WO2019154346A1 - 生物基磺酸盐作为营养源和调理剂的用途 - Google Patents

生物基磺酸盐作为营养源和调理剂的用途 Download PDF

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WO2019154346A1
WO2019154346A1 PCT/CN2019/074536 CN2019074536W WO2019154346A1 WO 2019154346 A1 WO2019154346 A1 WO 2019154346A1 CN 2019074536 W CN2019074536 W CN 2019074536W WO 2019154346 A1 WO2019154346 A1 WO 2019154346A1
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bio
salt
plant
monoester
composition
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English (en)
French (fr)
Inventor
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
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TH-UNIS INSIGHT Co Ltd
Xiamen University
Ningxia University
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TH-UNIS INSIGHT Co Ltd
Xiamen University
Ningxia University
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Priority to CN201980007000.5A priority Critical patent/CN111587282A/zh
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K17/00—Soil-conditioning materials or soil-stabilising materials
    • C09K17/14—Soil-conditioning materials or soil-stabilising materials containing organic compounds only
    • C09K17/18—Prepolymers; Macromolecular compounds
    • C09K17/32—Prepolymers; Macromolecular compounds of natural origin, e.g. cellulosic materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
    • Y02A40/22—Improving land use; Improving water use or availability; Controlling erosion

Definitions

  • the invention belongs to the field of protection and application of bio-based sulfonate compositions, and particularly relates to the use of bio-based sulfonates as nutrient sources and conditioning agents, including applications for regulating plant and microbial growth environments.
  • the existing desertified land area of the world is 36 million square kilometers, accounting for one quarter of the global land area.
  • Sandstorms, droughts and soil erosion are severe in the world, and natural disasters are frequent.
  • Desertification areas are also the areas with the most ecologically fragile and socially economically backward areas. Therefore, sand control and sand control work is important for maintaining regional ecological functions and sustainable economic and social development. Global significance.
  • saline-alkali soil The area of global saline soil (saline-alkali soil) is 95.6 million square kilometers. Soil salinization treatment can not always be effective for a single measure. It must be adapted to local conditions. It should be comprehensively controlled by water conservancy, physics, chemistry, biology and other measures. Water conservancy engineering technology is the foundation and soil improvement is the key and reasonable use is difficult.
  • Biomass resources such as cellulose, lignin, chitin, humic acid, protein, oil and fat are the most abundant and widely distributed, the most cost-effective and most degradable renewable biomass resources on the earth, accounting for the carbon content of the plant community. More than 60% of the plants produce about 1.5 x 10 12 tons of fiber per year through photosynthesis.
  • Biomass is the most basic raw material for development and application potential. China produces a large amount of biomass waste of about 5 billion tons of crop straw, animal husbandry, forestry and processing industry. At present, the method of directly returning straw or converting into organic fertilizer to return to the field has the problems of refractory degradation, large dosage, low utilization of crops, and most of the consumption by microorganisms. The development and utilization of good plants, especially straw resources, to solve the water-soluble problem of plant resources is the focus of soil remediation and conditioning.
  • the present invention provides a composition comprising a bio-based sulfonic acid and a sulfuric acid monoester or a salt substance which can well solve the above series of problems.
  • the compositions proposed by the present invention are used to support plant growth nutrition, and/or as a biological growth substrate, and/or to provide plant or microbial nutrient and biomass energy, and/or to slow release plant nutrients, and/or to promote plant nutrition Absorption of elements, and/or improvement of plant or microbial quality, and/or improvement of plant or microbial growth environment, said bio-based sulfonic acid and sulfate monoester or salt substance being bio-based sulfonic acid, bio-based sulfuric acid monoester, biological One or more of a sulfonate and a bio-based sulfate monoester.
  • the organism is a plant or a microorganism.
  • the composition is used for supporting plant growth nutrition, as a biological growth substrate, providing plant or microbial nutrition and biomass energy, slow release of plant nutrients, promoting plant nutrient absorption, Improve plant or microbial quality and improve the environment in which plants or microorganisms grow.
  • the growth substrate of the present invention is a biologically grown liquid or solid support and nutrient supply.
  • the growth substrate does not comprise a natural growth substrate such as sand, soil and water, and the bio-based sulfonic acid of the present invention
  • the composition of the sulfate monoester or the salt material as a growth substrate can simultaneously contain nutrients which are beneficial to biological growth, such as fertilizers, or add pesticide components which are beneficial to biological disease prevention and treatment, insect pest control, or addition of regulatory organisms. Regulatory components of growth, etc., but do not include conventional soils grown by sand, saline-alkali soils, and other organisms.
  • the growth environment is a solid growth environment or a liquid growth environment, or a growth environment in which solid and liquid are mixed; preferably, the solid growth environment is soil; preferably, the solid growth environment is sand. Soil or desert, preferably, the solid growth environment is saline soil or saline soil.
  • the growth environment refers to a solid or liquid environment to which the biological growth needs to be attached, such as a soil environment to which the root system is attached during the growth of the plant, a water environment, etc., for example, a medium to which the microorganism grows, etc., specifically, The nutrient groups and the like to which the edible fungus grows are all in the growth environment of the present invention.
  • the growth environment is sandy soil or desert, or saline-alkali soil or saline-alkali land.
  • the sandy soil generally means that the weight of the soil containing small particles of sand is more than 30% by weight of the soil.
  • the desert refers to the majority or all of the surface being sand.
  • the saline-alkali soil includes salt land and alkali land.
  • the salt soil refers to the soil salt weight and the soil weight ratio exceeding 0.05%
  • the alkaline soil refers to the soil pH greater than 7; the saline soil has a soil salt content greater than one thousandth.
  • the soil is alkaline, the organic matter content of the saline-alkaline soil is small, the soil fertility is low, the physical and chemical properties are poor, and the crops are difficult to grow.
  • the composition when the solid growth environment is sandy soil or desert, the composition can achieve skinning, wind erosion resistance, aging resistance, compression resistance, freeze-thaw resistance to sandy soil or desert. And improving the effect of one or more of the living environment of the microorganism; preferably, the use further comprises the composition realizing the skin fixation and sand fixation of the sandy soil or the desert, protecting the water and ensuring the fertilizer, improving the living environment of the microorganism, providing and promoting nutrition.
  • Element absorption sustained release of plant nutrients, assisting in complexing nutrients in sandy soil or desert, one or more of ion exchange, lowering pH, lowering salt concentration; preferably, the use also includes combination
  • the composition also realizes the skin-fixing, water-retaining and fertilizer-preserving, improving the microbial living environment, providing and promoting the mobile desert The role of nutrient absorption.
  • the use of the improved sandy soil or desert wherein the crust is applied to the sandy soil or the desert to form a consolidated layer on the surface of the sandy soil or desert, including the composition itself forming a consolidation layer and
  • the cohesive layer of the composition is cohesively bonded to the sand, and the effect of the crust includes the effect of sand fixation and water retention;
  • the application of the sand to the sandy soil or the desert can prevent the sandy soil or The flow of the desert due to the action of wind;
  • the application of the composition to the sandy soil or desert after the wind erosion resistance can make the sand or gravel of the sandy soil or desert difficult to be lost from the sandy soil or the desert surface under strong wind conditions;
  • Anti-aging After applying the composition to sandy soil or desert, it can exert its effects of sand fixation, skinning and compression on the surface of sandy soil or desert for a long time; the compressive composition is applied to sandy soil or desert.
  • the surface of the sandy soil or desert can then withstand the pressure from the upper or lower part without damage; the freeze-thaw resistance refers to the application of the composition in sandy soil or desert.
  • the surface of the soil or desert is not ruptured or damaged in a large area when it is frozen at a low temperature; the improvement of the living environment of the microorganism means that the application of the composition changes the adverse conditions such as lack of nutrition and water shortage in the desert, and can better maintain the growth of microorganisms. .
  • the use when the solid growth environment is a saline-alkali soil or a saline-alkali land, is a composition to achieve a salt-alkali soil or a saline-alkali soil salt concentration, pH, and a microbial environment. Or a plurality of effects; preferably, the use further comprises the composition to achieve ion exchange, neutralization, water retention, skinning, formation of soil aggregate structure to improve soil permeability, and provide plant and microbial nutrition to saline-alkali soil or saline-alkali soil.
  • the use also includes the composition to improve the salt-tolerance, drought-resistance, growth-promoting and plant quality of the saline-alkali soil or saline-alkali plants; preferably, the use further comprises the composition realizing the saline-alkali soil or the saline-alkali soil. Reduce salt concentration, lower pH, improve microbial living environment, and provide and promote the absorption of nutrients.
  • the anion and cation in the soil or saline-alkaline soil can be exchanged with the anion and cation in the composition to lower the salt.
  • the neutralization effect shown is the added composition or hydrolysis or oxidation to produce an acidic component that neutralizes the alkali in the soil;
  • the water retention is the composition itself It has the functions of absorbing water, drowning, inhibiting evaporation of water and preventing upward migration and transpiration of water in saline-alkaline soil or saline-alkali soil;
  • the skin can be made into saline-alkaline soil or saline-alkali soil by applying the composition to saline-alkali soil or saline-alkali soil.
  • the surface forms a consolidation layer, comprising a consolidation layer formed by the composition itself forming a consolidation layer and a cohesive bonded soil of the composition; the formation of the soil agglomerate structure improves the soil permeability for the soil formation after the composition is added
  • the agglomerate structure of the particles is beneficial to improve the permeability of the soil;
  • the nutrient supply of the plant and microorganisms is saline soil or After the composition is applied saline-alkali, the composition can provide the nutrients required for the roots or stems of the crop and the nutrients required for the associated symbiotic microorganisms; after the sustained-release plant nutrient is applied to the saline-alkaline soil or the saline-alkali soil, not only the composition, but also the composition
  • the nutrients contained in the nutrients can be slowly released for plant absorption, and the insoluble nutrients in the soil can be dissolved by the complexation and solubilization to ensure the nutrition of the plants.
  • the weight ratio of the bio-based sulfonic acid and the sulfuric acid monoester or salt material to the composition is from 1% to 99.99%; preferably, the composition is bio-based sulfonate.
  • the weight ratio of the acid and the sulfuric acid monoester or the salt substance to the composition is 10% to 80%, preferably, the weight of the bio-sulfonic acid and the sulfuric acid monoester or the salt substance in the composition accounts for the weight of the composition. The ratio is 20% to 60%.
  • the bio-based sulfonic acid or bio-based sulfuric acid monoester or a salt thereof is a cellulose, hemicellulose, starch, humic acid, chitin and a derivative thereof in the biological material.
  • a substance in which a hydroxy group or an aryl group is bonded to a sulfonyl group, the bio-based sulfonate or a bio-based sulfate monoester is a bio-sulfonic acid or a bio-based sulfuric acid monoester neutralized with a base, and the hydrogen ion is ionized by a metal ion or an ammonium Ion substitution
  • the metal ion is one of K + , Ca 2+ , Na + , Mg 2+ , Fe 2+ , Fe 3+ , Mn 2+ , Zn 2+ , Cu 2+ , Mo 6+ , Ni + Or a variety.
  • the metal ion is K + or Ca 2+ .
  • the bio-sulfonic acid and the sulfuric acid monoester or salt substance have a sulfur content of 1% by weight or more.
  • the sulfur content is measured by weighing a certain amount of the product into a regenerated cellulose dialysis bag with a molecular weight cut off (MW) of 200, placing it in deionized water, dialysis for 3 to 4 days, changing water for 6 to 8 times, and dialysis products. After drying at 60 ° C, the content of C, H, N, S and other elements in the dialysis powder was quantitatively analyzed by an elemental analyzer.
  • the average molecular weight of the multifunctional bio-sulfonate is 10,000 or more, and the larger the molecular weight, the better the water-retaining crust or film-forming effect.
  • the biological material is a plant material or an animal material; preferably, the plant material is crop straw, reed, sand willow, caragana, starch, slime, jujube, energy grass One or more of the high dans, the sudan grass, the giant grass, the forest resources and the processing residue thereof.
  • the material is one or more of sunflower stalk, shrimp shell and crab shell.
  • 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.
  • the composition further comprises one or more of a carrier or an additive, the carrier being water, humic acid, fiber, fertilizer, fly ash, slime, gasification One or more of slag, phosphate rock and straw smash, the additive being one or more of a fertilizer, a pesticide, a lignin salt, a lignosulfonate and a microorganism.
  • a carrier or an additive the carrier being water, humic acid, fiber, fertilizer, fly ash, slime, gasification One or more of slag, phosphate rock and straw smash
  • the additive being one or more of a fertilizer, a pesticide, a lignin salt, a lignosulfonate and a microorganism.
  • the total weight of the carrier and the additive is from 0.001 to 99.9% by weight of the composition; preferably, the total weight of the carrier and the additive is 0.01 to 99% by weight of the composition.
  • the total weight of the carrier and the additive other than the pesticide is from 20 to 90% by weight based on the weight of the composition.
  • the bio-based sulfonic acid and the sulfuric acid monoester or salt substance are cellulose sulfate monoester, cellulose sulfate monoester salt, hemicellulose sulfuric acid monoester, hemicellulose sulfuric acid single a combination of one or more of an ester salt, a starch sulfate, a starch sulfate, a chitin sulfate monoester, a chitin sulfate monoester salt, a humic acid sulfonic acid, and a humic acid sulfonate, preferably,
  • the bio-based sulfonic acid and the sulfuric acid monoester or salt substance are bio-based sulfonates and salts prepared by the sulfur trioxide sulfonation method.
  • the amount of the composition used when the plant or microorganism growth environment is improved, is from 1 kg to 100,000 kg/mu, preferably, the amount of the composition used is from 1 kg to 10,000 kg/mu, preferably, the composition The amount used is from 10kg to 1000kg/mu.
  • the invention also provides a conditioning agent for improving the growth environment of a plant or a microorganism, the conditioning agent comprising a bio-based sulfonic acid and a sulfuric acid monoester or a salt substance, the bio-based sulfonic acid and a sulfuric acid monoester or a salt
  • the conditioning agent comprising a bio-based sulfonic acid and a sulfuric acid monoester or a salt substance, the bio-based sulfonic acid and a sulfuric acid monoester or a salt
  • the sum of the weights of the substances is from 1% to 99.99% by weight of the conditioning agent.
  • the sum of the weight of the bio-based sulfonic acid and the sulfuric acid monoester or the salt-based substance is preferably from 10% to 80% by weight of the conditioning agent.
  • the bio-based The weight ratio of the sulfonic acid and the sulfuric acid monoester or salt to the composition is from 20% to 60% by weight.
  • the bio-based sulfonic acid and the sulfuric acid monoester or salt are one of bio-sulfonic acid, bio-based sulfuric acid monoester, bio-based sulfonate and bio-based sulfuric acid monoester salt. Or a variety.
  • the bio-based sulfonic acid and the sulfuric acid monoester or salt substance are bio-based sulfonates and salts prepared by a sulfur trioxide sulfonation method.
  • the step of the sulfur trioxide sulfonation method comprises adding a solid or gaseous SO 3 to or into the cooled 1,2-dichloroethane to form an appropriate concentration (concentration range of 0.5 mol/L to 4 mol/ L, wherein 0.5 mol / L ⁇ 2 mol / L of SO 3 /1,2-dichloroethane solution is preferred, and then the biological material (such as: (microcrystalline) cellulose, hemicellulose, lignin, chitin , humic acid, starch, etc.) according to a ratio of biological material to sulfur trioxide (nU (glucose unit): nSO 3 is 1:0.2 ⁇ 6.4, preferably 1:0.2 ⁇ 3.2) into the reactor, at room temperature or At a lower temperature (not more than 35 ° C, preferably 23 to 32 ° C), the reaction is stirred for 0.5 to 20 hours (preferably 1 to 5 hours) to obtain a bio-based sulfonic
  • the bio-based sulfonic acid or the bio-based sulfuric acid monoester is a hydroxyl group or a aryl group in the molecules of cellulose, hemicellulose, starch, humic acid, chitin and derivatives thereof in the biological material.
  • bio-sulfonate or bio-based sulfate monoester salt being a metal ion or an ammonium ion required for a sulfonate ion in a bio-based sulfonic acid or a bio-based sulfuric acid monoester, and a plant such as calcium Combined compounds.
  • the metal ions are K + , Ca 2+ , Na + , Mg 2+ , Fe 2+ , Fe 3+ , Mn 2+ , Zn 2+ , Cu 2+ , Mo 6+ , Ni One or more of + .
  • the metal ion is K + or Ca 2+ .
  • the conditioning agent further comprises one or two kinds of carriers or additives, and the carrier is water, humic acid, fiber (natural color paste, waste paper pulp), sulfonation reaction residue, One or more of fertilizer, manure, fly ash, slime, gasifier slag, phosphate rock and straw smash, the additive being fertilizer, pesticide, lignin salt, lignosulfonate and microorganism One or more.
  • the carrier is water, humic acid, fiber (natural color paste, waste paper pulp), sulfonation reaction residue, One or more of fertilizer, manure, fly ash, slime, gasifier slag, phosphate rock and straw smash, the additive being fertilizer, pesticide, lignin salt, lignosulfonate and microorganism One or more.
  • the total weight of the carrier and the additive is from 0.001 to 99.9% by weight of the composition; preferably, the total weight of the carrier and the additive is from 0.01 to 99% by weight of the composition; preferably The total weight of the carrier and the additive other than the pesticide is from 20 to 90% by weight based on the weight of the composition.
  • the biological material is a plant material or an animal material
  • the plant material is crop straw, reed, sand willow, caragana, coal slime, starch, jujube, energy grass, high grass, One or more of the Sudan grass, the giant grass, the forest resources, and the residue of the animal and plant processing, preferably, the material is one or more of sunflower stalk, shrimp shell and crab shell.
  • the crop straw is one or more of corn stalk, soybean stalk, flax stalk, sorghum stalk, rice straw, wheat straw, peanut stalk, broad bean stalk, rape stalk, sunflower stalk, and the like.
  • It may be a direct sulfonation of the plant or animal material to neutralize the unseparated mixture, or may be a product which has been subjected to solid-liquid separation or bio-sulfonated product size molecules which are initially separated by solubility in a mixed solvent.
  • the bio-based sulfonic acid and the sulfuric acid monoester or salt substance are cellulose sulfate monoester, cellulose sulfate monoester salt, hemicellulose sulfuric acid monoester, hemicellulose sulfate monoester salt , macromolecules and partially degraded small molecules of one or more of starch sulfate, starch sulfate, chitin sulfate monoester, chitin sulfate monoester, humic acid sulfonic acid, humic acid sulfonate combination.
  • the present invention also provides a method for using the above conditioning agent, characterized in that the method is applied to a plant or a microbial growth environment, or the conditioning agent is mixed with a solid substance or a liquid substance in a plant environment and then applied to the plant. The environment is grown, or the conditioning agent is applied to the foliage of the plant.
  • the manner of application is spraying, spreading, drip irrigation, root application, burying or pit burying, and particularly preferably, the application amount of the conditioning agent is 1 kg to 100000 kg per acre.
  • the agent preferably, is applied in an amount of from 1 kg to 10,000 kg of conditioning agent per acre.
  • the invention also provides the use of a bio-based sulfonic acid substance for the preparation of a sand-fixing agent.
  • the invention also provides the use of a bio-based sulfonic acid and a sulfuric acid monoester or salt for the preparation of a soil conditioner.
  • bio-sulfonic acid and sulfuric acid monoester or salt substance and “bio-sulfonate” are broadly understood to include not only acids containing a sulfonic acid group and salts thereof, but also some Certain substances of "sulfate monoester” or “sulfate monoester salt”. As long as it is a bio-based sulfonic acid and a salt substance or a mixture of a substance obtained by sulfonation to obtain a hydroxyl group or an aryl group-bonded sulfonyl group in a molecule, it is a “bio-sulfonic acid and a sulfuric acid monoester or a salt substance". "Bio-sulfonate”, without being limited to its name.
  • the ratio between the substances is by weight unless otherwise stated.
  • the composition containing the bio-based sulfonic acid and the monoester or salt thereof has a large molecular weight, and has an average molecular weight of about 50 to 1,000,000. It has good adsorptivity and ion exchange properties, and the bio-based ammonium salt. Or calcium salt products can neutralize, adsorb and ion exchange the saline-alkaline soil and saline-alkali soil, effectively reduce the pH and salt ion concentration in the soil, and the salt ions in the soil are enriched and exchanged into the macromolecules, avoiding the roots of the plants. Impact.
  • bio-based sulfonic acid and sulfuric acid monoester or salt can form a shell-like or membranous crust layer with the soil or increase the agglomerate structure of the soil, further promoting water retention and water absorption, improving soil structure and humidity.
  • the same effect can reduce the porosity of the soil surface, block the capillary structure to reduce water evaporation, increase the compactness, and improve the mechanical properties.
  • composition comprising the bio-based sulfonic acid and the monoester or salt thereof of the invention has all the elements required for the plant, and the water-soluble polymer sulfonate as the basic nutrient base can not only be well supplemented. It fully satisfies the soil organic matter and all nutrients needed for rapid growth of plants and microorganisms. It can also reduce soil salinity by ion exchange, effectively bind sodium ions, significantly improve soil water retention and fertilizer retention capacity, and make soil loose and pores. Large degree, high surface temperature, improved soil moisture, physical properties and structure.
  • composition comprising the bio-based sulfonic acid and the monoester or salt thereof has good sand-fixing effect on sandy soil and desert, strong crust ability, strong wind erosion resistance, good aging resistance, pressure resistance and resistance High freezing and thawing ability, while retaining water, reducing pH, reducing salt concentration, ion exchange, providing plant nutrition, releasing plant nutrients, complexing sandy soil or desert nutrients and releasing to sandy soil and desert Multiple functions of nutrients.
  • composition comprising the bio-based sulfonic acid and the monoester or the salt thereof of the invention can achieve the effects of reducing the salt concentration, lowering the pH, improving the biological growth environment on the saline-alkali soil or the saline-alkali soil, and simultaneously realizing the saline-alkali soil.
  • ion exchange, neutralization, water retention, skinning, formation of soil aggregate structure to improve soil permeability, provide plant and microbial nutrition, promote plant nutrient absorption, slow release of plant nutrients, help dissolve complex saline soil or saline land The nutrients in the nutrients and the dissolution of nutrients that are difficult to dissolve.
  • Figure 1 Infrared spectrum of cellulose sulfate and chitin sulfate
  • Figure 2 Nuclear magnetic spectrum of cellulose sulfate and chitin sulfate
  • composition of the bio-based sulfonic acid and the sulfuric acid monoester salt used in the following preparation examples is purchased or made, wherein the purchased product is a commercially available calcium lignosulfonate having an average molecular weight of about 5,000, and the self-made product can be prepared according to the following method. Corresponding bio-sulfonic acid and sulfuric acid monoester salts.
  • the bio-sulfonic acid and sulfuric acid monoester salts are prepared by adding solid or gaseous SO 3 to or into the cooled 1,2-dichloroethane to form an appropriate concentration (concentration range 0.5 mol/L). ⁇ 4mol/L) SO 3 /1,2-dichloroethane solution, then biomaterials (eg: (microcrystalline) cellulose, hemicellulose, lignin, humic acid, starch, chitin, sunflower Straw, Sudan grass, corn stover and other straw fibers, etc.) are added to the reactor at a certain ratio of biological material to sulfur trioxide (nU (glucose unit): nSO 3 1:0.2 to 6.4) at room temperature or lower.
  • nU sulfur trioxide
  • bio-based sulfonic acid is obtained.
  • the bio-sulfonic acid reaction mixture is neutralized with a calcium hydroxide emulsion of 27-50 g/100 g of biomass raw material or ammonia water mixed with 12-20 g/100 g of biomass raw material or mixed to the end point pH value 7 ⁇ 8, the production of bio-based sulfonate, according to the different raw materials can be obtained cellulose sulfate monoester salt, hemicellulose sulfate monoester salt, starch sulfate monoester salt, chitin sulfate monoester salt, lignosulfonate An aqueous solution of humic acid sulfonate or a mixture thereof.
  • the layered, recovered and distilled organic solvent can be recycled, and the aqueous solution is filtered to remove the unreacted solid raw material, and concentrated by evaporation to obtain a bio-based sulfuric acid monoester salt aqueous solution having a concentration of about 50%.
  • the application effect evaluation can be directly performed.
  • the samples subjected to the analysis were treated as follows: a certain amount of aqueous product solution was taken, and dialysis bags were used for dialysis to remove small molecules and inorganic salts below 200, and the samples were dried for content and structural analysis.
  • the molecular weight determination method is: wide-angle static/dynamic synchronous laser light scattering analysis method: the bio-sulfonate sample is dissolved in a pure aqueous solution, and is respectively formulated into 0.002 g/mL, 0.004 g/mL, 0.006 g/mL, 0.008 g/ The diluted solution of mL, 0.01g/mL was filtered through a 0.45 ⁇ m sterile filter and then dropped into the sample bottle that had been dedusted. The ALV/CGS-3 wide-angle static/dynamic synchronous laser light scattering system was measured and measured.
  • the intensity of the scattered light converts the scattered light intensity to KC/ ⁇ R ⁇ (K is a constant, ⁇ R ⁇ is the excess Rayleigh factor), and the KC/ ⁇ R ⁇ is used for the bio-sulfonate concentration C.
  • K is a constant
  • ⁇ R ⁇ is the excess Rayleigh factor
  • KC/ ⁇ R ⁇ is used for the bio-sulfonate concentration C.
  • Debye curve, the reciprocal of the curve intercept is the molecular weight of the bio-based sulfonate.
  • the sulfur element content and the weight average molecular weight of the dried product were respectively measured, and infrared (IR) and 13 C nuclear magnetic resonance (NMR) analysis were performed. See Table 1 and Figures 1 and 2 for the relevant results.
  • Example 1 Water retention properties of bio-based sulfonates
  • the bio-sulfonates in the following examples are calculated according to the solid dry weight.
  • the bio-based sulfonate (the commercially available calcium lignin sulfonate or the commercially available ammonium lignin sulfonate mentioned in the examples is a commercially available brand BASF product, and the other bio-based sulfonate products mentioned are The product prepared in the preparation example) was dissolved in a total of 40 g of water, stirred uniformly, weighed, the initial weight of the conditioning agent was obtained, the daily moisture change was followed, the average water retention rate of the bio-sulfonate was measured, and the weight of the remaining water was measured every day.
  • the ratio of the remaining water volume to the total water volume is the water retention rate.
  • the average water retention rate of the self-made series of bio-based sulfonate products of various raw materials is higher than that of the blank and the commercially available calcium lignosulfonate.
  • Example 2 Crust properties of bio-based sulfonates
  • bio-based sulfonate the commercially available calcium lignosulfonate or the commercially available ammonium lignosulfonate mentioned in the examples
  • the salt is purchased from the commercial brand BASF products, the other mentioned bio-based sulfonate products are all prepared in the preparation process, and the volume is adjusted to 160mL, and then sprayed onto the sand surface with a sprayer, weighed, and the initial weight is obtained.
  • the moisture content changes every day until the water content of the sand sample approaches 0, and the thickness of the crust is measured.
  • the thickness of the crust is measured by spraying the aqueous solution onto the surface of the desert, measuring it after drying with an aqueous solution to form a solid, and taking an average of 5 points per square meter, and then calculating the average value to start the measurement after forming the solid. Recorded as the initial measurement of the thickness of the crust. After one month after the initial measurement, the measurement is performed again. The measurement method is also an average of 5 points per square meter, and then the average value is calculated.
  • the self-made series of bio-based sulfonate products of various raw materials are thicker than the commercially available calcium lignosulfonate.
  • bio-based sulfonate the commercially available calcium lignosulfonate or the commercially available ammonium lignosulfonate mentioned in the examples
  • the salt is purchased from the commercial brand BASF products, the other mentioned bio-based sulfonate products are all prepared in the preparation process, stirred evenly, weighed, the initial weight is obtained, dried, and the sand column is measured by a pressure tester. Compressive strength, specific data participate in Table 5 below.
  • the crust-resistance performance of the self-made series of bio-based sulfonate products of various raw materials is superior to the commercially available calcium lignosulfonate.
  • Example 4 Crust resistance of freeze-thaw properties of bio-sulfonate
  • bio-based sulfonate the commercially available calcium lignosulfonate or the commercially available ammonium lignosulfonate mentioned in the examples
  • Salt is purchased from commercial brand BASF products
  • other bio-based sulfonate products are prepared in the preparation process, stirred evenly, weighed, obtained initial weight, dried, and frozen in a freezer (-18 °C) 12h, taken out and then placed outside (temperature 30-40 °C) for 12h, which is a cycle, 3 times, 7 freeze-thaw cycles, after drying, the compressive strength of the sand column is measured by a pressure tester. See Table 6 for the results.
  • the bio-based sulfonate (the commercially available calcium lignosulfonate or the commercially available ammonium lignosulfonate mentioned in the examples) at 100, 200, 400g/m 2 (folded).
  • the salt is purchased from the commercial brand BASF products, the other mentioned bio-based sulfonate products are all prepared in the preparation examples), stirred evenly, weighed, obtained the initial weight, dried, placed at 30cm under 40w UV lamp
  • the sealing conditions were continuously irradiated for 100 h and 200 h. After the end of the irradiation, the compressive strength of the sand column was measured by a pressure tester. The specific results are shown in Table 7 below.
  • the skin anti-ultraviolet aging properties of the self-made series of bio-based sulfonate products are relatively different, and the phenolic structure of lignin has good anti-aging properties.
  • the straw sulfonate prepared according to the preparation examples was sprayed to the surface of the desert at different dosages, and the wind erosion resistance was measured. The test was carried out when the angle between the test surface and the sand flow was 0 ° C. The specific results are as follows: Table 8.
  • Bio-based sulfonates are very resistant to wind erosion, and the more they are used, the stronger the ability to withstand wind erosion. As shown in Table 8, when the amount of the conditioning agent used is 60 g/m2, the seven-stage wind can be well protected; when the amount of the conditioning agent is 80 g/m2, the level 10 wind can be well protected.
  • Example 7 Significantly increase the number of nutrients and microorganisms
  • the straw sulfonate prepared in the preparation example (mainly sunflower stalk, corn stalk sulfonate) was selected, and the components were determined as follows: solid content 41%; fixed solid nutrient: all N 1%, K 2 O 0.7 %, organic matter 57%. Comparing the blank and carboxymethyl cellulose soil biological data before and after sunflower planting in the desert soil of the Wulanbu experimental area, the specific data are shown in Table 9:
  • the number of colonies in the bio-sulfonate-treated desert soil is 10-100 times higher than that of the carboxymethylcellulose-treated desert soil.
  • the soil calcium gluconate content (sucrose enzyme activity index) increased by 80%-140%, and 50-100Kg/mu sunflower stalk fiber sulfate was applied.
  • the soil fertility of the Ammonium Phosphate (35 kg) improver exceeds the efficacy of the modifier of 500-1000 Kg/mu.
  • the enzyme content of the catalase was increased by 2 times compared with the control group, which proved that the sunflower stalk fiber sulfate improver promoted the soil bioactivity and the effect.
  • the content of P 2 O 5 , Fe, Cu, Zn and other elements in the filtrate was determined by the corresponding national standard.
  • the experimental data show that the concentration of various nutrients in the soil/matrix of the sunflower sulphate sulfonate is sufficient to maintain the nutrient requirements of the plant, and can be used as an additive component of the controlled release fertilizer under the same amount of addition.
  • the acid-soluble ammonium salt has the same solubility for P, Fe, Ca, Mg, Zn and other elements as EDTA and citric acid.
  • the production cost of sunflower sulphate ammonium salt is much lower than that of EDTA and citric acid, and it requires a large amount of use.
  • the specific measurement data is shown in Table 11.
  • the bio-based sulfonate is selected (the control mentioned in the examples is conventional application of inorganic fertilizer, and the other bio-based sulfonate products used are all according to the products prepared in the preparation examples), and the solid content is 30 Kg/mu. It is used to plant trees with high-quality secondary eucalyptus trees.
  • the experimental site is the old solidification inspection line of Dongshe Village, Bushengbaoli Town, Bayanur City.
  • the fertilization method adopts pit application: firstly, the conditioning agent is laid on the bottom of the ditch (hole), or the slurry is poured into it to make it naturally formed, and the measurement results are shown in Table 12 below.
  • Example 9 Reducing the conductivity and pH of saline-alkali soil
  • the pH value has a direct impact on the growth and development of plants.
  • Water-soluble salts are an important attribute of saline-alkali soils and are limiting factors for growth.
  • Conductivity is an important parameter for the reaction of soil soluble salts.
  • Example 8 The test soil in Example 8 was tested for conductivity and pH. It can be seen from the following data that the soil pH value decreased by 0.4 on average after using the sunflower stalk fiber sulfate; the soil salt concentration (conductivity) decreased by 16%. Salt discharge and alkali reduction effect is remarkable.
  • the Ulan Bu and the field sand fixation test were carried out from May to October 2017.
  • the test scale was 20 mu.
  • the test was based on the preparation of the ammonium sulphate sulphate sulfonate prepared in the preparation examples for the consolidation of the sand-fixing material and the biological survival rate and growth. Significant results have been achieved.
  • the test crops include: giant grass, high grass, traditional grass check sand treatment as a control treatment, in which grass control group applied 50Kg fertilizer per acre; using sunflower sulphate ammonium sulfonate 25Kg+25Kg prepared in the preparation example Fertilizer, field trial began on May 8 and harvested on October 9.
  • the test results are shown in Tables 13 and 14.
  • the treatment of applied sunflower sulphate sulfonate can significantly promote the growth of forage grass.
  • the giant gram grass treated with ammonium sulphate sulfonate was applied.
  • the average stalk growth of the giant gram grass was the thickest, which was 26.1. Mm, the average plant height grew fastest, 195cm, the main shoots of the giant grasses sprouted long branches, more leaves, abundant leaf, high chlorophyll content, high photosynthesis products.
  • the average stem growth of the high-density grass was 26.1 mm, and the average plant height grew the fastest, 92 cm.
  • the long branches and leaves of the high-density grass sprouted after the growth of the high-density grass treated with the sunflower sulphate sulfonate. More, the amount of leaves is abundant, the chlorophyll content is the highest, and the products for photosynthesis are also high.
  • ammonium sulphate sulfonate can significantly promote the growth of pasture and improve the quality of pasture.
  • the crude fat content of giant grass, high danshen and sudangrass increased, and the crude fat content was 25.4%, 25.6%, and 16.2%, respectively.
  • the crude fat content is 0.1%, 3.8% and 4.5% higher than the crude fat content of the grass, the high grass and the Sudan grass.
  • the total sugar content of the plants After treatment with ammonium sulphate sulfonate, the total sugar content of the plants also increased.
  • the total sugar content of the giant grass and the high grass was 1.89% and 14.1%, respectively.
  • the total sugar content was 0.25% and 5.33% higher than the total sugar content of the giant grass and the high grass in the grass square.
  • the total carbohydrate content of the three herbage plants was only 74.7% higher than that of the high dandelion; the total carbohydrate of the high dancao was higher than that of the grass.
  • the total carbohydrate content of the grass is 26.9% higher.
  • the total carbohydrate content of the giant grass and the sudangrass did not increase the total carbohydrate compared to the grass square.
  • the calcium content in the plant increased, the calcium content of the giant grass was 3.04 g / kg; the calcium content of Sudan grass was 3.33 g / kg. They were higher than 0.06 g/kg and 0.41 g/kg of the calcium content of the giant grass and Sudan grass in the grass square, respectively.
  • ammonium sulphate sulfonate can significantly promote the growth and development of pasture and improve the quality and yield of pasture, as shown in Table 14.
  • Example 11 Promoting crop growth in a saline-alkali soil environment
  • the yield of corn treated with the sunflower sulphate sulfonate prepared in the preparation example was increased by 64 kg/mu compared with the conventional fertilization treatment, and the solid content of the bio-based sulfonate per acre was 30 kg, which increased the yield by 8%.
  • the application of bio-based sulfonate products decreased the ear weight and 1000-grain weight, but the total number of particles increased significantly.
  • the bio-based sulfonate was applied in the drip irrigation and fertilization of vegetables in the Helan County Horticultural Industrial Park in Ningxia in 2016.
  • the main crops were pepper, tomato and cucumber.
  • the comparative fertilizer uses Israel's imported water-soluble fertilizers such as Haifa Potassium, Magic Li and Bio-based Sulfonate.
  • the planting treatment schemes are all inorganic water-soluble fertilizers (CK), the application rate is 66Kg/mu; 100% inorganic water-soluble fertilizer + bio-sulfonate (treatment 1), the application rate is 66Kg/mu inorganic fertilizer + 40Kg/mu bio-based Sulfonate; 70% inorganic water-soluble fertilizer + bio-sulfonate (treatment 2), application rate 46Kg / mu inorganic fertilizer + 40Kg / mu bio-sulfonate; wherein the bio-sulfonate product used is prepared according to The sunflower sulphate sulfonate used in the examples.
  • CK inorganic water-soluble fertilizers
  • Chlorophyll Treatment with bio-sulfonate 1 was 10.89% to 27.08% higher than CK treatment;
  • Root length Treatment 1 and treatment 2 root lengths are 1.17 times and 1.80 times of CK, respectively;
  • Root surface area treatment 1 and treatment 2 root lengths increased by 13.84% and 48.93%, respectively, compared with CK;
  • Cucumber plant height The application of bio-based sulfonate treatment on the basis of conventional water-soluble fertilizer was consistently higher than that of CK, with a 42% increase.
  • Leaf area treated 1 plant with the largest leaf area, up to 818cm 2
  • Chlorophyll The chlorophyll content of treatment 1 and treatment 2 was significantly increased
  • Root length The root length of treatment 1 is 627mm, which is 101mm relative to CK.
  • Leaf area Treatments 1, 2 did not significantly change the leaf area
  • Example 13 Field application for weight loss and increased yield
  • the sunflower sulphate sulfonate produced in the preparation example was applied in drip irrigation and fertilization at the grape base of Jinshayuan Ecological Engineering Co., Ltd. in Inner Mongolia in 2016, and the sunflower sulphonate sulfonate used was 50% dry matter.
  • the dosage is 30kg/mu for the solid content
  • the comparative fertilizer is the amino acid fertilizer imported from Israel.
  • the amount of the solid is 30kg for the solid content.
  • the tea planting verification was carried out in Wuyishan, Nanping, Fujian, and the sunflower sulphate sulfonate produced in the example was prepared.
  • the dry matter content was 50%
  • the amount of arable was 30kg/mu of solid content
  • the comparative fertilizer was mixed with gold and silver beads. Fertilizer + amino acid BB fertilizer.
  • the sunflower stalk ammonium sulfonate fertilizer increased yield by 4 to 11.2% compared with the control fertilizer.
  • the comparative planting data of the grapes are shown in Table 15:
  • Example 14 Effects of different bio-based sulfonates on soil properties, ecology and crop yield
  • the sunflower stalk sulfonate sulfonate and the sunflower stalk sulfonate sulphate produced in the preparation examples were mixed according to the weight ratio of 1:1, and the crust permeability, crust water retention, compressive strength and resistance of the sand were determined.
  • Table 16 The specific data is shown in Table 16:

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Abstract

本发明涉及生物基磺酸盐作为营养源和调理剂的用途，本发明的包含生物基磺酸及硫酸单酯或盐类物质的组合物用于支持植物生长营养、和/或作为改良生物生长基质、和/或提供植物或微生物营养和生物质能、和/或缓释植物营养成分、和/或促进植物对营养元素的吸收、和/或提高植物或微生物品质、和/或改良植物或微生物生长环境的用途。包含生物基磺酸及硫酸单酯或盐类物质的组合物具有很好的吸附性和离子交换等性能，具有显著粘合性和保水性，改善土壤结构、湿度等作用，可降低土壤表面气孔率，阻断毛细结构减少水份蒸发、增加密实度，提高机械性能。

Description

生物基磺酸盐作为营养源和调理剂的用途 技术领域
本发明属于生物基磺酸盐组合物保护及应用领域，具体涉及生物基磺酸盐作为营养源和调理剂的用途，包括调节植物和微生物生长环境等应用。
背景技术
全球现有沙化土地面积3600万平方千米，占全球陆地面积的四分之一。全球范围内风沙、干旱和水土流失严重，自然灾害频繁,荒漠化地区也是生态环境最脆弱和社会经济发展最落后的地区，因此防沙治沙工作对维护区域生态功能和经济社会可持续发展具有重大全球性意义。
全球盐渍土(盐碱土)面积为9560万平方千米亿亩。土壤盐碱化治理往往不能单一措施一直有效，必须因地制宜，采用水利、物理、化学、生物等措施配套综合治理，其中水利工程技术是基础、土壤改良是关键、合理利用是难点。
目前国内外针对盐碱土壤改良技术主要有物理改良，如通过土地平整、深耕晒垄、及时松土等方法；水利改良技术，如灌排配套、灌水洗盐、地下排盐；化学改良，通过石膏、磷石膏、过磷酸钙、腐殖酸、泥炭、粗渣等；生物改良，种植水稻、种植耐盐植物、使用微生物菌肥等。以上各种盐碱地治理措施中，排水洗盐应用是基本方案，但存在耗水量大，工程投资大，实施成本高等系列难题。
纤维素、木质素、甲壳素、腐植酸、蛋白质、油脂等生物质资源是地球上最丰富、分布最广、获取成本最低廉、最易降解的可再生生物质资源，占植物界碳含量的60％以上，植物每年通过光合作用合成的纤维约有1.5×10 12吨。
由于转化利用技术瓶颈制约，仅有2.5％的纤维通过再生途径被利用。常用的草方格或沙障碍固沙技术功能单一，人工成本高，使用效果差无法大面积推广。应用石膏、磷石膏、过磷酸钙、秸秆、粉煤灰、腐殖酸等物质进行的盐碱地改良也由于其用量大排盐还主要靠水洗，每盐碱地亩地需要数吨改良剂和百吨以上的水，存在耗水量大、易返盐、土壤板结、生物生长困难、改造成本高，改造效果差等问题，也需要高效低成本的治理方案。
生物质是最有开发应用潜力的基础原料。中国每年产生的大量农作物秸秆、畜牧业、林业及其加工业的大量生物质废物约50亿吨。目前采用的秸秆直接还田或转化为有机肥还田的方法存在难降解、用量大，作物利用度低，绝大部分被微生物消耗的问题。开发利用好植物特别是秸秆资源，破解植物资源的水溶性难题是土壤修复和调理的重点。
发明内容
本发明提供了一种包含生物基磺酸及硫酸单酯或盐类物质的组合物可以很好破解上述系列难题。本发明提出的组合物用于支持植物生长营养、和/或作为生物生长基质、和/或提供植物或微生物营养和生物质能、和/或缓释植物营养成分、和/或促进植物对营养元素的吸收、和/或提高植物或微生物品质、和/或改良植物或微生物生长环境，所述生物基磺酸及硫酸单酯或盐类物质为生物基磺酸、生物基硫酸单酯、生物基磺酸盐和生物基硫酸单酯盐中的一种或多种。优选的，上述组合物的用途中，所述生物为植物或微生物。
优选的，上述组合物的用途中，所述组合物用于支持植物生长营养、作为生物生长基质、提供植物或微生物营养和生物质能、缓释植物营养成分、促进植物对营养元素的吸收、提高植物或微生物品质和改良植物或微生物生长环境。
本发明的生长基质是生物生长的液体或固体的支撑体和营养提供物，在本发明中，生长基质并不包含沙土、土壤和水等天然的生长基质，本发明的包含生物基磺酸及硫酸单酯或盐类物质的组合物作为生长基质的同时，可以同时包含有利于生物生长的营养物质，如肥料，或添加有利于生物防病治病防虫杀虫的农药成分、或添加调节生物生长的调节成分等，但是不包括沙土、盐碱土和其他生物生长的常规土壤。
优选的，上述组合物的用途中，所述生长环境为固体生长环境或液体生长环境，或为固体和液体混合的生长环境；优选的，固体生长环境为土壤；优选的，固体生长环境为沙质土壤或沙漠，优选的，固体生长环境为盐碱土壤地或盐碱地。
本发明中，所述生长环境是指生物生长所需要依附的固体或液体环境，例如植物生长过程中根系所依附的土壤环境，水体环境等，例如，微生物生长所依附的培养基等，具体，如可食用真菌生长所依附的营养基等，都属于本发明所述的生长环境。在本发明中只是优选生长环境为沙质土壤或沙漠，或盐碱土壤地或盐碱地。
所述沙质土壤一般是指土壤中含有小颗粒砂石的重量占土壤重量的30％以上。所述沙漠是指表面大部分或者是全部是沙。
所述盐碱土壤地包括盐土地和碱土地，盐土指土壤中含盐的重量和土壤的重量比超过0.05％，碱土指土壤的pH大于7的土壤；所述盐碱地土壤盐分大于千分之一，土壤呈碱性，盐碱土的有机质含量少，土壤肥力低，理化性状差，作物长苗难。
优选的，上述组合物的用途中，当固体生长环境为沙质土壤或沙漠时，所述组合物可实现对沙质土壤或沙漠的结皮、抗风蚀、耐老化、抗压、抗冻融、改善微生物生存环境中的一种或多种的作用；优选的，所述用途还包括组合物实现对沙质土壤或沙漠的结皮固沙、 保水保肥、改善微生物生存环境、提供和促进营养元素吸收，缓释植物营养成分，助溶络合沙质土壤或沙漠中的营养成分，离子交换、降低pH、降低盐浓度作用中的一种或多种；优选的，所述用途还包括组合物实现提高沙质土壤或沙漠植物的抗干旱能力、促生长能力和提高植物品质；优选的，还包括组合物实现对流动沙漠的结皮固沙、保水保肥、改善微生物生存环境、提供和促进营养元素吸收的作用。
上述改良沙质土壤或沙漠的用途，所述结皮为沙质土壤或沙漠施用了组合物后能够使得沙质土壤或沙漠的表面形成一层固结层，包括组合物自身形成固结层及组合物的粘结性粘结沙土后共同形成的固结层，所述的结皮的作用包括固沙保水的作用；所述固沙为沙质土壤或沙漠施用了组合物后能够防止沙质土壤或沙漠因风力作用产生的流动；所述抗风蚀为沙质土壤或沙漠施用了组合物后能够使得沙质土壤或沙漠在大风情况下沙尘或砂砾难从沙质土壤或沙漠表面流失；所述耐老化为沙质土壤或沙漠施用了组合物后能够在沙质土壤或沙漠的表面长时间发挥其固沙、结皮、抗压等作用；所述抗压为沙质土壤或沙漠施用了组合物后能够使沙质土壤或沙漠的表面能够承受来自于上部或下部的压力而不破损；所述抗冻融是指沙质土壤或沙漠施用了组合物后能够使得沙质土壤或沙漠的表面被低温冻结的情况下不会大面积破裂或损坏；所述改善微生物生存环境是指组合物的施用改变了沙漠缺乏营养、缺水等不利条件，可更好维持微生物生长。
优选的，上述组合物的用途中，当固体生长环境为盐碱土壤地或盐碱地时，所述用途为组合物实现对盐碱土壤地或盐碱地降低盐浓度、pH，改善微生物生存环境的一种或多种的作用；优选的，所述用途还包括组合物实现对盐碱土壤地或盐碱地的离子交换、中和、保水、结皮、形成土壤团粒结构改善土壤透气性，提供植物和微生物营养、促进植物营养元素吸收、缓释植物营养成分，助溶络合盐碱土壤或盐碱地中的营养成分，帮助难溶的营养元素的溶出的作用中的一种或多种；优选的，所述用途还包括组合物实现提高盐碱土壤地或盐碱地植物的抗盐碱能力、抗干旱能力、促生长能力和提高植物品质；优选的，所述用途还包括组合物实现对盐碱土壤或盐碱地的降低盐浓度、降低pH、改善微生物生存环境、提供和促进营养元素吸收的作用。
上述改良盐碱土壤地或盐碱地用途中，所述离子交换作用为盐碱土壤或盐碱地施用了组合物后，土壤或盐碱土中的阴阳离子能够和组合物中的阴阳离子进行交换，降低盐的有效浓度，减少了对于微生物和植物生长的不利影响的减少；所示中和作用为加入的组合物或水解或氧化产生为酸性组份可以中和土壤中的碱；所述保水为组合物自身具有吸水、囤水、抑制水分蒸发的作用并且能够防止盐碱土壤或盐碱地中的水分向上迁移和蒸腾；所述 结皮为盐碱土壤或盐碱地施用了组合物后能够使得盐碱土壤或盐碱地的表面形成固结层，包括组合物自身形成固结层和组合物的粘结性粘结土壤后共同形成的固结层；所述形成土壤团粒结构改善土壤透气性为组合物添加后土壤形成小颗粒的团粒结构，有利于改善土壤的透气性；所述提供植物和微生物营养为盐碱土壤或盐碱地施用了组合物后，组合物能够提供作物根部或茎叶部所需要的营养和相关共生微生物所需要的营养；所述缓释植物营养成分为盐碱土壤或盐碱地施用了组合物后，不但其含有的营养成分可缓慢释放供植物吸收，而且可通过络合助溶作用将土壤中难溶的营养成分溶出保证植物营养。
优选的，上述组合物的用途中，所述生物基磺酸及硫酸单酯或盐类物质的重量占组合物重量比为1％～99.99％；优选的，所述组合物中，生物基磺酸及硫酸单酯或盐类物质的重量占组合物重量比为10％～80％，优选的，所述组合物中，生物基磺酸及硫酸单酯或盐类物质的重量占组合物重量比为20％～60％。
优选的，上述组合物的用途中，所述生物基磺酸或生物基硫酸单酯或其盐为生物材料中的纤维素、半纤维素、淀粉、腐殖酸、甲壳素及其衍生物分子中羟基、芳基连接磺酰基官能团的物质，所述生物基磺酸盐或生物基硫酸单酯盐为生物基磺酸或生物基硫酸单酯被碱中和，氢离子被金属离子或铵根离子取代；
优选的，金属离子为K +、Ca 2+、Na +、Mg 2+、Fe 2+、Fe 3+、Mn 2+、Zn 2+、Cu 2+、Mo 6+、Ni +中的一种或多种。优选的，金属离子为K +或Ca 2+。
优选的，上述组合物的用途中，所述生物基磺酸及硫酸单酯或盐类物质中硫含量大于等于1％wt。硫含量测量方法为：称取一定量的产品置于截留分子量(MW)为200的再生纤维素透析袋中，放入去离子水中，透析3～4天，换水6～8次，透析产品于60℃下烘干，采用元素分析仪定量分析经过透析后的粉末中C、H、N、S等元素含量。
优选的，上述组合物的用途中，作为多功能生物基磺酸盐的平均分子量在一万以上，分子量越大，保水结皮或成膜效果越好。
优选的，上述组合物的用途中，所述生物材料为植物材料或动物材料；优选的，所述植物材料为作物秸秆、芦苇、沙柳、柠条、淀粉、煤泥、枣枝、能源草、高丹草、苏丹草、巨菌草、林木资源及其加工剩余物中的一种或多种，优选的，所述材料为葵花秆、虾壳和蟹壳中的一种或多种。优选的，作物秸秆为玉米秆、大豆秆、亚麻秆、高粱秆、水稻秸秆、小麦秸秆、花生干、蚕豆秆、油菜秆、葵花秆等中的一种或多种。
优选的，上述组合物的用途中，所述组合物中还包含载体或添加剂中的一种或多种，所述载体为水、腐植酸、纤维、肥料、粉煤灰、煤泥、气化炉渣、磷矿粉和秸秆粉碎物中 的一种或多种，所述添加剂为肥料、农药、木质素盐、木质素磺酸盐和微生物中的一种或多种。
优选的，上述组合物的用途中，所述载体和添加剂的总重量占组合物重量的百分比为0.001～99.9％；优选的，载体和添加剂的总重量占组合物重量的百分比为0.01～99％；优选的，载体和添加剂的除农药外总重量占组合物重量的百分比为20～90％。
优选的，上述组合物的用途中，所述生物基磺酸及硫酸单酯或盐类物质为纤维素硫酸单酯、纤维素硫酸单酯盐，半纤维素硫酸单酯、半纤维素硫酸单酯盐，淀粉硫酸酯、淀粉硫酸盐、甲壳素硫酸单酯、甲壳素硫酸单酯盐，腐殖酸磺酸和腐殖酸磺酸盐中的一种或多种的组合，优选的，所述生物基磺酸及硫酸单酯或盐类物质为通过三氧化硫磺化法制备得到的生物基磺酸盐及盐类物质。
优选的，上述组合物的用途中，改良植物或微生物生长环境时，组合物的使用量为1kg～100000kg/亩，优选的，组合物的使用量为1kg～10000kg/亩，优选的，组合物的使用量为10kg～1000kg/亩。
本发明还提供了一种用于改良植物或微生物生长环境的调理剂，所述调理剂包含生物基磺酸及硫酸单酯或盐类物质，所述生物基磺酸及硫酸单酯或盐类物质的重量之和占调理剂重量比为1％～99.99％。
优选的，上述调理剂中，所述生物基磺酸及硫酸单酯或盐类物质的重量之和占调理剂重量比优选为10％～80％，优选的，所述组合物中，生物基磺酸及硫酸单酯或盐类物质的重量占组合物重量比为20％～60％。
优选的，上述调理剂中，所述生物基磺酸及硫酸单酯或盐类物质为生物基磺酸、生物基硫酸单酯、生物基磺酸盐和生物基硫酸单酯盐中的一种或多种。优选的，所述生物基磺酸及硫酸单酯或盐类物质为通过三氧化硫磺化法制备得到的生物基磺酸盐及盐类物质。尤其优选的，所述三氧化硫磺化法的步骤为将固体或气体SO 3，加入或通入冷却的1，2-二氯乙烷中配成适量浓度(浓度范围0.5mol/L～4mol/L，其中优选0.5mol/L～2mol/L)的SO 3/1，2-二氯乙烷溶液，然后将生物材料(如：(微晶)纤维素、半纤维素、木质素、甲壳素、腐殖酸、淀粉等)按生物材料比三氧化硫一定比例下(nU(葡萄糖单元)∶nSO 3为1∶0.2～6.4，其中优选1∶0.2～3.2)加入反应器中，在室温或较低温度下(不超过35℃为宜，优选23～32℃)，搅拌反应0.5～20h(其中优选1～5h)后，即得到生物基磺酸。在生物基磺酸中加入一定量水后，与氨水或者氢氧化钙乳液混合中和至pH值7～8为终点，即得到纤维素硫酸铵/纤维素硫酸钙。优选的，上述调理剂中，所述生物基磺酸或生物基硫酸单酯 为生物材料中的纤维素、半纤维素、淀粉、腐殖酸、甲壳素及其衍生物分子中的羟基、芳基连接磺酰基官能团的物质，所述生物基磺酸盐或生物基硫酸单酯盐为生物基磺酸或生物基硫酸单酯中的磺酸根离子与钙等植物需要的金属离子或铵根离子结合的化合物。
优选的，上述调理剂中，金属离子为K +、Ca 2+、Na +、Mg 2+、Fe 2+、Fe 3+、Mn 2+、Zn 2+、Cu 2+、Mo 6+、Ni +中的一种或多种。优选的，金属离子为K +或Ca 2+。
优选的，上述调理剂中，所述调理剂中还包含载体或添加剂中的一种或两种，所述载体为水、腐植酸、纤维(本色浆、废纸浆)、磺化反应剩余物、肥料、粪便、粉煤灰、煤泥、气化炉渣、磷矿粉和秸秆粉碎物中的一种或多种，所述添加剂为肥料、农药、木质素盐、木质素磺酸盐和微生物中的一种或多种。
优选的，上述调理剂中，所述载体和添加剂的总重量占组合物重量的百分比为0.001～99.9％；优选的，载体和添加剂的总重量占组合物重量的百分比为0.01～99％；优选的，载体和添加剂除农药外的总重量占组合物重量的百分比为20～90％。
优选的，上述调理剂中，所述生物材料为植物材料或动物材料，所述植物材料为作物秸秆、芦苇、沙柳、柠条、煤泥、淀粉、枣枝、能源草、高丹草、苏丹草、巨菌草、林木资源及其动植物加工剩余物中的一种或多种，优选的，所述材料为葵花秆、虾壳和蟹壳中的一种或多种。优选的，作物秸秆为玉米秆、大豆秆、亚麻秆、高粱秆、水稻秸秆、小麦秸秆、花生秆、蚕豆秆、油菜秆、葵花秆等中的一种或多种。可以是植物或动物原料直接磺化中和未分离的混合物，也可以是进行了固液分离或生物基磺化产物的大小分子在混合溶剂中通过溶解度不同初步分离的产物。
优选的，上述调理剂中，所述生物基磺酸及硫酸单酯或盐类物质为纤维素硫酸单酯、纤维素硫酸单酯盐、半纤维素硫酸单酯、半纤维素硫酸单酯盐、淀粉硫酸酯、淀粉硫酸盐、甲壳素硫酸单酯、甲壳素硫酸单酯盐，腐殖酸磺酸、腐殖酸磺酸盐中的一种或多种的大分子及部分降解的小分子组合。
本发明还提供了上述调理剂的使用方法，其特征在于所述方法为将上述调理剂施用于植物或微生物生长环境，或者将调理剂与植物环境中的固体物质或液体物质混合后施用于植物生长环境，或者将调理剂施用于植物叶面。
优选的，上述调理剂中，所述施用的方式为喷施、撒施、滴灌、根施、垅埋或坑埋，尤其优选的，所述调理剂的施用量为每亩用1kg～100000kg调理剂，优选的，调理剂的施用量为每亩用1kg～10000kg调理剂。
本发明还提供了生物基磺酸类物质用于制备固沙剂的用途。
本发明还提供了生物基磺酸及硫酸单酯或盐类物质用于制备土壤调理剂的用途。
本发明的有益效果
在本发明中，“生物基磺酸及硫酸单酯或盐类物质”、“生物基磺酸盐”作广义理解，不仅包括含有磺酸基的酸及其盐类，也包括某些称为“硫酸单酯”或者“硫酸单酯盐”的某些物质。只要是生物质通过磺化制备得到分子中羟基、芳基连接磺酰基官能团的物质的生物基磺酸及盐类物质或混合物质，均属于“生物基磺酸及硫酸单酯或盐类物质”、“生物基磺酸盐”，而不拘泥于其名称。
在本发明中，如无其他说明，则物质之间的比例按重量比计。
在本发明中，如无其他说明，则所有操作均在室温、常压条件实施。
本发明的包含生物基磺酸及其单酯或盐类物质的组合物主要水溶性成份分子量大，平均约为50～100万，具有很好的吸附性和离子交换等性能，生物基铵盐或钙盐产品可对盐碱土壤和盐碱地产生中和、吸附和离子交换作用，有效降低土壤中的pH和盐离子浓度，土壤中的盐离子富集交换到大分子中，避免了对植物根系的影响。生物基磺酸及硫酸单酯或盐类物质的显著粘合性和保水性，使其与土壤形成壳状或膜状结皮层或增加土壤的团粒结构，进一步发挥保水吸水、改善土壤结构、湿度等作用，可降低土壤表面气孔率，阻断毛细结构减少水份蒸发、增加密实度，提高机械性能。
本发明的包含生物基磺酸及其单酯或盐类物质的组合物，自带含植物所需的全部元素，以水溶性高分子磺酸盐作为基本营养基不仅可以很好地补充了可完全满足植物和微生物快速生长需要的土壤有机质和全部营养成分，还可通过离子交换作用降低土壤盐碱度，有效束缚钠离子，显著提高土壤保水、保肥能力，可使土壤变得疏松，孔隙度大，表面温度高，土壤水分、物理性能和结构能得到改善。
本发明的包含生物基磺酸及其单酯或盐类物质的组合物对沙质土壤地和沙漠的固沙效果好、结皮能力强、抗风蚀能力强、耐老化好、抗压强、抗冻融能力高，同时对沙质土壤地和沙漠还具有保水、降低pH、降低盐浓度、离子交换、提供植物营养、缓释植物营养成分、络合沙质土壤或沙漠中的营养成分和释放营养成分的多种功能。
本发明的包含生物基磺酸及其单酯或盐类物质的组合物能够实现对盐碱土壤或盐碱地的降低盐浓度、降低pH、改善生物生长环境等效果，同时还能够实现对盐碱土壤或盐碱地的离子交换、中和、保水、结皮、形成土壤团粒结构改善土壤透气性，提供植物和微生物营养、促进植物营养元素吸收、缓释植物营养成分，助溶络合盐碱土壤或盐碱地中的营养成分、帮助难溶的营养元素的溶出等功能。
附图简要说明
图1:纤维素硫酸盐、甲壳素硫酸盐红外图谱
图2:纤维素硫酸盐、甲壳素硫酸盐核磁图谱
图3:淀粉硫酸单酯红外图谱
图4:淀粉硫酸单酯核磁图谱
图5:淀粉硫酸单酯不同含水量粘度图谱
图6：纤维素硫酸盐结皮效果
具体实施方式
下面制备实施例中所用的生物基磺酸及硫酸单酯盐类物质的组合物为购买或自制，其中购买产品为市售木质素磺酸钙平均分子量5000左右，自制产品按照以下方法可制备得到对应的生物基磺酸及硫酸单酯盐类物质。
制备实施例
生物基磺酸及硫酸单酯类盐类物质的制备方法为：将固体或气体SO 3，加入或通入冷却的1，2-二氯乙烷中配成适量浓度(浓度范围0.5mol/L～4mol/L)的SO 3/1，2-二氯乙烷溶液，然后将生物材料(如：(微晶)纤维素、半纤维素、木质素、腐殖酸、淀粉、甲壳素，葵花秆、苏丹草、玉米秸秆等秸秆纤维等)按生物材料比三氧化硫一定比例下(nU(葡萄糖单元)∶nSO 3为1∶0.2～6.4)加入反应器中，在室温或较低温度下(不超过35℃为宜)，搅拌反应1-5h(其中优选1～5h)后，即得到生物基磺酸。将生物基磺酸反应混合物与折百用量为27-50g/100g生物质原料的氢氧化钙乳液或需要量为12-20g/100g生物质原料的氨水或混合中和反应至终点pH值7～8，即制得生物基磺酸盐，根据原料的不同可以得到纤维素硫酸单酯盐、半纤维素硫酸单酯盐、淀粉硫酸单酯盐、甲壳素硫酸单酯盐、木质素磺酸盐、腐殖酸磺酸盐或其混合物水溶液。分层，回收蒸馏有机溶剂可循环套用，水溶液过滤除去未反应固体原料，蒸发浓缩可以得到浓度50％左右的生物基硫酸单酯盐水溶液产品。可直接进行应用效果评价。进行分析的样品进行如下处理：取一定量产品水溶液，用透析袋透析除去200以下小分子以及无机盐，样品烘干进行含量及结构分析。
分子量测定方法为：广角静态/动态同步激光光散射分析法：将生物基磺酸盐样品溶于纯净水溶液中，分别配成0.002g/mL，0.004g/mL，0.006g/mL，0.008g/mL，0.01g/mL的稀溶液，经0.45μm无菌滤膜过滤后依次滴入已经除尘过的样品瓶中，放入ALV/CGS-3型广角静态/动态同步激光光散射体系，测定其散射光强度，仪器自带的软件(ALV-Fit&Plot  Software)将散射光强度转换为KC/ΔRθ(K是常数，ΔRθ是过剩瑞利因子)，以KC/ΔRθ对生物基磺酸盐浓度C作Debye曲线，曲线截距的倒数即为生物基磺酸盐的分子量。
分别检测烘干产品的硫元素含量和重均分子量，进行红外(IR)和 13C核磁共振(NMR)分析。相关结果参见表1和附图1和图2。纤维素硫酸盐红外特征峰为1260cm -1和813cm -1，分别为-SO 3-(O＝S＝O)的不对称伸缩振动峰和C-O-S的伸缩振动峰(见图1)：甲壳素磺酸盐有1258cm -1和810cm -1两个特征峰，分别为-SO 3-(O＝S＝O)的不对称伸缩振动峰和C-O-S的伸缩振动峰(见图1)。
纤维素硫酸单酯 13CNMR中的66ppm处出现新峰，证明C6位伯羟基被硫酸酯基取代，未被酯化的C6位伯羟基的特征峰为60ppm(见图2)；甲壳素硫酸单酯在66ppm处出现新峰，这是C6位伯羟基被硫酸酯基取代的结果(见图2)；淀粉硫酸盐红外特征峰为1230cm -1和821cm -1，分别为-SO 3-(O＝S＝O)的不对称伸缩振动峰和C-O-S的伸缩振动峰(见图3)。核磁共振( 13CNMR)测得淀粉硫酸盐，在66ppm处出现新峰，这是C6位伯羟基被硫酸酯基取代的结果(见图4)；不同含水量淀粉硫酸盐的粘度(见图5)。
表1不同原料的生物基磺酸盐类/酯类产品数据
Figure PCTCN2019074536-appb-000001
应用实施例
实施例1：生物基磺酸盐的保水性能
取200g沙子，按照按沙子重量的0.1％、0.25％、0.5％、1％、2％称取固体折干相应质量(以下的实施例中的生物基磺酸盐均按照固体折干质量进行计算)的生物基磺酸盐(实 施例中所提及市售木质素磺酸钙或市售木质素磺酸铵盐为采购市售品牌巴斯夫产品，其他提及的生物基磺酸盐产品均为制备实施例中制备的产品)并溶于总计40g水中，搅拌均匀，称重，获得调理剂的初始重量，跟踪每天水分变化，测定生物基磺酸盐平均保水率，每天测定剩余水的重量，剩余水量与总水量的比值为保水率。各种原料自制的系列生物基磺酸盐产品的平均保水率均比空白及市售木质素磺酸钙保水率高。
表2生物基磺酸盐的保水性能表
Figure PCTCN2019074536-appb-000002
Figure PCTCN2019074536-appb-000003
实施例2：生物基磺酸盐的结皮性能
取800g沙子于塑料盒中，按照100、200、400g/m 2(折固)称量生物基磺酸盐(实施例中所提及市售木质素磺酸钙或市售木质素磺酸铵盐为采购市售品牌巴斯夫产品，其他提及的生物基磺酸盐产品均为制备实施中制备的产品)，定容至160mL，再用喷雾器喷洒至沙子表面，称重，获得初始重量，跟踪每天水分变化，直至沙样的含水量接近0，测量结皮厚度。
表3生物基磺酸盐结皮性能表
Figure PCTCN2019074536-appb-000004
取15kg生物基磺酸盐，制备成含量为30％的生物基磺酸盐的水溶液，测试不同用量的生物基磺酸及硫酸单酯或盐类物质的结皮效果。将不同的生物基磺酸盐喷施到沙漠的表面，效果参见附图6，然后测试沙漠的结皮情况，结皮情况参见如下表4。
结皮厚度的测量方法为：将水溶液喷施到沙漠的表面后，等水溶液干燥形成固体后进行测量，平均每个平方米随机取5个点，然后进行平均值计算，开始形成固体后的测量记为初始测量结皮厚度。初次测量后一个月后进行再次测量，测量方法也是平均每个平方米随机取5个点，然后进行平均值计算。
表4不同调理剂用量结皮厚度
Figure PCTCN2019074536-appb-000005
各种原料自制的系列生物基磺酸盐产品的均比市售木质素磺酸钙厚。
实施例3：生物基磺酸盐的结皮抗压性能
取80g沙子于表面皿中，按照100、200、400g/m 2(折固)称量生物基磺酸盐(实施例中所提及市售木质素磺酸钙或市售木质素磺酸铵盐为采购市售品牌巴斯夫产品，其他提及的生物基磺酸盐产品均为制备实施中制备的产品),搅拌均匀，称重，获得初始重量，烘干，用压力试验仪测定沙柱的抗压强度，具体数据参加如下表5。
表5生物基磺酸盐结皮抗压性能
Figure PCTCN2019074536-appb-000006
Figure PCTCN2019074536-appb-000007
各种原料自制的系列生物基磺酸盐产品的结皮抗压性能均优于市售木质素磺酸钙。
实施例4：生物基磺酸盐的结皮抗冻融性能
取80g沙子于表面皿中，按照100、200、400g/m 2(折固)称量生物基磺酸盐(实施例中所提及市售木质素磺酸钙或市售木质素磺酸铵盐为采购市售品牌巴斯夫产品，其他提及的生物基磺酸盐产品均为制备实施中制备的产品)，搅拌均匀，称重，获得初始重量，烘干，放入冰柜中冷冻(-18℃)12h，取出后再放入室外(温度30-40℃)融化12h，即为一个循环，进行3次、7次冻融循环，烘干后用压力试验仪测定沙柱的抗压强度，结果参见表6。
表6生物基磺酸盐结皮抗冻融性能
Figure PCTCN2019074536-appb-000008
Figure PCTCN2019074536-appb-000009
通过表6的数据可以看出，各种原料自制的系列生物基磺酸盐产品的结皮抗冻融性能大多优于市售木质素磺酸钙。
实施例5：生物基磺酸盐的结皮抗紫外老化性能
取80g沙子于表面皿中，按照100、200、400g/m 2(折固)称量生物基磺酸盐(实施例中所提及市售木质素磺酸钙或市售木质素磺酸铵盐为采购市售品牌巴斯夫产品，其他提及的生物基磺酸盐产品均为制备实施例中制备的产品)，搅拌均匀，称重，获得初始重量，烘干，放置40w紫外灯下30cm处封闭条件连续照射100h和200h，照射结束后，用压力试验仪测定沙柱的抗压强度，具体结果参见如下表7。
表7生物基磺酸盐的结皮抗紫外老化性能
Figure PCTCN2019074536-appb-000010
Figure PCTCN2019074536-appb-000011
Figure PCTCN2019074536-appb-000012
各种原料自制的系列生物基磺酸盐产品的结皮抗紫外老化性能差别比较大，木质素的酚类结构具有较好的抗老化性能。
实施例6：生物基磺酸盐结皮抗风蚀性能
应用按照制备实施例中制备的秸秆磺酸盐分别以不同用量喷施到沙漠的表面，测定其抗风蚀性能，测试时采用试验面与风沙流夹角为0℃时进行测试，具体结果参见如下表8。
表8秸秆磺酸盐调理剂抗风蚀性能
Figure PCTCN2019074536-appb-000013
生物基磺酸盐能够很好的抗击风蚀，使用量越多，抵御风蚀的能力越强。如表8所示，当调理剂的使用量为60g/㎡时，能够很好的抵御七级风；当调理剂的使用量为80g/㎡时，能够很好的抵御10级大风。
实施例7：显著增加养份和微生物数量
选取制备实施例中制备的秸秆磺酸盐(主要为葵花秆、玉米秆磺酸盐)，使用时测定成分如下：固含量41％；折固干基养分：全N 1％，K 2O 0.7％，有机质57％。对比空白和羧甲基纤维素在乌兰布试验区沙漠土壤中葵花种植前后土壤生物数据，具体数据如表9所示：
表9葵花秆纤维硫酸盐在沙漠土壤中生化数据分析
Figure PCTCN2019074536-appb-000014
生物基磺酸盐处理的沙漠土壤中菌落数量高出空白10-100倍，高出羧甲基纤维素处理的沙漠土壤2-4倍。
2018年于内蒙乌拉特后旗五原地区改盐增草(饲)兴牧工程的中度及重度盐碱地进行实验，施用量(50-100)Kg/亩种植油葵和苏丹草，喷施种植30天后取样测定土壤中酶活性，同时对比测定空白和其他微生物盐碱地改良技术的土壤中数据，具体数据如表10所示：
表10葵花秆纤维硫酸酯在盐碱地土壤中生化数据分析
Figure PCTCN2019074536-appb-000015
Figure PCTCN2019074536-appb-000016
施用了葵花秆纤维硫酸酯改良剂的土壤喷施一月后土壤的葡萄糖酸钙含量(蔗糖酶活性指标)提高80％-140％，施用50-100Kg/亩葵花秆纤维硫酸酯(其中混施磷酸铵35公斤)改良剂的土壤肥力超过了施用500-1000Kg/亩的改良剂的肥效。在重度盐碱地中过氧化氢酶较对照组的酶含量提高2倍，证明葵花秆纤维硫酸酯改良剂促进土壤生物活性能力和效果。
实施例8：释放土壤/基质中的微量元素
在200g土壤/基质/基质中加入300g蒸馏水，定量加入土壤/基质质量1.6-3.0％固含量折百用量的按照制备实施例中制备的葵花秆磺酸铵，对比实验在土壤/基质中加入土壤/基质质量2.0％的EDTA或者柠檬酸搅拌均匀后浸泡24h左右，以此对比秸秆磺酸铵、EDTA、柠檬酸对土壤/基质中营养元素的萃取率。固液分离后，将滤液定容到500ml，然后采用化学分析的方法测定溶液中的钙镁含量，采用相应的国标测定滤液中P 2O 5、Fe、Cu、Zn等元素的含量。实验数据表明，葵花秆磺酸铵盐对土壤/基质中的多种营养元素的溶出浓度已足以维持植物的营养需求，可以作为缓控释肥的添加成分在相同的添加量下，葵花秆磺酸铵盐对P、Fe、Ca、Mg、Zn等元素的助溶能力并不亚于EDTA、柠檬酸。而且，葵花秆磺酸铵盐的生产成本比EDTA和柠檬酸低得多，而且本来就需要较大的使用量，具体测定数据见表11。
表11络合助溶土壤/基质养分数据比较
Figure PCTCN2019074536-appb-000017
Figure PCTCN2019074536-appb-000018
选取生物基磺酸盐(实施例中所提及对照为常规施用无机肥，其他所用的生物基磺酸盐产品均为按照制备实施例中制备的产品)固含量折百用量为30Kg/亩，用于种植品种为优质二级榆树的树木，实验地点为巴彦淖尔市乌拉特后旗巴音宝力格镇东升村四社旧固察线。施肥方法采用坑施：先将调理剂铺垫于沟(穴)底，或将浆状物灌入其中，使其自然成型，测量结果如下表12。
表12处理间树木指标数据对比
Figure PCTCN2019074536-appb-000019
实施例9：降低盐碱土壤的电导率和pH
pH值的高低对植物的生长发育有直接的影响水溶性盐是盐碱土的一个重要属性，是限制作为生长的障碍因素。电导率是反应土壤可溶性盐分的重要参数。
将实施例8中试验土壤测试电导率和pH，通过以下数据可以看出，使用葵花秆纤维硫酸盐后土壤pH值平均下降0.4；土壤盐浓度(电导率)下降16％。排盐降碱效果显著。
实施例10：生物基磺酸盐提高作物品质
乌兰布和野外固沙试验先后于2017年5月～10月进行，试验规模20亩，测试按照制 备实施例中制备的葵花秆磺酸铵在固沙材料固结方面和生物成活率及生长方面都取得了显著的效果。
试验作物包括：巨菌草、高丹草，传统草方格固沙处理方式作为对照处理，其中草方格对照组每亩施加50Kg化肥；利用制备实施例中制备的葵花秆磺酸铵25Kg+25Kg化肥，现场试验5月8日开始播种，10月9日收获。测试结果如表13、14。
施用的葵花秆磺酸铵的处理可显著促进牧草生长，通过牧草种植试验，施用葵花秆磺酸铵处理后的巨菌草，生长一个月后，巨菌草平均茎秆生长最粗，为26.1mm，平均株高生长最快，为195cm，巨菌草萌发生长枝条、叶片较多，叶量丰富，叶绿素含量较高，进行光合作用的产物也较高。施用葵花秆磺酸铵处理后的高丹草，生长一个月后，高丹草平均茎秆生长最粗，为26.1mm，平均株高生长最快，为92cm，高丹草萌发生长枝条和叶片较多，叶量丰富，叶绿素含量最高，进行光合作用的产物也较高。
因此，施用葵花秆磺酸铵处理后，巨菌草、高丹草、苏丹草，生长发育较快，茎秆生长较粗，植物生长叶量数量多，叶绿素含量最高，进行光合作用的产物也较高，见表13。
表13处理间牧草生长指标数据对比
Figure PCTCN2019074536-appb-000020
施用葵花秆磺酸铵的处理可显著促进牧草生长，提高牧草品质。施用葵花秆磺酸铵处理后，巨菌草、高丹草、苏丹草的粗脂肪含量都增加，粗脂肪含量分别为25.4％、25.6％、16.2％。粗脂肪含量比草方格内巨菌草、高丹草和苏丹草的粗脂肪含量高0.1％、3.8％和4.5％。
施用葵花秆磺酸铵处理后，植物的总糖含量也增加了，巨菌草、高丹草的总糖含量分别为1.89％、14.1％。总糖含量比草方格内巨菌草、高丹草的总糖含量高0.25％和5.33％。
施用葵花秆磺酸铵处理后，三种牧草植物体内的总碳水化合物含量，仅有高丹草的总碳水化合物含量较高为74.7％；高丹草的总碳水化合物比草方格内高丹草的总碳水化合物 含量高26.9％。而巨菌草和苏丹草的总碳水化合物含量，与草方格内的相比，总碳水化合物没有增加。
施用葵花秆磺酸铵处理后，植物体内钙的含量增加了，巨菌草的钙含量为3.04g/kg；苏丹草的钙含量3.33g/kg。分别高于草方格内巨菌草和苏丹草钙含量的0.06g/kg和0.41g/kg。
施用葵花秆磺酸铵处理后，植物体内的酸性纤维ADF的含量下降了，巨菌草、高丹草植物体内的酸性纤维ADF的含量分别为43.1％和36.9％；植物体内的酸性纤维ADF的含量比草方格内植物体内的酸性纤维ADF的含量分别下降了3.5％和7.4％。
因此，施用葵花秆磺酸铵的处理可显著促进牧草的生长发育，提高牧草的品质和产量，见表14。
表14处理间牧草指标数据对比
Figure PCTCN2019074536-appb-000021
实施例11：促进盐碱土壤环境下作物生长
实验地点：内蒙古自治区阿拉善左旗巴彦木仁苏木上滩嘎查。土壤理化性质：pH值8.4-8.6，电导率0.55-0.79ms/cm，有机质0.83-1.08％；有效氮28.8-43.8ppm；有效磷28.8-43.8ppm；有效钾181-257ppm。玉米成熟收获后，对产品进行方差分析。
施用按照制备实施例中制备的葵花秆磺酸盐处理的玉米产量比常规施肥处理产量增加了64kg/亩，每亩应用生物基磺酸盐的固含量折百用量为30Kg，增产8％。通过对玉米主要构成因子(穗重和千粒重)分析，施用生物基磺酸盐产品虽然穗重及千粒重有所降低，但颗粒总数明显提升。
实施例12：减肥增产大棚应用
将生物基磺酸盐于2016年在宁夏贺兰县园艺产业园在蔬菜滴灌施肥中进行应用，主 要栽种作物有辣椒、番茄、黄瓜。对比肥料选用以色列进口水溶性肥料海法钾、魔力丰以及生物基磺酸盐。种植处理方案分别为全部无机水溶性肥料(CK)，施用量66Kg/亩；100％无机水溶性肥料+生物基磺酸盐(处理1)，施用量66Kg/亩无机肥+40Kg/亩生物基磺酸盐；70％无机水溶性肥料+生物基磺酸盐(处理2)，施用量46Kg/亩无机肥+40Kg/亩生物基磺酸盐；其中所用的生物基磺酸盐产品为按照制备实施例所用葵花秆磺酸铵。
作物的生产对比情况为：
番茄株高、茎粗无显著差异，减少常规肥30％用量基础上添加生物基磺酸盐仍很好保持良好生长；
叶绿素：施用生物基磺酸盐的处理1相对CK处理叶绿素含量高出10.89％～27.08％；
根长：处理1与处理2根长分别为CK的1.17倍与1.80倍；
根表面积：处理1与处理2根长分别比CK增加13.84％、48.93％；
产量：对照CK处理产量4790kg/亩，处理1产量5015kg/亩，增加4.7％；处理3产量4812kg/亩，增加22kg/亩；
品质：施用生物基磺酸盐的处理1果实Vc含量为69.63mg/kg，较CK(64.9mg/kg)增加7.97％；
黄瓜株高:常规水溶肥基础上施用生物基磺酸盐处理1植株长势始终显著高于CK，增长42％。
叶面积：处理1植株叶面积最大，高达818cm 2
叶绿素：处理1和处理2的叶绿素含量明显增高
根长：处理1的根最长为627mm，相对CK增加101mm
产量：处理1的黄瓜产量最高5600kg/亩，较对照(产量4596kg/亩)增产21.85％，处理2(产量4770kg/亩)较CK产量增加3.79％。
品质：可溶性固形物含量处理1与2较CK增加6.32％和10.64％
辣椒株高、茎粗:无显著差异，减少常规肥30％用量基础上添加生物基磺酸盐仍很好保持良好生长；
叶面积：处理1、2未显著改变叶面积；
产量：处理1的果实产量达4271.20kg/亩，是常规施肥处理组的1.34倍，处理2产量较CK增产6.39％。
品质：经生物基磺酸盐处理后，处理1的Vc含量最高达259.73mg/kg，较CK增长39.26％；果实硝酸盐含量处理1与处理2分别较CK降低3.95％与11.64％；处理1和处理2相对于 CK可溶性固形物含量明显增加，分别较CK提高14.55％与10.91％，试验说明，生物基磺酸盐的使用可以增加果实营养含量。
实施例13：减肥增产田间应用
将制备实施例中生产的葵花秆磺酸铵，于2016年在内蒙金沙苑生态工程有限责任公司葡萄基地进行滴灌施肥中进行应用，所用的葵花秆磺酸铵，干物质含量为50％，亩用量为固含量折百用量30kg/亩，对比肥料为以色列进口氨基酸肥，亩用量为固含量折百用量30kg。同时于2018年在福建南平武夷山进行了茶叶种植验证，制备实施例生产的葵花秆磺酸铵，干物质含量为50％，亩用量为固含量折百用量30kg/亩，对比肥料为金银珠参混肥料+氨基酸BB肥。葵花秆磺酸铵肥料比对照肥料的茶叶增产4～11.2％。葡萄的对比种植数据如表15所示：
表15生物基磺酸盐肥料与进口无机肥对葡萄及酒品质的影响
Figure PCTCN2019074536-appb-000022
实施例14：不同生物基磺酸盐对土壤性状、生态及作物产量的影响
将制备实施例生产的葵花秆磺酸铵、葵花秆磺酸钙,以及两者按照重量比1:1混合，分别测定其对沙土的结皮渗水性、结皮保水性、抗压强度、抗风蚀性能、抗紫外老化性能老化、冻融性能进行数据比较，不同性能在相同的生物基磺酸盐添加量下实验，经过验证，葵花秆磺酸铵与葵花秆磺酸钙混合物的性能优于单组份的生物基磺酸盐的性能。具体数据如表16所示：
表16不同组分生物基磺酸盐对土壤性状及生态等的影响
Figure PCTCN2019074536-appb-000023
Figure PCTCN2019074536-appb-000024

Claims (14)

  1. 一种包含生物基磺酸及硫酸单酯或盐类物质的组合物的用途，所述组合物用于支持植物生长营养、和/或作为生物生长基质、和/或提供植物或微生物营养和生物质能、和/或缓释植物营养成分、和/或促进植物对营养元素的吸收、和/或提高植物或微生物品质、和/或改良植物或微生物生长环境，所述生物基磺酸及硫酸单酯或盐类物质为生物基磺酸、生物基硫酸单酯、生物基磺酸盐和生物基硫酸单酯盐中的一种或多种。
  2. 根据权利要求1所述的用途，其特征在于所述生长环境为固体生长环境或液体生长环境，或为固体和液体混合的生长环境；优选的，固体生长环境为土壤，优选的，固体生长环境为沙质土壤或沙漠，优选的，固体生长环境为盐碱土壤地或盐碱地。
  3. 根据权利要求2所述的用途，当固体生长环境为沙质土壤或沙漠时，所述用途为组合物可实现对沙质土壤或沙漠的结皮、抗风蚀、耐老化、抗压、抗冻融、改善微生物生存环境中的一种或多种的作用；优选的，所述用途还包括组合物实现对沙质土壤或沙漠的结皮固沙、保水保肥、改善微生物生存环境、提供和促进营养元素吸收，缓释植物营养成分，助溶络合沙质土壤或沙漠中的营养成分，离子交换、降低pH、降低盐浓度作用中的一种或多种；优选的，还包括组合物实现提高沙质土壤或沙漠植物的抗干旱能力、促生长能力和提高植物品质；优选的，还包括组合物实现对流动沙漠的结皮固沙、保水保肥、改善微生物生存环境、提供和促进营养元素吸收的作用。
  4. 根据权利要求2所述的用途，当固体生长环境为盐碱土壤地或盐碱地时，所述用途为组合物实现对盐碱土壤地或盐碱地降低盐浓度、pH，改善微生物生存环境的一种或多种的作用；优选的，所述用途还包括组合物实现对盐碱土壤地或盐碱地的离子交换、中和、保水、结皮、形成土壤团粒结构改善土壤透气性，提供植物和微生物营养、促进植物营养元素吸收、缓释植物营养成分，助溶络合盐碱土壤或盐碱地中的营养成分的作用中的一种或多种；优选的，所述用途还包括组合物实现提高盐碱土壤地或盐碱地植物的抗盐碱能力、抗干旱能力、促生长能力和提高植物品质；优选的，所述用途还包括组合物实现对盐碱土壤或盐碱地的降低盐浓度、降低pH、改善微生物生存环境、提供和促进营养元素吸收的作用。
  5. 根据权利要求1-4任一项所述的用途，其特征在于所述生物基磺酸及硫酸单酯或盐类物质的重量占组合物重量比为1％～99.99％；优选的，所述组合物中，生物基磺酸及硫酸单酯或盐类物质的重量占组合物重量比为10％～80％，优选的，所述组合物中，生物基磺酸及硫酸单酯或盐类物质的重量占组合物重量比为20％～60％。
  6. 根据权利要求1-4任一项所述的用途，其特征在于所述生物基磺酸或生物基硫酸单酯或其盐为生物材料中的纤维素、半纤维素、淀粉、腐殖酸、甲壳素及其衍生物分子中羟基、芳基连接磺酰基官能团的物质，所述生物基磺酸盐或生物基硫酸单酯盐为生物基磺酸或生物基硫酸单酯被碱中和，氢离子被金属离子或铵根离子取代；优选的，金属离子为钾或钙离子；优选的，生物基磺酸及硫酸单酯或盐类物质中硫含量大于等于1％wt；优选的，作为多功能生物基磺酸盐的平均分子量在一万以上，分子量越大，保水结皮或成膜效果越好。
  7. 根据权利要求6所述的用途，其特征在于所述生物材料为植物材料或动物材料；优选的，所述植物材料为作物秸秆、芦苇、沙柳、柠条、淀粉、煤泥、枣枝、能源草、高丹草、苏丹草、巨菌草、林木资源及其加工剩余物中的一种或多种，优选的，所述材料为葵花秆、虾壳和蟹壳中的一种或多种。
  8. 根据权利要求1-4任一项所述的用途，其特征在于所述组合物中还包含载体或添加剂中的一种或多种，所述载体为水、腐植酸、纤维、肥料、粉煤灰、煤泥、气化炉渣、磷矿粉和秸秆粉碎物中的一种或多种，所述添加剂为肥料、农药、木质素盐、木质素磺酸盐和微生物中的一种或多种；所述载体和添加剂的总重量占组合物重量的百分比为0.001～99.9％；优选的，载体和添加剂的总重量占组合物重量的百分比为0.01～99％；优选的，载体和添加剂除农药外的总重量占组合物重量的百分比为20～90％。
  9. 根据权利要求1所述的用途，其特征在于所述生物基磺酸及硫酸单酯或盐类物质为纤维素硫酸单酯、纤维素硫酸单酯盐，半纤维素硫酸单酯、半纤维素硫酸单酯盐，淀粉硫酸酯、淀粉硫酸盐、甲壳素硫酸单酯、甲壳素硫酸单酯盐，腐殖酸磺酸和腐殖酸磺酸盐中的一种或多种的大分子及部分降解的小分子组合，优选的，所述生物基磺酸及硫酸单酯或盐类物质为通过三氧化硫磺化法制备得到的生物基磺酸盐及盐类混合物。
  10. 根据权利要求2所述的用途，其特征在于改良植物或微生物生长环境时，组合物的使用量为1kg～100000kg/亩，优选的，组合物的使用量为10kg～10000kg/亩。
  11. 一种用于改良植物或微生物生长环境的调理剂，所述调理剂包含生物基磺酸及硫酸单酯或盐类物质，所述生物基磺酸及硫酸单酯或盐类物质的重量之和占调理剂重量比为1％～99.99％，优选的，所述调理剂中，生物基磺酸及硫酸单酯或盐类物质的重量之和占调理剂重量比优选为10％～80％，优选的，所述组合物中，生物基磺酸及硫酸单酯或盐类物质的重量占组合物重量比为20％～60％，优选的，生物基磺酸及硫酸单酯或盐类物质为生物基磺酸、生物基硫酸单酯、生物基磺酸盐和生物基硫酸单酯盐中的一种或多种，优选的，所 述生物基磺酸或生物基硫酸单酯为生物材料中的纤维素、半纤维素、淀粉、腐殖酸、甲壳素及其衍生物分子中的羟基、芳基连接磺酰基官能团的物质，所述生物基磺酸盐或生物基硫酸单酯盐为生物基磺酸或生物基硫酸单酯中的磺酸根离子与植物需要的金属离子或铵根离子结合的化合物。
  12. 根据权利要求11所述的调理剂，其特征在于所述调理剂中还包含载体或添加剂中的一种或两种，所述载体为水、腐植酸、纤维(本色浆、废纸浆)、磺化反应剩余物、肥料、粪便、粉煤灰、煤泥、气化炉渣、磷矿粉和秸秆粉碎物中的一种或多种，所述添加剂为肥料、农药、木质素盐、木质素磺酸盐和微生物中的一种或多种；所述载体和添加剂的总重量占组合物重量的百分比为0.001～99.9％；优选的，载体和添加剂的总重量占组合物重量的百分比为0.01～99％；优选的，载体和添加剂除农药外的总重量占组合物重量的百分比为20～90％。
  13. 根据权利要求11所述的调理剂，其特征在于所述生物材料为植物材料或动物材料，所述植物材料为作物秸秆、芦苇、沙柳、柠条、煤泥、淀粉、枣枝、能源草、高丹草、苏丹草、巨菌草、林木资源及其动植物加工剩余物中的一种或多种，所述动物材料为虾壳和蟹壳中的一种或多种，优选的，所述生物基磺酸及硫酸单酯或盐类物质为纤维素硫酸单酯、纤维素硫酸单酯盐、半纤维素硫酸单酯、半纤维素硫酸单酯盐、淀粉硫酸单酯、淀粉硫酸单酯盐、甲壳素硫酸单酯、甲壳素硫酸单酯盐，腐殖酸磺酸、腐殖酸磺酸盐中的一种或多种的组合，优选的，所述生物基磺酸及硫酸单酯或盐类物质为通过三氧化硫磺化法制备得到的生物基磺酸盐及盐类物质混合物。
  14. 权利要求11-13任一项所述调理剂的使用方法，其特征在于所述方法为将调理剂施用于植物或微生物生长环境，或者将调理剂与植物环境中的固体物质或液体物质混合后施用于植物生长环境，或者将调理剂施用于植物叶面，优选的，施用的方式为喷施、撒施、滴灌、根施、垅埋或坑埋，尤其优选的，所述调理剂的施用量为每亩用1kg-100000kg调理剂，优选的，调理剂的施用量为每亩用1kg-10000kg调理剂。
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