CN114133058A - Resource utilization method of aluminum-containing wastewater by Friedel-crafts reaction - Google Patents
Resource utilization method of aluminum-containing wastewater by Friedel-crafts reaction Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 107
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 53
- 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 35
- 238000005727 Friedel-Crafts reaction Methods 0.000 title claims abstract description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 53
- 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 37
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 37
- 239000011734 sodium Substances 0.000 claims abstract description 37
- 239000003513 alkali Substances 0.000 claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 26
- 230000001590 oxidative effect Effects 0.000 claims abstract description 16
- 239000003463 adsorbent Substances 0.000 claims abstract description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 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 group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 239000006228 supernatant Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 238000004064 recycling Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 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
- 238000004321 preservation Methods 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims 3
- 239000002699 waste material Substances 0.000 abstract description 14
- 238000011282 treatment Methods 0.000 abstract description 10
- 230000000379 polymerizing effect Effects 0.000 abstract description 7
- 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
- 229920002521 macromolecule Polymers 0.000 abstract description 2
- 239000005416 organic matter Substances 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 8
- -1 alkyl hydrocarbon Chemical class 0.000 description 7
- 150000003839 salts Chemical class 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
- 238000001514 detection method Methods 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 150000002576 ketones Chemical class 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
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 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
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging 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
- 239000000575 pesticide Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000012629 purifying agent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 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
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- 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 resource utilization method of Friedel-crafts reaction aluminum-containing wastewater. The method comprises the steps of firstly oxidizing and removing organic matter macromolecules in the aluminum-containing wastewater by using an oxidizing agent, then adsorbing particle impurities in the waste liquid by using an adsorbent, refining the waste liquid, dividing the refined waste liquid into two parts, adding alkali into one part of the waste liquid to prepare sodium metaaluminate, dripping the prepared sodium metaaluminate into the other part of the waste liquid, and polymerizing and curing to prepare the polyaluminium chloride. The method for preparing 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 polyaluminium chloride prepared by the method has the basicity of 88-95 percent and the content of alumina can reach 28-30 percent.
Description
Technical Field
The invention relates to the technical field of aluminum-containing wastewater treatment, in particular to a resource utilization method of Friedel-crafts reaction aluminum-containing wastewater.
Background
During the production process of pesticides and intermediates thereof, alkyl hydrocarbon and aromatic ketone compounds are often synthesized by utilizing a Friedel-crafts reaction, aluminum trichloride is commonly used as a catalyst in the Friedel-crafts reaction, and the 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 flora poisoning can be caused by directly discharging the waste water to an oxidation pond for biodegradation, and the aim of treatment cannot be achieved. Meanwhile, aluminum ions have high toxicity to human bodies, and the aluminum ions in the industrial wastewater can be discharged only when the treatment amount is less than 5 ppm. The common treatment technology is to treat aluminum ions in the wastewater to the emission standard by a complexing method through a precipitation method, for example, a patent (cn201810019313. x: a treatment method of aluminum-containing wastewater generated by friedel-crafts reaction) by complexing and precipitating the aluminum ions, but the technology generates a large amount of aluminum mud solid waste, causes serious secondary pollution and high treatment cost, and wastes the aluminum mud as the solid waste. However, in the patent, the wastewater treatment needs to be carried out by extraction, rectification and other treatments, the process is long, the cost is high, and in the treatment, a ketone organic solvent is easily introduced, so that the ketone organic solvent is not easily removed, impurities are brought, and the product purity is influenced.
Disclosure of Invention
The invention aims to provide a resource utilization method of aluminum-containing wastewater in Friedel-crafts reaction, aiming at the technical problems of solid waste generated by aluminum-containing wastewater treatment and aluminum resource waste, and the resource utilization method can be used for treating the aluminum-containing wastewater in the Friedel-crafts reaction and simultaneously utilizing recycled aluminum for preparing polyaluminum chloride.
The invention provides a resource utilization method of Friedel-crafts reaction aluminum-containing wastewater, which comprises the following steps:
(1) adding an oxidant into the aluminum-containing wastewater, adding an adsorbent after oxidation, and filtering to obtain wastewater A;
(2) dividing the wastewater A into wastewater A1And wastewater A2；
(3) Preparing alkali liquor, and dripping the wastewater A into the alkali liquor1To prepare mixed liquor B containing sodium metaaluminate;
(4) waste water A is treated2Heating, starting stirring, dropwise adding the mixed solution B, preserving heat after dropwise adding is finished, cooling after heat preservation, standing and curing to obtain supernatant polyaluminium chloride liquid;
(6) and (4) concentrating and drying the supernatant liquid polyaluminium chloride liquid to obtain a finished solid polyaluminium chloride product.
