CN106345424A - Preparation method and application of hydroxypropyl guar gum/nanocellulose cross-linked adsorption film - Google Patents
Preparation method and application of hydroxypropyl guar gum/nanocellulose cross-linked adsorption film Download PDFInfo
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- CN106345424A CN106345424A CN201610889762.0A CN201610889762A CN106345424A CN 106345424 A CN106345424 A CN 106345424A CN 201610889762 A CN201610889762 A CN 201610889762A CN 106345424 A CN106345424 A CN 106345424A
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- Prior art keywords
- cellulose
- guar gum
- nano
- hydroxypropyl guar
- film
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Links
- 229920013818 hydroxypropyl guar gum Polymers 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000001179 sorption measurement Methods 0.000 title abstract description 20
- 229920001046 Nanocellulose Polymers 0.000 title abstract 4
- 238000004132 cross linking Methods 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 20
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims abstract description 17
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims abstract description 17
- 239000008108 microcrystalline cellulose Substances 0.000 claims abstract description 17
- 229940016286 microcrystalline cellulose Drugs 0.000 claims abstract description 17
- 238000004108 freeze drying Methods 0.000 claims abstract description 12
- 230000032050 esterification Effects 0.000 claims abstract description 10
- 238000005886 esterification reaction Methods 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000000376 reactant Substances 0.000 claims abstract description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 7
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims abstract description 7
- 239000011976 maleic acid Substances 0.000 claims abstract description 7
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000001913 cellulose Substances 0.000 claims description 85
- 229920002678 cellulose Polymers 0.000 claims description 83
- 239000000975 dye Substances 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 24
- 229910001385 heavy metal Inorganic materials 0.000 claims description 19
- 235000010980 cellulose Nutrition 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 16
- 229920002907 Guar gum Polymers 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 239000000665 guar gum Substances 0.000 claims description 7
- 235000010417 guar gum Nutrition 0.000 claims description 7
- 229960002154 guar gum Drugs 0.000 claims description 7
- -1 hydroxypropyl Chemical group 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000002699 waste material Substances 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 2
- 238000010494 dissociation reaction Methods 0.000 claims description 2
- 230000005593 dissociations Effects 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 150000008064 anhydrides Chemical class 0.000 claims 1
- 238000011001 backwashing Methods 0.000 claims 1
- 239000012429 reaction media Substances 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 229960000907 methylthioninium chloride Drugs 0.000 abstract description 10
- 150000002500 ions Chemical class 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000004140 cleaning Methods 0.000 abstract description 3
- 238000007493 shaping process Methods 0.000 abstract description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 abstract 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 abstract 1
- 230000000274 adsorptive effect Effects 0.000 abstract 1
- 229910001431 copper ion Inorganic materials 0.000 abstract 1
- ZXJXZNDDNMQXFV-UHFFFAOYSA-M crystal violet Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1[C+](C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 ZXJXZNDDNMQXFV-UHFFFAOYSA-M 0.000 abstract 1
- 239000010408 film Substances 0.000 description 53
- 239000000463 material Substances 0.000 description 18
- 238000005516 engineering process Methods 0.000 description 9
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 9
- 229920005615 natural polymer Polymers 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- 239000012528 membrane Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000003344 environmental pollutant Substances 0.000 description 6
- 231100000719 pollutant Toxicity 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229920002521 macromolecule Polymers 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 241000219112 Cucumis Species 0.000 description 4
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 238000010309 melting process Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011435 rock Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920001282 polysaccharide Polymers 0.000 description 3
- 239000012086 standard solution Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- 244000007835 Cyamopsis tetragonoloba Species 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229920002201 Oxidized cellulose Polymers 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002121 nanofiber Substances 0.000 description 2
- 229940107304 oxidized cellulose Drugs 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
- 101100136092 Drosophila melanogaster peng gene Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical compound N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000002519 galactosyl group Chemical group C1([C@H](O)[C@@H](O)[C@@H](O)[C@H](O1)CO)* 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000002103 nanocoating Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/08—Polysaccharides
- B01D71/10—Cellulose; Modified cellulose
-
- 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
-
- 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
- C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Analytical Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses s preparation method of a hydroxypropyl guar gum/nanocellulose cross-linked adsorption film. The method takes hydroxypropyl guar gum and microcrystalline cellulose as main raw materials, and comprises the steps: thinning the microcrystalline cellulose in a nano grinder and a high-strength ultrasonic wave generator successively to prepare nanocellulose, then respectively dispersing and dissolving the nanocellulose and hydroxypropyl guar gum in maleic acid, then adding maleic anhydride and sodium hypophosphite, stepwise heating to carry out esterification and cross-linking reaction, centrifuging and defoaming the reactant, shaping the reactant in a mold, forming a film by drying, and cleaning and freeze-drying the film to obtain the adsorption film. The film prepared by the method is light yellow and transparent, has good adsorptive capacity on copper ions, zinc ions, led ions, methylene blue and methyl violet, and simultaneously has higher mechanical properties.
