CN1216690C - Preparation method of modified beta zeolite catalyst for isobutane and butylene alkylation reaction - Google Patents
Preparation method of modified beta zeolite catalyst for isobutane and butylene alkylation reaction Download PDFInfo
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- CN1216690C CN1216690C CN 03107113 CN03107113A CN1216690C CN 1216690 C CN1216690 C CN 1216690C CN 03107113 CN03107113 CN 03107113 CN 03107113 A CN03107113 A CN 03107113A CN 1216690 C CN1216690 C CN 1216690C
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- zeolite
- catalyst
- preparation
- beta
- alkylation reaction
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Abstract
The present invention relates to a titanium containing supported beta zeolite catalyst which prepares high-octane petrol by making use of isobutane and butene alkylation reaction. The existing catalyst has the defects of short reaction service life and quick activity decrease. The present invention takes the beta-zeolite as parent population; after the beta-zeolite carries out dealuminization conventionally, the beta-zeolite carries out steam treatment by TiCl4 so as to make the titanium effectively load in the zeolite. Then, the treatment is promoted by sulfate through baking to make required particles (from 40 meshes to 60 meshes). The catalyst prepared by the method makes alkylation reaction activity and selectivity increase obviously.
Description
Technical field
The present invention relates to the preparation method of petrochemical industry with zeolite catalyst.
Background technology
High-quality gasoline alkylate is the fuel of current environmental protection and energy source of car active demand.The catalyst that prior art is produced this alkylate oil is the anhydrous concentrated sulfuric acid and hydrofluoric acid, has serious environmental pollution, equipment corrosion and produces uneasy congruent multiple factor.People attempt to adopt solid acid catalyst to replace above-mentioned catalyst always, though zeolite and super acids all show very high activity on alkylated reaction, their life-span is too short.H β zeolite is one of current generally acknowledged classic alkylation catalyst, but also has the deficiency of active decline fast response life-span weak point.
Summary of the invention
The objective of the invention is to develop the modification dealuminzation β zeolite titanium salt supported titanium that is used for iso-butane and butene alkylation that a class is pollution-free, the life-span long, activity is high
2/ SO
4 2-The preparation method of/D beta catalyst.
The preparation of dealuminzation β zeolite (D β):
The present invention is a parent with the Hydrogen β zeolite of routine, and their Si/Al is than about 15, and specific area is 450-550m
2/ g scope.Dealuminzation also is a conventional method of the prior art, promptly uses the H of 0.01-0.15N HCl and 0.01-0.15N
2C
2O
4Mixed liquor leaching 1-3 time, each 40-60 ℃ water-bath 1-3hr promptly gets dealuminzation β zeolite (D β).
Titanium salt supported catalyst preparation (TiO
2/ SO
4 2-/ D β):
The present invention makes the titanium salt loaded catalyst that is used for iso-butane and butene alkylation with above-mentioned dealuminzation β zeolite, is mainly used in and produces high-knock rating gasoline.With dealuminzation β zeolite TiCl
4Steam at 300-350 ℃, passes through zeolite to be processed with the 2-10mol/hr flow, by time 1-3 hour.Steam is logical finishes N
2Air-blowing is swept and is caught up with clean residual gas.Clean chlorion with rare nitric acid.Oven dry, then under 30-100 ℃ of temperature with the leaching of the ammonium sulfate of 3.0-6.0wt%, promoted that used ammonium sulfate is with on a small quantity repeatedly for well, with the 2-4 suboptimum during promotion.Oven dry at last, 540 ℃ of roastings 3 hours promptly get titanium salt loaded catalyst (TiO
2/ SO
4 2-/ D β).
