CN115582094B - Adsorption film and preparation method and application thereof - Google Patents
Adsorption film and preparation method and application thereof Download PDFInfo
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- CN115582094B CN115582094B CN202110758586.8A CN202110758586A CN115582094B CN 115582094 B CN115582094 B CN 115582094B CN 202110758586 A CN202110758586 A CN 202110758586A CN 115582094 B CN115582094 B CN 115582094B
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- 238000001179 sorption measurement Methods 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 152
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 84
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 43
- 239000010865 sewage Substances 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000011259 mixed solution Substances 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 26
- 239000002270 dispersing agent Substances 0.000 claims abstract description 19
- 238000012986 modification Methods 0.000 claims abstract description 18
- 230000004048 modification Effects 0.000 claims abstract description 18
- 238000005259 measurement Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 238000007789 sealing Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- -1 ammonia modified graphene Chemical class 0.000 claims description 29
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 15
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 13
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 230000010355 oscillation Effects 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 12
- 239000004698 Polyethylene Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 229920000573 polyethylene Polymers 0.000 claims description 10
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 10
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 28
- 230000003068 static effect Effects 0.000 abstract description 12
- 230000008021 deposition Effects 0.000 abstract description 4
- 238000002474 experimental method Methods 0.000 description 20
- 230000000694 effects Effects 0.000 description 9
- 238000004062 sedimentation Methods 0.000 description 9
- 238000009210 therapy by ultrasound Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000009096 changqing Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000033772 system development Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
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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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N5/00—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid
- G01N5/02—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid by absorbing or adsorbing components of a material and determining change of weight of the adsorbent, e.g. determining moisture content
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Abstract
The invention discloses an adsorption film, a preparation method and application thereof, wherein the adsorption film is prepared from a film solution, and raw materials of the film solution comprise graphene and/or modified graphene, collodion solution and a dispersing agent. The preparation method of the adsorption film comprises the following steps: adding graphene and/or modified graphene into the collodion solution, and then stirring; adding a dispersing agent, and continuing stirring until the solution is uniformly stirred to obtain a mixed solution; carrying out ultrasonic reaction on the mixed solution; sealing, standing and settling the mixed solution after ultrasonic reaction, and collecting an upper layer solution to obtain a collodion solution after graphene modification, namely a film solution; after the film solution is coated, the film solution is dried to form an adsorption film. The adsorption film prepared by using the graphene modified collodion can be used for adsorbing scale crystals on the wall of a container, and can effectively prevent measurement errors caused by deposition of scale crystals on the wall of a conical flask when the scale formation amount of sewage is measured by a common static method.
Description
Technical Field
The invention belongs to the technical field of petrochemical processing, and particularly relates to an adsorption film, a preparation method and application thereof.
Background
Along with the continuous and deep petroleum exploitation, water injection development has become the mainstream technology of oil field development in China. The water injection development technology can improve the recovery ratio and the oil well yield, but can produce a large amount of produced water. The ion constitution of the produced water is the same as or close to the reservoir, and the treated water is the optimal injection water source. Part of the oil fields (such as prolonged oil fields, changqing oil fields and the like) in China belong to multi-layer system development oil fields, the mineralization degree of produced water is high, the water type is complex, the compatibility of produced water in different layers is poor, and the mixed water has the reaction among ions to cause scaling. The scaling phenomenon in the petroleum exploitation and gathering and transportation process can cause the problems of high water injection pressure, pipeline blockage and the like in the process of exploitation and water injection, and can have serious influence on the safety production of oil fields.
An important index for evaluating the stability of the quality of injected water is the scale formation in water, and the main method for measuring the scale formation is a static bottle test method at present. The method for measuring the scale is greatly influenced by the wall of the container, and can generate larger error due to the fact that the deposition of scale crystals on the wall cannot be weighed. It is therefore important to prepare a suitable film material to overcome the above-mentioned errors.
Disclosure of Invention
One of the objects of the present invention is: an adsorption film is provided for the container wall to overcome the above-mentioned errors.
In order to achieve the above object, the present invention provides the following technical solutions:
The adsorption film is prepared from film solution, wherein the raw materials of the film solution comprise graphene and/or modified graphene, collodion solution and a dispersing agent.
Preferably, the concentration of the collodion solution is 5% -7%, the weight of the graphene and/or the modified graphene is 0.1% -0.5% of the weight of the collodion solution, the weight of the dispersing agent is 0.5% -2% of the weight of the collodion solution, and the percentages are mass percentages.
