CN104371748B - Preparation method of high-yield biochar - Google Patents

Abstract

The invention discloses a method for preparing high-yield biochar. The main steps include: (1) putting the collected biomass raw material into a catalyst solution, stirring and impregnating at room temperature, and filtering to obtain a biomass raw material containing water and a catalyst. The water content by weight ranges from 50 to 150%, and the weight content of the catalyst is 0.5 to 5%; (2) The biomass raw material containing water and catalyst is heated to 100 to 180 °C/min at 0.5 to 2 °C/min in an oxygen-free or oxygen-limited atmosphere. ℃, keep warm for 1-2 hours, then raise the temperature to 240-300°C at 0.5-3°C/min, keep warm for 1-3 hours, and finally raise the temperature to 500-900°C at 10-50°C/min, keep warm for 1-4 hours, The biochar is obtained after cooling, and the yield of the biochar is greater than 40% of the weight of the biomass raw material. The invention does not need to be dried in the preparation process of biochar, and utilizes the biomass raw material containing water and catalyst and step-by-step carbonization process to realize the purpose of increasing the yield of biochar, and saves energy while the prepared biochar has a specific surface area Large and high porosity, it can be widely used in water treatment, functional textiles and other fields.

Description

A kind of preparation method of high-yield biochar

technical field

The invention belongs to the technical field of biochar preparation, and relates to a method for preparing biochar with high yield. In particular, it relates to a method for preparing high-yield biochar from agricultural and forestry wastes.

Background technique

The waste generated in the process of agricultural and forestry processing in the world is a huge number. In my country alone, the output of rice husk in 2011 reached about 40 million tons, and the output of various crop straws exceeded 700 million tons per year. The disposal of these crop stalks, rice husks, etc. is a problem. Pyrolysis is to convert biomass raw materials into other products for utilization by thermal decomposition. It is relatively simple to implement, has a high energy conversion rate, and is also conducive to large-scale processing of biomass raw materials. It is one of the effective methods to solve the above-mentioned agricultural and forestry waste biomass raw materials. one.

Biochar is a kind of highly aromatized refractory solid material formed by pyrolysis and carbonization of biomass raw materials under complete or partial anoxic conditions. The commonly used pyrolysis method is often a one-stage pyrolysis, and a higher heating rate is used, and the yield of biochar is often lower.

The main components of biomass raw materials include cellulose, hemicellulose, lignin and inorganic salts. Among them, cellulose and hemicellulose are sugar compounds with more hydroxyl groups, and their structures are relatively unstable, and they are easy to decompose at lower temperatures. Many, relatively high thermal stability. Biochar prepared by conventional pyrolysis methods is mainly composed of charred products formed by pyrolysis of lignin and ash formed by inorganic salts, and the proportion of biochar formed by pyrolysis of cellulose and hemicellulose is relatively low. However, the proportion of cellulose and hemicellulose in biomass raw materials is as high as 50%. Therefore, increasing the yield of biochar formed by pyrolysis of cellulose and hemicellulose components can greatly improve the formation of biochar by pyrolysis of biomass. Yield of biochar.

Patent CN103328612A proposes to use biomass raw materials with low lignin content (10-30wt%) to stay in three temperature ranges of 130-280, 300-500, 650-900°C for 10-40, 5-30, 10-60 minutes respectively , to obtain carbon-rich solids for soil improvement. Although this patent proposes hierarchical pyrolysis for the three major organic components in biomass, the pyrolysis heating rate used is greater than 20°C/min, which is unfavorable for the pyrolysis conversion of hemicellulose and cellulose into charcoal The higher heating rate will promote the rapid decomposition of hemicellulose and cellulose into volatile substances and reduce the production of biochar. Patent CN101693845A also mentions a method of graded pyrolysis, which is mainly used to prepare bio-oil and chemicals, and is to convert the biochar converted from biomass into other products as much as possible, rather than improving the biochar. Yield. Patent CN101892106A mentions that boric acid is used to impregnate chestnut shells, followed by pre-oxidation and carbonization to prepare biochar, the purpose of which is to obtain a loose porous cross-linked structure and have a certain effect on improving the yield of biochar. Patent CN103213985A mentions a method of preparing biochar by zinc borate flame retardant method, and mentions that the yield of biochar is improved, but the first step of impregnating time is long, and the temperature of 105°C is too high.

Contents of the invention

The purpose of the present invention is to provide a high-yield biochar preparation method, aiming at the cellulose, hemicellulose and lignin components in the biomass, through the means of loading catalyst and step-by-step carbonization, making it in the pyrolysis process In the complex chemical reaction to form a cross-linked structure to reduce the escape of small molecules and trap tar, thereby increasing the yield of biochar and generating more pore structures. The preparation method includes two processes of impregnating the catalyst with the biomass raw material and stepwise carbonization.

