CN107010709B - Method for purifying high-concentration phenol-containing wastewater in production process of o/hydroquinone - Google Patents

Method for purifying high-concentration phenol-containing wastewater in production process of o/hydroquinone Download PDF

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CN107010709B
CN107010709B CN201710392082.2A CN201710392082A CN107010709B CN 107010709 B CN107010709 B CN 107010709B CN 201710392082 A CN201710392082 A CN 201710392082A CN 107010709 B CN107010709 B CN 107010709B
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fluidized bed
phenol
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wastewater
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CN107010709A (en
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乔旭
陈献
吴春辉
费兆阳
刘清
崔咪芬
汤吉海
张竹修
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Nanjing Zihuan Engineering Technology Research Institute Co ltd
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南京工业大学
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    • 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
    • C02F1/74—Treatment of water, waste water, or sewage by oxidation with air
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions

Abstract

The invention discloses a method for purifying high-concentration phenolic wastewater in the production process of o/hydroquinone, which comprises the following steps: 1 air inlet is respectively arranged at the upper expanding section and the bottom of the cyclone fluidized bed reactor, two air streams are simultaneously introduced, the air is taken as an oxidant, one air stream enters the fluidized section of the cyclone fluidized bed reactor from the bottom of the reactor, and the other air stream enters the reactor from the tangential direction of the expanding section; the phenol-containing wastewater is added into a fluidized section of a cyclone fluidized bed reactor from the top, phenols in the wastewater and air are subjected to catalytic cracking oxidation reaction under the action of a catalytic cracking oxidation catalyst, generated gas enters a fixed bed reactor from the top, deep oxidation reaction is carried out under the action of the deep oxidation catalyst, the gas is discharged from an outlet of the fixed bed reactor, the gas passes through a heat exchanger and a gas-liquid separator in sequence, obtained condensate is sent into a rain drainage system, and noncondensable gas is directly discharged in an air release mode. The invention can treat the phenol-containing wastewater with high efficiency, low cost and low energy consumption.

Description

Method for purifying high-concentration phenol-containing wastewater in production process of o/hydroquinone
Technical Field
The invention belongs to the field of treatment of high-concentration phenolic wastewater, and particularly relates to a method for purifying high-concentration phenolic wastewater in an o/p-dihydroxybenzene production process.
Background
The production process of the o/hydroquinone is mainly a hydroxylation method of oxydol oxidized phenol, and the reaction equation is as follows:
Figure BDA0001307750800000011
the process takes water as a reaction medium, about 30 wt% of hydrogen peroxide as an oxidant, and oxidizes phenol into o/hydroquinone under the action of a catalyst, and simultaneously generates water. After the oxidized reaction liquid is extracted by methyl isobutyl ketone, most of water can be recycled, but still part of water needs to be purified, and the part of water contains dangerous chemicals such as phenol, o/hydroquinone, phenol tar, methyl isobutyl ketone and the like.
Phenol and its derivatives are highly toxic, non-degradable organic materials and, due to their serious environmental and human health hazards, phenolic wastewater must be effectively dephenolized prior to discharge. The standard of direct discharge of volatile phenol wastewater in China (GB31571-2015) is 0.5mg/L, and the standard of direct discharge of volatile phenol-containing wastewater is 0.3mg/L in areas where special protection measures are needed because of the occurrence of serious water environment pollution problems. In recent years, researchers at home and abroad have made a lot of research on the treatment of phenol-containing wastewater, and developed various treatment methods, mainly including physical methods, catalytic oxidation methods, chemical oxidation methods, biochemical methods, electrochemical methods, photodegradation methods, and the like.
The physical method for treating the phenol-containing wastewater mainly comprises an extraction method and an adsorption method. The most key extractant in the extraction dephenolization technology is selected, in the United states patent 6071409, alkyl tert-amyl ether is adopted as the extractant, the primary extraction dephenolization rate can reach more than 90 percent (the phenol content in raw water is 7000mg/L), and the phenol content in raffinate is still about 700 mg/L; chinese patent 105540969 discloses that when eucalyptol is used as extractant to treat phenol waste water with phenol content of 5000mg/L, the single extraction dephenolizing rate can reach 96.2%. The technology for treating phenolic wastewater by an extraction method generally has the defects of high cost of an extracting agent and high regeneration energy consumption, and the content of phenol and the Chemical Oxygen Demand (COD) of organic matters in the extracted wastewater hardly reach the discharge standard of wastewater in a park, so the technology is often used as a pretreatment means of high-concentration phenolic wastewater for recovering phenols in the wastewater, raffinate is treated by other means, and a common treatment method is a biochemical method. In the adsorption dephenolization technology, most of the adsorbents are expensive, so that the adsorption regeneration cost is high, and secondary pollution is easy to generate.
