CN1218020C - First-stage selective hydrogenation catalyst for pyrolysis gasaline - Google Patents
First-stage selective hydrogenation catalyst for pyrolysis gasaline Download PDFInfo
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- CN1218020C CN1218020C CN 02111016 CN02111016A CN1218020C CN 1218020 C CN1218020 C CN 1218020C CN 02111016 CN02111016 CN 02111016 CN 02111016 A CN02111016 A CN 02111016A CN 1218020 C CN1218020 C CN 1218020C
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- selective hydrogenation
- catalyzer
- stage selective
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Abstract
The present invention relates to a catalyst for one-stage selective hydrogenation of gasoline cracking. The present invention mainly solves the problem of low diolefin hydrogenation selectivity when single component metal palladium is used in the past technique. The present invention uses the technical scheme that the palladium is loaded on a delta phase alumina supporter, wherein the pore volume of the supporter is from 0.6 to 0.9 ml / gram, the specific surface area is from 140 to 170 meters <2>, and the shell thickness of the catalyst is from 03 to 0.09 millimeter. The catalyst can be used in the industrial production of the one-stage selective hydrogenation of gasoline cracking.
Description
Technical field
The present invention relates to a kind of catalyzer that is used for one-stage selective hydrogenation of gasoline splitting.
Background technology
Liquid by-product C when pyrolysis gasoline is light oil (petroleum naphtha, gas wet goods) cracking production ethene, propylene
5～C
10The general name of cut.Pyrolysis gasoline is formed very complicated, mainly contain the organic compound of benzene,toluene,xylene, monoolefine, diolefin, straight-chain paraffin, naphthenic hydrocarbon and nitrogen, sulphur, oxygen, chlorine and heavy metal etc., more than totally 200 component, wherein benzene,toluene,xylene (being referred to as BTX) aromatic hydrocarbons is about 50～80%, unsaturated hydrocarbons 25～30%.Main cutting C on the industrial production
6～C
8Cut, through one-stage selective hydrogenation, remove the height unsaturated hydrocarbons, as chain conjugated dienes, vinylbenzene, cyclic conjugated diene etc., again through the secondary hydrogenation desulfurization, make the extractive raw material of aromatic hydrocarbons behind the organic compound of removal monoolefine and sulphur, nitrogen, oxygen, produce the usefulness of benzene,toluene,xylene, also can be only through one-stage hydrogenation, remove diolefin, keep most of monoolefine, thereby obtain stable motor spirit dopant, or the higher motor spirit of octane value.The pyrolysis gasoline hydrogenation catalyst of using on the Chemical Manufacture has Pd-Cr/Al at present
2O
3Deng bimetallic catalyst, Pd/Al is arranged also
2O
3Catalyzer.Existing P d-Cr/Al
2O
3The hydrogenation activity of bimetallic catalyst, many indexs such as diolefin hydrogenation selectivity are all not as existing P d/Al
2O
3Catalyzer.Diolefin in the pyrolysis gasoline is polymerization at high temperature easily, therefore one section catalyst hydrogenation activity is unsuitable too high, be advisable with moderate, and has a higher diolefin hydrogenation selectivity, temperature rise increases because monoolefin hydrogenation induces reaction to reduce, and then quickening carbonaceous and the deposition of burnt matter on catalyzer, catalyzer should have bigger appearance glue ability simultaneously, to prolong the regeneration period of catalyzer.The existing just Pd/Al of above-mentioned condition
2O
3Catalyzer is failed the problem of fine solution.In addition, the existence of micro amount of arsenic in the pyrolysis gasoline is to cause Pd/Al
2O
3How the important factor of poisoning of catalyst improves Pd/Al
2O
3The anti-arseniasis ability of catalyzer, promptly arsenic can not be adsorbed on the catalyst surface securely when arsenic content surpasses 50ppb, in case arsenic content returns to normally, the arsenic of absorption just can be washed out by qualified stock oil, catalyzer promptly recovers the hydrogenation performance fully, and this is very important in industrial application.
Introduced a kind of catalyzer that is used for one-stage selective hydrogenation of gasoline splitting among the document Chinese patent CN1071443A.Be carrier with δ, α mixing crystal formation aluminum oxide in the document, palladium metal of load 0.28～0.30% (weight) on it, being eggshell type at carrier surface distributes, the finished catalyst shell thickness is 0.09～0.15 millimeter, used carrier bulk density 0.75～0.85 grams per milliliter, specific pore volume 〉=0.45 milliliter/gram, 100～120 meters of specific surfaces
2/ gram, carrier is mechanical compression molding.This catalyzer is because its pore volume is less, so the colloidal sol ability is not high, requires the temperature in of reactor lower in addition, only 30 ℃, on the adiabatic reactor reaction unit, investigate, though have stability preferably, but the diolefin hydrogenation selectivity is also lower, generally about 25～30%.Introduced a kind of selective hydrogenation catalyst for pyrolysis gasoline that is used among the document Chinese patent CN1266085A.Be carrier with δ, α mixing crystal formation aluminum oxide in the document, supported precious metal palladium and basic metal and/or alkaline-earth metal isoreactivity component, the specific pore volume of carrier are 0.5～0.9 milliliter/gram, and specific surface is 70～140 meters
2/ gram, the shape of carrier can be that machinery is beaten sheet type, trifolium or cylinder extrusion.This catalyzer active result that investigates on adiabatic reactor has only the diene Value Data, does not disclose the raw material iodine number of raw material and reactor product.All be at least the catalyzer of dual-active component among same U.S. Pat 6054409 and the US5889187, but it does not announce catalyst activity, has only announced active deactivation data.
Summary of the invention
Technical problem to be solved by this invention is to overcome in the past when using the single-component palladium metal in the document, and the shortcoming that the diolefin hydrogenation selectivity is lower provides a kind of new catalyzer that is used for one-stage selective hydrogenation of gasoline splitting.It is moderate that this catalyzer has hydrogenation activity, and diolefin hydrogenation selectivity height has stronger anti-poisoning capability, the characteristics that operational stability is good.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of catalyzer that is used for one-stage selective hydrogenation of gasoline splitting, with the aluminum oxide is carrier, loaded metal palladium on alumina supporter, the charge capacity of palladium metal is 0.05～0.4% of a catalyst weight, and wherein the pore volume of alumina supporter is 0.6～0.9 a milliliter/gram, and the active constituent palladium is eggshell type at carrier surface and distributes, the crystalline phase of carrier is the δ phase, and the specific surface area of carrier is 140～170 meters
2/ gram, the catalyzer shell thickness is 0.03～0.09 millimeter.
The pore volume preferable range of alumina supporter is 0.6～0.7 a milliliter/gram in the technique scheme, and the charge capacity preferable range of palladium metal is 0.2～0.25% of a catalyst weight, and catalyzer shell thickness preferable range is 0.05～0.08 millimeter.The right cylinder that is shaped as 1～4 hole of alumina supporter, preferable range are the right cylinder in 1 hole.
The preparation method of alumina supporter is as follows: the employing hydrated aluminum oxide is a raw material, add pore-creating agent (gac, graphite etc.) by a certain percentage, caking agent (water, nitric acid or aluminium colloidal sol), through mechanically mixing, to mediate, extrusion molding is the right cylinder with 1～4 hole, then in low temperature (120 ℃) drying, through 900～1000 ℃ of roasting temperatures 4～6 hours, promptly making pore volume is 0.6～0.9 milliliter/gram, and specific surface is 140～170 meters
2The δ phase alumina carrier of/gram.
The Preparation of catalysts method is identical with common lamella catalyst dipping technique: earlier with a kind of liquid preimpregnation carrier that can dissolve each other with steeping fluid, again with the salt solution impregnation that contains precious metal palladium through the δ of preimpregnation crystal formation alumina supporter, soaked carrier through washing, dry, roasting promptly gets the oxidation catalyst finished product in air.Finished catalyst only needs to lead to hydrogen reducing and can use in reactor.
The present invention is because carrier adopts the right cylinder carrier that contains 1～4 hole, so the carrier geometrical surface is bigger, and the reaction bed pressure drop can be reduced, help reaction and remove heat, simultaneously can make bed temperature more even, help improving the purpose product selectivity, adapt to the high-speed running; Help the dispersion of palladium simultaneously, reduce the content of palladium.The pore volume of carrier is bigger, can improve the burnt ability of appearance of catalyzer.The palladium metal shell thickness is controlled at 0.03～0.09 millimeter, on the one hand helps suppressing the side reaction of deep hydrogenation, also help the homodisperse of palladium metal on the other hand, improve the utilization ratio of palladium, help to reach and improve optionally purpose.The catalyzer that the present invention makes, through evidence, the diolefin hydrogenation selectivity can reach more than 38%, has stability preferably simultaneously, has obtained better technical effect.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1～3]
With deionized water preimpregnation carrier, filter solid carbon dioxide part then, use the palladium chloride solution impregnated carrier, through washing, drying, in air, make catalyst A of the present invention, B or C, its physicals such as table 1 after the roasting respectively again.
Table 1
[embodiment 4]
In 30 milliliters isothermal trickle-bed reactor, carry out 150 hours activity ratings respectively with embodiment 1～3 described A, B, C catalyzer, appreciation condition is: loaded catalyst is 30 milliliters (bed height is 23.5～25 centimetres), reaction pressure is 2.7～2.8MPa, bathing temperature is 52～56 ℃, and raw material is C
5～C
9Fraction, liquid air speed are 8.0 hours
-1, hydrogen/oil ratio (volume/volume) is 60: 1, and temperature in is 44～45 ℃, and evaluation result sees Table 2.
Table 2
| Catalyzer | Stock oil | Product | Diolefin hydrogenation rate % | Diolefin hydrogenation selectivity % | ||
| Diene * | Iodine number * | Diene * | Iodine number * | |||
| A B C | 31.08 29.14 30.46 | 100.2 95.59 101.0 | 0.35 0.27 0.41 | 40.32 40.78 41.79 | 98.87 99.07 98.65 | 40.84 41.69 40.48 |
* restrain iodine/100 gram oil
[embodiment 5]
B catalyzer with embodiment 2 carries out estimating in 1000 hours in 100 milliliters of adiabatic trickle-bed reactors, and appreciation condition is: loaded catalyst is 100 milliliters (bed height is 30 centimetres), and reaction pressure is 2.7～2.8MPa, and bathing temperature is 52～56 ℃, and raw material is C
5～C
9Fraction, green oil air speed are 3.0 hours
-1(volume), turning oil air speed are 8.8 hours-1 (volume), and raw material is that green oil adds turning oil, hydrogen/green oil (volume/volume)=110: 1, and temperature in is 44～45 ℃, evaluation result sees Table 3.
Table 3
| Accumulative total reaction times hour | Raw material | Product | Temperature out ℃ | Diolefin hydrogenation rate % | Diolefin hydrogenation selectivity % | ||
| Diene * | Iodine number | Diene * | Iodine number | ||||
| 85 205 309 386 414 581 741 800 1003 | 8.51 6.87 6.87 7.82 6.44 10.40 16.97 16.97 10.99 | 47.74 50.31 50.31 64.67 64.23 72.53 78.45 78.45 74.99 | 0.70 0.36 0.54 0.07 0.12 0.73 0.47 0.50 0.36 | 32.32 36.97 37.93 48.29 52.46 53.65 45.18 47.03 53.89 | 104 97 98 93 98 99 98 98 98 | 91.77 94.76 92.14 99.10 98.14 92.98 97.23 97.05 96.72 | 40.61 39.24 40.73 38.27 42.32 40.78 39.74 41.53 40.24 |
* restrain iodine/100 gram oil
Claims (6)
1, a kind of catalyzer that is used for one-stage selective hydrogenation of gasoline splitting, with the aluminum oxide is carrier, loaded metal palladium on alumina supporter, the charge capacity of palladium metal is 0.05～0.4% of a catalyst weight, wherein the pore volume of alumina supporter is 0.6～0.9 a milliliter/gram, the active constituent palladium is eggshell type at carrier surface and distributes, and the crystalline phase that it is characterized in that carrier is the δ phase, and the specific surface area of carrier is 140～170 meters
2/ gram, the catalyzer shell thickness is 0.03～0.09 millimeter.
2, according to the described catalyzer that is used for one-stage selective hydrogenation of gasoline splitting of claim 1, the pore volume that it is characterized in that alumina supporter is 0.6～0.7 a milliliter/gram.
3, according to the described catalyzer that is used for one-stage selective hydrogenation of gasoline splitting of claim 1, the charge capacity that it is characterized in that palladium metal is 0.2～0.25% of a catalyst weight.
4,, it is characterized in that the catalyzer shell thickness is 0.05～0.08 millimeter according to the described catalyzer that is used for one-stage selective hydrogenation of gasoline splitting of claim 1.
5,, it is characterized in that the right cylinder that is shaped as 1～4 hole of alumina supporter according to the described catalyzer that is used for one-stage selective hydrogenation of gasoline splitting of claim 1.
6,, it is characterized in that the right cylinder that is shaped as 1 hole of alumina supporter according to the described catalyzer that is used for one-stage selective hydrogenation of gasoline splitting of claim 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02111016 CN1218020C (en) | 2002-03-13 | 2002-03-13 | First-stage selective hydrogenation catalyst for pyrolysis gasaline |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02111016 CN1218020C (en) | 2002-03-13 | 2002-03-13 | First-stage selective hydrogenation catalyst for pyrolysis gasaline |
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| CN1443829A CN1443829A (en) | 2003-09-24 |
| CN1218020C true CN1218020C (en) | 2005-09-07 |
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| CN 02111016 Expired - Lifetime CN1218020C (en) | 2002-03-13 | 2002-03-13 | First-stage selective hydrogenation catalyst for pyrolysis gasaline |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101423775B (en) | 2007-11-01 | 2010-05-12 | 中国石油天然气股份有限公司 | Selective nickel hydrogenation catalyst and preparation method thereof |
| CN101433841B (en) | 2007-12-13 | 2010-04-14 | 中国石油天然气股份有限公司 | Selective hydrogenation catalyst and preparation method thereof |
| CN101429453B (en) * | 2008-03-19 | 2010-05-12 | 中国石油天然气股份有限公司 | Pyrolysis gasoline fraction one-stage selective hydrogenation method |
| US20140235914A1 (en) * | 2013-02-19 | 2014-08-21 | Basf Corporation | Eggshell Catalyst Composites Containing Tungsten Oxide or Tungsten Oxide Hydrate |
| CN113249140B (en) * | 2020-02-11 | 2022-12-09 | 中国石油化工股份有限公司 | Method for hydrogenation of pyrolysis gasoline |
| CN113244914B (en) * | 2020-02-11 | 2023-04-07 | 中国石油化工股份有限公司 | Pyrolysis gasoline selective hydrogenation catalyst and preparation method and application thereof |
| CN115722221B (en) * | 2021-08-26 | 2024-04-09 | 中国石油化工股份有限公司 | Catalytic oxidation catalyst and preparation method thereof |
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