CN111587282A

CN111587282A - Use of biobased sulfonates as nutrient sources and conditioners

Info

Publication number: CN111587282A
Application number: CN201980007000.5A
Authority: CN
Inventors: 尹应武; 孙瑞; 保雄伟; 刘小舟; 张雪艳; 廖翠莺; 赵玉芬; 魏嘉成; 孙响响; 李德中; 刘泽涵; 杨少梅; 卢英华; 吐松; 叶李艺; 万鹏; 张海双; 陈红樱; 柴永清; 张议丹
Original assignee: Beijing Th Unis Insight Co ltd; Xiamen University; Ningxia University
Current assignee: Beijing Th Unis Insight Co ltd; Xiamen University; Ningxia University
Priority date: 2018-02-11
Filing date: 2019-02-02
Publication date: 2020-08-25
Also published as: WO2019154346A1

Abstract

The invention relates to the use of bio-based sulfonate as a nutrient source and a conditioner, and the composition containing bio-based sulfonic acid and sulfuric acid monoester or salt substances is used for supporting plant growth nutrition and/or used as a biological growth substrate and/or providing plant or microorganism nutrition and biomass energy and/or slowly releasing plant nutrient components and/or promoting the absorption of nutrient elements by plants and/or improving the quality of plants or microorganisms and/or improving the growth environment of plants or microorganisms. The composition containing the bio-based sulfonic acid and the sulfuric acid monoester or salt substance has good adsorbability, ion exchange performance and other performances, has obvious adhesion and water retention, has the effects of improving the soil structure, humidity and the like, can reduce the porosity of the soil surface, blocks a capillary structure, reduces the evaporation of water, increases the compactness and improves the mechanical performance.

Description

Use of biobased sulfonates as nutrient sources and conditioners

Technical Field

The invention belongs to the field of protection and application of bio-based sulfonate compositions, and particularly relates to application of bio-based sulfonate as a nutrient source and a conditioner, including application of regulating growth environments of plants and microorganisms and the like.

Background

The area of the existing desertified land in the world is 3600 ten thousand square kilometers, which occupies one fourth of the area of the land in the world. The wind, sand, drought and soil erosion are serious in global scope, natural disasters are frequent, and desertification areas are also the areas with the weakest ecological environment and the laggard social and economic development, so the sand prevention and control work has great global significance for maintaining the ecological function of the areas and the sustainable development of the economic and social.

The global saline soil (saline-alkali soil) area is 9560 million square kilometers per million acre. The soil salinization treatment often can not be effective all the time by a single measure, and must be comprehensively treated by adopting measures of water conservancy, physics, chemistry, biology and the like according to local conditions, wherein the water conservancy engineering technology is a foundation, and the soil improvement is a key and reasonable utilization problem.

At present, the saline-alkali soil improvement technology at home and abroad mainly comprises physical improvement, such as methods of land leveling, deep ploughing and ridge drying, timely soil loosening and the like; water conservancy improvement technology, such as irrigation and drainage matching, irrigation and salt washing, and underground salt drainage; chemical improvement is carried out by gypsum, phosphogypsum, calcium superphosphate, humic acid, peat, coarse slag and the like; biological improvement, planting rice, planting salt-tolerant plants, using microbial fertilizers and the like. In the various saline-alkali soil treatment measures, the drainage and salt washing application is a basic scheme, but the problems of large water consumption, large engineering investment, high implementation cost and the like exist.

The biomass resources such as cellulose, lignin, chitin, humic acid, protein, grease and the like are the most abundant, widely distributed, cheap and easily degradable renewable biomass resources on the earth, account for more than 60 percent of the carbon content of the plant boundary, and the fiber synthesized by the plant through photosynthesis is about 1.5 × 10¹²Ton.

Due to the technical bottleneck restriction of conversion utilization, only 2.5% of the fibers are utilized through the regeneration route. The common grass square grids or sand barriers prevent the sand fixing technology from being single in function, high in labor cost and poor in using effect, and cannot be popularized in a large area. The saline-alkali soil improvement by using gypsum, phosphogypsum, calcium superphosphate, straw, fly ash, humic acid and other substances is mainly carried out by washing due to large using amount of the substances, and each saline-alkali land per mu needs several tons of the modifying agent and more than one hundred tons of water, so that the problems of large water consumption, easy salt return, soil hardening, difficult biological growth, high modification cost, poor modification effect and the like exist, and a high-efficiency and low-cost treatment scheme is also needed.

Biomass is the most promising basic raw material for development and application. The annual large amount of crop straws, the animal husbandry, the forestry and the processing industry thereof produced in China is about 50 hundred million tons. The existing method for directly returning straws to the field or converting straws into organic fertilizer to return the straws to the field has the problems of difficult degradation, large using amount, low crop utilization degree and great consumption of microorganisms. The development and utilization of good plant resources, particularly straw resources, and the problem of water solubility in breaking plant resources are the key points of soil remediation and conditioning.

Disclosure of Invention

The invention provides a composition containing bio-based sulfonic acid and sulfuric acid monoester or salt substances, which can well solve the series of problems. The composition provided by the invention is used for supporting plant growth nutrition, and/or serving as a biological growth substrate, and/or providing plant or microorganism nutrition and biomass energy, and/or slowly releasing plant nutrient components, and/or promoting the absorption of nutrient elements by plants, and/or improving the quality of plants or microorganisms, and/or improving the growth environment of plants or microorganisms, wherein the bio-based sulfonic acid and sulfate monoester or salt substance is one or more of bio-based sulfonic acid, bio-based sulfate monoester, bio-based sulfonate and bio-based sulfate monoester salt. Preferably, in the use of the above composition, the organism is a plant or a microorganism.

Preferably, the composition is used for supporting plant growth nutrition, serving as a biological growth substrate, providing plant or microorganism nutrition and biomass energy, slowly releasing plant nutrient components, promoting the absorption of nutrient elements by plants, improving the quality of the plants or microorganisms and improving the growth environment of the plants or microorganisms.

The growth substrate of the invention is a liquid or solid support and a nutrition provider for biological growth, the growth substrate does not contain natural growth substrates such as sandy soil, water and the like, and the composition containing the bio-based sulfonic acid and the sulfuric acid monoester or salt substances of the invention is used as the growth substrate and simultaneously contains nutrient substances beneficial to biological growth, such as fertilizer, or pesticide ingredients beneficial to biological disease prevention, disease treatment, insect prevention and insect killing, or regulating ingredients for regulating biological growth, but does not contain sandy soil, saline alkali soil and other conventional soil for biological growth.

Preferably, in the use of the composition, the growth environment is a solid growth environment or a liquid growth environment, or a growth environment in which a solid and a liquid are mixed; preferably, the solid growth environment is soil; preferably, the solid growth environment is sandy soil or desert, and preferably, the solid growth environment is saline-alkali soil or saline-alkali soil.

In the present invention, the growth environment refers to a solid or liquid environment to which organisms need to attach, such as a soil environment to which roots attach during a plant growth process, a water environment, and the like, for example, a culture medium to which microorganisms attach during a growth process, and specifically, a nutrient medium to which edible fungi attach during a growth process, and the like, all belong to the growth environment of the present invention. In the invention, the preferable growing environment is sandy soil or desert, or saline-alkali soil.

The sandy soil generally means that the weight of small-particle sand contained in the soil accounts for more than 30% of the weight of the soil. The desert refers to the condition that most or all of the surface is sand.

The saline-alkali soil land comprises a saline land and an alkaline land, wherein the saline soil refers to the soil with the salt content more than 0.05 percent of the weight of the soil, and the alkaline earth refers to the soil with the pH value more than 7; the saline-alkali soil has the salinity of more than one thousandth, the soil is alkaline, the content of organic matters in the saline-alkali soil is low, the soil fertility is low, the physical and chemical properties are poor, and crops are difficult to grow.

Preferably, in the application of the composition, when the solid growth environment is sandy soil or desert, the composition can realize one or more of effects of skinning, weathering resistance, aging resistance, pressure resistance, freeze-thaw resistance and microbial living environment improvement on the sandy soil or desert; preferably, the application also comprises one or more of the effects of realizing the skinning, sand fixation, water retention and fertilizer retention, improving the living environment of microorganisms, providing and promoting nutrient element absorption, slowly releasing plant nutrient components, helping to dissolve and complex nutrient components in sandy soil or desert, ion exchange, pH reduction and salt concentration reduction of sandy soil or desert by the composition; preferably, the application also comprises the composition for improving the drought resistance, growth promotion capability and plant quality of sandy soil or desert plants; preferably, the composition also has the effects of solidifying sand, retaining water and fertilizer, improving the living environment of microorganisms and providing and promoting the absorption of nutrient elements on the flowing desert.

In the application of the composition for improving sandy soil or desert, the crust is a consolidated layer formed on the surface of the sandy soil or desert after the composition is applied to the sandy soil or desert, the consolidated layer comprises a consolidated layer formed by the composition and bonded sandy soil, and the crust has the functions of stabilizing sand and retaining water; the sand fixation is sandy soil or desert after the composition is applied, and the flow of the sandy soil or desert due to wind power can be prevented; the wind erosion resistance is that sand soil or desert can hardly lose sand dust or gravel from the surface of the sand soil or the desert under the condition of strong wind after the composition is applied to the sand soil or the desert; the ageing resistance is that after the composition is applied to sandy soil or desert, the effects of sand fixation, skinning, compression resistance and the like can be exerted on the surface of the sandy soil or desert for a long time; the compression resistance is that after the composition is applied to sandy soil or desert, the surface of the sandy soil or desert can bear the pressure from the upper part or the lower part without being damaged; the freeze-thaw resistance means that the sandy soil or the desert is not broken or damaged in a large area under the condition that the surface of the sandy soil or the desert is frozen at a low temperature after the composition is applied to the sandy soil or the desert; the improvement of the living environment of the microorganisms means that the application of the composition changes the unfavorable conditions of nutrient deficiency, water shortage and the like of the desert, and can better maintain the growth of the microorganisms.

Preferably, in the application of the composition, when the solid growth environment is saline-alkali soil or saline-alkali soil, the composition has one or more effects of reducing salt concentration and pH and improving the living environment of microorganisms on the saline-alkali soil or saline-alkali soil; preferably, the application also comprises one or more of the effects of realizing ion exchange, neutralization, water retention, skinning, soil aggregate structure formation, soil air permeability improvement, plant and microorganism nutrition providing, plant nutrient element absorption promoting, plant nutrient element slow release, dissolving and complexing of nutrient elements in saline-alkali soil or saline-alkali soil and dissolving out of insoluble nutrient elements by the composition; preferably, the application also comprises that the composition is used for improving the saline-alkali resistance, drought resistance and growth promotion capability of saline-alkali soil or saline-alkali land plants and improving the quality of the plants; preferably, the application also comprises the effects of reducing the salt concentration, reducing the pH, improving the living environment of microorganisms and providing and promoting the absorption of nutrient elements on saline-alkali soil or saline-alkali soil.

In the application of improving the saline-alkali soil or saline-alkali soil, the ion exchange effect is that after the composition is applied to the saline-alkali soil or saline-alkali soil, the anions and cations in the soil or saline-alkali soil can be exchanged with the anions and cations in the composition, so that the effective concentration of salt is reduced, and the adverse effect on the growth of microorganisms and plants is reduced; the neutralization is shown as the addition of a composition or hydrolysis or oxidation to produce an acid component that neutralizes the alkali in the soil; the water retention composition has the functions of absorbing water, storing water and inhibiting water evaporation, and can prevent water in saline-alkali soil or saline-alkali soil from migrating upwards and transpiring; the crust is a consolidated layer formed on the surface of saline-alkali soil or saline-alkali land after the composition is applied to the saline-alkali soil or saline-alkali land, and comprises a consolidated layer formed by the composition and a consolidated layer formed by the composition after the composition forms cohesive soil; the soil granular structure formed for improving the soil air permeability is a granular structure formed by the soil after the composition is added, and the soil air permeability is improved; after the composition is applied to saline-alkali soil or saline-alkali soil for providing plant and microorganism nutrition, the composition can provide nutrition required by crop roots or stems and leaves and nutrition required by related symbiotic microorganisms; after the composition is applied to the saline-alkali soil or saline-alkali soil, the slow-release plant nutrient components can be slowly released for the plant to absorb, and the indissolvable nutrient components in the soil can be dissolved out through the complexing and dissolving-assisting effects to ensure the plant nutrition.

Preferably, in the application of the composition, the weight of the bio-based sulfonic acid and the sulfuric acid monoester or salt substance accounts for 1 to 99.99 percent of the weight of the composition; preferably, the weight of the bio-based sulfonic acid and the sulfuric acid monoester or salt substance in the composition accounts for 10-80% of the weight of the composition, and preferably, the weight of the bio-based sulfonic acid and the sulfuric acid monoester or salt substance in the composition accounts for 20-60% of the weight of the composition.

Preferably, in the application of the composition, the bio-based sulfonic acid or the bio-based sulfuric acid monoester or the salt thereof is a substance in which the cellulose, the hemicellulose, the starch, the humic acid, the chitin and the derivative thereof in the biomaterial are connected with the sulfonyl functional group through hydroxyl and aryl groups, the bio-based sulfonate or the bio-based sulfuric acid monoester salt is obtained by neutralizing the bio-based sulfonic acid or the bio-based sulfuric acid monoester with alkali, and hydrogen ions are replaced by metal ions or ammonium ions;

preferably, the metal ion is K⁺、Ca²⁺、Na⁺、Mg²⁺、Fe²⁺、Fe³⁺、Mn²⁺、Zn²⁺、Cu²⁺、Mo⁶⁺、Ni⁺One or more of (a). Preferably, the metal ion is K⁺Or Ca²⁺。

Preferably, in the application of the composition, the sulfur content in the bio-based sulfonic acid and the sulfuric acid monoester or salt substance is more than or equal to 1 wt%. The sulfur content measuring method comprises the following steps: weighing a certain amount of product, placing the product in a regenerated cellulose dialysis bag with molecular weight cut-off (MW) of 200, placing the bag in deionized water, dialyzing for 3-4 days, changing water for 6-8 times, drying the dialyzed product at 60 ℃, and quantitatively analyzing the content of C, H, N, S and other elements in the dialyzed powder by using an element analyzer.

Preferably, in the application of the composition, the average molecular weight of the multifunctional bio-based sulfonate is more than ten thousand, and the higher the molecular weight is, the better the water retention and skinning or film forming effects are.

Preferably, in the use of the above composition, the biological material is a plant material or an animal material; preferably, the plant material is one or more of crop straws, reeds, salix mongolica, caragana microphylla, starch, coal slime, jujube branches, energy grass, sorghum sudanese, pennisetum hydridum, forest tree resources and processing residues thereof, and preferably, the material is one or more of sunflower straws, shrimp shells and crab shells. Preferably, the crop straw is one or more of corn stalk, soybean stalk, flax stalk, sorghum stalk, rice straw, wheat straw, dried peanut, broad bean stalk, rape stalk, sunflower stalk and the like.

Preferably, in the application of the composition, the composition further comprises one or more of a carrier and an additive, wherein the carrier is one or more of water, humic acid, fiber, fertilizer, fly ash, coal slime, gasification furnace slag, ground phosphate rock and straw crushed material, and the additive is one or more of fertilizer, pesticide, lignin salt, lignosulfonate and microorganism.

