CN104556460A - Defluorination and dephosphorization method of PSRY molecular sieve production wastewater - Google Patents

Defluorination and dephosphorization method of PSRY molecular sieve production wastewater Download PDF

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Publication number
CN104556460A
CN104556460A CN201310474332.9A CN201310474332A CN104556460A CN 104556460 A CN104556460 A CN 104556460A CN 201310474332 A CN201310474332 A CN 201310474332A CN 104556460 A CN104556460 A CN 104556460A
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molecular sieve
mixed system
accordance
psry
value
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CN104556460B (en
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桑军强
马欣
高峰
崔龙鹏
张超
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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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
    • 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
    • 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
    • C02F2101/105—Phosphorus compounds
    • 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
    • C02F2101/12—Halogens or halogen-containing 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

Abstract

The invention relates to a defluorination and dephosphorization method of PSRY molecular sieve production wastewater. The method comprises the following steps: (1) solid waste residues generated during treatment process of PSRY molecular sieve production wastewater and other molecular sieve production wastewater are mixed, and aluminum in the solid waste residues is dissolved in the form of Al<3+> in the wastewater, wherein pH value of the mixed system during the dissolution process is less than 4.5; (2) pH value of the mixed system obtained from the step (1) is adjusted to more than 6 to make Al<3+> reacts with F<-> and PO4<3-> so as to fully precipitate F<-> and PO4<3->; and (3) a coagulant aid is added into the mixed system obtained from the step (2), and solid-liquid separation is carried out on the mixed system which has undergone coagulantion enhancement, wherein dosage and dissolution conditions of the solid waste residues in the step (1) enable Al<3+> in the step (2) to fully precipitate F<-> and PO4<3->. By the method, fluorine and phosphor in the PSRY molecular sieve production wastewater can be effectively removed.

