CN106396227B - Recycling method of waste acid generated by preparing graphene oxide by liquid-phase chemical method - Google Patents
Recycling method of waste acid generated by preparing graphene oxide by liquid-phase chemical method Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 64
- 238000004064 recycling Methods 0.000 title claims abstract description 41
- 239000000126 substance Substances 0.000 title claims abstract description 37
- 239000007791 liquid phase Substances 0.000 title claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 88
- 239000010440 gypsum Substances 0.000 claims abstract description 38
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 38
- 238000000926 separation method Methods 0.000 claims abstract description 38
- 238000003756 stirring Methods 0.000 claims abstract description 35
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 claims abstract description 26
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 18
- 239000012716 precipitator Substances 0.000 claims abstract description 18
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 12
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- 238000000746 purification Methods 0.000 claims abstract description 3
- 238000005086 pumping Methods 0.000 claims description 87
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- 238000001914 filtration Methods 0.000 claims description 31
- 239000011572 manganese Substances 0.000 claims description 30
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 22
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 21
- 239000000460 chlorine Substances 0.000 claims description 21
- 229910052801 chlorine Inorganic materials 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 21
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- 238000007599 discharging Methods 0.000 claims description 17
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 10
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
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- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- OSVXSBDYLRYLIG-UHFFFAOYSA-N chlorine dioxide Inorganic materials O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
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- 229910001414 potassium ion Inorganic materials 0.000 claims description 3
- 229910001415 sodium ion Inorganic materials 0.000 claims description 3
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 claims description 3
- 238000000108 ultra-filtration Methods 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 229910003174 MnOOH Inorganic materials 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims 1
- 230000004048 modification Effects 0.000 claims 1
- 238000012986 modification Methods 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 abstract description 14
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 5
- 238000000053 physical method Methods 0.000 abstract description 4
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- 230000008901 benefit Effects 0.000 description 3
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- 238000003912 environmental pollution Methods 0.000 description 3
- 239000012286 potassium permanganate Substances 0.000 description 3
- 235000019398 chlorine dioxide Nutrition 0.000 description 2
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910001487 potassium perchlorate Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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Abstract
A resource method of waste acid generated by preparing graphene oxide (alkene) by a liquid phase chemical method. A recycling method for waste acid generated in the preparation of graphene oxide (graphene) by a liquid phase chemical method is characterized in that the waste acid is homogenized and is injected into a homogenizing tank by an acid-resistant pump for homogenization; recycling sulfate radicals, adding a precipitator according to the molar weight of sulfate ions in waste acid, and stirring for reaction to recover gypsum (CaSO 4 & 2H 2O); recycling manganese ions, adding inorganic base to adjust the pH value to form manganese hydroxide, adding an oxidant to react to form manganese oxide, and recovering the manganese hydroxide or oxide or a mixture of the manganese hydroxide and the oxide; through separation and purification, chloride ions are recycled, and water is recycled. The preparation method of graphene is mainly divided into a physical method and a chemical method, the physical method mainly comprises a micro-mechanical stripping method, a high-energy ball milling method and the like, and the method is low in yield and is not suitable for large-scale production. The method is applied to the fields of clean production of graphene oxide and comprehensive utilization of waste acid resources.
Description
The technical field is as follows:
the invention relates to a recycling method of waste acid generated in preparation of graphene oxide by a liquid-phase chemical method.
Background art:
graphene is a carbon nanomaterial with a two-dimensional planar structure, and has a plurality of unique physicochemical properties due to its specific monoatomic layer structure, and thus has been widely applied in the fields of energy, environment, electronics, biology, medicine, chemistry, and the like, and fundamental and application research on graphene has become one of the current leading-edge topics. The preparation method of graphene mainly comprises a physical method and a chemical method, wherein the physical method mainly comprises a micro-mechanical stripping method, a high-energy ball milling method and the like, and the method is low in yield and is not suitable for large-scale production. The chemical method mainly comprises a chemical vapor deposition method, a crystal epitaxial growth method and a redox method. Among them, the redox method is also called a liquid phase chemical method, and is a method in which graphite is oxidized with a strong acid to produce graphene oxide, and then reduced to produce graphene. The liquid phase chemical method is currently applied mostly in Hummers method, and is a main form for large-scale production and preparation of graphene oxide (graphene). However, the liquid phase chemical method produces a large amount of waste acid in the process of producing and preparing graphene oxide (alkene), and taking Hummers method as an example, every 1 ton of graphene oxide (alkene) is produced, 5-20 tons of waste acid liquor is produced, the acid content is high, and the pollution problem to the ecological environment is irreversible, so that the large-scale production of the graphene oxide (alkene) is severely restricted.
