CN114133058B - Friedel-crafts reaction aluminum-containing wastewater recycling method - Google Patents
Friedel-crafts reaction aluminum-containing wastewater recycling method Download PDFInfo
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- CN114133058B CN114133058B CN202111273721.6A CN202111273721A CN114133058B CN 114133058 B CN114133058 B CN 114133058B CN 202111273721 A CN202111273721 A CN 202111273721A CN 114133058 B CN114133058 B CN 114133058B
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- 239000002351 wastewater Substances 0.000 title claims abstract description 122
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 52
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000004064 recycling Methods 0.000 title claims abstract description 27
- 238000005727 Friedel-Crafts reaction Methods 0.000 title claims abstract description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 52
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 35
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 35
- 239000011734 sodium Substances 0.000 claims abstract description 35
- 239000003513 alkali Substances 0.000 claims abstract description 25
- 230000001590 oxidative effect Effects 0.000 claims abstract description 14
- 239000003463 adsorbent Substances 0.000 claims abstract description 10
- 239000007800 oxidant agent Substances 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 239000006228 supernatant Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims 2
- 239000005909 Kieselgur Substances 0.000 claims 1
- 238000007670 refining Methods 0.000 abstract description 7
- 238000004065 wastewater treatment Methods 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 229920002521 macromolecule Polymers 0.000 abstract description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 238000002156 mixing Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 13
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 7
- -1 alkyl hydrocarbon Chemical class 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 239000008235 industrial water Substances 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 5
- 239000002910 solid waste Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000012629 purifying agent Substances 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C01F7/00—Compounds of aluminium
- C01F7/48—Halides, with or without other cations besides aluminium
- C01F7/56—Chlorides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention relates to the technical field of aluminum-containing wastewater treatment, in particular to a Friedel-crafts reaction aluminum-containing wastewater recycling method. Firstly, oxidizing and removing organic macromolecules in aluminum-containing wastewater by using an oxidant, then adsorbing particle impurities in the wastewater by using an adsorbent, refining the wastewater, dividing the refined wastewater into two parts, adding alkali into one part of the wastewater to prepare sodium metaaluminate, dripping the prepared sodium metaaluminate into the other part of the wastewater, and polymerizing and curing to prepare the polyaluminium chloride. The method prepares the polyaluminium chloride while treating the aluminum-containing wastewater, has low three-waste generation amount, and greatly reduces the subsequent treatment cost and the influence on the environment. The basicity of the polyaluminum chloride prepared by the method is 88% -95%, and the content of the aluminum oxide can reach 28% -30%.
Description
Technical Field
The invention relates to the technical field of aluminum-containing wastewater treatment, in particular to a Friedel-crafts reaction aluminum-containing wastewater recycling method.
Background
In the production process of pesticides and intermediates thereof, alkyl hydrocarbon and aromatic ketone compounds are often synthesized by utilizing Friedel-crafts reaction, aluminum trichloride is commonly used as a catalyst in Friedel-crafts reaction, and waste water generated by the process contains the aluminum trichloride catalyst, so that the content of aluminum ions in the waste water is high, and the waste water is directly discharged to an oxidation pond for biodegradation, so that flora poisoning can be caused, and the aim of treatment cannot be achieved. Meanwhile, aluminum ions have high toxicity to human bodies, and the aluminum ions in industrial wastewater can be discharged only after being treated by less than 5 ppm. The common treatment technology is to treat aluminum ions in the wastewater to the emission standard by adopting a complexing method through a precipitation method, such as the treatment method of aluminum-containing wastewater generated by a Friedel-crafts reaction (CN201810019313. X), but the technology can generate a large amount of aluminum mud solid waste, so that serious secondary pollution is caused, the treatment cost is high, and meanwhile, the aluminum mud is discarded as the solid waste to cause waste. While CN202110180294.0 discloses a method for treating aluminum trichloride wastewater, which is used for preparing polyaluminium chloride by treating wastewater, however, the patent needs to be treated by extraction, rectification and the like during wastewater treatment, and has long flow, high cost, and is easy to introduce ketone organic solvents during treatment, difficult to remove, brings impurities and affects the purity of products.
Disclosure of Invention
Aiming at the technical problems that solid waste is generated and aluminum resources are wasted in aluminum-containing wastewater treatment in the prior art, the invention aims to provide a method for recycling aluminum-containing wastewater in Friedel-crafts reaction, which can treat the aluminum-containing wastewater in Friedel-crafts reaction and can simultaneously utilize the recovered aluminum to prepare polyaluminium chloride.
The invention provides a Friedel-crafts reaction aluminum-containing wastewater recycling method, which comprises the following steps:
(1) Adding an oxidant into the aluminum-containing wastewater, oxidizing, adding an adsorbent, and filtering to obtain wastewater A;
(2) Dividing wastewater A into wastewater A 1 And waste water A 2 ；
(3) Preparing alkali liquor, and dropwise adding wastewater A into the alkali liquor 1 Preparing a mixed solution B containing sodium metaaluminate;
(4) Waste water A 2 Heating, starting stirring, dropwise adding the mixed solution B, preserving heat after the dropwise adding is finished, cooling after the heat preservation, standing and curing to obtain supernatant polyaluminium chloride liquid;
(6) Concentrating and drying supernatant polyaluminium chloride liquid to obtain a solid polyaluminium chloride finished product.
Further, the total mass of the wastewater A is m, and the wastewater A 1 Mass is m 1 Waste water A 2 Is of mass m 2 ，m 1 ＝15％m，m 2 =85%m. Based on stable production in workshops, the same batch of wastewater has the mass of 15: 85% of the waste water is separated, 15% of the waste water is used for preparing sodium metaaluminate, the rest 85% of the waste water reacts with the prepared sodium metaaluminate to prepare polyaluminum chloride, the polyaluminum chloride obtained according to the proportion reaches the qualification standard, and a batch of waste water is just consumed, so that the waste water utilization rate is greatly improved.
Further, the oxidant is hydrogen peroxide, the consumption of the oxidant is 0.5-5% of the total mass of the aluminum-containing wastewater, and the oxidation time of the oxidant is 0.5-3h.
Further, the adsorbent is one of activated carbon, diatomite and activated alumina.
Further, the amount of the adsorbent is 0.5-2% of the total mass of the aluminum-containing wastewater, the wastewater is heated to 30-60 ℃ after being added with the adsorbent, and the wastewater is stirred and kept for 0.5-3 hours.
Further, the alkali liquor is sodium hydroxide solution, the mass concentration of the alkali liquor is 35-50%, and the dripping time is 4 hours.
Further, waste water A 2 Heating to 100-150deg.C, and stirring at 1500-3000r/min.
Further, the dripping time of the mixed solution B is 6-10h, the temperature is kept for 1-4h after the dripping is finished, and the temperature is reduced to 25-30 ℃ after the temperature is kept.
Further, standing and curing for 48-96h, mixing the lower layer solid insoluble substance with the mixed solution B after standing and curing, and continuing curing and polymerization to prepare sodium metaaluminate.
Further, in the step (5), concentrated and dried effluent is introduced into the alkali liquor in the step (3) for recycling.
The principle of the invention is as follows: firstly, oxidizing and removing organic macromolecules in aluminum-containing wastewater by using an oxidant, then, adsorbing granular impurities in the wastewater by using an adsorbent, refining the wastewater, dividing the refined wastewater into two parts, adding alkali into one part of the wastewater to prepare sodium metaaluminate, dripping the prepared sodium metaaluminate into the other part of the wastewater to react to generate aluminum hydroxide precipitate, and generating polyaluminium chloride under the conditions of high temperature and rapid stirring and the action of hydrochloric acid existing in a system, wherein the specific reaction equation is as follows:
the invention has the beneficial effects that (1) the aluminum-containing wastewater is divided into two parts, other polymerization raw materials are not needed, aluminum chloride is prepared while the aluminum-containing wastewater is treated, the three wastes are generated, the utilization rate of the wastewater is improved, and the subsequent treatment cost and the influence on the environment are greatly reduced. (2) The invention changes the aluminum element in the wastewater into valuable, and does not produce secondary pollution in the preparation process of the polyaluminium chloride. (3) The polyaluminium chloride prepared by the method has the basicity of 88% -95%, the content of alumina can reach 28% -30%, and the polyaluminium chloride has a good flocculation precipitation effect and can be used as a water purifying agent.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the description of the embodiments or the prior art will be briefly described below, and it will be obvious to those skilled in the art that other drawings can be obtained from these drawings without inventive effort.
FIG. 1 is a process flow diagram of an embodiment of the present invention.
Detailed Description
In order to make the technical solution of the present invention better understood by those skilled in the art, the technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
Examples 1-5 are aluminum-containing wastewater after Friedel-crafts reaction, and FIG. 1 shows a process flow of an embodiment of the invention.
Example 1
The invention relates to a Friedel-crafts reaction aluminum-containing wastewater recycling method, which comprises the following steps:
(1) Wastewater refining: adding 900kg of hydrogen peroxide into 30 tons of aluminum-containing wastewater, uniformly mixing, standing for oxidation for 2 hours, adding 600kg of fresh activated carbon after the oxidation is finished, heating to 60 ℃, stirring, preserving heat for 2 hours, and filtering to obtain 29.5 tons of refined wastewater;
(2) Preparation of sodium metaaluminate: mixing 4.43 tons of refined wastewater in the step (1) with industrial water and analytically pure sodium hydroxide solid, preparing alkali liquor with the mass concentration of 4.43 tons and 35 percent, and dripping the 4.43 tons of refined wastewater into the alkali liquor for 4 hours to obtain high-concentration sodium metaaluminate;
(3) And (3) polymerization curing: heating the remaining 25.07 tons of refined wastewater in the step (1) to 105 ℃, stirring at a rotating speed of 1500r/min, slowly and uniformly dropwise adding sodium metaaluminate in the step (2) for 8 hours, preserving heat for 2 hours after the dropwise adding is finished, cooling to 25-30 ℃ after the heat preservation is finished, standing and curing for 72 hours, and obtaining supernatant which is liquid polyaluminium chloride;
(4) And (3) drying and packaging: concentrating and drying the liquid polyaluminium chloride obtained after standing and curing in the step (3) to obtain finished solid polyaluminium chloride, introducing the concentrated and dried alkaline effluent into the alkali liquor in the step (2) for recycling, wherein the collection of the concentrated and dried effluent is realized by condensation;
(5) And (3) recycling: mixing the solid insoluble substance at the bottom left after standing and curing in the step (3) with the high-concentration sodium metaaluminate in the step (2), and continuing curing and polymerization to prepare the sodium metaaluminate.
By examining the polyaluminium chloride produced in this example, as shown in Table 1, the solid polyaluminium chloride index after the aluminum-containing wastewater produced in the Friedel-crafts reaction of example 1 is shown.
Table 1 example 1 preparation of polyaluminum chloride detection index
| Project | Alumina content | Basicity degree |
| Content of | 29.3％ | 88％ |
Example 2
(1) Wastewater refining: adding 900kg of hydrogen peroxide into 30 tons of aluminum-containing wastewater, uniformly mixing, standing for oxidation for 2 hours, adding 300kg of fresh activated carbon after the oxidation is finished, heating to 60 ℃, stirring, preserving heat for 2 hours, and filtering to obtain 29.5 tons of refined wastewater;
(2) Preparation of sodium metaaluminate: mixing 4.43 tons of refined wastewater in the step (1) with industrial water and analytically pure sodium hydroxide solid, preparing alkali liquor with the mass concentration of 4.43 tons and 35 percent, and dripping the 4.43 tons of refined wastewater into the alkali liquor for 4 hours to obtain high-concentration sodium metaaluminate;
(3) And (3) polymerization curing: heating the remaining 25.07 tons of refined wastewater in the step (1) to 105 ℃, stirring at a rotation speed of 2000r/min, slowly and uniformly dropwise adding sodium metaaluminate in the step (2) for 8 hours, preserving heat for 2 hours after the dropwise adding is finished, cooling to 25-30 ℃ after the heat preservation is finished, standing and curing for 96 hours, and obtaining supernatant which is liquid polyaluminium chloride;
(4) And (3) drying and packaging: concentrating and drying the liquid polyaluminium chloride obtained after standing and curing in the step (3) to obtain finished solid polyaluminium chloride, introducing the concentrated and dried alkaline effluent into the alkali liquor in the step (2) for recycling, wherein the collection of the concentrated and dried effluent is realized by condensation;
(5) And (3) recycling: mixing the solid insoluble substance at the bottom left after standing and curing in the step (3) with the high-concentration sodium metaaluminate in the step (2), and continuing curing and polymerization to prepare the sodium metaaluminate.
By examining the polyaluminium chloride produced in this example, as shown in Table 2, the solid polyaluminium chloride index after the aluminum-containing wastewater produced in the Friedel-crafts reaction of example 2 is shown.
Table 2 example 2 preparation of polyaluminum chloride detection index
| Project | Alumina content | Basicity degree |
| Content of | 29.8％ | 91％ |
Example 3
(1) Wastewater refining: adding 150kg of hydrogen peroxide into 30 tons of aluminum-containing wastewater, uniformly mixing, standing for oxidation for 0.5 hour, adding 150kg of fresh diatomite after oxidation, heating to 30 ℃, stirring, preserving heat for 0.5 hour, and filtering to obtain 29.8 tons of refined wastewater;
(2) Preparation of sodium metaaluminate: mixing 4.43 tons of refined wastewater in the step (1) with industrial water and analytically pure sodium hydroxide solid, preparing alkali liquor with the mass concentration of 4.43 tons and 50%, and dripping the 4.43 tons of refined wastewater into the alkali liquor for 4 hours to obtain high-concentration sodium metaaluminate;
(3) And (3) polymerization curing: heating the rest 25.33 tons of refined wastewater in the step (1) to 150 ℃, slowly and uniformly dropwise adding sodium metaaluminate in the step (2) at a stirring rotating speed of 3000r/min for 6 hours, preserving heat for 1 hour after the dropwise adding is finished, cooling to 25-30 ℃ after the heat preservation is finished, standing and curing for 48 hours, and obtaining supernatant which is liquid polyaluminium chloride;
(4) And (3) drying and packaging: concentrating and drying the liquid polyaluminium chloride obtained after standing and curing in the step (3) to obtain finished solid polyaluminium chloride, introducing the concentrated and dried alkaline effluent into the alkali liquor in the step (2) for recycling, wherein the collection of the concentrated and dried effluent is realized by condensation;
(5) And (3) recycling: mixing the solid insoluble substance at the bottom left after standing and curing in the step (3) with the high-concentration sodium metaaluminate in the step (2), and continuing curing and polymerization to prepare the sodium metaaluminate.
By examining the polyaluminium chloride produced in this example, as shown in Table 3, the solid polyaluminium chloride index after the aluminum-containing wastewater produced in the Friedel-crafts reaction of example 3 is shown.
TABLE 3 example 3 preparation of polyaluminum chloride detection index
| Project | Alumina content | Basicity degree |
| Content of | 30.2％ | 95％ |
Example 4
(1) Wastewater refining: adding 600kg of hydrogen peroxide into 30 tons of aluminum-containing wastewater, uniformly mixing, standing for oxidation for 3 hours, adding 600kg of fresh diatomite after oxidation, heating to 40 ℃, stirring, preserving heat for 3 hours, and filtering to obtain 29 tons of refined wastewater;
(2) Preparation of sodium metaaluminate: mixing 4.35 tons of refined wastewater in the step (1) with industrial water and analytically pure sodium hydroxide solid, preparing alkali liquor with the mass concentration of 4.43 tons and 50%, and dripping the 4.43 tons of refined wastewater into the alkali liquor for 4 hours to obtain high-concentration sodium metaaluminate;
(3) And (3) polymerization curing: heating the rest 15.65 tons of refined wastewater in the step (1) to 100 ℃, slowly and uniformly dropwise adding sodium metaaluminate in the step (2) at a stirring rotating speed of 2000r/min for 10 hours, preserving heat for 4 hours after the dropwise adding is finished, cooling to 25-30 ℃ after the heat preservation is finished, standing and curing for 50 hours, and obtaining supernatant which is liquid polyaluminium chloride;
(4) And (3) drying and packaging: concentrating and drying the liquid polyaluminium chloride obtained after standing and curing in the step (3) to obtain finished solid polyaluminium chloride, introducing the concentrated and dried alkaline effluent into the alkali liquor in the step (2) for recycling, wherein the collection of the concentrated and dried effluent is realized by condensation;
(5) And (3) recycling: mixing the solid insoluble substance at the bottom left after standing and curing in the step (3) with the high-concentration sodium metaaluminate in the step (2), and continuing curing and polymerization to prepare the sodium metaaluminate.
By examining the polyaluminium chloride produced in this example, as shown in Table 4, the solid polyaluminium chloride index after the aluminum-containing wastewater produced in the Friedel-crafts reaction of example 4 is shown.
TABLE 4 example 4 preparation of polyaluminum chloride detection index
| Project | Alumina content | Basicity degree |
| Content of | 28.3％ | 93％ |
Example 5
(1) Wastewater refining: adding 1500kg of hydrogen peroxide into 30 tons of aluminum-containing wastewater, uniformly mixing, standing for oxidization for 1 hour, adding 600kg of fresh diatomite after oxidization, heating to 50 ℃, stirring, preserving heat for 3 hours, and filtering to obtain 28.6 tons of purified wastewater;
(2) Preparation of sodium metaaluminate: mixing 4.29 tons of refined wastewater in the step (1) with industrial water and analytically pure sodium hydroxide solid, preparing alkali liquor with the mass concentration of 4.29 tons and 50%, and dripping the 4.29 tons of refined wastewater into the alkali liquor for 4 hours to obtain high-concentration sodium metaaluminate;
(3) And (3) polymerization curing: heating the rest 24.31 tons of refined wastewater in the step (1) to 100 ℃, slowly and uniformly dropwise adding sodium metaaluminate in the step (2) at a stirring rotating speed of 2000r/min for 10 hours, preserving heat for 4 hours after the dropwise adding is finished, cooling to 25-30 ℃ after the heat preservation is finished, standing and curing for 60 hours, and obtaining supernatant which is liquid polyaluminium chloride;
(4) And (3) drying and packaging: concentrating and drying the liquid polyaluminium chloride obtained after standing and curing in the step (3) to obtain finished solid polyaluminium chloride, introducing the concentrated and dried alkaline effluent into the alkali liquor in the step (2) for recycling, wherein the collection of the concentrated and dried effluent is realized by condensation;
(5) And (3) recycling: mixing the solid insoluble substance at the bottom left after standing and curing in the step (3) with the high-concentration sodium metaaluminate in the step (2), and continuing curing and polymerization to prepare the sodium metaaluminate.
By examining the polyaluminium chloride produced in this example, as shown in Table 5, the solid polyaluminium chloride index after the aluminum-containing wastewater produced in the Friedel-crafts reaction of example 5 is shown.
TABLE 5 example 5 preparation of polyaluminum chloride detection index
| Project | Alumina content | Basicity degree |
| Content of | 29.3％ | 94％ |
Comparative example 1
Comparative example 1 the process was as described in example 1, except that in comparative example 1, 2.95 tons of post-purification waste water was taken in step (2), and 26.55 tons of purified waste water was taken in step (3).
Comparative example 2
Comparative example 2 the procedure was as described in example 2, except that in comparative example 2, 5.9 tons of post-purification waste water was taken in step (2), and 23.6 tons of purified waste water was taken in step (3).
By examining the polyaluminium chloride prepared in comparative examples 1 and 2, the solid polyaluminium chloride index after the aluminum-containing wastewater preparation in comparative examples 1 and 2 is shown in Table 6.
Table 6 comparative examples 1 and 2 preparation of polyaluminum chloride detection index
| Project | Alumina content | Basicity degree |
| Comparative example 1 | 25.9％ | 75％ |
| Comparative example 2 | 23.3％ | 83％ |
As can be seen from the data in Table 6, the wastewater A was adjusted by comparative example 1 and comparative example 1, example 2 and comparative example 2 1 And waste water A 2 The proportion of the poly aluminum chloride is seriously influenced; waste water A 1 And waste water A 2 The influence of the proportion of the water-soluble polymer on the basicity of the polyaluminum chloride is obvious, and the utilization rate of the wastewater can be improved by reasonable proportion.
Although the present invention has been described in detail by way of preferred embodiments with reference to the accompanying drawings, the present invention is not limited thereto. Various equivalent modifications and substitutions may be made in the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and it is intended that all such modifications and substitutions be within the scope of the present invention/be within the scope of the present invention as defined by the appended claims.
Claims (9)
1. A Friedel-crafts reaction aluminum-containing wastewater recycling method is characterized by comprising the following steps:
(1) Adding an oxidant into the aluminum-containing wastewater, oxidizing, adding an adsorbent, and filtering to obtain wastewater A;
(2) Dividing wastewater A into wastewater A 1 And waste water A 2 The total mass of the wastewater A is m, and the wastewater A 1 Mass is m 1 Waste water A 2 Is of mass m 2 ，m 1 =15%m，m 2 =85%m；
(3) Preparing alkali liquor, and dropwise adding wastewater A into the alkali liquor 1 Preparing a mixed solution B containing sodium metaaluminate;
(4) Waste water A 2 Heating, starting stirring, dropwise adding the mixed solution B, preserving heat after the dropwise adding is finished, cooling after the heat preservation, standing and curing to obtain supernatant polyaluminium chloride liquid;
(5) Concentrating and drying supernatant polyaluminium chloride liquid to obtain a solid polyaluminium chloride finished product.
2. The method for recycling aluminum-containing wastewater of Friedel-crafts reaction according to claim 1, wherein the oxidant is hydrogen peroxide, the consumption of the oxidant is 0.5-5% of the total mass of the aluminum-containing wastewater, and the oxidation time of the oxidant is 0.5-3h.
3. The method for recycling aluminum-containing wastewater of friedel-crafts reaction according to claim 1, wherein the adsorbent is one of activated carbon, diatomaceous earth and activated alumina.
4. The method for recycling aluminum-containing wastewater by friedel-crafts reaction according to claim 3, wherein the amount of the adsorbent is 0.5-2% of the total mass of the aluminum-containing wastewater, the wastewater is heated to 30-60 ℃ after being added with the adsorbent, and the stirring and the heat preservation are carried out for 0.5-3 hours.
5. The method for recycling aluminum-containing wastewater of Friedel-crafts reaction according to claim 1, wherein the alkaline solution is sodium hydroxide solution, the mass concentration of the alkaline solution is 35-50%, and the dripping time is 4h.
6. The method for recycling aluminum-containing wastewater of Friedel-crafts reaction according to claim 1, wherein the wastewater A 2 Heating to 100-150deg.C, and stirring at 1500-3000r/min.
7. The method for recycling aluminum-containing wastewater of Friedel-crafts reaction according to claim 1, wherein the dropwise adding time of the mixed solution B is 6-10h, the temperature is kept for 1-4h after the dropwise adding is completed, and the temperature is reduced to 25-30 ℃ after the temperature is kept.
8. The method for recycling aluminum-containing wastewater of Friedel-crafts reaction according to claim 1, wherein the standing and curing time is 48-96h, and the lower layer solid insoluble substance is mixed with the mixed solution B after standing and curing, and the curing and polymerization are continued to prepare sodium metaaluminate.
9. The method for recycling aluminum-containing wastewater in Friedel-crafts reaction according to claim 1, wherein the concentrated and dried effluent in the step (5) is recycled in the alkali liquor in the step (3).
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