CN110835537A - Persistent coastal saline soil improvement salt absorbent, and preparation method and application thereof - Google Patents

Persistent coastal saline soil improvement salt absorbent, and preparation method and application thereof Download PDF

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CN110835537A
CN110835537A CN201911096018.5A CN201911096018A CN110835537A CN 110835537 A CN110835537 A CN 110835537A CN 201911096018 A CN201911096018 A CN 201911096018A CN 110835537 A CN110835537 A CN 110835537A
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salt
saline soil
component
coastal saline
inorganic
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CN110835537B (en
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林海涛
沈玉文
宋效宗
刘苹
王江涛
王梅
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Institute of Agricultural Resources and Environment of Shandong Academy of Agricultural Sciences
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Institute of Agricultural Resources and Environment of Shandong Academy of Agricultural Sciences
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    • C09K17/00Soil-conditioning materials or soil-stabilising materials
    • C09K17/40Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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Abstract

The invention relates to a lasting-effect type coastal saline soil improvement salt absorption agent and a preparation method and application thereof, and the lasting-effect type coastal saline soil improvement salt absorption agent comprises two functional components of a salt absorption component and a salt retention component, wherein the salt absorption component is prepared by sulfonating modified humic acid and an inorganic adsorption material according to the ratio of (75-85): (15-25) by weight; the storage salt component is prepared from an inorganic pore material and an organic pore filling material according to the weight ratio of (85-90): (10-15) in a weight ratio. The invention organically combines the adsorption of the inorganic adsorption material with the space storage of the inorganic porous material, and combines the physical adsorption and the chemical adsorption of the organic material to achieve the purposes of 'salt adsorption' and 'salt fixation', the organic adsorption material is combined with the inorganic adsorption material to strengthen the fixation of sodium ions, reduce the sodium ion content of the soil solution, play a role in high-efficiency salt reduction, can continuously realize the desalination and alkali inhibition of coastal saline soil, continuously improve the soil, have low cost, and are suitable for rapid mass production.

Description

Persistent coastal saline soil improvement salt absorbent, and preparation method and application thereof
Technical Field
The invention relates to a lasting effect type salt absorbent, in particular to a lasting effect type coastal saline soil improvement salt absorbent and a preparation method and application thereof, and belongs to the technical field of soil improvement.
Background
The saline soil is also called saline-alkali soil and is divided into inland saline soil and coastal saline soil, the saline soil area of China is wide and accounts for 4.88 percent of the available land area of the whole country, wherein the saline cultivated land area reaches 920.9 multiplied by 104hm2And accounts for 6.62 percent of the cultivated land area in China. Various salinized soils in China are distributed, but coastal salinized soil is most widely distributed, is almost distributed in various provinces, cities and autonomous regions along the coast, and has the area of about 211.4 multiplied by 104hm2. The coastal plain area in the north of the Yangtze river is the largest coastal saline soil distribution area in China and occupies about half of the area of the coastal saline soil. Due to natural factors and the lack of persistent-effect modifiers, about 80 percent of coastal saline soil is not developed and utilized in China. With the reduction of cultivated land area in China, the engineering construction of a Bohai sea granary is particularly promoted, so that the continuous improvement, development and utilization of coastal saline soil are urgently needed.
Coastal saline soil is different from inland saline soil. Firstly, the salt accumulation process of the coastal saline soil is prior to the soil formation process (which is a unique characteristic of the coastal saline soil), so that the salt accumulation on the surface layer of the coastal saline soil is heavy, the salt content of the whole profile is also very high, the structure is poor, the water level of underground water is high, and the mineralization degree is large. Secondly, because the salt of the coastal saline soil mainly comes from seawater, the salt composition of the soil and groundwater is consistent with that of the seawater, except for a few acidic coastal saline soil, chloride is used as an absolute advantage, and sodium chloride is used as a majority. Thirdly, coastal saline soil is mainly influenced by backflow of underground water and seawater, and biological influence is very little, so that the soil alkalinity is low, carbonate ions are hardly detected, and the pH is more than 7.5-8.0; and fourthly, the obstructive factors such as 'thin' and the like are more prominent, and because the salt content is high, the fertilizer is difficult to apply, and the coastal saline soil is generally lack of nutrition. Therefore, an improved technology aiming at the characteristics of the coastal saline soil and simultaneously aiming at the resource utilization in the coastal areas is urgently needed.
For the heavily saline soil (the salt content is more than 0.4%), the conditioner or the salt-absorbing agent is applied to reduce the salt content of the surface soil of the coastal saline soil, so that the problem of surface soil salt-covering caused by the traditional salt pressing by water can be effectively avoided.
For example, Chinese patent document CN102504825A discloses an ecological conditioner for coastal saline soil, a preparation method and an application thereof. The modifier neutralizes alkali through acid generated by physiological metabolism of thalli, so that the pH value of soil is reduced, meanwhile, the condition that salt content rises along capillary gaps along with water is blocked by the existence mode of microbial flora in the soil, the salt content of surface soil is reduced, the modifier can only reduce the salt content of the surface soil, salt absorption and salt fixation cannot be realized, and the modifier is easy to reduce the activity of a biological agent due to higher salt content and has poor effect on improving severe saline soil.
For another example, chinese patent document CN105993267A discloses a method for performing raw soil greening on coastal saline-alkali soil by using a salt absorbent containing fly ash, and chinese patent document CN105993268A discloses a method for performing raw soil greening on seawater-immersed saline-alkali soil by using a salt absorbent containing sugar residue mud, which are salt absorbents, but have the following disadvantages:
(1) the retention of salts, especially sodium ions, is not stable. Coastal saline soil, particularly severe saline soil, has over 90 percent of salt content of sodium chloride, so that the sodium ion is not stably held, which means that the salt absorption effect is not stable, and further the growth of crops is influenced, particularly the growth in the early emergence stage. The two documents absorb salt mainly through the adsorption and the hole-dwelling effect of inorganic materials such as bentonite, argil grains, zeolite powder, fly ash, fishbone powder and the like, but the fixing effect on salt is gradually reduced or disappears along with the desorption and the diffusion of the salt absorbed by the inorganic materials.
(2) The salt is not retained for a long time, and the long-acting property is poor. The two documents absorb salt mainly by absorbing organic materials such as straw powder, but the salt is gradually reduced or disappears by fixing along with the degradation of the straw powder and the organic materials.
(3) Is only suitable for greening the original soil of the coastal saline soil and is not suitable for field crops. The method is difficult to realize the simultaneous sowing of seed manure, and except that the simultaneous sowing of seed manure can not be realized because of no granulation, the key is that the adsorption effect of cations in the fertilizer on sodium ions is reduced because of competitive adsorption on the sodium ions during the simultaneous sowing of seed manure. Further, there is a problem of high cost.
(4) The problem of changing the soil into a plate due to rich alkali in the process of soil desalination cannot be controlled. The coastal saline soil is generally accompanied with an alkalization process in the process of desalting, and the alkalization process aggravates the hardening of the soil. Both of these documents, although also introducing acidic substances such as ammonium sulphate, superphosphate, etc., the materials release H rapidly+Cannot slowly and gradually release H+Therefore, the sodium ion desalting agent cannot play a role in desalting and inhibiting alkali, and can inhibit the adsorption of sodium ions, thereby influencing the salt absorption effect.
Disclosure of Invention
The invention aims to solve the technical problem of the prior art and provides a lasting-effect coastal saline soil improvement salt-absorbing agent, and a preparation method and application thereof.
The lasting effect type coastal saline soil improvement salt absorption agent simultaneously achieves the following purposes:
(1) the adsorption of inorganic adsorption material and the space occlusion of inorganic porous material are organically combined together, so that the salt absorption and the salt solidification are realized.
(2) The physical adsorption and the chemical adsorption of organic materials are combined to be used as 'salt adsorption' and 'salt fixation'.
(3) The organic adsorption material is combined with the inorganic adsorption material, so that the immobilization of sodium ions is strengthened, the sodium ion content of the soil solution is reduced, and the efficient salt reduction effect is achieved.
(4) The organic combination of the inorganic pore material and the organic pore-filling material is that firstly, salt is introduced into pores, and then the salt is firmly blocked in the pores, so as to achieve high-strength solid salt.
(5) Low cost, being suitable for rapid mass production, being capable of realizing 'simultaneous sowing of seed and fertilizer', and being convenient for popularization and application on field crops.
(6) Can continuously realize the desalination and alkali inhibition of the coastal saline soil and continuously improve the soil.
In order to achieve the above purpose, the invention is realized by the following technical scheme:
a lasting effect type coastal saline soil improvement salt absorption agent comprises two functional components of a salt absorption component and a salt occlusion component, wherein the weight ratio of the salt absorption component to the salt occlusion component is as follows: (60-90): (10-40), wherein the salt absorption component is prepared from sulfonated modified humic acid and an inorganic adsorbing material according to the weight ratio of (75-85): (15-25) by weight; the storage salt component is prepared from an inorganic pore material and an organic pore filling material according to the weight ratio of (85-90): (10-15) in a weight ratio.
According to the invention, the preferable sulfonated modified humic acid is prepared by modifying humic acid in a reaction kettle at 55-75 ℃ in the presence of sulfuric acid and then drying; the mass fraction of the sulfuric acid is 20-40%, and the solid-liquid weight ratio of the humic acid to the sulfuric acid is 1: 5-10.
Preferably, in the preparation process of the sulfonated modified humic acid, after the modification reaction is completed, filtering is performed, filter residues are dispersed in deionized water according to the solid-to-liquid ratio of 1:5, powdery calcium carbonate is slowly added during stirring, the pH value is adjusted to be 5.5-6.0, plate and frame filter pressing is performed, after the filter residues are sheared and crushed, air blowing drying is performed at the temperature of 120-150 ℃ until the water content is lower than 3%, and the filter residues are crushed and sieved by a 1mm sieve, so that the sulfonated modified humic acid is obtained.
