CN113880091A - Method for preparing magnetic activated carbon by treating papermaking black liquor with composite metal salt - Google Patents
Method for preparing magnetic activated carbon by treating papermaking black liquor with composite metal salt Download PDFInfo
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- CN113880091A CN113880091A CN202111323515.1A CN202111323515A CN113880091A CN 113880091 A CN113880091 A CN 113880091A CN 202111323515 A CN202111323515 A CN 202111323515A CN 113880091 A CN113880091 A CN 113880091A
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- metal salt
- activated carbon
- black liquor
- lignin
- composite metal
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- 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
- C01B32/348—Metallic compounds
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- 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
Abstract
The invention belongs to the field of activated carbon preparation methods, and particularly relates to a method for preparing magnetic activated carbon by treating papermaking black liquor with composite metal salt. The method comprises the following steps: adding FeCl into papermaking black liquor3And the lignin chelate is evenly mixed with another metal salt solution and centrifuged to obtain the metal lignin chelate, and the dried chelate is carbonized to obtain the magnetic activated carbon material. The method directly takes papermaking cooking black liquor as a raw material, and FeCl is added3And the metal salt is used as a flocculating agent to flocculate the black liquor lignin and is used as an activating agent to obtain porous and magnetic activated carbon through carbonization. The method has the advantages of simple conditions, short time period, quick operation and mild conditions, can be used for industrial large-scale production, and effectively reduces the production cost of the lignin activated carbon.
Description
[ technical field ] A method for producing a semiconductor device
The invention belongs to the field of activated carbon preparation methods, and particularly relates to a method for preparing magnetic activated carbon by treating papermaking black liquor with composite metal salt.
[ background of the invention ]
Black liquor is a waste liquor from the alkaline pulping process (soda and sulfate) of the paper industry, which contains a large amount of lignin and is dark brown, and is called black liquor. The black liquor contains a large amount of suspended solids, organic pollutants and toxic substances, and the direct discharge of the black liquor into a water body can cause serious pollution. The traditional black liquor treatment method adopts alkali to recover and burn organic matters in the black liquor so as to recover heat energy, thereby causing waste on resources. In actual production, the relative production ratio of black liquor to paper pulp is about 7: 1, and a large amount of black liquor by-products become a huge environmental burden for the paper industry. Therefore, how to utilize the black liquor more efficiently is an exploration direction for the high-value utilization of the papermaking wastes, and has very important significance.
In recent years, activated carbon has developed pore structure and abundant oxygen functional groups, so that the activated carbon can effectively remove color, odor, most organic pollutants and certain inorganic substances in water, including certain toxic heavy metals. Based on sustainability and economic benefits, there is an increasing interest in developing effective adsorbents from low cost biomass resources. In general, methods for preparing activated carbon can be classified into two major categories, physical activation and chemical activation. The carbonization and activation process can be accomplished in one step using chemical activation as opposed to physical activation. In recent years, FeCl has been used as a material3Its low cost and non-toxic properties, has been used as a new activator by more and more researchers, and research has shown that FeCl3The pyrolysis process of the solution pretreatment product can generate magnetism, and the problem of separation can be well solved due to the magnetism of the active carbon. Meanwhile, another metal salt is compounded to be used as an activating agent, so that the functional group is activated, the removal performance of the activated carbon pollutants is improved, and the functionality of the activated carbon pollutants is improved.
The method has the advantages that the black liquor is directly treated by the metal salt solution, the reaction condition is mild, the alkali loss in the treatment process is small, and in addition, as the lignin and the metal salt solution in the black liquor are in a uniformly dispersed state, the metal ions and the functional groups on the lignin can be accurately coordinated, so that the whole flocculation process is simple and rapid. The invention directly utilizes papermaking cooking black liquor as raw material and FeCl from the perspective of high-value utilization of solid waste3The lignin in the black liquor is separated out by taking another metal salt as a flocculating agent, and the composite metal salt is used for activationThe agent is used for preparing magnetic activated carbon with adsorption performance and is used for removing pollutants.