Further, the total mass of the wastewater A is m, and the wastewater A1Mass m1Waste water A2Has a mass of m2，m1＝15％m，m285% m. Based on stable production in a workshop, the quality of the same batch of wastewater is as follows: 85 percent of the sodium metaaluminate is separated, 15 percent of the sodium metaaluminate is used for preparing the polyaluminium chloride, the rest 85 percent of the sodium metaaluminate reacts with the prepared sodium metaaluminate to prepare the polyaluminium chloride, the polyaluminium chloride obtained according to the proportion reaches the qualified standard, a batch of wastewater is consumed exactly, and the wastewater utilization rate is greatly improved.
Furthermore, the oxidant is hydrogen peroxide, the dosage of the oxidant is 0.5-5% of the total mass of the aluminum-containing wastewater, and the oxidation time of the oxidant is 0.5-3 h.
Further, the adsorbent is one of activated carbon, diatomite and activated alumina.
Furthermore, the dosage of the adsorbent is 0.5-2% of the total mass of the aluminum-containing wastewater, the wastewater is heated to 30-60 ℃ after the adsorbent is added, and the stirring and heat preservation are carried out 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 dropping time is 4 hours.
Further, wastewater A2The temperature is raised to 100-150 ℃, and the stirring speed is 1500-3000 r/min.
Further, the dropping time of the mixed solution B is 6-10h, the temperature is kept for 1-4h after the dropping 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 substances with the mixed solution B after standing and curing, and continuously curing and polymerizing to prepare the sodium metaaluminate.
And (3) further, introducing the concentrated and dried effluent water in the step (5) into the alkali liquor in the step (3) for recycling.
The principle of the invention is as follows: the method comprises the following steps of firstly, oxidizing and removing organic matter macromolecules in the aluminum-containing wastewater by using an oxidant, then adsorbing particle impurities in the waste liquid by using an adsorbent, refining the waste liquid, dividing the refined waste liquid into two parts, adding alkali into one part of the waste liquid to prepare sodium metaaluminate, dripping the prepared sodium metaaluminate into the other part of the waste liquid to react to generate aluminum hydroxide precipitate, and generating polyaluminium chloride by the aluminum hydroxide precipitate under the conditions of high temperature and rapid stirring and under the action of hydrochloric acid existing in a system, wherein the specific reaction equation is as follows:
the method has the beneficial effects that (1) the method divides the aluminum-containing wastewater into two parts, does not need other polymerization reaction raw materials, treats the aluminum-containing wastewater and prepares the polyaluminum chloride at the same time, has low three-waste generation amount, improves the utilization rate of the wastewater, and greatly reduces the subsequent treatment cost and the influence of the subsequent treatment cost on the environment. (2) The method changes the aluminum element in the wastewater into valuable, and does not generate secondary pollution in the preparation process of the polyaluminium chloride. (3) The polyaluminium chloride prepared by the method has the basicity of 88-95 percent and the alumina content of 28-30 percent, has good flocculation and precipitation effects and can be used as a water purifying agent.
Drawings
In order to more clearly illustrate the embodiments or technical solutions in the prior art of the present invention, the drawings used in the description of the embodiments or prior art will be briefly described below, and it is obvious for those skilled in the art that other drawings can be obtained based on these drawings without creative efforts.
FIG. 1 is a process flow diagram of an embodiment of the present invention.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the technical solution in the embodiment of the present invention will be clearly and completely described below with reference to the drawings in the embodiment of the present invention, and it is obvious that the described embodiment is only a part of the embodiment of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Examples 1 to 5 are aluminum-containing wastewater after Friedel-crafts reaction, and FIG. 1 shows a process flow of an embodiment of the present invention.
Example 1
The resource utilization method of the Friedel-crafts reaction aluminum-containing wastewater comprises the following steps:
(1) refining wastewater: adding 900kg of hydrogen peroxide into 30 tons of aluminum-containing wastewater, uniformly mixing, standing, oxidizing 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) preparing sodium metaaluminate: taking 4.43 tons of refined wastewater in the step (1), mixing industrial water and analytically pure sodium hydroxide solid, preparing 4.43 tons of alkali liquor with the mass concentration of 35%, dropwise adding the 4.43 tons of refined wastewater into the alkali liquor for 4 hours, and obtaining high-concentration sodium metaaluminate after dropwise adding;
(3) polymerization and curing: heating 25.07 tons of refined waste water left in the step (1) to 105 ℃, stirring at a rotating speed of 1500r/min, slowly and uniformly dripping sodium metaaluminate in the step (2) for 8 hours, preserving heat for 2 hours after finishing dripping, cooling to 25-30 ℃ after finishing preserving heat, 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 after standing and curing in the step (3) to obtain a finished product solid polyaluminium chloride, introducing 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) recovering: mixing the residual bottom solid insoluble substances obtained after standing and curing in the step (3) with the high-concentration sodium metaaluminate obtained in the step (2), and continuing curing and polymerizing to prepare the sodium metaaluminate.
