CN113582174A - Preparation method of straw activated carbon, straw activated carbon and application - Google Patents
Preparation method of straw activated carbon, straw activated carbon and application Download PDFInfo
- Publication number
- CN113582174A CN113582174A CN202110846095.9A CN202110846095A CN113582174A CN 113582174 A CN113582174 A CN 113582174A CN 202110846095 A CN202110846095 A CN 202110846095A CN 113582174 A CN113582174 A CN 113582174A
- Authority
- CN
- China
- Prior art keywords
- straw
- activated carbon
- solid mixture
- washing
- straw activated
- 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.)
- Pending
Links
- 239000010902 straw Substances 0.000 title claims abstract description 232
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 229
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 87
- 239000008247 solid mixture Substances 0.000 claims abstract description 86
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 63
- 239000002245 particle Substances 0.000 claims abstract description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 239000011592 zinc chloride Substances 0.000 claims abstract description 31
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 31
- 238000005406 washing Methods 0.000 claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 27
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 13
- 238000004140 cleaning Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000007873 sieving Methods 0.000 claims abstract description 8
- 230000003213 activating effect Effects 0.000 claims abstract description 7
- 235000019441 ethanol Nutrition 0.000 claims abstract description 7
- 238000004042 decolorization Methods 0.000 claims abstract description 3
- 239000008367 deionised water Substances 0.000 claims description 26
- 229910021641 deionized water Inorganic materials 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 16
- 239000003513 alkali Substances 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 11
- 238000009210 therapy by ultrasound Methods 0.000 claims description 11
- 230000007935 neutral effect Effects 0.000 claims description 10
- 239000012670 alkaline solution Substances 0.000 claims description 8
- 230000000630 rising effect Effects 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 6
- 238000004332 deodorization Methods 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 44
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000012535 impurity Substances 0.000 abstract description 5
- 239000002023 wood Substances 0.000 abstract description 5
- 239000003245 coal Substances 0.000 abstract description 4
- 230000004913 activation Effects 0.000 description 23
- 239000011148 porous material Substances 0.000 description 20
- 230000000694 effects Effects 0.000 description 17
- 230000003197 catalytic effect Effects 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 241000209140 Triticum Species 0.000 description 4
- 235000021307 Triticum Nutrition 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 229960000907 methylthioninium chloride Drugs 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 240000006394 Sorghum bicolor Species 0.000 description 3
- 235000011684 Sorghum saccharatum Nutrition 0.000 description 3
- 240000008042 Zea mays Species 0.000 description 3
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 3
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 235000005822 corn Nutrition 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 238000009331 sowing Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- -1 timber Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
-
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
- C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/354—After-treatment
- C01B32/384—Granulation
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/485—Plants or land vegetals, e.g. cereals, wheat, corn, rice, sphagnum, peat moss
Abstract
The application relates to the technical field of activated carbon production, and particularly discloses a preparation method of straw activated carbon, straw activated carbon and application. The preparation method of the straw activated carbon comprises the following steps: cleaning, drying, crushing and sieving the straws to obtain straw particles; mixing straw particles with water, adding zinc chloride, heating for reaction under the protection of nitrogen, and cooling to obtain a solid mixture A; washing the solid mixture A with absolute ethyl alcohol, washing with water until no alcohol smell exists, and drying to obtain a solid mixture B; mixing the solid mixture B with phosphoric acid, activating, heating to react under the protection of nitrogen, introducing nitrogen to cool, and obtaining a solid mixture C; washing the solid mixture C with hydrochloric acid, washing with water to neutrality, and drying to obtain a solid mixture D; and extruding and granulating the solid mixture D to obtain the product. The straw activated carbon prepared by the method has the quality no different from that of coal and wood activated carbon, has good adsorption performance, and can be widely applied to decolorization and impurity removal treatment.
Description
Technical Field
The application relates to the technical field of activated carbon production, in particular to a preparation method of straw activated carbon, straw activated carbon and application.
Background
Corn, wheat and sorghum are three kinds of grain crops widely distributed in China, and with the improvement of grain yield, the by-product straws of the corn, the wheat and the sorghum are not fully utilized all the time, so that a large amount of surplus straws exist in rural areas, the using amount of the straws is far lower than the production amount, and meanwhile, with the use of modern chemical fertilizers, the requirement of agriculture on the fertilizer prepared from the straws is greatly reduced, and the treatment of the straws becomes a great problem. If the straws are not treated in time, the sowing of autumn sowing crops such as wheat and the like can be influenced, so that the phenomenon of burning the straws on a large scale frequently occurs. The consequence of burning straw on a large scale is environmental pollution and is not conducive to sustainable development.