[ summary of the invention ]
The main purpose of the invention is to directly utilize the papermaking black liquor, and add a composite metal salt solution into the black liquor, so that the black liquor lignin is flocculated as a flocculating agent on one hand, and is carbonized as an activating agent to obtain porous and magnetic activated carbon on the other hand. Compared with the commonly used impregnation method for preparing the activated carbon, the method provides a new idea which is cheaper and faster and can realize batch production, and the main steps are as follows:
(1) filtering the papermaking black liquor by a filter screen of 100-200 meshes for later use;
(2) flocculation of black liquor lignin by composite metal salt: respectively preparing 0.5-2 mol/L metal salt A, B solution, adding metal salt A and metal salt B into the cooking black liquor according to a certain proportion, mechanically stirring and centrifuging the mixed solution to remove supernatant to obtain flocculated lignin, drying the flocculated lignin, and grinding the flocculated lignin through a 60-100-mesh sieve for later use;
(3) and (3) putting a certain amount of the dried flocculated lignin obtained in the step (2) into a quartz boat, putting the quartz boat into a tube furnace, heating and carbonizing the quartz boat under the protection of nitrogen, taking out the activated carbon, boiling the activated carbon in a 5-15% acid solution for 5-15 min to remove residual impurities in the activated sample, washing the activated carbon with deionized water to be neutral, and drying the activated carbon to obtain the activated carbon sample.
[ detailed description ] embodiments
Example 1
Filtering the papermaking black liquor by a 100-mesh filter screen; flocculation of black liquor lignin by composite metal salt: FeCl prepared by 0.5mol/L3、ZnCl2Solution of black liquor FeCl3∶ZnCl2Adding into black liquor at a ratio of 1: 0.3, stirring the mixed solution at 50 deg.C at 300r/min for 1 hr, centrifuging, oven drying the precipitate at 60 deg.C, grinding, and sieving with 100 mesh sieve; placing the obtained dry flocculated lignin in quartz boat, placing in tube furnace, carbonizing at 700 deg.C for 50min under nitrogen atmosphere at heating rate of 10 deg.C/min, taking out activated carbon, and boiling in 10% hydrochloric acid solution for 10min to removeAnd (4) washing impurities remained in the activated sample to be neutral by using deionized water, and drying to obtain the activated carbon sample.
Example 2
Filtering the papermaking black liquor with a 200-mesh filter screen; flocculation of black liquor lignin by composite metal salt: FeCl prepared by 0.5mol/L3、CaCl2Solution of black liquor FeCl3∶CaCl2Adding into black liquor at a ratio of 1: 0.3, stirring the mixed solution at 60 deg.C and 400r/min for 2 hr, centrifuging, freeze drying the precipitate, grinding, and sieving with 80 mesh sieve; and putting the obtained dried flocculated lignin in a quartz boat, putting the quartz boat in a tubular furnace, carbonizing the quartz boat for 60min at the temperature rise rate of 5 ℃/min and 900 ℃ in a nitrogen atmosphere, taking out the activated carbon after carbonization, boiling the activated carbon in a 12% hydrochloric acid solution for 8min to remove residual impurities in the activated sample, washing the activated sample to be neutral by deionized water, and drying the activated sample to obtain the activated carbon sample.
Example 3
Filtering the papermaking black liquor by a 150-mesh filter screen; flocculation of black liquor lignin by composite metal salt: FeCl prepared with 1mol/L3、ZnCl2Solution of black liquor FeCl3∶ZnCl2Adding into black liquor at a ratio of 1: 0.1: 0.2, stirring the mixed solution at 80 deg.C at 600r/min for 2 hr, centrifuging, oven drying the precipitate at 80 deg.C, grinding, and sieving with 60 mesh sieve; and putting the obtained dried flocculated lignin in a quartz boat, putting the quartz boat in a tubular furnace, carbonizing the quartz boat for 90min at the temperature rise rate of 12 ℃/min and the temperature of 800 ℃ in the nitrogen atmosphere, taking out the activated carbon after the carbonization is finished, boiling the activated carbon in a 10% sulfuric acid solution for 15min to remove residual impurities in the activated sample, washing the activated carbon sample to be neutral by deionized water, and drying the activated carbon sample to obtain the activated carbon sample.
Example 4
Filtering the papermaking black liquor with a 200-mesh filter screen; flocculation of black liquor lignin by composite metal salt: FeCl prepared by 0.5mol/L3、Zn(NO3)2Solution of black liquor FeCl3∶Zn(NO3)2Adding into black liquor at a ratio of 1: 0.4: 0.2, stirring the mixed solution at 60 deg.C and 400r/min for 3 hr, centrifuging, oven drying the precipitate at 90 deg.C,grinding and sieving with a 100-mesh sieve for later use; and putting the obtained dried flocculated lignin in a quartz boat, putting the quartz boat in a tubular furnace, carbonizing the quartz boat for 50min at the temperature rise rate of 12 ℃/min at the temperature of 750 ℃ in the nitrogen atmosphere, taking out the activated carbon after the carbonization is finished, boiling the activated carbon in a 10% hydrochloric acid solution for 8min to remove residual impurities in the activated sample, washing the activated carbon sample to be neutral by deionized water, and drying the activated carbon sample to obtain the activated carbon sample.
Example 5
Filtering the papermaking black liquor by a 150-mesh filter screen; flocculation of black liquor lignin by composite metal salt: FeCl prepared with 1mol/L3、MgCl2Adding the solution into the black liquor according to the ratio of the black liquor to the metal salt A to the metal salt B of 1: 0.2, stirring the mixed solution at 80 ℃ for 3 hours at the rotating speed of 600r/min, centrifuging, taking the precipitate, freeze-drying, grinding and sieving with a 80-mesh sieve for later use; and putting the obtained dried flocculated lignin in a quartz boat, putting the quartz boat in a tubular furnace, carbonizing the quartz boat for 90min at the temperature rise rate of 15 ℃/min and the temperature of 500 ℃ in the nitrogen atmosphere, taking out the activated carbon after the carbonization is finished, boiling the activated carbon in a 10% hydrochloric acid solution for 15min to remove residual impurities in the activated sample, washing the activated carbon sample to be neutral by deionized water, and drying the activated carbon sample to obtain the activated carbon sample.
Example 6
Filtering the papermaking black liquor with a 200-mesh filter screen; flocculation of black liquor lignin by composite metal salt: FeCl prepared by 0.5mol/L3、CuCl2According to the ratio of black liquor to FeCl3∶CuCl2Adding into black liquor at a ratio of 1: 0.4: 0.3, stirring the mixed solution at 50 deg.C at 350r/min for 3 hr, centrifuging, oven drying the precipitate at 70 deg.C, grinding, and sieving with 100 mesh sieve; and putting the obtained dried flocculated lignin in a quartz boat, putting the quartz boat in a tubular furnace, carbonizing the quartz boat for 50min at the temperature rise rate of 10 ℃/min and 900 ℃ in the nitrogen atmosphere, taking out the activated carbon after carbonization, boiling the activated carbon in a 12% nitric acid solution for 10min to remove residual impurities in the activated sample, washing the activated carbon sample to be neutral by deionized water, and drying the activated carbon sample to obtain the activated carbon sample.
Claims (9)
1. A method for preparing magnetic activated carbon by treating papermaking black liquor with composite metal salt comprises the following steps:
(1) filtering the papermaking black liquor by a filter screen of 100-200 meshes for later use;
(2) flocculation of black liquor lignin by composite metal salt: respectively preparing 0.5-2 mol/L metal salt A, B solution, adding metal salt A and metal salt B into the cooking black liquor according to a certain proportion, mechanically stirring and centrifuging the mixed solution to remove supernatant to obtain flocculated lignin, drying the flocculated lignin, and grinding the flocculated lignin through a 60-100-mesh sieve for later use;
(3) and (3) putting a certain amount of the dried flocculated lignin obtained in the step (2) into a quartz boat, putting the quartz boat into a tube furnace, heating and carbonizing the quartz boat under the protection of nitrogen, taking out the activated carbon, boiling the activated carbon in a 5-15% acid solution for 5-15 min to remove residual impurities in the activated sample, washing the activated carbon with deionized water to be neutral, and drying the activated carbon to obtain the activated carbon sample.