By detecting the polyaluminium chloride prepared in the embodiment, as shown in Table 1, indexes of solid polyaluminium chloride after the preparation of the aluminum-containing wastewater of the Friedel-crafts reaction in the embodiment 1 are shown.
Table 1 example 1 test index for polyaluminium chloride preparation
| Item | Alumina content | Basicity of salt |
| Content (wt.) | 29.3％ | 88％ |
Example 2
(1) Refining wastewater: adding 900kg of hydrogen peroxide into 30 tons of aluminum-containing wastewater, uniformly mixing, standing, oxidizing 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) preparing sodium metaaluminate: taking 4.43 tons of refined wastewater in the step (1), mixing industrial water and analytically pure sodium hydroxide solid, preparing 4.43 tons of alkali liquor with the mass concentration of 35%, dropwise adding the 4.43 tons of refined wastewater into the alkali liquor for 4 hours, and obtaining high-concentration sodium metaaluminate after dropwise adding;
(3) polymerization and curing: heating 25.07 tons of refined waste water left in the step (1) to 105 ℃, stirring at a rotating speed of 2000r/min, slowly and uniformly dripping sodium metaaluminate in the step (2) for 8 hours, preserving heat for 2 hours after finishing dripping, cooling to 25-30 ℃ after finishing preserving heat, standing and curing for 96 hours, and obtaining supernatant fluid which is liquid polyaluminium chloride;
(4) and (3) drying and packaging: concentrating and drying the liquid polyaluminium chloride after standing and curing in the step (3) to obtain a finished product solid polyaluminium chloride, introducing 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) recovering: mixing the residual bottom solid insoluble substances obtained after standing and curing in the step (3) with the high-concentration sodium metaaluminate obtained in the step (2), and continuing curing and polymerizing to prepare the sodium metaaluminate.
By detecting the polyaluminium chloride prepared in the embodiment, as shown in Table 2, indexes of the solid polyaluminium chloride after the preparation of the aluminum-containing wastewater of the Friedel-crafts reaction in the embodiment 2 are shown.
Table 2 example 2 detection index for polyaluminium chloride
| Item | Alumina content | Basicity of salt |
| Content (wt.) | 29.8％ | 91％ |
Example 3
(1) Refining wastewater: adding 150kg of hydrogen peroxide into 30 tons of aluminum-containing wastewater, uniformly mixing, standing and oxidizing for 0.5 hour, adding 150kg of fresh diatomite after the oxidation is finished, heating to 30 ℃, stirring and preserving heat for 0.5 hour, and filtering to obtain 29.8 tons of refined wastewater;
(2) preparing sodium metaaluminate: taking 4.43 tons of refined wastewater in the step (1), mixing industrial water and analytically pure sodium hydroxide solid, preparing 4.43 tons of alkali liquor with the mass concentration of 50%, dropwise adding the 4.43 tons of refined wastewater into the alkali liquor for 4 hours, and obtaining high-concentration sodium metaaluminate after dropwise adding;
(3) polymerization and curing: heating the residual 25.33 tons of refined wastewater in the step (1) to 150 ℃, stirring at a rotating speed of 3000r/min, slowly and uniformly dripping sodium metaaluminate in the step (2) for 6 hours, preserving heat for 1 hour after finishing dripping, cooling to 25-30 ℃ after finishing preserving heat, standing and curing for 48 hours, and obtaining supernatant fluid which is liquid polyaluminium chloride;
(4) and (3) drying and packaging: concentrating and drying the liquid polyaluminium chloride after standing and curing in the step (3) to obtain a finished product solid polyaluminium chloride, introducing 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) recovering: mixing the residual bottom solid insoluble substances obtained after standing and curing in the step (3) with the high-concentration sodium metaaluminate obtained in the step (2), and continuing curing and polymerizing to prepare the sodium metaaluminate.