Description
Technical field
The present invention relates to a kind of natural polymer adsorbed film being capable of integrated treatment heavy metal ion and organic dyestuff waste liquid
Technology, the preparation method and application of especially a kind of hydroxypropyl guar gum/nano-cellulose crosslinking adsorbed film, belong to sky
So macromolecule modified field of material technology.
Background technology
With the fast development of process of industrialization, the dirt such as the plurality of heavy metal containing of many plant emissions and organic dyestuff
The waste water of dye thing drastically increases, and it is received environment cause serious pollution.Generally, heavy metal refers to that those can bring dirt
Dye and the metal of toxicity problem, such as lead, chromium, copper, zinc, nickel, hydrargyrum etc.[1].Different from most organic pollutants, heavy metal is same
When be present in rock and Ore；Under field conditions (factors), its in soil, deposit, the concentration in water body and vivo is all answered
This was maintained in normal range.But the production because of the mankind and life make substantial amounts of toxic heavy metal enter in environment, once
Beyond environment metabolic capacity, ecosystem will be destroyed, seriously threaten the mankind and hydrobiological presence[2].On the other hand,
Organic dyestuff is also the pollutant that a class poses a great threat to.In the many decades in past, a large amount of manufactures of dyestuff and use,
Environment is created with very big impact.Even if in very low concentration, waste water from dyestuff also has very high colourity, and this can be to aquatic ecological
System brings poisonous effect.Organic dyestuff has the enomosphore structure such as benzene, naphthalene, anthracene, quinone mostly, this make its in water environment very
Difficulty is biodegradable[3].With the demand more and more higher to color aspect for the people, the species of dyestuff also increases quick, and
Developing to the direction of anti-light solution property, antioxidation and antibiont degraded so that the intractability of waste water from dyestuff also increases continuous
Greatly[4].
At present, the method processing pollutant effluents has chemical precipitation, membrane filtration, coagulation-flocculation, air supporting, electroreduction, ion
Exchange and adsorb etc.[5].Comparatively speaking, absorption method is simple to operate with it, removes efficiently, process pollutant kind is many, low dense useless
Water treatment efficiency is good, becomes the more reliable water technology of one kind.For conventional synthesis adsorbent, natural polymer
Base adsorbent (generally presented in gel or film) has the high and low dense waste liquid of reactivity of wide material sources and pollutant
Treatment effect is good, easily separated the features such as, there is in terms of wastewater treatment and recovery the advantage of uniqueness, become current heavy metal and have
The emphasis of machine dye sorbent research[6], some of them natural macromolecular material and its material modified be applied in water body pollution
The removal of thing.
