CN111229254B - Method for treating organic wastewater by using waste catalyst of Fischer-Tropsch synthesis - Google Patents

Method for treating organic wastewater by using waste catalyst of Fischer-Tropsch synthesis Download PDF

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CN111229254B
CN111229254B CN202010078666.4A CN202010078666A CN111229254B CN 111229254 B CN111229254 B CN 111229254B CN 202010078666 A CN202010078666 A CN 202010078666A CN 111229254 B CN111229254 B CN 111229254B
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raw material
catalyst
waste catalyst
organic wastewater
heating
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CN111229254A (en
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刘红缨
杨玉立
于妍
秦子敬
郝国军
陈培研
李淑宇
林冰
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China University of Mining and Technology Beijing CUMTB
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
    • B01J38/52—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids oxygen-containing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/90—Regeneration or reactivation
    • B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
    • B01J35/33—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/02—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
    • B01J38/56—Hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
    • B01J38/60—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids
    • B01J38/62—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using acids organic
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C02F2101/345—Phenols
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/36—Organic compounds containing halogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/38—Organic compounds containing nitrogen

Abstract

The invention provides a method for treating organic wastewater by using a Fischer-Tropsch synthesis waste catalyst, which comprises the following steps: (1) removing hydrocarbon compounds on the surface of the waste catalyst raw material by dissolving and extracting by using an organic solvent to obtain an intermediate treatment substance A; (2) dissolving carboxylic acid and forming an inorganic complex pore structure on the surface of the intermediate treatment substance A to obtain an intermediate treatment substance B; (3) heating the intermediate treatment object B, and further consolidating the surface structure of the intermediate treatment object B to obtain a dry material; (4) carrying out magnetic separation on the dry materials to obtain a recovered iron catalyst; (5) the recovered catalyst and hydrogen peroxide are used for treating the organic wastewater at a certain pH value and temperature.

Description

Method for treating organic wastewater by using waste catalyst of Fischer-Tropsch synthesis
Technical Field
The invention belongs to the technical field of organic wastewater treatment, and particularly relates to a method for treating organic wastewater by using a Fischer-Tropsch synthesis waste catalyst.
Background
In the field of organic wastewater treatment, particularly the degradation problem of persistent organic pollutants, is a difficult problem in the field of water treatment, and due to the strong oxidizing property of a Fenton reagent, the Fenton reagent can treat most of persistent organic pollutants non-selectively and achieves the effect of thorough oxidation, so that the Fenton reagent is widely applied to the field of water treatment. Recent research shows that the Fenton reagent consisting of ferroferric oxide and hydrogen peroxide has a good treatment effect on organic wastewater or dye wastewater. However, the Fenton reagent is used in a large amount during treatment, and the treatment cost is high.
In the field of coal chemical industry, the Fischer-Tropsch synthesis of coal gasification is one of the technologies of coal indirect liquefaction, and has already been mature industrial application. Fischer-Tropsch synthesis is a synthesis reaction of synthesizing liquid fuel mainly comprising hydrocarbon compounds by using synthesis gas (carbon monoxide and hydrogen) as raw materials under the action of a catalyst, wherein the catalyst is mainly ferric oxide. Due to the special property of the Fischer-Tropsch synthesis reaction, after the reaction is finished, hydrocarbon compound products, filter aid and other auxiliary agents are usually adhered to the surfaces of catalyst particles, so that the surface property of the catalyst is complex, and the difficulty in recovering the catalyst with higher purity is correspondingly improved. The recovered iron catalyst has great economic value for Fischer-Tropsch synthesis reaction. However, the main component of the catalyst for Fischer-Tropsch synthesis is ferric oxide, so that the application of the recovered catalyst in organic wastewater treatment is only reported.
The patent CN200410012202.4 discloses a method for separating and recovering a waste iron-based catalyst and heavy hydrocarbons in slurry bed Fischer-Tropsch synthesis, the method uses light liquid paraffin with the initial boiling point of 210 ℃ to extract and separate a mixture of the waste iron-based catalyst and the heavy hydrocarbons for three to four times under the conditions of heating and stirring, so as to achieve the purpose of separating the catalyst and the heavy hydrocarbons, the extracted and separated waste iron-based catalyst is subjected to sanitary landfill treatment, and the recovered mixture of the light liquid paraffin and the heavy hydrocarbons can be directly used for oil product processing or returned to a descending bed reactor as a reaction medium for recycling without re-separation.
In the prior art, because the product of Fischer-Tropsch synthesis is complex, the selection of a proper solvent and the extraction condition for removing organic matters on the surface of the waste catalyst are complex; in addition, the surface of the waste catalyst also comprises other reaction auxiliary agents, especially the existence of inorganic filter aid, and the liquid hydrocarbon compounds are adhered and coated on the surface of the waste catalyst, so that the surface property of the waste catalyst is more complicated. The recovered waste catalyst has special conditions, and the process conditions for treating the organic wastewater also need to be further explored.
Disclosure of Invention
The invention unexpectedly discovers that the iron-based waste catalyst for Fischer-Tropsch synthesis has better magnetism after selecting a proper solvent and removing part of hydrocarbon compounds, and based on the discovery, the invention provides a method for treating organic wastewater by using the waste catalyst for Fischer-Tropsch synthesis, which comprises the following steps: (1) removing hydrocarbon compounds on the surface of the waste catalyst raw material by dissolving and extracting by using an organic solvent to obtain an intermediate treatment substance A; (2) dissolving carboxylic acid and forming an inorganic complex pore structure on the surface of the intermediate treatment substance A to obtain an intermediate treatment substance B; (3) heating the intermediate treatment object B, and further consolidating the surface structure of the intermediate treatment object B to obtain a dry material; (4) carrying out magnetic separation on the dry materials to obtain a recovered iron catalyst; (5) the recovered iron catalyst and hydrogen peroxide are used for treating organic wastewater at a certain pH value and temperature.
In the present invention, the complicated adhesion of organic/inorganic compounds on the surface of the spent catalyst raw material makes it difficult to remove organic substances on the surface of the catalytically active component, and to further separate inorganic substances such as a remaining filter aid from the iron-based catalyst active material even if the organic substances on the surface can be removed relatively well, thereby making the recovery of the catalyst for fischer-tropsch synthesis a difficult problem for those skilled in the art. The applicant of the present invention unexpectedly found that a combination of specific solvents can remove organic materials such as hydrocarbons on the surface of the active ingredient well, and unexpectedly found that the remaining waste material after removing the organic materials on the surface exhibits good magnetic properties, and the magnetic properties are unexpectedly found by the applicant because the active ingredient of ferric oxide itself does not have magnetic properties, and thus, the existence of such magnetic properties cannot be expected in advance by those skilled in the art, and thus, separation and recovery by magnetic properties cannot be expected. In the method, for the part for recovering the catalyst, an organic solvent extraction method is firstly used for dissolving and removing most of hydrocarbon compounds on the surface of the waste catalyst raw material; then, a small amount of residual hydrocarbon compounds and partial inorganic matters are removed by using carboxylic acid, so that a more complex pore structure is formed on the surface of the catalyst, the adsorption of pollutants is facilitated when organic wastewater is treated, and preferably, the carboxylic acid is matched with a polar solvent, so that the treatment effect is better; heating to further volatilize a small amount of hydrocarbon compounds on the surface of the waste catalyst, further break down inorganic substances, consolidate and shape the pore structure on the surface of the catalyst; and in the magnetic separation step, the magnetic iron catalyst is separated from other nonmagnetic impurities, and the purer iron catalyst is finally obtained.
Preferably, the method for treating organic wastewater by using the waste catalyst comprises the following steps:
(1) mixing an organic solvent with the waste catalyst raw material, extracting under the conditions of heating and stirring, dissolving the hydrocarbon compounds on the surface of the waste catalyst raw material by the organic solvent, and extracting the hydrocarbon compounds from a mixture system to obtain an intermediate treatment product A;
(2) adding carboxylic acid and a polar solvent into the intermediate treatment substance A, and dissolving inorganic substances and residual micromolecular organic substances in the intermediate treatment substance A by the carboxylic acid under the conditions of heating and stirring to obtain an intermediate treatment substance B with a complex pore structure;
(3) heating the intermediate treatment substance B obtained in the step (2) at the temperature of 100 ℃ and 250 ℃ for 3-4 hours to obtain a dry material;
(4) mixing the dry material with a magnetic separation medium, and then carrying out magnetic separation to obtain a recovered iron catalyst;
(5) mixing the recovered iron catalyst and hydrogen peroxide with organic wastewater in an acid environment, heating, degrading the wastewater, and filtering again to recover the catalyst.
The effective catalyst components of the waste catalyst raw material mainly comprise ferric oxide (carried out by ferric oxide) and ferroferric oxide (a compound of ferric oxide and ferric oxide in a certain form, which is a magnetic substance), the inorganic substances comprise diatomite, clay, metal oxide and metal, and the hydrocarbon compound is a hydrocarbon compound which is solid at normal temperature, such as C11The above hydrocarbon compounds, the pollutants contained in the organic wastewater include but are not limited to: carbohydrates, fats, proteins, cellulose, dyes, oils, and the like.
The organic solvent in the step (1) is selected from a combination of two or more of ethyl acetate, cyclohexane and morpholine, preferably, the organic solvent is a combination of ethyl acetate, cyclohexane and morpholine.
The organic solvent is a good solvent of hydrocarbon compounds, and contains low-boiling point, medium-boiling point and high-boiling point solvents in the boiling point distribution, and during the extraction process, the organic solvent continuously dissolves the hydrocarbon compounds on the surface of the waste catalyst raw material, and the hydrocarbon compounds are vaporized at different temperatures to be carried out of the raw material system.
The heating temperature of the step (1) is 60-200 ℃, the heating process of the step (1) is divided into three stages, the heating temperature of the first stage is 60-100 ℃, and the heating rate is 15-20 ℃/h; the heating temperature of the second stage is 100-140 ℃, and the heating rate is 20-25 ℃/h; the heating temperature of the third stage is 140-. The temperature control is the preferable condition of the present application, and by controlling the appropriate temperature range and temperature raising program, organic matter on the surface of the catalytically active component can be effectively removed, and at the same time, a large amount of the active component is not reduced, so that the catalytic activity of the recovered spent catalyst is retained to a relatively large extent.
Preferably, the stirring rate of the step (1) is 200-300 r/min.
The carboxylic acid in the step (2) is R-COOH, the R group is aliphatic hydrocarbon group, preferably, the number of carbon atoms of the aliphatic hydrocarbon group is 0-3, such as formic acid and acetic acid. The polar solvent is selected from water and/or ethanol. The carboxylic acid can be dissolved in a polar solvent to form an acidic solution environment, most of hydrocarbon compounds on the surface of the waste catalyst raw material are removed after extraction in the step (1), most of inorganic matters are exposed outside, the acidic solution environment interacts with oxides of the inorganic matters to dissolve and remold the structure of the inorganic matters to form an irregular and complex pore structure, namely, a plurality of pore channels are formed on the surface of the catalyst, the specific surface area of the catalyst is greatly increased, the adsorption capacity of the catalyst is enhanced, and the adsorption and treatment of pollutants in organic wastewater are facilitated. For example, the diatomite is used as an inorganic filter aid and has a special porous structure, and the diatomite is treated by using carboxylic acid and a polar solvent to dissolve part of oxides, so that the attachment structure of the diatomite on the surface of the catalyst is favorably remodeled, active catalytic sites are exposed, the adsorption capacity is enhanced, and the subsequent magnetic separation process and the organic wastewater treatment process are favorably carried out.
The heating temperature of the step (2) is 50-70 ℃, the stirring speed is 200-300r/min, and the heating temperature of the step (2) is preferably 60-70 ℃.
In the step (3), the intermediate treatment substance B obtained in the step (2) is heated for 3-4 hours at the temperature of 100 ℃ and 250 ℃ to obtain dry materials. Only a small amount of hydrocarbon compounds exist on the surface of the intermediate treatment object B, the hydrocarbon compounds are volatilized and removed in the heating process, inorganic matters on the surface of the intermediate treatment object B are easy to further crack and form new holes in a dry environment, and a complex pore structure on the surface of the intermediate treatment object B is further formed and consolidated.
