A high solid content plant-derived fulvic acid product based on salicylic acid and its production process

Abstract

The invention discloses a plant-based fulvic acid product with high solid content and a production process, and belongs to the fields of biochemical engineering, fermentation engineering, biorefining and synthetic biology industry. The plant-based fulvic acid product with high solid content of the invention has a stock solution pH of 5-6 and a solid content of not less than 60%. Its production process includes: the core agent SYS is mixed with sulfite as a cooking liquid; after the plant-based raw material is mixed with the cooking liquid, it is boiled, extracted, separated and concentrated to obtain a fulvic acid concentrated black liquid with high solid content; the core agent SYS includes salicylic acid and magnesium sulfate; the amount of salicylic acid added is 0.1%-10%, and the amount of magnesium sulfate added is 0.2%-10%. The solid content of fulvic acid of similar products currently available on the market is generally 40%-60%. The plant-based fulvic acid product provided by the invention can increase the solid content to more than 75%, with an increase of more than 60%, while improving the fertilizer efficiency.

Description

Technical Field

[0001] The invention belongs to the fields of biochemical engineering, comprehensive utilization of straw resources, separation of three elements, synthetic biology and fermentation engineering and biomass energy, and also belongs to the field of saline-alkali land soil improvement. The invention relates to a plant-derived fulvic acid product and also to a preparation method of the plant-derived fulvic acid product. Background Art

[0002] Fulvic acid is considered to be a plant growth activator. It is one of the humic acids with a smaller molecular weight. It is the core component of water-soluble humic acid and accounts for the vast majority of water-soluble humic acid. The main components include C, H, O, N, and S, of which the content of small molecular active organic carbon exceeds 50%. Humic acid-based organic materials include water-soluble humic acid materials and water-insoluble humic acid materials. Water-soluble humic acid materials include water-soluble straw-derived sulfonated fulvic acid, water-soluble straw-derived biochemical fulvic acid and water-soluble mineral-derived fulvic acid: Straw-derived sulfonated fulvic acid is a water-soluble low molecular weight humic acid obtained by sulfonation treatment of agricultural, forestry and fruit waste including straw; Straw-derived biochemical fulvic acid is a water-soluble fulvic acid obtained by composting and fermenting straw with biological bacteria; Mineral-derived fulvic acid refers to a water-soluble low molecular weight humic acid extracted by physical, chemical and biological methods using peat soil, lignite and weathered coal as raw materials, with an average molecular weight of 50-1000.

[0003] At present, there are four main methods for preparing fulvic acid. The extraction method includes acid extraction, alkali extraction, acid-organic solvent extraction, and ion exchange resin method. The main method for obtaining fulvic acid from weathered coal, lignite, peat, etc. is extraction. The typical product on the market is mineral potassium humate. The main problem is that the pH is too high, generally pH 9-11. The fermentation method is mainly based on some industrial and agricultural waste materials, sawdust, etc., and appropriate amounts of nutrients such as nitrogen, phosphorus, and potassium are added. First, the fermentation material rich in fulvic acid is obtained by biological fermentation technology, and then the product rich in fulvic acid is extracted from the fermentation material by leaching. The typical product on the market is bagasse molasses and yeast molasses fulvic acid. The main problem is the high salt content. The salt content of some products is detected to be 60%. Electrodialysis is a deep purification method, which is generally used for further processing and purification of fulvic acid primary products. The limitation is that the production and application scale is small. The extraction method uses ammonium sulfite as an auxiliary agent to obtain straw-derived fulvic acid and cellulose pulp through cooking and extraction. The common limitation of the above methods is the low solid content, generally 40%-60%.

[0004] The patent with the announcement number CN208308727U discloses a humic acid potassium phosphite ammonium phosphate solid compound fertilizer preparation system, which can generate humic acid potassium phosphite ammonium phosphate solid compound fertilizer by granulating, mixing potassium phosphite solution, ammonium phosphate solution and humic acid potassium solution. The patent application with the publication number CN 114044717 A includes the following steps: 1) crushing and dissolving inorganic raw materials: crushing the proportioned solid raw materials including urea, ammonium phosphate, potassium tripolyphosphate, diammonium phosphate, and boric acid through a raw material crushing device, placing them in a reactor, and adding proportioned soft water for dissolution; 2) dissolving auxiliary materials: adding fish protein powder, seaweed essence, potassium humate, NAM inhibitor, and phosphorus activator into the reactor for dissolution; 3) mixing and stirring; 4) subcontracting; 5) packaging to obtain a liquid fertilizer for cotton. The invention of publication number CN105503475A discloses a microcapsule-encapsulated amino acid liquid mineral fertilizer, which uses sodium hydroxide aqueous solution as a raw material and is obtained by producing liquid fertilizer and solid fertilizer and microencapsulating them to obtain a finished product.

[0005] The fulvic acid prepared by the above method has a wide range of uses in agriculture, animal husbandry and other fields due to its good nutritional value, natural environmental performance and low cost. For example, fulvic acid straw plant fiber can be made into degradable mulch film (CN112239960 A), glue-free and formaldehyde-free fiberboard (CN 112025906 A), cotton straw molded lunch boxes (CN 112127194 A), non-wood fiber pulping and papermaking (CN 108179650 A), and high-strength corrugated paper pulp (CN 111996827 A).

[0006] The advantages of fulvic acid produced by co-production of cellulose from plants are that the raw materials are widely available, fully utilized, and circularly economical. Fulvic acid is rich in vitamins and amino acids, and has a pH of 5-6. It is particularly suitable for saline-alkali soil improvement and saline-alkali fertilizer, saving fertilizer and increasing efficiency, and increasing yield. The co-produced cellulose can be used as paper products, and can also be used as raw materials for the downstream synthetic biology industry to replace oil and food.

[0007] The technical difficulty of plant-derived fulvic acid products is also to increase the solid base content of fulvic acid. Research by the Dalian Institute of Chemical Physics of the Chinese Academy of Sciences found that an important reason for the insufficient utilization of wood cellulose is that lignin is prone to disordered condensation during the reaction process, that is, uncontrollably forming carbon-carbon cross-links between and within molecules. Therefore, how to increase the solid base content of plant-derived fulvic acid products and increase their application value is an important topic in this field. Summary of the invention

[0008] The technical problem to be solved by the present invention is to increase the solid base content of fulvic acid and break through the upper limit of the solid base content of currently commonly used mineral-based fulvic acid and plant-based fulvic acid products, so as to expand application scenarios, improve application efficiency and reduce production costs.

[0009] The key problems commonly encountered in the production process and application of fulvic acid are how to improve the biological activity of fulvic acid, reduce the molecular weight of fulvic acid aggregates, and increase the solid base content of fulvic acid.

[0010] The increase in the solid content of humic acid is due to the decrease in the molecular weight of humic acid, which increases the proportion of molecular weights below 100. Increasing the activity of humic acid can increase the efficacy of humic acid at the same unit weight or unit volume, increase the effective yield of humic acid, and reduce the production cost of humic acid from straw raw materials. The solid content of humic acid on the market is generally 40%-60%, of which the estimated content of mineral humic acid (potassium) is 55%; plant-based humic acid products - generally below 57%; molasses humic acid - the highest value is 60%, and there has been no report of a plant-based humic acid product with a solid content exceeding 61%. Increasing the dry content of humic acid can increase the effective content of humic acid per unit product weight, improve the carbon sequestration benefit of the product, significantly improve the input-output ratio, improve production efficiency, save raw material consumption, and improve the economic benefits of the enterprise.

[0011] In order to solve the key technical bottleneck in production practice, the present invention proposes a plant-based high-solid content fulvic acid production technology solution with salicylic acid as the core and its related applications.

[0012] In a first aspect, the present invention provides a plant-derived fulvic acid product with a high solid base content.

[0013] The high solid content plant-derived fulvic acid product of the present invention has a pH of 5-6, a solid content (also referred to as solid content) of not less than 60%, preferably not less than 65%, and more preferably not less than 70%, by mass percentage. For example, the solid content is 60%-78%, 63%-75%, 65%-76%, 66%-72%, and so on. In a preferred example of the present invention, the stock solution of the plant-derived fulvic acid product contains salicylic acid, and the solid content is 58%-80%. The test results show that the addition of salicylic acid and magnesium sulfate in the production process of fulvic acid can greatly improve its comprehensive function, forming a superposition of the functions of fulvic acid, salicylic acid and magnesium sulfate.

[0014] The plant-derived fulvic acid product of the present invention is a low-molecular-weight fulvic acid obtained by sulfonation treatment of non-wood fiber biomass fiber raw materials and various plant fiber raw materials, and its indicators are: fulvic acid>60%, preferably fulvic acid content greater than 75%, organic matter content 50%-70%, humic acid content 60%-70%, average molecular weight <50, molecular weight <180 accounted for>95%, pH 4-6. The detection method of fulvic acid refers to HG / T 5332-2018 "Humic Acid Biological Organic Fertilizer".

[0015] In the present invention, the detection method of the component SYS in the fulvic acid can be NMR, MS, HPLC and the like.

[0016] In a second aspect, the present invention provides a production process for producing a plant-derived fulvic acid product with a high solid content using salicylic acid, using an ammonium sulfite method and a core auxiliary agent. The production process includes but is not necessarily completed in the order of S1 to S4:

[0017] S1, obtaining plant-derived raw materials (hereinafter referred to as raw materials);

[0018] S2, obtaining the core medicine SYS (also called core auxiliary agent or medicine, medicine SYS, SYS liquid);

[0019] S3, mixing the core agent SYS with liquid ammonium sulfite (i.e. ammonium sulfite) or solid ammonium sulfite dissolved in water to form a cooking liquid;

[0020] S4, after mixing the raw material with the cooking liquid, sequentially complete cooking extraction, separation, and concentration to obtain a concentrated black liquor of fulvic acid with a high solid content;

[0021] The core agent SYS includes salicylic acid and magnesium sulfate.