Preferably, the modified graphene is any one or a combination of two of ammonia modified graphene oxide and sulfuric acid modified graphene oxide.
Preferably, the ammonia-modified graphene oxide and the sulfuric acid-modified graphene oxide are prepared by an impregnation method.
Preferably, the preparation steps of the sulfuric acid modified graphene oxide are as follows: adding graphene oxide into concentrated sulfuric acid, reacting for 1-2 hours at 90-110 ℃, filtering, washing to neutrality, drying and grinding to obtain sulfuric acid modified graphene oxide;
The ammonia modified graphene oxide comprises the following steps: adding graphene oxide into an ammonia water solution for mixing and stirring, filtering, drying and grinding the mixed solution to obtain ammonia modified graphene oxide.
Preferably, the particle distribution of the graphene is 50-150 mu m, and the particle distribution of the modified graphene is 50-150 mu m.
Preferably, the dispersing agent is one of sodium dodecyl benzene sulfonate, polyethylene sulfonate and polyvinyl alcohol.
Preferably, the relative molecular mass range of the polyethylene sulfonate is 3000-5000; the relative molecular mass range of the polyvinyl alcohol is 2000-4000.
The second object of the present invention is: a method for preparing an adsorption film is provided.
In order to achieve the above object, the present invention provides the following technical solutions:
the preparation method of the adsorption film comprises the following steps:
(1) Adding graphene and/or modified graphene into the collodion solution, and then stirring;
(2) Adding a dispersing agent into the solution in the step (1), and continuing stirring until the solution is uniformly stirred to obtain a mixed solution;
(3) Carrying out ultrasonic reaction on the mixed solution in an ultrasonic device;
(4) Sealing, standing and settling the mixed solution after ultrasonic reaction, and collecting an upper layer solution to obtain a collodion solution after graphene modification, namely a film solution;
(5) After the film solution is coated, the film solution is dried to form an adsorption film.
Preferably, the rotation speed during stirring in the step (1) is 45-55 rpm, and the stirring time is 5-10 min;
the rotating speed of the stirring in the step (2) is 45-55 rpm, and the stirring time is more than 40 min;
and (3) standing for 11-13 h in the step (4).
Preferably, in the step (3), the ultrasonic reaction time is 35-45 min, the power of the ultrasonic device is 400-800W, and the frequency is 16-60 kHz.
The third object of the present invention is to: an application of the adsorption film is provided.
In order to achieve the above object, the present invention provides the following technical solutions:
The application of the adsorption film is that the adsorption film is coated on the wall of a container for containing sewage and is used for measuring the scale formation amount of the sewage.
Preferably, the specific measurement process of the sewage scaling amount is as follows:
Uniformly coating the film solution on the wall of a container, forming an adsorption film after the adsorption film is dried, adding a sewage sample into the adsorption film to react, pouring out the sewage sample, washing the adsorption film with clear water, taking the adsorption film out of the container, drying in vacuum, and measuring the mass change of the adsorption film before and after the reaction by a weighing method to obtain the sewage scaling amount.
Preferably, the temperature of the reaction after adding the sewage sample is 35-70 ℃, the time is 60-80 h, and the oscillation frequency of the sewage sample is 15-40 times/min.
The invention has the beneficial effects that:
The adsorption film prepared by using the graphene modified collodion can be used for adsorbing scale crystals on the wall of a container, and can effectively prevent measurement errors caused by deposition of scale crystals on the wall of a conical flask when the scale formation amount of sewage is measured by a common static method.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
200ML of the collodion solution (analytically pure, content 5%) was measured in a beaker, 0.5% sulfuric acid-modified graphene oxide (where 0.5% means that the weight of sulfuric acid-modified graphene oxide is 0.5% by weight of the collodion solution) was added and stirred slowly for 5min at 50 rpm. Then, a polyvinyl alcohol dispersant (1% in terms of weight of polyvinyl alcohol and 1% in terms of weight of collodion solution) with a relative molecular weight of 3000 was slowly added to the mixed solution, and stirring was continued for about 40 minutes until the solution was uniformly stirred. And carrying out ultrasonic treatment on the uniformly stirred mixed solution in an ultrasonic device for about 40min (the power of the ultrasonic device is 400W, the frequency is 16 kHz), then standing for 12h, and obtaining the upper layer solution after standing and sedimentation, namely the collodion solution (film solution) after graphene modification.
