CN1136051C - Middle-temp isomerizing catalyst and its preparing process - Google Patents

Middle-temp isomerizing catalyst and its preparing process Download PDF

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Publication number
CN1136051C
CN1136051C CNB001265938A CN00126593A CN1136051C CN 1136051 C CN1136051 C CN 1136051C CN B001265938 A CNB001265938 A CN B001265938A CN 00126593 A CN00126593 A CN 00126593A CN 1136051 C CN1136051 C CN 1136051C
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China
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catalyst
roasting
beta
molecular sieve
complex carrier
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CNB001265938A
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CN1305871A (en
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孙予罕
彭少逸
李芳�
任杰
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Shanxi Institute of Coal Chemistry of CAS
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Shanxi Institute of Coal Chemistry of CAS
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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
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The present invention relates to a moderate-temperature isomerization catalyst, more specifically to a Pt/Hbeta catalyst modified by a plurality of heteroatomic oxides (M=Nd, Ce, U or Cr). The catalyst comprises the following ingredients: 0.3 wt% of Pt, 1 to 25 wt% of heteroatomic oxides and 75 to 99 wt% of Hbeta. The catalyst is preapred by a mechanically mixing method and an immersion method. The catalyst can obviously improve the isomerizing selectivity to light hydrocarbon (such as n-C7) at a moderate temperature (240 to 280 DEG C), and simultaneously keep high conversion activity, particularly at 280 DEG C.

