CN109126883B - Petrochemical waste separation catalyst and preparation method thereof - Google Patents
Petrochemical waste separation catalyst and preparation method thereof Download PDFInfo
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- CN109126883B CN109126883B CN201811017994.2A CN201811017994A CN109126883B CN 109126883 B CN109126883 B CN 109126883B CN 201811017994 A CN201811017994 A CN 201811017994A CN 109126883 B CN109126883 B CN 109126883B
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
Abstract
The invention discloses a petrochemical waste separation catalyst which comprises the following raw materials in parts by weight: 20-40 parts of aluminum sulfate, 25-45 parts of ferrous sulfate, 10-20 parts of zinc sulfate, 15-30 parts of polyaluminium chloride, 20-30 parts of polyferric sulfate, 40-50 parts of powdered activated carbon prepared by modification after activation, 10-20 parts of bentonite, 10-20 parts of alumina and 30-40 parts of aryl zinc halide.
Description
Technical Field
The invention relates to the technical field of petrochemical industry, in particular to a petrochemical industry waste separation catalyst and a preparation method thereof.
Background
Petrochemical (also called Petrochemical industry), refers to the field of chemical industry in which petroleum is used as a raw material to produce chemicals, and also includes natural gas chemical industry in a broad sense. Petrochemical industry of the petrochemical industry limited company of China as a new industry is formed along with the development of the petroleum refining industry in the 20 th century and is grown during the world war II. After war, the rapid development of petrochemical industry has shifted the production of a large number of chemicals from the traditional production of coal and agricultural and forestry products to the production of petroleum and natural gas. Petrochemical industry has become the backbone industry in chemical industry, and plays an extremely important role in national economy.
In the petrochemical production process, a large amount of oil-containing petrochemical wastes such as acid sludge, waste engine oil, oil-containing alkaline water, oil-containing white clay, coke-oven plant coal tar residue, shale oil residue, oil sand slag, oil sludge of oil fields and oil refineries and the like are inevitably generated. The petrochemical industry waste is directly discharged without being treated, so that resource waste is caused, the environment is polluted, and meanwhile, petrochemical enterprises still need to pay pollution compensation fees with huge amounts, so that the operating cost of the enterprises is greatly increased. However, the treatment of the petrochemical oily waste is a problem which always troubles the petrochemical industry, and the problem is also a key issue concerned by all levels of governments and enterprises.
In the prior art, some chemical reagents can be used for separating and treating petrochemical wastes, but the treatment effect is poor, and water, oil, silt and the like in the petrochemical wastes are difficult to separate, so that the development of a petrochemical waste separation catalyst is very important.
Disclosure of Invention
The invention aims to provide a petrochemical waste separation catalyst to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme:
a petrochemical engineering waste separation catalyst comprises the following raw materials in parts by weight: 20-40 parts of aluminum sulfate, 25-45 parts of ferrous sulfate, 10-20 parts of zinc sulfate, 15-30 parts of polyaluminium chloride, 20-30 parts of polyferric sulfate, 40-50 parts of activated modified powdered activated carbon, 10-20 parts of bentonite, 10-20 parts of aluminum oxide and 30-40 parts of aryl zinc halide.
As a further scheme of the invention: the feed comprises the following raw materials in parts by weight: 25-35 parts of aluminum sulfate, 30-40 parts of ferrous sulfate, 12-18 parts of zinc sulfate, 20-25 parts of polyaluminium chloride, 22-28 parts of polyferric sulfate, 42-48 parts of activated modified powdered activated carbon, 12-18 parts of bentonite, 12-18 parts of alumina and 32-38 parts of aryl zinc halide.
As a still further scheme of the invention: the feed comprises the following raw materials in parts by weight: 30 parts of aluminum sulfate, 35 parts of ferrous sulfate, 15 parts of zinc sulfate, 22 parts of polyaluminium chloride, 25 parts of polyferric sulfate, 45 parts of activated modified powdered activated carbon, 15 parts of bentonite, 15 parts of aluminum oxide and 35 parts of aryl zinc halide.
As a still further scheme of the invention: the preparation method of the powdered activated carbon prepared by modification after activation comprises the following steps
The method comprises the following steps:
1) leaching the cellulose ethanol fermentation residues, and washing away organic acid and inorganic salt in the residues;
2) soaking the residue cleaned in the step 1) in a mixed solution of chitosan, glutaraldehyde and sodium dodecyl benzene sulfonate;
3) placing the residues soaked in the step 2) into a carbonization furnace, heating to 150-800 ℃ in air atmosphere for treatment for 20-60min, and then heating to 600-800 ℃ in inert atmosphere for carbonization for 60-120 min;
4) after carbonization treatment, introducing water vapor or carbon dioxide for activation treatment, wherein the activation process conditions are as follows: the activation temperature is 750-.