Preferably, in the application of the composition, the total weight of the carrier and the additive accounts for 0.001-99.9% of the weight of the composition; preferably, the total weight of the carrier and the additive accounts for 0.01-99% of the weight of the composition; preferably, the total weight of the carrier and the additive except the pesticide accounts for 20-90% of the weight of the composition.

Preferably, in the application of the composition, the bio-based sulfonic acid and the sulfate monoester or the salt substance are one or more combinations of cellulose sulfate monoester, cellulose sulfate monoester salt, hemicellulose sulfate monoester salt, starch sulfate, chitin sulfate monoester salt, humic acid sulfonic acid and humic acid sulfonate, and preferably, the bio-based sulfonic acid and the sulfate monoester or the salt substance are bio-based sulfonate and salt substance prepared by a sulfur trioxide sulfonation method.

Preferably, the composition is used in an amount of 1kg to 100000 kg/mu, preferably 1kg to 10000 kg/mu, and preferably 10kg to 1000 kg/mu, for improving the growing environment of plants or microorganisms.

The invention also provides a conditioner for improving the growth environment of plants or microorganisms, which comprises the bio-based sulfonic acid and the sulfuric acid monoester or salt substances, wherein the sum of the weights of the bio-based sulfonic acid and the sulfuric acid monoester or salt substances accounts for 1-99.99% of the weight of the conditioner.

Preferably, in the conditioner, the total weight of the bio-based sulfonic acid and the sulfuric acid monoester or salt substance accounts for 10-80% of the weight of the conditioner, and preferably, in the composition, the weight of the bio-based sulfonic acid and the sulfuric acid monoester or salt substance accounts for 20-60% of the weight of the composition.

Preferably, in the conditioner, the bio-based sulfonic acid and the sulfate monoester or salt is one or more of bio-based sulfonic acid, bio-based sulfate monoester, bio-based sulfonate and bio-based sulfate monoester salt. Preferably, the bio-based sulfonic acid and sulfuric acid monoester or salt substance is bio-based sulfonate and salt substance prepared by a sulfur trioxide sulfonation method. Particularly preferably, the step of the sulfur trioxide sulfonation process is to subject solid or gaseous SO₃Adding or introducing cooled 1, 2-dichloroethane to prepare SO with appropriate concentration (concentration range of 0.5-4 mol/L, preferably 0.5-2 mol/L)₃The 1, 2-dichloroethane solution is added with biological material (such as (microcrystalline) cellulose, hemicellulose, lignin, chitin, humic acid, starch, etc.) according to a certain ratio of sulfur trioxide to biological material (nU (glucose unit): nSO)₃Is 1: 0.2-6.4, preferably 1: 0.2-3.2), is added into a reactor, and is stirred and reacted for 0.5-20 hours (preferably 1-5 hours) at room temperature or lower temperature (preferably not more than 35 ℃, preferably 23-32 ℃) to obtain the bio-based sulfonic acid. Adding a certain amount of water into the bio-based sulfonic acid, mixing with ammonia water or calcium hydroxide emulsion, and neutralizing until the pH value is 7-8, so as to obtain the cellulose ammonium sulfate/cellulose calcium sulfate. Preferably, in the conditioner, the bio-based sulfonic acid or the bio-based sulfuric acid monoester is a substance in which a sulfonyl functional group is connected to a hydroxyl group and an aryl group in a molecule of cellulose, hemicellulose, starch, humic acid, chitin and derivatives thereof in a biological material, and the bio-based sulfonate or the bio-based sulfuric acid monoester salt is a compound in which a sulfonate ion in the bio-based sulfonic acid or the bio-based sulfuric acid monoester is combined with a metal ion or an ammonium ion required by plants such as calcium.

Preferably, in the conditioner, the metal ion is K⁺、Ca²⁺、Na⁺、Mg²⁺、Fe²⁺、Fe³⁺、Mn²⁺、Zn²⁺、Cu²⁺、Mo⁶⁺、Ni⁺One or more of (a). Preferably, the metal ion is K⁺Or Ca²⁺。

Preferably, in the conditioner, the conditioner further comprises one or two of a carrier and an additive, the carrier is one or more of water, humic acid, fiber (unbleached pulp and waste paper pulp), sulfonation reaction residues, fertilizer, excrement, fly ash, coal slime, gasification furnace slag, ground phosphate rock and straw crushed materials, and the additive is one or more of fertilizer, pesticide, lignin salt, lignosulfonate and microorganism.

Preferably, in the conditioner, the total weight of the carrier and the additive accounts for 0.001-99.9% of the weight of the composition; preferably, the total weight of the carrier and the additive accounts for 0.01-99% of the weight of the composition; preferably, the total weight of the carrier and the additive except the pesticide accounts for 20-90% of the weight of the composition.

Preferably, in the conditioner, the biological material is a plant material or an animal material, the plant material is one or more of crop straws, reeds, salix mongolica, caragana microphylla, coal slime, starch, jujube branches, energy grass, sorghum sudanense, forest and wood resources and animal and plant processing residues thereof, and preferably, the material is one or more of sunflower straws, shrimp shells and crab shells. Preferably, the crop straw is one or more of corn stalk, soybean stalk, flax stalk, sorghum stalk, rice stalk, wheat stalk, peanut stalk, broad bean stalk, rape stalk, sunflower stalk, and the like. The sulfonated product can be a mixture obtained by directly sulfonating and neutralizing plant or animal raw materials and not separating, or a product obtained by carrying out solid-liquid separation or preliminary separation of large and small molecules of a bio-based sulfonated product in a mixed solvent through different solubilities.

Preferably, in the conditioner, the bio-based sulfonic acid and the sulfate monoester or salt substance are a macromolecular and partially degraded micromolecular combination of one or more of cellulose sulfate monoester, cellulose sulfate monoester salt, hemicellulose sulfate monoester salt, starch sulfate, chitin sulfate monoester, humic acid sulfonic acid and humic acid sulfonate.

The invention also provides a use method of the conditioner, which is characterized in that the conditioner is applied to plants or a microorganism growing environment, or the conditioner is mixed with solid substances or liquid substances in the plant growing environment and then applied to the plant growing environment, or the conditioner is applied to plant leaf surfaces.

Preferably, in the conditioner, the application mode is spraying, broadcasting, drip irrigation, root application, ridge burying or pit burying, and particularly preferably, the application amount of the conditioner is 1kg-100000kg per mu, and preferably, the application amount of the conditioner is 1kg-10000kg per mu.

The invention also provides application of the bio-based sulfonic acid substances in preparing the sand-fixing agent.

The invention also provides application of the bio-based sulfonic acid and the sulfuric acid monoester or salt substance in preparing a soil conditioner.

The invention has the advantages of

In the present invention, "bio-based sulfonic acid and sulfuric acid monoester or salt-like substance" and "bio-based sulfonate" are to be understood in a broad sense and include not only acids containing sulfonic acid groups and salts thereof but also some substances called "sulfuric acid monoester" or "sulfuric acid monoester salt". Any bio-based sulfonic acid, salt substance or mixed substance of a substance with hydroxyl and aryl connected with sulfonyl functional groups in the molecule prepared by sulfonation of biomass belongs to the category of "bio-based sulfonic acid and sulfuric acid monoester or salt substance" and "bio-based sulfonate", without being limited by the name.

In the present invention, the ratio between substances is in terms of weight ratio unless otherwise specified.

In the present invention, all operations are carried out under room temperature and normal pressure unless otherwise specified.