A kind of preparation method of high yield biochar of the present invention comprises the steps:

(1) put the biomass raw material into the catalyst solution, stir and impregnate, and then filter to obtain the biomass raw material containing water and catalyst; wherein, the weight moisture content of the biomass raw material containing water and catalyst is 50% to 150%, and the catalyst The weight content is 0.5-5%;

(2) raising the temperature of the biomass raw material containing water and catalyst to 100-180°C at 0.5-2°C/min in an oxygen-free or oxygen-limited atmosphere, and then keeping it warm for 1-2 hours; moisture participates in and promotes the reaction, and Under the combined action of the catalyst, a relatively moderate internal environment is provided to promote the chemical cross-linking of the internal molecules of the biomass, immobilizing small molecules, and at the same time, the catalyst components are fixed in the random network formed by the internal molecules in the biomass raw materials;

(3) Then in an oxygen-free or oxygen-limited atmosphere, the temperature is raised to 240-300°C at 0.5-3°C/min, and the temperature is kept for 1-3 hours; Evaporate and etch the surface of biochar, loosen the structure of biochar, and form a pore structure to capture and decompose to produce tar and gas;

(4) Then raise the temperature to 500-900°C at 10-50°C/min in an oxygen-free or oxygen-limited atmosphere, and keep it warm for 1-4 hours; carry out final carbonization on the preliminary carbonization structure, fix the network structure and simultaneously capture the tar and gas react again to form char;

(5) The residual solid matter obtained after cooling is biochar, and the yield of biochar is greater than 40% of the weight of the biomass raw material. As a preferred technical solution:

A method for preparing high-yield biochar as described above, the biomass raw materials are rice straw, wheat straw, corn straw, cotton straw, rape straw, soybean straw, wheat husk, rice husk, peanut shell, bamboo, Bamboo chips, wood, wood chips, leaves, weeds, coconut shells, chestnut shells, coffee grounds, tea leaves, apple pomace, grape pomace, pear pomace, sugar cane pomace, olive pomace, mango pomace, watermelon rind, winter melon rind and pumpkin rind more than one of them.

A kind of preparation method of high-yield biochar as described above, described catalyst solution is potassium permanganate solution, zinc acetate solution, boric acid solution, sodium borate solution, zinc chloride solution, zinc sulfate solution, sodium chloride solution , phosphoric acid solution, ammonium phosphate solution, ammonium dihydrogen phosphate solution, diammonium hydrogen phosphate solution, sodium antimony tartrate solution, isocyanate solution, sodium p-toluenesulfonate solution, γ-aminopropyltriethoxysilane solution, γ-shrink Glyceryl ether oxypropyltrimethoxysilane solution, γ-(methacryloyloxy)propyltrimethoxysilane solution, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane solution, sodium methoxide solution, magnesium ethoxide solution, aluminum isopropoxide solution, ethyl orthosilicate solution, ethyl titanate solution or butyl phthalate solution, or a mixture of two of the above solutions in any volume ratio Mixed solution; the weight percent content of the catalyst in the catalyst solution is 0.5-10%.

A method for preparing high-yield biochar as described above, the amount of feed of the biomass raw material is 5 to 20 wt% of the sum of the biomass raw material and the catalyst solution; the stirring and impregnating time is 1 ~5 hours.

As mentioned above, a high-yield biochar preparation method, the oxygen-free or oxygen-limited atmosphere refers to a high-purity nitrogen or argon atmosphere, or a mixed gas of nitrogen and water vapor, or argon and water vapor.

A high-yield biochar preparation method as described above, the mixed gas of nitrogen and water vapor or argon and water vapor, the volume ratio of nitrogen or argon to water vapor is 90:10 to 98:2 .

A high-yield biochar preparation method proposed by the present invention fully utilizes the characteristics that the biomass raw material is composed of cellulose, hemicellulose and lignin, and impregnates it with a catalyst solution so that it is loaded with a lower content of catalyst molecules, Then, through the step-by-step carbonization process of undried hydrous biomass raw materials, at a low heating rate and carbonization temperature, water and catalyst molecules are used to fully esterify with the cellulose, hemicellulose and lignin molecules in the biomass raw materials The content of small molecules in the biomass raw material is reduced by reactions such as acetylation, acylation, and cross-linking and cyclization, and a complex heat-resistant network structure is formed, and then the surface of the biochar is etched by evaporation of water, and the structure of the biochar is loosened by its volume expansion. High heating rate and carbonization temperature fully carry out the carbonization process. This can not only increase the yield of biochar, but also increase the specific surface area of biochar, increase the pore structure of biochar, and greatly improve the practical value of biochar.

