CN1026494C - Catalyst for one-stage selective hydrogenation of gasoline splitting - Google Patents
Catalyst for one-stage selective hydrogenation of gasoline splitting Download PDFInfo
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- CN1026494C CN1026494C CN 91109503 CN91109503A CN1026494C CN 1026494 C CN1026494 C CN 1026494C CN 91109503 CN91109503 CN 91109503 CN 91109503 A CN91109503 A CN 91109503A CN 1026494 C CN1026494 C CN 1026494C
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Abstract
The present invention relates to a catalyst for one-stage selective hydrogenation of gasoline splitting, which is composed of delta and alpha mixing crystal type aluminum oxide and palladium metal which is loaded on the delta and alpha mixing crystal type aluminum oxide. The bulk density of a carrier is 0.75 to 0.85 gram /ml, specific pore volume is not smaller than 0.45 ml/ gram, a specific surface area is 100 to 120 meter <2>/ gram, a Na2O content is not larger than 0.07 wt%, radial crushing strength is 8 to 10 kgf/ grain, and axial crushing strength is 50 kgf/ grain. The content of palladium is from 0.28 to 0.30 wt% on the basis of the carrier, and the palladium is a shell catalyst. Compared with the existing catalyst, the present invention has the advantages of moderate hydrogenating activity, low reaction temperature rise and high diolefin hydrogenation selectivity, so that the present invention is favorable for prolonging the regeneration period of the catalyst. When an arsenic content is raised to 853 ppb from 50 ppb, the present invention displays strong arsenic poisoning resisting capability.
Description
The present invention relates to a kind of one-stage selective hydrogenation of gasoline splitting catalyzer.
Pyrolysis gasoline is the important by-product that ethylene industry is produced, and is C
5～C
9Fraction, according to the difference of cracking stock and cracking severity, its output accounts for more than 50% of ethylene production capacity, and wherein aromaticity content accounts for 40～80%, is the important source of aromatic hydrocarbons therefore.Main cutting C on the industrial production
6～C
8Fraction, 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 or dehydrogenative condensation 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 quickens carbonaceous and the deposition of burnt matter on catalyzer, and 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 its hydrogenation performance fully, and this is very important in industrial application.
It is moderate to the purpose of this invention is to provide a kind of hydrogenation activity, diolefin hydrogenation selectivity height, and reaction temperature rising is low, has stronger anti-poisoning capability and operational condition pyrolysis gasoline hydrogenation catalyst stably.
Catalyzer of the present invention supports precious metal palladium (Pd) by δ, α mixing crystal formation aluminum oxide and constitutes.Palladium is eggshell type at carrier surface and distributes, and the content that with the carrier is benchmark is that 0.28～0.30%(is heavy), 0.09～0.15 millimeter of shell thickness.δ, α mixing crystal formation alumina supporter bulk density 0.75～0.85 grams per milliliter, specific pore volume 〉=0.45 milliliter/gram, 100～120 meters of specific surfaces
2/ gram, Na
2O content≤0.07%(is heavy), horizontal crushing strength 8～10Kgf/ grain, vertically crushing strength is the mechanical wafers about the 50Kgf/ grain.Catalyzer of the present invention is applicable to that the diene value reaches 37 gram iodine/100 gram oil, and iodine number reaches the hydrogenation reaction of the pyrolysis gasoline of 148 gram iodine/100 gram oil.
Preparation of catalysts method of the present invention 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 containing δ, α the mixings crystal formation alumina supporter of the salt solution impregnation of precious metal palladium through preimpregnation, soaked carrier is through washing, drying, roasting promptly gets the oxidation catalyst finished product in air.Finished catalyst only needs to lead to hydrogen reducing and can use in reactor.
Catalyzer of the present invention and the one section Pd/Al of pyrolysis gasoline that uses at present
2O
3Catalyzer is compared has following advantage:
Therefore 1. hydrogenation activity is moderate, and the diolefin hydrogenation selectivity is higher, has reduced the thermal discharge in the reaction process relatively, and the corresponding reduction of reaction temperature rising makes smooth operation, has avoided causing because of catalyst activity is too high reaction uppity situation (data see Table 1).