Further preferably, the humic acid is weathered coal or lignite, the particle size is more than or equal to 100 meshes, the carbon content is more than or equal to 50 percent, and the aromaticity is more than or equal to 40 percent.
According to the invention, the inorganic adsorbing material is preferably one or more of aluminum sulfate hexahydrate, alum and silica gel in any combination.
According to the invention, the salt absorption component is preferably prepared according to the following steps:
and uniformly mixing the sulfonated modified humic acid and the inorganic adsorbing material at the temperature of less than or equal to 20 ℃ and the humidity of less than or equal to 50 percent to obtain the humic acid modified humic acid.
According to the invention, the inorganic porous material is preferably one or more of chabazite powder, pumice powder and palygorskite powder in any combination.
Further preferably, the pore diameter of chabazite powderThe grain size is more than or equal to 100 meshes, and the grain size of the pumice powder and the palygorskite powder is more than or equal to 100 meshes.
According to the invention, the organic pore-filling material is one or more of polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl methyl cellulose and hydroxyethyl cellulose in any combination.
Preferably, according to the invention, the occlusion salt component is prepared by the following steps:
adding distilled water into a temperature-controlled reaction kettle, heating to 80-100 ℃, then slowly adding an organic pore filling material according to a solid-to-liquid ratio of 1: 40-50 while stirring, controlling the temperature at 70-80 ℃, stirring for 30min, then slowly adding an inorganic pore material according to a weight ratio of 1: 5-6 to the organic pore filling agent while stirring, controlling the temperature and stirring for 30min, then transferring the mixture into a stainless steel container while the mixture is hot, putting the mixture into an ultrasonic cleaning machine for ultrasonic oscillation for 30-60 min, performing plate and frame filter pressing, performing air-blast drying on filter residues at 180-250 ℃ after shearing and crushing until the water content is lower than 3%, and crushing the filter residues through a 2mm sieve to obtain the occluded salt component.
More preferably, the ultrasonic oscillation has an oscillation frequency of 60 to 90 khz. The ultrasonic oscillation is used for removing air in the inorganic pore material and enabling the organic pore filling agent to enter pores along with water.
A preparation method of a lasting type coastal saline soil improvement salt absorption agent comprises the following steps:
mixing the salt absorption component and the dried salt occlusion and storage component for 10-20 min under the vacuum heat drying condition of vacuum degree of 90-95 kpa and temperature of 70 ℃ according to the weight ratio of 1: 1.5-9;
or spraying the salt absorption component and the salt retention component in a weight ratio of 1: 1.5-9 into the salt absorption component, granulating, drying and cooling.
More preferably, the granulated particle size is 2 to 5 mm.
Further preferably, the air inlet temperature of the dryer is controlled to be 180-250 ℃ and the air outlet temperature of the dryer is controlled to be 70-90 ℃ during drying.
It is further preferred that the temperature of the cooled particulate modifying agent should not exceed the natural ambient temperature.
The long-acting type coastal saline soil improvement salt-absorbing agent is applied to improving coastal saline soil, is used for long-acting improvement of a high-salinity coastal saline soil full plough layer, and is applied at the application amount of 50 kg/mu-200 kg/mu.
According to the invention, the preferable application amount is 100 kg/mu-200 kg/mu for the severe saline soil with the soluble salt content of more than or equal to 0.4 percent, and 50 kg/mu-100 kg/mu for the medium-low saline soil with the soluble salt content of less than 0.4 percent.
The preparation of the salt absorption component not only introduces the organic adsorbent with low salinity, namely the sulfonated modified humic acid, but also introduces inorganic adsorption materials such as aluminum sulfate hexahydrate and the like. The inorganic adsorption material is hydrolyzed to generate aluminum hydroxide inorganic colloid, so that sodium ions in the soil solution are adsorbed, the content of the sodium ions in the soil solution is reduced, the adsorption is reversible, the adsorbed sodium ions can be desorbed, and the adsorption of the sodium ions is enhanced by introducing the sulfonated modified humic acid, so that the physical adsorption is enhanced, the chemical adsorption is enhanced, the fixation of the sodium ions is enhanced, the content of the sodium ions in the soil solution is further reduced, and the salt reducing effect is achieved. The sodium ions absorbed by the salt absorbent can be desorbed during fresh water irrigation, and the desorbed sodium ions enter fresh water and move to deep soil along with the water under the action of gravity, so that the salt absorbent recovers the salt absorption function while desalting plough layer soil. The adsorption of the adsorbent to salt is limited, and in the process of dynamic balance, in order to further enhance the salt absorption capacity, keep the lower salt concentration of the soil solution and be beneficial to the growth of crops, the invention fixes a part of sodium ions and chloride ions by introducing the salt storage component, thereby effectively avoiding the increase of the content of the sodium ions and the chloride ions in the soil solution caused by the ion exchange effect generated by fertilization. This is because the dried occlusion salt component absorbs water rapidly in the soil, sodium ions and chloride ions in the soil solution enter the pores of the occlusion salt component along with the water, the organic pore-filling material in the pores absorbs water to swell and block the pores, and the sodium ions and chloride ions are "sealed" in the pores, so that the content of the sodium ions and chloride ions in the soil solution is greatly reduced and is not affected by fertilization. In addition, acidic factors and calcium ions are introduced through sulfonation modification of humic acid and an inorganic adsorbent or hydrolysate thereof, so that the pH value of soil can be reduced, sodium ions adsorbed by the soil can be replaced, the soil structure can be improved, and the effects of continuous desalination, alkali inhibition and plate modification can be achieved. The raw materials used for preparing the salt absorption agent are easy to obtain, the price is low, the salt absorption agent is suitable for large-scale production, and the seed manure can be sowed simultaneously by introducing the binding material for granulation, so that the salt absorption agent not only can be widely applied to improvement of coastal saline soil farmlands, but also can simplify the improvement operation.
