is 95~105 DEG C.
Preferably, the temperature crystallized in the step (4) is 25~40 DEG C.
Preferably, the temperature of cocrystallization is 5~25 DEG C in the step (5).
The present invention provides a kind of system of graphene Waste Sulfuric Acid recycling, the schematic diagram of the system is as shown in Figure 1.This
The system for inventing the graphene Waste Sulfuric Acid recycling provided includes: reaction kettle 1, and the reaction kettle 1 enters including solid inlet, liquid
Mouth, liquid outlet and gas vent；
The filter press 2 that entrance is connected to the liquid outlet of the reaction kettle 1, the filter press 2 is including liquid outlet and admittedly
Body outlet；
The dryer 3 that entrance is connected to the solid outlet of the filter press 2；
The evaporator 4 that entrance is connected to the liquid outlet of the filter press 2, the evaporator 4 include gas vent and liquid
Body outlet；
The first crystallizer 5 that entrance is connected to the liquid outlet of the evaporator 4；
First separator 6 of entrance and 5 outlet of the first crystallizer, first separator 6 go out including solid
Mouth and liquid outlet；
The second crystallizer 7 that entrance is connected to the liquid outlet of first separator 6；The liquid of first separator 6
Body outlet is also connected to the entrance of evaporator 4；
Second separator 8 of entrance and 7 outlet of the second crystallizer, second separator 8 go out including solid
Mouth and liquid outlet, the liquid outlet are connected to the entrance of the evaporator 4；
The tail gas absorption being connected to entrance with the gas vent of the gas vent of the reaction kettle 1 and the evaporator 4
System 9.
It is including following the present invention provides the method for carrying out graphene Waste Sulfuric Acid recycling using system described in above scheme
Step:
(a) graphene Waste Sulfuric Acid is mixed in reaction kettle 1 with magnesia and carries out neutralization reaction, obtain neutralization reaction liquid；
(b) the neutralization reaction liquid is mixed in reaction kettle 1 with oxidant and carries out oxidation reaction, obtain oxidation reaction
Liquid；
(c) oxidation liquid is mixed in reaction kettle 1 with flocculant after carrying out flocculation treatment, flocculation liquid enters pressure
Filter 2 is separated by solid-liquid separation, and sediment and filtrate are obtained；Sediment enters dryer 3 and is dried；
(d) filtrate sequentially enters evaporator 4, the first crystallizer 5 and the first separator 6 and is concentrated, is crystallized and is divided
From circulation the step of being concentrated, crystallized and separate in isolated separating liquid Returning evaporimeter 4, up to sulphur in separating liquid
The mass concentration of sour potassium >=10% terminates, using the separating liquid of potassium sulfate mass concentration >=10% as the first mother liquor；First separation
Isolated solid is magnesium sulfate in device 6；
(e) first mother liquor sequentially enters the second crystallizer 7 and the second separator 8 carries out cocrystallization and separation, obtains
Potassium magnesium sulfate cocrystallization object and the second mother liquor；The second mother liquor return step (d), repeats step (d), (e)；
The tail gas that reaction kettle 1 and evaporator 4 generate empties after the processing of tail gas absorbing system 9.
The present invention provides a kind of method of graphene Waste Sulfuric Acid recycling the following steps are included: (1) is by graphene sulfur waste
Acid is mixed with magnesia carries out neutralization reaction, obtains neutralization reaction liquid；(2) the neutralization reaction liquid is mixed into progress with oxidant
Oxidation reaction obtains oxidation liquid；(3) oxidation liquid is mixed with flocculant and carries out flocculation treatment, be separated by solid-liquid separation
After obtain sediment and filtrate；(4) filtrate is subjected to circulation concentration, crystallization and separation, until in separating obtained separating liquid
Potassium sulfate mass concentration >=10% terminates, separating obtained using the separating liquid of potassium sulfate mass concentration >=10% as the first mother liquor
Solid is magnesium sulfate；(5) the first mother liquor is successively subjected to cocrystallization and separation, obtains potassium magnesium sulfate cocrystallization object and the second mother
Liquid；The second mother liquor return step (4), repeats step (4), (5).The present invention uses in magnesia and graphene sulfur waste
Acid obtains magnesium sulfate and potassium magnesium sulfate product, realizes the recycling of sulfuric acid and potassium ion；Using in oxidizing process recycling graphene spent acid
Manganese ion can produce manganese fertilizer.Method provided by the invention is simple, and the full element of graphene Waste Sulfuric Acid obtains recycling treatment, realizes
Zero-emission, economic and social benefit are significant.