Table 1
Project has Pd/Al now
2O
3Catalyzer catalyzer of the present invention
Temperature in (℃) 30 30
Temperature out (℃) 118 109
Volume space velocity (time
-1) 99
Hydrogen/oil ratio (molecule) 0.2: 1 0.2: 1
Thermal insulation warming (℃) 88 79
Product diolefin hydrogenation selectivity
（%） 24.9 28.6
2. anti-arseniasis ability is strong (seeing example 4).
3. catalyst bulk density of the present invention is lower, when being applied to 300,000 tons of/year supporting pyrolysis gasoline of ethylene unit unit one-stage hydrogenation reactors, and its charge weitght and existing Pd/Al
2O
3Catalyzer is compared and can be reduced 29%, still can reach identical material treatment capacity.
4. catalyzer of the present invention is preserved with oxidation state, has therefore reduced the difficulty in the keeping, existing Pd/Al
2O
3Catalyzer is sold to go back ortho states.Catalyzer of the present invention logical on the spot hydrogen reducing in reactor can use.
Example 1
With deionized water preimpregnation carrier, filter solid carbon dioxide part then, use the palladium chloride solution impregnated carrier, again through washing, dry, in air, make catalyzer of the present invention, its physicals such as table 2 after the roasting.
Table 2
The catalyzer numbering
Project A B C
Carry apparent size Φ 4 * 4mm sheet Φ 4 * 4mm sheet Φ 4 * 5mm sheet
Surface area per unit volume (rice
2/ gram) 118 112 100～120
Rule specific pore volumes (milliliter/gram) 0.52 0.49 〉=0.45
Lattice Na
2O(weight %)＜0.05＜0.05≤0.07
Crushing strength (Kgf/ grain) radially 8.4 radially 9.8 radially 8～10
Axially＞50 axial 30 axially～50
Bulk density (grams per milliliter) 0.75 0.76 0.75～0.85
Palladium content (weight %) 0.3 0.3 0.28～0.30
Palladium layer thickness (millimeter) 0.12 0.14 0.09～0.15
Example 2
Carry out 150 hours activity ratings with example 1 described A, B, C on 300 milliliters of adiabatic reaction apparatus, evaluation result sees Table 3.
Table 3
Stock oil product diene adds diene and adds
Catalyzer hydrogen rate hydrogen is selected
Diene * iodine number * diene * iodine number * % %
A 12.0 87.5 0.12 46.8 99.0 25.5
B 15.2 90.5 0.36 44.8 97.6 27.9
C 12.5 87.7 0.14 43.4 98.9 24.5
Industrial 12.8 94.6 0.32 42.4 97.5 21.4
Pd/Al
2O
3
* restrain iodine/100 gram oil
Example 3
C catalyzer with example 1 carries out estimating in 1000 hours on 300ml adiabatic reactor reaction unit, and synthesis result sees Table 1.
Example 4
C catalyzer with example 1 carries out stability test in 1000 hours on 100ml isothermal trickle bed, synthesis result sees Table 4.
Table 4
The anti-raw produce diene diene of accumulative total adds
Hydrogenation rate hydrogen is selected between seasonable
(hr) diene * iodine number * diene * iodine number * % %
104 19.0 100.2 0.32 42.8 98.3 28.0
200 23.7 122.0 0.49 47.0 98.0 26.3
248 22.6 107.8 0.49 47.5 97.8 31.0
416 26.1 123.0 0.60 50.0 97.7 29.7
536 22.9 114.3 0.89 55.0 96.2 31.3
610 14.4 80.2 0.66 49.5 95.4 36.6
746 13.6 91.6 0.59 47.5 95.7 25.7
818 21.6 98.7 0.90 49.0 95.9 34.5
914 21.4 148.5 1.36 62.0 93.7 20.8
1004 37.0 117.6 2.15 60.5 94.2 46.8
* restrain iodine/100 gram oil
Example 5
It is on probation to carry out industry with the C catalyzer of example 1 in tonnage level ethylene unit pyrolysis gasoline unit first stage reactor, and its loadings is that prior art is used Pd/Al
2O
371% of catalyzer.Through running in 4000 hours, the charging diene is 18～28 gram iodine/100 gram oil, iodine number 65～86 gram iodine/100 gram oil, 16～25 ℃ of bed thermal insulation warmings, product diene value 1.7～2.5 gram iodine/100 gram oil, the diolefin hydrogenation rate is calculated as 86.5～93.3% by fresh feed oil, when iodine content when the 50ppb of design load increases to 853ppb, product diene value increases to 7.1 gram iodine/100 gram oil, and iodine content is reduced to just often, and product diene value can return to 2.23 gram iodine/100 gram oil.
Claims (2)
1, a kind of catalyzer that is used for one-stage selective hydrogenation of gasoline splitting, it is characterized in that it is the palladium metal that is supported 0.28～0.30% (weight) by σ, α mixing crystal formation aluminum oxide, the thickness that is the eggshell type distribution at carrier surface is 0.09～0.15 millimeter, carrier bulk density 0.75～0.85 grams per milliliter, specific pore volume 〉=0.45 grams per milliliter, 100～120 meters of specific surfaces
2/ gram, Na
2O content≤0.07% (weight), the horizontal 8～10kgf/ grain of crushing strength, vertically the 50kgf/ grain is machinery crushing moulding.
2, by the described hydrogenation catalyst of claim 1, it is characterized in that this catalyzer is applicable to that the diene value reaches 37 gram iodine/100 gram oil, iodine number reaches the adiabatic reactor and the isothermal reactor one-stage selective hydrogenation of gasoline splitting of 148 gram iodine/100 gram oil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91109503 CN1026494C (en) | 1991-10-04 | 1991-10-04 | Catalyst for one-stage selective hydrogenation of gasoline splitting |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91109503 CN1026494C (en) | 1991-10-04 | 1991-10-04 | Catalyst for one-stage selective hydrogenation of gasoline splitting |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1071443A CN1071443A (en) | 1993-04-28 |
| CN1026494C true CN1026494C (en) | 1994-11-09 |
Family
ID=4909870
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91109503 Expired - Lifetime CN1026494C (en) | 1991-10-04 | 1991-10-04 | Catalyst for one-stage selective hydrogenation of gasoline splitting |
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| Country | Link |
|---|---|
| CN (1) | CN1026494C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1107704C (en) * | 2000-02-03 | 2003-05-07 | 中国石油天然气股份有限公司兰州石化分公司 | Selective hydrogenation catalyst for pyrolysis gasoline |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1049680C (en) * | 1997-09-23 | 2000-02-23 | 中国石油化工集团公司 | Selective hydrogenation catalyst for alkyne in ethane-ethylene fraction |
| CN1084222C (en) * | 1998-06-10 | 2002-05-08 | 中国石化齐鲁石油化工公司 | Catalyst for selective hydrogenation of diolefin as raw material for alkylation of C4 and preparing method thereof |
| DE19839459A1 (en) * | 1998-08-29 | 2000-03-02 | Basf Ag | Catalyst used in refinery and petrochemical plants for hydrogenating hydrocarbon streams in gas or liquid phase comprises hydrogenation-active metal on aluminum oxide support |
| CN101121899B (en) * | 2006-08-11 | 2010-05-12 | 中国石油化工股份有限公司 | Selectivity hydrogenation method for whole fraction crack petroleum |
| 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 |
| CN102671657B (en) * | 2012-03-28 | 2014-06-04 | 中国科学院宁波材料技术与工程研究所 | 6-chloro-3-nitrotolyl-4-sulfonic acid liquid-phase hydrogenation catalyst and preparation method thereof |
| CN102698743B (en) * | 2012-05-18 | 2015-01-07 | 中国科学院宁波材料技术与工程研究所 | Catalyst for liquid-phase hydrogenation reduction reaction of 6-chloro-3-nitrotoluene-4-sulfonic acid (CLT acid) and method for preparing same |
| CN103657671B (en) | 2012-08-30 | 2015-07-08 | 中国科学院大连化学物理研究所 | Dialkenes selective hydrogenation catalyst and preparation method and application of dialkenes selective hydrogenation catalyst |
| CN112675837A (en) * | 2019-10-18 | 2021-04-20 | 中国石油化工股份有限公司 | Carbon four selective hydrogenation catalyst, preparation method and application thereof |
-
1991
- 1991-10-04 CN CN 91109503 patent/CN1026494C/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1107704C (en) * | 2000-02-03 | 2003-05-07 | 中国石油天然气股份有限公司兰州石化分公司 | Selective hydrogenation catalyst for pyrolysis gasoline |
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| Publication number | Publication date |
|---|---|
| CN1071443A (en) | 1993-04-28 |
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