CN110092396B - Method and system for recycling waste sulfuric acid of graphene - Google Patents
Method and system for recycling waste sulfuric acid of graphene Download PDFInfo
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- CN110092396B CN110092396B CN201910477238.6A CN201910477238A CN110092396B CN 110092396 B CN110092396 B CN 110092396B CN 201910477238 A CN201910477238 A CN 201910477238A CN 110092396 B CN110092396 B CN 110092396B
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 239000002699 waste material Substances 0.000 title claims abstract description 56
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 53
- 238000004064 recycling Methods 0.000 title claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 70
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims abstract description 58
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 45
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 40
- 238000000926 separation method Methods 0.000 claims abstract description 39
- 239000012452 mother liquor Substances 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 32
- 229910052939 potassium sulfate Inorganic materials 0.000 claims abstract description 32
- 235000011151 potassium sulphates Nutrition 0.000 claims abstract description 32
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims abstract description 30
- 235000019341 magnesium sulphate Nutrition 0.000 claims abstract description 30
- 239000000706 filtrate Substances 0.000 claims abstract description 25
- 239000007787 solid Substances 0.000 claims abstract description 24
- 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 21
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 20
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 20
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000001590 oxidative effect Effects 0.000 claims abstract description 20
- 239000007800 oxidant agent Substances 0.000 claims abstract description 19
- 238000002288 cocrystallisation Methods 0.000 claims abstract description 18
- 238000005189 flocculation Methods 0.000 claims abstract description 15
- 230000016615 flocculation Effects 0.000 claims abstract description 15
- 239000013078 crystal Substances 0.000 claims abstract description 12
- 239000012295 chemical reaction liquid Substances 0.000 claims description 41
- 238000002425 crystallisation Methods 0.000 claims description 34
- 230000008025 crystallization Effects 0.000 claims description 34
- 238000002156 mixing Methods 0.000 claims description 23
- 239000002244 precipitate Substances 0.000 claims description 21
- 239000008394 flocculating agent Substances 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 239000010413 mother solution Substances 0.000 claims description 10
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 6
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 claims description 5
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 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
- 229910001437 manganese ion Inorganic materials 0.000 abstract description 12
- 230000003647 oxidation Effects 0.000 abstract description 9
- 239000002253 acid Substances 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 7
- 229910001414 potassium ion Inorganic materials 0.000 abstract description 7
- 239000013049 sediment Substances 0.000 abstract description 4
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 39
- 239000007789 gas Substances 0.000 description 31
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 16
- 238000004891 communication Methods 0.000 description 13
- 239000003337 fertilizer Substances 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 11
- 239000011572 manganese Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 9
- 229910052748 manganese Inorganic materials 0.000 description 9
- 125000004122 cyclic group Chemical group 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 235000001055 magnesium Nutrition 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- -1 hydrogen peroxide manganese oxide ions Chemical class 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 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
- 239000012286 potassium permanganate Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 235000004789 Rosa xanthina Nutrition 0.000 description 1
- 241000109329 Rosa xanthina 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052796 boron Inorganic materials 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
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000008141 laxative Substances 0.000 description 1
- 230000002475 laxative effect Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 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
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 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
- 235000012015 potatoes Nutrition 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 235000013311 vegetables Nutrition 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Fertilizers (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention provides a method and a system for recycling waste sulfuric acid of graphene, and relates to the technical field of resource environment. The invention carries out neutralization reaction on graphene waste sulfuric acid and magnesium oxide, then carries out oxidation reaction on the graphene waste sulfuric acid and an oxidant, and then obtains sediment and filtrate through flocculation treatment; circularly concentrating, crystallizing and separating the filtrate until the mass concentration of potassium sulfate in the separated liquid is more than or equal to 10%, taking the separated liquid with the mass concentration of potassium sulfate being more than or equal to 10% as a first mother liquor, and separating to obtain solid magnesium sulfate; and sequentially performing co-crystallization and separation on the first mother liquor to obtain a potassium magnesium sulfate co-crystal and a second mother liquor, and returning the second mother liquor to the step of circulating, concentrating and crystallizing. According to the invention, magnesium oxide is used for neutralizing graphene waste sulfuric acid to obtain magnesium sulfate and potassium magnesium sulfate, so that sulfuric acid and potassium ions are recovered; and recovering manganese ions in the graphene waste acid by adopting an oxidation method. The method has the advantages of simple process, resource treatment of the whole element of the waste sulfuric acid of the graphene, and remarkable economic and social benefits.
