CN108514866A - A kind of preparation method of hemicellulose group high-efficiency environment friendly adsorbent for heavy metal - Google Patents
A kind of preparation method of hemicellulose group high-efficiency environment friendly adsorbent for heavy metal Download PDFInfo
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- CN108514866A CN108514866A CN201810259153.6A CN201810259153A CN108514866A CN 108514866 A CN108514866 A CN 108514866A CN 201810259153 A CN201810259153 A CN 201810259153A CN 108514866 A CN108514866 A CN 108514866A
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- hemicellulose
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- 229920002488 Hemicellulose Polymers 0.000 title claims abstract description 84
- 229910001385 heavy metal Inorganic materials 0.000 title claims abstract description 66
- 239000003463 adsorbent Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 26
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 13
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims abstract description 12
- -1 polyethylene Polymers 0.000 claims abstract description 9
- 229920000768 polyamine Polymers 0.000 claims abstract description 8
- 239000004698 Polyethylene Substances 0.000 claims abstract description 7
- 229920000573 polyethylene Polymers 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 18
- 239000012153 distilled water Substances 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 17
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 16
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 11
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- 239000003431 cross linking reagent Substances 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 5
- 238000012216 screening Methods 0.000 claims description 5
- KIZFHUJKFSNWKO-UHFFFAOYSA-M calcium monohydroxide Chemical compound [Ca]O KIZFHUJKFSNWKO-UHFFFAOYSA-M 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000008236 heating water Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims description 2
- 229960001124 trientine Drugs 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000012869 ethanol precipitation Methods 0.000 claims 1
- 238000011017 operating method Methods 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 23
- 238000001179 sorption measurement Methods 0.000 abstract description 19
- 238000010521 absorption reaction Methods 0.000 abstract description 14
- 239000011651 chromium Substances 0.000 abstract description 13
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052804 chromium Inorganic materials 0.000 abstract description 12
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 abstract description 12
- 238000000605 extraction Methods 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 9
- 238000002604 ultrasonography Methods 0.000 abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052802 copper Inorganic materials 0.000 abstract description 5
- 239000010949 copper Substances 0.000 abstract description 5
- 230000005855 radiation Effects 0.000 abstract description 5
- 229910052793 cadmium Inorganic materials 0.000 abstract description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000012629 purifying agent Substances 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000012043 crude product Substances 0.000 abstract 2
- 238000006735 epoxidation reaction Methods 0.000 abstract 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 abstract 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 13
- 239000002250 absorbent Substances 0.000 description 13
- 230000002745 absorbent Effects 0.000 description 13
- 241000609240 Ambelania acida Species 0.000 description 10
- 239000010905 bagasse Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 239000000706 filtrate Substances 0.000 description 9
- 239000011133 lead Substances 0.000 description 8
- 229910001431 copper ion Inorganic materials 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229920002678 cellulose Polymers 0.000 description 6
- 239000001913 cellulose Substances 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000010902 straw Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- 150000001412 amines Chemical group 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 229920005615 natural polymer Polymers 0.000 description 3
- 238000001637 plasma atomic emission spectroscopy Methods 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910001430 chromium ion Inorganic materials 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- 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
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
-
- 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
- B01J20/28016—Particle form
-
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0003—General processes for their isolation or fractionation, e.g. purification or extraction from biomass
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
Abstract
The invention discloses a kind of preparation methods of hemicellulose group high-efficiency environment friendly adsorbent for heavy metal, this method is using plant as raw material, by to plant material microwave radiation technology alkalinity extraction hemicellulose, hemicellulose epoxidation is crosslinked with diethylenetriamine or polyethylene polyamine again, use triethylamine is quaternary ammoniated to generate a large amount of branches again, crude product expands rapidly bulk multi-hole, and finally by crude product, grafted propylene is sour under ultrasound-enhanced effect, strengthens contents of many kinds of heavy metal ion absorption property.The method of the present invention is simple for process, the adsorbent for heavy metal bulk multi-hole prepared, it is nontoxic, it is biodegradable, counterweight metal adsorption performance capacity is big and selection is had excellent performance, and can adsorb the heavy metal ion such as chromium, lead, cadmium, the copper in waste liquid, especially have high absorption capacity to chromium and lead ion, there is excellent selective power to chromium, can be used as the effluent containing heavy metal ions purifying agent of high-efficiency environment friendly.