Description

A kind of PSRY molecular sieve factory effluent except fluorine phosphorus removing method
Technical field
The present invention relates to a kind of method for wastewater treatment, particularly a kind of PSRY molecular sieve factory effluent except fluorine phosphorus removing method.
Background technology
Phosphorous skeletal silicon-rich ultra-steady Y molecular sieve (i.e. PSRY molecular sieve) is the skeletal silicon-rich novel molecular sieve that NaY molecular sieve is obtained by hydrothermal calcine and the preparation of Compound-acid dealumination complement silicon, due to fluid catalytic cracking (FCC) catalyzer prepared for chief active constituent element with PSRY molecular sieve, to have coke selectivity good, gasoline octane rating is high, heavy oit pyrolysis ability is strong, diesel yield high, after successfully carrying out THE INDUSTRIAL TRIAL, the FCC catalyzer being chief active constituent element with PSRY molecular sieve uses on the many heavy oil catalytically cracking equipments in the whole nation, achieve good economic benefit and social benefit.
Owing to must use a certain amount of silicofluoric acid and phosphoric acid in process of production, there is significant difference with conventional molecular sieve factory effluent in the waste water that PSRY process of producing molecular sieve produces, and wherein most outstanding feature is F in waste water -, PO 4 3-the phosphorus that-P(exists with phosphate radical form) and SO 4 2-high (the F of content -content is often beyond 2000mg/L, PO 4 3--P content is generally 100 ~ 1000mg/L, SO 4 2-content is generally more than 20000mg/L), simultaneously to possess the silicon of conventional molecular sieve factory effluent, aluminium and ammonia-nitrogen content high for PSRY molecular sieve factory effluent, the feature that pH value is low.The main purpose of conventional molecular sieve production wastewater treatment removes the aluminium, silicon and the ammonia nitrogen that contain in water, this kind of wastewater processing technology is through improving development for many years, operational path is increasingly rationalized, and actual processing effect can meet molecular sieve and produce and environment protection emission requirement.Current molecular sieve and Catalyst Production producer process PSRY molecular sieve factory effluent together with after the molecular sieve factory effluent mixing of other types, and actual processing effect shows that this processing mode cannot make the fluorine in waste water and phosphorus content reach environmental emission standard.
Phosphoric excessive in water can cause the eutrophication of water body, and therefore phosphorus is one of strict main disposal of pollutants index controlled of country.Excessive fluorine can cause serious harm to environment, not only can cause the fluorosis of human body (show as to invade tooth and bone is main general chronic lesion), and fluoride pollution can make animal and plant poisoning, impact agricultural and animal husbandry are produced, and therefore the discharge of national wastewater discharge standard to fluorine has strict demand.Therefore, for ensureing the normal production of PSRY molecular sieve, fluorine and the phosphorus content discharge beyond standards problem of PSRY molecular sieve factory effluent must be solved.
Consult in existing document less than for PSRY molecular sieve factory effluent except the report of fluorine dephosphorization, but the relevant Patents technology except fluorine dephosphorization waste water and periodical literature can be found, representative Patents technology and periodical literature as follows:
CN 102070267 A(mono-kind processes the method for the phosphorous fluoride waste of high-concentration acidic wastewater) disclose a kind of method processing acid phosphorous fluoride waste.The method comprises the steps: 1) add calcium hydroxide in first oxytropism phosphor fluorine containing waste water, and the pH value of the hierarchy of control is between 12-14, obtains, containing the reaction system of precipitation, being designated as reaction system 1; 2) remove the precipitation in described reaction system 1, and in remaining liq, add sulfuric acid adjust ph between 9-11, then add Tai-Ace S 150 adjust ph between 6-7, obtain the reaction system 2 containing precipitation; 3) described reaction system 2 is precipitated, removing throw out wherein, obtain the waste water after processing.Waste water Oil repellent after the inventive method process is lower than 10mg/L, and phosphorus content is lower than 0.5mg/L, and pH value, between 6 ~ 7, reaches Phosphate Fertilizer Industry pollution discharge standard (GB15580-95).
CN 1185171C(treating method for high fluorice acid waste water) high fluorine-containing, high suspended matter process for treating acidic waste water in a kind of phophatic fertilizer production process is proposed, be applicable to containing suspended solid, high fluoric acid wastewater treatment.The method is with calcium carbonate for main defluorinating agent, and calcium oxide is auxiliary defluorinating agent, and is returned by fraction solids sediment as assembling crystal seed.Its control condition is sequentially added into main defluorinating agent, gathering crystal seed, auxiliary defluorinating agent, adjusted to ph 6-9, and settlement separate solid and process water, returned by part sediment in former water, part sediment fully utilizes.The method medicament source is wide, and price is low, and treatment time of water is short, and technique is simple, and cost of water treatment is low.
The method of CN 102267768 A(lime-flyash combination treatment high-concentration fluorine-containing waste water) disclose the method for a kind of lime-flyash combination treatment high-concentration fluorine-containing waste water, comprise the following steps: the lime one-level precipitation process stage: temperature is 10 DEG C, the every 50mL fluoride waste of lime adding amount 0.1 ~ 0.2g, adsorption time be 30 ~ 60min, pH are 5.0 ~ 8.0; The treatment stage of flyash secondary absorption: temperature is 15 DEG C ~ 45 DEG C, the every 50mL fluoride waste of flyash add-on 5.0 ~ 15.0g, adsorption time be 60 ~ 120min, pH are 5.0 ~ 7.0, and described flyash is in advance through peracid solutions modification.For Industrial Wastewater Treatment after flyash modified process, improve utilization of fly ash rate and utilizing status, and flyash belongs to twice-laid stuff, can be recycled by techniques such as pickling.