Description
Technical Field
The invention relates to the technical field of resource environment, in particular to a method and a system for recycling graphene waste sulfuric acid.
Background
Graphene is an emerging material, and has extremely wide application prospect; currently, the main production process of graphene is a redox method, wherein the oxidation process mainly adopts a modified Hummers method, and two methods are commonly used in the method: (1) potassium permanganate is taken as a strong oxidant, and sulfuric acid is used for intercalation; (2) firstly, pre-oxidizing graphite powder by using potassium persulfate and phosphorus pentoxide, and then, intercalation by using sulfuric acid by using potassium permanganate as a strong oxidant.
The oxidation process produces a large amount of spent sulfuric acid, wherein the sulfuric acid content is about 30% -59% (wt%), the manganese ion content is about 0.2% -2% (wt%), the potassium ion content is about 0.2% -2% (wt%), and trace heavy metals carried by the raw materials. At present, the waste sulfuric acid of graphene is mainly neutralized by a calcium method, and is not fully recycled.
Disclosure of Invention
In view of the above, the present invention aims to provide a method and a system for recycling waste sulfuric acid of graphene. The method and the system provided by the invention can realize the full element recycling of the waste sulfuric acid of the graphene, and achieve zero emission.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for recycling waste sulfuric acid of graphene, which comprises the following steps:
(1) Mixing waste sulfuric acid of graphene with magnesium oxide to perform a neutralization reaction to obtain a neutralization reaction liquid;
(2) Mixing the neutralization reaction liquid with an oxidant for oxidation reaction to obtain an oxidation reaction liquid;
(3) Mixing the oxidation reaction liquid with a flocculating agent for flocculation treatment, and carrying out solid-liquid separation to obtain a precipitate and a filtrate;
(4) Circularly concentrating, crystallizing and separating the filtrate until the mass concentration of potassium sulfate in the separated liquid is more than or equal to 10%, taking the separated liquid with the mass concentration of potassium sulfate being more than or equal to 10% as a first mother liquor, and separating to obtain solid magnesium sulfate;
(5) Sequentially performing co-crystallization and separation on the first mother solution to obtain a potassium magnesium sulfate co-crystal and a second mother solution; and (3) returning the second mother liquor to the step (4), and repeating the steps (4) and (5).
Preferably, the temperature of the neutralization reaction is 40-110 ℃, and the pH of the neutralization reaction solution is 4-8.
Preferably, the oxidant is one or more of hydrogen peroxide, sodium hypochlorite and potassium hypochlorite, and the mass of the oxidant is 0.01-2% of the mass of the neutralization reaction liquid.
Preferably, the time of the oxidation reaction is 0.1 to 1 hour.
Preferably, the flocculant is one or more of polyacrylamide, polymeric ferric sulfate, polymeric aluminum chloride and polymeric aluminum sulfate, and the mass of the flocculant is 0.01-0.2% of the mass of the oxidation reaction liquid.
Preferably, the concentration method in the circulating concentration crystallization is negative pressure evaporation concentration, and the temperature is 95-105 ℃.
Preferably, the crystallization temperature in the step (4) is 25 to 40 ℃.
Preferably, the temperature of the co-crystallization in the step (5) is 5-25 ℃.
The invention provides a system for recycling waste sulfuric acid of graphene, and a schematic diagram of the system is shown in fig. 1. The system for recycling the graphene waste sulfuric acid provided by the invention comprises the following components: a reaction kettle 1, wherein the reaction kettle 1 comprises a solid inlet, a liquid outlet and a gas outlet;
a filter press 2 with an inlet communicated with a liquid outlet of the reaction kettle 1, wherein the filter press 2 comprises a liquid outlet and a solid outlet;
a dryer 3 having an inlet communicating with the solid outlet of the filter press 2;
an evaporator 4 having an inlet in communication with the liquid outlet of the filter press 2, the evaporator 4 comprising a gas outlet and a liquid outlet;
a first crystallizer 5 with an inlet in communication with the liquid outlet of said evaporator 4;
a first separator 6 having an inlet in communication with the outlet of the first crystallizer 5, the first separator 6 comprising a solids outlet and a liquid outlet;
a second crystallizer 7 with an inlet communicating with the liquid outlet of said first separator 6; the liquid outlet of the first separator 6 is also in communication with the inlet of the evaporator 4;
a second separator 8 having an inlet in communication with the outlet of the second crystallizer 7, the second separator 8 comprising a solids outlet and a liquid outlet, the liquid outlet being in communication with the inlet of the evaporator 4;
and an exhaust gas absorption system 9 with an inlet communicated with the gas outlet of the reaction kettle 1 and the gas outlet of the evaporator 4.
