CN111011161A - Red mud soil matrix and preparation method thereof - Google Patents
Red mud soil matrix and preparation method thereof Download PDFInfo
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- CN111011161A CN111011161A CN201911366862.5A CN201911366862A CN111011161A CN 111011161 A CN111011161 A CN 111011161A CN 201911366862 A CN201911366862 A CN 201911366862A CN 111011161 A CN111011161 A CN 111011161A
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G24/00—Growth substrates; Culture media; Apparatus or methods therefor
- A01G24/20—Growth substrates; Culture media; Apparatus or methods therefor based on or containing natural organic material
- A01G24/22—Growth substrates; Culture media; Apparatus or methods therefor based on or containing natural organic material containing plant material
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G24/00—Growth substrates; Culture media; Apparatus or methods therefor
- A01G24/10—Growth substrates; Culture media; Apparatus or methods therefor based on or containing inorganic material
- A01G24/17—Growth substrates; Culture media; Apparatus or methods therefor based on or containing inorganic material containing slag
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G24/00—Growth substrates; Culture media; Apparatus or methods therefor
- A01G24/20—Growth substrates; Culture media; Apparatus or methods therefor based on or containing natural organic material
- A01G24/22—Growth substrates; Culture media; Apparatus or methods therefor based on or containing natural organic material containing plant material
- A01G24/23—Wood, e.g. wood chips or sawdust
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G24/00—Growth substrates; Culture media; Apparatus or methods therefor
- A01G24/60—Apparatus for preparing growth substrates or culture media
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F33/00—Other mixers; Mixing plants; Combinations of mixers
- B01F33/80—Mixing plants; Combinations of mixers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F33/00—Other mixers; Mixing plants; Combinations of mixers
- B01F33/80—Mixing plants; Combinations of mixers
- B01F33/83—Mixing plants specially adapted for mixing in combination with disintegrating operations
- B01F33/831—Devices with consecutive working receptacles, e.g. with two intermeshing tools in one of the receptacles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F33/00—Other mixers; Mixing plants; Combinations of mixers
- B01F33/80—Mixing plants; Combinations of mixers
- B01F33/836—Mixing plants; Combinations of mixers combining mixing with other treatments
- B01F33/8362—Mixing plants; Combinations of mixers combining mixing with other treatments with chemical reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F35/00—Accessories for mixers; Auxiliary operations or auxiliary devices; Parts or details of general application
- B01F35/71—Feed mechanisms
- B01F35/717—Feed mechanisms characterised by the means for feeding the components to the mixer
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Abstract
The application discloses a red mud soil matrix and a preparation method thereof, belongs to the technical field of red mud ecological restoration, and solves the problems of large consumption of red mud alkalinity regulation and control chemicals, complex other components, high cost and small red mud consumption in red mud soil chemical treatment. The preparation method comprises the following steps: crushing a biomass raw material; conveying biomass powder, water and a catalyst into a stirring tank and stirring to obtain a mixture; adding the mixture into a high-pressure reaction kettle, heating, preserving heat, and then cooling to room temperature to obtain a hydrothermal carbonization product; carrying out solid-liquid separation on part of the hydrothermal carbonization product to obtain hydrothermal carbon and hydrothermal carbon liquid; the remaining hydrothermal carbonization product is reserved; carbonizing the hydrothermal carbon to obtain modified hydrothermal carbon; mixing the modified hydrothermal carbon, the hydrothermal carbonization product and the red mud, putting the mixture into a stirring tank, stirring and placing the mixture to obtain the red mud soil matrix. The red mud soil matrix comprises a stirring mixture of modified hydrothermal carbon, hydrothermal carbonization products and red mud. The application realizes the ecological restoration of the red mud.
Description
Technical Field
The application relates to a red mud ecological restoration technology, in particular to a red mud soil matrix and a preparation method thereof.
Background
The red mud is solid waste residue generated in the production process of alumina, the total stock of the red mud in China exceeds 6 hundred million tons, the red mud is generated by about 1 hundred million tons every year, the stock of a large amount of the red mud not only occupies land resources, but also seriously harms the ecology near a stock dump, the grass on the stock dump is not grown due to the strong basicity of the red mud, dust is easily generated to pollute air, harmful elements in the red mud are easily transferred to underground water and soil to pollute the underground water and the soil, and certain cost is required for maintaining the stock dump. At present, a great deal of research is carried out on the comprehensive utilization of the red mud, and the research mainly comprises the steps of extracting valuable components, preparing functional materials, preparing building materials and the like; the red mud contains a certain amount of metal resources, and the problems of complex process, high cost, secondary pollution and the like exist in the extraction of valuable metals; the preparation of functional materials with high added values is basically in a research stage, and the technical idea has very limited red mud consumption; the red mud can be used for preparing building materials such as sintered bricks, non-steamed bricks, cement and the like, but the strong basicity of the red mud seriously affects the product quality, and the dealkalization technology has high cost and complex process.
The red mud is regulated into a soil matrix for plant growth to achieve ecological restoration, the reduction and harmlessness of the red mud are realized, and the application prospect is very good; the red mud has strong alkalinity and rich mineral elements, researches show that the red mud can better promote plant growth when used for regulating and controlling acid soil, but the red mud has very poor soil characteristics, strong alkalinity, low water retention rate, poor air permeability, easy hardening, low organic nutrient content and difficult direct soil utilization.