As a still further scheme of the invention: the preparation method of the aryl zinc halide comprises the following steps:
1) activating zinc powder by using trimethylchlorosilane;
2) adding lithium chloride for continuous activation treatment;
3) adding aromatic halide after catalyzing by phosgene, and obtaining the aryl zinc halide after overnight at room temperature.
The preparation method of the petrochemical waste separation catalyst comprises the following steps:
1) taking aluminum sulfate, ferrous sulfate, zinc sulfate, polyaluminium chloride, polyferric sulfate, activated modified powdered activated carbon, bentonite and alumina according to the formula ratio, and fully stirring and mixing the powdered activated carbon, the bentonite and the alumina in a mixing container to obtain a mixture A for later use;
2) fully grinding the mixture A obtained in the step 1) into powder with the granularity of 300-400 meshes to obtain powder B for later use;
3) adding aryl zinc halide with the formula amount into the powder B obtained in the step 2), and introducing chlorine dioxide gas for activation treatment, wherein the activation process conditions are as follows: the activation temperature is 200-.
The application of the petrochemical waste separation catalyst in the field of petrochemical industry.
Compared with the prior art, the invention has the beneficial effects that:
the petrochemical waste separation catalyst prepared by the invention can accelerate the separation of water, oil, silt and the like in the petrochemical waste under the combined action of various raw materials, and can effectively treat the petrochemical waste, thereby realizing the comprehensive utilization of harmless resources of the petrochemical waste, having good treatment effect, short treatment period, no secondary pollution in the treatment process, low treatment cost and being suitable for wide application.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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.
Example 1
A petrochemical engineering waste separation catalyst comprises the following raw materials in parts by weight: 20 parts of aluminum sulfate, 25 parts of ferrous sulfate, 10 parts of zinc sulfate, 15 parts of polyaluminium chloride, 20 parts of polyferric sulfate, 40 parts of activated modified powdered activated carbon, 10 parts of bentonite, 10 parts of aluminum oxide and 30 parts of aryl zinc halide.
The preparation method of the activated and modified powdered activated carbon comprises the following steps:
1) leaching the cellulose ethanol fermentation residues, and washing away organic acid and inorganic salt in the residues;
2) soaking the residue cleaned in the step 1) in a mixed solution of chitosan, glutaraldehyde and sodium dodecyl benzene sulfonate;
3) putting the residues soaked in the step 2) into a carbonization furnace, heating to 180 ℃ in air atmosphere for 40min, then heating to 700 ℃ in inert atmosphere, and carbonizing for 90 min;
4) after carbonization treatment, introducing water vapor or carbon dioxide for activation treatment, wherein the activation process conditions are as follows: the activation temperature is 850 ℃, the activation time is 15min, and the powdered activated carbon modified after activation is prepared after temperature reduction.
The preparation method of the aryl zinc halide comprises the following steps:
1) activating zinc powder by using trimethylchlorosilane;
2) adding lithium chloride for continuous activation treatment;
3) adding aromatic halide after catalyzing by phosgene, and obtaining the aryl zinc halide after overnight at room temperature.
In this embodiment, the preparation method of the petrochemical waste separation catalyst includes the following steps:
1) taking aluminum sulfate, ferrous sulfate, zinc sulfate, polyaluminium chloride, polyferric sulfate, activated modified powdered activated carbon, bentonite and alumina according to the formula ratio, and fully stirring and mixing the powdered activated carbon, the bentonite and the alumina in a mixing container to obtain a mixture A for later use;
2) fully grinding the mixture A obtained in the step 1) into powder with the granularity of 300-400 meshes to obtain powder B for later use;
3) adding aryl zinc halide with the formula amount into the powder B obtained in the step 2), and introducing chlorine dioxide gas for activation treatment, wherein the activation process conditions are as follows: the activation temperature is 280 ℃, the activation time is 40min, and the petrochemical waste separation catalyst is prepared after cooling.
Example 2
A petrochemical engineering waste separation catalyst comprises the following raw materials in parts by weight: 25 parts of aluminum sulfate, 30 parts of ferrous sulfate, 12 parts of zinc sulfate, 20 parts of polyaluminium chloride, 22 parts of polyferric sulfate, 42 parts of activated modified powdered activated carbon, 12 parts of bentonite, 12 parts of aluminum oxide and 32 parts of aryl zinc halide.
The preparation method of the activated and modified powdered activated carbon comprises the following steps:
1) leaching the cellulose ethanol fermentation residues, and washing away organic acid and inorganic salt in the residues;
2) soaking the residue cleaned in the step 1) in a mixed solution of chitosan, glutaraldehyde and sodium dodecyl benzene sulfonate;
3) putting the residues soaked in the step 2) into a carbonization furnace, heating to 180 ℃ in air atmosphere for 40min, then heating to 700 ℃ in inert atmosphere, and carbonizing for 90 min;
4) after carbonization treatment, introducing water vapor or carbon dioxide for activation treatment, wherein the activation process conditions are as follows: the activation temperature is 850 ℃, the activation time is 15min, and the powdered activated carbon modified after activation is prepared after temperature reduction.
The preparation method of the aryl zinc halide comprises the following steps:
1) activating zinc powder by using trimethylchlorosilane;
2) adding lithium chloride for continuous activation treatment;
3) adding aromatic halide after catalyzing by phosgene, and obtaining the aryl zinc halide after overnight at room temperature.
In this embodiment, the preparation method of the petrochemical waste separation catalyst includes the following steps:
1) taking aluminum sulfate, ferrous sulfate, zinc sulfate, polyaluminium chloride, polyferric sulfate, activated modified powdered activated carbon, bentonite and alumina according to the formula ratio, and fully stirring and mixing the powdered activated carbon, the bentonite and the alumina in a mixing container to obtain a mixture A for later use;
2) fully grinding the mixture A obtained in the step 1) into powder with the granularity of 300-400 meshes to obtain powder B for later use;
3) adding aryl zinc halide with the formula amount into the powder B obtained in the step 2), and introducing chlorine dioxide gas for activation treatment, wherein the activation process conditions are as follows: the activation temperature is 280 ℃, the activation time is 40min, and the petrochemical waste separation catalyst is prepared after cooling.
Example 3
A petrochemical engineering waste separation catalyst comprises the following raw materials in parts by weight: 30 parts of aluminum sulfate, 35 parts of ferrous sulfate, 15 parts of zinc sulfate, 22 parts of polyaluminium chloride, 25 parts of polyferric sulfate, 45 parts of activated modified powdered activated carbon, 15 parts of bentonite, 15 parts of aluminum oxide and 35 parts of aryl zinc halide.
The preparation method of the activated and modified powdered activated carbon comprises the following steps:
1) leaching the cellulose ethanol fermentation residues, and washing away organic acid and inorganic salt in the residues;
2) soaking the residue cleaned in the step 1) in a mixed solution of chitosan, glutaraldehyde and sodium dodecyl benzene sulfonate;
3) putting the residues soaked in the step 2) into a carbonization furnace, heating to 180 ℃ in air atmosphere for 40min, then heating to 700 ℃ in inert atmosphere, and carbonizing for 90 min;
4) after carbonization treatment, introducing water vapor or carbon dioxide for activation treatment, wherein the activation process conditions are as follows: the activation temperature is 850 ℃, the activation time is 15min, and the powdered activated carbon modified after activation is prepared after temperature reduction.
The preparation method of the aryl zinc halide comprises the following steps:
1) activating zinc powder by using trimethylchlorosilane;
2) adding lithium chloride for continuous activation treatment;
3) adding aromatic halide after catalyzing by phosgene, and obtaining the aryl zinc halide after overnight at room temperature.
In this embodiment, the preparation method of the petrochemical waste separation catalyst includes the following steps:
1) taking aluminum sulfate, ferrous sulfate, zinc sulfate, polyaluminium chloride, polyferric sulfate, activated modified powdered activated carbon, bentonite and alumina according to the formula ratio, and fully stirring and mixing the powdered activated carbon, the bentonite and the alumina in a mixing container to obtain a mixture A for later use;
2) fully grinding the mixture A obtained in the step 1) into powder with the granularity of 300-400 meshes to obtain powder B for later use;
3) adding aryl zinc halide with the formula amount into the powder B obtained in the step 2), and introducing chlorine dioxide gas for activation treatment, wherein the activation process conditions are as follows: the activation temperature is 280 ℃, the activation time is 40min, and the petrochemical waste separation catalyst is prepared after cooling.
Example 4
A petrochemical engineering waste separation catalyst comprises the following raw materials in parts by weight: 35 parts of aluminum sulfate, 40 parts of ferrous sulfate, 18 parts of zinc sulfate, 25 parts of polyaluminium chloride, 28 parts of polyferric sulfate, 48 parts of activated modified powdered activated carbon, 18 parts of bentonite, 18 parts of aluminum oxide and 38 parts of aryl zinc halide.
The preparation method of the activated and modified powdered activated carbon comprises the following steps:
1) leaching the cellulose ethanol fermentation residues, and washing away organic acid and inorganic salt in the residues;
2) soaking the residue cleaned in the step 1) in a mixed solution of chitosan, glutaraldehyde and sodium dodecyl benzene sulfonate;
3) putting the residues soaked in the step 2) into a carbonization furnace, heating to 180 ℃ in air atmosphere for 40min, then heating to 700 ℃ in inert atmosphere, and carbonizing for 90 min;
4) after carbonization treatment, introducing water vapor or carbon dioxide for activation treatment, wherein the activation process conditions are as follows: the activation temperature is 850 ℃, the activation time is 15min, and the powdered activated carbon modified after activation is prepared after temperature reduction.
The preparation method of the aryl zinc halide comprises the following steps:
1) activating zinc powder by using trimethylchlorosilane;
2) adding lithium chloride for continuous activation treatment;
3) adding aromatic halide after catalyzing by phosgene, and obtaining the aryl zinc halide after overnight at room temperature.
In this embodiment, the preparation method of the petrochemical waste separation catalyst includes the following steps:
1) taking aluminum sulfate, ferrous sulfate, zinc sulfate, polyaluminium chloride, polyferric sulfate, activated modified powdered activated carbon, bentonite and alumina according to the formula ratio, and fully stirring and mixing the powdered activated carbon, the bentonite and the alumina in a mixing container to obtain a mixture A for later use;
2) fully grinding the mixture A obtained in the step 1) into powder with the granularity of 300-400 meshes to obtain powder B for later use;
3) adding aryl zinc halide with the formula amount into the powder B obtained in the step 2), and introducing chlorine dioxide gas for activation treatment, wherein the activation process conditions are as follows: the activation temperature is 280 ℃, the activation time is 40min, and the petrochemical waste separation catalyst is prepared after cooling.
Example 5
A petrochemical engineering waste separation catalyst comprises the following raw materials in parts by weight: 40 parts of aluminum sulfate, 45 parts of ferrous sulfate, 20 parts of zinc sulfate, 30 parts of polyaluminium chloride, 30 parts of polyferric sulfate, 50 parts of activated modified powdered activated carbon, 20 parts of bentonite, 20 parts of aluminum oxide and 40 parts of aryl zinc halide.
The preparation method of the activated and modified powdered activated carbon comprises the following steps:
1) leaching the cellulose ethanol fermentation residues, and washing away organic acid and inorganic salt in the residues;
2) soaking the residue cleaned in the step 1) in a mixed solution of chitosan, glutaraldehyde and sodium dodecyl benzene sulfonate;
3) putting the residues soaked in the step 2) into a carbonization furnace, heating to 180 ℃ in air atmosphere for 40min, then heating to 700 ℃ in inert atmosphere, and carbonizing for 90 min;
4) after carbonization treatment, introducing water vapor or carbon dioxide for activation treatment, wherein the activation process conditions are as follows: the activation temperature is 850 ℃, the activation time is 15min, and the powdered activated carbon modified after activation is prepared after temperature reduction.
The preparation method of the aryl zinc halide comprises the following steps:
1) activating zinc powder by using trimethylchlorosilane;
2) adding lithium chloride for continuous activation treatment;
3) adding aromatic halide after catalyzing by phosgene, and obtaining the aryl zinc halide after overnight at room temperature.
In this embodiment, the preparation method of the petrochemical waste separation catalyst includes the following steps:
1) taking aluminum sulfate, ferrous sulfate, zinc sulfate, polyaluminium chloride, polyferric sulfate, activated modified powdered activated carbon, bentonite and alumina according to the formula ratio, and fully stirring and mixing the powdered activated carbon, the bentonite and the alumina in a mixing container to obtain a mixture A for later use;
2) fully grinding the mixture A obtained in the step 1) into powder with the granularity of 300-400 meshes to obtain powder B for later use;
3) adding aryl zinc halide with the formula amount into the powder B obtained in the step 2), and introducing chlorine dioxide gas for activation treatment, wherein the activation process conditions are as follows: the activation temperature is 280 ℃, the activation time is 40min, and the petrochemical waste separation catalyst is prepared after cooling.
Comparative example 1
The same procedure as in example 3 was repeated except that the powdery activated carbon obtained by modification after activation was not contained in the composition of example 3.
Comparative example 2
Compared with the example 3, the aryl zinc halide is not contained, and the rest is the same as the example 3.
Comparative example 3
Compared with the example 3, the powder active carbon and the aryl zinc halide prepared by modification after activation are not contained, and the rest is the same as the example 3.
The petrochemical waste separation catalysts prepared in examples 1 to 5 and comparative examples 1 to 3 were subjected to performance tests, and the test results are shown in table 1.
TABLE 1
From the results, the catalytic effect of the petrochemical waste separation catalyst prepared by adding the powdered activated carbon prepared by modification after activation and the aryl zinc halide raw material is more obvious.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (3)
1. The petrochemical waste separation catalyst is characterized by comprising the following raw materials in parts by weight: 20-40 parts of aluminum sulfate, 25-45 parts of ferrous sulfate, 10-20 parts of zinc sulfate, 15-30 parts of polyaluminium chloride, 20-30 parts of polyferric sulfate, 40-50 parts of activated modified powdered activated carbon, 10-20 parts of bentonite, 10-20 parts of alumina and 30-40 parts of aryl zinc halide; the preparation method of the activated and modified powdered activated carbon comprises the following steps: 1) leaching the cellulose ethanol fermentation residues, and washing away organic acid and inorganic salt in the residues; 2) soaking the residue cleaned in the step 1) in a mixed solution of chitosan, glutaraldehyde and sodium dodecyl benzene sulfonate; 3) placing the residues soaked in the step 2) into a carbonization furnace, heating to 150-800 ℃ in air atmosphere for treatment for 20-60min, and then heating to 600-800 ℃ in inert atmosphere for carbonization for 60-120 min; 4) after carbonization treatment, introducing water vapor or carbon dioxide for activation treatment, wherein the activation process conditions are as follows: the activation temperature is 750-; the preparation method of the aryl zinc halide comprises the following steps: 1) activating zinc powder by using trimethylchlorosilane; 2) adding lithium chloride for continuous activation treatment; 3) catalyzing with phosgene, adding aromatic halide, and standing overnight at room temperature to obtain aryl zinc halide; the preparation method of the petrochemical waste separation catalyst comprises the following steps: 1) taking aluminum sulfate, ferrous sulfate, zinc sulfate, polyaluminium chloride, polyferric sulfate, activated modified powdered activated carbon, bentonite and alumina according to the formula ratio, and fully stirring and mixing the powdered activated carbon, the bentonite and the alumina in a mixing container to obtain a mixture A for later use; 2) fully grinding the mixture A obtained in the step 1) into powder with the granularity of 300-400 meshes to obtain powder B for later use; 3) adding aryl zinc halide with the formula amount into the powder B obtained in the step 2), and introducing chlorine dioxide gas for activation treatment, wherein the activation process conditions are as follows: the activation temperature is 200-.
2. The petrochemical waste separation catalyst according to claim 1, comprising the following raw materials in parts by weight: 25-35 parts of aluminum sulfate, 30-40 parts of ferrous sulfate, 12-18 parts of zinc sulfate, 20-25 parts of polyaluminium chloride, 22-28 parts of polyferric sulfate, 42-48 parts of activated modified powdered activated carbon, 12-18 parts of bentonite, 12-18 parts of alumina and 32-38 parts of aryl zinc halide.
3. The petrochemical waste separation catalyst according to claim 2, comprising the following raw materials in parts by weight: 30 parts of aluminum sulfate, 35 parts of ferrous sulfate, 15 parts of zinc sulfate, 22 parts of polyaluminium chloride, 25 parts of polyferric sulfate, 45 parts of activated modified powdered activated carbon, 15 parts of bentonite, 15 parts of aluminum oxide and 35 parts of aryl zinc halide.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101327976A (en) * | 2008-07-15 | 2008-12-24 | 南通立源水处理技术有限公司 | Efficient water treatment flocculant |
| WO2013114068A3 (en) * | 2012-01-31 | 2013-10-10 | Cambridge Display Technology Limited | Process for the in situ activation of zinc metal |
| CN106672963A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Active carbon and preparation method thereof |
| CN106745351A (en) * | 2016-11-11 | 2017-05-31 | 广西新六合环保有限责任公司 | A kind of Industrial waste water treatment agent and preparation method thereof |
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| US20130109876A1 (en) * | 2011-10-31 | 2013-05-02 | Basf Se | Process for the preparation of organozinc halides |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101327976A (en) * | 2008-07-15 | 2008-12-24 | 南通立源水处理技术有限公司 | Efficient water treatment flocculant |
| WO2013114068A3 (en) * | 2012-01-31 | 2013-10-10 | Cambridge Display Technology Limited | Process for the in situ activation of zinc metal |
| CN106672963A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Active carbon and preparation method thereof |
| CN106745351A (en) * | 2016-11-11 | 2017-05-31 | 广西新六合环保有限责任公司 | A kind of Industrial waste water treatment agent and preparation method thereof |
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