CN102407145A - Catalyst for normal heptane isomerization reaction and preparation method thereof - Google Patents
Catalyst for normal heptane isomerization reaction and preparation method thereof Download PDFInfo
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- CN102407145A CN102407145A CN2011103248325A CN201110324832A CN102407145A CN 102407145 A CN102407145 A CN 102407145A CN 2011103248325 A CN2011103248325 A CN 2011103248325A CN 201110324832 A CN201110324832 A CN 201110324832A CN 102407145 A CN102407145 A CN 102407145A
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- isomerization reaction
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Abstract
The invention belongs to the technical field of catalysts, and in particular relates to a catalyst for a normal heptane isomerization reaction and a preparation method thereof. In the invention, Pt/WO3/ZrO2 solid acid modified by an oxide M2O3(M=In, Fe, Cr) is taken as a catalyst. The content of the components in the catalyst is as follows: the mole ratio of M to Zr is 0.001-0.1; the content of WO3 is 6-30wt% and the content of Pt is 0.1-2wt%. The catalyst achieves an excellent effect when being used for a normal heptane isomerization reaction, the conversion rate of normal heptane is high, the selectivity of isomerization product is high and the stability of the catalyst is better.
Description
Technical field
The invention belongs to the chemical catalyst technical field, be specifically related to a kind of Catalysts and its preparation method of normal heptane isomerization reaction.
Background technology
In order to improve gasoline quality, make it more compliance with environmental protection requirements, people urgently hope to find the clean fuel chemical technology that can produce high-octane rating, not contain aromatic hydrocarbon simultaneously again.
n-C
7+(carbon number is the n-alkane more than 7 and 7) hysomer is a kind of solution with big potentiality.In the crude oil
n-C
7+Cut is isomerizated into the branched paraffin with higher octane under the effect of catalyst, these isomerization products can join in the gasoline and use, thereby improves octane number, therefore,
n-C
7+Isomerization has caused people's research enthusiasm greatly again.
The normal alkane isomerization catalyst system therefor is mainly noble metal (like Pt, Pd, Ir etc.) and loads on the metal/carrier bifunctional catalyst on the solid strong acid.In recent years, it is found that Pt/WO
3/ ZrO
2The type catalyst is right
n-C
7+Isomerization has reactivity worth preferably, and it has been done a large amount of research.Compare Pt/WO with traditional P t/ zeolite molecular sieve catalyst
3/ ZrO
2Acidity stronger, so it is than just having higher activity under the low reaction temperatures, and than Pt/SO
4 2-/ ZrO
2Catalyst, Pt/WO
3/ ZrO
2Acidity slightly a little less than, but in isomerization reaction, demonstrate higher selectivity and better stability, and insensitive to benzene in the reaction raw materials and sulfide impurities.Bibliographical information Pt/WO is arranged
3/ ZrO
2The a small amount of Al of middle interpolation
2O
3Perhaps Ga
2O
3Can improve the activity of catalyst to the normal heptane isomerization reaction, but with In
2O
3, Fe
2O
3, Cr
2O
3The Pt/WO of modification
3/ ZrO
2Catalyst is used for the normal heptane isomerization reaction and does not appear in the newspapers as yet.
Summary of the invention
The purpose of this invention is to provide a kind of new normal heptane isomerization catalyst and preparation method thereof, this catalyst is used for the normal heptane isomerization reaction, has the active high and high advantage of isomerization product selectivity.
The normal heptane isomerization catalyst that the present invention proposes is a kind of M of using
2O
3The Pt/WO of oxide modifying
3/ ZrO
2Solid acid catalyst, it is formed as follows:
A) with molar ratio computing, the M/Zr ratio is 0.001 ~ 0.1;
B) by weight percentage, WO
3Content is 6 ~ 30%, and Pt content is 0.1 ~ 2%.
Among the present invention, M
2O
3M can be In, Fe or Cr in the oxide.Be M
2O
3Oxide can be In
2O
3, Fe
2O
3Or Cr
2O
3
Among the present invention, with molar ratio computing, the preferable range of M/Zr ratio is 0.01 ~ 0.02; By weight percentage, WO
3The preferable range of content is 15 ~ 24%, and the preferable range of Pt content is 0.5 ~ 1%.
The preparation method of the normal heptane isomerization catalyst that the present invention proposes, concrete steps are following:
1, at first under the condition of constant pH=8 ~ 10, the mixing salt solution with 4 ~ 8 mol/L ammoniacal liquor hydrolysis Zr and M obtains Zr (OH)
4-M (OH)
3Mixed hydroxides; Above-mentioned mixed hydroxides is filtered washing, 80 ~ 120
oDry 10 ~ 36 hours of C;
2, with equi-volume impregnating with the salt solution impregnation of the W of aequum in Zr (OH)
4-M (OH)
3On, 80 ~ 120
oDry 10 ~ 36 hours of C;
3, in air atmosphere 700 ~ 850
oC roasting 2 ~ 5 hours promptly obtains WO
3/ ZrO
2M
2O
3Solid acid;
4, then, with equi-volume impregnating with the salt solution impregnation of the Pt of aequum in WO
3/ ZrO
2-M
2O
3On, 80 ~ 120
oDry 10 ~ 36 hours of C is in air atmosphere 400 ~ 500
oC roasting 2 ~ 5 hours promptly gets required catalyst.
The raw material that uses in the catalyst of the present invention is following: the raw material of Zr is selected from ZrOCl
28H
2O or ZrO (NO
3)
27H
2O, the raw material of W is selected from ammonium metatungstate, and the raw material of Pt is selected from nitric acid four ammino platinum or chloroplatinic acids, and the raw material of In is selected from In (NO
3)
34.5H
2O, the raw material of Fe is selected from Fe (NO
3)
39H
2O, the raw material of Cr is selected from Cr (NO
3)
39H
2O.
Catalyst of the present invention is owing to adopt M
2O
3The Pt/WO of (M=In, Fe, Cr) oxide modifying
3/ ZrO
2Solid acid is used for the normal heptane isomerization reaction, and this catalyst is 200
oUnder C reaction temperature, the condition of normal pressure, the normal heptane conversion ratio can reach 75.2%, and the selectivity of isomerization product can reach more than 95%.
The appreciation condition of gained catalyst of the present invention is: the reaction procatalyst is earlier 450
oUnder the C air-activated 2 hours, then in 250
oHydrogen reducing is 2 hours under the C, and isomerization reaction is 200
oCarry out under the C, the mass space velocity of normal heptane is 0.9 h
-1, H
2/
n-C
7Mol ratio is 27.
The specific embodiment
Through embodiment the present invention is done further elaboration below.
Embodiment 1: with 34.800 gram ZrO (NO
3)
27H
2O and 0.394 gram Fe (NO
3)
39H
2O is dissolved in the 400 mL water, stirs down above-mentioned solution and 6 mol/L ammoniacal liquor are dropwise joined in the ammonia spirit of 200 mL pH=9 simultaneously, and it is constant in 9 to control whole dropping process pH.The gained deposition is through filtration, washing, 100
oBehind dry 24 hours of the C, ammonium metatungstate solution impregnated in Zr (OH) with equi-volume impregnating
4-Fe (OH)
3On, 100
oBehind dry 24 hours of the C, in air atmosphere 800
oC roasting 3 hours promptly obtains WO
3/ ZrO
2-Fe
2O
3Solid acid.Then, with equi-volume impregnating with nitric acid four ammino platinum solution impregnation in WO
3/ ZrO
2-Fe
2O
3On, 100
oBehind dry 24 hours of the C, in air atmosphere 450
oThe C roasting got required catalyst in 3 hours.The Fe/Zr mol ratio is 0.01 in the catalyst, WO
3Content is 18%, and Pt content is 1%.
Embodiment 2 ~ 6: each step and condition by embodiment 1 prepare catalyst, and the preparation condition of change comprises the kind of M, M/Zr mol ratio, WO
3Content, sintering temperature are seen table 1.
Table 1 Pt/WO
3/ ZrO
2-M
2O
3The preparation of solid acid catalyst
? | M | The M/Zr mol ratio | WO 3Content (%) | Sintering temperature ( oC) |
Embodiment 2 | In | 0.02 | 18 | 800 |
Embodiment 3 | Cr | 0.02 | 18 | 800 |
Embodiment 4 | Fe | 0.02 | 24 | 800 |
Embodiment 5 | Fe | 0.03 | 15 | 850 |
Embodiment 6 | In | 0.01 | 15 | 750 |
Embodiment 7 | In | 0.03 | 21 | 800 |
Comparative Examples 1: the Pt/WO for preparing non-modification by step and the condition of embodiment 1
3/ ZrO
2Solid acid catalyst, any M undopes in the preparation process
2O
3Oxide.
Embodiment 8: in the normal heptane isomerization reaction, concrete reaction condition is following with above-mentioned catalyst applications: the reaction procatalyst is earlier 450
oActivation 2 hours in the air under the C is then in 250
oHydrogen reducing is 2 hours under the C, and isomerization reaction is 200
oCarry out under the C, the mass space velocity of normal heptane is 0.9 h
-1, H
2/
n-C
7Mol ratio is 27.The reactivity worth of catalyst and stability are seen table 2 and table 3 respectively.
The normal heptane isomerization reaction performance of table 2 catalyst
? | Reaction time (h) | Conversion ratio (%) | Selectivity (%) |
Embodiment 1 | 2 | 75.2 | 95.2 |
Embodiment 2 | 2 | 72.0 | 95.8 |
Embodiment 3 | 2 | 55.8 | 97.9 |
Embodiment 4 | 2 | 58.2 | 98.3 |
Embodiment 5 | 2 | 42.3 | 98.6 |
Embodiment 6 | 2 | 39.1 | 98.6 |
Embodiment 7 | 2 | 55.9 | 98.3 |
Comparative Examples 1 | 2 | 36.9 | 97.8 |
The stability of table 3 embodiment 1 catalyst
Reaction time (h) | Conversion ratio (%) | Selectivity (%) |
1 | 75.3 | 95.1 |
2 | 75.2 | 95.2 |
10 | 75.3 | 95.2 |
30 | 75.2 | 95.2 |
60 | 75.2 | 95.2 |
100 | 75.1 | 95.3 |
Claims (5)
1. the catalyst of a normal heptane isomerization reaction is characterized in that being M
2O
3The Pt/WO of oxide modifying
3/ ZrO
2Solid acid, M are In, Fe or Cr, and catalytic component content is following:
(a) with molar ratio computing, the M/Zr ratio is 0.001 ~ 0.1;
(b) by weight percentage, WO
3Content is 6 ~ 30%, and Pt content is 0.1 ~ 2%.
2. the catalyst of normal heptane isomerization reaction according to claim 1 is characterized in that, with molar ratio computing, the M/Zr ratio is 0.01 ~ 0.02.
3. according to the catalyst of the said normal heptane isomerization reaction of claim 1, it is characterized in that, by weight percentage, WO
3Content is 15 ~ 24%, and Pt content is 0.5 ~ 1%.
4. like the Preparation of catalysts method of the said normal heptane isomerization reaction of claim 1-3, it is characterized in that concrete steps are following:
(1) at first under the condition of constant pH=8 ~ 10, the mixing salt solution with 4 ~ 8 mol/L ammoniacal liquor hydrolysis Zr and M obtains Zr (OH)
4~ M (OH)
3Mixed hydroxides; Above-mentioned mixed hydroxides is filtered washing, 80 ~ 120
oDry 10 ~ 36 hours of C;
(2) with equi-volume impregnating with the salt solution impregnation of the W of aequum in Zr (OH)
4~ M (OH)
3On, 80 ~ 120
oDry 10 ~ 36 hours of C;
(3) in air atmosphere 700 ~ 850
oC roasting 2 ~ 5 hours promptly obtains WO
3/ ZrO
2~ M
2O
3Solid acid;
(4) then, with equi-volume impregnating with the salt solution impregnation of the Pt of aequum in WO
3/ ZrO
2~ M
2O
3On, 80 ~ 120
oDry 10 ~ 36 hours of C is in air atmosphere 400 ~ 500
oC roasting 2 ~ 5 hours promptly gets required catalyst.
5. according to the Preparation of catalysts method of the said normal heptane isomerization reaction of claim 4, it is characterized in that the raw material of Zr salt is selected from ZrOCl
28H
2O or ZrO (NO
3)
27H
2O, the raw material of W salt is selected from ammonium metatungstate, and the raw material of Pt is selected from nitric acid four ammino platinum or chloroplatinic acids, and the raw material of In salt is selected from In (NO
3)
34.5H
2O, the raw material of Fe salt is selected from Fe (NO
3)
39H
2O, the raw material of Cr salt is selected from Cr (NO
3)
39H
2O.
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Cited By (7)
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CN103611552A (en) * | 2013-11-07 | 2014-03-05 | 复旦大学 | Solid superacid catalyst for n-heptane isomerization reaction and preparation method thereof |
CN106140197A (en) * | 2015-03-24 | 2016-11-23 | 中国石油天然气股份有限公司 | Solid super acidic catalyst, preparation method thereof and isomerization method of light normal paraffin |
CN106140198A (en) * | 2015-03-24 | 2016-11-23 | 中国石油天然气股份有限公司 | Preparation method of light alkane isomerization catalyst and isomerization method of light alkane |
CN108079988A (en) * | 2016-11-23 | 2018-05-29 | 中国科学院大连化学物理研究所 | The catalyst of C5, C6 alkane isomerization and preparation and application |
CN109718801A (en) * | 2017-10-27 | 2019-05-07 | 万华化学集团股份有限公司 | A kind of catalyst for normal paraffin isomerization and preparation method thereof |
CN110314684A (en) * | 2018-03-30 | 2019-10-11 | 中国石油化工股份有限公司 | A kind of n-heptane isomerization catalyst and preparation method thereof |
CN111569861A (en) * | 2020-05-29 | 2020-08-25 | 河北工业大学 | Catalyst for reaction for converting isoparaffin into normal paraffin and preparation method thereof |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN1564711A (en) * | 2001-08-07 | 2005-01-12 | 麻省理工学院 | Non-zeolitic nanocomposite materials for solid acid catalysis |
-
2011
- 2011-10-24 CN CN 201110324832 patent/CN102407145B/en not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1564711A (en) * | 2001-08-07 | 2005-01-12 | 麻省理工学院 | Non-zeolitic nanocomposite materials for solid acid catalysis |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103611552B (en) * | 2013-11-07 | 2016-09-28 | 复旦大学 | A kind of solid super acid catalyst of n-heptane isomerization reaction and preparation method thereof |
CN103611552A (en) * | 2013-11-07 | 2014-03-05 | 复旦大学 | Solid superacid catalyst for n-heptane isomerization reaction and preparation method thereof |
CN106140198B (en) * | 2015-03-24 | 2019-06-07 | 中国石油天然气股份有限公司 | Preparation method of light alkane isomerization catalyst and isomerization method of light alkane |
CN106140197A (en) * | 2015-03-24 | 2016-11-23 | 中国石油天然气股份有限公司 | Solid super acidic catalyst, preparation method thereof and isomerization method of light normal paraffin |
CN106140198A (en) * | 2015-03-24 | 2016-11-23 | 中国石油天然气股份有限公司 | Preparation method of light alkane isomerization catalyst and isomerization method of light alkane |
CN106140197B (en) * | 2015-03-24 | 2019-03-12 | 中国石油天然气股份有限公司 | Solid super acidic catalyst, preparation method thereof and isomerization method of light normal paraffin |
CN108079988A (en) * | 2016-11-23 | 2018-05-29 | 中国科学院大连化学物理研究所 | The catalyst of C5, C6 alkane isomerization and preparation and application |
CN109718801A (en) * | 2017-10-27 | 2019-05-07 | 万华化学集团股份有限公司 | A kind of catalyst for normal paraffin isomerization and preparation method thereof |
CN109718801B (en) * | 2017-10-27 | 2022-02-15 | 万华化学集团股份有限公司 | N-alkane isomerization catalyst and preparation method thereof |
CN110314684A (en) * | 2018-03-30 | 2019-10-11 | 中国石油化工股份有限公司 | A kind of n-heptane isomerization catalyst and preparation method thereof |
CN110314684B (en) * | 2018-03-30 | 2021-11-16 | 中国石油化工股份有限公司 | N-heptane isomerization catalyst and preparation method thereof |
CN111569861A (en) * | 2020-05-29 | 2020-08-25 | 河北工业大学 | Catalyst for reaction for converting isoparaffin into normal paraffin and preparation method thereof |
CN111569861B (en) * | 2020-05-29 | 2023-04-07 | 河北工业大学 | Catalyst for reaction for converting isoparaffin into normal paraffin and preparation method thereof |
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