Disclosure of Invention
In view of the above analysis, the present application aims to provide a red mud soil matrix and a preparation method thereof, which can solve at least one of the following technical problems: (1) in the prior art, the dosage of red mud alkaline regulation chemical substances is large, and a large amount of waste liquid is generated; (2) during the process of converting red mud into soil, the red mud is used as an additive component, and other components are complex (such as alkaline regulators, fertilizers, modifiers and the like), large in dosage and high in cost; (3) the utilization rate and the consumption of the red mud are low.
The purpose of the application is mainly realized by the following technical scheme:
the application provides a preparation method of a red mud soil matrix, which comprises the following steps:
step S1, crushing the biomass raw material into biomass powder by a crusher;
step S2, conveying the biomass powder, water and the catalyst into a stirring tank for stirring to obtain a mixture;
step S3, adding the mixture into a high-pressure reaction kettle at a speed V1Heating the high-pressure reaction kettle to T1Then, preserving the heat for 5-20 h; then cooling to room temperature to obtain a hydrothermal carbonization product;
step S4, performing solid-liquid separation on part of the hydrothermal carbonization product to obtain hydrothermal carbon and hydrothermal carbon liquid; the remaining hydrothermal carbonization product is reserved;
step S5, carbonizing the hydrothermal carbon to obtain modified hydrothermal carbon;
step S6, mixing the modified hydrothermal carbon, the residual hydrothermal carbonization product and the red mud, and putting the mixture into a stirring tank at a speed V3Stirring and placing to obtain the red mud soil matrix.
Furthermore, the granularity of the biomass powder is 1-5 mm.
Further, the mass ratio of the biomass powder to the water to the catalyst is 0.05-0.2: 1: 0.0025 to 0.01.
Further, the catalyst is one or more of red mud, potassium carbonate, potassium bicarbonate, potassium nitrate, potassium sulfate, ammonium sulfate, potassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, potassium pyrophosphate and potassium metaphosphate.
Further, V1Is 150 to 200 ℃/h.
Furthermore, the mass percentage of humic acid in the hydrothermal carbon is 5-30%.
Further, the hydrothermal carbonization product is prepared by adopting hydrothermal carbonization integrated process equipment, wherein the hydrothermal carbonization integrated process equipment comprises a crusher, a stirring tank and a high-pressure reaction kettle which are positioned on the same mounting plane;
the crusher is used for crushing biomass, and a discharge port of the crusher is connected with a first feed port of the stirring tank through a first conveying channel; the discharge hole of the stirring tank is connected with the feed hole of the high-pressure reaction kettle through a second conveying channel;
the first conveying channel is provided with at least 1 material lifting mechanism; the second delivery passage is provided with a fluid pump.
Further, material lifting mechanism includes: a square tube frame and 2 half square tube mechanisms;
half square tube mechanism includes: a half square tube, a rotatable baffle plate and a motor;
the square tube frame can splice the half square tubes of the 2 half square tube mechanisms into a square tube, and the motor is used for driving the half square tubes to slide along the axis direction of the square tube;
the half square tube comprises 1 whole side wall and 2 half side walls, the edge of the half side wall is provided with a sealing sliding chute, the whole side wall is hinged with a rotatable baffle, and the rotatable baffle can rotate towards the fluid flowing direction and enables materials to flow in the square tube;
the rotatable baffle is a rectangular plate, the length of the short edge of the rotatable baffle is equal to the width of the inner wall of the square tube, and the sealing strips are arranged on the edges of the periphery of the rotatable baffle.
On the other hand, the application also provides a red mud soil matrix which comprises a stirring mixture of the modified hydrothermal carbon, the hydrothermal carbonization product and the red mud.
Further, the mass ratio of the modified hydrothermal carbon to the hydrothermal carbonized product to the red mud is as follows: 5-10: 15-45: 50 to 75.
Compared with the prior art, the application can realize at least one of the following beneficial effects:
a) according to the method, the hydrothermal carbonization product obtained by hydrothermal carbonization of the biomass raw material is adopted, and part of hydrothermal carbon in the hydrothermal carbonization product is carbonized to obtain the modified hydrothermal carbon, and then the modified hydrothermal carbon and the rest hydrothermal carbonization product and the red mud are used as raw materials together to prepare the red mud soil matrix, so that the remediation and cyclic utilization of the biomass raw material, the red mud and other wastes are realized, the use of chemical substances in the prior art is reduced, the cost is saved, the method is environment-friendly, and the harmlessness and the reduction of the red mud can be realized.
b) The hydrothermal carbon in the hydrothermal carbonization product has a good pore structure and a large specific surface area; the hydrothermal carbon comprises organic carbon and humic acid (the mass percent of humic acid is 5-30%), so that the organic nutrients of the red mud can be effectively increased; moreover, a large number of oxygen-containing functional groups with weak acidity are arranged on the surface of the hydrothermal carbon, so that the acidity and alkalinity of the red mud can be stabilized for a long time by slowly releasing acid sites through neutralization; the modified hydrothermal carbon obtained by carbonizing the hydrothermal carbon can improve the air permeability and porosity of the red mud.
c) The hydrothermal carbon liquid in the application comprises small-molecular organic acidic substances (such as furfural, propionic acid and acetic acid); the small molecular organic acidic substances in the hydrothermal carbon liquid can quickly reduce the alkalinity of the red mud. And can provide carbon sources for microorganisms and improve the microbial growth environment of the red mud.
d) This application is with the breaker, agitator tank and high-pressure batch autoclave install on same horizontal plane, can adopt closed mode to carry to the eminence from the low with the solid-liquid mixture after the breakage through material lifting mechanism, carry the eminence to the liquid mixture after will stirring from the low through the fluid pump simultaneously, the high space that whole equipment took has been saved, and make the breaker, such main equipment of agitator tank and high-pressure batch autoclave can set up simply on the horizontal plane can, need not to set up two sets of solitary equipment and carry out the processing of solid-state material and liquid material respectively.
Additional features and advantages of the application will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by the practice of the application. The objectives and other advantages of the application may be realized and attained by the structure particularly pointed out in the written description and drawings.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the application, wherein like reference numerals are used to designate like parts throughout.
Fig. 1 is a schematic flow diagram of a method for preparing a red mud soil matrix according to the present application;
FIG. 2 is a schematic diagram of the overall structure of the hydrothermal carbonization integrated process equipment of the present application;
FIG. 3 is a partial cross-sectional view of the material lifting mechanism of the present application;
FIG. 4 is a schematic cross-sectional view of a material lifting mechanism of the present application;
FIG. 5 is a schematic longitudinal cross-sectional view of a material lifting mechanism of the present application;
FIG. 6 is a first schematic diagram of a material lifting mechanism of the present application;
fig. 7 is a second schematic diagram of the material lifting mechanism of the present application.
Reference numerals:
1-a crusher; 2-a stirring tank; 3-high pressure reactor; 4-a material lifting mechanism; 5-sleeving a pipe; a 6-four-way structure; 7-half square tube; 8-a rotatable baffle; 9-square tube frame.
Detailed Description
The preferred embodiments of the present application will now be described in detail with reference to the accompanying drawings, which form a part hereof, and which together with the embodiments of the application serve to explain the principles of the application.
The application provides a preparation method of a red mud soil matrix, as shown in figure 1, comprising the following steps:
step S1, crushing the biomass raw material into biomass powder by a crusher;
step S2, conveying the biomass powder, water and the catalyst into a stirring tank for stirring to obtain a mixture;
step S3, adding the mixture into a high-pressure reaction kettle at a speed V1Heating the high-pressure reaction kettle to T1Then, preserving the heat for 5-20 h; then cooling to room temperature to obtain a hydrothermal carbonization product;
step S4, performing solid-liquid separation on part of the hydrothermal carbonization product to obtain hydrothermal carbon and hydrothermal carbon liquid; the remaining hydrothermal carbonization product is reserved;
step S5, carbonizing the hydrothermal carbon to obtain modified hydrothermal carbon;
step S6, mixing the modified hydrothermal carbon, the residual hydrothermal carbonization product and the red mud and putting the mixture into a stirring poolAt a speed V3Stirring at a speed of (for example, 600-1000 rpm) for a period of time (for example, 30-100 min), and standing for 20-24 h to obtain the red mud soil matrix.
The biomass raw material in the step S1 is one or more of agricultural and forestry waste such as straw, fallen leaves and wood chips, livestock manure, kitchen waste or industrial waste residue; the specific surface area of the biomass raw material of the agricultural and forestry waste is 0.2-10 m2/g。
The particle size of the biomass powder in the step S1 is 1-5 mm, because the requirement on crushing equipment is high if the particle size of the biomass powder is too small, the crushing time is long, and the cost is high; if the particle size of the biomass powder is too large, adverse effects such as difficulty in stirring or insufficient reaction may be caused in the later reaction process.
The mass ratio of the biomass powder, the water and the catalyst in the step S2 is 0.05-0.2: 1: 0.0025-0.01, because the water consumption is too small, the stirring is difficult, and different components are not fully contacted; the water consumption is too large, and the yield of the carbonized product can be reduced in the subsequent steps.
In the step S2, considering that the stirring speed is too low, the materials cannot be sufficiently mixed, the stirring speed is too high, and the requirement on the performance of the equipment is high, the stirring speed is controlled to be 100-500 rpm, and the stirring time is 10-60 min; this ensures homogeneity of the mix.
In the above step S2, the catalyst may be one or more of red mud, potassium carbonate, potassium bicarbonate, potassium nitrate, potassium sulfate, ammonium sulfate, potassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, potassium pyrophosphate, or potassium metaphosphate.
In a possible design, the catalyst in step S2 is red mud, because alkaline substances, metal oxides and the like in the red mud have a certain catalytic effect on the hydrothermal carbonization process of biomass, so that the hydrothermal carbonization product of biomass is more suitable for red mud regulation and control.
In the step S3, if the temperature rising speed is too fast, the performance requirement of the high-pressure reactor is high, if the temperature rising speed is too slow, the hydrothermal carbonization time is prolonged, and the proper temperature rising rate is controlled to be beneficial to obtaining the productThe hydrothermal carbonization product suitable for red mud regulation and control is obtained, and V is controlled1Is 150 to 200 ℃/h.
In the above step S3, T1The temperature is 200-380 ℃, and hydrothermal carbonization products suitable for red mud regulation and control can be obtained in the temperature range.
Specifically, in step S3, the hydrothermal carbonization product mainly includes hydrothermal carbon and hydrothermal carbon liquid; the hydrothermal carbon has larger specific surface area and rich oxygen-containing groups; exemplarily, the specific surface area of the hydrothermal carbon is 40-90 m2The hydrothermal carbon has good hydrophilicity due to a large amount of oxygen-containing polar groups on the surface, the water holding rate of the red mud is obviously improved, and the weakly acidic oxygen-containing functional groups can slowly release acidic sites and stabilize the acidity and alkalinity of the red mud for a long time through neutralization; the yield of the hydrothermal carbon is 80-95%.
In step S3, the hydrothermal carbon includes organic carbon and humic acid; illustratively, the mass percentage of humic acid in the hydrothermal carbon is 5% -30%, and the humic acid and organic carbon in the hydrothermal carbon can effectively increase organic nutrients of the red mud, provide a carbon source for microorganisms and improve the microbial growth environment of the red mud.