Cellulose is to be distributed the widest and stock number natural polymer the abundantest in nature, is the master of plant fiber material
Want chemical composition, account for 35% ~ 50%, global annual output is 200,000,000,000 tons[7].Cellulose has amorphous region and crystal region to constitute,
Using chemical reaction, for example, acid hydrolysis, oxidation reaction etc., its amorphous region of degrading, separate in combination with mechanical treatment and received
Cellulose crystals in the range of metrical scale.Nano-cellulose has that density is low, specific surface area is big, intensity is high and biodegradable
Property etc. is so as to have larger development prospect in terms of the cutting edge technologies such as nano coating, filler and film preparation[8].Hydroxypropyl guar
Glue is a kind of water-soluble nonionic polysaccharide[9], it is in the basic conditions, etherification modified institute is carried out by expoxy propane to guar gum
Product, its main chemical composition is similar to guar gum, is d type mannose and is formed by connecting as main chain by β-(1-4), with
D type galactosyl is the macromolecule of side chain.Compared with guar gum, hydroxypropyl guar gum has more preferable hydrophilic and film forming
Property, it is obtained in terms of crude oil recovery, food industry, coating and ammunition formula and be widely applied.Hydroxypropyl guar gum and
Nano-cellulose top layer is respectively provided with substantial amounts of activity hydroxy, and therefore, both have the preferable compatibility, thus preparing homogenizing
Composite, and can preferably play the intrinsic advantage of two kinds of natural polymers.It will be appreciated, however, that passing through the hydrogen between-oh
The composite membrane mechanical strength that key combination is formed by connecting is not high, easily disintegrate dispersion in aqueous medium, and pollutant absorbability
Weaker the shortcomings of, is so that the application of this hybrid films is very restricted.Not enough for these, this seminar is drawn by research
From suitable cross-linking agent, while introducing the active function groups that other have absorbability, two kinds of macromolecules are carried out crosslinking
In conjunction with the hydroxypropyl guar gum/nano-cellulose adsorbed film of excellent performance can be prepared.
The heavy metal in water causing in conjunction with modern industry and the pollution problem of organic dyestuff, the application describes in detail with hydroxypropyl melon
That glue and Microcrystalline Cellulose prepare the hydroxypropyl guar gum of two kinds of pollutant of efficient absorption/nano-cellulose cross linking membrane for raw material
Technological process.The comprehensive utilization ratio of the natural polymers such as guar gum, cellulose not only can be improved, and be heavy metal and have
One feasible program of the offer of the adsorbing and removing in machine waste water from dyestuff.
List of references
[1] j.wang, b.l.chen. adsorption and coadsorption of organic pollutants
and a heavy metal by grapheme oxide and reduced grapheme materials [j].
chemical engineering journal, 2015, 281:379-388.
[2] m.j. xie, l.x. zeng, q.y. zhang, y.kang, h.j.xiao, y.n.peng,
x.c.chen, j.w.luo. synthesis and adsorption behavior of magnetic microspheres
based on chitosan/organic rectorite for low-concentration heavy metal removal
[j]. journal of alloys and compounds, 2015, 647: 892-905.
[3] q.w.lin, m.f.gao, j.l.chang, h.z.ma. adsorption properties of
crosslinking carboxymethyl cellulose grafting dimethyldiallylammonium
chloride for cationic and anionic dyes [j]. carbohydrate polymers, 2016, 151:
283-294.
[4] v.nair, r.vinu. peroxide-assisted microwave activation of pyrolysis
char for adsorption of dyes from wastewater [j]. bioresource technology,
2016, 216:511-519.
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Content of the invention
Adsorbed film due to processing heavy metal and organic dyestuff waste liquid depends on synthesis class or semi-synthetic family macromolecule,
The exploitation having the environmentally friendly adsorbed film with good physical behavior concurrently with natural polymer as main matrix does not also have enough
Basis and technology support.Therefore, the invention provides a kind of can integrated treatment heavy metallic salt and organic dyestuff hydroxypropyl
The preparation method of guar gum/nano-cellulose crosslinking adsorbed film, the method utilizes aboundresources, develops extensive crystallite fibre
Dimension element and new type natural polymeric derivative --- hydroxypropyl guar gum be raw material, through nano-level grinder repeatedly grind with ultrasonic
Microcrystalline Cellulose is refined as nano-cellulose by ripple dissociation, and hydroxypropyl guar gum is dissolved in maleic acid, adds nanometer
Cellulose, maleic anhydride and sodium hypophosphite, after being uniformly dispersed, zone heating is esterified and cross-linking reaction, after cooling room temperature, hands over
Connection thing shapes, cold dry, cleaning, re-dry, obtain hydroxypropyl guar gum/nano-cellulose crosslinking adsorbed film, expand melon further
Your gum derivative and the application of cellulose, make such environmentally friendly regeneration macromolecule obtain more extensive high-valued profit
With.