The magnetic separation medium in the step (4) is a dilute sodium hydroxide solution, and the magnetic separation medium not only can neutralize the residual carboxylic acid on the surface of the dry material, but also can chemically react with the silicon dioxide in the inorganic substance to further remold the pore structure of the silicon dioxide attached to the surface of the catalyst; in the magnetic separation equipment, the non-magnetic substance and the magnetic separation medium are separated from the magnetic iron catalyst, and finally the recovered iron catalyst is obtained and can be used for organic wastewater treatment.
And (3) the magnetic separation device or equipment in the step (4) is a device or equipment with a magnetic separation function applied to the market.
In the step (5), the recycled iron-based catalyst needs an acidic environment for treating the organic wastewater, and the pH value is 2-5, preferably 3-4. The treatment temperature is 30-60 ℃, and preferably, the treatment temperature is 40-50 ℃. The treatment time is 0.5-2 hours.
After the wastewater is degraded, the catalyst recovered by filtration may be discarded or may be recovered and reused in the above steps (1) to (4) depending on the actual conditions and the type and amount of the wastewater to be treated.
In the organic solvent, the volume mass ratio of the ethyl acetate to the waste catalyst raw material is (100-150) mL: 1mg, and the volume mass ratio of the cyclohexane to the waste catalyst raw material is (100-150) mL: 1mg, wherein the volume mass ratio of morpholine to the waste catalyst raw material is (70-100) mL: 1 mg.
The mass ratio of the carboxylic acid to the waste catalyst raw material is (0.1-0.3): 1.
the volume mass ratio of the polar solvent to the waste catalyst raw material is (100-120) mL: 1 mg. The volume mass ratio of the magnetic separation medium to the waste catalyst raw material is (150-180) mL: 1mg, and the concentration of the magnetic separation medium is 0.007-0.01 g/mL.
The mass volume ratio of the recycled iron catalyst to the organic wastewater is (3-20) g: 100L, wherein the mass volume ratio of the hydrogen peroxide to the organic wastewater is (5-15) g: 100L. The amount of the recovered iron-based catalyst and the amount of the recovered hydrogen peroxide may vary depending on the kind and content of organic contaminants contained in the organic wastewater to be actually treated, and the reaction time may also vary.
Detailed Description
In the following preparation examples, examples and comparative examples, the main components of the spent catalyst were an iron-based catalyst mainly composed of iron sesquioxide and iron tetroxide, and diatomaceous earth and hydrocarbon compounds blended therewith or attached to the outer surface thereof. In the following examples and comparative examples, the effect of catalyst recovery is expressed in terms of the number of recovered parts, which is the amount of the recovered catalyst parts by mass based on 100 parts by mass of the waste catalyst raw material. In the following examples and comparative examples, the treated organic wastewater was rhodamine B wastewater and phenol wastewater.
Preparation example 1
The recovery method of the Fischer-Tropsch synthesis catalyst comprises the following steps:
(1) adding ethyl acetate, cyclohexane and morpholine into the waste catalyst raw material in sequence, wherein the heating temperature in the first stage is 60-100 ℃, the heating rate is 15 ℃/h, the heating temperature in the second stage is 100-140 ℃, the heating rate is 20 ℃/h, the heating temperature in the third stage is 140-200 ℃, the heating rate is 20 ℃/h, the stirring rate is 200r/min, extracting is carried out, and the organic solvent dissolves the hydrocarbon compounds on the surface of the waste catalyst raw material and extracts the hydrocarbon compounds to leave the mixture system to obtain an intermediate treatment substance A;
wherein the volume mass ratio of the ethyl acetate to the waste catalyst raw material is 100 mL: 1mg, wherein the volume mass ratio of the cyclohexane to the waste catalyst raw material is 100 mL: 1mg, wherein the volume mass ratio of morpholine to the waste catalyst raw material is 70 mL: 1 mg;
(2) adding acetic acid and water into the intermediate treatment substance A, heating at 70 deg.C under reflux, stirring at a speed of 200r/min, dissolving partial oxide in diatomaceous earth with acetic acid, and disintegrating diatomaceous earth to obtain intermediate treatment substance B; wherein the mass ratio of the acetic acid to the waste catalyst raw material is 0.3: 1, the volume mass ratio of water to the waste catalyst raw material is 100 mL: 1 mg;
(3) heating the intermediate treatment substance B obtained in the step (2) for 3 hours at 150 ℃ to obtain a dry material;
(4) mixing the dry material obtained in the step (3) with a sodium hydroxide solution, and then carrying out magnetic separation to obtain a recovered iron catalyst; wherein the concentration of the sodium hydroxide solution is 0.007g/mL, and the volume-to-mass ratio of the sodium hydroxide solution to the waste catalyst raw material is 150 mL: 1 mg.