And then uniformly coating the prepared film solution into an experimental conical flask, and forming a film after the film solution is dried. 200ml of sewage sample is added into the solution, the solution is placed for 72 hours at the oscillation frequency of 20 times/min and the temperature of 50 ℃, and the scale crystal can be fully deposited on the film when the scale amount in the sewage is measured by a laboratory static method by utilizing the adsorption effect of the modified graphene on the scale crystal. After the experiment is finished, the film is washed 3 times by clean water, carefully taken out of the conical flask, dried in vacuum, and the mass change of the film before and after the experiment is measured by a weighing method, so that the scaling amount of the water sample can be obtained.
Comparative example
200Ml of the wastewater sample was placed in an Erlenmeyer flask and left at 50℃for 72h with 20 oscillations/min. After the experiment is finished, pouring out water, filtering by using a solvent filter, washing a filter membrane of the filter with clear water for 3 times, vacuum drying, and measuring the mass change of the filter membrane before and after the experiment by a weighing method to obtain the scaling quantity of the water sample. From the experimental phenomenon, a certain scale sample adheres to the bottle wall, so that the test bottle becomes not transparent enough.
Example 2
200ML of a collodion solution (analytically pure, content 5%) was measured and placed in a beaker, 0.5% ammonia-modified graphene oxide (where 0.5% means that the weight of ammonia-modified graphene oxide is 0.5% by weight of the collodion solution) was added and stirred slowly for 5min at 50 rpm. Then slowly adding a sodium dodecyl benzene sulfonate dispersing agent with the mass concentration of 1% (1% in the specification refers to that the weight of the sodium dodecyl benzene sulfonate accounts for 1% of the weight of the collodion solution in the specification) into the mixed solution, and continuously stirring for about 40 minutes until the solution is uniformly stirred. And carrying out ultrasonic treatment on the uniformly stirred mixed solution in an ultrasonic device for about 40min (the power of the ultrasonic device is 500W, the frequency is 30 kHz), then standing for 12h, and obtaining an upper layer solution after standing and sedimentation, namely the collodion solution (film solution) after graphene modification.
And then uniformly coating the prepared film solution into an experimental conical flask, and forming a film after the film solution is dried. 200ml of sewage sample is added into the solution, the solution is placed for 64 hours at the oscillation frequency of 15 times/min and the temperature of 50 ℃, and the scale crystal can be fully deposited on the film when the scale amount in the sewage is measured by a laboratory static method by utilizing the adsorption effect of the modified graphene on the scale crystal. After the experiment is finished, the film is washed 3 times by clean water, carefully taken out of the conical flask, dried in vacuum, and the mass change of the film before and after the experiment is measured by a weighing method, so that the scaling amount of the water sample can be obtained.
Example 3
200ML of a collodion solution (analytically pure, content 6%) was measured and placed in a beaker, sulfuric acid-modified graphene oxide (0.1% herein means that the weight of the sulfuric acid-modified graphene oxide is 0.1% by weight of the collodion solution) was added in a particle size of 150 μm, and the mixture was slowly stirred at 50rpm for 5 minutes. Then, a polyethylene sulfonate dispersant (2% herein means that the weight of the polyethylene sulfonate is 2% of the weight of the collodion solution by weight) with a relative molecular weight of 4000 is slowly added into the mixed solution, and stirring is continued for about 40 minutes until the solution is uniformly stirred. And carrying out ultrasonic treatment on the uniformly stirred mixed solution in an ultrasonic device for about 40min (the power of the ultrasonic device is 600W, the frequency is 40 kHz), then standing for 12h, and obtaining an upper layer solution after standing and sedimentation, namely the collodion solution (film solution) after graphene modification.
And then uniformly coating the prepared film solution into an experimental conical flask, and forming a film after the film solution is dried. 200ml of sewage sample is added into the solution, the solution is placed for 72 hours at the oscillation frequency of 40 times/min and the temperature of 35 ℃, and the scale crystal can be fully deposited on the film when the scale amount in the sewage is measured by a laboratory static method by utilizing the induced adsorption effect of the modified graphene on the scale crystal. After the experiment is finished, the film is washed 3 times by clean water, carefully taken out of the conical flask, dried in vacuum, and the mass change of the film before and after the experiment is measured by a weighing method, so that the scaling amount of the water sample can be obtained.