Realize the process technology scheme that the object of the invention takes as follows:
(1) Microcrystalline Cellulose priority adopts grinder and ultrasonic Treatment, obtains nano-cellulose；
(2) dissolving and dispersion hydroxypropyl guar gum, the nano-cellulose of step (1) and cross-linking agent (Herba Kalimeridis acid in Herba Kalimeridis acid
Acid anhydride and sodium hypophosphite), and temperature-gradient method heating be esterified and cross-linking reaction；
(3) reactant is centrifuged de-bubble, and pours in mould, shape, be dried, form solid film, sample deionized water is carried out
Cyclic washing, after drying, obtain lamellar hydroxypropyl guar gum/nano-cellulose crosslinking adsorbed film.
The present invention is capable of the hydroxypropyl guar gum/nano-cellulose cross linking membrane of comprehensive Adsorption of Heavy Metal Ions and organic dyestuff
Preparation method, concrete operations are as follows:
(1) melting process of nano-cellulose: add water in Microcrystalline Cellulose, be allowed to mass concentration and adjust to 0.5 ~ 5.0%,
Put in nano-level grinder, regulation speed of grinding plate is 1000 ~ 3000rpm, mill spacing is -10 ~ -80 μm, circular grinding 10 ~ 60
Secondary, after being disposed, collect sample, ice-water bath proceeds supersound process, wherein, and ultrasonic power 100 ~ 1200w, surpass
Sound wave acts on 1 ~ 5min every 1 ~ 5min, and total action time is 10 ~ 60min, and the sample after process passes through 5000～
10000rpm is centrifuged 10～30min, collects supernatant liquid, lyophilization is completely dried to material, obtains final product nano-cellulose；
(2) esterification of hydroxypropyl guar gum/nano-cellulose and cross-linking reaction: add hydroxypropyl guar gum and step in maleic acid
Suddenly the nano-cellulose of (1), is sufficiently stirred for, in hydroxypropyl guar gum dissolving, and on the premise of nano-cellulose is uniformly dispersed,
Add maleic anhydride and sodium hypophosphite, agitating heating boiling 10 ~ 30min, sealing, be heated to 120 ~ 150 DEG C in a kettle. instead
Answer 20 ~ 60min, wherein, mass volume ratio concentration in reaction system for the hydroxypropyl guar gum is 3 ~ 20%, hydroxypropyl guar gum:
The mass ratio of nano-cellulose is 1:0.005 ~ 1:0.5 (g/g), maleic anhydride quality: over dry nano-cellulose and hydroxypropyl melon
Your glue quality sum is 2.0 ~ 10.0 (g/g), and sodium hypophosphite consumption is the 1 ~ 10% of maleic anhydride quality；After esterification terminates,
Reaction vessel is put in frozen water and is quickly down to room temperature, continuously add over dry nano-cellulose and hydroxypropyl guar gum quality sum 8 ~
25% sodium hypophosphite, continues after sealing to react 10 ~ 20min at 130 ~ 170 DEG C, after cross-linking reaction terminates, cooling, and standby；
(3) preparation process of hydroxypropyl guar gum/nano-cellulose cross linking membrane: be down to the reactant of room temperature 7000～
It is centrifuged 15～30min under 15000rpm, remove undissolved cellulose and bubble, collect and obtain clear liquid；Clear liquid is taken to pour mould into
In, shape, be dried, form solid film, sample deionized water carries out cyclic washing, lyophilization, obtains lamellar hydroxypropyl melon
The crosslinked adsorbed film of your glue/nano-cellulose.
The present invention another object is that hydroxypropyl guar gum/nano-cellulose crosslinking adsorbed film application that said method is obtained
Processing containing in heavy metal ion, organic dyestuff waste liquid.
The invention has the beneficial effects as follows: using hydroxypropyl guar gum and Microcrystalline Cellulose as preparing natural polymer adsorbed film
Main raw material(s), dissociated Microcrystalline Cellulose, and centrifugation by mechanical lapping and ultrasound wave, dialysis cleaning lyophilization,
Obtain nano-cellulose, gained nano-cellulose is dispersed or dissolved in horse with hydroxypropyl guar gum, maleic anhydride and sodium hypophosphite
In sour, zone heating is esterified and cross-linking reaction, through centrifugation de-bubble, shaping, is dried, obtains Adsorption of Heavy Metals and have engine dyeing
Hydroxypropyl guar gum/nano-cellulose the cross linking membrane of material.Natural polymer subclass adsorbed film has synthesis high score subclass adsorbing material
General character, can be in waste liquid produced by multiple industry such as mining, metallurgy, machine-building, weaving, printing and dyeing, papermaking and printing
Process aspect can play good application prospect.Meanwhile, this natural polymer subbase adsorbed film is also equipped with hypotoxicity, good
Absorption/desorption performance, the relatively advantage such as high-mechanical property and environment friendly, are that a class of mainstream development now is new, green
Functional material.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but the scope of the present invention be not limited to described interior
Hold.
