CN115722211A - Phenol adsorbent and preparation method and application thereof - Google Patents
Phenol adsorbent and preparation method and application thereof Download PDFInfo
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- CN115722211A CN115722211A CN202211483128.9A CN202211483128A CN115722211A CN 115722211 A CN115722211 A CN 115722211A CN 202211483128 A CN202211483128 A CN 202211483128A CN 115722211 A CN115722211 A CN 115722211A
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000003463 adsorbent Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000003245 coal Substances 0.000 claims abstract description 61
- 238000002309 gasification Methods 0.000 claims abstract description 58
- 239000002893 slag Substances 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000000926 separation method Methods 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 74
- 239000000243 solution Substances 0.000 claims description 57
- 239000003431 cross linking reagent Substances 0.000 claims description 26
- 239000011259 mixed solution Substances 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 238000004132 cross linking Methods 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 6
- 238000004065 wastewater treatment Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 abstract description 72
- 229920002451 polyvinyl alcohol Polymers 0.000 abstract description 72
- 238000001179 sorption measurement Methods 0.000 abstract description 31
- 239000002699 waste material Substances 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 6
- 238000011161 development Methods 0.000 abstract description 5
- 239000003344 environmental pollutant Substances 0.000 abstract description 5
- 231100000719 pollutant Toxicity 0.000 abstract description 5
- 239000002910 solid waste Substances 0.000 abstract description 5
- 238000001556 precipitation Methods 0.000 abstract description 4
- 238000012216 screening Methods 0.000 abstract description 4
- 239000008367 deionised water Substances 0.000 description 18
- 229910021641 deionized water Inorganic materials 0.000 description 18
- 239000000843 powder Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 12
- 238000007865 diluting Methods 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 238000005303 weighing Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000004971 Cross linker Substances 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RLFWWDJHLFCNIJ-UHFFFAOYSA-N 4-aminoantipyrine Chemical compound CN1C(C)=C(N)C(=O)N1C1=CC=CC=C1 RLFWWDJHLFCNIJ-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 238000010382 chemical cross-linking Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003517 fume Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 210000004877 mucosa Anatomy 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- -1 papermaking Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Abstract
The invention provides a phenol adsorbent and a preparation method and application thereof. The phenol adsorbent comprises PVA gel and coal gasification fine slag loaded in the PVA gel. The phenol adsorbent comprises PVA gel and coal gasification fine slag loaded in the PVA gel. Coal Gasification Fine Slag (CGFS) belongs to solid waste, but due to the excellent adsorption capacity of the CGFS on phenol, the application obtains a granular phenol adsorbent by fixing the CGFS in a porous polyvinyl alcohol (PVA) three-dimensional gel network. The adsorbent has the performance of adsorbing phenolic pollutants in water and the characteristic of simple separation through screening or precipitation, so that the resource utilization of CGFS is realized, the purpose of treating wastes with wastes is achieved, and the effect of resource utilization of wastes is achieved, so that the adsorbent has feasibility of popularization and application, and conforms to the strategy of sustainable development.
Description
Technical Field
The invention relates to the technical field of environmental protection, and particularly relates to a phenol adsorbent and a preparation method and application thereof.
Background
Phenol is a simple phenolic organic weak acid and is a common organic pollutant in industrial wastewater of petroleum, papermaking, rubber and the like. In addition to the industrial wastewater, the excrement and the nitrogenous organic matters also generate phenolic compounds in the decomposition process, so a large amount of excrement sewage discharged by an urban sewage pipe network is also an important source of phenolic pollution in water. Phenol has strong toxic action on a plurality of organisms, can cause certain toxic action on human bodies through direct contact of skin and mucosa, is listed in a list of key pollutants by a plurality of countries, and how to remove phenolic compounds in wastewater becomes one of the key research problems in the field of modern environment.
Under the energy structure of rich coal, lean oil and less gas, the coal gasification process becomes the front-stage pillar industry of modern coal chemical industry, and is an important technical means for realizing comprehensive utilization and clean and efficient utilization of coal. However, the coal gasification process generates a large amount of solid waste, namely, coal gasification fine slag. The gasification slag of more than 3300 ten thousand tons is produced in China every year, and the main disposal mode is landfill and stockpiling at present, so that the land is occupied, the environmental pollution is caused, higher environmental cost is brought to enterprises, and the sustainable development of the coal gasification industry is restricted. The coal gasification fine slag has rich specific surface area and pore structure, and researches show that the coal gasification fine slag has certain phenol adsorption performance and is an ideal raw material for preparing the phenol adsorbent. However, the coal gasification fine slag is directly used for wastewater treatment, and has the problem of difficult separation, thereby restricting the recovery and the recycling of the coal gasification fine slag.