Example 4
200ML of a collodion solution (analytically pure, content 6%) was measured and placed in a beaker, sulfuric acid-modified graphene oxide (0.3% herein means that the weight of the sulfuric acid-modified graphene oxide is 0.3% by weight of the collodion solution) was added in a particle size of 70 μm, and the mixture was slowly stirred at 50rpm for 5 minutes. Then, a polyvinyl alcohol dispersant (1.5% in terms of weight of polyvinyl alcohol and 1.5% in terms of weight of collodion solution) with a relative molecular weight of 2500 was slowly added to the mixed solution, and stirring was continued for about 40 minutes until the solution was uniformly stirred. And carrying out ultrasonic treatment on the uniformly stirred mixed solution in an ultrasonic device for about 40min (the power of the ultrasonic device is 700W, the frequency is 50 kHz), then standing for 12h, and obtaining the upper layer solution after standing and sedimentation, namely the collodion solution (film solution) after graphene modification.
And then uniformly coating the prepared film solution into an experimental conical flask, and forming a film after the film solution is dried. 200ml of sewage sample is added into the solution, the solution is placed for 80 hours at the oscillation frequency of 30 times/min and the temperature of 40 ℃, and the scale crystal can be fully deposited on the film when the scale amount in the sewage is measured by a laboratory static method by utilizing the adsorption effect of the modified graphene on the scale crystal. After the experiment is finished, the film is washed 3 times by clean water, carefully taken out of the conical flask, dried in vacuum, and the mass change of the film before and after the experiment is measured by a weighing method, so that the scaling amount of the water sample can be obtained.
Example 5
200ML of collodion solution (analytically pure, content 7%) was measured and placed in a beaker, 0.5% sulfuric acid-modified graphene oxide (0.5% herein means that the weight of graphene oxide is 0.5% by weight of the collodion solution) was added and stirred slowly at 50rpm for 5min. Then, a polyvinyl alcohol dispersant (1% in terms of weight of polyvinyl alcohol and 1% in terms of weight of collodion solution) with a relative molecular weight of 3000 was slowly added to the mixed solution, and stirring was continued for about 40 minutes until the solution was uniformly stirred. And carrying out ultrasonic treatment on the uniformly stirred mixed solution in an ultrasonic device for about 40min (the power of the ultrasonic device is 800W, the frequency is 60 kHz), then standing for 12h, and obtaining the upper layer solution after standing and sedimentation, namely the collodion solution (film solution) after graphene modification.
And then uniformly coating the prepared film solution into an experimental conical flask, and forming a film after the film solution is dried. 200ml of sewage sample is added into the solution, the solution is placed for 60 hours at the oscillation frequency of 20 times/min and the temperature of 45 ℃, and the scale crystal can be fully deposited on the film when the scale amount in the sewage is measured by a laboratory static method by utilizing the induced adsorption effect of the modified graphene on the scale crystal. After the experiment is finished, the film is washed 3 times by clean water, carefully taken out of the conical flask, dried in vacuum, and the mass change of the film before and after the experiment is measured by a weighing method, so that the scaling amount of the water sample can be obtained.
Example 6
200ML of the collodion solution (analytically pure, content 7%) was measured in a beaker, 0.5% sulfuric acid-modified graphene oxide (where 0.5% means that the weight of sulfuric acid-modified graphene oxide is 0.5% by weight of the collodion solution) was added and stirred slowly for 5min at 50 rpm. Then, 0.5% of a polyvinyl alcohol dispersing agent (0.5% of polyvinyl alcohol herein means that the weight of the polyvinyl alcohol accounts for 0.5% of the weight of the collodion solution in weight percent) with relative molecular weight of 4000 is slowly added into the mixed solution, and stirring is continued for about 40 minutes until the solution is uniformly stirred. And carrying out ultrasonic treatment on the uniformly stirred mixed solution in an ultrasonic device for about 40min (the power of the ultrasonic device is 400W, the frequency is 16 kHz), then standing for 12h, and obtaining the upper layer solution after standing and sedimentation, namely the collodion solution (film solution) after graphene modification.
