CN116081756B - Water purifying agent for petroleum refining wastewater and preparation method thereof - Google Patents
Water purifying agent for petroleum refining wastewater and preparation method thereof Download PDFInfo
- Publication number
- CN116081756B CN116081756B CN202310355773.0A CN202310355773A CN116081756B CN 116081756 B CN116081756 B CN 116081756B CN 202310355773 A CN202310355773 A CN 202310355773A CN 116081756 B CN116081756 B CN 116081756B
- Authority
- CN
- China
- Prior art keywords
- fly ash
- parts
- mixture
- petroleum refining
- water purifying
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
- C02F2103/365—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention belongs to the technical field of water purifying agents, and particularly relates to a water purifying agent for petroleum refining wastewater and a preparation method thereof. The water purifying agent for the petroleum refining wastewater consists of the following raw materials: the modified fly ash comprises polyepoxy chloropropane amine, polyethyleneimine, polyphosphoric ferric sulfate, polysilicic aluminum magnesium chloride, 1-butyl-3-methylimidazole hexafluorophosphate, a mixture of modified bentonite and pretreated fly ash, sodium silicate and sodium humate. According to the water purifying agent for petroleum refining wastewater, the raw materials are synergistic, a mixture of modified bentonite and pretreated fly ash, an organic flocculant and an inorganic polymer flocculant are compounded for use, 1-butyl-3-methylimidazole hexafluorophosphate is added to reduce the strength of an oil-water interface film, sodium silicate is used as an inorganic dispersing agent, and sodium humate is added to remove heavy metals in the petroleum refining wastewater. The water purifying agent prepared by the method has the advantages of high efficiency, thorough treatment, high oil removal rate and high COD removal rate.
Description
Technical Field
The invention belongs to the technical field of water purifying agents, and particularly relates to a water purifying agent for petroleum refining wastewater and a preparation method thereof.
Background
The refining wastewater refers to wastewater generated in the production process of petrochemical enterprises, and comprises not only wastewater generated in the petroleum processing production process, but also process condensate water and other water in factories. The refining wastewater has the advantages of large discharge amount, large water fluctuation, high pollutant content, more mineral oil, ammonia nitrogen, suspended impurities and organic pollutants, and great environmental hazard.
The refining wastewater includes a plurality of different chemical substances such as petroleum, phenols, sulfides, ammonia, cyanide, nitrides, heavy metals (such as chromium, iron, nickel, copper, molybdenum, selenium, vanadium, zinc) and suspended substances. Petroleum is a saturated acyclic hydrocarbon, cyclic hydrocarbon, olefin, aromatic hydrocarbon, and non-hydrocarbon, respectively. The refining wastewater often contains more polycyclic aromatic hydrocarbons, which are more toxic and more durable in the environment.
If the oily wastewater generated in the petroleum refining process is directly discharged into the environment, the water body is polluted, the use value of water resources is affected, and the aromatic hydrocarbon compounds in the oily wastewater can poison aquatic organisms and enter human bodies after being enriched by food chains, so that the health of human beings is endangered. The existing water purifying agent for petroleum refining wastewater treatment has the problems of low treatment efficiency, single action, large dosage and the like, and has poor treatment effect on petroleum refining wastewater. Therefore, the development of a simple, convenient, efficient and thorough water purifying agent for petroleum refining wastewater has important significance.
Disclosure of Invention
The purpose of the invention is that: provides a water purifying agent for petroleum refining wastewater. The water purifying agent is used for petroleum refining wastewater and has the characteristics of small dosage, high COD removal rate, high oil removal rate and the like; the invention also provides a preparation method of the composite.
The invention relates to a water purifying agent for petroleum refining wastewater, which comprises the following raw materials in parts by weight: 2.5-3.5 parts of polyepichlorohydrin, 1-3 parts of polyethyleneimine, 7-9 parts of polyphosphoric ferric sulfate, 10-13 parts of polysilicate aluminum magnesium chloride, 0.8-1.3 parts of 1-butyl-3-methylimidazole hexafluorophosphate, 18-21 parts of a mixture of modified bentonite and pretreated fly ash, 5-7 parts of sodium silicate and 4-6 parts of sodium humate.
Preferably, the water purifying agent for petroleum refining wastewater provided by the invention comprises the following raw materials in parts by weight: 3.0 parts of polyepichlorohydrin, 2 parts of polyethyleneimine, 9 parts of polyphosphoric ferric sulfate, 11.5 parts of polysilicate aluminum magnesium chloride, 1.0 part of 1-butyl-3-methylimidazole hexafluorophosphate, 19.5 parts of a mixture of modified bentonite and pretreated fly ash, 7 parts of sodium silicate and 5 parts of sodium humate.