In step S3, a large amount of small organic acidic substances (e.g., furfural, propionic acid, and acetic acid) generated by pyrolysis of biomass in the hydrothermal char solution can rapidly reduce the alkalinity of the red mud.
Specifically, the solid-liquid separation of the part of the hydrothermal carbonization product in step S4 means that a part (for example, 5% to 10%) of the hydrothermal carbonization product in step S3 is subjected to solid-liquid separation, so that the remaining hydrothermal carbonization product is ready for use, and the amount of treatment can be reduced, thereby reducing the production cost. And although the carbonization can increase pores and improve air permeability, organic matters in the hydrothermal carbon can be lost by carbonization, so that only a part of hydrothermal carbonization products need to be subjected to solid-liquid separation to obtain the hydrothermal carbon and hydrothermal carbon liquid, the separated hydrothermal carbon is carbonized, and the rest hydrothermal carbonization products are continuously used for preparing raw materials of the red mud soil matrix subsequently.
In the step S5, the carbonization includes the following steps:
step S51: hydrothermal charcoal is put into a high temperature furnace at room temperature at a speed V2Heating the high-temperature furnace to T2Then, preserving the heat;
step S52: and cooling to room temperature to obtain the modified hydrothermal carbon.
In the step S51, it should be noted that, since too fast temperature rise will have higher requirement on the performance of the high temperature furnace, too slow temperature rise will result in longer production time and increased cost, and controlling a proper temperature rise rate is favorable for obtaining modified hydrothermal carbon with a proper pore structure and a proper specific surface area, therefore, controlling V is favorable for obtaining modified hydrothermal carbon with a proper pore structure and a proper specific surface area2Is 200 to 220 ℃/h.
In the step S51, T is controlled considering that too low temperature will increase the production time and the carbonization effect is not good, and too high temperature or too long holding time will cause the collapse of the pores of the hydrothermal carbon, resulting in the failure of the pores2Keeping the temperature for 2-5 h at 400-600 ℃.
Specifically, in step S51, in order to ensure the oxygen-free environment of the high-temperature furnace, an inert gas is introduced into the high-temperature furnace.
Specifically, in step S5, the specific surface area of the modified hydrothermal carbon is 250-400 m2The modified hydrothermal carbon has the pore structure that the number proportion of micropores is 5-15%, the number proportion of mesopores is 20-40%, the number proportion of macropores is 45-75%, and the modified hydrothermal carbon can obviously improve the air permeability of the red mud. Wherein, the pore diameter is smaller than 2nm and is micropore, the pore diameter is 2-50 nm and is mesopore, and the pore diameter is larger than 50nm and is macropore.
In the step S6, the hydrothermal carbon liquid obtained in the step S4 may be added to the stirring tank as a raw material in consideration of resource recycling.
In the step S6, the pH value of the red mud is 10-12, and the pH value of the red mud soil matrix is 6-8.
It should be noted that in the preparation method of the red mud soil matrix, a hydrothermal carbonization integrated process device is adopted to prepare the hydrothermal carbonization product, as shown in fig. 2, the hydrothermal carbonization integrated process device comprises a crusher 1, a stirring tank 2 and a high-pressure reaction kettle 3 which are located on the same mounting plane; the crusher 1 is used for crushing biomass raw materials, and a discharge port of the crusher 1 is connected with a first feed port of the stirring tank 2 through a first conveying channel; the second feed inlet of the stirring tank 2 is used for adding water and a catalyst; the discharge hole of the stirring tank 2 is connected with the feed inlet of the high-pressure reaction kettle 3 through a second conveying channel; the first sub-channel of the first conveying channel is provided with at least 1 material lifting mechanism 4; the second delivery passage is provided with a fluid pump.
In one possible design, the second conveying channel is provided with a material lifting mechanism 4.
During implementation, the biomass raw material is firstly crushed by the crusher 1, then the biomass material is conveyed to the first feed inlet of the stirring tank 2 through the material lifting mechanism 4 of the first conveying channel, then water and a catalyst are added into the stirring tank 2 through the second feed inlet, the biomass material, the water and the catalyst entering the stirring tank 2 are stirred and mixed to obtain a mixture, the mixture is conveyed to the high-pressure reaction kettle 3 through the second conveying channel, and a hydrothermal carbonization reaction is carried out in the high-pressure reaction kettle 3 until a hydrothermal carbonization product with a good pore structure, a large amount of acidic surface functional groups and organic matters is obtained.
Specifically, a discharge port of the crusher 1 is arranged at the bottom of the crusher 1; the first feed inlet and the second feed inlet of agitator tank 2 set up at agitator tank 2's top, and agitator tank 2's discharge gate setting is in agitator tank 2's bottom. Because the integrated process equipment adopts the material lifting mechanism 4, the whole equipment can process the biomass in a solid-liquid mixed state on the premise of ensuring that the crusher 1, the stirring tank 2 and the high-pressure reaction kettle 3 are arranged on the same plane, and the equipment is simple to install and simple in structure.
The material lifting mechanism 4 is structured as shown in fig. 3 to 5, and the material lifting mechanism 4 includes: a square tube frame 9 and 2 half square tube mechanisms; half square tube mechanism includes: a half square tube 7, a rotatable baffle 8 and a motor; the square tube frame 9 can splice the half square tubes 7 of the 2 half square tube mechanisms into a square tube, and the motor is used for driving the half square tubes 7 to slide along the axis direction of the square tube; the half square tube 7 comprises a whole side wall and 2 half side walls, the edge of the half side wall is provided with a sealing sliding chute, the whole side wall is hinged with a rotatable baffle 8, and the rotatable baffle 8 can rotate towards the fluid flowing direction to enable materials to flow in the square tube; the rotatable baffle 8 is a rectangular plate, the length of the short edge of the rotatable baffle 8 is equal to the width of the inner wall of the square tube, and sealing strips are arranged on the edges of the periphery of the rotatable baffle 8; the 2 rotatable baffle plates 8 are arranged in sequence along the material flowing direction and do not interfere with each other when rotating.
For convenience of explanation, as shown in fig. 6 and 7, the 2 half-pipe mechanisms are a first mechanism and a second mechanism, respectively: when the half-direction pipe of the first mechanism moves upwards relative to the half-direction pipe of the second mechanism, the rotatable baffle of the first mechanism is abutted against the inner side of the whole side wall of the half-direction pipe of the second mechanism, the rotatable baffle of the second mechanism rotates upwards under the action of materials and is separated from the inner side of the whole side wall of the half-direction pipe of the first mechanism, and the materials enter between the rotatable baffle of the first mechanism and the rotatable baffle of the second mechanism from the lower part of the rotatable baffle of the second mechanism through the separated opening; when the half-square pipe of the second mechanism moves upwards relative to the half-square pipe of the first mechanism, the rotatable baffle of the second mechanism is abutted against the inner side of the whole side wall of the half-square pipe of the first mechanism, the rotatable baffle of the first mechanism rotates upwards under the action of the materials, and the materials enter the upper part of the rotatable baffle of the first mechanism from the position between the rotatable baffle of the first mechanism and the rotatable baffle of the second mechanism through the separated opening; when the first mechanism and the second mechanism continuously slide up and down relatively, the materials are lifted up gradually from bottom to top. And the sealing strip at the edge of the rotatable baffle can prevent the solid-liquid mixed material from falling back when the rotatable baffle abuts against the whole side wall.
In order to guarantee that 2 half square tube mechanisms can slide relatively, the cross sectional shape of the sealing chute of the first mechanism is in a shape like a Chinese character 'tu', a sealing slide block with a cross sectional shape like a Chinese character 'tu' is arranged at a corresponding position of the second mechanism, the sealing chute and the sealing slide block can perform relative sliding and can also play a role in limiting to prevent the separation of the 2 half square tube mechanisms, and in addition, a sealing strip arranged on a contact surface of the sealing chute and the sealing slide block can prevent materials from leaking from the splicing position of the 2 half square tube mechanisms.
Specifically, the mode that motor control half square pipe 7 reciprocating motion does:
the motor controls the ball screw pair, the motor is fixed with the square tube frame 9, an output gear is arranged at the output end of the motor, the output gear drives a screw rod to rotate through a reduction gear set, a screw nut on the screw rod moves up and down, the screw nut is fixed with the half square tube 7, and reciprocating motion of the half square tube 7 is achieved.
Or, the motor controls the hydraulic cylinder, the cylinder body of the hydraulic cylinder is fixed with the square pipe frame 9, and the piston of the hydraulic cylinder is fixed with the half square pipe 7, so that the reciprocating motion of the half square pipe 7 is realized.
Or, the motor controls the gear-rack pair, the motor is fixed with the square tube frame 9, the output end of the motor is provided with an output gear, the output gear drives the rack gear to rotate through the reduction gear set, so that the rack moves up and down, and the rack is fixed with the half square tube 7, so that the reciprocating motion of the half square tube 7 is realized.
In order to simplify first transfer passage, need not all to set up material lifting mechanism 4 on whole first transfer passage, only need set up many material lifting mechanism 4 make the material that solid-liquid mixes can be lifted to the eminence can, first transfer passage still is equipped with a plurality of sleeve pipes 5, the both ends of sleeve pipe 5 are the square connector of rigidity, the outside of square pipe can be established to square connector, and with square pipe frame 9 fixed connection, and square connector directly is equipped with the sealing washer with square pipe, can prevent that the material from leaking from square pipe and square connector junction. It should be noted that, a square connecting pipe is arranged between the two square connectors, the square connecting pipe can be set as a straight pipe or an elbow pipe according to the situation, and the square connecting pipe should be a rigid pipe to prevent the square connecting pipe from being damaged by the material in the square connecting pipe.
Correspondingly, the discharge gate of breaker 1 and the first feed inlet of agitator tank 2 all are equipped with can with square connector sealing connection and fixed connection's interface.
Specifically, the structure that first transfer passage connects into by square tubular frame 9 and sleeve pipe 5 is rigid structure, guarantees first transfer passage's fixed route and shape, and 2 half square tubular mechanisms reciprocating motion relative to corresponding square tubular frame 9 make the material of solid-liquid mixture state can follow first transfer passage and carry to the eminence from the low place to realize the lift and the transport of the material of solid-liquid mixture state.
Water and a catalyst are added to the biomass in the agitation tank 2, and the water, the catalyst, and the biomass are agitated and mixed. Specifically, the stirring tank 2 is provided with a stirring device, the stirring device is arranged inside the stirring tank 2, and in order to enable stirring to be more uniform, the stirring device comprises a rotating shaft, a rotating motor, blades and a lifting motor; the rotating motor is used for controlling the rotating shaft to rotate in the circumferential direction, and the lifting motor is used for controlling the rotating shaft to move in the axial direction; the blade is equipped with a plurality ofly, and the equipartition is fixed to be set up in the pivot. In the embodiment of the invention, the mixture in the stirring tank 2 is stirred in the circumferential direction through the circumferential rotation of the blades along with the rotating shaft, and the mixture in the stirring tank 2 is turned in the axial direction through the axial movement of the blades along with the rotating shaft.
