CN113117737B - Catalyst for treating oily sewage and preparation method and application thereof - Google Patents

Catalyst for treating oily sewage and preparation method and application thereof Download PDF

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Publication number
CN113117737B
CN113117737B CN202011603565.0A CN202011603565A CN113117737B CN 113117737 B CN113117737 B CN 113117737B CN 202011603565 A CN202011603565 A CN 202011603565A CN 113117737 B CN113117737 B CN 113117737B
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catalyst
carrier
preparing
treating oily
oily sewage
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CN113117737A (en
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周建华
蒋广安
赵越
李宝忠
郭宏山
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • B01J29/7607—A-type
    • B01J35/615—
    • B01J35/633—
    • B01J35/643—
    • B01J35/647—
    • 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
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/32—Reaction with silicon compounds, e.g. TEOS, siliconfluoride
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
    • C02F2103/365—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)

Abstract

The invention discloses a catalyst for treating oily sewage and a preparation method and application thereof, wherein the preparation method comprises the steps of contacting a slurry containing chopped fibers, silicon-aluminum composite oxide and active carbon to form a uniform material, adding a binder and water, and obtaining a first carrier after molding, drying and curing; then adding the mixture into caustic soda solution for treatment, and drying, roasting and cooling the separated solid particles to obtain a second carrier; contacting the second carrier with silicon tetrachloride under nitrogen or inert atmosphere to obtain a carrier; and introducing active metal, and drying and roasting to obtain the catalyst. The catalyst prepared by the method has good catalytic activity stability, and can greatly improve the use efficiency of the oxidant.

Description

Catalyst for treating oily sewage and preparation method and application thereof
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a catalytic material for treating oily wastewater and a preparation method thereof.
Background
During the processing and use of petroleum products, part of oily wastewater, such as stripping of petrochemical enterprises, washing of acid gas, leakage of petroleum substances and the like, is generated. The treatment method of the oily wastewater is mainly a physical method and a biological degradation method. Biodegradation is one of the effective methods for degrading petroleum hydrocarbon, but the biochemical method has the limitation that petroleum pollutants are difficult to thoroughly remove or reach the emission index. The ozone catalytic oxidation technology can excite ozone to generate hydroxyl free radicals, and the hydroxyl free radicals and organic pollutants are subjected to a series of free radical chain reactions to be gradually degraded into harmless low-molecular-weight organic matters, and finally the harmless low-molecular-weight organic matters are degraded into CO2, H2O and other mineral salts, so that the problem of COD reduction of sewage difficult to biochemically treat can be effectively solved.
The key of the treatment effect of the ozone catalytic oxidation process is the reactivity of the catalyst. In the common ozone catalytic oxidation catalysts sold in the market, the catalyst prepared by loading metal with active carbon has better activity, but has poor mechanical strength and is easy to abrade; the ceramsite supported catalyst has low specific surface area and poor activity; alumina supported catalyst raw materials are expensive and the pore structure is not suitable for handling complex component contaminants. When these catalysts treat organic matters in wastewater, the adsorption effect on complex molecular components is poor, so that the reaction rate is low, the driving force is insufficient, and the pollutant removal effect at high concentration is difficult to achieve, so that the activity of treating organic pollutants is affected. The development of a new catalytic material with gradient pore diameter, three-dimensional pore channel structure and certain hydrophobicity can efficiently adsorb organic pollutants, improve the mass transfer rate of the pollutants and the initial concentration of catalytic treatment reactants, realize in-situ and real-time catalytic degradation of the pollutants, and improve the removal of the organic pollutants under the condition of the same catalyst and oxidant consumption.
CN201711288309.5 discloses a high-efficiency catalytic sodium hypochlorite reclaimed water treatment system based on a composite catalytic bed layer, which comprises an oxidation tower, wherein an active carbon catalyst bed layer and a molecular sieve catalyst bed layer are arranged in the oxidation tower. The invention also discloses a high-efficiency catalytic sodium hypochlorite water treatment process based on the composite catalytic bed layer. The invention realizes the activation of the catalytic bed layer to the sodium hypochlorite, effectively reduces the content of refractory organic matters in reclaimed water, and realizes the advanced treatment of reclaimed water.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a catalyst for treating oily sewage, and a preparation method and application thereof. The catalyst prepared by the method has good catalytic activity stability, and can greatly improve the use efficiency of the oxidant.