Disclosure of Invention
The invention mainly aims to provide a phenol adsorbent and a preparation method and application thereof, and aims to solve the problem that coal gasification fine slag is difficult to separate when used for wastewater treatment in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a phenol adsorbent comprising PVA gel and coal gasification fine slag carried in the PVA gel.
Further, the particle size of the phenol adsorbent is 2-4 mm, and preferably, the particle size of the coal gasification fine slag loaded in the PVA gel is 125-250 μm; more preferably, the loading amount of the coal gasification fine slag is 10 to 30wt%.
Further, the coal gasification fine slag is residue separated and discharged in the purification process of the coal gasification gas; the specific surface area of the coal gasification fine slag is preferably 500-570 m 2 ·g -1 The total pore volume is 0.4-0.5 m 2 ·g -1 The average pore diameter is 3-4 nm, and the fixed carbon content is 60-75%.
In order to achieve the above object, according to an aspect of the present invention, there is provided a method for producing the above phenol adsorbent, comprising: preparing PVA-NaOH sol by using NaOH aqueous solution and PVA aqueous solution; mixing the coal gasification fine slag with PVA-NaOH sol to obtain a mixed solution, and carrying out ultrasonic treatment on the mixed solution to form PVA-NaOH-CGFS sol; and crosslinking the PVA-NaOH-CGFS sol with the crosslinking agent solution to obtain the phenol adsorbent.
Further, the preparation method of the aqueous PVA solution comprises the following steps: mixing PVA with water, and heating to dissolve the PVA to obtain a PVA aqueous solution; the preferable heating comprises water bath heating, the preferable heating temperature is 80-90 ℃, and the preferable heating time is 60-90 min.
Further, the mass concentration of the NaOH aqueous solution is 5 to 10%, preferably the mass concentration of the PVA aqueous solution is 11 to 13%, and preferably the mass concentration of PVA in the mixed solution is 8 to 10%.
Further, the content ratio of the coal gasification fine slag to the PVA-NaOH sol is 1.5-4 g:130mL.
Further, the crosslinker solution includes a solution containing H 3 BO 3 And CaCl 2 One or more of glutaraldehyde and polyethylene oxide, preferably H 3 BO 3 Has a mass concentration of 3-5%, preferably CaCl 2 The mass concentration of (A) is 1 to 3%.
Furthermore, the volume ratio of the PVA-NaOH-CGFS sol to the cross-linking agent solution is 1:2-1:5; the crosslinking time is 3-12 h.
According to another aspect of the present invention, there is provided a use of the above phenol adsorbent for wastewater treatment.
By applying the technical scheme of the invention, the Coal Gasification Fine Slag (CGFS) belongs to solid waste, but the CGFS has excellent adsorption capacity on phenol, so that the granular phenol adsorbent is obtained by fixing the CGFS in a porous polyvinyl alcohol (PVA) three-dimensional gel network. The adsorbent has the performance of adsorbing phenolic pollutants in water, and also has the characteristic of simple separation through screening or precipitation, so that the resource utilization of the CGFS is realized, the aim of treating wastes with processes of wastes against one another and the effect of resource utilization of wastes are achieved, the feasibility of popularization and application is realized, and the sustainable development strategy is met.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As analyzed by the background art of the application, the coal gasification fine slag serving as the phenol adsorbent in the prior art has the problem of difficult separation. In order to solve the problem, the application provides a phenol adsorbent and a preparation method and application thereof.
In an exemplary embodiment of the present application, a phenol adsorbent is provided, which includes PVA gel and coal gasification fine slag carried in the PVA gel.
Coal Gasification Fine Slag (CGFS) belongs to solid waste, but due to the excellent adsorption capacity of the CGFS on phenol, the application obtains a granular phenol adsorbent by fixing the CGFS in a porous polyvinyl alcohol (PVA) three-dimensional gel network. The adsorbent has the performance of adsorbing phenolic pollutants in water and the characteristic of simple separation through screening or precipitation, so that the resource utilization of CGFS is realized, the purpose of treating wastes with wastes is achieved, and the effect of resource utilization of wastes is achieved, so that the adsorbent has feasibility of popularization and application, and conforms to the strategy of sustainable development.
It should be noted that the adsorbent should include and only include chemical components used, such as polyvinyl alcohol, coal gasification fine slag, calcium chloride, boric acid, and the like. The polyvinyl alcohol and the coal gasification fine slag are main components, and the rest components play a role in assisting the structural stability of the gel carrier, account for a small amount and can be ignored.
In some embodiments, the phenol adsorbent has a particle size of 2 to 4mm. The phenol adsorbent is in a gel pellet form, is uniform in size after being dried, and does not need to be screened. The particle size of the coal gasification fine slag influences the phenol adsorption rate, and according to the adsorption rule of the coal gasification fine slag, the particle size of the coal gasification fine slag loaded in the PVA gel is preferably 125-250 μm; the particle size of the coal gasification fine slag is out of this range, and the adsorption rate may be reduced. More preferably, the loading amount of the coal gasification fine slag is 10 to 30wt%. The loading capacity of the coal gasification fine slag is in the range, the CGFS can be stably loaded in the gel without falling off, and the obtained gel beads have excellent phenol adsorption performance. The coal gasification fine slag has small particle size, and when the coal gasification fine slag is used for adsorbing phenol without treatment, the filter screen is easily blocked when the coal gasification fine slag is filtered in the adsorption column. The coal gasification fine slag is wrapped into the gel small ball form, so that the coal gasification fine slag is easily intercepted by the filter screen without causing the blockage of the filter screen, and the separation of the adsorbent and the solvent can be easily realized. The operation method is simple and easy, and effectively avoids the inherent defect of difficult separation and recovery of the CGFS powder.
The source of the CGFS is not particularly limited, and for the purpose of recycling the waste, in some embodiments, the coal gasification gas may be entrained and the discharged residue may be separated during the purification process after the coal gasification gas leaves the coal gasifier; in order to make the phenol adsorbent have more excellent phenol adsorption capacity, CGFS with rich specific surface area, pores and carbon content can be selected, and in some embodiments, the specific surface area of the gasified fine slag is preferably 500-570 m 2 ·g -1 The total pore volume is 0.4-0.5 m 2 ·g -1 The average pore diameter is 3-4 nm, and the fixed carbon content is 60-75%.
In another exemplary embodiment of the present application, there is provided a method for preparing a phenol adsorbent, the method comprising: preparing PVA-NaOH sol by using NaOH aqueous solution and PVA aqueous solution; mixing the coal gasification fine slag with PVA-NaOH sol to obtain a mixed solution, and carrying out ultrasonic treatment on the mixed solution to form PVA-NaOH-CGFS sol; and crosslinking the PVA-NaOH-CGFS sol with the crosslinking agent solution to obtain the phenol adsorbent.
The method mixes the Coal Gasification Fine Slag (CGFS) with PVA-NaOH sol, naOH aqueous solution firstly catalyzes PVA to realize complete alcoholysis, and expands PVA long-chain molecules to enable the side chains of the PVA long-chain molecules to be full of active hydroxyl groups, and when saturated boric acid and CaCl are dripped in 2 After the solution is obtained, naOH can further catalyze hydroxyl of a side chain of a PVA molecule and boric acid molecules to generate chemical crosslinking through ester bonds, and CGFS with excellent adsorption capacity on phenol can be fixed in a porous PVA three-dimensional gel network through physical hydrogen bonds and chemical bonds through the chemical crosslinking. The raw materials are cheap and easy to obtain, and the method has the potential of large-scale popularization and use.
The preparation method of the aqueous PVA solution in the present application may refer to conditions commonly used in the art. In some embodiments, the method of preparing the aqueous PVA solution comprises: the PVA was mixed with water and dissolved by heating to obtain an aqueous PVA solution. In order to sufficiently dissolve PVA, the heating preferably includes water bath heating, preferably at a temperature of 80 to 90 ℃ for 60 to 90min.
To prepare the aqueous PVA solution into a sol state, a three-dimensional gel network is provided for CGFS. In some embodiments, the aqueous NaOH solution has a mass concentration of 5 to 10%, preferably the aqueous PVA solution has a mass concentration of 11 to 13%, and preferably the mixed solution has a mass fraction of PVA of 8 to 10%. If the mass fraction of the mixed solution is too high, the viscosity of the sol is too high, the cross-linking solution is not easy to drop into the sol to be solidified into spheres, and if the mass fraction is too low, the stability of the gel is poor.
In some embodiments, the content ratio of the coal gasification fine slag to the PVA-NaOH sol is 1.5-4g. The content of the coal gasification fine slag and PVA-NaOH sol can be stably cross-linked and solidified with a cross-linking agent solution within the range, CGFS is stably loaded in gel and cannot fall off, and the obtained gel beads have excellent phenol adsorption performance.
To better crosslink PVA and CGFS and avoid the crosslinker solution from disrupting the three-dimensional network of the PVA gel, in some embodiments, the crosslinker solution comprises a polymer comprising H 3 BO 3 And CaCl 2 The solution of the phenol adsorbent can form the gel spherical phenol adsorbent with good mechanical property by adopting the cross-linking agent solution, and the cross-linking agent has low price, simple and convenient cross-linking method, stability, greenness and no pollution. Preferably H 3 BO 3 Has a mass concentration of 3-5%, preferably CaCl 2 The mass concentration of (b) is 1 to 3%.
In order to fully crosslink the PVA and the CGFS, the dosage of the crosslinking agent can be properly increased, in some embodiments, the volume ratio of the PVA-NaOH-CGFS sol to the crosslinking agent solution is greater than 1:2, and the volume ratio of the PVA-NaOH-CGFS sol to the crosslinking agent solution is preferably 1:2 to 1:5 in consideration of economic cost; the crosslinking time is 3-12 h.
In yet another exemplary embodiment of the present application, there is provided a use of the above phenol adsorbent for wastewater treatment.
The phenol adsorbent is used for wastewater treatment, so that the purpose of treating wastes with processes of wastes against one another and the effect of recycling wastes are achieved, and the phenol adsorbent has feasibility of popularization and application.
In some embodiments, the steps of the adsorption experiments of the present application comprise: a100 mL conical flask is adopted, phenol solution with the concentration of 50-100 mg/L is added, then 0.5-1.0 g of PVA-CGFS adsorbent is added, the mixture is placed on a constant temperature shaking table (120rpm, 25 ℃) to carry out adsorption experiment, and the adsorption rate is measured after 5-12 h of adsorption.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
CGFS specific surface area 562.22m for use in the examples herein 2 ·g -1 Total pore volume of 0.43m 2 ·g -1 The average pore diameter is 3.71nm, and the fixed carbon content is 60 to 75 percent。
Example 1
Preparation of PVA-CGFS phenol adsorbent
(1) Weighing 12g of PVA powder by an electronic balance, adding the PVA powder into 100mL of deionized water, and continuously and mechanically stirring the mixture in a water bath kettle at the temperature of 85 ℃ until the PVA powder is completely dissolved to form a homogeneous PVA solution with the concentration of 12%;
(2) Dissolving 1.5g of NaOH into 30mL of deionized water, diluting the PVA solution to obtain a mixed solution with the PVA mass concentration of 9.2%, uniformly stirring, and removing internal bubbles by ultrasonic treatment for 30min to form PVA-NaOH homogeneous sol;
(3) Mixing 2g of CGFS (particle size of 150 mu m) with the PVA-NaOH homogeneous sol obtained in the step (2) and uniformly stirring to form PVA-NaOH-CGFS sol;
(4) Mixing 40g H 3 BO 3 And 10g of CaCl 2 Dissolving in deionized water, and diluting to 1000mL in a volumetric flask to obtain a solution containing 4% H 3 BO 3 And 1% of CaCl 2 The mixed solution of (3) as a crosslinking agent solution for crosslinking reaction; dropwise adding the PVA-NaOH-CGFS sol obtained in the step (3) into a cross-linking agent solution (the mass ratio of the PVA-NaOH-CGFS sol to the cross-linking agent solution is 1:3) under continuous magnetic stirring by using an injector and an injection pump, and taking out after cross-linking for 12 hours to obtain PVA-CGFS particles with the uniform load CGFS and the particle size of 2-4 mm; washing the granules with deionized water for 3 times, and drying for later use.
Example 2
Preparation of PVA-CGFS phenol adsorbent
(1) Weighing 12g of PVA powder by an electronic balance, adding the PVA powder into 100mL of deionized water, and continuously and mechanically stirring the mixture in a water bath kettle at the temperature of 85 ℃ until the PVA powder is completely dissolved to form a homogeneous PVA solution with the mass concentration of 12%;
(2) Dissolving 1.5g of NaOH into 30mL of deionized water, diluting the PVA solution to obtain a mixed solution with the PVA mass concentration of 9.2%, uniformly stirring, and removing internal bubbles by ultrasonic treatment for 30min to form PVA-NaOH homogeneous sol;
(3) Mixing 3g of CGFS with the PVA-NaOH homogeneous sol obtained in the step (2) and uniformly stirring to form PVA-NaOH-CGFS sol;
(4) Mixing 40g H 3 BO 3 And 10g of CaCl 2 Dissolving in deionized water, and diluting to 1000mL in a volumetric flask to obtain a solution containing 4% H 3 BO 3 And 1% of CaCl 2 The mixed solution of (3) as a crosslinking agent solution for crosslinking reaction; dropwise adding the PVA-NaOH-CGFS sol obtained in the step (3) into a cross-linking agent solution (the mass ratio of the PVA-NaOH-CGFS sol to the cross-linking agent solution is 1:3) under continuous magnetic stirring by using an injector and an injection pump, and taking out after cross-linking for 12 hours to obtain PVA-CGFS particles with the uniform load CGFS and the particle size of 2-4 mm; washing the granules with deionized water for 3 times, and drying for later use.
Example 3
Preparation of PVA-CGFS phenol adsorbent
(1) Weighing 12g of PVA powder by an electronic balance, adding the PVA powder into 100mL of deionized water, and continuously and mechanically stirring the mixture in a water bath kettle at the temperature of 85 ℃ until the PVA powder is completely dissolved to form a homogeneous PVA solution with the concentration of 12%;
(2) Dissolving 1.5g of NaOH into 30mL of deionized water, diluting the PVA solution to obtain a mixed solution with the PVA mass concentration of 9.2%, uniformly stirring, and removing internal bubbles by ultrasonic treatment for 30min to form PVA-NaOH homogeneous sol;
(3) Mixing 4g of CGFS with the PVA-NaOH homogeneous sol obtained in the step (2) and uniformly stirring to form PVA-NaOH-CGFS sol;
(4) Mixing 40g H 3 BO 3 And 10g of CaCl 2 Dissolving in deionized water, and diluting to 1000mL in volumetric flask to obtain solution containing 4% H 3 BO 3 And 1% of CaCl 2 The mixed solution of (3) as a crosslinking agent solution for crosslinking reaction; dropwise adding the PVA-NaOH-CGFS sol obtained in the step (3) into a cross-linking agent solution (the mass ratio of the PVA-NaOH-CGFS sol to the cross-linking agent solution is 1:3) under continuous magnetic stirring by using an injector and an injection pump, and taking out after cross-linking for 12 hours to obtain PVA-CGFS particles with the uniform load CGFS and the particle size of 2-4 mm; washing the granules with deionized water for 3 times, and drying for later use.
Example 4
(1) Weighing 11g of PVA powder by using an electronic balance, adding the PVA powder into 100mL of deionized water, and continuously and mechanically stirring the PVA powder in a water bath kettle at the temperature of 85 ℃ until the PVA powder is completely dissolved to form a homogeneous PVA solution with the concentration of 11%;
(2) Dissolving 0.5g of NaOH into 10mL of deionized water, diluting the PVA solution to obtain a mixed solution with the PVA mass concentration of 10%, uniformly stirring, and removing internal bubbles by ultrasonic treatment for 30min to form PVA-NaOH homogeneous sol;
(3) Mixing 4g of CGFS with the PVA-NaOH homogeneous sol obtained in the step (2) and uniformly stirring to form PVA-NaOH-CGFS sol;
(4) Mixing 40g H 3 BO 3 And 10g of CaCl 2 Dissolving in deionized water, and diluting to 1000mL in volumetric flask to obtain solution containing 4% H 3 BO 3 And 1% of CaCl 2 The mixed solution of (3) as a crosslinking agent solution for crosslinking reaction; dropwise adding the PVA-NaOH-CGFS sol obtained in the step (3) into a cross-linking agent solution (the mass ratio of the PVA-NaOH-CGFS sol to the cross-linking agent solution is 1:2) under continuous magnetic stirring by using an injector and an injection pump, and taking out after cross-linking for 12 hours to obtain PVA-CGFS particles with the uniform load CGFS and the particle size of 2-4 mm; washing the granules with deionized water for 3 times, and drying for later use.
(5) The PVA-CGFS particles were used for phenol adsorption experiments: 0.100g of phenol is weighed in a fume hood, dissolved in deionized water and then fixed to the volume of 1000mL in a volumetric flask, thus obtaining 100mg/L of phenol solution. A50 mL phenol solution was added to a 100mL Erlenmeyer flask, and 0.9g PVA-CGFS adsorbent was added, and the Erlenmeyer flask was placed on a constant temperature shaker (120rpm, 25 ℃ C.) to conduct adsorption experiments. After 8h, the phenol adsorption rate in the system was 94.0%.
Example 5
Unlike example 1, the mass concentration of PVA in the mixed solution in step (2) was 12%.
Example 6
Unlike example 1, the mass concentration of the mixed solution PVA in step (2) was 6%.
Example 7
In step (3), 1g of CGFS was mixed with the PVA-NaOH homogeneous sol obtained in step (2) and stirred uniformly, unlike example 1.
Example 8
In step (3), 4.5g of CGFS was mixed with the PVA-NaOH homogeneous sol obtained in step (2) and stirred uniformly, unlike example 1.
Comparative example 1
An adsorption experiment was carried out using 0.129g of the same coal gasification fine slag as in example 1.
Adsorption experiments were performed on the adsorbents prepared in the above examples and comparative examples:
the above adsorbent was used in phenol adsorption experiments: weighing 0.100g of phenol in a fume hood, dissolving the phenol in deionized water, and then metering the volume to 1000mL in a volumetric flask to obtain a phenol solution of 100 mg/L. A50 mL phenol solution was added to a 100mL Erlenmeyer flask, and 0.9g PVA-CGFS adsorbent was added, and the Erlenmeyer flask was placed on a constant temperature shaker (120rpm, 25 ℃ C.) to conduct adsorption experiments. After 8h, the phenol adsorption rate in the system is measured by adopting a 4-aminoantipyrine spectrophotometry, and the test result is shown in table 1.
TABLE 1
| Granular state of gel adsorbent | Phenol adsorption (%) | Adsorbent recovery (%) | |
| Example 1 | Easy to form and stable | 79.3 | 100 |
| Example 2 | Easy to form and stable | 82.5 | 100 |
| Example 3 | Easy to form and stable | 92.7 | 100 |
| Example 4 | Easy to form and stable | 94.0 | 100 |
| Example 5 | No formation and corrosion | / | / |
| Example 6 | No formation and corrosion | / | / |
| Example 7 | Easy to form and stable | 65.8 | 100 |
| Example 8 | Difficult and unstable to mold | 91.5 | 100 |
| Comparative example 1 | / | 83.7 | 93 |
When the concentration of the sol is too low, the gel adsorbent obtained by crosslinking is unstable and is easy to dissolve in water; when the viscosity of the sol is too high, the tailing is serious when the sol is dropped into the cross-linking agent, so that the sol cannot be formed into balls, and a stable adsorbent cannot be prepared. Therefore, the sol concentration should be strictly controlled within the range, i.e., 11 to 13%.
Examples 1 to 3 show that the adsorption rate of the adsorbents obtained by gradually increasing the loading amounts (2 g, 3g, and 4 g) of the coal gasification fine slag with the same PVA concentration (12%) was increased as the loading amount was increased.
It is understood from examples 1 to 3 and examples 5 to 8 that since the phenol adsorption capacity is almost completely provided by the coal gasification fine slag, the adsorption rate of the adsorbent gradually increases with the increase of the doping amount within a certain range. However, if the doping amount of CGFS is too high (as in example 8), i.e., the gel content is relatively too low, on the one hand, the properties of the mixed sol fluid are affected due to the too high solid content, resulting in difficulty in dropping into the crosslinking agent in the form of droplets; on the other hand, as the amount of gel is relatively reduced, the stability of the adsorbent is deteriorated, and the gasified fine slag may fall off when the adsorbent is immersed in an aqueous solution for a long time, thereby causing secondary pollution to the water body.
Compared with the comparative example 1, the phenol adsorbent in the example 1 is in a gel sphere shape, the gel wraps the coal gasification fine slag and occupies a certain adsorption site, and the adsorption rate of the directly used coal gasification fine slag is slightly higher than that of the gel adsorbent. But compared with the phenol adsorbent coated by the gel, the phenol adsorbent coated by the gel is easier to separate and is not easy to block a filter screen.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects: coal Gasification Fine Slag (CGFS) belongs to solid waste, but due to the excellent adsorption capacity of the CGFS on phenol, the application obtains a granular phenol adsorbent by fixing the CGFS in a porous polyvinyl alcohol (PVA) three-dimensional gel network. The adsorbent has the performance of adsorbing phenolic pollutants in water, and also has the characteristic of simple separation through screening or precipitation, so that the resource utilization of the CGFS is realized, the aim of treating wastes with processes of wastes against one another and the effect of resource utilization of wastes are achieved, the feasibility of popularization and application is realized, and the sustainable development strategy is met.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The phenol adsorbent is characterized by comprising PVA gel and coal gasification fine slag loaded in the PVA gel.
2. The phenol adsorbent according to claim 1, wherein the phenol adsorbent has a particle size of 2 to 4mm, and preferably the coal gasification fine slag supported in the PVA gel has a particle size of 125 to 250 μm; more preferably, the loading amount of the coal gasification fine slag is 10-30 wt%.
3. The phenol adsorbent according to claim 1 or 2, wherein the coal gasification fine slag is a residue discharged by separation of coal gasification gas during purification; preferably, the specific surface area of the coal gasification fine slag is 500-570 m 2 ·g -1 The total pore volume is 0.4-0.5 m 2 ·g -1 The average pore diameter is 3-4 nm, and the fixed carbon content is 60-75%.
4. A method for producing the phenol adsorbent according to any one of claims 1 to 3, characterized in that the production method comprises:
preparing PVA-NaOH sol by using NaOH aqueous solution and PVA aqueous solution;
mixing the coal gasification fine slag with the PVA-NaOH sol to obtain a mixed solution, and carrying out ultrasonic treatment on the mixed solution to form PVA-NaOH-CGFS sol;
and crosslinking the PVA-NaOH-CGFS sol with a crosslinking agent solution to obtain the phenol adsorbent.
5. The method according to claim 4, wherein the aqueous PVA solution is prepared by a method comprising:
mixing PVA with water, and heating to dissolve the PVA to obtain the PVA aqueous solution;
preferably, the heating comprises water bath heating, preferably, the heating temperature is 80-90 ℃, and preferably, the heating time is 60-90 min.
6. The method according to claim 4 or 5, wherein the aqueous NaOH solution has a mass concentration of 5 to 10%, preferably the aqueous PVA solution has a mass concentration of 11 to 13%, and preferably the mixed solution has a mass concentration of 8 to 10%.
7. The preparation method according to any one of claims 4 to 6, wherein the content ratio of the coal gasification fine slag to the PVA-NaOH sol is 1.5 to 4g:130mL.
8. The method according to any one of claims 4 to 7, wherein the crosslinking agent solution comprises a solution containing H 3 BO 3 And CaCl 2 Preferably said H, glutaraldehyde, polyethylene oxide, and optionally one or more of 3 BO 3 The mass concentration of (3) to (5%) preferably said CaCl 2 The mass concentration of (A) is 1 to 3%.
9. The method according to any one of claims 4 to 8, wherein the volume ratio of the PVA-NaOH-CGFS sol to the cross-linking agent solution is 1:2 to 1:5; the crosslinking time is 3-12 h.
10. Use of the phenol adsorbent according to any one of claims 1 to 3, characterized in that the phenol adsorbent is used for wastewater treatment.
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| CN103936134A (en) * | 2014-05-06 | 2014-07-23 | 南京大学 | Method for treating phenolic wastewater by using synthetic ammonia gasification slag |
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| CN110723775A (en) * | 2019-10-29 | 2020-01-24 | 陕西延长石油（集团）有限责任公司 | Coking wastewater purification treatment device and method thereof |
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| CN103936134A (en) * | 2014-05-06 | 2014-07-23 | 南京大学 | Method for treating phenolic wastewater by using synthetic ammonia gasification slag |
| CN107081140A (en) * | 2017-05-23 | 2017-08-22 | 西安交通大学 | A kind of water treatment absorbent based on coal gasification lime-ash and preparation method thereof |
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