The present invention provides a kind of system of graphene Waste Sulfuric Acid recycling, the system flow is simple, principle is rigorous, investment
Less, at low cost, graphene sulfur waste sour component whole resource utilization has broad application prospects.
Detailed description of the invention
Fig. 1 is the schematic diagram of the system of graphene Waste Sulfuric Acid recycling provided by the invention, and 1 indicates reaction kettle in Fig. 1,2
Indicate filter press, 3 indicate dryer, and 4 indicate evaporator, and 5 indicate the first crystallizer, and 6 indicate the first separator, and 7 indicate second
Crystallizer, 8 indicate the second separator, and 9 indicate tail gas absorbing system；
Fig. 2 is the flow chart of graphene Waste Sulfuric Acid recycling provided by the invention.
Specific embodiment
The present invention provides a kind of methods of graphene Waste Sulfuric Acid recycling, comprising the following steps:
(1) graphene Waste Sulfuric Acid is mixed with magnesia and carries out neutralization reaction, obtain neutralization reaction liquid；
(2) the neutralization reaction liquid is mixed with oxidant and carries out oxidation reaction, obtain oxidation liquid；
(3) oxidation liquid is mixed with flocculant and carries out flocculation treatment, obtain sediment and filter after separation of solid and liquid
Liquid；
(4) filtrate is subjected to circulation concentration, crystallization and separation, until potassium sulfate quality is dense in separating obtained separating liquid
Degree >=10% terminates, and using the separating liquid of potassium sulfate mass concentration >=10% as the first mother liquor, separating obtained solid is magnesium sulfate；
(5) the first mother liquor is successively subjected to cocrystallization and separation, obtains potassium magnesium sulfate cocrystallization object and the second mother liquor；It is described
Second mother liquor return step (4), repeats step (4), (5).
The present invention, which mixes graphene Waste Sulfuric Acid with magnesia, carries out neutralization reaction, obtains neutralization reaction liquid, i.e., of the invention
By in magnesium sulfate and graphene Waste Sulfuric Acid.In the present invention, the temperature of the neutralization reaction is preferably 40~110 DEG C, more excellent
It is selected as 60~100 DEG C；The pH value of the neutralization reaction liquid is preferably 4~8, and more preferably 6~7, the pH value passes through magnesia
Additional amount control.The present invention controls the pH of neutralization reaction liquid in 4~8 ranges, and the utilization rate of magnesia can be improved,
And within the scope of the pH, facilitate subsequent oxidation divalent manganesetion.
After neutralization reaction, the present invention, which mixes the neutralization reaction liquid with oxidant, carries out oxidation reaction, and it is anti-to obtain oxidation
Answer liquid.In the present invention, the oxidant is preferably one or more of hydrogen peroxide, sodium hypochlorite and postassium hypochlorite, described
The quality of oxidant is preferably the 0.01~2% of the neutralization reaction liquid quality, and more preferably 0.1~1%.The present invention preferably will
The oxidant is added in neutralization reaction liquid and is mixed, and the present invention does not require the mixed method particularly, adopts
Guarantee to be uniformly mixed with mixed method well known in the art.In the present invention, the time of the oxidation reaction is preferably 0.1
~1h.Manganese ion in graphene Waste Sulfuric Acid is oxidized to manganese dioxide by oxidizing process by the present invention, wherein hydrogen peroxide oxidation manganese
The reaction equation of ion is as shown in Equation 1；Sodium hypochlorite and postassium hypochlorite are hypochlorite, aoxidize the reaction equation such as formula of manganese ion
Shown in 2:
H2O2+Mn2++2OH-→MnO2↓+2H2O formula 1；
ClO-+Mn2++2OH-→MnO2↓+H2O+Cl-Formula 2.
After oxidation reaction, the present invention, which mixes the oxidation liquid with flocculant, carries out flocculation treatment, after separation of solid and liquid
Obtain sediment and filtrate.In the present invention, the flocculant is preferably polyacrylamide, bodied ferric sulfate, aluminium polychloride
One or more of with polyaluminium sulfate, the quality of the flocculant be preferably the oxidation liquid quality 0.01~
0.2%, more preferably 0.1~0.15%.The flocculant is preferably added in oxidation liquid by the present invention, to the oxidation
Reaction solution carries out flocculation treatment.In the present invention, the time of the flocculation treatment is preferably 0.2~2h.The present invention passes through addition
Flocculant improves the subsequent separative efficiency to sediment.After flocculation treatment, the present invention is separated by solid-liquid separation gained flocculation liquid, obtains
To sediment and filtrate.The present invention does not require the method for the separation of solid and liquid particularly, using method well known in the art
, such as filter press technique.In the present invention, the main component of the sediment is impurity and the dioxies such as the silico-calcium in raw materials of magnesium oxide
Change manganese, the main component in filtrate is magnesium sulfate and a small amount of potassium sulfate；Sediment can be used as manganese fertilizer after drying.
After being separated by solid-liquid separation, the filtrate is carried out circulation concentration, crystallization and separation by the present invention, until separating obtained point
Potassium sulfate mass concentration >=10% terminates in chaotropic, using the separating liquid of potassium sulfate mass concentration >=10% as the first mother liquor, point
It is magnesium sulfate from obtained solid.In the present invention, the circulation concentration, crystallization and separation i.e. concentration, crystallization and isolated process
Circulation carries out；Method for concentration in the circulation condensing crystallizing is preferably negative pressure evaporation concentration, and temperature is preferably 95~105 DEG C,
More preferably 100 DEG C；The crystallization temperature of the circulation condensing crystallizing is preferably 25~40 DEG C, and more preferably 30~35 DEG C.At this
In invention, the circulation condensing crystallizing specifically: the filtrate is successively concentrated, is crystallized, crystal solution is isolated
Separating liquid returns to the step of enrichment process repeats concentration, crystallization and separation, up to the mass concentration of potassium sulfate in separating liquid
>=10%.In the process, potassium sulfate exists in solution, and concentration is lower, and the crystallization process is that magnesium sulfate is tied
Crystalline substance, therefore, the solid matter obtained after Crystallization Separation are magnesium sulfate.Magnesium sulfate industrially may be used as process hides, explosive, papermaking,
The raw material of porcelain, chemical synthesis etc.；Medically it is used as oral purgative；It is agriculturally widely used as foliar fertilizer and soil fertiliser containing magnesium, because
It is one of the main component of chlorophyll for magnesium, is normally used for the crops of veterinary antibiotics or magnesium deficiency, such as tomato, Ma Ling
Potato, rose etc..
After the concentration of above-mentioned circulation, crystallization and separation, the first mother liquor is successively carried out cocrystallization and separation by the present invention, is obtained
To potassium magnesium sulfate cocrystallization object and the second mother liquor.In the present invention, in first mother liquor potassium sulfate mass concentration >=10%,
Sulphate of potash and magesium can carry out cocrystallization, and in the process, the temperature of the cocrystallization is preferably 5~25 DEG C, more preferably
It is 15~20 DEG C；Time preferred > 0.5h, more preferably 4~5h.
After cocrystallization, the present invention separates gained cocrystallization liquid, obtains potassium magnesium sulfate cocrystallization object and the second mother
Liquid；The step of second mother liquor contains a large amount of magnesium sulfate and a small amount of potassium sulfate, returns to above-mentioned circulation condensing crystallizing, repeat
The step of above-mentioned circulation condensing crystallizing, separation, cocrystallization；The molecular formula of the potassium magnesium sulfate cocrystallization object is K2SO4·
mMgSO4·nH2O, wherein m=1~2, n=0~6.Obtained potassium magnesium sulfate can be used as NEW TYPE OF COMPOSITE fertilizer, have nutrient content
The features such as abundant, improving soil is good, can effectively facilitate plant growth, remarkable in economical benefits；It is a kind of multi-element K fertilizer, except containing
Potassium, magnesium outside sulphur, can also add microelement in calcium, silicon, boron, iron, zinc etc., generally make base manure, can also make top dressing, with equal potassium amount
Traditional simple substance potash fertilizer become apparent from compared to effect of increasing production.