Embodiment 1: the preparation method of this hydroxypropyl guar gum/nano-cellulose crosslinking adsorbed film, concrete operations are as follows:
(1) melting process of nano-cellulose
Weigh 5.6g and air-dry Microcrystalline Cellulose (if Microcrystalline Cellulose mass dryness fraction is 90%, 5g over dry material/90%=5.6g air-dries material), turn
Move to and add 1000ml deionized water in glass beaker so as to concentration is adjusted to 0.5%, pour in nano-level grinder, adjust mill
Rotating speed is 1000rpm, and mill spacing is -10 μm, circular grinding 10 times, after being disposed, collects sample, continues in ice-water bath
Carry out supersound process, set ultrasonic power 100w, every 1min interval 1min, total contribution time 10min, after process for ultrasound wave
Sample by 5000rpm be centrifuged 10min, collect supernatant liquid, lyophilization is completely dried to material, obtains final product nanofiber
Element；Through dynamic laser particle size analyzer determination, the number of products therefrom all a size of 80 ~ 100nm under this process conditions；
(2) esterification of hydroxypropyl guar gum/nano-cellulose and cross-linking reaction
Add 3g hydroxypropyl guar gum (concentration 3%) in the maleic acid of 100ml, and the nano-cellulose of 0.015g step (1)
(hydroxypropyl guar gum: the quality of nano-cellulose is 1:0.005 g/g), is sufficiently stirred for, fully dissolves in hydroxypropyl guar gum
On the premise of, add 6.03g maleic anhydride (maleic anhydride consumption: over dry hydroxypropyl guar gum and nano-cellulose gross mass are
2.0 g/g) and 0.06g sodium hypophosphite (sodium hypophosphite consumption is the 1% of maleic anhydride quality), agitating heating boiling 10min, close
Envelope, is heated to 120 DEG C of reaction 20min, after esterification terminates, retort is put into and is quickly down to room in frozen water in a kettle.
Temperature, continuously adds the consumption of 0.24g(8%) sodium hypophosphite, continue after sealing at 130 DEG C react 10min, cross-linking reaction tie
Shu Hou, cooling, standby；
(3) preparation process of hydroxypropyl guar gum/nano-cellulose cross linking membrane
It is down to the reactant after room temperature and is centrifuged 15min under 7000rpm, remove undissolved cellulose and bubble, collect and obtain
Clear liquid, and take 10g clear liquid to pour in the circular die of a diameter of 20cm, shape, be dried, form solid film, sample deionization
Water carries out cyclic washing, lyophilization, obtains lamellar hydroxypropyl guar gum/nano-cellulose crosslinking adsorbed film；
(4) hydroxypropyl guar gum/nano-cellulose crosslinking adsorbed film
The mensure of adsorbed film physical strength: according to astm d638 method of testing, be that anti-tensile is strong using universal testing machine measurement result
Spend and draw high coefficient and be respectively 36mpa and 107%.
The determining adsorption method of heavy metallic salt: the desciccator diaphragm measuring peek piece 50mg is immersed in 1ml concentration respectively for 1mg/
The cuso of ml4、znso4With pb (no3)2In standard solution, under 25 DEG C of water temperatures, stand 72h, after adsorption equilibrium, take out film, wipe
Striping top layer liquid, detects the content of the heavy metal element of absorption in film respectively using elemental analyser.Result can obtain, and this film has
There is higher metal absorbability, adsorb 2.9mmol/g(cu respectively2+), 3.5mmol/g(zn2+) and 1.0mmol/g(pb2+).
Organic dyestuff determining adsorption method: measure take 50mg about desciccator diaphragm be immersed in respectively 100ml concentration be 25mg/
In the methylene blue (anionic dye) and crystal violet (cationic dye) solution of l, under the conditions of 25 DEG C, shaking table rocks 48h, inhales
After attached balance, take out film, detect that remaining dye content in each solution, its Methylene Blue and crystal violet are divided using UV, visible light
Light pass degree meter detects its content.Result can obtain, and this film has comparatively ideal organic dyestuff absorbability, to methylene blue and methyl
Purple absorbability respectively reaches 22mg/g and 175mg/g.
Embodiment 2: the preparation method of this hydroxypropyl guar gum/nano-cellulose crosslinking adsorbed film, concrete operations are as follows:
(1) melting process of nano-cellulose
Weigh 8.7g and air-dry Microcrystalline Cellulose (if Microcrystalline Cellulose mass dryness fraction is 92%, 8g over dry material/92%=8.7g air-dries material), turn
Move to and add 266ml deionized water in glass beaker so as to concentration is adjusted to 3.0%, pour in nano-level grinder, adjust mill
Rotating speed is 2000rpm, and mill spacing is -60 μm, circular grinding 40 times, after being disposed, collects sample, continues in ice-water bath
Carry out supersound process, set ultrasonic power 900w, ultrasound wave often acts on 3min interval 3min, total contribution time 30min, processes
Sample by 8000rpm be centrifuged 20min, collect supernatant liquid, lyophilization is completely dried to material, obtains final product nanofiber
Element；Through dynamic laser particle size analyzer determination, the number of products therefrom all a size of 50 ~ 80nm under this process conditions；
(2) esterification of hydroxypropyl guar gum/nano-cellulose and cross-linking reaction
Add 30g hydroxypropyl guar gum (concentration 15%) in the maleic acid of 200ml, and the nano-cellulose of 6g step (1)
(hydroxypropyl guar gum: the quality of nano-cellulose is 1:0.2 g/g), is sufficiently stirred for, in hydroxypropyl guar gum fully dissolving
Under the premise of, add 288g maleic anhydride (maleic anhydride consumption: over dry nano-cellulose with hydroxypropyl guar gum quality sum is
8.0 g/g) and 20.2g sodium hypophosphite (sodium hypophosphite consumption is the 7% of maleic anhydride quality), agitating heating boiling 20min, close
Envelope, is heated to 140 DEG C of reaction 35min, after esterification terminates, retort is put into and is quickly down to room in frozen water in a kettle.
Temperature, continuously adds the consumption of 7.2g(20%) sodium hypophosphite, continue after sealing at 160 DEG C react 15min, cross-linking reaction tie
Shu Hou, cooling, standby；
(3) preparation process of hydroxypropyl guar gum/nano-cellulose cross linking membrane
It is down to the reactant after room temperature and is centrifuged 20min under 10000rpm, remove undissolved cellulose and bubble, collect and obtain
Clear liquid, and take 80g clear liquid to pour in the circular die of a diameter of 85cm, shape, be dried, form solid film, sample deionization
Water carries out cyclic washing, lyophilization, obtains lamellar hydroxypropyl guar gum/nano-cellulose crosslinking adsorbed film；
(4) hydroxypropyl guar gum/nano-cellulose crosslinking adsorbed film
The mensure of adsorbed film physical strength: according to astm d638 method of testing, be that anti-tensile is strong using universal testing machine measurement result
Spend and draw high coefficient and be respectively 33mpa and 90%.
The determining adsorption method of heavy metallic salt: the desciccator diaphragm measuring peek piece 50mg is immersed in 1ml concentration respectively for 1mg/
The cuso of ml4、znso4With pb (no3)2In standard solution, under 25 DEG C of water temperatures, stand 72h, after adsorption equilibrium, take out film, wipe
Striping top layer liquid, detects the content of the heavy metal element of absorption in film respectively using elemental analyser.Result can obtain, and this film has
There is higher metal absorbability, adsorb 5.0mmol/g(cu respectively2+), 6.1mmol/g(zn2+) and 1.7mmol/g(pb2+).
Organic dyestuff determining adsorption method: measure take 50mg about desciccator diaphragm be immersed in respectively 100ml concentration be 25mg/
In the methylene blue (anionic dye) and crystal violet (cationic dye) solution of l, under the conditions of 25 DEG C, shaking table rocks 48h, inhales
After attached balance, take out film, detect that remaining dye content in each solution, its Methylene Blue and crystal violet are divided using UV, visible light
Light pass degree meter detects its content.Result can obtain, and this film has comparatively ideal organic dyestuff absorbability, to methylene blue and methyl
Purple absorbability respectively reaches 26mg/g and 220mg/g.