Wet oxidation is an effective oxidation technology for treating toxic, harmful and high-concentration organic wastewater developed by american scientists Zimmermann in the 50 s of the 20 th century, and is now applied to the treatment of phenol-containing wastewater. Inchaurrondo et Al developed a wet catalytic oxidation catalyst CuO- γ Al2O3And is applied to phenol wastewater treatment, under the optimal condition, the phenol removal rate can reach 100 percent, and the Total Organic Carbon (TOC) reaches 80 percent (CHEMICAL ENGINEERING JOURNAL,2012.198: 426-434.). Chinese patent 201510245064.2 discloses a preparation method of a wet catalytic oxidation catalyst and a purification method of phenol wastewater based on the catalyst, wherein the phenol content in the wastewater is 1000mg/L, and the space velocity is 6h-1When the reaction pressure is 1.0MPa and the reaction temperature is 160 ℃, the removal rate of phenol can reach 96.4 percent and the removal rate of COD is 75 percent. The wet catalytic oxidation completely degrades COD, the temperature needs to reach about 250 ℃, the operating pressure is 4-8 MPa, the reactor material is required to have high temperature resistance, high pressure resistance and corrosion resistance, meanwhile, the wet oxidation method can reach the discharge standard of phenolic wastewater treatment by being difficult to be treated in one step, secondary harmless treatment is still required, and therefore the industrial application of the wet catalytic oxidation is restricted.
The biodegradation method is the most important method for treating the phenol-containing wastewater at present. Gonzalez et al use calcium alginate to gel pseudounicellular bacteria into spider bodies, successfully apply the spider bodies in a fluidized bed bioreactor, treat phenolic wastewater generated in a phenolic resin plant, dilute the phenolic concentration to 1000mg/L before entering a fluidized bed, control the pH to 6.6 during operation, control the temperature to 30 ℃, control the air inflow to 85L/h, and control the phenol removal rate to be more than 90% when the dissolved oxygen is 2-4.5 mg/L (bioreasoure TECHNOLOGY,2001.80(2):137 and 142). The biological degradation method has the disadvantages that phenolic substances have toxic action on strains and cannot treat high-concentration phenolic wastewater. Therefore, when the phenol-containing wastewater is treated by a biodegradation method, the phenol-containing wastewater needs to be pretreated, so that the phenol content in the wastewater is reduced, and microorganisms can survive. In general, when phenolic wastewater enters a biochemical pool, the concentration of phenol in the wastewater needs to be controlled not to exceed 1000mg/L, and meanwhile, the biological treatment method has the defects of large occupied area of a device, high operation management requirement and the like.
In recent years, photocatalytic technology has been widely studied as an advanced oxidation technology. Patent CN201310338889.X discloses a device and a method for photocatalytic degradation of phenol-containing wastewater, the core of the device is a turntable reactor, which comprises a shell, a turntable, a rotating shaft, an excitation light source, a liquid inlet pipe and a liquid outlet pipe. The inner walls of the turntable and the shell are loaded with catalysts, and excitation light sources are arranged above and below the turntable so as to increase the photocatalytic reaction time and strengthen the mass transfer effect. The wastewater with the phenol content of 500mg/L is taken as a simulation object, when the rotating speed of a rotating disc is 500r/min, a light source is a 254nm low-pressure mercury lamp, and the light intensity is 18.35mW/cm2The space velocity is 50L/h, the removal rate of phenol is 98.34 percent by sampling analysis after 4h, and the concentration of residual phenol is about 8 mg/L. The method has the defects of difficult separation of the catalyst, complex reactor structure, low light energy utilization rate and the like. Chinese patent CN20131029323.3 discloses a method for photodegradation of phenol wastewater by using chlorine dioxide as an oxidant and activated carbon loaded nano-titanium dioxide as a catalyst under the irradiation of an ultraviolet lamp. The COD and phenol contents of the wastewater before treatment are 433.7mg/L and 195mg/L respectively, the COD and phenol contents of the wastewater after treatment are 78.5mg/L and 1.09mg/L respectively, and the removal rates of the COD and the phenol reach 81.6% and 99.5%. The phenol-containing wastewater after photocatalytic treatment still needs secondary treatment, and the light degradation method needs illumination, so the transparency of the wastewater is related to the degradation effect, and the method cannot treat the wastewater with turbidity or poor water quality transparency.
Disclosure of Invention
The invention aims to provide a purification treatment method for phenol-containing wastewater generated in an extraction process in a phenol hydroxylation production process.
The purpose of the invention is realized by the following technical scheme:
a method for purifying high-concentration phenol-containing wastewater in the production process of catechol/hydroquinone comprises the following steps:
(1) 1 air inlet is respectively arranged at the upper expanding section and the bottom of the cyclone fluidized bed reactor, two air streams are simultaneously introduced, the air is taken as an oxidant, one air stream enters the fluidizing section of the cyclone fluidized bed reactor from the bottom of the reactor, the other air stream enters the reactor from the tangential direction of the expanding section, and catalyst particles and organic matter molecules in the expanding section return to the fluidizing section under the action of air cyclone; phenol-containing wastewater generated in the process of producing o/hydroquinone through phenol hydroxylation is added into a fluidization section of a cyclone fluidized bed reactor from the top of the cyclone fluidized bed reactor, and organic matters in the wastewater and air undergo catalytic cracking oxidation reaction under the action of a catalytic cracking oxidation catalyst;
(2) the gas generated after catalytic cracking oxidation enters a fixed bed reactor connected with the cyclone fluidized bed reactor in series from the top, and is subjected to deep oxidation reaction under the action of a deep oxidation catalyst, so that micromolecular organic matters after organic matters in the gas are cracked are further reduced;
(3) and discharging the deeply oxidized gas from an outlet of the fixed bed reactor, sequentially passing through a heat exchanger and a gas-liquid separator, feeding the obtained condensate into a rain drainage system, and directly discharging the non-condensable gas in an emptying manner.
The phenolic wastewater is generated by an extraction process in the process of producing the o/hydroquinone through phenol hydroxylation. The main organic matters in the phenol-containing wastewater are phenol, hydroquinone, catechol, resorcinol, phenol tar and an extracting agent methyl isobutyl ketone.
The Chemical Oxygen Demand (COD) of the phenolic wastewater is 1000-100000 mgO2L; the total phenol concentration in the phenol-containing wastewater is 100-10000 mg/L, wherein the total phenol concentration refers to the total concentration of phenol, hydroquinone, catechol and resorcinol in the wastewater, and is measured in mg/L.
In the step (1)The feeding airspeed of the phenol-containing wastewater is 0.05-0.6L/(kg)cat, gas cyclone fluidized bedH) the total air feeding space velocity is 400-1500L/(kg)cat, gas cyclone fluidized bedH), the volume ratio of the air entering the fluidization section from the bottom of the cyclone fluidized bed reactor to the air entering the expansion section tangentially is 9/1-2/1. In the invention, the feeding airspeed of the phenol-containing wastewater and the air feeding airspeed refer to the airspeed relative to the catalyst in the cyclone fluidized bed.
The reaction pressure of the catalytic cracking oxidation reaction is 0.1-0.25 MPa (absolute pressure, the same below), and the reaction temperature is 300-450 ℃.
The catalytic cracking oxidation catalyst is a metal oxide catalyst, 1 or no more than 3 of metal oxides in ruthenium, palladium, platinum, gold, rubidium, chromium, manganese and other metal oxides are used as active components, one of a Y molecular sieve, ZSM-5, MCM-22, MCM-41, SBA-15 and β molecular sieves is used as a carrier, the load capacity of the active components is 1-20%, the particle size of the catalytic cracking oxidation catalyst is 40-200 mu m, and the catalytic cracking oxidation catalyst is prepared by adopting a spray drying method2、PdO、RuO2、Au2O3When the precursor is a chloride salt; the active component is MnO2、Rb2O、Cr2O3When the precursor is nitrate, the corresponding precursor is nitrate.
In the step (2), the filling amount of the deep oxidation catalyst in the fixed bed reactor is the same as the mass of the catalytic cracking oxidation catalyst in the cyclone fluidized bed reactor; the reaction pressure of deep oxidation in the fixed bed reactor is kept consistent with the pressure of the cyclone fluidized bed reactor, and the reaction temperature is 300-400 ℃. The gas at the outlet of the fixed bed reactor contains water vapor, carbon dioxide and unreacted organic matter vapor, the gas is cooled to 40-60 ℃ in a heat exchanger, and the gas is obtained by a gas-liquid separatorCOD in the condensate is less than or equal to 80mgO2The total phenol concentration is lower than 0.5mg/L and reaches the rain drainage standard (surface water environment quality standard GB 3838-2002), and the content of VOCs in the non-condensable gas leaving from the top of the gas-liquid separator is not more than 20mg/m3And the emission standard reaches the comprehensive emission standard of atmospheric pollutants (GB16297-1996) and the emission standard of volatile organic compounds in the chemical industry of Jiangsu province.
The deep oxidation catalyst is a metal oxide catalyst, the active component is a composite of 1 or no more than 3 of metal oxides in metal oxides such as lanthanum, iron, cobalt, nickel, cerium, copper, iridium and the like, one of alumina, silicon oxide, activated clay and attapulgite is used as a carrier, and the loading capacity of the active component is 10-20%. The particle size of the deep oxidation catalyst is 2-5 mm, the deep oxidation catalyst is prepared by adopting an immersion method, and the deep oxidation catalyst is formed by extruding strips: dissolving a precursor of an active component in water, mixing and rolling the precursor with a carrier uniformly, then extruding and molding the mixture in a strip extruding machine, drying the mixture at 120 ℃, and roasting the dried mixture at 550 ℃ for 3 hours to obtain a metal oxide catalyst; wherein the active component is La2O3、CuO、NiO、Co2O3、Fe2O3、CeO2When the precursor is nitrate; the active component is IrO2When the precursor is a chloride salt, the corresponding precursor is a chloride salt.
The invention also aims to provide a purification system for high-concentration phenol-containing wastewater in the production process of catechol/hydroquinone, which comprises a cyclone fluidized bed reactor, a fixed bed reactor, a heat exchanger and a gas-liquid separator which are connected in series in sequence; the cyclone fluidized bed reactor comprises a lower fluidized section and an upper expanding section, wherein a catalytic cracking oxidation catalyst is filled in the fluidized section, a tangential air inlet is formed in the expanding section of the cyclone fluidized bed reactor to realize tangential air inlet, an axial air inlet is formed in the bottom of the cyclone fluidized bed reactor, and a wastewater inlet and a gas outlet are formed in the top of the cyclone fluidized bed reactor; the gas outlet of the cyclone fluidized bed reactor is connected with the gas inlet at the top of the fixed bed reactor, the fixed bed reactor is filled with a deep oxidation catalyst, and the outlet at the bottom of the fixed bed reactor is connected with the heat exchanger.
The cyclonic fluidized bed reactor in the present invention is a conventional reactor.
