CN102407145B - Catalyst for normal heptane isomerization reaction and preparation method thereof - Google Patents
Catalyst for normal heptane isomerization reaction and preparation method thereof Download PDFInfo
- Publication number
- CN102407145B CN102407145B CN 201110324832 CN201110324832A CN102407145B CN 102407145 B CN102407145 B CN 102407145B CN 201110324832 CN201110324832 CN 201110324832 CN 201110324832 A CN201110324832 A CN 201110324832A CN 102407145 B CN102407145 B CN 102407145B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- hour
- normal heptane
- zro
- isomerization reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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 wish 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 (as 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 Pt/ 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 selective and better stability, and insensitive to the 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 catalyst to the activity of 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 selective high advantage of isomerization product.
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 composed as follows:
A) with molar ratio computing, the M/Zr ratio is 0.001 ~ 0.1;
B) by weight percentage, WO
3Content is that 6 ~ 30%, 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 that the preferable range of 15 ~ 24%, Pt content is 0.5 ~ 1%.
The preparation method of the normal heptane isomerization catalyst that the present invention proposes, concrete steps are as follows:
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
oC drying 10 ~ 36 hours;
2, with equi-volume impregnating with the salt solution impregnation of the W of aequum in Zr (OH)
4-M (OH)
3On, 80 ~ 120
oC drying 10 ~ 36 hours;
3, in air atmosphere 700 ~ 850
oC roasting 2 ~ 5 hours namely 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
oC drying 10 ~ 36 hours is in air atmosphere 400 ~ 500
oC roasting 2 ~ 5 hours namely gets required catalyst.
The raw material that uses in the catalyst of the present invention is as follows: 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%, selectively can the reaching more than 95% of isomerization product.
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
The invention will be further elaborated below by embodiment.
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.Gained precipitates after filtration, washing, 100
oBehind dry 24 hours of the C, with equi-volume impregnating ammonium metatungstate solution be impregnated in Zr (OH)
4-Fe (OH)
3On, 100
oBehind dry 24 hours of the C, in air atmosphere 800
oC roasting 3 hours namely 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, WO in the catalyst
3Content is that 18%, 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 see 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: above-mentioned catalyst is applied in the normal heptane isomerization reaction, and concrete reaction condition is as follows: the reaction procatalyst is earlier 450
oActivate 2 hours in the air under the C, 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 see Table 2 and table 3 respectively.
The normal heptane isomerization reaction performance of table 2 catalyst
| ? | Reaction time (h) | Conversion ratio (%) | Selectively (%) |
| 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 (%) | Selectively (%) |
| 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 as follows:
(a) with molar ratio computing, M/Zr is than being 0.001-0.1;
(b) by weight percentage, WO
3Content is 6-30%, and Pt content is 0.1-2%;
This catalyst is prepared by following step:
(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 hour 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 hour of C;
(3) 700-850 in air atmosphere
oC roasting 2-5 hour namely 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 hour of C, 400-500 in air atmosphere
oC roasting 2-5 hour namely gets required catalyst.
2. the catalyst of normal heptane isomerization reaction according to claim 1 is characterized in that, with molar ratio computing, M/Zr is than being 0.01-0.02.
3. according to the catalyst of the described normal heptane isomerization reaction of claim 2, it is characterized in that, by weight percentage, WO
3Content is 15-24%, and Pt content is 0.5-1%.
4. the Preparation of catalysts method of normal heptane isomerization reaction according to claim 1 is characterized in that concrete steps are as follows:
(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 hour 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 hour of C;
(3) 700-850 in air atmosphere
oC roasting 2-5 hour namely 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 hour of C, 400-500 in air atmosphere
oC roasting 2-5 hour namely gets required catalyst.
5. according to the Preparation of catalysts method of the described 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110324832 CN102407145B (en) | 2011-10-24 | 2011-10-24 | Catalyst for normal heptane isomerization reaction and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110324832 CN102407145B (en) | 2011-10-24 | 2011-10-24 | Catalyst for normal heptane isomerization reaction and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102407145A CN102407145A (en) | 2012-04-11 |
| CN102407145B true CN102407145B (en) | 2013-07-10 |
Family
ID=45909668
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110324832 Expired - Fee Related CN102407145B (en) | 2011-10-24 | 2011-10-24 | Catalyst for normal heptane isomerization reaction and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102407145B (en) |
Families Citing this family (7)
| 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 |
| CN106140198B (en) * | 2015-03-24 | 2019-06-07 | 中国石油天然气股份有限公司 | The preparation method of Performance of Isomerization Catalysts for Light n-Paraffin and the isomerization method of light paraffins |
| CN106140197B (en) * | 2015-03-24 | 2019-03-12 | 中国石油天然气股份有限公司 | The isomerization method of solid super acid catalyst and preparation method thereof and 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 |
| 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 |
| 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 |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004537404A (en) * | 2001-08-07 | 2004-12-16 | マサチューセッツ・インスティチュート・オブ・テクノロジー | Non-zeolitic nanocomposite materials for solid acidic catalysts |
-
2011
- 2011-10-24 CN CN 201110324832 patent/CN102407145B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN102407145A (en) | 2012-04-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102407145B (en) | Catalyst for normal heptane isomerization reaction and preparation method thereof | |
| CN102302934B (en) | Novel auxiliary-modified catalyst for preparing methanol by catalytic hydrogenation of carbon dioxide and preparation method of catalyst | |
| CN105289710B (en) | A kind of CO2Catalyst of Hydrogenation isoparaffin and its preparation method and application | |
| CN104998659A (en) | Catalyst for catalyzing furfural or furfuryl alcohol to prepare cyclopentanol through hydrogenation rearrangement and preparation method and application method thereof | |
| CN100556544C (en) | A kind of preparation method of high isomerization active solid super acidic catalyst | |
| CN102626640B (en) | Monolithic catalyst for low temperature oxidation of methane and preparation thereof | |
| CN103157460B (en) | Rare earth oxide modified Cr2O3-ZrO2 catalyst, preparation method and application | |
| CN100548480C (en) | A kind of hydro carbons Working liquids product modifying catalyst and method for modifying | |
| CN103752306B (en) | Preparation method of a kind of prepared from benzene and hydrogen thiacyclohexane catalyst and products thereof and application | |
| CN102228834A (en) | Catalyst for catalytic hydrogenation and application thereof | |
| CN103785462B (en) | A kind of cycloalkane hydrogenation catalyst and its preparation method and application | |
| CN101979138B (en) | Cobalt-copper Fischer-Tropsch synthesis catalyst and preparation method thereof | |
| CN112705220B (en) | Catalyst for skeletal isomerization reaction of carbon tetra-alkane, preparation method and application thereof | |
| CN102649746A (en) | Method for producing glycolic acid ester through adding hydrogen in oxalic ester | |
| CN103611552B (en) | A kind of solid super acid catalyst of n-heptane isomerization reaction and preparation method thereof | |
| CN102757298B (en) | Method for preparing cyclohexane by benzene hydrogenation | |
| CN104437596A (en) | Methanol to arene catalyst and preparation method thereof | |
| CN104588022A (en) | High-activity Fischer-Tropsch synthesis catalyst, and preparation method and application thereof | |
| CN110882696B (en) | Catalyst for producing cyclane by hydrogenation of aromatic hydrocarbon and preparation method thereof | |
| CN1318134C (en) | Prepn of nickel-base catalyst for decomposing ammonia | |
| CN102533315A (en) | Method for hydro-dearomatization in catalytic cracking of diesel | |
| CN102641734B (en) | Catalyst for aryl hydrogen peroxide hydrogenation reduction and preparation and application thereof | |
| CN104725187A (en) | Technology for directly preparing ethyl alcohol and co-generating methane from synthesis gas | |
| CN103752327A (en) | Catalyst for producing isopropyl alcohol through acetone hydrogenation and method for catalytically producing isopropyl alcohol | |
| CN104109080B (en) | Through the method that acetic acid gas-phase catalytic hydrogenation prepares ethanol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130710 Termination date: 20141024 |
|
| EXPY | Termination of patent right or utility model |