The present invention obtains magnesium sulfate and potassium magnesium sulfate product using in magnesia and graphene Waste Sulfuric Acid, realize sulfuric acid and
The recycling of potassium ion；Manganese fertilizer can be produced using the manganese ion in oxidizing process recycling graphene spent acid.Therefore, on provided by the invention
The method of stating can make the full element of graphene Waste Sulfuric Acid obtain recycling treatment, realize zero-emission, and economic and social benefit is significant.
The present invention provides a kind of systems of graphene Waste Sulfuric Acid recycling, as shown in Figure 1, comprising:
Reaction kettle 1, the reaction kettle 1 include solid inlet, liquid inlet, liquid outlet and gas vent；
The filter press 2 that entrance is connected to the liquid outlet of the reaction kettle 1, the filter press 2 is including liquid outlet and admittedly
Body outlet；
The dryer 3 that entrance is connected to the solid outlet of the filter press 2；
The evaporator 4 that entrance is connected to the liquid outlet of the filter press 2, the evaporator 4 include gas vent and liquid
Body outlet；
The first crystallizer 5 that entrance is connected to the liquid outlet of the evaporator 4；
First separator 6 of entrance and 5 outlet of the first crystallizer, first separator 6 go out including solid
Mouth and liquid outlet；
The second crystallizer 7 that entrance is connected to the liquid outlet of first separator 6；The liquid of first separator 6
Body outlet is also connected to the entrance of evaporator 4；
Second separator 8 of entrance and 7 outlet of the second crystallizer, second separator 8 go out including solid
Mouth and liquid outlet, the liquid outlet are connected to the entrance of the evaporator 4；
The tail gas absorption being connected to entrance with the gas vent of the gas vent of the reaction kettle 1 and the evaporator 4
System 9.
In the present invention, the liquid outlet of the reaction kettle 1 and gas vent are located at the lower end and top of reaction kettle 1
End；The liquid outlet and gas vent of the evaporator 4 are located at the bottom and top of evaporator 4；First separator 6
Solid outlet and liquid outlet be located at the top and bottom of the first separator 6；The solid outlet of second separator 8
The top and bottom of the second separator 8 are located at liquid outlet.
The present invention is to the reaction kettle, filter press, dryer, evaporator, the first crystallizer, the first separator, the second knot
Brilliant device, the second separator, tail gas absorbing system concrete type there is no particular/special requirement, on well known to those skilled in the art
Equipment is stated to be connected to according to mode of communicating described in above scheme.Graphene Waste Sulfuric Acid recycling provided by the invention is
System, process is simple, principle is rigorous, small investment, at low cost, can have graphene sulfur waste sour component whole resource utilization
Wide application prospect.
The present invention provides a kind of method for carrying out graphene Waste Sulfuric Acid recycling using system described in above scheme, processes
As shown in Figure 2, comprising the following steps:
(a) graphene Waste Sulfuric Acid is mixed in reaction kettle 1 with magnesia and carries out neutralization reaction, obtain neutralization reaction liquid；
(b) the neutralization reaction liquid is mixed in reaction kettle 1 with oxidant and carries out oxidation reaction, obtain oxidation reaction
Liquid；
(c) oxidation liquid is mixed in reaction kettle 1 with flocculant after carrying out flocculation treatment, flocculation liquid enters pressure
Filter 2 is separated by solid-liquid separation, and sediment and filtrate are obtained；Sediment enters dryer 3 and is dried；
(d) filtrate sequentially enters evaporator 4, the first crystallizer 5 and the first separator 6 and is concentrated, is crystallized and is divided
From circulation the step of being concentrated, crystallized and separate in isolated separating liquid Returning evaporimeter 4, up to sulphur in separating liquid
The mass concentration of sour potassium >=10% terminates, using the separating liquid of potassium sulfate mass concentration >=10% as the first mother liquor；First separation
Isolated solid is magnesium sulfate in device 6；
(e) first mother liquor sequentially enters the second crystallizer 7 and the second separator 8 carries out cocrystallization and separation, obtains
Potassium magnesium sulfate cocrystallization object and the second mother liquor；The second mother liquor return step (d), repeats step (d), (e)；
The tail gas that reaction kettle 1 and evaporator 4 generate empties after the processing of tail gas absorbing system 9.