Environmental pollution and resource shortage are not only major problems of priority consideration for implementing sustainable development strategy in China, but also major challenges for human society in the 21 st century. The waste acid is used as an important environmental pollution source, and the comprehensive treatment and the reutilization of the waste acid cause wide attention of people. At present, the waste acid recycling treatment technology mainly comprises a direct roasting method, an evaporation method, a membrane separation method, an extraction method and a chemical conversion method. The methods have advantages and disadvantages in the actual application process, the single process hardly meets practical requirements, and particularly, the waste acid liquid generated in the process of preparing the graphene oxide (alkene) by the liquid phase chemical method has high acid content and contains a large amount of metal ions, so that serious environmental pollution is caused and resources are greatly wasted if the waste acid liquid is not properly comprehensively treated. Aiming at waste acid generated by preparing graphene oxide by a liquid phase chemical method, an effective comprehensive recycling treatment technology is still unavailable, and the method is still blank in China.
Taking Hummers method as an example, the main components of the waste acid generated in the process of preparing graphene oxide (alkene) by the liquid phase chemical method are water, sulfuric acid, hydrochloric acid, nitric acid, manganese ions, potassium ions and sodium ions. According to the physicochemical characteristics of the components, a set of simple and feasible combined process method is developed, the waste acid is recycled, and the gypsum and the chlorine-containing composite salt are recovered; the recycling of manganese ions is realized, and hydroxides or oxides of manganese are recovered; the recycling of water is realized. The product recovered by the process method can be used as an electrode material, a building material, a decorative material and other chemical raw materials, water can be recycled in a graphene oxide (alkene) production line, the whole process realizes closed circulation, and the basic requirements of clean production are met. In addition, the method is simple to operate, compact in process, easy to control, low in cost, green and environment-friendly in process, and has practical significance in popularization and application.
The invention content is as follows:
the invention aims to provide a recycling method of waste acid generated in the preparation of graphene oxide (graphene) by a liquid-phase chemical method.
The above purpose is realized by the following technical scheme:
a resource method for waste acid generated in preparation of graphene oxide by a liquid phase chemical method is characterized by comprising the following process steps:
(1) waste acid homogenization: injecting waste acid into a homogenizing pool by an acid-resistant pump for homogenization;
(2) recycling sulfate radicals: recovering gypsum (CaSO 4 & 2H 2O), pumping the homogenized waste acid into a reaction sedimentation tank A, adding a precipitator according to the molar weight of sulfate ions in the waste acid, stirring for reaction to form gypsum, precipitating, pumping supernatant into a reaction sedimentation tank B, pumping the precipitate into a filter, performing solid-liquid separation, discharging filtrate into the reaction sedimentation tank B, and drying filter cakes to obtain gypsum for external sale as building materials or decorative materials.
(3) Recycling manganese ions: recovering manganese hydroxide or oxide or a mixture of the manganese hydroxide and the oxide, adding inorganic base into a reaction sedimentation tank B, adjusting the pH value, stirring to form manganese hydroxide, adding an oxidant, reacting to form manganese oxide, precipitating, pumping supernatant to the next procedure, pumping sediment to a filter device, performing solid-liquid separation, pumping filtrate to the next procedure, drying filter cakes to obtain a recovered product, and externally selling the recovered product to be used as an electrode material or other chemical raw materials.
(4) Resource utilization of chloride ions: and (4) recycling the water, separating and purifying the waste liquid generated in the step (3) to obtain chlorine-containing composite salt and water, drying the chlorine-containing composite salt to be used as other chemical raw materials, and recycling the water in the process for preparing the graphene oxide by the redox method.
The resource method for the waste acid generated by preparing the graphene oxide (alkene) by the liquid phase chemical method is characterized in that the waste acid in the step 1 is from a process for preparing the graphene oxide (alkene) by the chemical method, and the main components of the waste acid are one or more of water, sulfuric acid, hydrochloric acid, nitric acid, manganese ions, potassium ions and sodium ions.
The method for recycling waste acid generated by preparing graphene oxide (graphene) by the liquid phase chemical method is used for producing gypsum (CaSO 4 & 2H 2O) according to the recycled product in the step 2.
According to the resource method for preparing the waste acid generated by the graphene oxide (alkene) by the liquid phase chemical method, the precipitator in the step 2 is CaO, Ca (OH)2 or the combination of the CaO and the Ca (OH) 2.
According to the resource method for waste acid generated by preparing graphene oxide by the liquid phase chemical method, the recovered product in the step 3 is manganese hydroxide or oxide or a mixture of the manganese hydroxide and the manganese oxide, wherein the manganese hydroxide comprises Mn (OH)2, Mn (OH)4 and MnOOH and variants of different crystal forms of the manganese hydroxide, and the manganese oxide comprises MnO, MnO2, Mn2O3 and Mn3O4 and variants of different crystal forms of the manganese oxide.
According to the method for recycling waste acid generated in the preparation of graphene oxide (alkene) by the liquid phase chemical method, the inorganic alkali added in the step 3 is one or more of NaOH, KOH, Ca (OH)2 and Mg (OH) 2.
The recycling method for waste acid generated in the preparation of graphene oxide (graphene) by the liquid phase chemical method is characterized in that the pH value adjusting range is 8-14 according to the step 3.
According to the method for recycling waste acid generated in the step 3 for preparing graphene oxide (alkene) by the liquid phase chemical method, the oxidant is one or more of permanganate, manganate, perchlorate, hypochlorite, persulfate, thiosulfate, O3, H2O2 and ClO 2.
The method for recycling waste acid generated by preparing the graphene oxide (graphene) by the liquid phase chemical method is used for recycling chlorine-containing composite salt and water according to the step 4.
The method for recycling waste acid generated in the preparation of graphene oxide (graphene) by the liquid phase chemical method is characterized in that the purification and separation method in the step 4 is one or more of an ultrafiltration method, a nanofiltration method, an electrodialysis method, a reverse osmosis method and a crystallization and evaporation method.
The invention has the beneficial effects that:
1. the invention selects green, general, environment-friendly and nontoxic chemical agents and a method which is easy to operate and simple in procedure, the recovered products can be used as electrode materials, building materials, decorative materials and other chemical raw materials, water can be recycled in the production line of the graphene oxide, and the whole process realizes closed circulation, zero pollution and zero emission. In addition, the method is simple to operate, compact in process, easy to control and low in operation cost, has practical significance in popularization and application, and paves a way for large-scale production of the graphene oxide (graphene).
The implementation of the invention can obviously reduce the production cost of enterprises and maximally improve the economic benefits of the enterprises. The resource recycling product can be sold for profit or extend an industrial chain, so that the operation cost of comprehensive treatment of waste acid can be reduced to zero. Taking an enterprise producing 500 tons of graphene annually as an example, 5000-10000 tons of waste acid are expected to be produced each year, if a third party is entrusted to treat the waste acid, the treatment price per kilogram is about 80 yuan, and the enterprise pays 4-8 million yuan of treatment cost each year, so that the production cost of the enterprise is greatly increased, and the economic benefit of the enterprise is reduced. By adopting the process technology, 4-8 million yuan of production cost can be saved for enterprises every year, and the method has small investment and quick response.
Description of the drawings:
FIG. 1 is a process flow diagram of a recycling method of the present invention.
The specific implementation mode is as follows:
example 1
Injecting waste acid into a homogenizing tank by using an acid-resistant pump for homogenizing, pumping the homogenized waste acid into a reaction sedimentation tank A, adding a mixture of a precipitator CaO and Ca (OH)2 according to the molar quantity of sulfate ions in the waste acid, stirring for reaction to form gypsum (CaSO 4.2H 2O), pumping supernatant liquid after precipitation into a reaction sedimentation tank B, and pumping sediment into filtering equipment. And (4) carrying out solid-liquid separation, discharging the filtrate into a reaction sedimentation tank B, and obtaining a filter cake, namely the gypsum. Adding KOH into a reaction sedimentation tank B, adjusting the pH value to 9, stirring to form Mn (OH)4, adding potassium permanganate into the reaction sedimentation tank B to react to form Mn3O4, pumping supernatant after sedimentation to the next procedure, and pumping sediments to a filtering device. And (4) carrying out solid-liquid separation, sending the filtrate to the next procedure, and drying the filter cake to obtain Mn3O 4. The collected waste liquid is evaporated and crystallized to recover chlorine-containing double salt, and the water is recycled in the production line of graphene oxide.
Example 2
Injecting waste acid into a homogenizing tank by using an acid-resistant pump for homogenizing, pumping the homogenized waste acid into a reaction sedimentation tank A, adding a precipitator CaO according to the molar weight of sulfate ions in the waste acid, stirring for reaction to form gypsum (CaSO 4.2H 2O), pumping supernatant after precipitation into a reaction sedimentation tank B, and pumping sediment into a filtering device. And (4) carrying out solid-liquid separation, discharging the filtrate into a reaction sedimentation tank B, and obtaining the filter cake as the gypsum. And (3) adding NaOH into the reaction sedimentation tank B, adjusting the pH value to 10, stirring to form Mn (OH)2, adding potassium permanganate, reacting to form MnO, pumping supernatant after sedimentation to the next procedure, and pumping sediments to filtering equipment. And (4) carrying out solid-liquid separation, sending the filtrate to the next procedure, and drying the filter cake to obtain MnO. And recovering chlorine-containing double salt from the collected waste liquid by adopting an evaporative crystallization method, and recycling water in a graphene oxide production line.
Example 3
Injecting waste acid into a homogenizing tank by using an acid-resistant pump for homogenizing, pumping the homogenized waste acid into a reaction sedimentation tank A, adding a mixture of a precipitator CaO and Ca (OH)2 according to the molar quantity of sulfate ions in the waste acid, stirring for reaction to form gypsum (CaSO 4.2H 2O), pumping supernatant liquid after precipitation into a reaction sedimentation tank B, and pumping sediment into filtering equipment. And (4) carrying out solid-liquid separation, discharging the filtrate into a reaction sedimentation tank B, and obtaining a filter cake, namely the gypsum. Adding KOH and NaOH into a reaction sedimentation tank B, adjusting the pH value to 9.5, stirring to form Mn (OH)2, adding sodium hypochlorite and potassium permanganate, reacting to form MnO2, pumping supernatant after sedimentation to the next procedure, and pumping sediments to a filtering device. And (4) carrying out solid-liquid separation, sending the filtrate to the next procedure, and drying the filter cake to obtain MnO 2. And recovering chlorine-containing double salt from the collected waste liquid by an electrodialysis method, and recycling water for the production line of the graphene oxide (alkene).
Example 4
Injecting waste acid into a homogenizing tank by using an acid-resistant pump for homogenizing, pumping the homogenized waste acid into a reaction sedimentation tank A, adding a precipitator Ca (OH)2 according to the molar quantity of sulfate ions in the waste acid, stirring for reaction to form gypsum (CaSO 4.2H 2O), pumping supernatant liquid after precipitation into a reaction sedimentation tank B, and pumping sediments into filtering equipment. And (4) carrying out solid-liquid separation, discharging the filtrate into a reaction sedimentation tank B, and obtaining the filter cake as the gypsum. Adding KOH into a reaction sedimentation tank B, adjusting the pH value to 9, stirring to form Mn (OH)4, adding potassium perchlorate to react to form Mn3O4 and MnO, pumping supernatant after sedimentation to the next procedure, and pumping sediment to a filtering device. Solid-liquid separation, sending the filtrate to the next procedure, and drying the filter cake to obtain a mixture of Mn3O4, MnO and Mn (OH) 4. The collected waste liquid is subjected to nanofiltration to recover chlorine-containing double salt, and water is recycled in the graphene oxide production line.
Example 5
Injecting waste acid into a homogenizing tank by using an acid-resistant pump for homogenizing, pumping the homogenized waste acid into a reaction sedimentation tank A, adding a precipitator CaO according to the molar weight of sulfate ions in the waste acid, stirring for reaction to form gypsum (CaSO 4.2H 2O), pumping supernatant after precipitation into a reaction sedimentation tank B, and pumping sediment into a filtering device. And (4) carrying out solid-liquid separation, discharging the filtrate into a reaction sedimentation tank B, and obtaining the filter cake as the gypsum. Adding Ca (OH)2 into a reaction sedimentation tank B, adjusting the pH value to 14, stirring to form Mn (OH)2, adding O3, reacting to form MnO2 and MnO, pumping supernatant after sedimentation to the next procedure, and pumping sediment to a filtering device. Solid-liquid separation, sending the filtrate to the next procedure, and drying the filter cake to obtain a mixture of MnO2, MnO and Mn (OH) 2. And recycling chlorine-containing double salt from the collected waste liquid by adopting a reverse osmosis method, and recycling water for the graphene oxide production line.
Example 6
Injecting waste acid into a homogenizing tank by using an acid-resistant pump for homogenizing, pumping the homogenized waste acid into a reaction sedimentation tank A, adding a precipitator CaO according to the molar weight of sulfate ions in the waste acid, stirring for reaction to form gypsum (CaSO 4.2H 2O), pumping supernatant after precipitation into a reaction sedimentation tank B, and pumping sediment into a filtering device. And (4) carrying out solid-liquid separation, discharging the filtrate into a reaction sedimentation tank B, and obtaining the filter cake as the gypsum. Adding Ca (OH)2 into a reaction sedimentation tank B, adjusting the pH value to 11.5, stirring to form Mn (OH)2, adding H2O2, reacting to form MnO2 and MnO, pumping supernatant after sedimentation to the next procedure, and pumping sediment to a filtering device. And (4) carrying out solid-liquid separation, sending filtrate to the next procedure, and drying a filter cake to obtain a MnO2 and MnO mixture. And recycling chlorine-containing double salt from the collected waste liquid by an ultrafiltration method, and recycling water for the graphene oxide production line.
Example 7
Injecting waste acid into a homogenizing tank by using an acid-resistant pump for homogenizing, pumping the homogenized waste acid into a reaction sedimentation tank A, adding a precipitator Ca (OH)2 according to the molar quantity of sulfate ions in the waste acid, stirring for reaction to form gypsum (CaSO 4.2H 2O), pumping supernatant liquid after precipitation into a reaction sedimentation tank B, and pumping sediments into filtering equipment. And (4) carrying out solid-liquid separation, discharging the filtrate into a reaction sedimentation tank B, and obtaining the filter cake as the gypsum. Adding Mg (OH)2 into a reaction sedimentation tank B, adjusting the pH value to 13.5, stirring to form Mn (OH)4, adding O3, reacting to form MnO2, pumping supernatant after sedimentation to the next procedure, and pumping sediment to a filtering device. Solid-liquid separation, sending the filtrate to the next procedure, and drying the filter cake to obtain a mixture of MnO2 and Mn (OH) 4. The collected waste liquid is subjected to nanofiltration to recover chlorine-containing double salt, and water is recycled in the graphene oxide production line.
Example 8
Injecting waste acid into a homogenizing tank by using an acid-resistant pump for homogenizing, pumping the homogenized waste acid into a reaction sedimentation tank A, adding a precipitator CaO according to the molar weight of sulfate ions in the waste acid, stirring for reaction to form gypsum (CaSO 4.2H 2O), pumping supernatant after precipitation into a reaction sedimentation tank B, and pumping sediment into a filtering device. And (4) carrying out solid-liquid separation, discharging the filtrate into a reaction sedimentation tank B, and obtaining the filter cake as the gypsum. Adding NaOH into a reaction sedimentation tank B, adjusting the pH value to 10.5, stirring to form Mn (OH)2, adding H2O2, reacting to form MnO2, pumping supernatant after sedimentation to the next procedure, and pumping sediment to a filtering device. And (4) carrying out solid-liquid separation, sending the filtrate to the next procedure, and drying the filter cake to obtain MnO 2. And recovering chlorine-containing double salt from the collected waste liquid by adopting an evaporative crystallization method, and recycling water in a graphene oxide production line.
Example 9
Injecting waste acid into a homogenizing tank by using an acid-resistant pump for homogenizing, pumping the homogenized waste acid into a reaction sedimentation tank A, adding a precipitator Ca (OH)2 according to the molar quantity of sulfate ions in the waste acid, stirring for reaction to form gypsum (CaSO 4.2H 2O), pumping supernatant liquid after precipitation into a reaction sedimentation tank B, and pumping sediments into filtering equipment. And (4) carrying out solid-liquid separation, discharging the filtrate into a reaction sedimentation tank B, and obtaining the filter cake as the gypsum. Adding NaOH and Ca (OH)2 into a reaction sedimentation tank B, adjusting the pH value to 12.5, stirring to form Mn (OH)2 and Mn (OH)4, adding persulfate, reacting to form Mn3O4, pumping supernatant after sedimentation to the next procedure, and pumping sediment to a filtering device. Solid-liquid separation, sending the filtrate to the next procedure, and drying the filter cake to obtain a mixture of Mn3O4 and Mn (OH) 4. The collected waste liquid is subjected to nanofiltration to recover chlorine-containing double salt, and water is recycled in the graphene oxide production line.
Example 10
Injecting waste acid into a homogenizing tank by using an acid-resistant pump for homogenizing, pumping the homogenized waste acid into a reaction sedimentation tank A, adding a precipitator Ca (OH)2 according to the molar quantity of sulfate ions in the waste acid, stirring for reaction to form gypsum (CaSO 4.2H 2O), pumping supernatant liquid after precipitation into a reaction sedimentation tank B, and pumping sediments into filtering equipment. And (4) carrying out solid-liquid separation, discharging the filtrate into a reaction sedimentation tank B, and obtaining the filter cake as the gypsum. Adding Ca (OH)2 into a reaction sedimentation tank B, adjusting the pH value to 14, stirring to form Mn (OH)2 and Mn (OH)4, adding thiosulfate, reacting to form Mn3O4, pumping supernatant after sedimentation to the next procedure, and pumping sediment to a filtering device. Solid-liquid separation, sending the filtrate to the next procedure, and drying the filter cake to obtain a mixture of Mn3O4 and Mn (OH) 4. The collected waste liquid is ultrafiltered to recover chlorine-containing double salt, and the water is reused in the graphene oxide production line.
Example 11
Injecting waste acid into a homogenizing tank by using an acid-resistant pump for homogenizing, pumping the homogenized waste acid into a reaction sedimentation tank A, adding a precipitator CaO according to the molar weight of sulfate ions in the waste acid, stirring for reaction to form gypsum (CaSO 4.2H 2O), pumping supernatant after precipitation into a reaction sedimentation tank B, and pumping sediment into a filtering device. And (4) carrying out solid-liquid separation, discharging the filtrate into a reaction sedimentation tank B, and obtaining the filter cake as the gypsum. Adding KOH into a reaction sedimentation tank B, adjusting the pH value to 13, stirring to form Mn (OH)2, adding hypochlorite, reacting to form Mn3O4, pumping supernatant after sedimentation to the next procedure, and pumping sediment to a filtering device. Solid-liquid separation, sending the filtrate to the next procedure, and drying the filter cake to obtain a mixture of Mn3O4 and Mn (OH) 2. And (3) recovering chlorine-containing double salt from the collected waste liquid by adopting a reverse osmosis method, and recycling water for the graphene oxide production line.
Example 12
Injecting waste acid into a homogenizing tank by using an acid-resistant pump for homogenizing, pumping the homogenized waste acid into a reaction sedimentation tank A, adding precipitants CaO and Ca (OH)2 according to the molar weight of sulfate ions in the waste acid, stirring for reaction to form gypsum (CaSO 4.2H 2O), pumping supernatant liquid into a reaction sedimentation tank B after precipitation, and pumping sediment into filtering equipment. And (4) carrying out solid-liquid separation, discharging the filtrate into a reaction sedimentation tank B, and obtaining a filter cake, namely the gypsum. Adding KOH and Ca (OH)2 into a reaction sedimentation tank B, adjusting the pH value to 9.5, stirring to form Mn (OH)2, adding ClO2, reacting to form Mn3O4, pumping supernatant after sedimentation to the next procedure, and pumping sediment to a filtering device. And (4) carrying out solid-liquid separation, sending the filtrate to the next procedure, and drying the filter cake to obtain Mn3O 4. And recovering chlorine-containing double salt from the collected waste liquid by an electrodialysis method, and recycling water for the production line of the graphene oxide (alkene).
Example 13
Injecting waste acid into a homogenizing tank by using an acid-resistant pump for homogenizing, pumping the homogenized waste acid into a reaction sedimentation tank A, adding a precipitator CaO according to the molar weight of sulfate ions in the waste acid, stirring for reaction to form gypsum (CaSO 4.2H 2O), pumping supernatant after precipitation into a reaction sedimentation tank B, and pumping sediment into a filtering device. And (4) carrying out solid-liquid separation, discharging the filtrate into a reaction sedimentation tank B, and obtaining the filter cake as the gypsum. Adding KOH into a reaction sedimentation tank B, adjusting the pH value to 10, stirring to form Mn (OH)2, adding hypochlorite, reacting to form MnO, pumping supernatant after sedimentation to the next procedure, and pumping sediment to a filtering device. And (4) carrying out solid-liquid separation, sending the filtrate to the next procedure, and drying a filter cake to obtain a mixture of MnO and Mn (OH) 2. And recovering chlorine-containing double salt from the collected waste liquid by adopting an evaporative crystallization method, and recycling water for the oxidized graphene production line.
Example 14
Injecting waste acid into a homogenizing tank by using an acid-resistant pump for homogenizing, pumping the homogenized waste acid into a reaction sedimentation tank A, adding a precipitator CaO according to the molar weight of sulfate ions in the waste acid, stirring for reaction to form gypsum (CaSO 4.2H 2O), pumping supernatant after precipitation into a reaction sedimentation tank B, and pumping sediment into a filtering device. And (4) carrying out solid-liquid separation, discharging the filtrate into a reaction sedimentation tank B, and obtaining the filter cake as the gypsum. Adding KOH into a reaction sedimentation tank B, adjusting the pH value to 10, stirring to form Mn (OH)2, adding persulfate, reacting to form MnO2, pumping supernatant after sedimentation to the next procedure, and pumping sediment to a filtering device. And (4) carrying out solid-liquid separation, sending the filtrate to the next procedure, and drying the filter cake to obtain MnO 2. And recovering chlorine-containing double salt from the collected waste liquid by an electrodialysis method, and recycling water in a graphene oxide (graphene) production line.
Example 15
Injecting waste acid into a homogenizing tank by using an acid-resistant pump for homogenizing, pumping the homogenized waste acid into a reaction sedimentation tank A, adding a precipitator CaO according to the molar weight of sulfate ions in the waste acid, stirring for reaction to form gypsum (CaSO 4.2H 2O), pumping supernatant after precipitation into a reaction sedimentation tank B, and pumping sediment into a filtering device. And (4) carrying out solid-liquid separation, discharging the filtrate into a reaction sedimentation tank B, and obtaining the filter cake as the gypsum. Adding Ca (OH)2 into a reaction sedimentation tank B, adjusting the pH value to 10.5, stirring to form Mn (OH)2, adding ClO2, reacting to form Mn3O4, pumping supernatant after sedimentation to the next procedure, and pumping sediment to a filtering device. And (4) carrying out solid-liquid separation, sending the filtrate to the next procedure, and drying the filter cake to obtain Mn3O 4. And recycling chlorine-containing double salt from the collected waste liquid by adopting a reverse osmosis method, and recycling water for the graphene oxide production line.
Claims (2)
1. A resource method for waste acid generated in preparation of graphene oxide by a liquid phase chemical method is characterized by comprising the following process steps:
(1) waste acid homogenization: injecting waste acid into a homogenizing pool by an acid-resistant pump for homogenization;
(2) recycling sulfate radicals: recovering gypsum
) Pumping the homogenized waste acid into a reaction sedimentation tank A, adding a precipitator according to the molar weight of sulfate ions in the waste acid, stirring for reaction to form gypsum, precipitating, pumping supernatant into a reaction sedimentation tank B, pumping sediment into a filtering device, carrying out solid-liquid separation, discharging filtrate into the reaction sedimentation tank B, drying filter cakes to obtain the gypsumAn outer pin used as a building material or a finishing material;
(3) recycling manganese ions: recovering manganese hydroxide or oxide or a mixture of the manganese hydroxide and the oxide, adding inorganic base into a reaction sedimentation tank B, adjusting the pH value, stirring to form manganese hydroxide, adding an oxidant, reacting to form manganese oxide, precipitating, pumping supernatant to the next procedure, pumping sediment to a filter device, performing solid-liquid separation, pumping filtrate to the next procedure, drying filter cakes to obtain a recovered product, and externally selling the recovered product to be used as an electrode material or other chemical raw materials;
(4) resource utilization of chloride ions: recycling water, separating and purifying the waste liquid generated in the step (3) to obtain chlorine-containing composite salt and water, drying the chlorine-containing composite salt to be used as other chemical raw materials, and recycling the water in the process for preparing the graphene oxide by the liquid-phase chemical method;
the waste acid is derived from a process for preparing graphene oxide by a chemical method, and the main components of the waste acid are one or more of water, sulfuric acid, hydrochloric acid, nitric acid, manganese ions, potassium ions and sodium ions;
the precipitant is CaO, CaO,
Or a combination thereof;
the recovered product is manganese hydroxide or oxide or a mixture of the two, wherein the manganese hydroxide comprises Mn (OH)2、Mn(OH)4And MnOOH and its different crystal modification, oxides of manganese including MnO, MnO2、 Mn2O3And Mn3O4And variants of different crystalline forms thereof;
the oxidant is permanganate, manganate, perchlorate, hypochlorite, persulfate, thiosulfate or O3、H2O2、ClO2One or more of the above;
the inorganic base added according to the step (3) is NaOH, KOH, Ca (OH)2、Mg(OH)2One or more of the above;
and (4) adjusting the pH value in the step (3) to be 8-14.
2. The resource utilization method of waste acid generated in the preparation of graphene oxide by the liquid phase chemical method according to claim 1, which is characterized in that: the separation and purification method in the step (4) is one or more of an ultrafiltration method, a nanofiltration method, an electrodialysis method, a reverse osmosis method and a crystallization and evaporation method.
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| CN107459373A (en) * | 2017-08-02 | 2017-12-12 | 上海交通大学 | The method and system of potassium manganese mixed fertilizer are prepared based on graphene oxide generation spent acid |
| CN108046481A (en) * | 2018-01-26 | 2018-05-18 | 黑龙江科技大学 | A kind of expanded graphite wastewater treatment method |
| CN108516589B (en) * | 2018-05-18 | 2020-10-02 | 山东道恩钛业有限公司 | Method for recycling manganese hydroxide in titanium dioxide waste acid treatment process |
| CN109052383A (en) * | 2018-09-05 | 2018-12-21 | 七台河宝泰隆石墨烯新材料有限公司 | A kind of technique of electroosmose process separation graphene oxide |
| CN109081621B (en) * | 2018-10-19 | 2021-04-30 | 昂星新型碳材料常州有限公司 | Treatment method and application of waste liquid in graphite oxide/graphene production, cement retarder and cement |
| CN109319999B (en) * | 2018-11-13 | 2021-10-08 | 新疆烯金石墨烯科技有限公司 | Treatment method for resource utilization of waste liquid in graphene oxide production |
| 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 |
| CN109775729B (en) * | 2018-12-07 | 2021-02-02 | 四川聚创石墨烯科技有限公司 | Processing system of oxidation graphite alkene waste liquid |
| CN109437181B (en) * | 2018-12-07 | 2021-01-22 | 四川聚创石墨烯科技有限公司 | Comprehensive treatment system for graphene oxide slurry |
| CN109319773B (en) * | 2018-12-07 | 2021-03-19 | 四川聚创石墨烯科技有限公司 | Comprehensive treatment method of graphene oxide slurry |
| CN109502864A (en) * | 2018-12-07 | 2019-03-22 | 四川聚创石墨烯科技有限公司 | A kind of processing method of graphene oxide waste liquid |
| CN113511746B (en) * | 2021-03-11 | 2024-02-13 | 广东聚石科技研究有限公司 | Treatment method and application of graphene production wastewater |
| CN114229882B (en) * | 2021-12-31 | 2023-03-17 | 山东利特纳米技术有限公司 | Comprehensive utilization method of waste sulfuric acid and washing wastewater in graphene oxide preparation process |
| CN114380337A (en) * | 2021-12-31 | 2022-04-22 | 山东利特纳米技术有限公司 | Preparation of MnO from waste liquid of graphene oxide production2Method for producing/GO composite materials |
| CN114162841A (en) * | 2022-01-17 | 2022-03-11 | 山东金利特新材料有限责任公司 | Comprehensive treatment method for graphene oxide waste acid |
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