CN111841500A - Method and system for synthesizing VOCs adsorbent by using fly ash and waste oil - Google Patents
Method and system for synthesizing VOCs adsorbent by using fly ash and waste oil Download PDFInfo
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- CN111841500A CN111841500A CN202010873942.6A CN202010873942A CN111841500A CN 111841500 A CN111841500 A CN 111841500A CN 202010873942 A CN202010873942 A CN 202010873942A CN 111841500 A CN111841500 A CN 111841500A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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Abstract
The invention discloses a method and a system for synthesizing VOCs adsorbent by using fly ash and waste oil, wherein the fly ash of a circulating fluidized bed which is difficult to utilize by using the conventional technology is utilized, and simultaneously, the waste oil is utilized to obtain the VOCs adsorbent and a compound fertilizer byproduct, so that the waste is treated by waste.
Description
Technical Field
The invention belongs to the field of comprehensive utilization of wastes, and particularly relates to a method and a system for synthesizing VOCs adsorbent by using fly ash and waste oil.
Background
Volatile Organic Compounds (VOCs) are organic chemicals having a high vapor pressure at room temperature, typically organic substances having a boiling point of less than 250 ℃, such as benzene, formaldehyde, ethanol, acetone, and the like. VOCs are in various types, mainly come from decoration, coating, industrial production, fuel combustion, oil storage and transportation, automobiles and cooking, and most of odors are VOCs. Many VOCs can adversely affect human health, such as irritation of the eyes and respiratory system, causing symptoms of headache, nausea, epistaxis, allergies, memory impairment, fatigue, weakness, etc., and damage to the liver, kidneys and central nervous system, some of which are also closely associated with cancer. In addition, VOCs are also one of the main pollutants causing atmospheric pollution such as haze and photochemical smog.
Common methods for removing VOCs include adsorption, absorption, condensation, catalytic combustion, biotransformation, etc., with adsorption being the most widely used and being able to remove low concentrations of VOCs that are difficult to process by other methods. The adsorbent used in the adsorption method is active carbon, zeolite molecular sieve, diatomite, etc. The activated carbon is low in price, but the safety of regeneration operation is poor, and the performance of regeneration recovery is poor, so that the cost of the whole life cycle is high. The zeolite molecular sieve is high temperature resistant and long in service life, and a molecular sieve adsorption method represented by a zeolite rotating wheel is widely applied to the field of VOCs treatment, but the cost of the zeolite molecular sieve is usually high. In recent years, the technology for synthesizing the molecular sieve by using the fly ash is developed, the cost of the zeolite molecular sieve is hopefully reduced by using the fly ash as a raw material to synthesize the zeolite molecular sieve, and the zeolite molecular sieve with high adsorbability, high reproducibility and high regeneration safety can be economically applied to the adsorption of VOCs on a large scale.
The fly ash refers to fine fly ash obtained after the flue gas of the coal-fired boiler is collected by a dust remover, and the fly ash in a broad sense also comprises bottom ash. China is a big coal country, consumes half of the coal worldwide and generates about 5 million tons of fly ash every year. If a large amount of fly ash is not treated but simply stored, a large amount of land is occupied, and environmental hazards are generated. The fly ash is mostly used in the fields with low added values such as cement, building materials and road construction, so that the development of a new way for utilizing the fly ash and the preparation of products with high added values by utilizing the fly ash are urgent. In recent years, a batch of fly ash synthetic molecular sieve technology has been developed.
Chinese patent CN201710393382.2 applies for a method for preparing VOCs molecular sieve adsorbing material by taking fly ash as raw material, the fly ash is calcined by alkali fusion, and then structural directing agents such as CTAB and the like are added for hydrothermal treatment to obtain the material with the highest specific surface area of 67.52m2The use of/g adsorbent material, but expensive structure directing agents, limits the large scale application of this process.
Chinese patents CN201911057138.4 and CN201911057140.1 propose a preparation method of modified fly ash adsorbent for VOCs and a new process for treating VOCs with modified fly ash, the fly ash is subjected to acid washing, water washing, drying, grinding, and alkali dissolution with 60 ℃ microwave to obtain the modified fly ash adsorbent, and the VOCs are treated by adsorption and high temperature oxidation methods. However, the technology uses 20% hydrochloric acid solution, the acid consumption is large, the amount of waste liquid generated is large, and the treatment effect on VOCs gas needs to be further improved.
