CN115197372B - Preparation method and application of cellulose-based material for absorbing oily wastewater - Google Patents
Preparation method and application of cellulose-based material for absorbing oily wastewater Download PDFInfo
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- CN115197372B CN115197372B CN202210955396.XA CN202210955396A CN115197372B CN 115197372 B CN115197372 B CN 115197372B CN 202210955396 A CN202210955396 A CN 202210955396A CN 115197372 B CN115197372 B CN 115197372B
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 54
- 239000001913 cellulose Substances 0.000 title claims abstract description 54
- 239000000463 material Substances 0.000 title claims abstract description 43
- 239000002351 wastewater Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000000178 monomer Substances 0.000 claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003999 initiator Substances 0.000 claims abstract description 27
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 239000000725 suspension Substances 0.000 claims abstract description 10
- 238000000944 Soxhlet extraction Methods 0.000 claims abstract description 5
- 238000001291 vacuum drying Methods 0.000 claims abstract description 5
- 239000012467 final product Substances 0.000 claims abstract description 4
- 235000010980 cellulose Nutrition 0.000 claims description 48
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims description 38
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims description 38
- 239000008108 microcrystalline cellulose Substances 0.000 claims description 38
- 229940016286 microcrystalline cellulose Drugs 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 10
- 238000011282 treatment Methods 0.000 claims description 9
- 238000002203 pretreatment Methods 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 abstract description 11
- 238000001035 drying Methods 0.000 abstract description 4
- 238000004140 cleaning Methods 0.000 abstract description 2
- 238000004065 wastewater treatment Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 71
- 235000019198 oils Nutrition 0.000 description 71
- 238000010521 absorption reaction Methods 0.000 description 44
- 238000001179 sorption measurement Methods 0.000 description 43
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000011358 absorbing material Substances 0.000 description 13
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000003960 organic solvent Substances 0.000 description 12
- 239000003502 gasoline Substances 0.000 description 11
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 10
- 238000010559 graft polymerization reaction Methods 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000005303 weighing Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- -1 butyl acrylate-N, N' -methylenebisacrylamide Chemical compound 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229920000578 graft copolymer Polymers 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000004745 nonwoven fabric Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 235000019476 oil-water mixture Nutrition 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- CHIHQLCVLOXUJW-UHFFFAOYSA-N benzoic anhydride Chemical compound C=1C=CC=CC=1C(=O)OC(=O)C1=CC=CC=C1 CHIHQLCVLOXUJW-UHFFFAOYSA-N 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000000053 physical method Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- FHNINJWBTRXEBC-UHFFFAOYSA-N Sudan III Chemical compound OC1=CC=C2C=CC=CC2=C1N=NC(C=C1)=CC=C1N=NC1=CC=CC=C1 FHNINJWBTRXEBC-UHFFFAOYSA-N 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 239000003305 oil spill Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229940099373 sudan iii Drugs 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
- C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
-
- 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
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
-
- 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
- B01J20/28002—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 physical properties
-
- 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
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a preparation method and application of a cellulose-based material for absorbing oily wastewater, wherein the cellulose-based material is butyl acrylate-N, N ʹ -methylene bisacrylamide, and the preparation method comprises the following steps: step 1, dropwise adding an initiator into cellulose suspension, and then continuously dropwise adding butyl acrylate monomer to carry out grafting reaction; and step 2, dropwise adding N, N ʹ -methylene bisacrylamide and butyl acrylate monomers into the step 1, and continuing to perform polymerization reaction to obtain the cellulose-based material, wherein in the step 3, acetone and deionized water are used for cleaning the cellulose-based material in the step 2, soxhlet extraction is carried out for 24 hours, and a vacuum drying box is used for drying to obtain a final product, and the material is applied to oily wastewater treatment.
Description
Technical Field
The invention belongs to the technical field of oil absorption materials, and particularly relates to a cellulose-based material for absorbing oily wastewater, a preparation method and application of the material.
Background
At present, petroleum and organic solvents are frequently leaked during the exploration, transportation, storage, processing, refining and use of offshore petroleum, and in addition, a large amount of oily wastewater is generated during normal shipping and production in the petroleum, food, textile, steel, leather and metal processing industries. The frequent oil spill accidents and the discharge of oily industrial wastewater cause serious damage to the marine ecological environment and huge economic loss, not only comprise the waste of petroleum resources, but also bring negative economic influence to marine product breeding industry and marine travel industry, and the marine ecological environment restoration and recovery also need a great deal of funds.