2. The method for preparing magnetic activated carbon by treating papermaking black liquor with composite metal salt according to claim 1 is characterized in that: the papermaking black liquor is waste water generated by soda process or sulfate process cooking.
3. The method for preparing magnetic activated carbon by treating papermaking black liquor with composite metal salt according to claim 1 is characterized in that: the metal salt A is FeCl3。
4. The method for preparing magnetic activated carbon by treating papermaking black liquor with composite metal salt according to claim 1 is characterized in that: the cation of the metal salt B is Zn2+、Ca2+、Mg2+、Cu2+The anion is one of chloride, sulfate, nitrate and acetate in any combination.
5. The method for preparing magnetic activated carbon by treating papermaking black liquor with composite metal salt according to claim 1 is characterized in that: the mixing proportion of the metal salt A, the metal salt B and the black liquor in the step (2) is that the black liquor: metal salt A: the volume ratio of the metal salt B is 1: 0.05-0.6.
6. The method for preparing magnetic activated carbon by treating papermaking black liquor with composite metal salt according to claim 1 is characterized in that: the stirring condition of the mixed solution in the step (2) is that the mixed solution is stirred for 1-5 hours at the temperature of 50-90 ℃ and the rotating speed of 300-600 r/min.
7. The method for preparing magnetic activated carbon by treating papermaking black liquor with composite metal salt according to claim 1 is characterized in that: the drying method of the flocculation lignin is freeze drying or drying.
8. The method for preparing magnetic activated carbon by treating papermaking black liquor with composite metal salt according to claim 1 is characterized in that: and (3) carbonizing at 500-900 ℃ for 10-90 min at a temperature rise rate of 5-20 ℃/min.
9. The method for preparing magnetic activated carbon by treating papermaking black liquor with composite metal salt according to claim 1 is characterized in that: the acid solution used for the active carbon acid cleaning is hydrochloric acid, sulfuric acid or nitric acid.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114433167A (en) * | 2022-02-25 | 2022-05-06 | 天津科技大学 | Preparation and use method of iron-based heterogeneous catalyst |
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| WO2011162420A1 (en) * | 2010-06-25 | 2011-12-29 | ロペスアンドエヌティ有限会社 | Method for recovering lignin in the neutral range from spent pulp cooking liquor |
| CN103408010A (en) * | 2013-07-26 | 2013-11-27 | 福建农林大学 | Method for preparing activated carbon by using papermaking black liquor as active agent |
| CN105197926A (en) * | 2015-08-18 | 2015-12-30 | 南京林业大学 | Method for preparing activated carbon with enzymatic hydrolysis lignin as raw material |
| CN106517190A (en) * | 2016-10-27 | 2017-03-22 | 陕西科技大学 | Co-production method of monophenol compound and activated carbon by lignin catalytic pyrolysis |
| CN111760549A (en) * | 2020-06-10 | 2020-10-13 | 昆明理工大学 | Method for preparing porous carbon-based adsorbent from papermaking black liquor |
| CN113247887A (en) * | 2021-04-13 | 2021-08-13 | 齐鲁工业大学 | Preparation method of hierarchical porous graphene and application of hierarchical porous graphene |
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Patent Citations (7)
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| CN101847481A (en) * | 2009-03-25 | 2010-09-29 | 中国科学院生态环境研究中心 | Novel process for preparing C-Fe shell-core magnetic active carbon by utilizing waste biomasses |
| WO2011162420A1 (en) * | 2010-06-25 | 2011-12-29 | ロペスアンドエヌティ有限会社 | Method for recovering lignin in the neutral range from spent pulp cooking liquor |
| CN103408010A (en) * | 2013-07-26 | 2013-11-27 | 福建农林大学 | Method for preparing activated carbon by using papermaking black liquor as active agent |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114433167A (en) * | 2022-02-25 | 2022-05-06 | 天津科技大学 | Preparation and use method of iron-based heterogeneous catalyst |
| CN114433167B (en) * | 2022-02-25 | 2024-04-23 | 天津科技大学 | Preparation and use methods of iron-based heterogeneous catalyst |
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