The invention has the following beneficial effects:
the invention aims at the method for treating the phenol-containing wastewater generated in the process of producing the o/hydroquinone by hydroxylation of the phenol, has the characteristics of simple process, mild conditions and easy realization, can realize the treatment of the phenol-containing wastewater which is difficult to degrade, high in toxicity and high in concentration with high efficiency, low cost and low energy consumption, and can realize that after the phenol-containing wastewater passes through a purification system formed by connecting a cyclone fluidized bed reactor and a fixed bed reactor in series, the chemical oxygen demand and the phenol content in the effluent reach the corresponding discharge standards, the discharge can be realized without secondary treatment, the VOCs content in the obtained gas reaches the discharge standards, and the gas can be directly discharged without further treatment. The method of the invention can greatly reduce the equipment investment and simultaneously realize the purpose of protecting the environment.
Drawings
FIG. 1 is a flow chart of a method for purifying high-concentration phenol-containing wastewater in the production process of catechol/hydroquinone according to the present invention;
in FIG. 1, 1 is a cyclonic fluidized bed reactor, 2 is a fixed bed reactor, 3 is a heat exchanger, and 4 is a gas-liquid separator.
Detailed Description
As shown in figure 1, a purification system for high-concentration phenol-containing wastewater in the production process of catechol/hydroquinone, which comprises a cyclone fluidized bed reactor 1, a fixed bed reactor 2, a heat exchanger 3 and a gas-liquid separator 4 which are connected in series in sequence; the cyclone fluidized bed reactor 1 comprises a lower part fluidization section and an upper part expansion section, a catalytic cracking oxidation catalyst is filled in the fluidization section, a tangential air inlet is arranged at the expansion section of the cyclone fluidized bed reactor 1 to realize the tangential entry of air, an axial air inlet 1 is arranged at the bottom of the cyclone fluidized bed reactor, and a wastewater inlet and an air outlet are arranged at the top of the cyclone fluidized bed reactor 1; the gas outlet of the cyclone fluidized bed reactor 1 is connected with the gas inlet at the top of the fixed bed reactor 2, the fixed bed reactor 2 is filled with a deep oxidation catalyst with the same mass as that of the catalytic cracking oxidation catalyst in the cyclone fluidized bed reactor, and the outlet at the bottom of the fixed bed reactor 2 is connected with the heat exchanger 3.
The process flow of the purification treatment of the phenol-containing wastewater comprises the following steps: introducing two air flows into the cyclone fluidized bed reactor, wherein the air 1 enters the fluidized section from the bottom of the cyclone fluidized bed to enable the catalytic cracking oxidation catalyst to be in a fluidized state, and the air 2 enters the expansion section from the expansion section of the cyclone fluidized bed reactor tangentially, so that catalyst particles and organic matter molecules in the expansion section generate a cyclone effect under the drive of tangential air flow and enter the fluidized section to be fully contacted with the catalyst; introducing the phenol-containing wastewater into a fluidized section at the top of the cyclone fluidized bed to perform catalytic cracking oxidation reaction; the gas at the outlet of the cyclone fluidized bed reactor contains a small amount of unpurified organic matter steam, the gas enters a fixed bed reactor connected with the cyclone fluidized bed reactor in series for deep oxidation reaction, the gas is subjected to serial catalytic purification of the cyclone fluidized bed reactor and the fixed bed reactor, and COD (chemical oxygen demand) in condensate obtained by heat exchange and cooling of the gas at the outlet of the fixed bed reactor through a heat exchanger is less than or equal to 80mgO2The total phenol concentration is less than 0.5mg/L, the gas can directly enter a rain drainage system, and the content of VOCs in the evacuated non-condensable gas is not more than 40mg/m3And can be directly emptied.
The content of phenol in water is analyzed by adopting a liquid spectrum, and the analysis conditions are as follows: the mobile phase is a methanol-water mixed solution with the volume ratio of 2:3, the liquid spectrum column is a C18 column, and the wavelength is 277 nm.
The COD detection is carried out by adopting a 6B-200 type COD rapid detector. Analyzing the content of the gas-phase VOCs by adopting a chromatography, wherein the chromatography column is a capillary column, the standard gas is methane, and the gas chromatography conditions are as follows: the column temperature was 100 ℃ and the detector and the vaporization chamber were both 200 ℃.
The present invention will be described in further detail with reference to examples.
Example 1
The reaction adopts a purification device with a cyclone fluidized bed and a fixed bed connected in series, and the COD of the phenolic wastewater is 10000mgO2The total phenol concentration was 100 mg/L. The catalytic cracking oxidation catalyst filled in the cyclone fluidized bed reactor is PtO2/MCM-41，PtO2The loading amount of the catalyst is 1.5 percent, the loading amount is 40g, the catalyst is prepared by a spray drying method, and the preparation method comprises the following steps: 27.1g H2PtCl6Dissolving in 300ml water, soaking 900g MCM-41 molecular sieve in the above water solution for 12h, adding 333g silica Sol (SiO)2Content of 30 percent), spray-forming in a spray dryer, drying at 120 ℃, roasting at 550 ℃ for 3 hours, and the particle size of the catalyst is 60-200 mu m. The deep oxidation catalyst filled in the fixed bed reactor is CuO-Fe2O3/Al2O3The supported amount of CuO was 15%, Fe2O3The loading amount of the catalyst is 5 percent, the catalyst is prepared by a mixed rolling method, and the preparation method comprises the following steps: mixing 351.7gCu (NO)3)2、253gFe(NO3)3·9H2O dissolved in 350ml of water with 1000g of Al2O3And after uniformly mixing and rolling, extruding and molding in a strip extruding machine, drying at 120 ℃, roasting at 550 ℃ for 3 hours, wherein the particle size of the catalyst is 2-4 mm. The pressure of the cyclone fluidized bed reactor and the fixed bed reactor is kept consistent, the operating pressure is 0.11MPa (absolute pressure, the same below), the temperature of the catalytic cracking oxidation reaction is 300 ℃, and the temperature of the deep oxidation reaction is 361 ℃.
The air feeding space velocity entering the fluidization section from the bottom of the cyclone fluidized bed is 320L/(kg)cat, gas cyclone fluidized bedH) the feed rate of air entering tangentially from the expanded section of the cyclonic fluidized bed reactor was 80L/(kg)cat, gas cyclone fluidized bedH) the space velocity of the feeding of the phenol-containing wastewater is 0.1L/(kg)cat, gas cyclone fluidized bedH); the deeply oxidized gas is discharged from the outlet of the fixed bed reactor and sequentially passes through a heat exchanger and a gas-liquid separator, and the COD in the condensate obtained is 71.4mgO2The total phenol concentration is 0.47mg/L, and the VOCs in the non-condensable gas is 17.1mg/m3。
Example 2
The reaction adopts a purification device with a cyclone fluidized bed and a fixed bed connected in series, and the COD of the phenol-containing wastewater is 18000mgO2The total phenol concentration was 1650 mg/L. The catalytic cracking oxidation catalyst filled in the cyclone fluidized bed reactor is RuO2-MnO2/SBA-15，RuO2The supported amount of (B) is 1%, MnO2The loading amount of the catalyst is 15 percent, the loading amount is 40g, the catalyst is prepared by a spray drying method, and the preparation method comprises the following steps: 15.6g of RuCl3·3H2O, 401ml of 50% Mn (NO)3)2The solution was dissolved in 200ml of water, 900g/SBA-15 molecular sieve was immersed in the above aqueous solution for 12 hours, and 333g of silica Sol (SiO)2Content of 30 percent), spray-forming in a spray dryer, drying at 120 ℃, roasting at 550 ℃ for 3 hours, and the particle size of the catalyst is 60-200 mu m. The deep oxidation catalyst filled in the fixed bed reactor is La2O3Attapulgite, La2O3The loading capacity of the catalyst is 20 percent, the catalyst is prepared by a mixed rolling method, and the preparation method comprises the following steps: 718gLa (NO)3)3·6H2Dissolving O in 300ml of water, mixing and rolling uniformly with 1000g of attapulgite, then extruding and molding in a strip extruding machine, drying at 120 ℃, roasting at 550 ℃ for 3 hours, wherein the particle size of the catalyst is 2-4 mm. The pressure of the cyclone fluidized bed reactor and the fixed bed reactor is kept consistent, the operating pressure is 0.15MPa, the temperature of catalytic cracking oxidation reaction is 350 ℃, and the temperature of deep oxidation reaction is 367 ℃.
The air feeding airspeed from the bottom of the cyclone fluidized bed to the fluidizing section is 400L/(kg)cat, gas cyclone fluidized bedH) the feed rate of air entering tangentially from the expanded section of the cyclonic fluidized bed reactor is 150L/(kg)cat, gas cyclone fluidized bedH) the space velocity of the feeding of the phenol-containing wastewater is 0.23L/(kg)cat, gas cyclone fluidized bedH). The deeply oxidized gas is discharged from the outlet of the fixed bed reactor and sequentially passes through a heat exchanger and a gas-liquid separator, and the COD in the obtained condensate is 58.2mgO2The total phenol concentration is 0.39mg/L, and the VOCs in the non-condensable gas is 19.5mg/m3。
Example 3
The reaction adopts a purification device with a cyclone fluidized bed and a fixed bed connected in series, and the COD of the phenolic wastewater is 26000mgO2The catalyst is prepared by a spray drying method, wherein the catalyst is PdO/β molecular sieve, the loading amount of PdO is 2%, the loading amount is 40g, and the catalyst is prepared by 29g of PdCl2Dissolving in 300ml water, soaking 900g β molecular sieve in the above water solution for 12h, adding 333g silica Sol (SiO)2Content of 30 percent), spray-forming in a spray dryer, drying at 120 ℃, roasting at 550 ℃ for 3 hours, and the particle size of the catalyst is 60-200 mu m.The deep oxidation catalyst filled in the fixed bed reactor is Co2O3White clay, Co2O3The loading capacity is 10%, the catalyst is prepared by a mixed rolling method, and the preparation method comprises the following steps: 350.6gCo (NO)3)2·6H2Dissolving O in 300ml of water, mixing with 1000g of argil, uniformly rolling, extruding and molding in a strip extruding machine, drying at 120 ℃, roasting at 550 ℃ for 3 hours, and enabling the particle size of the catalyst to be 2-4 mm. The pressure of the cyclone fluidized bed reactor and the fixed bed reactor is kept consistent, the operating pressure is 0.18MPa, the temperature of the catalytic cracking oxidation reaction is 380 ℃, and the temperature of the deep oxidation reaction is 377 ℃.
The air feeding airspeed from the bottom of the cyclone fluidized bed to the fluidizing section is 480L/(kg)cat, gas cyclone fluidized bedH) the feed rate of air entering tangentially from the expanded section of the cyclonic fluidized bed reactor is 120L/(kg)cat, gas cyclone fluidized bedH) a phenolic wastewater feed of 0.33L/(kg)cat, gas cyclone fluidized bedH). The deeply oxidized gas is discharged from the outlet of the fixed bed reactor and sequentially passes through a heat exchanger and a gas-liquid separator, and the COD in the obtained condensate is 32.8mgO2The total phenol concentration in the condensate was 0.29mg/L and the VOCs in the non-condensable gases was 10.3mg/m3。
Example 4
The reaction adopts a purification device with a cyclone fluidized bed and a fixed bed connected in series, and the COD of the phenolic wastewater is 34000mgO2The total phenol concentration was 5075 mg/L. The catalytic cracking oxidation catalyst filled in the cyclone fluidized bed reactor is Cr2O3Molecular sieve,/Y, Cr2O3The loading amount of the catalyst is 15 percent, the loading amount is 40g, the catalyst is prepared by a spray drying method, and the preparation method comprises the following steps: 790g Cr (NO)3)3·9H2O was dissolved in 300ml of water, and a 900gY molecular sieve was immersed in the above aqueous solution for 12 hours, and 500g of alumina sol (Al)2O3Content 20%), spray-forming in a spray dryer, drying at 120 ℃, roasting at 550 ℃ for 3h, and the particle size of the catalyst is 60-200 μm. The deep oxidation catalyst filled in the fixed bed reactor is NiO-CeO2/SiO2The amount of NiO supported was 10% and CeO2Supported amount of 5%, catalyst recoveryThe preparation method is as follows: 389.3gNi (NO)3)2·6H2O、126gCe(NO3)3·6H2Dissolving O in 300ml of water, mixing and rolling uniformly with 1000g of silicon oxide powder, then extruding and molding in a strip extruding machine, drying at 120 ℃, roasting at 550 ℃ for 3 hours, and enabling the particle size of the catalyst to be 2-4 mm. The pressure of the cyclone fluidized bed reactor and the fixed bed reactor is kept consistent, the operating pressure is 0.12MPa, the temperature of catalytic cracking oxidation reaction is 360 ℃, and the temperature of deep oxidation reaction is 300 ℃.
The air feeding airspeed from the bottom of the cyclone fluidized bed to the fluidizing section is 400L/(kg)cat, gas cyclone fluidized bedH) the feed rate of air entering tangentially from the expanded section of the cyclonic fluidized bed reactor was 80L/(kg)cat, gas cyclone fluidized bedH) the space velocity of the feeding of the phenol-containing wastewater is 0.46L/(kg)cat, gas cyclone fluidized bedH). The deeply oxidized gas is discharged from the outlet of the fixed bed reactor and sequentially passes through a heat exchanger and a gas-liquid separator, and the COD in the condensate obtained is 42.7mgO2The total phenol concentration in the condensate was 0.38mg/L and the VOCs in the non-condensable gases was 12.1mg/m3。
Example 5
The reaction adopts a purification device with a cyclone fluidized bed and a fixed bed connected in series, and the COD of the phenolic wastewater is 46240mgO2The total phenol content was 8034 mg/L. The catalytic cracking oxidation catalyst filled in the cyclone fluidized bed reactor is Au2O3-MnO2-Rb2O/H- β molecular sieve, Au2O3Supported amount of (2%), MnO2The loading of (1) is 12%, Rb2The load capacity of O is 1 percent, the load capacity is 40g, the catalyst is prepared by adopting a spray drying method, and the preparation method comprises the following steps: 37.3g of HAuCl4·4H2O, 321ml 50% Mn (NO)3)2Solution, 15.8gRBNO3Dissolving in 200ml water, soaking 900g H- β molecular sieve in the above water solution for 12h, adding 500g aluminum sol (Al)2O3Content 20%), spray-forming in a spray dryer, drying at 120 ℃, roasting at 550 ℃ for 3h, and the particle size of the catalyst is 60-200 μm. The deep oxidation catalyst filled in the fixed bed reactor is IrO2-NiO-CuO/Clay, IrO2The loading capacity of the catalyst is 1 percent, the loading capacity of NiO is 4 percent, the loading capacity of CuO is 15 percent, the catalyst is prepared by a mixed rolling method, and the preparation method comprises the following steps: will 23gH2IrCl6·6H2O、155.7gNi(NO3)2·6H2O、352gCu(NO3)2Dissolving the mixture in 300ml of water, mixing and rolling the mixture with 1000g of silicon oxide powder uniformly, then extruding and molding the mixture in a strip extruding machine, drying the mixture at 120 ℃, roasting the mixture for 3 hours at 550 ℃, and enabling the particle size of the catalyst to be 2-4 mm. The pressure of the cyclone fluidized bed reactor and the fixed bed reactor is kept consistent, the operating pressure is 0.24MPa, the temperature of catalytic cracking oxidation reaction is 390 ℃, and the temperature of deep oxidation reaction is 394 ℃.
The air feeding airspeed from the bottom of the cyclone fluidized bed to the fluidizing section is 800L/(kg)cat, gas cyclone fluidized bedH) the feed rate of air entering tangentially from the expanded section of the cyclonic fluidized bed reactor is 200L/(kg)cat, gas cyclone fluidized bedH) the space velocity of the feeding of the phenol-containing wastewater is 0.05L/(kg)cat, gas cyclone fluidized bedH). The deeply oxidized gas is discharged from the outlet of the fixed bed reactor and passes through a heat exchanger and a gas-liquid separator in sequence to obtain 26.9mgO in condensate2The total phenol concentration in the condensate is 0.16mg/L, and the VOCs in the non-condensable gas is 10mg/m3。
Example 6
The reaction adopts a purification device with a cyclone fluidized bed and a fixed bed connected in series, and the COD of the phenol-containing wastewater is 68000mgO2The total phenol concentration is 876 mg/L. The catalytic cracking oxidation catalyst filled in the cyclone fluidized bed reactor is PtO2-Cr2O3Molecular sieves, PtO, MCM-222Supported amount of (2) Cr2O3The loading amount of the catalyst is 14 percent, the loading amount is 40g, the catalyst is prepared by a spray drying method, and the preparation method comprises the following steps: 18g of HPtCl6、737.9gCr(NO3)3·9H2Dissolving O in 300ml water, soaking 900g MCM-22 molecular sieve in the above water solution for 12h, adding 500g aluminium sol (Al)2O3Content 20%), spray-forming in a spray dryer, drying at 120 ℃, roasting at 550 ℃ for 3h, and the particle size of the catalyst is 60-200 μm. Fixed bed reactorThe filled deep oxidation catalyst is CuO-CeO2CeO/terra alba, the loading of CuO is 15%2The loading amount of the catalyst is 5 percent, the catalyst is prepared by a mixed rolling method, and the preparation method comprises the following steps: mixing 352gCu (NO)3)2、126gCe(NO3)3·6H2Dissolving O in 300ml of water, mixing and rolling uniformly with 1000g of silicon oxide powder, then extruding and molding in a strip extruding machine, drying at 120 ℃, roasting at 550 ℃ for 3 hours, and enabling the particle size of the catalyst to be 2-4 mm. The pressure of the cyclone fluidized bed reactor and the fixed bed reactor is kept consistent, the operating pressure is 0.18MPa, the temperature of catalytic cracking oxidation reaction is 410 ℃, and the temperature of deep oxidation reaction is 400 ℃.
The air feeding space velocity entering the fluidization section from the bottom of the cyclone fluidized bed is 540L/(kg)cat, gas cyclone fluidized bedH) the feed rate of air entering tangentially from the expanded section of the cyclonic fluidized bed reactor is 60L/(kg)cat, gas cyclone fluidized bedH) the space velocity of the feeding of the phenol-containing wastewater is 0.15L/(kg)cat, gas cyclone fluidized bedH). The deeply oxidized gas is discharged from the outlet of the fixed bed reactor and sequentially passes through a heat exchanger and a gas-liquid separator, and the COD in the condensate obtained is 24.5mgO2The total phenol concentration in the condensate was 0.09mg/L and the VOCs in the non-condensable gases was 7.9mg/m3。
Example 7
The reaction adopts a purification device with a cyclone fluidized bed and a fixed bed connected in series, and the COD of the phenolic wastewater is 100000mgO2Phenol concentration was 10000 mg/L. MnO is used as catalytic cracking oxidation catalyst filled in the cyclone fluidized bed reactor2-PtO2-Cr2O3/MCM-41，MnO2The supported amount of (A) is 10%, PtO2Supported amount of (2) Cr2O3The loading amount of the catalyst is 5 percent, the loading amount is 40g, the catalyst is prepared by a spray drying method, and the preparation method comprises the following steps: 267.3ml of 50% Mn (NO)3)2Solution, 18g of HPtCl6、263gCr(NO3)3·9H2Dissolving O in 300ml water, soaking 900g MCM-41 molecular sieve in the above water solution for 12h, adding 500g aluminium sol (Al)2O3Content of 20%), spray-drying at 120 deg.C, and stirringAnd (3) drying, roasting at 550 ℃ for 3 hours, wherein the particle size of the catalyst is 60-200 mu m. The deep oxidation catalyst filled in the fixed bed reactor is Fe2O3-CuO-CeO2Aluminum oxide, Fe2O3The supported amount of (A) is 15%, the supported amount of CuO is 3%, and CeO2The loading capacity of the catalyst is 2 percent, the catalyst is prepared by a mixed rolling method, and the preparation method comprises the following steps: 759gFe (NO)3)3·9H2O、70.34gCu(NO3)2、50.5g Ce(NO3)2·6H2Dissolving O in 300ml of water, mixing and rolling uniformly with 1000g of silicon oxide powder, then extruding and molding in a strip extruding machine, drying at 120 ℃, roasting at 550 ℃ for 3 hours, and enabling the particle size of the catalyst to be 2-4 mm. The pressure of the cyclone fluidized bed reactor and the fixed bed reactor is kept consistent, the operating pressure is 0.13MPa, the temperature of the catalytic cracking oxidation reaction is 450 ℃, and the temperature of the catalytic oxidation reaction is 400 ℃.
The air feeding airspeed from the bottom of the cyclone fluidized bed to the fluidizing section is 1200L/(kg)cat, gas cyclone fluidized bedH) the feed rate of air entering tangentially from the expanded section of the cyclonic fluidized bed reactor is 300L/(kg)cat, gas cyclone fluidized bedH) the space velocity of the feeding of the phenol-containing wastewater is 0.6L/(kg)cat, gas cyclone fluidized bedH). The deeply oxidized gas is discharged from the outlet of the fixed bed reactor and sequentially passes through a heat exchanger and a gas-liquid separator, and the COD in the obtained condensate is 15mgO2The total phenol concentration in the condensate was 0.03mg/L and the VOCs in the non-condensable gases was 6.1mg/m3。

Claims (8)

1. A method for purifying phenol-containing wastewater in the production process of catechol/hydroquinone is characterized by comprising the following steps:
(1) 1 air inlet is respectively arranged at the upper expanding section and the bottom of the cyclone fluidized bed reactor, two air streams are simultaneously introduced, the air is taken as an oxidant, one air stream enters the fluidizing section of the cyclone fluidized bed reactor from the bottom of the reactor, and the other air stream enters the reactor from the tangential direction of the expanding section; phenol-containing wastewater generated in the process of producing o/hydroquinone through phenol hydroxylation is added into a fluidized section of a cyclone fluidized bed reactor from the top of the cyclone fluidized bed reactor and is subjected to catalytic crackingUnder the action of the de-oxidation catalyst, organic matters in the wastewater and air undergo catalytic cracking oxidation reaction; wherein the chemical oxygen demand of the phenolic wastewater is 1000-100000 mgO2L; the total phenol concentration in the phenol-containing wastewater is 100-10000 mg/L; the reaction pressure of the catalytic cracking oxidation reaction is 0.1-0.25 MPa, and the reaction temperature is 300-450 ℃;
(2) gas generated after catalytic cracking oxidation enters a fixed bed reactor connected with the cyclone fluidized bed reactor in series from the top, and is subjected to deep oxidation reaction under the action of a deep oxidation catalyst;
(3) and discharging the deeply oxidized gas from an outlet of the fixed bed reactor, sequentially passing through a heat exchanger and a gas-liquid separator, feeding the obtained condensate into a rain drainage system, and directly discharging the non-condensable gas in an emptying manner.
2. The method according to claim 1, wherein the total phenol concentration is the total concentration of phenol, hydroquinone, catechol, and resorcinol in the wastewater.
3. The method for purifying the phenol-containing wastewater in the production process of o/hydroquinone as claimed in claim 1, wherein in the step (1), the feeding space velocity of the phenol-containing wastewater is 0.05-0.6L/(kg)cat, gas cyclone fluidized bedH) the total air feeding space velocity is 400-1500L/(kg)cat, gas cyclone fluidized bedH), the volume ratio of the air entering the fluidization section from the bottom of the cyclone fluidized bed reactor to the air entering the expansion section tangentially is 9/1-2/1.
4. The method for purifying phenol-containing wastewater in the production process of o/hydroquinone as claimed in claim 1, wherein the catalytic cracking oxidation catalyst is a metal oxide catalyst, 1 or not more than 3 of oxides of ruthenium, palladium, platinum, gold, rubidium, chromium and manganese is used as an active component, one of Y molecular sieve, ZSM-5, MCM-22, MCM-41, SBA-15 and beta molecular sieve is used as a carrier, and the loading capacity of the active component is 1-20%.
5. The method for purifying phenol-containing wastewater in the production process of o/hydroquinone as claimed in claim 1, wherein in the step (2), the reaction pressure of the deep oxidation reaction in the fixed bed reactor is kept consistent with the pressure of the cyclonic fluidized bed reactor, and the reaction temperature of the deep oxidation reaction is 300-400 ℃.
6. The method for purifying phenol-containing wastewater in an o/hydroquinone production process as claimed in claim 1, wherein the loading amount of the deep oxidation catalyst in the fixed bed reactor is the same as the mass of the catalytic cracking oxidation catalyst in the cyclonic fluidized bed reactor.
7. The method for purifying phenol-containing wastewater in the production process of o/hydroquinone as claimed in claim 1, characterized in that the deep oxidation catalyst is a metal oxide catalyst, 1 or not more than 3 of oxides of lanthanum, iron, cobalt, nickel, cerium, iridium and copper are used as active components, one of alumina, silica, activated clay and attapulgite is used as a carrier, and the loading amount of the active components is 10-20%.
8. A system for realizing the purification method of the phenol-containing wastewater in the production process of the catechol/hydroquinone as described in claim 1, which is characterized in that the purification system comprises a cyclone fluidized bed reactor, a fixed bed reactor, a heat exchanger and a gas-liquid separator which are connected in series in sequence; the cyclone fluidized bed reactor comprises a lower fluidized section and an upper expanding section, wherein a catalytic cracking oxidation catalyst is filled in the fluidized section, a tangential air inlet is formed in the expanding section of the cyclone fluidized bed reactor to realize tangential air inlet, an axial air inlet 1 is formed in the bottom of the cyclone fluidized bed reactor, and a wastewater inlet and a gas outlet are formed in the top of the cyclone fluidized bed reactor; the gas outlet of the cyclone fluidized bed reactor is connected with the gas inlet at the top of the fixed bed reactor, and the outlet at the bottom of the fixed bed reactor is connected with the heat exchanger.
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