The treatment methods of oil pollution can be broadly divided into four categories, namely chemical, in situ combustion, biological and physical. The chemical method and the in-situ combustion method can rapidly treat oil pollution on the water surface, but have the defects of secondary pollution, resource waste and the like. Bioremediation is an environmentally friendly treatment, but in practical applications stringent environmental conditions are required to sustain microbial proliferation and the treatment of oil pollution is slow. The mechanical method in the physical method is suitable for large oil spilling accidents, has low cost and high treatment speed, but has low oil-water separation efficiency, a large amount of floating oil is remained after treatment, and is not suitable for complex oil-water mixing systems and other problems, and simultaneously, environmental factors such as ocean currents, stormy waves and the like can also influence on site operation. Compared with the method, the method using the oil absorbing material in the physical method is insensitive to sea conditions, is more economical and environment-friendly, and is one of the most effective methods for thoroughly removing oil pollution, for example, a light filter material for treating oily wastewater and sewage is disclosed in China patent with the classification number of C02F and the publication number of CN104961190A, and can be used for adsorbing the oily wastewater.
In the prior art, oil absorbing materials can be generally classified into three main categories: inorganic mineral materials, natural organic materials, and organic synthetic materials. Inorganic mineral materials are generally low in oil absorption, unreusable and poor in buoyancy performance, and the risk of dust formation is also caused when the inorganic mineral materials are used in open places; the natural organic material has limited adsorption capacity, needs a large amount of space for storage when in use, has poor hydrophobicity, absorbs oil and absorbs a large amount of water at the same time, so that the oil absorption efficiency is low; synthetic organic materials have stronger oil absorption properties, but are not biodegradable, and their use in oil pollution treatments may further lead to environmental problems.
The ideal oil-absorbing material has good hydrophobic and oleophilic properties, high oil-absorbing capacity and oil-retaining property, is easy to recover from water, can be biologically degraded and can be repeatedly used for a plurality of times, and has the advantages of low cost, abundant raw material reserves and the like. Cellulose is the most abundant renewable biological resource in nature, and has very wide sources, low price, good biodegradability, biocompatibility and mechanical properties. Therefore, the invention aims to carry out surface functionalization modification on the cellulose-based oil absorption material with more excellent performance.
Disclosure of Invention
The invention provides a preparation method and application of a cellulose-based material for absorbing oily wastewater, the preparation method of the cellulose-based material is simple, and the prepared cellulose-based material has good hydrophobic and oleophilic and regeneration performances, has excellent adsorption effect on various oils and organic solvents, and has the capability of rapidly treating floating oil on the water surface.
The technical scheme of the invention is realized as follows: a method for preparing a cellulose-based material for absorbing oily wastewater, comprising the steps of:
step 1, dropwise adding an initiator into cellulose suspension, and then continuously dropwise adding butyl acrylate monomer to carry out grafting reaction;
and 2, dropwise adding N, N' -methylene bisacrylamide and butyl acrylate monomers in the step 1, and continuing to perform polymerization reaction to obtain the cellulose-based material.
As a preferred embodiment, the preparation method of the cellulose suspension in step 1 comprises the following steps: soaking microcrystalline cellulose in a mixed solution of acetone and water for 12 hours to obtain a cellulose suspension;
in the step 1, the initiator is dibenzoyl peroxide, and the initiator is pretreated before use, wherein the pretreatment method comprises the following steps: the dibenzoyl oxide is purified by adopting a recrystallization method.
As a preferred embodiment, the butyl acrylate monomer in step 1 and step 2 is pretreated before use, and the pretreatment method is as follows: and (3) performing alkali washing on the butyl acrylate monomer by using sodium hydroxide to obtain the refined butyl acrylate monomer.
In the step 1, the grafting reaction temperature is 60-80 ℃, the mass ratio of microcrystalline cellulose to butyl acrylate monomer is 1:5-1:9, and the mass ratio of microcrystalline cellulose to dibenzoyl oxide is 1:0.05-1:0.20;
in the step 2, the mass ratio of the butyl acrylate monomer to the N, N' -methylene bisacrylamide is 1:0.002-1:0.008.
The grafting polymerization temperature is 60-80 ℃, the optimal grafting polymerization temperature is 70 ℃ by further optimizing, the size of the grafting polymerization temperature can influence the decomposition rate of an initiator, and further influence the grafting rate and the crosslinking density of cellulose-grafting-polymerization (butyl acrylate-N, N '-methylene bisacrylamide) [ Cell-g-P (BA-MBA) ] and the use amount of the initiator is too high or too low, so that the oil absorption performance of the cellulose-grafting-polymerization (butyl acrylate-N, N' -methylene bisacrylamide) [ Cell-g-P (BA-MBA) ] is not beneficial to improvement.
As a preferred embodiment, in step 2, N, N' -methylenebisacrylamide is used in an amount of 0.2 to 0.8wt% based on the amount of butyl acrylate monomer.
As a preferred embodiment, dibenzoyl peroxide is used in an amount of 0.05g to 0.2g;
the amount of butyl acrylate monomer is 5g-9g.
The oil absorption process mainly utilizes a long carbon chain structure on butyl acrylate, so that the consumption level of the butyl acrylate has a great influence on the oil absorption performance of cellulose-grafting-polymerization (butyl acrylate-N, N' -methylene bisacrylamide) [ Cell-g-P (BA-MBA) ], the consumption level of the butyl acrylate is lower, the quantity of monomers grafted onto the cellulose is limited, the consumption level of the butyl acrylate is higher, the steric hindrance of a grafted polymer is large after the grafting rate reaches a certain value, the continuous grafting is not facilitated, meanwhile, the homopolymerization reaction among the butyl acrylate is easier to occur, and the oil absorption effect is reduced.
The amount of the initiator can influence the grafting rate and grafting efficiency of the cellulose-graft-polymerization (butyl acrylate-N, N '-methylene bisacrylamide) [ Cell-g-P (BA-MBA) ] and the crosslinking density, and the excessive or the insufficient amount of the initiator can reduce the oil absorption performance of the cellulose-graft-polymerization (butyl acrylate-N, N' -methylene bisacrylamide) [ Cell-g-P (BA-MBA) ], so that the invention selects the proper amount of the initiator.
In a preferred embodiment, step 2 is followed by step 3, in which the cellulose-based material in step 2 is washed with acetone and deionized water, soxhlet extracted for 24 hours, and dried in a vacuum oven to obtain the final product.
As a preferred embodiment, steps 1, 2 and 3 are all performed under nitrogen protection.
The application of the cellulose-based material for absorbing the oily wastewater prepared by adopting the preparation method of the cellulose-based material for absorbing the oily wastewater in the treatment of the oily wastewater.
After the technical scheme is adopted, the invention has the beneficial effects that:
1. the method has the advantages of simple implementation mode process, no need of high temperature and high pressure in reaction conditions, purification of the crude product by simple cable extraction, and low cost and high efficiency.
2. The invention selects microcrystalline cellulose as grafting base, and the microcrystalline cellulose can be obtained from agricultural waste, and has the advantages of low cost, abundant reserves, biodegradability, certain mechanical strength and the like. The butyl acrylate monomer with moderate carbon chain length is selected, so that the butyl acrylate monomer has certain lipophilicity, and is easily grafted onto microcrystalline cellulose in an acetone/water reaction system.
3. The cellulose-based oil absorption material prepared by the invention has a certain adsorption capacity to various oils and organic solvents.
4. The adsorption capacity of the cellulose-based oil absorption material prepared by the invention after 15 adsorption and desorption cycles is basically the same as the primary adsorption capacity, and the cellulose-based oil absorption material has excellent recycling performance.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions of the prior art, the drawings which are used in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that other drawings can be obtained according to these drawings without inventive faculty for a person skilled in the art.
FIG. 1 is an infrared spectrum of microcrystalline cellulose, cell-g-PBA, cell-g-P (BA-MBA) and P (BA-MBA) in example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of microcrystalline cellulose, cell-g-PBA, cell-g-P (BA-MBA), and P (BA-MBA) in example 1 of the present invention;
FIG. 3 is a schematic diagram showing the results of water contact angle test of microcrystalline cellulose and Cell-g-P (BA-MBA) in example 1 of the present invention;
FIGS. 4 and 5 are schematic diagrams showing adsorption capacities of Cell-g-P (BA-MBA) prepared in example 1 of the present invention for various oils and organic solvents;
FIGS. 6 and 7 are schematic diagrams showing adsorption capacities of Cell-g-P (BA-MBA) prepared in example 1 according to the present invention as a function of contact time;
FIGS. 8 and 9 are graphs showing the results of the quasi-first order and quasi-second order kinetic fitting of Cell-g-P (BA-MBA) prepared in example 1 of the present invention;
FIGS. 10 and 11 are schematic diagrams showing the results of fitting Langmuir adsorption isotherms and Freundlich adsorption isotherms of Cell-g-P (BA-MBA) prepared in example 1 of the present invention;
FIG. 12 is a graph showing the fitting result of the adsorption thermodynamic data of Cell-g-P (BA-MBA) prepared in example 1 of the present invention;
FIG. 13 is a graph showing the actual oil-water separation effect of Cell-g-P (BA-MBA) prepared in example 1 of the present invention;
FIG. 14 is a graph showing the results of the regeneration performance test of Cell-g-P (BA-MBA) prepared in example 1 of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. 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.
A preparation method of a cellulose-based material for absorbing oily wastewater comprises the steps of firstly grafting part of butyl acrylate onto cellulose under the action of an initiator, adding butyl acrylate and N, N '-methylenebisacrylamide to react for a period of time, and continuing to react to obtain cellulose-graft-polymerization (butyl acrylate-N, N' -methylenebisacrylamide) [ Cell-g-P (BA-MBA) ], and comprises the following steps:
step 1, dropwise adding an initiator into cellulose suspension, and then continuously dropwise adding butyl acrylate monomer to carry out grafting reaction;
and 2, dropwise adding N, N' -methylene bisacrylamide and butyl acrylate monomers in the step 1, and continuing to perform polymerization reaction to obtain the cellulose-based material.
The preparation method of the cellulose suspension in the step 1 comprises the following steps: soaking microcrystalline cellulose in a mixed solution of acetone and water for 12 hours to obtain a cellulose suspension;
in the step 1, the initiator is dibenzoyl peroxide, and the initiator is pretreated before use, wherein the pretreatment method comprises the following steps: the dibenzoyl peroxide is purified by adopting a recrystallization method.
The butyl acrylate monomer in the step 1 and the step 2 is pretreated before use, and the pretreatment method comprises the following steps: and (3) performing alkali washing on the butyl acrylate monomer by using sodium hydroxide to obtain the refined butyl acrylate monomer.
In the step 1, the grafting reaction temperature is 60-80 ℃, the optimal grafting polymerization temperature is 70 ℃ by further optimizing, the size of the grafting polymerization temperature can influence the decomposition rate of an initiator, and further influence the grafting rate and the crosslinking density of cellulose-grafting-polymerization (butyl acrylate-N, N '-methylene bisacrylamide) [ Cell-g-P (BA-MBA) ] so that the oil absorption performance of the cellulose-grafting-polymerization (butyl acrylate-N, N' -methylene bisacrylamide) ] is not improved due to the fact that the using amount of the initiator is too high or too low. The mass ratio of the microcrystalline cellulose to the butyl acrylate monomer is 1:5-1:9, and the mass ratio of the microcrystalline cellulose to the dibenzoyl peroxide is 1:0.05-1:0.20;
in the step 2, the mass ratio of the butyl acrylate monomer to the N, N' -methylene bisacrylamide is 1:0.002-1:0.008.
In the step 2, the dosage of N, N' -methylene bisacrylamide is 0.2 to 0.8 weight percent of the dosage of butyl acrylate monomer. Further optimization results in an optimum amount of 0.35wt%. The cross-linking density is affected by the amount of the cross-linking agent, the three-dimensional network structure of cellulose-graft-polymerization (butyl acrylate-N, N '-methylene bisacrylamide) [ Cell-g-P (BA-MBA) ] is loose, collapse is easy in the oil absorption process, the amount of the cross-linking agent is too high, the stretching capacity of the three-dimensional network structure is poor, and oil molecules are not easy to enter, so that the oil absorption capacity of the cellulose-graft-polymerization (butyl acrylate-N, N' -methylene bisacrylamide) is reduced.
In the step 1, the dosage of dibenzoyl peroxide is 0.05g-0.2g; further optimization results in an optimum amount of 0.09g, the amount of initiator affects the grafting ratio and grafting efficiency of the cellulose-graft-polymerization (butyl acrylate-N, N '-methylenebisacrylamide) [ Cell-g-P (BA-MBA) ] and also affects the crosslinking density thereof, and too much or too little amount of initiator causes the oil absorption performance of the cellulose-graft-polymerization (butyl acrylate-N, N' -methylenebisacrylamide) [ Cell-g-P (BA-MBA) ] to be lowered.
In the step 1 and the step 2, the dosage of the butyl acrylate monomer is 5g-9g, the optimal dosage is 7g, the oil absorption process mainly utilizes a long carbon chain structure on butyl acrylate, so that the dosage has a larger influence on the oil absorption performance of cellulose-grafting-polymerization (butyl acrylate-N, N' -methylene bisacrylamide) [ Cell-g-P (BA-MBA) ] and the dosage of butyl acrylate is lower, the quantity of the monomer grafted onto cellulose is limited, the dosage of butyl acrylate is higher, the steric hindrance of the grafted polymer is larger after the grafting rate reaches a certain value, the continuous grafting is not facilitated, and meanwhile, the homopolymerization reaction among the butyl acrylate is easier to occur, so that the oil absorption effect is reduced.
And step 2 is followed by step 3, wherein step 3 is that acetone and deionized water are used for cleaning the cellulose-based material in step 2, soxhlet extraction is carried out for 24 hours, and a vacuum drying oven is used for drying, so that a final product is obtained.
Step 1, step 2 and step 3 are all carried out under the protection of nitrogen.
Use of a cellulose-based material absorbing oily wastewater in the treatment of oily wastewater.
The cellulose-based oil absorption material prepared by the invention has certain adsorption capacity to various oils and organic solvents, wherein the maximum average adsorption capacity to chloroform, toluene, acetone, N-dimethylformamide and gasoline are respectively 37.55g g-1, 18.72g g-1, 9.46g g-1, 7.37g g-1 and 10.41g g-1.
Example 1
According to the method for preparing the cellulose-based oil absorbing material shown in fig. 1 to 14, the method comprises the following steps:
1. pretreatment process
Pretreatment of an initiator: 10g of BPO (dibenzoyl peroxide) is slowly added into 40mL of chloroform at room temperature, the solid is dissolved by stirring, insoluble impurities are removed by filtration, then the filtrate is poured into 100mL of pre-cooled methanol, the mixture is taken out after being stored for 3 hours in a refrigerator at the temperature of 4 ℃, the obtained mixture is subjected to suction filtration, white crystals are washed for multiple times by using methanol, and the product is stored in a sealed light-resistant small bottle after being dried in vacuum.
Pretreatment of cellulose: accurately weighing 1g of microcrystalline cellulose, measuring 10mL of acetone and deionized water, sequentially adding into a four-necked flask, and soaking for 12 hours under the action of magnetic stirring.
Monomer pretreatment: 50mL of butyl acrylate is measured in a separating funnel, 10mL of pre-prepared sodium hydroxide solution with the mass fraction of 5% is used for multiple alkaline washing until the lower layer liquid is not discolored, the residual sodium hydroxide is removed by washing with deionized water, finally, the activated molecular sieve is added to remove the residual moisture in the BA monomer, and the BA monomer is placed in a brown bottle for storage.
2. Synthesis of cellulose graft Polymer (butyl acrylate-N, N' -methylenebisacrylamide)
A 250mL four-necked flask, in which cellulose was previously soaked, was placed in a thermostatic water bath of a prescribed temperature, and purged with nitrogen gas for 30 minutes. Firstly adding 0.13g of initiator, initiating for 30min, then dripping 1g of BA monomer, dripping 0.35wt% of MBA (N, N' -methylene bisacrylamide) and 6g of BA (butyl acrylate) monomer after 0.5h, continuing to react for 4h, carrying out the whole reaction process under the stirring effect and the protection of nitrogen, carrying out suction filtration after the reaction is finished to obtain a crude product, washing with acetone and deionized water for multiple times to remove unreacted initiator and monomer, then carrying out Soxhlet extraction in acetone for 24h, drying the product in a vacuum drying oven at 60 ℃ to constant weight, and finally weighing the dried product.
Example 2
According to the method for preparing the cellulose-based oil absorbing material shown in fig. 1 to 14, the method comprises the following steps:
1. pretreatment process
Pretreatment of an initiator: 10g of BPO (dibenzoyl peroxide) is slowly added into 40mL of chloroform at room temperature, the solid is dissolved by stirring, insoluble impurities are removed by filtration, then the filtrate is poured into 100mL of pre-cooled methanol, the mixture is taken out after being stored for 3 hours in a refrigerator at the temperature of 4 ℃, the obtained mixture is subjected to suction filtration, white crystals are washed for multiple times by using methanol, and the product is stored in a sealed light-resistant small bottle after being dried in vacuum.
Pretreatment of cellulose: accurately weighing 1g of microcrystalline cellulose, measuring 10mL of acetone and deionized water, sequentially adding into a four-necked flask, and soaking for 12 hours under the action of magnetic stirring.
Monomer pretreatment: 50mL of butyl acrylate is measured in a separating funnel, 10mL of pre-prepared sodium hydroxide solution with the mass fraction of 5% is used for multiple alkaline washing until the lower layer liquid is not discolored, the residual sodium hydroxide is removed by washing with deionized water, finally, the activated molecular sieve is added to remove the residual moisture in BA (butyl acrylate) monomers, and the mixture is placed in a brown bottle for storage.
2. Synthesis of cellulose graft Polymer (butyl acrylate-N, N' -methylenebisacrylamide)
A 250mL four-necked flask, in which cellulose was previously soaked, was placed in a thermostatic water bath of a prescribed temperature, and purged with nitrogen gas for 30 minutes. Firstly adding 0.09g of initiator, initiating for 30min, then dripping 1g of BA monomer, dripping 0.50wt% of MBA (N, N' -methylene bisacrylamide) and 7g of BA monomer after 0.5h, continuing to react for 4h, carrying out the whole reaction process under the stirring effect and the protection of nitrogen, carrying out suction filtration after the reaction is finished to obtain a crude product, washing with acetone and deionized water for multiple times to remove unreacted initiator and monomer, carrying out Soxhlet extraction in acetone for 24h, drying the product in a vacuum drying oven at 60 ℃ until the weight is constant, and finally weighing the dried product.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Test example:
the IR spectra of microcrystalline cellulose, cell-g-PBA, cell-g-P (BA-MBA) and P (BA-MBA) in example 1 are shown in FIG. 1.
The infrared spectrum of microcrystalline cellulose is shown in curve (a) at 3335cm -1 The nearby broad peak is the telescopic vibration absorption peak of hydroxyl H-O bond, 2893cm -1 The weak peak at 1159cm is the stretching vibration absorption peak of methylene C-H bond -1 Weak C-O-C bond symmetrical telescopic vibration absorption peaks appear. In contrast to microcrystalline cellulose, the infrared spectra of Cell-g-PBA and Cell-g-P (BA-MBA) show some new absorption peaks: 2959cm -1 And 2874cm -1 Two asymmetric and symmetric telescopic vibration absorption peaks of methyl and methylene C-H bond at 1730cm -1 The strong absorption peak is caused by stretching vibration of ester carbonyl C=O bond, 1450cm -1 The asymmetric flexural vibration absorption peak of the methyl C-H bond is shown. These new absorption peaks substantially coincide with the characteristic absorption peaks appearing in the P (BA-MBA) infrared spectrum, demonstrating that the P (BA-MBA) copolymer has been successfully grafted to the surface of microcrystalline cellulose. Further, it was found by comparison that 1159cm in the curve (b) (c) -1 The intensity of the symmetrical telescopic vibration absorption peak of the C-O-C bond is obviously higher than that of microcrystalline cellulose, because the C-O-C content in the ester group is increased due to the grafting of butyl acrylate. Since the graft polymerization product Cell-g-P (BA-MBA) has the characteristic absorption peaks of microcrystalline cellulose and P (BA-MBA), the graft polymerization reaction between butyl acrylate and N, N' -methylenebisacrylamide and cellulose can be judged to occur under the action of an initiator BPO, namely, the Cell-g-P (BA-MBA) is successfully prepared.
The scanning electron microscope images of the microcrystalline cellulose, cell-g-PBA, cell-g-P (BA-MBA) and P (BA-MBA) in example 1 are shown in FIG. 2, wherein FIG. 2 (a) is a scanning electron microscope image of the microcrystalline cellulose; FIG. 2 (b) is a scanning electron microscope image of Cell-g-PBA; FIG. 2 (c) is a scanning electron microscope image of Cell-g-P (BA-MBA); FIG. 2 (d) is a scanning electron microscope image of P (BA-MBA).
As can be seen from FIG. 2 (a), the original microcrystalline cellulose has a rod shape and a nonuniform size, and the longitudinal length is less than or equal to 25 μm, and further enlarged pictures show that the microcrystalline cellulose has a nearly smooth surface and slight wrinkles. As can be seen from fig. 2 (b) and 2 (c), the polymer chains cross-link and entangle, and accumulate on the surface of microcrystalline cellulose, making the surface of Cell-g-PBA and Cell-g-P (BA-MBA) more rough. FIG. 2 (d) shows the surface morphology of P (BA-MBA), which is very smooth. As can be seen from the enlarged picture in fig. 2 (c), the surface of the Cell-g-P (BA-MBA) has rich wrinkles and a small amount of pore structures, so that oil molecules can enter the interior of the material more easily, and the existence of the three-dimensional network structure increases the specific surface area of the oil absorbing material, thereby improving the oil absorbing performance of the Cell-g-P (BA-MBA).
The contents of three elements C, H, N in microcrystalline cellulose, cell-g-PBA, cell-g-P (BA-MBA) and P (BA-MBA) were tested by elemental analysis, and the test results are shown in Table 1.
Table 1 shows the C, H, N content of microcrystalline cellulose, cell-g-PBA, cell-g-P (BA-MBA) and P (BA-MBA).
Wherein the content of C and H in the Cell-g-PBA is significantly higher than that of microcrystalline cellulose, further proving that butyl acrylate has been successfully grafted onto microcrystalline cellulose. In addition, N element was also detected in Cell-g-P (BA-MBA) and P (BA-MBA), demonstrating that MBA monomer was also successfully grafted onto cellulose. In order to ensure the oil absorption performance of the oil absorption material, only a small amount of MBA monomer is used in the preparation process, so that the element analysis only detects the existence of a small amount of N element.
As shown in fig. 3, cell-g-P (BA-MBA) has been demonstrated to have hydrophobic and oleophilic properties by a water contact angle test, wherein fig. 3 (a) is a water contact angle test result of microcrystalline cellulose; FIG. 3 (b) is the water contact angle test result of Cell-g-PBA; as shown in fig. 3 (a), the microcrystalline cellulose has a water contact angle of 18.9 °, because a large number of hydroxyl groups exist on the surface of the microcrystalline cellulose to make it hydrophilic. Fig. 3 (b) shows that the water contact angle of Cell-g-P (BA-MBA) is 101.3 °, because when hydrophobic BA monomer is graft polymerized onto microcrystalline cellulose, the formed polymer chains are entangled and accumulated to the surface thereof, so that Cell-g-P (BA-MBA) exhibits good hydrophobic and oleophilic properties.
Oil absorption performance study:
the adsorption capacity of Cell-g-P (BA-MBA) for 10 different oils and organic solvents was determined by weighing. Firstly, weighing dry oil absorption material with the mass m1 (about 0.1 g) and placing the dry oil absorption material in a non-woven fabric bag, completely immersing the bag in 150mL of oil or organic solvent to be tested at room temperature, taking out the bag immediately after absorbing oil for 12h, draining for 1min until no liquid drops drop, wiping residual oil on the surface of a sample by using filter paper, immediately weighing and recording the mass m2 of the residual oil, and minimizing the influence of volatilization of the oil and the organic solvent on experimental results. The adsorption capacities of Cell-g-P (BA-MBA) for different oils and organic solvents were calculated according to the following formula:
wherein Q (g.g) -1 ) Represents the adsorption capacity of the dry oil absorbing material per unit mass, and m1 (g) and m2 (g) represent the mass of the oil absorbing material before and after adsorption, respectively.
A control experiment was set up under the same conditions with microcrystalline cellulose as the oil absorbing material.
The adsorption of Cell-g-P (BA-MBA) and microcrystalline cellulose on different oils and organic solvents was repeated three times under the same experimental conditions, and the final average was taken as the experimental result.
The adsorption capacities of the Cell-g-P (BA-MBA) prepared in example 1 for various oils and organic solvents are shown in FIGS. 4 and 5, and the maximum average adsorption capacity for chloroform is 37.55 g.g -1 The maximum average adsorption capacity of toluene is 18.72 g.g-1, and the maximum average adsorption capacity of acetone is 9.46 g.g -1 The maximum average adsorption capacity for N, N-dimethylformamide was 7.37 g.g -1 The maximum average adsorption capacity to gasoline is 10.41 g.g -1 The maximum average adsorption capacity of the oil for normal hexane, diesel oil, soybean oil, engine oil and vacuum pump oil is 0.54 g.g -1 -0.90g·g -1 Between them.
The adsorption kinetics experiment was performed on the Cell-g-P (BA-MBA) prepared in example 1, a known weight of dry Cell-g-P (BA-MBA) was weighed and placed in a non-woven fabric bag, the non-woven fabric bag was completely immersed in the oil or organic solvent (chloroform, toluene and gasoline) to be tested, and the non-woven fabric bag was taken out, weighed and recorded at different time points, respectively, the adsorption capacity of Cell-g-P (BA-MBA) at each time point was calculated, and the adsorption capacity change curve was plotted with time. Three experiments were repeated at the same conditions at each time point, and the average value was finally taken as an experimental result.
The adsorption capacity of Cell-g-P (BA-MBA) prepared in example 1 shows the same trend as shown in FIGS. 6 and 7: the adsorption rate of chloroform, toluene and gasoline is relatively fast in the first 180min, the increase of the oil absorption capacity in 7h is obviously reduced, the adsorption rate is slowed down, and the adsorption process almost reaches equilibrium after the contact time reaches 10 h.
The adsorption capacities of the Cell-g-P (BA-MBA) prepared in example 1 were compared with those of several other oil absorbing materials, and the results are shown in Table 2.
Table 2 comparison of adsorption capacities with several other oil absorbing materials
The results of the quasi-first order kinetics and quasi-second order kinetics fitting of Cell-g-P (BA-MBA) prepared in example 1 are shown in FIGS. 8 and 9, k 1 (min -1 )、k 2 (g·g -1 min -1 )、Q e,calc (g·g -1 ) Specific values of the parameters associated with the R2 kinetic model are listed in table 3.
Table 3 shows parameters related to the quasi-primary and quasi-secondary dynamics models
Adsorption isotherm experiments were performed on Cell-g-P (BA-MBA) prepared in example 1: pre-disposition of initial concentrations of 1.5, 3.0, 4.5, 6.0, 7.5, 9.0, 10.5, 12.0gL before experiment -1 0.05g of Cell-g-P (BA-MBA) was weighed and placed in 50mL glass bottles, and 50mL of oil-water mixtures of different concentrations were added to the glass bottles (minimal headspace was reserved to prevent gasoline evaporation). The glass bottle is placed in a water bath constant temperature shaking box at 30 ℃ and is subjected to constant temperature shaking for 12 hours at the speed of 100rpm, and then the oil absorption material after oil absorption is weighed, and the adsorption capacity and the gasoline equilibrium concentration of the oil absorption material are calculated. Each set of experiments was repeated three times under the same conditions, and the average value was finally taken as the experimental result. Experimental results were performed by means of two adsorption isotherm models, langmuir and FreundlichAnd (5) line fitting.
Table 4 shows parameters relating to Langmuir and Freundlich adsorption isotherms
Adsorption thermodynamic experiments were performed on Cell-g-P (BA-MBA) prepared in example 1:0.05 g of Cell-g-P (BA-MBA) is weighed and placed in a 50mL glass bottle, and 50mL of a known concentration of oil-water mixture is added to the glass bottle (with minimal headspace reserved to prevent gasoline evaporation). The glass bottles are respectively placed in water bath constant temperature shaking boxes with the temperatures of 293.15, 303.15, 313.15 and 323.15K, and are adsorbed for 12 hours by constant temperature shaking at the speed of 100 rpm. The oil-absorbed Cell-g-P (BA-MBA) was then weighed and its adsorption capacity and gasoline equilibrium concentration were calculated.