The first aspect of the invention provides a preparation method of a catalyst for treating oily sewage, which comprises the following steps:
(1) The alkali-soluble chopped fiber yarn is contacted with water, and fully and uniformly mixed to obtain slurry containing chopped fiber;
(2) Carrying out heat treatment on the silicon-aluminum composite oxide at 600-1000 ℃ to obtain a modified silicon-aluminum composite oxide;
(3) Contacting the slurry containing chopped fibers and the modified silicon-aluminum composite oxide with activated carbon to form a uniform material, adding a binder and water, and forming, drying and curing to obtain a first carrier;
(4) Adding the first carrier obtained in the step (3) into caustic soda solution for treatment, then carrying out solid-liquid separation, and drying, roasting and cooling the separated solid particles to obtain a second carrier;
(5) Contacting the second carrier with silicon tetrachloride under nitrogen or inert atmosphere to obtain a carrier;
(6) And (3) introducing active metal to the carrier obtained in the step (5), and then drying and roasting to obtain the catalyst.
The preparation method of the catalyst for treating oily sewage is characterized by comprising the following steps: the length of the alkali-soluble chopped fiber in the step (1) is 2-5 mm, the diameter of the monofilament is 10-70 nm, and the alkali-soluble chopped fiber can be specifically selected from any one or more of alkali-soluble polyester fiber, carboxymethyl cellulose fiber and hydroxyethyl cellulose fiber.
In the preparation method of the catalyst for treating oily sewage, in the step (2), the silicon-aluminum composite oxide is powder particles, and the oxides of Si and Al in the particles account for 8More than 0wt percent, wherein the oxide of Si accounts for 25-60 wt percent. The specific surface area of the silicon-aluminum composite oxide is 5-500 m 2 And/g, wherein the average pore diameter is 2.0-30.0 nm, the particle diameter is 1-100 mu m, and more than 80% of pores with pore volume metering pore diameter of 5.0-15.0 nm are occupied.
In the preparation method of the catalyst for treating oily sewage, the active carbon in the step (3) is ground wood, coal or fruit shell granular active carbon, the average pore diameter is 0.4-5.0 nm, and the specific surface area is 400-3500 m 2 And/g, the grain diameter is 1-100 μm, and the pore volume is used for measuring the pore diameter of 1.2-3.6 nm to account for more than 90%.
In the preparation method of the catalyst for treating oily sewage, in the step (3), the mass ratio of the active carbon to the modified silicon-aluminum composite oxide to the alkali-soluble chopped fiber to the binder is (10-40): 30-85: 5-15: 2 to 5.
In the preparation method of the catalyst for treating oily sewage, the binder in the step (3) is a silicate inorganic binder and/or a phosphate inorganic binder; wherein, the silicate inorganic binder can be one or more of aluminum silicate, sodium silicate, calcium silicate, dicalcium silicate and tricalcium silicate, preferably sodium silicate and/or aluminum silicate; the phosphate inorganic binder can be one or more of aluminum phosphate, aluminum dihydrogen phosphate, sodium pyrophosphate, sodium tripolyphosphate and sodium hexametaphosphate, and is preferably aluminum dihydrogen phosphate and/or sodium tripolyphosphate.
In the preparation method of the catalyst for treating oily sewage, the adding amount of the caustic soda solution in the step (4) is as follows: the ratio of the amount of NaOH substance was 1: 3-4, and the concentration of the caustic soda solution is 7-10 wt%.
In the preparation method of the catalyst for treating oily sewage, the drying temperature in the step (4) is 50-150 ℃, preferably 60-120 ℃ and the drying time is 2-12 h.
In the preparation method of the catalyst for treating oily sewage, the roasting temperature in the step (4) is 300-1000 ℃, preferably 400-800 ℃, and the roasting treatment time is 2-8 hours. The calcination is carried out under anaerobic conditions, for example under nitrogen or under inert gas.
In the preparation method of the catalyst for treating oily sewage, any means capable of realizing solid-liquid two-phase separation in the field is adopted for the solid-liquid separation in the step (4), such as filtration, centrifugation, inclined filtration and the like.
In the preparation method of the catalyst for treating oily sewage, the specific process of the contact treatment of the second carrier and silicon tetrachloride in the step (5) is as follows: and adding a second carrier into the container under nitrogen or inert atmosphere, and then injecting silicon tetrachloride into the container at 300-600 ℃, wherein the silicon tetrachloride is gasified and is contacted with the second carrier for treatment, and the silicon tetrachloride dosage is 0.1-10 times of the weight of the treated material.
In the preparation method of the catalyst for treating oily sewage, the active metal in the step (6) is iron.
In the preparation method of the catalyst for treating oily sewage, the method for introducing the active metal into the carrier obtained in the step (5) in the step (6) adopts any conventional method existing in the field, such as an impregnation method, a kneading method and the like, and preferably adopts the impregnation method. The active metal component loaded on the carrier by adopting an impregnation method is manufactured by adopting a conventional impregnation method, and a spray impregnation method, a saturation impregnation method or a supersaturation impregnation method can be adopted. The method for supporting the active metal component on the carrier is, for example, an impregnation method, which comprises preparing a solution of the active metal-containing compound and impregnating the carrier with the solution. The active metal-containing compound is an iron-containing salt solution, and can be one or more of sulfate, nitrate, acetate and chloride.
In the preparation method of the catalyst for treating oily sewage, the drying temperature in the step (6) is 50-150 ℃, preferably 60-120 ℃ and the drying time is 2-12 h.
In the preparation method of the catalyst for treating oily sewage, the roasting temperature in the step (6) is 300-1000 ℃, preferably 400-800 ℃, and the heating time is 2-8 hours. The calcination is carried out under anaerobic conditions, for example under nitrogen or under inert gas.
The invention provides a catalyst for treating oily sewage, which is prepared by the method, and comprises an active component and a carrier, wherein iron is used as the active component, and the composite carrier contains active carbon, a 4A molecular sieve, a silicon-aluminum composite oxide and a binder; wherein the content of the active component is 2-20wt%.
In the catalyst for treating oily sewage, the content of active carbon in the composite carrier is 10-50wt%; the content of the 4A molecular sieve is 15-40 wt%; 30-60 wt% of silicon-aluminum composite oxide; the content of the binder is 2-15 wt%, the relative crystallinity of the 4A molecular sieve is 30-60, and the 4A molecular sieve is mainly positioned on the outer surface of the carrier and is formed by treating silicon-aluminum composite oxide with caustic soda solution.
In the catalyst for treating oily sewage, the composite carrier is provided with three-dimensional pore channels and good pore distribution, wherein the pore volume of pores with the pore diameter of 0.1-1.5 nm accounts for 20-45% of the total pore volume, the pore volume of pores with the pore diameter of 1.5-5 nm accounts for 20-35% of the total pore volume, the pore volume of pores with the pore diameter of 5-50 nm accounts for 20-60% of the total pore volume, and multi-pore channels in the whole carrier are in three-dimensional intercommunication connection.
In a third aspect, the present invention provides a treatment method for oily sewage, wherein the treatment method is to make the oily sewage and ozone enter a reactor to react in contact with the catalyst for treating oily sewage.
In the above-described oily sewage treatment method, the oily sewage may be from oily wastewater produced during petroleum exploitation, transportation, processing, and storage.
In the oil-containing sewage treatment method, the reaction conditions are room temperature, normal pressure and volume space velocity of 0.1-3 h -1 The ozone adding amount is 10-1000 g/t of wastewater.
Compared with the prior art, the catalyst for treating oily sewage, and the preparation method and application thereof have the following advantages:
in the preparation method of the catalyst for treating the oily sewage, in the preparation process of the composite carrier and the catalyst, the composite carrier has good structural support strength by heat treatment of the silicon-aluminum composite oxide and the binder; performing in-situ crystal transformation on the outer layer of the composite carrier through alkali treatment and heat treatment of the silicon-aluminum composite oxide to generate a 4A molecular sieve; the chopped fibers in the composite carrier are removed through alkali liquor treatment, and a three-dimensional porous penetrating hole structure is generated, so that the composite carrier and the catalyst have good reactant product diffusion performance; the silicon tetrachloride gas phase treatment is beneficial to further dealumination and silicon supplementation of the generated 4A molecular sieve, increases the silicon-aluminum ratio of the molecular sieve in the material, and enhances the hydrophobicity of the carrier material, thereby promoting the adsorption performance on organic matters; the catalyst has good reaction activity due to good adsorptivity of the active carbon and the molecular sieve, initiation activity of active carbon chain reaction and catalytic activity of active metal, and is beneficial to improving the capability of treating organic pollutants. The catalyst can effectively reduce COD and improve biochemical value of wastewater.
Detailed Description
The preparation method of the present invention will be further described with reference to specific examples, but the scope of the present invention is not limited to the examples.
In the embodiment and the comparative example of the invention, the pore volume, the specific surface area and the pore distribution are measured by adopting a low-temperature liquid nitrogen physical adsorption method. In the invention, the weight percent is the mass fraction. In the examples and comparative examples of the present invention, the relative crystallinity was obtained by an X-ray diffraction method (Xu Ruren, pang Wenqin, etc.. Molecular sieves and porous materials chemistry. Beijing: science Press. 2014).
The specific surface area of the commercial powdery coconut charcoal used in the present invention is 920m 2 Per gram, pore volume 1.0cm 3 Per gram, average pore radius of 1.1nm, iodine adsorption value of 700mg/g, particle diameter of 45 μm.
The specific surface area of the inorganic oxide composite soil used in the invention is 105m 2 The mass ratio of the silica to the alumina was 3:2 and the particle diameter was 45. Mu.m.
Example 1
Adding water into alkali-soluble polyester fiber chopped fibers, fully and uniformly mixing, adding silicon-aluminum composite oxide treated for 4 hours at 650 ℃, adding silicon tetrachloride treated for 4 hours under the protection of nitrogen, adding silica sol with the silicon content of 20%, fully mixing and kneading, extruding and molding, drying for 4 hours at 100 ℃, solidifying for 8 hours at 275 ℃, cooling, adding the particles into alkali liquor, circularly treating the solid particles for 4 hours, carrying out solid-liquid separation, washing the solid particles to be neutral by using distilled water, drying for 4 hours at 100 ℃, roasting for 6 hours at 600 ℃ in nitrogen atmosphere, cooling, placing the solid particles into a closed and breathable tubular furnace, introducing silicon tetrachloride for 4 hours under the protection of nitrogen, cooling to obtain carrier ZA, carrying out quantitative loading on ZA and an iron-containing solution, drying for 8 hours at 90 ℃, roasting for 6 hours in nitrogen atmosphere at 500 ℃, and obtaining catalyst A, wherein the amounts of the reagents used for preparation are shown in Table 1, the distribution results of carrier ZA are shown in Table 2, and the physicochemical properties of the catalyst A are shown in Table 3.
Example 2
Adding water into alkali-soluble carboxymethyl cellulose chopped fibers, fully and uniformly mixing, adding silicon-aluminum composite oxide treated at 700 ℃ for 3.5 hours and active carbon, uniformly mixing, adding water glass with 25% of silicon content, fully mixing and kneading, extruding and molding, drying at 100 ℃ for 4 hours, solidifying at 300 ℃ for 6 hours, cooling, adding the particles into alkali liquor, carrying out circulating treatment on the solid particles for 4 hours, carrying out solid-liquid separation, washing the solid particles to be neutral by using distilled water, drying at 100 ℃ for 4 hours, roasting at 650 ℃ for 6 hours in a nitrogen atmosphere, cooling, placing the solid particles into a closed and aerated tubular furnace, introducing silicon tetrachloride under the condition of 425 ℃ under the protection of nitrogen for 3.5 hours, cooling to obtain a carrier ZB, carrying out quantitative loading on ZB by contacting with an iron-containing solution, drying at 90 ℃ for 8 hours, roasting at 550 ℃ for 5 hours in a nitrogen atmosphere, and obtaining the catalyst B, wherein the amounts of the prepared reagents are shown in Table 1, the pore distribution results of the carrier ZB are shown in Table 2, and the properties of the catalyst B are shown in Table 3.
Example 3
Adding water into alkali-soluble hydroxyethyl cellulose chopped fibers, fully and uniformly mixing, adding silicon-aluminum composite oxide treated at 700 ℃ for 3 hours and active carbon, uniformly mixing, adding silica sol with the silicon content of 25%, carrying out extrusion molding after fully mixing and kneading, drying at 100 ℃ for 4 hours, solidifying at 350 ℃ for 5 hours, cooling, adding particles into alkali liquor, carrying out circulating treatment on the solid particles for 4 hours, carrying out solid-liquid separation, washing the solid particles to be neutral by using distilled water, drying at 100 ℃ for 4 hours, roasting at 700 ℃ for 5 hours in nitrogen atmosphere, cooling, placing the solid particles into a closed and breathable tubular furnace, introducing silicon tetrachloride for 3 hours under the condition of 450 ℃ under the protection of nitrogen, cooling to obtain a carrier ZC, carrying out quantitative loading on ZC and an iron-containing solution, drying at 90 ℃ for 8 hours, roasting at 600 ℃ for 4 hours in nitrogen atmosphere, and obtaining a catalyst C, wherein the amounts of reagents used for preparation are shown in Table 1, and the distribution results of the carrier ZC are shown in Table 2, and the materialized properties of the catalyst C are shown in Table 3.