The catalytic performance of titanium salt loaded catalyst:
The present invention titanium salt support type β zeolite and H β zeolite facies ratio, supported titanium
2/ SO
4 2-/ D β zeolite is because the interaction between its each component, Bronsted acid position strong/Y is compared in the weak acid position
BBe improved, alkylating activity and selectivity are improved.Modified beta zeolite catalyst of the present invention is used for iso-butane and butene alkylation, and its alkylating activity all can reach 80%, desired product TMP (three side chain isooctane, its octane number 100 or on) selectivity at 30-50%.Its performance obviously is better than H β zeolite.
The specific embodiment
Example one:
With H β zeolite is parent (Si/Al=14-15), with 0.1N HCl+0.1N H
2C
2O
4Mixed liquor leaching 3-4 time, each 2hr.The D β (Si/Al=20-25) that obtains, logical TiCl
4Steam (5ml/hr) heats 250 ℃, allows it adsorb 1.5 hours.Be cooled to room temperature, catch up with clean residual gas.With (NH
4)
2SO
4(30%)+HNO of 0.1wt%
3Solution washing is to there not being chlorion.Dried 2 hours for 110 ℃.540 ℃ of roastings 3 hours.Ti% ≈ 3 in the final sample, SO
4 2-%=1.5.
Example two:
The alkylation performance of each catalyst:
Above-mentioned sample is levigate, and compressing tablet is made 40-60 order particle.Sample is put into fixed bed central authorities, and seal with silica the bottom up and down, and nitrogen is carrier gas (30ml/min).300 ℃ activate 2 hours, nebulizer gas pressure 2.1Mpa, iso-butane 1-butylene mol ratio 11,1-butylene mass space velocity WHSV=1.3h
-1, 80 ℃ of reaction temperatures.Alkylated reaction proceeds to TOS=60, and 90, during 120min, the conversion ratio of 1-butylene and the selectivity of TMP see the following form 1:
Table 1:
| TOS(min) | TiO 2/SO 4 2-/Dβ 1-C 4 ＝Conversion ratio %TMP/C 5+％ |
| 60 | 85 43 |
| 90 | 77 37 |
| 120 | 58 32 |
Claims (3)
1. a preparation method who is used for the modified beta zeolite catalyst of iso-butane and butene alkylation is characterized in that with the β zeolite be parent, uses TiCl behind dealuminzation
4Steam treatment, oven dry back promote 2-4 time with the sulfuric acid saline solution of 3.0-6.0wt%, oven dry again, and after roasting can be used, sulfate is to use ammonium sulfate.
2. the preparation method who is used for the modified beta zeolite catalyst of iso-butane and butene alkylation according to claim 1 is characterized in that with Hydrogen β zeolite be parent, the Si/Al=20-25 of zeolite behind the dealuminzation.
3. the preparation method who is used for the modified beta zeolite catalyst of iso-butane and butene alkylation according to claim 1 is characterized in that behind the dealuminzation TiCl
4Steam passes through zeolite, TiCl down at 300-350 ℃
4Flow be 2-10mol/hr, TiCl
4Steam is 1-3 hour by the time, removes chlorion then, and oven dry, promotion get final product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03107113 CN1216690C (en) | 2003-02-28 | 2003-02-28 | Preparation method of modified beta zeolite catalyst for isobutane and butylene alkylation reaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03107113 CN1216690C (en) | 2003-02-28 | 2003-02-28 | Preparation method of modified beta zeolite catalyst for isobutane and butylene alkylation reaction |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00117060 Division CN1124891C (en) | 2000-07-05 | 2000-07-05 | Method for preparing modified beta zeolite catalyst used for alkylation reaction of isobutane/butylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1443602A CN1443602A (en) | 2003-09-24 |
| CN1216690C true CN1216690C (en) | 2005-08-31 |
Family
ID=27814483
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03107113 Expired - Fee Related CN1216690C (en) | 2003-02-28 | 2003-02-28 | Preparation method of modified beta zeolite catalyst for isobutane and butylene alkylation reaction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1216690C (en) |
-
2003
- 2003-02-28 CN CN 03107113 patent/CN1216690C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1443602A (en) | 2003-09-24 |
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