CN109046263B - Carboxymethylation and phosphorylation bamboo fiber and preparation method and application thereof - Google Patents
Carboxymethylation and phosphorylation bamboo fiber and preparation method and application thereof Download PDFInfo
- Publication number
- CN109046263B CN109046263B CN201810749552.0A CN201810749552A CN109046263B CN 109046263 B CN109046263 B CN 109046263B CN 201810749552 A CN201810749552 A CN 201810749552A CN 109046263 B CN109046263 B CN 109046263B
- Authority
- CN
- China
- Prior art keywords
- bamboo
- carboxymethylated
- bamboo fiber
- phosphorylated
- carboxymethylation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 235000017166 Bambusa arundinacea Nutrition 0.000 title claims abstract description 101
- 235000017491 Bambusa tulda Nutrition 0.000 title claims abstract description 101
- 241001330002 Bambuseae Species 0.000 title claims abstract description 101
- 235000015334 Phyllostachys viridis Nutrition 0.000 title claims abstract description 101
- 239000011425 bamboo Substances 0.000 title claims abstract description 101
- 239000000835 fiber Substances 0.000 title claims abstract description 73
- 238000006366 phosphorylation reaction Methods 0.000 title claims abstract description 27
- 230000026731 phosphorylation Effects 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 42
- 238000001179 sorption measurement Methods 0.000 claims abstract description 33
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000000227 grinding Methods 0.000 claims abstract description 19
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229940106681 chloroacetic acid Drugs 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 11
- 238000006467 substitution reaction Methods 0.000 claims abstract description 11
- 238000003746 solid phase reaction Methods 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 230000008961 swelling Effects 0.000 claims abstract description 9
- 239000000428 dust Substances 0.000 claims abstract description 6
- 239000000080 wetting agent Substances 0.000 claims abstract description 6
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims abstract description 5
- 235000011180 diphosphates Nutrition 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 9
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 8
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 8
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 8
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000010842 industrial wastewater Substances 0.000 claims description 3
- 230000001737 promoting effect Effects 0.000 claims description 3
- 229940048084 pyrophosphate Drugs 0.000 claims description 3
- 238000009736 wetting Methods 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims 2
- 150000002500 ions Chemical class 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 10
- 239000002351 wastewater Substances 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 8
- 239000003463 adsorbent Substances 0.000 abstract description 5
- 239000002657 fibrous material Substances 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 230000003113 alkalizing effect Effects 0.000 abstract 1
- 239000002131 composite material Substances 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000004065 wastewater treatment Methods 0.000 abstract 1
- 239000001913 cellulose Substances 0.000 description 13
- 229920002678 cellulose Polymers 0.000 description 13
- 239000003513 alkali Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- 229910001430 chromium ion Inorganic materials 0.000 description 4
- 229910001431 copper ion Inorganic materials 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000000498 cooling water Substances 0.000 description 3
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- HLVXFWDLRHCZEI-UHFFFAOYSA-N chromotropic acid Chemical compound OS(=O)(=O)C1=CC(O)=C2C(O)=CC(S(O)(=O)=O)=CC2=C1 HLVXFWDLRHCZEI-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 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
- 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
- B01J20/28023—Fibres or filaments
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention relates to a carboxymethylation and phosphorylation bamboo fiber material and a preparation method and application thereof. The raw materials are prepared from the following materials in parts by mass through solid-phase reaction: 1 part of bamboo dust, 1-2 parts of sodium hydroxide, 1-5 parts of chloroacetic acid and 1-5 parts of pyrophosphate. The preparation method of the carboxymethylation and phosphorylation bamboo fiber mainly comprises the following steps: crushing bamboo scraps, adding sodium hydroxide solid and a trace wetting agent according to a certain proportion for alkalizing and swelling, then sequentially adding chloroacetic acid and pyrophosphate, and grinding at normal temperature to perform carboxymethylation reaction and phosphorylation reaction. The carboxymethylated and phosphorylated bamboo fibers prepared by the solid-phase reaction have high substitution degree, large specific surface area and high activity. The composite adsorbent is applied to the field of wastewater treatment, and has good adsorption performance on heavy metal ions in wastewater. The method has the advantages of wide raw material source, low cost, simple and easy operation, realization of the utilization of wastes and contribution to environmental protection.
Description
Technical Field
The invention relates to the technical field of heavy metal adsorption materials in wastewater, and particularly relates to carboxymethylation and phosphorylation bamboo fibers and a preparation method and application thereof.
