CN108355670A - A kind of preparation method and application of the carbon monoxide-olefin polymeric of degradation low concentration formaldehyde - Google Patents
A kind of preparation method and application of the carbon monoxide-olefin polymeric of degradation low concentration formaldehyde Download PDFInfo
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- CN108355670A CN108355670A CN201711418263.4A CN201711418263A CN108355670A CN 108355670 A CN108355670 A CN 108355670A CN 201711418263 A CN201711418263 A CN 201711418263A CN 108355670 A CN108355670 A CN 108355670A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2257/00—Components to be removed
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- B01D2257/708—Volatile organic compounds V.O.C.'s
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The present invention provides a kind of preparation method and application of the carbon monoxide-olefin polymeric of degradation low concentration formaldehyde.Composite oxides in the carbon monoxide-olefin polymeric are bismuth antimony Cu-Mn complex oxide.The method follows these steps to carry out：1, dissolution of raw material and basified；2, potassium persulfate solution is added；3, it dries；4, it calcines.Carbon monoxide-olefin polymeric activity prepared by the present invention is high, can in a relatively short period of time quickly and also efficiently catalyzing and oxidizing degrading waste water in formaldehyde, wastewater treatment method can carry out under normal temperature and pressure and without oxidant and illumination, technological process is simple, non-secondary pollution generates, and the features such as operating cost is low, and catalyst is reusable repeatedly, there is very high actual application value.
Description
Technical field：
The present invention relates to field of inorganic material preparing technology, it is related specifically to a kind of carbon monoxide-olefin polymeric of degradation low concentration formaldehyde
Preparation method and application.
Background technology：
Formaldehyde is soluble easily in water and has intense stimulus smell.It is a kind of important industrial chemicals, is widely used in sterilizing, kill
The industries such as bacterium, anti-corrosion, pharmacy, pesticide, dyestuff, plastics and building.But formaldehyde has the toxicity of height, by world health group
It knits and is determined as carcinogenic and causes deformed material.Currently, the method for removing formaldehyde in waste water has absorption method, Ozonation, photocatalysis
Method, hot wet oxidation process, bioanalysis, blow-off method etc..Absorption method poor selectivity, regeneration are difficult.The ozone that Ozonation utilizes
It is very big to human health damage.Photocatalytic method processing is needed with specific excitation light source.Current most popular titanium dioxide
Photochemical catalyst can only utilize ultraviolet light.Hot wet oxidation process energy expenditure is high.Biochemical method is at low cost, but reaction speed is slow,
Treatment facility takes up a large area.Blow-off method is ineffective.
Catalysis oxidation formaldehyde is a kind of method effectively removing formaldehyde at room temperature.It receives extensive attention in recent years.But
The catalyst for being this method all includes at least one noble metal.The Pt/SnO of United States Patent (USP) US5585083 inventions2Catalyst is in room
Temperature can be degradable for carbon dioxide and water by formaldehyde.But the noble metal for being 12% containing mass fraction in the catalyst
Pt.Chinese patent CN103071489A discloses a kind of preparation side of the carried active carbon catalysis material of the formaldehyde of removal at room temperature
Method.Include in the catalysis material 0.1~2% gold, palladium, platinum, rhodium, a kind of or combinations thereof noble metal active group in ruthenium
Point.Chinese patent CN102139234A discloses a kind of loaded catalyst removing formaldehyde at room temperature.Its active component be gold,
The noble metal of one or more of palladium, platinum, rhodium, ruthenium.Bullion content accounts for the 0.1~2% of catalyst weight.Precious Metals Resources
Rare and price is high, and the promotion and application for touching formaldehyde are gone which has limited greenhouse catalysis oxidation.
Invention content：
Present invention aims at provide a kind of preparation method and application of the carbon monoxide-olefin polymeric of degradation low concentration formaldehyde.In view of
This, design philosophy of the invention is to solve the above-mentioned technical problems in the prior art, provides a kind of simple and effective processing
The preparation method and application of the carbon monoxide-olefin polymeric of formaldehyde in waste water.
To achieve the above object, the technical scheme is that:
A kind of carbon monoxide-olefin polymeric of degradation low concentration formaldehyde, including composite oxides are compound in the carbon monoxide-olefin polymeric
Oxide is bismuth antimony Cu-Mn complex oxide, and the bismuth antimony Cu-Mn complex oxide is as in catalyst energy catalyzing oxidizing degrading waste water
Formaldehyde.
A kind of carbon monoxide-olefin polymeric preparation method of degradation low concentration formaldehyde, the method carry out as follows：
1, dissolution of raw material and basified：Using bismuth nitrate, antimony trichloride, copper nitrate and manganese nitrate as raw material, it is added in beaker
Deionized water is simultaneously stirred to dissolving, and the ammonium hydroxide of a concentration of 6mol/L is then added dropwise, until solution is alkalescent, pH value is 8 at this time
~10；
2, potassium persulfate solution is added：The mistake that concentration of volume percent is 5% is added in the weakly alkaline solution obtained to step 1
Potassium sulfate solution 5mL is heated to boiling, and is filtered after being cooled to room temperature；
3, it dries：The sediment that step 2 is obtained is put into baking oven and is dried at a temperature of 105-150 DEG C；
4, it calcines：Drying sediment obtained by step 3 is put into Muffle furnace, in 300 DEG C~900 DEG C temperature lower calcinations 3-8 hours,
Bismuth antimony Cu-Mn complex oxide powder is obtained after calcining.
The molar ratio of bismuth nitrate, antimony trichloride, copper nitrate and manganese nitrate in the method is 22.6:16.9：8.9:
1.0。
A kind of application of the carbon monoxide-olefin polymeric of degradation low concentration formaldehyde, is added in waste water in the ratio of 0.5~4.0g/L
Enter the bismuth antimony Cu-Mn complex oxide of acquisition, stir process 30-60 minutes at normal temperatures and pressures.
The present invention bismuth antimony Cu-Mn complex oxide catalyst be applied to formaldehyde waste water processing method be：With combined oxidation
Object is catalyst, and degradation conditions are：Concentration of formaldehyde be less than 5%, processing every liter of formaldehyde waste water catalyst amount be 0.5~
4.0g, waste water system are in normal temperature and pressure.In experiment, when formaldehyde waste water volume is 40mL, when a concentration of 1.0%, under stiring plus
Enter catalyst 0.1g, catalytic degradation 30 minutes, the degradation rate of formaldehyde reaches 90% or more.Residual solution is replaced with to new formaldehyde
It is recycled that catalyst is carried out after solution again.The result shows that first of the catalyst in second of cycle, third time recycle
The degradation rate of aldehyde all reaches 90.0% or more.
The positive effect of the present invention is
1, carbon monoxide-olefin polymeric preparation method used in the present invention is simple, and raw materials are of low cost, easy to operate；
2, the carbon monoxide-olefin polymeric activity of the invention for preparing processing is high, quick and efficient degradation can pollute in a relatively short period of time
Object；
3, wastewater treatment method of the invention can carry out under normal temperature and pressure and without oxidant and without illumination, technique stream
The features such as journey is simple, and non-secondary pollution generates, and operating cost is low, there is very high actual application value；
4, it is reusable repeatedly to prepare the carbon monoxide-olefin polymeric handled by the present invention.
Specific embodiment
Clear, complete description further is carried out to technical scheme of the present invention with reference to embodiment.
Embodiment 1：
1, dissolution of raw material and basified：Weigh 1.82g（5.04×10-3mol）Five water bismuth nitrates, 0.86g（3.77×10- 3mol）Antimony trichloride, 0.48g（1.99×10-3mol）Nitrate trihydrate copper and 0.08g（2.23×10-4mol）(50% is molten for manganese nitrate
Liquid), addition deionized water is stirred to being completely dissolved in beaker, and the ammonium hydroxide of a concentration of 6mol/L is then added dropwise, until solution is
Alkalescent, pH value is 8~10 at this time；
2, potassium persulfate solution is added：The mistake that concentration of volume percent is 5% is added in the weakly alkaline solution obtained to step 1
Potassium sulfate 5mL is heated to boiling, and is filtered after being cooled to room temperature；
3, it dries：The sediment that step 2 is obtained is put into baking oven and is dried at a temperature of 105-150 DEG C；
4, it calcines：Drying sediment obtained by step 3 is put into Muffle furnace, it is multiple that bismuth antimony copper manganese is obtained after being calcined 8 hours at 300 DEG C
Close oxide powder.
It is 40mL to take 0.1 gram of bismuth antimony Cu-Mn complex oxide catalyst being prepared as stated above and volume is added,
In a concentration of 1.0% formaldehyde waste water, in normal temperature and pressure catalytic degradation formaldehyde 30 minutes under stirring.Then in centrifuge
Upper centrifugation 10 minutes, takes supernatant to measure residual formaldehyde concentration.The results are shown in Table 1, when degradation time is 30 minutes, formaldehyde
Degradation rate is 90.0%.
The degradation rate of table 1 degradation time and formaldehyde in waste water
| The catalyst degradation time/min | 15 | 30 | 45 | 60 |
| Degradation Formaldehyde rate/% | 85.6 | 90.0 | 91.3 | 92.0 |
Embodiment 2
1, dissolution of raw material and basified：Weigh 1.82g（5.04×10-3mol）Five water bismuth nitrates, 0.86g（3.77×10- 3mol）Antimony trichloride, 0.48g（1.99×10-3mol）Nitrate trihydrate copper and 0.08g（2.23×10-4mol）(50% is molten for manganese nitrate
Liquid), addition deionized water is stirred to being completely dissolved in beaker, and the ammonium hydroxide of a concentration of 6mol/L is then added dropwise, until solution is
Alkalescent, pH value is 8~10 at this time；
2, potassium persulfate solution is added：The mistake that concentration of volume percent is 5% is added in the weakly alkaline solution obtained to step 1
Potassium sulfate 5mL is heated to boiling, and is filtered after being cooled to room temperature；
3, it dries：The sediment that step 2 is obtained is put into baking oven and is dried at a temperature of 105-150 DEG C；
4, it calcines:Drying sediment obtained by step 3 is put into Muffle furnace, it is multiple that bismuth antimony copper manganese is obtained after being calcined 5 hours at 750 DEG C
Close oxide powder.
It is 40mL to take 0.1 gram of bismuth antimony Cu-Mn complex oxide catalyst being prepared as stated above and volume is added,
In a concentration of 1.0% formaldehyde waste water, in normal temperature and pressure catalytic degradation formaldehyde 30 minutes under stirring.Then in centrifuge
Upper centrifugation 10 minutes, takes supernatant to measure residual formaldehyde concentration.When degradation time is 30 minutes, Degradation Formaldehyde rate is 92.2%.
Embodiment 3
1, dissolution of raw material and basified：Weigh 1.82g（5.04×10-3mol）Five water bismuth nitrates, 0.86g（3.77×10- 3mol）Antimony trichloride, 0.48g（1.99×10-3mol）Nitrate trihydrate copper and 0.08g（2.23×10-4mol）(50% is molten for manganese nitrate
Liquid), addition deionized water is stirred to being completely dissolved in beaker, and the ammonium hydroxide of a concentration of 6mol/L is then added dropwise, until solution is
Alkalescent, pH value is 8~10 at this time；
2, potassium persulfate solution is added：The mistake that concentration of volume percent is 5% is added in the weakly alkaline solution obtained to step 1
Potassium sulfate 5mL is heated to boiling, and is filtered after being cooled to room temperature；
3, it dries：The sediment that step 2 is obtained is put into baking oven and is dried at a temperature of 105-150 DEG C；
4, it calcines：Drying sediment obtained by step 3 is put into Muffle furnace, bismuth antimony copper manganese composite oxygen is obtained after being calcined at 900 DEG C
Compound powder.
It is 40mL to take 0.1 gram of bismuth antimony Cu-Mn complex oxide catalyst being prepared as stated above and volume is added,
In a concentration of 1.0% formaldehyde waste water, in normal temperature and pressure catalytic degradation formaldehyde 30 minutes under stirring.Then in centrifuge
Upper centrifugation 10 minutes, takes supernatant to measure residual formaldehyde concentration.When degradation time is 30 minutes, Degradation Formaldehyde rate is 92.8%.
Embodiment 4
In order to investigate the recycling situation of catalyst, the preparation method of catalyst obtains described in Example 2 bismuth antimony copper manganese
Composite oxides carry out continuous catalyzing oxidizing degrading aldehyde test three times, and each degradation time is 30 minutes.
It is added in the beaker for a concentration of 1.0% formalin for filling 40mL and closes oxide by the bismuth antimony copper manganese of 0.10g
Catalyst, under magnetic agitation effect, in normal temperature and pressure catalytic degradation formaldehyde 30 minutes under stirring.Then in centrifuge
Upper centrifugation 10 minutes, takes supernatant to measure residual formaldehyde concentration.Supernatant after centrifugation is sucked out with dropper, leaves behind catalyst
1.0% new formalins of 40mL are added in solid portion, repeat above-mentioned degradation of formaldehyde process, and so cycle is followed for the second time
Ring, third time cycle down solution aldehyde test, the results are shown in Table 2.
2 catalyst circulation degradation of formaldehyde of table
| Catalyst access times | 1 | 2 | 3 |
| Degradation Formaldehyde rate/% | 92.2 | 91.0 | 90.3 |
As can be seen from Table 2, for the degradation rate of catalyst degradation of formaldehyde in recycling three times all 90.0% or more, this shows bismuth antimony
Cu-Mn complex oxide catalyst being capable of circulating repetition use.
All features disclosed in this specification or disclosed all preparation method and application, in addition to mutually exclusive spy
Sign and/or step, using in addition, can combine in any way.This specification（Including claim, abstract）Disclosed in
Any feature can be replaced by other alternative features that are equivalent or have similar purpose unless specifically stated.It is i.e. unless special
It does not describe, each feature is an example in a series of equivalent or similar characteristics.
Described above is only the non-limiting embodiment of invention, a large amount of embodiment can also be derived, for this field
Those of ordinary skill for, not departing from the invention design and under the premise of do not make creative work, can also do
Go out the embodiment of several modifications and improvements, these are all within the scope of protection of the present invention.
Claims (4)
1. a kind of carbon monoxide-olefin polymeric of degradation low concentration formaldehyde, including composite oxides, it is characterised in that：The catalyst group
The composite oxides closed in object are bismuth antimony Cu-Mn complex oxide, which can be catalyzed oxygen as catalyst
Change the formaldehyde in degrading waste water.
2. a kind of carbon monoxide-olefin polymeric preparation method of degradation low concentration formaldehyde, it is characterised in that：The method is as follows
It carries out：
（1）Dissolution of raw material and basified：Using bismuth nitrate, antimony trichloride, copper nitrate and manganese nitrate as raw material, it is added in beaker
Deionized water is simultaneously stirred to dissolving, and the ammonium hydroxide of a concentration of 6mol/L is then added dropwise, until solution is alkalescent, pH value is 8 at this time
~10；
（2）Add potassium persulfate solution：To step（1）It is 5% that concentration of volume percent is added in the weakly alkaline solution obtained
Potassium persulfate solution 5mL is heated to boiling, and is filtered after being cooled to room temperature；
（3）Drying：By step（2）The sediment obtained is put into baking oven and is dried at a temperature of 105-150 DEG C；
（4）Calcining：By step（3）Gained drying sediment is put into Muffle furnace, small in 300 DEG C~900 DEG C temperature lower calcination 3-8
When, bismuth antimony Cu-Mn complex oxide powder is obtained after calcining.
3. the carbon monoxide-olefin polymeric preparation method and application of degradation low concentration formaldehyde according to claim 2, feature exist
In：The molar ratio of bismuth nitrate, antimony trichloride, copper nitrate and manganese nitrate in the method is 22.6:16.9：8.9: 1.0.
4. a kind of application of the carbon monoxide-olefin polymeric of degradation low concentration formaldehyde, it is characterised in that：0.5~4.0g/L is pressed in waste water
Ratio be added obtain bismuth antimony Cu-Mn complex oxide, stir process 30-60 minutes at normal temperatures and pressures.
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Citations (5)
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|---|---|---|---|---|
| CN102139234A (en) * | 2011-01-06 | 2011-08-03 | 梁耀彰 | Loaded reduced precious metal catalyst as well as preparation method and application thereof |
| CN103071489A (en) * | 2011-10-25 | 2013-05-01 | 上海纳米技术及应用国家工程研究中心有限公司 | Supported active carbon catalytic material capable of eliminating formaldehyde at room temperature and preparation method thereof |
| CN106238065A (en) * | 2016-07-08 | 2016-12-21 | 宁波钛安新材料科技有限公司 | A kind of composite catalyst being catalyzed Formaldehyde decomposition and preparation method thereof |
| CN106622260A (en) * | 2016-12-09 | 2017-05-10 | 湖北工业大学 | Preparation method and application of catalyst for treating low-concentration formaldehyde wastewater |
| CN106824172A (en) * | 2016-12-09 | 2017-06-13 | 湖北工业大学 | The carbon monoxide-olefin polymeric preparation method and application of low concentration formaldehyde in treatment waste water |
-
2017
- 2017-12-25 CN CN201711418263.4A patent/CN108355670B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102139234A (en) * | 2011-01-06 | 2011-08-03 | 梁耀彰 | Loaded reduced precious metal catalyst as well as preparation method and application thereof |
| CN103071489A (en) * | 2011-10-25 | 2013-05-01 | 上海纳米技术及应用国家工程研究中心有限公司 | Supported active carbon catalytic material capable of eliminating formaldehyde at room temperature and preparation method thereof |
| CN106238065A (en) * | 2016-07-08 | 2016-12-21 | 宁波钛安新材料科技有限公司 | A kind of composite catalyst being catalyzed Formaldehyde decomposition and preparation method thereof |
| CN106622260A (en) * | 2016-12-09 | 2017-05-10 | 湖北工业大学 | Preparation method and application of catalyst for treating low-concentration formaldehyde wastewater |
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| Title |
|---|
| 伊邦跃等: "《陶瓷核燃料工艺》", 28 February 2015, 哈尔滨工程大学出版社 * |
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