Design and working (the Treatment of Industrial Water of fluorine-containing treatment of Phosphorus Containing Waste Water technique, 25th volume the 2nd phase in 2005) a Wen Zhongshao will state, Wang Qichao, Quan Yulian adopt the acid waste water of fluorine-containing, the phosphorous acid group of method process of limestone vegetation precipitation, the reaction pH controlling waste water is respectively 8.5 and 11.0, and add excessive strong electrolyte calcium chloride, fluorion and phosphate anion are precipitated respectively.Make throw out be separated with waste water again, reach the object removing fluorion in acid-bearing wastewater and phosphate anion.Finally adopt dilute hydrochloric acid neutralization, make fluorine-containing, phosphate anion waste water qualified discharge after treatment.This technical process is simple, and plant efficiency is high, easy and simple to handle, has good environmental benefit.
Various method is all with Ca above 2+as the main reactant except fluorine (and dephosphorization), pass through Ca 2+with F -(and PO 4 3-) react the water-fast calcium precipitation of generation and reach the object removing most of fluorine, phosphorus in waste water.Waste water handled by above method does not all have silicon and the high feature of sulfate radical content.Owing to containing a large amount of SO in PSRY molecular sieve factory effluent 4 2-ion, CaSO 4generation can severe jamming calcium salt particularly CaF 2formation efficiency and sedimentation function, and in PSRY molecular sieve factory effluent the silicon of high-content can have a strong impact on sorbent material recycle efficiency.Therefore above various method be all difficult to effectively to be applied to PSRY molecular sieve factory effluent except fluorine dephosphorization process.
Summary of the invention
The object of the invention is to develop a kind of be applicable to PSRY molecular sieve factory effluent except fluorine phosphorus removing method.The method effectively can remove fluorine in PSRY molecular sieve factory effluent and phosphorus.
PSRY molecular sieve factory effluent except a fluorine phosphorus removing method, comprising:
(1) PSRY molecular sieve factory effluent is mixed with the solid slag produced in other molecular sieve production wastewater treatment processes, make aluminium in described solid slag with Al 3+form be dissolved in described waste water, in dissolution process, the pH value of mixed system is less than 4.5;
(2) more than the pH value to 6 of mixed system that regulating step (1) obtains, Al is made 3+with F -and PO 4 3-reaction, by F -and PO 4 3-abundant precipitation;
(3) coagulant aids is added in the mixed system obtained to step (2), to through helping the mixed system of solidifying process to carry out solid-liquid separation;
Wherein, in step (1), solid slag consumption and dissolution conditions make the Al in step (2) 3+amount is enough to F -and PO 4 3-abundant precipitation.
Should be understood that, the object of the invention is to remove the fluorine in PSRY molecular sieve factory effluent and phosphorus, therefore the scope of other molecular sieves described in step (1) should not contradiction with it.Usually, other molecular sieves described in step (1) refer to molecular sieve that is not phosphorous, fluorine.
Should be understood that equally, the aluminium content of PSRY molecular sieve factory effluent, Oil repellent and phosphorus content are changes, and due to the difference of molecular sieve and preparation technology thereof, the aluminium content of step (1) described solid slag is also different, and therefore the consumption of step (1) described solid slag should be determined as the case may be.On the basis of dissolving disclosed by the invention and deposition condition, those skilled in the art can the easily consumption of determining step (1) described solid slag and other reaction conditions.
Generally, the consumption of step (1) described solid slag makes the total amount of contained aluminium in mixed system and precipitation F -and PO 4 3-the ratio of the theoretical amount of required aluminium is 4 ~ 10:1.
In general, the dissolution time of step (1) is not less than 10min, and preferably dissolution time is 30 ~ 120min.
The present invention has no particular limits the solvent temperature in step (1), adopts normal temperature.
The pH value of PSRY molecular sieve factory effluent is lower (generally about 3.0), and solid slag is then neutral or alkaline.In step (1), acidity remaining in general PSRY molecular sieve factory effluent just can reach the Al in stripping solid slag 3+object.For ensureing the Al in solid slag 3+effective stripping, in dissolution process, the pH value of mixed system should be less than 4.5, if desired (acidity of PSRY molecular sieve factory effluent be not enough to make in dissolution process, the pH value of mixed system remains on the state being less than 4.5 under), technique means then by adjust ph reaches this purpose, the means of pH are regulated to be well known to those skilled in the art, consider price and the factor such as easy to use, the general mode adding the mineral acids such as sulfuric acid, hydrochloric acid or nitric acid that adopts is to turn down the pH value of mixed system.
In step (2), for ensureing F -and PO 4 3-abundant precipitation, the pH value of mixed system answers > 6, and pH value effect between 6 to 9 is better.
Regulate the means of pH to be well known to those skilled in the art, consider price and the factor such as easy to use, the general pH value adopting the mineral alkali such as sodium hydroxide or potassium hydroxide to heighten mixed system.
In general, the reaction times of step (2) is not less than 10min, and preferably the reaction times is 30 ~ 120min.
In step (3), in order to ensure that the mixed system to step (2) obtains carries out solid-liquid separation effectively, need to add coagulant aids.Use polyacrylamide (PAM) as coagulant aids, dosage is 0.5 ~ 2mg/L, can carry out good solid-liquid separation to the mixed system that step (2) obtain.
In step (3), conventional wastewater treatment equipment for separating liquid from solid can be adopted, comprise horizontal sedimentation tank, radial-flow sedimentation tank and common slurry tank.
In step (3), the solid waste concentrating unit that the precipitating sludge that solid-liquid separation produces is transported to molecular sieve manufacturing enterprise carries out sludge condensation process.
In preferred situation, after the water outlet of step (3) solid-liquid separation being mixed with other high ammonia-nitrogen wastewaters of molecular sieve manufacturing enterprise, jointly carry out the process of stripping ammonia nitrogen removal.
Should be understood that, each concrete technical characteristic described in the invention, when without prejudice to thought of the present invention and not conflicting, can at random combine, it should be considered as content disclosed in this invention equally.
The present invention has taken into full account the water quality characteristics of PSRY molecular sieve factory effluent, the practical situation of binding molecule sieve manufacturing enterprise, the Al making full use of PSRY molecular sieve factory effluent and contain 3+as removing on the basis of fluorine dephosphorization reactant, the solid slag being rich in aluminium produced in other molecular sieve production wastewater treatment processes, as the supplementary medicament except fluorine dephosphorization, is utilizing Al 3+with F -and PO 4 3-reaction is by F -and PO 4 3-after abundant precipitation, only need add a small amount of coagulant aids, can Al be made 3+with F -and PO 4 3-the precipitation that reaction produces and the solid slag added effectively are separated with waste water, and PSRY molecular sieve factory effluent, completing after except fluorine dephosphorization, is mixed into stripping deamination apparatus with other high ammonia-nitrogen wastewaters.
The present invention possesses following outstanding advantages:
1. the present invention does not use Ca 2+, but utilize Al 3+as the precipitation positively charged ion except fluorine dephosphorization, avoid the SO that PSRY molecular sieve factory effluent contains in a large number 4 2-on the impact except fluorine dephosphorization process.
2. the present invention makes full use of contained Al in PSRY molecular sieve factory effluent 3+as the precipitation positively charged ion except fluorine dephosphorization, be rich in the solid slag of aluminium as Al using molecular sieve manufacturing enterprise simultaneously 3+supplementary source, both can ensure raw-material sufficient supplies, reach again resource recycling, not increase the object of extra solids waste residue.
3. because other high ammonia-nitrogen wastewaters of molecular sieve manufacturing enterprise are not fluorine-containing and phosphorus, its water yield is then more than 2 times of PSRY molecular sieve factory effluent, therefore use that the Oil repellent in PSRY molecular sieve factory effluent only need be reduced to below 30mg/L by the present invention, phosphorus content is reduced to below 3mg/L and can meets emission request, thus reduce operating cost and the management difficulty of the present invention's application.Stripping deamination process need brings up to 12 the pH value of waste water simultaneously, the alkali lye that neutralisation unit of the present invention consumes dissolves except the mineral acid that adds of unit for neutralizing except small portion, major part still acts on stripping deamination process, does not substantially increase the alkali consumption of whole treatment unit for waste water.
4. the present invention utilizes the acidity of PSRY molecular sieve factory effluent itself molecular sieve manufacturing enterprise to be rich in aluminium stripping in the solid slag of aluminium, as the Al of precipitation agent 3+derive from the solid slag of PSRY molecular sieve factory effluent itself and molecular sieve manufacturing enterprise.In addition, the major part adding alkali in step (2) still acts on stripping deamination process.Although the present invention adds solid slag in PSRY molecular sieve factory effluent, but only need can by Al by adding a small amount of coagulant aids 3+with F -and PO 4 3-the precipitation that reaction produces and the solid slag added effectively are separated with waste water.These characteristics makes reagent cost of the present invention lower, compared with prior art has obvious advantage.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated, but the scope of protection of present invention is not limited to the scope that embodiment represents.In embodiment, the number-average molecular weight of PAM is 8,000,000, purchased from Beijing Xitao Development Tech Co., Ltd..
Embodiment 1
PSRY molecular sieve factory effluent water sample: F -content: 1936mg/L; PO 4 3--P content: 286mg/L; SO 4 2-content: 21638mg/L; Aluminium content: 4075mg/L; PH:3.28.
Solid slag: water ratio: 80%; Al 2o 3content: 7.2%.
Getting 100g solid slag adds in the PSRY molecular sieve factory effluent of 1000mL, stirring reaction 60min under normal temperature, and it is 4.0 that reaction terminates rear pH; Subsequently to the sodium hydroxide solution adding 35m% in waste water, adjust ph, to 7.2, continues stirring reaction 60min; Backward waste water in add 1mg/L PAM carry out helping solidifying reaction 1min; Finally 120min is left standstill to water sample and carry out solid-liquid separation.Get supernatant liquor and measure F -content is 18mg/L; PO 4 3--P content is 0.5mg/L.
Embodiment 2
PSRY molecular sieve factory effluent water sample: F -content: 2257mg/L; PO 4 3--P content: 297mg/L; SO 4 2-content: 22713mg/L; Aluminium content: 4371mg/L; PH:3.24.
Solid slag: water ratio: 85%; Al 2o 3content: 5.2%.
Getting 200g solid slag adds in the PSRY molecular sieve factory effluent of 1000mL, supplements a small amount of hydrochloric acid, stirring reaction 80min simultaneously, and it is 3.8 that reaction terminates rear pH; Subsequently to the sodium hydroxide solution adding 35m% in waste water, adjust ph, to 7.8, continues stirring reaction 90min; Backward waste water in add 1mg/L PAM carry out helping solidifying reaction 1min; Then 120min is left standstill to water sample and carry out solid-liquid separation; The PAM getting the polymerize aluminum chloride and 1mg/L that supernatant liquor adds 40mg/L carries out helping solidifying reaction 1min again; Solid-liquid separation is carried out after finally 120min being left standstill to water sample.Getting supernatant liquor mensuration F-content is 4mg/L; PO 4 3--P content is 0.1mg/L.
Embodiment 3
PSRY molecular sieve factory effluent water sample: F -content: 2223mg/L; PO 4 3--P content: 331mg/L; SO 4 2-content: 21830mg/L; Aluminium content: 4441mg/L; PH:2.96.
Solid slag: water ratio: 75%; Al 2o 3content: 7.8%.
Getting 80g solid slag adds in the PSRY molecular sieve factory effluent of 1000mL, stirring reaction 90min, and it is 3.7 that reaction terminates rear pH; Subsequently to the sodium hydroxide solution adding 35m% in waste water, adjust ph, to 7.0, continues stirring reaction 90min; Backward waste water in add 1mg/L PAM carry out helping solidifying reaction 1min; Finally 120min is left standstill to water sample and carry out solid-liquid separation.Getting supernatant liquor mensuration F-content is 13mg/L; PO 4 3--P content is 0.3mg/L.

Claims (9)

1. PSRY molecular sieve factory effluent except a fluorine phosphorus removing method, comprising:
(1) PSRY molecular sieve factory effluent is mixed with the solid slag produced in other molecular sieve production wastewater treatment processes, make aluminium in described solid slag with Al 3+form be dissolved in described waste water, in dissolution process, the pH value of mixed system is less than 4.5;
(2) more than the pH value to 6 of mixed system that regulating step (1) obtains, Al is made 3+with F -and PO 4 3-reaction, by F -and PO 4 3-abundant precipitation;
(3) coagulant aids is added in the mixed system obtained to step (2), to through helping the mixed system of solidifying process to carry out solid-liquid separation;
Wherein, in step (1), solid slag consumption and dissolution conditions make the Al in step (2) 3+amount is enough to F -and PO 4 3-abundant precipitation.
2. in accordance with the method for claim 1, it is characterized in that, the consumption of step (1) described solid slag makes the total amount of contained aluminium in mixed system and precipitation F -and PO 4 3-the ratio of the theoretical amount of required aluminium is 4 ~ 10:1.
3. in accordance with the method for claim 1, it is characterized in that, the dissolution time of step (1) is 30 ~ 120min.
4. in accordance with the method for claim 1, it is characterized in that, in step (2), regulate the pH value of mixed system between 6 to 9.
5. in accordance with the method for claim 1, it is characterized in that, the reaction times of step (2) is 30 ~ 120min.
6. in accordance with the method for claim 1, it is characterized in that, in step (3), use polyacrylamide as coagulant aids, dosage is 0.5 ~ 2mg/L.
7. in accordance with the method for claim 1, it is characterized in that, in step (3), the solid waste concentrating unit that the precipitating sludge that solid-liquid separation produces is transported to molecular sieve manufacturing enterprise carries out sludge condensation process.
8. in accordance with the method for claim 1, it is characterized in that, if desired, add under sulfuric acid, hydrochloric acid or nitric acid makes the pH value of mixed system in step (1) described dissolution process remain on the state being less than 4.5.
9. in accordance with the method for claim 1, it is characterized in that, in step (2), adopt sodium hydroxide or potassium hydroxide to regulate the pH value of mixed system.
CN201310474332.9A 2013-10-12 2013-10-12 A kind of PSRY molecular sieve produces the fluorine removal phosphorus removing method of waste water Active CN104556460B (en)

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Publication number Priority date Publication date Assignee Title
CN107381526A (en) * 2017-07-11 2017-11-24 高嵘 Spent acid processing method after aluminium section bar and aluminium alloy cleaning
CN111530410A (en) * 2020-04-28 2020-08-14 北京工业大学 Method for preparing phosphorus removal adsorbent based on natural zeolite synthesized molecular sieve waste
CN112694142A (en) * 2019-10-22 2021-04-23 中国石油化工股份有限公司 Modifier for treating wastewater and application thereof

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CN103253788A (en) * 2012-12-28 2013-08-21 中国科学院生态环境研究中心 Method for removing fluorides in water through aluminum base composite metal oxide-based fluorine removing absorption material complexation-absorption

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CN102249457A (en) * 2011-05-26 2011-11-23 瓮福（集团）有限责任公司 Method for retreating wastewater reclaimed water containing phosphorus and fluorine
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Publication number Priority date Publication date Assignee Title
CN107381526A (en) * 2017-07-11 2017-11-24 高嵘 Spent acid processing method after aluminium section bar and aluminium alloy cleaning
CN112694142A (en) * 2019-10-22 2021-04-23 中国石油化工股份有限公司 Modifier for treating wastewater and application thereof
CN112694142B (en) * 2019-10-22 2022-12-09 中国石油化工股份有限公司 Modifier for treating wastewater and application thereof
CN111530410A (en) * 2020-04-28 2020-08-14 北京工业大学 Method for preparing phosphorus removal adsorbent based on natural zeolite synthesized molecular sieve waste

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