By detecting the polyaluminium chloride prepared in the embodiment, as shown in Table 3, indexes of the solid polyaluminium chloride after the preparation of the aluminum-containing wastewater of the Friedel-crafts reaction in the embodiment 3 are shown.
Table 3 example 3 test index for polyaluminium chloride preparation
| Item | Alumina content | Basicity of salt |
| Content (wt.) | 30.2％ | 95％ |
Example 4
(1) Refining wastewater: adding 600kg of hydrogen peroxide into 30 tons of aluminum-containing wastewater, uniformly mixing, standing, oxidizing for 3 hours, adding 600kg of fresh diatomite after the oxidation is finished, heating to 40 ℃, stirring, preserving heat for 3 hours, and filtering to obtain 29 tons of refined wastewater;
(2) preparing sodium metaaluminate: taking 4.35 tons of refined wastewater in the step (1), mixing industrial water and analytically pure sodium hydroxide solid, preparing 4.43 tons of alkali liquor with the mass concentration of 50%, dropwise adding the 4.43 tons of refined wastewater into the alkali liquor for 4 hours, and obtaining high-concentration sodium metaaluminate after dropwise adding;
(3) polymerization and curing: heating the 15.65 tons of refined waste water left in the step (1) to 100 ℃, stirring at the rotating speed of 2000r/min, slowly and uniformly dripping sodium metaaluminate in the step (2) for 10 hours, preserving heat for 4 hours after finishing dripping, cooling to 25-30 ℃ after finishing preserving heat, standing and curing for 50 hours, and obtaining the supernatant which is liquid polyaluminium chloride;
(4) and (3) drying and packaging: concentrating and drying the liquid polyaluminium chloride after standing and curing in the step (3) to obtain a finished product solid polyaluminium chloride, introducing 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) recovering: mixing the residual bottom solid insoluble substances obtained after standing and curing in the step (3) with the high-concentration sodium metaaluminate obtained in the step (2), and continuing curing and polymerizing to prepare the sodium metaaluminate.
By detecting the polyaluminium chloride prepared in the embodiment, as shown in Table 4, indexes of the solid polyaluminium chloride after the preparation of the aluminum-containing wastewater of the Friedel-crafts reaction in the embodiment 4 are shown.
Table 4 example 4 detection index for polyaluminium chloride
| Item | Alumina content | Basicity of salt |
| Content (wt.) | 28.3％ | 93％ |
Example 5
(1) Refining wastewater: adding 1500kg of hydrogen peroxide into 30 tons of aluminum-containing wastewater, uniformly mixing, standing and oxidizing for 1 hour, adding 600kg of fresh diatomite after the oxidation is finished, heating to 50 ℃, stirring and preserving heat for 3 hours, and filtering to obtain 28.6 tons of refined wastewater;
(2) preparing sodium metaaluminate: taking 4.29 tons of refined wastewater in the step (1), mixing industrial water and analytically pure sodium hydroxide solid, preparing 4.29 tons of alkali liquor with the mass concentration of 50%, dropwise adding the 4.29 tons of refined wastewater into the alkali liquor for 4 hours, and obtaining high-concentration sodium metaaluminate after dropwise adding;
(3) polymerization and curing: heating the residual 24.31 tons of refined wastewater in the step (1) to 100 ℃, stirring at the rotating speed of 2000r/min, slowly and uniformly dripping sodium metaaluminate in the step (2) for 10 hours, preserving heat for 4 hours after finishing dripping, cooling to 25-30 ℃ after finishing preserving heat, standing and curing for 60 hours, and obtaining the supernatant which is liquid polyaluminium chloride;
(4) and (3) drying and packaging: concentrating and drying the liquid polyaluminium chloride after standing and curing in the step (3) to obtain a finished product solid polyaluminium chloride, introducing 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) recovering: mixing the residual bottom solid insoluble substances obtained after standing and curing in the step (3) with the high-concentration sodium metaaluminate obtained in the step (2), and continuing curing and polymerizing to prepare the sodium metaaluminate.
By detecting the polyaluminium chloride prepared in the embodiment, as shown in Table 5, indexes of solid polyaluminium chloride after the preparation of the aluminum-containing wastewater of the Friedel-crafts reaction in the embodiment 5 are shown.
TABLE 5 test results for polyaluminum chloride prepared in example 5
| Item | Alumina content | Basicity of salt |
| Content (wt.) | 29.3％ | 94％ |
Comparative example 1
Comparative example 1 the process was as in example 1, except that in comparative example 1, 2.95 tons of refined wastewater was taken in step (2) and 26.55 tons of refined wastewater was taken in step (3).
Comparative example 2
The process in comparative example 2 was as described in example 2, except that in comparative example 2, 5.9 tons of refined wastewater was taken in step (2) and 23.6 tons of refined wastewater was taken in step (3), unlike example 1.
By detecting the polyaluminium chloride prepared in the comparative examples 1 and 2, as shown in the table 6, indexes of the solid polyaluminium chloride prepared by the Friedel-crafts reaction of the aluminiferous waste water in the comparative examples 1 and 2 are shown.
TABLE 6 detection indexes of polyaluminium chloride prepared in comparative examples 1 and 2
| Item | Alumina content | Basicity of salt |
| Comparative example 1 | 25.9％ | 75％ |
| Comparative example 2 | 23.3％ | 83％ |
From the data in Table 6, it can be seen from comparative example 1 and comparative example 1, and from example 2 and comparative example 2 that wastewater A was adjusted1And wastewater A2The ratio of (A) to (B) seriously affects the basicity and the content of the polyaluminium chloride; waste water A1And wastewater A2The proportion of (A) has obvious influence on the basicity of the polyaluminium chloride, and the reasonable proportion can improve the utilization rate of the wastewater.
Although the present invention has been described in detail by referring to the drawings in connection with the preferred embodiments, the present invention is not limited thereto. Various equivalent modifications or substitutions can be made on the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and these modifications or substitutions are within the scope of the present invention/any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention.
Claims (10)
1. A resource utilization method of Friedel-crafts reaction aluminum-containing wastewater is characterized by comprising the following steps:
(1) adding an oxidant into the aluminum-containing wastewater, adding an adsorbent after oxidation, and filtering to obtain wastewater A;
(2) dividing the wastewater A into wastewater A1And wastewater A2；
(3) Preparing alkali liquor, and dripping the wastewater A into the alkali liquor1To prepare mixed liquor B containing sodium metaaluminate;
(4) waste water A is treated2Heating, starting stirring, dropwise adding the mixed solution B, preserving heat after dropwise adding is finished, cooling after heat preservation, standing and curing to obtain supernatant polyaluminium chloride liquid;
(5) and (4) concentrating and drying the supernatant liquid polyaluminium chloride liquid to obtain a finished solid polyaluminium chloride product.
2. The resource utilization method of Friedel-crafts reaction aluminum-containing wastewater as claimed in claim 1, characterized in that the total mass of wastewater A is m, and the wastewater A is1Mass m1Waste water A2Has a mass of m2，m1＝15％m，m2＝85％m。
3. The resource utilization method of Friedel-crafts reaction aluminum-containing wastewater as claimed in claim 1 or 2, characterized in that the oxidant is hydrogen peroxide, the dosage of the oxidant is 0.5-5% of the total mass of the aluminum-containing wastewater, and the oxidation time of the oxidant is 0.5-3 h.
4. The resource utilization method of Friedel-crafts reaction aluminum-containing wastewater as claimed in claim 1 or 2, characterized in that the adsorbent is one of activated carbon, diatomite and activated alumina.
5. The resource utilization method of Friedel-crafts reaction aluminum-containing wastewater as claimed in claim 4, characterized in that 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 the adsorbent is added, and the stirring and heat preservation are carried out for 0.5-3 hours.
6. The resource utilization method of Friedel-crafts reaction aluminum-containing wastewater as claimed in claim 1 or 2, characterized in that the alkali liquor is sodium hydroxide solution, the mass concentration of the alkali liquor is 35-50%, and the dropping time is 4 h.
7. The resource utilization method of Friedel-crafts reaction aluminum-containing wastewater as claimed in claim 1 or 2, characterized in that wastewater A is2The temperature is raised to 100-150 ℃, and the stirring speed is 1500-3000 r/min.
8. The resource utilization method of Friedel-crafts reaction aluminum-containing wastewater as claimed in claim 1 or 2, characterized in that the dropping time of the mixed solution B is 6-10h, the temperature is kept for 1-4h after the dropping is finished, and the temperature is reduced to 25-30 ℃ after the temperature is kept.
9. The resource utilization method of Friedel-crafts reaction aluminum-containing wastewater as claimed in claim 1 or 2, characterized in that the standing and aging time is 48-96h, the lower layer solid insoluble substances are mixed with the mixed solution B after standing and aging, and aging polymerization is continued to prepare sodium metaaluminate.
10. The resource utilization method of Friedel-crafts reaction aluminum-containing wastewater as claimed in claim 1 or 2, characterized in that the effluent of concentration and drying in the step (5) is introduced into the lye in the step (3) for recycling.
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