And then uniformly coating the prepared film solution into an experimental conical flask, and forming a film after the film solution is dried. 200ml of sewage sample is added into the solution, the solution is placed for 72 hours at the oscillation frequency of 20 times/min and the temperature of 70 ℃, and the scale crystal can be fully deposited on the film when the scale amount in the sewage is measured by a laboratory static method by utilizing the adsorption effect of the modified graphene on the scale crystal. After the experiment is finished, the film is washed 3 times by clean water, carefully taken out of the conical flask, dried in vacuum, and the mass change of the film before and after the experiment is measured by a weighing method, so that the scaling amount of the water sample can be obtained.
Example 7
200ML of a collodion solution (analytically pure, content 7%) was measured and added to a beaker, sulfuric acid-modified graphene oxide (here, 0.1% means that the weight of sulfuric acid-modified graphene oxide is 0.1% by weight of the collodion solution) was added in a particle size of 150 μm, and the mixture was stirred slowly at 50rpm for 5 minutes. Then, a polyethylene sulfonate dispersant (2% herein means that the weight of the polyethylene sulfonate is 2% of the weight of the collodion solution by weight) with a relative molecular weight of 3000 was slowly added to the mixed solution, and stirring was continued for about 40 minutes until the solution was uniformly stirred. And carrying out ultrasonic treatment on the uniformly stirred mixed solution in an ultrasonic device for about 40min (the power of the ultrasonic device is 600W, the frequency is 40 kHz), then standing for 12h, and obtaining an upper layer solution after standing and sedimentation, namely the collodion solution (film solution) after graphene modification.
And then uniformly coating the prepared film solution into an experimental conical flask, and forming a film after the film solution is dried. 200ml of sewage sample is added into the solution, the solution is placed for 72 hours at the oscillation frequency of 40 times/min and the temperature of 35 ℃, and the scale crystal can be fully deposited on the film when the scale amount in the sewage is measured by a laboratory static method by utilizing the induced adsorption effect of the modified graphene on the scale crystal. After the experiment is finished, the film is washed 3 times by clean water, carefully taken out of the conical flask, dried in vacuum, and the mass change of the film before and after the experiment is measured by a weighing method, so that the scaling amount of the water sample can be obtained.
Example 8
200ML of a collodion solution (analytically pure, content 5%) was measured and placed in a beaker, sulfuric acid-modified graphene oxide (0.1% herein means that the weight of the sulfuric acid-modified graphene oxide is 0.1% by weight of the collodion solution) was added in a particle size of 150 μm, and the mixture was slowly stirred at 50rpm for 5 minutes. Then slowly adding 2% of polyethylene sulfonate dispersant with relative molecular weight of 5000 (2% refers to the weight of polyethylene sulfonate accounting for 2% of the weight of collodion solution) into the mixed solution, and continuously stirring for about 40min until the solution is uniformly stirred. And carrying out ultrasonic treatment on the uniformly stirred mixed solution in an ultrasonic device for about 40min (the power of the ultrasonic device is 600W, the frequency is 40 kHz), then standing for 12h, and obtaining an upper layer solution after standing and sedimentation, namely the collodion solution (film solution) after graphene modification.
And then uniformly coating the prepared film solution into an experimental conical flask, and forming a film after the film solution is dried. 200ml of sewage sample is added into the solution, the solution is placed for 72 hours at the oscillation frequency of 40 times/min and the temperature of 35 ℃, and the scale crystal can be fully deposited on the film when the scale amount in the sewage is measured by a laboratory static method by utilizing the induced adsorption effect of the modified graphene on the scale crystal. After the experiment is finished, the film is washed 3 times by clean water, carefully taken out of the conical flask, dried in vacuum, and the mass change of the film before and after the experiment is measured by a weighing method, so that the scaling amount of the water sample can be obtained.
Example 9
200ML of collodion solution (analytically pure, content 5%) was measured in a beaker, 0.5% graphene with particle size 70 μm (0.5% herein means 0.5% by weight of graphene based on the weight of collodion solution) was added and stirred slowly for 5min at 50 rpm. Then, a polyvinyl alcohol dispersant (1% in terms of weight of polyvinyl alcohol and 1% in terms of weight of collodion solution) with a relative molecular weight of 3000 was slowly added to the mixed solution, and stirring was continued for about 40 minutes until the solution was uniformly stirred. And carrying out ultrasonic treatment on the uniformly stirred mixed solution in an ultrasonic device for about 40min (the power of the ultrasonic device is 400W, the frequency is 16 kHz), then standing for 12h, and obtaining the upper layer solution after standing and sedimentation, namely the collodion solution (film solution) after graphene modification.
And then uniformly coating the prepared film solution into an experimental conical flask, and forming a film after the film solution is dried. 200ml of sewage sample is added into the solution, the solution is placed for 72 hours at the oscillation frequency of 20 times/min and the temperature of 50 ℃, and the scale crystal can be fully deposited on the film when the scale amount in the sewage is measured by a laboratory static method by utilizing the adsorption effect of the modified graphene on the scale crystal. After the experiment is finished, the film is washed 3 times by clean water, carefully taken out of the conical flask, dried in vacuum, and the mass change of the film before and after the experiment is measured by a weighing method, so that the scaling amount of the water sample can be obtained.
Example 10
In comparison with example 1, example 10 used an unmodified collodion solution as an adsorption film to determine the amount of fouling, and the other measurement conditions were the same as in example 1.
The ammonia-modified graphene oxide and the sulfuric acid-modified graphene oxide of examples 1-10 were prepared by an impregnation method.
The preparation method of the sulfuric acid modified graphene oxide comprises the following steps:
Adding graphene oxide into concentrated sulfuric acid with the mass concentration of 98% (the mass ratio of the graphene oxide to the concentrated sulfuric acid is preferably 1:6-1:8), reacting for 1-2 hours at 90-110 ℃, filtering, washing to be neutral, drying and grinding to obtain the sulfuric acid modified graphene oxide.
The steps of the ammonia modified graphene oxide are as follows:
adding graphene oxide into an ammonia water solution with the mass concentration of 25% (the mass ratio of the graphene oxide to the ammonia water solution is preferably 1:6-1:8) for mixing and stirring, then filtering, drying and grinding the mixed solution to obtain ammonia modified graphene oxide;
the graphene oxide used in the preparation process is purchased from Jiangsu Xianfeng nano materials science and technology Co.
The measurement results of the amount of scale in the examples are shown in Table 1.
Table 1 experimental scale measurement
In the present invention, in the actual scale measurement, the scale sample mass is obtained by subtracting the mass of the membrane solution before sewage treatment from the mass of the membrane solution after sewage treatment, so that the larger the membrane mass difference is, the larger the experimental error is represented.
As can be seen from table 1:
1. From the poor film quality data of examples 1-9, it can be seen that: the quality difference of the film (the film modified by the graphene) is very small and is lower than 5mg and the minimum is 2mg, so that the error caused by the drying of the film is very small when the film is adopted to treat sewage samples, and the film can be ignored in measurement.
2. The films of comparative examples 1, 10 are of poor quality, as can be seen: the film quality difference of the film after graphene modification is far smaller than that of the film without modification, which shows that the film measurement scaling amount obtained by utilizing the graphene modified collodion can obviously reduce experimental errors caused by film drying and improve the accuracy of scaling amount measurement.
3. The scale mass of comparative examples 1, 10 can be seen: the mass of the scale sample adsorbed by the film after the graphene modification is increased compared with that of the scale sample adsorbed by the film without the graphene modification, because the capacity of adsorbing the scale crystals of the adsorption film after the graphene modification is enhanced.
4. Comparative example 1 and comparative example can be seen: the mass of the scale sample measured in example 1 is significantly higher than that of the comparative example, because the comparative example fails to measure the mass of the scale crystals deposited on the wall of the conical flask, and thus the film of the present invention can avoid measurement errors caused by deposition of the scale crystals on the wall of the conical flask when measuring the mass of the scale sample.
5. As can be seen from comparative examples 1 and 9, the ammonia-modified and sulfuric acid-modified graphene oxide has the advantages that the surface of the graphene oxide contains SO 4 2-, COO-, OH-and other anions which can form coordination bonds with scale forming cations such as Ca 2+、Mg2+ and the like in water, SO that scale crystals can be induced to be adsorbed and aggregated on the surface of the film, the number of small-particle scale crystals in water can be reduced, and the accuracy of scale formation amount measurement is improved.