Background
With the acceleration of the industrialization process, the industrial wastewater gradually becomes the most harmful and difficult wastewater to treat. Heavy metal pollutants have certain toxicity and biological aggregation, are difficult to degrade under natural conditions, and if the heavy metal pollutants are not treated, the heavy metal pollutants containing high concentration are directly discharged, so that the heavy metal pollutants can cause serious influence on human beings and the environment. The adsorption method in the existing method for removing heavy metals is widely applied due to simple and convenient operation and high efficiency. The currently developed adsorption materials generally have the following characteristics: (1) the adsorbing material is expensive, and the modification process is less; (2) the specific surface area of the adsorption material is small, the liquid phase dispersibility is poor, the adsorption capacity is low, and the removal rate is low; (3) the adsorption is not easy to separate, and the recycling effect is poor. Therefore, the development of high performance adsorbents is the key to the adsorption process.
After a piece of whole bamboo is cut as required, it is only about 70% of the final product, and the remaining 30% becomes useless waste. Each bamboo product is subjected to the working procedures of shaping, polishing and the like to generate a large amount of bamboo chips. The bamboo dust contains high cellulose which is an organic compound with the largest amount in the nature, and the processing application of the bamboo dust is seriously influenced because the cellulose molecules are straight-chain molecules, the crystallinity is high, and the water solubility is poor. Carboxymethyl cellulose is the most important modified product, and has good water solubility; and phosphorylation can increase the adsorption of cellulose to heavy metals, so that the prepared carboxymethylated and phosphorylated bamboo fiber adsorbent has good application prospect.
Disclosure of Invention
The invention aims to solve the problems and provide carboxymethylation and phosphorylation bamboo fibers and a preparation method and application thereof. The raw materials used in the invention have low cost, large specific surface area and good adsorption performance, and particularly, the absorption effect on heavy metal ions is remarkable after the phosphating reaction, and the heavy metal ions can be easily separated by a filtering method after the adsorption. The preparation process is simple and the process is easy to control.
The technical scheme adopted by the invention is as follows:
carboxymethylation and phosphorylation bamboo fiber is prepared from the following raw materials in parts by weight through solid-phase reaction: 1 part of bamboo dust, 1-2 parts of sodium hydroxide solid, 1-5 parts of chloroacetic acid and 1-5 parts of sodium pyrophosphate.
Preferably, the substitution degree of the carboxymethylated and phosphorylated bamboo fibers ranges from 0.85 to 0.95. The high substitution degree ensures that the obtained carboxymethylated and phosphorylated bamboo fiber has excellent heavy metal ion adsorption performance.
The bamboo fiber has a porous structure, a large specific surface area and good adsorption performance, but is insoluble in water and easy to aggregate and precipitate. The addition of alkali can not only fully activate the bamboo fiber, but also improve the hydrophilic property of the bamboo fiber and improve the adsorption effect; carboxymethylation can also make the bamboo fiber have better water solubility; and phosphorylation can increase the adsorption performance of the bamboo fiber to heavy metals. The carboxymethylation and phosphorylation bamboo fiber are prepared by adopting a solid-phase reaction, and have high substitution degree and good adsorption effect.
A method for preparing carboxymethylation and phosphorylation bamboo fiber, which is a solid phase reaction and comprises the following steps:
(1) crushing dry bamboo scraps according to the formula amount, weighing sodium hydroxide solid according to the formula amount, adding a trace wetting agent for wetting, cooling, adding the mixture into the bamboo scraps, grinding at normal temperature, and promoting alkalization and swelling for 4-5 hours to obtain alkalized bamboo fibers;
(2) weighing chloroacetic acid with a formula amount, gradually adding the chloroacetic acid into the alkalized bamboo fiber obtained in the step (1), uniformly stirring, controlling the temperature to be 40-80 ℃, and grinding to promote carboxymethylation reaction for 2-5 hours to obtain carboxymethylated bamboo fiber;
(3) weighing pyrophosphate with a formula amount, gradually adding into the carboxymethylated bamboo fiber obtained in the step (2), controlling the temperature at 40-80 ℃, and grinding to promote phosphorylation reaction for 2-5 hours;
(4) and (4) washing the product obtained in the step (3) until the PH value is equal to 7, thus obtaining the carboxymethylated and phosphorylated bamboo fiber.
