CN1128250A - Catalyst for hydration of olefines and its preparation method - Google Patents
Catalyst for hydration of olefines and its preparation method Download PDFInfo
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- CN1128250A CN1128250A CN 95101005 CN95101005A CN1128250A CN 1128250 A CN1128250 A CN 1128250A CN 95101005 CN95101005 CN 95101005 CN 95101005 A CN95101005 A CN 95101005A CN 1128250 A CN1128250 A CN 1128250A
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Abstract
The said catalyst consists of H-beta zeolite with silicon-to-aluminium ratio 10-50 in 40-95 wt%, ZrO2 in 3-40 wt% and sulphuric radical 1-20 wt%. In the prepn, H-beta zeolite is passed through ammonium exchange and ZrO2 precipitation to obtain ZrNH4-beta. ZrNH4-beta and zirconium- hydroxide are soaked separately with sulphuric radical, mixed in the certain ratio, ground, formed, stoved and roasted to produce the H-beta/ZrO2/sulphuric radical catalyst. The catalyst is used in the hydration of C2-C7 olefines to prepare corresponding alcohols, esp suitable for the hydration of propylene to prepare isopropanol.
Description
The present invention relates to a kind of catalyst for hydration of olefines and preparation method thereof, exactly is a kind of H β/ZrO that is used for olefin hydration prepared in reaction alcohol
2/ SO
4 2-Catalysts and its preparation method.
Low-carbon alkene hydration reaction system alcohol is a kind of important catalytic process, and its product lower alcohols such as Virahol (IPA) are not only a kind of important petrochemicals, but also is a kind of good gasoline octane rating auxiliary agent.In recent years, each refinery owing to added the ZSM-5 auxiliary agent, when improving gasoline octane rating, has also produced a large amount of C in FCC (Fluid catalyticcracking) process
2-C
7Alkene mixture, and olefin hydration is the important channel that consumes alkene, also is industrial important method of producing alcohol.The olefin hydration reaction is typical acid catalyzed reaction, and its catalyzer is generally sulfuric acid and phosphoric acid, because there are problems such as burn into loss in above-mentioned two kinds of catalyzer, is progressively replaced by zeolite catalyst and strong resin catalyzer in recent years.Though strong resin has advantages of high catalytic activity since its have preparation complexity, facile hydrolysis inactivation, can not regenerate, shortcoming such as throughput is low, therefore, present many major companies have been devoted to the research to zeolite catalyst.US4214107 has reported silica alumina ratio and has been used for the method that low-carbon alkene, particularly propylene hydration prepare Virahol greater than 12 HZSM-5 zeolite catalyst.It is catalyzer that US4499313 discloses with H type mordenite and Y zeolite, is used for the method that olefin hydration prepares correspondent alcohol.People such as E.Equchi (Apply.Catalysis34,1987,275) have investigated various zeolites and have been used for the olefin hydration reactive activity, and point out, the hydrophobic and hydrophilic nmature of zeolite has considerable influence to activity of such catalysts.EP323137,323138, patents such as 323268 have been reported with H-β zeolite as the catalyst activity constituent element, with Al
2O
3Or SiO
2As carrier, light olefin is changed into the technological process of alcohol or ether.US5144084 discloses the method that a kind of converted olefin is alcohol or ether, the catalyzer that this method is used, and its active ingredient is that beta-zeolite, IVA and/or IVB family metal oxide are (as TiO
2, ZrO
2) be carrier.
The purpose of this invention is to provide a kind of high reactivity that has, Virahol is had the H β/ZrO of highly selective
2/ SO
4 2-Catalyst for hydration of olefines and preparation method thereof.
The said catalyzer of the present invention, it consists of: (1) 40-95 heavy %, preferably 60-85 heavy % silica alumina ratios are 10-50 H β zeolite; (2) 3-40 heavy %, the preferably ZrO of 5-30 heavy %
2(3) 1-20 heavy %, the preferably SO of 4-10 heavy %
4 2-
Preparation of catalysts method of the present invention comprises the steps:
(1) NH
4The preparation of β: being 10-50 Na-β zeolite with silica alumina ratio carries out ion-exchange with the ammonium salt solution of 0.5-3N, and its liquid-solid ratio is 5-20: 1, makes Na
2The heavy % in O content＜0.01 filters, and gets NH
4β;
(2) ZrNH
4The preparation of β: with NH
4β places the saturated zirconium salt solution of 0.5 heavy %, under agitation slowly splashes into the ammoniacal liquor of 0.1-28 heavy %, and regulating PH is 5-9, filters, and washing is not to there being acid group, and oven dry makes ZrNH
4β;
(3) preparation of zirconium hydroxide: with the saturated zirconium salt solution of 0.5 heavy %, under agitation slow dropping ammonia, control PH=5-9, washing in 100-200 ℃ of oven dry, makes zirconium hydroxide to there not being acid group;
(4) with ZrNH
4β and zirconium hydroxide are respectively with the excessive SO that contains
4 2-Solution impregnation, or with saturated pickling process dipping;
(5) two kinds of macerates that step (4) is obtained mix according to the proportion of composing of this catalyzer, porphyrize, and extruded moulding, oven dry in 500-650 ℃ of roastings 0.5-10 hours, promptly gets H β/ZrO
2/ SO
4 2-Catalyst for hydration of olefines.
The said ammonium salt solution of the present invention is (NH
4)
2SO
4, NH
4Cl, NH
4NO
3The said zirconium salt solution of the present invention is ZrOCl
2, ZrO (NO
3)
2Or Zr (NO
3)
4The aqueous solution or ethanolic soln, wherein said Zr also can replace with other metals of IVB family such as Ti, Hf.
The said SO of the present invention
4 2-Precursor be H
2SO
4Or (NH
4)
2SO
4Solution, SO
4 2-Also can when extruded moulding, add and the catalyzer extruded moulding is finished simultaneously.
H β/ZrO that the present invention makes
2/ SO
4 2-Catalyzer can be used for C
2-C
7The corresponding alcohol of low-carbon alkene hydration preparation is specially adapted to propylene hydration and prepares Virahol.This catalyzer and H β/ZrO
2Catalyzer is compared, and has high reactivity and to the highly selective of Virahol.As 200 ℃, 2MPa, water/alkene mol ratio (W/O)=2.81, LHSV=6 hour
-1Reaction conditions under, the selectivity that propylene conversion reaches 14.65 heavy %, Virahol reaches 100%, and H β/ZrO
2Catalyzer, propylene conversion have only 8.24 heavy %.
Fig. 1 has described 100 hours activity rating figure of catalyzer of the present invention, and appreciation condition is with example 3.As seen from Figure 1: catalyzer initial activity of the present invention is very high, propylene conversion is greater than 14 heavy %, after reaction for some time, propylene conversion maintains 9.5-11.5 heavy % basically, it can be said that bright: catalyzer of the present invention not only has advantages of high catalytic activity, and also has good activity stability.
The following examples will the invention will be further described.
Example 1
50 gram Na-β zeolites are (according to CN94102213.7 preparation, silica alumina ratio=30, Na
2O=1), be under 10 the condition, to use 1N NH in liquid-solid ratio
4Cl (bioid factory of Beijing ProMos, chemical pure) solution exchange 1 hour exchanges twice altogether, the filter cake that obtains and 500 milliliter 1.13 heavy %ZrOCl
2(ZrOCl
28H
2O, Beijing Chemical Plant, analytical pure) solution pulls an oar together, under agitation slowly splashes into 2 heavy % ammoniacal liquor (the new Photochemical agents in Beijing factory, analytical pure), regulates PH=7, filters, and is washed till no Cl
-, oven dry makes ZrNH
4β contains 8 heavy %SO with 140 milliliters then
4 2-(NH
4)
2SO
4Solution impregnation is filtered, and oven dry makes ZrSNH
4β.
With 1000 milliliter 7.22 heavy %ZrOCl
2The ammoniacal liquor of the aqueous solution and 8.0 heavy % under agitation is added drop-wise in 1000 milliliters of deionized waters simultaneously, control PH=7, precipitate complete after-filtration, washing is to there not being Cl-, in 120 ℃ of oven dry, obtain 64.75 gram zirconium hydroxides, below zirconium hydroxide porphyrize to 150 order with gained, and flood 32.2 milliliters and contain 16%SO
4 2-(NH
4)
2SO
4Solution, oven dry gets zirconium hydroxide.
With 12.24 gram zirconium hydroxides and 57.78 gram ZrSNH
4β mixes, porphyrize, and extruded moulding, the oven dry back promptly gets catalyst A in 550 ℃ of roastings 2 hours, and it consists of: 74.86 heavy %H-β zeolites, 17.18 heavy %ZrO
2, 7.96 heavy %SO
4 2-
Comparative example 1
The Preparation of catalysts method is not just flooded SO with example 1
4 2-, making catalyst B, it consists of: H β zeolite 74.86 heavy %, the ZrO of equal amount
2
Example 2
Catalyst A, B are carried out activity rating.
The small fixed flow reactor is adopted in the catalyst activity evaluation, the loadings of catalyzer is 5 milliliters (20-40 orders), used propylene is polymerization-grade (the heavy % of purity 98.6, Yanshan Petrochemical company face south chemical plant), and institute's water is a deionized water, be interrupted sampling, product is analyzed with 3400 type chromatographic instruments, and chromatographic column is the OV-101 capillary column, and the gained result is 2-4 hours average result of reaction, reaction conditions: 200 ℃, 3.0MPa, W/O mol ratio=2.81, LHSV
Propylene=6 hours
-1, reaction result sees Table 1.
As can be seen from Table 1, adopt H β/ZrO provided by the invention
2/ SO
4 2-Catalyzer carries out hydration reaction to propylene, its catalytic activity and the selectivity of Virahol is higher than H β/ZrO
2Catalyzer.
Table 1
| Example number | The catalyzer title | The catalyzer constituent element | Propylene conversion (heavy %) | IPA selectivity (%) |
| Example 1 | ?A | ?Hβ/ZrO 2/SO 4 2- | ??19.56 | ????100 |
| Comparative example 1 | ?B | ?Hβ/ZrO 2 | ??14.76 | ????100 |
* annotate: IPA is meant Virahol
Example 3
Catalyst A, B are carried out activity rating, and appreciation condition is with example 2, and just reaction pressure is 2.0MPa, the results are shown in Table 2.
As can be seen from Table 2: when reaction pressure is 2.0MPa, H β/ZrO of the present invention
2/ SO
4 2-Activity of such catalysts is much higher than H β/ZrO
2Catalyzer.As catalyst A of the present invention, at 200 ℃, 2MPa, W/O mol ratio=2.81, LHSV
Propylene=6 hours
-1Under the condition, the selectivity that propylene conversion reaches 14.65 heavy %, IPA reaches 100%, and H β/ZrO
2Catalyzer, propylene conversion have only 8.24 heavy %.
Table 2
| Example number | The catalyzer title | The catalyzer constituent element | Propylene conversion (heavy %) | IPA selectivity (%) |
| Example 1 | ????A | ?Hβ/ZrO 2/SO 4 2- | ????14.65 | ????100 |
| Comparative example 1 | ????B | ?Hβ/ZrO 2 | ????8.24 | ????100 |
Example 4-7
Preparation of catalysts method and the beta-zeolite content in catalyzer just floods the SO of different amounts with example 1
4 2-And the ZrO of equal amount
2, make catalyzer C, D, E, F.
Example 8
Catalyzer C, D, E, F are carried out activity rating, and appreciation condition is seen example 2, the results are shown in Table 3.
As can be seen from Table 3: catalyzer of the present invention, SO
4 2-Content bigger to catalytic activity influence, SO
4 2-Content in catalyzer is 1-20 heavy %, preferably 4-10 heavy %.
Table 3
| Example number | The catalyzer title | SO 4 2-Content in catalyzer (heavy %) | Propylene conversion (heavy %) |
| ????4 | ????C | ????1.00 | ????15.30 |
| ????5 | ????D | ????5.03 | ????18.23 |
| ????6 | ????E | ????12.10 | ????16.85 |
| ????7 | ????F | ????16.07 | ????14.97 |
Example 9
The Preparation of catalysts method is the composition difference of catalyzer with example 1: H β zeolite 64.90 heavy %, ZrO
226.98 heavy %, SO
4 2-8.12 heavy % makes catalyzer G.
Example 10
Catalyzer G is carried out activity rating, and appreciation condition is with example 2, and the result is: propylene conversion is 16.50 heavy %, and the Virahol selectivity is 100%.
Example 11
Catalyst A is carried out 100 hours activity ratings, and appreciation condition the results are shown in Figure 1 with example 3.
As seen from Figure 1: catalyst A initial activity of the present invention is very high, propylene conversion is greater than 14 heavy %, and after reaction for some time, propylene conversion maintains 9.5-11.5 heavy % basically, illustrate that catalyzer of the present invention not only has advantages of high catalytic activity, and also have good activity stability.
Claims (7)
1. catalyst for hydration of olefines, it is characterized in that consisting of of this catalyzer: (1) 40-95 heavy % silica alumina ratio is 10-50 H-β zeolite; (2) 3-40 heavy %ZrO
2(3) 1-20 heavy %SO
4 2-
2. according to the said catalyzer of claim 1, it is characterized in that the content of H-β zeolite in catalyzer is 60-85 heavy %.
3. according to the said catalyzer of claim 1, it is characterized in that ZrO
2Content in catalyzer is 5-30 heavy %.
4. according to the said catalyzer of claim 1, it is characterized in that SO
4 2-Content in catalyzer is 4-10 heavy %.
5. the said Preparation of catalysts method of claim 1 is characterized in that:
(1) be that 10-50 Na-β zeolite exchanges with 0.5-3N ammonium salt solution with silica alumina ratio, its liquid-solid ratio is 5-20: 1, makes NaO
2The heavy % in content＜0.01 filters, and obtains NH
4β;
(2) with NH
4β places the saturated zirconium salt solution of 0.5 heavy %, under agitation slowly splashes into the ammoniacal liquor of 0.1-28 heavy %, and regulating PH is 5-9, filters, and washing is not to there being acid group, and oven dry makes ZrNH
4β;
(3) with the saturated zirconium salt solution of 0.5 heavy %, under agitation slow dropping ammonia, control PH=5-9, washing in 100-200 ℃ of oven dry, makes zirconium hydroxide to there not being acid group;
(4) with ZrNH
4β and zirconium hydroxide are respectively with the excessive SO that contains
4 2-Solution impregnation, or with saturated pickling process dipping;
(5) two kinds of macerates that step (4) is obtained promptly got H β/ZrO according to proportion of composing mixing, porphyrize, extruded moulding, the oven dry of this catalyzer in 0.5-10 hours in 500-650 ℃ of roastings
2/ SO
4 2-Catalyst for hydration of olefines.
6. according to the said preparation method of claim 5, it is characterized in that said zirconium salt solution is ZrOCl in (2), (3) step
2, ZrO (NO
3)
2Or Zr (NO
3)
4The aqueous solution or ethanolic soln, wherein said Zr also can replace with Ti, the Hf of IVB family.
7. according to the said preparation method of claim 5, it is characterized in that in the step (4) SO
4 2-Precursor be H
2SO
4Or (NH
4)
2SO
4Solution contains SO
4 2-Solution also can when extruded moulding, add and the catalyzer extruded moulding is finished simultaneously.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95101005A CN1051028C (en) | 1995-01-03 | 1995-01-03 | Catalyst for hydration of olefines and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95101005A CN1051028C (en) | 1995-01-03 | 1995-01-03 | Catalyst for hydration of olefines and its preparation method |
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| Publication Number | Publication Date |
|---|---|
| CN1128250A true CN1128250A (en) | 1996-08-07 |
| CN1051028C CN1051028C (en) | 2000-04-05 |
Family
ID=5073724
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95101005A Expired - Fee Related CN1051028C (en) | 1995-01-03 | 1995-01-03 | Catalyst for hydration of olefines and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1051028C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1060686C (en) * | 1998-01-12 | 2001-01-17 | 南开大学 | Compounded active carbon fibre solid catalyst |
| CN104549463B (en) * | 2013-10-22 | 2017-01-25 | 中国石油化工股份有限公司 | Cracking catalyst containing metallic oxide modified beta zeolite |
| CN106925259A (en) * | 2015-12-31 | 2017-07-07 | 中国石油天然气股份有限公司 | Catalyst for preparing isopropanol by propylene hydration through gas-liquid phase method and preparation method and application thereof |
| CN107206368A (en) * | 2014-11-12 | 2017-09-26 | 日立造船株式会社 | Aldehyde decomposition catalyst, waste gas treatment equipment and waste gas processing method |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1339382C (en) * | 1987-12-30 | 1997-08-26 | Tracy Jau-Hua Huang | Process for the catalytic hydration of olefins |
| US4918041A (en) * | 1988-09-21 | 1990-04-17 | Sun Refining And Marketing Company | Catalyst for hydrocarbon conversion and conversion process utilizing the same |
| IT1248591B (en) * | 1991-06-28 | 1995-01-19 | Eniricerche Spa | SUPERACID CATALYST AND PROCEDURE FOR ITS PREPARATION |
| CN1028840C (en) * | 1992-02-24 | 1995-06-14 | 中国石油化工总公司 | Preparation method for ultra-strong acid of oxide system |
-
1995
- 1995-01-03 CN CN95101005A patent/CN1051028C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1060686C (en) * | 1998-01-12 | 2001-01-17 | 南开大学 | Compounded active carbon fibre solid catalyst |
| CN104549463B (en) * | 2013-10-22 | 2017-01-25 | 中国石油化工股份有限公司 | Cracking catalyst containing metallic oxide modified beta zeolite |
| CN107206368A (en) * | 2014-11-12 | 2017-09-26 | 日立造船株式会社 | Aldehyde decomposition catalyst, waste gas treatment equipment and waste gas processing method |
| CN107206368B (en) * | 2014-11-12 | 2020-03-17 | 日立造船株式会社 | Aldehyde decomposition catalyst, exhaust gas treatment device, and exhaust gas treatment method |
| CN106925259A (en) * | 2015-12-31 | 2017-07-07 | 中国石油天然气股份有限公司 | Catalyst for preparing isopropanol by propylene hydration through gas-liquid phase method and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1051028C (en) | 2000-04-05 |
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