The composition containing the bio-based sulfonic acid and the monoester or salt substance thereof has the advantages that the main water-soluble components are large in molecular weight, the average water-soluble components are about 50-100 ten thousand, the composition has good adsorbability, ion exchange performance and other performances, the bio-based ammonium salt or calcium salt product can perform neutralization, adsorption and ion exchange effects on saline-alkali soil and saline-alkali soil, the pH value and the salt ion concentration in the soil are effectively reduced, the salt ions in the soil are enriched and exchanged into macromolecules, and the influence on plant root systems is avoided. The biological sulfonic acid and the sulfuric acid monoester or the salt substance have obvious adhesiveness and water retention, so that the biological sulfonic acid and the sulfuric acid monoester or the salt substance form a shell-shaped or film-shaped crust layer with soil or increase the aggregate structure of the soil, further play the roles of water retention and absorption, soil structure improvement, humidity improvement and the like, can reduce the porosity of the soil surface, block a capillary structure, reduce water evaporation, increase compactness and improve mechanical performance.

The composition containing the bio-based sulfonic acid and the monoester or salt substance thereof contains all elements required by plants, and the water-soluble polymer sulfonate is used as a basic nutrient medium, so that soil organic matters and all nutrient components which can completely meet the requirements of rapid growth of the plants and microorganisms can be well supplemented, the salinity and alkalinity of the soil can be reduced through ion exchange, sodium ions can be effectively bound, the water and fertilizer retention capacity of the soil can be remarkably improved, the soil can be loosened, the porosity is large, the surface temperature is high, and the soil moisture, the physical properties and the structure can be improved.

The composition containing the bio-based sulfonic acid and the monoester or salt substance thereof has good sand fixing effect, strong skinning capability, strong wind erosion resistance, good aging resistance, high pressure resistance and high freeze-thaw resistance on sandy soil and desert, and has multiple functions of water retention, pH reduction, salt concentration reduction, ion exchange, plant nutrition providing, plant nutrient slow release, complexing of nutrient components in the sandy soil or desert and nutrient component release on the sandy soil and desert.

The composition containing the bio-based sulfonic acid and the monoester or salt substance thereof can realize the effects of reducing the salt concentration, reducing the pH, improving the biological growth environment and the like on saline-alkali soil or saline-alkali soil, and simultaneously can realize the functions of ion exchange, neutralization, water retention, skinning, forming a soil aggregate structure, improving the soil air permeability, providing plant and microorganism nutrition, promoting the absorption of plant nutrient elements, slowly releasing plant nutrient components, assisting in dissolving and complexing the nutrient components in the saline-alkali soil or saline-alkali soil, assisting in dissolving out insoluble nutrient elements and the like on the saline-alkali soil or saline-alkali soil.

Brief description of the drawings

FIG. 1 is an infrared spectrum of cellulose sulfate and chitin sulfate

FIG. 2 NMR spectra of cellulose sulfate and chitin sulfate

FIG. 3 Infrared Spectroscopy of starch sulfate monoester

FIG. 4 nuclear magnetic spectrum of starch sulfuric acid monoester

FIG. 5 viscosity diagram for starch sulfate monoesters at different water contents

FIG. 6: cellulose sulphate skinning effect

Detailed Description

The composition of bio-based sulfonic acid and sulfate monoester salt used in the following preparation examples was purchased or made by oneself, wherein the purchased product was about 5000 average molecular weight of commercially available calcium lignosulfonate, and the made-by-oneself product was prepared according to the following method to obtain the corresponding bio-based sulfonic acid and sulfate monoester salt.

Preparation examples

The preparation method of the bio-based sulfonic acid and sulfuric acid monoester salt substance comprises the following steps: by introducing solid or gaseous SO₃Adding or introducing cooled 1, 2-dichloroethane to prepare SO with appropriate concentration (concentration range of 0.5-4 mol/L)₃The 1, 2-dichloroethane solution is added with biological materials (such as (microcrystalline) cellulose, hemicellulose, lignin, humic acid, starch, chitin, straw fiber of sunflower stalk, Sudan grass, corn stalk and the like) according to a certain proportion of sulfur trioxide of the biological materials (nU (glucose unit): nSO)₃1: 0.2-6.4) is added into a reactor, and stirred and reacted for 1-5 hours (preferably 1-5 hours) at room temperature or lower temperature (preferably not higher than 35 ℃), thus obtaining the bio-based sulfonic acid. And (2) neutralizing the reaction mixture of the bio-based sulfonic acid with calcium hydroxide emulsion with a folding dosage of 27-50g/100g of biomass raw material or ammonia water with a required dosage of 12-20g/100g of biomass raw material or a mixture until the pH value is 7-8 at the end point to obtain bio-based sulfonate, and obtaining cellulose sulfate monoester salt, hemicellulose sulfate monoester salt, starch sulfate monoester salt, chitin sulfate monoester salt, lignosulfonate, humic acid sulfonate or a mixture water solution thereof according to different raw materials. Stratify and returnThe distilled organic solvent can be recycled, the water solution is filtered to remove unreacted solid raw materials, and the product of the bio-based sulfuric acid monoester salt water solution with the concentration of about 50 percent can be obtained by evaporation and concentration. The application effect evaluation can be directly carried out. The samples to be analyzed were treated as follows: taking a certain amount of product water solution, dialyzing by using a dialysis bag to remove less than 200 micromolecules and inorganic salts, and drying a sample for content and structure analysis.

The molecular weight determination method comprises the following steps: wide-angle static/dynamic synchronous laser light scattering analysis method: dissolving a bio-based sulfonate sample in a pure water solution to respectively prepare 0.002g/mL, 0.004g/mL, 0.006g/mL, 0.008g/mL and 0.01g/mL of dilute solution, filtering the dilute solution by a 0.45-micrometer sterile filter membrane, sequentially dropping the filtered solution into a dedusted sample bottle, putting the dedusted sample bottle into an ALV/CGS-3 wide-angle static/dynamic synchronous laser light scattering system, measuring the scattered light intensity, converting the scattered light intensity into KC/delta R theta (K is a constant, delta R theta is an excessive Rayleigh factor) by Software (ALV-Fit & Plsoftware) carried by an instrument, making a Debye curve on the bio-based sulfonate concentration C by using KC/delta R theta, and obtaining the reciprocal of the curve intercept as the molecular weight of the bio-based sulfonate.

Respectively detecting sulfur content and weight average molecular weight of the oven-dried product, and performing Infrared (IR) and¹³c Nuclear Magnetic Resonance (NMR) analysis. See table 1 and accompanying figures 1 and 2 for relevant results. The infrared characteristic peak of the cellulose sulfate is 1260cm^-1And 813cm^-1Are each-SO₃Asymmetric stretching vibration peak of- (O ═ S ═ O) and stretching vibration peak of C — O — S (see fig. 1): the chitin sulfonate has a density of 1258cm^-1And 810cm^-1Two characteristic peaks of-SO₃An asymmetric stretching vibration peak of- (O ═ S ═ O) and a stretching vibration peak of C — O — S (see fig. 1).

Cellulose sulfuric acid monoester¹³A new peak appears at 66ppm in the CNMR, which proves that the primary hydroxyl at the C6 position is substituted by sulfate ester group, and the characteristic peak of the un-esterified primary hydroxyl at the C6 position is 60ppm (see figure 2); the chitin sulfuric monoester showed a new peak at 66ppm, which is the result of the substitution of the primary hydroxyl group at C6 with a sulfate group (see fig. 2); the infrared characteristic peak of the starch sulfate is 1230cm^-1And 821cm^-1Are each-SO₃Asymmetry of- (O ═ S ═ O)A stretching vibration peak and a stretching vibration peak of C-O-S (see FIG. 3). Nuclear magnetic resonance (¹³CNMR) and a new peak at 66ppm, which is the result of substitution of the primary hydroxyl group at C6 with a sulfate group (see fig. 4); viscosity of starch sulfate at various water contents (see FIG. 5).

TABLE 1 Bio-based sulfonate product data for different materials

Application examples

Example 1: water retention of bio-based sulfonates

Taking 200g of sand, weighing the bio-based sulfonate (the commercial calcium lignosulfonate or the commercial ammonium lignosulfonate in the embodiment is a purchased commercial brand basf product, and the other mentioned bio-based sulfonate products are products prepared in the preparation embodiment) according to the corresponding mass (the bio-based sulfonate in the following embodiment is calculated according to the mass of the dry solid) of the dry solid according to 0.1%, 0.25%, 0.5%, 1% and 2% of the weight of the sand, dissolving the bio-based sulfonate in 40g of water in total, uniformly stirring, weighing to obtain the initial weight of the conditioner, tracking the change of water per day, measuring the average water retention rate of the bio-based sulfonate, measuring the weight of the remaining water per day, and measuring the ratio of the remaining water to the total water to obtain the water retention rate. The average water retention rate of series of bio-based sulfonate products prepared by various raw materials is higher than that of blank and commercial calcium lignosulfonate.

TABLE 2 Water retention Performance of Bio-based sulfonates

Example 2: skinning performance of biobased sulfonates

Taking 800g of sand in a plastic box according to the ratio of 100, 200 and 400g/m²Weighing bio-based sulfonate (the commercial calcium lignosulfonate or the commercial ammonium lignosulfonate mentioned in the examples is a purchased commercial brand basf product, and the other mentioned bio-based sulfonate products are products prepared in the preparation implementation), fixing to 160mL, spraying to the surface of sand by using a sprayer, weighing, obtaining an initial weight, tracking daily moisture change until the moisture content of the sand sample is close to 0, and measuring the skinning thickness.

TABLE 3 Bio-based sulfonate skinning Performance Table

15kg of bio-based sulfonate is taken to prepare an aqueous solution of bio-based sulfonate with the content of 30 percent, and the skinning effect of bio-based sulfonic acid and sulfuric acid monoester or salt substances with different dosages is tested. The effect of spraying different bio-based sulfonates on the surface of a desert is shown in fig. 6, and then the desert is tested for skinning, as shown in table 4 below.

The measurement method of the crust thickness comprises the following steps: after the aqueous solution is sprayed on the surface of the desert, the measurement is carried out after the aqueous solution is dried to form solids, 5 points are randomly taken for each square meter on average, then the average value calculation is carried out, and the measurement after the solids are formed is recorded as the initial measurement of the crust thickness. And measuring again after one month after the initial measurement, wherein 5 points are randomly taken for each square meter on average, and then the average value is calculated.

TABLE 4 crusting thickness for different conditioner dosages

The series of bio-based sulfonate products prepared by various raw materials are thicker than the calcium lignosulfonate sold in the market.

Example 3: crusting compression resistance of bio-based sulfonate

Taking 80g of sand in a watch glass according to the ratio of 100, 200 and 400g/m²Weighing (solid breaking) the bio-based sulfonate (the commercially available calcium lignosulfonate or the commercially available ammonium lignosulfonate mentioned in the examples is purchased under the brand name of basf, and the other mentioned bio-based sulfonate products are all prepared in the preparation), uniformly stirring, weighing, obtaining an initial weight, drying, and measuring the compressive strength of the sand column by using a pressure tester, wherein the specific data are shown in the following table 5.

TABLE 5 Bio-based sulfonate crusting compression resistance

The crusting and pressure resistance of series of bio-based sulfonate products prepared by various raw materials are superior to that of the calcium lignosulfonate sold in the market.

Example 4: skinning freeze-thaw resistance of bio-based sulfonate

Taking 80g of sand in a watch glass according to the ratio of 100, 200 and 400g/m²Weighing (solid breaking) bio-based sulfonate (the commercially available calcium lignosulfonate or commercially available ammonium lignosulfonate mentioned in the examples is a purchased commercially available brand basf product, and other mentioned bio-based sulfonate products are all prepared products in the preparation implementation), uniformly stirring, weighing to obtain an initial weight, drying, freezing in a freezer for 12h at (-18 ℃), taking out, then placing outside a room (at 30-40 ℃) for melting for 12h, namely a cycle, performing freeze-thaw cycles for 3 times and 7 times, and measuring the compressive strength of the sand column by using a pressure tester after drying, wherein the results are shown in table 6.

TABLE 6 Bio-based sulfonate skinning freeze-thaw resistance

As can be seen from the data in Table 6, the skinning freeze-thaw resistance of the series of bio-based sulfonate products prepared by various raw materials is mostly superior to that of the commercial calcium lignosulfonate.

Example 5: anti-ultraviolet ageing performance of crust of bio-based sulfonate

Taking 80g of sand in a watch glass according to the ratio of 100, 200 and 400g/m²Weighing (solid breaking) bio-based sulfonate (the commercially available calcium lignosulfonate or commercially available ammonium lignosulfonate mentioned in the examples is a purchased commercially available brand basf product, and other mentioned bio-based sulfonate products are all products prepared in the preparation examples), uniformly stirring, weighing to obtain an initial weight, drying, continuously irradiating for 100 hours and 200 hours under a 40w ultraviolet lamp under a closed condition at a position of 30cm, and measuring the compressive strength of the sand column by using a pressure tester after the irradiation is finished, wherein the specific results are shown in the following table 7.

TABLE 7 skinning anti-UV aging Properties of biobased sulfonates

The crust ultraviolet aging resistance of series of bio-based sulfonate products prepared by various raw materials is greatly different, and the phenolic structure of lignin has better aging resistance.

Example 6: biological sulfonate crust anti-weathering performance

The straw sulfonate prepared in the preparation examples is respectively sprayed on the surface of desert in different dosage to measure the wind erosion resistance, and the test is carried out when the included angle between the test surface and the wind-sand flow is 0 ℃, and the specific results are shown in the following table 8.

TABLE 8 weather resistance of straw sulfonate conditioner

The bio-based sulfonate can well resist wind erosion, and the more the usage amount is, the stronger the wind erosion resistance is. As shown in Table 8, when the conditioner is used in an amount of 60 grams per square meter, seven grades of wind can be well resisted; when the using amount of the conditioning agent is 80 g/square meter, the conditioning agent can well resist 10-grade strong wind.

Example 7: obviously increase the number of nutrients and microorganisms

The straw sulfonate (mainly sunflower straw sulfonate and corn straw sulfonate) prepared in the preparation example is selected, and the measured components in use are as follows: the solid content is 41 percent; and (3) folding and fixing dry base nutrients: all N1%, K₂0.7 percent of O and 57 percent of organic matter. Comparing the soil biological data before and after sunflower planting in desert soil of Ulanbu test area with blank and carboxymethyl cellulose, the concrete data is shown in Table 9:

TABLE 9 analysis of biochemical data of sunflower stalk fiber sulfate in desert soil

The number of bacterial colonies in the desert soil treated by the bio-based sulfonate is 10-100 times higher than that of the blank desert soil and 2-4 times higher than that of the desert soil treated by the carboxymethyl cellulose.

In 2018, after Nemenglatt, in flag five-original areas, salt and grass improvement (feeding) are performed on moderate and severe saline-alkali soil in the Xingmu pasture project, oil sunflowers and sudan grass are planted at an application rate of 50-100 Kg/mu, sampling is performed after 30 days of spraying and planting to measure the enzyme activity in the soil, and meanwhile, the specific data are shown in Table 10:

TABLE 10 analysis of biochemical data of sunflower stalk fiber sulfate in saline-alkali soil

After the sunflower stalk fiber sulfate modifier is applied to the soil, the content of calcium gluconate (the activity index of sucrase) in the soil is improved by 80-140% after the soil is sprayed for one month, and the soil fertility of the sunflower stalk fiber sulfate modifier applied to 50-100 Kg/mu (wherein 35 Kg of ammonium phosphate is applied in a mixed mode) exceeds the fertility of the modifier applied to 500-1000 Kg/mu. The enzyme content of catalase in severe saline-alkali soil is improved by 2 times compared with that of a control group, and the sunflower stalk fiber sulfate modifier is proved to promote the soil bioactivity and effect.

Example 8: release of trace elements from soil/substrate

300g of distilled water is added into 200g of soil/matrix, the sunflower stalk sulfonic acid ammonium prepared according to the preparation example with the solid content of 1.6-3.0% of the mass of the soil/matrix and the dosage of hundreds of percent is added quantitatively, and in a comparative experiment, EDTA or citric acid with the mass of 2.0% of the mass of the soil/matrix is added into the soil/matrix, is uniformly stirred and is soaked for about 24 hours, so that the extraction rates of the straw sulfonic acid ammonium, the EDTA and the citric acid on the nutrient elements in the soil/matrix are compared. After solid-liquid separation, the filtrate is subjected to constant volume of 500ml, then the calcium and magnesium content in the solution is determined by adopting a chemical analysis method, and the P content in the filtrate is determined by adopting a corresponding national standard₂O₅And Fe, Cu, Zn, etc. The experimental data show that the dissolving-out concentration of the sunflower stalk ammonium sulfonate salt to various nutrient elements in the soil/matrix is enough to maintain the nutrient requirement of the plants, and the sunflower stalk ammonium sulfonate salt can be used for maintaining the nutrient requirement of the plantsUnder the same addition amount of the additive component used as the slow and controlled release fertilizer, the solubilizing capacity of the sunflower stalk ammonium sulfonate to elements such as P, Fe, Ca, Mg, Zn and the like is not inferior to that of EDTA and citric acid. Moreover, the production cost of the sunflower stalk sulfonic acid ammonium salt is much lower than that of EDTA and citric acid, and a larger using amount is originally required, and specific determination data are shown in a table 11.

TABLE 11 comparison of Complex solubilized soil/matrix nutrient data

The bio-based sulfonate (the control mentioned in the examples is the conventional application of inorganic fertilizer, and other bio-based sulfonate products used are the products prepared in the preparation examples) was selected to have a solid content of 30 Kg/mu in hundred, and was used to plant trees of high quality second grade elm at the experimental site of the old guchi line of the four society of yangtze, guan-tongbaoling, yangmu, yangmuie. The fertilizing method adopts pit application: the conditioner was first applied to the bottom of the trench (cavity) or the slurry was poured into it and allowed to set naturally, and the results of the measurements are shown in Table 12 below.

TABLE 12 inter-treatment Tree index data comparison

Example 9: reducing the conductivity and pH of saline-alkali soil

The water-soluble salt is an important attribute of saline-alkali soil and is a barrier factor for limiting the growth of plants. Conductivity is an important parameter for reflecting the soluble salt content of soil.

The soil tested in example 8 was tested for conductivity and pH, and as can be seen from the data below, the pH of the soil was reduced by an average of 0.4 using sunflower stalk fiber sulfate; the soil salt concentration (conductivity) is reduced by 16%. The effect of removing salt and reducing alkali is obvious.

Example 10: bio-based sulfonate salts for improving crop quality

The uraria cloth and the field sand fixation test are carried out in 2017 in 5-10 months in sequence, the test scale is 20 mu, and the sunflower stem ammonium sulfonate prepared in the preparation example is tested to obtain remarkable effects on the sand fixation material consolidation, the biological survival rate and the growth.

The test crops include: jujun grass, Gaodan grass, the traditional grass square sand-fixing treatment mode is used as contrast treatment, wherein 50Kg of chemical fertilizer is applied to each mu of grass square contrast group; by using 25Kg plus 25Kg of fertilizer for sunflower stalk ammonium sulfonate prepared in the preparation examples, the seeds are sown in 5 months and 8 days and harvested in 10 months and 9 days in field tests. The test results are shown in tables 13 and 14.

The applied ammonium sunflower stalk sulfonate can remarkably promote the growth of pasture, and after one month of growth, the average stalk of the giant fungus grass grows coarsely to be 26.1mm, the average plant height grows fastest to be 195cm, the giant fungus grass germinates to grow branches and leaves more, the leaf quantity is rich, the chlorophyll content is higher, and the product for photosynthesis is also higher. After the sorghum sudanense treated by the ammonium sunflower stalk sulfonate grows for one month, the average stem of the sorghum sudanense grows coarsely and is 26.1mm, the average plant height grows fastest and is 92cm, the number of branches and leaves of the sorghum sudanense germinates and grows is large, the leaf amount is rich, the chlorophyll content is highest, and the product for photosynthesis is also high.

Therefore, after the treatment with ammonium sulfonate sunflower stalks, pennisetum hydridum, sorghum halepense and sudan grass grow faster, stalks grow thicker, the number of growing leaves of the plants is large, the chlorophyll content is highest, and the products for photosynthesis are also higher, as shown in table 13.

TABLE 13 comparison of grass growth index data between treatments

The application of the sunflower stalk ammonium sulfonate can obviously promote the growth of the pasture and improve the quality of the pasture. After the sunflower stalk ammonium sulfonate treatment is applied, the crude fat contents of the pennisetum hydridum, the sorghum sudanense and the sudanese are increased, and the crude fat contents are respectively 25.4%, 25.6% and 16.2%. The crude fat content is 0.1%, 3.8% and 4.5% higher than that of Megasphaera cordifolia, sorghum sudanense and Sudan grass.

After the treatment of the sunflower stalk ammonium sulfonate, the total sugar content of the plants is also increased, and the total sugar content of the pennisetum hydridum and the sorghum sudanense is 1.89 percent and 14.1 percent respectively. The total sugar content is 0.25% and 5.33% higher than that of Meristotheca papulosa and Gaodan grass.

After the treatment of the ammonium sulfonate of the sunflower stalk, the total carbohydrate content in the bodies of the three pasture plants is only 74.7 percent higher than that of the sorghum vulgare; the total carbohydrate content of sorghum sudanense is 26.9 percent higher than that of sorghum sudanense in grass squares. The total carbohydrate content of pennisetum and sudan grass was not increased compared to that in the grass squares.

After the sunflower stalk ammonium sulfonate is applied for treatment, the content of calcium in the plant body is increased, and the content of calcium in the pennisetum hydridum is 3.04 g/kg; the calcium content of Sudan grass is 3.33 g/kg. Is respectively higher than 0.06g/kg and 0.41g/kg of calcium content of the Membrerophytes dichotoma and the Sudan grass in the grass grid.

After the sunflower stalk ammonium sulfonate treatment is applied, the content of the acid fiber ADF in the plant body is reduced, and the content of the acid fiber ADF in the Jujun grass and the Gaodan grass plant body is respectively 43.1 percent and 36.9 percent; the content of the acid fiber ADF in the plant bodies is reduced by 3.5 percent and 7.4 percent respectively compared with the content of the acid fiber ADF in the plant bodies in the grass squares.

Therefore, the treatment with the sunflower stalk ammonium sulfonate can significantly promote the growth and development of the pasture grass and improve the quality and yield of the pasture grass, see table 14.

TABLE 14 comparison of grass index data between treatments

Example 11: promoting the growth of crops in saline-alkali soil environment

The experimental site: an Alxa-L Bayanmu ren Shantan Gazhan in inner Mongolia autonomous region. Physical and chemical properties of soil: the pH value is 8.4-8.6, the conductivity is 0.55-0.79ms/cm, and the organic matter is 0.83-1.08%; effective nitrogen 28.8-43.8 ppm; effective phosphorus of 28.8-43.8 ppm; effective potassium 181-257 ppm. After the corn is ripe and harvested, the product is subjected to analysis of variance.

The corn yield treated by applying the sunflower stalk sulfonate prepared in the preparation example is increased by 64 Kg/mu compared with the conventional fertilization treatment yield, the solid content of the applied bio-based sulfonate per mu is reduced by 30Kg, and the yield is increased by 8%. By analyzing the main constituent factors (ear weight and thousand kernel weight) of the corn, the total number of the particles is obviously improved although the ear weight and the thousand kernel weight are reduced by applying the bio-based sulfonate product.

Example 12: application of weight-reducing and yield-increasing greenhouse

The bio-based sulfonate is applied to vegetable drip irrigation and fertilization in a gardening industrial park in Ningxia Helan county in 2016, and mainly crops such as pepper, tomato and cucumber are planted. The contrast fertilizer adopts Israel imported water-soluble fertilizers such as HALF, Molifeng and bio-based sulfonate. The planting treatment scheme is that all inorganic water-soluble fertilizers (CK) are applied at 66 Kg/mu; 100% of inorganic water-soluble fertilizer and bio-based sulfonate (treatment 1), and the application amount is 66 Kg/mu of inorganic fertilizer and 40 Kg/mu of bio-based sulfonate; 70% of inorganic water-soluble fertilizer + bio-based sulfonate (treatment 2), and the application amount is 46 Kg/mu of inorganic fertilizer +40 Kg/mu of bio-based sulfonate; the bio-based sulfonate product used therein was ammonium sunflower stalk sulfonate used according to the preparation examples.

The production comparison of the crops is as follows:

tomato plant height and stem thickness have no obvious difference, and good growth can be maintained by adding bio-based sulfonate on the basis of reducing the use amount of 30 percent of conventional fertilizer;

chlorophyll: treatment 1 with application of bio-based sulfonate is 10.89% -27.08% higher in chlorophyll content than CK treatment;

root length: the lengths of the treatment 1 and the treatment 2 are respectively 1.17 times and 1.80 times of the CK;

root surface area: the lengths of the roots of the treatment 1 and the treatment 2 are respectively increased by 13.84 percent and 48.93 percent compared with the length of the root of CK;

yield: compared with CK treatment yield of 4790 kg/mu and 1 treatment yield of 5015 kg/mu, the increase is 4.7 percent; the yield is 4812 kg/mu after 3 times of treatment, and is increased by 22 kg/mu;

quality: the Vc content of the fruit 1 treated by applying the bio-based sulfonate is 69.63mg/kg, which is increased by 7.97 percent compared with CK (64.9 mg/kg);

the plant height of the cucumber is obviously higher than CK all the time and is increased by 42 percent by applying the bio-based sulfonate to treat 1 plant on the basis of the conventional water soluble fertilizer.

Leaf area: the leaf area of the treated 1 plant is the largest and reaches 818cm²

Chlorophyll: chlorophyll content of treatment 1 and treatment 2 was significantly increased

Root length: the longest root of treatment 1 was 627mm, and the relative CK increased by 101mm

Yield: the cucumber yield of the treatment 1 is 5600 kg/mu at the highest, the cucumber yield is increased by 21.85% compared with the control (yield 4596 kg/mu), and the cucumber yield of the treatment 2 (yield 4770 kg/mu) is increased by 3.79% compared with the CK yield.

Quality: the soluble solid content of the treatments 1 and 2 is increased by 6.32 percent and 10.64 percent compared with the CK

The plant height and stem thickness of the pepper are not obviously different, and the addition of bio-based sulfonate on the basis of reducing the dosage of 30 percent of the conventional fertilizer can still well keep good growth;

leaf area: treatments 1, 2 did not significantly change leaf area;

yield: the fruit yield of the treated 1 reaches 4271.20 kg/mu, which is 1.34 times of that of the conventional fertilization treatment group, and the yield of the treated 2 is increased by 6.39 percent compared with CK.

Quality: after the treatment of the bio-based sulfonate, the Vc content of the treated 1 can reach 259.73mg/kg as high as 39.26 percent higher than that of CK; the nitrate content of the fruits is reduced by 3.95 percent and 11.64 percent respectively in the treatment 1 and the treatment 2 compared with the CK; compared with CK, the soluble solid content of the treatment 1 and the treatment 2 is obviously increased by 14.55 percent and 10.91 percent respectively, and tests show that the use of the bio-based sulfonate can increase the nutritional content of the fruits.

Example 13: weight-reducing and yield-increasing field application

The ammonium sunflower stalk sulfonate produced in the preparation examples is applied to the grape base of Mengjin flatstem milkvetch ecological engineering Limited liability company in 2016, the dry matter content of the used ammonium sunflower stalk sulfonate is 50%, the dosage per mu is 30kg per mu in terms of solid content, the comparative fertilizer is an Israel imported amino acid fertilizer, and the dosage per mu is 30kg in terms of solid content. Meanwhile, tea planting verification is carried out on Fujian south-Ping Wuyi mountain in 2018, the dry matter content of the sunflower stalk ammonium sulfonate produced in the preparation example is 50%, the dosage per mu is 30 kg/mu in terms of solid content, and the comparative fertilizer is a honeysuckle-radix salviae miltiorrhizae mixed fertilizer and an amino acid BB fertilizer. The sunflower stalk ammonium sulfonate fertilizer is increased by 4-11.2% compared with the tea of the reference fertilizer. Comparative planting data for grapes are shown in table 15:

TABLE 15 Effect of Bio-based sulfonate fertilizers and imported inorganic fertilizers on grape and wine quality

Example 14: influence of different bio-based sulfonates on soil characteristics, ecology and crop yield

The ammonium sunflower stalk sulfonate and the calcium sunflower stalk sulfonate produced in the preparation example and the mixture of the ammonium sunflower stalk sulfonate and the calcium sunflower stalk sulfonate in the weight ratio of 1:1 are respectively measured, the crusting water permeability, the crusting water retention property, the compressive strength, the wind erosion resistance, the ultraviolet aging resistance and the freezing and thawing performance of the mixture on sandy soil are compared, different performances are tested under the same addition amount of the bio-based sulfonate, and the verification proves that the performance of the mixture of the ammonium sunflower stalk sulfonate and the calcium sunflower stalk sulfonate is superior to that of the mono-component bio-based sulfonate. Specific data are shown in table 16:

TABLE 16 influence of different components of bio-based sulfonates on soil properties and ecology

Claims

Use of a composition comprising a bio-based sulphonic acid and sulphate monoester or salt species, the composition being one or more of a bio-based sulphonic acid, a bio-based sulphate monoester, a bio-based sulphonate and a bio-based sulphate monoester salt, to support plant growth nutrition, and/or to act as a biological growth substrate, and/or to provide plant or microbial nutrition and biomass energy, and/or to slow the release of plant nutrients, and/or to promote the absorption of nutrient elements by plants, and/or to enhance the quality of plants or microorganisms, and/or to improve the plant or microorganism growth environment.
Use according to claim 1, characterized in that the growth environment is a solid growth environment or a liquid growth environment, or a mixed solid and liquid growth environment; preferably, the solid growth environment is soil, preferably, the solid growth environment is sandy soil or desert, and preferably, the solid growth environment is saline-alkali soil or saline-alkali soil.
The use according to claim 2, wherein when the solid growth environment is sandy soil or desert, the use is that the composition can achieve one or more of the effects of crusting on sandy soil or desert, weathering resistance, aging resistance, pressure resistance, freeze-thaw resistance, and improving the microbial survival environment; preferably, the application also comprises one or more of the effects of realizing the skinning, sand fixation, water retention and fertilizer retention, improving the living environment of microorganisms, providing and promoting nutrient element absorption, slowly releasing plant nutrient components, helping to dissolve and complex nutrient components in sandy soil or desert, ion exchange, pH reduction and salt concentration reduction of sandy soil or desert by the composition; preferably, the composition is used for improving the drought resistance, growth promotion capability and plant quality of sandy soil or desert plants; preferably, the composition also has the effects of solidifying sand, retaining water and fertilizer, improving the living environment of microorganisms and providing and promoting the absorption of nutrient elements on the flowing desert.
The use according to claim 2, when the solid growth environment is a saline-alkali soil or a saline-alkali land, the use is one or more of the effects of reducing salt concentration, pH, and improving the living environment of microorganisms on the saline-alkali soil or the saline-alkali land; preferably, the application also comprises one or more of the functions of realizing ion exchange, neutralization, water retention, skinning, soil aggregate structure formation, soil air permeability improvement, plant and microorganism nutrition providing, plant nutrient element absorption promoting, plant nutrient component slow release and dissolving and complexing of nutrient components in saline-alkali soil or saline-alkali soil by the composition; preferably, the application also comprises that the composition is used for improving the saline-alkali resistance, drought resistance and growth promotion capability of saline-alkali soil or saline-alkali land plants and improving the quality of the plants; preferably, the application also comprises the effects of reducing the salt concentration, reducing the pH, improving the living environment of microorganisms and providing and promoting the absorption of nutrient elements on saline-alkali soil or saline-alkali soil.
Use according to any one of claims 1 to 4, characterised in that the weight of the bio-based sulphonic acid and sulphate mono-ester or salt forms is between 1% and 99.99% by weight of the composition; preferably, the weight of the bio-based sulfonic acid and the sulfuric acid monoester or salt substance in the composition accounts for 10-80% of the weight of the composition, and preferably, the weight of the bio-based sulfonic acid and the sulfuric acid monoester or salt substance in the composition accounts for 20-60% of the weight of the composition.
Use according to any one of claims 1 to 4, characterized in that the bio-based sulfonic acid or mono-ester of bio-based sulfuric acid or salt thereof is a substance in which the hydroxyl and aryl groups in the molecule of cellulose, hemicellulose, starch, humic acid, chitin and derivatives thereof in the biomaterial are linked to sulfonyl functional groups, the bio-based sulfonate or mono-ester of bio-based sulfuric acid is neutralized by a base, the hydrogen ions are replaced by metal ions or ammonium ions; preferably, the metal ion is potassium or calcium ion; preferably, the sulfur content in the bio-based sulfonic acid and the sulfuric acid monoester or salt substance is more than or equal to 1 percent by weight; preferably, the multifunctional bio-based sulfonate has an average molecular weight of ten thousand or more, and the higher the molecular weight, the better the water retention and skinning or film forming effects.
Use according to claim 6, characterized in that the biological material is a plant material or an animal material; preferably, the plant material is one or more of crop straws, reeds, salix mongolica, caragana microphylla, starch, coal slime, jujube branches, energy grass, sorghum sudanese, pennisetum hydridum, forest tree resources and processing residues thereof, and preferably, the material is one or more of sunflower straws, shrimp shells and crab shells.
Use according to any one of claims 1 to 4, characterized in that the composition further comprises one or more of a carrier or an additive, the carrier being one or more of water, humic acid, fiber, fertilizer, fly ash, coal slurry, gasifier slag, ground phosphate rock and straw pulverizate, the additive being one or more of a fertilizer, a pesticide, a lignin salt, a lignin sulfonate and a microorganism; the total weight of the carrier and the additive accounts for 0.001-99.9% of the weight of the composition; preferably, the total weight of the carrier and the additive accounts for 0.01-99% of the weight of the composition; preferably, the total weight of the carrier and the additive except the pesticide accounts for 20-90% of the weight of the composition.
The use according to claim 1, characterized in that the bio-based sulfonic acid and sulfate monoester or salt substance is cellulose sulfate monoester, cellulose sulfate monoester salt, hemicellulose sulfate monoester salt, starch sulfate, chitin sulfate monoester salt, and one or more of humic acid sulfonic acid and humic acid sulfonate, preferably, the bio-based sulfonic acid and sulfate monoester or salt substance is bio-based sulfonate and salt mixture prepared by sulfur trioxide sulfonation.
Use according to claim 2, characterized in that the composition is used in an amount of 1kg to 100000 kg/acre, preferably 10kg to 10000 kg/acre, for improving the growing environment of plants or microorganisms.
A conditioner for improving the growth environment of plants or microorganisms, which comprises bio-based sulfonic acid and sulfuric acid monoester or salt substances, wherein the weight sum of the bio-based sulfonic acid and the sulfuric acid monoester or salt substances accounts for 1-99.99% of the weight ratio of the conditioner, preferably, the weight sum of the bio-based sulfonic acid and the sulfuric acid monoester or salt substances in the conditioner accounts for 10-80% of the weight ratio of the conditioner, preferably, the weight sum of the bio-based sulfonic acid and the sulfuric acid monoester or salt substances in the composition accounts for 20-60% of the weight ratio of the composition, preferably, the bio-based sulfonic acid and the sulfuric acid monoester or salt substances are one or more of bio-based sulfonic acid, bio-based sulfuric acid monoester, bio-based sulfonic acid salt and bio-based sulfuric monoester salt, preferably, the bio-based sulfonic acid or bio-based sulfuric monoester is cellulose, sulfuric acid monoester salt and bio-based sulfuric monoester salt in biological materials, Hydroxyl and aryl in molecules of hemicellulose, starch, humic acid, chitin and derivatives thereof are connected with sulfonyl functional groups, and the bio-based sulfonate or bio-based sulfuric acid monoester salt is a compound formed by combining sulfonate ions in bio-based sulfonic acid or bio-based sulfuric acid monoester with metal ions or ammonium ions required by plants.
The conditioner according to claim 11, wherein the conditioner further comprises one or two of a carrier and an additive, the carrier is one or more of water, humic acid, fiber (unbleached pulp, waste paper pulp), sulfonation reaction residue, fertilizer, feces, fly ash, coal slurry, gasification furnace slag, ground phosphate rock and straw crushed material, and the additive is one or more of fertilizer, pesticide, lignin salt, lignosulfonate and microorganism; the total weight of the carrier and the additive accounts for 0.001-99.9% of the weight of the composition; preferably, the total weight of the carrier and the additive accounts for 0.01-99% of the weight of the composition; preferably, the total weight of the carrier and the additive except the pesticide accounts for 20-90% of the weight of the composition.
The conditioner according to claim 11, characterized in that the biological material is a plant material or an animal material, the plant material is one or more of crop straw, reed, salix mongolica, caragana microphylla, coal slime, starch, jujube branches, energy grass, sorghum grass, sudan grass, Jujun grass, forest and wood resources and animal and plant processing residues, the animal material is one or more of shrimp shell and crab shell, preferably, the bio-based sulfonic acid and the sulfate monoester or salt substance is one or more of cellulose sulfate monoester, cellulose sulfate monoester salt, hemicellulose sulfate monoester salt, starch sulfate monoester salt, chitin sulfate monoester, humic acid sulfonic acid and humic acid sulfonate, preferably, the bio-based sulfonic acid and sulfuric acid monoester or salt substance is a mixture of bio-based sulfonate and salt substance prepared by a sulfur trioxide sulfonation method.
Method of using the conditioner according to any of claims 11 to 13, characterized in that the conditioner is applied to plants or a microbial growth environment, or the conditioner is mixed with solid or liquid substances in the plant environment and then applied to the plant growth environment, or the conditioner is applied to plant foliage, preferably by spraying, spreading, drip irrigation, root application, ridge burying or pit burying, particularly preferably, the conditioner is applied in an amount of 1kg to 100000kg of conditioner per acre, preferably, the conditioner is applied in an amount of 1kg to 10000kg of conditioner per acre.