CN105692864A - Method for processing wastewater - Google Patents
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- CN105692864A CN105692864A CN201410705506.2A CN201410705506A CN105692864A CN 105692864 A CN105692864 A CN 105692864A CN 201410705506 A CN201410705506 A CN 201410705506A CN 105692864 A CN105692864 A CN 105692864A
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Abstract
The invention discloses a method for processing wastewater. The wastewater is high-acid heavy crude oil processing wastewater. The method comprises the following step: the high-acid heavy crude oil processing wastewater is successively contacted with an assistant catalyst A, an ozone catalytic oxidation catalyst and an assistant catalyst B, wherein the ozone catalytic oxidation catalyst contains a carrier and active components and auxiliaries which are loaded on the carrier. The carrier contains gamma-alumina. The active component elements contain Fe, Mn, Cu and Co. The auxiliary elements contain Ce and Mg. By the method for processing wastewater, physical and chemical performance stability of the ozone catalytic oxidation catalyst can be maintained for a long time, and COD cr value of wastewater is remarkably reduced. In addition, by the above method, the ozone catalytic oxidation catalyst used has long service life and high catalytic activity.
Description
Technical field
The present invention relates to a kind of method processing waste water, especially, relate to a kind of method processing high-acid heavy crude oil processing waste water。
Background technology
Refinery(waste) water is petroleum refining and a class waste water of generation in the course of processing。Owing to the kind of crude oil is many, therefore, refinery(waste) water water-quality constituents is complicated, and changes greatly, and biodegradability is poor, COD, NH3-N concentration is high, and biochemical processing process is easily subject to impact, and treatment effect is unstable。
Along with the propelling of national energy-saving emission reduction work, country and local priority have been put into effect stricter discharge standard and reduced discharging index。But, on the one hand, owing to discharge standard improves constantly, the clearance of pollutant requires just to improve constantly, on the other hand, enterprise's emission reduction is increasing, solve this problem, it is crucial that research and development refinery(waste) water advanced treating and reuse technology, while the Sewage advanced treatment of qualified discharge reduces the concentration of emission of pollutant, also can be back to use recirculating cooling water system, realize the target of water-saving and emission-reducing, kill two birds with one stone。
Ozonation technology is an extremely important link in Refinery Wastewater integrated technique; this technology utilizes the catalytic action of catalyst; ozone can be rapidly decomposed into hydroxyl radical free radical; hydroxyl radical free radical is very active; alcohol, ketone, organic acid and the Ester decomposed difficult in waste water can be continued oxidation Decomposition; organic pollution oxidation is more thorough, and removal efficiency is high。
But, various defect is there is when being used in catalytic ozonation technology by the catalyst that prior art provides, such as, publication number is the preparation method of a kind of Refinery Wastewater ozone catalytic oxidation catalyst disclosed in CN101982237A, the method adopts the mixture that amorphous alumina and hydroxyl oxidize iron powder are formed to carry out pelletize, maintenance, dry, finished catalyst is obtained after roasting, the preparation method simplicity of this catalyst and environmental protection, but, use the service life of catalyst during this catalyst treatment refinery(waste) water short, and the performance such as catalytic efficiency is not good。The defect that above-mentioned catalyst service life is short and catalytic performance is not good is there is also when utilizing publication number for involved in CN102923913A catalyst treatment refinery(waste) water。
Therefore, the method developing the process high-acid heavy crude oil processing waste water that a kind of new ozone catalytic oxidation catalyst making to use has stable physical and chemical performance for a long time seems particularly necessary。
Summary of the invention
It is an object of the invention to overcome the defect of prior art, the method that the stable process high-acid heavy crude oil processing waste water of a kind of physical and chemical performance that can maintain catalyst for a long time is provided, and, the method of above-mentioned process waste water provided by the invention enables to the ozone catalytic oxidation catalyst long service life, the catalysis activity height that use, it is possible to significantly reduce the CODcr value in described high-acid heavy crude oil processing waste water。
To achieve these goals, the present invention provides a kind of method processing high-acid heavy crude oil processing waste water, the method includes: contacted with cocatalyst A, ozone catalytic oxidation catalyst and cocatalyst B successively by high-acid heavy crude oil processing waste water, wherein, described ozone catalytic oxidation catalyst includes carrier and load active component on the carrier and auxiliary agent, described carrier includes gama-alumina, described active component element includes Fe, Mn, Cu and Co, and described auxiliary element includes Ce and Mg。
The method of process high-acid heavy crude oil processing waste water provided by the invention can maintain the physical and chemical performance of catalyst long-term and stably, and, said method provided by the invention enables to the ozone catalytic oxidation catalyst long service life, the catalysis activity height that use, and can significantly reduce the CODcr value in described high-acid heavy crude oil processing waste water。Such as, gather the physicochemical data of catalyst in each embodiment of the process high-acid heavy crude oil processing waste water of 6 months and the load capacity of active component element and auxiliary element can be seen that, when adopting method of the present invention to process high-acid heavy crude oil processing waste water, the physical and chemical performance of the ozone catalytic oxidation catalyst used in the method for the present invention is stable, and can substantially reduce the CODcr value in described waste water。
Under preferable case, when the method adopting process high-acid heavy crude oil processing waste water of the present invention processes high-acid heavy crude oil processing waste water, enterprise wastewater qualified discharge can not only be made, also can be back to use circulating water water system, realize emission reduction targets for enterprise and technical support is provided。
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently。
Detailed description of the invention
Hereinafter the specific embodiment of the present invention is described in detail。It should be appreciated that detailed description of the invention described herein is merely to illustrate and explains the present invention, it is not limited to the present invention。
In the present invention, it is necessary to special instruction, when not contrary explanation, described Fe, Mn, Cu, Co, Ce and Mg represent corresponding element。
In the present invention, described " first " and " second " are only used for distinguishing, and do not represent precedence, and those skilled in the art should not be construed as the restriction to technical scheme。
On the one hand, the invention provides a kind of method processing high-acid heavy crude oil processing waste water, the method includes: contacted with cocatalyst A, ozone catalytic oxidation catalyst and cocatalyst B successively by high-acid heavy crude oil processing waste water, wherein, described ozone catalytic oxidation catalyst includes carrier and load active component on the carrier and auxiliary agent, described carrier includes gama-alumina, and described active component element includes Fe, Mn, Cu and Co, and described auxiliary element includes Ce and Mg。
In the present invention, in described ozone catalytic oxidation catalyst, the gama-alumina as carrier can be spherical。
In the present invention, the not special requirement of kind to described active component, can be conventional use of one or more compounds including Fe element, Mn element, Cu element and Co element containing the present invention in this area, preferably comprising Fe element, Mn element, Cu element and Co element at interior oxide, namely described active component is preferably the oxide of described active component element。In the present invention, as long as described active component at least can provide Fe element, Mn element, Cu element and Co element, it is preferable that described active component is the oxide of described active component element。
In the present invention, to the not special requirement of the kind of described auxiliary agent, it is possible to for one or more compounds including Ce element and Mg element containing the present invention conventional use of in this area。In the present invention, as long as described auxiliary agent at least can provide Ce element and Mg element, it is preferred to Ce element and the oxide of Mg element can be provided。
When the method for the process high-acid heavy crude oil processing waste water that the employing present invention is described above processes high-acid heavy crude oil processing waste water, can substantially reduce the CODcr value in high-acid heavy crude oil processing waste water, and, the said method of the present invention makes the advantage that the ozone catalytic oxidation catalyst used has long service life, catalysis activity height and stable in catalytic performance。
Method according to process high-acid heavy crude oil processing waste water of the present invention, wherein, with the gross weight gauge of described ozone catalytic oxidation catalyst, described active component element can for 6-12 weight % with the total content that oxide is counted；Preferably, the total content that described active component element is counted with oxide is for 8-10 weight %。In the present invention, described active component element refers in the total content of oxide, and all active component elements contained in the described ozone catalytic oxidation catalyst of the present invention are with the total content of its corresponding oxide timing。
Method according to process high-acid heavy crude oil processing waste water of the present invention, wherein, with the gross weight gauge of described ozone catalytic oxidation catalyst, described auxiliary element can for 1.5-2.5 weight % with the total content that oxide is counted；Preferably, the total content that described auxiliary element is counted with oxide is for 1.8-2.2 weight %。In the present invention, described auxiliary element refers in the total content of oxide, and all auxiliary elements contained in the described ozone catalytic oxidation catalyst of the present invention are with the total content of its corresponding oxide timing。
In the method for process high-acid heavy crude oil processing waste water of the present invention, described Fe, Mn, Cu and Co content can be identical or different。Under preferable case, in the method for process high-acid heavy crude oil processing waste water of the present invention, in described ozone catalytic oxidation catalyst, gross weight gauge with described ozone catalytic oxidation catalyst, described Fe, Mn, Cu and Co can respectively 1.5-2.5 weight % in the content of oxide, it is further preferred that described Fe, Mn, Cu and Co can respectively 1.8-2.2 weight % in the content of oxide。
In the method for process high-acid heavy crude oil processing waste water of the present invention, the content of described Ce and Mg can be identical or different。Under preferable case, in the method for process high-acid heavy crude oil processing waste water of the present invention, in described ozone catalytic oxidation catalyst, gross weight gauge with described ozone catalytic oxidation catalyst, described Ce and Mg can respectively 0.7-1.5 weight % in the content of oxide, it is further preferred that described Ce and Mg can respectively 0.9-1.1 weight % in the content of oxide。
Method according to process high-acid heavy crude oil processing waste water of the present invention, wherein, the specific surface area of described ozone catalytic oxidation catalyst can be 270-290m2/ g, it is preferred to 274-285m2/g。
Method according to process high-acid heavy crude oil processing waste water of the present invention, wherein, the pore volume of described ozone catalytic oxidation catalyst can be 0.4-0.55mL/g, it is preferred to 0.44-0.51mL/g。In the present invention, described pore volume refers to the total hole volume in 1g ozone catalytic oxidation catalyst, namely the specific pore volume in conventional meaning。
Method according to process high-acid heavy crude oil processing waste water of the present invention, wherein, the aperture of described ozone catalytic oxidation catalyst can be 6-7.8nm, it is preferred to 6.4-7.3nm。In the present invention, described aperture refers to the bore dia in ozone catalytic oxidation catalyst。
In the method for process high-acid heavy crude oil processing waste water of the present invention, to the preparation method of the above-mentioned active component containing carrier and load on carrier and the ozone catalytic oxidation catalyst of auxiliary agent, there is no particular limitation, and those skilled in the art can by adopting the preparation method of conventional use of catalyst in this area prepare。Such as, in the present invention, can the compound containing active component element of the present invention and the compound containing adjuvant component element of the present invention be dissolved in water or other solvent, and contact with described carrier, make described active component element and described auxiliary element load on the carrier, then carry out the dry of routine and namely baking operation can obtain ozone catalytic oxidation catalyst of the present invention。
Particularly preferably in situation, the inventors found that the catalytic performance adopting the ozone catalytic oxidation catalyst prepared with the following method is more stable, the catalysis activity of ozone catalytic oxidation catalyst is higher。Therefore, the present invention provides following preferred preparation method to prepare the described ozone catalytic oxidation catalyst in the method for the process high-acid heavy crude oil processing waste water of the present invention。
A kind of preparation method of ozone catalytic oxidation catalyst, the method includes:
(1) the impregnation liquid A containing auxiliary element is contacted with carrier, obtain the carrier containing auxiliary element；
(2) the described carrier containing auxiliary element is contacted with the impregnation liquid B containing active component element,
Wherein, described carrier includes gama-alumina, and described active component element includes Fe, Mn, Cu and Co, and described auxiliary element includes Ce and Mg。
In the present invention, in step (1) and/or step (2), the mode of described contact has multiple, it is preferable that the mode of described contact is the mode of dipping。In the present invention, the mode of described dipping can have multiple, for instance equi-volume impregnating can be adopted in the present invention to impregnate。In the present invention, to the temperature and time of described dipping, there is no particular limitation, those skilled in the art can select according to dipping temperature conventional in this area and dip time, as long as enabling to carrier to reach adsorption equilibrium, the present invention does not repeat them here。
The concrete operation method of equi-volume impregnating as well known to those skilled in the art, the present invention does not repeat them here。
Preparation method according to ozone catalytic oxidation catalyst of the present invention, to the concentration of compound containing auxiliary element in described impregnation liquid A and in described impregnation liquid B the concentration of compound containing active component element there is no particular limitation, those skilled in the art can prepare the described impregnation liquid A and impregnation liquid B of suitable concn according to the load capacity of required active component element and/or auxiliary element and the way of contact adopted, and the present invention does not repeat them here。
Preparation method according to ozone catalytic oxidation catalyst of the present invention, the method is additionally included in before carrying out step (2), and the described carrier containing auxiliary element obtained after contact in step (1) is sequentially carried out first dry and the first roasting。
In the present invention, it is preferred to the described first temperature dried is 80-150 DEG C, the described first time dried specifically was not limited by the present invention, and the present invention can be 10-100min preferably the described first time dried。
In the present invention, preferably the temperature of described first roasting is 500-600 DEG C, the present invention to time of described first roasting also without special restriction, those skilled in the art can select according to the conventional roasting time in this area, and the time of the present invention preferably described first roasting can be 30-300min。
According to method of the present invention, the method also includes carrier obtained after being contacted with the impregnation liquid B containing active component element by the described carrier containing auxiliary element is carried out post processing, the method of described post processing can include being sequentially carried out second dry and the second roasting, in this post-processing approach second be dry and the temperature of the second roasting and the time can dry from aforesaid first and the temperature and time of the first roasting is identical or different, the temperature that in the present invention preferably this post processing second dries is 80-150 DEG C, second time dried can be 10-100min；The temperature of the second roasting is 500-600 DEG C, and the time of the second roasting can be 30-300min。
A kind of preferred embodiment according to the present invention, the preparation method of the described ozone catalytic oxidation catalyst in the method for the process high-acid heavy crude oil processing waste water of the present invention may include that
(1) the impregnation liquid A containing auxiliary element is contacted with carrier, obtain the carrier containing auxiliary element；
(2) the described carrier containing auxiliary element is sequentially carried out first dry and the first roasting；
(3) carrier containing auxiliary element described in after the first roasting is contacted with the impregnation liquid B containing active component element, and the catalyst obtained after described contact is sequentially carried out second dry and the second roasting, obtain described ozone catalytic oxidation catalyst；
Wherein, described carrier includes gama-alumina, and described active component element includes Fe, Mn, Cu and Co, and described auxiliary element includes Ce and Mg。
Adopt the CODcr value that described high-acid heavy crude oil processing waste water can be substantially provided during the catalyst treatment high-acid heavy crude oil processing waste water of the above-mentioned offer of the present invention, and the ozone catalytic oxidation catalyst in the present invention has stable in catalytic performance and the active high advantage of catalysis, it is possible to react suitable in various catalytic ozonations。
Method according to process high-acid heavy crude oil processing waste water of the present invention, the present invention preferred cocatalyst A and described cocatalyst B can be TS-3 cocatalyst, in the present invention, described TS-3 cocatalyst is purchased from Zhonghai Asphalt (Taizhou) Co., Ltd.。
Method according to process high-acid heavy crude oil processing waste water of the present invention, it is preferable that the admission space of described cocatalyst A, ozone catalytic oxidation catalyst and cocatalyst B is than for 1.5-2.5:4.5-8.5:1。
Method according to process high-acid heavy crude oil processing waste water of the present invention, the condition contacted with cocatalyst A, ozone catalytic oxidation catalyst and cocatalyst B successively by high-acid heavy crude oil processing waste water can be identical, can also be different, in method of the present invention, the condition of preferred described contact is identical, and the condition of described contact includes: pH value can be 7-8, and during liquid, volume space velocity can be 1.5-4.5h-1。
In the method for process high-acid heavy crude oil processing waste water of the present invention, the Organic substance contained in described high-acid heavy crude oil processing waste water can include at least one in indone, cycloolefin, cycloalkane, nitrogen-containing heterocycle compound and phthalic acid ester and aphthenic acids。It is to say, high-acid heavy crude oil processing waste water of the present invention can contain the Organic substance of at least one and aphthenic acids included in indone, cycloolefin, cycloalkane, nitrogen-containing heterocycle compound and phthalic acid ester。
Method according to process high-acid heavy crude oil processing waste water of the present invention, wherein, described aphthenic acids can be the aphthenic acids of C12-C18, it is particularly preferred in situation, in the present invention, described aphthenic acids is the aphthenic acids of C18, is the aphthenic acids that carbon number is 18。
Method according to process high-acid heavy crude oil processing waste water of the present invention, wherein, the CODcr of described high-acid heavy crude oil processing waste water can be 140-250mg/L。
Hereinafter will be described the present invention by embodiment。Hereinafter preparing in example, contrast preparation example, embodiment and comparative example, in case of no particular description, the various raw materials used are all from commercially available, and the water used is deionized water。
In following preparation example and contrast preparation example, in the impregnation liquid A used, the compound containing auxiliary element is cerous nitrate and magnesium nitrate；In the impregnation liquid B used, the compound containing active component element is ferric nitrate, manganese nitrate, cobalt nitrate and copper nitrate。
The dipping below prepared in example and contrast preparation example all adopts equi-volume impregnating to carry out。
In the following Examples and Comparative Examples, the load capacity of described auxiliary element and active component element is all in its corresponding oxide form。
Preparation example 1
This prepares example for preparing ozone catalytic oxidation catalyst of the present invention, and this is prepared example and adopts and prepare described catalyst with the following method:
(1) adopt equi-volume impregnating to be contacted by the gamma-aluminium oxide carrier of impregnation liquid A and 25kg, obtain the carrier containing auxiliary element；
(2) the described carrier containing auxiliary agent is sequentially carried out first dry and the first roasting, and wherein, the first temperature dried is 110 DEG C, and the first time dried was 20min, and the temperature of the first roasting is 550 DEG C, and the time of the first roasting is 50min；
(3) equi-volume impregnating is adopted to be contacted with impregnation liquid B by carrier containing auxiliary element described in after the first roasting, and the catalyst obtained after described contact is sequentially carried out second dry and the second roasting, wherein, second temperature dried is 110 DEG C, second time dried was 20min, the temperature of the second roasting is 550 DEG C, the time of the second roasting is 50min, obtaining catalyst cat1, the physico-chemical property of this catalyst cat1 and the load capacity of active component element and auxiliary element are as shown in table 1。
Preparation example 2
This prepares example for preparing ozone catalytic oxidation catalyst of the present invention, and this is prepared example and adopts and prepare described catalyst with the following method:
Equi-volume impregnating is adopted to be contacted by the gamma-aluminium oxide carrier of impregnation liquid A with impregnation liquid B and 25kg, the catalyst obtained after contact is sequentially carried out dry and roasting, wherein, dry temperature is 110 DEG C, the dry time is 30min, and the temperature of roasting is 550 DEG C, and the time of roasting is 80min, obtaining catalyst cat2 after roasting, the physico-chemical property of this catalyst cat2 and the load capacity of active component element and auxiliary element are as shown in table 1。
Preparation example 3
This prepares example for preparing ozone catalytic oxidation catalyst of the present invention, and this is prepared example and adopts and prepare described catalyst with the following method:
Equi-volume impregnating is adopted to be contacted by the gamma-aluminium oxide carrier of impregnation liquid A with impregnation liquid B and 25kg, the catalyst obtained after contact is sequentially carried out dry and roasting, wherein, dry temperature is 120 DEG C, the dry time is 45min, and the temperature of roasting is 580 DEG C, and the time of roasting is 70min, obtaining catalyst cat3 after roasting, the physico-chemical property of this catalyst cat3 and the load capacity of active component element and auxiliary element are as shown in table 1。
Preparation example 4
This is prepared example and adopts such as method as described in preparation example 2 to prepare catalyst, wherein, institute the difference is that:
The load capacity of described active component element is different, obtains catalyst cat4 after roasting, and the physico-chemical property of this catalyst cat4 and the load capacity of active component element and auxiliary element are as shown in table 1。
Preparation example 5
This is prepared example and adopts such as method as described in preparation example 4 to prepare catalyst, wherein, institute the difference is that:
The load capacity of described active component element is different, obtains catalyst cat5 after roasting, and the physico-chemical property of this catalyst cat5 and the load capacity of active component element and auxiliary element are as shown in table 1。
Preparation example 6
This is prepared example and adopts such as method as described in preparation example 3 to prepare catalyst, wherein, institute the difference is that:
The load capacity of described auxiliary element is different, obtains catalyst cat6 after roasting, and the physico-chemical property of this catalyst cat6 and the load capacity of active component element and auxiliary element are as shown in table 1。
Preparation example 7
This is prepared example and adopts such as method as described in preparation example 6 to prepare catalyst, wherein, institute the difference is that:
The load capacity of described auxiliary element is different, obtains catalyst cat7 after roasting, and the physico-chemical property of this catalyst cat7 and the load capacity of active component element and auxiliary element are as shown in table 1。
Table 1
Contrast preparation example 1
This contrast preparation example adopts the method identical with preparation example 1 to carry out, the difference is that active constituent compound contained in impregnation liquid B be copper nitrate, manganese nitrate, nickel nitrate and ferric nitrate, and the load capacity of Cu, Mn, Cu and Ni is identical with the load capacity of Cu, Mn, Cu and Co in preparation example 1 respectively。
Catalyst called after D-cat1 obtained in this contrast preparation example, the physico-chemical property of this catalyst D-cat1 and the load capacity of active component element and auxiliary element are as shown in table 2。
Table 2
Contrast preparation example 2
This contrast preparation example adopts and carries out with the preparation identical method of example 1, and institute is magnesium nitrate and antimony chloride the difference is that auxiliary compound contained in impregnation liquid A, and the load capacity of Mg and Sb is identical with the load capacity of Mg and Ce prepared in example 1 respectively。
Catalyst called after D-cat2 obtained in this contrast preparation example, the physico-chemical property of this catalyst D-cat2 and the load capacity of active component element and auxiliary element are as shown in table 3。
Table 3
Contrast preparation example 3
This contrast preparation example adopts and carries out with the preparation identical method of example 1, institute the difference is that in impregnation liquid A without there being auxiliary element。
Catalyst called after D-cat3 obtained in this contrast preparation example, the physico-chemical property of this catalyst D-cat3 and the load capacity of active component element and auxiliary element are as shown in table 4。
Table 4
Contrast preparation example 4
This contrast preparation example adopts and carries out with the preparation identical method of example 1, and institute is Alpha-alumina the difference is that the carrier used in this contrast preparation example。
Catalyst called after D-cat4 obtained in this contrast preparation example, the physico-chemical property of this catalyst D-cat4 and the load capacity of active component element and auxiliary element are as shown in table 5。
Table 5
Contrast preparation example 5
This contrast preparation example adopts and carries out with the preparation identical method of example 1, and institute is activated carbon the difference is that the carrier used in this contrast preparation example。
Catalyst called after D-cat5 obtained in this contrast preparation example, the physico-chemical property of this catalyst D-cat5 and the load capacity of active component element and auxiliary element are as shown in table 6。
Table 6
Embodiment 1
The present embodiment adopts process high-acid heavy crude oil processing waste water with the following method。
In the present embodiment, experimental water is high-acid heavy crude oil processing waste water water outlet, water temperature 30 DEG C, and pH value is 7.6, CODcr is 226mg/L。
Experimental provision: 50mL tetra-manages parallel catalyst experiment room evaluating apparatus (being provided by China National Offshore Oil Corporation)。
Above-mentioned experimental water is introduced vapour-liquid contacting column, and tower bottom blasts ozone, filling inert ceramic balls in tower, and after making gas-liquid be fully contacted, the waste water dissolved with ozone enters the catalytic reactor equipped with the catalyst cat1 prepared in preparation example 1。Ozone under the effect of catalyst by catalytic oxidation by the organic matter degradation in waste water, fluid reservoir is finally collected in the water outlet through catalytic reaction, and from described fluid reservoir the CODcr of sampling and measuring water outlet。
Major parameter condition in aforementioned four catalytic reactor is identical, and particularly as follows: wastewater flow is 150mL/h, the ratio of height to diameter of catalytic reactor is 4:1, the cumulative volume of Catalyst packing is 50mL, wherein, TS-3 cocatalyst is loaded at the bottom of described catalytic reactor and top respectively, and each catalytic reactor all loads successively according to by the order of bottom to top, it is TS-3 cocatalyst by the kind of the catalyst of the filling of bottom to top and volume ratio: ozone catalytic oxidation catalyst: TS-3 cocatalyst=2:5:1, reaction temperature is 27 DEG C, ozone generating capacity is 5g/h。
Under these experimental conditions, device runs 6 months continuously, the CODcr of sampling and measuring water outlet every day, and wherein, 6 months interior peaks of water outlet CODcr, minimum and meansigma methods are as shown in table 7 below。The analysis method adopted is according to State Environmental Protection Administration " water and effluent monitoring analyze method ", and wherein CODcr adopts potassium dichromate method to carry out。
Embodiment 2
The present embodiment adopts the method similar to embodiment 1 to process high-acid heavy crude oil processing waste water, wherein, the difference is that:
The ozone catalytic oxidation catalyst used in the present embodiment is by preparing the cat2 that example 2 prepares, and TS-3 cocatalyst: ozone catalytic oxidation catalyst: TS-3 cocatalyst=2:6:1, wastewater flow is 125mL/h。
All the other are all identical with the method described in embodiment 1。Under these experimental conditions, device runs 6 months continuously, the CODcr of sampling and measuring water outlet every day, and wherein, 6 months interior peaks of water outlet CODcr, minimum and meansigma methods are as shown in table 7 below。
Embodiment 3
The present embodiment adopts the method similar to embodiment 1 to process high-acid heavy crude oil processing waste water, wherein, the difference is that:
The ozone catalytic oxidation catalyst used in the present embodiment is by preparing the cat3 that example 3 prepares, and TS-3 cocatalyst: ozone catalytic oxidation catalyst: TS-3 cocatalyst=2:7:1, wastewater flow is 175mL/h。
All the other are all identical with the method described in embodiment 1。Under these experimental conditions, device runs 6 months continuously, the CODcr of sampling and measuring water outlet every day, and wherein, 6 months interior peaks of water outlet CODcr, minimum and meansigma methods are as shown in table 7 below。
Embodiment 4-5
Embodiment 4-5 adopts the method similar to embodiment 2 to process high-acid heavy crude oil processing waste water, wherein, the difference is that:
The ozone catalytic oxidation catalyst used in embodiment 4 and embodiment 5 is respectively by preparing example 4 and preparing cat4 and the cat5 that example 5 prepares。
All the other are all identical with the method described in embodiment 2。Under these experimental conditions, device runs 6 months continuously, the CODcr of sampling and measuring water outlet every day, and wherein, 6 months interior peaks of water outlet CODcr, minimum and meansigma methods are as shown in table 7 below。
Embodiment 6-7
Embodiment 6-7 adopts the method similar to embodiment 3 to process high-acid heavy crude oil processing waste water, wherein, the difference is that:
The ozone catalytic oxidation catalyst used in embodiment 6 and embodiment 7 is respectively by preparing example 6 and preparing cat6 and the cat7 that example 7 prepares。
All the other are all identical with the method described in embodiment 3。Under these experimental conditions, device runs 6 months continuously, the CODcr of sampling and measuring water outlet every day, and wherein, 6 months interior peaks of water outlet CODcr, minimum and meansigma methods are as shown in table 7 below。
Comparative example 1-5
Comparative example 1-5 adopts the method similar to embodiment 1 to process high-acid heavy crude oil processing waste water, wherein, the difference is that:
The ozone catalytic oxidation catalyst used in comparative example 1-5 respectively by contrast preparation example 1-5 prepare D-cat1, D-cat2, D-cat3, D-cat4 and D-cat5。
All the other are all identical with the method described in embodiment 1。Under these experimental conditions, device runs 6 months continuously, the CODcr of sampling and measuring water outlet every day, and wherein, 6 months interior peaks of water outlet CODcr, minimum and meansigma methods are as shown in table 7 below。
Comparative example 6
This comparative example adopts the method similar to embodiment 1 to process high-acid heavy crude oil processing waste water, wherein, the difference is that:
Catalyst in this comparative example is all ozone catalytic oxidation catalyst cat1。
All the other are all identical with the method described in embodiment 1。Under these experimental conditions, device runs 6 months continuously, the CODcr of sampling and measuring water outlet every day, and wherein, 6 months interior peaks of water outlet CODcr, minimum and meansigma methods are as shown in table 7 below。
Table 7
Be can be seen that by the result of table 7, compared with comparative example, method of wastewater treatment according to the present invention, 6 months interior peaks of continuous service differ less with minimum, namely when carrying out the process of high-acid heavy crude oil processing waste water according to the method for the present invention, the ozone catalytic oxidation catalyst used can maintain stable and higher catalysis activity for a long time。
Test case
Gather the physicochemical data of the above-described embodiment after 6 months process and the ozone catalytic oxidation catalyst in comparative example and the load capacity of active component and auxiliary agent, be listed in the table below 8-14 respectively。
Table 8
Table 9
Table 10
Table 11
Table 12
Table 13
Table 14
Gather the physicochemical data of catalyst in each embodiment of the process high-acid heavy crude oil processing waste water of 6 months and the load capacity of active component element and auxiliary element can be seen that, when adopting method of the present invention to process high-acid heavy crude oil processing waste water, the physical and chemical performance of the ozone catalytic oxidation catalyst used in the method for the present invention is stable, and can substantially reduce the CODcr value in described waste water。
And the result contrasting the physicochemical data of the catalyst cat1 in the embodiment 1 after the wastewater treatment of 6 months and the catalyst cat1 in comparative example 6 and the load capacity of active component element and auxiliary element can be seen that, the physicochemical data of the catalyst cat1 in embodiment 1 and the load capacity of active component element and auxiliary element to be stablized many compared with the result in comparative example 6, it is to say, adopt the stability of ozone catalytic oxidation catalyst that method of the present invention enables to use higher。
The preferred embodiment of the present invention described in detail above; but, the present invention is not limited to the detail in above-mentioned embodiment, in the technology concept of the present invention; technical scheme can being carried out multiple simple variant, these simple variant belong to protection scope of the present invention。
It is further to note that, each concrete technical characteristic described in above-mentioned detailed description of the invention, in reconcilable situation, it is possible to be combined by any suitable mode, in order to avoid unnecessary repetition, various possible compound modes are no longer illustrated by the present invention separately。
Additionally, can also carry out combination in any between the various different embodiment of the present invention, as long as it is without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally。
Claims (12)
1. the method processing waste water, wherein, this waste water is high-acid heavy crude oil processing waste water, the method includes: contacted with cocatalyst A, ozone catalytic oxidation catalyst and cocatalyst B successively by described high-acid heavy crude oil processing waste water, wherein, described ozone catalytic oxidation catalyst includes carrier and load active component on the carrier and auxiliary agent, it is characterized in that, described carrier includes gama-alumina, described active component element includes Fe, Mn, Cu and Co, and described auxiliary element includes Ce and Mg。
2. method according to claim 1, wherein, with the gross weight gauge of described ozone catalytic oxidation catalyst, the total content that described active component element is counted with oxide is for 6-12 weight %, and the total content that described auxiliary element is counted with oxide is for 1.5-2.5 weight %；
Preferably, the total content that described active component element is counted with oxide is for 8-10 weight %, and the total content that described auxiliary element is counted with oxide is for 1.8-2.2 weight %。
3. method according to claim 1, wherein, in described ozone catalytic oxidation catalyst, described Fe, Mn, Cu and Co content identical or different, and with the gross weight gauge of described ozone catalytic oxidation catalyst, described Fe, Mn, Cu and Co are in the content respectively 1.5-2.5 weight % of oxide。
4. method according to claim 3, wherein, described Fe, Mn, Cu and Co are in the content respectively 1.8-2.2 weight % of oxide。
5. method according to claim 1, wherein, in described ozone catalytic oxidation catalyst, the content of described Ce and Mg is identical or different, and with the gross weight gauge of described ozone catalytic oxidation catalyst, described Ce and Mg is in the content respectively 0.7-1.5 weight % of oxide。
6. method according to claim 5, wherein, described Ce and Mg is in the content respectively 0.9-1.1 weight % of oxide。
7. method according to claim 1, wherein, the specific surface area of described ozone catalytic oxidation catalyst is 270-290m2/ g, pore volume are 0.4-0.55mL/g, aperture is 6-7.8nm；
Preferably, the specific surface area of described ozone catalytic oxidation catalyst is 274-285m2/ g, pore volume are 0.44-0.51mL/g, aperture is 6.4-7.3nm。
8. method according to claim 1, wherein, described cocatalyst A and described cocatalyst B is TS-3 cocatalyst；The admission space of preferred described cocatalyst A, ozone catalytic oxidation catalyst and cocatalyst B is than for 1.5-2.5:4.5-8.5:1。
9. the method according to any one in claim 1-8, wherein, the preparation method of described ozone catalytic oxidation catalyst includes:
(1) the impregnation liquid A containing auxiliary element is contacted with carrier, obtain the carrier containing auxiliary element；
(2) the described carrier containing auxiliary element is sequentially carried out first dry and the first roasting；
(3) carrier containing auxiliary element described in after the first roasting is contacted with the impregnation liquid B containing active component element, and the catalyst obtained after described contact is sequentially carried out second dry and the second roasting, obtain described ozone catalytic oxidation catalyst。
10. method according to claim 1, wherein, described high-acid heavy crude oil processing waste water is identical with the condition that cocatalyst A, ozone catalytic oxidation catalyst and cocatalyst B contact successively, and the condition of described contact includes: pH value is 7-8, and during liquid, volume space velocity is 1.5-4.5h-1。
11. method according to claim 1, wherein, the Organic substance contained in described high-acid heavy crude oil processing waste water includes at least one in indone, cycloolefin, cycloalkane, nitrogen-containing heterocycle compound and phthalic acid ester and aphthenic acids。
12. method according to claim 10, wherein, described aphthenic acids is the aphthenic acids of C12-C18；The CODcr of preferred described high-acid heavy crude oil processing waste water is 140-250mg/L。
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