CN111072991A - Preparation method of bio-based sulfonate for improving saline-alkali soil - Google Patents
Preparation method of bio-based sulfonate for improving saline-alkali soil Download PDFInfo
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- CN111072991A CN111072991A CN201911345130.8A CN201911345130A CN111072991A CN 111072991 A CN111072991 A CN 111072991A CN 201911345130 A CN201911345130 A CN 201911345130A CN 111072991 A CN111072991 A CN 111072991A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
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- 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
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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
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- 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
- C09K2109/00—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE pH regulation
Abstract
The invention relates to a bio-based sulfonate for improving saline-alkali soil and a preparation method thereof, wherein leaf particles and SO are added under the conditions that the temperature is 60-200 ℃ and the pressure is 2-4 atmospheres3Sulfonation of 1, 2-dichloroethane solution, and removal of SO by distillation3And then adding the solid material into an alkaline solution for neutralization, finally dialyzing with an aqueous solution, cleaning with ethanol to remove impurities, separating and purifying, and drying to obtain the product. The bio-based sulfonate prepared by the invention can improve the soil quality, promote the growth of plants and improve the quality and yield of the plants. And the leaves, the urban waste, are recycled, and have the characteristics of environmental protection and economy.
Description
Technical Field
The invention relates to the technical field of resource utilization of solid wastes and soil environment treatment, in particular to a preparation method of bio-based sulfonate for improving saline-alkali soil.
Background
With the increasing of the challenge of the red line of cultivated land in China and the need of grain productivity enhancement, saline-alkali land is taken as an important backup cultivated land resource, and the reasonable development and scientific configuration of the saline-alkali land affect the agricultural development and the grain safety. The coastal saline-alkali soil in China has huge area, is in urgent need of development and utilization, and urgently requires the research and development of new improvement measures for the development of the coastal saline-alkali soil. The coastal saline-alkali soil is mainly distributed on offshore beaches and river delta and belongs to chloride saline soil. The coastal saline-alkali soil is characterized by low soil humus content and nutrient, high salt content, quick water loss and the like.
The method for producing the bio-based sulfonate comprises ① catalytic oxidation, hydroxymethylation and final sulfonation, ② catalytic oxidation and direct sulfohydroxymethylation, ③ catalytic oxidation and direct hydroxymethylation with formaldehyde, and the technical scheme disclosed in the patent application No. CN201510078598.0 is that the bio-based sulfonate is used as a concrete mixing agent in the building field and is used as a cement for bonding metals, glass, paper, wood and the like, wherein the technical scheme disclosed in the patent application No. CN2 is that the bio-based sulfonate is used as a cement for bonding metal, glass, paper, wood and the like.
At present, the reagents for producing the cement water reducing agent or the adhesive are disclosed in the patent, the reaction temperature is controlled below 35 ℃ to prepare the product, because different reaction temperatures can cause sulfonation sites (-SO)3H) Different.
Disclosure of Invention
The invention aims to provide a new bio-based sulfonate which is suitable for saline-alkali soil remediation and is prepared by a high-temperature sulfonation reaction method, and compared with the bio-based sulfonate used as a water reducing agent or an adhesive, the bio-based sulfonate has low viscosity and good wetting and adsorption properties.
The technical scheme of the invention is as follows:
the preparation method of the bio-based sulfonate for improving the saline-alkali soil is characterized by comprising the following steps of:
(1) and (3) processing leaves: drying the leaves at the temperature of 100-110 ℃ for 2-5 h, and crushing the leaves to obtain leaf particles with the particle size of 2-5 cm;
(2)SO3preparation of the 1, 2-dichloroethane solution: 100.0g of phosphorus pentoxide was put into a flask, 80.0mL of 98% sulfuric acid was added dropwise, the temperature was raised to 150 ℃ and the generated gas SO was purged3Dissolved in 200.0mL of 1, 2-dichloroethane to contain SO3The concentration of (b) is 2.8-3.0 mol/L;
(3) and (3) sulfonation reaction: putting the leaf particles obtained in the step (1) into a reaction kettle, and firstly, injecting the SO prepared in the step (2) into the reaction kettle3The mass ratio of the addition amount of the/1, 2-dichloroethane solution to the leaves is 1: 1-1: 5, the reaction temperature is 60-200 ℃, the pressure is 2-4 atmospheric pressures, and the reaction time is 0.5-5 h;
(4) and (3) purification: passing the solution after the sulfonation reaction of the step (3) through a 20-mesh sieve at the temperature of 20-25 ℃, and distilling at the temperature of 110-120 ℃ to remove SO3And then adding 1mol/L sodium hydroxide solution or calcium hydroxide solution to adjust the pH value to 6.5-7.5, dialyzing with aqueous solution, cleaning with ethanol to remove impurities, centrifugally separating precipitates, and drying to obtain the compound.
The preparation method of the bio-based sulfonate for improving the saline-alkali soil is characterized in that SO is generated in the sulfonation reaction in the step (3)3The mass ratio of the/1, 2-dichloroethane solution to the leaves is 1: 3-1: 5.
The preparation method of the bio-based sulfonate for improving the saline-alkali soil is characterized in that the temperature of the sulfonation reaction in the step (3) is 70-150 ℃, the pressure is 2-4 atmospheric pressures, and the time is 0.5-4 hours.
The raw material for preparing the bio-based sulfonate is leaf or other raw materials rich in lignin. Lignin is a biopolymer widely existing in plants and having an amorphous three-dimensional network structure, and an aromatic polymer containing structural units of oxyphenbutamol or derivatives thereof in the molecular structure. Lignin molecules are network molecules connected together by its basic structural units, and the molecules contain active functional groups such as methoxy, hydroxyl, phenolic hydroxyl and the like, so that lignin can be subjected to various chemical modification reactions such as sulfonation. The sulfonated bio-based sulfonate contains a large number of-OH bonds, and can be combined with water molecules in a hydrogen bond mode. After the bio-based sulfonate is added into soil, the bio-based sulfonate is associated with hydrogen bonds in water molecules to release excessive water; meanwhile, a stable solvation water film is formed on the soil surface, particles are lubricated due to the isolation of the water film, and the sulfonated bio-based sulfonate has multiple properties of biomacromolecules and polyelectrolyte, so that the bio-based sulfonate has good adsorption performance and can adsorb salt ions generated due to moisture release, thereby achieving the effects of moistening and loosening the soil and reducing the salinity.
In many cases, sulfonation temperatures can affect the location of the sulfo groups into the aromatic ring. Sulfonated groups (-SO) sulfonated at low temperatures3H) Often in the ortho position of the benzene ring in the lignin molecule, and high temperature sulfonated-SO3H is often in the meta position of the benzene ring in the lignin molecule.
The content of the bio-based sulfonate obtained by the high-temperature sulfonation reaction is 25-57%, and the molecular formula of the main components is as follows:
the molecular weight is about 300 ten thousand.
Compared with the prior art, the invention is characterized in that:
1. the invention adopts a preparation method of high-temperature sulfonation reaction, and the prepared bio-based sulfonate has low viscosity and good wetting and adsorption properties, and is suitable for saline-alkali soil remediation.
2. The bio-based sulfonate prepared by the invention has the effects of loosening soil and reducing salt content, can be widely used for improving coastal saline-alkali soil, can effectively improve the physicochemical property of the saline-alkali soil, improves the survival rate of plants and promotes the growth of the plants.
3. The bio-based sulfonate is extracted from leaves, is rich in various trace elements, has certain fertility, has a good effect of promoting the growth of plants, and has the characteristics of environmental protection and economy due to the resource utilization of the leaves, namely urban waste.
4. The invention adopts sulfonation reaction under high temperature and high pressure, and the sulfonation temperature can influence the position of sulfo group entering aromatic ring. Sulfonated groups (-SO) sulfonated at low temperatures3H) Often in the ortho position of the benzene ring in the lignin molecule, while-SO 3H, after high temperature sulfonation, is often in the meta position of the benzene ring in the lignin molecule.
Detailed Description
The present invention is not limited by the following examples, and specific embodiments may be determined according to the technical solutions and practical situations of the present invention.
All the chemical reagents and chemical articles mentioned in the invention are mass fractions unless otherwise specified; the solution in the present invention is an aqueous solution of water as a solvent unless otherwise specified.
The invention is further described below with reference to the following examples:
example 1:
(1) and (3) processing leaves: drying the leaves in a forced air drying oven at 105 deg.C for 3h, and pulverizing to obtain leaf granules with particle diameter of 3 cm;
(2)SO3preparation of the 1, 2-dichloroethane solution: 100.0g of phosphorus pentoxide was quantitatively weighed and placed in a two-necked flask, 80.0mL of 98% sulfuric acid was added dropwise using a constant pressure dropping funnel, and then the temperature was raised to 150 ℃ to generate SO gas3Gas SO3Dissolving in 200.0mL of 1, 2-dichloroethane at 25 ℃ to form SO3Solution of/1, 2-dichloroethane containing SO3The concentration of (A) is 2.9 mol/L;
(3) and (3) sulfonation reaction: putting the leaf particles into a reaction kettle according to SO3Slowly adding SO into the reaction kettle according to the mass ratio of the 1, 2-dichloroethane solution to the leaves being 1: 53SO with a concentration of 2.9mol/L3The reaction temperature of the 1, 2-dichloroethane solution is 150 ℃, the pressure is 2 atmospheres, the reaction time is 2 hours, and after the reaction is finished, a pressure reducing valve and a low-temperature circulating pump are started and cooled to 25 ℃;
(4) and (3) purification: and (3) sieving the solution subjected to the sulfonation reaction in the step (3) by a 20-mesh sieve at 25 ℃, placing the solution in a distillation flask, distilling the solution at 115 ℃ to remove sulfur trioxide gas, then adding 1mol/L NaOH solution to adjust the pH to 7.0, dialyzing the solution by using aqueous solution to remove micromolecules and inorganic salt impurities, washing the solution by using 3 times of ethanol for 3 times to remove the impurities, centrifugally separating precipitates, and drying to obtain a solid sample.
Example 2:
SO was added in step (3) of example 13The mass ratio of the 1, 2-dichloroethane solution to the leaves is 1: 4, the reaction temperature is 130 ℃, the reaction pressure is 2.5 atmospheric pressures, and the reaction time is 3 hours;
using 1mol/L of Ca (OH) to the 1mol/L NaOH solution in the step (4)2Replacing the solution;
the other steps are the same as in example 1.
Example 3:
the reaction temperature of the step (3) of the above example 1 is 70 ℃, the reaction pressure is 4 atmospheric pressures, and the reaction time is 0.5 h;
the other steps are the same as in example 1.
Example 4:
SO was added in step (2) of example 13The mass ratio of the amount of the 1, 2-dichloroethane to the leaves is 1: 3;
the reaction temperature in the step (3) is 100 ℃, the reaction pressure is 3 atmospheric pressures, and the reaction time is 1 h;
the other steps are the same as in example 1.
The yield of the bio-based sulfonate in examples 1 to 4 was: and (3) obtaining 1-1.7 kg of solid sample per kg of dried leaves, wherein the content of the bio-based sulfonate in the solid sample is 25-57%.
The observation conditions of the effect of the bio-based sulfonate of the embodiment 1-4 and the comparative example of the blank test without adding the bio-based sulfonate solution on the saline-alkali soil are as follows:
the test soil for saline-alkali soil in the white city Zhen 361699 of Jilin province has a pH value of 10.15 and a total salt content of 4.25 g/kg. And 5 groups of experiments are carried out, 500g of coastal saline-alkali soil is added into a flowerpot, the bio-based sulfonate prepared in each embodiment is diluted by 20 times by adding water and is uniformly mixed, 250ml of bio-based sulfonate is weighed and poured into the corresponding flowerpot, and black nightshade seeds with full seeds are selected and planted in the flowerpot, wherein 12 grains are planted in each flowerpot. The flowerpot is placed in a greenhouse, and water is irrigated every 3 days after seeding. After 60 days, various indexes of the black nightshade, the pH value of the coastal saline-alkali soil and the total salt content are recorded as shown in the following table 1.
Table 1, plant indexes, pH value of coastal saline-alkali soil and total salt content
| Index (I) | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example |
| pH | 8.65 | 8.94 | 8.01 | 7.87 | 9.91 |
| Total salt amount (g/kg) | 1.73 | 2.05 | 0.51 | 0.35 | 4.17 |
| Rate of emergence | 80.55％ | 74.38％ | 90.61％ | 91.57％ | 16.15％ |
| Plant height (cm) after 60 days | 36.39 | 31.12 | 40.11 | 42.38 | 10.64 |
The application test results prove that the bio-based sulfonate for the saline-alkali soil can effectively improve the physicochemical property of the saline-alkali soil, effectively reduce the total salt content of the soil, improve the survival rate of plants and promote the growth of the plants.
Claims (3)
1. A preparation method of bio-based sulfonate for improving saline-alkali soil is characterized by comprising the following steps:
(1) and (3) processing leaves: drying the leaves at the temperature of 100-110 ℃ for 2-5 h, and crushing the leaves to obtain leaf particles with the particle size of 2-5 cm;
(2)SO3preparation of the 1, 2-dichloroethane solution: 100.0g of phosphorus pentoxide is put into a flask, 80.0mL of 98% sulfuric acid is added dropwise, the temperature is raised to 150 ℃, and the generated gas SO is3Dissolved in 200.0mL of 1, 2-dichloroethane to contain SO3The concentration of (b) is 2.8-3.0 mol/L;
(3) and (3) sulfonation reaction: putting the leaf particles obtained in the step (1) into a reaction kettle, and firstly, injecting the SO prepared in the step (2) into the reaction kettle3The mass ratio of the added amount of the 1, 2-dichloroethane solution to the leavesThe ratio of the reaction time to the reaction temperature is 1: 1-1: 5, the reaction temperature is 60-200 ℃, the reaction pressure is 2-4 atm, and the reaction time is 0.5-5 h;
(4) and (3) purification: passing the solution obtained after the sulfonation reaction in the step (3) through a 20-mesh sieve at 20-25 ℃, and distilling at 110-120 ℃ to remove SO3And then adding 1mol/L sodium hydroxide solution or calcium hydroxide solution to adjust the pH value to 6.5-7.5, dialyzing with aqueous solution, cleaning with ethanol to remove impurities, centrifugally separating precipitates, and drying to obtain the compound.
2. The method for preparing bio-based sulfonate used for improving saline-alkali soil according to claim 1, wherein SO is generated in the sulfonation reaction in the step (3)3The mass ratio of the/1, 2-dichloroethane solution to the leaves is 1: 3-1: 5.
3. The method for preparing the bio-based sulfonate used for improving the saline-alkali soil according to claim 1, wherein the temperature of the sulfonation reaction in the step (3) is 70-150 ℃, the pressure is 2-4 atm, and the time is 0.5-4 h.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103539952A (en) * | 2012-07-10 | 2014-01-29 | 厦门大学 | Novel humic acid sulfonatiion process |
| CN104592529A (en) * | 2013-10-31 | 2015-05-06 | 厦门大学 | Novel lignin sulfonation technology |
| CN105985043A (en) * | 2015-02-13 | 2016-10-05 | 厦门大学 | New production technology of high-efficiency water reducer bio-based sulfate ester/sulfonate |
| CN105985527A (en) * | 2015-02-13 | 2016-10-05 | 北京紫光英力化工技术有限公司 | New synthesis technology of highly-substituted lignosulfonate water reducer |
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- 2019-12-24 CN CN201911345130.8A patent/CN111072991A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103539952A (en) * | 2012-07-10 | 2014-01-29 | 厦门大学 | Novel humic acid sulfonatiion process |
| CN104592529A (en) * | 2013-10-31 | 2015-05-06 | 厦门大学 | Novel lignin sulfonation technology |
| CN105985043A (en) * | 2015-02-13 | 2016-10-05 | 厦门大学 | New production technology of high-efficiency water reducer bio-based sulfate ester/sulfonate |
| CN105985527A (en) * | 2015-02-13 | 2016-10-05 | 北京紫光英力化工技术有限公司 | New synthesis technology of highly-substituted lignosulfonate water reducer |
Non-Patent Citations (1)
| Title |
|---|
| 李娜: "生物基磺酸盐改良剂对盐碱土的改良效果及油葵生长的影响", 《西北农业学报》 * |
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