Comparative example 1
The method for recovering the Fischer-Tropsch synthesis catalyst comprises the following steps:
(1) adding water into the waste catalyst raw material, wherein the heating temperature of the first stage is 60-100 ℃, the heating rate is 15 ℃/h, the heating temperature of the second stage is 100-: 100.
the other steps of this comparative example were the same as in preparation example 1.
Comparative example 2
The method for recovering the Fischer-Tropsch synthesis catalyst comprises the following steps:
(1) same as in step (1) of preparation example 1;
(2) adding water into the intermediate treatment substance A, heating at 70 ℃, stirring at a speed of 200r/min, wherein the volume mass ratio of the water to the waste catalyst raw material is 100 mL: 1 mg.
The other steps of this comparative example were the same as in preparation example 1.
Comparative example 3
Steps (1) to (3) of the recovery method of the Fischer-Tropsch synthesis catalyst of this comparative example are the same as steps (1) to (3) of preparation example 1.
(4) Mixing the dry material obtained in the step (3) with water, and then carrying out magnetic separation to obtain a recovered iron catalyst; wherein the volume mass ratio of water to the waste catalyst raw material is 150 mL: 1 mg.
TABLE 1 comparison of catalyst recoveries of preparative example 1 and comparative examples 1-3
Preparation example 1 Comparative example 1 Comparative example 2 Comparative example 3
Fraction recovery 49 12 36 41
As can be seen from table 1, comparative example 1 uses no organic solvent, the catalyst recovery rate is low, and there is a possibility that the catalyst inside cannot be sufficiently exposed and released due to adhesion of hydrocarbon compounds on the surface of the waste catalyst raw material. Comparative example 2, using an organic solvent, catalyst recovery doubled, indicating that the organic solvent was very effective for catalyst recovery, however, without the use of a carboxylic acid, it was likely that the diatomaceous earth was not strongly disintegrated, resulting in insufficient exposure of the catalyst inside. The magnetic separation medium of comparative example 3 was water, which may still not sufficiently disrupt the diatomaceous earth attachment, resulting in a poor catalyst recovery. Preparation example 1 has the technical key points of the recovery part of the method of the present invention, and can fully dissolve and destroy the adhering substances on the surface of the waste catalyst raw material, solve the problem of complex external environment, fully expose the catalyst core, and greatly improve the catalyst recovery rate.
Selection of organic solvent
Preparation example 2
The recovery method of the Fischer-Tropsch synthesis catalyst comprises the following steps:
(1) adding ethyl acetate and morpholine into the waste catalyst raw material in sequence, wherein the heating temperature in the first stage is 60-100 ℃, the heating rate is 15 ℃/h, the heating temperature in the second stage is 100-140 ℃, the heating rate is 20 ℃/h, the heating temperature in the third stage is 140-200 ℃, the heating rate is 20 ℃/h, the stirring rate is 200r/min, extracting is carried out, and the organic solvent dissolves the hydrocarbon compounds on the surface of the waste catalyst raw material and extracts the hydrocarbon compounds from the mixture system to obtain an intermediate treatment substance A;
wherein the volume mass ratio of the ethyl acetate to the waste catalyst raw material is 100 mL: 1mg, wherein the volume mass ratio of morpholine to the waste catalyst raw material is 70 mL: 1 mg.
