CN117383559A - Method for preparing active carbon precursor by removing biomass ash through wood vinegar combined with hydrothermal carbonization - Google Patents
Method for preparing active carbon precursor by removing biomass ash through wood vinegar combined with hydrothermal carbonization Download PDFInfo
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- 239000002028 Biomass Substances 0.000 title claims abstract description 118
- 239000002023 wood Substances 0.000 title claims abstract description 107
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- 235000021419 vinegar Nutrition 0.000 title claims abstract description 89
- 238000003763 carbonization Methods 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 72
- 239000007833 carbon precursor Substances 0.000 title claims abstract description 53
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 137
- 239000002994 raw material Substances 0.000 claims abstract description 64
- 239000002243 precursor Substances 0.000 claims abstract description 47
- 238000000197 pyrolysis Methods 0.000 claims abstract description 39
- 238000005406 washing Methods 0.000 claims abstract description 39
- 239000007791 liquid phase Substances 0.000 claims abstract description 23
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 52
- 229910052799 carbon Inorganic materials 0.000 description 31
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 30
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 27
- 229910052783 alkali metal Inorganic materials 0.000 description 26
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- 230000000052 comparative effect Effects 0.000 description 20
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- 229910021641 deionized water Inorganic materials 0.000 description 9
- 150000007522 mineralic acids Chemical class 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
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- 238000001027 hydrothermal synthesis Methods 0.000 description 3
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- 229910052751 metal Inorganic materials 0.000 description 3
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- 239000011591 potassium Substances 0.000 description 3
- 235000019260 propionic acid Nutrition 0.000 description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 229920002488 Hemicellulose Polymers 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
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- 230000007613 environmental effect Effects 0.000 description 2
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- 238000006386 neutralization reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
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- 150000001720 carbohydrates Chemical class 0.000 description 1
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- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 229910052801 chlorine Inorganic materials 0.000 description 1
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- 239000012530 fluid Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
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- 239000005416 organic matter Substances 0.000 description 1
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- 239000000049 pigment Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
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- 239000000779 smoke Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
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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
- C01B32/318—Preparation characterised by the starting materials
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a method for preparing an active carbon precursor by removing biomass ash through wood vinegar combined with hydrothermal carbonization. And (3) taking wood vinegar as a liquid phase medium, and performing hydrothermal carbonization on biomass raw materials to obtain a biomass-based activated carbon precursor. The invention innovatively utilizes the organic acid active ingredient in the acid wood vinegar, combines hydrothermal carbonization, and avoids the use of strong acid, strong alkali and pollution caused in the washing process. The method is easy to realize industrialized popularization and application and is environment-friendly under the condition of not obviously increasing the process cost. In addition, the method fully utilizes the acid liquid byproduct wood vinegar in the process of preparing the charcoal by biomass pyrolysis, and realizes high-value comprehensive utilization of biomass pyrolysis products on the basis of preparing biomass-based activated charcoal precursors.
Description
Technical Field
The invention relates to the technical field of preparation of biomass-based activated carbon precursors, in particular to a method for preparing an activated carbon precursor by removing biomass ash through hydrothermal carbonization of wood vinegar.
Background
By using the innovative technology or method, the agriculture and forestry waste biomass resources such as straws and the like are converted into products such as chemicals, energy products, functional materials and the like with high added value and multiple functions and purposes, so that the high-value recycling of agricultural wastes is realized, waste materials are changed into valuable materials, and the problem of environmental pollution caused by straw burning is solved. By utilizing advanced pyrolysis technology, under the anaerobic or anoxic condition, the agriculture and forestry biomass waste such as straw, wood and the like is subjected to high-temperature pyrolysis, and the biomass raw material can be efficiently converted into products such as biochar, combustible gas, wood vinegar, pyrolysis oil and the like. The biochar is a carbon-rich solid product, has remarkably improved carbon content, larger specific surface area and abundant micropore structures, and has abundant oxygen-containing functional groups on the surface. The unique characteristics enable the biochar to be used as a high-quality adsorption material, and have high application value in the aspects of wastewater and waste gas treatment, pollution control, agricultural production, ecological environment restoration and the like. On the other hand, the biochar can also be used as a precursor for preparing the activated carbon, and the activated carbon with better performance and higher value can be prepared by activating the biochar through a physical activation method, a chemical activation method or a physical and chemical combined activation method. Activated carbon, also known as carbon molecular sieves, generally has a high specific surface area, a developed pore structure, and a large adsorption capacity. The high-quality activated carbon is used as a high-quality adsorption material, has great application prospect in the fields of gas purification, wastewater treatment, environmental protection, food, medicine, chemical industry, military industry and the like, and becomes an indispensable material for national economy development.
Typically, the straw component has about 70% carbohydrate, about 20% lignin, and the balance impurities such as ash, pigments, fat, and the like. The mass fraction of polysaccharide high molecular polymer cellulose and hemicellulose in the straw and the mass fraction of carbon elements are higher, and the prepared straw-based biomass carbon can be used as an activated carbon precursor for preparing activated carbon with higher value and quality through high-temperature controllable pyrolysis of the straw. However, compared with the traditional active carbon raw materials such as wood, coconut shells, fruit shells and the like, the straw-based active carbon has higher ash content and lower carbon content, so that the yield and quality of the active carbon prepared by taking straw as the raw material are lower. The ash content of the biomass is an inorganic substance in the biomass and mainly comprises alkali metals such as potassium and sodium and alkaline earth metals such as magnesium and calcium absorbed from soil in the growth process of biomass resources. In addition, the components of a portion of the ash can act as a catalyst during pyrolysis, so that more biomass feedstock is converted into liquid or gaseous products, and the yield of solid products is reduced. Ash removal from biomass can reduce the ash content in the biochar produced by pyrolysis, thereby improving the quality of the produced biochar.
Removal of biomass ash is an important and effective way of pretreatment of biomass. Currently, the deashing process of biomass feedstock mainly comprises water washing or mineral acid washing. The alkali and alkaline earth metals in the biomass feedstock are predominantly present in ionic form or in the form of covalent compounds. The ash components are washed by water, although the cost is low, the ash removal efficiency is not high, the ash removal effect on sand and partial water-soluble metal elements is better, and the ash removal effect on other ash is not ideal. The inorganic acid washing mode involves a large amount of strong acid such as hydrochloric acid, sulfuric acid, nitric acid and the like, and a large amount of inorganic strong base and water for neutralization are possibly needed in the subsequent washing process, so that the cost is high, and the environment pollution or secondary pollution is caused. In addition, the acid washing can damage organic matter components in the biomass raw material, and part of acid washing residual liquid can be attached to the surface of the pretreated biomass raw material, so that the quality of the biochar is reduced. These disadvantages limit the industrial application of the mineral acid washing process.
Disclosure of Invention
The invention aims at overcoming the defects in the existing biomass-based active carbon precursor preparation technology at present, and provides a method for preparing an active carbon precursor by removing ash in biomass raw materials through combining refined pyroligneous liquor with hydrothermal carbonization. The biomass-based high-quality activated carbon precursor can be prepared by adopting the refined aqueous phase pyroligneous liquor rich in organic acid, which is generated in the biomass pyrolysis process, as a liquid phase medium and carrying out pretreatment on biomass raw materials by combining hydrothermal carbonization, so that ash content in the biomass raw materials can be effectively reduced. The method can reduce ash in biomass raw materials at low cost, thereby improving the quality of biomass-based activated carbon precursors. The method fully utilizes the combination of organic acid active ingredients in the acid wood vinegar and hydrothermal carbonization to pretreat the biomass raw material, solves the problems of low efficiency and poor effect of a single deashing method in the biomass pretreatment field, and avoids strong acid and strong alkali used in the process of washing and deashing by using inorganic acid and pollution caused in the washing process. The method can prepare the biomass-based high-quality activated carbon precursor without obviously increasing the process cost. The method has the characteristics of low cost, easiness in realizing industrialized popularization and application, environmental friendliness and comprehensive utilization of biomass pyrolysis products.
In order to achieve the above purpose, the invention is realized by the following technical scheme:
a method for preparing a biomass-based activated carbon precursor by removing biomass ash through combining wood vinegar with hydrothermal carbonization, which takes wood vinegar as a liquid phase medium, carries out hydrothermal carbonization on biomass raw materials to obtain the biomass-based activated carbon precursor.
Wherein the pyroligneous liquor is pyroligneous liquor generated by condensing volatile smoke in the biomass pyrolysis process;
the biomass raw material is a biomass raw material with high ash content.
Specifically, the method for preparing the biomass-based activated carbon precursor comprises the following steps:
pulverizing and sieving biomass raw materials for preparing an activated carbon precursor, adding wood vinegar into the biomass raw materials according to a certain solid-liquid ratio, stirring the obtained mixture, heating the mixture in an inert atmosphere for hydrothermal carbonization, filtering after the reaction is finished, and collecting a solid product, namely the biomass-based activated carbon precursor;
in the method, the wood vinegar is prepared by the following steps:
pulverizing biomass raw materials, sieving, drying, performing high-temperature pyrolysis in an anaerobic environment, performing fractional condensation on high-temperature flue gas generated in the pyrolysis process to obtain pyroligneous liquor, pyrolysis oil, biochar and combustible gas, and refining the obtained pyroligneous liquor to obtain the biomass;
the biomass raw material is lignocellulose biomass, and can be at least one of wheat straw, corn straw, rice straw, bamboo wood, wood dust, peanut shell and rice hull;
sieving with 10-100 mesh sieve;
the high-temperature pyrolysis is to place the dried biomass raw material in inert atmosphere or vacuum, pyrolyze for 1-3 hours at 400-800 ℃, collect flue gas, and carry out fractional condensation to obtain yellow brown acidic liquid wood vinegar;
the refining comprises standing wood vinegar, filtering, removing impurities, and collecting water phase filtrate.
The biomass raw material for preparing the activated carbon precursor is lignocellulose biomass, and can be specifically at least one of wheat straw, corn straw, rice straw, bamboo wood, wood dust, peanut shell and rice hull;
sieving with 10-100 mesh sieve;
the biomass raw material for preparing the active carbon precursor is the same as or different from the biomass raw material for preparing the wood vinegar;
as a further improved technical scheme of the invention, the ratio of the biomass raw material for preparing the active carbon precursor to the wood vinegar is 1:5-1:30 (w/w);
according to the technical scheme, the hydrothermal carbonization process is that a mixture of the biomass raw material for preparing the active carbon precursor and wood vinegar is stirred, the temperature is raised to 160-220 ℃ at a heating rate of 10-20 ℃/min in an inert atmosphere, the system pressure is 10-60bar, the hydrothermal carbonization is carried out, and the mixture is kept for 1-2h at the temperature and the pressure.
The above method may further comprise washing the obtained solid product with water at 20-60deg.C until it is neutral, and drying.
The drying is drying at 80-110 deg.C for 12-24 hr.
The biomass-based activated carbon precursor prepared by the method and the biomass-based activated carbon prepared by the biomass-based activated carbon precursor also belong to the protection scope of the invention.
According to the invention, inorganic ash in biomass is removed by combining wood vinegar with hydrothermal carbonization, and straw biomass raw materials such as wheat straw, corn straw and the like can be converted into precursors of high-quality activated carbon by reducing the inorganic content in the product and improving the organic carbon content. The ash in biomass raw materials mainly comprises alkali metals such as potassium and sodium and alkaline earth metals such as magnesium and calcium, and the metal ions are taken up from soil during the growth of biomass as important nutrient elements and exist in the biomass in a free state or in a covalent compound form. In conventional biomass pretreatment processes, water washing or mineral acid washing is typically employed to remove ash from the biomass. In the invention, the acidic pyroligneous liquor produced by biomass in the pyrolysis carbonization process is used as a liquid phase, and inorganic metal elements in biomass raw materials can be efficiently removed in a hydrothermal carbonization mode. Because the main components of the wood vinegar are water and organic acids such as formic acid, acetic acid, propionic acid, glycollic acid and the like, the mode has the advantages of water washing and inorganic acid washing in the traditional method. The water can remove the metallic elements which are easy to dissolve in water and exist in a majority of free state in the biomass raw material, and the organic acid component which is rich in the pyroligneous liquor can convert the metallic ions which are not easy to dissolve in water and exist in a majority of organic covalent compound form in the biomass raw material into water-soluble compounds such as water-soluble salt and the like and remove the water-soluble compounds. In addition, the byproduct acid wood vinegar in the process of preparing the biochar by biomass pyrolysis is a liquid phase of a hydrothermal reaction, so that the use of additional added water, organic acid and possible pollution and production cost rise are avoided.
Compared with the prior art, the invention has the beneficial effects that:
according to the method for preparing the high-quality active carbon precursor by removing biomass ash through combining the pyroligneous liquor with the hydrothermal carbonization, disclosed by the invention, the pyroligneous liquor rich in organic acid is used as a liquid phase eluent, and various alkali metal and alkaline earth metal inorganic matters in biomass raw materials can be efficiently removed through combining the hydrothermal carbonization, so that the high-quality active carbon precursor is prepared. The wood vinegar is an acidic liquid product which is a byproduct in the process of preparing the biochar by biomass pyrolysis, and is rich in moisture and various organic acids produced by thermal degradation of high molecular polymers such as cellulose, hemicellulose and the like. The acidic wood vinegar is used as the liquid-phase eluent, and the water-thermal carbonization is combined, so that the method has the advantages of water washing or inorganic acid washing in the traditional pretreatment method, and the waste of water resources and the possible environmental pollution and the increase of production cost caused by chemicals such as acid, alkali and the like are avoided. The wood vinegar is adopted to replace sulfuric acid, hydrochloric acid, nitric acid and other strong acid liquids in the inorganic acid washing process, so that inorganic bases such as sodium hydroxide, potassium hydroxide and the like used in the neutralization and washing processes are avoided, and strong corrosive pollutants such as chlorine, sulfur and the like are not introduced into a production system, and corrosion and damage to production equipment are avoided. Compared with the traditional method, the byproduct wood vinegar produced in the preparation of the biochar by biomass pyrolysis is used as eluent and a liquid phase component in the hydrothermal carbonization, so that the environmental pollution is avoided, the cost is reduced, the resource utilization rate is improved, and the recycling and high-value utilization of biomass pyrolysis byproducts are realized.
Drawings
FIG. 1 shows a schematic diagram of the biomass pyrolysis and formation of pyroligneous and other major products according to the present invention.
Fig. 2 shows a schematic flow chart of the preparation of high-quality activated carbon precursor by using refined wood vinegar as liquid phase fluid for hydrothermal carbonization.
Fig. 3 shows the yields of the activated carbon precursors prepared in examples 1 to 10 and comparative examples 1 to 3 provided by the present invention.
Fig. 4 shows the carbon element content of the activated carbon precursors and biomass raw materials (wheat straw, corn straw, fir wood chips) prepared in examples 1 to 10 and comparative examples 1 to 3 provided by the present invention.
Fig. 5 shows the removal rates of alkali metals and alkaline earth metals in examples 1 to 10 and comparative examples 1 to 3 provided by the present invention.
Detailed Description
The following detailed description of the invention is provided in connection with the accompanying drawings that are presented to illustrate the invention and not to limit the scope thereof. The examples provided below are intended as guidelines for further modifications by one of ordinary skill in the art and are not to be construed as limiting the invention in any way.
The experimental methods in the following examples, unless otherwise specified, are conventional methods, and are carried out according to techniques or conditions described in the literature in the field or according to the product specifications. Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Example 1
The embodiment provides a method for preparing a high-quality activated carbon precursor by removing wheat straw ash through wood vinegar combined with hydrothermal carbonization, which comprises the following steps:
pulverizing wheat straw, sieving to 30 mesh, and drying. And (3) heating the dried wheat straw to the pyrolysis temperature of 500 ℃ at a heating rate of 20 ℃/min in nitrogen atmosphere, preserving heat for 1h, collecting flue gas, and performing fractional condensation to obtain the wheat straw pyroligneous liquor. And (3) standing, filtering, removing impurities, collecting water phase filtrate, and refining the obtained wood vinegar to obtain refined wheat straw wood vinegar.
The wheat straw was crushed and sieved to 30 mesh. Mixing the obtained wheat straw raw material with the refined wheat straw wood vinegar in a hydrothermal carbonization reactor according to a ratio of 1:10 (w/w), uniformly stirring, then heating to 160 ℃ in nitrogen at a heating rate of 10 ℃/min, keeping the pressure of a reaction system at 30bar by adjusting the flow rate of the nitrogen, keeping the reaction system at the set temperature and the pressure for 1 hour, carrying out hydrothermal carbonization reaction, after the reaction is finished, continuing to cool the reaction system to room temperature in a nitrogen atmosphere, filtering the obtained solid product, repeatedly washing to be neutral with ionized water at 30 ℃, and drying at 105 ℃ to obtain the high-quality active carbon precursor. The obtained high-quality active carbon precursor is placed in a mixed solution of hydrochloric acid and nitric acid (volume ratio: 3:1), stirred and digested for 24 hours at 100 ℃, and the content of alkali metal and alkaline earth metal is measured by adopting an inductively coupled plasma mass spectrometer ICP-MS. And measuring the carbon element content of the obtained high-quality active carbon precursor by adopting an elemental analyzer.
Example 2
The embodiment provides a method for preparing a high-quality activated carbon precursor by removing wheat straw ash through wood vinegar combined with hydrothermal carbonization, which comprises the following steps:
pulverizing wheat straw, sieving to 30 mesh, and drying. And (3) heating the dried wheat straw to the pyrolysis temperature of 500 ℃ at a heating rate of 20 ℃/min in nitrogen atmosphere, preserving heat for 1h, collecting flue gas, and performing fractional condensation to obtain the wheat straw pyroligneous liquor. And (3) standing, filtering, removing impurities, collecting water phase filtrate, and refining the obtained wood vinegar to obtain refined wheat straw wood vinegar.
The wheat straw was crushed and sieved to 30 mesh. Mixing the obtained wheat straw raw material with the refined wheat straw wood vinegar in a hydrothermal carbonization reactor according to a ratio of 1:20 (w/w), uniformly stirring, then heating to 160 ℃ in nitrogen at a heating rate of 10 ℃/min, keeping the pressure of a reaction system at 30bar by adjusting the flow rate of the nitrogen, keeping the reaction system at the set temperature and the pressure for 1 hour, carrying out hydrothermal carbonization reaction, after the reaction is finished, continuing to cool the reaction system to room temperature in a nitrogen atmosphere, filtering the obtained solid product, repeatedly washing to be neutral with ionized water at 30 ℃, and drying at 105 ℃ to obtain the high-quality active carbon precursor. The obtained high-quality active carbon precursor is placed in a mixed solution of hydrochloric acid and nitric acid (volume ratio: 3:1), stirred and digested for 24 hours at 100 ℃, and the content of alkali metal and alkaline earth metal is measured by adopting an inductively coupled plasma mass spectrometer ICP-MS. And measuring the carbon element content of the obtained high-quality active carbon precursor by adopting an elemental analyzer.
Example 3
The embodiment provides a method for preparing a high-quality activated carbon precursor by removing wheat straw ash through wood vinegar combined with hydrothermal carbonization, which comprises the following steps:
pulverizing wheat straw, sieving to 30 mesh, and drying. And (3) heating the dried wheat straw to the pyrolysis temperature of 500 ℃ at a heating rate of 20 ℃/min in nitrogen atmosphere, preserving heat for 1h, collecting flue gas, and performing fractional condensation to obtain the wheat straw pyroligneous liquor. Standing, filtering, removing impurities, collecting water phase filtrate, and refining to obtain refined wheat straw wood vinegar
The wheat straw was crushed and sieved to 30 mesh. Mixing the obtained wheat straw raw material with the refined wheat straw wood vinegar in a hydrothermal carbonization reactor according to a ratio of 1:20 (w/w), uniformly stirring, then heating to 180 ℃ in nitrogen at a heating rate of 10 ℃/min, keeping the pressure of a reaction system at 30bar by adjusting the flow rate of the nitrogen, keeping the reaction system at the set temperature and the pressure for 1 hour, carrying out hydrothermal carbonization reaction, after the reaction is finished, continuing to cool the reaction system to room temperature in a nitrogen atmosphere, filtering the obtained solid product, repeatedly washing to be neutral with ionized water at 30 ℃, and drying at 105 ℃ to obtain the high-quality active carbon precursor. The obtained high-quality active carbon precursor is placed in a mixed solution of hydrochloric acid and nitric acid (volume ratio: 3:1), stirred and digested for 24 hours at 100 ℃, and the content of alkali metal and alkaline earth metal is measured by adopting an inductively coupled plasma mass spectrometer ICP-MS. And measuring the carbon element content of the obtained high-quality active carbon precursor by adopting an elemental analyzer.
Example 4
The embodiment provides a method for preparing a high-quality activated carbon precursor by removing wheat straw ash through wood vinegar combined with hydrothermal carbonization, which comprises the following steps:
pulverizing wheat straw, sieving to 30 mesh, and drying. And (3) heating the dried wheat straw to the pyrolysis temperature of 500 ℃ at a heating rate of 20 ℃/min in nitrogen atmosphere, preserving heat for 1h, collecting flue gas, and performing fractional condensation to obtain the wheat straw pyroligneous liquor. And (3) standing, filtering, removing impurities, collecting water phase filtrate, and refining the obtained wood vinegar to obtain refined wheat straw wood vinegar.
The wheat straw was crushed and sieved to 30 mesh. Mixing the obtained wheat straw raw material with the refined wheat straw wood vinegar in a hydrothermal carbonization reactor according to a ratio of 1:20 (w/w), uniformly stirring, then heating to 160 ℃ in nitrogen at a heating rate of 10 ℃/min, keeping the pressure of the reaction system at 50bar by adjusting the flow rate of the nitrogen, keeping the reaction system at the set temperature and the pressure for 1 hour, carrying out hydrothermal carbonization reaction, after the reaction is finished, continuing to cool the reaction system to room temperature in a nitrogen atmosphere, filtering the obtained solid product, repeatedly washing to be neutral with ionized water at 30 ℃, and drying at 105 ℃ to obtain the high-quality active carbon precursor. The obtained high-quality active carbon precursor is placed in a mixed solution of hydrochloric acid and nitric acid (volume ratio: 3:1), stirred and digested for 24 hours at 100 ℃, and the content of alkali metal and alkaline earth metal is measured by adopting an inductively coupled plasma mass spectrometer ICP-MS. And measuring the carbon element content of the obtained high-quality active carbon precursor by adopting an elemental analyzer.
Example 5
The embodiment provides a method for preparing a high-quality activated carbon precursor by removing wheat straw ash through wood vinegar combined with hydrothermal carbonization, which comprises the following steps:
pulverizing wheat straw, sieving to 30 mesh, and drying. And (3) heating the dried wheat straw to the pyrolysis temperature of 600 ℃ at the heating rate of 20 ℃/min in nitrogen atmosphere, preserving heat for 1h, collecting flue gas, and performing fractional condensation to obtain the wheat straw pyroligneous liquor. And (3) standing, filtering, removing impurities, collecting water phase filtrate, and refining the obtained wood vinegar to obtain refined wheat straw wood vinegar.
The wheat straw was crushed and sieved to 30 mesh. Mixing the obtained wheat straw raw material with the refined wheat straw wood vinegar in a hydrothermal carbonization reactor according to a ratio of 1:20 (w/w), uniformly stirring, then heating to 160 ℃ in nitrogen at a heating rate of 10 ℃/min, keeping the pressure of the reaction system at 50bar by adjusting the flow rate of the nitrogen, keeping the reaction system at the set temperature and the pressure for 1 hour, carrying out hydrothermal carbonization reaction, after the reaction is finished, continuing to cool the reaction system to room temperature in a nitrogen atmosphere, filtering the obtained solid product, repeatedly washing to be neutral with ionized water at 30 ℃, and drying at 105 ℃ to obtain the high-quality active carbon precursor. The obtained high-quality active carbon precursor is placed in a mixed solution of hydrochloric acid and nitric acid (volume ratio: 3:1), stirred and digested for 24 hours at 100 ℃, and the content of alkali metal and alkaline earth metal is measured by adopting an inductively coupled plasma mass spectrometer ICP-MS. And measuring the carbon element content of the obtained high-quality active carbon precursor by adopting an elemental analyzer.
Example 6
The embodiment provides a method for preparing a high-quality activated carbon precursor by removing wheat straw ash through wood vinegar combined with hydrothermal carbonization, which comprises the following steps:
pulverizing wheat straw, sieving to 50 mesh, and drying. And (3) heating the dried wheat straw to the pyrolysis temperature of 600 ℃ at the heating rate of 20 ℃/min in nitrogen atmosphere, preserving heat for 1h, collecting flue gas, and performing fractional condensation to obtain the wheat straw pyroligneous liquor. And (3) standing, filtering, removing impurities, collecting water phase filtrate, and refining the obtained wood vinegar to obtain refined wheat straw wood vinegar.
The wheat straw was crushed and sieved to 50 mesh. Mixing the obtained wheat straw raw material with the refined wheat straw wood vinegar in a hydrothermal carbonization reactor according to a ratio of 1:20 (w/w), uniformly stirring, then heating to 160 ℃ in nitrogen at a heating rate of 10 ℃/min, keeping the pressure of the reaction system at 50bar by adjusting the flow rate of the nitrogen, keeping the reaction system at the set temperature and the pressure for 1 hour, carrying out hydrothermal carbonization reaction, after the reaction is finished, continuing to cool the reaction system to room temperature in a nitrogen atmosphere, filtering the obtained solid product, repeatedly washing to be neutral with ionized water at 30 ℃, and drying at 105 ℃ to obtain the high-quality active carbon precursor. The obtained high-quality active carbon precursor is placed in a mixed solution of hydrochloric acid and nitric acid (volume ratio: 3:1), stirred and digested for 24 hours at 100 ℃, and the content of alkali metal and alkaline earth metal is measured by adopting an inductively coupled plasma mass spectrometer ICP-MS. And measuring the carbon element content of the obtained high-quality active carbon precursor by adopting an elemental analyzer.
Example 7
The embodiment provides a method for preparing a high-quality activated carbon precursor by removing corn straw ash through wood vinegar combined with hydrothermal carbonization, which comprises the following steps:
crushing corn stalk, sieving to 50 mesh, and drying. And (3) heating the dried corn straw to the pyrolysis temperature of 500 ℃ at a heating rate of 20 ℃/min in nitrogen atmosphere, preserving heat for 1h, collecting flue gas, and performing fractional condensation to obtain the corn straw wood vinegar. And (3) standing, filtering, removing impurities and collecting aqueous phase filtrate for refining the obtained wood vinegar to obtain refined corn straw wood vinegar.
Crushing corn stalk and sieving to 50 mesh. Mixing the obtained corn stalk raw material with the refined corn stalk pyroligneous liquor in a hydrothermal carbonization reactor according to a ratio of 1:10 (w/w), uniformly stirring, then heating to 160 ℃ in nitrogen at a heating rate of 10 ℃/min, keeping the pressure of a reaction system at 30bar by adjusting the flow rate of the nitrogen, keeping the reaction system at a set temperature and pressure for 1 hour, carrying out hydrothermal carbonization reaction, after the reaction is finished, continuing to cool the reaction system to room temperature in a nitrogen atmosphere, filtering the obtained solid product, repeatedly washing to be neutral with ionized water at 30 ℃, and drying at 105 ℃ to obtain the high-quality active carbon precursor. The obtained high-quality active carbon precursor is placed in a mixed solution of hydrochloric acid and nitric acid (volume ratio: 3:1), stirred and digested for 24 hours at 100 ℃, and the content of alkali metal and alkaline earth metal is measured by adopting an inductively coupled plasma mass spectrometer ICP-MS. And measuring the carbon element content of the obtained high-quality active carbon precursor by adopting an elemental analyzer.
Example 8
The embodiment provides a method for preparing a high-quality activated carbon precursor by removing corn straw ash through wood vinegar combined with hydrothermal carbonization, which comprises the following steps:
crushing corn stalk, sieving to 50 mesh, and drying. And (3) heating the dried corn straw to the pyrolysis temperature of 500 ℃ at a heating rate of 20 ℃/min in nitrogen atmosphere, preserving heat for 1h, collecting flue gas, and performing fractional condensation to obtain the corn straw wood vinegar. And (3) standing, filtering, removing impurities and collecting aqueous phase filtrate for refining the obtained wood vinegar to obtain refined corn straw wood vinegar.
Crushing corn stalk and sieving to 50 mesh. Mixing the obtained corn stalk raw material with the refined corn stalk pyroligneous liquor in a hydrothermal carbonization reactor according to a ratio of 1:20 (w/w), uniformly stirring, then heating to 160 ℃ in nitrogen at a heating rate of 20 ℃/min, keeping the pressure of a reaction system at 50bar by adjusting the flow rate of the nitrogen, keeping the reaction system at a set temperature and pressure for 1 hour, carrying out hydrothermal carbonization reaction, after the reaction is finished, continuing to cool the reaction system to room temperature in a nitrogen atmosphere, filtering the obtained solid product, repeatedly washing to be neutral with ionized water at 30 ℃, and drying at 105 ℃ to obtain the high-quality active carbon precursor. The obtained high-quality active carbon precursor is placed in a mixed solution of hydrochloric acid and nitric acid (volume ratio: 3:1), stirred and digested for 24 hours at 100 ℃, and the content of alkali metal and alkaline earth metal is measured by adopting an inductively coupled plasma mass spectrometer ICP-MS. And measuring the carbon element content of the obtained high-quality active carbon precursor by adopting an elemental analyzer.
Example 9
The embodiment provides a method for preparing a high-quality activated carbon precursor by removing fir wood chip ash through wood vinegar combined with hydrothermal carbonization, which comprises the following steps:
pulverizing fir wood chip, sieving to 50 mesh, and drying. And (3) heating the dried fir wood chips to the pyrolysis temperature of 500 ℃ at a heating rate of 20 ℃/min in nitrogen atmosphere, preserving heat for 1h, collecting flue gas, and performing fractional condensation to obtain the fir wood chip wood vinegar. And (3) standing, filtering, removing impurities, collecting water phase filtrate, and refining the obtained wood vinegar to obtain refined fir wood chip wood vinegar.
Pulverizing fir wood chip, and sieving to 50 mesh. Mixing the obtained fir wood chip raw material with the refined fir wood chip wood vinegar in a hydrothermal carbonization reactor according to a ratio of 1:20 (w/w), uniformly stirring, then heating to 160 ℃ in nitrogen at a heating rate of 20 ℃/min, keeping the pressure of a reaction system at 30bar by adjusting the flow rate of the nitrogen, keeping for 1 hour at a set temperature and pressure for hydrothermal carbonization reaction, after the reaction is finished, continuing to cool the reaction system to room temperature in a nitrogen atmosphere, filtering the obtained solid product, repeatedly washing to be neutral with ionized water at 30 ℃, and drying at 105 ℃ to obtain the high-quality active carbon precursor. The obtained high-quality active carbon precursor is placed in a mixed solution of hydrochloric acid and nitric acid (volume ratio: 3:1), stirred and digested for 24 hours at 100 ℃, and the content of alkali metal and alkaline earth metal is measured by adopting an inductively coupled plasma mass spectrometer ICP-MS. And measuring the carbon element content of the obtained high-quality active carbon precursor by adopting an elemental analyzer.
Example 10
The embodiment provides a method for preparing a high-quality activated carbon precursor by removing fir wood chip ash through wood vinegar combined with hydrothermal carbonization, which comprises the following steps:
pulverizing wheat straw, sieving to 30 mesh, and drying. And (3) heating the dried wheat straw to the pyrolysis temperature of 500 ℃ at a heating rate of 20 ℃/min in nitrogen atmosphere, preserving heat for 1h, collecting flue gas, and performing fractional condensation to obtain the wheat straw pyroligneous liquor. And (3) standing, filtering, removing impurities, collecting water phase filtrate, and refining the obtained wood vinegar to obtain refined wheat straw wood vinegar.
Pulverizing fir wood chip, and sieving to 50 mesh. Mixing the obtained fir wood chip raw material with the refined wheat straw wood vinegar in a hydrothermal carbonization reactor according to a ratio of 1:10 (w/w), uniformly stirring, then heating to 160 ℃ in nitrogen at a heating rate of 10 ℃/min, keeping the pressure of a reaction system at 30bar by adjusting the flow rate of the nitrogen, keeping for 1 hour at a set temperature and pressure for hydrothermal carbonization reaction, continuing cooling the reaction system to room temperature in a nitrogen atmosphere after the reaction is finished, filtering the obtained solid product, repeatedly washing to be neutral with ionized water at 30 ℃, and drying at 105 ℃ to obtain the high-quality active carbon precursor. The obtained high-quality active carbon precursor is placed in a mixed solution of hydrochloric acid and nitric acid (volume ratio: 3:1), stirred and digested for 24 hours at 100 ℃, and the content of alkali metal and alkaline earth metal is measured by adopting an inductively coupled plasma mass spectrometer ICP-MS. And measuring the carbon element content of the obtained high-quality active carbon precursor by adopting an elemental analyzer.
Comparative example 1
The comparative example is different from example 1 only in that wood vinegar is not used as a liquid phase medium for the hydrothermal reaction in the process of preparing the wheat straw-based activated carbon precursor, and deionized water is used instead of wood vinegar as a liquid phase medium for the hydrothermal carbonization reaction, and the rest are the same. I.e. the wheat straw is crushed and sieved to 30 meshes. Mixing the obtained wheat straw raw material with deionized water in a hydrothermal carbonization reactor according to a ratio of 1:10 (w/w), uniformly stirring, heating to 160 ℃ in nitrogen at a heating rate of 10 ℃/min, maintaining the pressure of a reaction system at 30bar by adjusting the flow rate of the nitrogen, maintaining the temperature at a set temperature and the pressure for 1 hour, carrying out hydrothermal carbonization reaction, continuing cooling the reaction system to room temperature in a nitrogen atmosphere after the reaction is completed, filtering the obtained solid product, repeatedly washing to be neutral with ionized water at 30 ℃, and drying at 105 ℃ to obtain the active carbon precursor. The obtained active carbon precursor is placed in a mixed solution of hydrochloric acid and nitric acid (volume ratio: 3:1), stirred and digested for 24 hours at 100 ℃, and the content of alkali metal and alkaline earth metal is measured by adopting an inductively coupled plasma mass spectrometer ICP-MS. And measuring the carbon element content of the obtained active carbon precursor by adopting an elemental analyzer.
Comparative example 2
The comparative example is different from example 7 only in that wood vinegar is not used as a liquid phase medium for the hydrothermal reaction in the process of preparing the corn stalk-based activated carbon precursor, and deionized water is used as a liquid phase medium instead of wood vinegar to perform the hydrothermal carbonization reaction, and the rest are the same. The corn stalk is crushed and sieved to 50 meshes. Mixing the corn stalk material with deionized water in a hydrothermal carbonization reactor according to a ratio of 1:10 (w/w), stirring uniformly, heating to 160 ℃ in nitrogen at a heating rate of 10 ℃/min, maintaining the pressure of a reaction system at 30bar by adjusting the flow of the nitrogen, maintaining the temperature and the pressure for 1 hour for hydrothermal carbonization reaction, continuing cooling the reaction system to room temperature in nitrogen atmosphere after the reaction is completed, filtering the obtained solid product, repeatedly washing to be neutral with ionized water at 30 ℃, and drying at 105 ℃ to obtain the active carbon precursor. The obtained active carbon precursor is placed in a mixed solution of hydrochloric acid and nitric acid (volume ratio: 3:1), stirred and digested for 24 hours at 100 ℃, and the content of alkali metal and alkaline earth metal is measured by adopting an inductively coupled plasma mass spectrometer ICP-MS. And measuring the carbon element content of the obtained active carbon precursor by adopting an elemental analyzer.
Comparative example 3
This comparative example differs from example 1 only in that the hydrothermal carbonization reaction temperature employed in the process of preparing the wheat straw based activated carbon precursor is lower, and the remainder are the same. Namely, the wheat straw is crushed, sieved to 30 meshes and dried. And (3) heating the dried wheat straw to the pyrolysis temperature of 500 ℃ at a heating rate of 20 ℃/min in nitrogen atmosphere, preserving heat for 1h, collecting flue gas, and performing fractional condensation to obtain the wheat straw pyroligneous liquor. And (3) standing, filtering, removing impurities, collecting water phase filtrate, and refining the obtained wood vinegar to obtain refined wheat straw wood vinegar.
The wheat straw was crushed and sieved to 30 mesh. Mixing the obtained wheat straw raw material with the refined wheat straw wood vinegar in a hydrothermal carbonization reactor according to a ratio of 1:10 (w/w), uniformly stirring, then heating to 120 ℃ in nitrogen at a heating rate of 10 ℃/min, keeping the pressure of a reaction system at 30bar by adjusting the flow rate of the nitrogen, keeping the reaction system at the set temperature and the pressure for 1 hour, carrying out hydrothermal carbonization reaction, after the reaction is finished, continuing to cool the reaction system to room temperature in a nitrogen atmosphere, filtering the obtained solid product, repeatedly washing to be neutral with ionized water at 30 ℃, and drying at 105 ℃ to obtain the high-quality active carbon precursor. The obtained high-quality active carbon precursor is placed in a mixed solution of hydrochloric acid and nitric acid (volume ratio: 3:1), stirred and digested for 24 hours at 100 ℃, and the content of alkali metal and alkaline earth metal is measured by adopting an inductively coupled plasma mass spectrometer ICP-MS. And measuring the carbon element content of the obtained high-quality active carbon precursor by adopting an elemental analyzer.
Fig. 3 shows the yields of the activated carbon precursors prepared in examples 1 to 10 and comparative examples 1 to 3.
Fig. 4 shows the carbon element content of the activated carbon precursors and biomass raw materials (wheat straw, corn straw, fir wood chips) prepared in examples 1 to 10 and comparative examples 1 to 3.
FIG. 5 shows the removal rates of alkali metals and alkaline earth metals in examples 1 to 10 and comparative examples 1 to 3.
The experimental test data of the above examples and comparative examples show that the high-quality biomass-based activated carbon precursor can be prepared by using an acidic pyroligneous liquor rich in organic acids such as acetic acid and propionic acid as a liquid-phase eluent and combining hydrothermal carbonization to efficiently remove various alkali metals and alkaline earth metals in biomass raw materials. From the yields of the activated carbon precursors prepared in examples 1 to 10 and comparative examples 1 to 3 provided by the present invention (fig. 3), it can be seen that whether or not the acid pyroligneous liquor is used as a liquid phase medium for hydrothermal carbonization does not significantly affect the yield of the solid product under the experimental conditions, i.e., under the conditions, the pyroligneous liquor is used as a liquid phase medium for hydrothermal carbonization (examples 1 to 10) and deionized water is used as a liquid phase medium for hydrothermal carbonization (comparative examples 1 to 2). The yield of the solid product is mainly distributed between 70 and 80%. The yields of examples 9 and 10 show that the yield of solid products prepared from fir wood chips is slightly higher than that prepared from straw-based biomass such as wheat straw, corn straw, etc. In addition, the data of example 1 and comparative example 3 show that higher hydrothermal carbonization reaction temperatures increase the carbonization degree of the raw material, and thus, the yield of the solid product decreases with an increase in the hydrothermal carbonization reaction temperature. Fig. 4 shows the carbon element content of the activated carbon precursors and biomass raw materials (wheat straw, corn straw, fir wood chips) prepared in examples 1 to 10 and comparative examples 1 to 3 provided by the present invention. In examples 1-10, wood vinegar was used as the liquid medium for hydrothermal carbonization, and the carbon content of the obtained solid product was increased as compared with the corresponding biomass raw material. In comparative examples 1-2, deionized water was used as the liquid phase medium for hydrothermal carbonization, and the carbon element content of the obtained solid product was also improved. Under the experimental conditions, deionized water or wood vinegar is adopted as a liquid medium, so that the degree of increasing the content of carbon elements in the solid product is not greatly influenced, but the content of the carbon elements is obviously increased compared with the corresponding biomass raw material, and the prepared solid product is a high-quality active carbon precursor. Fig. 5 shows the removal rates of alkali metals and alkaline earth metals in examples 1 to 10 and comparative examples 1 to 3 provided by the present invention. Wood vinegar or deionized water is used as a liquid phase medium for hydrothermal carbonization, so that alkali metal and alkaline earth metal rich in biomass raw materials can be removed. The effect of using acid pyroligneous liquor as a liquid phase medium (examples 1-10) on the removal of alkali metals and alkaline earth metals was significantly better than deionized water (comparative examples 1-2). The higher temperature of the hydrothermal carbonization reaction is also more beneficial to the removal of alkali metals and alkaline earth metals in the raw materials. The wood vinegar prepared by pyrolyzing biomass in an anaerobic or inert atmosphere is rich in water and organic acids such as formic acid, acetic acid, propionic acid, glycolic acid and the like, and the acidic wood vinegar rich in the organic acids is used as a liquid phase medium for hydrothermal carbonization, so that the wood vinegar has the advantages of washing with water and washing with inorganic acid, and simultaneously alkali metals such as potassium, sodium, magnesium, calcium and the like in biomass raw materials are easier to remove at a higher temperature. In summary, the acid wood vinegar which is generated in the process of preparing the biochar by biomass pyrolysis and is rich in organic acid is used as a liquid phase medium, and the content of alkali metal and alkaline earth metal in the biomass material can be obviously reduced by combining with hydrothermal carbonization, so that the content of carbon element in the prepared product is improved, and the biomass-based high-quality active carbon precursor is prepared. The method has the advantages of washing biomass raw materials with water, washing the biomass raw materials with inorganic acid and the like, can efficiently remove alkali metal and alkaline earth metal in the biomass raw materials, directly prepares the high-quality biomass-based activated carbon precursor, and also avoids strong acid and alkali used in the washing and deashing process with inorganic acid and pollution caused in the washing process. The method does not obviously increase the production cost, is easy to realize industrialized popularization and application and is environment-friendly. In addition, the method fully utilizes the acid liquid byproduct wood vinegar in the process of preparing the biochar by biomass pyrolysis, and realizes high-value comprehensive utilization of biomass pyrolysis products.
The present invention is described in detail above. It will be apparent to those skilled in the art that the present invention can be practiced in a wide range of equivalent parameters, concentrations, and conditions without departing from the spirit and scope of the invention and without undue experimentation. While the invention has been described with respect to specific embodiments, it will be appreciated that the invention may be further modified. In general, this application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains.
Claims (10)
1. A method for preparing a biomass-based activated carbon precursor by removing biomass ash through combining wood vinegar with hydrothermal carbonization, which takes wood vinegar as a liquid phase medium, carries out hydrothermal carbonization on biomass raw materials to obtain the biomass-based activated carbon precursor.
2. The method according to claim 1, characterized in that: the method comprises the following steps:
the biomass raw materials for preparing the activated carbon precursor are crushed and sieved, wood vinegar is added into the biomass raw materials according to a certain solid-liquid ratio, the obtained mixture is stirred and heated in an inert atmosphere for hydrothermal carbonization, and after the reaction is finished, the solid products are filtered and collected, so that the biomass-based activated carbon precursor is obtained.
3. The method according to claim 1 or 2, characterized in that: the wood vinegar is prepared by the following steps:
pulverizing biomass raw materials, sieving, drying, performing high-temperature pyrolysis in an anaerobic environment, performing fractional condensation on high-temperature flue gas generated in the pyrolysis process to obtain pyroligneous liquor, pyrolysis oil, biochar and combustible gas, and refining the obtained pyroligneous liquor.
4. A method according to claim 3, characterized in that: the biomass raw material is lignocellulose biomass, and specifically is at least one of wheat straw, corn straw, rice straw, bamboo wood, wood dust, peanut shell and rice hull;
sieving with 10-100 mesh sieve;
the high-temperature pyrolysis is to place the dried biomass raw material in inert atmosphere or vacuum, pyrolyze for 1-3 hours at 400-800 ℃, collect flue gas, and carry out fractional condensation to obtain yellow brown acidic liquid wood vinegar;
the refining comprises standing wood vinegar, filtering, removing impurities, and collecting water phase filtrate.
5. The method according to claim 2, characterized in that: the biomass raw material for preparing the activated carbon precursor is lignocellulose biomass, and specifically is at least one of wheat straw, corn straw, rice straw, bamboo, wood dust, peanut shell and rice hull;
the sieving is carried out by sieving with a 10-100 mesh sieve.
6. The method according to claim 2, characterized in that: the ratio of the biomass raw material for preparing the active carbon precursor to the wood vinegar is 1:5-1:30, w/w.
7. The method according to claim 2, characterized in that: the hydrothermal carbonization process is to stir the mixture of the biomass raw material for preparing the active carbon precursor and the wood vinegar, heat the mixture to 160-220 ℃ at a heating rate of 10-20 ℃/min in an inert atmosphere, and carry out hydrothermal carbonization under a system pressure of 10-60bar, wherein the mixture is kept for 1-2h at the temperature and the pressure.
8. The method according to claim 2, characterized in that: the method further comprises the operation of washing the obtained solid product with water at a low temperature of 20-60 ℃ until the solid product is neutral and dried.
9. A biomass-based activated carbon precursor produced by the method of any one of claims 1-8.
10. A biomass-based activated carbon prepared from the biomass-based activated carbon precursor of claim 9.
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