Wherein:
the preparation method of the mixture of the modified bentonite and the pretreated fly ash comprises the following steps:
(1) Adding sulfuric acid into the fly ash for stirring and mixing reaction, then carrying out vacuum suction filtration, drying and crushing the filtered fly ash at 120 ℃, and sieving the dried fly ash with a 200-mesh sieve to prepare pretreated fly ash;
(2) Adding bentonite and the pretreated fly ash prepared in the step (1) into water, and carrying out oscillation reaction for 2-3h at 55-60 ℃;
(3) Adding polyacrylamide into the mixed solution prepared in the step (2) for reaction for 2-3 hours, and then adding polydimethyldiallyl ammonium chloride for continuous reaction for 1.5-2 hours;
(4) Cooling to room temperature after the reaction is finished, standing for 48 hours, filtering, washing with deionized water, vacuum filtering, finally drying at 83-85 ℃, grinding and sieving with a 325-mesh sieve to obtain the mixture of the modified bentonite and the pretreated fly ash.
Wherein:
in the step (1), the liquid-solid ratio of sulfuric acid to fly ash is 3.5:1, the concentration of sulfuric acid is 1.5mol/L, the stirring and mixing reaction temperature is 50 ℃, and the reaction time is 1.2h.
In the step (2), the mass ratio of the bentonite to the pretreated fly ash is 1:0.3-0.5.
In the step (2), the mass volume ratio of the mixture of bentonite and pretreated fly ash to water is 1:60-70, and the unit is g/mL.
In the step (3), the mass-volume ratio of the mixture of bentonite and pretreated fly ash to polyacrylamide is 1:10-12, the unit is g/mL, and the mass fraction of the polyacrylamide solution is 1 per mill; the mass ratio of the mixture of bentonite and pretreated fly ash to polydimethyl diallyl ammonium chloride is 1:0.05-0.1.
The preparation method of the mixture of the modified bentonite and the pretreated fly ash comprises the steps of firstly pretreating the fly ash by sulfuric acid, so as to increase the specific surface area of the fly ash and the adsorption capacity of the fly ash, and simultaneously, more metal active sites in the fly ash are exposed, and acidic substances and SiO in the fly ash are also exposed 2 Al and 2 O 3 reaction takes place and the released Fe 3+ 、Al 3+ Has a certain flocculation sedimentation effect and promotes the adsorption effect of the fly ash. Bentonite and pretreated fly ash are selected for compounding, because the fly ash is a porous loose solid substance and is a porous aluminosilicate substance, and the bentonite has cation exchange property, larger specific surface area and higher ion exchange capacity. The oil removal rate and COD removal rate of the petroleum refining wastewater can be greatly improved after the modified treatment. Unmodified bentonite and fly ash have strong hydrophilicity and poor adsorption capability on organic matters in petroleum refining wastewater. The polyacrylamide has the property of oleophylic and hydrophobic after cation exchange with alkali metal ions between bentonite layers, and simultaneously increases the interlayer spacing of the bentonite, improves the specific surface area and has good application effect in weak acid and neutral environments. Alkoxy in the polydimethyl diallyl ammonium chloride can react with silanol groups on the surface of the fly ash after being hydrolyzed, so that the modified polydimethyl diallyl ammonium chloride has certain antibacterial performance. The addition of the fly ash expands the application range of the mixture of the modified bentonite and the pretreated fly ash in the petroleum refining wastewater, and greatly improves the capability of the mixture of the modified bentonite and the pretreated fly ash in adsorbing low-solubility organic pollutants in the petroleum refining wastewater.
