CN101031359B - Ex-situ reduction and dry passivation of noble metal catalysts - Google Patents
Ex-situ reduction and dry passivation of noble metal catalysts Download PDFInfo
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Abstract
A method of ex-situ activation and dry passivation of supported noble metal catalysts including the steps of reducing in the presence of hydrogen and dry passivation by cooling in an inert atmosphere and exposing to air or by filling the pores of the catalyst with a low sulfur oil before exposing to air.
Description
Background of invention
The present invention relates to ex situ (ex-situ) activation and the passivating method of catalyst.Especially, these methods relate to the noble metal catalyst that loads on mesopore or the zeolitic material.These technology are applicable to that also all absorb the catalyst of the noble metal of water and working load.
The original position nitrogen drying of noble metal catalyst and hydrogen reduction are difficult to realize sometimes in industrial equipment.Catalyst must be at first at inert gas (N
2) following bone dry, must in the hydrogen reduction process, water partial pressure be remained on extremely low level to prevent the noble metal of destruction height dispersion then.Industrial equipment contains multiple processing gas composition, and minimum operational pressure and purge gas speed are had restriction.Therefore, for big catalytic amount, in-situ activation sustainable several weeks, and success greatly depends on accurate processing gas dew point and measures, and this is quite insecure.In addition, desiccant nitrogen is not that total energy obtains, and is very expensive and buy fully dry required enormous amount.
Ex-situ reduction and dry passivation have been eliminated the demand to extensive in-situ treatment.This has reduced start-up time, and eliminated destroy in the industrial in-situ reducing process in the presence of moisture that noble metal disperses may.
At present, most of noble metal catalysts are the reactor of packing under the situation of oxide form at metal, then in this commercial plant on the spot with noble metal activation/reduction.As mentioned above, in-situ activation sustainable several weeks, and cross humid existence meeting in the reduction process and obviously destroy noble metal and disperse.For limited purposes,, and in inert atmosphere, the catalyst that reduces is immersed in excessive oil, wax or the liquid with the passivation noble metal immediately the activation of noble metal ex situ.But, be immersed in the extremely difficult processing of catalyst in the excess liq, and in most of many bed bioreactors of can not packing into.
Brief summary of the invention
The present invention contains the ex-situ reduction of the loaded noble metal catalyst of mesopore or zeolite matrix and dry passivation method.This method comprise with this catalyst reduction and under the situation that does not have excess liq with the step of this catalyst structure.In a kind of preferred embodiment, at first in inert atmosphere, the catalyst that reduces is cooled off, be exposed in the air then.In another kind of preferred embodiment, can in inert atmosphere, fill the hole of the catalyst of reduction with oil.Because only the hole is filled by oil, described catalyst still keeps dry and flows freely.
In a kind of preferred embodiment, load type metal catalyst is at U.S.5, described in 098,684 load on MCM-41 that aluminium oxide combines on palladium and platinum.
The accompanying drawing summary
That Fig. 1 has shown in-situ reducing and the comparison of the palladium of ex-situ reduction and platinum loaded catalyst performance according to the present invention as in Example 2.
Fig. 2 has shown the catalyst performance of embodiment 4.
Fig. 3 has shown the catalyst performance of the air passivation of embodiment 4.
Fig. 4 has shown the catalyst performance of the oily filler opening of embodiment 5.
DESCRIPTION OF THE PREFERRED
The present invention is the ex situ activation and the dry passivation method of loaded noble metal catalyst.This method comprises two step procedure.At first, with the at first dry and reduction in single step in the presence of hydrogen and noble gas mixtures of the metal oxide containing precious metals of load.Secondly, also be exposed in the air then, or before in being exposed to air, use super-low sulfur mineral oil catalyst filling hole, the catalyst dry passivation of reduction by cooling in inert atmosphere.Passivated catalyst is dry and free-pouring, and heating promptly begins the handling oil charging without further processing then to remove the free water and the oxygen of passivation in the industrial reactor of can easily packing into, in hydrogen.
Ex-situ reduction and passivation can reduce start-up time, and destroy the possibility that noble metal disperses in the in-situ reducing process of elimination in the presence of moisture.Although in the industrial ex situ passivation of catalyst in excessive oil or wax of having carried out reduction, be novel with air or by the dry passivation that oil-hole filling is carried out, and the advantage that flows freely catalyst is provided.In addition, the pilot plant data show, the catalyst of ex-situ reduction and dry passivation has with gas with bone dry and carries out the performance that the catalyst of controlled dried in place and reduction step is equal to.Method described in the following examples be used to load on MCM-41 that aluminium oxide combines on palladium and platinum.
Embodiment 1: in-situ reducing
Catalyst contain load on MCM-41 that aluminium oxide combines on 0.3 weight % platinum and 0.9 weight % palladium.At first the aqueous solution with nitric acid four ammino platinum and nitric acid four ammino palladiums is adsorbed onto on the carrier, thus with platinum and palladium high degree of dispersion on the surface of this catalyst carrier.Behind metal coat, with carrier drying, calcining stays the platinum and the palladium oxide of fine dispersion so that tetrammine decomposes in air then.Before using, must be by reduction platinum and palladium oxide under the situation of not destroying the metal dispersion so that catalyst be activated.
Current practice is with these noble metal catalysts industrial reactor of packing into, and at first dry this catalyst in nitrogen, this noble metal of reduction in hydrogen then.As shown in following table 1, must be with the catalyst bone dry in the inert gas at nitrogen and so on before the reduction, and must water partial pressure be remained on extremely low-levelly to prevent to destroy the dispersion of noble metal in the hydrogen reduction process, simultaneous temperature is necessary at least 150 ℃ to reduce noble metal fully.
Table 1
The influence of drying condition
Concerning some limited purposes, can be with the noble metal ex-situ reduction, the catalyst that is about to reduction of existing side by side immerses in excessive oil, wax or other liquid (in inert atmosphere) with the passivation noble metal.But, be immersed in the extremely difficult processing of catalyst in the excess liq, and because they can not be packed in most of many bed bioreactors, it only can be used for single bed bioreactor.
Embodiment 2: ex-situ reduction and passivation
In ex-situ reduction, at first in the rotary calcining stove, in the presence of the mixture of hydrogen and inert gas with metal oxide containing precious metals dry and reduction in single step of load.As shown in table 2, the result of the absorption of the oxidation on the sample that nitrogen covers shows that catalyst reduces fully after the ex-situ reduction in the rotary calcining stove, and noble metal does not gather.
In nitrogen,, the catalyst of reduction at room temperature is exposed in the air, prepares the catalyst of air passivation thus the catalyst cooling of reduction.In this step, oxygen is absorbed on the catalyst surface, with the noble metal oxidation that prevents to reduce.Oxidation absorption measured value (0.01O/M) shown in the table 2 shows that the noble metal position is covered by oxygen.In addition, chemisorbed test also shows, can easily remove oxide coating under as mild as a dove condition (in hydrogen＞35 ℃), to expose the active noble metals position of reduction fully and high degree of dispersion.
At inert gas (N
2) under, use oily filler opening passivating technique to prepare oily filler opening passivated catalyst.In this case, the pharmaceutical grade white oil is added in the catalyst of reduction to pore volume to fill about 95%.Can not be by the reducing catalyst sample of oxidation absorption method analysis with oily passivation.
Table 2
The metal of the catalyst of ex-situ reduction disperses
Embodiment 3: the evaluation and test of the catalyst of ex-situ reduction and dry passivation
To pack in the pilot plant reactor from the reduction of embodiment 2 and passivated catalyst sample, and evaluate and test the hydrorefined performance of 600N dewaxed oil that every kind of catalyst is crossed hydrogenation treatment.With dewaxed oil in advance hydrogenation treatment so that sulfur content is reduced to about 200wppm.
The noble metal catalyst of the three kinds of ex-situ reductions of about 5cc and passivation packed into go up in the fluid micro-reactor.These comprise all by the noble metal catalyst of ex-situ reduction and passivation: (1) is flooded in excessive oil by present employing, (2) by be exposed in the surrounding air or (3) by using the mineral oil filler opening.Catalyst is heated to 150 ℃ in the hydrogen with 2psi water partial pressure, simulation has recycle hydrogen and handles the typical industry startup of gas scrubbing.Begin oily charging then, and service condition is adjusted to 2LHSV, 100psig and 2,500scf/bbl.Temperature of reactor rises to 275 ℃, keeps then constant about 7 to 10 days.Hydrogen purity is 100%, not using gases recirculation.