Embodiment 3: the preparation method of this hydroxypropyl guar gum/nano-cellulose crosslinking adsorbed film, concrete operations are as follows:
(1) melting process of nano-cellulose
Weigh 21.1g and air-dry Microcrystalline Cellulose (if Microcrystalline Cellulose mass dryness fraction is 95%, 20g over dry material/95%=21.1g air-dries material),
It is transferred in glass beaker and adds 400ml deionized water so as to concentration is adjusted to 5.0%, pour in nano-level grinder, adjust mill
Disk rotating speed is 3000rpm, and mill spacing is -80 μm, circular grinding 60 times, after being disposed, collects sample, in ice-water bath relaying
Continuous carry out supersound process, set ultrasonic power 1200w, ultrasound wave often acts on 5min interval 5min, total contribution time 60min,
The sample processing is centrifuged 30min by 10000rpm, collects supernatant liquid, lyophilization is completely dried to material, obtains final product nanometer
Cellulose；Through dynamic laser particle size analyzer determination, the number of products therefrom all a size of 28 ~ 50nm under this process conditions；
(2) esterification of hydroxypropyl guar gum/nano-cellulose and cross-linking reaction
Add 30g hydroxypropyl guar gum (concentration 20%) in the maleic acid of 150ml, and the nano-cellulose of 15g step (1)
(hydroxypropyl guar gum: the quality of nano-cellulose is 1:0.5 g/g), is sufficiently stirred for, in hydroxypropyl guar gum fully dissolving
Under the premise of, add 450g maleic anhydride (maleic anhydride consumption: over dry nano-cellulose with hydroxypropyl guar gum quality sum is
10.0 g/g) and 45g sodium hypophosphite (sodium hypophosphite consumption is the 10% of maleic anhydride quality), agitating heating boiling 30min, close
Envelope, is heated to 150 DEG C of reaction 60min, after esterification terminates, retort is put into and is quickly down to room in frozen water in a kettle.
Temperature, continuously adds the consumption of 11.3g(25%) sodium hypophosphite, continue after sealing at 170 DEG C react 20min, cross-linking reaction tie
Shu Hou, cooling, standby；
(3) preparation process of hydroxypropyl guar gum/nano-cellulose cross linking membrane
It is down to the reactant after room temperature and is centrifuged 30min under 15000rpm, remove undissolved cellulose and bubble, collect and obtain
Clear liquid, and take 100g clear liquid to pour in the circular die of a diameter of 100cm, shapes, is dried, form solid film, sample spend from
Sub- water carries out cyclic washing, lyophilization, obtains lamellar hydroxypropyl guar gum/nano-cellulose crosslinking adsorbed film；
(4) hydroxypropyl guar gum/nano-cellulose crosslinking adsorbed film
The mensure of adsorbed film physical strength: according to astm d638 method of testing, be that anti-tensile is strong using universal testing machine measurement result
Spend and draw high coefficient and be respectively 20mpa and 72%.
The determining adsorption method of heavy metallic salt: the desciccator diaphragm measuring peek piece 50mg is immersed in 1ml concentration respectively for 1mg/
The cuso of ml4、znso4With pb (no3)2In standard solution, under 25 DEG C of water temperatures, stand 72h, after adsorption equilibrium, take out film, wipe
Striping top layer liquid, detects the content of the heavy metal element of absorption in film respectively using elemental analyser.Result can obtain, and this film has
There is higher metal absorbability, adsorb 4.8mmol/g(cu respectively2+), 7.0mmol/g(zn2+) and 2.0mmol/g(pb2+).
Organic dyestuff determining adsorption method: measure take 50mg about desciccator diaphragm be immersed in respectively 100ml concentration be 25mg/
In the methylene blue (anionic dye) and crystal violet (cationic dye) solution of l, under the conditions of 25 DEG C, shaking table rocks 48h, inhales
After attached balance, take out film, detect that remaining dye content in each solution, its Methylene Blue and crystal violet are divided using UV, visible light
Light pass degree meter detects its content.Result can obtain, and this film has comparatively ideal organic dyestuff absorbability, to methylene blue and methyl
Purple absorbability respectively reaches 28mg/g and 291mg/g.
