CN116764634A - Ionizing radiation catalyst, polyacrylamide solution and viscosity reduction method for polymer-containing sewage in oil field - Google Patents
Ionizing radiation catalyst, polyacrylamide solution and viscosity reduction method for polymer-containing sewage in oil field Download PDFInfo
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- 229920002401 polyacrylamide Polymers 0.000 title claims abstract description 60
- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 229920000642 polymer Polymers 0.000 title claims abstract description 45
- 239000010865 sewage Substances 0.000 title claims abstract description 45
- 230000005865 ionizing radiation Effects 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 36
- 230000009467 reduction Effects 0.000 title claims abstract description 22
- 238000010894 electron beam technology Methods 0.000 claims abstract description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 35
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 36
- 238000010521 absorption reaction Methods 0.000 claims description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 238000006460 hydrolysis reaction Methods 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 4
- 230000005855 radiation Effects 0.000 abstract description 21
- 229910052799 carbon Inorganic materials 0.000 abstract description 10
- 238000005516 engineering process Methods 0.000 abstract description 9
- 230000033558 biomineral tissue development Effects 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 239000003921 oil Substances 0.000 description 21
- 230000000694 effects Effects 0.000 description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000002957 persistent organic pollutant Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 231100000987 absorbed dose Toxicity 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000013043 chemical agent Substances 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 102000003992 Peroxidases Human genes 0.000 description 1
- 241000612118 Samolus valerandi Species 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
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- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000005025 nuclear technology Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 108040007629 peroxidase activity proteins Proteins 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/305—Treatment of water, waste water, or sewage by irradiation with electrons
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/09—Viscosity
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Materials Engineering (AREA)
- Physical Water Treatments (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses an ionization radiation catalyst, a polyacrylamide solution and a viscosity reduction method for polymer-containing sewage in an oil field, wherein the ionization radiation catalyst comprises nano Fe 3 O 4 The nanometer Fe 3 O 4 Loading on active carbon; the polyacrylamide solution and the viscosity reduction method for the polymer-containing sewage in the oil field are characterized by comprising the following steps: carrying out irradiation treatment on polyacrylamide solution or polymer-containing sewage of an oil field by using electron beams; the ionizing radiation catalyst is added into the polyacrylamide solution or the oilfield polymer-containing sewage; solving the problems of adoptingThe electron beam irradiation technology is used for viscosity reduction treatment of the polymer-containing sewage in the oil field, and the removal rate, the removal rate and the mineralization rate of the polyacrylamide by the ionization irradiation are obviously affected due to the complex components.
Description
Technical Field
The invention relates to the field of oilfield produced water treatment, in particular to a method for degrading polyacrylamide in oilfield polymer-containing sewage by utilizing an electron beam irradiation technology so as to reduce the viscosity of the oilfield polymer-containing sewage.
Background
In tertiary oil recovery technology, polymer oil displacement is most widely applied, and a large amount of polymer-containing sewage is generated. The polymer flooding is to add high molecular polymers such as polyacrylamide and the like into water to increase the viscosity and viscoelasticity of a polymer-matching system, improve the fluidity ratio, increase the swept area of the oil-flooding system and further increase the crude oil extraction rate.
The oilfield produced water is usually subjected to coagulation sedimentation and filtration to remove the concentration of crude oil and suspended matters, and is subjected to sterilization treatment and reused as stratum oil extraction reinjection water. The recovery of the produced water not only can save fresh water resources and reduce environmental pollution, but also has high temperature and good compatibility with stratum, thereby being beneficial to oil displacement. The polymer-containing sewage in the oil field contains high-concentration polyacrylamide, has high viscosity, high emulsification degree and difficult oil-water separation, and remarkably reduces the treatment effect of the sedimentation filtration process, so that the effluent is difficult to meet the reinjection water quality standard.
At present, more polymer viscosity reduction technologies are studied, such as Fenton oxidation, ultraviolet rays, ultrasonic waves, demulsification and viscosity reduction by adding chemical agents and other chemical methods and biological methods. The produced water of the oil field has high oil content, complex components and extremely strong biological resistance, and is difficult to be biodegraded. Most of the existing chemical methods need to be added with chemical agents, so that the cost is high, the ion concentration and the salinity of the oilfield produced water are further increased, and the quality of reinjection water is affected. The viscosity reduction effect of ultrasonic treatment is not ideal, liu Xinliang, etc. (Liu Xinliang, iris, yin Hailiang, zhang, yang Jiangang, research on ultrasonic degradation of polymer-containing oilfield sewage, workers)Industrial water treatment 34 (3) (2014) -74) the polymer-containing sewage of the victory oil field (viscosity of 2.49 mPa.s) was treated by ultrasonic waves. At a temperature of 20 DEG C o And C, the microwave power is 300W, the ultrasonic frequency is 45 kHz, and the viscosity of sewage is reduced to 1.47 mPa.s under the condition of ultrasonic treatment for 60 min and is far higher than the viscosity of pure water (1.01 mPa.s) at the same temperature. Wei Chaodeng (Wei Chao, wei Li, zhao Yunfa, li Chunying, wei Dong, liu Pu, ultraviolet technology is applied to the research of rapid viscosity reduction of oilfield polymer-containing produced water, environmental science and management 42 (7) (2017) -73) research on viscosity reduction effect of ultraviolet on oilfield polymer-containing sewage, and viscosity of sewage after 30 min treatment is reduced from 2.902 mPa.S to 1.096 mPa.S. However, the study did not mention the experimental temperature, and it was not known whether the viscosity was lowered to be consistent with pure water at the same temperature.
Ionizing radiation refers to radiation that carries enough electrons in atoms or molecules of a substance to become free, thereby ionizing those atoms or molecules, and belongs to the field of nuclear technology applications, mainly including gamma rays and electron beams. The application of irradiation technology in environmental protection is listed by the international agency for atomic energy (IAEA) as one of the main research directions for atomic energy applications in the 21 st century.
The electron beam irradiation technique is to treat pollutants by electron beams generated by an electron accelerator. Electron beam irradiation is a unique advanced oxidation-reduction technology, and the action principle comprises the direct irradiation of high-energy electron beams and the excitation of water molecules by the electron beams to generate OH and e aq − Oxidation-reduction of active particles such as H. The electron beam irradiation is carried out by direct irradiation of high-energy electron beams, and by OH oxidation and e aq − And degrading polyacrylamide in the polymer-containing sewage of the oil field under the combined action of H and H, so that the viscosity of the sewage of the oil field is reduced, and the subsequent flocculation degreasing process is ensured to be smoothly carried out.
The electron beam irradiation has higher decomposition efficiency on organic pollutants, but the mineralized organic pollutants usually need larger dosage, which affects the application economy. Moreover, the oilfield sewage has complex components, higher salt content, and a large amount of petroleum substances and CO existing in the sewage 3 2- 、NO 3 - The plasma anions compete with the polyacrylamide and degradation products thereof for free radicals generated by irradiation, and the removal rate, the removal rate and the mineralization rate of the ionizing radiation on the polyacrylamide are obviously affected.
Disclosure of Invention
In view of this, the present invention provides an ionizing radiation catalyst and a method for preparing the same.
In addition, the invention also provides a polyacrylamide solution and a viscosity reduction method for the polymer-containing sewage in the oil field, which solve the problems that the removal rate, the removal rate and the mineralization rate of the polyacrylamide are obviously affected by the ionizing radiation due to the complex components of the polymer-containing sewage in the oil field by adopting an electron beam irradiation technology to reduce the viscosity of the polymer-containing sewage in the oil field.
In a first aspect, the ionizing radiation catalyst is characterized by comprising:
nano Fe 3 O 4 ；
The nanometer Fe 3 O 4 Loaded on the activated carbon.
In a second aspect, the preparation method of the ionizing radiation catalyst is characterized by comprising the following steps:
at nanometer Fe 3 O 4 Activated carbon is added in the preparation process of (2).
Further, the nano Fe 3 O 4 The preparation method of (2) comprises the following steps:
by FeSO 4 ·7H 2 O and Fe 2 (SO 4 ) 3 Carrying out hydrolysis reaction;
argon is introduced during the hydrolysis reaction to maintain an anaerobic state.
Further, the addition amount of the activated carbon is as follows: the Fe is 3 O 4 The mass ratio of the activated carbon to the activated carbon is 2-1: 1.
further, concentrated sulfuric acid is added during the hydrolysis reaction to prevent oxidation of ferrous iron.
In a third aspect, the method for reducing viscosity of a polyacrylamide solution is characterized by comprising the following steps:
carrying out irradiation treatment on the polyacrylamide solution by using electron beams;
the ionizing radiation catalyst according to the first aspect is added to the polyacrylamide solution.
In a third aspect, the method for reducing viscosity of the oilfield polymer-containing sewage is characterized by comprising the following steps:
carrying out irradiation treatment on the polymer-containing sewage of the oil field by utilizing electron beams;
the ionizing radiation catalyst of the first aspect is added into the oilfield polymer-containing sewage.