Description
Technical field
The present invention relates to the technical field of adsorbent, specifically a kind of hemicellulose group high-efficiency environment friendly is heavy metal ion adsorbed
The preparation method of agent.
Technical background
With the fast development of modern industry, the discharge of the industrial wastewater containing heavy metal ion has seriously polluted the environment,
Compromise health.Heavy metal ion pollution administering method include mainly:Restore a precipitation method, absorption method and ion exchange
Method etc., wherein a defects of precipitation method are difficult to handle, easily cause secondary pollution because presence precipitates, processing cost is higher is restored,
Application aspect is limited by very large.In ion-exchange and absorption method, activated carbon is most widely used, most in world wide
Effective adsorbent, but the non-selective adsorption of activated carbon restore of high cost wait of its activity using thermally and chemically method and limit
Extensive use of the activated carbon in water treatment field.Ion exchange resin have large specific surface area, porous performance it is good, to aromatic hydrocarbon
The advantages that molecule adsorption selectivity is high, while also there is resource is limited, manufacturing cost is high, complex process and hydrophilicity are low etc.
Disadvantage.However ideal heavy metal ion exchange and sorbing material should have the characteristics that it is efficient, cheap.With both adsorption materials
Material is compared, the hemicellulose separated from biomass, especially bagasse hemicellulose, is agricultural wastes cycling and reutilization, is
It is relatively cheap in nature, abundant it is renewable, there is good biocompatibility, nontoxic and renewable degradability, but also
Material rich in hydroxyl can be modified bagasse hemicellulose by a variety of chemical reactions, the ion to greatly improve it
Switching performance and absorption property.Therefore, reproducible plant hemicellulose resource is developed, being compatible with the environment property of preparation is good, and adsorbs
Performance is good, and the wider array of modified hemicellulose heavy-metal adsorption material of application field is of great practical significance.
Hemicellulose level is only second to cellulose, is a kind of abundant, cheap, renewable natural polymer.Hemicellulose is inhaled
Attached dose, due to being taken from agriculture and forestry by-product, makes it have environmentally friendly recyclability, degradability, biocompatibility and special reason
Change performance, and natural resources is nervous now, and hemicellulose is refined out from biomass and prepares novel environment friendly absorbent-type material,
It will be as the development trend of the following polymeric sorbent.But due to by the detaching of hemicellulose, extracting and molecular structure is restricted,
Compared with the natural polymers feature capability material such as cellulose, starch, hemicellulose and its derivative prepare new type functional material
It is less.Especially research hemicellulose prepares the researches of adsorbent for heavy metal, and this respect works out hemicellulose
Adsorbent for heavy metal adsorption effect is not very good, the journey such as south China science and engineering and beautiful research hemicellulose in ionic liquid
Modified absorption heavy metal be also 56.32mg/g and 64.40mg/g to copper ion, the absorption of lead ion highest.Guangxi University Wang Li
The hemicellulose adsorbent for heavy metal that army doctor works out is also in 100mg/ to copper ion, lead ion and cadmium sorption
Within g, therefore the heavy metal absorbent of hemicellulose group high-efficiency environment friendly, it is the key breakthrough mouth of this research direction.