The other steps of this preparation example were the same as in preparation example 1.
Preparation example 3
The recovery method of the Fischer-Tropsch synthesis catalyst comprises the following steps:
(1) adding cyclohexane and morpholine into the waste catalyst raw material in sequence, wherein the heating temperature in the first stage is 60-100 ℃, the heating rate is 15 ℃/h, the heating temperature in the second stage is 100-;
wherein the volume mass ratio of the cyclohexane to the waste catalyst raw material is 100 mL: 1mg, wherein the volume mass ratio of morpholine to the waste catalyst raw material is 70 mL: 1 mg.
The other steps of this preparation example were the same as in preparation example 1.
TABLE 2 comparison of catalyst recoveries from preparative examples 1-3
Preparation example 1 Preparation example 2 Preparation example 3
Fraction recovery 49 42 45
As can be seen from Table 2, preparation example 1, which used three organic solvents, reached a catalyst recovery ratio of 49, and was able to effectively contact and dissolve the hydrocarbon compound throughout the heating process, probably because the three organic solvents covered a wide boiling point range. Cyclohexane and morpholine were used in preparation example 3, and the catalyst recovery ratio reached 45, while ethyl acetate and morpholine were used in preparation example 2, and the catalyst recovery ratio reached 42, which is slightly less effective than preparation example 3.
Example 1
The method for treating rhodamine B wastewater by using the waste catalyst comprises the following steps:
(1) adding ethyl acetate, cyclohexane and morpholine into the waste catalyst raw material in sequence, wherein the heating temperature in the first stage is 60-100 ℃, the heating rate is 20 ℃/h, the heating temperature in the second stage is 100-140 ℃, the heating rate is 25 ℃/h, the heating temperature in the third stage is 140-200 ℃, the heating rate is 25 ℃/h, the stirring rate is 200r/min, extracting is carried out, and the organic solvent dissolves the hydrocarbon compounds on the surface of the waste catalyst raw material and extracts the hydrocarbon compounds to leave the mixture system to obtain an intermediate treatment substance A;
wherein the volume mass ratio of the ethyl acetate to the waste catalyst raw material is 150 mL: 1mg, wherein the volume mass ratio of the cyclohexane to the waste catalyst raw material is 150 mL: 1mg, wherein the volume mass ratio of morpholine to the waste catalyst raw material is 100 mL: 1 mg;
(2) adding acetic acid and water into the intermediate treatment substance A, heating to 70 ℃, stirring at the speed of 300r/min, dissolving partial oxides in the diatomite by the acetic acid, and collapsing and remolding the pore structure of the diatomite to obtain an intermediate treatment substance B; wherein the mass ratio of the acetic acid to the waste catalyst raw material is 0.3: 1, the volume mass ratio of water to the waste catalyst raw material is 120 mL: 1 mg;
(3) heating the intermediate treatment substance B obtained in the step (2) for 3 hours at 250 ℃ to obtain a dry material;
(4) mixing the dry material obtained in the step (3) with a sodium hydroxide solution, and then carrying out magnetic separation to obtain a recovered iron catalyst; wherein the concentration of the sodium hydroxide solution is 0.01g/mL, and the volume-to-mass ratio of the sodium hydroxide solution to the waste catalyst raw material is 180 mL: 1 mg;
(5) the pH value is 3, the treatment temperature is 40 ℃, the recovered iron catalyst and hydrogen peroxide are mixed with rhodamine B wastewater and heated for 30 minutes, and the mass volume ratio of the recovered iron catalyst to the rhodamine B wastewater is 3 g: 100L, the mass-volume ratio of hydrogen peroxide to rhodamine B wastewater is 5 g: 100L, filtering and recycling the catalyst after degrading the wastewater.