The water purifying agent for petroleum refining wastewater uses the mixture of modified bentonite and pretreated fly ash as main components, and is compounded with an inorganic polymeric flocculant and an organic flocculant to enable the water purifying agent to have higher oil removal rate and COD removal rate. The addition of the mixture of the modified bentonite and the pretreated fly ash greatly improves the adsorption capacity of low-solubility organic pollutants in the petroleum refining wastewater, has good application effect under weak acid and neutral conditions, and generates ion exchange reaction under strong acid conditions to reduce the oleophilic hydrophobicity of the mixture, so that the adsorption effect on organic matters in the petroleum refining wastewater is reduced, and the oil particles themselves generate saponification under strong alkaline conditions. Therefore, inorganic polymeric flocculants such as polyphosphoric ferric sulfate and polysilicic acid aluminum magnesium chloride and organic flocculants such as polyepoxypropylamine and polyethyleneimine are additionally added. The inorganic polymeric flocculant of the polyphosphoric ferric sulfate, polysilicic acid aluminum magnesium chloride and the organic flocculant of the polyepichlorohydrin amine and the polyethylenimine are compounded for use, and the four substances have synergistic effect. The polysilicate aluminum magnesium chloride is an inorganic high molecular substance formed by copolymerization of aluminum and magnesium metal ions and polysilicic acid, the polysilicic acid is crosslinked into a net shape in the polymerization process, has larger specific surface area, interacts with an aluminum hydrolysis polymerization product to generate an aluminum-silicon polymer with higher polymer, and is favorable for polysilicic acid chlorideThe adsorption bridging and net capturing effects of the aluminum magnesium oxide have good flocculation effects under acidic, neutral and alkaline conditions, and the low-temperature flocculation effect is excellent. The polyphosphoric ferric sulfate is a high-charge polyhydroxy polynuclear complex, phosphate radical participates in the complexing reaction of Fe (III), and can form bridging between iron atoms to generate polynuclear complex, and Fe-OH-Fe or Fe-PO can be used 4 3- The structure of Fe alters the nature of the substance. Therefore, the two are selected for combination use, and the adsorption bridging and net capturing and rolling functions of the poly-phosphorus ferric sulfate on colloid in petroleum refining wastewater are enhanced by utilizing the advantages of the space three-dimensional net structure of the poly-phosphorus ferric sulfate and the longer length of the poly-silicate aluminum magnesium chloride aggregate. The introduction of the polyepichlorohydrin enhances the oil removal capability of the water purifying agent, and the state of flocs can be improved by introducing hydrophobic micelles, so that the adhesion of the water purifying agent to equipment is reduced. The polyethyleneimine exists in the petroleum refining wastewater in a form of polymeric cations, can neutralize and adsorb anionic substances in the petroleum refining wastewater, and can chelate heavy metals in the petroleum refining wastewater. The inorganic polymeric flocculant and the organic flocculant are selected for compounding use, and the addition of the polyepichlorohydrin amine and the polyethyleneimine can greatly improve the electric neutralization capacity and the adsorption bridging capacity of the polyphosphoric ferric sulfate and the polysilicic acid aluminum magnesium chloride.
The water purifying agent for petroleum refining wastewater is also added with a small amount of 1-butyl-3-methylimidazole hexafluorophosphate, sodium silicate and sodium humate. Wherein, the 1-butyl-3-methylimidazole hexafluorophosphate can form a conjugation effect with aromatic ring substances, thereby reducing the strength of the interface film. Sodium silicate is added as an inorganic dispersing agent to improve the dispersibility of the water purifying agent. The removal of heavy metals in petroleum refining wastewater is realized by utilizing the cation exchange property of sodium humate and the chelation with heavy metals.
The invention relates to a preparation method of a water purifying agent for petroleum refining wastewater, which comprises the following steps:
(1) Preparing a mixture of modified bentonite and pretreated fly ash, and then uniformly mixing with sodium silicate;
(2) And (2) stirring and mixing the polyepoxy chloropropane amine, the polyethyleneimine, the polyphosphoric ferric sulfate and the polysilicate aluminum magnesium chloride for 2-3 hours at the temperature of 40-45 ℃ according to a certain weight portion ratio, and then adding the mixture prepared in the step (1), the 1-butyl-3-methylimidazole hexafluorophosphate and the sodium humate into the mixture for stirring and mixing to prepare the water purifying agent for the petroleum refining wastewater.
The water purifying agent for petroleum refining wastewater is added into petroleum refining wastewater with the addition amount of 0.8-1.0g/L.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the water purifying agent for petroleum refining wastewater, the raw materials are synergistic, a mixture of modified bentonite and pretreated fly ash, an organic flocculant (polyepichlorohydrin amine and polyethylenimine) and an inorganic polymer flocculant (polyphosphoric ferric sulfate and polysilicic acid aluminum magnesium chloride) are compounded for use, 1-butyl-3-methylimidazole hexafluorophosphate is added to reduce the strength of an oil-water interface film, sodium silicate is used as an inorganic dispersing agent, and sodium humate is added to remove heavy metals in the petroleum refining wastewater. The water purifying agent prepared by the method is applied to petroleum refining wastewater and has the advantages of high efficiency, thorough treatment, high oil removal rate and high COD removal rate.
(2) The preparation method of the water purifying agent for the petroleum refining wastewater is simple and easy to implement, and the prepared water purifying agent for the petroleum refining wastewater has the characteristics of small consumption and good property stability.
Detailed Description
The invention is further described below with reference to examples.
Example 1: the water purifying agent for petroleum refining wastewater described in the embodiment 1 comprises the following raw materials in parts by weight: 3.0 parts of polyepichlorohydrin, 2 parts of polyethyleneimine, 9 parts of polyphosphoric ferric sulfate, 11.5 parts of polysilicate aluminum magnesium chloride, 1.0 part of 1-butyl-3-methylimidazole hexafluorophosphate, 19.5 parts of a mixture of modified bentonite and pretreated fly ash, 7 parts of sodium silicate and 5 parts of sodium humate.
Wherein:
the preparation method of the mixture of the modified bentonite and the pretreated fly ash comprises the following steps:
(1) Adding sulfuric acid into the fly ash for stirring and mixing reaction, then carrying out vacuum suction filtration, drying and crushing the filtered fly ash at 120 ℃, and sieving the dried fly ash with a 200-mesh sieve to prepare pretreated fly ash;
(2) Adding bentonite and the pretreated fly ash prepared in the step (1) into water, and carrying out oscillation reaction for 2.5h at 58 ℃;
(3) Adding polyacrylamide into the mixed solution prepared in the step (2) for reaction for 2.5 hours, and then adding polydimethyldiallyl ammonium chloride for continuous reaction for 1.8 hours;
(4) Cooling to room temperature after the reaction is finished, standing for 48 hours, filtering, washing with deionized water, vacuum filtering, finally drying at 83 ℃, grinding and sieving with a 325-mesh sieve to obtain the mixture of modified bentonite and pretreated fly ash.
Wherein:
in the step (1), the liquid-solid ratio of sulfuric acid to fly ash is 3.5:1, the concentration of sulfuric acid is 1.5mol/L, the stirring and mixing reaction temperature is 50 ℃, and the reaction time is 1.2h.
In the step (2), the mass ratio of bentonite to pretreated fly ash is 1:0.3.
In the step (2), the mass-volume ratio of the mixture of bentonite and pretreated fly ash to water is 1:65, and the unit is g/mL.
In the step (3), the mass-volume ratio of the mixture of bentonite and pretreated fly ash to polyacrylamide is 1:11, the unit is g/mL, and the mass fraction of the polyacrylamide solution is 1 per mill; the mass ratio of the mixture of bentonite and pretreated fly ash to polydimethyl diallyl ammonium chloride is 1:0.08.
The preparation method of the water purifying agent for petroleum refining wastewater of the embodiment 1 comprises the following steps:
(1) Preparing a mixture of modified bentonite and pretreated fly ash, and then uniformly mixing with sodium silicate;
(2) And (2) stirring and mixing the polyepoxy chloropropane amine, the polyethyleneimine, the polyphosphoric ferric sulfate and the polysilicate aluminum magnesium chloride for 3 hours at 45 ℃ according to a certain weight portion ratio, and then adding the mixture prepared in the step (1), the 1-butyl-3-methylimidazole hexafluorophosphate and the sodium humate into the mixture for stirring and mixing to prepare the water purifying agent for the petroleum refining wastewater.
In the use of the water purifying agent for petroleum refining wastewater described in example 1, the water purifying agent was added to petroleum refining wastewater in an amount of 0.8g/L. The oil removal rate in the petroleum refining wastewater after treatment is 99.5%, the COD removal rate is 98.3%, and the SS removal rate is 99.4%.
Example 2: the water purifying agent for petroleum refining wastewater described in the embodiment 2 comprises the following raw materials in parts by weight: 3.5 parts of polyepichlorohydrin, 1 part of polyethylenimine, 7 parts of polyphosphoric ferric sulfate, 10 parts of polysilicate aluminum magnesium chloride, 0.8 part of 1-butyl-3-methylimidazole hexafluorophosphate, 21 parts of a mixture of modified bentonite and pretreated fly ash, 5 parts of sodium silicate and 6 parts of sodium humate.
Wherein:
the preparation method of the mixture of the modified bentonite and the pretreated fly ash comprises the following steps:
(1) Adding sulfuric acid into the fly ash for stirring and mixing reaction, then carrying out vacuum suction filtration, drying and crushing the filtered fly ash at 120 ℃, and sieving the dried fly ash with a 200-mesh sieve to prepare pretreated fly ash;
(2) Adding bentonite and the pretreated fly ash prepared in the step (1) into water, and carrying out oscillation reaction for 2h at 60 ℃;
(3) Adding polyacrylamide into the mixed solution prepared in the step (2) for reaction for 2 hours, and then adding polydimethyldiallyl ammonium chloride for continuous reaction for 1.5 hours;
(4) Cooling to room temperature after the reaction is finished, standing for 48 hours, filtering, washing with deionized water, vacuum filtering, finally drying at 85 ℃, grinding and sieving with a 325-mesh sieve to obtain the mixture of modified bentonite and pretreated fly ash.
Wherein:
in the step (1), the liquid-solid ratio of sulfuric acid to fly ash is 3.5:1, the concentration of sulfuric acid is 1.5mol/L, the stirring and mixing reaction temperature is 50 ℃, and the reaction time is 1.2h.
In the step (2), the mass ratio of bentonite to pretreated fly ash is 1:0.5.
In the step (2), the mass volume ratio of the mixture of bentonite and pretreated fly ash to water is 1:60, and the unit is g/mL.
In the step (3), the mass-volume ratio of the mixture of bentonite and pretreated fly ash to polyacrylamide is 1:10, the unit is g/mL, and the mass fraction of the polyacrylamide solution is 1 per mill; the mass ratio of the mixture of bentonite and pretreated fly ash to polydimethyl diallyl ammonium chloride is 1:0.05.
The preparation method of the water purifying agent for petroleum refining wastewater described in the embodiment 2 comprises the following steps:
(1) Preparing a mixture of modified bentonite and pretreated fly ash, and then uniformly mixing with sodium silicate;
(2) And (2) stirring and mixing the polyepoxy chloropropane amine, the polyethyleneimine, the polyphosphoric ferric sulfate and the polysilicate aluminum magnesium chloride for 2 hours at a certain weight portion ratio at a temperature of 40 ℃, and then adding the mixture prepared in the step (1), the 1-butyl-3-methylimidazole hexafluorophosphate and the sodium humate into the mixture for stirring and mixing to prepare the water purifying agent for the petroleum refining wastewater.
In the use of the water purifying agent for petroleum refining wastewater described in example 2, the water purifying agent was added to petroleum refining wastewater in an amount of 1.0g/L. The oil removal rate in the petroleum refining wastewater after treatment is 98.3%, the COD removal rate is 96.2%, and the SS removal rate is 98.6%.
Example 3: the water purifying agent for petroleum refining wastewater described in the embodiment 3 comprises the following raw materials in parts by weight: 2.5 parts of polyepichlorohydrin, 3 parts of polyethylenimine, 8 parts of polyphosphoric ferric sulfate, 13 parts of polysilicate aluminum magnesium chloride, 1.3 parts of 1-butyl-3-methylimidazole hexafluorophosphate, 18 parts of a mixture of modified bentonite and pretreated fly ash, 6 parts of sodium silicate and 4 parts of sodium humate.
Wherein:
the preparation method of the mixture of the modified bentonite and the pretreated fly ash comprises the following steps:
(1) Adding sulfuric acid into the fly ash for stirring and mixing reaction, then carrying out vacuum suction filtration, drying and crushing the filtered fly ash at 120 ℃, and sieving the dried fly ash with a 200-mesh sieve to prepare pretreated fly ash;
(2) Adding bentonite and the pretreated fly ash prepared in the step (1) into water, and carrying out oscillation reaction for 3 hours at 55 ℃;
(3) Adding polyacrylamide into the mixed solution prepared in the step (2) for reaction for 3 hours, and then adding polydimethyldiallyl ammonium chloride for continuous reaction for 2 hours;
(4) Cooling to room temperature after the reaction is finished, standing for 48 hours, filtering, washing with deionized water, vacuum filtering, finally drying at 85 ℃, grinding and sieving with a 325-mesh sieve to obtain the mixture of modified bentonite and pretreated fly ash.
Wherein:
in the step (1), the liquid-solid ratio of sulfuric acid to fly ash is 3.5:1, the concentration of sulfuric acid is 1.5mol/L, the stirring and mixing reaction temperature is 50 ℃, and the reaction time is 1.2h.
In the step (2), the mass ratio of bentonite to pretreated fly ash is 1:0.4.
In the step (2), the mass-volume ratio of the mixture of bentonite and pretreated fly ash to water is 1:70, and the unit is g/mL.
In the step (3), the mass-volume ratio of the mixture of bentonite and pretreated fly ash to polyacrylamide is 1:12, the unit is g/mL, and the mass fraction of the polyacrylamide solution is 1 per mill; the mass ratio of the mixture of bentonite and pretreated fly ash to the polydimethyl diallyl ammonium chloride is 1:0.1.