Traditional hemicellulose extraction, if alkaline process, acid system, hot-water process extract hemicellulose, extraction step is complicated, takes
Long, extraction efficiency is not high, and microwave radiation technology alkalinity extraction hemicellulose, the influence generated to molecular motion using microwave radiation,
Promote intermolecular friction, lead to cell rupture, to separate and extract the hemicellulose components during cell is started.It is this novel pre-
Processing method has proved to be time-consuming shortest hemicellulose rope extracting method, extraction time in a few minutes between more than ten minutes,
And traditional alkali carries take and generally require a few houres.Another advantage of microwave radiation exaraction be the loss of acetyl group in extraction process not
Greatly, the hemicellulose molecule matter that extract molecular mass and alkali carries obtain is most like.
Diethylenetriamine and polyethylene polyamine modified cellulose and hemicellulose had had many people to study in the past, but straight
It connects bad with diethylenetriamine and polyethylene polyamine modified cellulose hemicellulose adsorption effect.And the electronics of epoxychloropropane molecule
Cloud is intensive on oxygen atom, causes ring epoxychloropropane molecule very active, easily forms carbonium ion and makes three-membered ring open loop,
It is used as " bridge " with higher chemism, therefore using epoxychloropropane, amine groups is then re-introduced into, can be formed positively charged
Amine salt.Amino modified is related with nitrogen content to adsorption of metal ions ability, and epoxychloropropane can improve diethylenetriamine
Crosslinking rate, to improve Nitrogen content.And quaternary amines are successfully introduced into hemicellulose, the absorption in adsorbent would be more advantageous
Effect.It is equal using native cellulose as raw material to open jade-like stone, by alkalization, by being reacted with epoxychloropropane and DETA, is prepared for polyamines
Type heavy metal ion adsorbing material, the removal rate to Cr in water (VI) are 91.1%.Tan Ting etc. is using straw rice straw as raw material, with more
Kind amido reagent is modified straw rice straw through chlorination and aminating reaction, is prepared for a variety of modified amido rice-straw fibres, and will
It is used for heavy metal out of electroplating wastewater ion Fe3+、Ni2+、Cu2+、Zn2+Absorption.And there are no passed through using hemicellulose in document
Epichlorohydrin epoxy is crosslinked diethylenetriamine or polyethylene polyamine, a large amount of branch is acutely crosslinked out under 100 DEG C or so
Chain makes reactant expand rapidly, finally uses the quaternary ammoniated relevant report of triethylamine.
Ultrasonic wave can play the role of accelerating chemical reaction, utilize ultrasonic technique as a kind of special form of energy
Accelerating chemical reaction, there are many reports, using being almost related to organic chemistry every field.But ultrasound is utilized, to what is be modified
Hemicellulose makes the unemployed site further upper carboxyl of grafting, strengthens hemicellulose weight further with acrylic acid modified
The absorption property of metal absorbent has not been reported.
Invention content
Technical problem to be solved by the invention is to provide a kind of of low cost, easy to operate, high absorption properties and right
The preparation method of environmental-friendly hemicellulose group high-efficiency environment friendly adsorbent for heavy metal.
The present invention solves above-mentioned technical problem with following technical solution：
A kind of preparation method of hemicellulose group high-efficiency environment friendly adsorbent for heavy metal of the present invention, it includes following operation
Step：
A, plant material is crushed and is placed in lye with screening process, then by said mixture in a constant temperature
It is separated by solid-liquid separation after degree, power microwave irradiation 10min~30min, by the liquid tune pH value after separation to acidity, then concentration,
Again with absolute ethyl alcohol precipitation, washing, filtering, then obtained by freeze drying hemicellulose；
B, by hemicellulose in step a and epoxychloropropane, N, after N methacrylamide (DMF) mixing water-bath is carried out to add
Heat is stirred to react 60~90min at 90 DEG C~100 DEG C, adds crosslinking agent and stirs 60min at 90 DEG C~100 DEG C, finally
Be added triethylamine stir 90~180min at 60 DEG C~100 DEG C, after reaction use distilled water immersion, suction filtration, by solid into
Solid powder is obtained after row is dry；
C, the solid powder of step b is mixed with distilled water, acrylic acid or methacrylic acid, through ultrasonic reaction 30min
~60min, then use 1molL-1NaOH impregnates, and regulation system pH=12, obtained sediment are washed with distilled water, then through dry
After dry to get to the present invention hemicellulose group high-efficiency environment friendly adsorbent for heavy metal.