In the present invention, the alkali swelling in the step (1) is preferably carried out at a temperature of less than 25 ℃. The reason is that the formation of alkali cellulose is an exothermic reaction process, and the adsorption amount of cellulose to alkali is reduced with the increase of temperature, while the hydrolysis reaction of alkali cellulose is greatly increased, which is not favorable for the generation of alkali fiber. And the alkalization temperature is reduced, so that the generation of the alkali cellulose is facilitated and the hydrolysis reaction of the alkali cellulose is inhibited.
Preferably, the bamboo dust in the step (1) is crushed to a particle size of 50-200 meshes. The sufficient crushing of the bamboo chips can increase the reaction area, accelerate the subsequent reaction speed and increase the adsorption area.
Preferably, the wetting agent in the step (1) is distilled water. Water is a strong swelling agent for cellulose reaction, and can break hydrogen bonds among cellulose molecular chains, open a microporous structure, greatly increase the internal surface area of cellulose and improve the reaction performance of cellulose.
The invention has the following beneficial effects:
1. in the invention, the addition of the alkali liquor can fully activate the bamboo fiber, simultaneously improve the hydrophilic property of the bamboo fiber, the carboxymethylation can also ensure that the bamboo fiber has better water solubility, the bamboo fiber can be fully dispersed in water and has more probability of contacting with heavy metal ions, and the phosphorylation can increase the adsorption property of the bamboo fiber to the heavy metal. The invention is prepared by solid phase reaction, has high degree of substitution and good adsorption effect on heavy metal ions.
2. The invention has the advantages of simple and easily obtained raw materials, low cost, reasonable process design and simple and easily realized preparation process.
Detailed Description
The technical solution of the present invention will be further specifically described below by way of specific examples.
Example 1:
in the embodiment, the carboxymethylation and phosphorylation bamboo fiber is prepared from the following raw materials in parts by weight through a solid-phase reaction: 20g of bamboo sawdust, 20g of sodium hydroxide solid, 20g of chloroacetic acid and 20g of sodium pyrophosphate. The preparation method comprises the following steps:
(1) crushing the bamboo scraps according to the formula amount to 50 meshes, adding 4mL of water to wet the sodium hydroxide solid according to the formula amount, cooling, adding the mixture into the bamboo scraps, and grinding to promote alkalization and swelling for 4-5 hours to obtain alkalized bamboo fibers;
(2) gradually adding chloroacetic acid (sodium chloroacetate) with a formula amount into the alkalized bamboo fibers obtained in the step (1), uniformly stirring, adjusting the cooling water flow of a mechanical device in the stirring process, controlling the temperature at 40 ℃, and grinding to promote carboxymethylation reaction for 2 hours to obtain carboxymethylated bamboo fibers;
(3) gradually adding sodium pyrophosphate with formula amount into the carboxymethylated bamboo fiber obtained in the step (2), controlling the temperature to be 40 ℃, and grinding to promote phosphorylation reaction for 2 hours;
(4) and (4) washing the product obtained in the step (3) until the PH value is equal to 7, thus obtaining the carboxymethylated and phosphorylated bamboo fiber.
Example 2:
in the embodiment, the carboxymethylation and phosphorylation bamboo fiber is prepared from the following raw materials in parts by mass through a solid-phase reaction: 20g of bamboo sawdust, 30g of sodium hydroxide solid, 50g of chloroacetic acid and 50g of sodium pyrophosphate. The preparation method comprises the following steps:
(1) crushing the bamboo scraps according to the formula amount to 100 meshes, adding 5mL of water to wet the sodium hydroxide solid according to the formula amount, cooling, adding the mixture into the bamboo scraps, and grinding to promote alkalization and swelling for 4-5 hours to obtain alkalized bamboo fibers;
(2) gradually adding chloroacetic acid (sodium chloroacetate) with a formula amount into the alkalized bamboo fibers obtained in the step (1), uniformly stirring, adjusting cooling water flow in a mechanical device in the stirring process, controlling the temperature at 60 ℃, and grinding to promote carboxymethylation reaction for 3 hours to obtain carboxymethylated bamboo fibers;
(3) gradually adding sodium pyrophosphate with formula amount into the carboxymethylated bamboo fiber obtained in the step (2), controlling the temperature to be 60 ℃, and grinding to promote phosphorylation reaction for 3 hours;
(4) and (4) washing the product obtained in the step (3) until the PH value is equal to 7, thus obtaining the carboxymethylated and phosphorylated bamboo fiber.
Example 3:
in the embodiment, the carboxymethylation and phosphorylation bamboo fiber is prepared from the following raw materials in parts by mass through a solid-phase reaction: 20g of bamboo sawdust, 40g of sodium hydroxide solid, 100g of chloroacetic acid and 100g of sodium pyrophosphate.
The preparation process of the carboxymethylation and phosphorylation bamboo fiber comprises the following steps:
(1) crushing the bamboo scraps to 100 meshes, adding 6mL of water to wet the solid sodium hydroxide according to the formula amount, cooling, adding the wet solid sodium hydroxide into the bamboo scraps, grinding to promote alkalization and swelling for 4-5 hours to obtain alkalized bamboo fibers;
(2) gradually adding chloroacetic acid (sodium chloroacetate) into the alkalized bamboo fibers obtained in the step (1), uniformly stirring, adjusting the flow rate of cooling water in a mechanical device in the stirring process, controlling the temperature at 80 ℃, and grinding to promote carboxymethylation reaction for 5 hours to obtain carboxymethylated bamboo fibers;
(3) gradually adding sodium pyrophosphate into the carboxymethylated bamboo fiber obtained in the step (2), controlling the temperature to be 80 ℃, and grinding to promote phosphorylation reaction for 5 hours;
(4) and (4) washing the product obtained in the step (3) until the PH value is equal to 7, thus obtaining the carboxymethylated and phosphorylated bamboo fiber.
And (3) performance detection:
method for measuring degree of substitution: heating carboxymethylated and phosphorylated bamboo fibers and concentrated sulfuric acid at 100 ℃ for 1 hour to quantitatively release formaldehyde, cooling, adding chromium acid-changing acid, reacting the formaldehyde and the chromium acid-changing acid (4, 5-dihydroxy-2, 7-naphthalenedisulfonic acid) to generate a chromogenic dye, measuring the absorbance of the solution at the wavelength of 570nm according to the Lambert-beer law, and determining the substitution degree of carboxymethyl; the degree of substitution of the phosphate group was determined by measuring the absorbance at a wavelength of 700 nm.
The measured degrees of substitution of the carboxymethylated phosphorylated bamboo fibers prepared in examples 1 to 3 were respectively: 0.92,0.89,0.88, with a high degree of substitution.
The carboxymethylated and phosphorylated cellulose materials prepared by the methods of examples 1 to 3 were used for determining the adsorption effect of simulated wastewater containing heavy metals of copper ions, lead ions and chromium ions, respectively:
respectively preparing 100mL of simulated wastewater containing copper ions, lead ions and chromium ions with the concentrations of 10mg/L, 50mg/L and 100mg/L, and adjusting the pH to 6.0; respectively weighing 0.1g, 0.3g and 0.5g of carboxymethylation and phosphorylation bamboo fiber materials prepared in the embodiment, and adding the materials into simulated wastewater; and oscillating and adsorbing for 3 hours at the temperature of 30 ℃ at the speed of 200 rpm, filtering by a 200-mesh filter screen after reaching balance, drying the filtered product at the temperature of 95 ℃ to constant weight, weighing, comparing, measuring the concentration of heavy metal ions in the filtrate and calculating the adsorption quantity and the absorption rate, wherein the results are shown in tables 1, 2 and 3:
table 1: table of adsorption effect of prepared carboxymethylated and phosphorylated bamboo fiber on copper ion in simulated wastewater
Table 2: table of adsorption effect of prepared carboxymethylated and phosphorylated bamboo fiber on lead ion in simulated wastewater
Table 3: adsorption effect of prepared carboxymethylated and phosphorylated bamboo fibers on chromium ions in simulated wastewater
As can be seen from the results in table 2 in table 1 above, the carboxymethylated and phosphorylated bamboo fibers prepared in example 1 and example 2 have good absorptivity to heavy metals, which are both 92% or more, and the absorption amount is greatly increased with the great increase of the heavy ion content in the wastewater, and the change of the absorptivity is small.
According to the Langmuir isotherm equation, Ce/qe is 1/KLqmax + Ce/qmax (when Ce is the concentration of a system and qe is the amount of an adsorbent when adsorption is balanced, qmax is the theoretical maximum adsorption amount of the adsorbent, and KL is a Langmuir adsorption constant), the carboxymethylation and phosphorylation bamboo fiber provided by the invention has the maximum theoretical adsorption amount of 476.5mg/g on copper ions, 456.32mg/g on lead ions and 437.2mg/g on chromium ions, and shows that the adsorption material has high adsorption capacity on heavy metal ions.
The above description is only a preferred embodiment of the present invention and should not be taken as limiting the invention, and any modification, replacement, or improvement made on the principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. The carboxymethylation and phosphorylation bamboo fiber is characterized in that the carboxymethylation and phosphorylation bamboo fiber is used for adsorption and separation of heavy metals in industrial wastewater and is prepared from the following raw materials in parts by weight through solid-phase reaction: 1 part of bamboo dust, 1-2 parts of sodium hydroxide solid, 1-5 parts of chloroacetic acid and 1-5 parts of sodium pyrophosphate;
the preparation method comprises the following steps:
(1) crushing dry bamboo scraps according to the formula amount, weighing sodium hydroxide according to the formula amount, adding a trace amount of wetting agent for wetting, cooling, adding the mixture into the bamboo scraps, grinding at normal temperature, and promoting alkalization and swelling for 4-5 hours to obtain alkalized bamboo fibers;
(2) weighing chloroacetic acid with a formula amount, gradually adding the chloroacetic acid into the alkalized bamboo fiber obtained in the step (1), uniformly stirring, controlling the temperature to be 40-80 ℃, and grinding to promote carboxymethylation reaction for 2-5 hours to obtain carboxymethylated bamboo fiber;
(3) weighing pyrophosphate with a formula amount, gradually adding into the carboxymethylated bamboo fiber obtained in the step (2), controlling the temperature at 40-80 ℃, and grinding to promote phosphorylation reaction for 2-5 hours;
(4) and (4) washing the product obtained in the step (3) until the pH value is equal to 7, thus obtaining the carboxymethylated and phosphorylated bamboo fiber.
2. The carboxymethylated and phosphorylated bamboo fibre according to claim 1, wherein the degree of substitution of the carboxymethylated and phosphorylated bamboo fibre is in the range of 0.85 to 0.92.
3. A method of preparing carboxymethylated and phosphorylated bamboo fibers according to claim 1, wherein the method comprises the steps of:
(1) crushing dry bamboo scraps according to the formula amount, weighing sodium hydroxide according to the formula amount, adding a trace amount of wetting agent for wetting, cooling, adding the mixture into the bamboo scraps, grinding at normal temperature, and promoting alkalization and swelling for 4-5 hours to obtain alkalized bamboo fibers;
(2) weighing chloroacetic acid with a formula amount, gradually adding the chloroacetic acid into the alkalized bamboo fiber obtained in the step (1), uniformly stirring, controlling the temperature to be 40-80 ℃, and grinding to promote carboxymethylation reaction for 2-5 hours to obtain carboxymethylated bamboo fiber;
(3) weighing pyrophosphate with a formula amount, gradually adding into the carboxymethylated bamboo fiber obtained in the step (2), controlling the temperature at 40-80 ℃, and grinding to promote phosphorylation reaction for 2-5 hours;
(4) and (4) washing the product obtained in the step (3) until the pH value is equal to 7, thus obtaining the carboxymethylated and phosphorylated bamboo fiber.
4. The method for preparing carboxymethylated and phosphorylated bamboo fibers according to claim 3, wherein the wetting agent in the step (1) is distilled water.
5. The method for preparing carboxymethylated and phosphorylated bamboo fiber according to claim 3, wherein the bamboo chips in the step (1) are pulverized to have a particle size of 50-200 mesh.