[0022] The present invention can process common crop raw materials (or plant-based raw materials) in agriculture into fulvic acid. Preferably, the raw materials that can be used to produce fulvic acid are selected from various plants: one or more of corn stalks, corn cobs, lignin sludge, bamboo, reeds, cotton stalks, wheat stalks, and rice straw.

[0023] Preferably, the order of addition during cooking is to first dissolve the core agent in water, and then charge it into the cooker simultaneously with the ammonium sulfite (also referred to as ammonium sulfite in the present invention) solid or liquid, and then load it into the pot according to the set liquid ratio.

[0024] The neutral imine method is adopted for cooking, and conventional methods in the art can be used. Preferably, the pH of the cooking in the present invention is 6-7 (a buffer without Na ions can be used to reduce the salt content and the sodium ion content), and the fiber and raw material cooking liquid are obtained; the cooking is carried out at 160-173°C and kept warm for 30-180 minutes.

[0025] Preferably, the temperature is raised and kept warm according to the ammonium sulfite pulping process. The cooking temperature and the keeping time are set according to the raw materials and the target pulp performance requirements.

[0026] The core additive SYS is used to further increase the solid content of the fulvic acid product. Its dosage is 0.1%-10% of the weight of the raw material, preferably 0.5%-5%, more preferably 2%-3%, by mass percentage. The added core agent SYS includes salicylic acid, magnesium sulfate, etc., all of which are commercially available.

[0027] The addition amount of each component in the core agent SYS is the percentage by weight of raw materials, wherein the addition amount of salicylic acid is 0.1%-10%, preferably 0.5%-5% of the weight of the raw materials, more preferably 1%-3%, such as 1.2%, 1.5%, 1.6%, 1.8%, 2%, 2.2%, 2.5%, 2.6%, 2.8%, by mass percentage. In a preferred embodiment of the present invention, the addition amount of salicylic acid is 2%. With the increase of the addition amount of salicylic acid, the solid base content of the obtained fulvic acid product has increased, but it does not show a dose-dependent type. The test results of the present invention show that, when the addition amount of magnesium sulfate and subammonium is the same, when the addition amount of salicylic acid is 0.5%, 1%, 5%, 10%, the solid base content of the obtained fulvic acid product does not present a trend of gradually increasing as imagined, which may be because a variety of additives and reaction parameters are involved in the production process, so there will be more changes.

[0028] Magnesium sulfate, also known as magnesium sulphate (Magnesium sulfate heptahydrate), can be used for leather making, explosives, papermaking, porcelain, fertilizer, and medical oral laxatives. Magnesium sulfate is used as a fertilizer in agriculture because magnesium is one of the main components of chlorophyll. It is usually used for potted plants or magnesium-deficient crops, such as tomatoes, potatoes, roses, etc. The advantage of magnesium sulfate over other fertilizers is that it has a higher solubility. In the SYS core additive of the present invention, the addition amount of magnesium sulfate is 0.2%-10% of the weight of the raw material, preferably 0.5%-1.5%, and more preferably 0.8%-1.0%.

[0029] Preferably, sulfite can be added to the mixture of raw materials and medicaments to interact with salicylic acid and the like to increase the solid content of fulvic acid. Ammonium sulfite is an inorganic compound with a chemical formula of (NH4)2SO3. It is a colorless crystalline powder, soluble in water, almost insoluble in ethanol and acetone, and is mainly used as a reducing agent and a lubricant for metal cold working. It can also be used as an efficient absorbent for removing a small amount of hydrogen sulfide in coal gas, and can also be used in medicine, photographic reducing agent, dye intermediate, papermaking, food additive, water treatment, etc. In the present invention, the amount of sulfite is preferably 15%-35% of the weight of the raw material, for example, 15%-30%, 20%-35%, and more preferably 20%-30%, by mass percentage.

[0030] Correspondingly, the present invention provides a core agent for producing a plant-derived fulvic acid product, wherein the core agent contains salicylic acid and magnesium sulfate; the salicylic acid content accounts for 0.1%-10% of the weight of the raw material, and the magnesium sulfate content is 0.2%-10%, by mass percentage.

[0031] When fulvic acid is produced using the production process of the present invention, the solid base content of the fulvic acid product produced is not less than 55%, for example, not less than 57%. Preferably, the solid base content of the concentrated fulvic acid product can reach more than 60%, reaching 60%-80%, and more preferably 65%-75%. In a preferred embodiment of the present invention, corn cob raw material is used, 30% ammonium sulfite, 2% salicylic acid, and 2% magnesium sulfate are added, and the solid base content of the obtained fulvic acid can reach 75.79%, and the water-soluble humic acid content is 78.71%.

[0032] Preferably, after adding the core auxiliary agent SYS, the produced plant-derived fulvic acid product retains the component of salicylic acid. The plant-derived fulvic acid finished product produced by this technical solution contains fulvic acid, ammonium sulfate, ammonium sulfite and salicylic acid.

[0033] The produced plant-derived fulvic acid product retains the component of salicylic acid. Preferably, the fulvic acid solid base content is 66%-74%, the average molecular weight of fulvic acid is 38, and the molecular weight distribution is: <180 accounts for 95.13%, 500-180 accounts for 4.85%, and 1000-500 accounts for 0.07%.

[0034] In a third aspect, the present invention provides the application of the high-solid-base fulvic acid product and its production process.

[0035] The cellulose obtained by co-producing fulvic acid can be used for pulp molding production and is also a high-quality raw material for the production of straw cellulose glucose.

[0036] The test results show that in the fulvic acid product of the present invention, the carboxyl content and the phenolic hydroxyl content do not change significantly, but the total amount of groups increases with the increase of dry matter content, thereby increasing the total amount of active matter and increasing the content of water-soluble small molecule organic carbon. Molecules containing carboxyl and phenolic hydroxyl groups are an important part of the activity of fulvic acid, which can significantly improve the nutritional effects of fulvic acid products as food additives, feed additives, fertilizers, soil conditioners, etc., and promote crop growth. The activity of active groups in the unit mass product increases, indicating that after using the production process of the present invention, the activity of fulvic acid is significantly improved, the production and use efficiency of fulvic acid is improved, and the cost is reduced from another perspective.

[0037] At present, the solid base content of fulvic acid products on the market is about 40%-60%. However, only a 5% increase in the solid base content can broaden the application range of fulvic acid products and achieve better application results. In the method of the present invention, after adding the core additive SYS, the solid base content of fulvic acid can be increased by at least 40%, for example, from 40%-53% to 56%-75%. The increase in solid base content means the improvement of the active performance of fulvic acid products, providing a higher cost-effectiveness for subsequent applications.

[0038] In the description of the present invention, % not specifically specified refers to mass percentage.

[0039] In the description of the present invention, the terms "comprises", "comprising" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device comprising a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device. In the absence of further restrictions, the elements defined by the statement "comprising a reference structure" do not exclude the presence of other identical elements in the process, method, article or device comprising the elements. It should be noted that, in this article, relational terms such as "first", "second", etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations.

[0040] The beneficial effects of the present invention are:

[0041] 1. The high solid base content fulvic acid provided by the present invention has a high solid base content and is rich in salicylic acid, which greatly improves the comprehensive performance of plant-derived fulvic acid.

[0042] 2. Significantly increase the solid content of plant-derived fulvic acid products from 40%-53% to more than 75%, with the lowest increase exceeding 40%. This is much higher than the common fulvic acid products on the market, including mineral fulvic acid (fulvic acid solid content 55%), molasses fulvic acid (fulvic acid solid content 60%), and similar plant-derived fulvic acid products (fulvic acid solid content up to 53%).

[0043] 3. The increase in the dry basis content of humic acid is due to the reduction in the molecular weight of humic acid and the increase in the specific surface area of ​​humic acid aggregates, which increases the activity of humic acid, improves the efficacy of humic acid, and increases the absorption rate of crops; at the same time, it greatly increases the content of small molecular organic carbon, which can quickly improve the fertilizer effect of organic matter and effectively solve the problem of slow fertilizer effect of organic fertilizer.

[0044] 4. The increase in the solid base content of humic acid increases the effective content of humic acid per unit weight or unit volume, reduces transportation costs, improves the efficiency of fertilizer substitution, and can effectively promote fertilizer saving and efficiency improvement.

[0045] 5. Along with the increase of humic acid dry basis content, the organic matter content in the product also increases synchronously. When the humic acid solid basis content reaches 70%-75%, the organic matter content can generally be maintained at around 60%.

[0046] 6. The production efficiency of plant-based fulvic acid products has been greatly improved, with high marginal returns, which greatly improves production efficiency and enhances carbon sequestration effects.

[0047] 7. The present invention uses salicylic acid. Salicylic acid itself is a plant growth regulator, which has the effects of increasing crop growth, increasing yield, inhibiting natural aging of crops, prolonging life, improving stress resistance, and enhancing rooting ability of crops. After further research, it was found that the presence of salicylic acid in fulvic acid greatly improved the comprehensive function of the plant source, forming a superposition of the functions of fulvic acid and salicylic acid. BRIEF DESCRIPTION OF THE DRAWINGS

[0048] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0049] Figure 1 This is a physical picture of the Hegang corn cob xylose residue raw material.

[0050] Figure 2 This is a physical picture of the lignin sludge of Anhui Fengyuan Group.

[0051] Figure 3 This is a real picture of bamboo chips in Jiujiang, Jiangxi.

[0052] Figure 4 This is a real picture of corn stalks.

[0053] Figure 5 This is a real picture of reed.

[0054] Figure 6 This is the NMR test chart of salicylic acid content before and after the sample is dried.

[0055] Figure 7 This is the MS test chart of salicylic acid.

[0056] Figure 8 This is the HPLC test chart of salicylic acid.

[0057] Fig. 9 The figure below is a comparison of wheat rhizomes after applying different fulvic acids. The left figure is the result after using a common fulvic acid product, and the right figure is the result after applying the fulvic acid product of the present invention.

[0058] Fig.10 It is a comparison chart of wheat root system. Among them, the left picture shows the result after using ordinary fulvic acid products, and the right picture shows the result after using the fulvic acid product of the present invention. DETAILED DESCRIPTION

[0059] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0060] Example 1 Production of fulvic acid using corncob xylose residue as raw material

[0061] (1) Raw materials: Take Hegang corn cob xylose residue as an example, see Figure 1 .

[0062] (2) Preparation: Prepare SYS solution according to the predetermined dosage. For example: 2% salicylic acid, 0.5% magnesium sulfate, both solid, calculated by raw material mass. Dilute the agent with clean water at a volume ratio of 1:10-30 and set aside.

[0063] The amount of solid ammonium sulfite (which may be referred to as ammonium sulfite for short) used is 30%, calculated based on the mass of the raw materials.

[0064] (3) Cooking method: intermittent ball steaming.

[0065] (4) Loading the pot:

[0066] When solid ammonium sulfite is used, the raw material, ammonium sulfite and SYS solution are added and transported along the conveyor belt in proportion.

[0067] When liquid ammonium sulfite is used, the SYS solution and the liquid ammonium sulfite are first mixed to form a mixed solution, and then the mixed solution and the raw materials are added and transported according to a proportion.

[0068] If liquid ammonium sulfide with a solid content of 30% is used, the amount of water added is (1+0.002+0.002+0.002+0.3)×3.5-0.7=3.8 tons.

[0069] (5) Steaming: Heat to 170°C and keep warm for 70 minutes.

[0070] (6) Spraying.

[0071] (7) Solid-liquid separation. Solid-liquid separation is performed in a conventional manner. In this scheme, a screw squeezer is used to separate straw cellulose and fulvic acid black liquor. Four-stage reverse washing is used to obtain fulvic acid dilute black liquor with a solid content of 16% and cellulose coarse pulp.

[0072] (8) Concentration of fulvic acid black liquor. The 16% fulvic acid dilute black liquor is concentrated by multi-effect evaporation to obtain commercial fulvic acid concentrated black liquor with a solid content of 55% (volume concentration).

[0073] (9) Drying: The humic acid concentrated black liquor with a solid content of 55% is spray-dried to obtain humic acid dry powder.

[0074] (10) Test results. The test method of fulvic acid refers to HG / T 5332-2018 Humic Acid Bio-Organic Fertilizer, O / STHJ02-2003 (carbon coefficient: 0.50), etc.

[0075] The samples were sent to the Taiyuan Testing Center of China Humic Acid Testing Industry Association for testing. The test results are shown in Table 1. The indicators are:

[0076] Fulvic acid (dry basis) 75.79%, water-soluble humic acid content 78.71%, carboxyl group 0.47 (ad mmol / g), phenolic hydroxyl group 0.47 (ad mmmol / g).

[0077] The solid content of fulvic acid refers to the content of fulvic acid in the dry state. The fulvic acid product needs to be dried into dry powder and then the content of fulvic acid is detected and calculated. The corresponding calculation formula is:

[0078] Solid base content = (weight of fulvic acid (FA) / total weight of plant-based fulvic acid products (dry basis))%, mass percentage.

[0079] Table 1 Test results of high solid content plant-derived fulvic acid products in Example 1

[0080]

[0081] Note: The percentages in the table are all mass percentages. Mad% is the analytical base moisture, the moisture content of the sample itself; d% is the dry matter content of the sample, which is the mass percentage of the dry matter after removing the moisture content in the sample.

[0082] ad is the analytical basis content, the wet basis content of the sample, the content without removing water.

[0083] Example 2 Production of fulvic acid using lignin sludge as raw material

[0084] (1) Raw material: lignin sludge from Anhui Fengyuan Group, see Figure 2 .

[0085] (2) Production process: same as in Example 1.

[0086] (3) Drug formula: 30% imine, 0.5% magnesium sulfate, and 2% salicylic acid.

[0087] (4) Test results: See Table 2.

[0088] Fulvic acid (dry basis) 70.13%, carboxyl 0.23 (ad mmol / g), phenolic hydroxyl 0.21 (ad mmmol / g).

[0089] Table 2 Test results of Example 2

[0090]

[0091] Example 3 Production of fulvic acid using bamboo scraps as raw material

[0092] Raw materials: Jiangxi Jiujiang bamboo chips, Figure 3 .

[0093] (1) Production process: same as in Example 1.

[0094] (2) Drug formula: 30% imine, 0.5% magnesium sulfate, and 2% salicylic acid.

[0095] Test results: See Table 3.

[0096] Fulvic acid (dry basis) 72.32%, water-soluble humic acid content 72.62%, carboxyl group 0.52 (ad mmol / g), phenolic hydroxyl group 0.10 (ad mmmol / g).

[0097] Table 3 Test results of Example 3

[0098]

[0099] Example 4 Production of fulvic acid using corn stalks as raw material

[0100] (1) Raw materials: corn stalks (see Figure 4 ).

[0101] (2) Production process: same as in Example 1.

[0102] (3) Drug formula: 30% imine, 0.5% magnesium sulfate, and 0.1% salicylic acid.

[0103] (4) Test results: See Table 4.

[0104] Fulvic acid (dry basis) 59.69%, water-soluble humic acid content 68.07%, carboxyl 0.55 (ad mmol / g), phenolic hydroxyl 0.17 (ad mmmol / g).

[0105] Table 4 Test results of Example 4

[0106]

[0107] Example 5 Production of fulvic acid using reed as raw material

[0108] (1) Raw materials: reed, see Figure 5 .

[0109] (2) Production process: same as in Example 1.

[0110] (3) Drug formula: 30% ammonium sulfide, 2% magnesium sulfate, and 1% salicylic acid.

[0111] (4) Test results: See Table 5.

[0112] Fulvic acid (dry basis) 55.85%, water-soluble humic acid content 56.09%, carboxyl group 0.31 (ad mmol / g), phenolic hydroxyl group 0.2 (ad mmmol / g).

[0113] Table 5 Test results of Example 5

[0114]

[0115] Example 6 Effect of different imine contents on fulvic acid solid content

[0116] (1) Raw materials: Reed, see Figure 5 .

[0117] (2) Production process: same as in Example 1.

[0118] (3) Drug formula: see Table 6 for imine, magnesium sulfate 0.5%, salicylic acid 0%.

[0119] (4) Test results: see Table 6

[0120] Table 6 Effect of different amounts of ammonium sulfide added on the solid content of fulvic acid

[0121]

[0122] Example 7 Effect of different salicylic acid contents on fulvic acid solid content

[0123] (1) Raw materials: straw (see Figure 4 ).

[0124] (2) Production process: same as in Example 1.

[0125] (3) Drug formula: 30% imine, 0.5% magnesium sulfate, salicylic acid content see Table 8.

[0126] (4) Test results: See Table 7.

[0127] Table 7 Effect of adding salicylic acid on the solid content of fulvic acid

[0128]

[0129] Example 8 Comparative Experiment

[0130] This example tests the fulvic acid solid base content, fulvic acid molecular weight and distribution changes in the obtained product.

[0131] (1) Raw material: reed.

[0132] (2) Production process: same as in Example 1.

[0133] (3) Formula: Comparative experiment:

[0134] 8.1 Pharmaceutical formula: 30% imine, 2% magnesium sulfate, 2% salicylic acid

[0135] Test results:

[0136] The solid base content of fulvic acid is 73.5%, the average molecular weight (MW) of fulvic acid is 38 (g / mol), and the molecular weight distribution is: <180 accounts for 95.13%, 500-180 accounts for 4.85%, and 1000-500 accounts for 0.07%.

[0137] 8.2 Pharmaceutical formula: 30% ammonium sulfite, 2% magnesium sulfate

[0138] The solid base content of fulvic acid is 57.1%, the average molecular weight (MW) of fulvic acid is 53 (g / mol), and the molecular weight distribution is: <180 accounts for 89.47%, 500-180 accounts for 10.47%, and 1000-500 accounts for 0.05%.

[0139] It can be seen that salicylic acid can greatly increase the solid base content of fulvic acid.

[0140] Example 9 Comparative Test (Comparison with Example 1)

[0141] Fulvic acid is produced using corncob xylose residue as raw material.

[0142] (1) Raw materials: Take Hegang corn cob xylose residue as an example, see Figure 1 .

[0143] (2) Preparation: Prepare SYS solution according to the predetermined dosage, for example: 2% acetic acid, 0.5% magnesium sulfate, both solid, calculated by the mass of raw materials. Dilute the agent with clean water at a volume ratio of 1:10-30 and set aside.

[0144] The amount of solid ammonium sulfite (which may be referred to as ammonium sulfite for short) used is 30%, calculated based on the mass of the raw materials.

[0145] (3) Cooking method: intermittent bulb cooking.

[0146] (4) Loading the pot:

[0147] When solid ammonium sulfite is used, the raw material, ammonium sulfite and SYS solution are added and transported along the conveyor belt in proportion.

[0148] When liquid ammonium sulfite is used, the SYS solution and the liquid ammonium sulfite are first mixed to form a mixed solution, and then the mixed solution and the raw materials are added and transported according to a proportion.

[0149] If liquid ammonium sulfide with a solid content of 30% is used, the amount of water added is (1+0.002+0.002+0.002+0.3)×3.5-0.7=3.8 tons.

[0150] (5) Steaming: Heat to 170°C and keep warm for 70 minutes.

[0151] (6) Spraying.

[0152] (7) Solid-liquid separation. Solid-liquid separation is performed in a conventional manner. In this scheme, a screw squeezer is used to separate straw cellulose and fulvic acid black liquor. Four-stage reverse washing is used to obtain fulvic acid dilute black liquor with a solid content of 16% and cellulose coarse pulp.

[0153] (8) Concentration of fulvic acid black liquor. The 16% fulvic acid dilute black liquor is concentrated by multi-effect evaporation to obtain commercial fulvic acid concentrated black liquor with a solid content of 55% (volume concentration).

[0154] (9) Drying: The humic acid concentrated black liquor with a solid content of 55% is spray-dried to obtain humic acid dry powder.

[0155] (10) Test results. See Table 8.

[0156] Test indicators, see Table 8:

[0157] Fulvic acid (dry basis) 51.08%, water-soluble humic acid content 54.65%, carboxyl group 0.26 (ad mmol / g), phenolic hydroxyl group 0.08 (ad mmmol / g).

[0158] Table 8 Comparison of test data between Example 1 and Example 9

[0159]

[0160] Example 10 Effect of solid base content on the activity of fulvic acid

[0161] Table 9 Comparison of calculated values ​​of total active groups corresponding to solid base content

[0162]

[0163] The results showed that the increase in solid base content means that the content of pure fulvic acid in the unit weight of fulvic acid product increases, and the corresponding total content of active groups increases. The solid base content of fulvic acid in the table increased from 55.79 (g / kg) to 75.79 (g / kg), corresponding to the carboxyl content increased from 26221.3 (ad, mmol / g) to 35621.3 (ad, mmol / g), and the phenolic hydroxyl content (ad, mmol / g) increased from 10600.1 to 14400.1 (ad, mmol / g), (ad, mmol / g).

[0164] The present invention forms a comprehensive product advantage including high solid content + salicylic acid + magnesium sulfate. The high solid content brings about an increase in the total amount of active groups and an increase in the content of water-soluble small molecule organic carbon. The test results show that the carboxyl content and phenolic hydroxyl content mmol / g in the product do not change significantly, but the increase in solid content indicates that the total amount of fulvic acid has increased, and the carboxyl and hydroxyl groups in the unit fulvic acid product have increased. At the same time, the total amount of active organic carbon in the unit fulvic acid product has also increased. According to the calculation of 50% carbon content, the small molecule organic carbon content in the comparison table has also increased from 55.79*50%=27.895% to 75.79*50 / =37.895%. The active groups containing small molecule organic carbon and carboxyl phenolic hydroxyl groups are prominent signs of fulvic acid activity. These characteristic components have irreplaceable advantages in improving the nutritional effects of fulvic acid products as food additives, feed additives, fertilizers, etc., promoting crop growth, improving soil structure, and complexing soil heavy metals.

[0165] Example 11 Fulvic Acid Material Composition

[0166] According to qualitative analysis, the plant-derived fulvic acid product obtained by the present invention contains, but is not limited to, fulvic acid, ammonium sulfite, ammonium sulfate, salicylic acid, and other ingredients. The following table is used to show the important ingredients in the fulvic acid product.

[0167] The test methods refer to "Determination of copper, iron, manganese, zinc, boron and molybdenum content in water-soluble fertilizers" NY / T 1974-2010, magnesium, "Determination of calcium, sulfur and chlorine content in water-soluble fertilizers" NY / T 1117-2010, "Determination of sodium, selenium and silicon content in water-soluble fertilizers" NY / T1972-2010, and "Determination of total nitrogen, phosphorus and potassium content in water-soluble fertilizers" NY / T 1977-2010. Some test results are shown in Table 10.

[0168] Table 10 Composition of fulvic acid

[0169]

[0170] Example 12 Detection of salicylic acid components

[0171] The plant-derived fulvic acid product obtained by the present invention was subjected to NMR, MS, and HPLC detection of salicylic acid:

[0172] NMR testing

[0173] Figure 6 The upper part of the picture is the NMR test picture of the sample. Figure 6 The lower half of the figure is the NMR test graph of the dried sample.

[0174] It can be seen that salicylic acid is indeed present in the samples, and its concentrations are 7.7ppm, 7.4ppm, and 6.9ppm respectively.

[0175] MS detection NMR

[0176] Figure 7 This is the MS test chart of the sample salicylic acid.

[0177] It can be seen that the sample contains the following structures:

[0178] Structure 1: 137 is the characteristic peak of salicylic acid.

[0179] Structure 2: 97 and 195 are characteristic peaks of sulfate.

[0180] Structure three: 282 and 563 are system impurity peaks.

[0181] (3) HPLC

[0182] Figure 8 The sample was diluted to about 1.0 × 10 4 The HPLC test chart shows that the salicylic acid content in the sample is about 5.81%, by mass percent.

[0183] Example 13 Comparison of the development effects of wheat lines fed with fulvic acid with different solid base contents

[0184] Use time: After the wheat turns green in April, apply the high-solid-base fulvic acid (solid-base content 60%) of Example 4 of the present invention, and use the same application amount of ordinary fulvic acid (solid-base content 45%) as a control group. The application amount of fulvic acid is 5 kg / mu. After the wheat turns green, apply compound fertilizer and water it, and apply it mechanically in the field. After 20 days, observe the development of the wheat seedling root system.

[0185] 1. For details, see Fig. 9 and Fig.10 :

[0186] 1. Use fulvic acid with normal solid content (left, solid content 45%)

[0187] Effect: ① The rhizomes turn yellow and rot, ② The root system turns yellow.

[0188] 2. Use high solid content fulvic acid (right, solid content 60%)

[0189] Effect: ① The rhizome is strong and white, ② The root system is white.

[0190] 91 is the wheat stem base treated with fulvic acid of normal solid content, 92 is the wheat root system treated with fulvic acid of normal solid content, 93 is the wheat stem base treated with fulvic acid of high solid content of the present invention, and 94 is the wheat root system treated with fulvic acid of high solid content of the present invention.

[0191] In addition to the results of Example 4, the present invention also used Example 3 to obtain high solid content fulvic acid (ZZ 1220 ①, solid content 69%), and applied it to wheat according to the above method. After 20 days, the average root length of wheat was 10.0 cm, and the average root length of the control group was 3.6 cm.

[0192] 2. Conclusion:

[0193] The use of high-solid content fulvic acid significantly enhances the development of wheat root system, which is manifested by strong rhizomes, white roots and strong vitality ( Fig. 9 and Fig.10 ).

[0194] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the claims and their equivalents.

Claims

1. A production process of a plant-derived fulvic acid product with high solid base content, characterized in that: The production process comprises: S1, obtaining plant-derived raw materials; S2, obtain the medicine SYS; S3, mixing the reagent SYS with ammonium sulfite as a cooking liquid; S4, after mixing the plant-derived raw materials with the cooking liquid, cooking, extracting, separating and concentrating are completed to obtain a concentrated black liquor of fulvic acid with a high solid content; The medicine SYS comprises salicylic acid and magnesium sulfate; the amount of salicylic acid added is not less than 0.1% of the weight of the raw materials, and the amount of magnesium sulfate added is 0.2%-10%.

2. The production process according to claim 1, characterized in that: After the reagent is dissolved in water, it is simultaneously loaded into the digester with the ammonium sulfite solid or liquid and the raw material, and then loaded into the pot according to the set liquid ratio; The neutral ammonium sulfite method is used for cooking, and the pH value is 6-7; The cooking temperature range is 160-180°C, and the insulation time range is 30-180min.

3. The production process according to claim 1, characterized in that: The dosage of ammonium sulfite is 15%-35% of the weight of the raw material; the dosage of the agent SYS is 0.5%-10% of the weight of the raw material, and the amount of salicylic acid added is 0.5%-5% of the weight of the raw material, calculated in mass percentage.

4. The production process according to claim 1, characterized in that: The dosage of the agent SYS is 1%-8% of the weight of the raw material, and the added amount of salicylic acid is 1%-5% of the weight of the raw material, calculated in mass percentage.

5. The production process according to claim 1, characterized in that: The dosage of the agent SYS is 3%-10% of the weight of the raw materials, calculated as a percentage by mass; The amount of salicylic acid in the agent SYS is 2%-3% of the weight of the raw material.

6. The production process according to claim 1, characterized in that: The produced plant-derived fulvic acid product retains the component of salicylic acid; The plant-derived raw materials for producing fulvic acid are selected from one or more of corn stalks, corn cobs, lignin sludge, bamboo, reeds, cotton stalks, wheat stalks, and rice straw; The solid base content of the produced humic acid is 58%-76%.

7. The production process according to claim 1, characterized in that: The plant-derived fulvic acid product obtained using corn cob raw materials has a fulvic acid content of 76% and a water-soluble humic acid content of 78.71%, calculated by mass percentage.

8. A plant-derived fulvic acid product with a high solid content, characterized in that: The pH of the fulvic acid product solution obtained after concentration is 5-6, and the solid content is not less than 58%, calculated by mass percentage; The production process of the high solid base content plant-derived fulvic acid product includes: S1, obtaining plant-derived raw materials; S2, obtain the medicine SYS; S3, mixing the reagent SYS with ammonium sulfite as a cooking liquid; S4, after mixing the plant-derived raw materials with the cooking liquid, cooking, extracting, separating and concentrating are completed to obtain a concentrated black liquor of fulvic acid with a high solid content; The medicine SYS comprises salicylic acid and magnesium sulfate; the amount of salicylic acid added is not less than 0.1% of the weight of the raw materials, and the amount of magnesium sulfate added is 0.2%-10.

9. The plant-derived fulvic acid product with high solid content according to claim 8, characterized in that: The concentrated fulvic acid product contains salicylic acid, with a solid base content of 60%-76%.

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