In step a, the plant material crushed the mesh sieve of 60 mesh~80.
In step a, the mass concentration of the lye is 5%, and lye is using in NaOH solution, KOH solution, CaOH solution
It is a kind of；The solid-to-liquid ratio of lye and plant material is：Plant material:Lye=1g:30ml.
In step a, it is 300w~800w that the temperature of the microwave, which is 50 DEG C~80 DEG C microwave powers,.
In step a, after being separated by solid-liquid separation, then with the half amount of above-mentioned lye to isolated solid carry out 2h~
4h, extracting, the liquid after extracting is mixed with last isolated liquid, and adjusts pH value to 5~6.
In step b, the hemicellulose and epoxychloropropane and N, the ratio of N methacrylamide (DMF) are：Half fiber
Dimension element:Epoxychloropropane:N-N Methacrylamides=1g:2~5ml:10~20ml.
In step b, the crosslinking agent be diethylenetriamine, triethylene tetramine or polyethylene polyamine, hemicellulose with crosslinking
The proportioning of agent is：Hemicellulose:Crosslinking agent=1g:The proportioning of 2~10ml, hemicellulose and triethylamine is：Hemicellulose:Three second
Amine=1g:6~30ml.
In step c, the proportioning of the solid powder and distilled water, acrylic acid or methacrylic acid of the step b is：Solid
Powder:Distilled water:Acrylic acid or methacrylic acid=1g:80~120ml:0.8~2ml.
In step c, the temperature of ultrasonic wave is 60 DEG C~80 DEG C, and power is 200w~400w.
In step b and step c, drying condition is dried for 24 hours at 50~60 DEG C.
The high-efficiency environment friendly adsorbent for heavy metal maximal absorptive capacity that the method for the present invention prepares is：In 700mg/L
Gr6+Adsorbance reaches 669.09mg/g, removal rate 92.71% in simulated solution；In 400mg/L Pb2+Adsorbance is in simulated solution
243.75mg/g removal rate 62.47%；In 300mg/L Cu2+Adsorbance is 151.03mg/g in simulated solution, and removal rate is
52.35%, hemicellulose group heavy metal absorbent is to Gr6+、Pb2+Adsorptivity, selectivity are good.
The method of the present invention has the advantages that：
(1) present invention is a kind of agricultural cyclic utilization of waste object using the bagasse hemicellulose separated from biomass,
It is relatively cheap in nature, enriches renewable, there is good biocompatibility, nontoxic and renewable degradability, and
Also be rich in hydroxyl material, can by it is a variety of chemical reaction bagasse hemicellulose is modified, to greatly improve it from
Sub- switching performance and absorption property, are also beneficial to environmental protection.
(2) present invention utilizes microwave radiation technology alkalinity extraction hemicellulose, and time-consuming most short, extraction time is in a few minutes to more than ten
Between minute, and traditional alkali carries take and generally require a few houres；And in extraction process acetyl group loss it is little, extract molecule
Quality and the hemicellulose molecule matter that alkali carries obtain are most like；The method of the present invention uses microwave dissolver, reaction to be more uniformly distributed,
Controllability is good, and more preferably, extraction efficiency is high for reaction effect.
(3) present invention is crosslinked diethylenetriamine or polyethylene polyamine, 100 by hemicellulose through epichlorohydrin epoxy
DEG C or so under be acutely crosslinked out a large amount of nitrogenous branches, so that reactant is expanded rapidly, improve the grafting rate of final product, then with three
Ethamine is quaternary ammoniated, it is therefore intended that quaternary amines are successfully introduced into hemicellulose；The adsorption effect in adsorbent would be more advantageous, most
The adsorption capacity for greatly improving hemicellulose adsorbing material eventually, than general simple diethylenetriamine modified cellulose,
The adsorption effect of hemicellulose is good.