The preparation method of the water purifying agent for petroleum refining wastewater described in the embodiment 3 comprises the following steps:
(1) Preparing a mixture of modified bentonite and pretreated fly ash, and then uniformly mixing with sodium silicate;
(2) And (2) stirring and mixing the polyepoxy chloropropane amine, the polyethyleneimine, the polyphosphoric ferric sulfate and the polysilicate aluminum magnesium chloride for 2.5 hours at the temperature of 43 ℃ according to a certain weight portion ratio, and then adding the mixture prepared in the step (1), the 1-butyl-3-methylimidazole hexafluorophosphate and the sodium humate into the mixture for stirring and mixing to prepare the water purifying agent for the petroleum refining wastewater.
In the use of the water purifying agent for petroleum refining wastewater described in example 3, the water purifying agent was added to petroleum refining wastewater in an amount of 0.9g/L. The oil removal rate in the petroleum refining wastewater after treatment is 99.0%, the COD removal rate is 97.5%, and the SS removal rate is 99.1%.
Comparative example 1
The preparation method of the water purifying agent for petroleum refining wastewater described in this comparative example 1 is the same as that of example 1, except that the mixture of modified bentonite and pretreated fly ash is not added to the raw material. The water purifying agent for petroleum refining wastewater, which is described in the comparative example 1, comprises the following raw materials in parts by weight: 3.0 parts of polyepichlorohydrin, 2 parts of polyethyleneimine, 9 parts of polyphosphoric ferric sulfate, 11.5 parts of polysilicate aluminum magnesium chloride, 1.0 part of 1-butyl-3-methylimidazole hexafluorophosphate, 7 parts of sodium silicate and 5 parts of sodium humate.
The use of the water purifying agent for petroleum refining wastewater of comparative example 1 was carried out by adding the prepared water purifying agent for petroleum refining wastewater to petroleum refining wastewater in an amount of 0.8g/L. The oil removal rate in the petroleum refining wastewater after treatment is 76.8%, the COD removal rate is 73.4%, and the SS removal rate is 88.3%.
Comparative example 2
The preparation method of the water purifying agent for petroleum refining wastewater described in this comparative example 2 is the same as that of example 1, except that the raw material composition is different. The water purifying agent for petroleum refining wastewater described in the comparative example 2 comprises the following raw materials in parts by weight: 3.0 parts of polyepichlorohydrin, 2 parts of polyethyleneimine, 9 parts of polyphosphoric ferric sulfate, 11.5 parts of polysilicate aluminum magnesium chloride, 1.0 part of 1-butyl-3-methylimidazole hexafluorophosphate, 19.5 parts of modified bentonite, 7 parts of sodium silicate and 5 parts of sodium humate.
The preparation method of the modified bentonite comprises the following steps:
(1) Adding bentonite into water, and carrying out oscillation reaction for 2.5h at 58 ℃;
(2) Adding polyacrylamide into the mixed solution prepared in the step (1) for reaction for 2.5 hours, and then adding polydimethyldiallyl ammonium chloride for continuous reaction for 1.8 hours;
(3) Cooling to room temperature after the reaction is finished, standing for 48 hours, filtering, washing with deionized water, vacuum filtering, finally drying at 83 ℃, grinding and sieving with a 325-mesh sieve to obtain the modified bentonite.
Wherein:
in the step (1), the mass-volume ratio of bentonite to water is 1:65, and the unit is g/mL.
In the step (2), the mass-volume ratio of bentonite to polyacrylamide is 1:11, the unit is g/mL, and the mass fraction of the polyacrylamide solution is 1 per mill; the mass ratio of bentonite to polydimethyl diallyl ammonium chloride is 1:0.08.
The use of the water purifying agent for petroleum refining wastewater described in comparative example 2 was carried out by adding the prepared water purifying agent for petroleum refining wastewater to petroleum refining wastewater in an amount of 0.8g/L. The oil removal rate in the petroleum refining wastewater after treatment is 83.6%, the COD removal rate is 80.5%, and the SS removal rate is 89.7%.
Comparative example 3
The preparation method of the water purifying agent for petroleum refining wastewater described in this comparative example 3 is the same as in example 1, except that the raw materials are not added with polyepichlorohydrin amine and polyethyleneimine. The water purifying agent for petroleum refining wastewater, which is described in the comparative example 3, comprises the following raw materials in parts by weight: 9 parts of polyphosphoric ferric sulfate, 11.5 parts of polysilicate aluminum magnesium chloride, 1.0 part of 1-butyl-3-methylimidazole hexafluorophosphate, 19.5 parts of a mixture of modified bentonite and pretreated fly ash, 7 parts of sodium silicate and 5 parts of sodium humate.
The use of the water purifying agent for petroleum refining wastewater according to comparative example 3 was carried out by adding the prepared water purifying agent for petroleum refining wastewater to petroleum refining wastewater in an amount of 0.8g/L. The oil removal rate in the petroleum refining wastewater after treatment is 88.9%, the COD removal rate is 86.8%, and the SS removal rate is 92.3%.
