CN1067604C - Regeneration of catalyst for dehydrogenating normal paraffin hydrocarbon - Google Patents
Regeneration of catalyst for dehydrogenating normal paraffin hydrocarbon Download PDFInfo
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- CN1067604C CN1067604C CN95111129A CN95111129A CN1067604C CN 1067604 C CN1067604 C CN 1067604C CN 95111129 A CN95111129 A CN 95111129A CN 95111129 A CN95111129 A CN 95111129A CN 1067604 C CN1067604 C CN 1067604C
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Abstract
The present invention relates to a regeneration method of a halgen-free supported platinum-containing catalyst, which has the steps that after being treated by three stages under the different conditions by hot air in a rotary kiln, a deactivated catalyst is immersed in a platinum-containing solution, dried, calcined and reduced. The deactivated catalyst can be completely regenerated by the method in a short time.
Description
The present invention is a kind of holomorphosis method of catalyst for dehydrogenating normal paraffin hydrocarbon.Specifically, be about a kind of nC of being applicable to
10～nC
18Normal paraffin dehydrogenation generates the renovation process of the support type catalyst made from platonic of corresponding positive structure monoolefine.
Catalyst for dehydrogenating normal paraffin hydrocarbon is a kind of main catalytic element with noble metal platinum, and one or more cocatalytic elements load on the catalyst of making on the high-temperature inorganic oxide carrier.In the process of dehydrogenation reaction, because the sintering of the carbon distribution of catalyst surface and carried metal and losing activity gradually, thereby need regenerate.
US 3,875, and a kind of renovation process of platinum reforming catalyst is provided in 049 patent, promptly be in oxygen-containing gas, to add an amount of chlorine, under such atmosphere, decaying catalyst is heat-treated, both replenished the chlorine that runs off on the catalyst, the platinum particle of sintering is disperseed again.This renovation process can make activity, selectivity and the stability restoring of regenerated catalyst to the level near raw catelyst.
Yet for catalyst for dehydrogenating normal paraffin hydrocarbon, be purpose particularly, from C to produce biological degradability good linear alkylbenzene (LAB)
10～C
18Normal paraffin dehydrogenation generates the corresponding positive used support type catalyst made from platonic of structure monoolefine, in order to improve the selectivity of its reaction, suppresses cracking and isomerization reaction, and requiring must not have chlorine in the catalyst, does not also allow to use chlorine in regenerative process certainly.Therefore, the renovation process that can successfully be applied to reforming catalyst but is difficult to be applied to this class catalyst made from platonic.
For halogen-free, the catalyst of picture dehydrating alkanes one class, the renovation process that discloses in the GB1257282 patent is with decaying catalyst heat treatment in being lower than 550 ℃ oxygen-containing gas earlier, reduce in being lower than 500 ℃ hydrogeneous atmosphere then, so repeatedly reprocessing can make metal dispersity near raw catelyst.However, this method but can not make the stability restoring of catalytic performance, particularly catalyst of catalyst to the level of fresh catalyst.
The applicant had once disclosed a kind of C of being used in CN1015513.B
10～C
18Normal paraffin dehydrogenation generates the renovation process of the non-acid loading type platinum catalyst of monoolefine.According to this method, decaying catalyst at first will divide three phases to handle with containing oxygen nitrogen: 150～300 ℃, oxygen content less than 0.1% (body), handled 1～6 hour; 330～420 ℃, oxygen content 0.3～1.0% (body), handled 10～30 hours; 460～520 ℃, handled 2～10 hours with dry air.Catalyst after the heat treatment uses the mixed liquor of being made up of chloroplatinic acid or cobalt nitrate, sodium or lithium salts, hydrochloric acid and ethanol to flood 0.5～1 hour.Then drying, at 400～550 ℃, gas hourly space velocity 500～2000 o'clock
-1Air in roasting after 1～8 hour, with the air dechlorination of moisture vapor 20～30% (body), use water content at last again less than 20PPM, 300～520 ℃, gas hourly space velocity 500～2000 o'clock
-1Hydrogen reducing 1～10 hour.Though can reach the level of fresh catalyst according to the activity of such catalysts after this method regeneration, but not only to prepare the nitrogen of low oxygen content at the decaying catalyst heat treatment stages, and heat treatment takes time and reaches 13～46 hours, and this makes troubles to industrial production.
The purpose of this invention is to provide a kind of be used for normal paraffin dehydrogenation generate corresponding positive structure monoolefine the support type catalyst made from platonic, that save time manyly than prior art, make the method that decaying catalyst can holomorphosis.
Renovation process provided by the invention is that decaying catalyst was handled respectively 0.5～2 hour with hot-air under 200～350 ℃, 350～500 ℃, 500～550 ℃ in rotary kiln successively, uses mixed liquor dipping drying, roasting, reduction after 0.5～1 hour of being made up of chloroplatinic acid, stannous chloride, sodium chloride, hydrochloric acid and ethanol then.
Sodium chloride can replace with lithium chloride or potassium chloride in the mixed liquor of said dipping usefulness, and the content of each component (by catalyst weight) is platinum 0.01～0.15% in the mixed liquor, tin 0.01～0.50%, sodium or lithium or potassium 0.01～0.50%, hydrochloric acid 1～10%.
Said drying is to carry out under 60～120 ℃ 2～4 hours.
Said roasting is 480～500 ℃, gas hourly space velocity 500～2000 hours
-1Condition under in dry air, carried out 4～8 hours successively; Under similarity condition, in the air of moisture vapor 20～30% (percentage by volume), carried out 2～6 hours.
Said reduction is 300～550 ℃, gas hourly space velocity 500～2000 hours
-1Condition under with water content less than the hydrogen reducing of 20ppm 1～10 hour.
Renovation process provided by the invention not only can make decaying catalyst be able to holomorphosis, and the catalytic performance of the catalyst after the regeneration surpasses the level of former fresh catalyst.Compare with prior art, though renovation process required time provided by the invention shortens dramatically regeneration effect and not second to prior art.
To be that the present invention is given further instruction by embodiment below, but not thereby limiting the invention.
The support type catalyst made from platonic A and the B of two kinds of inactivations under the industrial operation condition have been used among the embodiment.The active constituent of deactivator A is platinum-Xi-indium-lithium, and its carrier is γ-Al
2O
3The active constituent of deactivator B is platinum-Xi-lithium, and its carrier is γ-Al
2O
3
Embodiment one:
The regeneration of decaying catalyst
Decaying catalyst A was handled respectively 70～80 minutes with hot-air under 200～350 ℃, 350～500 ℃, 500～550 ℃ in rotary kiln successively.
Mix with the stannous chloride aqueous solution of the chloroplatinic acid of 4.0 milliliters of platiniferous 12.5 mg/ml, 1.88 milliliters of stanniferous 40mg/ml, 2 milliliters of sodium-chloride water solutions that contain sodium 25 mg/ml, 14.8 milliliter of 15% (weight) hydrochloric acid and 62 milliliters of absolute ethyl alcohols and to make maceration extract.
Get 50 after heat treatment deactivator A of gram and in above-mentioned maceration extract, flooded 45 minutes, then 90 ± 10 ℃ of dryings 3 hours, again 480～500 ℃, during gas hourly space velocity 1200
-1Condition under successively with dry air roasting 6 hours, use the air roasting 4 hours of moisture vapor 20～30% (body) again, when using gas hourly space velocity 1200 at last
-1Dry hydrogen (water content is less than 20ppm) under 450 ℃ of conditions, reduced 4 hours, obtain regenerated catalyst note and make regenerative agent C.
Embodiment two:
The regeneration of decaying catalyst
Deactivator B is regenerated according to method described in the embodiment 1, and different is that roasting is when gas hourly space velocity 1800
-1Condition under with dry air roasting 4 hours, roasting 2 hours in the moisture vapor air: reduction be 300 ℃, during gas hourly space velocity 1800
-1Condition carried out 6 hours, the regenerated catalyst that obtains note is made regenerative agent D.
Embodiment three:
The regeneration of decaying catalyst
Deactivator A is regenerated according to method described in the embodiment 1, and the sodium chloride that different is in the maceration extract is replaced by lithium chloride, and the content of platinum, tin and lithium accounts for 0.1%, 0.15%, 0.1% of catalyst weight respectively; Roasting is when gas hourly space velocity 1500
-1Condition under with dry air roasting 8 hours, roasting 6 hours in the moisture vapor air: reduction be 550 ℃, during gas hourly space velocity 1500
-1Condition carried out 2 hours, the regenerated catalyst that obtains note is made regenerative agent E.
Embodiment four:
The regeneration of decaying catalyst
Deactivator A is regenerated according to method described in the embodiment 1, and the content of different is platinum in the maceration extract, tin and sodium accounts for 0.05%, 0.15% and 0.10% of catalyst weight respectively, and the regenerated catalyst note that obtains is made regenerative agent F.
Comparative Examples:
Catalyst according to the regeneration of deactivated of method described in the CN1015513.B
When deactivator A is used oxygen content 0.1% (body), gas hourly space velocity 1000 successively under 250 ℃
-1Nitrogen treatment 4 hours; When using oxygen content 0.7% (body), gas hourly space velocity 900 down for 380 ℃
-1Nitrogen treatment 20 hours; At 490 ℃ during with gas hourly space velocity 1200
-1Dry air handled 6 hours.
With the deactivator after the heat treatment according to the method described in the embodiment 1 flood, drying, roasting, reduction, the regenerated catalyst that obtains note is made regenerative agent G.
Embodiment five:
The reactivity worth evaluation of regeneration rear catalyst
With fresh dose and under identical condition, on mini-reactor, carry out the evaluation of catalytic perfomance respectively with catalyst C, D, E and F after the method provided by the invention regeneration.The catalyst sample loading amount is that 5 milliliters, reaction raw materials are C
10～C
13The mixing n-alkane, liquid hourly space velocity (LHSV) is 20 o'clock
-1, hydrogen/hydrocarbon mol ratio is 5.0, bed temperature is that 480 ℃, pressure are 0.1 MPa (gauge pressure).Products of dehydrogenation reactions is analyzed the back with chromatogram and is calculated its conversion ratio.Evaluation result is listed in table 1.
For comparison purpose, the sample G that prior art in the comparative example is born again estimates under condition same as described above, and the result also one is listed in table 1.
From table 1 data as can be seen: the catalytic perfomance with the catalyst that the invention provides method regeneration is better than fresh dose.Though renovation process required time provided by the invention shortens dramatically than prior art, regeneration effect and not second to prior art.
Table-1 regenerated catalyst catalytic perfomance evaluating data table
| Reaction time (hour) | Conversion ratio (%) | |||||
| Fresh dose | Regenerative agent C | Regenerative agent D | Regenerative agent E | Regenerative agent F | Regenerative agent G | |
| 8 | 20.6 | 22.0 | 21.0 | 21.2 | 21.9 | 20.9 |
| 16 | 19.8 | 21.6 | 20.6 | 20.6 | 20.8 | 20.2 |
| 24 | 19.1 | 20.9 | 20.1 | 19.7 | 19.8 | 19.5 |
| 32 | 18.8 | 19.8 | 19.2 | 18.9 | 19.1 | 18.8 |
| 40 | 18.2 | 19.6 | 18.7 | 18.6 | 18.9 | 18.5 |
| 48 | 17.1 | 19.5 | 18.0 | 18.1 | 18.5 | 17.7 |
| 66 | 16.8 | 19.0 | 17.6 | 17.2 | 18.0 | 17.3 |
| 61 | 16.8 | 18.1 | 17.2 | 16.4 | 17.8 | 16.8 |
Claims (2)
1, a kind of renovation process of halogen-free support type catalyst made from platonic, it is characterized in that: decaying catalyst in rotary kiln in 200～350 ℃, 350～500 ℃, 500～550 ℃ hot-air, handled respectively successively 0.5～2 hour, dried catalyst was used the mixed impregnant liquor dipping be made up of chloroplatinic acid, stannous chloride, sodium chloride, hydrochloric acid and ethanol 0.5～1 hour, and the content of each component (by catalyst weight) is platinum 0.01～0.15%, tin 0.01～0.50%, sodium or lithium or potassium 0.01～0.50%, hydrochloric acid 1～10% in the mixed impregnant liquor; Catalyst behind the dipping 60～120 ℃ dry 2～4 hours down, dried catalyst is at 480～500 ℃, gas hourly space velocity 500～2000 hours
-1Condition under roasting 4～8 hours in dry air successively, roasting is 2～6 hours in containing 20～30% (percentage by volume) water vapour, again at 300～550 ℃, gas hourly space velocity 500～2000 hours
-1Condition under with water content less than the hydrogen reducing of 20PPm 1～10 hour.
2, method according to claim 1 is characterized in that: the sodium chloride in the mixed impregnant liquor can replace with lithium chloride or potassium chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95111129A CN1067604C (en) | 1995-07-25 | 1995-07-25 | Regeneration of catalyst for dehydrogenating normal paraffin hydrocarbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95111129A CN1067604C (en) | 1995-07-25 | 1995-07-25 | Regeneration of catalyst for dehydrogenating normal paraffin hydrocarbon |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1141218A CN1141218A (en) | 1997-01-29 |
| CN1067604C true CN1067604C (en) | 2001-06-27 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95111129A Expired - Fee Related CN1067604C (en) | 1995-07-25 | 1995-07-25 | Regeneration of catalyst for dehydrogenating normal paraffin hydrocarbon |
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| CN (1) | CN1067604C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101623643B (en) * | 2008-07-08 | 2011-07-20 | 中国石油化工股份有限公司 | Method for regenerating deactivated styrene catalyst through ethylbenzene dehydrogenation |
| CN102806094B (en) * | 2011-06-03 | 2014-06-04 | 中国石油天然气股份有限公司 | Regeneration method of C10-C13 long-chain n-alkanes dehydrogenation deactivated catalyst |
| US20140371501A1 (en) | 2012-02-20 | 2014-12-18 | Dow Global Technologies Llc | Reconstituted dehydrogenation catalyst showing slowed activity loss when compared with fresh catalyst |
| CN104588037B (en) * | 2013-11-03 | 2017-01-18 | 中国石油化工股份有限公司 | Regeneration method for dehydrogenation catalyst |
| CN113441110A (en) * | 2021-08-13 | 2021-09-28 | 成都中科普瑞净化设备有限公司 | Method for preparing adsorbent for adsorbing and separating carbon monoxide |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3803052A (en) * | 1969-11-26 | 1974-04-09 | Universal Oil Prod Co | Regeneration of a coke-deactivated catalyst comprising a combination of platinum,tin and halogen with a porous carrier material |
| 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 |
| US5227566A (en) * | 1991-01-09 | 1993-07-13 | Uop | Process for the dehydrogenation of hydrocarbons |
| CA2098651A1 (en) * | 1992-06-23 | 1993-12-24 | Rodolfo Iezzi | Process for dehydrogenating light paraffins in a fluidized bed reactor |
-
1995
- 1995-07-25 CN CN95111129A patent/CN1067604C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3803052A (en) * | 1969-11-26 | 1974-04-09 | Universal Oil Prod Co | Regeneration of a coke-deactivated catalyst comprising a combination of platinum,tin and halogen with a porous carrier material |
| 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 |
| US5227566A (en) * | 1991-01-09 | 1993-07-13 | Uop | Process for the dehydrogenation of hydrocarbons |
| CA2098651A1 (en) * | 1992-06-23 | 1993-12-24 | Rodolfo Iezzi | Process for dehydrogenating light paraffins in a fluidized bed reactor |
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| Publication number | Publication date |
|---|---|
| CN1141218A (en) | 1997-01-29 |
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