(4) ultrasonic wave can play the role of accelerating chemical reaction as a kind of special form of energy, using ultrasound,
To the hemicellulose that has been modified further with acrylic acid modified, makes the unemployed site further upper carboxyl of grafting, strengthen
The adsorption effect of hemicellulose heavy metal absorbent improves absorption property.
(5) the hemicellulose group high-efficiency environment friendly adsorbent for heavy metal that the method for the present invention obtains has biodegradable
Property, stability it is good, renewable, can recycle, combine natural polymer and synthesize high molecular advantage, meet green ring
Factoring is read and low-carbon economy development.
(6) the hemicellulose group high-efficiency environment friendly adsorbent for heavy metal that the method for the present invention obtains can be used in various waste water
The heavy metal ion such as chromium, lead, copper, cadmium, especially have high absorption capacity to chromium and lead ion, there is excellent selection energy to chromium
Power can be used as the effluent containing heavy metal ions purifying agent of high-efficiency environment friendly.
Specific implementation mode
Technical scheme of the present invention is further described with reference to example.
Embodiment 1
A, Bagasse Material is crushed and after screening process, took the quality that the bagasse 40g of 80 mesh is placed in 1200ml dense
Degree is to be then placed in microwave dissolver in 5%NaOH solution, and microwave reaction power is 300w, is reacted at 80 DEG C
30min, reaction terminate to filter, and filter residue uses the 5%NaOH solution of 600ml to extract 2h again, and filtering finally mixes filtrate twice
It closes, is 5~6 with acetic acid regulation system pH, rotary evaporation concentration adds 3~4 times of absolute ethyl alcohol precipitation, finally uses nothing again
Water-ethanol washs 4 times, centrifugal filtration, and white powder hemicellulose is made in freeze-drying for 24 hours.
B, by hemicellulose 2g in step a, epoxychloropropane 10mL, N-N Methacrylamide (DMF) 40mL mixing is added
Heating water bath in three-necked flask is stirred to react 60min under the conditions of 90 DEG C, adds 4mL diethylenetriamines, under the conditions of 90 DEG C
It is stirred to react 60min, 12mL triethylamines is eventually adding and is stirred to react 180min under the conditions of 90 DEG C.Sintetics distillation water logging
Bubble filters, dry in 50 DEG C of vacuum drying chambers to obtain yellow-white grafting solid powder for 24 hours.
C, step b yellow-whites grafting solid powder 2g is added in the distilled water of 160mL, adds 1.6mL acrylic acid,
1h is reacted under 70 DEG C of temperature ultrasounds of power of 200W, reaction uses 1molL after terminating-1Sodium hydroxide solution, which impregnates, adjusts pH=
12 are precipitated, and are finally washed with distilled water 3 times, dry in 60 DEG C of vacuum drying chambers to obtain hemicellulose group Efficient Ring for 24 hours
Take care of yourself metal ion adsorbent.
The application of heavy metal absorbent
Make adsorption experiment with heavy metal chromium, lead, copper
Take heavy metal absorbent prepared by three parts of 0.0200g embodiments 1 in 3 100mL conical flasks respectively, respectively to three
20mL 700mg/L Gr are sequentially added in a conical flask6+、400mg/L Pb2+With 300mg/L Cu2+, at 35 DEG C, rotating speed is
4h is shaken in the water bath chader of 135r/min, is filtered, and filtrate is taken to measure the institute in solution with induced coupled plasma atomic emission spectrometry
Remaining chromium, lead, content of copper ion calculate adsorbance and adsorption rate according to following formula：
In formula：
Q --- unit mass heavy metal absorbent is to the adsorbance of heavy metal ion, mg/g；
The removal rate of η --- heavy metal ion, %；
C0--- the initial concentration of heavy metal ion, mg/L；
C --- after filtering in filtrate heavy metal ion concentration, mg/L；
The volume of V --- solution, L；
Experimental result：In 700mg/L Gr6+Adsorbance is 669.09mg/g, removal rate 92.71% in simulated solution；
400mg/L Pb2+Adsorbance is 243.75mg/g, removal rate 62.47% in simulated solution；300mg/L Cu2+It is inhaled in simulated solution
Attached amount is 151.03mg/g, removal rate 52.35%.