Example 4
According to the proportions of example 2, without adding carboxymethylcellulose during the preparation, the support ZD and the catalyst D were prepared, the amounts of the reagents used for the preparation being given in Table 1, the results of the pore distribution of the support ZD being given in Table 2 and the physicochemical properties of the catalyst D being given in Table 3.
Comparative example 1
According to the active carbon: silicon-aluminum composite oxide: the ratio of the 4A molecular sieves was 30:35:35, alkali-soluble fibers were not added, alkali treatment was not performed, siCl4 gas treatment was not used, and carrier ZDA and catalyst DA were prepared in the same manner as in example 2, the pore distribution results of carrier ZDA are shown in Table 2, and the physicochemical properties of catalyst DA are shown in Table 3.
TABLE 1 amount of reagents used to prepare catalysts
Figure 275036DEST_PATH_IMAGE001
TABLE 2 Carrier pore distribution results
Figure 926597DEST_PATH_IMAGE002
TABLE 3 physicochemical Properties of catalyst
Figure 503072DEST_PATH_IMAGE003
As can be seen from the physical and chemical properties of the carrier and the catalyst in tables 2 and 3, the catalyst obtained by adding the chopped alkali-soluble fiber has reduced pore distribution and increased macropore content compared with the catalyst obtained without adding the chopped alkali-soluble fiber; the specific surface area of the catalyst increases.
The treatment method of the oily sewage comprises the following steps: filling a catalyst in a fixed bed, treating oily sewage by using an ozone catalytic oxidation process at normal temperature and normal pressure, wherein the COD (chemical oxygen demand) of the oily sewage is 200mg/L, and the treatment condition airspeed is 1h -1 The ozone adding amount is 100mg/L. The results of the treatment after 100 hours are shown in Table 4.
TABLE 4 ozone catalytic oxidation treatment results
Figure 898281DEST_PATH_IMAGE004
As can be seen from the treatment results of Table 4, the catalyst obtained by the treatment with the addition of the chopped alkali-soluble fiber has a good treatment activity in treating oily sewage as compared with the catalyst obtained without the addition of the catalyst and the catalyst obtained by physical mixing.

Claims (23)

1. A method for preparing a catalyst for treating oily sewage, which comprises the following steps:
(1) The alkali-soluble chopped fiber yarn is contacted with water, and fully and uniformly mixed to obtain slurry containing chopped fiber;
(2) Carrying out heat treatment on the silicon-aluminum composite oxide at 600-1000 ℃ to obtain a modified silicon-aluminum composite oxide;
(3) Contacting the slurry containing chopped fibers and the modified silicon-aluminum composite oxide with activated carbon to form a uniform material, adding a binder and water, and forming, drying and curing to obtain a first carrier;
(4) Adding the first carrier obtained in the step (3) into caustic soda solution for treatment, then carrying out solid-liquid separation, and drying, roasting and cooling the separated solid particles to obtain a second carrier;
(5) Contacting the second carrier with silicon tetrachloride under nitrogen or inert atmosphere to obtain a carrier;
(6) And (3) introducing active metal to the carrier obtained in the step (5), and then drying and roasting to obtain the catalyst.
2. The process for preparing a catalyst for treating oily sewage according to claim 1, wherein: the length of the alkali-soluble chopped fiber in the step (1) is 2-5 mm, the diameter of a single filament is 10-70 nm, and the alkali-soluble chopped fiber is selected from any one or more of alkali-soluble polyester fibers, carboxymethyl cellulose fibers and hydroxyethyl cellulose fibers.
3. The process for preparing a catalyst for treating oily sewage according to claim 1, wherein: the silicon-aluminum composite oxide in the step (2) is powder particles, wherein the oxides of Si and Al in the particles account for more than 80wt%, and the oxides of Si account for 25-60 wt%.
4. The process for preparing a catalyst for treating oily sewage according to claim 1, wherein: the average pore diameter of the activated carbon in the step (3) is 0.4-5.0 nm, and the specific surface area is 400-3500 m 2 And/g, the grain diameter is 1-100 μm, and the pore volume is used for measuring the pore diameter of 1.2-3.6 nm to account for more than 90%.
5. The process for preparing a catalyst for treating oily sewage according to claim 1, wherein: in the step (3), the mass ratio of the active carbon to the modified silicon-aluminum composite oxide to the alkali-soluble chopped fiber to the binder is 10-40: 30-85: 5-15: 2 to 5.
6. The process for preparing a catalyst for treating oily sewage according to claim 1, wherein: the binder in the step (3) is a silicate inorganic binder and/or a phosphate inorganic binder.
7. The process for preparing a catalyst for treating oily wastewater according to claim 6, wherein: the silicate inorganic binder is one or more of aluminum silicate, sodium silicate, calcium silicate, dicalcium silicate and tricalcium silicate; the phosphate inorganic binder is one or more of aluminum phosphate, aluminum dihydrogen phosphate, sodium pyrophosphate, sodium tripolyphosphate and sodium hexametaphosphate.
8. The process for preparing a catalyst for treating oily wastewater according to claim 7, wherein: the silicate inorganic binder is sodium silicate and/or aluminum silicate; the phosphate inorganic binder is aluminum dihydrogen phosphate and/or sodium tripolyphosphate.
9. The process for preparing a catalyst for treating oily sewage according to claim 1, wherein: the addition amount of the caustic soda solution in the step (4) is as follows: the ratio of the amount of NaOH substance was 1: 3-4, and the concentration of the caustic soda solution is 7-10 wt%.
10. The process for preparing a catalyst for treating oily sewage according to claim 1, wherein: in the step (4), the drying temperature is 50-150 ℃ and the drying time is 2-12 h.
11. The process for preparing a catalyst for treating oily sewage according to claim 1, wherein: in the step (4), the drying temperature is 60-120 ℃ and the drying time is 2-12 h.
12. The process for preparing a catalyst for treating oily sewage according to claim 1, wherein: the roasting temperature in the step (4) is 300-1000 ℃, and the roasting treatment time is 2-8 hours; the calcination is performed under anaerobic conditions.
13. The process for preparing a catalyst for treating oily wastewater according to claim 12, wherein: the roasting temperature in the step (4) is 400-800 ℃.
14. The process for preparing a catalyst for treating oily sewage according to claim 1, wherein: the contact treatment process of the second carrier and the silicon tetrachloride in the step (5) is as follows: and adding the second carrier into a container under an inert atmosphere, then injecting silicon tetrachloride into the container at 300-600 ℃, gasifying the silicon tetrachloride and contacting the silicon tetrachloride with the second carrier for treatment, wherein the silicon tetrachloride is 0.1-10 times of the weight of the treated material.
15. The process for preparing a catalyst for treating oily sewage according to claim 1, wherein: the active metal in the step (6) is iron.
16. The process for preparing a catalyst for treating oily sewage according to claim 1, wherein: in the step (6), the drying temperature is 50-150 ℃ and the drying time is 2-12 h.
17. The process for preparing a catalyst for treating oily wastewater according to claim 16, wherein: the drying temperature in the step (6) is 60-120 ℃.
18. The process for preparing a catalyst for treating oily sewage according to claim 1, wherein: the roasting temperature in the step (6) is 300-1000 ℃ and the heating time is 2-8 hours; the calcination is performed under the protection of nitrogen or inert gas.
19. The process for preparing a catalyst for treating oily wastewater as set forth in claim 18, wherein: the roasting temperature in the step (6) is 400-800 ℃.
20. A catalyst for treating oily sewage obtained by the preparation method of any one of claims 1 to 19, the catalyst comprising an active component and a composite carrier, wherein iron is used as the active component, and the composite carrier comprises activated carbon, a 4A molecular sieve, a silicon-aluminum composite oxide and a binder.
21. The oily wastewater treatment catalyst according to claim 20, wherein: in the composite carrier, the content of the activated carbon is 10-50 wt%; the content of the 4A molecular sieve is 15-40 wt%; 30-60 wt% of silicon-aluminum composite oxide; the content of the binder is 2-15 wt%, and the relative crystallinity of the 4A molecular sieve is 30-60.
22. The oily wastewater treatment catalyst according to claim 20, wherein: the composite carrier has three-dimensional pore channels and good pore distribution, wherein the pore volume of pores with the pore diameter of 0.1-1.5 nm accounts for 20-45% of the total pore volume, the pore volume of pores with the pore diameter of 1.5-5 nm accounts for 20-35% of the total pore volume, and the pore volume of pores with the pore diameter of 5-50 nm accounts for 20-60% of the total pore volume.
23. A process for treating oily sewage by bringing oily sewage into contact with ozone in a reactor and reacting with the catalyst for treating oily sewage as claimed in any one of claims 20 to 22.
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