The active carbon is a black porous solid carbon, the main component of the active carbon is carbon, and the active carbon contains a small amount of elements such as oxygen, hydrogen, sulfur, nitrogen, chlorine and the like, has strong adsorption performance, and is an industrial adsorbent with wide application. The raw materials for preparing the activated carbon mainly comprise coal, wood and fruit shells, and are limited by the source of the raw materials, so that the price of the activated carbon is high, and a large amount of wood, coal and other resources are consumed for preparing the activated carbon, thereby causing very serious resource waste. Therefore, the preparation of the activated carbon by using the waste straws is more and more concerned by people, so that the production cost can be reduced, the waste of resources can be reduced, and the problem of straw treatment is solved.
Aiming at the related technologies, when the waste straws are used for preparing the activated carbon, compared with the activated carbon prepared by taking the wood and the fruit shell as raw materials, the quality of the straw activated carbon is poor, and the adsorption performance of the straw activated carbon needs to be improved.
Disclosure of Invention
In order to improve the quality of the straw activated carbon and improve the adsorption performance of the straw activated carbon, the application provides a preparation method of the straw activated carbon.
In a first aspect, the application provides a preparation method of straw activated carbon, which adopts the following technical scheme:
a preparation method of straw activated carbon comprises the following steps:
s1, cleaning the straws, drying the straws at the temperature of 100-120 ℃ until the water content is lower than 5%, crushing the straws, and sieving the straws with 80-mesh and 120-mesh sieves to obtain straw particles;
s2, mixing the straw particles with deionized water, adding zinc chloride, stirring and mixing, reacting for 20-40min at the temperature of 200-250 ℃ under the protection of nitrogen, and naturally cooling to 25 ℃ after the reaction is finished to obtain a solid mixture A;
s3, cleaning the solid mixture A by using absolute ethyl alcohol, cleaning the solid mixture A by using deionized water until no alcohol smell exists, and drying the solid mixture A at the temperature of 100-120 ℃ until the water content is lower than 5% to obtain a solid mixture B;
s4, mixing the solid mixture B with phosphoric acid, activating at 220 ℃ of 180-2 h, heating to 550 ℃ of 450-2 h under the protection of nitrogen, reacting for 1-2h, and cooling to 25 ℃ by introducing nitrogen after the reaction is finished to obtain a solid mixture C;
s5, cleaning the solid mixture C by using a hydrochloric acid solution with the mass concentration of 3-5%, cleaning the solid mixture C to be neutral by using deionized water, and drying the solid mixture C at the temperature of 100-120 ℃ until the water content is lower than 5% to obtain a solid mixture D;
and S6, extruding and granulating the solid mixture D to obtain the straw activated carbon.
Through adopting above-mentioned technical scheme, after smashing the edulcoration of straw raw materials, carry out preliminary reaction with zinc chloride as the catalyst, improve the activation reaction rate of straw, promote the production in the inside hole of straw, improve the adsorption effect of straw, after preliminary reaction, use absolute ethyl alcohol to detach remaining zinc chloride, wash after the drying, use phosphoric acid to carry out the second step reaction as the catalyst, macromolecule among the catalysis straw splits, participate in the formation of new bond in the straw simultaneously, promote the fracture of carbon bond, restrain the production of tar, thereby improve the activation reaction speed of straw, further promote the production of straw pore structure, increase the hole quantity in the straw, thereby obviously improve the adsorption effect of the straw activated carbon who makes.
This application is through the substep reaction, when initial temperature is lower, use zinc chloride earlier as the catalyst to promote activation reaction forward going, the later stage is under higher temperature, use phosphoric acid to promote activation reaction forward going for the catalyst, combine zinc chloride and phosphoric acid to use, zinc chloride high temperature easy decomposition has been improved, the defect that phosphoric acid low temperature catalytic activity is low, make the straw all take place abundant activation reaction at the overall process, thereby improve the quality of straw active carbon, improve the adsorption effect of the straw active carbon who makes.
Preferably, in S2, before the straw particles are mixed with deionized water, the straw particles are further subjected to alkali treatment, and the alkali treatment includes: and (3) soaking the straw particles in an alkaline solution, washing the straw particles to be neutral by using deionized water after the soaking is finished, and drying the straw particles for later use.
By adopting the technical scheme, the straw particles are soaked by using the alkaline solution, so that wax, ash and other water-soluble impurities on the surfaces of the straw particles can be effectively removed, and the influence of the impurities on the performance of the final product straw activated carbon is reduced, so that the quality of the prepared straw activated carbon is improved, and the adsorption performance of the straw activated carbon is improved.
Preferably, the alkaline solution is a sodium hydroxide solution with the mass concentration of 3-5%, and the soaking time is 24-48 h.