For relatively, with commercial catalysts sample in-situ reducing, evaluation and test is used for the same hydrorefined performance of 600N dewaxed oil then.In this case, use the same program catalyst of packing into, then in nitrogen 260 ℃ of dryings, be cooled to room temperature, in dry hydrogen,, be cooled to 150 ℃ then in about 260 ℃ of reduction.This order representative is used for " optimal cases " of the perfect in-situ reducing of noble metal catalyst.Add oily charging then, and regulate service condition as mentioned above.
The product quality that every day, monitoring was determined by aromatic compounds, sulphur and nitrogen content.Aromatic compounds is measured (mM/kilogram) by the UV absorption process.Fig. 1 has shown the aromatic compounds total amount of conduct at the function of the time of using.As shown in the figure, initial aromatics saturation degree (arosat) performance of all ex situ hydrogen reductions and catalyst deactivation is equal to or is better than the in-situ reducing catalyst.In addition, the sample of ex-situ reduction and dry passivation (with air or by carrying out passivation with oily filler opening) has better aromatic compounds saturation degree performance with comparing by the ex-situ reduction sample that is immersed in passivation in the white oil.
Dry oil is better than the advantage of air passivation
The following examples have compared the performance of the two kinds of dry passivation catalyst (empty G﹠O filler opening is with the noble metal of protection reduction) of embodiment 2 under stricter entry condition.Except that the passivation of metal of reduction, oily filler opening technology also provide make catalyst store and processing procedure in to the minimized advantage of the absorption of water, so reduced the generation of water in the start-up course, and further reduced the risk of metal sintering.
Dewaxed oil the processing raw material of using hydrogenation treatment to cross as catalyst evaluation and test usefulness.This oil is the dewaxed oil (18 ℃) that contains Trace Sulfur (4.7wppm) and about 5.5 weight % aromatic compounds (124 mM/kilogram).
Embodiment 4: oxide catalyst
It is basic example that humid gas on oxide catalyst is handled, and compares sky G﹠O passivated catalyst performance with it.Make the noble metal catalyst process drying steps (140 ℃) of oxide state and the reduction step (220 ℃) of carrying out with the humid gas that contains about 2.2psia water partial pressure.Metal sintering can take place in studies show that before under these reducing conditions, thereby generates the lower catalyst of performance.
In the process that humid gas is handled, and when the device condition changes, before transferring dry hydrogen to, be increased to 3.5psia about 1 hour at 150 ℃ of water partial pressures with catalyst.To install pressure then and slowly be increased to the 2000psig operating pressure, and add dewaxed oil.Then, temperature of reactor is risen to 220 ℃ operating temperature.
In addition, again the performance of catalyst performance with the oxide catalyst of and the reduction dry with dry gas of using traditional pilot plant to start compared.With this catalyst at N
2In 150 ℃ of dryings, and at H
2In 250 ℃ the reduction 8 hours.
As expected, handle oxide catalyst with humid gas and produce the performance catalyst lower than the catalyst of dry-cure.The performance of in table 3 and Fig. 2, having summarized the oxide catalyst of humid gas and dry gas processing.
Table 3
Embodiment 5: air passivation and oily filler opening passivated catalyst
Empty G﹠O filler opening is all imposed humid gas with reduction and passivated catalyst to be handled.The catalyst of the air passivation of in two reactors, packing into.A kind of catalyst is through 2 hours drying steps (140 ℃) and 16 hours reduction steps (140 ℃) of carrying out with the humid gas that contains about 1psia water partial pressure.Second kind of air passivation catalyst directly reduced 16 hours at 140 ℃ with wet hydrogen, the cancellation drying steps.
The oily filler opening passivated catalyst of packing in two other reactor, it is extrudate or crushing form.When handling other catalyst, these two reactors remain under the static dried nitrogen pressure (200psig).Before transferring dry hydrogen gas to, wet hydrogen (1psia) was handled about 4 hours on oily filler opening passivated catalyst at 140 ℃.
The result
Fig. 3 and table 4 have shown the lower-performance of air catalyst deactivation when with wet nitrogen and hydrogen treat.Obviously, this catalyst activity is starkly lower than the catalyst of and reduction dry with dry gas.
Find that the hydrogenation property of air passivation catalyst that only imposes wet hydrogen is a little more than the oxide catalyst of the embodiment 4 that handles with wet nitrogen and wet hydrogen.
Fig. 4 and table 4 show that oily filler opening passivated catalyst performance is similar with the oxide catalyst that uses the dry also embodiment 4 of reduction of dry gas according to traditional pilot plant program.These results show, tangible metal sintering does not take place, and reactive metal can carry out hydrogenation reaction fully.
At observed little performance difference between extrudate and the crushing catalyst is to fill result preferably when using the crushing catalyst in the minor diameter reactor, maybe may be the result of mass transfer limitations.
Claims (10)
1. have the ex-situ reduction and the dry passivation method of the loaded noble metal catalyst hole and that contain mesopore or zeolite matrix, comprising:
(a) dry and reduce described catalyst under the situation of the mixture that has hydrogen and inert gas in single step, make the catalyst that is reduced,
(b) by under the situation that does not have excess liq, filling the hole of the described catalyst that is reduced with oil, with the described catalyst structure that is reduced, make the described catalyst that is reduced keep dry and flow freely and
(c) with the described catalyst exposure that is passivated in air.
2. the process of claim 1 wherein that described oil is white oil.
3. the process of claim 1 wherein that described oil is paraffin oil.
4. the process of claim 1 wherein that described oil is mineral oil.
5. the process of claim 1 wherein that described catalyst is palladium and the platinum that loads on the MCM-41.
6. the process of claim 1 wherein that described noble metal is palladium and platinum.
7. have the ex-situ reduction and the dry passivation method of the loaded noble metal catalyst hole and that contain mesopore or zeolite matrix, comprising:
(a) dry and reduce described catalyst under the situation of the mixture that has hydrogen and inert gas in single step, make the catalyst that is reduced,
(b) by in inert atmosphere the cooling with the described catalyst structure that is reduced, make the described catalyst that is reduced keep dry and flow freely and
(c) with the described catalyst exposure that is passivated in air.
8. the method for claim 7, wherein said inert atmosphere is a nitrogen.
9. the method for claim 7, wherein said noble metal is palladium and platinum.
10. the method for claim 7, wherein said catalyst is palladium and the platinum that loads on the MCM-41.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US61501604P | 2004-10-01 | 2004-10-01 | |
| US60/615,016 | 2004-10-01 | ||
| US11/228,366 | 2005-09-16 | ||
| US11/228,366 US7407909B2 (en) | 2004-10-01 | 2005-09-16 | Ex-situ reduction and dry passivation of noble metal catalysts |
| PCT/US2005/034752 WO2006039316A2 (en) | 2004-10-01 | 2005-09-27 | Ex-situ reduction and dry passivation of noble metal catalysts |
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| CN101031359A CN101031359A (en) | 2007-09-05 |
| CN101031359B true CN101031359B (en) | 2010-10-27 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4372841A (en) * | 1979-12-31 | 1983-02-08 | Exxon Research And Engineering Co. | Process for reducing coke formation in heavy feed catalytic cracking |
| CN1136070A (en) * | 1996-01-30 | 1996-11-20 | 中国石油化工总公司 | Catalyst for removing arsentic from liquid hydrocarbon and its preparation |
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2005
- 2005-09-27 CN CN2005800331982A patent/CN101031359B/en active Active
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- 2007-03-30 ZA ZA200702698A patent/ZA200702698B/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4372841A (en) * | 1979-12-31 | 1983-02-08 | Exxon Research And Engineering Co. | Process for reducing coke formation in heavy feed catalytic cracking |
| CN1136070A (en) * | 1996-01-30 | 1996-11-20 | 中国石油化工总公司 | Catalyst for removing arsentic from liquid hydrocarbon and its preparation |
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| ZA200702698B (en) | 2008-08-27 |
| CN101031359A (en) | 2007-09-05 |
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