Example 2
The method for treating rhodamine B wastewater by using the waste catalyst comprises the following steps:
(1) adding ethyl acetate, cyclohexane and morpholine into the waste catalyst raw material in sequence, wherein the heating temperature in the first stage is 60-100 ℃, the heating rate is 18 ℃/h, the heating temperature in the second stage is 100-140 ℃, the heating rate is 23 ℃/h, the heating temperature in the third stage is 140-200 ℃, the heating rate is 22 ℃/h, the stirring rate is 300r/min, extracting is carried out, and the organic solvent dissolves the hydrocarbon compounds on the surface of the waste catalyst raw material and extracts the hydrocarbon compounds to leave the mixture system to obtain an intermediate treatment substance A;
wherein the volume mass ratio of the ethyl acetate to the waste catalyst raw material is 130 mL: 1mg, wherein the volume mass ratio of the cyclohexane to the waste catalyst raw material is 120 mL: 1mg, wherein the volume mass ratio of morpholine to the waste catalyst raw material is 80 mL: 1 mg;
(2) adding acetic acid and water into the intermediate treatment substance A, heating to 60 ℃, stirring at a speed of 250r/min, dissolving part of oxides in the diatomite by the acetic acid, and collapsing and remolding the pore structure of the diatomite to obtain an intermediate treatment substance B; wherein the mass ratio of the acetic acid to the waste catalyst raw material is 0.2: 1, the volume mass ratio of water to the waste catalyst raw material is 110 mL: 1 mg;
(3) heating the intermediate treatment substance B obtained in the step (2) for 4 hours at 100 ℃ to obtain a dry material;
(4) mixing the dry material obtained in the step (3) with a sodium hydroxide solution, and then carrying out magnetic separation to obtain a recovered iron catalyst; wherein the concentration of the sodium hydroxide solution is 0.008g/mL, and the volume mass ratio of the sodium hydroxide solution to the waste catalyst raw material is 160 mL: 1 mg;
(5) the pH value is 4, the treatment temperature is 50 ℃, the recovered iron catalyst and hydrogen peroxide are mixed with rhodamine B wastewater and heated for 40 minutes, and the mass volume ratio of the recovered iron catalyst to the rhodamine B wastewater is 5 g: 100L, the mass-volume ratio of hydrogen peroxide to rhodamine B wastewater is 10 g: 100L, filtering and recycling the catalyst after degrading the wastewater.
Example 3
The method for treating phenol wastewater by using the waste catalyst comprises the following steps:
(1) adding ethyl acetate, cyclohexane and morpholine into the waste catalyst raw material in sequence, wherein the heating temperature in the first stage is 60-100 ℃, the heating rate is 15 ℃/h, the heating temperature in the second stage is 100-140 ℃, the heating rate is 24 ℃/h, the heating temperature in the third stage is 140-200 ℃, the heating rate is 23 ℃/h, the stirring rate is 240r/min, extracting is carried out, and the organic solvent dissolves the hydrocarbon compounds on the surface of the waste catalyst raw material and extracts the hydrocarbon compounds to leave the mixture system to obtain an intermediate treatment substance A;
wherein the volume mass ratio of the ethyl acetate to the waste catalyst raw material is 110 mL: 1mg, wherein the volume mass ratio of the cyclohexane to the waste catalyst raw material is 140 mL: 1mg, wherein the volume mass ratio of morpholine to the waste catalyst raw material is 90 mL: 1 mg;
(2) adding formic acid and water into the waste catalyst coated with the diatomite, heating to 50 ℃, stirring at a speed of 280r/min, dissolving partial oxides in the diatomite by the formic acid, and disrupting and remolding the pore structure of the diatomite to obtain an intermediate treatment substance B; wherein the mass ratio of the formic acid to the diatomite is 0.1: 1, the volume mass ratio of water to the waste catalyst raw material is 120 mL: 1 mg;
(3) heating the intermediate treatment substance B obtained in the step (2) for 4 hours at 200 ℃ to obtain a dry material;
(4) mixing the dry material obtained in the step (3) with a sodium hydroxide solution, and then carrying out magnetic separation to obtain a recovered iron catalyst; wherein the concentration of the sodium hydroxide solution is 0.009g/mL, and the volume-to-mass ratio of the sodium hydroxide solution to the waste catalyst raw material is 170 mL: 1 mg.
(5) The pH value is 5, the treatment temperature is 30 ℃, the recovered iron-based catalyst and hydrogen peroxide are mixed with the phenol wastewater and heated for 30 minutes, and the mass volume ratio of the recovered iron-based catalyst to the phenol wastewater is 7 g: 100L, the mass volume ratio of hydrogen peroxide to phenol wastewater is 9 g: 100L, filtering and recycling the catalyst after degrading the wastewater.
In the embodiments 1 and 2, the recovered catalyst is used for treating rhodamine B wastewater, the degradation rates are respectively 95% and 97%, and the treatment effect is good.
In example 3, the recovered catalyst was used for treating phenol wastewater with a degradation rate of 94% and a good treatment effect.

Claims (8)

1. A method for treating organic wastewater by using a Fischer-Tropsch synthesis waste catalyst is characterized by comprising the following steps:
(1) mixing an organic solvent with the waste catalyst raw material, extracting under the conditions of heating and stirring, dissolving the hydrocarbon compounds on the surface of the waste catalyst raw material by the organic solvent, and extracting the hydrocarbon compounds from a mixture system to obtain an intermediate treatment product A;
(2) adding carboxylic acid and a polar solvent into the intermediate treatment substance A, and dissolving inorganic substances and residual micromolecular organic substances in the intermediate treatment substance A by the carboxylic acid under the conditions of heating and stirring to obtain an intermediate treatment substance B with a pore structure;
(3) heating the intermediate treatment substance B obtained in the step (2) at the temperature of 100 ℃ and 250 ℃ for 3-4 hours to obtain a dry material;
(4) mixing the dry material with a magnetic separation medium, and then carrying out magnetic separation to obtain a recovered iron catalyst;
(5) mixing the recovered iron catalyst and hydrogen peroxide with organic wastewater in an acid environment, heating, degrading the wastewater, and filtering again to recover the catalyst;
the organic solvent in the step (1) is selected from the combination of two or more of ethyl acetate, cyclohexane and morpholine; the effective catalyst component of the waste catalyst raw material is mainly ferric oxide;
in the step (2), the inorganic substance is diatomite;
in the step (4), the magnetic separation medium is a dilute sodium hydroxide solution;
in the step (1), the heating process is divided into three stages, wherein the heating temperature in the first stage is 60-100 ℃, and the heating rate is 15-20 ℃/hour; the heating temperature of the second stage is 100-140 ℃, and the heating rate is 20-25 ℃/h; the heating temperature of the third stage is 140-.
2. The method of treating organic wastewater according to claim 1, wherein the organic solvent is a combination of ethyl acetate, cyclohexane and morpholine.
3. The method for treating organic wastewater according to claim 2, wherein the carboxylic acid in the step (2) is R-COOH, the R group is an aliphatic hydrocarbon group, and the polar solvent is selected from water and/or ethanol;
the heating temperature of the step (2) is 50-70 ℃, and the stirring speed is 200-300 r/min.
4. The method for treating organic wastewater according to claim 2, wherein the volume-to-mass ratio of the ethyl acetate to the waste catalyst raw material in the organic solvent is (100-150) mL: 1mg, and the volume mass ratio of the cyclohexane to the waste catalyst raw material is (100-150) mL: 1mg, wherein the volume mass ratio of morpholine to the waste catalyst raw material is (70-100) mL: 1 mg.
5. The method for treating organic wastewater according to claim 3, wherein the mass ratio of the carboxylic acid to the spent catalyst raw material is (0.1-0.3): 1.
6. the method for treating organic wastewater according to claim 1, wherein the volume-to-mass ratio of the polar solvent to the waste catalyst raw material is (100-120) mL: 1 mg.
7. The method for treating organic wastewater according to claim 1, wherein the volume-to-mass ratio of the magnetic separation medium to the waste catalyst raw material is (150-180) mL: 1mg, and the concentration of the magnetic separation medium is 0.007-0.01 g/mL.
8. The method for treating organic wastewater according to claim 1, wherein the mass-to-volume ratio of the recovered iron-based catalyst to the organic wastewater is (3-20) g: 100L, wherein the mass volume ratio of the hydrogen peroxide to the organic wastewater is (5-15) g: 100L.
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