CN1049163C - Oxidation charking regeneration of thermal instability catalyst - Google Patents
Oxidation charking regeneration of thermal instability catalyst Download PDFInfo
- Publication number
- CN1049163C CN1049163C CN95109800A CN95109800A CN1049163C CN 1049163 C CN1049163 C CN 1049163C CN 95109800 A CN95109800 A CN 95109800A CN 95109800 A CN95109800 A CN 95109800A CN 1049163 C CN1049163 C CN 1049163C
- Authority
- CN
- China
- Prior art keywords
- catalyst
- coke
- heavy
- oxidant
- clo
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a charking regeneration method of thermally unstable catalysts, which comprises the steps: an aqueous solution of oxidizing agents selected from one or many kinds of perchloric acid and salt thereof, hypochlorous acid and salts thereof is added to catalysts to be regenerated and having carbon deposit, and mixtures are charked and regenerated for 0.5 to 5 hours in an atmosphere of air, oxygen or mixed gas thereof at a temperature of 280 to 450 DEG C. The charking temperature can be decreased by the method, carbon deposited on the surfaces of the thermally unstable catalysts can be effectively removed, and the structure of the catalysts can not be destroyed.
Description
The present invention relates to the coke-burning regeneration method of catalyst.
For structural unstable catalyst, for example a problem running in application such as laminated clay column type catalyst, super macroporous molecular sieve catalyst is how to remove the carbon deposit of catalyst surface effectively and do not influence its structure when regeneration.At present the renovation process of conventional catalyst mainly is to adopt high-temperature roasting method, the catalyst that is about to coking deactivation greater than 550 ℃ in addition up to 700 ℃ hot conditions under in oxygen-containing atmosphere (being generally air atmosphere) roasting direct make the surface area char combustion decomposition of catalyst and overflow with gas form.This coke-burning regeneration method is effective for structural stability good catalyst such as Y zeolite catalyst, but for structural instability, especially heat-labile catalyst, when high temperature regeneration, can destroy the structure of catalyst, causing its degree of crystallinity decline even its structure is destroyed fully, is example with the Pd laminated clay column catalyst, after its high temperature coke-burning regeneration method regeneration routinely, its degree of crystallinity can descend 60～70%, and this has just limited these catalyst in industrial application prospect.In addition, for some load type metal catalyst, for example hydrogenation and reforming catalyst etc. can make active the reduction because of the gathering of reactive metal when the high temperature coke-burning regeneration, if coke-burning regeneration at a lower temperature then helps prolonging its service life.Therefore, for these heat-labile catalyst, need a kind of low temperature coke-burning regeneration technology of development.
The report of at present relevant low temperature coke-burning regeneration catalyst is still rare.USP5 has described the renovation process of a kind of platinum and many metal platinum reforming catalyst in 183,789, this method be with carbon deposited catalyst with contain O
3Its concentration be the air-flow contact of 1～50 volume % and under 20～200 ℃ temperature coke-burning regeneration, make activity of such catalysts return to the level of fresh catalyst.
Copperthwaite, people such as R.G. reported low-temp recovery method (J.Chem.Soc., Chem.Commun, 1985, the 644-645 pages or leaves of ZSM-5 molecular sieve; J.Chem.Soc., Faraday Trans.1,1986,82,1007-1017 page or leaf), people such as Hutchings G. J. also reported the low-temp recovery method (Applied Catalysis, 34,1987, the 153-161 page or leaf) of Y zeolite catalyst.The common trait of these three pieces of documents is with containing O with carbon deposited catalyst
3Air-flow coke-burning regeneration under 100～200 ℃ lower temperature, make in regenerative process not can saboteur's sieve structure.
Add ozone when the catalyst coke-burning regeneration, though the coke-burning regeneration temperature is reduced greatly, ozone is not a kind of raw material that is easy to get, and cost is higher, and harmful, so this is not a kind of practicable coke-burning regeneration method.
The Mobil oil company is at USP4,335,020 and USP4,410, the method of organic formwork agent in a kind of ZSM of removing series molecular sieve has been described in 452, this method be with molecular sieve with contain standard oxidation potential greater than the solution of 0.25 volt oxidant stir process 0.5～72 hour under less than 100 condition, these oxidants comprise perchlorate, hypochlorite, permanganate, bichromate, hydrogen peroxide etc.
The coke-burning regeneration method that the purpose of this invention is to provide a kind of thermally labile catalyst, make catalyst at a lower temperature coke-burning regeneration can remove its surperficial carbon deposit effectively and not influence its structure.
The coke-burning regeneration method of thermally labile catalyst provided by the present invention be in the reclaimable catalyst of carbon deposit, add a certain amount of aqueous solution that contains one or more oxidants then in the atmosphere of air, oxygen or their gaseous mixture in 280～450 ℃ of coke-burning regenerations 0.5～5 hour.
Said catalyst is meant the catalyst that laminated clay column type catalyst, super macroporous molecular sieve type catalyst, load type metal catalyst and other can the reductions of making property when handling more than 500 ℃.Load type metal catalyst wherein can be that metal is loaded on hydrogenation or reforming catalyst on the inorganic oxide carrier.
Said oxidant comprises HClO for being selected from
4, KClO
4, NH
4ClO
4, NaClO
4At interior perchloric acid and salt thereof and comprise HClO, KClO, NH
4ClO, NaClO are at interior hypochlorous acid and salt thereof.
Total consumption of said oxidant is 3～35 heavy % of catalyst weight, is preferably 5～30 heavy %.
The concentration of said aqueous oxidizing agent solution is 5～30 heavy %, is preferably 10～20 heavy %.
Said in reclaimable catalyst, add aqueous oxidizing agent solution then the process of coke-burning regeneration can be to divide under the situation of 5～35 heavy % to carry out for several times keeping the total addition of oxidant, preferably divide and carry out for 2～4 times, each oxidant addition can be identical or different, adds behind the oxidant all 280～450 ℃ of roastings 0.5～2 hour in oxygen-containing atmosphere at every turn.
When carrying out the coke-burning regeneration of catalyst according to method provided by the invention, charcoal temperature is lower, can remove the surperficial carbon deposit of thermally labile catalyst effectively and can not destroy the structure of catalyst.
The present invention is described further below by example.Carbon content in each example (carbon deposit or carbon residue amount) is measured with LecocS-444 charcoal sulphur instrument, and relative crystallinity is to be that benchmark (degree of crystallinity is 100%) is measured by X-ray diffraction method (XRD) with the spent agent.
Embodiment 1
The explanation of this example contains the preparation of the Pd/ laminated clay column catalyst of carbon deposit.
Make the Pd/ laminated clay column catalyst that Pd content is 0.58 heavy % by the 1 described method of the example among the CN1042668A, be designated as Pd-PM.
The Pd-PM catalyst that makes is carried out hydrogenation reaction in medium-sized the facing of 10 liters in the hydrogen production device.Raw materials used is Nanjing Refinery hydrocracking diesel oil, and density (20 ℃) 0.8089g/ml, 232～344 ℃ of boiling ranges, arene content are 6.4 heavy %; Reaction condition is: 220～230 ℃ of reaction temperatures, pressure 6.0 MPas; During liquid hourly space velocity (LHSV) 1.6
-1, hydrogen-oil ratio 1000/1, successive reaction draws off the catalyst of carbon deposit as reclaimable catalyst after 300 hours, and recording its coke content is 2.82 heavy %, and this reclaimable catalyst note is made X.
Embodiment 2
The explanation of this example can reduce charcoal temperature with renovation process provided by the invention.
The reclaimable catalyst X that gets 6.0 gram embodiment, 1 gained puts into porcelain crucible, and adding concentration is the NH of 20 heavy %
4ClO
4(commercial reagent, chemical pure) aqueous solution makes spent agent complete wetting, NH
4ClO
4Consumption be spent agent butt weight 20% (promptly 1.2 the gram NH
4ClO
4).After spent agent soaks into fully,, obtain sample A 110 ℃ of oven dry.
With sample X and sample A with differential scanning calorimeter (DSC) under air atmosphere with different its charcoal temperatures of speed intensification assay determination, the results are shown in Table 1 for it.Add oxidant NH as can be seen from Table 1 in the spent agent
4ClO
4Can reduce charcoal temperature later on.
Table 1
Embodiment 3～6
This example illustrates the different oxidant consumptions in the method provided by the invention.