By adopting the technical scheme, when the concentration of the alkaline solution is too high, the surface and the pore structure of the straw can be damaged, so that the pore structure is collapsed, the number of effective pores in the straw is reduced, and the adsorption performance of the prepared straw activated carbon is reduced. When the concentration of the alkaline solution is too low, the zinc chloride on the surface and in the pores of the straw can not be sufficiently eluted, so that the subsequent steps are affected, and the adsorption performance of the prepared straw activated carbon is affected.
Preferably, in the S2, the weight ratio of the straw particles to the zinc chloride is 1 (2-3).
By adopting the technical scheme, when the weight ratio of the straw particles to the zinc chloride is in the range, the zinc chloride has a better promotion effect on the generation of the straw pore structure, so that the active reaction of the straw is promoted to be carried out positively, and the prepared straw activated carbon has better adsorption performance.
Preferably, in S4, the solid mixture B is mixed with phosphoric acid and then subjected to ultrasonic treatment.
Through adopting above-mentioned technical scheme, the frequency of ultrasonic wave is higher than 20kHz, has better cavitation effect and heat effect, can impel solute molecule migration velocity in the mixed solution to accelerate, thereby improve the catalytic effect of phosphoric acid, further impel the activation reaction forward of straw to go on, show the formation that improves the interior pore structure of straw, thereby improve the adsorption performance of straw activated carbon.
Preferably, the temperature of the ultrasonic treatment is 30-50 ℃, and the treatment time is 20-40 min.
By adopting the technical scheme, within the temperature and treatment time range, the ultrasonic treatment can play a good promoting role in the catalytic effect of the phosphoric acid, so that the formation of the pore structure in the straw is improved, and the adsorption performance of the prepared straw activated carbon is improved.
Preferably, in the S4, the weight ratio of the solid mixture B to the phosphoric acid is 1 (2-3).
By adopting the technical scheme, when the using amount of the solid mixture B and the phosphoric acid is in the range of the proportion, the phosphoric acid can fully promote the forward progress of the straw activation reaction, accelerate the formation of the pore structure in the straw, generate a fine and dense pore structure on the surface of the straw, and improve the adsorption performance of the straw activated carbon. When the usage amount of the phosphoric acid is less than the proportion, the phosphoric acid cannot sufficiently generate a catalytic effect, so that the number of pores is reduced, and the adsorption performance of the straw activated carbon is reduced.
Preferably, in S4, the temperature increase rate is 5-7 ℃/min.
By adopting the technical scheme, when the temperature rising speed is in the range, the prepared straw activated carbon has better adsorption performance. The reason for analyzing the above is that when the temperature rising speed is low, the activation reaction of the straw is slow, so that the generation rate of the pore structure of the straw is slow, and the adsorption effect of the straw activated carbon is not favorably improved. When the temperature rising speed is high, the activation reaction is rapidly carried out and is violent, so that volatile components in the straws are gathered in the pore structures of the straws to form carbon black, the pore structures are blocked, and the adsorption effect of the straw activated carbon is reduced.
In a second aspect, the present application provides a straw activated carbon, which adopts the following technical scheme:
straw activated carbon prepared by the method for preparing straw activated carbon according to any one of claims 1 to 8.
Through adopting above-mentioned technical scheme, the straw activated carbon of this application is inside to have more pore structure to make it have good adsorption efficiency, have the quality that is no different from the activated carbon who makes with coal, timber, shell as the material.
In a third aspect, the application provides an application of straw activated carbon, which adopts the following technical scheme:
an application of straw activated carbon in decoloring and deodorizing.
By adopting the technical scheme, the straw activated carbon has excellent adsorption performance, so that the straw activated carbon can be widely applied to decolorization and deodorization treatment of foods or products.
In summary, the present application has the following beneficial effects:
1. according to the method, the straw is subjected to segmented catalytic activation reaction by adopting zinc chloride and phosphoric acid, and the zinc chloride has higher sensitivity at an initial low temperature and the phosphoric acid has a wide catalytic activity temperature range, so that the straw activation reaction is promoted by segmented catalysis, the straw is fully reacted, and the adsorption effect of the straw activated carbon is improved;
2. in the application, the ultrasonic wave is preferably adopted to assist the phosphoric acid catalytic reaction, and the ultrasonic wave has a cavitation effect, so that the movement of molecules in the mixed solution is accelerated, the catalytic reaction activity of the phosphoric acid is improved, the straw is more fully reacted, and the adsorption performance of the straw activated carbon is improved;
3. according to the method, the temperature rise speed of the phosphoric acid catalytic reaction is controlled, so that the severe reaction of the straws due to overhigh temperature is avoided, the condition that the carbon black blocks the pore structures of the straws is generated, and the adsorption performance of the straw activated carbon is ensured.
Detailed Description
The present application will be described in further detail with reference to examples.
The raw materials used in the examples of the present application are commercially available, except for the following specific descriptions:
the straw is corn straw or wheat straw or sorghum straw;
zinc chloride was obtained from Shanghai Michelin Biochemical technology Ltd, cat #: z820755, CAS No.: 7646-85-7, analytically pure; the absolute ethyl alcohol is obtained from Shanghai Michelin Biochemical technology Co., Ltd, CAS No. 64-17-5, and is analytically pure;
phosphoric acid is collected from Shanghai Maxlin Biotechnology Limited, CAS No. 7664-38-2, and is analytically pure, with a mass percent concentration of 85%;
the hydrochloric acid solution is self-prepared, and the mass percentage concentration is 3 percent, 4 percent and 5 percent respectively;
the sodium hydroxide solution is self-prepared, and the mass percentage concentrations are respectively 2%, 3%, 4%, 5% and 6%;
the sodium bicarbonate solution is self-prepared, and the mass percentage concentration is 4%.
Examples
Example 1
Straw activated carbon is prepared by the following steps:
s1, cleaning the straws, drying the straws at 110 ℃ until the water content is lower than 5%, crushing the straws, and sequentially sieving the straws with 80-120 meshes to obtain straw particles with the particle size of 80-120 meshes;
s2, weighing 1kg of straw particles, mixing with 5kg of deionized water, adding 1kg of zinc chloride, stirring and mixing for 10min under the condition of 120r/min, reacting for 30min at 225 ℃ under the protection of nitrogen, and naturally cooling to 25 ℃ after the reaction is finished to obtain a solid mixture A;
s3, washing the solid mixture A by using absolute ethyl alcohol, then continuously washing by using deionized water until no alcohol smell exists, and drying at 110 ℃ until the water content is lower than 5% to obtain a solid mixture B;
s4, weighing 0.5kg of solid mixture B, mixing with 0.5kg of phosphoric acid (the mass percentage concentration is 85%), activating at 180 ℃ for 1.5h, heating to 500 ℃ at the speed of 3 ℃/min under the protection of nitrogen, reacting for 1.5h, and cooling to 25 ℃ after the reaction is finished by introducing nitrogen (the flow rate is 10L/min), so as to obtain a solid mixture C;
s5, washing the solid mixture C by using a hydrochloric acid solution (the mass percentage concentration is 3%), then washing the solid mixture C to be neutral by using deionized water, and drying the solid mixture C at 110 ℃ until the water content is lower than 5% to obtain a solid mixture D;
and S6, extruding and granulating the solid mixture D to obtain the solid mixture D.
Example 2
A straw activated carbon is different from that in the embodiment 1, in the preparation process S2 of the straw activated carbon, before straw particles are mixed with deionized water, the straw particles are further subjected to alkali treatment, and the alkali treatment comprises the following steps: soaking the straw particles in a sodium bicarbonate solution (the mass percent solubility is 4%) for 60 hours, washing the straw particles to be neutral by using deionized water after the soaking is finished, and drying the straw particles at the temperature of 110 ℃ until the water content is lower than 5% for later use.
Example 3
A straw activated carbon is different from that in the embodiment 1, in the preparation process S2 of the straw activated carbon, before straw particles are mixed with deionized water, the straw particles are further subjected to alkali treatment, and the alkali treatment comprises the following steps: soaking the straw particles in a sodium hydroxide solution (the mass percent solubility is 2%) for 60 hours, washing the straw particles to be neutral by deionized water after the soaking is finished, and drying the straw particles at the temperature of 110 ℃ until the water content is lower than 5% for later use.
Examples 4 to 7
A straw activated carbon, which is different from example 3 in that the mass percentage concentration and the soaking time of the sodium hydroxide solution are shown in table 1.
TABLE 1 Mass percent concentration of sodium hydroxide solution in examples 3-7
Examples 8 to 11
A straw activated carbon is different from the straw activated carbon in example 5 in that in the preparation process of the straw activated carbon, in S2, the use amounts of straw particles and zinc chloride are shown in Table 2.
TABLE 2 use of straw pellets and Zinc chloride in examples 5, 8-11
Example 12
A difference between the straw activated carbon and the embodiment 9 is that in the preparation process of the straw activated carbon, in S4, after the solid mixture B is mixed with phosphoric acid, ultrasonic treatment is further carried out, wherein the frequency of the ultrasonic treatment is 28kHz, the temperature is 25 ℃, and the time is 10 min.
Examples 13 to 16
A straw activated carbon was different from example 9 in that the temperature and time of ultrasonic treatment were as shown in Table 3.
TABLE 3 temperature and time of sonication for examples 12-16
Examples 17 to 20
A straw activated carbon, which is different from example 14 in that the solid mixture B and phosphoric acid are used in amounts shown in Table 4 in S4 in the preparation process of the straw activated carbon.
TABLE 4 examples 14, 17-20 solid mixture B and phosphoric acid amounts used
Examples 21 to 24
A straw activated carbon, which is different from that of example 18 in that the temperature rise rate in S4 in the preparation process of the straw activated carbon is shown in Table 5.
TABLE 5 examples 18, 21 to 24 rates of temperature rise
Example 25
Straw activated carbon is prepared by the following steps:
s1, cleaning the straws, drying the straws at 100 ℃ until the water content is lower than 5%, crushing the straws, and sequentially sieving the straws with 80-120 meshes to obtain straw particles with the particle size of 80-120 meshes;
s2, weighing 1kg of straw particles, mixing with 5kg of deionized water, adding 1kg of zinc chloride, stirring and mixing for 10min under the condition of 120r/min, reacting for 20min at 200 ℃ under the protection of nitrogen, and naturally cooling to 25 ℃ after the reaction is finished to obtain a solid mixture A;
s3, washing the solid mixture A by using absolute ethyl alcohol, then continuously washing by using deionized water until no alcohol smell exists, and drying at 100 ℃ until the water content is lower than 5% to obtain a solid mixture B;
s4, weighing 0.5kg of solid mixture B, mixing with 0.5kg of phosphoric acid (the mass percentage concentration is 85%), activating at 200 ℃ for 1h, heating to 450 ℃ at the speed of 3 ℃/min under the protection of nitrogen, reacting for 1h, and cooling to 25 ℃ after the reaction is finished in a nitrogen introducing (the flow rate is 10L/min), so as to obtain a solid mixture C;
s5, washing the solid mixture C by using a hydrochloric acid solution (the mass percentage concentration is 4%), then washing the solid mixture C to be neutral by using deionized water, and drying the solid mixture C at 100 ℃ until the water content is lower than 5% to obtain a solid mixture D;
and S6, extruding and granulating the solid mixture D to obtain the solid mixture D.
Example 26
Straw activated carbon is prepared by the following steps:
s1, cleaning the straws, drying the straws at 120 ℃ until the water content is lower than 5%, crushing the straws, and sequentially sieving the straws with 80-120 meshes to obtain straw particles with the particle size of 80-120 meshes;
s2, weighing 1kg of straw particles, mixing with 5kg of deionized water, adding 1kg of zinc chloride, stirring and mixing for 10min under the condition of 120r/min, reacting for 40min at 250 ℃ under the protection of nitrogen, and naturally cooling to 25 ℃ after the reaction is finished to obtain a solid mixture A;
s3, washing the solid mixture A by using absolute ethyl alcohol, then continuously washing by using deionized water until no alcohol smell exists, and drying at 120 ℃ until the water content is lower than 5% to obtain a solid mixture B;
s4, weighing 0.5kg of solid mixture B, mixing with 0.5kg of phosphoric acid (the mass percentage concentration is 85%), activating at 220 ℃ for 2h, heating to 550 ℃ at the speed of 3 ℃/min under the protection of nitrogen, reacting for 2h, and cooling to 25 ℃ by introducing nitrogen (the flow rate is 10L/min) after the reaction is finished to obtain a solid mixture C;
s5, washing the solid mixture C by using a hydrochloric acid solution (the mass percentage concentration is 5%), then washing the solid mixture C to be neutral by using deionized water, and drying the solid mixture C at 120 ℃ until the water content is lower than 5% to obtain a solid mixture D;
and S6, extruding and granulating the solid mixture D to obtain the solid mixture D.
Comparative example
Comparative example 1
An activated carbon which differs from example 1 in that it is obtained by the following steps:
s1, cleaning the straws, drying the straws at 110 ℃ until the water content is lower than 5%, crushing the straws, and sequentially sieving the straws with 80-120 meshes to obtain straw particles with the particle size of 80-120 meshes;
s2, weighing 1kg of straw particles, mixing with 5kg of deionized water, adding 1kg of zinc chloride, stirring and mixing for 10min under the condition of 120r/min, reacting for 30min at 225 ℃ under the protection of nitrogen, and naturally cooling to 25 ℃ after the reaction is finished to obtain a solid mixture A;
s3, washing the solid mixture A by using absolute ethyl alcohol, then continuously washing by using deionized water until no alcohol smell exists, and drying at 110 ℃ until the water content is lower than 5% to obtain a solid mixture B;
and S4, extruding and granulating the solid mixture B to obtain the solid mixture B.