Further, the addition amount of the ionizing radiation catalyst is 0.5-1.0 g/L.
Further, the irradiation absorption dose of the irradiation treatment is less than 10kGy.
Further, the ionizing radiation catalyst was recovered by magnet separation.
The invention has the following beneficial effects:
the ionizing radiation catalyst is a metal catalytic oxidant, and enhances electron transfer through multivalent metal, so that the generation of active free radicals such as OH and the like is promoted, and the decomposition mineralization efficiency of organic pollutants is improved. In addition, organic pollutants in the water body are adsorbed on the metal catalyst and then oxidized and degraded, so that the influence of anions, oils and other substances in the polymer-containing sewage can be reduced.
While magnetic nano material Fe 3 O 4 The catalyst has larger specific surface area and catalytic reaction activity, and can be recycled by a magnetic separation method; meanwhile, the iron element is rich in reserves, nontoxic and harmless, and environment-friendly, and is an ionizing radiation catalyst with great application prospect. With common Fe 3 O 4 In comparison, nano Fe 3 O 4 Exhibit specific properties such as excellent surface activity, higher magnetic properties, higher electrical conductivity, and small size and quantum tunneling effects. Recent studies have found that nano Fe 3 O 4 Has catalytic properties similar to those of peroxidase, and the catalytic activity increases with the decrease of the particle size. Nano Fe 3 O 4 Can promote gamma rays/electron beams to excite water molecules to generate OH and H generated in the process of water molecule irradiation 2 O 2 Fenton-like reaction and Fe 2+ /Fe 3+ Electron pair transferVarious ways promote the generation of hydroxyl radicals, thereby enhancing the decomposition and mineralization of polyacrylamide.
However, the nano iron oxide has high surface energy and is easy to agglomerate to affect the catalytic efficiency, and the nano iron oxide is loaded on the porous active carbon material with large specific surface area, so that the agglomeration of the nano iron oxide can be prevented, the catalytic activity can be improved, and meanwhile, the stability and the recycling property of the catalyst can be enhanced. So that the activated carbon loads nano Fe 3 O 4 As an ionizing radiation catalyst, the catalyst has the characteristics of high catalytic activity, stable performance, easy separation and recovery and the like; meanwhile, the iron element has rich reserves, is nontoxic and harmless, is environment-friendly, and has great application potential.
According to the viscosity reduction method for the polymer-containing sewage in the oil field, the high-energy electron beam is used for treating the polymer-containing sewage in the oil field by utilizing the ionization radiation catalyst, so that the polyacrylamide can be efficiently degraded and mineralized. The method is efficient and wide in application range, electron beam irradiation can be performed at normal temperature, and the ionizing radiation catalyst can be reused. The method can be applied to pretreatment of oilfield produced water and has wide application prospect in the petrochemical field.
Detailed Description
The present invention is described below based on examples, but it should be noted that the present invention is not limited to these examples. In the following detailed description of the present invention, certain specific details are set forth in detail. However, for the part not described in detail, the present invention is also fully understood by those skilled in the art.
Meanwhile, unless the context clearly requires otherwise, throughout the description and the claims, the words "comprise", "comprising", and the like are to be construed in an inclusive sense as opposed to an exclusive or exhaustive sense; that is, it is the meaning of "including but not limited to".
Example 1
1. Preparation of ionizing radiation catalyst
Adopts a Massart hydrolysis method in a coprecipitation method to prepare nano Fe 3 O 4 ，FeSO 4 ·7H 2 O and Fe 2 (SO 4 ) 3 Argon is introduced into the reaction solution for protectionAnd (5) keeping the anaerobic state, and adding concentrated sulfuric acid to prevent ferrous iron from being oxidized. At nanometer Fe 3 O 4 Adding a certain proportion of active carbon (Fe) 3 O 4 And the active carbon with the mass ratio of 2:1) are reacted together to prepare the active carbon loaded nano Fe 3 O 4 And (3) the composite material to obtain the ionizing radiation catalyst.
2. Electron beam irradiation viscosity reduction experiment of polyacrylamide solution
Dissolving polyacrylamide with molecular weight of 1200-1600 ten thousand in deionized water to prepare polyacrylamide solution, wherein the initial concentration of the polyacrylamide is 500 mg/L. Dividing the polyacrylamide solution into two parts, directly placing one part into a sample bag, and then conveying the sample bag to an irradiation chamber of an electron accelerator by using a conveyor belt for irradiation; the other part was added with 0.5g/L of the ionizing radiation catalyst of the first embodiment, and after mixing uniformly, the mixture was placed in a sample bag, and then was transported to an irradiation chamber of an electron accelerator by a conveyor belt for irradiation. Different radiation absorption doses of 0.25kGy, 0.5kGy,1.0kGy,5.0kGy and 10kGy are obtained by controlling the beam intensity and the transmission speed. After the irradiation is finished, the added ionizing radiation catalyst is separated and recovered by a magnet.
3. Performance detection of polyacrylamide solution subjected to electron beam irradiation viscosity reduction
The supernatant in the sample bag after electron beam irradiation was filtered through a 0.45 μm filter membrane, and then the polyacrylamide concentration and COD viscosity were measured (COD concentration corresponds to mineralization rate, which may be expressed by COD removal efficiency or TOC removal efficiency).
The COD viscosity of the initial polyacrylamide solution was 531mg/L and the viscosity was 7.0 mPa.s. The experimental temperature is 26+/-0.5 o C。
The polyacrylamide concentration was analyzed by a turbidity method, the COD concentration was analyzed by a potassium dichromate oxidation method, and the viscosity (mPas) was analyzed by a viscometer (NDJ-79 rotary viscometer, bunge's Instrument technology (Shanghai)).
The viscosity can be obviously reduced to 1.70 mPa.s when the irradiation absorption dose is 0.25kGy without adding the independent irradiation of the ionizing irradiation catalyst; the irradiation absorbed doses were 0.5kGy,1.0kGy,5.0kGy and 10kGy, respectively, and the viscosity of the polyacrylamide solution continued to decrease to 1.6 mPas, 1.25 mPas, 1.2mPas and 1.2 mPas. The viscosity remained substantially unchanged after the irradiation absorbed dose was more than 5.0kGy, and the viscosity of pure water (1.0 mPas) was detected at slightly higher temperature.
When the ionizing radiation catalyst is added for radiation, the viscosity of the polyacrylamide solution is reduced to 1.5 mPas, 1.2mPas, 1.0 mPas and 1.0 mPas when the radiation absorption doses are 0.5kGy,1.0kGy,5.0kGy and 10kGy, and the solution viscosity can be reduced to be consistent with that of pure water when the radiation absorption doses are 5.0 kGy.
The concentration of the polyacrylamide can be respectively reduced to 451mg/L,411mg/L,354 mg/L and 323mg/L when the irradiation absorption doses are respectively 0.5kGy,1.0kGy,5.0kGy and 10kGy without separate irradiation of an ionizing irradiation catalyst, and the removal rate is 10%,18%,30% and 37%; COD concentration can be reduced to 497mg/L,498mg/L,487mg/L and 480mg/L, and removal rate is 7%,7%,9% and 10%.
When the irradiation is carried out by adding the ionizing radiation catalyst, the concentration of the polyacrylamide can be respectively reduced to 406 mg/L,387mg/L,300mg/L and 226mg/L when the irradiation absorption doses are 0.5kGy,1.0kGy,5.0kGy and 10kGy, and the removal rate is 19%,23%,40% and 55%; COD concentration can be reduced to 436mg/L,359mg/L,307mg/L and 235 mg/L, and removal rates are 18%,33%,43% and 56%.
The ionizing radiation catalyst is reused for 5 times, and still has high activity.
From the detection data, the viscosity reduction effect of the electron beam irradiation on the polyacrylamide solution is good. The removal rate of polyacrylamide and COD after adding the ionizing radiation catalyst is increased by 11-46% compared with the removal rate of polyacrylamide and COD after adopting electron beam irradiation alone.
Example 2
1. Preparation of ionizing radiation catalyst
Adopts a Massart hydrolysis method in a coprecipitation method to prepare nano Fe 3 O 4 ，FeSO 4 ·7H 2 O and Fe 2 (SO 4 ) 3 Argon is introduced into the reaction solution to keep an anaerobic state, and concentrated sulfuric acid is added to prevent ferrous iron from being oxidized. At nanometer Fe 3 O 4 Adding active carbon with a certain proportion in the preparation processReaction (Fe) 3 O 4 The mass ratio of the active carbon to the active carbon is 1:1) to prepare the active carbon loaded nano Fe 3 O 4 Composite materials, i.e. ionizing radiation catalysts.
2. Electron beam irradiation viscosity reduction experiment of polyacrylamide solution
The polyacrylamide with the molecular weight of 2500 ten thousand is dissolved in tap water to prepare a polyacrylamide solution, and the initial concentration of the polyacrylamide is 250 mg/L. Dividing the polyacrylamide solution into two parts, directly placing one part into a sample bag, and then conveying the sample bag to an irradiation chamber of an electron accelerator by using a conveyor belt for irradiation; the other part of the ionization radiation catalyst of the second example of 1.0g/L is added, and the mixture is placed into a sample bag after being uniformly mixed, and then is sent to an irradiation chamber of an electron accelerator for irradiation by a conveyor belt. Different radiation absorption doses of 0.25kGy, 0.5kGy,1.0kGy and 2.0kGy are obtained by controlling the beam intensity and the transmission speed. And after the irradiation is finished, separating and recycling the ionizing radiation catalyst through a magnet.
3. Performance detection of polyacrylamide solution subjected to electron beam irradiation viscosity reduction
The supernatant in the sample bag after electron beam irradiation was filtered through a 0.45 μm filter membrane, and then the polyacrylamide concentration and COD viscosity were measured.
The COD of the initial polyacrylamide solution was 275mg/L and the viscosity was 5.3 mPa.s. The experimental temperature is 26+/-0.5 o C。
The viscosity can be obviously reduced to 1.2mPas when the irradiation absorption dose is 0.25kGy without adding an ionization irradiation catalyst and performing independent irradiation; the viscosities of the polyacrylamide solutions continued to decrease to 1.15 mPas, 1.1 mPas and 1.1 mPas at irradiation absorption doses of 0.5kGy,1.0kGy and 2.0kGy, and the pure water viscosities (1.0 mPas) were detected at approximately the same temperature.
When the ionizing radiation catalyst is added, and the radiation absorption doses are respectively 0.25kGy, 0.5kGy,1.0kGy and 10kGy, the viscosity of the solution is respectively reduced to 1.15 mPas, 1.1 mPas and 1.0 mPas, and the viscosity of the solution can be reduced to be consistent with that of pure water.
The method is characterized in that an ionization radiation catalyst is not added, but electron beam radiation is adopted singly, when the radiation absorption doses are respectively 1.0kGy and 2.0kGy, the concentration of polyacrylamide can be respectively reduced to 209mg/L and 175mg/L, and the removal rate is respectively 17% and 30%; COD concentration can be reduced to 252mg/L and 201mg/L respectively, and removal rates are 9% and 17% respectively.
Adding an ionization radiation catalyst and simultaneously carrying out electron beam radiation, wherein when the radiation absorption doses are respectively 1.0kGy and 2.0kGy, the concentration of polyacrylamide can be respectively reduced to 169mg/L and 123mg/L, and the removal rates are respectively 33% and 51%; COD concentration can be reduced to 179 mg/L and 135mg/L respectively, the removal rate is 35% and 51% respectively, and the removal rate of polyacrylamide is increased by 16% -21% compared with the single electron beam irradiation. The COD removal rate is increased by 26-34% compared with the single electron beam irradiation.
Example 3
1. Preparation of ionizing radiation catalyst
Adopts a Massart hydrolysis method in a coprecipitation method to prepare nano Fe 3 O 4 ，FeSO 4 ·7H 2 O and Fe 2 (SO 4 ) 3 Argon is introduced into the reaction solution to keep an anaerobic state, and concentrated sulfuric acid is added to prevent ferrous iron from being oxidized. At nanometer Fe 3 O 4 Adding a certain proportion of active carbon to react together (Fe 3 O 4 The mass ratio of the catalyst to the activated carbon is 1: 1) To prepare the activated carbon loaded nano Fe 3 O 4 Composite materials, i.e. ionizing radiation catalysts.
2. Electron beam irradiation viscosity reduction experiment for polymer-containing sewage in oil field
The polymer-containing sewage of a certain oil extraction factory in the north of China is divided into two parts. Directly placing a part of the sample into a sample bag, spreading the sample as thin as possible, and then conveying the sample to an irradiation chamber of an electron accelerator by using a conveyor belt for irradiation; another portion of the ionizing radiation catalyst of example III was added at 1.0. 1.0g/L 4 Mixing, placing into sample bag, and conveying to irradiation chamber of electron accelerator for irradiation. Different radiation absorption doses of 1.0kGy,5.0kGy and 10kGy are obtained by controlling the beam intensity and the transmission speed. After the irradiation is finished, the added ionizing radiation catalyst is separated and recovered by a magnet.
3. Performance detection after viscosity reduction experiment of polymer-containing sewage in oil field
After the electron beam is irradiatedThe supernatant in the sample bag was filtered through a 0.45 μm filter membrane, and then the polyacrylamide viscosity, COD concentration and polyacrylamide concentration were measured. The experimental temperature is 25+/-0.5 o C。
The viscosity of the oilfield polymer-containing sewage is 5.33 mPas, and the COD concentration and the polyacrylamide concentration are 350mg/L and 575mg/L respectively.
When the electron beam irradiation is adopted singly and the irradiation absorption dose is 1kGy, the viscosity, COD concentration and polyacrylamide concentration of the polymer-containing sewage basically do not change. When the irradiation absorption dose is 5kGy, the viscosity of the polymer-containing sewage is reduced to 3.2 mPas, and the COD concentration and the polyacrylamide concentration are respectively reduced to 325 mg/L and 475 mg/L. When the irradiation absorption dose is 10kGy, the viscosity of the polymer-containing sewage is further reduced to 1.7 mPas, the COD concentration and the polyacrylamide concentration are respectively reduced to 300mg/L and 375mg/L, and the removal rates are respectively 15% and 35%.
And adding an ionization radiation catalyst and simultaneously carrying out electron beam radiation, wherein when the radiation absorption dose is 1kGy, the viscosity of the polymer-containing sewage is reduced to 1.7 mPa.s, and the COD concentration and the polyacrylamide concentration are respectively reduced to 330mg/L and 453mg/L. When the irradiation absorption dose is 5kGy, the viscosity of the polymer-containing sewage is reduced to 1.2mPas, and the COD concentration and the polyacrylamide concentration are respectively reduced to 280 mg/L and 295mg/L. When the irradiation absorption dose is 10kGy, the viscosity of the polymer-containing sewage is further reduced to 1.05 mPas, the COD concentration and the polyacrylamide concentration are respectively reduced to 225mg/L and 235 mg/L, and the removal rates are respectively 36% and 60%, and are improved by 11% and 25% compared with the single electron beam irradiation.
The above examples are merely illustrative embodiments of the present invention, which are described in more detail and are not to be construed as limiting the scope of the invention. It should be noted that modifications, equivalent substitutions, improvements, etc. can be made by those skilled in the art without departing from the spirit of the present invention, and these are all within the scope of the present invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. An ionizing radiation catalyst, characterized by comprising:
nano Fe 3 O 4 ；
The nanometer Fe 3 O 4 Loaded on the activated carbon.
2. A method for preparing an ionizing radiation catalyst, comprising:
at nanometer Fe 3 O 4 Activated carbon is added in the preparation process of (2).
3. The method for preparing ionizing radiation catalyst according to claim 2, wherein the nano Fe 3 O 4 The preparation method of (2) comprises the following steps:
by FeSO 4 ·7H 2 O and Fe 2 (SO 4 ) 3 Carrying out hydrolysis reaction;
argon is introduced during the hydrolysis reaction to maintain an anaerobic state.
4. A method for preparing an ionizing radiation catalyst according to claim 3, wherein:
concentrated sulfuric acid is added during the hydrolysis reaction to prevent oxidation of ferrous iron.
5. The method for preparing an ionizing radiation catalyst according to claim 4, wherein the amount of the activated carbon added is:
the Fe is 3 O 4 The mass ratio of the activated carbon to the activated carbon is 2-1: 1.
6. a method for reducing viscosity of a polyacrylamide solution, comprising:
carrying out irradiation treatment on the polyacrylamide solution by using electron beams;
the ionizing radiation catalyst of claim 1 is added to the polyacrylamide solution.
7. A method for reducing viscosity of polymer-containing sewage in an oil field, which is characterized by comprising the following steps:
carrying out irradiation treatment on the polymer-containing sewage of the oil field by utilizing electron beams;
the ionizing radiation catalyst of claim 1 is added into the polymer-containing sewage of the oil field.
8. The oilfield polymer-containing sewage viscosity reduction method according to claim 7, wherein:
the addition amount of the ionizing radiation catalyst is 0.5-1.0 g/L.
9. The oilfield polymer-containing sewage viscosity reduction method according to claim 8, wherein:
the irradiation absorption dose of the irradiation treatment is less than or equal to 10kGy.
10. The oilfield polymer-containing sewage viscosity reduction method according to any one of claims 7 to 9, wherein:
the ionizing radiation catalyst was recovered by magnet separation.
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