The invention provides a method for recycling graphene waste sulfuric acid by utilizing the system, which comprises the following steps:
(a) Mixing graphene waste sulfuric acid and magnesium oxide in a reaction kettle 1 to perform a neutralization reaction to obtain a neutralization reaction liquid;
(b) Mixing the neutralization reaction liquid with an oxidant in a reaction kettle 1 for oxidation reaction to obtain an oxidation reaction liquid;
(c) Mixing the oxidation reaction liquid with a flocculating agent in a reaction kettle 1 for flocculation treatment, and allowing the flocculated liquid to enter a filter press 2 for solid-liquid separation to obtain precipitate and filtrate; the precipitate enters a dryer 3 for drying;
(d) The filtrate sequentially enters an evaporator 4, a first crystallizer 5 and a first separator 6 for concentration, crystallization and separation, separated liquid obtained by separation returns to the evaporator 4 for circulation for concentration, crystallization and separation until the mass concentration of potassium sulfate in the separated liquid is more than or equal to 10%, and the separated liquid with the mass concentration of potassium sulfate being more than or equal to 10% is used as a first mother liquor; the solid separated in the first separator 6 is magnesium sulfate;
(e) The first mother liquor sequentially enters a second crystallizer 7 and a second separator 8 for co-crystallization and separation to obtain potassium magnesium sulfate co-crystals and a second mother liquor; the second mother liquor returns to the step (d), and the steps (d) and (e) are repeated;
the tail gas generated by the reaction kettle 1 and the evaporator 4 is processed by a tail gas absorption system 9 and then is exhausted.
The invention provides a method for recycling waste sulfuric acid of graphene, which comprises the following steps: (1) Mixing waste sulfuric acid of graphene with magnesium oxide to perform a neutralization reaction to obtain a neutralization reaction liquid; (2) Mixing the neutralization reaction liquid with an oxidant for oxidation reaction to obtain an oxidation reaction liquid; (3) Mixing the oxidation reaction liquid with a flocculating agent for flocculation treatment, and carrying out solid-liquid separation to obtain a precipitate and a filtrate; (4) Circularly concentrating, crystallizing and separating the filtrate until the mass concentration of potassium sulfate in the separated liquid is more than or equal to 10%, taking the separated liquid with the mass concentration of potassium sulfate being more than or equal to 10% as a first mother liquor, and separating the obtained solid to obtain magnesium sulfate; (5) Sequentially performing co-crystallization and separation on the first mother solution to obtain a potassium magnesium sulfate co-crystal and a second mother solution; and (3) returning the second mother liquor to the step (4), and repeating the steps (4) and (5). According to the invention, waste sulfuric acid of graphene is neutralized by using magnesium oxide to obtain magnesium sulfate and potassium magnesium sulfate products, so that the recovery of sulfuric acid and potassium ions is realized; manganese ions in the graphene waste acid are recovered by an oxidation method to produce the manganese fertilizer. The method provided by the invention is simple, the whole element of the waste sulfuric acid of the graphene is subjected to resource treatment, zero emission is realized, and the economic and social benefits are obvious.
The invention provides a system for recycling waste sulfuric acid of graphene, which has the advantages of simple flow, strict principle, low investment and low cost, and the system has wide application prospect due to the full recycling of the waste sulfuric acid of graphene.
Drawings
Fig. 1 is a schematic diagram of a system for recycling waste sulfuric acid of graphene, in fig. 1, 1 represents a reaction kettle, 2 represents a filter press, 3 represents a dryer, 4 represents an evaporator, 5 represents a first crystallizer, 6 represents a first separator, 7 represents a second crystallizer, 8 represents a second separator, and 9 represents an exhaust gas absorption system;
fig. 2 is a flow chart of the resource utilization of the graphene waste sulfuric acid.
Detailed Description
The invention provides a method for recycling waste sulfuric acid of graphene, which comprises the following steps:
(1) Mixing waste sulfuric acid of graphene with magnesium oxide to perform a neutralization reaction to obtain a neutralization reaction liquid;
(2) Mixing the neutralization reaction liquid with an oxidant for oxidation reaction to obtain an oxidation reaction liquid;
(3) Mixing the oxidation reaction liquid with a flocculating agent for flocculation treatment, and carrying out solid-liquid separation to obtain a precipitate and a filtrate;
(4) Circularly concentrating, crystallizing and separating the filtrate until the mass concentration of potassium sulfate in the separated liquid is more than or equal to 10%, taking the separated liquid with the mass concentration of potassium sulfate being more than or equal to 10% as a first mother liquor, and separating the obtained solid to obtain magnesium sulfate;
(5) Sequentially performing co-crystallization and separation on the first mother solution to obtain a potassium magnesium sulfate co-crystal and a second mother solution; and (3) returning the second mother liquor to the step (4), and repeating the steps (4) and (5).
According to the invention, the waste sulfuric acid of graphene is mixed with magnesium oxide for neutralization reaction, so that a neutralization reaction liquid is obtained, namely, the waste sulfuric acid of graphene is neutralized by magnesium sulfate. In the present invention, the temperature of the neutralization reaction is preferably 40 to 110 ℃, more preferably 60 to 100 ℃; the pH of the neutralization reaction liquid is preferably 4 to 8, more preferably 6 to 7, and is controlled by the addition amount of magnesium oxide. The pH of the neutralization reaction liquid is controlled within the range of 4-8, so that the utilization rate of magnesium oxide can be improved, and the subsequent oxidation of divalent manganese ions is facilitated within the pH range.
After the neutralization reaction, the neutralization reaction liquid is mixed with an oxidant for oxidation reaction, so that an oxidation reaction liquid is obtained. In the present invention, the oxidizing agent is preferably one or more of hydrogen peroxide, sodium hypochlorite and potassium hypochlorite, and the mass of the oxidizing agent is preferably 0.01 to 2% of the mass of the neutralization reaction liquid, more preferably 0.1 to 1%. The oxidant is preferably added into the neutralization reaction liquid for mixing, the mixing method is not particularly required, and the mixing method is well known in the art, so that the uniform mixing is ensured. In the present invention, the time of the oxidation reaction is preferably 0.1 to 1 hour. The method comprises the steps of oxidizing manganese ions in graphene waste sulfuric acid into manganese dioxide by an oxidation method, wherein the reaction formula of hydrogen peroxide manganese oxide ions is shown in a formula 1; the sodium hypochlorite and the potassium hypochlorite are hypochlorite, and the reaction formula of manganese oxide ions is shown as formula 2:
H 2 O 2 +Mn 2+ +2OH - →MnO 2 ↓+2H 2 o is 1;
ClO - +Mn 2+ +2OH - →MnO 2 ↓+H 2 O+Cl - formula 2.
After the oxidation reaction, the invention mixes the oxidation reaction liquid with a flocculating agent for flocculation treatment, and precipitates and filtrate are obtained after solid-liquid separation. In the present invention, the flocculant is preferably one or more of polyacrylamide, polymeric ferric sulfate, polymeric aluminum chloride and polymeric aluminum sulfate, and the flocculant is preferably 0.01 to 0.2% by mass, more preferably 0.1 to 0.15% by mass of the oxidation reaction liquid. In the present invention, the flocculant is preferably added to an oxidation reaction solution, and the oxidation reaction solution is subjected to flocculation treatment. In the present invention, the flocculation treatment time is preferably 0.2 to 2 hours. The invention improves the subsequent separation efficiency of the sediment by adding the flocculating agent. After flocculation treatment, the invention carries out solid-liquid separation on the obtained flocculation liquid to obtain sediment and filtrate. The method of the present invention for solid-liquid separation is not particularly limited, and methods well known in the art, such as a press filtration method, may be employed. In the invention, the main components of the precipitate are impurities such as calcium silicate and manganese dioxide in magnesium oxide raw materials, and the main components in filtrate are magnesium sulfate and a small amount of potassium sulfate; the precipitate can be used as a manganese fertilizer after being dried.
After solid-liquid separation, the filtrate is circularly concentrated, crystallized and separated until the mass concentration of potassium sulfate in the separated liquid is more than or equal to 10%, the separated liquid with the mass concentration of potassium sulfate being more than or equal to 10% is used as a first mother liquor, and the separated solid is magnesium sulfate. In the present invention, the cyclic concentration, crystallization and separation, i.e., the processes of concentration, crystallization and separation, are cyclically performed; the concentration method in the circulating concentration crystallization is preferably negative pressure evaporation concentration, and the temperature is preferably 95-105 ℃, more preferably 100 ℃; the crystallization temperature of the cyclic concentrated crystals is preferably 25 to 40 ℃, more preferably 30 to 35 ℃. In the invention, the cyclic concentrated crystallization is specifically as follows: and (3) sequentially concentrating and crystallizing the filtrate, and returning the separating liquid obtained by separating the crystallization liquid to a concentration process to repeat the steps of concentrating, crystallizing and separating until the mass concentration of potassium sulfate in the separating liquid is more than or equal to 10%. In this process, potassium sulfate is present in the solution at a low concentration, and the crystallization process is only crystallization of magnesium sulfate, so that the solid substance obtained after crystallization separation is magnesium sulfate. The magnesium sulfate can be used as raw materials for leather making, explosive, papermaking, porcelain, chemical synthesis and the like in industry; is used as an oral laxative in medical treatment; agricultural is widely used as foliar and soil magnesium fertilizer because magnesium is one of the main components of chlorophyll, and is commonly used for vegetables, fruits or magnesium-deficient crops such as tomatoes, potatoes, roses, and the like.
After the cyclic concentration, crystallization and separation, the first mother liquor is subjected to co-crystallization and separation in sequence to obtain a potassium magnesium sulfate co-crystal and a second mother liquor. In the invention, the mass concentration of the potassium sulfate in the first mother solution is more than or equal to 10%, and the potassium sulfate and the magnesium sulfate can be subjected to co-crystallization, wherein the temperature of the co-crystallization is preferably 5-25 ℃, more preferably 15-20 ℃; the time is preferably > 0.5h, more preferably 4-5 h.
After co-crystallization, the method separates the obtained co-crystallization liquid to obtain a magnesium potassium sulfate co-crystal and a second mother liquid; the second mother liquor contains a large amount of magnesium sulfate and a small amount of potassium sulfate, returns to the step of circulating concentration crystallization, and repeatedly performs the steps of circulating concentration crystallization, separation and co-crystallization; the molecular formula of the potassium magnesium sulfate cocrystal is K 2 SO 4 ·mMgSO 4 ·nH 2 O, where m=1 to 2 and n=0 to 6. The obtained potassium magnesium sulfate can be used as a novel compound fertilizer, and has the characteristics of rich nutrient content, good soil improvement effect, capability of effectively promoting crop growth, obvious economic benefit and the like; the multi-element potash fertilizer contains potassium, magnesium and sulfur, and can be added with medium trace elements such as calcium, silicon, boron, iron, zinc and the like, and is generally used as a base fertilizer and can also be used as an additional fertilizer.
According to the invention, waste sulfuric acid of graphene is neutralized by using magnesium oxide to obtain magnesium sulfate and potassium magnesium sulfate products, so that the recovery of sulfuric acid and potassium ions is realized; manganese ions in the graphene waste acid are recovered by an oxidation method to produce the manganese fertilizer. Therefore, the method provided by the invention can realize the recycling treatment of the graphene waste sulfuric acid all elements, realizes zero emission and has remarkable economic and social benefits.
The invention provides a system for recycling waste sulfuric acid of graphene, which is shown in fig. 1 and comprises the following steps:
a reaction kettle 1, wherein the reaction kettle 1 comprises a solid inlet, a liquid outlet and a gas outlet;
a filter press 2 with an inlet communicated with a liquid outlet of the reaction kettle 1, wherein the filter press 2 comprises a liquid outlet and a solid outlet;
a dryer 3 having an inlet communicating with the solid outlet of the filter press 2;
an evaporator 4 having an inlet in communication with the liquid outlet of the filter press 2, the evaporator 4 comprising a gas outlet and a liquid outlet;
a first crystallizer 5 with an inlet in communication with the liquid outlet of said evaporator 4;
a first separator 6 having an inlet in communication with the outlet of the first crystallizer 5, the first separator 6 comprising a solids outlet and a liquid outlet;
a second crystallizer 7 with an inlet communicating with the liquid outlet of said first separator 6; the liquid outlet of the first separator 6 is also in communication with the inlet of the evaporator 4;
a second separator 8 having an inlet in communication with the outlet of the second crystallizer 7, the second separator 8 comprising a solids outlet and a liquid outlet, the liquid outlet being in communication with the inlet of the evaporator 4;
and an exhaust gas absorption system 9 with an inlet communicated with the gas outlet of the reaction kettle 1 and the gas outlet of the evaporator 4.
In the invention, the liquid outlet and the gas outlet of the reaction kettle 1 are respectively positioned at the lower end and the top end of the reaction kettle 1; the liquid outlet and the gas outlet of the evaporator 4 are respectively positioned at the bottom and the top of the evaporator 4; the solid outlet and the liquid outlet of the first separator 6 are respectively positioned at the upper end and the lower end of the first separator 6; the solids outlet and the liquid outlet of the second separator 8 are located at the upper and lower ends of the second separator 8, respectively.
The invention has no special requirements on the specific types of the reaction kettle, the filter press, the dryer, the evaporator, the first crystallizer, the first separator, the second crystallizer, the second separator and the tail gas absorption system, and the equipment well known to the person skilled in the art can be used for communicating according to the communication mode described in the scheme. The system for recycling the waste sulfuric acid of the graphene, provided by the invention, has the advantages of simple flow, strict principle, low investment and low cost, can fully recycle the waste sulfuric acid of the graphene, and has a wide application prospect.
The invention provides a method for recycling graphene waste sulfuric acid by using the system, which is shown in a flow chart in fig. 2 and comprises the following steps:
(a) Mixing graphene waste sulfuric acid and magnesium oxide in a reaction kettle 1 to perform a neutralization reaction to obtain a neutralization reaction liquid;
(b) Mixing the neutralization reaction liquid with an oxidant in a reaction kettle 1 for oxidation reaction to obtain an oxidation reaction liquid;
(c) Mixing the oxidation reaction liquid with a flocculating agent in a reaction kettle 1 for flocculation treatment, and allowing the flocculated liquid to enter a filter press 2 for solid-liquid separation to obtain precipitate and filtrate; the precipitate enters a dryer 3 for drying;
(d) The filtrate sequentially enters an evaporator 4, a first crystallizer 5 and a first separator 6 for concentration, crystallization and separation, separated liquid obtained by separation returns to the evaporator 4 for circulation for concentration, crystallization and separation until the mass concentration of potassium sulfate in the separated liquid is more than or equal to 10%, and the separated liquid with the mass concentration of potassium sulfate being more than or equal to 10% is used as a first mother liquor; the solid separated in the first separator 6 is magnesium sulfate;
(e) The first mother liquor sequentially enters a second crystallizer 7 and a second separator 8 for co-crystallization and separation to obtain potassium magnesium sulfate co-crystals and a second mother liquor; the second mother liquor returns to the step (d), and the steps (d) and (e) are repeated;
the tail gas generated by the reaction kettle 1 and the evaporator 4 is processed by a tail gas absorption system 9 and then is exhausted.
According to the invention, the waste sulfuric acid of graphene and magnesium oxide are mixed in a reaction kettle 1 to carry out neutralization reaction, so that a neutralization reaction liquid is obtained. According to the invention, graphene waste sulfuric acid and magnesium oxide are respectively added into a reaction kettle through a liquid inlet and a solid inlet of the reaction kettle 1 to be mixed for neutralization reaction; the mixing is preferably carried out under stirring; the neutralization reaction temperature and pH conditions are the same as those of the above scheme, and will not be described here. The invention neutralizes the waste sulfuric acid of graphene by magnesium sulfate. In the process, the main component of the tail gas generated by the reaction kettle 1 is water vapor, and the tail gas is exhausted after being treated by the tail gas absorption system 9.
After the neutralization reaction, the obtained neutralization reaction liquid and an oxidant are mixed in a reaction kettle 1 for oxidation reaction; the type of the oxidizing agent and the conditions of the oxidation reaction are the same as those of the above scheme, and will not be described in detail herein. In the invention, hydrogen peroxide is preferably added through a liquid inlet of the reaction kettle 1, and sodium hypochlorite and potassium hypochlorite are preferably added through a solid inlet of the reaction kettle 1. The invention oxidizes manganese ions in the waste sulfuric acid of graphene into manganese dioxide by an oxidation method.
After the oxidation reaction, the obtained oxidation reaction liquid and a flocculating agent are mixed in a reaction kettle 1 for flocculation treatment, and the flocculation liquid enters a filter press 2 for solid-liquid separation to obtain a precipitate and filtrate; the precipitate enters a dryer 3 for drying. In the present invention, the types and the addition amounts of the flocculating agent are the same as those of the above-described schemes, and are not described herein. After the oxidation reaction and flocculation treatment, the tail gas generated by the reaction kettle 1 mainly comprises water vapor and a small amount of dust, and the tail gas is emptied after being treated by a tail gas absorption system 9. The invention improves the subsequent separation efficiency of the sediment by adding the flocculating agent. In the invention, the main components of the precipitate are impurities such as calcium silicate and manganese dioxide in magnesium oxide raw materials, and the filtrate is mainly magnesium sulfate and a small amount of potassium sulfate solution; the precipitate can be used as a manganese fertilizer after being dried.
