CN1068564C - Catalyst for treatment of waste water and its preparation method - Google Patents
Catalyst for treatment of waste water and its preparation method Download PDFInfo
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- CN1068564C CN1068564C CN 96109161 CN96109161A CN1068564C CN 1068564 C CN1068564 C CN 1068564C CN 96109161 CN96109161 CN 96109161 CN 96109161 A CN96109161 A CN 96109161A CN 1068564 C CN1068564 C CN 1068564C
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- catalyzer
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Abstract
The present invention relates to a waste water treating catalyst and a preparing method thereof, particularly to a catalyst for treating sulfuric organic waste water of high concentration and high salt content in petrochemical industry and a preparing method thereof. The catalyst contains Pd or Pt, V2O5, TiO2 and Al2O3. The preparing method comprises the steps that V2O5 and TiO2 are added to alumina collosol acidified by dilute acid; a carrier is prepared through drying and roasting activation; the carrier is soaked in nitrate solution of Pd and Pt, and the catalyst is prepared through drying and roasting activation. The catalyst of the present invention contains V2O5 and TiO2; consequently, Pd or Pt is protected from being poisoned by sulfide, and favorable oxidation performance is ensured.
Description
The present invention relates to a kind of Catalysts and its preparation method of handling waste water, especially relate to a kind of processing petrochemical complex high density, high saliniferous sulfur-bearing organic wastewater Catalysts and its preparation method.
The petrochemical complex high concentrated organic wastewater owing to contain the organism of higher difficult for biological degradation, particularly contains inorganic, the organic salt of the sulfide of high density, and intractability is big, and is seriously polluted, thereby is subjected to paying attention to widely.Organic polymer and cyanide waste liquor as the production device for acrylic nitrile discharge; Contain catalytic gasoline, the kerosene of high density volatile phenol, naphthenic acid, sulfide and sodium sulfate salt, the alkaline wash or the alkaline wash acidified water of diesel oil; The waste lye that contains high density octenal, butanols, isopropylcarbinol, butyraldehyde that discharges in the octenol production process; Cracking of ethylene liquid; The Organic Chemicals production equipment is discharged contains waste liquids such as benzene, toluene, ethylbenzene and various halogenated alkane, alkene.These organic waste waters because of big to bio-toxicity, volatile sulfur compounds content high or because of salt concn too high, and more difficult.
Processing for this waste water, a lot of researchs have been done by various countries, as introducing among the US3997440, with Cu, Mn is major constituent, with a certain component among Ca, Sr, Ba, the Zn is auxiliary agent, with at least a metal in second subgroup is the catalyzer of second auxiliary agent, organic pollutant in the waste water is oxidized to the sour gas of solubility, the atomic ratio that its catalyzer consists of Cu, Mn is 0.25: 1-4: 1, certain metal in second subgroup and the atomic ratio of Mn are 0.02: 1-4: 1, and the surface-area and the tap density of obtained catalyzer are respectively 8-50m
2/ g, 0.8-1.7g/cm
3It is first component that US4268399 introduces with Cu, Mn, and Ti, Zn are the catalyzer of second component, and wherein, first components contents is 0.05-20w%, and the atomic ratio of Zn and Ti is 1: 1-3: 1; Introduce with the metal catalyzer of Cu, Mn and Fe family among the US4072608, its content is respectively 20-65w%, 20-65w%, 5-50w%.The surface-area and the tap density of obtained catalyzer are respectively 8-50m
2/ g, 1.5g/cm
3Above catalyzer is mainly used on the gaseous oxidation waste water treatment process under high temperature, highly compressed liquid-phase oxidation and the normal pressure, particularly under the liquid-phase oxidation operational condition, can basic oxidations such as the alkane of 0.01-0.5W%, alkene, aromatic hydrocarbons, alcohol, aldehyde, acid, ether is complete.And it is for the oxidation effectiveness under the gaseous oxidation condition, and unspecified.
For the organic waste water of greater concn, the processing of the brine waste particularly a certain amount of, that the organism relative volatility is relatively poor, U.S. Oil﹠amp for containing; Gas J., 1992,90 (25), the disclosed PO of 43-4
*WW
*ER
TMPropose among the PROCESS with evaporation-catalytic gas phase oxidation technology, but the used catalyzer of unexposed this technology, and whether contain the volatile sulfur compounds that very easily causes poisoning of catalyst in the waste water of handling.
