CN105688928A - Ozone catalytic oxidation catalyst and preparation method and application thereof - Google Patents
Ozone catalytic oxidation catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN105688928A CN105688928A CN201410705751.3A CN201410705751A CN105688928A CN 105688928 A CN105688928 A CN 105688928A CN 201410705751 A CN201410705751 A CN 201410705751A CN 105688928 A CN105688928 A CN 105688928A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- present
- active component
- catalytic oxidation
- roasting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of an ozone catalytic oxidation catalyst and the ozone catalytic oxidation catalyst prepared by the method. The method comprises the following steps: (1) steeping liquor A containing auxiliary elements is contacted with a carrier to obtain a carrier containing the auxiliary elements; and (2) the carrier containing the auxiliary elements is contacted with steeping liquor B containing active component elements, wherein the carrier contains gamma-alumina; the active component elements contain Fe, Mn, Cu and Co; and the auxiliary elements contain Ce and Mg. The invention also discloses an application of the ozone catalytic oxidation catalyst in treating high-acid heavy crude oil processing wastewater. The method for preparing the catalyst is low-cost, has simple process and is green and environmentally friendly. In addition, the catalyst prepared by the method has advantages of long service life, high catalytic activity and stable catalytic performance.
Description
Technical field
The present invention relates to the preparation method of a kind of ozone catalytic oxidation catalyst and the ozone catalytic oxidation catalyst prepared by the method, the application in processing high-acid heavy crude oil processing waste water of a kind of ozone catalytic oxidation catalyst。
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, develop a kind of new ozone catalytic oxidation catalyst with stable physical and chemical performance and seem particularly necessary。
Summary of the invention
It is an object of the invention to overcome the defect of prior art, a kind of ozone catalytic oxidation catalyst with stable physical and chemical performance is provided, simultaneously, the method preparing ozone catalytic oxidation catalyst provided by the invention has inexpensively, technique simple and the advantage of environmental protection, and the catalyst prepared by the method for the present invention also has long service life and the active high advantage of catalysis。
To achieve these goals, the preparation method that the present invention provides a kind 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。
On the other hand, the present invention also provides for a kind of ozone catalytic oxidation catalyst prepared by the said method of the present invention。
On the other hand, the present invention also provides for the application in processing high-acid heavy crude oil processing waste water of a kind of catalyst of the present invention。
The preparation method of ozone catalytic oxidation catalyst provided by the invention is cheap, technique simple and environmental protection, the catalyst prepared by the said method of the present invention can maintain stable physical and chemical performance for a long time, and ozone catalytic oxidation catalyst provided by the invention also has long service life and the active high advantage of catalysis。Such as, the result of comparative example 1 and comparative example 6 it can also be seen that, even under the active component element of identical load amount and the premise of auxiliary element, adopt the active result apparently higher than comparative example 6 of catalysis of the ozone catalytic oxidation catalyst of the preparation method acquisition of the present invention, and after the wastewater treatment of 6 months, the content of auxiliary agent Ce elements is apparently higher than the result in comparative example 6。And, from the data of embodiments of the invention and test case it can be seen that utilize the ozone catalytic oxidation catalyst of the present invention when processing high-acid heavy crude oil processing waste water, the clearance of water outlet CODcr is apparently higher than water outlet CODcr clearance during with catalyst treatment high-acid heavy crude oil processing waste water in comparative example。
Under preferable case, when the ozone catalytic oxidation catalyst adopting preparation method of the present invention to prepare is used for processing 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 preparation method that the invention provides a kind 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, can be spherical as the gama-alumina of carrier。
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, it is preferred to include Ce element and the oxide of Mg element。In the present invention, as long as described auxiliary agent at least can provide Ce element and Mg element。
The preparation method of the ozone catalytic oxidation catalyst that the present invention is described above is cheap, technique simple and environmental protection。The advantage that the ozone catalytic oxidation catalyst prepared by the said method of the present invention has long service life, catalysis activity height and stable in catalytic performance。
Preparation method according to ozone catalytic oxidation catalyst of the present invention, wherein, the consumption of described active component makes the gross weight gauge with described catalyst, and 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, by all active component elements contained in the described ozone catalytic oxidation catalyst that preparation method of the present invention the prepares total content with its corresponding oxide timing。