Although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (11)
1. An application of an adsorption film, which is characterized in that: coating an adsorption film on the wall of a container for containing sewage, and measuring the scale formation amount of the sewage;
The adsorption film is prepared from film solution, wherein the raw materials of the film solution comprise graphene and/or modified graphene, collodion solution and dispersing agent; the concentration of the collodion solution is 5-7%, the weight of the graphene and/or the modified graphene is 0.1-0.5% of the weight of the collodion solution, the weight of the dispersing agent is 0.5-2% of the weight of the collodion solution, and the percentages are mass percentages;
The preparation method of the adsorption film comprises the following steps:
(1) Adding graphene and/or modified graphene into the collodion solution, and then stirring;
(2) Adding a dispersing agent into the solution in the step (1), and continuing stirring until the solution is uniformly stirred to obtain a mixed solution;
(3) Carrying out ultrasonic reaction on the mixed solution in an ultrasonic device;
(4) Sealing, standing and settling the mixed solution after ultrasonic reaction, and collecting an upper layer solution to obtain a collodion solution after graphene modification, namely a film solution;
(5) After the film solution is coated, the film solution is dried to form an adsorption film.
2. Use of an adsorption film according to claim 1, characterized in that: the modified graphene is any one or the combination of two of ammonia modified graphene oxide and sulfuric acid modified graphene oxide.
3. Use of an adsorption film according to claim 2, characterized in that: the ammonia modified graphene oxide and the sulfuric acid modified graphene oxide are prepared by an impregnation method.
4. Use of an adsorption film according to claim 3, wherein:
the preparation method of the sulfuric acid modified graphene oxide comprises the following steps: adding graphene oxide into concentrated sulfuric acid, reacting for 1-2 hours at 90-110 ℃, filtering, washing to neutrality, drying and grinding to obtain sulfuric acid modified graphene oxide;
The ammonia modified graphene oxide comprises the following steps: adding graphene oxide into an ammonia water solution for mixing and stirring, filtering, drying and grinding the mixed solution to obtain ammonia modified graphene oxide.
5. Use of an adsorption film according to claim 1, characterized in that: the particle distribution of the graphene is 50-150 mu m, and the particle distribution of the modified graphene is 50-150 mu m.
6. Use of an adsorption film according to claim 1, characterized in that: the dispersing agent is one of sodium dodecyl benzene sulfonate, polyethylene sulfonate and polyvinyl alcohol.
7. The use of an adsorption film according to claim 6, wherein: the relative molecular mass range of the polyethylene sulfonate is 3000-5000; the relative molecular mass range of the polyvinyl alcohol is 2000-4000.
8. Use of an adsorption film according to claim 1, characterized in that:
the rotation speed during stirring in the step (1) is 45-55 rpm, and the stirring time is 5-10 min;
the rotating speed of the stirring in the step (2) is 45-55 rpm, and the stirring time is more than 40 min;
and (3) standing for 11-13 h in the step (4).
9. Use of an adsorption film according to claim 1, characterized in that:
In the step (3), the ultrasonic reaction time is 35-45 min, the power of the ultrasonic device is 400-800W, and the frequency is 16-60 kHz.
10. Use of an adsorption film according to claim 1, characterized in that: the specific measurement process of the sewage scaling amount is as follows:
Uniformly coating the film solution on the wall of a container, forming an adsorption film after the adsorption film is dried, adding a sewage sample into the adsorption film to react, pouring out the sewage sample, washing the adsorption film with clear water, taking the adsorption film out of the container, drying in vacuum, and measuring the mass change of the adsorption film before and after the reaction by a weighing method to obtain the sewage scaling amount.
11. Use of an adsorption film according to claim 10, wherein: the reaction temperature is 35-70 ℃ after adding the sewage sample, the time is 60-80 h, and the oscillation frequency of the sewage sample is 15-40 times/min.
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| CN107174973A (en) * | 2017-06-30 | 2017-09-19 | 宁波千仁环保科技有限公司 | A kind of preparation method of the plain composite membrane of graphene fiber |
| EP3530617A1 (en) * | 2018-02-27 | 2019-08-28 | Fundacio Privada Institut Catala de Nanociencia I Nanotecnologia (ICN2) | Method of forming a porous graphene-based macroscopic structure |
| CN113018503A (en) * | 2021-03-25 | 2021-06-25 | 中国科学院兰州化学物理研究所 | Nano-pore graphene/nitrocellulose membrane with antibacterial and wound healing promoting functions and preparation method thereof |
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| CN107174973A (en) * | 2017-06-30 | 2017-09-19 | 宁波千仁环保科技有限公司 | A kind of preparation method of the plain composite membrane of graphene fiber |
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