Table 5 shows the thermodynamic parameters of the adsorption of gasoline by Cell-g-P (BA-MBA).
The actual oil-water separation performance test was performed on the Cell-g-P (BA-MBA) prepared in example 1: 5mL of toluene that had been stained with Sudan III was added dropwise to a beaker containing 100mL of water, after which 0.3g of Cell-g-P (BA-MBA) was weighed into the oil-water mixture, which was observed and photographed every two minutes for recording. The Cell-g-P (BA-MBA) prepared in the example 1 always floats on the water surface in the oil absorption process, shows good buoyancy, can completely remove toluene on the water surface within about 12 minutes, and shows excellent practical application value.
The Cell-g-P (BA-MBA) prepared in example 1 was subjected to regeneration performance test: 0.1g of oil absorbing material is weighed, placed in a non-woven bag, kept stand at room temperature in 150mL of gasoline for 12 hours for absorption, taken out, drained, weighed and recorded, and the absorption capacity is calculated according to the formula. The saturated oil absorbing material was then immersed in 30mL of n-hexane solution for 5h for soaking and elution, after which it was taken out, drained and weighed and the mass recorded. The same procedure was repeated 15 times in gasoline and n-hexane to obtain the adsorption capacity of Cell-g-P (BA-MBA) after each adsorption and desorption, and each experiment was repeated three times under the same conditions, and the average value was finally taken as the experimental result.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (4)
1. A method for preparing a cellulose-based material for absorbing oily wastewater, comprising the steps of:
step 1, dropwise adding an initiator into cellulose suspension, and then continuously dropwise adding butyl acrylate monomer to carry out grafting reaction;
step 2, dropwise adding N, N ʹ -methylene bisacrylamide and butyl acrylate monomers into the step 1, and continuing to perform polymerization reaction to obtain the cellulose-based material;
the preparation method of the cellulose suspension in the step 1 comprises the following steps: soaking microcrystalline cellulose in a mixed solution of acetone and water for 12 hours to obtain a cellulose suspension;
the initiator in the step 1 is dibenzoyl peroxide, and the initiator is pretreated before use, and the pretreatment method comprises the following steps: purifying dibenzoyl peroxide by adopting a recrystallization method;
the butyl acrylate monomer in the step 1 and the step 2 is pretreated before use, and the pretreatment method comprises the following steps: alkali washing is carried out on butyl acrylate monomer by using sodium hydroxide to obtain refined butyl acrylate monomer;
the grafting reaction temperature in the step 1 is 70 ℃;
the mass ratio of microcrystalline cellulose to dibenzoyl peroxide in the step 1 is 1:0.13, wherein the dosage of dibenzoyl peroxide is 0.13g;
the mass ratio of microcrystalline cellulose to butyl acrylate monomer in the step 1 and the step 2 is 1:7;
the dosage of the butyl acrylate monomer in the step 1 and the step 2 is 7g, wherein the dosage of the butyl acrylate monomer in the step 1 is 1g, and the dosage of the butyl acrylate monomer in the step 2 is 6g;
the mass ratio of the butyl acrylate monomer to the N, N ʹ -methylene bisacrylamide in the step 2 is 1:0.0035; wherein the amount of N, N ʹ -methylenebisacrylamide is 0.35wt% of the amount of the butyl acrylate monomer.
2. The method for preparing a cellulose-based material absorbing oily wastewater according to claim 1, wherein the step 2 is further followed by a step 3, and the step 3 is that after the cellulose-based material in the step 2 is washed with acetone and deionized water, the soxhlet extraction is performed for 24 hours, and after the washing is performed with a vacuum drying oven, the final product is obtained.
3. The method for preparing a cellulose-based material absorbing oily wastewater according to claim 2, wherein the steps 1, 2 and 3 are all performed under the protection of nitrogen.
4. Use of a cellulose-based material absorbing oily wastewater prepared by the steps of any one of claims 1 to 3 in the treatment of oily wastewater.
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| CN101565488A (en) * | 2009-06-01 | 2009-10-28 | 新疆大学 | Preparation method of cellulose-based oil-absorption material |
| CN101565487A (en) * | 2009-06-01 | 2009-10-28 | 新疆大学 | Method for preparing oil absorption material from cellulose and alkyl acrylate by graft copolymerization |
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| CN101565488A (en) * | 2009-06-01 | 2009-10-28 | 新疆大学 | Preparation method of cellulose-based oil-absorption material |
| CN101565487A (en) * | 2009-06-01 | 2009-10-28 | 新疆大学 | Method for preparing oil absorption material from cellulose and alkyl acrylate by graft copolymerization |
| CN103304820A (en) * | 2013-03-15 | 2013-09-18 | 山东大学（威海） | Preparation method of efficient polyethyleneimine modified cellulose-based heavy metal adsorbent |
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