CN111646856A - Preparation method of biomass sulfonated carbon-based compound fertilizer - Google Patents
Preparation method of biomass sulfonated carbon-based compound fertilizer Download PDFInfo
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- CN111646856A CN111646856A CN202010536249.XA CN202010536249A CN111646856A CN 111646856 A CN111646856 A CN 111646856A CN 202010536249 A CN202010536249 A CN 202010536249A CN 111646856 A CN111646856 A CN 111646856A
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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
- C05B—PHOSPHATIC FERTILISERS
- C05B17/00—Other phosphatic fertilisers, e.g. soft rock phosphates, bone meal
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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
- C05G3/70—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting wettability, e.g. drying agents
-
- 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 a biomass sulfonated carbon-based compound fertilizer, 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 potassium salt, and mixing to obtain a uniform suspension; (4) and adding ammonia into the suspension, and drying to obtain the biomass sulfonated carbon-based compound fertilizer. 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 a biomass sulfonated carbon-based compound fertilizer, 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 effect of biomass charcoal includes improving soilStructure, improved aggregate stability, improved soil water capacity, promoted microbial growth, and ultimately improved soil productivity (10%). The biomass charcoal can also quickly improve the organic carbon content of soil and reduce N while improving the crop yield2O 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 biomass charcoal and the auxiliary materials containing nitrogen, phosphorus, potassium and the like are directly mixed to prepare the carbon-based slow-release compound fertilizer, so that the compound fertilizer has certain slow release property.
Chinese patent CN108911847A discloses a preparation method of biomass charcoal-based organic compound fertilizer, wherein the biomass charcoal is crop straw biomass charcoal, the fertilizer is cake fertilizer, and the preparation method of the organic compound fertilizer actually needs fermentation and decomposition, and has complex and difficult-to-control process.
Chinese patent CN109879696A discloses a preparation method of biomass charcoal-based compound fertilizer, wherein biomass charcoal is selected as straw biomass charcoal, the biomass charcoal needs to be prepared first, the preparation process is long, and the process is relatively complex.
Disclosure of Invention
The method 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 the biomass as a raw material, reduces reaction steps, reduces energy consumption, converts the biomass into the biomass sulfonated carbon, has high conversion rate, greatly reduces the recycling energy consumption due to lower reaction temperature, has no dioxin in the discharged gas, and has great economic benefit and environmental benefit. The obtained biomass sulfonated carbon-based compound fertilizer has high water-retaining property 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 a biomass sulfonated carbon-based compound fertilizer comprises the steps of 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 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 potassium salt, and stirring and mixing uniformly;
(4) and (4) adding ammonia into the suspension obtained in the step (3), adjusting the pH of the reaction solution to 3-6, and drying to obtain the biomass sulfonated carbon-based compound fertilizer.
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 potassium salt is potassium sulfate or potassium chloride; the addition amount of the sylvite is 0.1-5 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 the biomass sulfonated carbon-based compound fertilizer.
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, phosphoric acid solution and potassium salt are directly added into the obtained biomass sulfonated carbon, and ammonia gas is added after the uniform mixing to react to prepare the biomass sulfonated carbon-based compound fertilizer, wherein the fertilizer contains nitrogen, phosphorus, potassium 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 up to 82 percent, and the specific surface area is up to 278m2G, pore diameter of 1.2-2.5nm, pore volume of 120-175mm3/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
160.2g of waste alkylated sulfuric acid (acid concentration: 89.2%, containing 6.8% of organic matter) was weighed into a round-bottomed flask (250mL), 48.06g of rice husk was added, 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. After the reaction is finished, cooling to room temperature, weighing 20% phosphoric acid with the mass of 1 time of that of the waste acid and 40g of potassium sulfate, adding the phosphoric acid and the potassium sulfate into a 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 compound fertilizer 1 is obtained after drying.
The embodiment is carried out under negative pressure, the carbonization rate of the prepared biomass sulfonated carbon is 82 percent, and the specific surface area is 260m2Per g, pore diameter of 2.1nm and pore volume of 155mm3The water-retaining agent has rich pores, can play a good role in water retention and slow release, and can be used for farmingThe product can provide nutrient elements such as nitrogen, phosphorus, potassium and the like.
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 109KPa, the carbonization rate of the sulfonated carbon of the biomass is 70 percent, and the specific surface area is 78m2G, pore diameter of 2.8nm and pore volume of 61mm3/g。
Example 2
148.7g of waste alkylated sulfuric acid (acid concentration: 89.2%, containing 6.8%) was weighed into a round-bottomed flask (250mL), 49.48g of reed straw was added, the temperature was raised from room temperature to 220 ℃ and then the flask pressure was maintained at 75kpa (absolute), and the reaction was carried out for 2 hours. After the reaction is finished, cooling to room temperature, weighing 24% phosphoric acid with the mass of 1 time of that of the waste acid and 35g of potassium sulfate, adding the phosphoric acid and the potassium sulfate into a 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 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 compound fertilizer 2 is obtained after drying.
The embodiment is carried out under negative pressure, the carbonization rate of the prepared biomass sulfonated carbon is 77 percent, and the specific surface area is 278m2Per g, pore diameter of 2.5nm 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, potassium 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 107KPa, the carbonization rate of the sulfonated carbon of the biomass is 69 percent, and the specific surface area is 82m2Per g, pore diameter of 2.9nm and pore volume of 77mm3/g。
Example 3
154.6g of waste sulfuric acid from alkylation (acid concentration: 89.2%, organic content: 6.8%) was weighed into a round-bottomed flask (250mL), 30.92g of corn stover was added, the temperature was raised from room temperature to 200 ℃ and 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 24% phosphoric acid with the mass 1 time that of sulfuric acid and 20g of potassium sulfate, adding the phosphoric acid and the potassium sulfate into a 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 compound fertilizer 3 is obtained after drying.
The embodiment is carried out under negative pressure, the carbonization rate of the prepared biomass sulfonated carbon is 71 percent, and the specific surface area is 265m2G, pore diameter of 1.2nm and pore volume of 175mm3The 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, potassium 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 110KPa, the carbonization rate of the sulfonated carbon of the biomass is 70 percent, and the specific surface area is 83m2G, pore diameter of 2.6nm and pore volume of 68mm3/g。
Example 4
158.2g 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. After the reaction is finished, cooling to room temperature, weighing 24% phosphoric acid with the mass of 1 time of that of the waste acid and 75g of potassium chloride, adding the phosphoric acid and the potassium chloride into a 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 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 compound fertilizer 4 is obtained after drying.
The embodiment is carried out under negative pressure, the carbonization rate of the prepared biomass sulfonated carbon is 77 percent, and the specific surface area is 272m2Per g, pore diameter of 2.2nm 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, potassium 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 104KPa, the carbonization rate of the sulfonated carbon of the biomass is 70 percent, and the specific surface area is 79m2Per g, pore diameter2.7nm, pore volume 76mm3/g。
Example 5
152.7g of waste alkylated sulfuric acid (acid concentration: 89.2%, organic content: 6.8%) was weighed into a round-bottomed flask (250mL), and 45.81g of wheat straw was added, and the temperature was raised from room temperature to 180 ℃ and then the flask pressure was maintained at 55kpa (absolute), and reacted for 2 hours. After the reaction is finished, cooling to room temperature, weighing 24% phosphoric acid with the mass of 1 time of that of the waste acid and 30g of potassium sulfate, adding the phosphoric acid and the potassium sulfate into a 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 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 compound fertilizer 5 is obtained after drying.
The embodiment is carried out under negative pressure, the carbonization rate of the prepared biomass sulfonated carbon is 74 percent, and the specific surface area is 268m2Per g, pore diameter of 2.0nm and pore volume of 156mm3The 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, potassium 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 108KPa, the carbonization rate of the sulfonated carbon of the biomass is 68 percent, and the specific surface area is 90m2Per g, pore diameter of 2.9nm and pore volume of 81mm3/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.
Detecting the content of total nitrogen in the C, GB/T8572-2010 compound fertilizer in the biomass sulfonated carbon-based compound fertilizer by using elemental analysis (a titration method after distillation); measuring the content of available phosphorus in the GB/T8573-2010 compound fertilizer; the potassium content in the GB/T8574-2010 compound fertilizer is determined (potassium tetraphenylborate gravimetric method), and the results are shown in the following table:
| sample (I) | C | P2O5 | N | K2O |
| 1 | 12.20 | 11.23 | 10.36 | 10.46 |
| 2 | 14.38 | 12.33 | 10.29 | 9.03 |
| 3 | 11.22 | 15.20 | 12.69 | 6.12 |
| 4 | 5.96 | 12.34 | 10.30 | 18.20 |
| 5 | 13.44 | 13.47 | 11.24 | 8.23 |
The applicant states that the invention is illustrated by the above examples to describe the preparation method of the biomass sulfonated carbon based compound fertilizer, but the invention is not limited to the above process steps, i.e. the invention is not meant to be dependent on the above process steps to be implemented. It will be apparent to those skilled in the art that any modifications to the invention, equivalent substitutions of selected materials for the invention and selection of specific modes of addition of adjunct ingredients, etc. may be made, for example: urea, ammonium sulfate, ammonium chloride, monoammonium phosphate, diammonium phosphate and other medium trace elements and the like are all within the protection scope and the disclosure of the invention.
Claims (8)
1. A preparation method of a biomass sulfonated carbon-based compound fertilizer 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 potassium salt, and stirring and mixing uniformly;
(4) and (4) adding ammonia into the suspension obtained in the step (3), adjusting the pH of the reaction solution to 3-6, and drying to obtain the biomass sulfonated carbon-based compound fertilizer.
2. The preparation method of the biomass sulfonated carbon-based compound fertilizer according to claim 1, which is 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 the biomass sulfonated carbon-based compound fertilizer according to claim 1, which is 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 the biomass sulfonated carbon-based compound fertilizer according to claim 1, which is characterized by comprising the following steps: and (3) the reaction pressure in the step (2) is 0-99 KPa.
5. The preparation method of the biomass sulfonated carbon-based compound fertilizer according to claim 1, which is 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 the biomass sulfonated carbon-based compound fertilizer according to claim 1, which is 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 the biomass sulfonated carbon-based compound fertilizer according to claim 1, which is characterized by comprising the following steps: the potassium salt is potassium sulfate or potassium chloride; the addition amount of the sylvite is 0.1-5 times of the weight of the waste sulfuric acid.
8. The preparation method of the biomass sulfonated carbon-based compound fertilizer according to claim 1, which is 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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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112897503A (en) * | 2021-01-25 | 2021-06-04 | 上海应用技术大学 | Acid modification preparation method of biomass charcoal material with toluene adsorption effect |
| CN113617332A (en) * | 2021-08-27 | 2021-11-09 | 郑子渝洋 | Sulfonated biochar for treating heavy metal waste liquid |
| CN117158281A (en) * | 2023-08-26 | 2023-12-05 | 湖北农康生物科技有限公司 | Vegetable seedling substrate based on pig manure ferment and production method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160023959A1 (en) * | 2011-06-06 | 2016-01-28 | Cool Planet Energy Systems, Inc. | Biochars and biochar treatment processes |
| CN105858622A (en) * | 2016-05-19 | 2016-08-17 | 广西南宁东和新赢环保技术有限公司 | Alkylation waste sulfuric acid resource recycling method |
| 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 |
| CN108164330A (en) * | 2018-01-02 | 2018-06-15 | 北京三聚绿能科技有限公司 | A kind of biomass carbon base and preparation method thereof |
| CN108946697A (en) * | 2018-08-02 | 2018-12-07 | 中国科学院过程工程研究所 | A kind of processing method using waste sulfuric acid from alkylation production biomass carbon |
-
2020
- 2020-06-12 CN CN202010536249.XA patent/CN111646856A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160023959A1 (en) * | 2011-06-06 | 2016-01-28 | Cool Planet Energy Systems, Inc. | Biochars and biochar treatment processes |
| CN105858622A (en) * | 2016-05-19 | 2016-08-17 | 广西南宁东和新赢环保技术有限公司 | Alkylation waste sulfuric acid resource recycling method |
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