CN1051028C - 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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- CN1051028C CN1051028C CN95101005A CN95101005A CN1051028C CN 1051028 C CN1051028 C CN 1051028C CN 95101005 A CN95101005 A CN 95101005A CN 95101005 A CN95101005 A CN 95101005A CN 1051028 C CN1051028 C CN 1051028C
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Abstract
The present invention relates to a catalyst for olefin hydration, which is composed of 40 to 95 wt% of H-beta zeolite, 3 to 40 wt% of ZrO2 and 1 to 20 wt% of SO4 <2->, wherein the silica to alumina ratio of the H-beta zeolite is from 10 to 50. A preparation method for the catalyst comprises: Na beta zeolite is prepared into ZrNH4 beta through ammonium exchange and ZrO2 precipitation, the ZrNH4 beta and zirconium hydroxide are respectively immersed in the SO4 <2-> to be mixed according to the proportion of the catalyst, and the H-beta /ZrO2 /SO4 <2-> catalyst is prepared by steps of porphyrization, shaping, drying, baking, etc. The catalyst can be used for the olefin hydration of C2 to C7 to prepare corresponding alcohol, and is particularly suitable for propylene hydration to prepare isopropyl alcohol.
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 isopropyl alcohol (IPA) are not only a kind of important petrochemicals, but also is a kind of good octane number auxiliary agent.In recent years, each oil plant owing to added the ZSM-5 auxiliary agent, when improving octane number, 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 catalyst is generally sulfuric acid and phosphoric acid, because there are problems such as burn into loss in above-mentioned two kinds of catalyst, is progressively replaced by zeolite catalyst and strong resin catalyst 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 production capacity is low, therefore, present many major companies have been devoted to the research to zeolite catalyst.US 4214107 has reported silica alumina ratio and has been used for the method that low-carbon alkene, particularly propylene hydration prepare isopropyl alcohol greater than 12 HZSM-5 zeolite catalyst.It is catalyst that US 4499313 discloses with H type modenite and Y zeolite, is used for the method that olefin hydration prepares correspondent alcohol.People such as E.Equchi (Apply.Catalysis 34,1987,275) 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.Patents such as EP 323137,323138,323268 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 technical process of alcohol or ether.US5144084 discloses the method that a kind of converted olefin is alcohol or ether, the catalyst that this method is used, and its active component 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 activity that has, isopropyl alcohol is had the H β/ZrO of high selectivity
2/ SO
4 2-Catalyst for hydration of olefines and preparation method thereof.
The said catalyst of the present invention, it consists of: the heavy % of (1) 40-95, preferably the heavy % silica alumina ratio of 60-85 is the H β zeolite of 10-50; (2) the heavy % of 3-40, the preferably ZrO of the heavy % of 5-30
2(3) the heavy % of 1-20, the preferably SO of the heavy % of 4-10
4 2-
Preparation of catalysts method of the present invention comprises the steps:
(1) NH
4The preparation of β: the Na-β zeolite that with silica alumina ratio is 10-50 carries out ion-exchange with the ammonium salt solution of 0.5-3N, and its liquid-solid ratio is 5-20: 1, make 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 the heavy % of 0.1-28, and adjusting 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 infusion process dipping;
(5) two kinds of macerates that step (4) is obtained mix according to the proportion of composing of this catalyst, porphyrize, and extruded moulding, oven dry in 500-650 ℃ of roasting 0.5-10 hour, 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 solution, 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 catalyst extruded moulding is finished simultaneously.
β/ZrO that the present invention makes
2/ SO
4 2-Catalyst can be used for C
2--C
7The corresponding alcohol of low-carbon alkene hydration preparation is specially adapted to propylene hydration and prepares isopropyl alcohol.This catalyst and H β/ZrO
2Catalyst is compared, and has high activity and to the high selectivity of isopropyl alcohol.As 200 ℃, 2MPa, water/alkene mol ratio (W/O)=2.81, LHSV=6 hour
-1Reaction condition under, the selectivity that propylene conversion reaches 14.65 heavy %, isopropyl alcohol reaches 100%, and H β/ZrO
2Catalyst, propylene conversion have only 8.24 heavy %.
Fig. 1 has described 100 hours activity rating figure of catalyst of the present invention, and appreciation condition is with example 3.As seen from Figure 1: catalyst initial activity of the present invention is very high, propylene conversion is greater than 14 heavy %, after reaction a period of time, propylene conversion maintains the heavy % of 9.5-11.5 basically, it can be said that bright: catalyst 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 CN 94102213.7 preparations, 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, the Beijing Chemical Plant analyzes pure) solution pulls an oar together, under agitation slowly splashes into 2 heavy % ammoniacal liquor (the new Photochemical agents in Beijing factory analyzes pure), regulates PH=7, and filtration is washed till no Cl
-, oven dry makes ZrNH
4β is little, 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, and precipitation back is fully filtered, and washing is to there not being CI
-, 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 must contain SO
4 -2Zirconium hydroxide.
12.24 grams are contained SO
4 -2Zirconium hydroxide and 57.78 the 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 7486 heavy %, the ZrO of aequum
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 catalyst is 5 milliliters (20-40 orders), used propylene is polymer 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 chromatographs, and chromatographic column is the OV-101 capillary column, and the gained result is 2-4 hour average result of reaction, reaction condition: 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-Catalyst carries out hydration reaction to propylene, its catalytic activity and the selectivity of isopropyl alcohol is higher than H β/ZrO
2Catalyst.
Table 1
* annotate: IPA is meant isopropyl alcohol
| Example number | The catalyst title | The catalyst 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 |
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
2Catalyst.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
2Catalyst, propylene conversion have only 8.24 heavy %.
Table 2
| Example number | The catalyst title | The catalyst 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 catalyst just floods the SO of different amounts with example 1
4 2-And the ZrO of aequum
2, make catalyst C, D, E, F.
Example 8
Catalyst 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: catalyst of the present invention, SO
4 2-Content bigger to catalytic activity influence, SO
4 2-Content in catalyst is the heavy % of 1-20, preferably the heavy % of 4-10.
Table 3
| Example number | The catalyst title | SO 4 2-Content in catalyst (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 catalyst with example 1: H β zeolite 64.90 heavy %, ZrO
226.98 heavy %, SO
4 2-8.12 heavy % makes catalyst G.
Example 10
Catalyst 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 isopropyl alcohol 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 a period of time, propylene conversion maintains the heavy % of 9.5-11.5 basically, illustrate that catalyst 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 is characterized in that consisting of of this catalyst: (1) 40-95 is heavy, and the % silica alumina ratio is the H-β zeolite of 10-50; (2) the heavy %ZrO of 3-40
2(3) the heavy %SO of 1-20
4 2-
2. according to the said catalyst of claim 1, it is characterized in that the content of H-β zeolite in catalyst is the heavy % of 60-85.
3. according to the said catalyst of claim 1, it is characterized in that ZrO
2Content in catalyst is the heavy % of 5-30.
4. according to the said catalyst of claim 1, it is characterized in that SO
4 2-Content in catalyst is the heavy % of 4-10.
5. the said Preparation of catalysts method of claim 1 is characterized in that:
(1) be that the Na-β zeolite of 10-50 exchanges with the 0.5-3N ammonium salt solution with silica alumina ratio, its liquid-solid ratio is 5-20: 1, make 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 the heavy % of 0.1-28, and adjusting 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 infusion 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 catalyst in 500-650 ℃ of roasting 0.5-10 hour
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 solution.
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 catalyst 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 CN1128250A (en) | 1996-08-07 |
| CN1051028C true CN1051028C (en) | 2000-04-05 |
Family
ID=5073724
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| 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 |
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| Country | Link |
|---|---|
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Families Citing this family (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 |
| JP6546738B2 (en) * | 2014-11-12 | 2019-07-17 | 日立造船株式会社 | Aldehyde decomposition catalyst, exhaust gas treatment facility 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 | FCC Off-Gas over Zeolite Catalyst propylene hydration prepares catalyst of isopropanol and its preparation method and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1035492A (en) * | 1987-12-30 | 1989-09-13 | 无比石油公司 | Process for 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 |
| EP0520543A1 (en) * | 1991-06-28 | 1992-12-30 | ENIRICERCHE S.p.A. | Superacidic catalyst and process for preparing it |
| CN1075900A (en) * | 1992-02-24 | 1993-09-08 | 中国石油化工总公司 | The preparation method of ultra-strong acid of oxide system |
-
1995
- 1995-01-03 CN CN95101005A patent/CN1051028C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1035492A (en) * | 1987-12-30 | 1989-09-13 | 无比石油公司 | Process for 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 |
| EP0520543A1 (en) * | 1991-06-28 | 1992-12-30 | ENIRICERCHE S.p.A. | Superacidic catalyst and process for preparing it |
| CN1075900A (en) * | 1992-02-24 | 1993-09-08 | 中国石油化工总公司 | The preparation method of ultra-strong acid of oxide system |
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|---|---|
| CN1128250A (en) | 1996-08-07 |
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