Claims (3)
1. a kind of preparation method of hydroxypropyl guar gum/nano-cellulose crosslinking adsorbed film is it is characterised in that enter as follows
OK:
(1) Microcrystalline Cellulose adopts grinder to grind, and is then dissociated by ultrasound wave, obtains nano-cellulose；
(2) dissolve hydroxypropyl guar gum in Herba Kalimeridis acid, and add the nano-cellulose of dispersion steps (1), add Herba Kalimeridis anhydride
After sodium hypophosphite, temperature-gradient method heating is esterified and cross-linking reaction；
(3) reactant is centrifuged de-bubble, and pours in mould, shape, be dried, form solid film, sample deionized water is carried out
Cyclic washing, after drying, obtain lamellar hydroxypropyl guar gum/nano-cellulose crosslinking adsorbed film.
2. the preparation method of hydroxypropyl guar gum according to claim 1/nano-cellulose crosslinking adsorbed film, its feature exists
As follows in concrete operations:
(1) Microcrystalline Cellulose is mixed homogeneously with water, adjustment over dry Microcrystalline Cellulose mass concentration is 0.5 ~ 5.0%, puts into and receives
In rice grinder, regulation speed of grinding plate is 1000 ~ 3000rpm, and mill spacing is -10 ~ -80 μm, circular grinding 10 ~ 60 times, place
After reason finishes, collect sample, ice-water bath proceed ultrasonic dissociation, ultrasonic power 100 ~ 1200w, ultrasound wave every 1 ~
5min acts on 1 ~ 5min, and total action time is 10 ~ 60min, the sample after process by 5000～10000rpm centrifugation 10～
30min, collects supernatant liquid, and lyophilization obtains nano-cellulose；
(2) with maleic acid as reaction medium, add the nano-cellulose of hydroxypropyl guar gum and step (1), be sufficiently stirred for, dissolving
After hydroxypropyl guar gum, and dispersed nano-cellulose, add maleic anhydride and sodium hypophosphite, stirring, ebuillition of heated 10 ~
30min, sealing, react 20 ~ 60min, wherein mass volume ratio in reaction system for the hydroxypropyl guar gum at 120 ~ 150 DEG C
Concentration is 3 ~ 20%, hydroxypropyl guar gum: the mass ratio of nano-cellulose is 1:0.005 ~ 1:0.5, maleic anhydride quality: over dry
Nano-cellulose and hydroxypropyl guar gum quality sum are 2.0 ~ 10.0, and sodium hypophosphite consumption is the 1 ~ 10% of maleic anhydride quality；
After esterification terminates, reaction vessel is put in frozen water and is quickly down to room temperature, continuously adds over dry nano-cellulose and hydroxypropyl
The sodium hypophosphite of guar gum quality sum 8 ~ 25%, continues to react 10 ~ 20min at 130 ~ 170 DEG C after sealing, cross-linking reaction is tied
Shu Hou, cooling, standby；
(3) reactant being down to room temperature is centrifuged 15～30min under 7000～15000rpm, removes undissolved cellulose and gas
Bubble, collects and obtains clear liquid；Clear liquid is poured in mould, shapes, be dried, form solid film, sample deionized water is carried out instead
After backwashing is washed, lyophilization, obtains lamellar hydroxypropyl guar gum/nano-cellulose crosslinking adsorbed film.
3. the hydroxypropyl that the preparation method of the hydroxypropyl guar gum described in claim 1/nano-cellulose crosslinking adsorbed film is obtained
Guar gum/nano-cellulose crosslinking adsorbed film is being processed containing the application in heavy metal ion, organic dyestuff waste liquid.
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| CN110302564A (en) * | 2019-06-28 | 2019-10-08 | 陕西科技大学 | It is a kind of based on nano-cellulose/guar gum composite hydrogel water-oil separating material and its preparation method and application |
| CN111978793A (en) * | 2020-08-18 | 2020-11-24 | 江南大学 | Preparation method of biological composite coating and intelligent colorimetric film material |
| CN111978793B (en) * | 2020-08-18 | 2021-07-27 | 江南大学 | Preparation method of biological composite coating and intelligent colorimetric film material |
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| WO2024148004A1 (en) * | 2023-01-03 | 2024-07-11 | Texas Tech University System | Guar and guar-cellulose composite materials |
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