CN111018089A - Catalytic wet oxidation treatment method for propylene oxide wastewater - Google Patents
Catalytic wet oxidation treatment method for propylene oxide wastewater Download PDFInfo
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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
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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
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/32—Hydrocarbons, e.g. oil
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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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
- 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
Abstract
The invention discloses a catalytic wet oxidation treatment method of propylene oxide production wastewater, which takes the wastewater generated in the production process of propylene oxide as a raw material, mixes the wastewater with air, and then passes through a fixed bed reactor filled with a catalyst; the temperature in the reactor is 200-310 ℃, the system pressure is 1-10 MPa, and the liquid airspeed is 0.5-4 h‑1The method effectively solves the problem that the high-concentration epoxypropane wastewater is difficult to degrade, and particularly adopts Ru as an active component for loadingThe catalyst prepared on titanium dioxide has the reaction temperature of 270 ℃, the pressure of 7.0MPa and the liquid airspeed of 1h‑1Under the condition, the COD value in the high-concentration wastewater can be effectively reduced, after wet oxidation treatment, the COD value of the industrial epoxypropane wastewater is reduced from 65647mg/L to 69mg/L, the ammonia nitrogen value is reduced from 152.7mg/L to 0.24mg/L, the COD value and the ammonia nitrogen removal rate are respectively 99.89% and 99.84%, and better technical effects are achieved. The method has the advantages of simple process route and small occupied area of used equipment, and is suitable for industrial application.
Description
Technical Field
The invention belongs to the field of wastewater treatment, and particularly relates to a catalytic oxidation technology for treating high-concentration degradation-resistant propylene oxide wastewater.
Background
Propylene Oxide (PO) is the third largest propylene derivative second to polypropylene and acrylonitrile, is used for producing polyether, propylene glycol, surfactant and the like in large quantity, is widely applied to industries such as petroleum, chemical engineering, pesticides, textile, daily chemicals and the like, and is a very important basic organic chemical raw material. However, the wastewater produced by the direct hydrogen peroxide oxidation method for producing propylene oxide (HPPO method for short) is complex in composition, mainly contains dichloromethane, propylene glycol, propylene oxide, ethylbenzene, m-xylene, pentanediol and other derivatives, and has a COD value as high as several tens of thousands or even hundreds of thousands, a deep color, a large odor and poor biodegradability.
At present, the high-concentration organic wastewater is treated at home and abroad mainly by a method combining a biochemical method and an advanced oxidation method, for example, CN104773928A discloses a method for treating wastewater produced by propylene oxide. Although the method can effectively reduce the concentration of organic matters in the propylene oxide wastewater, the process is complex, and the operation difficulty and the production cost are increased.
The catalytic wet oxidation (CWAO) is a high-temperature high-pressure oxidation treatment technology developed in the last 70 th century, and has a good treatment effect on high-concentration organic wastewater difficult to degrade. The method adopts air or oxygen as an oxidant, can effectively oxidize organic matters in the sewage into inorganic matters such as carbon dioxide, nitrogen, water and the like or micromolecular organic matters under the conditions of high temperature (125-320 ℃) and high pressure (0.5-20 MPa), achieves the aim of purifying water quality, and is an efficient, green, energy-saving and environment-friendly sewage treatment technology.
CN108067225A discloses a "preparation method of catalytic wet oxidation catalyst and an organic wastewater treatment method", wherein Ce, Zr and other elements are used to modify the carrier twice, the prepared catalyst has larger pore volume and strength, higher activity and stability, and improves the utilization rate of noble metals, but the preparation process of the catalyst is complex and is not beneficial to large-scale industrial application.
CN109292956A discloses a catalytic wet oxidation treatment method for dye wastewater treatment, which adopts Cu-Fe as an active component and Al2O3The carrier is the Cu-Fe modified by Ce and doped by La, so that the activity of the catalyst is improved, the dissolution of Ce in the catalyst is reduced, and the specific surface area of the catalyst is increased by doping La. The active component particles on the surface of the catalyst are finer and more uniform, and the activity and the stability of the catalyst are improved. However, the method is only suitable for treating low-concentration organic wastewater.
CN105923854A discloses a method for treating high-concentration organic wastewater, which utilizes a method combining wet oxidation and electrocatalysis to treat the organic wastewater, wherein the catalyst used in the wet oxidation process is soluble metal salt or a supported noble metal catalyst, the noble metal or noble metal oxide is used as the catalyst in the electrocatalysis process, and the chroma and COD removal rate of the organic wastewater can reach more than 90%. However, the method has complex process and large consumption of noble metal, which greatly increases the cost.
Disclosure of Invention
The invention aims to solve the technical problem that the COD (chemical oxygen demand) efficiency of high-concentration and difficult-to-degrade propylene oxide wastewater treated by the prior art is low, and provides a wet oxidation method for treating organic wastewater. The method effectively solves the problem that the high-concentration epoxypropane wastewater is difficult to degrade, and has the advantages of simple process route, small equipment floor area, low energy consumption, high efficiency of reducing COD in the wastewater and the like.
A catalytic wet oxidation treatment method for propylene oxide production wastewater is characterized in that the propylene oxide production wastewater is mixed with air and then passes through a fixed bed reactor filled with a supported catalyst; the temperature in the fixed bed reactor is 200-310 ℃, the reaction pressure is 1-10 MPa, and the liquid space velocity is 0.5-4 h-1(ii) a The supported catalyst comprises 95-99.9 parts by weight of titanium dioxide molded carrier and 0.1-5 parts by weight of one or more noble metal elements selected from Au, Pt, Pd, Ru and Rh. Air conditionerThe amount of the gas is 1.0-4.0 times of the theoretical amount of the air required by the COD value of the propylene oxide production wastewater. The waste water and air are mixed and preheated by the preheater, enter the fixed bed and contact with the catalyst, and the organic waste water reacts with oxygen in the air under the action of the catalyst so as to achieve the purpose of degradation.
Further, the specific surface area of the titanium dioxide carrier is 15-25 m2A diameter of 3-5 mm and a length of 5-10 mm.
Further, in the fixed bed reactor filled with the catalyst, the volume ratio of the catalyst bed layer to the carrier bed layer is as follows: 0.3-0.5: 1.0.
Further, the reaction temperature is 230-280 ℃.
Further, the reaction pressure is 5-8 MPa.
Further, the liquid airspeed is 0.5-2 h-1The air consumption is 1.6-2.6 times of the theoretical air consumption required by the COD value of the propylene oxide production wastewater.
Furthermore, the propylene oxide production wastewater is prepared by mixing one or more of salt-containing wastewater, alcohol, ether, oil and alkali wastewater generated in the process of producing propylene oxide by an HPPO method according to different proportions, the main components of the wastewater are dichloromethane, propylene glycol, propylene oxide, ethylbenzene, m-xylene, pentanediol and other derivatives, and the COD of the mixed wastewater is 2000-300000 mg/L.
The invention has the beneficial effects that: the method effectively solves the problem that the high-concentration propylene oxide wastewater is difficult to degrade, and particularly the catalyst prepared by taking Ru as an active component and loading the Ru on titanium dioxide has the reaction temperature of 270 ℃, the pressure of 7.0MPa and the liquid airspeed of 1h-1Under the condition, the COD value in the high-concentration wastewater can be effectively reduced, after wet oxidation treatment, the COD value of the industrial epoxypropane wastewater is reduced from 65647mg/L to 69mg/L, the ammonia nitrogen value is reduced from 152.7mg/L to 0.24mg/L, the COD value and the ammonia nitrogen removal rate are respectively 99.89% and 99.84%, and better technical effects are achieved. The method has the advantages of simple process route and small occupied area of used equipment, and is suitable for industrial application.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples.
In examples 1-8, the titania supports were: the specific surface area is 15-25 m2A diameter of 3-5 mm and a length of 5-10 mm.
Example 1
The epoxy propane industrial wastewater is used as a raw material, the COD value of the wastewater is 65647mg/L, and the ammonia nitrogen value is 152.7 mg/L. The wastewater is mixed with air and then enters a reactor filled with 130g of 2 wt% Ru/TiO2The reaction temperature in the reactor is 270 ℃, the reaction pressure is 7.0MPa, and the liquid space velocity is 1h-1. The amount of the air is 1.6 times of the theoretical amount of the air required by the COD value of the propylene oxide production wastewater. The reaction results are shown in Table 1.
Example 2
The epoxy propane industrial wastewater is used as a raw material, the COD value of the wastewater is 65647mg/L, and the ammonia nitrogen value is 152.7 mg/L. The wastewater is mixed with air and then enters a reactor filled with 130g of 0.5 wt% Pt-1.5 wt% Ru/TiO2A fixed bed reactor of the catalyst, wherein the reaction temperature in the reactor is 245 ℃, the reaction pressure is 7.0MPa, and the liquid space velocity is 2h-1. The amount of the air is 1.0 time of the theoretical amount of the air required by the COD value of the propylene oxide production wastewater. The reaction results are shown in Table 1.
Example 3
The epoxy propane industrial wastewater is used as a raw material, the COD value of the wastewater is 29630 mg/L, and the ammonia nitrogen value is 150.17 mg/L. The waste water is mixed with air and then enters a reactor filled with 130g of Ru/TiO with the weight percent of 0.52A fixed bed reactor of the catalyst, wherein the reaction temperature in the reactor is 225 ℃, the reaction pressure is 4.0MPa, and the liquid space velocity is 1h-1. The amount of the air is 3.6 times of the theoretical amount of the air required by the COD value of the propylene oxide production wastewater. The reaction results are shown in Table 1.
Example 4
The epoxy propane industrial wastewater is taken as a raw material, the COD value of the wastewater is 40987 mg/L, and the ammonia nitrogen value is 207.38 mg/L. The wastewater is mixed with air and then enters a reactor filled with 130g of 2.5 wt% Pt-2.5 wt% Ru/TiO2A fixed bed reactor of the catalyst, the reaction temperature in the reactor is 280 ℃, the reaction pressure is 7.0MPa, and the reaction solution isThe space velocity is 1h-1. The amount of the air is 2.6 times of the theoretical amount of the air required by the COD value of the propylene oxide production wastewater. The reaction results are shown in Table 1.
Example 5
The epoxy propane industrial wastewater is taken as a raw material, the COD value of the wastewater is 40987 mg/L, and the ammonia nitrogen value is 207.38 mg/L. The wastewater is mixed with air and then enters a reactor filled with 130g of 1.5 percent Ru/TiO2The reaction temperature in the reactor is 265 ℃, the reaction pressure is 7.0MPa, and the liquid airspeed is 1h-1. The amount of the air is 2.6 times of the theoretical amount of the air required by the COD value of the propylene oxide production wastewater. The reaction results are shown in Table 1.
Example 6
The epoxy propane industrial wastewater is taken as a raw material, the COD value of the wastewater is 40987 mg/L, and the ammonia nitrogen value is 207.38 mg/L. The waste water is mixed with air and then enters a reactor filled with 130g of 0.5 wt% Pd-1.5 wt% Ru/TiO2The reaction temperature in the reactor is 270 ℃, the reaction pressure is 7.0MPa, and the liquid space velocity is 1h-1. The amount of the air is 2.6 times of the theoretical amount of the air required by the COD value of the propylene oxide production wastewater. The reaction results are shown in Table 1.
Example 7
The epoxy propane industrial wastewater is taken as a raw material, the COD value of the wastewater is 40987 mg/L, and the ammonia nitrogen value is 207.38 mg/L. The wastewater is mixed with air and then enters a reactor filled with 130g of 1.9 wt% Ru-0.1 wt% Rh/TiO2The reaction temperature in the reactor is 270 ℃, the reaction pressure is 6.5MPa, and the liquid space velocity is 1h-1. The amount of the air is 2.6 times of the theoretical amount of the air required by the COD value of the propylene oxide production wastewater. The reaction results are shown in Table 1.
Example 8
The epoxy propane industrial wastewater is used as a raw material, the COD value of the wastewater is 113946 mg/L, and the ammonia nitrogen value is 134.63 mg/L. The wastewater is mixed with air and then enters a reactor filled with 130g of 5 wt% Ru/TiO2The reaction temperature in the reactor is 270 ℃, the reaction pressure is 8MPa, and the liquid space velocity is 0.5h-1. The amount of the air is 1.9 times of the theoretical amount of the air required by the COD value of the propylene oxide production wastewater. Results of the reactionSee table 1.
Table 1: wet oxidation reaction result of industrial waste water of propylene oxide
The above examples illustrate that the method of the present invention can effectively solve the problem of difficult degradation of high concentration propylene oxide wastewater, especially the catalyst prepared by loading Ru as active component on titanium dioxide, at a reaction temperature of 270 ℃, a pressure of 7.0MPa and a liquid space velocity of 1h-1Under the condition, the COD value in the high-concentration wastewater can be effectively reduced, after wet oxidation treatment, the COD value of the industrial epoxypropane wastewater is reduced from 65647mg/L to 69mg/L, the ammonia nitrogen value is reduced from 152.7mg/L to 0.24mg/L, the COD value and the ammonia nitrogen removal rate are respectively 99.89% and 99.84%, and better technical effects are achieved. The method has the advantages of simple process route and small occupied area of used equipment, and is suitable for industrial application.
Claims (7)
1. A catalytic wet oxidation treatment method of propylene oxide production wastewater is characterized in that the propylene oxide production wastewater is mixed with air and then passes through a fixed bed reactor filled with a supported catalyst; the temperature in the fixed bed reactor is 200-310 ℃, the reaction pressure is 1-10 MPa, and the liquid space velocity is 0.5-4 h-1(ii) a The supported catalyst comprises 95-99.9 parts by weight of titanium dioxide molded carrier and 0.1-5 parts by weight of one or more noble metal elements selected from Au, Pt, Pd, Ru and Rh. The amount of the air is 1.0-4.0 times of the theoretical amount of the air required by the COD value of the propylene oxide production wastewater.
2. The method according to claim 1, wherein the titania support has a specific surface area of 15 to 25m2A diameter of 3-5 mm and a length of 5-10 mm.
3. The method of claim 1, wherein in a fixed bed reactor containing the catalyst, the volume ratio of the catalyst bed to the support bed is: 0.3-0.5: 1.0.
4. The method according to claim 1, wherein the reaction temperature is 230 to 280 ℃.
5. The method according to claim 1, wherein the reaction pressure is 5 to 8 MPa.
6. The method of claim 1, wherein the liquid space velocity is 0.5-2 h-1The air consumption is 1.6-2.6 times of the theoretical air consumption required by the COD value of the propylene oxide production wastewater.
7. The method according to claim 1, wherein the propylene oxide production wastewater is prepared by mixing one or more of salt-containing wastewater, alcohol, ether, oil and alkali wastewater generated in the process of producing propylene oxide by an HPPO method according to different proportions, the main components are dichloromethane, propylene glycol, propylene oxide, ethylbenzene, meta-xylene, pentanediol and other derivatives, and the COD of the mixed wastewater is 2000-300000 mg/L.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113003785A (en) * | 2021-03-25 | 2021-06-22 | 华东理工大学 | Method for treating heavy alcohol kettle bottom liquid based on catalytic wet oxidation method |
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| CN103523891A (en) * | 2012-07-03 | 2014-01-22 | 中国石油化工股份有限公司 | Method for realizing catalytic wet oxidation of wastewater containing organic substances |
| CN105236547A (en) * | 2014-07-11 | 2016-01-13 | 中国石油化工股份有限公司 | Method for reducing COD in wastewater by catalytic wet air oxidation |
| CN105600909A (en) * | 2014-11-20 | 2016-05-25 | 中国石油化工股份有限公司 | Catalytic wet oxidation treatment method for organic waste water |
| CN109153588A (en) * | 2016-05-25 | 2019-01-04 | 国际壳牌研究有限公司 | The method for handling waste water |
| CN109336332A (en) * | 2018-11-13 | 2019-02-15 | 中石化炼化工程（集团）股份有限公司 | A kind of processing method and organic sewage treatment device suitable for high COD organic sewage |
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- 2019-11-08 CN CN201911088335.2A patent/CN111018089A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103523891A (en) * | 2012-07-03 | 2014-01-22 | 中国石油化工股份有限公司 | Method for realizing catalytic wet oxidation of wastewater containing organic substances |
| CN105236547A (en) * | 2014-07-11 | 2016-01-13 | 中国石油化工股份有限公司 | Method for reducing COD in wastewater by catalytic wet air oxidation |
| CN105600909A (en) * | 2014-11-20 | 2016-05-25 | 中国石油化工股份有限公司 | Catalytic wet oxidation treatment method for organic waste water |
| CN109153588A (en) * | 2016-05-25 | 2019-01-04 | 国际壳牌研究有限公司 | The method for handling waste water |
| CN109336332A (en) * | 2018-11-13 | 2019-02-15 | 中石化炼化工程（集团）股份有限公司 | A kind of processing method and organic sewage treatment device suitable for high COD organic sewage |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113003785A (en) * | 2021-03-25 | 2021-06-22 | 华东理工大学 | Method for treating heavy alcohol kettle bottom liquid based on catalytic wet oxidation method |
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