CN102976465A - Method for degrading polyacrylamide in sewage - Google Patents
Method for degrading polyacrylamide in sewage Download PDFInfo
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- CN102976465A CN102976465A CN2012105640560A CN201210564056A CN102976465A CN 102976465 A CN102976465 A CN 102976465A CN 2012105640560 A CN2012105640560 A CN 2012105640560A CN 201210564056 A CN201210564056 A CN 201210564056A CN 102976465 A CN102976465 A CN 102976465A
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Abstract
The invention relates to a method for degrading polyacrylamide in sewage. The method is used for effectively degrading polyacrylamide in the sewage through adding a polyacrylamide sewage solution into catalyst metal ion modified clay and catalyzing a system under the ultrasonic action. The method has the advantages that operation is simple, degradation is rapid, process is simple, cost is low and the like, and has wide application prospect in the aspect of treatment of sewage containing polyacrylamide.
Description
Technical field
The present invention relates to the method for polyacrylamide in a kind of degradation of sewage, specifically refer to the method for degradation of polypropylene acid amides in oilfield sewage, the chemical engineering industry sewage.
Background technology
At present, the most of oil field of China enters tertiary phase in succession, and using polyacrylamide to carry out tertiary oil recovery is the most typical chemical flooding oil production technology, is used widely.Along with the application of oilfield polymer flooding technology, the output that contains polyacrylamide sewage water is increasing year by year.Polyacrylamide has also increased considerably viscosity and the emulsifying property of mixed solution when improving oil recovery factor for field produces, the oily water separation difficulty is strengthened, and causes recovered water oleaginousness severe overweight.Contain polyacrylamide sewage water and have the characteristics such as viscosity height, the oily water separation difficulty is large, biodegradability is poor, cause oil, moisture to strengthen from the difficulty with oily water treatment, also more and more obvious to the negative impact of environment.In addition, slow degradation can occur in the polyacrylamide that remains in the environment, discharges poisonous acrylamide monomer, and this will bring immeasurable long-term hazards to ecotope.The traditional sedimentation in oil field-filtration re-injection treatment process can not satisfy and contained the requirement that polyacrylamide sewage water is processed.Therefore, the processing that contains polyacrylamide sewage water has become a problem demanding prompt solution.
Mainly comprise physical method, chemical process and biological method for the polymer-bearing waste-water treatment technology.Physical method can improve oily water separation efficient to a certain extent, reduces oil-contg and the suspension content of water outlet, but the high molecular polymer in the sewage is not had removal effect substantially, and the water after the processing does not reach the index of oil field reinjection water at all.Biological rule process more complicated, restive and have stronger selectivity, the breeding breakneck acceleration of the function yeast of using in the biological process is slower, therefore, biological process degradation of polypropylene acid amides is still immature at present, and existing technique can't satisfy the requirement of degradation of polypropylene acid amides.Its principle of oxidation style is that the chain reaction that utilizes strong oxidizer, luminous energy or other energy catalysis to produce free radical initiation free radical makes long polyacrylamide molecular rupture become small organic molecule, finally is degraded to inorganics.The more oxygenant of research has Fenton reagent, potassium ferrate etc. at present, and these method for oxidation are once invested and the working cost height, and easily causes secondary pollution, is not suitable for large-scale application.
Summary of the invention
The object of the invention provides the method for polyacrylamide in a kind of degradation of sewage, the method will add polyacrylamide sewage water solution in the metal ion-modified clay of Kaolinite Preparation of Catalyst, by the ultrasonication catalyst system, thereby the effective polyacrylamide in the degradation of sewage, that the method has is simple to operate, degraded fast, the advantage such as technique is simple, with low cost.Have broad application prospects aspect the polyacrylamide sewage water processing containing.