Comparative example 2
An activated carbon which differs from example 1 in that it is obtained by the following steps:
s1, cleaning the straws, drying the straws at 110 ℃ until the water content is lower than 5%, crushing the straws, and sequentially sieving the straws with 80-120 meshes to obtain straw particles with the particle size of 80-120 meshes;
s2, weighing 0.5kg of straw particles, mixing with 0.5kg of phosphoric acid (the mass percentage concentration is 85%), activating at 180 ℃ for 1.5h, heating to 500 ℃ at the speed of 3 ℃/min under the protection of nitrogen, reacting for 1.5h, and cooling to 25 ℃ by introducing nitrogen (the flow rate is 10L/min) after the reaction is finished to obtain a solid mixture A;
s3, washing the solid mixture A by using a hydrochloric acid solution (the mass percentage concentration is 3%), then washing the solid mixture A to be neutral by using deionized water, and drying the solid mixture A at 100 ℃ until the water content is lower than 5% to obtain a solid mixture B;
and S4, extruding and granulating the solid mixture B to obtain the solid mixture B.
Performance test
Respectively taking the straw activated carbon prepared in examples 1-26 and comparative examples 1-2 as a test object, and testing the iodine adsorption value of the straw activated carbon by referring to a method in GB/T12496.8-2015 'test method for wood activated carbon-determination of iodine adsorption value'; the methylene blue adsorption value of the straw activated carbon is tested by referring to the method in GB/T12496.10-1999 test method of wooden activated carbon-determination of methylene blue adsorption value, and the test results are shown in the following table 6.
TABLE 6 straw activated carbon adsorption Performance test results
As can be seen from the data in Table 6, the straw activated carbon prepared by the preparation method of the present application (namely, the examples 1 to 26) has iodine adsorption values of more than 95mg/g and methylene blue adsorption values of more than 670mg/g, so that the straw activated carbon prepared by the examples of the present application has high quality and good adsorption performance.
The difference between example 1 and comparative examples 1 and 2 is that in comparative example 1, only zinc chloride is used as a catalyst to catalyze the straw activation reaction, and in comparative example 2, only phosphoric acid is used as a catalyst to catalyze the straw activation reaction, and as can be seen from the data in table 6, the straw activated carbon prepared by using zinc chloride and phosphoric acid to catalyze the straw activation reaction in a staged manner in example 1 of the present application has better adsorption performance, and the adsorption values of iodine and methylene blue are far higher than those of the straw activated carbon prepared in comparative example 1 and comparative example 2. Therefore, the absorption performance of the prepared straw activated carbon can be obviously improved by using zinc chloride and phosphoric acid to catalyze straw activation in a segmented manner, and the reason for analyzing the absorption performance is that the zinc chloride has high catalytic sensitivity at the temperature of 200-250 ℃ and has good catalytic activity, and when the temperature is too high, the zinc chloride is heated and decomposed to cause the collapse of the internal pore structure of the straw, so that the absorption effect of the straw activated carbon is reduced; the activation temperature range of the phosphoric acid is wider, but the activation effect of the phosphoric acid is not as good as that of zinc chloride at the temperature of 200-250 ℃, so that the adsorption performance of the straw activated carbon can be obviously improved through step-by-step activation when the straw activated carbon is prepared.
The difference between the embodiment 1 and the embodiment 2 is that in the embodiment 2, the straw particles are further subjected to alkali treatment in the step S2, and it can be known from data in table 6 that the alkali treatment can improve the adsorption effect of the worthy straw activated carbon, and the reason for analyzing the alkali treatment is that the alkali treatment can effectively remove wax, ash and other water-soluble impurities on the surfaces of the straw particles, and reduce the influence of the impurities on the performance of the final product straw activated carbon, thereby improving the adsorption performance of the prepared straw activated carbon.
The difference between the example 2 and the examples 3-7 is that the alkaline solution used in the alkaline treatment process is different, and the data in table 6 show that the adsorption performance of the prepared straw activated carbon can be remarkably improved when the alkaline treatment is carried out by using the sodium hydroxide solution with the mass percent solubility of 3-5%.
The difference between the example 5 and the examples 2-11 is that the straw particles and the zinc chloride are used in different proportions in the preparation process of the straw activated carbon, and the data in the table 6 show that the prepared straw activated carbon has better adsorption performance when the weight ratio of the straw particles to the zinc chloride is 1 (2-3). The reason for analyzing the above is that when the weight ratio of the straw particles to the zinc chloride is in the above range, the zinc oxide has a relatively high-efficiency catalytic action on the activation reaction of the straw, so that the straw activation reaction is accelerated, the formation speed of the pore structure in the straw is increased, and the adsorption performance of the straw activated carbon is improved.
