CN104492454A - Catalyst for eliminating benzene dichloride through complete catalytic oxidation and preparation method of catalyst - Google Patents
Catalyst for eliminating benzene dichloride through complete catalytic oxidation and preparation method of catalyst Download PDFInfo
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- CN104492454A CN104492454A CN201410785851.1A CN201410785851A CN104492454A CN 104492454 A CN104492454 A CN 104492454A CN 201410785851 A CN201410785851 A CN 201410785851A CN 104492454 A CN104492454 A CN 104492454A
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- coxmnyo
- benzenes
- dichloro
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Abstract
The invention relates to a catalyst for eliminating benzene dichloride through complete catalytic oxidation and a preparation method of the catalyst. The catalyst is prepared by the following steps: adding citric acid monohydrate into a 0.1mol/L mixed solution containing a cobalt salt and a manganese salt according to a mole ratio of citric acid monohydrate to the sum of cobalt and manganese of 0.50-0.70, wherein the mole ratio of Mn/(Co+Mn) is equal to 0.08-0.75; when the citric acid monohydrate is completely dissolved, transferring the mixed solution to a spin steaming instrument; performing spin steaming at 20-25 DEG C until colloid is generated; then heating to 60-75 DEG C, and performing spin steaming for a whole night; drying obtained citrate at 80-110 DEG C; and roasting for 4 hours at 350-600 DEG C to obtain a manganese doped cobalt tetroxide catalyst. The catalyst provided by the invention is used for eliminating benzene dichloride through low-temperature catalytic combustion, is high in activity, less in byproduct and good in stability.
Description
Technical field
The invention belongs to catalysis environmental technology field, particularly a kind of Catalysts and its preparation method eliminated for dichloro-benzenes complete catalysts oxidation.
Background technology
Many chlorination aromatic hydrocarbons organic pollution is present in city garbage burning waste gas, industrial waste gas, power plant exhaust widely, wherein many chlorodiphenyls and to dioxin (PCDD) and many chlorine biphenyl furans (PCDF) stable chemical nature, accumulation can be produced in vivo, belong to highly toxic, carcinogenic, can to the ecosystem can cause lasting, accumulate sex organic pollution.Therefore, a lot of country has formulated stricter environmental legislation for the discharge of PCDD/PCDF now.
Owing to still not possessing possibility from pollution abatement on source, and adopt the method for post processing to eliminate pollution that many chlorination aromatic hydrocarbons bring becomes the approaches and methods of unique feasible.Removing method at present about many chlorination aromatic hydrocarbons is mainly divided into physical method, biological method and chemical method.Wherein chemical method is divided into again catalytic hydrogenation and dechlorination method, photocatalytic degradation method and complete oxidation method.Catalytic combustion possesses that operating temperature low (250 DEG C-550 DEG C), pollution abatement substrate concentration are wide, product (CO
2, HCl and H
2o) selective high.Therefore, complete oxidation method is widely used in elimination volatile organic compound.
Because bioxin has hypertoxicity, so generally adopt the presomas such as chlorobenzene, dichloro-benzenes or chlorophenol to screen catalyst as Model Molecule and investigate under experimental conditions.As far back as the forties in 20th century, people is just had to be studied its bio-toxicity and mutagenesis, teratogenesis and carcinogenicity with dichloro-benzenes Mo Ni bioxin pollutant abroad.
The catalyst eliminated completely for bioxin pollutant catalytic oxidation at present mainly comprises noble metal catalyst, solid acid catalyst and catalyst of transition metal oxide.Wherein catalyst of transition metal oxide is because it is cheap, relatively stable the obtaining of character is studied widely.Mainly V is concentrated at present for the good catalyst of transition metal oxide of chlorohydrocarbon low-temperature catalytic oxidation elimination activity
2o
5-TiO
2-catalyst based, CaCO
3/-Fe
2o
3, Fe-Ca-Ox/TiO
2deng.But due to V
2o
5-TiO
2-catalyst based middle V
2o
5there is toxicity, easily cause secondary pollution, limit its application; CaCO
3/-Fe
2o
3catalyst is easy inactivation in the reaction atmosphere having water.In addition, the catalyst much eliminated about chlorohydrocarbon complete catalysts oxidation can produce a large amount of polystream in application process, pollutes more serious.Therefore, develop cheap, high-efficiency environment friendly, stable in properties catalyst still to have great importance.
Summary of the invention
In order to overcome the deficiency that prior art exists, the invention provides the Catalysts and its preparation method that a kind of dichloro-benzenes complete catalysts oxidation is eliminated.
Dichloro-benzenes complete catalysts oxidation eliminates a preparation method for catalyst, it is characterized in that, comprises the following steps:
According to mol ratio monohydrate potassium/(cobalt+manganese)=0.50 ~ 0.70, monohydrate potassium being joined 0.1 mole often liter contains in the mixed solution of cobalt salt and manganese salt, wherein mol ratio Mn/ (Co+Mn)=0.08-0.75, being transferred to by mixed solution to revolve after monohydrate potassium dissolves completely steams on instrument, steam until there is colloid to generate at 20 ~ 50 DEG C of condition backspins, then be warming up to 60 ~ 75 DEG C to spend the night and revolve steaming, by dry under 80 ~ 110 DEG C of conditions for the citrate obtained, roasting 2 ~ 4 hours at 350 ~ 600 DEG C, can obtain four cobalt oxide catalysts of additive Mn.
Described cobalt salt is cobalt nitrate or cobalt chloride, and described manganese salt is manganese nitrate or manganese acetate.
The catalyst that dichloro-benzenes complete catalysts oxidation is eliminated, is characterized in that, prepare according to above-mentioned either method.
The catalyst that described dichloro-benzenes complete catalysts oxidation is eliminated, is characterized in that, reactivity order is: CoxMnyO
4(y/ (x+y)=0.10) >CoxMnyO
4(0.14) >CoxMnyO
4(0.08) > CoxMnyO
4(0.18) > Co
3o
4>CoxMnyO
4(0.25) > CoxMnyO
4(0.50).
The catalyst that described dichloro-benzenes complete catalysts oxidation is eliminated, is characterized in that, in reaction end gas, the most high selectivity order of trichloro-benzenes is: Co
3o
4> CoxMnyO
4(0.08) > CoxMnyO
4(0.10) > CoxMnyO
4(0.14) > CoxMnyO
4(0.18) > CoxMnyO
4(0.25)=CoxMnyO
4(0.50).
The catalyst that described dichloro-benzenes complete catalysts oxidation is eliminated, it is characterized in that, dichloro-benzenes concentration is 1000ppm, and air speed is 15000mlg
-1h
-1under condition, CoxMnyO
4(y/ (x+y)=0 ~ 0.18) catalyst has no inactivation in 100h.
Catalyst provided by the invention has the features such as preparation technology is simple, cheap, catalytic activity is high, anti-fluorine poisoning ability is strong, accessory substance is few, the life-span is long; Technology path is convenient and practical, can be widely used in the low-temperature catalyzed purification of dioxin contamination thing in the catalytic combustion elimination of the chloride volatile organic pollution in papermaking, pharmacy, process hides, washing and city garbage burning, power plant exhaust.
Detailed description of the invention
Embodiment 1:
3.5g monohydrate potassium is joined in 250ml 0.1mol/L cobalt nitrate solution, being transferred to by mixed solution to revolve after monohydrate potassium dissolves completely steams on instrument, steam until there is colloid to generate at 40 DEG C of condition backspins, then be warming up to 65 DEG C to spend the night and revolve steaming, by dry under 110 DEG C of conditions for the citrate obtained, at 550 DEG C, roasting 4 hours, obtains Co
3o
4catalyst, is denoted as Co
3o
4.
Embodiment 2:
3.5g monohydrate potassium being joined 250ml 0.1mol/L contains in the mixed solution of cobalt nitrate and manganese nitrate, wherein mol ratio Mn/ (Co+Mn)=0.08, being transferred to by mixed solution to revolve after monohydrate potassium dissolves completely steams on instrument, steam until there is colloid to generate at 40 DEG C of condition backspins, then be warming up to 65 DEG C to spend the night and revolve steaming, by dry under 110 DEG C of conditions for the citrate obtained, roasting 4 hours at 550 DEG C, four cobalt oxide catalysts of additive Mn can be obtained, be denoted as CoxMnyO
4(0.08).
Embodiment 3:
Prepare the cobalt Mn complex oxide catalyst of Mn/ (Co+Mn)=0.10 according to the method for embodiment 2, be denoted as CoxMnyO
4(0.10).
Embodiment 4:
Prepare the cobalt Mn complex oxide catalyst of Mn/ (Co+Mn)=0.14 according to the method for embodiment 2, be denoted as CoxMnyO
4(0.14).
Embodiment 5:
Prepare the cobalt Mn complex oxide catalyst of Mn/ (Co+Mn)=0.18 according to the method for embodiment 2, be denoted as CoxMnyO
4(0.18).
Embodiment 6:
Prepare the cobalt Mn complex oxide catalyst of Mn/ (Co+Mn)=0.25 according to the method for embodiment 2, be denoted as CoxMnyO
4(0.25).
Embodiment 7:
Prepare the cobalt Mn complex oxide catalyst of Mn/ (Co+Mn)=0.50 according to the method for embodiment 2, be denoted as CoxMnyO
4(0.50).
Embodiment 8:
Used catalyst activity rating for o-dichlorohenzene catalytic combustion carries out in fixed-bed micro-reactor (internal diameter 3mm quartz), and the consumption of catalyst is 200mg, and temperature adopts K type thermocouple automatically to control.Adopt 100 serial KDS120 type micro-injection pumps of Stoelting company of the U.S. that o-dichlorohenzene injection is entered vaporizer, be then mixed into reactor with air and burn.Total flow adopts mass flowmenter to control, and the concentration of o-dichlorohenzene is 0.1vol%, and the exhausted air quantity of every gram of catalyst process per hour is 15L, and the linear velocity through the gas of reactor is 100m/h, and reaction pressure is 0.1MPa.The conversion ratio of o-dichlorohenzene and the relation of reaction temperature are in table 1, and in table, T10%, T50%, T90% are respectively conversion ratio and reach 10%, 50%, 90% time institute
The reaction temperature needed.Reaction end gas is through chromatogram and mass spectrum on-line tracing, and key reaction product is carbon dioxide, hydrogen chloride and a small amount of chlorine, and the amount of the trichloro-benzenes wherein different catalysts produced is in table 2.
O-dichlorohenzene catalytic oxidation performance in table 1 different catalysts
Shown in table 1, result shows, additive Mn can significantly improve the activity of cobalt oxide catalyst for dichloro-benzenes catalytic combustion, especially CoxMnyO
4(0.10) catalyst, concentration is 1000ppm, and air speed is 15000mlg
-1h
-1t under condition
50be 265 DEG C, T
90be 330 DEG C, the catalyst based activity of the V-Ti that its activity that is active and current industrial application is the highest is close, and CoxMnyO is described
4(0.10) catalyst application prospect is considerable.
Table 2 different catalysts produces the most high selectivity of trichloro-benzenes
Shown in table 2, result shows, and pure Co
3o
4compare, prepared CoxMnyO
4on catalyst, trichloro-benzenes is selective extremely low, as can be seen here, and prepared CoxMnyO
4catalyst can greatly reduce secondary pollution, and this exploitation for environmental protection catalyst has very important significance.
Embodiment 9:
Adopt the evaluating catalyst system identical with embodiment 8, keep reaction condition constant: the concentration of o-dichlorohenzene is 0.1vol%, and the exhausted air quantity of every gram of catalyst process per hour is 15L, and the linear velocity through the gas of reactor is 100m/h, and reaction pressure is 0.1MPa.Each catalyst life at investigating 300 DEG C, its result is as shown in table 3.
The o-dichlorohenzene catalytic oxidation life-span in table 3 different catalysts
Table 3 result shows CoxMnyO
4(y/ (x+y)=0 ~ 0.18) catalyst 100h not in see inactivation, good stability, key reaction product is carbon dioxide, hydrogen chloride and a small amount of chlorine, and this commercial Application for reality has very important significance.
Claims (6)
1. dichloro-benzenes complete catalysts oxidation eliminates a preparation method for catalyst, it is characterized in that, comprises the following steps:
According to mol ratio monohydrate potassium/(cobalt+manganese)=0.50 ~ 0.70, monohydrate potassium being joined 0.1 mole often liter contains in the mixed solution of cobalt salt and manganese salt, wherein mol ratio Mn/ (Co+Mn)=0.08-0.75, being transferred to by mixed solution to revolve after monohydrate potassium dissolves completely steams on instrument, steam until there is colloid to generate at 20 ~ 50 DEG C of condition backspins, then be warming up to 60 ~ 75 DEG C to spend the night and revolve steaming, by dry under 80 ~ 110 DEG C of conditions for the citrate obtained, roasting 2 ~ 4 hours at 350 ~ 600 DEG C, can obtain four cobalt oxide catalysts of additive Mn.
2. dichloro-benzenes complete catalysts oxidation according to claim 1 eliminates the preparation method of catalyst, and it is characterized in that, described cobalt salt is cobalt nitrate or cobalt chloride, and described manganese salt is manganese nitrate or manganese acetate.
3. a catalyst for dichloro-benzenes complete catalysts oxidation elimination, it is characterized in that, according to above-mentioned arbitrary claim, method prepares.
4. the catalyst of dichloro-benzenes complete catalysts oxidation elimination according to claim 3, is characterized in that, reactivity order is: CoxMnyO
4(y/ (x+y)=0.10) >CoxMnyO
4(0.14) >CoxMnyO
4(0.08) > CoxMnyO
4(0.18) > Co
3o
4>CoxMnyO
4(0.25) > CoxMnyO
4(0.50).
5. the catalyst eliminated of dichloro-benzenes complete catalysts oxidation according to claim 3, is characterized in that, in reaction end gas, the most high selectivity order of trichloro-benzenes is: Co
3o
4> CoxMnyO
4(0.08) > CoxMnyO
4(0.10) > CoxMnyO
4(0.14) > CoxMnyO
4(0.18) > CoxMnyO
4(0.25)=CoxMnyO
4(0.50).
6. the catalyst of dichloro-benzenes complete catalysts oxidation elimination according to claim 3, it is characterized in that, dichloro-benzenes concentration is 1000ppm, and air speed is 15000mlg
-1h
-1under condition, CoxMnyO
4(y/ (x+y)=0 ~ 0.18) catalyst has no inactivation in 100h.
Priority Applications (1)
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|---|---|---|---|
| CN201410785851.1A CN104492454B (en) | 2014-12-18 | 2014-12-18 | Catalyst for eliminating benzene dichloride through complete catalytic oxidation and preparation method of catalyst |
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|---|---|---|---|
| CN201410785851.1A CN104492454B (en) | 2014-12-18 | 2014-12-18 | Catalyst for eliminating benzene dichloride through complete catalytic oxidation and preparation method of catalyst |
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| CN104492454B CN104492454B (en) | 2017-02-22 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112547091A (en) * | 2019-09-26 | 2021-03-26 | 中国石油化工股份有限公司 | Combined catalyst and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08113543A (en) * | 1994-10-17 | 1996-05-07 | Toagosei Co Ltd | Production of monochlorobenzene and production of para-and ortho-dichlorobenzene utilizing the same |
| CN103894200A (en) * | 2014-04-22 | 2014-07-02 | 华东理工大学 | Method and catalyst for low-temperature catalytic combustion elimination of polychlorinated aromatic hydrocarbon |
-
2014
- 2014-12-18 CN CN201410785851.1A patent/CN104492454B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08113543A (en) * | 1994-10-17 | 1996-05-07 | Toagosei Co Ltd | Production of monochlorobenzene and production of para-and ortho-dichlorobenzene utilizing the same |
| CN103894200A (en) * | 2014-04-22 | 2014-07-02 | 华东理工大学 | Method and catalyst for low-temperature catalytic combustion elimination of polychlorinated aromatic hydrocarbon |
Non-Patent Citations (1)
| Title |
|---|
| 蔡婷: ""CoxMny催化剂低温催化燃烧1,2-二氯苯的研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112547091A (en) * | 2019-09-26 | 2021-03-26 | 中国石油化工股份有限公司 | Combined catalyst and preparation method and application thereof |
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| CN104492454B (en) | 2017-02-22 |
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