After solid-liquid separation, the obtained filtrate sequentially enters an evaporator 4, a first crystallizer 5 and a first separator 6 for concentration, crystallization and separation, and the separated liquid obtained by separation returns to the evaporator 4 for circulation for concentration, crystallization and separation until the mass concentration of potassium sulfate in the separated liquid is more than or equal to 10%, and the separated liquid with the mass concentration of potassium sulfate more than or equal to 10% is used as a first mother liquor. In the present invention, the temperature of concentration and crystallization is the same as that of the above scheme, and will not be described herein. In this process, potassium sulfate is present in the solution at a low concentration, and the crystallization process is only crystallization of magnesium sulfate, and thus the solid separated in the first separator 6 is magnesium sulfate. The main component of the tail gas generated by the evaporator 4 is water vapor, and the tail gas is exhausted after being treated by a tail gas absorption system 9.
After the concentration, crystallization and separation, the first mother liquor sequentially enters a second crystallizer 7 and a second separator 8 for co-crystallization and separation to obtain a potassium magnesium sulfate co-crystal and a second mother liquor; the second mother liquor is returned to the evaporator 4, and the above steps of concentration, crystallization and separation are repeated. In the invention, the mass concentration of potassium sulfate in the first mother solution is more than or equal to 10%, and potassium sulfate and magnesium sulfate can be subjected to co-crystallization to obtain potassium magnesium sulfate co-crystals; the temperature of the co-crystallization in this process is consistent with the above scheme and will not be described again.
The method and system for recycling the waste sulfuric acid of graphene provided by the invention are described in detail below with reference to examples, but they are not to be construed as limiting the scope of the invention.
Example 1
(1) Starting the reaction kettle for stirring, adding 1000kg of graphene waste sulfuric acid with the sulfuric acid mass content of 40% and 182kg of light burned magnesium oxide with the sulfuric acid mass content of 90% into the reaction kettle through a sulfuric acid metering tank until the pH value reaches 7, and keeping the reaction temperature at 90 ℃ for 30 minutes;
(2) Adding 6.5kg of hydrogen peroxide with the mass concentration of 30% into the solution in the step (1), and oxidizing divalent manganese ions (the manganese ion content of waste acid is 0.3%) to generate manganese dioxide precipitate; after reacting for 1 hour, adding 1kg of polyaluminium sulfate flocculant, filtering and separating manganese dioxide precipitate, and drying the precipitate to obtain 5kg of manganese fertilizer (the mass content of manganese is 60%);
(3) The filtrate from the step (2) is mainly magnesium sulfate and a small amount of potassium sulfate solution (waste acid contains 0.4 percent of potassium ions), and 950kg of magnesium sulfate product meeting the technical requirements of HG/T2680-2017 is obtained through cyclic concentration and cooling crystallization;
(4) Transferring the mother liquor from the step (3) to a potassium magnesium sulfate crystallizer when the concentration of potassium sulfate is more than or equal to 10% through cyclic crystallization, controlling the crystallization temperature to be 10 ℃, and crystallizing to obtain a potassium magnesium sulfate product (K) meeting the technical requirements of GB/T20937-2018 2 SO 4 ·2MgSO 4 ·6H 2 O) 20kg; and (3) returning the residual mother liquor to the step (3) for magnesium sulfate cyclic crystallization.
(5) And (3) enabling tail gas of each reaction system to enter a tail gas absorption tower, and evacuating after reaching the standard through treatment.
Example 2
(1) Starting the reaction kettle for stirring, adding 1000kg of graphene waste sulfuric acid with the sulfuric acid mass content of 50% and 227kg of light burned magnesium oxide with the sulfuric acid mass content of 90% into the reaction kettle through a sulfuric acid metering tank until the pH value reaches 6, and keeping the reaction temperature at 90 ℃ for 30 minutes;
(2) Adding 7.2kg of sodium hypochlorite into the solution obtained in the step (1), and oxidizing divalent manganese ions (the manganese ion content of waste acid is 0.5%) to generate manganese dioxide precipitate; after reacting for 1 hour, adding 1.2kg of polyaluminium sulfate flocculant, filtering and separating manganese dioxide precipitate, and drying the precipitate to obtain 8kg of manganese fertilizer (the manganese content is 60%);
(3) The filtrate from the step (2) is mainly magnesium sulfate and a small amount of potassium sulfate solution (waste acid contains 0.2 percent of potassium ions), and 1225kg of magnesium sulfate product meeting the technical requirements of HG/T2680-2017 is obtained through cyclic concentration and cooling crystallization;
(4) Transferring the mother liquor from the step (3) to a potassium magnesium sulfate crystallizer when the concentration of potassium sulfate is more than or equal to 10% through cyclic crystallization, controlling the crystallization temperature to be 10 ℃, and crystallizing to obtain a potassium magnesium sulfate product (K) meeting the technical requirements of GB/T20937-2018 2 SO 4 ·2MgSO 4 ·6H 2 O) 10kg; returning the residual mother liquor to the step (3) for magnesium sulfate cyclic crystallization;
(5) And (3) enabling tail gas of each reaction system to enter a tail gas absorption tower, and evacuating after reaching the standard through treatment.
From the above examples, the invention uses magnesium oxide to neutralize waste sulfuric acid of graphene to obtain magnesium sulfate and potassium magnesium sulfate products, thereby realizing the recovery of sulfuric acid and potassium ions; manganese ions in the graphene waste acid are recovered by an oxidation method to produce the manganese fertilizer. Therefore, the invention can realize the full element recycling of the waste sulfuric acid of the graphene.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (7)
1. The method for recycling the waste sulfuric acid of the graphene is characterized by comprising the following steps of:
(1) Mixing waste sulfuric acid of graphene with magnesium oxide to perform a neutralization reaction to obtain a neutralization reaction liquid; the pH value of the neutralization reaction liquid is 6-7;
(2) Mixing the neutralization reaction liquid with an oxidant for oxidation reaction to obtain an oxidation reaction liquid;
(3) Mixing the oxidation reaction liquid with a flocculating agent for flocculation treatment, and carrying out solid-liquid separation to obtain a precipitate and a filtrate;
(4) Circularly concentrating, crystallizing and separating the filtrate until the mass concentration of potassium sulfate in the separated liquid is more than or equal to 10%, taking the separated liquid with the mass concentration of potassium sulfate being more than or equal to 10% as a first mother liquor, and separating the obtained solid to obtain magnesium sulfate;
(5) Sequentially performing co-crystallization and separation on the first mother solution to obtain a potassium magnesium sulfate co-crystal and a second mother solution; returning the second mother liquor as filtrate to the step (4), and repeating the steps (4) and (5); the temperature of the co-crystallization is 5-25 ℃.
2. The method according to claim 1, wherein the neutralization reaction temperature is 40 to 110 ℃.
3. The method according to claim 1, wherein the oxidant is one or more of hydrogen peroxide, sodium hypochlorite and potassium hypochlorite, and the mass of the oxidant is 0.01-2% of the mass of the neutralization reaction liquid.
4. The method of claim 1, wherein the time of the oxidation reaction is 0.1 to 1 hour.
5. The method according to claim 1, wherein the flocculant is one or more of polyacrylamide, polymeric ferric sulfate, polymeric aluminum chloride and polymeric aluminum sulfate, and the flocculant is 0.01-0.2% of the oxidation reaction liquid.
6. The method according to claim 1, wherein the concentration method in the circulating concentration is negative pressure evaporation concentration, and the temperature is 95-105 ℃.
7. The method according to claim 1, wherein the crystallization temperature in the step (4) is 25 to 40 ℃.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104192850A (en) * | 2014-08-18 | 2014-12-10 | 连云港正道新能源有限公司 | Method for treating waste graphene sulfuric acid solution by using serpentine |
| CN105923628A (en) * | 2016-06-13 | 2016-09-07 | 南京工业大学 | Wastewater treatment method in graphene preparation process |
| CN109485176A (en) * | 2018-11-30 | 2019-03-19 | 北京圣盟科技有限公司 | A kind of high-efficient treatment method of graphene production waste water |
| CN109809447A (en) * | 2019-03-27 | 2019-05-28 | 宋纯 | The recovery method of Waste Sulfuric Acid |
| CN210048502U (en) * | 2019-06-03 | 2020-02-11 | 易科力（天津）环保科技发展有限公司 | System for graphite alkene waste sulfuric acid resourceization |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104192850A (en) * | 2014-08-18 | 2014-12-10 | 连云港正道新能源有限公司 | Method for treating waste graphene sulfuric acid solution by using serpentine |
| CN105923628A (en) * | 2016-06-13 | 2016-09-07 | 南京工业大学 | Wastewater treatment method in graphene preparation process |
| CN109485176A (en) * | 2018-11-30 | 2019-03-19 | 北京圣盟科技有限公司 | A kind of high-efficient treatment method of graphene production waste water |
| CN109809447A (en) * | 2019-03-27 | 2019-05-28 | 宋纯 | The recovery method of Waste Sulfuric Acid |
| CN210048502U (en) * | 2019-06-03 | 2020-02-11 | 易科力（天津）环保科技发展有限公司 | System for graphite alkene waste sulfuric acid resourceization |
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