Example 9 is different from example 12 in that in example 12, when the solid mixture B is catalyzed by phosphoric acid, ultrasonic treatment is also performed, and as can be seen from the data in table 6, the adsorption performance of the straw activated carbon prepared by ultrasonic treatment of the mixture of the solid mixture B and phosphoric acid can be remarkably improved. The reason for this is that the cavitation effect of the ultrasonic wave promotes the molecular motion, thereby improving the catalytic effect of phosphoric acid.
The difference between the example 12 and the examples 13-16 is that the temperature and the treatment time are different during the ultrasonic treatment, and the data in the table 6 show that when the temperature is 30-50 ℃ and the treatment time is 20-40min, the prepared straw activated carbon has better adsorption performance.
The difference between the example 14 and the examples 17-20 is that the solid mixture B and the phosphoric acid are used in different amounts, and the data in Table 6 show that when the weight ratio of the solid mixture B to the phosphoric acid is 1 (2-3), the phosphoric acid has the best catalytic effect on the straw, so that a large amount of pore structures are generated in the straw, and the adsorption performance of the straw activated carbon is improved.
The difference between the example 18 and the examples 21 to 24 is that the temperature rising speed is different in the process of the phosphoric acid catalytic activation reaction, and as can be seen from the data in table 6, when the temperature rising speed is 5 to 7 ℃/min, the prepared straw activated carbon has better adsorption performance, and the reason for analyzing the difference is that when the temperature rising speed is too slow, the catalytic efficiency of phosphoric acid is low, the promotion effect on the activation reaction is poor, and when the temperature rising speed is too fast, the activation reaction is severe, so that volatile components in the straw are aggregated to form carbon black, and the pore structure is blocked, so that the adsorption effect of the prepared straw activated carbon is reduced.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. A preparation method of straw activated carbon is characterized by comprising the following steps:
s1, cleaning the straws, drying, crushing and sieving to obtain straw particles;
s2, mixing the straw particles with deionized water, adding zinc chloride, stirring and mixing, reacting for 20-40min at the temperature of 200-250 ℃ under the protection of nitrogen, and naturally cooling to 25 ℃ after the reaction is finished to obtain a solid mixture A;
s3, washing the solid mixture A by using absolute ethyl alcohol, then washing by using deionized water until no alcohol smell exists, and drying to obtain a solid mixture B;
s4, mixing the solid mixture B with phosphoric acid, activating at 220 ℃ of 180-2 h, heating to 550 ℃ of 450-2 h under the protection of nitrogen, reacting for 1-2h, and cooling to 25 ℃ by introducing nitrogen after the reaction is finished to obtain a solid mixture C;
s5, washing the solid mixture C by using a hydrochloric acid solution with the mass percentage concentration of 3-5%, then washing the solid mixture C to be neutral by using deionized water, and drying to obtain a solid mixture D;
and S6, extruding and granulating the solid mixture D to obtain the straw activated carbon.
2. The method for preparing straw activated carbon according to claim 1, wherein in S2, before mixing the straw particles with deionized water, the straw particles are further subjected to alkali treatment, and the alkali treatment comprises the following steps: and (3) soaking the straw particles in an alkaline solution, washing the straw particles to be neutral by using deionized water after the soaking is finished, and drying the straw particles for later use.
3. The preparation method of straw activated carbon as claimed in claim 2, wherein the alkaline solution is a sodium hydroxide solution with a mass concentration of 3-5%, and the soaking time is 24-48 h.
4. The preparation method of straw activated carbon as claimed in claim 1, wherein in S2, the weight ratio of straw particles to zinc chloride is 1 (2-3).
5. The method for preparing straw activated carbon according to claim 1, wherein in the step S4, after the solid mixture B is mixed with phosphoric acid, ultrasonic treatment is further performed.
6. The preparation method of straw activated carbon according to claim 5, wherein the temperature of the ultrasonic treatment is 30-50 ℃, and the treatment time is 20-40 min.
7. The preparation method of straw activated carbon as claimed in claim 1, wherein in S4, the weight ratio of the solid mixture B to the phosphoric acid is 1 (2-3).
8. The preparation method of straw activated carbon as claimed in claim 1, wherein in the step S4, the temperature rising speed is 5-7 ℃/min.
9. Straw activated carbon, characterized in that the straw activated carbon is prepared by the method for preparing straw activated carbon according to any one of claims 1 to 8.
10. The application of the straw activated carbon is characterized in that the straw activated carbon is applied to decolorization and deodorization.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110846095.9A CN113582174A (en) | 2021-07-26 | 2021-07-26 | Preparation method of straw activated carbon, straw activated carbon and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110846095.9A CN113582174A (en) | 2021-07-26 | 2021-07-26 | Preparation method of straw activated carbon, straw activated carbon and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113582174A true CN113582174A (en) | 2021-11-02 |
Family
ID=78250106
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110846095.9A Pending CN113582174A (en) | 2021-07-26 | 2021-07-26 | Preparation method of straw activated carbon, straw activated carbon and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113582174A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116173902A (en) * | 2023-02-10 | 2023-05-30 | 成都华域环保有限公司 | Preparation method of modified activated carbon |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101070155A (en) * | 2007-06-08 | 2007-11-14 | 山东大学 | Method for preparing active charcoal of scripus tubernaemontani stem |
| CN103288084A (en) * | 2013-06-07 | 2013-09-11 | 上海交通大学 | Method for preparing modified activated carbon at normal pressure |
| CN107804848A (en) * | 2017-11-21 | 2018-03-16 | 浙江省林业科学研究院 | A kind of preparation method of the straw base porous activated carbon of surface active |
| CN110683539A (en) * | 2019-10-25 | 2020-01-14 | 潍坊科技学院 | Method for preparing biological activated carbon by utilizing tomato and eggplant straw mixture |
-
2021
- 2021-07-26 CN CN202110846095.9A patent/CN113582174A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101070155A (en) * | 2007-06-08 | 2007-11-14 | 山东大学 | Method for preparing active charcoal of scripus tubernaemontani stem |
| CN103288084A (en) * | 2013-06-07 | 2013-09-11 | 上海交通大学 | Method for preparing modified activated carbon at normal pressure |
| CN107804848A (en) * | 2017-11-21 | 2018-03-16 | 浙江省林业科学研究院 | A kind of preparation method of the straw base porous activated carbon of surface active |
| CN110683539A (en) * | 2019-10-25 | 2020-01-14 | 潍坊科技学院 | Method for preparing biological activated carbon by utilizing tomato and eggplant straw mixture |
Non-Patent Citations (2)
| Title |
|---|
| XIANJUN XING ET AL: ""Preparation and analysis of straw activated carbon synergetic catalyzed by ZnCl2-H3PO4 through hydrothermal carbonization combined with ultrasonic assisted immersion pyrolysis"", 《WASTE MANAGEMENT》, vol. 84, pages 275 - 72 * |
| 王迎春等: "《热处理工艺学》", 北京理工大学出版社, pages: 125 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116173902A (en) * | 2023-02-10 | 2023-05-30 | 成都华域环保有限公司 | Preparation method of modified activated carbon |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lu et al. | An aggregated understanding of cellulase adsorption and hydrolysis for ball-milled cellulose | |
| CN105000558B (en) | A kind of method that activated carbon is directly produced in spent acid | |
| CN111492986A (en) | Hydrophilic modified plant fiber cat litter material and preparation method thereof | |
| CN103833425B (en) | Treatment method for hyperosmosis concentrated mash waste liquor | |
| CN106699449A (en) | Double-layer coated slow-release nitrogen fertilizer for improving saline-alkali soil and preparation method thereof | |
| CN106334549A (en) | Porous composite material for purifying formaldehyde and TVOCs and preparation method of porous composite material | |
| CN111848291A (en) | Environment-friendly coated slow-release organic fertilizer and preparation method thereof | |
| CN113582174A (en) | Preparation method of straw activated carbon, straw activated carbon and application | |
| CN111644158A (en) | Carbon-based adsorbent for removing phosphate in solution | |
| CN104860779A (en) | Soil improvement type fertilizer and preparation method thereof | |
| CN103408006B (en) | Manufacturing technology for low-sulfur activated carbon | |
| CN114956079A (en) | Method for preparing activated carbon by wood biomass ammonia baking pretreatment | |
| CN108841114A (en) | A kind of novel environment friendly Wood-plastic material and preparation method thereof | |
| CN110817869A (en) | Zinc phosphate-organic acid composite activator and method for preparing activated carbon by using same | |
| CN111530436A (en) | Method for modifying shells | |
| CN110683539A (en) | Method for preparing biological activated carbon by utilizing tomato and eggplant straw mixture | |
| JP2010509167A5 (en) | ||
| CN104876681A (en) | Fertilizer combining organic carbon and inorganic nutrients and preparation method of fertilizer | |
| CN105645468B (en) | A kind of preparation method of metatitanic acid | |
| CN110386989B (en) | Preparation method of low-viscosity high-resistance starch | |
| CN106519050A (en) | Preparing technology of adipic acid porous crosslinked starch | |
| CN107043293A (en) | A kind of vegetables fertilizer of microelement-supplementing | |
| CN1557787A (en) | Binding agent for pelletization of organic-inorganic compound fertilizer and method for preparing the same | |
| CN106622147A (en) | Method for preparing adsorbent from corncob powder | |
| CN109336109A (en) | A kind of preparation method of active carbon |
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 |