The waste oil generally refers to waste edible oil, including swill oil produced in catering and food industries, frying waste oil, range hood condensate oil, oil which is produced in oil processing, storage and transportation and does not meet the use standard, urban sewer oil floating material and the like, and is commonly called as swill oil. If the waste oil and fat is processed by illegal merchants and then flows into the food market again, the waste oil and fat can cause serious harm to human health.
The use of waste fats and oils has also attracted attention and researchers have developed new applications in addition to conventional soap making techniques. CN 201410468577.5 provides a method for preparing polyhydric alcohol from waste oil, which comprises the steps of catalyzing the waste oil and methanol to carry out esterification and ester exchange reaction by using a solid acid catalyst with a large hydrophobic surface and a sulfonic acid group and a carboxylic acid group, separating, carrying out acid catalysis epoxidation, carrying out ring opening, filtering and recovering the catalyst, and carrying out reduced pressure distillation and water removal to obtain the biological oil-based polyhydric alcohol. CN 201710839683.3 discloses a method for preparing high-purity bio-alkane by using waste oil, which comprises the steps of removing water impurities from the waste oil, carrying out hydrodeoxygenation and denitrification modification under the action of a modification catalyst, and carrying out oil-water separation to obtain a biomass long-chain straight-chain alkane oil product. CN 201310245928.1 discloses a method for preparing acetylene by thermal plasma cracking of waste grease, which comprises filtering and atomizing the waste grease, mixing with a transport gas, introducing into a thermal plasma jet of a plasma generator, and performing millisecond cracking and quenching to obtain a cracked gas containing acetylene. CN 201910976259.2 provides a method for preparing an environment-friendly plasticizer by using waste oil and application thereof, which adopts high-grade fatty acid, methanol, 50% hydrogen peroxide, trimellitic anhydride and acetic anhydride purified by the waste oil as main raw materials to prepare an environment-friendly plasticizer product, namely acetyl fatty acid methyl ester-trimellitic ester through four steps of reactions, namely esterification, epoxidation, ring-opening esterification and acetylation. CN 201410166050.7 proposes an emulsifier for oil-based drilling fluid, which is prepared by reacting waste oil with alkali to obtain saponified substance, and reacting with organic amine under the catalysis of alkali to obtain amidate as the component of the emulsifier. Although the utilization of waste oil and fat has been advanced in recent years, the application of the waste oil and fat in the field of adsorbents, particularly VOCs gas adsorbents, is not reported.
Disclosure of Invention
The invention aims to provide a method and a system for synthesizing VOCs adsorbent by using fly ash and waste oil, which overcome the defects of the prior art, solve the problem of utilization of fly ash waste and waste oil, treat VOCs atmospheric pollutants and treat wastes with wastes.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for synthesizing VOCs adsorbent by using fly ash and waste oil comprises the following steps:
s1: grinding and screening the fly ash of the circulating fluidized bed to obtain fly ash fine powder screen educt with the mesh size below 60;
s2: taking a potassium hydroxide solution, adding a urea buffer solution to obtain a mixed solution, dissolving and heating to 60-95 ℃, adding the fly ash fine powder screen educt obtained in the step S1, wherein the solid-liquid ratio is 1: 5-1: 20, the feeding process is controlled to be 5-30 min, and then keeping stirring to obtain a first solid-liquid mixture;
s3: taking out a part of the first solid-liquid mixture and remaining the part of the first solid-liquid mixture to form a first solid-liquid mixture A, and taking out the remaining part of the first solid-liquid mixture to form a first solid-liquid mixture B;
s4: quenching the temperature of the first solid-liquid mixture B to 30-60 ℃, adding waste grease with the water content of less than 10% under the condition of strong stirring until the apparent viscosity reaches 10-400 mPa & s, and obtaining a second solid-liquid mixture;
s5: treating the second solid-liquid mixture in a colloid mill, and repeatedly starting and standing for a plurality of times to obtain a third solid-liquid mixture;
s6: mixing the first solid-liquid mixture A with the third solid-liquid mixture, and performing crystallization reaction at the pressure of 0.1-2.0 MPa to obtain a fourth solid-liquid mixture;
s7: continuously introducing sulfur dioxide into the fourth solid-liquid mixture, and cooling to obtain a fifth solid-liquid mixture;
s8: centrifugally separating and washing the fifth solid-liquid mixture, drying and granulating the solid phase to obtain the VOCs adsorbent; and neutralizing the liquid phase, and then drying to obtain a compound fertilizer byproduct.
Further, in the mixed solution in the step S2, the molar ratio of urea to potassium hydroxide is 0.01-0.2, and the concentration of potassium hydroxide is 0.5-5 mol/L; in the step S2, the stirring time is kept for 15-90 min.
Further, in step S3, the first solid-liquid mixture is taken out and left at 5 to 30% to be the first solid-liquid mixture a, and the remainder is the first solid-liquid mixture B.
Further, in step S5, the colloid mill is started for 5-15 min, and then the mixture is allowed to stand for 10-30 min, and the starting-standing process is repeated for 3 times.
Further, the temperature of the crystallization reaction in step S6 is 80-120 ℃ for 4-72 hr.
Further, in the step S7, the total introduction volume of sulfur dioxide is 1-50 times of that of the fourth solid-liquid mixture, and the introduction time is 10 min.
A system for synthesizing VOCs adsorbent by fly ash and waste oil comprises an air flow grinder for grinding the fly ash of a circulating fluidized bed, wherein a grinder hopper is arranged at the outlet of the air flow grinder, the outlet of the grinder hopper is connected to a first stirring kettle through a vibrating screen, a lye pump for conveying potassium hydroxide solution and a buffer pump for conveying urea solution are connected to the first stirring kettle, the outlet of the first stirring kettle is connected to a second stirring kettle, the outlet of the second stirring kettle is divided into two paths, one path is connected to a third stirring kettle, the other path is connected to a strong stirring and mixing kettle through a heat exchanger, a waste oil conveying rotor pump for conveying waste oil with the water content of less than 10% and an apparent viscosity probe for detecting the apparent viscosity are connected to the strong stirring and mixing kettle, the outlet of the strong stirring and mixing kettle is connected to a colloid mill, the outlet of the colloid mill and the outlet of the third stirring kettle are connected to a high-pressure crystallization kettle together, be connected with the sulfur dioxide gas distributor on the high-pressure crystallization cauldron, the exit linkage of high-pressure crystallization cauldron to centrifugal filter, centrifugal filter's liquid phase exit linkage to fourth stirred tank, be connected with the neutralization pump on the fourth stirred tank, the exit linkage of fourth stirred tank to first drying tower, the exit linkage of first drying tower has compound fertilizer receiving hopper, centrifugal filter's solid phase exit linkage to emulsification shearing homogeneity cauldron, be connected with carrier and binder delivery pump on the emulsification shearing homogeneity cauldron, emulsification shearing homogeneity cauldron's exit linkage to second drying tower, the exit linkage of second drying tower has VOCs adsorbent receiving hopper.
Further, a fly ash fine powder belt conveyor is arranged between the vibrating screen and the first stirring kettle, and a VOCs adsorbent precursor belt conveyor is arranged between a solid phase outlet of the centrifugal filter and the emulsifying shearing homogenizing kettle.
Further, an outlet of the compound fertilizer receiving hopper is connected with a compound fertilizer packaging machine; and the outlet of the VOCs adsorbent receiving hopper is connected with a VOCs adsorbent packaging machine.
Further, an outlet of the first stirring kettle is provided with a first delivery pump, an outlet of the second stirring kettle is provided with a second delivery pump, an outlet of the powerful stirring and mixing kettle is provided with a third delivery pump, an outlet of the third stirring kettle is provided with a fourth delivery pump, and an outlet of the high-pressure crystallization kettle is provided with a fifth delivery pump.
