CN1015513B - Regeneration of non-acid loading type platinum catalyst - Google Patents
Regeneration of non-acid loading type platinum catalystInfo
- Publication number
- CN1015513B CN1015513B CN88109981A CN88109981A CN1015513B CN 1015513 B CN1015513 B CN 1015513B CN 88109981 A CN88109981 A CN 88109981A CN 88109981 A CN88109981 A CN 88109981A CN 1015513 B CN1015513 B CN 1015513B
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- catalyst
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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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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a regeneration method for a hydrocarban conversion catalyst, which is used for the regeneration of a non-acid loading type platinum catalyst for dehydrogenating normal alkane (nc10 to nc16) to generate corresponding monoolefin. Nitrogen containing oxygen is used for processing a deactivated catalyst by sections under different conditions; the methods of immersion by solution containing platinum or cobalt, drying, air calcination, water vapor dechlorination and hydrogen reduction are used for regenerating the deactivated catalyst once. The method that the once regenerated catalyst can be directly reduced by chark and hydrogen after the devitalization of the once regenerated catalyst is used for regenerating the catalyst twice; the catalytic activity of the regenerated catalyst reaches a novel catalytic level; the service life is longer than that of a novel catalyst, namely that the stability of the regenerated catalyst is higher than that of the novel 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, dehydrogenations 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 catalyst 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 metallic particles of sintering disperse fully again.
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 that the metallic particles of sintering disperses again on the catalyst, thereby platinum reforming catalyst is by this method regeneration, the catalytic activity of catalyst is restored.Activity, selectivity and the stability of regeneration rear catalyst tap into raw catelyst (US3875049).
Dehydrogenation, be purpose particularly to produce good linear alkylbenzene (LAB) or the higher aliphatic of biological degradability, (nC10～nC16) dehydrogenation generates the corresponding positive used dehydrogenation of structure monoolefine from high grade normal paraffin, in order to improve the selectivity of reaction, suppress cracking and isomerization reaction, this class catalyst 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 catalyst obtain regeneration.To this class catalyst, existing renovation process (GB1257282) is earlier logical oxygen-containing gas (＜550 ℃), the logical hydrogen reducing (＜500 ℃) in back repeatedly reprocessing can make metal dispersity near raw catelyst, but still the catalytic performance that can not make catalyst particularly the stability of catalyst reach the level of raw catelyst.
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 catalyst reaches the level of raw catelyst.
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 catalyst can directly adopt the method for making charcoal with hydrogen reducing to make catalyst obtain secondary recycling after reusing inactivation.
Dehydrogenation 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 catalyst for carrier.
The catalyst 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) phase I: 150 ℃～300 ℃ of temperature, oxygen content＜0.1%, gas hourly space velocity 500～1500 hours
-1, 1～6 hour time; (2) second stage: 330 ℃～420 ℃ of temperature, oxygen content 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 catalyst of handling through above-mentioned condition, with the solution impregnation of platiniferous or cobalt 0.5～1 hour, maceration extract was made up of chloroplatinic acid or cobalt nitrate, hydrochloric acid, ethanol and water.Calculate by catalyst weight, the solution platinum containing amount is 0～0.09
Wt% or to contain the cobalt amount be 0.1～0.5
Wt%, the addition of hydrochloric acid is 1～10
Wt%, the addition of ethanol is calculated as 10～60% by the maceration extract volume, can add alkali metal salt (particularly lithium, sodium salt) in the maceration extract, and its addition is calculated as 0～0.5 by the weight of catalyst
Wt%.
Catalyst 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 catalyst 1～8 hour, to remove the chlorine in the catalyst.
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 catalyst can directly adopt the method for making charcoal with hydrogen reducing to make catalyst obtain secondary recycling after reusing inactivation.
When the normal paraffin dehydrogenation that is used for nC10～nC16 with the dehydrogenation after this method regeneration generated corresponding monoolefine, its catalytic activity reached the level of raw catelyst, and its service life is longer than raw catelyst, and promptly stability is better than raw catelyst.
The catalytic perfomance evaluation of catalyst is to carry out in a mini-reactor.The catalyst loading amount is 3～5 milliliters, and charging is mixing n-alkane and the hydrogen of nC10～nC13, and the control reaction bed temperature is 480 ℃, and pressure is 9.8 * 10
4Crust (table), liquid hourly space velocity (LHSV) 20 hours
-1, hydrogen-hydrocarbon ratio is 5.0mol/mol.Analyze products of dehydrogenation reactions, calculate conversion ratio.
Embodiment one.
(1) platiniferous 0.375
Wt%, tin 0.48
Wt%, lithium 0.45
WtThe dehydrogenation of the r-AL2O3 load of % is at 460 ℃～500 ℃ of temperature, pressure 15.68～20.58 * 10
4Crust (table), liquid hourly space velocity (LHSV) 28～33 hours
-1(dehydrogenation reaction of nC10～nC13), the catalyst behind the reaction inactivation unloads and is dead catalyst to carry out long chain alkane under the industrial condition of hydrogen-hydrocarbon ratio 5～8mol/mol.
(2) dead 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 content 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 solutions, contains 2 milliliters of the lithium nitrate solutions of lithium 20 mg/ml, contains 48 milliliters of the maceration extracts 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-treatment 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 catelyst 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 solutions, 48 milliliters of dippings of 24 milliliters of maceration extracts of ethanol 0.5～1 hour.Then by embodiment one .(3) condition handle catalyst C.
The catalytic perfomance evaluating data of raw catelyst 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 catalyst 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..
Conversion ratio (%)
Reaction time raw catelyst regeneration regeneration secondary recycling
(hour) catalyst B catalyst C catalyst D
2 21.2 22.2 20.8 21.0
12 17.6 19.9 17.5 18.2
24 16.3 18.6 16.5 17.4
48 14.4 16.2 14.6 15.0
72 12.9 15.6 13.2 14.2
Claims (2)
1, a kind of normal paraffin dehydrogenation that is used for six carbon of ten carbon to ten generates the renovation process of the non-acid loading type platinum catalyst of monoolefine, it is characterized in that:
Handle decaying catalyst in three stages with containing oxygen nitrogen, the condition in each stage is: 150 ℃-300 ℃ of (1) temperature, oxygen content＜0.1vol%, gas hourly space velocity 300-1500 hour
-1, time 1-6 hour; (2) temperature is 330 ℃-420 ℃, oxygen content 0.3-1vol%, gas hourly space velocity 300-1500 hour
-1, time 10-30 hour; (3) temperature is 460 ℃-520 ℃, dry air, gas hourly space velocity 500-2000 hour
-1, time 2-10 hour;
Use platiniferous (chloroplatinic acid) amount for 0-0.09wt% (by catalyst weight) or contain cobalt (cobalt nitrate) amount and be 0.1-0.5wt% then, hydrochloric acid is 1-10wt%, solution impregnation 0.5-1 hour of forming of ethanol and alkali metal salt (particularly lithium, sodium salt).Catalyst drying behind the dipping was 400 ℃-550 ℃ of temperature, gas hourly space velocity 500-2000 hour
-1Air in after roasting 1-8 hour, with the air dechlorination of moisture vapor 20-30vol%;
Use hydrogen reducing again, its reducing condition: water content is less than 20ppm, 300 ℃-520 ℃ of temperature, gas hourly space velocity 500-2000 hour
-1, time 1-10 hour.Make catalyst obtain regeneration.
2, according to the method for claim 1, the catalyst of reusing once more inactivation after it is characterized in that regenerating can directly adopt the method for burning carbon and hydrogen reducing to make catalyst obtain secondary recycling, at first handle decaying catalyst in three stages with containing oxygen nitrogen, the condition in each stage is 150 ℃-300 ℃ of (1) temperature, oxygen content＜0.1vol%, gas hourly space velocity 300-1500 hour
-1, time 1-6 hour; (2) temperature is 330 ℃-420 ℃, oxygen content 0.3-1vol%, gas hourly space velocity 300-1500 hour
-1, time 10-30 hour; (3) temperature is 460 ℃-520 ℃, dry air, gas hourly space velocity 500-2000 hour
-1, time 2-10 hour; And then use hydrogen reducing, its reducing condition: water content is less than 20ppm, 300 ℃-520 ℃ of temperature, gas hourly space velocity 500-2000 hour
-1, time 1-10 hour.
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 CN1042094A (en) | 1990-05-16 |
| CN1015513B true 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) |
Families Citing this family (8)
| 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 |
| WO2008081792A1 (en) * | 2006-12-28 | 2008-07-10 | Mitsubishi Rayon Co., Ltd. | 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 |
| 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 |
-
1988
- 1988-10-22 CN CN88109981A patent/CN1015513B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN1042094A (en) | 1990-05-16 |
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