Embodiment 2
A, Bagasse Material is crushed and after screening process, took the quality that the bagasse 40g of 60 mesh is placed in 1200ml dense
Degree is to be then placed in microwave dissolver in 5%KOH solution, and microwave reaction power is 500w, reacts 30min at 60 DEG C,
Reaction terminates to filter, and filter residue uses the 5%KOH solution of 600ml to extract 3h again, and filtrate twice is finally mixed, uses acetic acid by filtering
Regulation system pH is 5~6, rotary evaporation concentration, adds 3~4 times of absolute ethyl alcohol precipitation, is finally washed again with absolute ethyl alcohol
4 times, white powder hemicellulose is made in centrifugal filtration, freeze-drying for 24 hours.
B, hemicellulose 2g in step a is mixed into addition with epoxychloropropane 4mL, N-N Methacrylamide (DMF) 20mL
Heating water bath in three-necked flask is stirred to react 60min under the conditions of 100 DEG C, adds 20mL diethylenetriamines, in 100 DEG C of items
It is stirred to react 60min under part, 60mL triethylamines is eventually adding and is stirred to react 180min under the conditions of 100 DEG C.Sintetics steams
Distilled water is impregnated, is filtered, dry in 50 DEG C of vacuum drying chambers to obtain yellow-white grafting solid powder for 24 hours.
C, step b yellow-whites grafting solid powder 1g is added in the distilled water of 100mL, adds 0.8mL acrylic acid,
30min is reacted under the power of 200W, 60 DEG C of temperature ultrasounds, uses 1molL later after reaction-1Sodium hydroxide solution, which impregnates, to be adjusted
Section pH=12 is precipitated, and is finally washed with distilled water 4 times, dry in 60 DEG C of vacuum drying chambers to obtain hemicellulose group for 24 hours
High-efficiency environment friendly adsorbent for heavy metal.
The application of heavy metal absorbent
Make adsorption experiment with heavy metal chromium, lead, copper
Take heavy metal absorbent prepared by three parts of 0.0200g embodiments 1 in 3 100mL conical flasks respectively, respectively to three
The chromium ion solution, lead ion solution and copper ion solution that 20mL 400mg/L are sequentially added in a conical flask, at 40 DEG C, rotating speed
To shake 4h in the water bath chader of 135r/min, filters, filtrate is taken to be measured in solution with induced coupled plasma atomic emission spectrometry
Remaining chromium, lead, content of copper ion calculate adsorbance and adsorption rate according to following formula：
In formula：
Q --- unit mass heavy metal absorbent is to the adsorbance of heavy metal ion, mg/g；
The removal rate of η --- heavy metal ion, %；
C0--- the initial concentration of heavy metal ion, mg/L；
C --- after filtering in filtrate heavy metal ion concentration, mg/L；
The volume of V --- solution, L；
Experimental result：In 400mg/L Gr6+Adsorbance is 243.04mg/g, removal rate 82.26% in simulated solution；
400mg/L Pb2+Adsorbance is 131.69mg/g, removal rate 30.19% in simulated solution；400mg/L Cu2+It is inhaled in simulated solution
Attached amount is 52.99mg/g, removal rate 16.28%.