Further, a first program control valve is arranged between the first conveying pump and the second stirring kettle, a second program control valve is arranged between the second conveying pump and the third stirring kettle, a third program control valve is arranged between the second conveying pump and the heat exchanger, a fourth program control valve is arranged between the third conveying pump and the colloid mill, a fifth program control valve is arranged between the fourth conveying pump and the high-pressure crystallization kettle, and a sixth program control valve is arranged between the fifth conveying pump and the centrifugal filter.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention simultaneously utilizes the fly ash waste and the waste grease to synthesize the adsorbent capable of adsorbing the VOCs of the atmospheric pollutants, thereby realizing the treatment of wastes with processes of wastes against one another. The urea buffer solution and potassium hydroxide are used for synergistic action, the controllable matching of the alkali dissolution rate of the fly ash, the hydrolysis rate of the waste oil, the gelling rate and the micelle conversion rate can be realized, and the synthesis of the high-performance VOCs adsorbent can be realized through the coupling action of the alkali dissolution hydrolysis of the fly ash, the alkali hydrolysis of the oil and the surface modification of the adsorbent. The synthesized VOCs adsorbent product has large specific surface area which can reach 230m2The benzene adsorption capacity can reach 118 mg/g. The invention can utilize the high-calcium circulating fluidized bed fly ash which is difficult to utilize in the prior art, and solves the problem of utilization of the fly ash of the circulating fluidized bed. The invention can realize continuous production, has high production efficiency, green process, environment-friendly property and low discharge of three wastes, and the by-product of the product can be used as a chemical fertilizer.
Drawings
The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a schematic diagram of the system of the present invention.
Wherein, 1-a jet mill, 2-a mill hopper, 3-a vibrating screen, 4-a fly ash fine powder belt conveyor, 5-an alkali liquor pump, 6-a buffer liquor pump, 7-a first stirring kettle, 8-a first delivery pump, 9-a first program control valve, 10-a second stirring kettle, 11-a second delivery pump, 12-a second program control valve, 13-a third stirring kettle, 14-a third program control valve, 15-a heat exchanger, 16-a powerful stirring and mixing kettle, 17-a waste grease delivery rotor pump, 18-a powerful stirring paddle, 19-an apparent viscosity probe, 20-a third delivery pump, 21-a fourth program control valve, 22-a colloid mill, 23-a fourth delivery pump, 24-a fifth program control valve, 25-a crystallization high-pressure kettle and 26-a sulfur dioxide gas distributor, 27-a fifth delivery pump, 28-a sixth program control valve, 29-a centrifugal filter, 30-a solid material port, 31-a liquid material port, 32-a neutralization pump, 33-a fourth stirring kettle, 34-a first drying tower, 35-a compound fertilizer receiving hopper, 36-a compound fertilizer packaging machine, 37-a VOCs adsorbent precursor belt conveyor, 38-a carrier and binder delivery pump, 39-an emulsifying shearing homogenizing kettle, 40-a second drying tower, 41-a VOCs adsorbent receiving hopper and 42-a VOCs adsorbent packaging machine.
Detailed Description
The invention is described in further detail below:
a method for synthesizing VOCs adsorbent by using fly ash and waste oil comprises the following steps:
s1: taking the circulating fluidized bed fly ash, grinding the fly ash by using a jet mill 1, then passing through a grinding machine hopper 2 to a vibrating screen 3, and screening to obtain a fly ash fine powder screen educt with the particle size of below 60 meshes;
s2: adding a potassium hydroxide solution into a first stirring kettle 7 through an alkaline liquid pump 5, adding a urea buffer solution into the first stirring kettle 7 through a buffer liquid pump 6 to obtain a mixed solution, wherein the molar concentration of potassium hydroxide in the mixed solution is 0.5-5 mol/L, and the molar ratio of urea to potassium hydroxide is 0.01-0.2, then heating to 60-95 ℃, slowly adding a fly ash fine powder sieve-out product obtained in the step S1 into the first stirring kettle 7 through a fly ash fine powder belt conveyor 4, wherein the solid-liquid ratio is 1: 5-1: 20, the feeding process is controlled to be 5-30 min, then conveying to a second stirring kettle 10 through a first conveying pump 8 and a first program control valve 9, and stirring in the second stirring kettle 10 for 15-90 min to obtain a first solid-liquid mixture;
s3: taking out 5-30% of the first solid-liquid mixture, conveying the first solid-liquid mixture to a third stirring kettle 13 through a second conveying pump 11 and a second program control valve 12 to obtain a first solid-liquid mixture A, and taking the rest as a second solid-liquid mixture B;
s4: conveying the rest first solid-liquid mixture B to a heat exchanger 15 through a second conveying pump 11 and a third program control valve 14, quenching the temperature to 30-60 ℃, then conveying the mixture to a strong stirring mixing kettle 16, adding waste oil with the water content of less than 10% through a waste oil conveying rotor pump 17 under the strong stirring action of a strong stirring paddle 18 until the apparent viscosity is detected by an apparent viscosity probe 19 (adopting a rotary apparent viscosity probe) to reach 10-400 mPa & s, and obtaining a second solid-liquid mixture;
s5: conveying the second solid-liquid mixture to a colloid mill 22 through a third conveying pump 20 and a fourth program control valve 21 for treatment, starting the colloid mill for 5-15 min, standing for 10-30 min, and repeating the step of starting and standing for three times to obtain a third solid-liquid mixture;
s6: mixing the remained first solid-liquid mixture A with the third solid-liquid mixture through a fourth delivery pump 23 and a fifth program control valve 24, transferring the mixture to a high-pressure crystallization kettle 25, maintaining the pressure of 0.1-2.0 MPa, and crystallizing at 80-120 ℃ for 4-72 hours to obtain a fourth solid-liquid mixture;
s7: continuously introducing sulfur dioxide into the fourth solid-liquid mixture for 10min through a sulfur dioxide gas distributor 26, and cooling to obtain a fifth solid-liquid mixture;
s8: conveying the fifth solid-liquid mixture to a centrifugal filter 29 through a fifth conveying pump 27 and a sixth program control valve 28 for centrifugal separation and washing, conveying a solid phase discharged from a solid phase material port 30 of the centrifugal filter 29 (adopting a horizontal centrifugal filter) to an emulsification shearing homogenizing kettle 39 through a VOCs adsorbent precursor belt conveyor 37, conveying a carrier and an adhesive to the emulsification shearing homogenizing kettle 39 through a carrier and adhesive conveying pump 38, granulating together with the solid phase, drying through a second drying tower 40, and conveying the obtained VOCs adsorbent to a VOCs adsorbent packaging machine 42 through a VOCs adsorbent receiving hopper 41 for packaging;
and the liquid phase discharged from the liquid phase material port 31 of the centrifugal filter 29 is conveyed to a fourth stirring kettle 33, a neutralizing agent is added into the fourth stirring kettle 33 through a neutralizing pump 32, the liquid phase is conveyed to a first drying tower 34 for drying after being neutralized, and the dried compound fertilizer byproduct is conveyed to a compound fertilizer packaging machine 35 for packaging through a compound fertilizer receiving hopper 35.
In order to clearly illustrate the present invention, the present invention will be further described in detail with reference to examples.
Example 1
A method for synthesizing VOCs adsorbent by using fly ash and waste oil comprises the following steps:
s1: taking the fly ash of the circulating fluidized bed, grinding by using an air bed, and screening to obtain a fine powder screen educt of the fly ash with 100 meshes;
s2: taking a potassium hydroxide solution, adding a urea buffer solution to obtain a mixed solution, wherein the concentration of potassium hydroxide in the mixed solution is 2.8mol/L, the molar ratio of urea to potassium hydroxide is 0.05, heating to 80 ℃, slowly adding a fly ash fine powder screen-out substance obtained in the step S1, the solid-liquid ratio is 1:8.2, controlling the feeding process for 15min, and then keeping stirring for 30min to obtain a first solid-liquid mixture;
s3: taking out 10% of the first solid-liquid mixture and remaining to obtain a first solid-liquid mixture A;
s4: quenching the temperature of the rest first solid-liquid mixture B to 50 ℃, adding the waste grease with the water content of less than 10% under the condition of strong stirring until the apparent viscosity reaches 65mPa & s, and obtaining a second solid-liquid mixture;
s5: treating the second solid-liquid mixture in a colloid mill, starting the colloid mill for 10min, standing for 20min, and repeating the step of starting and standing for three times to obtain a third solid-liquid mixture;
s6: transferring the remained first solid-liquid mixture A and the third solid-liquid mixture to a stirring kettle, maintaining the pressure of 0.15MPa, and crystallizing at 100 deg.C for 18hr to obtain a fourth solid-liquid mixture;
s7: continuously introducing sulfur dioxide into the fourth solid-liquid mixture for 10min, and cooling to obtain a fifth solid-liquid mixture;
s8: and carrying out centrifugal separation and washing on the fifth solid-liquid mixture, drying the solid phase, and granulating to obtain the VOCs adsorbent.
S9: and (4) performing centrifugal separation on the fifth solid-liquid mixture, washing to obtain a liquid phase, neutralizing with carbon dioxide, and drying to obtain a compound fertilizer byproduct.
Example 2
A method for synthesizing VOCs adsorbent by using fly ash and waste oil comprises the following steps:
s1: taking the fly ash of the circulating fluidized bed, grinding by using an air bed, and screening to obtain a 60-mesh fly ash fine powder screen educt;
s2: taking a potassium hydroxide solution, adding a urea buffer solution to obtain a mixed solution, wherein the concentration of potassium hydroxide in the mixed solution is 5mol/L, the molar ratio of urea to potassium hydroxide is 0.01, heating to 95 ℃, slowly adding a fly ash fine powder screen educt obtained in the step S1, the solid-liquid ratio is 1:20, controlling the feeding process at 5min, and then keeping stirring for 15min to obtain a first solid-liquid mixture;
s3: taking out 30% of the first solid-liquid mixture and remaining to obtain a first solid-liquid mixture A;
s4: quenching the temperature of the rest first solid-liquid mixture B to 60 ℃, adding waste grease with the water content of less than 10% under the condition of strong stirring until the apparent viscosity reaches 10mPa & s, and obtaining a second solid-liquid mixture;
s5: treating the second solid-liquid mixture in a colloid mill, starting the colloid mill for 5min, standing for 10min, and repeating the step of starting and standing for three times to obtain a third solid-liquid mixture;
s6: transferring the remained first solid-liquid mixture A and the third solid-liquid mixture to a stirring kettle, maintaining the pressure of 0.1MPa, and crystallizing at 80 deg.C for 72hr to obtain a fourth solid-liquid mixture;
s7: continuously introducing sulfur dioxide into the fourth solid-liquid mixture for 10min, and cooling to obtain a fifth solid-liquid mixture;
s8: and carrying out centrifugal separation and washing on the fifth solid-liquid mixture, drying the solid phase, and granulating to obtain the VOCs adsorbent.
S9: and (4) performing centrifugal separation on the fifth solid-liquid mixture, washing to obtain a liquid phase, neutralizing with carbon dioxide, and performing spray drying to obtain a compound fertilizer byproduct.
Example 3
A method for synthesizing VOCs adsorbent by using fly ash and waste oil comprises the following steps:
s1: taking the fly ash of the circulating fluidized bed, grinding by using an air bed, and screening to obtain a fine powder screen educt of fly ash of 200 meshes;
s2: taking a potassium hydroxide solution, adding a urea buffer solution to obtain a mixed solution, wherein the concentration of potassium hydroxide in the mixed solution is 0.5mol/L, the molar ratio of urea to potassium hydroxide is 0.2, heating to 60 ℃, slowly adding a fly ash fine powder screen-out substance obtained in the step S1, wherein the solid-liquid ratio is 1:5, the feeding process is controlled to be 30min, and then keeping stirring for 90min to obtain a first solid-liquid mixture;
s3: taking out 5% of the first solid-liquid mixture and remaining to obtain a first solid-liquid mixture A;
s4: quenching the temperature of the rest first solid-liquid mixture B to 30 ℃, adding the waste grease with the water content of less than 10% under the condition of strong stirring until the apparent viscosity reaches 400mPa & s, and obtaining a second solid-liquid mixture;
s5: treating the second solid-liquid mixture in a colloid mill, starting the colloid mill for 15min, standing for 30min, and repeating the step of starting and standing for three times to obtain a third solid-liquid mixture;
s6: transferring the remained first solid-liquid mixture A and the third solid-liquid mixture to a stirring kettle, introducing nitrogen to maintain the pressure of 2.0MPa, and crystallizing at 120 deg.C for 4hr to obtain a fourth solid-liquid mixture;
s7: continuously introducing sulfur dioxide into the fourth solid-liquid mixture for 10min, and cooling to obtain a fifth solid-liquid mixture;
s8: and carrying out centrifugal separation and washing on the fifth solid-liquid mixture, drying the solid phase, and granulating to obtain the VOCs adsorbent.
S9: and (4) performing centrifugal separation on the fifth solid-liquid mixture, washing to obtain a liquid phase, neutralizing with sulfuric acid, and performing spray drying to obtain a compound fertilizer byproduct.
Effects of the embodiment: examples 1, 2, 3 SynthesisThe VOCs adsorbents in the (1) have higher specific surface area, and the specific surface area of the product in the example is 230m2In g, the product of example 2 has a specific surface area of 103m2In g, the product of example 3 has a specific surface area of 110m2(ii) in terms of/g. The adsorbents of VOCs synthesized in examples 1, 2 and 3 all have higher adsorption capacity for VOCs, and the adsorption capacity of the product of example 1 is 118mg/g, the adsorption capacity of the product of example 2 is 62mg/g and the adsorption capacity of the product of example 3 is 70mg/g by taking benzene as a model compound.
It should be noted that the above description is only one embodiment of the present invention, and all equivalent changes of the system described in the present invention are included in the protection scope of the present invention. Persons skilled in the art to which this invention pertains may substitute similar alternatives for the specific embodiments described, all without departing from the scope of the invention as defined by the claims.
Claims (10)
1. A method for synthesizing VOCs adsorbent by using fly ash and waste oil is characterized by comprising the following steps:
s1: grinding and screening the fly ash of the circulating fluidized bed to obtain fly ash fine powder screen educt with the mesh size below 60;
s2: taking a potassium hydroxide solution, adding a urea buffer solution to obtain a mixed solution, dissolving and heating to 60-95 ℃, adding the fly ash fine powder screen educt obtained in the step S1, wherein the solid-liquid ratio is 1: 5-1: 20, the feeding process is controlled to be 5-30 min, and then keeping stirring to obtain a first solid-liquid mixture;
s3: taking out a part of the first solid-liquid mixture and remaining the part of the first solid-liquid mixture to form a first solid-liquid mixture A, and taking out the remaining part of the first solid-liquid mixture to form a first solid-liquid mixture B;
s4: quenching the temperature of the first solid-liquid mixture B to 30-60 ℃, adding waste grease with the water content of less than 10% under the condition of strong stirring until the apparent viscosity reaches 10-400 mPa & s, and obtaining a second solid-liquid mixture;
s5: treating the second solid-liquid mixture in a colloid mill, and repeatedly starting and standing for a plurality of times to obtain a third solid-liquid mixture;
s6: mixing the first solid-liquid mixture A with the third solid-liquid mixture, and performing crystallization reaction at the pressure of 0.1-2.0 MPa to obtain a fourth solid-liquid mixture;
s7: continuously introducing sulfur dioxide into the fourth solid-liquid mixture, and cooling to obtain a fifth solid-liquid mixture;
s8: centrifugally separating and washing the fifth solid-liquid mixture, drying and granulating the solid phase to obtain the VOCs adsorbent; and neutralizing the liquid phase, and then drying to obtain a compound fertilizer byproduct.
2. The method for synthesizing VOCs adsorbent from fly ash and waste oil and fat according to claim 1, wherein in the mixed solution in step S2, the molar ratio of urea to potassium hydroxide is 0.01-0.2, and the concentration of potassium hydroxide is 0.5-5 mol/L; in the step S2, the stirring time is kept for 15-90 min.
3. The method for synthesizing VOCs adsorbent from fly ash and waste oil and fat according to claim 1, wherein 5-30% of the first solid-liquid mixture is taken out and left in step S3 to become a first solid-liquid mixture A, and the balance is a first solid-liquid mixture B;
in step S5, the colloid mill is started for 5-15 min, and then is kept stand for 10-30 min, and the starting-standing process is repeated for 3 times.
4. The method for synthesizing VOCs adsorbent from fly ash and waste oil and fat according to claim 1, wherein the temperature of the crystallization reaction in step S6 is 80-120 ℃ for 4-72 hr.
5. The method for synthesizing VOCs adsorbent from fly ash and waste oil and fat according to claim 1, wherein the total volume of sulfur dioxide introduced in step S7 is 1-50 times of that of the fourth solid-liquid mixture, and the introduction time is 10 min.
6. The utility model provides a system of synthetic VOCs adsorbent of fly ash and waste oil, a serial communication port, including being used for carrying out the jet mill (1) ground to circulating fluidized bed fly ash, the export of jet mill (1) is provided with grinding machine hopper (2), the export of grinding machine hopper (2) is connected to first stirred tank (7) through shale shaker (3), be connected with lye pump (5) that are used for carrying potassium hydroxide solution and buffer liquid pump (6) that are used for carrying urea solution on first stirred tank (7), the exit linkage of first stirred tank (7) is to second stirred tank (10), the export of second stirred tank (10) is divided into two routes, be connected to third stirred tank (13) all the way, another way is connected to intensive mixing cauldron (16) through heat exchanger (15), be connected with waste oil transport rotor pump (17) that are used for carrying the waste oil of moisture content < 10% and be used for detecting apparent viscosity probe that apparent viscosity is surveyed on intensive mixing cauldron (16) (19) The outlet of the powerful stirring and mixing kettle (16) is connected to a colloid mill (22), the outlet of the colloid mill (2) and the outlet of the third stirring kettle (13) are jointly connected to a high-pressure crystallization kettle (25), a sulfur dioxide gas distributor (26) is connected to the high-pressure crystallization kettle (25), the outlet of the high-pressure crystallization kettle (25) is connected to a centrifugal filter (29), a liquid phase outlet (31) of the centrifugal filter (29) is connected to a fourth stirring kettle (33), a neutralization pump (32) is connected to the fourth stirring kettle (33), the outlet of the fourth stirring kettle (33) is connected to a first drying tower (34), the outlet of the first drying tower (34) is connected with a compound fertilizer receiving hopper (35), a solid phase outlet (30) of the centrifugal filter (29) is connected to an emulsifying and shearing kettle (39), and the emulsifying and shearing kettle (39) is connected with a carrier and a binder conveying pump (38), the outlet of the emulsifying shearing homogenizing kettle (39) is connected to a second drying tower (40), and the outlet of the second drying tower (40) is connected with a VOCs adsorbent receiving hopper (41).
7. The system for synthesizing VOCs adsorbent from fly ash and waste oil and fat according to claim 6, wherein a fly ash fine powder belt conveyor (4) is arranged between the vibrating screen (3) and the first stirring kettle (7), and a VOCs adsorbent precursor belt conveyor (37) is arranged between the solid phase outlet (30) of the centrifugal filter (29) and the emulsifying shear homogenizing kettle (39).
8. The system for synthesizing VOCs adsorbent by using fly ash and waste oil and fat as recited in claim 6, wherein the outlet of the compound fertilizer receiving hopper (35) is connected with a compound fertilizer packaging machine (36); and the outlet of the VOCs adsorbent receiving hopper (41) is connected with a VOCs adsorbent packing machine (42).
9. The system for synthesizing VOCs adsorbent from fly ash and waste oil and fat according to claim 6, wherein the outlet of the first stirring kettle (7) is provided with a first delivery pump (8), the outlet of the second stirring kettle (10) is provided with a second delivery pump (11), the outlet of the intensive stirring and mixing kettle (16) is provided with a third delivery pump (20), the outlet of the third stirring kettle (13) is provided with a fourth delivery pump (23), and the outlet of the high-pressure crystallization kettle (25) is provided with a fifth delivery pump (27).
10. The system for synthesizing VOCs adsorbent from fly ash and waste oil and fat according to claim 9, wherein a first program control valve (9) is arranged between the first delivery pump (8) and the second stirring kettle (10), a second program control valve (12) is arranged between the second delivery pump (11) and the third stirring kettle (13), a third program control valve (14) is arranged between the second delivery pump (11) and the heat exchanger (15), a fourth program control valve (21) is arranged between the third delivery pump (20) and the colloid mill (22), a fifth program control valve (24) is arranged between the fourth delivery pump (23) and the high-pressure crystallization kettle (25), and a sixth program control valve (28) is arranged between the fifth delivery pump (27) and the centrifugal filter (29).
Priority Applications (1)
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| WO2022042367A1 (en) * | 2020-08-26 | 2022-03-03 | 华能国际电力股份有限公司 | System for synthesizing adsorbent of vocs from fly ash and waste grease |
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