In a word, the invention has the advantages that the salt absorption and the salt fixation are improved, and the salt reduction effect is more obvious; the lasting effect and the high efficiency are synchronous, so that the salt content of the soil is maintained at a lower level; the 'desalting' and the 'salt inhibiting and plate changing' are coordinated, so that the method is more beneficial to the growth of crops and the improvement of soil structure; the fertilizer has the advantages of easily obtained materials, simple preparation, lower cost, suitability for rapid mass production, capability of being used for 'sowing seeds and fertilizers simultaneously', simplified improvement operation and wide market prospect.
Detailed Description
The present invention is further described in conjunction with the following examples, which are included to explain and illustrate the present invention and are not to be construed as limiting the scope of the present invention.
The raw materials used in the examples are illustrated below:
sulfuric acid: available from Nanjing Union speciality chemical Co., Ltd;
weathered coal humic acid, lignite humic acid, available from Jinan Yunze chemical Limited;
powdered calcium carbonate, available from jingzi 38473;
aluminum sulfate hexadecahydrate, which is sold in the chemical industry of Jinan Shiteng to a limited extent;
alum, available from chemical Limited of Jinan Dewang;
silica gel, available from chemical Limited of Jinan Suzuki;
chabazite powder with standard pore diameter
Figure BDA0002268365180000051
Sold by mineral processing plants in Wachwan of Lingshu county;
pumice powder, available from the manufacturer of Baifeng mineral products in lingshou county;
palygorskite powder, available from Shijiazhuang morning refractory Co., Ltd;
93 percent of light magnesium oxide, which is produced and sold by Shijiazhuang Tianyu magnesium industry Co Ltd;
dolomite powder, available from Lingshou county Henchang mineral processing factories;
polyvinyl alcohol (1799), available from Anhui Uygur, Inc.;
carboxymethyl cellulose, hydroxypropylmethyl cellulose, hydroxyethyl cellulose, commercially available from Hebei Chemicals, Inc.
Example 1:
a lasting-effect type coastal saline soil improvement salt absorption agent:
(1) preparation of salt absorption component:
a. mixing aluminum sulfate hexadecahydrate and silica gel according to the weight ratio of 2:3 to form an inorganic adsorbent for later use;
b. adding 100L of sulfuric acid with the mass fraction of 20% into a temperature-controlled reaction kettle, slowly adding weathered coal humic acid with the particle size of less than or equal to 200 meshes according to the liquid-solid volume ratio of 10:1 while stirring, controlling the temperature to be 70-75 ℃, refluxing for 4.0-4.5 hours, filtering, dispersing filter residues into deionized water according to the solid-liquid ratio of 1:5, slowly adding powdery calcium carbonate while stirring, adjusting the pH to be 5.8-6.0, stopping adding, performing plate and frame filter pressing, performing air blast drying after shearing and crushing the filter residues, stopping drying when the drying temperature is 120-125 ℃, and crushing the filter residues and the water content is less than 3%, and obtaining sulfonated modified humic acid by sieving with a 1mm sieve;
c. and physically mixing 85 parts by weight of dried sulfonated modified humic acid and 15 parts by weight of dried inorganic adsorbent at the temperature of 30 ℃ and the relative humidity of below 40% to obtain a salt absorbing component.
(2) Preparation of the occlusion salt component:
a. mixing polyvinyl alcohol and carboxymethyl cellulose according to a weight ratio of 4:1 to obtain an organic pore-filling material; mixing chabazite powder and pumice powder according to the weight ratio of 3:1 to obtain an inorganic porous material for later use;
b. adding 100L of distilled water into a temperature-controlled reaction kettle, heating to 98-100 ℃, then slowly adding an organic pore filling material according to a solid-to-liquid ratio of 1:40 while stirring, controlling the temperature to 78-80 ℃, stirring for 30min after all the organic pore filling material is added to obtain an organic pore filling agent, slowly adding an inorganic pore material according to a weight ratio of 1:6 to the organic pore filling agent while stirring, controlling the temperature and stirring for 30min after all the materials are added, then transferring the materials into a stainless steel container while the materials are hot, putting the stainless steel container into an ultrasonic cleaning machine, and carrying out ultrasonic oscillation for 60min with an oscillation frequency of 90 kHz to remove air in the inorganic pore material and enable the organic pore filling agent to enter pores along with water. Preferably, the treatment solution is subjected to plate-and-frame filter pressing, filter residues are subjected to forced air drying at 190 ℃ after being sheared and crushed, drying is stopped when the water content is lower than 3%, and the filter residues are crushed and screened by a 2mm sieve to obtain a salt storage component;
(3) the preparation method of the lasting type coastal saline soil improvement salt absorption agent comprises the following steps:
firstly, mixing a salt absorption component and a salt storage component according to a weight ratio of 1.5:1, and then carrying out vacuum drying at a vacuum degree of 90-95 kpa and a drying temperature of 70 ℃ for 20 min.
The lasting-effect type special salt absorbent for improving the coastal saline soil prepared in the embodiment 1 is suitable for improving the whole plough layer of the high-salinity coastal saline soil.
Example 2:
a lasting-effect type coastal saline soil improvement salt absorption agent:
(1) preparation of salt absorption component:
a. mixing alum and silica gel according to the weight ratio of 1:1 to form an inorganic adsorbent for later use;
b. adding 100L of sulfuric acid with the mass fraction of 30% into a temperature-controlled reaction kettle, slowly adding weathered coal humic acid with the particle size of less than or equal to 200 meshes according to the liquid-solid volume ratio of 8:1 while stirring, controlling the temperature to be 68-73 ℃, refluxing for 5.0-5.5 h, filtering, dispersing filter residues into deionized water according to the solid-liquid ratio of 1:5, slowly adding powdery calcium carbonate while stirring, adjusting the pH to be 5.6-5.8, stopping adding, performing plate and frame filter pressing, performing forced air drying after shearing and crushing the filter residues, stopping drying at the drying temperature of 140-145 ℃, and obtaining sulfonated modified humic acid after crushing through a 1mm sieve, wherein the mass fraction of the sulfuric acid is 30%;
c. and physically mixing 80 parts by weight of dried sulfonated modified humic acid and 20 parts by weight of dried inorganic adsorbent at the temperature of 30 ℃ and the relative humidity of below 40% to obtain a salt absorbing component.
(2) Preparation of the occlusion salt component:
a. mixing polyvinyl alcohol and hydroxypropyl methyl cellulose according to the weight ratio of 2:1 to obtain an organic pore-filling material; mixing chabazite powder and pumice powder according to the weight ratio of 2:1 to obtain an inorganic porous material for later use;
b. adding 100L of distilled water into a temperature-controlled reaction kettle, heating to 90-95 ℃, then slowly adding an organic pore filling material according to a solid-to-liquid ratio of 1:45 while stirring, controlling the temperature to be 75-78 ℃, stirring for 30min after all the organic pore filling material is added to obtain an organic pore filling agent, then slowly adding an inorganic pore material according to a weight ratio of 1:5.5 to the organic pore filling agent while stirring, controlling the temperature and stirring for 30min after all the materials are added, then transferring the mixture into a stainless steel container while the mixture is hot, putting the stainless steel container into an ultrasonic cleaning machine, and carrying out ultrasonic oscillation for 60min with an oscillation frequency of 80 kHz to remove air in the inorganic pore material and enable the organic pore filling agent to enter pores along with water. Preferably, the treatment solution is subjected to plate-and-frame filter pressing, the filter residue is subjected to air-blast drying at 200 ℃ after being sheared and crushed, the drying is stopped when the water content is lower than 3%, and the occluded salt component is obtained after crushing and sieving by a 2mm sieve.
(3) The preparation method of the lasting type coastal saline soil improvement salt absorption agent comprises the following steps:
firstly, mixing the salt-storage-salt-retention component and the salt-absorption component according to the weight ratio of 1:3, and then carrying out vacuum drying at the vacuum degree of 90-95 kpa and the drying temperature of 70 ℃ for 15 min.
The lasting-effect special salt absorbent for improving the coastal saline soil prepared in the embodiment 2 is suitable for improving the whole plough layer of the coastal saline soil with medium and high salinity and medium nutrition.
Example 3:
a lasting-effect type coastal saline soil improvement salt absorption agent:
(1) preparation of salt absorption component:
a. mixing aluminum sulfate hexadecahydrate and silica gel according to the weight ratio of 2:3 to form an inorganic adsorbent for later use;
b. adding 100L of sulfuric acid with the mass fraction of 20% into a temperature-controlled reaction kettle, slowly adding weathered coal humic acid with the particle size of less than or equal to 200 meshes according to the liquid-solid volume ratio of 10:1 while stirring, controlling the temperature to be 70-75 ℃, refluxing for 4.0-4.5 hours, filtering, dispersing filter residues into deionized water according to the solid-liquid ratio of 1:5, slowly adding powdery calcium carbonate while stirring, adjusting the pH to be 5.8-6.0, stopping adding, performing plate and frame filter pressing, performing air blast drying after shearing and crushing the filter residues, stopping drying when the drying temperature is 120-125 ℃, and crushing the filter residues and the water content is less than 3%, and obtaining sulfonated modified humic acid by sieving with a 1mm sieve;
c. and physically mixing 85 parts by weight of dried sulfonated modified humic acid and 15 parts by weight of dried inorganic adsorbent at the temperature of 30 ℃ and the relative humidity of below 40% to obtain a salt absorbing component.
(2) Preparation of the occlusion salt component:
a. mixing polyvinyl alcohol and carboxymethyl cellulose according to a weight ratio of 4:1 to obtain an organic pore-filling material; mixing chabazite powder and pumice powder according to the weight ratio of 3:1 to obtain an inorganic porous material for later use;
b. adding 100L of distilled water into a temperature-controlled reaction kettle, heating to 98-100 ℃, then slowly adding an organic pore filling material according to a solid-to-liquid ratio of 1:40 while stirring, controlling the temperature to 78-80 ℃, stirring for 30min after all the organic pore filling material is added, then slowly adding an inorganic pore material according to a weight ratio of 1:5 to the organic pore filling material while stirring, controlling the temperature and stirring for 30min after all the materials are added, then transferring the materials into a stainless steel container while the materials are hot, putting the materials into an ultrasonic cleaning machine, carrying out ultrasonic oscillation for 60min, wherein the oscillation frequency is 90 KHz, removing air in the inorganic pore material, enabling the organic pore filling agent to enter pores along with water, carrying out plate and frame filter pressing, and carrying out shear crushing on filter residues to obtain an undried occluded salt component.
(3) The preparation method of the lasting type coastal saline soil improvement salt absorption agent comprises the following steps:
according to the weight ratio of the dried occluded salt component to the adsorbed salt component of 1:1.5, spraying the non-dried occluded salt component on the mixed dried material of the adsorbed salt component in a drum granulator or a disc granulator, granulating, drying, cooling, screening and packaging to obtain the product. The method comprises the following steps: during drying, the air inlet temperature of the dryer is controlled to be 220-250 ℃, the air outlet temperature is controlled to be 85-90 ℃, and the cooled salt absorbent particles are close to the room temperature. The preferable granulation particle size is 2 mm-5 mm, the particle size is too large or too small, and the granulated particles are pulverized to be used as the powdery lasting salt absorbent special for improving the coastal saline soil.
The sustained-effect special salt absorbent for improving the coastal saline soil prepared in the embodiment 3 is used for improving the whole plough layer of the high-salinity coastal saline soil in a powdery manner, and is used for improving the planting plough layer of the high-salinity coastal saline soil under the condition of sowing seeds and fertilizers at the same time.
Example 4:
a lasting-effect type coastal saline soil improvement salt absorption agent:
(1) preparation of salt absorption component:
a. mixing alum and silica gel according to the weight ratio of 1:1 to form an inorganic adsorbent for later use;
b. adding 100L of sulfuric acid with the mass fraction of 30% into a temperature-controlled reaction kettle, slowly adding weathered coal humic acid with the particle size of less than or equal to 200 meshes according to the liquid-solid volume ratio of 8:1 while stirring, controlling the temperature to be 68-73 ℃, refluxing for 5.0-5.5 h, filtering, dispersing filter residues into deionized water according to the solid-liquid ratio of 1:5, slowly adding powdery calcium carbonate while stirring, adjusting the pH to be 5.6-5.8, stopping adding, performing plate and frame filter pressing, performing forced air drying after shearing and crushing the filter residues, stopping drying at the drying temperature of 140-145 ℃, and obtaining sulfonated modified humic acid after crushing through a 1mm sieve, wherein the mass fraction of the sulfuric acid is 30%;
c. and physically mixing 80 parts by weight of dried sulfonated modified humic acid and 20 parts by weight of dried inorganic adsorbent at the temperature of 30 ℃ and the relative humidity of below 40% to obtain a salt absorbing component.
(2) Preparation of the occlusion salt component:
a. mixing polyvinyl alcohol and hydroxypropyl methyl cellulose according to the weight ratio of 2:1 to obtain an organic pore-filling material; mixing chabazite powder and pumice powder according to the weight ratio of 2:1 to obtain an inorganic porous material for later use;
b. adding 100L of distilled water into a temperature-controlled reaction kettle, heating to 90-95 ℃, then slowly adding an organic pore filling material according to a solid-to-liquid ratio of 1:45 while stirring, controlling the temperature to be 75-78 ℃, stirring for 30min after all the organic pore filling material is added to obtain an organic pore filling agent, then slowly adding an inorganic pore material according to a weight ratio of 1:5.5 to the organic pore filling agent while stirring, controlling the temperature and stirring for 30min after all the materials are added, then transferring the mixture into a stainless steel container while the mixture is hot, putting the stainless steel container into an ultrasonic cleaning machine, and carrying out ultrasonic oscillation for 60min with an oscillation frequency of 80 kHz to remove air in the inorganic pore material and enable the organic pore filling agent to enter pores along with water. Preferably, the treatment solution is subjected to plate-and-frame filter pressing, and the filter residue is sheared and crushed to obtain an undried occluded salt component.
(3) The preparation method of the lasting type coastal saline soil improvement salt absorption agent comprises the following steps: :
according to the weight ratio of the dried occluded salt component to the adsorbed salt component of 1:3, the non-dried occluded salt component is sprayed on the mixed dry material of the adsorbed salt component in a drum granulator or a disc granulator, and the product is prepared by granulation, drying, cooling, screening and packaging. The method comprises the following steps: during drying, the air inlet temperature of the dryer is controlled to be 180-210 ℃, the air outlet temperature is controlled to be 70-75 ℃, and the cooled salt absorbent particles are close to the room temperature. The preferable granulation particle size is 2 mm-5 mm, the particle size is too large or too small, and the granulated particles are pulverized to be used as the powdery lasting salt absorbent special for improving the coastal saline soil.
The sustained-effect special salt absorbent for improving the coastal saline soil prepared in the embodiment 4 is used for improving the whole plough layer of the coastal saline soil with medium and high salinity in a powdery manner and is used for improving the planting plough layer of the coastal saline soil with medium and high salinity in a granular manner under the condition of sowing seeds and fertilizers at the same time.
Application test example:
the sustained-effect type coastal saline soil improvement salt absorption agent prepared according to the embodiment is applied to a severe salinization coastal saline soil improvement test of yellow river estuary towns in reclamation areas of Shandong province, Dongying cities, and the tested crop is winter wheat.
Before sowing winter wheat:
the salt and nutrient content conditions of the plough layer soil are as follows: the soil surface layer (0-20 cm) has the soluble salt content of 0.48 percent, belongs to heavy saline soil (the salt content is more than or equal to 0.40 percent), has the sodium chloride content of 93 percent, the pH value of 7.2, the alkaline hydrolysis nitrogen content of 44.5mg/Kg, the effective phosphorus content of 19.8mg/Kg and the effective potassium content of 131.1 mg/Kg.
After harvesting winter wheat:
(1) improving effect on soil salinity and pH value
The content of soluble salt in the soil on the surface layer (0-20 cm) is reduced by 47.7-57.3%, the content of sodium ions in the soil is reduced by 60.3-68.9%, the content of chloride ions is reduced by 35.1-45.7%, and the pH is reduced to 6.7-7.0. Specific indexes are shown in a table 1:
TABLE 1 salt content and pH changes in the surface soil of harvested winter wheat
Soil index Example 1 Example 2 Example 3 Example 4
Soluble salt content (%) 0.205 0.237 0.234 0.251
Decrease in soluble salt content (%) 57.3 50.6 51.3 47.7
Reduction of soil sodium ion content (%) 68.9 63.4 62.8 60.3
Reduction of soil chloride ion content (%) 45.7 37.9 39.7 35.1
pH of soil 7.0 7.1 7.0 7.2
(2) Persistent effect on soil salinity and pH improvement
After the salt absorbent is applied to the coastal saline soil improved by the salt absorbent, the salt absorbent is not applied any more, the content of soluble salt and the pH value of the soil on the surface soil (0-20 cm) are measured after 6 months, and the test results are shown in the following table 2:
TABLE 2 physicochemical Properties of the coastal saline soil after 6 months after improvement of the salt absorbent
Soil index Example 1 Example 2 Example 3 Example 4
Soluble salt content (%) 0.207 0.241 0.235 0.256
pH of soil 7.0 7.1 7.0 7.2
As can be seen from the table 2, even if the salt absorbent is not applied to the improved coastal saline soil, the content of soluble salt and the pH value of the soil are basically unchanged after 6 months, which shows that the salt absorbent has lasting effect and long lasting period.
(3) Influence on growth and yield of winter wheat
Compared with the contrast, the emergence rate of the wheat field which is applied with the special salt absorbent for improving the coastal saline soil is improved by 25.8-29.5%, the ear number per mu is increased by 32.1-36.8%, and the yield per mu of winter wheat is improved by 35.9-42.6%. The specific indexes are shown in Table 2:
TABLE 3 winter wheat growth and yield conditions
Soil index Example 1 Example 2 Example 3 Example 4
Emergence rate increase (%) 29.5 26.2 28.1 25.8
Increase in ear per mu (%) 36.8 33.4 34.2 32.1
Mu yield increase (%) 42.6 37.3 39.8 35.9
The above embodiments are only exemplary, so as to enable those skilled in the art to better understand the present disclosure, and should not be construed as limiting the scope of the present invention, but as merely providing the modifications to the technical solution of the present invention, which fall within the scope of the present invention.

Claims (10)

1. A lasting effect type coastal saline soil improvement salt absorption agent comprises two functional components of a salt absorption component and a salt occlusion component, wherein the weight ratio of the salt absorption component to the salt occlusion component is as follows: (60-90): (10-40), wherein the salt absorption component is prepared from sulfonated modified humic acid and an inorganic adsorbing material according to the weight ratio of (75-85): (15-25) by weight; the storage salt component is prepared from an inorganic pore material and an organic pore filling material according to the weight ratio of (85-90): (10-15) in a weight ratio.
2. The lasting-effect coastal saline soil improvement salt absorption agent as claimed in claim 1, wherein the sulfonated modified humic acid is prepared by modifying humic acid in a reaction kettle at 55-75 ℃ in the presence of sulfuric acid and then drying; the mass fraction of the sulfuric acid is 20-40%, and the solid-liquid weight ratio of the humic acid to the sulfuric acid is 1: 5-10.
3. The lasting-effect coastal saline soil improvement salt absorption agent according to claim 1, characterized in that in the preparation process of the sulfonated modified humic acid, after the modification reaction is completed, filtration is carried out, filter residues are dispersed in deionized water according to a solid-to-liquid ratio of 1:5, powdery calcium carbonate is slowly added while stirring, the pH is adjusted to be 5.5-6.0, plate and frame filter pressing is carried out, after the filter residues are sheared and crushed, air-blast drying is carried out at a temperature of 120-150 ℃ until the water content is lower than 3%, and the filter residues are crushed by a sieve of 1mm to obtain the sulfonated modified humic acid, preferably, the humic acid is weathered coal or lignite, the particle size is larger than or equal to 100 meshes, the carbon content is larger than or equal to.
4. The lasting coastal saline soil improvement salt adsorbent of claim 1, wherein the inorganic adsorbing material is one or more of aluminum sulfate hexadecahydrate, alum and silica gel in any combination.
5. The lasting type coastal saline soil improvement salt absorption agent according to claim 1, wherein the salt absorption component is prepared by the following steps:
and uniformly mixing the sulfonated modified humic acid and the inorganic adsorbing material at the temperature of less than or equal to 20 ℃ and the humidity of less than or equal to 50 percent to obtain the humic acid modified humic acid.
6. The lasting type coastal saline soil improvement salt absorption agent as claimed in claim 1, wherein the inorganic porous material is one or more of chabazite powder, pumice powder and palygorskite powder, and the pore diameter of the chabazite powder is any combination of two or more of the chabazite powder, the pumice powder and the palygorskite powder
Figure FDA0002268365170000011
The grain size is more than or equal to 100 meshes, and the grain size of the pumice powder and the palygorskite powder is more than or equal to 100 meshes; the organic pore-filling material is one or more of polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl methyl cellulose and hydroxyethyl cellulose.
7. The lasting coastal saline soil improvement salt absorption agent according to claim 1, wherein the salt sequestration component is prepared by the following steps:
adding distilled water into a temperature-controlled reaction kettle, heating to 80-100 ℃, then slowly adding an organic pore filling material according to a solid-to-liquid ratio of 1: 40-50 while stirring, controlling the temperature at 70-80 ℃, stirring for 30min, then slowly adding an inorganic pore material according to a weight ratio of 1: 5-6 to the organic pore filling agent while stirring, controlling the temperature and stirring for 30min, then transferring the mixture into a stainless steel container while the mixture is hot, putting the mixture into an ultrasonic cleaning machine for ultrasonic oscillation for 30-60 min, performing plate and frame filter pressing, performing air-blast drying on filter residues at 180-250 ℃ after shearing and crushing until the water content is lower than 3%, and crushing the filter residues through a 2mm sieve to obtain the occluded salt component.
8. A preparation method of a lasting type coastal saline soil improvement salt absorption agent comprises the following steps:
mixing the salt absorption component and the dried salt occlusion and storage component for 10-20 min under the vacuum heat drying condition of vacuum degree of 90-95 kpa and temperature of 70 ℃ according to the weight ratio of 1: 1.5-9;
or spraying the salt absorption component and the salt retention component in a weight ratio of 1: 1.5-9 into the salt absorption component, granulating, drying and cooling.
9. The preparation method of claim 8, wherein the grain size of the granulated material is 2-5 mm, the inlet air temperature of the dryer is controlled to be 180-250 ℃ during drying, the outlet air temperature is controlled to be 70-90 ℃, and the temperature of the cooled granular modifying agent is not higher than the natural environment temperature.
10. The application of the lasting-effect type coastal saline soil improvement salt absorption agent in improving coastal saline soil is used for long-acting improvement of a high-salinity coastal saline soil full plough layer, and the application amount is 50 kg/mu to 200 kg/mu;
the application amount is 100 kg/mu to 200 kg/mu for severe saline soil with the soluble salt content of more than or equal to 0.4 percent, and is 50 kg/mu to 100 kg/mu for medium and low-degree saline soil with the soluble salt content of less than 0.4 percent.
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