Comparative example 4
The process for producing a water purifier for petroleum refining wastewater according to comparative example 4 is the same as in example 1, except that iron polyphosphate sulfate and magnesium aluminum polysilicate chloride are not added to the raw materials. The water purifying agent for petroleum refining wastewater described in the comparative example 4 comprises the following raw materials in parts by weight: 3.0 parts of polyepichlorohydrin amine, 2 parts of polyethylenimine, 1.0 part of 1-butyl-3-methylimidazole hexafluorophosphate, 19.5 parts of a mixture of modified bentonite and pretreated fly ash, 7 parts of sodium silicate and 5 parts of sodium humate.
The use of the water purifying agent for petroleum refining wastewater of comparative example 4 was carried out by adding the prepared water purifying agent for petroleum refining wastewater to petroleum refining wastewater in an amount of 0.8g/L. The oil removal rate in the petroleum refining wastewater after treatment is 68.1%, the COD removal rate is 64.2%, and the SS removal rate is 83.9%.
Claims (3)
1. The water purifying agent for the petroleum refining wastewater is characterized by comprising the following raw materials in parts by weight: 2.5-3.5 parts of polyepichlorohydrin, 1-3 parts of polyethyleneimine, 7-9 parts of polyphosphoric ferric sulfate, 10-13 parts of polysilicate aluminum magnesium chloride, 0.8-1.3 parts of 1-butyl-3-methylimidazole hexafluorophosphate, 18-21 parts of a mixture of modified bentonite and pretreated fly ash, 5-7 parts of sodium silicate and 4-6 parts of sodium humate;
wherein: the preparation method of the mixture of the modified bentonite and the pretreated fly ash comprises the following steps:
(1) Adding sulfuric acid into the fly ash for stirring and mixing reaction, then carrying out vacuum suction filtration, drying and crushing the filtered fly ash at 120 ℃, and sieving the dried fly ash with a 200-mesh sieve to prepare pretreated fly ash;
(2) Adding bentonite and the pretreated fly ash prepared in the step (1) into water, and carrying out oscillation reaction for 2-3h at 55-60 ℃;
(3) Adding polyacrylamide into the mixed solution prepared in the step (2) for reaction for 2-3 hours, and then adding polydimethyldiallyl ammonium chloride for continuous reaction for 1.5-2 hours;
(4) Cooling to room temperature after the reaction is finished, standing for 48 hours, filtering, washing with deionized water, vacuum filtering, finally drying at 83-85 ℃, grinding and sieving with a 325-mesh sieve to obtain a mixture of modified bentonite and pretreated fly ash;
wherein:
in the step (1), the liquid-solid ratio of sulfuric acid to fly ash is 3.5:1, the concentration of sulfuric acid is 1.5mol/L, the stirring and mixing reaction temperature is 50 ℃, and the reaction time is 1.2h;
in the step (2), the mass ratio of bentonite to pretreated fly ash is 1:0.3-0.5;
in the step (2), the mass volume ratio of the mixture of bentonite and pretreated fly ash to water is 1:60-70, and the unit is g/mL;
in the step (3), the mass-volume ratio of the mixture of bentonite and pretreated fly ash to polyacrylamide is 1:10-12, the unit is g/mL, and the mass fraction of the polyacrylamide solution is 1 per mill; the mass ratio of the mixture of bentonite and pretreated fly ash to polydimethyl diallyl ammonium chloride is 1:0.05-0.1.
2. The water purifying agent for petroleum refining wastewater according to claim 1, which is characterized by comprising the following raw materials in parts by weight: 3.0 parts of polyepichlorohydrin, 2 parts of polyethyleneimine, 9 parts of polyphosphoric ferric sulfate, 11.5 parts of polysilicate aluminum magnesium chloride, 1.0 part of 1-butyl-3-methylimidazole hexafluorophosphate, 19.5 parts of a mixture of modified bentonite and pretreated fly ash, 7 parts of sodium silicate and 5 parts of sodium humate.
3. A method for preparing the water purifying agent for petroleum refining wastewater according to claim 1, which is characterized by comprising the following steps:
(1) Preparing a mixture of modified bentonite and pretreated fly ash, and then uniformly mixing with sodium silicate;
(2) And (2) stirring and mixing the polyepoxy chloropropane amine, the polyethyleneimine, the polyphosphoric ferric sulfate and the polysilicate aluminum magnesium chloride for 2-3 hours at the temperature of 40-45 ℃ according to a certain weight portion ratio, and then adding the mixture prepared in the step (1), the 1-butyl-3-methylimidazole hexafluorophosphate and the sodium humate into the mixture for stirring and mixing to prepare the water purifying agent for the petroleum refining wastewater.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310355773.0A CN116081756B (en) | 2023-04-06 | 2023-04-06 | Water purifying agent for petroleum refining wastewater and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310355773.0A CN116081756B (en) | 2023-04-06 | 2023-04-06 | Water purifying agent for petroleum refining wastewater and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116081756A CN116081756A (en) | 2023-05-09 |
| CN116081756B true CN116081756B (en) | 2023-06-23 |
Family
ID=86201084
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310355773.0A Active CN116081756B (en) | 2023-04-06 | 2023-04-06 | Water purifying agent for petroleum refining wastewater and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116081756B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114751499A (en) * | 2022-06-16 | 2022-07-15 | 山东艾维斯特精细化工有限公司 | Composite flocculant for treating dye wastewater and preparation method and application thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107651737A (en) * | 2017-10-31 | 2018-02-02 | 广西贝仕特环保科技有限公司 | A kind of industrial waste water purifying agent of high oil removal rate and preparation method thereof |
| CN109626483B (en) * | 2018-12-24 | 2022-01-18 | 深圳市发科达表面处理技术有限公司 | Industrial wastewater treatment agent and preparation method thereof |
| CN111547828A (en) * | 2020-04-10 | 2020-08-18 | 佛山华清智业环保科技有限公司 | Composite flocculant and preparation method and application thereof |
| CN111704194B (en) * | 2020-06-30 | 2022-09-13 | 广西夏阳环保科技有限公司 | Composite sewage treatment agent based on inorganic non-metallic mineral material and application |
| CN113684053B (en) * | 2021-10-25 | 2021-12-21 | 胜利油田海发环保化工有限责任公司 | Composite demulsifier and preparation process thereof |
-
2023
- 2023-04-06 CN CN202310355773.0A patent/CN116081756B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114751499A (en) * | 2022-06-16 | 2022-07-15 | 山东艾维斯特精细化工有限公司 | Composite flocculant for treating dye wastewater and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116081756A (en) | 2023-05-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103641245B (en) | A kind of paper-making waste water treating agent and preparation method thereof | |
| CN101298038B (en) | Gel adsorbing agent for wastewater treatment | |
| CN103641226A (en) | Heavy metal sewage treating agent and preparation method thereof | |
| CN103708631A (en) | Multifunctional sewage treatment agent and preparation method thereof | |
| CN109292933B (en) | COD (chemical oxygen demand) remover with oxidation and flocculation combined function for sewage treatment | |
| CN101941755B (en) | Modified coal ash, preparation method thereof and method thereof for treating humic acid | |
| WO2013123780A1 (en) | Advanced treatment method for biochemical tail water of coking wastewater | |
| CN101475252A (en) | Integrated method for processing arsenic-containing wastewater by using iron composite bentonite | |
| CN102557218B (en) | Composite flocculating agent containing various polyacrylamides and preparation method for composite flocculating agent | |
| CN111732169A (en) | Efficient water treatment agent and preparation method and application thereof | |
| CN108067185A (en) | A kind of preparation of high-efficient sewage water treatment absorbent and production method | |
| CN104692612A (en) | Paper sludge dewatering composite flocculant | |
| CN116081756B (en) | Water purifying agent for petroleum refining wastewater and preparation method thereof | |
| CN106746475B (en) | Composite polymer sludge dewatering flocculant and preparation method thereof | |
| CN102583672B (en) | Polysilicate ferro-copper sulfate composite with wastewater deodorizing and flocculating function and preparation method thereof | |
| CN101381136A (en) | High-efficiency broadspectrum flocculant and preparation method thereof | |
| CN113636631B (en) | Composite water quality agglutination purifying agent and preparation method thereof | |
| CN106669640A (en) | Polyaniline modified bentonite nano-microsphere adsorption material and preparation method thereof | |
| CN113083216B (en) | Two-dimensional nickel-based composite metal oxide adsorbent, preparation method and application of adsorbent in removing phosphate radical | |
| CN114940547A (en) | Treatment method of nickel wastewater | |
| Visa | Heavy Metals Removal on Dye–Modified Fly Ash Substrates | |
| CN104628105A (en) | Organic sewage treatment complex reagent | |
| CN110404500A (en) | A kind of multiple-effect compound type sewage-treating agent and preparation method thereof | |
| CN101786645A (en) | Basic silica-based aluminate serial waste water treating agent and waste water treatment method | |
| CN111039370A (en) | Composite flocculant and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |