CN1045076C - Catalyst for wet oxidation and purification of industrial sewage containing high-enriched organics and ammonia - Google Patents
Catalyst for wet oxidation and purification of industrial sewage containing high-enriched organics and ammonia Download PDFInfo
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- CN1045076C CN1045076C CN92109904A CN92109904A CN1045076C CN 1045076 C CN1045076 C CN 1045076C CN 92109904 A CN92109904 A CN 92109904A CN 92109904 A CN92109904 A CN 92109904A CN 1045076 C CN1045076 C CN 1045076C
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- tio
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- precious metal
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Abstract
The present invention relates to a catalyst for the wet oxidation and the purification of industrial sewage containing high-enriched organic substances and ammonia, which is prepared by loading one of precious metal ingredients, such as Pt, Pd, Ru, Ir and Rh, and rare-earth elements on TIO2. The present invention uses the preparation technique of double activity ingredient co-immersion or separated immersion. Compared with a single precious metal catalyst, the catalyst prepared in the present invention has the advantages of high oxidation activity, low precious metal content (0.3 to 1 wt%), operation availability at a high processing airspeed (2.0 hours <-1>, more than 98.5% of CODcr removing rate and more than 99.6% of NH3-N removing rate. Therefore, the present invention can improve the purification efficiency of the sewage and lower purification expenses.
Description
The present invention is for containing high-enriched organics and ammonia industrial sewage wet oxidation purification techniques provides a kind of new catalyst, and this catalyzer is specially adapted to contain high density chemical oxygen demand (COD) and NH
3The oxidation, purification of coked waste water handle.
Catalytic Wet Oxidation is a kind of purification techniques of handling high-enriched organics sewage that external the eighties grows up, promptly under certain temperature, pressure, with the organism in the sewage and contain N, the S objectionable impurities resolves into CO through atmospheric oxidation
2, N
2, SO
4 -And H
2Innoxious substances such as O reach the purpose of purification.The catalyzer that is adopted (as Japanese Patent 59-29317, United States Patent (USP) 4294706, Japanese Patent 60-272082, United States Patent (USP) 4699720 etc.), with precious metals such as platinum, palladium, ruthenium, rhodium, iridium, gold be active ingredient, with TiO
2Or ZrO
2Be carrier.The weak point of this catalyzer is that activity is lower, uses air speed lower, and air speed is 1.0 o'clock
-1(volume), and active ingredient is higher, contains precious metal 2.0% (weight), thereby catalyzer cost and waste disposal plant investment cost are higher.Recent technology such as the rare-earth element modified carrier TiO of Europe patent 431932 usefulness
2, the rare earth element add-on is 5-30% (weight), the adding method adopts coprecipitation method.Prepared catalyzer contains precious metal 1.5-2.0%, and the air speed that is used to dispose of sewage only was increased to 1.2 o'clock
-1, be 98-99% to the clearance of COD, its catalytic activity is not still improved.
The objective of the invention is to prepare a kind of being applicable to and contain high-enriched organics and NH
3The oxygenolysis of industrial sewage is specially adapted to contain high concentration COD and NH
3The dual-active component catalyst that purifies of coked waste water, its catalytic activity height, the noble metal active component concentration is low, can use under higher sewage disposal air speed, reduces the purification expense.
Catalyzer of the present invention is with Pt, Pd, and Ru, Rh or Ir precious metal are main active ingredient (1), with rare earth element ce, La, Pr, Nd or Sm are for helping active ingredient (2), and active ingredient (1) supports in TiO by co-impregnation or branch pickling process with (2)
2On, the weight percent that catalyzer is formed, noble metal component (1) 0.3-1.0%, rare earth element (2) 0.05-2.0%, all the other are TiO
2Its optimum weight percentage composition is precious metal 0.5-0.8%, rare earth element 0.15-0.75%.Carrier TiO
2Can adopt commodity or prepare the TiO that makes with titanium sulfate precipitator method technology
2100% is Detitanium-ore-type, and specific surface area is higher, is 60-90 rice
2/ gram is beneficial to active ingredient in the carrier surface high dispersing.The titanium sulfate precipitator method are less to equipment corrosion, are convenient to industry and apply.
Preparation of catalysts method of the present invention is characterized in that it being by co-impregnation or branch pickling process active ingredient to be supported on the carrier, specifically adopts following step:
One, the preparation of carrier
The precipitator method prepare TiO
2Process be at room temperature to use the ammonia precipitation process titanium sulfate aqueous solution, generate titanium hydroxide glue.Filter then, washing is carried out roasting, moulding (physical dimension is the right cylinder of φ 1.5～2.0 * 2～4mm) at last to not having SO4 radical ion aftershaping, oven dry under 500～800 ℃.Its physico-chemical property of gained carrier is a bulk density 1.25-1.86 grams per milliliter, specific surface area 60-90 rice
2/ gram, TiO
2Crystal formation is an anatase octahedrite.
Two, Preparation of catalysts
1, with Pt, Pd, Ru, Rh or Ir salt and rare earth element ce, La, Pr, Nd or Sm salt, for example nitrate or muriate are mixed with the aqueous solution.
2, select a kind of precious metal salt solution and the mixing of a kind of rare earth element salt solution in 1, be immersed in commodity TiO
2Or by a TiO who makes
2On the carrier, after 110-120 ℃ of drying, carry out roasting (above-mentioned is co-impregnation) in 300-600 ℃.Or a kind of rare earth element salt in 2 is dipped in TiO earlier
2Carrier, through 110-120 ℃ of dry back in 300-600 ℃ of roasting, and then flood in 1 a kind of precious metal salt through 10-120 ℃ dry after in 300-600 ℃ of roasting (being the branch pickling process).Roasting time is no less than 1 hour, makes finished catalyst of the present invention.Below by example technology of the present invention is given to illustrate further.
Embodiment 1 carrier TiO
2Preparation
With concentration is 10% (with NH
3Meter) ammoniacal liquor at room temperature precipitates the titanium sulfate solution that concentration is 83 grams per liters, control pH～6, generate titanium glue after filtration, be washed to no SO
4Radical ion, the filter cake extruded moulding, in 110～120 ℃ of dryings, the gained titanium hydroxide is 500-800 ℃ of roasting in activation furnace, and roasting time is 3 hours.
Embodiment 2 Preparation of catalysts
Get 10 milliliters of the ruthenium trichloride aqueous solution that contain ruthenium 0.05 grams per milliliter, 6.4 milliliters of the cerous nitrate aqueous solution that contain cerium 0.117 grams per milliliter, in steeping cell, and add an amount of water, add carrier 100 grams that example 1 makes then, dipping evenly the back in 110～120 ℃ of dryings 4 hours, then in 4 hours catalyzer that get product (A) of 300-600 ℃ of activation, its composition (active ingredient weight) is a ruthenium 0.5%, cerium 0.75%.
Embodiment 3 Preparation of catalysts 2
After getting 6.4 milliliters of lanthanum nitrate aqueous solutions that contain lanthanum 0.117 grams per milliliter and in steeping cell, adding suitable quantity of water, add carrier 100 grams that example 1 makes, dipping evenly the back 110～120 ℃ dry 4 hours down, 500 ℃ of following air roastings 4 hours, again with 10 milliliters of the palladium chloride aqueous solutions that contain palladium 0.07 grams per milliliter, flood above-mentioned baked catalyzer, drying is 4 hours under 110～120 ℃, activate 4 hours catalyzer that get product (B) down at 300-600 ℃ then, its composition (active ingredient weight) is a palladium 0.7%, lanthanum 0.75%.
Embodiment 4 Preparation of catalysts 3
Make 0.5%Ru-1.0%Ce/TiO by the method in the example 3
2(catalyzer C).0.5%Ru-0.5%Ce/TiO
2(catalyzer D), 0.5% Ru-0.25%Ce/TiO
2(catalyzer E); Contrast with single noble metal catalyst 2%Ru/TiO by the same terms preparation in the example 2
2(catalyzer F) and 1%Ru/TiO
2(catalyzer G).
Embodiment 5 catalyzer are used for coked waste water and purify experiment
Be to estimate the decontamination effect improving of two-pack wet type oxide catalyst to coked waste water on the fixed bed bubbling style reaction unit of 15ml in the catalyzer loading amount, it the results are shown in table 1.
Table 1 two-pack wet type oxide catalyst contains CoDer clearance % treating water to the oxidation activity catalyst treatment water of coked waste water and contains NH
3-N goes
CODcr mg/l NH
3-N, mg/l removes rate, %A 70.1 98.7 17.1 99.6B 64.4 98.8 16.0 99.6C 83.0 98.5 18.0 99.6D 47.0 99.1 10.0 99.8E 33.9 99.4 6.6 99.9
Reaction conditions: 280 ℃, 8.0MPa handles air speed 1.0 time-1
Coked waste water contains CODcr 5457mg/l, NH
3-N 4205mg/l.
By the data of table 1 as can be seen co-impregnation and the bicomponent catalyst that divides immersion process for preparing to COD and NH
3-N has very high clearance.
Comparative example 1 catalyst performance relatively
By the reaction conditions comparative evaluation bicomponent catalyst in the example 5 and the catalytic performance of single noble metal catalyst, its as a result example in table 2.
The performance of table 2 bicomponent catalyst and single noble metal catalyst relatively
| Catalyzer | Air speed hour | Treating water contains COD removal treating water and contains NH 3-N removes CODcr, and mg/l leads, % NH 3-N, mg/l removes rate, % |
| E | 1 | 33.9 99.4 6.6 99.9 |
| 2 | 229 95.8 14.2 99.7 | |
| F | 1 | 32.0 99.5* 5.0 99.9* |
| G | 1 | 280 94.9 51 98.8 |
| 2 | 493 91.0 786 81.3 |
* contain CODcr6305mg/l, NH before the coked waste water reaction
3-N 3775mg/l.
From table 2 data as can be seen, bicomponent catalyst of the present invention has higher oxidation activity than existing single noble metal component catalyzer, with single noble metal catalyst of 2% identical activity is arranged when bullion content is 0.5% (weight), in air speed=2.0 o'clock
-1, than containing single noble metal catalyst of 1% in air speed=1.0 o'clock
-1Active taller.
By last example, dual-active component catalyst of the present invention, because the adding of the 2nd component rare earth element, improved the oxidation activity of catalyzer, compare with existing single noble metal catalyst, bullion content can reduce by 50%, uses air speed to double, and therefore can reduce catalyzer cost and sewage purification expense.
Claims (3)
1. precious metals pt that contains that is used to handle high-enriched organics sewage, Pd, Ru, Rh or Ir and rare earth element ce, La, Pr, Nd or Sm carrier are the catalyzer of titanium oxide, the weight percent that it is characterized in that each component is: precious metal 0.3～1%, and rare earth element 0.15～2%, all the other are TiO
2And TiO
2Be 60～90 meters of surface-area
2The TiO of/gram anatase crystal
2
2. according to the described catalyzer of claim 1, it is characterized in that the weight percent of each component is: precious metal 0.5～0.8%, rare earth element 0.15～0.75%, all the other are TiO
2
3. one kind is to adopt pickling process that precious metal and rare earth element component are supported on the carrier according to the described Preparation of catalysts method of claim 1, it is characterized in that carrier TiO
2Be to adopt the titanium sulfate precipitator method, generate titanium hydroxide with the ammonia precipitation process titanium sulfate aqueous solution, then after filtration, washing, oven dry, and to carry out roasting and make specific surface area under 500～800 ℃ be 60～90 meters
2The TiO of the anatase crystal of/gram
2Carrier.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92109904A CN1045076C (en) | 1992-09-22 | 1992-09-22 | Catalyst for wet oxidation and purification of industrial sewage containing high-enriched organics and ammonia |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92109904A CN1045076C (en) | 1992-09-22 | 1992-09-22 | Catalyst for wet oxidation and purification of industrial sewage containing high-enriched organics and ammonia |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1084496A CN1084496A (en) | 1994-03-30 |
| CN1045076C true CN1045076C (en) | 1999-09-15 |
Family
ID=4944455
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92109904A Expired - Fee Related CN1045076C (en) | 1992-09-22 | 1992-09-22 | Catalyst for wet oxidation and purification of industrial sewage containing high-enriched organics and ammonia |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1045076C (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1095447C (en) * | 2000-10-20 | 2002-12-04 | 清华大学 | Non-noble metal catalyst for catalytic wet oxidation and its preparation method |
| CN100460070C (en) * | 2005-07-12 | 2009-02-11 | 沈阳化工研究院 | Preparation of multi-component titanium-based catalyst carrier |
| CN103041811A (en) * | 2011-10-17 | 2013-04-17 | 中国石油化工股份有限公司 | Preparation method of catalytic wet oxidation catalyst and treatment method of organic wastewater |
| CN103043773B (en) * | 2011-10-17 | 2016-03-30 | 中国石油化工股份有限公司 | A kind of Catalytic Wet Oxidation method of flue gas desulphurization waste solution |
| CN103041810B (en) * | 2011-10-17 | 2014-10-15 | 中国石油化工股份有限公司 | Cellulosic ethanol wastewater treatment catalyst, preparation method thereof and wastewater treatment method |
| CN103272614B (en) * | 2013-05-03 | 2015-04-08 | 南京德磊科技有限公司 | Special palladium catalyst for sewage treatment and application thereof |
| CN104148048B (en) * | 2013-05-16 | 2016-05-18 | 中国石油化工股份有限公司 | The Preparation method and use of wet oxidizing catalyst carrier |
| CN105268435B (en) * | 2014-07-24 | 2019-01-25 | 中国石油化工股份有限公司 | Heterogeneous catalysis wet oxidizing catalyst |
| CN105347573B (en) * | 2015-12-10 | 2018-05-15 | 浙江奇彩环境科技股份有限公司 | A kind of processing method of pyridine waste water |
| CN109824135A (en) * | 2017-11-23 | 2019-05-31 | 中国科学院大连化学物理研究所 | A kind of method of catalytic wet oxidation processing cephalo-type waste water |
| CN110523413B (en) * | 2018-05-25 | 2021-03-12 | 中国科学院大连化学物理研究所 | Preparation method of supported catalyst and application of supported catalyst in catalytic oxidation reaction of benzene |
| CN115487808B (en) * | 2021-06-18 | 2024-05-03 | 中国石油化工股份有限公司 | Wet oxidation catalyst, preparation method and application thereof, and wet oxidation treatment method of imidazole-containing wastewater |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86108846A (en) * | 1985-12-03 | 1987-07-29 | 大阪瓦斯株式会社 | Temperature oxidation technique is handled the flow process of waste water |
| EP0431932A1 (en) * | 1989-12-06 | 1991-06-12 | Nippon Shokubai Co., Ltd. | Method for treatment of waste water |
-
1992
- 1992-09-22 CN CN92109904A patent/CN1045076C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4699720A (en) * | 1985-03-12 | 1987-10-13 | Osaka Gas Company Limited | Process for treating waste water by wet oxidations |
| CN86108846A (en) * | 1985-12-03 | 1987-07-29 | 大阪瓦斯株式会社 | Temperature oxidation technique is handled the flow process of waste water |
| EP0431932A1 (en) * | 1989-12-06 | 1991-06-12 | Nippon Shokubai Co., Ltd. | Method for treatment of waste water |
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| Publication number | Publication date |
|---|---|
| CN1084496A (en) | 1994-03-30 |
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Granted publication date: 19990915 Termination date: 20100922 |