The high-pressure reaction kettle 3 is provided with a heating pipeline which is a snake-shaped or spiral pipeline filled with hot fluid and is arranged on the inner wall of the high-pressure reaction kettle 3, the hot fluid can be liquid or gas, and the temperature in the high-pressure reaction kettle 3 can be more uniform through the snake-shaped or spiral pipeline;
specifically, in order to improve the reaction rate of hydrothermal carbonization, the uniformity of the materials in the high-pressure reaction kettle 3 can be further improved by improving the feeding structure, so that the reaction rate of hydrothermal carbonization is further improved. Specifically, the second conveying channel is provided with a four-way structure 6, the four-way structure 6 comprises 1 input end and 3 output ends, and the 1 input end and the 3 input ends form a regular triangular pyramid; 3 feed inlets of the high-pressure reaction kettle 3 are uniformly distributed along the circumferential direction of the high-pressure reaction kettle 3; the output end of each four-way structure 6 is respectively connected with the feed inlets of 1 high-pressure reaction kettle 3; through the four-way structure 6 of regular triangular pyramid, come to add the material in the feed inlet to high pressure reation kettle 3 through three circumference equipartition for the material in high pressure reation kettle 3 is more even, makes hydrothermal carbomorphism's reaction can be more abundant, thereby improves hydrothermal carbomorphism's reaction rate.
In order to ensure that the materials can be subjected to hydrothermal carbonization reaction uniformly in the high-pressure reaction kettle 3, the tank body of the high-pressure reaction kettle 3 is a revolving body with the axis vertical to the installation plane, and the lower part of the tank body is of a round table-shaped structure with a thick upper part and a thin lower part; the discharge hole of the high-pressure reaction kettle 3 is arranged at the bottom end of the tank body. In the high-pressure reaction kettle 3, the viscosity and the solid content of the material show a descending trend under the action of hydrothermal carbonization, the trend can be gradually increased from top to bottom in the vertical direction and gradually increased from the periphery to the center in the horizontal direction in the high-pressure reaction kettle 3, and the material subjected to hydrothermal carbonization can be discharged from the bottom of the high-pressure reaction kettle 3 by using a discharge pump by using the self gravity of the material and the cone angle of the circular truncated cone-shaped structure.
The application also provides a red mud soil matrix, which comprises the stirring mixture of the modified hydrothermal carbon, the hydrothermal carbonization product and the red mud.
Specifically, the mass ratio of the modified hydrothermal carbon to the hydrothermal carbonized product to the red mud is as follows: 5-10: 15-45: 50 to 75.
Specifically, the pH value of the red mud soil matrix is 6-8.
Compared with the prior art, the method has the advantages that the hydrothermal carbonization product obtained by hydrothermal carbonization of the biomass raw material is adopted, and part of hydrothermal carbon in the hydrothermal carbonization product is carbonized to obtain the modified hydrothermal carbon, and then the modified hydrothermal carbon, the hydrothermal carbonization product and the red mud are used as raw materials together to prepare the red mud soil matrix, so that the remediation and the cyclic utilization of the biomass raw material and the red mud waste are realized, the use of chemical substances in the prior art is reduced, the cost is saved, the method is environment-friendly, and the effect of the red mud soil matrix for plant growth is better.
The hydrothermal carbon has a good pore structure and a large specific surface area; the hydrothermal carbon comprises organic carbon and humic acid (the mass percent of humic acid is 5-30%), so that the organic nutrients of the red mud can be effectively increased; in addition, the surface of the hydrothermal carbon has a large number of weakly acidic oxygen-containing functional groups, so that the acidity and alkalinity of the red mud can be stabilized for a long time through the slow-release acid site neutralization effect.
The hydrothermal carbon liquid in the application comprises small-molecular organic acidic substances (such as furfural, propionic acid and acetic acid); the small molecular organic acidic substances in the hydrothermal carbon liquid can quickly reduce the alkalinity of the red mud. And can provide carbon sources for microorganisms and improve the microbial growth environment of the red mud.
Example one
The preparation method of the red mud soil matrix of the embodiment comprises the following steps:
step S1, adding a biomass raw material (straws in the embodiment) into a crusher 1, and crushing the straws into powder with the granularity of 1mm by the crusher 1;
step S2, conveying the powder into the stirring tank 2 through the first feeding hole by using the material lifting mechanism 4, then adding water and a catalyst (in this embodiment, the catalyst is red mud) into the stirring tank 2 through the second feeding hole, and stirring to obtain a mixture, wherein the stirring speed is 500rpm, the stirring time is 10min, and the mass ratio of the powder to the water to the catalyst is: 0.05: 1: 0.0025;
step S3, adding the mixture into a high-pressure reaction kettle 3, heating the high-pressure reaction kettle 3 at a speed of 200 ℃/h, and keeping the temperature for 20h after the temperature is raised to 200 ℃; then cooling to room temperature to obtain a hydrothermal carbonization product; wherein the volume of the mixture is 1/3 of the volume of the high-pressure reaction kettle 3;
step S4, performing solid-liquid separation on part (5%) of the hydrothermal carbonization product to obtain hydrothermal carbon and hydrothermal carbon liquid; the remaining hydrothermal carbonization product is reserved; wherein the specific surface area of the hydrothermal carbon is 40m2The yield of the hydrothermal carbon is 95 percent; the mass percentage of humic acid in the hydrothermal carbon is 5 percent;
step S5, putting the hydrothermal carbon into a high-temperature furnace at room temperature, heating the high-temperature furnace at the speed of 200 ℃/h, and keeping the temperature for 5h after the temperature is raised to 600 ℃; then cooling to room temperature to obtain the modified hydrothermal carbon, wherein the specific surface area of the modified hydrothermal carbon is 250m2(ii)/g; in the pore structure of the modified hydrothermal carbon, the number proportion of micropores is 15%, the number proportion of mesopores is 40%, and the number proportion of macropores is 45%.
S6, mixing the modified hydrothermal carbon, the residual hydrothermal carbonization product, the red mud and the hydrothermal carbon liquid obtained in the step S4, putting the mixture into a stirring tank, stirring the mixture at the speed of 600rpm for 100min, and standing the mixture for 20h to obtain a red mud soil matrix; wherein the mass ratio of the modified hydrothermal carbon to the hydrothermal carbonized product to the red mud is as follows: 5: 15: 75; the pH value of the red mud is 10, and the pH value of the red mud soil matrix is 7.
After the red mud soil matrix is placed for 10 days, the pH value is measured to be 7.1, and therefore, the acid-base stability of the red mud soil matrix is better; the red mud soil matrix is added into the ryegrass with poor growth vigor, the ryegrass growth vigor slowly becomes better after 2 days, and the ryegrass normally grows after 7 days, so that the red mud soil matrix can be better suitable for plant growth.
Example two
The preparation method of the red mud soil matrix of the embodiment comprises the following steps:
step S1, adding a biomass raw material (fallen leaves in the embodiment) into a crusher 1, and crushing the fallen leaves into powder with the particle size of 3mm by the crusher 1;
step S2, conveying the powder into the stirring tank 2 through the first feeding hole by using the material lifting mechanism 4, then adding water and a catalyst (in this embodiment, the catalyst is potassium carbonate) into the stirring tank 2 through the second feeding hole, and stirring to obtain a mixture, wherein the stirring speed is 200rpm, the stirring time is 30min, and the mass ratio of the powder to the water to the catalyst is: 0.2: 1: 0.01;
step S3, adding the mixture into a high-pressure reaction kettle 3, heating the high-pressure reaction kettle 3 at a speed of 150 ℃/h, and preserving heat for 10h after the temperature is raised to 380 ℃; then cooling to room temperature to obtain a hydrothermal carbonization product; wherein the volume of the mixture is 2/3 of the volume of the high-pressure reaction kettle 3;
step S4, performing solid-liquid separation on part (8%) of the hydrothermal carbonization product to obtain hydrothermal carbon and hydrothermal carbon liquid; the remaining hydrothermal carbonization product is reserved; wherein the specific surface area of the hydrothermal carbon is 90m2The yield of the hydrothermal carbon is 95 percent; the mass percentage of humic acid in the hydrothermal carbon is 30 percent;
step S5, putting the hydrothermal carbon into a high-temperature furnace at room temperature, heating the high-temperature furnace at a speed of 220 ℃/h, and keeping the temperature for 2h after the temperature is raised to 600 ℃; then cooling to room temperature to obtain the modified hydrothermal carbon, wherein the specific surface area of the modified hydrothermal carbon is 400m2(ii)/g; in the pore structure of the modified hydrothermal carbon, the number proportion of micropores is 5%, the number proportion of mesopores is 20%, and the number proportion of macropores is 75%.
Step S6, mixing the modified hydrothermal carbon, the residual hydrothermal carbonization product and the red mud, putting the mixture into a stirring tank, stirring the mixture for 30min at the speed of 1000rpm, and standing the mixture for 24h to obtain a red mud soil matrix; wherein the mass ratio of the modified hydrothermal carbon to the hydrothermal carbonized product to the red mud is as follows: 8: 21: 63; the pH value of the red mud is 10.5, and the pH value of the red mud soil matrix is 7.5.
After the red mud soil matrix is placed for 10 days, the pH value is 7.5, and therefore, the acid-base stability of the red mud soil matrix is better; the red mud soil matrix is added into the ryegrass with poor growth vigor, the ryegrass growth vigor slowly becomes better after 2 days, and the ryegrass normally grows after 7 days, so that the red mud soil matrix can be better suitable for plant growth.
EXAMPLE III
The preparation method of the red mud soil matrix of the embodiment comprises the following steps:
step S1, adding a biomass raw material (wood chips in this embodiment) into a crusher 1, and crushing the wood chips into powder with a particle size of 2mm by the crusher 1; then adding water and a catalyst into the crusher 1;
step S2, conveying the powder into the stirring tank 2 through the first feeding hole by using the material lifting mechanism 4, then adding water and a catalyst (in this embodiment, the catalyst is dipotassium hydrogen phosphate) into the stirring tank 2 through the second feeding hole, and stirring to obtain a mixture, wherein the stirring speed is 100rpm, the stirring time is 60min, and the mass ratio of the powder to the water to the catalyst is as follows: 0.1: 1: 0.006;
step S3, adding the mixture into a high-pressure reaction kettle 3, heating the high-pressure reaction kettle 3 at a speed of 180 ℃/h, and keeping the temperature for 15h after the temperature is raised to 300 ℃; then cooling to room temperature to obtain a hydrothermal carbonization product; wherein the volume of the mixture is 1/2 of the volume of the high-pressure reaction kettle 3;
step S4, performing solid-liquid separation on part (10%) of the hydrothermal carbonization product to obtain hydrothermal carbon and hydrothermal carbon liquid; the remaining hydrothermal carbonization product is reserved; wherein the specific surface area of the hydrothermal carbon is 70m2The yield of the hydrothermal carbon is 80 percent; the mass percentage of humic acid in the hydrothermal carbon is 20%;
step S5, putting the hydrothermal carbon into a high-temperature furnace at room temperature, heating the high-temperature furnace at the speed of 200 ℃/h, and keeping the temperature for 4h after the temperature is raised to 500 ℃; then cooling toObtaining the modified hydrothermal carbon at room temperature, wherein the specific surface area of the modified hydrothermal carbon is 300m2(ii)/g; in the pore structure of the modified hydrothermal carbon, the number proportion of micropores is 10%, the number proportion of mesopores is 35%, and the number proportion of macropores is 55%.
Step S6, mixing the modified hydrothermal carbon, the residual hydrothermal carbonization product and the red mud, putting the mixture into a stirring tank, stirring the mixture for 30min at the speed of 1000rpm, and standing the mixture for 22h to obtain a red mud soil matrix; wherein the mass ratio of the modified hydrothermal carbon to the hydrothermal carbonized product to the red mud is as follows: 10: 45: 50; the pH value of the red mud is 10.2, and the pH value of the red mud soil matrix is 7.
In particular, the present embodiment may be a continuous production.
After the red mud soil matrix is placed for 10 days, the pH value is measured to be 7.1, and therefore, the acid-base stability of the red mud soil matrix is better; the red mud soil matrix is added into the ryegrass with poor growth vigor, the ryegrass growth vigor slowly becomes better after 2 days, and the ryegrass normally grows after 7 days, so that the red mud soil matrix can be better suitable for plant growth.
The above description is only for the preferred embodiment of the present application, but the scope of the present application is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present application should be covered within the scope of the present application.
Claims (10)
1. The preparation method of the red mud soil matrix is characterized by comprising the following steps:
step S1, crushing the biomass raw material into biomass powder by a crusher;
step S2, conveying the biomass powder, water and the catalyst into a stirring tank for stirring to obtain a mixture;
step S3, adding the mixture into a high-pressure reaction kettle at a speed V1Heating the high-pressure reaction kettle to T1Then, preserving the heat for 5-20 h; then cooling to room temperature to obtain a hydrothermal carbonization product;
step S4, performing solid-liquid separation on part of the hydrothermal carbonization product to obtain hydrothermal carbon and hydrothermal carbon liquid; the remaining hydrothermal carbonization product is reserved;
step S5, carbonizing the hydrothermal carbon to obtain modified hydrothermal carbon;
step S6, mixing the modified hydrothermal carbon, the residual hydrothermal carbonization product and the red mud, and putting the mixture into a stirring tank at a speed V3Stirring and placing to obtain the red mud soil matrix.
2. The method for preparing the red mud soil matrix according to claim 1, wherein the particle size of the biomass powder is 1-5 mm.
3. The preparation method of the red mud soil matrix according to claim 1, wherein the mass ratio of the biomass powder, water and the catalyst is 0.05-0.2: 1: 0.0025 to 0.01.
4. The method for preparing the red mud soil matrix according to claim 3, wherein the catalyst is one or more of red mud, potassium carbonate, potassium bicarbonate, potassium nitrate, potassium sulfate, ammonium sulfate, potassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, potassium pyrophosphate and potassium metaphosphate.
5. The method for preparing a red mud soil matrix according to claim 1, wherein V is1Is 150 to 200 ℃/h.
6. The method for preparing the red mud soil matrix according to any one of claims 1 to 5, wherein the mass percentage of humic acid in the hydrothermal carbon is 5 to 30%.
7. The method for preparing the red mud soil matrix according to any one of claims 1 to 5, wherein the hydrothermal carbonization product is prepared by using hydrothermal carbonization integrated process equipment, and the hydrothermal carbonization integrated process equipment comprises a crusher (1), a stirring tank (2) and a high-pressure reaction kettle (3) which are positioned on the same mounting plane;
the crusher (1) is used for crushing biomass, and a discharge hole of the crusher (1) is connected with a first feed hole of the stirring tank (2) through a first conveying channel; the discharge hole of the stirring tank (2) is connected with the feed inlet of the high-pressure reaction kettle (3) through a second conveying channel;
the first conveying channel is provided with at least 1 material lifting mechanism (4); the second conveying channel is provided with a fluid pump.
8. The method for preparing a red mud soil matrix according to claim 7, wherein the material lifting mechanism (4) comprises: a square tube frame (9) and 2 half square tube mechanisms;
the half square tube mechanism includes: a half square tube (7), a rotatable baffle (8) and a motor;
the square tube frame (9) can be used for splicing the half square tubes (7) of the 2 half square tube mechanisms into a square tube, and the motor is used for driving the half square tubes (7) to slide along the axis direction of the square tube;
the half square pipe (7) comprises 1 whole side wall and 2 half side walls, a sealing sliding groove is formed in the edge of each half side wall, the whole side wall is hinged with the rotatable baffle (8), and the rotatable baffle (8) can rotate in the fluid flowing direction and enables materials to flow in the square pipe;
rotatable baffle (8) are rectangular shaped plate, just the minor face length of rotatable baffle (8) equals with the inner wall width of square pipe, the edge all around of rotatable baffle (8) all is equipped with the sealing strip.
9. The red mud soil matrix is characterized by being prepared by the preparation method of claims 1-8, and comprises a stirred mixture of modified hydrothermal carbon, hydrothermal carbonization products and red mud.
10. The red mud soil matrix according to claim 9, wherein the mass ratio of the modified hydrothermal carbon to the hydrothermal carbonized product to the red mud is: 5-10: 15-45: 50 to 75.
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