Beneficial effect:

The present invention does not need to carry out the drying step of the biomass raw material before the pyrolysis carbonization, which saves time and energy consumption; reduces the generation of volatile substances in the pyrolysis carbonization process, forms more solid carbon, and is beneficial to reduce carbon emissions; at the same time The prepared biochar has a large specific surface area and high porosity, and has a wide range of applications.

detailed description

The present invention will be further described below in combination with specific embodiments. It should be understood that these examples are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the teachings of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims of the present application.

Example 1

Put the collected rice stalks into an aqueous solution containing 0.5% by weight of boric acid, the weight of the rice stalks is 5% of the weight of the whole system, stir and soak at room temperature for 1 hour, and filter out the liquid with a filter screen to obtain 0.5wt% boric acid, water by weight 50% rice straw, the rice straw on the filter screen was transferred to the pyrolysis furnace, under the protective atmosphere of high-purity nitrogen, the heating rate was raised to 100°C at a rate of 0.5°C/min, kept for 1 hour, and then Raise the temperature at a rate of 0.5 °C/min to 240 °C, keep the temperature for 1 hour, and finally raise the temperature at a rate of 10 °C/min to 500 °C, keep the temperature for 1 hour, and cool with the furnace to obtain biochar with a yield of 55 wt%.

Example 2

Put the collected rice husks into an aqueous solution containing 10% by weight of potassium permanganate, the weight of the rice husks is 20% of the weight of the whole system, stir and soak at room temperature for 5 hours, and filter out the liquid with a filter screen to obtain potassium permanganate-containing 5wt% rice husk with a weight moisture content of 150%, the rice husk on the filter screen is transferred to the pyrolysis furnace, under the protective atmosphere of high-purity argon, the temperature rises to 180°C at a rate of 2°C/min, and the temperature is kept for 2 hours, then raised to 300°C at a heating rate of 3°C/min, kept for 3 hours, and finally raised to 900°C at a heating rate of 50°C/min, kept at a temperature of 4 hours, and then cooled with the furnace to obtain biochar, with a yield of 40.1 wt%.

Example 3

Put the collected bamboo into a solution containing 5% by weight of γ-aminopropyltriethoxysilane, the weight of the bamboo is 10% of the weight of the whole system, stir and soak at room temperature for 5 hours, and filter the liquid with a filter screen to obtain γ-aminopropyltriethoxysilane 1wt%, the bamboo material of weight moisture content 80%, the bamboo material on the filter screen is transferred in the pyrolysis furnace, under the atmosphere that nitrogen and water vapor volume ratio are 90:10, with 2 The heating rate of ℃/min was raised to 180°C, kept for 2 hours, then raised to 300°C at a rate of 3°C/min, kept for 3 hours, and finally raised to 900°C at a rate of 50°C/min, kept for 4 hours Hours, the biochar is obtained with furnace cooling, and the yield is 49wt%.

Example 4

The bamboo chips collected are put into an aqueous solution containing 2% by weight of sodium borate, the weight of bamboo chips is 10% of the weight of the whole system, stirred and soaked at room temperature for 5 hours, and the liquid is filtered out with a filter screen to obtain sodium borate containing 2wt%, by weight Bamboo chips with a moisture content of 70%, transfer the bamboo chips on the filter to the pyrolysis furnace, in an atmosphere with a volume ratio of nitrogen and water vapor of 98:2, raise the temperature to 160°C at a rate of 2°C/min, and keep warm 2 hours, then raised to 280°C at a heating rate of 3°C/min, held for 2 hours, and finally raised to 800°C at a heating rate of 50°C/min, held for 2 hours, and then cooled with the furnace to obtain biochar, yield It is 47wt%.

Example 5

The collected wood is dropped into an aqueous solution containing 3% by weight of zinc chloride, and the weight of the wood is 15% of the weight of the whole system. After stirring and soaking at room temperature for 4 hours, filter out the liquid with a filter screen to obtain 3% by weight of zinc chloride. For wood with a moisture content of 66%, transfer the wood on the filter to the pyrolysis furnace, in an atmosphere with a volume ratio of argon and water vapor of 98:2, raise the temperature to 180 °C at a rate of 2 °C/min, and keep the temperature for 2 hour, then raised to 300°C at a heating rate of 3°C/min, held for 2 hours, and finally raised to 900°C at a heating rate of 50°C/min, kept at a temperature of 4 hours, and then cooled with the furnace to obtain biochar, with a yield of 43 wt%.

Example 6

The collected leaves are dropped into an aqueous solution containing 4% by weight of sodium chloride, and the weight of the leaves is 13% of the weight of the whole system. After stirring and soaking at room temperature for 2 hours, filter the liquid with a strainer to obtain 3.5 wt% sodium chloride. Leaves with a water content of 80% by weight, transfer the leaves on the filter to the pyrolysis furnace, and raise the temperature to 180°C at a rate of 2°C/min in an atmosphere with a volume ratio of argon and water vapor of 90:10, and keep warm 2 hours, then raised to 300°C at a heating rate of 3°C/min, held for 2 hours, and finally raised to 900°C at a heating rate of 50°C/min, held at a temperature of 2 hours, and then cooled with the furnace to obtain biochar, yield It is 41wt%.

Example 7

Put the collected weeds into an aqueous solution containing 8% by weight of phosphoric acid, the weight of the weeds is 7% of the weight of the whole system, stir and soak at room temperature for 3 hours, and filter out the liquid with a filter screen to obtain a solution containing 4.5wt% phosphoric acid and water by weight. Weeds with a rate of 55% were transferred to the pyrolysis furnace, and the temperature was raised to 180°C at a rate of 2°C/min in an atmosphere with a volume ratio of nitrogen and water vapor of 95:5, and the heat preservation time was 2°C. hour, then raised to 270°C at a heating rate of 3°C/min, held for 2 hours, and finally raised to 900°C at a heating rate of 35°C/min, kept at a temperature of 3 hours, and then cooled with the furnace to obtain biochar, with a yield of 48wt%.

Example 8

The coconut shell that collects is put into the aqueous solution containing 9% by weight of ammonium phosphate, and the weight of coconut shell is 12% of whole system weight, removes liquid with strainer after stirring and soaking at room temperature for 1 hour, obtains 4.2wt% containing ammonium phosphate, For coconut shells with a water content of 79%, the coconut shells on the filter screen are transferred to the pyrolysis furnace. Raise the heating rate to 250°C in min, keep it warm for 2 hours, and finally raise the temperature to 555°C at a heating rate of 50°C/min, keep it warm for 2 hours, and cool down with the furnace to get biochar with a yield of 51wt%.

Example 9

Put the collected chestnut shells into an aqueous solution containing 9.5% by weight of isocyanate. The weight of chestnut shells is 12% of the weight of the whole system. After stirring and soaking at room temperature for 1 hour, filter out the liquid with a filter screen to obtain 3.9% by weight of isocyanate. Chestnut shells with a yield of 81%, the chestnut shells on the filter are transferred to the pyrolysis furnace, and in an argon atmosphere, the heating rate is raised to 120°C at a rate of 1.5°C/min, kept for 2 hours, and then heated at a rate of 2.5°C/min The heating rate was raised to 240°C, kept for 2 hours, and finally raised to 730°C at a heating rate of 40°C/min, kept for 2 hours, and cooled with the furnace to obtain biochar, with a yield of 53wt%.

Example 10

Put the collected coffee grounds into a mixed aqueous solution containing 10% by weight of ammonium dihydrogen phosphate and diammonium hydrogen phosphate in total, wherein the weight ratio of ammonium dihydrogen phosphate and diammonium hydrogen phosphate is 7:3, and the weight of coffee grounds is the whole 20% of the system weight, stirred and soaked at room temperature for 5 hours and filtered out the liquid with a filter screen to obtain coffee grounds containing 4.1wt% of ammonium phosphate and diammonium hydrogen phosphate and a weight moisture content of 74%. The coffee grounds on the filter screen were transferred to In the pyrolysis furnace, under a nitrogen atmosphere, the temperature was raised to 180°C at a rate of 2°C/min, kept for 1.6 hours, then raised to 240°C at a rate of 3°C/min, kept for 3 hours, and finally heated at 50°C The heating rate was raised to 900° C., kept at a temperature of 4 hours, and cooled with the furnace to obtain biochar with a yield of 47.5 wt%.

Example 11

Put the collected tea leaves into a mixed aqueous solution containing 9.8% by weight of ammonium dihydrogen phosphate and diammonium hydrogen phosphate in total, wherein the weight ratio of ammonium dihydrogen phosphate and diammonium hydrogen phosphate is 8:3, and the weight of tea leaves is the whole 19.9% of the system weight, after stirring and soaking at room temperature for 4.6 hours, remove the liquid with a strainer to obtain a total of 2.1wt% of ammonium phosphate and diammonium phosphate, and the tea leaves with a weight moisture content of 87%. The tea leaves on the strainer are transferred to In the pyrolysis furnace, under argon atmosphere, the temperature was raised to 180°C at a rate of 2°C/min, and kept for 2 hours, then raised to 289°C at a rate of 3°C/min, kept for 3 hours, and finally heated at 44 The heating rate of °C/min was increased to 900 °C, the temperature was maintained for 4 hours, and the biochar was obtained by cooling with the furnace, with a yield of 46.5 wt%.

Example 12

Put the collected watermelon rind into a mixed aqueous solution containing 0.5% by weight of zinc acetate and zinc sulfate in total, wherein the weight ratio of zinc acetate and zinc sulfate is 9:4, and the weight of watermelon rind is 5% of the weight of the whole system, and stir at room temperature After soaking for 1 hour, remove the liquid with a strainer to obtain a total of 1.4wt% of zinc acetate and zinc sulfate, watermelon rind with a weight moisture content of 122%. The watermelon rind on the strainer is transferred to the pyrolysis furnace, and the In an atmosphere with a vapor volume ratio of 98:2, raise the temperature to 100°C at a rate of 0.5°C/min, keep it for 1 hour, then raise it to 240°C at a rate of 0.5°C/min, keep it for 3 hours, and finally heat it at 10°C The heating rate of °C/min was increased to 510 °C, the temperature was maintained for 2 hours, and the biochar was obtained by cooling with the furnace, with a yield of 53.5 wt%.

Example 13

Put the collected cotton stalks into a mixed aqueous solution containing 2% by weight of sodium antimony tartrate and sodium p-toluenesulfonate in total, wherein the weight ratio of sodium antimony tartrate and sodium p-toluenesulfonate is 1:1, and the weight of cotton straw is the whole 11% of the system weight, stirred and soaked at room temperature for 2 hours and then filtered out the liquid with a filter screen to obtain a total of 1.7wt% of sodium antimony tartrate and sodium p-toluenesulfonate, cotton stalks with a weight moisture content of 91%, and the cotton stalks on the filter screen Transfer to the pyrolysis furnace, in an atmosphere with a volume ratio of nitrogen and water vapor of 94:6, raise the temperature to 130°C at a rate of 1°C/min, keep it warm for 2 hours, and then increase the temperature at a rate of 2°C/min Heat to 250°C, hold for 2 hours, and finally raise the temperature to 800°C at a rate of 20°C/min, hold for 3 hours, and cool with the furnace to obtain biochar, with a yield of 42.2wt%.

Example 14

Put the collected grape marc into a mixed aqueous solution containing 3% by weight of sodium antimony tartrate and sodium chloride in total, wherein the weight ratio of sodium antimony tartrate and sodium chloride is 1:3, and the weight of grape marc is 16% of the weight of the whole system. %, stirred and soaked at room temperature for 3 hours, filtered out the liquid with a strainer to obtain a total of 2.4wt% sodium antimony tartrate and sodium chloride, and a grape marc with a weight moisture content of 66%. The grape marc on the strainer was transferred to the pyrolysis furnace , in an atmosphere with a volume ratio of argon to water vapor of 93:7, the temperature was raised to 160°C at a rate of 1°C/min, kept for 1 hour, and then raised to 270°C at a rate of 2°C/min, kept After 2 hours, the temperature was raised to 700°C at a rate of 20°C/min, held for 3 hours, and cooled with the furnace to obtain biochar, with a yield of 47.7wt%.

Example 15

Put the collected wheat straw into a mixed solution containing a total of 3% by weight of sodium methoxide and magnesium ethoxide, wherein the weight ratio of sodium methoxide and magnesium ethoxide is 1:2, and the weight of wheat straw is 19% of the weight of the whole system, stirring at room temperature After soaking for 3 hours, remove the liquid with a filter screen to obtain a total of 4.4wt% of sodium methylate and magnesium ethylate, and a wheat straw with a water content of 144% by weight. The wheat straw on the filter screen is transferred to the pyrolysis furnace. Under nitrogen atmosphere, Raise to 166°C at a heating rate of 1°C/min, hold for 1 hour, then raise to 266°C at a heating rate of 2°C/min, hold for 2 hours, and finally rise to 777°C at a heating rate of 20°C/min, Heat preservation for 3 hours, and then cool down with the furnace to obtain biochar, with a yield of 40.7wt%.

Example 16

Put the collected mango pomace into a mixed solution containing 3% by weight of γ-glycidyl etheroxypropyl trimethoxysilane and γ-(methacryloyloxy)propyl trimethoxysilane, wherein γ-glycidol The weight ratio of etheroxypropyltrimethoxysilane to γ-(methacryloyloxy)propyltrimethoxysilane is 1:5, and the weight of mango pomace is 19% of the weight of the whole system. After stirring and impregnating at room temperature for 3 hours Filter out the liquid with a strainer to obtain mango pomace containing 3.4wt% of gamma-glycidyl etheroxypropyltrimethoxysilane and gamma-(methacryloxy)propyltrimethoxysilane and a weight moisture content of 74%. , transfer the mango pomace on the filter to the pyrolysis furnace, and raise the temperature to 136°C at a rate of 1.5°C/min in an argon atmosphere, keep it warm for 1 hour, and then raise it to 256°C at a rate of 2°C/min. ℃, heat preservation for 2 hours, and finally raised to 567°C at a heating rate of 20°C/min, heat preservation for 3 hours, and then cooled with the furnace to obtain biochar, with a yield of 49.7wt%.

Example 17

Put the collected corn stalks into a solution containing 6.9% by weight of aluminum isopropoxide, the weight of the corn stalks is 18% of the weight of the whole system, stir and impregnate at room temperature for 1 hour, and filter the liquid with a filter screen to obtain aluminum isopropoxide containing 4wt% corn stalks with a moisture content of 55% by weight, transfer the corn stalks on the filter to the pyrolysis furnace, raise the temperature to 110°C at a rate of 1°C/min under a high-purity nitrogen atmosphere, keep it warm for 1 hour, and then Then raise the temperature to 250°C at a rate of 2°C/min, keep it warm for 2 hours, and finally raise it to 600°C at a rate of 20°C/min, keep it at a temperature of 3 hours, and cool it with the furnace to get biochar, with a yield of 50.7wt% .

Example 18

Put the collected rape stalks into a solution containing 4% by weight of tetraethyl orthosilicate, the weight of the rape stalks is 15% of the weight of the whole system, stir and soak at room temperature for 3 hours, and filter the liquid with a filter screen to obtain orthosilicic acid-containing Rapeseed straw with 4.5wt% ethyl ester and 50% water content by weight, the rape straw on the filter screen is transferred to the pyrolysis furnace, under the high-purity argon atmosphere, the temperature rises to 160°C at a rate of 0.6°C/min, and the temperature is kept 1 hour, then raised to 270°C at a heating rate of 2.5°C/min, held for 2 hours, and finally raised to 700°C at a heating rate of 10°C/min, held for 1 hour, and then cooled with the furnace to obtain biochar, yield It is 53wt%.

Example 19

Put the collected soybean stalks into a mixed solution containing potassium permanganate and tetraethyl orthosilicate with a total weight percentage of 8%, wherein the weight ratio of potassium permanganate and tetraethyl orthosilicate is 2:7, and the weight of soybean stalks is the whole 16% of the system weight, stirring and impregnating at room temperature for 3 hours and then filtering out the liquid with a strainer to obtain a total of 4.8wt% potassium permanganate and tetraethylorthosilicate, soybean straw with a weight moisture content of 60%, and the soybean straw on the strainer Transfer to the pyrolysis furnace, in an atmosphere with argon and water vapor volume ratio of 96:4, raise the temperature to 175°C at a rate of 1.5°C/min, keep it warm for 1.5 hours, and then increase the temperature at a rate of 2.1°C/min Raise it to 250°C, keep it warm for 2 hours, and finally raise it to 600°C at a rate of 35°C/min, keep it warm for 4 hours, and cool down with the furnace to get biochar, with a yield of 56wt%.

Example 20

Put the collected wheat husks into a solution containing 6% by weight of ethyl titanate, the weight of wheat husks is 19% of the weight of the whole system, stir and impregnate at room temperature for 2 hours, and filter out the liquid with a filter to obtain ethyl titanate 2.6wt%, wheat husks with a weight moisture content of 150%, the wheat husks on the filter screen are transferred to the pyrolysis furnace, and the temperature rises at a rate of 1°C/min in an atmosphere with a volume ratio of nitrogen and water vapor of 92:8. to 168°C, hold for 2 hours, then raise the temperature to 280°C at a rate of 3°C/min, hold for 2 hours, and finally raise the rate of temperature to 800°C at a rate of 25°C/min, hold for 3 hours, and cool in the furnace. Biochar, the yield is 52wt%.

Example 21

Put the collected peanut shells into a solution containing 6.5% by weight of butyl phthalate, the weight of the peanut shells is 20% of the weight of the whole system, stir and soak at room temperature for 2.5 hours, and filter the liquid with a filter screen to obtain butyl phthalate containing 3.5wt%, peanut shells with a weight moisture content of 120%, the peanut shells on the filter screen are transferred to the pyrolysis furnace, and under a nitrogen atmosphere, the temperature rises to 170°C at a rate of 0.6°C/min, kept for 1 hour, and then Raise to 300°C at a heating rate of 2.6°C/min, hold for 3 hours, and finally raise to 850°C at a heating rate of 50°C/min, hold for 3 hours, and cool with the furnace to obtain biochar with a yield of 51wt%.

Example 22

Put the collected wood chips into a mixed solution containing 10% by weight of ethyl titanate and butyl phthalate in total, wherein the weight ratio of ethyl titanate and butyl phthalate is 3:10, and the weight of wood chips is the weight of the entire system 5% of phthalate, stirring and impregnating at room temperature for 3 hours, then filtering out the liquid with a filter screen to obtain wood chips containing 0.5wt% of ethyl titanate and butyl phthalate, and a weight moisture content of 60%. The wood chips on the filter screen are transferred to pyrolysis In the furnace, in the atmosphere with the volume ratio of argon and water vapor at 96:4, the temperature was raised to 100°C at a rate of 2°C/min, kept for 1 hour, and then raised to 250°C at a rate of 2.5°C/min , keep it warm for 2 hours, and finally raise the temperature to 600° C. at a rate of 10° C./min, keep it warm for 2 hours, and cool down with the furnace to get biochar, with a yield of 48wt%.

Example 23

Put the collected apple pomace into a mixed solution containing 4% by weight of aluminum isopropoxide and tetraethyl orthosilicate, wherein the weight ratio of aluminum isopropoxide and tetraethyl orthosilicate is 2:9, and the weight of apple pomace is the whole 5% of the system weight, stirred and soaked at room temperature for 5 hours, and filtered out the liquid with a filter screen to obtain apple pomace containing 2wt% aluminum isopropoxide and tetraethyl orthosilicate, and a weight moisture content of 75%. Transfer the apple pomace on the screen In the pyrolysis furnace, in a high-purity nitrogen atmosphere, the temperature was raised to 100°C at a rate of 1.8°C/min, and kept for 1.2 hours, and then raised to 290°C at a rate of 2.8°C/min, kept for 2.2 hours, and finally Raise the temperature to 850°C at a rate of 26°C/min, hold the temperature for 3 hours, and cool down with the furnace to obtain biochar, with a yield of 47wt%.

Example 24

Put the collected pear pomace into a mixed solution containing aluminum isopropoxide and ethyl titanate with a total weight percentage of 9.9%, wherein the weight ratio of aluminum isopropoxide and ethyl titanate is 1:11, and the weight of pear pomace is the whole 14% of the system weight, stirred and soaked at room temperature for 2.5 hours, then filtered out the liquid with a filter screen to obtain a total of 2.6wt% of aluminum isopropoxide and ethyl titanate, pear residue with a weight moisture content of 90%, and the pear residue on the filter screen Transfer to the pyrolysis furnace, under high-purity argon atmosphere, raise the temperature to 170°C at a rate of 0.9°C/min, keep it for 1.2 hours, then raise it to 300°C at a rate of 2.2°C/min, and keep it for 2 hours , and finally raised to 750° C. at a heating rate of 25° C./min, held for 3.5 hours, and cooled with the furnace to obtain biochar, with a yield of 46 wt%.

Example 25

Put the collected bagasse into a solution containing 8.5% by weight of N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, the weight of bagasse is 6% of the whole system weight, and After stirring and soaking for 3.2 hours, filter out the liquid with a strainer to obtain bagasse containing N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane 0.9wt%, and a weight moisture content of 86%. The bagasse on the filter screen was transferred to the pyrolysis furnace, and in the high-purity nitrogen atmosphere, the temperature was raised to 154°C at a rate of 1.9°C/min, kept for 1 hour, and then raised to 255°C at a rate of 0.9°C/min , keep it warm for 2 hours, and finally raise the temperature to 777° C. at a rate of 25° C./min, keep it warm for 3 hours, and cool down with the furnace to get biochar, with a yield of 47wt%.

Example 26

The olive pomace of collection is put into the mixed solution that contains zinc sulfate and sodium chloride total weight percentage 3%, wherein the weight ratio of zinc sulfate and sodium chloride is 3:4, and the weight of olive pomace is 20% of whole system weight, Stir and soak at room temperature for 3 hours and filter out the liquid with a filter screen to obtain 4.9wt% zinc sulfate and sodium chloride and olive pomace with a weight moisture content of 58%. The olive pomace on the screen is transferred to the pyrolysis furnace, and the In an atmosphere with a water vapor volume ratio of 98:2, raise the temperature to 180°C at a rate of 1°C/min, keep it for 1 hour, then raise it to 240°C at a rate of 3°C/min, keep it for 2 hours, and finally Raise the temperature to 900°C at a heating rate of 10°C/min, keep the temperature for 3 hours, and cool down with the furnace to obtain biochar with a yield of 48wt%.

Example 27

Put the collected wax gourd skin into a mixed solution containing 7% by weight of sodium chloride and phosphoric acid in total, wherein the weight ratio of sodium chloride and phosphoric acid is 11:3, and the weight of wax gourd skin is 10% of the whole system weight, and stir at room temperature After soaking for 1 hour, filter the liquid with a strainer to obtain a total of 0.8wt% of sodium chloride and phosphoric acid, and a wax gourd skin with a weight moisture content of 55%. In an atmosphere with a volume ratio of 92:8, raise the temperature to 150°C at a rate of 0.8°C/min, hold for 1.3 hours, then raise the temperature to 280°C at a rate of 2°C/min, hold for 2 hours, and finally heat at 40°C The heating rate per minute was raised to 850°C, kept at a temperature of 3 hours, and cooled with the furnace to obtain biochar, with a yield of 54wt%.

Example 28

Put the collected pumpkin skin into a mixed solution containing 9% by weight of zinc chloride and zinc sulfate, wherein the weight ratio of zinc chloride and zinc sulfate is 11:1, and the weight of the pumpkin skin is 10% of the whole system weight, After stirring and soaking at room temperature for 4 hours, filter out the liquid with a filter screen to obtain a total of 3.2wt% zinc chloride and zinc sulfate, pumpkin skin with a weight moisture content of 65%, transfer the pumpkin skin on the filter screen to a pyrolysis furnace, and In an atmosphere with a volume ratio of air and water vapor of 95:5, raise the temperature to 120°C at a rate of 1°C/min, hold for 1 hour, then raise the rate of temperature to 285°C at a rate of 2.6°C/min, and hold for 2 hours. Finally, the temperature was raised to 620° C. at a rate of 18° C./min, kept for 2.5 hours, and cooled with the furnace to obtain biochar, with a yield of 58 wt%.

Claims (6)

1. a kind of preparation method of high yield pulp1 charcoal, is characterized in that comprising the steps:

(1) biomass material is rendered in catalyst solution, stirring dipping, then filter, obtain aqueous and catalyst life Raw material of substance；Wherein, the weight moisture capacity of the described aqueous biomass material with catalyst is 50～150%, catalyst weight Content is 0.5～5%；The inventory of described biomass material is the 5 of described biomass material and described catalyst solution sum ～20wt%；

(2) described aqueous and catalyst biomass material is warming up to 0.5～2 DEG C/min under anaerobic or limit oxygen atmosphere 100～180 DEG C, then it is incubated 1～2 hour；

(3) then under anaerobic or limit oxygen atmosphere, it is warming up to 240～300 DEG C with 0.5～3 DEG C/min, be incubated 1～3 hour；

(4) and then it is warming up to 500～900 DEG C with 10～50 DEG C/min under anaerobic or limit oxygen atmosphere, be incubated 1～4 hour；

(5) obtain residual solids after cooling down and be charcoal, the yield of charcoal is more than the 40% of biomass material weight.

2. a kind of preparation method of high yield pulp1 charcoal according to claim 1 is it is characterised in that described biomass material For rice straw, wheat stalk, corn straw, cotton stalk, rape stalk, soybean stalk, wheat shell, rice husk, Pericarppium arachidis hypogaeae, bamboo Material, bamboo scraps, timber, wood flour, leaveves, weeds, coconut husk, chestnut shell, coffee groundss, tealeaf residue, pomace, treaster, pears slag, Caulis Sacchari sinensis One or more of slag, Fructus Canarii albi slag, Fructus Mangifera Indicae slag, Exocarpium Citrulli, Exocarpium Benincasae and pumpkin peel.

3. a kind of preparation method of high yield pulp1 charcoal according to claim 1 is it is characterised in that described catalyst solution It is that potassium permanganate solution, zinc acetate solution, boric acid solution, dobell's solution, liquor zinci chloridi, solution of zinc sulfate, sodium chloride are molten Liquid, phosphoric acid solution, ammonium phosphate solution, ammonium dihydrogen phosphate, ammonium dibasic phosphate solution, antimony tartrate sodium solution, isocyanates Solution, p-methyl benzenesulfonic acid sodium solution, gamma-aminopropyl-triethoxy-silane solution, γ-glycidyl ether oxygen propyl trimethoxy silicon Alkane solution, γ-(methacryloxypropyl) propyl trimethoxy silicane solution, N- β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxy Base silane solution, sodium methoxide solution, ethanol magnesium solution, aluminum isopropylate. solution, teos solution, tetraethyl titanate solution or phthalein Acid butyl ester solution, or the mixed solution being made up of according to the mixing of arbitrary volume ratio two kinds of above-mentioned solution；Described catalyst In solution, catalyst weight content is 0.5～10%.

4. a kind of high yield pulp1 charcoal according to claim 1 preparation method it is characterised in that described stirring dipping Time is 1～5 hour.

5. a kind of high yield pulp1 charcoal according to claim 1 preparation method it is characterised in that described anaerobic or limit oxygen Atmosphere refers to high pure nitrogen or argon atmosphere, or the gaseous mixture for nitrogen and vapor, argon and vapor.

6. a kind of preparation method of high yield pulp1 charcoal according to claim 5 is it is characterised in that described nitrogen is steamed with water Gas or the gaseous mixture of argon and vapor, its nitrogen or argon are 90 with the volume ratio of vapor:10～98:2.