Embodiment 3
A, Bagasse Material is crushed and after screening process, took the quality that the bagasse 40g of 60 mesh is placed in 1200ml dense
Degree is to be then placed in microwave dissolver in 5%CaOH solution, and microwave reaction power is 800w, is reacted at 80 DEG C
10min, reaction terminate to filter, and filter residue uses the 5%CaOH solution of 600ml to extract 3h again, and filtering finally mixes filtrate twice
It closes, is 5~6 with acetic acid regulation system pH, rotary evaporation concentration adds 3~4 times of absolute ethyl alcohol precipitation, finally uses nothing again
Water-ethanol washs 4 times, centrifugal filtration, and white powder hemicellulose is made in freeze-drying for 24 hours.
B, hemicellulose 2g in step a is mixed with epoxychloropropane 10mL, N-N Methacrylamide (DMF) 20mL and is added
Enter heating water bath in three-necked flask, be stirred to react 90min under the conditions of 90 DEG C, add 12mL triethylene tetramines, in 100 DEG C of items
It is stirred to react 60min under part, 30mL triethylamines is eventually adding and is stirred to react 90min under the conditions of 90 DEG C.Sintetics distills
Water is impregnated, is filtered, dry in 50 DEG C of vacuum drying chambers to obtain yellow-white grafting solid powder for 24 hours.
C, step b yellow-whites grafting solid powder 3g is added in the distilled water of 360mL, adds 6mL methacrylic acids,
50min is reacted under 80 DEG C of temperature ultrasounds of power of 400W, uses 1molL later after reaction-1Sodium hydroxide solution impregnates
It adjusts pH=12 to be precipitated, finally be washed with distilled water 4 times, it is dry in 60 DEG C of vacuum drying chambers to obtain hemicellulose for 24 hours
Base high-efficiency environment friendly adsorbent for heavy metal.
The application of heavy metal absorbent
Make adsorption experiment with heavy metal chromium, lead, copper
Take heavy metal absorbent prepared by three parts of 0.0200g embodiments 1 in 3 100mL conical flasks respectively, respectively to three
The chromium ion solution, lead ion solution and copper ion solution that 20mL 200mg/L are sequentially added in a conical flask, at 30 DEG C, rotating speed
To shake 4h in the water bath chader of 135r/min, filters, filtrate is taken to be measured in solution with induced coupled plasma atomic emission spectrometry
Remaining chromium, lead, content of copper ion calculate adsorbance and adsorption rate according to following formula：
In formula：
Q --- unit mass heavy metal absorbent is to the adsorbance of heavy metal ion, mg/g；
The removal rate of η --- heavy metal ion, %；
C0--- the initial concentration of heavy metal ion, mg/L；
C --- after filtering in filtrate heavy metal ion concentration, mg/L；
The volume of V --- solution, L；
Experimental result：In 200mg/L Gr6+Adsorbance is 147.89mg/g, removal rate 92.47% in simulated solution；
200mg/L Pb2+Adsorbance is 104.98mg/g, removal rate 46.64% in simulated solution；200mg/L Cu2+It is inhaled in simulated solution
Attached amount is 33.508mg/g, removal rate 19.72%.
Claims (10)
1. a kind of preparation method of hemicellulose group high-efficiency environment friendly adsorbent for heavy metal, which is characterized in that it includes as follows
Operating procedure：
A, plant material is crushed and is placed in lye with screening process, then by said mixture in certain temperature, work(
It is separated by solid-liquid separation after rate microwave irradiation 10min~30min, by the liquid tune pH value after separation to acidity, then concentration, then uses nothing
Water-ethanol precipitation, washing, filtering, then obtained by freeze drying hemicellulose；
B, by hemicellulose in step a and epoxychloropropane, N, heating water bath is carried out after N methacrylamide (DMF) mixing,
It is stirred to react 60~90min at 90 DEG C~100 DEG C, crosslinking agent is added and stirs 60min at 90 DEG C~100 DEG C, is finally added
Enter triethylamine and stir 90~180min at 60 DEG C~100 DEG C, uses distilled water immersion after reaction, filters, solid is carried out
Solid powder is obtained after drying；
C, the solid powder of step b is mixed with distilled water, acrylic acid or methacrylic acid, through ultrasonic reaction 30min~
60min, then use 1molL-1NaOH impregnates, and regulation system pH=12, obtained sediment are washed with distilled water, then through drying
After obtain hemicellulose group high-efficiency environment friendly adsorbent for heavy metal.
2. the preparation method of hemicellulose group high-efficiency environment friendly adsorbent for heavy metal, feature exist according to claim 1
In in step a, the plant material crushed the mesh sieve of 60 mesh~80.
3. the preparation method of hemicellulose group high-efficiency environment friendly adsorbent for heavy metal, feature exist according to claim 1
In in step a, the mass concentration of the lye is 5%, and lye is using one kind in NaOH solution, KOH solution, CaOH solution；
The solid-to-liquid ratio of lye and plant material is：Plant material:Lye=1g:30ml.
4. the preparation method of hemicellulose group high-efficiency environment friendly adsorbent for heavy metal, feature exist according to claim 1
In in step a, it is 300w~800w that the temperature of the microwave, which is 50 DEG C~80 DEG C microwave powers,.
5. the preparation method of hemicellulose group high-efficiency environment friendly adsorbent for heavy metal, feature exist according to claim 1
In in step a, after being separated by solid-liquid separation, then with the half amount of above-mentioned lye carrying out 2h~4h to isolated solid, take out
It carries, the liquid after extracting is mixed with last isolated liquid, and adjusts pH value to 5~6.
6. the preparation method of hemicellulose group high-efficiency environment friendly adsorbent for heavy metal, feature exist according to claim 1
In in step b, the hemicellulose and epoxychloropropane and N, the ratio of N methacrylamide (DMF) are：Hemicellulose:
Epoxychloropropane:N-N Methacrylamides=1g:2~5ml:10~20ml.
7. the preparation method of hemicellulose group high-efficiency environment friendly adsorbent for heavy metal, feature exist according to claim 1
In in step b, the crosslinking agent is diethylenetriamine, triethylene tetramine or polyethylene polyamine, and hemicellulose and crosslinking agent are matched
Than for：Hemicellulose:Crosslinking agent=1g:The proportioning of 2~10ml, hemicellulose and triethylamine is：Hemicellulose:Triethylamine=
1g:6~30ml.
8. the preparation method of hemicellulose group high-efficiency environment friendly adsorbent for heavy metal, feature exist according to claim 1
In in step c, the proportioning of the solid powder and distilled water, acrylic acid or methacrylic acid of the step b is：Solid powder:
Distilled water:Acrylic acid or methacrylic acid=1g:80~120ml:0.8~2ml.
9. the preparation method of hemicellulose group high-efficiency environment friendly adsorbent for heavy metal, feature exist according to claim 1
In in step c, the temperature of ultrasonic wave is 60 DEG C~80 DEG C, and power is 200w~400w.
10. the preparation method of hemicellulose group high-efficiency environment friendly adsorbent for heavy metal, feature exist according to claim 1
In in step b and step c, drying condition is dried for 24 hours at 50~60 DEG C.
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| CN116143227A (en) * | 2023-04-19 | 2023-05-23 | 新乡学院 | Method for treating low-concentration heavy metal pollution wastewater by combining adsorption and ultrafiltration |
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| CN117801126A (en) * | 2024-03-01 | 2024-04-02 | 山东百川集大环境工程有限公司 | Cellulose-based multiple binding site heavy metal sewage treatment agent and preparation method and application thereof |
| CN117801126B (en) * | 2024-03-01 | 2024-05-03 | 山东百川集大环境工程有限公司 | Cellulose-based multiple binding site heavy metal sewage treatment agent and preparation method and application thereof |
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