CN105709833A - Preparation of light gasoline etherification catalyst - Google Patents
Preparation of light gasoline etherification catalyst Download PDFInfo
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- CN105709833A CN105709833A CN201610068817.1A CN201610068817A CN105709833A CN 105709833 A CN105709833 A CN 105709833A CN 201610068817 A CN201610068817 A CN 201610068817A CN 105709833 A CN105709833 A CN 105709833A
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- molecular sieve
- beta
- sulfonic acid
- propyl sulfonic
- catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Liquid Carbonaceous Fuels (AREA)
Abstract
The invention discloses preparation of a light gasoline etherification catalyst. A Hbeta molecular sieve serves as a carrier and loaded with 1-propylsulfonic-3-methyliMidazolium dihydrogen phosphate and propylsulfonic pyridine lactone, and the light gasoline etherification conversion rate can be increased.
Description
Technical field
The present invention relates to a kind of method producing catalyst for etherification, particularly the preparation of a kind of Etherification of Light FCC Gasoline catalyst.
Technical background
Etherification of Light FCC Gasoline technology is that the C5～C7 active olefin in catalytic cracking unit stable gasoline reacts the corresponding ether of generation with methanol, thus reducing the content of alkene in gasoline.Octane number after etherified can improve 1～3 unit.The relatively low methanol of price can be made to be the gasoline products of high added value by etherification conversion by ether-based device, improve the economic benefit of oil plant.Etherification of Light FCC Gasoline technology specifically includes that the operations such as weight vapour oil separating, selective hydrogenation, catalyst etherifying, product separation, Methanol Recovery.
CN102553616A relates to the catalyst that light FCC gasoline etherificate is prepared etherified benzine, and described catalyst comprises amorphous silicon alumina supporter and load oxysulfide on the carrier.The application further relates to the method preparing described catalyst, and described method includes, with ammonium sulfate, ammonium bisulfate solution, sulfuric acid solution or its mixed solution dipping amorphous silicon alumina supporter, then being dried and baking inphases by impregnated amorphous silica-alumina carrier segments.The application further relates to the method that prepared by light FCC gasoline etherificate etherified benzine, and described method includes making light gasoline and the mixed material of methanol contact with described catalyst and react.
CN1654602 provides one can be greatly shortened technological process, thus reducing production equipment and bringing and operate olefin-containing Etherification of Light FCC Gasoline method easily, the method does not adopt noble metal catalyst, thus solves noble metal and easily run off and the technological deficiency of sulfur poisoning.Technical scheme is as follows: olefin-containing Etherification of Light FCC Gasoline method, including olefin-containing light gasoline being removed diene, elimination alkali nitrogen and carrying out etherification reaction of hydro-refining, it is characterized in that: elimination diene and elimination alkali nitrogen are combined into one section and carry out selective hydrogenation by adopting difunctional non-precious metal catalyst by first paragraph, second segment is heterogeneous activity alkene and carries out etherification reaction of hydro-refining with methanol, produces etherified gasoline.
Above patent and the used catalyst of known technology has low temperature active difference all to a certain extent, active acid constituent is easy to run off, regenerate difficulty etc. deficiency.
Summary of the invention
For the deficiencies in the prior art, invent the preparation of a kind of Etherification of Light FCC Gasoline catalyst.By certain proportioning in a kettle., adding H beta-molecular sieve, dehydrated alcohol, 1-propyl sulfonic acid-3-Methylimidazole. dihydric phosphate under stirring, propyl sulfonic acid pyridine lactone participates in reaction.
The invention provides the preparation of a kind of Etherification of Light FCC Gasoline catalyst, realized by following steps:
In a kettle., add H beta-molecular sieve under stirring, add the dehydrated alcohol of H beta-molecular sieve quality 2-4 times, adding the 1-propyl sulfonic acid-3-Methylimidazole. dihydric phosphate of H beta-molecular sieve mass percentage content 0.5-2%, the propyl sulfonic acid pyridine lactone being subsequently adding H beta-molecular sieve weight/mass percentage composition 0.5-2 participates in reaction, and charge temperature controls at 0-10 DEG C, after having fed in raw material, it is warming up to 20-50 DEG C, reacts 2-5h, after reaction terminates, filter, it is washed to neutrality, dries, obtain qualified products.
Described H beta-molecular sieve is commercially available prod；Described 1-propyl sulfonic acid-3-Methylimidazole. dihydric phosphate, propyl sulfonic acid pyridine lactone is commercially available prod, such as the product of Chinese Academy of Sciences's Lanzhou Chemical Physics Research Institute.
This product has the advantages that
1) H beta-molecular sieve can keep being simultaneously generated of microcellular structure mesoporous to the full extent, and the B-acid amount of suitable etherification reaction is moderate.
2) H beta-molecular sieve load strong acidic ion liquid 1-propyl sulfonic acid-3-Methylimidazole. dihydric phosphate, propyl sulfonic acid pyridine lactone, the advantage such as this system has catalyst amount height little, active, can be easily separated, substrate universality is wide, can improve the conversion ratio of Etherification of Light FCC Gasoline.
Detailed description of the invention
Following instance is only further illustrate the present invention, is not restriction the scope of protection of the invention.
Embodiment 1:
In 1000L reactor, add H beta-molecular sieve 100Kg, dehydrated alcohol 300Kg, adding 1Kg1-propyl sulfonic acid-3-Methylimidazole. dihydric phosphate, 1Kg propyl sulfonic acid pyridine lactone participates in reaction, and charge temperature controls at 5 DEG C, after having fed in raw material, it is warming up to 40 DEG C, reacts 3h, after reaction terminates, filter, be washed to neutrality, dry, obtaining qualified products, products obtained therefrom is numbered B-1.
Embodiment 2
In 1000L reactor, add H beta-molecular sieve 100Kg, dehydrated alcohol 200Kg, adding 0.5Kg1-propyl sulfonic acid-3-Methylimidazole. dihydric phosphate, 0.5Kg propyl sulfonic acid pyridine lactone participates in reaction, and charge temperature controls at 0 DEG C, after having fed in raw material, it is warming up to 20 DEG C, reacts 5h, after reaction terminates, filter, be washed to neutrality, dry, obtaining qualified products, products obtained therefrom is numbered B-2.
Embodiment 3
In 1000L reactor, add H beta-molecular sieve 100Kg, dehydrated alcohol 400Kg, adding 2Kg1-propyl sulfonic acid-3-Methylimidazole. dihydric phosphate, 2Kg propyl sulfonic acid pyridine lactone participates in reaction, and charge temperature controls at 10 DEG C, after having fed in raw material, it is warming up to 50 DEG C, reacts 2h, after reaction terminates, filter, be washed to neutrality, dry, obtaining qualified products, products obtained therefrom is numbered B-3.
Comparative example 1
Being added without 1-propyl sulfonic acid-3-Methylimidazole. dihydric phosphate, the other the same as in Example 1, products obtained therefrom is numbered B-4.
Comparative example 2
Being added without propyl sulfonic acid pyridine lactone, the other the same as in Example 1, products obtained therefrom is numbered B-5.
Comparative example 3
Being added without propyl sulfonic acid pyridine lactone, 1-propyl sulfonic acid-3-Methylimidazole. dihydric phosphate, the other the same as in Example 1, products obtained therefrom is numbered B-6.
Embodiment 4. catalyst activity evaluation
Etherification reaction carries out in laboratory room small-sized continuous flowing type fixed bed reactor. the catalyst prod of embodiment 1-3 and comparative example 1-3 is loaded on flat-temperature zone in the middle part of reaction tube, loading amount 20ml, feedstock amount JW Miniature plunger dosing pump controls. and catalytically active assessment condition is temperature 70 C, pressure 1MPa, alcohol: mol ratio=1 of total olefin, air speed 1h in gasoline-1. reaction 100h sampling detection reaction raw materials and product chromatographic.
The comparison of the total Tertiary olefin conversion ratio of catalyst test sample that different process is made.
| Numbering | Total Tertiary olefin conversion ratio % |
| B-1 | 66 |
| B-2 | 61 |
| B-3 | 69 |
| B-4 | 50 |
| B-5 | 51 |
| B-6 | 42 |
Claims (1)
1. a preparation for Etherification of Light FCC Gasoline catalyst, is characterized by comprise the following steps:
In a kettle., add H beta-molecular sieve under stirring, add the dehydrated alcohol of H beta-molecular sieve quality 2-4 times, adding the 1-propyl sulfonic acid-3-Methylimidazole. dihydric phosphate of H beta-molecular sieve mass percentage content 0.5-2%, the propyl sulfonic acid pyridine lactone being subsequently adding H beta-molecular sieve weight/mass percentage composition 0.5-2 participates in reaction, and charge temperature controls at 0-10 DEG C, after having fed in raw material, it is warming up to 20-50 DEG C, reacts 2-5h, after reaction terminates, filter, it is washed to neutrality, dries, obtain qualified products.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610068817.1A CN105709833A (en) | 2016-01-22 | 2016-01-22 | Preparation of light gasoline etherification catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610068817.1A CN105709833A (en) | 2016-01-22 | 2016-01-22 | Preparation of light gasoline etherification catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105709833A true CN105709833A (en) | 2016-06-29 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201610068817.1A Withdrawn CN105709833A (en) | 2016-01-22 | 2016-01-22 | Preparation of light gasoline etherification catalyst |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102553616A (en) * | 2010-12-30 | 2012-07-11 | 中国石油化工股份有限公司 | Catalyst for preparing etherified benzine by etherifying catalytic cracking benzine, preparation method thereof and application thereof |
| CN102688774A (en) * | 2012-05-30 | 2012-09-26 | 凯瑞化工股份有限公司 | Resin catalyst for light gasoline etherification and preparation method thereof |
| CN103586075A (en) * | 2013-11-26 | 2014-02-19 | 凯瑞化工股份有限公司 | Light petrol etherification catalyst and preparation method thereof |
| CN103611568A (en) * | 2013-12-02 | 2014-03-05 | 江南大学 | Preparation method of dual-core acidic ionic liquid immobilized SBA-15 molecular sieve catalyst used for synthesizing tert butyl glycidyl ether |
-
2016
- 2016-01-22 CN CN201610068817.1A patent/CN105709833A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102553616A (en) * | 2010-12-30 | 2012-07-11 | 中国石油化工股份有限公司 | Catalyst for preparing etherified benzine by etherifying catalytic cracking benzine, preparation method thereof and application thereof |
| CN102688774A (en) * | 2012-05-30 | 2012-09-26 | 凯瑞化工股份有限公司 | Resin catalyst for light gasoline etherification and preparation method thereof |
| CN103586075A (en) * | 2013-11-26 | 2014-02-19 | 凯瑞化工股份有限公司 | Light petrol etherification catalyst and preparation method thereof |
| CN103611568A (en) * | 2013-12-02 | 2014-03-05 | 江南大学 | Preparation method of dual-core acidic ionic liquid immobilized SBA-15 molecular sieve catalyst used for synthesizing tert butyl glycidyl ether |
Non-Patent Citations (1)
| Title |
|---|
| 刘淑芝等: "改性Hβ-分子筛催化FCC轻汽油醚化反应性能的研究", 《分子催化》 * |
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Application publication date: 20160629 |
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| WW01 | Invention patent application withdrawn after publication |