CN1042094A - The regeneration of non-acid loading type platinum catalyst - Google Patents
The regeneration of non-acid loading type platinum catalyst Download PDFInfo
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- CN1042094A CN1042094A CN88109981A CN88109981A CN1042094A CN 1042094 A CN1042094 A CN 1042094A CN 88109981 A CN88109981 A CN 88109981A CN 88109981 A CN88109981 A CN 88109981A CN 1042094 A CN1042094 A CN 1042094A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
The invention discloses a kind of renovation process of Hydrocarban coversion catalysts, be applicable to normal paraffin (nC
10～nC
16) dehydrogenation generates the regeneration of the non-acid loading type platinum catalyst of corresponding monoolefine.
Employing contains oxygen nitrogen treatment by stages decaying catalyst under different condition, and with the solution impregnation of platiniferous or cobalt, drying, air roasting, steam dechlorination, the method for hydrogen reducing makes decaying catalyst obtain primary recycling.The primary recycling catalyzer can directly adopt the method for making charcoal with hydrogen reducing to make catalyzer obtain secondary recycling after reusing inactivation.
The catalytic activity of regeneration rear catalyst reaches the level of raw catalyst, and its work-ing life is longer than raw catalyst, and promptly stability is better than raw catalyst.
Description
The invention relates to the renovation process of Hydrocarban coversion catalysts, be applicable to that normal paraffin dehydrogenation generates the regeneration of the non-acid loading type platinum catalyst of monoolefine.
Hydrocarban coversion catalysts such as platinum-reforming catalyst, dehydrogenation catalysts etc. all are to be the main catalytic element with the noble metal platinum, one or more cocatalytic elements load on carrier (as r-AL
2O
3) on make catalyzer with good catalytic.In the process of catalysis hydrocarbon conversion reactions,, be necessary to regenerate because carbon distribution and sintering lose catalytic activity gradually.
Common renovation process be with oxygen-containing gas under the condition that heats up gradually, by the decaying catalyst bed,, use hydrogen reducing then at a certain temperature with decarbonizing.But common renovation process can not make the sufficient redispersion of agglomerating metallic particles.
For platinum-reforming catalyst, must in oxygen-containing gas, add an amount of chlorine, with the chlorine that runs off on the make-up catalyst, make agglomerating metallic particles redispersion on the catalyzer, thereby platinum-reforming catalyst is by the regeneration of this method, the catalytic activity of catalyzer is restored.Activity, selectivity and the stability of regeneration rear catalyst tap into raw catalyst (US3875049).
Dehydrogenation catalyst, be purpose particularly to produce good linear alkylbenzene or the high fatty alcohol of biological degradability, (nC10～nC16) dehydrogenation generates the corresponding positive used dehydrogenation catalyst of structure monoolefine from high grade normal paraffin, in order to improve the selectivity of reaction, suppress cracking and isomerization reaction, this class catalyzer must be not chloride non-acidic catalyst as far as possible.In regenerative process, do not allow to introduce chlorine, thereby common renovation process can not make this class catalyzer obtain regeneration.To this class catalyzer, existing renovation process (GB1257282) is earlier logical oxygen-containing gas (＜550 ℃), the logical hydrogen reducing (＜500 ℃) in back repeatedly re-treatment can make metal dispersity near raw catalyst, but still the catalytic performance that can not make catalyzer particularly the stability of catalyzer reach the level of raw catalyst.
The objective of the invention is that normal paraffin dehydrogenation is generated the used non-acid loading type platinum catalyst of corresponding monoolefine and propose a kind of renovation process, the catalytic activity that the makes the regeneration rear catalyst particularly stability of catalyzer reaches the level of raw catalyst.
The present invention adopts and contains oxygen nitrogen under different condition, the treatment by stages decaying catalyst, and with the solution impregnation of platiniferous or cobalt, drying, air roasting, steam dechlorination, the method for hydrogen reducing makes decaying catalyst obtain primary recycling.The primary recycling catalyzer can directly adopt the method for making charcoal with hydrogen reducing to make catalyzer obtain secondary recycling after reusing inactivation.
Dehydrogenation catalyst involved in the present invention is that the normal paraffin dehydrogenation for carbon number ten to 16 generates the used non-acid loading type platinum catalyst of corresponding monoolefine, and its platinum is the main catalytic element, and tin and lithium are cocatalytic element, r-AL
2O
3Many dehydrogenation metals catalyzer for carrier.
The catalyzer of inactivation under different conditions, is handled stage by stage with the oxygen-containing gas that air and nitrogen are formed, and the condition in each stage is: (1) fs: 150 ℃～300 ℃ of temperature, oxygen level＜0.1%, gas hourly space velocity 500～1500 hours
-1, 1～6 hour time; (2) subordinate phase: 330 ℃～420 ℃ of temperature, oxygen level 0.3～1%, gas hourly space velocity 300～1500 hours
-1, 10～30 hours time; (3) phase III: 460 ℃～520 ℃ of temperature, dry air, gas hourly space velocity 500～2000 hours
-1, 2～10 hours time.
The catalyzer of handling through above-mentioned condition, with the solution impregnation of platiniferous or cobalt 0.5～1 hour, steeping fluid was made up of Platinic chloride or Xiao Suangu, hydrochloric acid, ethanol and water.Calculate by catalyst weight, the solution platinum containing amount is 0～0.09
% or to contain the cobalt amount be 0.1～0.5
%, the add-on of hydrochloric acid is 1～10
%, the alcoholic acid add-on is calculated as 10～60% by the steeping fluid volume, can add an alkali metal salt (particularly lithium, sodium salt) in the steeping fluid, and its add-on is calculated as 0～0.5 by the weight of catalyzer
Wt%.
Catalyzer behind the dipping is 60～120 ℃ of dryings 1～6 hour, then 400 ℃～550 ℃ of temperature with dry air roasting 1～8 hour, gas hourly space velocity 500～2000 hours
-1The air of using moisture vapor 20～30% again is at 400 ℃～550 ℃ of temperature, gas hourly space velocity 500～2000 hours
-1, handled catalyzer 1～8 hour, to remove the chlorine in the catalyzer.
Use dry hydrogen (water content＜then 20ppm) at 300 ℃～520 ℃ reducing catalysts, gas hourly space velocity 500～2000 hours
-1, 1～10 hour recovery time.
The invention is characterized in containing oxygen nitrogen treatment by stages decaying catalyst under different condition, then with the solution impregnation of platiniferous or cobalt, drying, air roasting, steam dechlorination, the method for hydrogen reducing makes decaying catalyst obtain primary recycling.The primary recycling catalyzer can directly adopt the method for making charcoal with hydrogen reducing to make catalyzer obtain secondary recycling after reusing inactivation.
When the normal paraffin dehydrogenation that is used for nC10～nC16 with the dehydrogenation catalyst after present method regeneration generated corresponding monoolefine, its catalytic activity reached the level of raw catalyst, and its work-ing life is longer than raw catalyst, and promptly stability is better than raw catalyst.
The catalytic perfomance evaluation of catalyzer is to carry out in a mini-reactor.The catalyzer loading amount is 3～5 milliliters, and charging is mixing normal paraffin and the hydrogen of nC10～nC13, and the control catalyst bed temperature is 480 ℃, and pressure is 9.8 * 10
4Crust (table), liquid hourly space velocity 20 hours
-1, hydrogen-hydrocarbon ratio is 5.0mol/mol.Analyze products of dehydrogenation reactions, calculate transformation efficiency.
Embodiment one.
(1) platiniferous 0.375
Wt%, tin 0.48
Wt%, lithium 0.45
WtThe dehydrogenation catalyst of the r-AL2O3 load of % is at 460 ℃～500 ℃ of temperature, pressure 15.68～20.58 * 10
4Crust (table), liquid hourly space velocity 28～33 hours
-1(dehydrogenation reaction of nC10～nC13), the catalyzer behind the reaction inactivation unloads and is spent catalyst to carry out long chain alkane under the industrial condition of hydrogen-hydrocarbon ratio 5～8mol/mol.
(2) spent catalyst is at 150～300 ℃, with containing the nitrogen of oxygen less than 0.1%, gas hourly space velocity 500～1500 hours
-1, handled 1～6 hour; 330 ℃～420 ℃ of temperature, with the nitrogen of oxygen level 0.3～1%, gas hourly space velocity 300～1500 hours
-1, handled 10～30 hours; Use dry air for 460 ℃～520 ℃ in temperature, gas hourly space velocity 500～2000 hours
-1, handled 2～10 hours, get catalyst A.
(3) catalyst A 20 gram with 1.3 milliliters of the platinum acid chloride solutions of platiniferous 12 mg/ml, 6.7 milliliters of 15% hydrochloric acid solns, contains 2 milliliters of the lithium nitrate solutions of lithium 20 mg/ml, contains 48 milliliters of the steeping fluids of 24 milliliters of ethanol, floods 0.5～1 hour.60～120 ℃ of dryings 2～4 hours, at 480～500 ℃ with dry air roasting 4～8 hours, gas hourly space velocity 500～2000 hours
-1, under identical conditions, use the air handling 2～6 hours of containing water vapor 20%～30% again, use dry hydrogen (water content＜then 20ppm) at 300 ℃～520 ℃ reducing catalysts, gas hourly space velocity 500～2000 hours
-1, 1～10 hour recovery time, get catalyst B.
The catalytic perfomance evaluating data of raw catalyst and regenerated catalyst B sees Table-1.
Embodiment two.
Catalyst A 20 grams, with 5 milliliters of the cobalt nitrate solutions that contains cobalt 20 mg/ml, 6.7 milliliters of 15% hydrochloric acid solns, 48 milliliters of dippings of 24 milliliters of steeping fluids of ethanol 0.5～1 hour.Press embodiment one then.(3) condition handle catalyzer C.
The catalytic perfomance evaluating data of raw catalyst and regenerated catalyst C sees Table-1.
Embodiment three.
After regenerated catalyst B uses inactivation, press earlier embodiment one .(2) the condition processing, use dry hydrogen (water content＜then 20ppm) at 300 ℃～520 ℃ reducing catalysts, gas hourly space velocity 500～2000 hours
-1, recovery time 1-10 hour, obtain secondary recycling catalyzer D.
The catalytic perfomance evaluating data of raw catelyst and regenerated catalyst D sees Table-1.
The catalytic perfomance evaluating data of raw catelyst and regenerated catalyst B, C, D of table-1..
| Reaction time (hour) | Conversion ratio (%) | |||
| Raw catelyst | Regenerated catalyst B | Regenerated catalyst C | Secondary recycling catalyst D | |
| 2 12 24 48 72 | 21.2 17.6 16.3 14.4 12.9 | 22.2 19.9 18.6 16.2 15.6 | 20.8 17.5 16.5 14.6 13.2 | 21.0 18.2 17.4 15.0 14.2 |
Claims (8)
1, a kind of renovation process that is used for the non-acid loading type platinum catalyst of normal paraffin dehydrogenation generation monoolefine, it is characterized in that with containing oxygen nitrogen treatment by stages decaying catalyst under different condition, then with the solution impregnation of platiniferous or cobalt, dry, air roasting, steam dechlorination, the method for hydrogen reducing makes decaying catalyst obtain primary recycling.The primary recycling catalyzer can directly adopt the method for making charcoal with hydrogen reducing to make catalyzer obtain secondary recycling after reusing inactivation.
2,, it is characterized in that normal paraffin dehydrogenation that this class catalyzer is used to contain six carbon of ten carbon to ten generates the process of monoolefine according to the described catalyst for dehydrogenating normal paraffin hydrocarbon of claim 1..
3, contain oxygen nitrogen treatment by stages decaying catalyst under different condition according to claim 1. described usefulness, it is characterized in that the branch three phases carries out, the condition in each stage is:
(1) temperature is 150 ℃～300 ℃, oxygen level＜0.1%, gas hourly space velocity 500～1500 hours
-1, 1～6 hour time;
(2) temperature is 330 ℃～420 ℃, oxygen level 0.3～1%, gas hourly space velocity 300～1500 hours
-1, 10～30 hours time;
(3) temperature is 460 ℃～520 ℃, dry air, gas hourly space velocity 500～2000 hours
-1, 2～10 hours time.
4,, it is characterized in that steeping fluid is made up of Platinic chloride or Xiao Suangu, hydrochloric acid, ethanol and water according to claim 1. described solution impregnation with platiniferous or cobalt.Calculate by catalyst weight, the solution platinum containing amount is 0～0.09
% or to contain the cobalt amount be 0.1～0.5
%, the add-on of hydrochloric acid is 1～10
% can add an alkali metal salt (particularly lithium, sodium salt) in the steeping fluid.
5, be after dipping, drying, to carry out according to claim 1. described air roastings, it is characterized in that the condition of air roasting is:
(1) temperature is 400 ℃～550 ℃;
(2) gas hourly space velocity is 500～2000 hours
-1;
(3) 1～8 hour time.
6, be behind air roasting, to carry out according to claim 1, described steam dechlorination, it is characterized in that air handling catalyzer with moisture vapor 20～30%.
7, be after the water vapour dechlorination, to carry out according to claim 1. described hydrogen reducings, it is characterized in that the condition of hydrogen reducing is:
(1) in the hydrogen water-content less than 20ppm;
(2) temperature is 350 ℃～520 ℃;
(3) gas hourly space velocity is 500～2000 hours
-1;
(4) 1～10 hour time.
8,1. described direct employings are made charcoal and the method for hydrogen reducing makes catalyzer obtain secondary recycling according to claim, and it is characterized in that making charcoal is to handle decaying catalyst with containing oxygen nitrogen under different condition, uses hydrogen reducing then.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN88109981A CN1015513B (en) | 1988-10-22 | 1988-10-22 | Regeneration of non-acid loading type platinum catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN88109981A CN1015513B (en) | 1988-10-22 | 1988-10-22 | Regeneration of non-acid loading type platinum catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1042094A true CN1042094A (en) | 1990-05-16 |
| CN1015513B CN1015513B (en) | 1992-02-19 |
Family
ID=4835490
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN88109981A Expired CN1015513B (en) | 1988-10-22 | 1988-10-22 | Regeneration of non-acid loading type platinum catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1015513B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1049163C (en) * | 1995-08-28 | 2000-02-09 | 中国石油化工总公司石油化工科学研究院 | Oxidation charking regeneration of thermal instability catalyst |
| CN1067604C (en) * | 1995-07-25 | 2001-06-27 | 中国石化金陵石化公司烷基苯厂 | Regeneration of catalyst for dehydrogenating normal paraffin hydrocarbon |
| CN101279273B (en) * | 2007-04-04 | 2010-10-06 | 中国石油化工股份有限公司 | Method for regenerating inactivated phenylethylene catalyst |
| CN101622067B (en) * | 2006-12-28 | 2012-08-15 | 三菱丽阳株式会社 | Method for regenerating palladium-containing metal loaded catalyst, palladium-containing metal loaded catalyst and method for producing the same |
| CN103801331A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Regeneration method for low-carbon alkane dehydrogenation catalyst |
| CN103801330A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Regeneration method for dehydrogenation catalyst |
| CN105689014A (en) * | 2016-03-14 | 2016-06-22 | 辽宁石油化工大学 | Regeneration method of precious metal dehydrogenation catalyst |
| CN105797788B (en) * | 2016-03-18 | 2018-07-20 | 辽宁石油化工大学 | A kind of regeneration method of alkane dehydrogenating catalyst |
-
1988
- 1988-10-22 CN CN88109981A patent/CN1015513B/en not_active Expired
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1067604C (en) * | 1995-07-25 | 2001-06-27 | 中国石化金陵石化公司烷基苯厂 | Regeneration of catalyst for dehydrogenating normal paraffin hydrocarbon |
| CN1049163C (en) * | 1995-08-28 | 2000-02-09 | 中国石油化工总公司石油化工科学研究院 | Oxidation charking regeneration of thermal instability catalyst |
| CN101622067B (en) * | 2006-12-28 | 2012-08-15 | 三菱丽阳株式会社 | Method for regenerating palladium-containing metal loaded catalyst, palladium-containing metal loaded catalyst and method for producing the same |
| CN101279273B (en) * | 2007-04-04 | 2010-10-06 | 中国石油化工股份有限公司 | Method for regenerating inactivated phenylethylene catalyst |
| CN103801331A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Regeneration method for low-carbon alkane dehydrogenation catalyst |
| CN103801330A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Regeneration method for dehydrogenation catalyst |
| CN103801331B (en) * | 2012-11-07 | 2015-09-30 | 中国石油化工股份有限公司 | A kind of renovation process of catalyst for dehydrogenation of low-carbon paraffin |
| CN103801330B (en) * | 2012-11-07 | 2015-12-16 | 中国石油化工股份有限公司 | A kind of renovation process of dehydrogenation |
| CN105689014A (en) * | 2016-03-14 | 2016-06-22 | 辽宁石油化工大学 | Regeneration method of precious metal dehydrogenation catalyst |
| CN105797788B (en) * | 2016-03-18 | 2018-07-20 | 辽宁石油化工大学 | A kind of regeneration method of alkane dehydrogenating catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1015513B (en) | 1992-02-19 |
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