The present invention propose a kind of processing contain the organic substance volatility relatively poor relatively, contain the catalyzer and the preparation method of the brine waste of high density volatile sulfur compounds simultaneously.
The wastewater treatment catalyst that the present invention proposes is to be the noble metal catalyst of major constituent by Pd or Pt.It is generally acknowledged that precious metal (Pd, Pt etc.) activity of such catalysts is extremely responsive to sulfide, under the condition that a large amount of water vapors exists, is easy to cause the permanent poisoning of catalyzer especially.For this reason, the present invention has added a certain amount of V in catalyzer
2O
5, to have avoided when processing contains the high density volatile sulfur compounds, catalyzer is because of the sulphur inactivation.Again at Al
2O
3The middle TiO that adds
2Make carrier, to improve the oxidation activity of catalyzer.
The wastewater treatment catalyst that the present invention proposes is first component by precious metals pd or Pt mainly, and the oxide compound of V is second component, and the oxide compound of Ti and Al is the catalyzer that the 3rd component is formed.Wherein the content of Pd or Pt is 0.005-0.5w%, is preferably 0.01-0.3w%; V
2O
5Content be 5-30w%, be preferably 8-15w%; TiO
2Content is 20-60w%, is preferably 40-50w%; Al
2O
3Content is 30-70w%, is preferably 40-50w%.
Preparation of catalysts method of the present invention is, by the catalyst content requirement with Al
2O
3With diluted acid acidifying 30-60min, add TiO then respectively
2, V
2O
5, be rolled into paste, on banded extruder, be extruded into the rectangular of φ 1.2-1.7mm, in loft drier, carry out 110 ℃ of dry 2-6h down, be cut into the strip of 3-5mm then, this strip is made carrier at 450-600 ℃ of following calcination activation 1-4h.
According to the water-intake rate of carrier and the component concentration of catalyzer requirement, with Pd (NO
3)
2Or Pt (NO
3)
2Make a certain amount of aqueous solution.
With containing Pd (NO
3)
2Or Pt (NO
3)
2Solution impregnating carrier, at 80-120 ℃ of following dry 1-3h, send into stoving oven then, at 450-600 ℃ of following calcination activation 1-4h, make the catalyzer finished product.Also can adopt supersaturated solution impregnation catalyst agent carrier, make catalyzer.The surface-area and the tap density of obtained catalyzer are respectively 100-200m
2/ g, 0.8-1.5g/cm
3
Used diluted acid can be nitric acid or hydrochloric acid, and concentration of nitric acid is 20-40%, and concentration of hydrochloric acid is 10-30%.
Catalyzer of the present invention is specially adapted to handle and contains the brine waste that organic material volatility is relatively poor relatively, contain the high density volatile sulfur compounds, this waste water is evaporation at atmospheric or low pressure earlier, volatile material and water vapor are together under catalyst action of the present invention, with oxygen or air is medium, carry out catalyzed oxidation under 280-400 ℃, oxidation products can require direct discharging, reuse according to the different processing degree of depth or further handle; Non-volatile salt can be used as product and reclaims, or carries out dilution discharge with handling back water.
Catalyzer of the present invention is at 370 ℃ of temperature of reaction, air speed LHSV2.0h
-1, to containing phenol 7000mg/l, the waste water of sulfide 1200mg/l has carried out 2000 hours oxidation stability tests.Test-results shows that the oxidation activity of this catalyzer does not show downward trend.
Catalyzer of the present invention has good oxidation activity and stability to easy volatile in the high concentrated organic wastewater with relative difficult volatile organism, with its disposable low molecular acid thing that is oxidized to carbonic acid gas or minute quantity.This catalyzer has good anti-poisoning performance to high density sulfide, and can as requested sulfide be changed into elemental sulfur or sulfurous gas owing to contain the oxide compound of vanadium.Thereby solved the problem that petrochemical complex high density, sulfur-bearing, salt-containing organic wastewater are difficult to handle.
Specify the present invention below in conjunction with embodiment.
Embodiment 1
Catalyzer is first component by precious metals pd, V
2O
5Be second component, TiO
2And Al
2O
3It is the catalyzer that the 3rd component is formed.Wherein Pd is 0.22w%, V
2O
5Be 9.78w%, TiO
2Be 60w%, Al
2O
3Be 30w%.
Its preparation method is to get 30g Al
2O
3, add 65ml H
2Among the O, stir, slowly drip 40%HNO
330ml, acidifying 40min adds 60g TiO more respectively
2, 10g V
2O
5, weigh, be rolled into paste, be extruded into the rectangular of φ 1.3mm, dry 4h under 110 ℃ is cut into the rectangular of 3-5mm, activates 3h down at 550 ℃, forms carrier.Claim 0.5g Pd (NO
3)
2Be dissolved in 80ml H
2Among the O, stir, the carrier that makes is immersed in the solution, dry 3h under 110 ℃ at 550 ℃ of following roasting 1h, makes catalyzer.
With Zhenghai general petrochemicals factory catalytic gasoline alkaline wash acidified water is process object, COD 29786mg/l, volatile phenol 8000mg/l, volatile sulfur compounds 170mg/l, Na
2SO
4Salt 15g/l evaporates under 0.1MPa, 115 ℃ of vaporization temperatures, evaporated liquor COD28114mg/l, volatile phenol 7563mg/l, sulfide 166.2mg/l.With the catalyzer that makes above, evaporated liquor is carried out gaseous oxidation, 300 ℃ of temperature of reaction, liquid air speed LHSV1.99h
-1, water outlet COD59mg/l, volatile phenol and sulfide do not detect; 350 ℃ of temperature of reaction, liquid air speed LHSV2.60h
-1, water outlet COD34mg/l, volatile phenol and sulfide do not detect; 400 ℃ of temperature of reaction, liquid air speed LHSV2.37h
-1, water outlet COD15mg/l, volatile phenol and sulfide do not detect.
Embodiment 2
Catalyzer is first component by precious metals pd, V
2O
5Second component, TiO
2And Al
2O
3It is the catalyzer that the 3rd component is formed.Wherein Pd is 0.09w%, V
2O
5Be 9.91w%, TiO
2Be 40w%, Al
2O
3Be 50w%.
Its preparation method is to get 50g Al
2O
3, add 80ml H
2Among the O, stir, slowly drip 20% HCl 80ml, acidifying 50min adds 40g TiO again
2, 10g V
2O
5, weigh, be rolled into paste, be extruded into the rectangular of φ 1.3mm, dry 3h under 110 ℃ is cut into the rectangular of 3-5mm, activates 4h down at 500 ℃, forms carrier.Claim 0.2g Pd (NO
3)
2Be dissolved in 75ml H
2Among the O, stir, the carrier that makes is immersed in the solution, dry 4h under 110 ℃ at 450 ℃ of following roasting 4h, makes catalyzer.
With Jiujiang general petrochemicals factory mixed base washing lotion acidified water is process object, COD 18596mg/l, volatile phenol 6000mg/l, volatile sulfur compounds 80mg/l, Na
2SO
4Salt 35g/l evaporates under 0.1MPa, 115 ℃ of vaporization temperatures, evaporated liquor CODl8375mg/l, volatile phenol 6474mg/l, sulfide 81.4mg/l.With the catalyzer that makes above, evaporated liquor is carried out gaseous oxidation, 350 ℃ of temperature of reaction, liquid air speed LHSV4.0h
-1, water outlet COD600mg/l, volatile phenol 2.5mg/l, sulfide does not detect; 370 ℃ of temperature of reaction, liquid air speed LHSV3.0h
-1, water outlet COD66.2mg/l, volatile phenol 0.23mg/l, sulfide does not detect.
Embodiment 3
Catalyzer is first component by precious metals pd, V
2O
5Second component, TiO
2And Al
2O
3It is the catalyzer that the 3rd component is formed.Wherein Pd is 0.35w%, V
2O
5Be 19.65w%, TiO
2Be 40w%, Al
2O
3Be 40w%.
Under the room temperature, get 40g Al
2O
3, add 80ml H
2Among the O, stir, slowly drip 40%HNO
340ml, acidifying 30min adds 40g TiO more respectively
2, 20g V
2O
5, weigh, be rolled into paste, be extruded into the rectangular of φ 1.5mm, dry 4h under 110 ℃ is cut into the rectangular of 3-5mm, activates 1h down at 600 ℃, forms carrier.Claim 0.8g Pd (NO
3)
2Be dissolved in 70ml H
2Among the O, stir, the carrier that makes is immersed in the solution, dry 2h under 110 ℃ at 550 ℃ of following roasting 2h, makes catalyzer.
With Zhenghai general petrochemicals factory catalytic diesel oil alkaline wash acidified water is process object, COD25636mg/l, volatile phenol 4500mg/l, volatile sulfur compounds 64mg/l, Na
2SO
4Salt 20g/l evaporates under 0.1MPa, 116 ℃ of vaporization temperatures, evaporated liquor COD21340mg/l, volatile phenol 4360mg/l, sulfide 61mg/l.With the catalyzer that makes above, evaporated liquor is carried out gaseous oxidation, 350 ℃ of temperature of reaction, liquid air speed LHSV2.0h
-1, water outlet COD86mg/l, volatile phenol 0.5mg/l, sulfide does not detect; 370 ℃ of temperature of reaction, liquid air speed LHSV3.0h
-1, water outlet COD46.2mg/l, volatile phenol 0.2mg/l, sulfide does not detect.
Embodiment 4
Catalyzer is first component by precious metals pd, V
2O
5Second component, TiO
2And Al
2O
3It is the catalyzer that the 3rd component is formed.Wherein Pd is 0.02w%, V
2O
5Be 9.98w%, TiO
2Be 60w%, Al
2O
3Be 30w%.
Its preparation method is to get 30g Al
2O
3, add 60ml H
2Among the O, stir, slowly drip 40%HNO
350ml, acidifying 40min adds 60g TiO more respectively
2, 10g V
2O
5, weigh, be rolled into paste, be extruded into the rectangular of φ 1.3mm, dry 4h under 110 ℃ is cut into the rectangular of 3-5mm, activates 4h down at 450 ℃, forms carrier.Claim 0.05g Pd (NO
3)
2Be dissolved in 90ml H
2Among the O, stir, the carrier that makes is immersed in the solution, dry 3h under 110 ℃ at 600 ℃ of following roasting 1h, makes catalyzer.
Phenol, ammonium sulfide waste water with testing laboratory's preparation are process object, COD 20580mg/l, volatile phenol 7526mg/l, volatile sulfur compounds 2138mg/l evaporates under 0.1MPa, 105 ℃ of vaporization temperatures, with the catalyzer that makes above, evaporated liquor is carried out gaseous oxidation, 370 ℃ of temperature of reaction, liquid air speed LHSV2.2h
-1, water outlet COD940mg/l, volatile phenol 0.5mg/l, sulfide 0.8mg/l; 390 ℃ of temperature of reaction, liquid air speed LHSV3.2h
-1, water outlet COD760mg/l, volatile phenol and sulfide do not detect.
Embodiment 5
Catalyzer is first component by precious metals pd, V
2O
5Second component, TiO
2And Al
2O
3It is the catalyzer that the 3rd component is formed.Wherein Pd is 0.005w%, V
2O
5Be 10w%, TiO
2Be 60w%, Al
2O
3Be 30w%.
Its preparation method is to get 30g Al
2O
3, add 70mlH
2Among the O, stir, slowly drip 40%HNO
340ml, acidifying 50min adds 60g TiO more respectively
2, 10g V
2O
5, weigh, be rolled into paste, be extruded into the rectangular of φ 1.3mm, dry 4h under 110 ℃ is cut into the rectangular of 3-5mm, activates 4h down at 500 ℃, forms carrier.Claim 0.01g Pd (NO
3)
2Be dissolved in 65ml H
2Among the O, stir, the carrier that makes is immersed in the solution, dry 3h under 110 ℃ at 550 ℃ of following roasting 2h, makes catalyzer.
Phenol, ammonium sulfide waste water with testing laboratory's preparation are process object, COD 27648mg/l, volatile phenol 11134mg/l, volatile sulfur compounds 1751mg/l, evaporate under 0.1MPa, 105 ℃ of vaporization temperatures are with the catalyzer that makes above, evaporated liquor is carried out gaseous oxidation, 350 ℃ of temperature of reaction, liquid air speed LHSV3.5h-1, water outlet COD1530mg/l, volatile phenol 25mg/l, sulfide 32.5mg/l; 390 ℃ of temperature of reaction, liquid air speed LHSV3.42h
-1, water outlet COD826mg/l, volatile phenol does not detect, sulfide 38mg/l.
Embodiment 6
Catalyzer is first component by precious metals pt, V
2O
5Second component, TiO
2And Al
2O
3It is the catalyzer that the 3rd component is formed.Wherein Pt is 0.2w%, V
2O
5Be 9.8w%, TiO
2Be 60w%, Al
2O
3Be 30w%.
Its preparation method is to get 30g Al
2O
3, add 60ml H
2Among the O, stir, slowly drip 40%HNO
350ml, acidifying 30min adds 60g TiO more respectively
2, 10g V
2O
5Weigh, be rolled into paste, be extruded into the rectangular of φ 1.3mm, dry 4h under 110 ℃ is cut into the rectangular of 3-5mm, activates 4h down at 500 ℃, forms carrier.Claim 0.5g Pt (NO
3)
2Be dissolved in 60ml H
2Among the O, stir, the carrier that makes is immersed in the solution, dry 3h under 110 ℃ at 500 ℃ of following roasting 3h, makes catalyzer.
Phenol, ammonium sulfide waste water with testing laboratory's preparation are process object, COD 25620mg/l, volatile phenol 5362mg/l, volatile sulfur compounds 1106mg/l evaporates under 0.1MPa, 105 ℃ of vaporization temperatures, with the catalyzer that makes above, carry out gaseous oxidation, 350 ℃ of temperature of reaction, liquid air speed LHSV2.4h
-1, water outlet COD389mg/l, volatile phenol 0.5mg/l, sulfide 2.1mg/l; 390 ℃ of temperature of reaction, liquid air speed LHSV3.2h
-1, water outlet COD760mg/l, volatile phenol and sulfide do not detect.
Embodiment 7
Catalyzer is first component by precious metals pt, V
2O
5Second component, TiO
2And Al
2O
3It is the catalyzer that the 3rd component is formed.Wherein Pt is 0.08w%, V
2O
5Be 9.92w%, TiO
2Be 40W%, Al
2O
3Be 50w%.
Under the room temperature, get 50g Al
2O
3, add 100ml H
2Among the O, stir, slowly drip 25%HCl 150ml, acidifying 60min adds 40g TiO more respectively
2, 10g V
2O
5, weigh, be rolled into paste, be extruded into the rectangular of φ 1.3mm, dry 3h under 110 ℃ is cut into the rectangular of 3-5mm, activates 4h down at 550 ℃, forms carrier.Claim 0.2g Pt (NO
3)
2Be dissolved in 60ml H
2Among the O, stir, the carrier that makes is immersed in the solution, dry 4h under 110 ℃ at 550 ℃ of following roasting 1h, makes catalyzer.
Phenol, ammonium sulfide waste water with testing laboratory's preparation are process object, COD 28000mg/l, volatile phenol 7600mg/l, volatile sulfur compounds 983mg/l evaporates under 0.1MPa, 105 ℃ of vaporization temperatures, with the catalyzer that makes above, carry out gaseous oxidation, 370 ℃ of temperature of reaction, liquid air speed LHSV 3.2h
-1, water outlet COD567mg/l, volatile phenol 0.6mg/l, sulfide 1.9mg/l; 390 ℃ of temperature of reaction, liquid air speed LHSV3.0h
-1, water outlet COD460mg/l, volatile phenol and sulfide do not detect.
Comparative example 8
Catalyzer is first component by precious metals pd, V
2O
5Second component, Al
2O
3It is the catalyzer that the 3rd component is formed.Wherein Pd is 0.005w%, V
2O
5Be 10w%, Al
2O
3Be 90w%.
Under the room temperature, get 90g Al
2O
3, add 170ml H
2Among the O, stir, slowly drip 40%HNO
340ml, acidifying 35min adds 10g V again
2O
5, weigh, be rolled into paste, be extruded into the rectangular of φ 1.3mm, dry 4h under 110 ℃ is cut into the rectangular of 3-5mm, activates 4h down at 550 ℃, forms carrier.Claim 0.01g Pd (NO
3)
2Be dissolved in 75ml H
2Among the O, stir, the carrier that makes is immersed in the solution, dry 3h under 110 ℃ at 550 ℃ of following roasting 1h, makes catalyzer.
Phenol, ammonium sulfide waste water with testing laboratory's preparation are process object, COD 27648mg/l, volatile phenol 11134mg/l, volatile sulfur compounds 1751mg/l evaporates under 0.1MPa, vaporization temperature l05 ℃, with the catalyzer that makes above, carry out gaseous oxidation, 350 ℃ of temperature of reaction, liquid air speed LHSV2.5h
-1, water outlet COD4530mg/l, volatile phenol 125mg/l, sulfide 36.5mg/l; 390 ℃ of temperature of reaction, liquid air speed LHSV2.42h
-1, water outlet COD3826mg/l, volatile phenol 87mg/l, sulfide 38mg/l.
From the foregoing description and comparative example result, as can be seen, catalyzer of the present invention has good effect to the processing of high concentrated organic wastewater.Also can find out simultaneously the TiO in the catalyzer
2Component is fairly obvious to the influence of handling.
Claims (6)
1, a kind of catalyzer of handling waste water contains V
2O
5, TiO
2And Al
2O
3, it is characterized in that also containing Pd or Pt in the catalyzer, each component concentration is respectively, Pd or Pt:0.005-0.5w%, V
2O
5: 5-30w%, TiO
2: 20-60w%, Al
2O
3: 30-70w%.
2,, it is characterized in that each component concentration is respectively, Pd or Pt:0.01-0.3w%, V according to the catalyzer of claim 1
2O
5: 8-15w%, TiO
2: 40-50w%, Al
2O
3: 40-50w%.
3, the described Preparation of catalysts method of a kind of claim 1 comprises carrier making processes and catalyzer making processes, contains Pd or Pt0.005-0.5w%, V by final catalyzer
2O
55-30w%, TiO
220-60w%, Al
2O
3The ratio of 30-70w% adds various raw materials, it is characterized in that, carrier making processes is carried out in the following order: at room temperature get Al
2O
3, add water and stir, add the diluted acid acidifying after, add TiO more respectively
2And V
2O
5, the extruding slivering, after the drying, calcination activation; Catalyzer making processes is carried out in the following order: carrier and Pd (NO
3)
2Or Pt (NO
3)
2Solution mixes, the dry roasting activation.
4,, it is characterized in that diluted acid is HNO according to the method for claim 3
3Or HCl, its concentration is respectively 20-40% and 10-30%.
5,, it is characterized in that acidificatoin time 30-60 minute according to the method for claim 3.
6, according to the method for claim 3, it is characterized in that in the carrier making processes that maturing temperature is 450-600 ℃, roasting time is 1-4h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96109161 CN1068564C (en) | 1996-08-02 | 1996-08-02 | Catalyst for treatment of waste water and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96109161 CN1068564C (en) | 1996-08-02 | 1996-08-02 | Catalyst for treatment of waste water and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1172776A CN1172776A (en) | 1998-02-11 |
| CN1068564C true CN1068564C (en) | 2001-07-18 |
Family
ID=5120266
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 96109161 Expired - Lifetime CN1068564C (en) | 1996-08-02 | 1996-08-02 | Catalyst for treatment of waste water and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1068564C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101543790B (en) * | 2009-04-28 | 2012-07-04 | 九江学院 | An energizing agent and its preparing technology and a method for processing sewage water |
| CN101658793B (en) * | 2009-09-29 | 2011-10-05 | 浙江三龙催化剂有限公司 | Titania-based catalytic agent in coal steam-electric plant smoke SCR denitration and preparation method thereof |
| WO2017202863A1 (en) * | 2016-05-25 | 2017-11-30 | Shell Internationale Research Maatschappij B.V. | Process for preparing a catalyst and use thereof |
| US11168011B2 (en) | 2016-05-25 | 2021-11-09 | Shell Oil Company | Process for the treatment of waste water |
| CN106315818B (en) * | 2016-09-23 | 2019-05-03 | 郑州航空工业管理学院 | V2O5/CeO2Application of the nanocomposite in degradation waste water containing cefalexin |
| CN115304222B (en) * | 2022-08-24 | 2023-08-15 | 南京工大环境科技有限公司 | Treatment process of oil-containing storage wastewater |
-
1996
- 1996-08-02 CN CN 96109161 patent/CN1068564C/en not_active Expired - Lifetime
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|---|---|
| CN1172776A (en) | 1998-02-11 |
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Owner name: CHINA PETROCHEMICAL CORPORATION; CHINA PETROLEUM & Free format text: FORMER NAME OR ADDRESS: CHINA PETRO-CHEMICAL CORP.; FUSHUN PETROCHEMICAL INSTITUTE., CHINA PETROCHEMICAL CORP. |
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| CP01 | Change in the name or title of a patent holder |
Patentee after: China Petrochemical Group Corp. Patentee after: Sinopec Group Fushun Research Institute of Petroleum and Petrochemicals Patentee before: China Petrochemical Corporation Patentee before: Fushun Research Inst. of Petroleum Processing, China Petro-chem. Corp. |
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| CX01 | Expiry of patent term |
Granted publication date: 20010718 |
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| EXPY | Termination of patent right or utility model |