6. Use of carboxymethylated and phosphorylated bamboo fibers prepared by the preparation method according to claim 3, wherein the carboxymethylated and phosphorylated bamboo fibers are used for adsorption and separation of heavy metals in industrial wastewater.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810749552.0A CN109046263B (en) | 2018-07-10 | 2018-07-10 | Carboxymethylation and phosphorylation bamboo fiber and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810749552.0A CN109046263B (en) | 2018-07-10 | 2018-07-10 | Carboxymethylation and phosphorylation bamboo fiber and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109046263A CN109046263A (en) | 2018-12-21 |
| CN109046263B true CN109046263B (en) | 2021-10-15 |
Family
ID=64819282
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810749552.0A Active CN109046263B (en) | 2018-07-10 | 2018-07-10 | Carboxymethylation and phosphorylation bamboo fiber and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109046263B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1871260A (en) * | 2003-10-31 | 2006-11-29 | 兴和株式会社 | Cellulose II phosphate ester and metal-adsorbing material using the same |
| CN102476044A (en) * | 2010-11-26 | 2012-05-30 | 中国科学院理化技术研究所 | Cellulose base adsorbing material for removing cations of heavy metal in water and preparation method of cellulose base adsorbing material |
| CN106378102A (en) * | 2016-11-01 | 2017-02-08 | 内江师范学院 | Carboxymethylated paper pulp fiber heavy-metal adsorbing material, and preparation method and application thereof |
-
2018
- 2018-07-10 CN CN201810749552.0A patent/CN109046263B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1871260A (en) * | 2003-10-31 | 2006-11-29 | 兴和株式会社 | Cellulose II phosphate ester and metal-adsorbing material using the same |
| CN102476044A (en) * | 2010-11-26 | 2012-05-30 | 中国科学院理化技术研究所 | Cellulose base adsorbing material for removing cations of heavy metal in water and preparation method of cellulose base adsorbing material |
| CN106378102A (en) * | 2016-11-01 | 2017-02-08 | 内江师范学院 | Carboxymethylated paper pulp fiber heavy-metal adsorbing material, and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| Carboxymethylated Cellulose Fibers as Low-Cost and Renewable Adsorbent Materials;Jian Wang et al.;《Ind. Eng. Chem. Res.》;20171205;第56卷;第14940-14948页 * |
| 竹屑制备高取代度羧甲基纤维素钠的优化及其表征;余小龙等;《现代化工》;20150831;第35卷(第8期);第114页结论 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109046263A (en) | 2018-12-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Jin et al. | Polyethyleneimine-bacterial cellulose bioadsorbent for effective removal of copper and lead ions from aqueous solution | |
| CN102500333B (en) | Magnetic cationic surfactant modified chitosan / hydroxyapatite / zeolite composite and preparation method and application thereof | |
| CN103007896A (en) | Preparation method of cellulose adsorbent for adsorbing heavy metal cations | |
| CN101357325B (en) | Globular cellulose chelate sorbent containing amidoxime group and carboxy and preparation method thereof | |
| CN101992064A (en) | Method for preparing novel tannic acid curing chitosan heavy metal ion adsorbent | |
| CN102430390B (en) | Modified nanometer cellulose adsorbent and preparation method thereof | |
| CN105921121B (en) | A kind of preparation method for the nano-cellulose tannin microgel adsorbent being easily recycled | |
| CN101121516A (en) | Multifunctional active carbon | |
| CN104226259A (en) | Threonine modified attapulgite adsorbent and application thereof | |
| AU2020244447A1 (en) | Method for preparing efficient dyeing wastewater adsorbent from waste goat hair | |
| CN107473467A (en) | A kind of method of hexavalent chromium in Adsorption industrial wastewater | |
| CN108295820A (en) | A kind of preparation method and applications of plant fiber adsorbing material | |
| CN105056902A (en) | Method for treatment of anionic pollutant containing wastewater with modified tobacco straw | |
| CN104030305B (en) | A kind of preparation method of active calcium silicate | |
| CN102908998B (en) | Preparation method of xanthate macro-pore dextrangel adsorbent | |
| CN114276817B (en) | Soil restoration agent and preparation method and application thereof | |
| CN115124757A (en) | Cellulose-based aerogel small ball capable of efficiently removing chromium, and preparation method and application thereof | |
| CN107583620A (en) | A kind of chitosan-based metal ion adsorbent and preparation method thereof | |
| CN101912767A (en) | Method for preparing modified furfural residue heavy metal adsorbent | |
| CN111167851A (en) | Remediation method for applying humic acid to soil remediation | |
| CN109046263B (en) | Carboxymethylation and phosphorylation bamboo fiber and preparation method and application thereof | |
| CN106540652A (en) | Modified flying dust of a kind of quaternary ammonium salt cationic and preparation method thereof | |
| CN109759024A (en) | A kind of preparation method of the light sorbent based on plant cellulose | |
| CN108031443B (en) | Preparation and application of chromium-containing wastewater treatment agent | |
| CN107413314A (en) | The preparation method and application of the modified adsorbents of PEI/ZSM 5 of chromium in a kind of removal waste water |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |