CN1253987A - Gasoline hydrogenation treatment catalyst - Google Patents
Gasoline hydrogenation treatment catalyst Download PDFInfo
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- CN1253987A CN1253987A CN 98114481 CN98114481A CN1253987A CN 1253987 A CN1253987 A CN 1253987A CN 98114481 CN98114481 CN 98114481 CN 98114481 A CN98114481 A CN 98114481A CN 1253987 A CN1253987 A CN 1253987A
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- gasoline
- catalyzer
- treatment catalyst
- hydrogenation treatment
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Abstract
The gasoline hydrofining catalyst is formed from active component and carrier, and is characterized by that the active component composition consists of (wt%) Ni 5-30%, Fe 0.1-5%, Mn 0.1-5% and X 0.1-10%, in which X is one or several kinds selected from W, Sn, V, Cr, Ru, Pd, Co and Cu, and its carrier is active alumina. Said invented catalyst is high in hydrogenation selectivity, and possesses strong resistance to sulfur, nitrogen and other toxic material.
Description
The present invention relates to catalyzer, a kind of gasoline hydrogenation treatment catalyst is provided especially.
Gasoline by explained hereafter such as water vapour thermo-cracking or catalytic pyrolysiss generally all contains diolefin and sulfur-nitrogen compound, causes the stability of this gasoline very poor, remove these impurity and generally adopt catalytic hydrofinishing technology.Adopt two-section hydrotreating art breading water vapour pyrolysis gasoline such as US 4113603, first section is used the Ni-W catalyzer, and this catalyzer sulfur tolerance is good, can handle the high gasoline of sulphur content, and second section is used Pd/Al
2O
3Catalyzer; US 3492220 uses the Ni catalyzer, can only handle low-sulfur content gasoline; GB 2131043 uses the catalyzer of different Ni content and different operational conditions, two-stage hydrogenation, and this mode helps control reaction temperature, optionally removes the diolefin in the gasoline, and shortcoming is not to be suitable for the high gasoline of sulfur-bearing.
The object of the present invention is to provide a kind of gasoline hydrogenation treatment catalyst, its hydrogenation selectivity height, and the nitrogen of anti-sulphur poisonous substance ability is strong.
The invention provides a kind of gasoline hydrogenation treatment catalyst, form, it is characterized in that the weight percentage of active ingredient is by live generation part and carrier
Ni??????????5～30％
Fe??????????0.1～5％
Mn??????????0.1～5％
X???????????0.1～10％
Wherein X is selected from W, Sn, V, Cr, Ru, Pd, Co, one or more of Cu; Carrier is an activated alumina.
The optimum content of active constituent is among the present invention
Ni??????????8～15％
Fe??????????0.5～2.5％
Mn??????????0.5～2.5％
X???????????0.5～3.5％
But catalyzer of the present invention prevulcanized is before use handled, and prevulcanized can make the hydrogenation selectivity of catalyzer and stability improve.Prevulcanized can be carried out in reactor or outside the reactor, can use conventional vulcanization process.
Catalyzer of the present invention is a kind of novel catalyzer, and the formation of catalyzer is different with other patent, and this catalyzer is to the hydrogenation selectivity height of diolefin, and the few hydrogenation of monoolefine, and poisonous substance such as the nitrogen of anti-sulphur.
Below by embodiment in detail the present invention is described in detail.
Embodiment 1
Preparation of Catalyst: take by weighing a certain amount of nickelous nitrate, iron nitrate, Manganous chloride tetrahydrate, sodium wolframate is put into a large beaker, adds the suitable quantity of water dissolving, more a certain amount of active aluminum oxide carrier is immersed, and stirs gently, and placement is spent the night.Then in 110 ℃ of oven dry, 450 ℃ of roastings are 8 hours again.The catalyzer that obtains consist of 10%Ni-0.8% Fe-1.2%Mn-0.3%W/Al
2O
3Also will carry out prevulcanized to catalyzer generally speaking and handle, prevulcanized is handled and can be carried out outside reactor, also can carry out in reactor, and this example is carried out in reactor according to a conventional method.
Catalyst performance test: take by weighing 15 gram catalyzer (granularity 20～40 orders), in the reactor of the internal diameter 10mm that packs into.In hydrogen, be warming up to 450 ℃, reduced 8 hours, reduce to 150 ℃, feed and to contain the solvent of sulphur, and slowly be warming up to 300 ℃, 300 ℃ of constant temperature 5 hours.Be cooled to 150 ℃, under a certain amount of flow hydrogen gas, feed gasoline.The rerum natura of gasoline is as follows before the hydrogenation:
Diolefin content: 2.8wt%
Monoolefine content: 31.5wt%
Octane value: 95
Total sulfur content: 800PPm
Total nitrogen content: 360PPm
Oxidation induction period: 42 minutes
The rerum natura of gasoline is as follows behind the hydrogenation:
Diolefin content: 0.03wt%
Monoolefine content: 32.3wt%
Octane value: 94
Oxidation induction period:＞480 minutes
Embodiment 2～12 and relevant comparative example 1～3 are listed in the table 1.
Need to prove: the composition of catalyzer has only provided the percentage composition of each metallic element, and all the other are made of oxygen element and activated alumina; It is identical with embodiment 1 to test used gasoline, and test condition is also identical.
Table 1 catalyzer is selected the hydrogenation The performance test results to gasoline
| Gasoline is behind shortening | ||||||
| Numbering | Catalyzer is formed (wt%) | Diolefin content (%) | Monoolefine content (%) | Octane value | Inductive phase (minute) | The nitrogen of anti-sulphur ability |
| Embodiment 2 | 10Ni-0.2Fe-0.2Mn-0.7W -0.7V/Al 2O 3 | ???0.03 | ???32.6 | ??94 | ?＞480 | By force |
| Embodiment 3 | 5Ni-0.5Fe-0.8Mn-1.2Co /Al 2O 3 | ???0.03 | ???31.6 | ??93 | ?＞480 | By force |
| Embodiment 4 | 8Ni-1.0Fe-0.8Mn-0.01Pd -0.1Sn/Al 2O 3 | ???0.04 | ???32.3 | ??94 | ?＞480 | By force |
| Embodiment 5 | 12Ni-0.1Fe-0.3Mn-0.3Sn -0.2Cr/Al 2O 3 | ???0.03 | ???32.9 | ??94 | ?＞480 | By force |
| Embodiment 6 | 15Ni-0.8Fe-0.1Mn-1.0W /Al 2O 3 | ???0.02 | ???31.3 | ??94 | ?＞480 | By force |
| Embodiment 7 | 27Ni-0.1Fe-0.4Mn-0.1Co /Al 2O 3 | ???0.03 | ???32.2 | ??94 | ?＞480 | By force |
| Embodiment 8 | 10Ni-0.8Fe-1.8Mn/Al 2O 3 | ???0.05 | ???32.0 | ??94 | ?＞480 | By force |
| Embodiment 9 | 10Ni-4.2Fe-0.1Mn/Al 2O 3 | ???0.03 | ???32.1 | ??94 | ?＞480 | By force |
| Embodiment 10 | 10Ni-0.2Fe-5Mn/Al 2O 3 | ???0.02 | ???30.1 | ??93 | ?＞480 | By force |
| Embodiment 11 | 6Ni-0.7Fe-0.8Mn-3W- 0.1Ru-6Cu/Al 2O 3 | ???0.05 | ???31.8 | ??94 | ?＞480 | By force |
| Embodiment 12 | 9Ni-1.5Fe-1.5Mn-0.1Sn- 0.2V-0.8Co-1.2Cu/Al 2O 3 | ???0.03 | ???33.1 | ??94 | ?＞480 | By force |
| Comparative example 1 | 10Ni/Al 2O 3 | ???0.11 | ???23.5 | ??83 | ?182 | Difference |
| Comparative example 2 | 15Ni-1.5Fe/Al 2O 3 | ???0.15 | ???25.3 | ??85 | ?150 | Difference |
| Comparative example 3 | 10Ni-2.3Mn/Al 2O 3 | ???0.12 | ???26.3 | ??86 | ?163 | Difference |
Claims (2)
1. a gasoline hydrogenation treatment catalyst is made up of live generation part and carrier, it is characterized in that the weight percentage of active ingredient is
Ni????????5～30％
Fe????????0.1～5％
Mn????????0.1～5％
X?????????0.1～10％
Wherein X is selected from W, Sn, V, Cr, Ru, Pd, Co, one or more of Cu; Carrier is an activated alumina.
2. according to the described gasoline hydrogenation treatment catalyst of claim 1, it is characterized in that the content of active constituent is
Ni????????8～15％
Fe????????0.5～2.5％
Mn????????0.5～2.5％
X?????????0.5～3.5％。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98114481 CN1100853C (en) | 1998-11-18 | 1998-11-18 | Gasoline hydrogenation treatment catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98114481 CN1100853C (en) | 1998-11-18 | 1998-11-18 | Gasoline hydrogenation treatment catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1253987A true CN1253987A (en) | 2000-05-24 |
| CN1100853C CN1100853C (en) | 2003-02-05 |
Family
ID=5224140
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 98114481 Expired - Fee Related CN1100853C (en) | 1998-11-18 | 1998-11-18 | Gasoline hydrogenation treatment catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1100853C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1101454C (en) * | 2000-08-22 | 2003-02-12 | 中国石油化工股份有限公司 | Hydrodesulfurizing catalyst for fraction oil and its preparing method |
| CN101191079B (en) * | 2006-11-21 | 2011-03-23 | 中国石油化工股份有限公司上海石油化工研究院 | Selectivity hydrogenation method for whole fraction crack petroleum |
| CN101480618B (en) * | 2009-01-22 | 2011-04-13 | 江苏佳誉信实业有限公司 | Gasoline hydrogenation pretreatment catalyst as well as production method and use thereof |
| CN101590411B (en) * | 2008-05-28 | 2012-11-07 | 北京三聚环保新材料股份有限公司 | Non-noble metal hydrogenation catalyst and preparation method thereof |
| CN104383923A (en) * | 2013-07-18 | 2015-03-04 | 中国石油大学(北京) | Gasoline and diesel hydrogenation iron-based catalyst and application thereof |
| US10335773B2 (en) | 2013-07-18 | 2019-07-02 | China University of Petroleum—Beijing | Fe-based hydrogenation catalyst and use thereof |
-
1998
- 1998-11-18 CN CN 98114481 patent/CN1100853C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1101454C (en) * | 2000-08-22 | 2003-02-12 | 中国石油化工股份有限公司 | Hydrodesulfurizing catalyst for fraction oil and its preparing method |
| CN101191079B (en) * | 2006-11-21 | 2011-03-23 | 中国石油化工股份有限公司上海石油化工研究院 | Selectivity hydrogenation method for whole fraction crack petroleum |
| CN101590411B (en) * | 2008-05-28 | 2012-11-07 | 北京三聚环保新材料股份有限公司 | Non-noble metal hydrogenation catalyst and preparation method thereof |
| CN101480618B (en) * | 2009-01-22 | 2011-04-13 | 江苏佳誉信实业有限公司 | Gasoline hydrogenation pretreatment catalyst as well as production method and use thereof |
| CN104383923A (en) * | 2013-07-18 | 2015-03-04 | 中国石油大学(北京) | Gasoline and diesel hydrogenation iron-based catalyst and application thereof |
| CN104383923B (en) * | 2013-07-18 | 2016-07-06 | 中国石油大学(北京) | A kind of gasoline, diesel hydrogenation ferrum-based catalyst and application thereof |
| US10335773B2 (en) | 2013-07-18 | 2019-07-02 | China University of Petroleum—Beijing | Fe-based hydrogenation catalyst and use thereof |
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| Publication number | Publication date |
|---|---|
| CN1100853C (en) | 2003-02-05 |
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