CN106466603A - Resistance to high salt ozone catalyst and preparation method thereof - Google Patents
Resistance to high salt ozone catalyst and preparation method thereof Download PDFInfo
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- CN106466603A CN106466603A CN201510508937.4A CN201510508937A CN106466603A CN 106466603 A CN106466603 A CN 106466603A CN 201510508937 A CN201510508937 A CN 201510508937A CN 106466603 A CN106466603 A CN 106466603A
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Abstract
The present invention discloses a kind of resistance to high salt ozone catalyst, is grouped into by the group of following weight portion：Particle diameter is 88.7～91.3 parts of the activated alumina particle of 2～4mm, 1.4～1.6 parts of copper oxide, 0.8～1.2 part of titanium dioxide, 4～7 parts of Polyethylene Glycol, 1.9～2.1 parts of polyvinyl alcohol, by described particle diameter be 2～4mm 88.7～91.3 parts of activated alumina particle and 1.4～1.6 parts of copper oxide, 0.8～1.2 part of titanium dioxide, 4～7 parts of Polyethylene Glycol, 1.9～2.1 parts of polyvinyl alcohol mixes in stirring mixer, so that uniform 1.4～1.6 parts of mixed copper oxide, 0.8～1.2 part of titanium dioxide, 4～7 parts of Polyethylene Glycol, 1.9～2.1 parts of polyvinyl alcohol is covered in described activated alumina particle surface and forms catalyst mother bulb；Again catalyst mother bulb is dried successively, roasting obtains described resistance to high salt ozone catalyst.The present invention improves the tolerance to high salts substances so that in the catalytic oxidation treatment process to saline sewage, keeping good effect to the biodegradability of the removal of waste water COD, decolouring, de- stench, degraded toxic pollutant and raising waste water.
Description
Technical field
The present invention relates to a kind of resistance to high salt ozone catalyst and preparation method thereof, belong to ozonation technology field.
Background technology
RO technology has been widely used for the numerous areas such as electronics, chemical industry, desalinization, chemical engineering sewage reuse,
There is irreplaceable advantage.Using RO PROCESS FOR TREATMENT sewage, 1/3 condensed water (concentrated water) can be produced,
Contain the refractory organic compounds being detrimental to health with ecological environment in concentrated water, its concentration exceedes discharge mark more
The appropriate process of standard, therefore concentrated water is the widely used bottleneck of RO technology.
Reverse osmosiss (RO) membrane process, while producing high-quality water, also creates the high saliferous being concentrated organic
Waste water.In such waste water, COD is generally more than discharge standard it is impossible to directly discharge.This water process difficulty is very big,
Method effectively is there is no to carry out this waste water of individual processing at present.Dense Organic substance in water is essentially the Organic substance of the dissolved,
The chemical property of micro quantity organic pollutant and biochemical property are all relatively stable, and the TDS in concentrated water is (always molten simultaneously
Solution property solid) concentration higher (TDS ＞ 4000mg/L), particularly it is rich in the inorganic ionss such as chloride ion.Such
The feature of sewage makes this sewage can neither be processed by the way of biological oxidation, again can not be using flocculation
The physical treatment method such as filtration.Similarly, since the presence of substantial amounts of inorganic salt have impact on oxidation processes effect in water
Rate is so that independent efficiency by the way of oxidation processes is also affected.
Degradation speed is fast, oxidation efficiency is high, do not produce secondary dirt because having for heterogeneous catalytic ozonation technology
The features such as dye, reaction condition are gentle, is widely used in advanced treatment of wastewater field at present, but in saline sewage
Process in, by salts substances such as C1-, SO42-, Na+, Ca2+, catalytic oxidation process is affected, smelly
Oxygen catalytic oxidation technique can not obtain good treatment effect all the time.The impact of salts substances becomes ozone and urges
Change the bottleneck influence factor of oxidation processes brine waste.
Content of the invention
It is an object of the present invention to provide a kind of resistance to high salt ozone catalyst, it is right that this resistance to high salt ozone catalyst improves
The tolerance of high salts substances is so that in the catalytic oxidation treatment process to saline sewage, catalyst
Ozone, produces active hydroxyl radical free radical, poisonous to the removal of waste water COD, decolouring, de- stench, degraded
Pollutant and the biodegradability good effect of holding improving waste water；Meanwhile, provide a kind of above-mentioned resistance to high salt
The preparation method of ozone catalyst.
For reaching above-mentioned purpose, the first technical scheme that the present invention adopts is：A kind of resistance to high salt ozone catalyst,
Described resistance to high salt ozone catalyst is grouped into by the group of following weight portion：
By described particle diameter be 2～4mm 88.7～91.3 parts of activated alumina particle and 1.4～1.6 parts of copper oxide,
0.8～1.2 part of titanium dioxide, 4～7 parts of Polyethylene Glycol, 1.9～2.1 parts of polyvinyl alcohol are mixed in stirring mixer
Close so that uniformly 1.4～1.6 parts of mixed copper oxide, 0.8～1.2 part of titanium dioxide, Polyethylene Glycol 4～7
Part, 1.9～2.1 parts of polyvinyl alcohol are covered in described activated alumina particle surface and form catalyst mother bulb；Again will
Catalyst mother bulb is dried successively, roasting obtains described resistance to high salt ozone catalyst.
For reaching above-mentioned purpose, the second technical scheme that the present invention adopts is：A kind of above-mentioned ozone of resistance to high salt
The preparation method of catalyst, comprises the following steps：
Step one, 88.7～91.3 parts of activated alumina distilled water are cleaned for several times to remove the miscellaneous of its surface
Matter, and be dried to quality constant weight, the particle diameter of described activated alumina is 2～4mm；
Step 2,88.7～91.3 parts of activated aluminas that step one is obtained and 1.4～1.6 parts of copper oxide,
0.8～1.2 part of titanium dioxide, 4～7 parts of Polyethylene Glycol, 1.9～2.1 parts of polyvinyl alcohol are mixed in stirring mixer
Close so that uniformly 1.4～1.6 parts of mixed copper oxide, 0.8～1.2 part of titanium dioxide, Polyethylene Glycol 4～7
Part, 1.9～2.1 parts of polyvinyl alcohol are covered in described activated alumina particle surface and form catalyst mother bulb；
Step 3, take out described catalyst mother bulb from stirring mixer, after drying at room temperature, put into baking
Case, is dried under the conditions of 100～120 DEG C and obtains dried catalyst mother bulb；
Step 4, dried catalyst mother bulb is put in Muffle furnace, roasting under the conditions of 350～520 DEG C obtains
Obtain resistance to high salt ozone catalyst.
In technique scheme, further improved technical scheme is as follows：
Preferably, under the conditions of 100～120 DEG C, drying time is 4～6 hours in described step 3.
Preferably, under the conditions of 350～520 DEG C, roasting time is 7～9 hours in described step 4.
Because technique scheme is used, the present invention compared with prior art has following advantages and effect：
1st, the present invention resistance to high salt ozone catalyst and preparation method thereof, which raises the tolerance to high salts substances
Ability is so that in the catalytic oxidation treatment process to saline sewage, catalyst ozone produces active hydroxyl
Base free radical, to the removal of waste water COD, decolouring, de- stench, degraded toxic pollutant and raising waste water
Biodegradability keep good effect.
2nd, the present invention resistance to high salt ozone catalyst and preparation method thereof, its physical capacity of resistance to salt is strong, can be in TDS
Normally use in the waste water being not more than 8000mg/L, catalyst activity is high, low cost, and preparation method be simple,
Therefore for catalytic ozonation technology, the extensive application in saline sewage advanced treating has highly important meaning
Justice.
Specific embodiment
With reference to embodiment, the invention will be further described：
Embodiment 1～4：A kind of resistance to high salt ozone catalyst, described resistance to high salt ozone catalyst is by following weight portion
Group be grouped into, as shown in table 1：
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Activated alumina particle | 90 parts | 89.5 parts | 89 parts | 91 parts |
| Copper oxide | 1.55 part | 1.4 part | 1.6 part | 1.5 part |
| Titanium dioxide | 1.2 part | 0.85 part | 0.95 part | 1.1 part |
| Polyethylene Glycol | 5.5 part | 4.8 part | 6 parts | 6.5 part |
| Polyvinyl alcohol | 2 parts | 1.9 part | 1.95 part | 2.1 part |
Described activated alumina particle particle diameter is 2～4mm；
By described particle diameter be 2～4mm 88.7～91.3 parts of activated alumina particle and 1.4～1.6 parts of copper oxide,
0.8～1.2 part of titanium dioxide, 4～7 parts of Polyethylene Glycol, 1.9～2.1 parts of polyvinyl alcohol are mixed in stirring mixer
Close so that uniformly 1.4～1.6 parts of mixed copper oxide, 0.8～1.2 part of titanium dioxide, Polyethylene Glycol 4～7
Part, 1.9～2.1 parts of polyvinyl alcohol are covered in described activated alumina particle surface and form catalyst mother bulb；Again will
Catalyst mother bulb is dried successively, roasting obtains described resistance to high salt ozone catalyst.
The preparation method of the resistance to high salt ozone catalyst of above-described embodiment, comprises the following steps：
Step one, 88.7～91.3 parts of activated alumina distilled water are cleaned for several times to remove the miscellaneous of its surface
Matter, and be dried to quality constant weight, the particle diameter of described activated alumina is 2～4mm；
Step 2,88.7～91.3 parts of activated aluminas that step one is obtained and 1.4～1.6 parts of copper oxide,
0.8～1.2 part of titanium dioxide, 4～7 parts of Polyethylene Glycol, 1.9～2.1 parts of polyvinyl alcohol are mixed in stirring mixer
Close so that uniformly 1.4～1.6 parts of mixed copper oxide, 0.8～1.2 part of titanium dioxide, Polyethylene Glycol 4～7
Part, 1.9～2.1 parts of polyvinyl alcohol are covered in described activated alumina particle surface and form catalyst mother bulb；
Step 3, take out described catalyst mother bulb from stirring mixer, after drying at room temperature, put into baking
Case, is dried under the conditions of 100～120 DEG C and obtains dried catalyst mother bulb；
Step 4, dried catalyst mother bulb is put in Muffle furnace, roasting under the conditions of 350～520 DEG C obtains
Obtain resistance to high salt ozone catalyst.
In above-mentioned steps three under the conditions of 100～120 DEG C drying time be 5 hours, in above-mentioned steps four
Under the conditions of 350～520 DEG C, roasting time is 8 hours.
The present invention resistance to high salt ozone catalyst catalytic effect is evaluated, and experimental technique data is shown in Table 2：
In the test of dynamic continuous flow catalytic ozonation, catalyst amountses are 1.5L, ozone dosage
100mg/L, hydraulic detention time 1h, utilize gas flowmeter to control ozone dosage, by wriggling in experiment
Pump continuum micromeehanics.After running 3 cycle catalytic effect stabilities, repeatedly COD is measured by sampling, averages.
Experiment condition：Dynamic continuous flow operational mode, ozone dosage 100mg/L, HRT=1h.
Water inlet source：Certain factory RO concentrated water, COD about 350mg/L, TDS are 3500mg/L.
The Contrast on effect of the different ozone catalyst catalysis oxidation RO concentrated water of table 2
From table 2, data understands, urges with respect to Zhonghai Asphalt's conventional alumina ozone
Agent, resistance to high salt ozone catalyst catalysis oxidation RO concentrated water, is 100mg/L in ozone dosage, waterpower is stopped
The time is stayed to be under 1h service condition, COD clearance is up to 31%, ozone efficiency is 1.03, far superior to
Conventional ozone catalyst.
When therefore, using above-mentioned resistance to high salt ozone catalyst and preparation method thereof, which raises to high salt thing
The tolerance of matter is so that in the catalytic oxidation treatment process to saline sewage, catalyst ozone produces
Active hydroxyl radical free radical, to the removal of waste water COD, decolouring, de- stench, degraded toxic pollutant and
The biodegradability improving waste water keeps good effect；Secondly, its physical capacity of resistance to salt is strong, can be in TDS
Normally use in the waste water being not more than 8000mg/L, catalyst activity is high, low cost, and preparation method be simple,
Therefore for catalytic ozonation technology, the extensive application in saline sewage advanced treating has highly important meaning
Justice.
Above-described embodiment only technology design to illustrate the invention and feature, its object is to allow and is familiar with this skill
The personage of art will appreciate that present disclosure and implements according to this, can not limit the protection model of the present invention with this
Enclose.All equivalence changes made according to spirit of the invention or modification, all should cover the protection in the present invention
Within the scope of.
Claims (4)
1. a kind of resistance to high salt ozone catalyst it is characterised in that：Described resistance to high salt ozone catalyst is by following heavy
The group of amount part is grouped into：
By described particle diameter be 2～4mm 88.7～91.3 parts of activated alumina particle and 1.4～1.6 parts of copper oxide,
0.8～1.2 part of titanium dioxide, 4～7 parts of Polyethylene Glycol, 1.9～2.1 parts of polyvinyl alcohol are mixed in stirring mixer
Close so that uniformly 1.4～1.6 parts of mixed copper oxide, 0.8～1.2 part of titanium dioxide, Polyethylene Glycol 4～7
Part, 1.9～2.1 parts of polyvinyl alcohol are covered in described activated alumina particle surface and form catalyst mother bulb；Again will
Catalyst mother bulb is dried successively, roasting obtains described resistance to high salt ozone catalyst.
2. a kind of preparation method for the resistance to high salt ozone catalyst described in claim 1 it is characterised in that：
Comprise the following steps：
Step one, 88.7～91.3 parts of activated alumina distilled water are cleaned for several times to remove the miscellaneous of its surface
Matter, and be dried to quality constant weight, the particle diameter of described activated alumina is 2～4mm；
Step 2,88.7～91.3 parts of activated aluminas that step one is obtained and 1.4～1.6 parts of copper oxide,
0.8～1.2 part of titanium dioxide, 4～7 parts of Polyethylene Glycol, 1.9～2.1 parts of polyvinyl alcohol are mixed in stirring mixer
Close so that uniformly 1.4～1.6 parts of mixed copper oxide, 0.8～1.2 part of titanium dioxide, Polyethylene Glycol 4～7
Part, 1.9～2.1 parts of polyvinyl alcohol are covered in described activated alumina particle surface and form catalyst mother bulb；
Step 3, take out described catalyst mother bulb from stirring mixer, after drying at room temperature, put into baking
Case, is dried under the conditions of 100～120 DEG C and obtains dried catalyst mother bulb；
Step 4, dried catalyst mother bulb is put in Muffle furnace, roasting under the conditions of 350～520 DEG C obtains
Obtain resistance to high salt ozone catalyst.
3. resistance to high salt ozone catalyst according to claim 1 preparation method it is characterised in that：Institute
Stating in step 3 drying time under the conditions of 100～120 DEG C is 4～6 hours.
4. resistance to high salt ozone catalyst according to claim 1 preparation method it is characterised in that：Institute
Stating in step 4 roasting time under the conditions of 350～520 DEG C is 7～9 hours.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108704646A (en) * | 2018-05-10 | 2018-10-26 | 山东理工大学 | Composite ozone catalyst and preparation method thereof for COD in treated sewage |
Citations (4)
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|---|---|---|---|---|
| CN103127934A (en) * | 2011-12-01 | 2013-06-05 | 上海纳米技术及应用国家工程研究中心有限公司 | Metal net immobilization titanium dioxide photocatalyst and preparing method |
| CN104399464A (en) * | 2014-12-09 | 2015-03-11 | 齐鲁工业大学 | Photocatalyst for activation of organic chlorine inert pollutant molecules in water treatment process, as well as preparation method and application of photocatalyst |
| CN104646020A (en) * | 2013-11-18 | 2015-05-27 | 北京天灏柯润环境科技有限公司 | Ozone catalyst and preparation method |
| CN104759286A (en) * | 2015-03-12 | 2015-07-08 | 苏州清然环保科技有限公司 | Ozone catalyst preparation method |
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2015
- 2015-08-19 CN CN201510508937.4A patent/CN106466603A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103127934A (en) * | 2011-12-01 | 2013-06-05 | 上海纳米技术及应用国家工程研究中心有限公司 | Metal net immobilization titanium dioxide photocatalyst and preparing method |
| CN104646020A (en) * | 2013-11-18 | 2015-05-27 | 北京天灏柯润环境科技有限公司 | Ozone catalyst and preparation method |
| CN104399464A (en) * | 2014-12-09 | 2015-03-11 | 齐鲁工业大学 | Photocatalyst for activation of organic chlorine inert pollutant molecules in water treatment process, as well as preparation method and application of photocatalyst |
| CN104759286A (en) * | 2015-03-12 | 2015-07-08 | 苏州清然环保科技有限公司 | Ozone catalyst preparation method |
Non-Patent Citations (1)
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| 盛军波: "《苯加氢操作技术》", 31 January 2014 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108704646A (en) * | 2018-05-10 | 2018-10-26 | 山东理工大学 | Composite ozone catalyst and preparation method thereof for COD in treated sewage |
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Application publication date: 20170301 |