Description

Middle temp isomerizing catalyst and preparation method thereof
The invention belongs to a kind of middle temp isomerizing catalyst, relate in particular to Pt/H-Beta (Pt/H β) catalyst with hetero atom (M=Nd, Ce, U or Cr) oxide modifying.
Acid catalyzed alkane isomerization reaction is subjected to extensively attracting attention as the important reaction that synthetic high-knock rating gasoline adds component.At present, to C 7A large amount of research, C have been made in following alkane isomerization reaction 7And the alkane (C of longer carbochain 7+) higher and high-octane rating multibranched paraffin (containing quaternary carbon) is less because of lytic activity, application is restricted.So in actual applications, the application that makes isomerization process of cracking reaction is limited in C 4-C 6On the hydrocarbon.
The used catalyst of alkane isomerization mainly contains two types, is noble metal catalyst.Class is Pt-chloride/aluminium chloride, and operating temperature is lower, is 120-150 ℃, the reactivity height of this type of catalyst, and selectivity is good, but strict to sulphur in the raw material, water, and needs to replenish the chloride auxiliary agent.Another kind of is middle temperature Pt (or Pd)/molecular sieve catalyst, reaction temperature 260-280 ℃.Studies show that, at normal pressure and H 2/ n-C 7Under the condition of=15: 1 (mol), the C of Pt/H beta catalyst in the time of 240 ℃ 7Conversion ratio is 47.27%, isomerization selectivity 37.05%; After being warming up to 280 ℃, although C 7Conversion ratio rises to 97.88%, but isomerization selectivity＜5%.J.A.I.Ch.E.1993,39 (4): in 607 1 literary compositions, T.F.Degnan and C.R.Kennedy find, with Pt/Al 2O 3After the beta-molecular sieve physical mixed, below 300 ℃ to n-C 7Conversion reaction does not have activity substantially.
The object of the present invention is to provide a profit to have the optionally middle temp isomerizing catalyst of high activity, high isomerization.
The present invention at first adopts mechanical mixing to prepare M-H β complex carrier (M=Nd, Ce, U or Cr), again precious metals pt is immersed on this complex carrier, because of hetero atom and H β interact, make catalyst in the time of 240-280 ℃ to n-C 7Conversion reaction has greater activity and high isomerization selectivity.
Catalyst of the present invention is formed (weight ratio):
Pt 0.3 hetero atom oxide 1-25 H β 75-99
As above said hetero atom oxide is Nd, Ce, U or Cr oxide.
Catalyst of the present invention is to adopt mechanical mixing and immersion process for preparing.
(1) respectively with various heteroatomic nitrate and H beta-molecular sieve mechanical mixture evenly after, 800-825 ℃ of roasting 3h.
(2) product of roasting compression molding sieves out 20-40 purpose particle H 2PtCl 6Solution impregnation 24h, dried overnight behind 500 ℃ of roasting 5h, makes required catalyst.
The present invention compares with existing catalyst, has the following advantages:
(1) the paraffin hydro activity of conversion is higher, middle temp isomerizing selectivity height, and stability is also better.
(2) preparation process is simple, easy operating.
Embodiment 1
Take by weighing 0.08gNd (NO respectively 3) 36H 2O and 6gH beta-molecular sieve after mechanical mixture is even, through 800-825 ℃ of roasting 3h, obtain Nd-H β complex carrier, with the H of 3g complex carrier at 1.2ml 2PtCl 6Solution (1gH 2PtCl 66H 2O/50ml water) dipping 24h in, dried overnight in 500 ℃ of roasting 5h, makes catalyst A 1, catalyst is formed (weight ratio) and is: Pt0.3, Nd 2O 31, H β 99.
Embodiment 2
Take by weighing 0.78gNd (NO respectively 3) 36H 2O and 6gH beta-molecular sieve after mechanical mixture is even, through 800-825 ℃ of roasting 3h, obtain Nd-H β complex carrier, and all the other preparation process make catalyst A with embodiment 1 2, catalyst is formed (weight ratio) and is: Pt0.3, Nd 2O 310, H β 90.
Embodiment 3
Take by weighing 1.95gNd (NO respectively 3) 36H 2O and 6gH beta-molecular sieve after mechanical mixture is even, through 800-825 ℃ of roasting 3h, obtain Nd-H β complex carrier, and all the other preparation process make catalyst A with embodiment 1 3, catalyst is formed (weight ratio) and is: Pt0.3, Nd 2O 325, H β 75.
Embodiment 4
Take by weighing 0.08gCe (NO respectively 3) 36H 2O and 6gH beta-molecular sieve after mechanical mixture is even, through 800-825 ℃ of roasting 3h, obtain Ce-H β complex carrier, with the H of 3g complex carrier at 1.2ml 2PtCl 6Flood 24h in the solution, dried overnight in 500 ℃ of roasting 5h, makes catalyst B 1, catalyst is formed (weight ratio) and is: Pt0.3, Ce 2O 31, H β 99.
Embodiment 5
Take by weighing 0.79gCe (NO respectively 3) 36H 2O and 6gH beta-molecular sieve after mechanical mixture is even, through 800-825 ℃ of roasting 3h, obtain Ce-H β complex carrier, and all the other preparation process make catalyst B with embodiment 1 2, catalyst is formed (weight ratio) and is: Pt0.3, Ce 2O 310, H β 90.
Embodiment 6
Take by weighing 1.98gCe (NO respectively 3) 36H 2O and 6gH beta-molecular sieve after mechanical mixture is even, through 800-825 ℃ of roasting 3h, obtain Ce-H β complex carrier, and all the other preparation process make catalyst B with embodiment 1 3, catalyst is formed (weight ratio) and is: Pt0.3, Ce 2O 325, H β 75.
Embodiment 7
Take by weighing 0.1gUO respectively 2(NO 3) 26H 2O and 6gH beta-molecular sieve after mechanical mixture is even, through 800-825 ℃ of roasting 3h, obtain U-H β complex carrier, with the H of 3g complex carrier at 1.2ml 2PtCl 6Flood 24h in the solution, dried overnight in 500 ℃ of roasting 5h, makes catalyst C 1, catalyst is formed (weight ratio) and is: Pt0.3, UO 31, H β 99.
Embodiment 8
Take by weighing 1.05gUO respectively 2(NO 3) 26H 2O and 6gH beta-molecular sieve after mechanical mixture is even, through 800-825 ℃ of roasting 3h, obtain U-H β complex carrier, and all the other preparation process make catalyst C with embodiment 1 2, catalyst is formed (weight ratio) and is: Pt0.3, UO 310, H β 90.
Embodiment 9
Take by weighing 2.63gUO respectively 2(NO 3) 26H 2O and 6gH beta-molecular sieve after mechanical mixture is even, through 800-825 ℃ of roasting 3h, obtain U-H β complex carrier, and all the other preparation process make catalyst C with embodiment 1 3, catalyst is formed (weight ratio) and is: Pt0.3, UO 325, H β 75.
Embodiment 10
Take by weighing 0.16gCr (NO respectively 3) 39H 2O and 6g H beta-molecular sieve after mechanical mixture is even, through 800-825 ℃ of roasting 3h, get Cr-H β complex carrier, with the H of 3g complex carrier at 1.2ml 2PtCl 6Flood 24h in the solution, dried overnight in 500 ℃ of roasting 5h, makes catalyst D 1, catalyst is formed (weight ratio) and is: Pt0.3, Cr 2O 31, H β 99.
Embodiment 11
Take by weighing 1.58gCr (NO respectively 3) 39H 2O and 6gH beta-molecular sieve after mechanical mixture is even, through 800-825 ℃ of roasting 3h, obtain Cr-H β complex carrier, and all the other preparation process make catalyst D with embodiment 1 2, catalyst is formed (weight ratio) and is: Pt0.3, Cr 2O 310, H β 90.
Embodiment 12
Take by weighing 3.95gCr (NO respectively 3) 39H 2O and 6gH beta-molecular sieve after mechanical mixture is even, through 800-825 ℃ of roasting 3h, obtain Cr-H β complex carrier, and all the other preparation process make catalyst D with embodiment 1 3, catalyst is formed (weight ratio) and is: Pt0.3, Cr 2O 325, H β 75.
The evaluating catalyst method that each embodiment makes is:
Make raw material with normal heptane, the weight (hourly) space velocity (WHSV) (WHSV) of micro-amounts of liquids pump feed liquor is 2ml/g.h, H 2: n-C 7=15: 1 (mol).Elder generation, faces hydrogen again and is warming up to 470 ℃ at 250 ℃ of preliminary treatment 1.5h with Ar gas before the reaction, behind the reductase 12 h, and the sample introduction reaction.Product ov-101 capillary chromatographic column on-line analysis, fid detector, sample analysis behind the reaction 1h.
Catalyst Reaction temperature (℃) C 7Conversion ratio (%) Selectivity of product (%)
Isomerized products Pyrolysis product The aromatization product
A 1 240 20.37 95.35 3.87 0.78
280 80.61 84.07 12.28 3.65
A 2 280 35.06 90.38 6.96 2.67
A 3 280 48.65 90.04 7.55 2.41
B 1 240 26.69 95.04 4.21 0.75
280 85.12 77.16 18.57 4.27
B 2 240 23.93 94.26 4.94 0.8
280 88.92 67.01 28.59 4.4
B 3 240 19.44 93.57 5.58 0.85
280 83.44 76.75 19.64 3.61
C 1 240 29.37 93.66 5.44 0.9
280 83.74 79.19 16.79 4.02
C 2 240 16.1 96.65 2.42 0.93
280 77.86 83.56 12.49 3.95
C 3 240 17.46 97.63 1.64 0.73
280 77.34 87.52 8.14 4.34
D 1 240 18.02 94.3 4.96 0.74
280 75.35 84.53 11.58 3.89
D 2 240 24.28 93.6 5.68 0.72
280 81.72 82.29 14.34 3.37
D 3 240 18.89 95.47 3.78 0.75
280 85.18 78.15 17.68 4.17
Annotate: this reaction result refers to one way reaction conversion ratio and isomerization selectivity.

Claims (3)

1. temp isomerizing catalyst in a kind is characterized in that the weight ratio constituent of described catalyst is:
Pt 0.3
Hetero atom oxide 1-25
Hβ 75-99。
2. temp isomerizing catalyst in as claimed in claim 1 is characterized in that the hetero atom oxide in the described catalyst is the oxide of Nd, Ce, U or Cr.
3. Preparation of catalysts method as claimed in claim 1 or 2 is characterized in that:
(1) respectively with various heteroatomic nitrate and H beta-molecular sieve mechanical mixture evenly after, 800-825 ℃ of roasting 3h;
(2) product of roasting compression molding sieves out 20-40 purpose particle H 2PtCl 6Solution impregnation 24h, dried overnight, 500 ℃ of roasting 5h.
CNB001265938A 2000-09-30 2000-09-30 Middle-temp isomerizing catalyst and its preparing process Expired - Fee Related CN1136051C (en)

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Application Number Priority Date Filing Date Title
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CN1136051C true CN1136051C (en) 2004-01-28

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Publication number Priority date Publication date Assignee Title
CN101172248B (en) * 2006-10-31 2010-08-25 中国石油化工股份有限公司 C7-C20alkane isomerization catalyst and isomerization process

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