The method of polyacrylamide in a kind of degradation of sewage of the present invention follows these steps to carry out:
A, the metal ion-modified clay material of Kaolinite Preparation of Catalyst: with montmorillonite, kaolinite or attapulgite clay dispersion of materials in the 200-1000mL deionized water, compound concentration is the 20-100g/L slurry, at room temperature stirred 12 hours with mechanical stirrer, in the whizzer that 4000 turn after centrifugal 40 minutes, get upper strata suspension, the adding metallic cation is Na
+, Zn
2+, Cu
2+, Ni
2+, Co
3+, Al
3+Or Fe
3+, at room temperature stir and carried out ion-exchange in 8 hours, the clay material after the exchange is carried out centrifugation, washing according to a conventional method, obtain the clay material of catalyst metal ion modification;
The ultrasonic degradation of b, Polyacrylamide in Sewage Water: will add polyacrylamide sewage water solution in the step a catalyst metal ion modified clay, under the 10-100kHz ultrasonication, temperature 0-60 ℃, degraded 1-30 minute, carry out according to a conventional method centrifugation and go out the catalyst metal ion modified clay, catalyst metal ion modified clay after centrifugal is put into again the sewage of polyacrylamide and degraded, until complete the getting final product of Polyacrylamide in Sewage Water degraded.
The mass concentration of step b catalyst metal ion modified clay is 0.5-10g/L.
The mass concentration of the step b polyacrylamide pollutent aqueous solution is 1-1000mg/L.
The volume of the step b polyacrylamide pollutent aqueous solution is 50-1000mL.
Embodiment
For ease of understanding, the present invention is described further below in conjunction with specific examples, but protection scope of the present invention is not limited to this, also because of the succession of each embodiment the present invention do not caused any restriction.
Embodiment 1
The metal ion-modified clay material of Kaolinite Preparation of Catalyst:
Take by weighing the montmorillonitic clay dispersion of materials of 10g in the 200mL deionized water, compound concentration is the suspension of 50g/L, at room temperature stirred 12 hours with mechanical stirrer, in the whizzer that 4000 turn, after centrifugal 40 minutes, get upper strata suspension, fixed molten to 200mL with deionized water, add iron trichloride 0.972g, at room temperature stir and carried out ion-exchange in 8 hours, the montmorillonite clay material after the exchange is carried out centrifugation, washing, obtain the montmorillonite material of catalyzer iron ion modification;
The ultrasonic degradation of Polyacrylamide in Sewage Water:
It is in the 1mg/L polyacrylamide sewage water solution that the catalyzer iron ion modified clay 0.05g that obtains is added the 100mL mass concentration, and under the 10kHz ultrasonication, 0 ℃ of temperature was degraded 2 minutes, and the degradation efficiency of polyacrylamide can reach 82%.
Simultaneous test and result:
The polyacrylamide sewage water (100mL) of 1mg/L is directly used the 25kHz ultrasonication, and 20 minutes time, degradation efficiency only is 2%;
It is in the 1mg/L polyacrylamide sewage water solution that montmorillonitic clay 0.05g is added the 100mL mass concentration, uses the 25kHz ultrasonication, and 20 minutes time, degradation efficiency only is 5%;
It is in the 1mg/L polyacrylamide sewage water solution that the catalyzer iron ion modified clay 0.05g that obtains is added the 100mL mass concentration, processes with the 25kHz ultrasonic degradation, and degradation efficiency has reached 82% after 2 minutes time.
Embodiment 2
Take by weighing the kaolinite clay dispersion of materials of 20g in the 400mL deionized water, compound concentration is the suspension of 50g/L, at room temperature stirred 12 hours with mechanical stirrer, in the whizzer that 4000 turn, after centrifugal 40 minutes, get upper strata suspension, fixed molten to 400mL with deionized water, add SODIUMNITRATE 1.944g, at room temperature stir and carried out ion-exchange in 8 hours, the kaolinite clay material after the exchange is carried out centrifugation, washing, obtain the kaolinite clay material of sodium ion modification.
It is in the 100mg/L polyacrylamide sewage water solution that the catalyzer sodium ion modification kaolinite clay 0.2g that obtains is added the 300mL mass concentration, and under the 20kHz ultrasonication, 10 ℃ of temperature were degraded 5 minutes, and the degradation efficiency of polyacrylamide can reach 75%
Simultaneous test and result:
The polyacrylamide sewage water (300mL) of 100mg/L is directly used the 20kHz ultrasonication, and 30 minutes time, degradation efficiency only is 3%;
It is in the 100mg/L polyacrylamide sewage water solution that kaolinite clay 0.2g is added the 300mL mass concentration, uses the 20kHz ultrasonication, and 20 minutes time, degradation efficiency only is 5%;
It is in the 100mg/L polyacrylamide sewage water solution that the kaolinite clay 0.2g of sodium ion modification is added the 300mL mass concentration, processes with the 20kHz ultrasonic degradation, and degradation efficiency has reached 75% after 2 minutes time.
Embodiment 3
Take by weighing the attapulgite clay dispersion of materials of 15g in the 500mL deionized water, compound concentration is the suspension of 75g/L, at room temperature stirred 12 hours with mechanical stirrer, in the whizzer that 4000 turn, after centrifugal 40 minutes, get upper strata suspension, fixed molten to 200mL with deionized water, add Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 0.874g, at room temperature stir and carried out ion-exchange in 8 hours, the attapulgite clay material after the exchange is carried out centrifugation, washing, obtain the attapulgite clay material of catalyst cobalt ion modification;
It is in the 150mg/L polyacrylamide sewage water solution that the catalyst cobalt ion modification attapulgite clay 0.5g that obtains is added the 500mL mass concentration, and under the 40kHz ultrasonication, 20 ℃ of temperature were degraded 10 minutes, and the degradation efficiency of polyacrylamide can reach 80%
Simultaneous test and result:
The polyacrylamide sewage water (500mL) of 150mg/L is directly used the 40kHz ultrasonication, and 15 minutes time, degradation efficiency only is 3%;
It is in the 150mg/L polyacrylamide sewage water solution that attapulgite clay 0.5g is added the 500mL mass concentration, uses the 40kHz ultrasonication, and 15 minutes time, degradation efficiency only is 7%;
It is in the 150mg/L polyacrylamide sewage water solution that the attapulgite clay 0.5g of cobalt ion modification is added the 500mL mass concentration, processes with the 40kHz ultrasonic degradation, and degradation efficiency has reached 80% after 10 minutes time.
Embodiment 4
The metal ion-modified clay material of Kaolinite Preparation of Catalyst:
Take by weighing the montmorillonitic clay dispersion of materials of 10g in the 300mL deionized water, compound concentration is the suspension of 50g/L, at room temperature stirred 12 hours with mechanical stirrer, in the whizzer that 4000 turn, after centrifugal 40 minutes, get upper strata suspension, fixed molten to 200mL with deionized water, add nickelous nitrate 0.972g, at room temperature stir and carried out ion-exchange in 8 hours, the montmorillonite clay material after the exchange is carried out centrifugation, washing, obtain the montmorillonite material of catalyzer nickel ion modification;
The ultrasonic degradation of Polyacrylamide in Sewage Water:
It is in the 500mg/L polyacrylamide sewage water solution that the catalyzer nickel ion modified clay 0.8g that obtains is added the 800mL mass concentration, and under the 60kHz ultrasonication, 40 ℃ of temperature were degraded 15 minutes, and the degradation efficiency of polyacrylamide can reach 85%
Simultaneous test and result:
The polyacrylamide sewage water (800mL) of 500mg/L is directly used the 60kHz ultrasonication, and 20 minutes time, degradation efficiency only is 1%;
It is in the 500mg/L polyacrylamide sewage water solution that montmorillonitic clay 0.8g is added the 800mL mass concentration, uses the 60kHz ultrasonication, and 20 minutes time, degradation efficiency only is 5%;
It is in the 500mg/L polyacrylamide sewage water solution that the modified montmorillonite used clay 0.8g of nickel ion is added the 800mL mass concentration, processes with the 60kHz ultrasonic degradation, and degradation efficiency has reached 85% after 15 minutes time.
Embodiment 5
Take by weighing the kaolinite clay dispersion of materials of 20g in the 600mL deionized water, compound concentration is the suspension of 50g/L, at room temperature stirred 12 hours with mechanical stirrer, in the whizzer that 4000 turn, after centrifugal 40 minutes, get upper strata suspension, fixed molten to 400mL with deionized water, add cupric nitrate 0.883g, at room temperature stir and carried out ion-exchange in 8 hours, the kaolinite clay material after the exchange is carried out centrifugation, washing, obtain the kaolinite clay material of copper ion modified.
It is in the 1000mg/L polyacrylamide sewage water solution that the catalyzer copper ion modified kaolinite clay 1g that obtains is added the 600mL mass concentration, and under the 100kHz ultrasonication, temperature 60 C was degraded 10 minutes, and the degradation efficiency of polyacrylamide can reach 80%
Simultaneous test and result:
The polyacrylamide sewage water (600mL) of 1000mg/L is directly used the 100kHz ultrasonication, and 30 minutes time, degradation efficiency only is 2%;
It is in the 1000mg/L polyacrylamide sewage water solution that kaolinite clay 1g is added the 600mL mass concentration, uses the 100kHz ultrasonication, and 10 minutes time, degradation efficiency only is 6%;
It is in the 1000mg/L polyacrylamide sewage water solution that copper ion modified kaolinite clay 1g is added the 600mL mass concentration, processes with the 100kHz ultrasonic degradation, and degradation efficiency has reached 80% after 10 minutes time.
Embodiment 6
Take by weighing the attapulgite clay dispersion of materials of 15g in the 1000mL deionized water, compound concentration is the suspension of 75g/L, at room temperature stirred 12 hours with mechanical stirrer, in the whizzer that 4000 turn, after centrifugal 40 minutes, get upper strata suspension, fixed molten to 200mL with deionized water, add zinc acetate 0.769g, at room temperature stir and carried out ion-exchange in 8 hours, the attapulgite clay material after the exchange is carried out centrifugation, washing, obtain the attapulgite clay material of catalyzer zine ion modification;
It is in the 800mg/L polyacrylamide sewage water solution that the attapulgite clay 0.7g of the catalyzer zine ion modification that obtains is added the 700mL mass concentration, and under the 80kHz ultrasonication, temperature 50 C was degraded 7 minutes, and the degradation efficiency of polyacrylamide can reach 70%
Simultaneous test and result:
The polyacrylamide sewage water (700mL) of 800mg/L is directly used the 80kHz ultrasonication, and 10 minutes time, degradation efficiency only is 1%;
It is in the 800mg/L polyacrylamide sewage water solution that attapulgite clay 0.7g is added the 700mL mass concentration, uses the 80kHz ultrasonication, and 10 minutes time, degradation efficiency only is 4%;
It is in the 800mg/L polyacrylamide sewage water solution that the attapulgite clay 0.7g of zine ion modification is added the 700mL mass concentration, processes with the 80kHz ultrasonic degradation, and degradation efficiency has reached 70% after 7 minutes time.
Embodiment 7
Take by weighing the attapulgite clay dispersion of materials of 15g in the 700mL deionized water, compound concentration is the suspension of 75g/L, at room temperature stirred 12 hours with mechanical stirrer, in the whizzer that 4000 turn, after centrifugal 40 minutes, get upper strata suspension, fixed molten to 200mL with deionized water, add aluminum chloride 0.677g, at room temperature stir and carried out ion-exchange in 8 hours, the attapulgite clay material after the exchange is carried out centrifugation, washing, obtain the attapulgite clay material of catalyzer aluminum ion modification;
It is in the 400mg/L polyacrylamide sewage water solution that the catalyzer aluminum ion modified attapulgite clay 0.4g that obtains is added the 300mL mass concentration, and under the 70kHz ultrasonication, 30 ℃ of temperature were degraded 15 minutes, and the degradation efficiency of polyacrylamide can reach 60%
Simultaneous test and result:
The polyacrylamide sewage water (300mL) of 400mg/L is directly used the 70kHz ultrasonication, and 20 minutes time, degradation efficiency only is 2%;
It is in the 400mg/L polyacrylamide sewage water solution that attapulgite clay 0.4g is added the 300mL mass concentration, uses the 70kHz ultrasonication, and 20 minutes time, degradation efficiency only is 5%;
It is in the 400mg/L polyacrylamide sewage water solution that the attapulgite clay 0.4g of aluminum ion modification is added the 300mL mass concentration, processes with the 70kHz ultrasonic degradation, and degradation efficiency has reached 60% after 15 minutes time.
Claims (3)
1. the method for polyacrylamide in the degradation of sewage is characterized in that following these steps to carrying out:
A, the metal ion-modified clay material of Kaolinite Preparation of Catalyst: with montmorillonite, kaolinite or attapulgite clay dispersion of materials in the 200-1000mL deionized water, compound concentration is the 20-100g/L slurry, at room temperature stirred 12 hours with mechanical stirrer, in the whizzer that 4000 turn after centrifugal 40 minutes, get upper strata suspension, the adding metallic cation is Na
+, Zn
2+, Cu
2+, Ni
2+, Co
3+, Al
3+Or Fe
3+, at room temperature stir and carried out ion-exchange in 8 hours, the clay material after the exchange is carried out centrifugation, washing according to a conventional method, obtain the clay material of catalyst metal ion modification;
The ultrasonic degradation of polyacrylamide in b, the pollutent: will add polyacrylamide sewage water solution in the step a catalyst metal ion modified clay, under the 10-100kHz ultrasonication, temperature 0-60 ℃, degraded 1-10 minute, carry out according to a conventional method centrifugation and go out the catalyst metal ion modified clay, catalyst metal ion modified clay after centrifugal is put into again the sewage of polyacrylamide and degraded, until complete the getting final product of Polyacrylamide in Sewage Water degraded.
2. method according to claim 1 is characterized in that the mass concentration of step b catalyst metal ion modified clay is 0.5-10g/L.
3. method according to claim 1 is characterized in that the mass concentration of the step b polyacrylamide pollutent aqueous solution is 0.01-1000mg/L.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105668752A (en) * | 2016-04-19 | 2016-06-15 | 兰州交通大学 | Preparing method for sulfhydrylation polyacrylamide heavy metal flocculant |
| CN109504359A (en) * | 2019-01-17 | 2019-03-22 | 山东滨州昱诚化工科技有限公司 | A kind of oil extraction in oil field high polymer polyacrylamide degradation de-plugging agent and preparation method |
| CN111234861A (en) * | 2020-03-06 | 2020-06-05 | 宁夏医科大学 | Method for removing composite oil displacement agent in crude oil |
| CN113371911A (en) * | 2021-06-17 | 2021-09-10 | 浙江金龙再生资源科技股份有限公司 | Improve papermaking effluent treatment plant of paper pulp rate of recovery |
| CN113403055A (en) * | 2021-08-18 | 2021-09-17 | 北京石大瑞伽石油技术开发有限公司 | Water-soluble polymer degradation agent and preparation and application thereof |
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| MD3508F1 (en) * | 2007-02-05 | 2008-02-29 | Universitatea De Stat Din Moldova | Process for obtaining a catalyst for water purification from organic compounds |
| CN101439918A (en) * | 2008-11-28 | 2009-05-27 | 南京大学 | Method for processing wastewater from polyacrylamide production |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105668752A (en) * | 2016-04-19 | 2016-06-15 | 兰州交通大学 | Preparing method for sulfhydrylation polyacrylamide heavy metal flocculant |
| CN109504359A (en) * | 2019-01-17 | 2019-03-22 | 山东滨州昱诚化工科技有限公司 | A kind of oil extraction in oil field high polymer polyacrylamide degradation de-plugging agent and preparation method |
| CN109504359B (en) * | 2019-01-17 | 2022-06-28 | 山东滨州昱诚化工科技有限公司 | High-molecular polyacrylamide degradation blocking remover for oil extraction in oil field and preparation method thereof |
| CN111234861A (en) * | 2020-03-06 | 2020-06-05 | 宁夏医科大学 | Method for removing composite oil displacement agent in crude oil |
| CN113371911A (en) * | 2021-06-17 | 2021-09-10 | 浙江金龙再生资源科技股份有限公司 | Improve papermaking effluent treatment plant of paper pulp rate of recovery |
| CN113403055A (en) * | 2021-08-18 | 2021-09-17 | 北京石大瑞伽石油技术开发有限公司 | Water-soluble polymer degradation agent and preparation and application thereof |
| CN113403055B (en) * | 2021-08-18 | 2021-11-09 | 北京石大瑞伽石油技术开发有限公司 | Water-soluble polymer degradation agent and preparation and application thereof |
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