The present invention mixes graphene Waste Sulfuric Acid with magnesia in reaction kettle 1 carries out neutralization reaction, obtains neutralization reaction
Liquid.Graphene Waste Sulfuric Acid and magnesia are passed through the liquid inlet of reaction kettle 1 to the present invention respectively and solid inlet is added to reaction
It is mixed in kettle, carries out neutralization reaction；The mixing preferably carries out under stirring conditions；The temperature and pH item of the neutralization reaction
Part is consistent with above scheme, and details are not described herein.The present invention passes through in magnesium sulfate and graphene Waste Sulfuric Acid.In the process, instead
The tail gas main component for answering kettle 1 to generate is water vapour, and the tail gas empties after the processing of tail gas absorbing system 9.
After neutralization reaction, the present invention mixes gained neutralization reaction liquid with oxidant in reaction kettle 1 carries out oxidation reaction；
The type of the oxidant and the condition of oxidation reaction are consistent with above scheme, and details are not described herein.The present invention is preferably by dioxygen
Water is added by the liquid inlet of the reaction kettle 1, and sodium hypochlorite and postassium hypochlorite are passed through to the solid inlet of the reaction kettle 1
It is added.Manganese ion in graphene Waste Sulfuric Acid is oxidized to manganese dioxide by oxidizing process by the present invention.
After oxidation reaction, the present invention mixes gained oxidation liquid with flocculant in reaction kettle 1 carries out flocculation treatment
Afterwards, flocculation liquid enters filter press 2 and is separated by solid-liquid separation, and obtains sediment and filtrate；Sediment enters dryer 3 and is dried.
In the present invention, the type of the flocculant and additive amount are consistent with above scheme, and details are not described herein.It is anti-by the oxidation
Should be with after flocculation treatment, the tail gas that reaction kettle 1 generates is mainly water vapour and a small amount of dust, and the tail gas passes through tail gas absorption system
It is emptied after 9 processing of system.The present invention improves the subsequent separative efficiency to sediment by adding flocculant.In the present invention, described
The main component of sediment is that impurity and manganese dioxide, the filtrates such as the silico-calcium in raw materials of magnesium oxide are mainly magnesium sulfate and a small amount of sulphur
Sour potassium solution；Sediment can be used as manganese fertilizer after drying.
After separation of solid and liquid, gained filtrate sequentially enter evaporator 4, the first crystallizer 5 and the first separator 6 be concentrated,
It crystallizes and separates, the step of being concentrated, crystallized and being separated is recycled in isolated separating liquid Returning evaporimeter 4, until point
The mass concentration of potassium sulfate >=10% terminates in chaotropic, using the separating liquid of potassium sulfate mass concentration >=10% as the first mother liquor.
In the present invention, the concentration, the temperature of crystallization are consistent with above scheme, and details are not described herein.In the process, potassium sulfate is deposited
It is in solution, concentration is lower, and the crystallization process is that magnesium sulfate is crystallized, therefore, isolated in the first separator 6
Solid be magnesium sulfate.The tail gas main component that evaporator 4 generates is water vapour, and the tail gas is by tail gas absorbing system 9
It is emptied after reason.
After above-mentioned concentration, crystallization and separation, the first mother liquor is sequentially entered the second crystallizer 7 and second point by the present invention
Cocrystallization and separation are carried out from device 8, obtains potassium magnesium sulfate cocrystallization object and the second mother liquor；The second mother liquor Returning evaporimeter 4,
The step of repeating above-mentioned concentration, crystallization, separation.In the present invention, in first mother liquor potassium sulfate mass concentration >=
10%, sulphate of potash and magesium can carry out cocrystallization, obtain potassium magnesium sulfate cocrystallization object；The temperature of this process cocrystallization with it is upper
It is consistent to state scheme, details are not described herein.
It is carried out below with reference to method and system of the embodiment to graphene Waste Sulfuric Acid recycling provided by the invention detailed
Illustrate, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
(1) reaction kettle stirring is opened, the graphene Waste Sulfuric Acid that sulfuric acid mass content is 40% is added by sulfuric acid measuring tank
The light calcined magnesia 182kg of 1000kg and 90%, until pH value reaches 7, reaction temperature is kept for 30 minutes at 90 DEG C；
(2) step (1) solution be added 6.5kg mass concentration 30% hydrogen peroxide, oxidation divalent manganesetion (spent acid manganese from
Sub- content is 0.3%), to generate manganese dioxide precipitate；After reaction 1 hour, 1kg polyaluminum sulfate aluminium flocculating agent is added, is separated by filtration
Manganese dioxide precipitate, sediment dry to obtain manganese fertilizer 5kg (manganese mass content is 60%)；
(3) filtrate from step (2) is mainly magnesium sulfate and a small amount of potassium sulfate solution (spent acid contains potassium ion 0.4%),
By circulation concentration and crystallisation by cooling, the sulfuric acid magnesium products that 950kg meets HG/T 2680-2017 technical requirements are obtained；
(4) when the mother liquor from step (3) reaches sulfuric acid potassium concn >=10% by circulation crystallization, mother liquor is transferred to sulfuric acid
Potassium magnesium crystallizer, control crystallization temperature are 10 DEG C, crystallize out the potassium magnesium sulfate product for meeting GB/T20937-2018 technical requirements
(K2SO4·2MgSO4·6H2O)20kg；Remaining mother liquor return step (3) carries out magnesium sulfate circulation crystallization.
(5) each reaction system tail gas enters tail gas absorber, empties after processing is up to standard.
Embodiment 2
(1) reaction kettle stirring is opened, the graphene Waste Sulfuric Acid that sulfuric acid mass content is 50% is added by sulfuric acid measuring tank
The light calcined magnesia 227kg of 1000kg and 90%, until pH value reaches 6, reaction temperature is kept for 30 minutes at 90 DEG C；
(2) 7.2kg sodium hypochlorite is added in the solution of step (1), and (spent acid manganese ion content is oxidation divalent manganesetion
0.5%) manganese dioxide precipitate, is generated；After reaction 1 hour, 1.2kg polyaluminum sulfate aluminium flocculating agent is added, is separated by filtration titanium dioxide
Manganese precipitating, sediment dry to obtain manganese fertilizer 8kg (manganese content 60%)；
(3) filtrate from step (2) is mainly magnesium sulfate and a small amount of potassium sulfate solution (spent acid contains potassium ion 0.2%),
By circulation concentration and crystallisation by cooling, the sulfuric acid magnesium products that 1225kg meets HG/T 2680-2017 technical requirements are obtained；
(4) when the mother liquor from step (3) reaches sulfuric acid potassium concn >=10% by circulation crystallization, mother liquor is transferred to sulfuric acid
Potassium magnesium crystallizer, control crystallization temperature are 10 DEG C, crystallize out the potassium magnesium sulfate product for meeting GB/T20937-2018 technical requirements
(K2SO4·2MgSO4·6H2O)10kg；Remaining mother liquor return step (3) carries out magnesium sulfate circulation crystallization；
(5) each reaction system tail gas enters tail gas absorber, empties after processing is up to standard.
As seen from the above embodiment, the present invention uses in magnesia with graphene Waste Sulfuric Acid, obtains magnesium sulfate and potassium sulfate
Magnesium products realize the recycling of sulfuric acid and potassium ion；Manganese fertilizer can be produced using the manganese ion in oxidizing process recycling graphene spent acid.It can
See, the full element resource of graphene Waste Sulfuric Acid can be achieved in the present invention.
The present invention is the above is only a preferred embodiment of the present invention, it is noted that for the common of the art
For technical staff, various improvements and modifications may be made without departing from the principle of the present invention, these are improved and profit
Decorations also should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of method of graphene Waste Sulfuric Acid recycling, which comprises the following steps:
(1) graphene Waste Sulfuric Acid is mixed with magnesia and carries out neutralization reaction, obtain neutralization reaction liquid；
(2) the neutralization reaction liquid is mixed with oxidant and carries out oxidation reaction, obtain oxidation liquid；
(3) oxidation liquid is mixed with flocculant and carries out flocculation treatment, obtain sediment and filtrate after separation of solid and liquid；
(4) filtrate is subjected to circulation concentration, crystallization and separation, until potassium sulfate mass concentration in separating obtained separating liquid >=
10% terminates, and using the separating liquid of potassium sulfate mass concentration >=10% as the first mother liquor, separating obtained solid is magnesium sulfate；
(5) the first mother liquor is successively subjected to cocrystallization and separation, obtains potassium magnesium sulfate cocrystallization object and the second mother liquor；By described
Two mother liquors repeat step (4), (5) as filtrate return step (4).
2. the method according to claim 1, wherein the temperature of the neutralization reaction be 40~110 DEG C, it is described in
PH value with reaction solution is 4~8.
3. the method according to claim 1, wherein the oxidant is hydrogen peroxide, sodium hypochlorite and hypochlorous acid
One or more of potassium, the quality of the oxidant are the 0.01~2% of the neutralization reaction liquid quality.
4. the method according to claim 1, wherein the time of the oxidation reaction is 0.1~1h.
5. the method according to claim 1, wherein the flocculant is polyacrylamide, bodied ferric sulfate, gathers
One or more of aluminium chloride and polyaluminium sulfate are closed, the quality of the flocculant is the 0.01 of the oxidation liquid quality
~0.2%.
6. the method according to claim 1, wherein the method for concentration in the circulation condensing crystallizing is negative pressure steaming
Hair concentration, temperature are 95~105 DEG C.
7. the method according to claim 1, wherein the temperature crystallized in the step (4) is 25~40 DEG C.
8. the method according to claim 1, wherein the temperature of cocrystallization is 5~25 DEG C in the step (5).
9. a kind of system of graphene Waste Sulfuric Acid recycling characterized by comprising
Reaction kettle (1), the reaction kettle (1) includes solid inlet, liquid inlet, liquid outlet and gas vent；
The filter press (2) that entrance is connected to the liquid outlet of the reaction kettle (1), the filter press (2) include liquid outlet and
Solid outlet；
The dryer (3) that entrance is connected to the solid outlet of the filter press (2)；
The evaporator (4) that entrance is connected to the liquid outlet of the filter press (2), the evaporator (4) include gas vent and
Liquid outlet；
The first crystallizer (5) that entrance is connected to the liquid outlet of the evaporator (4)；
The first separator (6) of entrance and the first crystallizer (5) outlet, first separator (6) includes solid
Outlet and liquid outlet；
The second crystallizer (7) that entrance is connected to the liquid outlet of first separator (6)；First separator (6)
Liquid outlet is also connected to the entrance of evaporator (4)；
The second separator (8) of entrance and the second crystallizer (7) outlet, second separator (8) includes solid
Outlet and liquid outlet, the liquid outlet are connected to the entrance of the evaporator (4)；
The tail gas absorption being connected to entrance with the gas vent of the gas vent of the reaction kettle (1) and the evaporator (4)
System (9).
10. a kind of method for carrying out graphene Waste Sulfuric Acid recycling using system described in claim 9, which is characterized in that including
Following steps:
(a) graphene Waste Sulfuric Acid is mixed in reaction kettle (1) with magnesia and carries out neutralization reaction, obtain neutralization reaction liquid；
(b) the neutralization reaction liquid is mixed in reaction kettle (1) with oxidant and carries out oxidation reaction, obtain oxidation liquid；
(c) oxidation liquid is mixed in reaction kettle (1) with flocculant after carrying out flocculation treatment, flocculation liquid enters filters pressing
Machine (2) is separated by solid-liquid separation, and sediment and filtrate are obtained；Sediment enters dryer (3) and is dried；
(d) filtrate sequentially enter evaporator (4), the first crystallizer (5) and the first separator (6) be concentrated, crystallize and
The step of separation, the middle circulation of isolated separating liquid Returning evaporimeter (4) is concentrated, is crystallized and is separated, until separating liquid
The mass concentration of middle potassium sulfate >=10% terminates, using the separating liquid of potassium sulfate mass concentration >=10% as the first mother liquor；First
Isolated solid is magnesium sulfate in separator (6)；
(e) first mother liquor sequentially enters the second crystallizer (7) and the second separator (8) carries out cocrystallization and separation, obtains
Potassium magnesium sulfate cocrystallization object and the second mother liquor；Using second mother liquor as filtrate, return step (d) repeats step
(d),(e)；
The tail gas that reaction kettle (1) and evaporator (4) generate empties after tail gas absorbing system (9) processing.
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