The NH that in four parts of Pd/ laminated clay column catalyst X to be generated, adds 5,10,20,30 heavy % of butt weight according to the method for embodiment 2 respectively
4ClO
4Then in 110 ℃ of oven dry, the sample after the oven dry is placed in the muffle furnace in 350 ℃ of coke-burning regenerations 2 hours (air atmosphere), the sample after obtaining regenerating, note is made B, C, D, E respectively.The analysis result of its carbon residue amount and relative crystallinity is listed in the table 2.
Comparative Examples 1
The effect of coke-burning regeneration is carried out in the explanation of this Comparative Examples according to a conventional method.
The spent agent X6.0 gram of getting in the example 1 is directly put into muffle furnace in 550 ℃ of following coke-burning regenerations 2 hours (air atmosphere), gets sample T-1 after the taking-up, analyzes carbon residue and relative crystallinity then, and the results are shown in Table 2 for it.From table 2 data as can be known, adopt the conventional regeneration method effect of making charcoal bad, and degree of crystallinity destroys seriously, and adopt method provided by the invention not only can improve the efficient of making charcoal, and can keep the structure of catalyst not to be destroyed.
Table 2
| Example 1 | Example 3 | Example 4 | Example 5 | Example 6 | Comparative Examples 1 | |
| Sample number into spectrum | X | B | C | D | E | T-1 |
| Add NH 4ClO 4Amount (heavy %) | - | 5 | 10 | 20 | 30 | - |
| The coke-burning regeneration temperature (℃) | - | 350 | 350 | 350 | 350 | 550 |
| The coke-burning regeneration time (hr) | - | 2 | 2 | 2 | 2 | 2 |
| Carbon residue is (heavy %) | 2.82 | 0.96 | 0.85 | 0.80 | 0.62 | 1.62 |
| Relative crystallinity (%) | 100 | 76 | Do not analyze | 80 | 85 | 32 |
Embodiment 7
Oxidant can add in gradation in this example explanation the inventive method.
By feeding intake of embodiment 5, but NH
4ClO
4Add at twice, promptly take by weighing 6.0g spent agent X and put into porcelain crucible, add the NH of 20 heavy %
4ClO
4The aqueous solution 3.0 gram makes catalyst wetting, after 100 ℃ of oven dry, puts into muffle furnace roasting 30 minutes under 380 ℃ of air atmospheres, is chilled to room temperature after the taking-up, adds the NH of 20 heavy % again in this catalyst
4ClO
4Solution 3.0 gram makes catalyst wetting, puts into muffle furnace after the oven dry again in 380 ℃ of following air atmosphere roastings 1.5 hours, obtains the sample behind the coke-burning regeneration, and note is made F, and the results are shown in Table 3 in its carbon residue quantitative analysis.
Embodiment 8
Repeat the step of embodiment 7, that different is NH
4ClO
4The aqueous solution divides four addings, adds the NH of 10 heavy % at every turn
4ClO
4The aqueous solution 3.0 gram (total NH
4ClO
4Amount is 20% of spent agent weight), add NH at every turn
4ClO
4Directly 330 ℃ of following air atmosphere roastings 30 minutes, the catalyst after obtaining at last regenerating remembers and makes G that the results are shown in Table 3 in its carbon residue quantitative analysis after making catalyst wetting behind the aqueous solution.
Table 3
| Embodiment 5 | Embodiment 7 | Embodiment 8 | |
| Sample number into spectrum | D | F | G |
| Total NH 4ClO 4Consumption (heavy %) | 20 | 20 | 20 |
| NH 4ClO 4Add indegree | 1 | 2 | 4 |
| The coke-burning regeneration temperature (℃) | 350 | 380 | 330 |
| Total burning recovery time (hr) | 2 | 2 | 2 |
| Carbon residue amount (heavy %) | 0.80 | 0.61 | 0.45 |
Embodiment 9～12
This example illustrates that method provided by the invention adopts different oxidants.
Repeat the step of embodiment 5, but oxidant changes commercially available chemically pure reagent KClO respectively into
4, NaClO, NH
4ClO and HClO, the consumption of oxidant is all identical with embodiment 5 with the coke-burning regeneration condition, and the regenerated catalyst that obtains at last remembers respectively and makes H, I, J and K that the results are shown in Table 4 in its carbon residue quantitative analysis.
Table 4
| Embodiment 9 | Embodiment 10 | Embodiment 11 | Embodiment 12 | |
| Sample number into spectrum | H | I | J | K |
| Oxidant | KClO 4 | NaClO | NH 4ClO | HClO |
| Carbon residue amount (heavy %) | 0.64 | 0.70 | 0.72 | 0.68 |
Embodiment 13～15
This example illustrates regeneration temperature and the recovery time in the renovation process provided by the invention.
Repeat the operating procedure of embodiment 5, just the coke-burning regeneration temperature changes 300 ℃, 400 ℃ and 450 ℃ respectively into, the coke-burning regeneration time changes 4 hours respectively into, 3 hours and 1 hour, the gained regenerated catalyst remembers respectively and makes L, M and N that the results are shown in Table 5 in its carbon residue quantitative analysis.
Table 5
| Embodiment 13 | Embodiment 14 | Embodiment 15 | |
| Sample number into spectrum | L | M | N |
| The coke-burning regeneration temperature (℃) | 300 | 400 | 450 |
| The coke-burning regeneration time (hr) | 4 | 3 | 1 |
| Carbon residue amount (heavy %) | 0.65 | 0.53 | 0.50 |
Embodiment 16～17
The metallic catalyst that the explanation of this example loads on the inorganic oxide carrier can be regenerated with method provided by the invention.
The used spent agent of this example is that the catalyst trade mark of taking from Guangzhou general petrochemicals factory High-pressure Hydrogenation Unit is the hydrogenation catalyst to be generated (catalyst is that Chang Ling, Hunan oil-refining chemical factory produces, and is supported non-precious metal catalyst) of RN-1, and its coke content is 6.09 heavy %.
Get two parts of each 6.0 grams of above-mentioned RN-1 reclaimable catalyst and place in the porcelain crucible, add the HClO of 20 heavy % respectively
4(commercial reagent, chemical pure) aqueous solution 1.5 grams and 6.0 grams make catalyst wetting, make HClO
4Consumption is respectively 5% and 20% of catalyst weight.After 110 ℃ of oven dry, put it in the muffle furnace in 350 ℃ of following air atmosphere coke-burning regenerations 2 hours, the regenerated catalyst sample, note is made O and P respectively, the results are shown in Table 6 in its carbon residue component analysis.
Embodiment 18
Repeat embodiment 8, but spent agent is used the RN-1 spent agent described in the example 16～17 instead, and each coke-burning regeneration temperature changes 350 ℃ into, other conditions are identical, the regenerated catalyst sample, note is made Q, the results are shown in Table 6 in its carbon residue quantitative analysis.
Embodiment 19～20
Get two parts of each 6.0 grams of the RN-1 reclaimable catalyst described in the embodiment 16～17 and place in the porcelain crucible, add the HClO aqueous solution 4.5 grams of 20 heavy % and the KClO of 20 heavy % respectively
4The aqueous solution 4.5 grams, the consumption that makes oxidant is 15% of a catalyst weight.After 110 ℃ of oven dry, put it in the muffle furnace in 350 ℃ of air atmosphere coke-burning regenerations 2 hours, the regenerated catalyst sample, note is made R and S respectively, the results are shown in Table 6 in its carbon residue component analysis.
Comparative Examples 2
Get RN-1 spent agent 6.0 gram described in the embodiment 16～17 and place and directly put into muffle furnace in the porcelain crucible in 550 ℃ of following air atmosphere coke-burning regenerations 2 hours, after the taking-up the regenerated catalyst sample, note is made T-2, the results are shown in Table 6 in its carbon residue component analysis.
Table 6
| Example 16 | Example 17 | Example 18 | Example 19 | Example 20 | Comparative Examples 2 | ||
| Sample number into spectrum | The RN-1 spent agent | O | P | Q | R | S | T-2 |
| Oxidant | - | HClO 4 | HClO 4 | HClO 4 | HClO | KClO 4 | - |
| Total oxidant consumption (heavy %) | - | 5 | 20 | 20 | 15 | 15 | - |
| Oxidant adds indegree | - | 1 | 1 | 4 | 1 | 1 | - |
| The coke-burning regeneration temperature (℃) | - | 350 | 350 | 350 | 350 | 350 | 550 |
| The coke-burning regeneration time (hr) | - | 2 | 2 | 0.5×4 | 2 | 2 | 2 |
| Carbon residue amount (heavy %) | 6.09 | 0.99 | 0.62 | 0.42 | 0.84 | 0.74 | 5.60 |
Embodiment 21
The regenerative agent L that regenerative agent D that embodiment 5 is obtained and Comparative Examples 1 obtain carries out the aromatic hydrogenation saturation testing on 10 milliliters small stationary bed reaction device.Raw materials used jet fuel (aviation kerosine) for Guangzhou Petrochemical Complex production, its density (20 ℃) is 0.7868g/ml, and boiling range is 166～258 ℃, and arene content is 7.3 heavy % (ultraviolet absorption spectroscopy).Earlier catalyst is packed into during reaction in the reactor, in the H2 air-flow in 350 ℃ of reductase 12s hour, be transferred to desired reaction temperature then, feeding reaction raw materials oil, under the listed condition of table 7, carry out evaluation test continuously, the stable back sampling of waiting to turn round is measured its arene content with ultraviolet absorption spectroscopy, and the results are shown in Table 7 for it.After using method provided by the invention to catalyst regeneration as can be seen by the result of table 7, activity of such catalysts is well recovered.
Table 7
| Catalyst | D T-1 |
| Reaction temperature (℃) pressure (MPa) air speed (h -1) hydrogen-oil ratio (v/v) liquid receipts (%) | 250 280 250 280 6.0 6.0 3 3 1000/1 1000/1 100 100 |
| Arene content in the product (heavy %) | 0.02 0.20 0.42 0.55 |
Claims (6)
1. the coke-burning regeneration method of a thermally labile catalyst, it is characterized in that this method comprises adds the aqueous solution that contains one or more oxidants in the reclaimable catalyst of carbon deposit, then in the atmosphere of air, oxygen or their gaseous mixture in 280～450 ℃ of coke-burning regenerations 0.5～5 hour, wherein said oxidant comprises HClO for being selected from
4, KClO
4, NH
4ClO
4And NaClO
4At interior perchloric acid and salt thereof and comprise HClO, KClO, NH
4ClO and NaClO are at interior hypochlorous acid and salt thereof.
2. according to the process of claim 1 wherein that said catalyst is laminated clay column type catalyst, super macroporous molecular sieve type catalyst and load type metal catalyst and other catalyst that when handling more than 500 ℃ activity is reduced.
3. according to the method for claim 2, wherein said load type metal catalyst is for loading on metal hydrogenation or the reforming catalyst on the inorganic oxide carrier.
4. according to the process of claim 1 wherein that total consumption of said oxidant is 3～35 heavy % of said catalyst weight.
5. according to the process of claim 1 wherein that the concentration of said aqueous oxidizing agent solution is 5～30 heavy %.
According to the process of claim 1 wherein said in reclaimable catalyst, add aqueous oxidizing agent solution then the process of coke-burning regeneration can be to divide under the situation of 5～35 heavy % to carry out for several times keeping the total addition of oxidant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95109800A CN1049163C (en) | 1995-08-28 | 1995-08-28 | Oxidation charking regeneration of thermal instability catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95109800A CN1049163C (en) | 1995-08-28 | 1995-08-28 | Oxidation charking regeneration of thermal instability catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1144143A CN1144143A (en) | 1997-03-05 |
| CN1049163C true CN1049163C (en) | 2000-02-09 |
Family
ID=5077380
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95109800A Expired - Fee Related CN1049163C (en) | 1995-08-28 | 1995-08-28 | Oxidation charking regeneration of thermal instability catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1049163C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101585007B (en) * | 2009-07-13 | 2011-05-18 | 北京化工大学 | Regeneration method for removing catalyst carbon deposit |
| CN102039207B (en) * | 2009-10-16 | 2014-08-20 | 中国石油化工股份有限公司 | Method for regenerating and prevulcanizing hydrogenation catalysts |
| CN102310006A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Method for regenerating and pre-vulcanizing hydrogenation catalyst |
| CN110803706B (en) * | 2019-12-04 | 2023-03-28 | 宝鸡文理学院 | Method for quickly and efficiently removing mesoporous silicon oxide material template agent |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3898173A (en) * | 1971-08-26 | 1975-08-05 | Universal Oil Prod Co | Four-step procedure for regenerating a carbon-containing deactivated bimetallic acidic catalyst |
| US4335020A (en) * | 1981-01-06 | 1982-06-15 | Mobil Oil Corporation | Method of preparation of composite zeolite catalysts |
| US4517076A (en) * | 1984-08-24 | 1985-05-14 | Exxon Research And Engineering Co. | Reactivation of iridium-containing catalysts |
| CN1042094A (en) * | 1988-10-22 | 1990-05-16 | 金陵石油化工公司南京烷基苯厂 | The regeneration of non-acid loading type platinum catalyst |
| US5183789A (en) * | 1991-03-11 | 1993-02-02 | Exxon Research And Engineering Company | Ozone regeneration of platinum, and polymetallic platinum reforming catalysts |
| CN1092377A (en) * | 1993-01-14 | 1994-09-21 | 国际壳牌研究有限公司 | The burn-off process of carbon |
-
1995
- 1995-08-28 CN CN95109800A patent/CN1049163C/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3898173A (en) * | 1971-08-26 | 1975-08-05 | Universal Oil Prod Co | Four-step procedure for regenerating a carbon-containing deactivated bimetallic acidic catalyst |
| US4335020A (en) * | 1981-01-06 | 1982-06-15 | Mobil Oil Corporation | Method of preparation of composite zeolite catalysts |
| US4517076A (en) * | 1984-08-24 | 1985-05-14 | Exxon Research And Engineering Co. | Reactivation of iridium-containing catalysts |
| CN1042094A (en) * | 1988-10-22 | 1990-05-16 | 金陵石油化工公司南京烷基苯厂 | The regeneration of non-acid loading type platinum catalyst |
| US5183789A (en) * | 1991-03-11 | 1993-02-02 | Exxon Research And Engineering Company | Ozone regeneration of platinum, and polymetallic platinum reforming catalysts |
| CN1092377A (en) * | 1993-01-14 | 1994-09-21 | 国际壳牌研究有限公司 | The burn-off process of carbon |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1144143A (en) | 1997-03-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107866285B (en) | Regeneration method of isodewaxing catalyst | |
| CN1323754C (en) | Catalyst for synthesizing dimethyl carbonate and its preparing process | |
| CN101678341A (en) | Method of regenerating lower hydrocarbon aromatizing catalyst | |
| CN101657527A (en) | Composition and process for the removal of sulfur from middle distillage fuels | |
| CN1129470C (en) | Catalytic reforming catalyst activation | |
| CN1289388A (en) | Regeneration of catalyst/absorber | |
| CN1129471C (en) | Process for activating reforming catalyst | |
| CN101428235B (en) | Regeneration method of molecular sieve catalysts | |
| CN1059918C (en) | Improved steam reforming catalysts for lower hydrocarbons | |
| CN1049163C (en) | Oxidation charking regeneration of thermal instability catalyst | |
| EP0515270B1 (en) | Hydrocracking of Fischer-Tropsch paraffines with catalysts based on zeolithe-H-Y | |
| CN100339152C (en) | Trichloroethylene waste gas catalytic purification method | |
| CN1345629A (en) | Copper aluminium-cerium aluminium compound oxide combustion catalyst, its preparation and use | |
| EP0009819A1 (en) | Cracking catalyst, process for cracking hydrocarbons and method for passivating contaminating metals on hydrocarbon cracking catalysts | |
| CN1051479C (en) | Carbon carrier hydrogenation catalyst | |
| CN1175478A (en) | High-strength, high heat-resistance and poisoning-resistance deoxidation catalyst | |
| CN1031030A (en) | The preparation of low content of rare earth super-stable Y molecular sieves | |
| US4283274A (en) | Process for cracking hydrocarbons with a cracking catalyst passivated with thallium | |
| CN1506299A (en) | Prepn and application of nickel-based catalyst for decomposing ammonia to prepare mixed H2-N2 gas | |
| CN1015513B (en) | Regeneration of non-acid loading type platinum catalyst | |
| CN1034222C (en) | Method for preparation of catalyst cracking combustion-supporting agent | |
| US3673108A (en) | Hydrocracking catalyst activation treatment | |
| CN1234666C (en) | Preparation method of Ru-B load type catalyst | |
| CN1166453C (en) | Copper-aluminium-cerium-aluminium composite oxide three-effect FCC adjuvant and its preparation method | |
| CN1197052A (en) | Process for elminating arsenic from liquid hydrocarbon feeds |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |