CN111533584A - Preparation method of biomass sulfonated carbon based diammonium phosphate - Google Patents
Preparation method of biomass sulfonated carbon based diammonium phosphate Download PDFInfo
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- CN111533584A CN111533584A CN202010536256.XA CN202010536256A CN111533584A CN 111533584 A CN111533584 A CN 111533584A CN 202010536256 A CN202010536256 A CN 202010536256A CN 111533584 A CN111533584 A CN 111533584A
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D9/00—Other inorganic fertilisers
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B7/00—Fertilisers based essentially on alkali or ammonium orthophosphates
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/40—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting fertiliser dosage or release rate; for affecting solubility
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/80—Soil conditioners
Abstract
The invention discloses a preparation method of biomass sulfonated carbon-based diammonium phosphate, belonging to the field of fertilizer preparation. The method comprises the following steps: (1) drying and crushing biomass; (2) mixing the waste sulfuric acid, heating and reacting, and keeping negative pressure to obtain the biomass sulfonated carbon material adsorbed with sulfuric acid; (3) cooling the carbon material generated in the step (2) to room temperature, adding a phosphoric acid solution, and mixing to obtain a uniform suspension; (4) and (4) adding ammonia into the suspension obtained in the step (3), and drying to obtain the biomass sulfonated carbon-based diammonium phosphate. The method has the advantages of short route, simple operation, low energy consumption and wide application range, takes the biomass as the raw material, realizes the resource recycling of organic matters and acid in the biomass and the high-concentration organic waste sulfuric acid, reduces reaction steps and energy consumption, converts the biomass into the biomass sulfonated carbon, has high conversion rate, greatly reduces the recycling energy consumption at lower reaction temperature, has no dioxin in the discharged gas, and has great economic benefit and environmental benefit.
Description
Technical Field
The invention relates to a preparation method of biomass sulfonated carbon based diammonium phosphate, belonging to the field of fertilizer preparation.
Background
Biomass char (biocar), also known as Biochar, biomass char, and the like. As a soil amendment, biochar forms a tough carbon negative soil carbon complex and stores atmospheric carbon dioxide into a highly resistant soil carbon reservoir. After the biochar is applied to soil, the nutrition durability of the biochar is enhanced, the requirement of crops on fertilizers is reduced, and certain influence is exerted on climate and environment.
The raw material sources of the biochar are very wide, and a plurality of agricultural and forestry byproducts such as date pits, walnut shells, waste tea leaves, corn cobs, coconut shells, beet roots, peanut shells, rice husks, cotton shells, banana skins, bamboo wastes, olive pits, cherry pits, orange peels, coffee bean pods, corn stalks, cassava skins and the like are reported in the literature to be tried to prepare the biochar with low cost. Since the carbon atoms are bound with each other with a very strong affinity, the biochar has very high chemical and biological stability and very low solubility. The basic properties of the biochar enable the biochar to have adsorption performance, catalytic performance and biological decomposition resistance, and the biochar can be widely applied to the fields of agriculture, energy, environment and the like.
The effects of biomass char include improving soil structure, increasing aggregate stability, increasing soil water capacity, promoting microbial growth, and ultimately increasing soil productivity (10%). The biomass charcoal can also quickly improve the organic carbon content of soil while improving the crop yield,reduction of N2O discharge amount and bioavailability of heavy metal in polluted soil. Soil improvement and upgrading effects, particularly carbon sequestration and emission reduction, remain the current outstanding needs. The carbonization of the wastes not only treats the wastes such as straws and the like, avoids the discharge of direct incineration or landfill decomposition, increases the organic carbon reservoir of the soil, but also greatly improves the physical properties of the soil, promotes the biological growth and activity, improves the fertility and reduces the environmental pollution risk, thus being an important way for the sustainable management of the soil. Agricultural wastes such as straws and the like are not effectively utilized, and a large amount of direct incineration aggravates atmospheric pollution. Under the framework of the national green development strategy, the sustainable management of soil and the recycling of wastes become the complementary path of sustainable agricultural development.
The most common method for preparing biochar is thermal cracking, i.e. the organic material is thermally decomposed in an oxygen-free or limited oxygen supply environment to form a solid substance, the main components of which are carbon, hydrogen, oxygen, nitrogen and the like, and a small amount of trace elements are also contained, and the carbon content is generally more than 60%. During carbonization, non-carbon elements are decomposed and escape to form a pore structure, so that the carbon material has certain porosity and specific surface area. The biochar surface has abundant functional groups, and contains various groups such as carboxyl, phenolic hydroxyl, acid anhydride and the like. The adaptability of the pyrolysis method for processing the biomass is relatively good, the pyrolysis method has certain advantages in the aspect of processing performance indexes, the decrement ratio reaches over 95 percent, auxiliary fuel is not needed in operation, energy can be recycled, and waste is not needed to be classified and pretreated. But the incineration waste gas treatment device is seriously acidified, dioxin cannot be stably discharged up to the standard, and the overhaul cost is high. And the control of dioxin is the most difficult problem of biomass incineration. Because the dioxin generation mechanism is quite complex, according to domestic literature, the known generation route is summarized in 2 aspects: 1) the precursors react heterogeneously to form dioxins. Namely, organic compounds such as polychlorinated benzene, chlorophenols, PVC and the like react to generate dioxin at 450-700 ℃ in a metal catalyst (copper chloride, ferric chloride and the like); 2) and (3) re-synthesizing to react to form dioxin, namely, oxidizing, chlorinating and polymerizing granular organic carbon (such as propylene, methylbenzene and chlorobenzene) and macromolecular carbon structures (such as coke, fly ash and residual carbon) in the fly ash at 250-850 ℃ through different catalysts to form the dioxin. Therefore, the optimal synthesis temperature of dioxin is 250-400 ℃.
The sulfuric acid carbonization method is a process of dehydrating and carbonizing a carbon-containing biomass raw material at a lower temperature by utilizing the dehydration property and strong acidity of concentrated sulfuric acid to obtain a biomass charcoal material. Chinese patents CN103157509A and CN103157512A disclose that concentrated sulfuric acid and bagasse (or rice hull) are mixed and partially carbonized to prepare solid sulfonic acid catalyst, and chinese patents CN1915507A and CN1951563A disclose methods for preparing solid sulfonic acid catalyst from plant raw materials or carbohydrates, but concentrated sulfuric acid is adopted in the reaction, the biomass is not completely carbonized, and the acid solution contains a large amount of small molecular organic matters. The study on the catalytic carbonization of sludge and cotton by sulfuric acid has been made, but the carbonization degree is low, the twice carbonization is needed, the generated carbonized substance has small granularity, is easy to dissolve in the sulfuric acid and difficult to separate, and the organic matter content in the acid after filtration is high, so that the comprehensive utilization cannot be realized. Chinese patent CN108946697A discloses a treatment method for producing biomass charcoal by using alkylated waste sulfuric acid, which comprises the steps of taking biomass as a raw material, adding the biomass into alkylated waste acid, heating to ensure that acid-soluble oil in the biomass and the waste sulfuric acid is polymerized and carbonized under the action of sulfuric acid to obtain the biomass charcoal, wherein the acid-soluble oil is used for polymerizing and carbonizing micromolecule organic matters decomposed by the biomass, so that the content of the organic matters in an acid solution is reduced, but the technology needs heating to separate the biomass charcoal from reaction produced gas and sulfuric acid, and the energy consumption is high.
The biomass charcoal has the properties of more pores, large specific surface area, charge on the surface of particles and the like, has the characteristic of adsorbing and holding fertilizer nutrients, and is mostly processed from cheap raw materials such as farmland wastes and the like. Therefore, the slow-release carrier can be used as a slow-release carrier of the fertilizer, not only can the utilization rate of the nutrients of the quick-acting fertilizer be effectively improved, but also the raw material cost and the environmental cost can be reduced compared with the traditional slow/controlled release fertilizer. Therefore, the biomass charcoal fertilizer has an important application prospect. The preparation method comprises the following steps of directly mixing biomass charcoal and auxiliary materials containing diammonium phosphate to prepare the charcoal-based slow-release fertilizer rod, so that diammonium phosphate has certain slow release property, and the patent CN108046934 discloses charcoal-based diammonium phosphate and a preparation process thereof, wherein the preparation process comprises the steps of mixing the biomass charcoal and concentrated phosphoric acid, enabling the concentrated phosphoric acid to permeate into pores of the biomass charcoal, and forming primary slurry with the biomass charcoal and the concentrated phosphoric acid uniformly mixed; mixing the primary slurry with liquid ammonia, wherein the liquid ammonia can perform a neutralization reaction with concentrated phosphoric acid in pores of the biomass charcoal, so that the content of diammonium phosphate in the biomass charcoal is increased, and the remaining liquid ammonia can be uniformly mixed with the primary slurry and performs a neutralization reaction with the concentrated phosphoric acid therein to prepare secondary slurry; finally, the secondary slurry can ensure that the biomass charcoal is distributed more uniformly in the processes of granulation, drying, screening and cooling to prepare the carbon-based diammonium phosphate, and the carbon-based diammonium phosphate has high fertilizer utilization rate and slow release effect by the specific method. However, in the biomass charcoal fertilizer, the biomass charcoal is usually used as a slow release material, the biomass charcoal needs to be prepared first, the preparation process is long, and the process is complex.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention aims to solve the technical problems of providing a preparation method of biomass sulfonated carbon based diammonium phosphate, which has the advantages of short route, simple operation, low energy consumption and wide application range, realizes resource recycling of organic matters and acid in biomass and high-concentration organic waste sulfuric acid by taking biomass as a raw material, reduces reaction steps, reduces energy consumption, converts the biomass into biomass sulfonated carbon, has high conversion rate, greatly reduces recycling energy consumption due to lower reaction temperature, has no dioxin in exhaust gas, and has great economic benefit and environmental benefit. The obtained biomass sulfonated carbon based diammonium phosphate has high water retention and good fertilizer slow release performance, and realizes low-cost carbonization treatment of biomass.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a preparation method of biomass sulfonated carbon based diammonium phosphate comprises the steps of adding biomass into waste sulfuric acid, heating to 100-300 ℃ to polymerize and carbonize acid-soluble oil in the biomass and the waste sulfuric acid under the action of sulfuric acid to obtain biomass carbon, and comprises the following steps:
(1) drying and crushing biomass into biomass powder;
(2) mixing the waste sulfuric acid, heating to 100-300 ℃ for reaction, and keeping the reaction at negative pressure to obtain a biomass sulfonated carbon material adsorbed with sulfuric acid;
(3) cooling the carbon material generated in the step (2) to room temperature, adding a phosphoric acid solution, and stirring and mixing uniformly;
(4) and (4) adding ammonia into the mixed solution of phosphoric acid, sulfuric acid and biomass charcoal obtained in the step (3), adjusting the pH of the reaction solution to 3-6, and drying to obtain the biomass sulfonated charcoal based diammonium phosphate.
The weight ratio of the waste sulfuric acid to the biomass in the step (2) is 10: 0.1 to 0.8.
The heating reaction in the step (2) is carried out at the temperature of 80-250 ℃ for 0.5-4 hours.
And (3) the reaction pressure in the step (2) is 0-99 KPa.
In the step (2), the waste sulfuric acid is organic waste sulfuric acid with the acid concentration of more than 65% and the organic matter content of more than 2%.
In the step (3), the concentration of the phosphoric acid is 10-50%; the adding amount of the phosphoric acid solution is 1-10 times of the weight of the waste sulfuric acid.
The drying temperature in the step (4) is 60-200 ℃; the drying pressure is-0.1 MPa; the drying time is 0.5-4 hours.
And (4) drying to obtain ammonium phosphate, sulfate and biomass sulfonated carbon-based diammonium phosphate.
According to the invention, biomass is used as a raw material, the biomass and high-concentration organic waste sulfuric acid are mixed and heated, organic matters in the waste sulfuric acid and biomass hydrolysate react and are carbonized into biomass sulfonated carbon, generated gas is discharged in time in the reaction process, a phosphoric acid solution is directly added into the obtained biomass sulfonated carbon, ammonia gas is added after uniform mixing to react to prepare the biomass sulfonated carbon based diammonium phosphate, and the fertilizer contains nitrogen, phosphorus and biomass carbon. The treatment method has the advantages of few reaction steps, low energy consumption, realization of carbonization treatment of biomass with low cost, wide application range and accordance with green chemical requirements.
The invention has the beneficial effects that:
in the invention, the biomass is mixed with high-concentration organic waste sulfuric acid and then heated, the biomass and acid-soluble oil in the waste sulfuric acid are subjected to hydrolysis, polymerization, carbonization, sulfonation and other reactions to generate biomass sulfonated carbon, the reaction process keeps negative pressure, so that gas generated in the reaction process is discharged in time, and compared with the original method of removing the reaction gas by heating and drying, the obtained biomass sulfonated carbon has more and richer pore passages and functional groups and has good water retention and slow release performance. The biomass sulfonated carbon obtained by carbonizing the biomass with sulfuric acid has the advantages of rich raw material sources, low price, large specific surface area, developed pore structure, good thermal stability and chemical stability and the like, can be widely applied to a plurality of fields of agriculture, environmental remediation, chemical industry, energy storage and the like, and has wide application prospect as a biomass carbon fertilizer and a soil conditioner.
The reaction process of the invention keeps negative pressure, the carbonization rate of the prepared biomass sulfonated carbon is as high as 81 percent, and the specific surface area is as high as 280m2(ii)/g, pore diameter of 1.3-2.6nm, pore volume of 120-185mm3/g。
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
102.5g of waste alkylated sulfuric acid (acid concentration: 89.2%, organic content: 6.8%) was weighed into a round-bottomed flask (250mL), and rice husk was added thereto in an amount of 20% by mass of the waste acid, and the temperature was raised from room temperature to 160 ℃ and then the flask pressure was maintained at 98kpa (absolute), and the reaction was carried out for 3.5 hours. And cooling to room temperature after the reaction is finished, weighing 30% phosphoric acid with the mass 5 times that of the waste acid, adding the phosphoric acid into the round-bottom flask, and stirring for 30min to obtain a mixed solution of the biomass charcoal, the phosphoric acid and the sulfuric acid. And then ammonia gas is introduced to adjust the pH value of the solution to 4.5, the solution is heated to 120 ℃, the drying pressure is 20Kpa, the drying time is 3 hours, and the biomass sulfonated carbon-based diammonium phosphate 1 is obtained after drying.
The embodiment is carried out under negative pressure, the carbonization rate of the prepared biomass sulfonated carbon is 81 percent, and the specific surface area is 260m2Per g, pore diameter of 2.0nm and pore volume of 125mm3G, has rich pore passages, and can play a good role in water retentionAnd has slow release effect, and can provide nutrient elements such as nitrogen, phosphorus and the like for crops.
Comparative example 1
The difference from the example 1 is only that the reaction pressure of the biomass powder and the waste sulfuric acid is 110KPa, the carbonization rate of the sulfonated carbon of the biomass is 71 percent, and the specific surface area is 95m2Per g, pore diameter of 2.8nm and pore volume of 76mm3/g。
Example 2
103.4g of alkylated waste sulfuric acid (acid concentration is 89.2%, and organic matter content is 6.8%) is weighed into a round-bottom flask (250mL), reed straws with the mass percent of the waste acid being 40% are added, the temperature is raised to 220 ℃ from room temperature, then the flask pressure is maintained at 75kpa (absolute pressure), and the reaction is carried out for 2 hours. And cooling to room temperature after the reaction is finished, weighing 24% phosphoric acid with the mass 4 times that of the waste acid, adding the phosphoric acid into the round-bottom flask, and stirring for 30min to obtain a mixed solution of the biomass charcoal, the phosphoric acid and the sulfuric acid. And then ammonia gas is introduced to adjust the pH value of the solution to 4.5, the solution is heated to 100 ℃, the drying pressure is 10Kpa, the drying time is 2 hours, and the biomass sulfonated carbon-based diammonium phosphate 2 is obtained after drying.
The embodiment is carried out under negative pressure, the carbonization rate of the prepared biomass sulfonated carbon is 78 percent, and the specific surface area is 280m2G, pore diameter of 1.9nm and pore volume of 165mm3The water-retaining agent has rich pores, can play a good role in water retention and slow release, and can provide nutrient elements such as nitrogen, phosphorus and the like for crops.
Comparative example 2
The difference from the example 2 is only that the reaction pressure of the biomass powder and the waste sulfuric acid is 105KPa, the carbonization rate of the sulfonated carbon of the biomass is 70 percent, and the specific surface area is 86m2Per g, pore diameter of 2.9nm and pore volume of 65mm3/g。
Example 3
102.9g of waste alkylated sulfuric acid (acid concentration: 89.2%, organic content: 6.8%) was weighed into a round-bottomed flask (250mL), and corn stover was added in an amount of 1 time the mass of the waste acid, and the temperature was raised from room temperature to 200 ℃ and then the flask pressure was maintained at 80kpa (absolute), and the reaction was carried out for 2.5 hours. After the reaction is finished, cooling to room temperature, weighing 30% phosphoric acid with 6 times of the mass of sulfuric acid, adding the phosphoric acid into the round-bottom flask, and stirring for 30min to obtain a mixed solution of the biomass charcoal, the phosphoric acid and the sulfuric acid. And then ammonia gas is introduced to adjust the pH value of the solution to 5.5, the solution is heated to 140 ℃, the drying pressure is 30Kpa, the drying time is 1 hour, and the biomass sulfonated carbon-based diammonium phosphate 3 is obtained after drying.
The embodiment is carried out under negative pressure, the carbonization rate of the prepared biomass sulfonated carbon is 79 percent, and the specific surface area is 255m2Per g, pore diameter of 2.4nm and pore volume of 120mm3The water-retaining agent has rich pores, can play a good role in water retention and slow release, and can provide nutrient elements such as nitrogen, phosphorus and the like for crops.
Comparative example 3
The difference from the example 3 is only that the reaction pressure of the biomass powder and the waste sulfuric acid is 111KPa, the carbonization rate of the sulfonated carbon of the biomass is 70 percent, and the specific surface area is 81m2G, pore diameter of 2.7nm and pore volume of 72mm3/g。
Example 4
101.5g of waste alkylated sulfuric acid (acid concentration: 89.2%, organic content: 6.8%) was weighed into a round-bottomed flask (250mL), 10% by mass of corn stover was added to the waste alkylated sulfuric acid, the temperature was raised from room temperature to 240 ℃ and the flask pressure was maintained at 95kpa (absolute), followed by reaction for 2 hours. And cooling to room temperature after the reaction is finished, weighing 30% phosphoric acid with the mass 5 times that of the waste acid, adding the phosphoric acid into the round-bottom flask, and stirring for 30min to obtain a mixed solution of the biomass charcoal, the phosphoric acid and the sulfuric acid. And then ammonia gas is introduced to adjust the pH value of the solution to 5.5, the solution is heated to 130 ℃, the drying pressure is 80Kpa, the drying time is 2 hours, and the biomass sulfonated carbon-based diammonium phosphate 4 is obtained after drying.
The embodiment is carried out under negative pressure, the carbonization rate of the prepared biomass sulfonated carbon is 72 percent, and the specific surface area is 265m2Per g, pore diameter of 2.6nm and pore volume of 185mm3The water-retaining agent has rich pores, can play a good role in water retention and slow release, and can provide nutrient elements such as nitrogen, phosphorus and the like for crops.
Comparative example 4
The difference from the example 4 is only that the reaction pressure of the biomass powder and the waste sulfuric acid is 106KPa, the carbonization rate of the sulfonated carbon of the biomass is 69 percent, and the specific surface area is 79m2Per g, pore diameter of2.8nm, pore volume 71mm3/g。
Example 5
103.8g of waste alkylated sulfuric acid (acid concentration: 89.2%, organic content: 6.8%) was weighed into a round-bottomed flask (250mL), wheat straw was added in an amount of 50% by mass of the waste acid, the temperature was raised from room temperature to 180 ℃ and then the flask pressure was maintained at 55kpa (absolute), and the reaction was carried out for 2 hours. And cooling to room temperature after the reaction is finished, weighing 30% phosphoric acid with the mass 6 times that of the waste acid, adding the phosphoric acid into the round-bottom flask, and stirring for 30min to obtain a mixed solution of the biomass charcoal, the phosphoric acid and the sulfuric acid. And then ammonia gas is introduced to adjust the pH value of the solution to 6.5, the solution is heated to 130 ℃, the drying pressure is 80Kpa, the drying time is 2 hours, and the biomass sulfonated carbon-based diammonium phosphate 5 is obtained after drying.
The embodiment is carried out under negative pressure, the carbonization rate of the prepared biomass sulfonated carbon is 75 percent, and the specific surface area is 261m2G, pore diameter of 1.3nm and pore volume of 155mm3The water-retaining agent has rich pores, can play a good role in water retention and slow release, and can provide nutrient elements such as nitrogen, phosphorus and the like for crops.
Comparative example 5
The difference from the example 5 is only that the reaction pressure of the biomass powder and the waste sulfuric acid is 109KPa, the carbonization rate of the biomass sulfonated carbon is 70 percent, and the specific surface area is 90m2Per g, pore diameter of 2.9nm and pore volume of 66mm3/g。
According to the results of the above examples and comparative examples, the reaction of the biomass powder and the waste sulfuric acid is performed under negative pressure, so that gas generated in the reaction process is discharged in time, and the obtained biomass sulfonated carbon has more and richer pore passages and functional groups, and has good water retention and slow release properties.
The method for detecting CHS in biomass sulfonated carbon-based diammonium phosphate by using elemental analysis comprises the following steps of (1) detecting CHS in biomass sulfonated carbon-based diammonium phosphate according to a method for measuring total nitrogen content in GB/T10209.1 monoammonium phosphate and diammonium phosphate (titration method after distillation) and a method for measuring phosphorus content in GB/T10209.2 monoammonium phosphate and diammonium phosphate, wherein the results are as follows:
the applicant states that the invention is illustrated by the above examples to describe a method for preparing diammonium phosphate from biomass charcoal, but the invention is not limited to the above process steps, i.e. the invention does not depend on the above process steps to be implemented. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (7)
1. A preparation method of biomass sulfonated carbon based diammonium phosphate is characterized by comprising the following steps: adding biomass into waste sulfuric acid, heating to 100-300 ℃ to enable acid-soluble oil in the biomass and the waste sulfuric acid to be polymerized and carbonized under the action of sulfuric acid to obtain biomass charcoal, and the method comprises the following steps:
(1) drying and crushing biomass into biomass powder;
(2) mixing the waste sulfuric acid, heating to 100-300 ℃ for reaction, and keeping the reaction at negative pressure to obtain a biomass sulfonated carbon material adsorbed with sulfuric acid;
(3) cooling the carbon material generated in the step (2) to room temperature, adding a phosphoric acid solution, and stirring and mixing uniformly;
(4) and (4) adding ammonia into the mixed solution of phosphoric acid, sulfuric acid and biomass charcoal obtained in the step (3), adjusting the pH of the reaction solution to 3-6, and drying to obtain the biomass sulfonated charcoal based diammonium phosphate.
2. The preparation method of biomass sulfonated carbon-based diammonium phosphate according to claim 1, characterized by comprising the following steps: the weight ratio of the waste sulfuric acid to the biomass in the step (2) is 10: 0.1 to 0.8.
3. The preparation method of biomass sulfonated carbon-based diammonium phosphate according to claim 1, characterized by comprising the following steps: the heating reaction in the step (2) is carried out at the temperature of 80-250 ℃ for 0.5-4 hours.
4. The preparation method of biomass sulfonated carbon-based diammonium phosphate according to claim 1, characterized by comprising the following steps: and (3) the reaction pressure in the step (2) is 0-99 KPa.
5. The preparation method of biomass sulfonated carbon-based diammonium phosphate according to claim 1, characterized by comprising the following steps: in the step (2), the waste sulfuric acid is organic waste sulfuric acid with the acid concentration of more than 65% and the organic matter content of more than 2%.
6. The preparation method of biomass sulfonated carbon-based diammonium phosphate according to claim 1, characterized by comprising the following steps: in the step (3), the concentration of the phosphoric acid is 10-50%; the adding amount of the phosphoric acid solution is 1-10 times of the weight of the waste sulfuric acid.
7. The preparation method of biomass sulfonated carbon-based diammonium phosphate according to claim 1, characterized by comprising the following steps: the drying temperature in the step (4) is 60-200 ℃; the drying pressure is-0.1 MPa; the drying time is 0.5-4 hours.
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| CN109320374A (en) * | 2018-10-26 | 2019-02-12 | 昆明理工大学 | A kind of production method of charcoal base slow-release compound fertilizer |
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- 2020-06-12 CN CN202010536256.XA patent/CN111533584A/en active Pending
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| CN108046934A (en) * | 2018-01-22 | 2018-05-18 | 北京三聚绿能科技有限公司 | A kind of charcoal base Diammonium phosphate (DAP) and its preparation process |
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