CN113003785A - Method for treating heavy alcohol kettle bottom liquid based on catalytic wet oxidation method - Google Patents

Method for treating heavy alcohol kettle bottom liquid based on catalytic wet oxidation method Download PDF

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CN113003785A
CN113003785A CN202110319675.2A CN202110319675A CN113003785A CN 113003785 A CN113003785 A CN 113003785A CN 202110319675 A CN202110319675 A CN 202110319675A CN 113003785 A CN113003785 A CN 113003785A
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heavy alcohol
wet oxidation
liquid
catalytic wet
precipitation
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杨雪晶
朱碧莲
李佳男
汪华林
李先如
卫皇曌
孙承林
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East China University of Science and Technology
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East China University of Science and Technology
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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
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • 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
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • 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
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • 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
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • 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
    • C02F1/727—Treatment of water, waste water, or sewage by oxidation using pure oxygen or oxygen rich gas
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • 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 method for treating heavy alcohol kettle bottom liquid based on a catalytic wet oxidation method. Firstly, adding a coagulant to remove suspended matters in the waste liquid, then adjusting the pH value of the waste liquid containing the heavy alcohol to a value required by precipitation, carrying out chemical flocculation precipitation, continuously adjusting the pH value of inlet water in the precipitation process, filtering after precipitation, carrying out unit operation of precipitation and filtration on the waste water containing the heavy alcohol, then placing the softened waste water containing the heavy alcohol in a high-temperature high-pressure reaction device, and selecting a proper catalyst for wet catalytic oxidation treatment. The invention adopts a wet oxidation method to treat the heavy alcohol wastewater generated in the process of generating the ethylene glycol by hydrating the ethylene oxide, the process is mature and simple, the treatment effect is good, and the wastewater treated by the wet catalytic oxidation has no harmful organic matters and other substances which are difficult to degrade by heavy alcohols.

Description

Method for treating heavy alcohol kettle bottom liquid based on catalytic wet oxidation method
Technical Field
The invention relates to the technical field of novel heavy alcohol kettle bottom liquid treatment, in particular to a method for treating heavy alcohol refractory substances by a catalytic wet oxidation technology.
Background
Glycol is an important chemical raw material and strategic material, is a polyol with the largest consumption in the world, can be used for manufacturing polyester (for further producing terylene, beverage bottles and films), explosives and glyoxal, and can be used as an antifreezing agent, a plasticizer, hydraulic fluid, a solvent and the like. The main industrial production method of ethylene glycol is ethylene oxide direct hydration method, in which ethylene and oxygen are used as main raw material, under the condition of a certain mixing ratio, temp. and pressure, gas-phase ethylene oxide is produced, and after the ethylene oxide and water are washed with water and stripped, they are directly liquid-phase hydrated in tubular reactor under the condition of pressurization (2.23MPa) and high temp. (190-200 deg.C), and at the same time the by-products are diethylene glycol, triethylene glycol and polyglycols.
The process wastewater generated in the process of producing ethylene glycol is mainly high polymeric alcohols and is characterized by high COD value, high salinity and poor biochemical performance, so the process treatment of the wastewater is needed.
At present, the methods for treating complex wastewater at home and abroad comprise two methods, namely a physicochemical method and a biological method. The physical and chemical methods comprise: ozone oxidation, ozone/activated carbon, ozone/UV, sodium hypochlorite oxidation, supercritical oxidation, Fenton technology, membrane separation and other methods and resource utilization methods. The biological method comprises an intermittent hydrolysis aerobic process (SBR process), a continuous hydrolysis (anaerobic) aerobic process, a UASB (upflow anaerobic sludge blanket reactor) -facultative-aerobic process and the like. In the method, the ozone oxidation cost is high, the sodium hypochlorite oxidation effect is not ideal, and the Fenton method is easy to form iron mud deposition to cause secondary pollution. Because the biodegradability of the waste water is poor, the biological method has poor effect on the waste water, and the introduction of an anaerobic technology results in huge equipment and long reaction time.
In order to improve the treatment effect of the heavy alcohol kettle bottom liquid and reach higher and higher wastewater discharge requirements or wastewater reuse requirements, the aspects needing important research are as follows: (1) improving the pretreatment technology of the kettle bottom liquid; (2) the economic and effective kettle bottom liquid treatment technology strengthens the condition control of the catalytic wet oxidation technology and finds the limit working condition that the kettle bottom liquid treatment meets the emission requirement.
Disclosure of Invention
The invention aims to solve the defects of the prior art, the softened heavy alcohol wastewater is treated by a wet catalytic oxidation method, and the existing mature wet catalytic oxidation technology is combined with equipment for generating ethylene glycol by hydrating ethylene oxide to form a heavy alcohol kettle bottom liquid treatment method which is industrialized, strong in operability and good in treatment effect.
The technical scheme adopted by the invention is as follows:
a method for treating heavy alcohol kettle bottom liquid based on a catalytic wet oxidation method is characterized by comprising the following steps:
(1) adding a coagulant into the thick heavy alcohol kettle bottom liquid, wherein the volume of the coagulant is not more than 20% of that of the heavy alcohol kettle bottom liquid, removing suspended matters in the waste liquid, and filtering by adopting a filtering device to obtain clear liquid;
(2) adjusting the pH of the clear liquid obtained in the step (1), introducing alkali liquor, keeping the pH between 9 and 11, precipitating metal ions in the waste liquid, standing for 30 minutes, and filtering;
(3) adding the liquid filtered in the step (2) into a catalytic wet oxidation device for catalytic wet oxidation reaction at the reaction temperature of 200-; the mass ratio of the amount of the catalyst to the liquid is (1: 22) - (1.2: 22), and oxygen is continuously introduced as an oxidant in the treatment process.
And (3) carrying out catalytic wet oxidation reaction in the step (3), wherein the reaction temperature is controlled at 250 ℃, the reaction pressure is 7.5MPa, and the reaction time is 3 hours.
And (3) in the precipitation process of the step (2), the pH value of the outlet water is kept at about 10, and the pH value of the inlet water is adjusted at any time to ensure the pH condition of the subsequent catalytic wet oxidation.
The coagulant in the step (1) is polyaluminium chloride or polyaluminium ferric chloride.
The catalyst in the step (3) is a supported catalyst, and the carrier is selected from activated carbon and SiO2Or TiO2The load is selected from Ru and RuO2，Pt，Ir,IrO2One kind of (1).
And (4) arranging blades in the catalytic wet oxidation device in the step (3), wherein the stirring speed is 600r/min-700 r/min.
The COD concentration of the heavy alcohol kettle bottom liquid is up to 60-70 ten thousand mg/L, the TOC concentration is 50 ten thousand mg/L, the kettle bottom liquid takes ethylene glycol as a main pollutant, the content of the ethylene glycol accounts for 70% of the total components, the diethylene glycol, the triethylene glycol accounts for 20%, the polyethylene glycol accounts for 10%, and the heavy alcohol kettle bottom liquid contains a large amount of Fe element, a considerable concentration of K, Na, Cr and other elements, and a small amount of Mn, Ca and the like.
The heterogeneous catalyst is utilized to reduce the activation energy of the reaction and improve the reaction efficiency. The catalyst for the high-temperature high-pressure wet catalytic oxidation is selected from common catalyst carriers, such as TiO2Active alumina, active carbon and the like, and the load is selected from noble metals such as Pt, ruthenium, rubidium and the like, and is prepared by a common preparation method of the catalyst.
The catalyst with high removal rate of alcohol substances in the kettle bottom liquid wastewater is selected, and the loaded metal oxide and noble metal are also characterized by high degradation effect, the removal rate of TOC and COD of the kettle bottom liquid treated by the method can reach more than 99 percent, and the biodegradability of the wastewater is obviously improved. The invention is also suitable for the pretreatment of other alcohol-containing wastewater.
Compared with the prior art, the invention has the advantages that:
(1) by adopting the technical scheme of the invention, the pretreated kettle bottom liquid is placed in a high-temperature high-pressure device for reaction for a period of time, high-polymer alcohols are converted into substances with small molecular weight, the biodegradability of the wastewater is improved, and the effluent quality of the subsequent biological treatment is improved;
(2) by adopting the technical scheme of the invention, secondary pollutants such as NOx, SOx, HCl and the like generated by an incineration method are avoided;
(3) by adopting the technical scheme of the invention, the process method is mature and simple, the reaction device occupies less land, the operation and management are simple, the personnel investment is less, and the treatment cost is reduced.
Drawings
FIG. 1 shows a typical treatment process of ethylene glycol kettle bottom liquid wastewater at present
FIG. 2 is a process for treating waste water of glycol kettle bottom liquid based on the invention
Detailed Description
The above-described scheme is further illustrated below with reference to specific examples. It should be understood that these examples are for illustrative purposes and are not intended to limit the scope of the present invention. The conditions used in the examples may be further adjusted according to the conditions of the particular manufacturer, and the conditions not specified are generally the conditions in routine experiments.
Example 1
The ethylene glycol wastewater of a company by an ethylene method has a pH value of 3.4, COD of about 750000mg/L, TOC of about 650000mg/L and a pH value of about 3. The waste water contains 55mg/kg of Ca; cr, 139 mg/kg; cu, 50mg/kg, Fe, 4860 mg/kg; k, 303 mg/kg; mn, 54 mg/kg; na, 131mg/kg, and the existence of a large amount of metal ions also has certain influence on the treatment of the wastewater. Firstly, adding coagulant polyaluminum ferric chloride into a water sample, filtering the generated precipitate, then introducing sodium hydroxide solution to adjust the pH of the bottom liquid of the kettle to 10, simultaneously diluting wastewater, introducing the rest liquid into a catalytic wet oxidation device after precipitation and filtration, and selecting RuO loaded by activated carbon2As a catalyst for reaction, the reaction temperature of the device is set to be 250 ℃, the operation pressure is 7MPa, and the rotating speed is 600 r/min. The reaction time was 2.5 h. The main performance indexes of the wastewater before and after treatment are shown in Table 1. It is obvious from the results of COD and TOC that the biodegradability of the wastewater treated by catalytic wet oxidation is greatly improved, and the color of the effluent is changed from original grey black to clear and transparent, and can be directly recovered or discharged.
TABLE 1 Current laboratory wastewater treatment results
Figure BDA0002992294070000041
Example 2
A certain company utilizes an ethylene method to produce ethylene glycol, an oxidation unit mainly generates ethylene oxide, and a refining unit pressurizes and hydrates the ethylene oxide in a reaction evaporation system of the ethylene glycol to generate the ethylene glycol and simultaneously generates a large amount of waste liquid at the bottom of a kettle. Directly introducing the waste liquid into a precipitation reaction tank, adding a coagulant of polyaluminum ferric chloride, filtering the generated precipitate, introducing alkali liquor sodium hydroxide to adjust the pH value of the bottom liquid of the kettle to 11, diluting the waste water, introducing the rest liquid into a catalytic wet oxidation device after precipitation and filtration, and introducing SiO into a catalytic wet oxidation device2/IrO2As a reaction catalyst, the reaction temperature of the device is set to be 200 ℃, the operation pressure is 8MPa, and the rotating speed is 650 r/min. The reaction time was 2 h. Finally, the liquid was recovered or discharged, and the results before and after the treatment are shown in Table 2. Obviously, the COD and TOC values of the treated wastewater are obviously reduced, and the treatment effect is excellent.
Figure BDA0002992294070000042
Figure BDA0002992294070000051

Claims (6)

1. A method for treating heavy alcohol kettle bottom liquid based on a catalytic wet oxidation method is characterized by comprising the following steps:
(1) adding a coagulant into the thick heavy alcohol kettle bottom liquid, wherein the volume of the coagulant is not more than 20% of that of the heavy alcohol kettle bottom liquid, removing suspended matters in the waste liquid, and filtering to obtain clear liquid;
(2) adjusting the pH of the clear liquid obtained in the step (1), introducing alkali liquor, keeping the pH between 9 and 11, precipitating metal ions in the liquid, standing for 30 minutes, and filtering;
(3) the liquid filtered in the step (2) enters a catalytic wet oxidation device for catalytic wet oxidation reaction at the reaction temperature of 200-; the mass ratio of the amount of the catalyst to the liquid is (1: 22) - (1.2: 22), and oxygen is continuously introduced as an oxidant in the treatment process.
2. The method for treating heavy alcohol kettle bottoms according to claim 1, wherein the coagulant in step (1) is polyaluminum chloride or polyaluminum ferric chloride.
3. The method for treating heavy alcohol still bottoms according to claim 1, wherein the effluent pH is maintained at 10 during the precipitation in step (2), and the influent pH is adjusted at all times to ensure the pH conditions for the subsequent catalytic wet oxidation.
4. The method for treating heavy alcohol still bottoms according to claim 1, wherein the catalytic wet oxidation reaction of step (3) is carried out at a reaction temperature of 250 ℃, a reaction pressure of 7.5MPa, and a reaction time of 3 hours.
5. The method for treating heavy alcohol still bottoms according to claim 1 wherein the catalyst of step (3) is a supported catalyst and the support is selected from the group consisting of activated carbon, SiO2Or TiO2The load is selected from Ru and RuO2，Pt，Ir,IrO2One kind of (1).
6. The method for treating heavy alcohol kettle bottoms according to claim 1, wherein blades are arranged in the catalytic wet oxidation device in the step (3), and the stirring speed is 600r/min-700 r/min.
CN202110319675.2A 2021-03-25 2021-03-25 Method for treating heavy alcohol kettle bottom liquid based on catalytic wet oxidation method Pending CN113003785A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114751576A (en) * 2022-06-16 2022-07-15 北京惠宇乐邦环保科技有限公司 Method for treating dialkoxybenzene production wastewater

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1552519A (en) * 2003-12-19 2004-12-08 吉林大学 Heterogeneous catalyst and method for treating refuse percolate by catalytic oxidation wet process
CN111018089A (en) * 2019-11-08 2020-04-17 康纳新型材料(杭州)有限公司 Catalytic wet oxidation treatment method for propylene oxide wastewater

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1552519A (en) * 2003-12-19 2004-12-08 吉林大学 Heterogeneous catalyst and method for treating refuse percolate by catalytic oxidation wet process
CN111018089A (en) * 2019-11-08 2020-04-17 康纳新型材料(杭州)有限公司 Catalytic wet oxidation treatment method for propylene oxide wastewater

Non-Patent Citations (1)

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Title
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Publication number Priority date Publication date Assignee Title
CN114751576A (en) * 2022-06-16 2022-07-15 北京惠宇乐邦环保科技有限公司 Method for treating dialkoxybenzene production wastewater

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Application publication date: 20210622