Preparation method according to ozone catalytic oxidation catalyst of the present invention, wherein, the consumption of described auxiliary agent makes the gross weight gauge with described catalyst, and 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, by all auxiliary elements contained in the described ozone catalytic oxidation catalyst that preparation method of the present invention the prepares total content with its corresponding oxide timing。
In the preparation method of ozone catalytic oxidation catalyst of the present invention, described Fe, Mn, Cu and Co consumption can be identical or different。Under preferable case, in the preparation method of ozone catalytic oxidation catalyst of the present invention, described Fe, Mn, Cu and Co consumption make and with the gross weight gauge of described 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 preparation method of ozone catalytic oxidation catalyst of the present invention, the consumption of described Ce and Mg can be identical or different。Under preferable case, in the preparation method of ozone catalytic oxidation catalyst of the present invention, the consumption of described Ce and Mg makes the gross weight gauge with described 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。
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 in described impregnation liquid A auxiliary compound concentration and in described impregnation liquid B the concentration of active constituent compound 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 agent 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 by the described carrier containing auxiliary agent 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, and the 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 described ozone catalytic oxidation catalyst 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 contact with the impregnation liquid B containing active component element, and the catalyst obtained after described contact is sequentially carried out second dries and the second roasting, obtain described 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。
The catalyst that said method of the present invention prepares is adopted to have stable in catalytic performance and the active high advantage of catalysis, it is adaptable to various catalytic ozonations react。
On the other hand, the present invention also provides for a kind of ozone catalytic oxidation catalyst prepared by the said method of the present invention。
The specific surface area of the described ozone catalytic oxidation catalyst prepared by said method of the present invention can be 270-290m2/ g, it is preferred to 274-285m2/g。
The pore volume of the described ozone catalytic oxidation catalyst prepared by said method of the present invention 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 catalyst, namely the specific pore volume in conventional meaning。
The aperture of the described ozone catalytic oxidation catalyst prepared by said method of the present invention 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 catalyst。
On the other hand, present invention also offers the application in processing high-acid heavy crude oil processing waste water of a kind of catalyst of the present invention。
According to catalyst of the present invention in the application processed in high-acid heavy crude oil processing waste water, wherein, 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, catalyst of the present invention is particularly suitable for processing the organic high-acid heavy crude oil processing waste water containing at least one and aphthenic acids included in indone, cycloolefin, cycloalkane, nitrogen-containing heterocycle compound and phthalic acid ester。
According to catalyst of the present invention in the application processed in high-acid heavy crude oil processing waste water, wherein, described aphthenic acids can be the aphthenic acids of C12-C18, particularly preferably in situation, in the present invention, described aphthenic acids is the aphthenic acids of C18, is the aphthenic acids that carbon number is 18。
According to catalyst of the present invention in the application processed in high-acid heavy crude oil processing waste water, wherein, the pH value of described high-acid heavy crude oil processing waste water can be 7-8, CODcr can be 140-250mg/L。
Hereinafter will be described the present invention by embodiment。In following 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 the examples below, the auxiliary compound contained in the impregnation liquid A used is cerous nitrate and magnesium nitrate；The active constituent compound contained in the impregnation liquid B used is ferric nitrate, manganese nitrate, cobalt nitrate and copper nitrate。
Dipping in following example and comparative 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。
In following test case, the TS-3 cocatalyst used is purchased from Zhonghai Asphalt (Taizhou) Co., Ltd.。
Embodiment 1
The present embodiment is for the preparation method that ozone catalytic oxidation catalyst of the present invention is described and the ozone catalytic oxidation catalyst prepared by the method, and the present embodiment is adopted and prepared 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 element 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。
Embodiment 2
The present embodiment is for the preparation method that ozone catalytic oxidation catalyst of the present invention is described and the ozone catalytic oxidation catalyst prepared by the method, and the present embodiment is adopted and prepared 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 element is sequentially carried out first dry and the first roasting, and wherein, the first temperature dried is 120 DEG C, and the first time dried was 30min, and the temperature of the first roasting is 560 DEG C, and the time of the first roasting is 70min；
(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 130 DEG C, second time dried was 40min, the temperature of the second roasting is 570 DEG C, the time of the second roasting is 40min, obtaining catalyst cat2, 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。
Embodiment 3
The present embodiment is for the preparation method that ozone catalytic oxidation catalyst of the present invention is described and the ozone catalytic oxidation catalyst prepared by the method, and the present embodiment is adopted and prepared 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 element is sequentially carried out first dry and the first roasting, and wherein, the first temperature dried is 100 DEG C, and the first time dried was 45min, and the temperature of the first roasting is 580 DEG C, and the time of the first roasting is 65min；
(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 125 DEG C, second time dried was 60min, the temperature of the second roasting is 575 DEG C, the time of the second roasting is 50min, obtaining catalyst cat3, 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。
Embodiment 4
The present embodiment adopt method as described in Example 1 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。
Embodiment 5
The present embodiment adopt method as described in Example 4 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。
Embodiment 6
The present embodiment adopt method as described in Example 2 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。
Embodiment 7
The present embodiment adopt method as described in Example 6 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
Comparative example 1
This comparative example adopts the method identical with embodiment 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 embodiment 1 respectively。
Catalyst called after D-cat1 obtained in this comparative 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
Comparative example 2
This comparative example adopts and carries out with the identical method of embodiment 1, and institute is magnesium nitrate and antimony chloride the difference is that the auxiliary compound contained by impregnation liquid A, and the load capacity of Mg and Sb is identical with the load capacity of Mg and Ce in embodiment 1 respectively。
Catalyst called after D-cat2 obtained in this comparative 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
Comparative example 3
This comparative example adopts and carries out with the identical method of embodiment 1, institute the difference is that in impregnation liquid A without there being auxiliary agent。
Catalyst called after D-cat3 obtained in this comparative 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
Comparative example 4
This comparative example adopts and carries out with the identical method of embodiment 1, the difference is that the carrier used in this comparative example be Alpha-alumina。
Catalyst called after D-cat4 obtained in this comparative 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
Comparative example 5
This comparative example adopts and carries out with the identical method of embodiment 1, the difference is that the carrier used in this comparative example be activated carbon。
Catalyst called after D-cat5 obtained in this comparative 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
Comparative example 6
This comparative example is adopted and is prepared catalyst with the following method so that in the catalyst prepared, active component element is identical with embodiment 1 with the load capacity of auxiliary element:
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 D-cat6 after roasting, the physico-chemical property of this catalyst D-cat6 and the load capacity of active component element and auxiliary element are as shown in table 7。
Table 7
Test case 1
This test case adopts the following experiment condition catalyst to preparing in above-described embodiment and comparative example to carry out activity rating。
Experiment condition: experimental water is high-acid heavy crude oil processing waste water water outlet, water temperature 30 DEG C, 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)。
Concrete operations flow process is when experiment starts, and 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 catalytic reactor。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: 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 8 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。
Table 8
Test case 2
Take above-mentioned catalyst in test case 1, gather the physicochemical data of each catalyst after 6 months process and the load capacity of active component and auxiliary agent, be listed in the table below 9-15 respectively。
Table 9
Table 10
Table 11
Table 12
Table 13
Table 14
Table 15
By the evaluating data of above-mentioned test case it can be seen that the catalysis activity of the catalyst prepared by the preparation method of the present invention is high, and stable at the physical and chemical performance of 6 months rear catalysts of Continuous Wastewater Treatment, COD removal efficiency is stable and higher。
The result of comparative example 1 and comparative example 6 can be seen that, even under the active component element of identical load amount and the premise of auxiliary element, adopt the active result apparently higher than comparative example 6 of catalysis of the ozone catalytic oxidation catalyst of the preparation method acquisition of the present invention, and after the wastewater treatment of 6 months, the content of auxiliary agent Ce elements is apparently higher than the result in comparative example 6。It can also be seen that from the data of embodiments of the invention and test case: when utilizing the ozone catalytic oxidation catalyst prepared by the preparation method of the present invention to process high-acid heavy crude oil processing waste water, the clearance of water outlet CODcr is apparently higher than water outlet CODcr clearance during with catalyst treatment high-acid heavy crude oil processing waste water in comparative example。
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 (10)
1. the preparation method of an ozone catalytic oxidation catalyst, it is characterised in that 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。
2. method according to claim 1, wherein, the consumption of described active component makes the gross weight gauge with described catalyst, and the total content that described active component is counted with oxide is for 6-12 weight %, it is preferred to 8-10 weight %；
The consumption of described auxiliary agent makes the gross weight gauge with described catalyst, and the total content that described auxiliary agent is counted with oxide is for 1.5-2.5 weight %, it is preferred to 1.8-2.2 weight %。
3. method according to claim 1, wherein, described Fe, Mn, Cu and Co consumption identical or different, and the consumption of described Fe, Mn, Cu and Co makes the gross weight gauge with described catalyst, described Fe in the catalyst, Mn, Cu and Co are in the content respectively 1.5-2.5 weight % of oxide；Preferred respectively 1.8-2.2 weight %。
4. method according to claim 1, wherein, the consumption of described Ce and Mg is identical or different, and the consumption of described Ce and Mg makes the gross weight gauge with described catalyst, and described Ce and Mg in the catalyst is in the content respectively 0.7-1.5 weight % of oxide；Preferred respectively 0.9-1.1 weight %。
5. method according to claim 1, wherein, 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；Preferably the described first dry temperature respectively 80-150 DEG C and 500-600 DEG C with the first roasting。
6. method according to claim 1, wherein, the method also includes the catalyst obtained after the contact described in step (2) is sequentially carried out second dry and the second roasting, it is preferable that the described second dry temperature respectively 80-150 DEG C and 500-600 DEG C with the second roasting。
7. the ozone catalytic oxidation catalyst that the method described in any one in claim 1-6 prepares。
8. the application in processing high-acid heavy crude oil processing waste water of the catalyst described in claim 7。
9. application according to claim 8, 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。
10. application according to claim 9, wherein, described aphthenic acids is the aphthenic acids of C12-C18；The pH value of preferred described high-acid heavy crude oil processing waste water is 7-8, CODcr is 140-250mg/L。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410705751.3A CN105688928B (en) | 2014-11-27 | 2014-11-27 | A kind of ozone catalytic oxidation catalyst and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410705751.3A CN105688928B (en) | 2014-11-27 | 2014-11-27 | A kind of ozone catalytic oxidation catalyst and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105688928A true CN105688928A (en) | 2016-06-22 |
| CN105688928B CN105688928B (en) | 2018-05-15 |
Family
ID=56230408
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410705751.3A Active CN105688928B (en) | 2014-11-27 | 2014-11-27 | A kind of ozone catalytic oxidation catalyst and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105688928B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106669726A (en) * | 2016-12-20 | 2017-05-17 | 上海纳米技术及应用国家工程研究中心有限公司 | Ozone catalyst for effectively stabilizing ammonia nitrogen content in iron and steel wastewater and preparation and application |
| CN110479302A (en) * | 2019-08-07 | 2019-11-22 | 上海尚析环保设备有限公司 | A kind of preparation method of micropore iron carbon composite catalytic agent and thus obtained micropore iron carbon composite catalytic agent and its application |
| CN111298803A (en) * | 2018-12-12 | 2020-06-19 | 金风环保有限公司 | Ozone catalytic oxidation catalyst for treating wastewater and preparation method thereof |
| CN114289029A (en) * | 2021-12-14 | 2022-04-08 | 煤炭科学技术研究院有限公司 | Ozone catalytic oxidation composite catalyst and preparation method and application thereof |
| CN114289022A (en) * | 2021-12-14 | 2022-04-08 | 煤炭科学技术研究院有限公司 | Ozone catalytic oxidation catalyst and preparation method and application thereof |
| CN114849719A (en) * | 2022-06-08 | 2022-08-05 | 北京碧水源膜科技有限公司 | Composite catalyst, preparation method thereof and wastewater treatment method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102029165A (en) * | 2010-11-09 | 2011-04-27 | 中国海洋石油总公司 | Method for preparing ozone catalytic oxidation catalyst for treating coking wastewater |
| CN102941084A (en) * | 2012-11-22 | 2013-02-27 | 大连理工大学 | Method for preparing double-component metallic oxide catalytic ozonation catalyst |
| KR20130058138A (en) * | 2011-11-25 | 2013-06-04 | 부산대학교 산학협력단 | Porous composite for removing volatile organic compounds and ozone catalytic oxidation reactor using the composite |
-
2014
- 2014-11-27 CN CN201410705751.3A patent/CN105688928B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102029165A (en) * | 2010-11-09 | 2011-04-27 | 中国海洋石油总公司 | Method for preparing ozone catalytic oxidation catalyst for treating coking wastewater |
| KR20130058138A (en) * | 2011-11-25 | 2013-06-04 | 부산대학교 산학협력단 | Porous composite for removing volatile organic compounds and ozone catalytic oxidation reactor using the composite |
| CN102941084A (en) * | 2012-11-22 | 2013-02-27 | 大连理工大学 | Method for preparing double-component metallic oxide catalytic ozonation catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 卫学玲等: "Al2O3负载Cu2O-臭氧催化氧化芴酮生产废水", 《环境科学与管理》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106669726A (en) * | 2016-12-20 | 2017-05-17 | 上海纳米技术及应用国家工程研究中心有限公司 | Ozone catalyst for effectively stabilizing ammonia nitrogen content in iron and steel wastewater and preparation and application |
| CN111298803A (en) * | 2018-12-12 | 2020-06-19 | 金风环保有限公司 | Ozone catalytic oxidation catalyst for treating wastewater and preparation method thereof |
| CN110479302A (en) * | 2019-08-07 | 2019-11-22 | 上海尚析环保设备有限公司 | A kind of preparation method of micropore iron carbon composite catalytic agent and thus obtained micropore iron carbon composite catalytic agent and its application |
| CN114289029A (en) * | 2021-12-14 | 2022-04-08 | 煤炭科学技术研究院有限公司 | Ozone catalytic oxidation composite catalyst and preparation method and application thereof |
| CN114289022A (en) * | 2021-12-14 | 2022-04-08 | 煤炭科学技术研究院有限公司 | Ozone catalytic oxidation catalyst and preparation method and application thereof |
| CN114289029B (en) * | 2021-12-14 | 2024-05-10 | 煤炭科学技术研究院有限公司 | Ozone catalytic oxidation composite catalyst and preparation method and application thereof |
| CN114289022B (en) * | 2021-12-14 | 2024-05-10 | 煤炭科学技术研究院有限公司 | Ozone catalytic oxidation catalyst and preparation method and application thereof |
| CN114849719A (en) * | 2022-06-08 | 2022-08-05 | 北京碧水源膜科技有限公司 | Composite catalyst, preparation method thereof and wastewater treatment method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105688928B (en) | 2018-05-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105688927A (en) | Ozone catalytic oxidation catalyst and application thereof | |
| CN105688928A (en) | Ozone catalytic oxidation catalyst and preparation method and application thereof | |
| CN105692864A (en) | Method for processing wastewater | |
| Zhao et al. | Catalytic ozonation for the degradation of nitrobenzene in aqueous solution by ceramic honeycomb-supported manganese | |
| Chen et al. | Biodegradability enhancement of coking wastewater by catalytic wet air oxidation using aminated activated carbon as catalyst | |
| WO2017128600A1 (en) | Ozone catalytic oxidation catalyst for wastewater treatment and preparation method therefor | |
| WO2018035882A1 (en) | Catalyst for catalytic oxidation treatment of organic wastewater, preparation method therefor, and application thereof | |
| CN105692865A (en) | Method for processing high-acid heavy crude oil processing wastewater | |
| CN108970620A (en) | A kind of preparation method removing Organic substance in water and total nitrogen ozone oxidation catalyst | |
| CN105664963A (en) | Ozone catalyst for water treatment and preparation method thereof | |
| CN1817455A (en) | Production of 3,4-dichloroaniline catalyst with 3,4-mirbane oil dichloride hydrogenation | |
| CN108623457A (en) | The catalytic decomposition process of formic acid | |
| CN102941084A (en) | Method for preparing double-component metallic oxide catalytic ozonation catalyst | |
| CN103406091B (en) | Method for preparation of titanate adsorbent from (methyl) acrylic acid production wastewater | |
| CN105854900A (en) | Catalytic wet oxidation catalyst applied to harmless treatment of ammonia-nitrogen wastewater and preparation method thereof | |
| CN111111664A (en) | Catalyst for Fenton-like continuous treatment of low-concentration organic wastewater and preparation method and application thereof | |
| CN1947840A (en) | Method for preparing heteropoly acid/ordered mesic porous silicon oxide catalyst, and its application | |
| CN104628118B (en) | Catalytic Wet Air Oxidation for Wastewater processing method | |
| CN103990452A (en) | Catalyst and catalyst carrier for deep treatment of waste water and preparation methods of catalyst and catalyst carrier | |
| CN106881090A (en) | A kind of ozone catalytic oxidation catalyst method of modifying | |
| CN109985616A (en) | Catalyst for photocatalytic degradation of organic wastewater and preparation method thereof | |
| CN107552067A (en) | A kind of material for water treatment and its application | |
| CN101323794B (en) | Spherical active carbon fuel oil adsorption desulfurizing agent and preparation thereof | |
| CN105439311A (en) | Coal chemical industrial wastewater deep treatment apparatus and method | |
| CN103320159A (en) | Method for removing mercaptan sulfur contained in catalytically cracked gasoline |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20170427 Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Applicant after: China National Offshore Oil Corporation Applicant after: China National Offshore Oil Corporation Applicant after: CNOOC Huizhou Petrochemical Co., Ltd. Address before: 100010 Beijing City, Dongcheng District Chaoyangmen No. 25 North Street CNOOC building Applicant before: China National Offshore Oil Corporation Applicant before: China National Offshore Oil Corporation Applicant before: Huizhou Refinery Branch, CNOOC Oil & Petrochemicals Co., Ltd. |
|
| TA01 | Transfer of patent application right | ||
| CB02 | Change of applicant information |
Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Applicant after: China Offshore Oil Group Co., Ltd. Applicant after: China National Offshore Oil Corporation Applicant after: CNOOC Huizhou Petrochemical Co., Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Applicant before: China National Offshore Oil Corporation Applicant before: China National Offshore Oil Corporation Applicant before: CNOOC Huizhou Petrochemical Co., Ltd. |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |