CN1048198C - Catalyst using for process of ether and its processing method - Google Patents
Catalyst using for process of ether and its processing method Download PDFInfo
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- CN1048198C CN1048198C CN95107789A CN95107789A CN1048198C CN 1048198 C CN1048198 C CN 1048198C CN 95107789 A CN95107789 A CN 95107789A CN 95107789 A CN95107789 A CN 95107789A CN 1048198 C CN1048198 C CN 1048198C
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Abstract
The present invention relates to a beta-zeolite catalyst in a hydrogen modification type for methyl tert-butyl ether (MTBE) and isopropyl ether (IPE) and a preparation method thereof. The beta-zeolite catalyst in a hydrogen modification type is composed of 50 to 100 portions of beta-zeolite in a hydrogen type, 0 to 50 portions of gamma-alumina and 0.5 to 25 portions of boron oxide by weight. The preparation method comprises the three steps: preparing the beta-zeolite in a hydrogen type; preparing a strip-shaped mixture of the beta-zeolite in a hydrogen type and the alumina; immersing the boron oxide. The beta-zeolite catalyst in a hydrogen modification type has high catalytic activity and high selectivity for the synthesis reaction of MTBE or IPE. Particularly, the beta-zeolite catalyst in a hydrogen modification type is slightly influenced by the change of reaction temperature, and has the advantages of no environment pollution, no reaction equipment corrosion, easy regeneration, high stability, easy preparation, etc.
Description
The present invention relates to a kind of Catalysts and its preparation method that contains zeolite molecular sieve, aluminium oxide and boron oxide.
At present both at home and abroad used catalyst is strongly acidic cation-exchange mostly in methyl tertiary butyl ether(MTBE) and isopropyl ether preparation, as Amberlyst-15, and D72 etc.This class catalyst has pair variations in temperature sensitivity, reaction temperature surpass 90 ℃ then active constituent obviously run off, cause to the corrosion of equipment with to the pollution of environment easy swelling in the course of reaction simultaneously, weakness (Chu, P., Ind.Eng.Chem.Res. such as can not regenerate, 1987,26 (2), 365-369; Qian Ruilong, petrochemical industry chemical fibre, 4,12-21,1992).It is heteropoly acid and phosphoric acid series catalysts that human titanium and zirconium are also arranged, and the disadvantage of such catalyst is that very big (JP 54,55507A for the by-products content of reaction
2, JP 01,283234A
2).The employing molecular sieve catalyst though existing now people begins one's study, wherein mainly be with Hydrogen ZSM-5 and Y two molecular sieve analogs, with Hydrogen β zeolite introduction also arranged, mainly be the technological problems of research reaction, all do not obtain good effect about catalyst, subject matter is the not high enough (Chu of catalytic activity, P., Ind.Eng.Chem.Res., 1987,26 (2), 365-369; Goodwin, Jr.J.G., J.Catal., 1994,148,1557-163; U.S.P.5,114,086)
The purpose of this invention is to provide a kind of methyl tertiary butyl ether(MTBE) (MTBE) or isopropyl ether (IPE) preparation of can being used for, higher catalytic activity is arranged, the influence that changed by reaction temperature is little, has good selectivity, the modification Hydrogen beta-zeolite catalyst of regeneration and good stability easily simultaneously again.
The object of the present invention is achieved like this: the present invention is by Hydrogen β zeolite (H β), gama-alumina (γ-Al
2O
3) and boron oxide (B
2O
3) the composite modified Hydrogen beta-zeolite catalyst that constitutes, the weight ratio of its component is H β: γ-Al
2O
3: B
2O
3=50～100: 0～50: 0.5～25.
Catalyst component weight ratio of the present invention is preferably in H β: γ-Al
2O
3: B
2O
3=70～90: 10～25: in 1～7 the scope.
Preparation of catalysts method of the present invention comprises the preparation and the boron oxide dipping three process of Hydrogen β prepare zeolite, Hydrogen β zeolite and aluminium oxide strip mixture.
(1) Hydrogen β prepare zeolite:, the zeolite after the exchange reaction was promptly made Hydrogen β zeolite in 4 hours 550 ℃ of following roastings with 1.0 centinormal 1 ammonium chloride solutions, 4 times (keeping each swap time 2 hours) of exchange under 90 ℃ of a certain amount of sodium type β zeolite with enough reacting doses.
(2) preparation of Hydrogen β zeolite and aluminium oxide strip mixture: the Hydrogen β zeolite that makes in (1) step and the solids content of getting weight and be 50～100 parts is that the aluminium glue of 0～500 part of weight of 10% (percetage by weight) mixes, and adding concentration is 2% HNO
3Solution is till make solid mixture by complete wetting, and adding weight is the starch of Hydrogen β zeolite and aluminium glue mixture weight 3%, is pressed into strip after they are mixed, dried 4～12 hours at 120 ℃, and bar diameter 2mm, length is not limit.
(3) oxide impregnation boron, getting constant weight analyzes pure BAS make the aqueous solution that boric acid content is 10.0% (weight) in the deionized water of proportional quantity, the strip mixture of the Hydrogen β zeolite that makes in (2) step of institute's expense and aluminium oxide is diluted to 0.1%～10.00% BAS with the BAS of 10.00% concentration to be flooded, each dipping 12 hours, all will soak after the oven dry below 100 ℃ behind each dipping, what make thus consists of H β: γ-Al again
2O
3: B
2O
3=50～100: 0～50: 0.5～25 modification Hydrogen beta-zeolite catalyst was deposited in the drier in case the moisture absorption is standby 200 ℃～850 ℃ following roastings in 1～20 hour again.
Compared with prior art, the advantage that has of the present invention is: A. catalytic activity height.Modification Hydrogen beta-zeolite catalyst of the present invention all has very high catalytic activity to synthesizing of MTBE or IPE.In the reaction of synthetic MTBE with the catalytic activity of the Amberlyst-15 (Am-15) of the catalytic activity the best of generally acknowledging in the world at present quite (seeing accompanying drawing 2).In synthetic IPE reaction with anhydrous AlCl
3On propylene conversion suitable.Be higher than the catalytic activity that does not have through the single Hydrogen β zeolite of modification processing significantly.The influence that changed by reaction temperature is little.Catalyst of the present invention is that 25 ℃～120 ℃ scope all has catalytic activity (seeing accompanying drawing 1) preferably to synthetic MTBE in reaction temperature.And strongly acidic cation-exchange does not at room temperature almost have catalytic activity, and temperature can cause active constituent obviously to run off again when surpassing 90 ℃, to synthetic IPE, and under 180 ℃, the catalytic activity of catalyst of the present invention and AlCl
3Quite, and Am-15 can only be 80 ℃ of reactions, and its activity is well below catalyst of the present invention.C. selectivity is good.In synthetic MTBE reaction, do not have accessory substance to produce with catalyst of the present invention, and strongly acidic cation-exchange also have minor by-products and produce when 80 ℃ of its optimal reaction temperatures.D. do not pollute the environment and etching apparatus.Strongly acidic cation-exchange is in catalytic reaction process, and its active constituent sulfonate radical can produce environment is had the acid of polluting and equipment being had corrosion because of swelling and leakage take place.AlCl
3Consersion unit is also had corrosiveness, can emit the acid of contaminated environment after the suction.Can etching apparatus and catalyst of the present invention was in use both free from environmental pollution.E. regeneration easily, good stability.Catalyst of the present invention can repeat regeneration and use more than 4 times.And strongly acidic cation-exchange and anhydrous AlCl
3Can not regenerate.
The drawing of accompanying drawing is described as follows:
Accompanying drawing 1. is presented at H β-γ-Al under the differential responses temperature
2O
3-B
2O
3The catalytic activity of catalyst is among the figure
Be 40 ℃,
Be 60 ℃,
It is 100 ℃.When accompanying drawing 2. is presented at reaction temperature and is 60 ℃, H β-γ of the present invention-Al
2O
3-B
2O
3The catalytic activity of catalyst and Amberlyst-15 catalyst compares, among the figure
Be Am-15,
Be H β-γ-Al
2O
3-B
2O
3
Following experimental example can further embody the substantive distinguishing features that the present invention gives prominence to, but is not that the present invention is imposed any restrictions.
Embodiment 1
Get 20.0g sodium type β zeolite, with the NH of 1.0N concentration
4Cl solution 250ml exchanges 4 times down at 90 ℃, and the zeolite that obtains in the exchange was promptly made Hydrogen β zeolite in 4 hours 550 ℃ of following roastings.The aluminium glue of getting 7.5g Hydrogen β zeolite and 25.0g solids content and be 10% (percetage by weight) mixes mutually, adds concentration then and be 2% HNO
3Solution made the hybrid solid complete wetting, adds 0.8g starch again, is pressed into strip (diameter is 2mm, and length is not limit) after they are mixed, 120 ℃ of oven dry 4～12 hours.Get this strip mixture 10.0g, use by analyze pure boric acid in deionized water and 3.0% the borate dipping that makes flooded 12 hours at every turn, all will be behind each dipping in oven dry below 100 ℃.Make thus and form H β: γ-Al
2O
3: B
2O
3=75: 25: 6 modification Hydrogen beta-zeolite catalyst, through depositing in the drier standby after 4 hours 550 ℃ of following roastings.
Embodiment 2
Be taken at the catalyst 2.0g that makes among the embodiment 1, placing volume is the tank reactor of 150ml, adds 17.5ml methyl alcohol in reactor, and reactor is sealed, the rising reaction temperature arrives the experimental temperature (being respectively 40 ℃, 60 ℃ and 100 ℃) of appointment rapidly, uses N
2The isobutene of 38.5ml is pressed in the reactor, picks up counting, take a sample once every 5 minutes in preceding half an hour, sampling interval time can be more longer after half an hour.Sample is analyzed by gas chromatograph, adopts internal standard method to determine the content of each composition in the sample.At differential responses temperature H β-γ-Al
2O
3-B
2O
3The catalytic activity of catalyst the results are shown in accompanying drawing 1.
Embodiment 3
Getting the catalyst 2.0g and the Amberlyst-15 resin catalyst 2.0g that make among the embodiment 1 is the reaction that compares catalytic performance under 60 ℃ of conditions in reaction temperature, other reaction conditions are with embodiment 2, the result as shown in Figure 2, visible catalyst of the present invention is suitable with Amber-lyst-15 isobutene conversion in the time of 60 ℃.After reaction is carried out 3 hours, in being the product of catalyst, Am-berlyst-15 have accessory substance-isobutene dimer of 1% to produce, in the reaction of catalyst of the present invention, then do not find to have the accessory substance generation.
Embodiment 4
Reaction temperature is decided to be 60 ℃, reaction time is decided to be 3 hours, other conditions are all identical with embodiment 2, but carry out the reaction experiment of 4 repetitions, after each reaction finishes catalyst was regenerated 550 ℃ of following roastings in 4 hours, secondary response under the catalyst after the regeneration is used for, the result shows, activity of such catalysts of the present invention and selectivity be not decay almost, and conversion for isobutene does not have accessory substance to generate between 80～83% yet.
Embodiment 5
The Preparation of catalysts step is identical with embodiment 1, but forms component H β, γ-Al
2O
3And B
2O
3The ratio difference, make the modification Hydrogen beta-zeolite catalyst of different component ratios.Reaction condition is decided to be 3 hours other conditions with the reaction time and to execute example 2 identical except that reaction temperature is decided to be 60 ℃.The modification Hydrogen beta-zeolite catalyst of variant component ratio is listed in the table 1 performance of synthetic MTBE.
Embodiment 6
The catalyst that makes among the embodiment 1 is carried out roasting respectively under different temperatures, its catalytic performance the results are shown in Table 2 (reaction condition is identical with embodiment 5)
Embodiment 7
Get by the catalyst 2.0g that makes among the embodiment 1, put into the reactor that volume is 250ml, add isopropyl alcohol 22.0ml,, be heated to 130 ℃, by high pressure N with the reactor sealing
2The 12.0g propylene is pressed in the reactor, the stainless steel quantity tube accurately weighing on balance of propylene consumption, reaction temperature is 180 ℃, pressure is 5.0MPa, and the time is 3 hours, and the product sample is by gas chromatographic analysis, propylene conversion is 13.7%, and the productive rate of IPE is 29.8%.Its reactivity worth and known use anhydrous AlCl
3For the result of catalyst suitable.
The relation of table 1 catalyst composition and performance of the present invention
| Numbering | Hβ | γ-Al 2O 3 | B 2O 3 | Isobutene conversion (W%) |
| 1 | 100 | 0 | 5 | 62 |
| 2 | 90 | 10 | 1 | 81 |
| 3 | 75 | 25 | 7 | 82 |
| 4 | 65 | 35 | 3 | 72 |
| 5 | 50 | 50 | 5 | 66 |
| 6 | 65 | 35 | 7 | 74 |
| 7 | 75 | 25 | 10 | 78 |
| 8 | 85 | 15 | 20 | 72 |
| 9 | 90 | 10 | 25 | 64 |
The sintering temperature of table 2 catalyst of the present invention and the relation of catalytic performance
| Numbering | Sintering temperature ℃ | Conversion for isobutene (W%) |
| 1 | 200 | 52 |
| 2 | 450 | 67 |
| 3 | 550 | 83 |
| 4 | 650 | 72 |
| 5 | 750 | 63 |
| 6 | 850 | 51 |
Claims (3)
1. Hydrogen beta-zeolite catalyst that is used for synthesize methyl tert-butyl ether or isopropyl ether, it is characterized in that: it is the composite modified Hydrogen beta-zeolite catalyst that is made of Hydrogen β zeolite and gama-alumina and boron oxide, the weight ratio of its component is Hydrogen β zeolite (H β): gama-alumina (γ-Al
2O
3): boron oxide (B
2O
3)=50～100: 0～50: 0.5～25.
2. modification Hydrogen beta-zeolite catalyst according to claim 1 is characterized in that: the weight ratio of the composition component of this catalyst is H β: γ-Al
2O
3: B
2O
3=70～90: 10～25: 1～7.
3. method that is used for preparing the said catalyst of claim 1 is characterized in that having comprised following three process:
(1) Hydrogen β prepare zeolite, the 1.0 centinormal 1 ammonium chloride solutions of a certain amount of sodium type β zeolite with enough reacting doses are exchanged 4 times at 90 ℃, kept each swap time 2 hours, the zeolite after the exchange reaction was promptly made Hydrogen β zeolite in 4 hours 550 ℃ of roastings;
(2) preparation of Hydrogen β zeolite and aluminium oxide strip mixture, the Hydrogen β zeolite that makes in (1) step and the solids content of getting weight and be 50～100 parts are that the aluminium glue of 0～500 part of weight of 10% (percetage by weight) mixes, and adding concentration is 2% HNO
3Solution adds weight and is 3% starch of Hydrogen β zeolite and aluminium glue mixture weight till make the solid mixture complete wetting, is pressed into strip after they are mixed, and dries 4～12 hours down at 120 ℃, and the bar diameter is 2.0mm, and length is not limit;
(3) oxide impregnation boron, getting constant weight analyzes in the deionized water that pure boric acid is dissolved in proportional quantity and makes the aqueous solution that boric acid content is 10.0% (weight), use BAS to be diluted to 0.1%～10.0% BAS dipping in the Hydrogen β zeolite that in (2) step, makes of institute's expense and the strip mixture of aluminium oxide by 10.0% concentration, each dipping 12 hours, all will be after oven dry below 100 ℃ behind each dipping dipping again, what make thus consists of H β: γ-Al
2O
3: B
2O
3=50～100: 0～50: 0.5～25 modification Hydrogen beta-zeolite catalyst is again 200 ℃～850 ℃ following roastings 1～20 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95107789A CN1048198C (en) | 1995-07-18 | 1995-07-18 | Catalyst using for process of ether and its processing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95107789A CN1048198C (en) | 1995-07-18 | 1995-07-18 | Catalyst using for process of ether and its processing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1140629A CN1140629A (en) | 1997-01-22 |
| CN1048198C true CN1048198C (en) | 2000-01-12 |
Family
ID=5076436
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95107789A Expired - Fee Related CN1048198C (en) | 1995-07-18 | 1995-07-18 | Catalyst using for process of ether and its processing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1048198C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1123389C (en) * | 1998-08-26 | 2003-10-08 | 中国科学院大连化学物理研究所 | Preparation of catalyst for preparing low-carbon alcohol by low-carbon oleffine hydration and its application |
| CN101773848B (en) * | 2010-01-14 | 2012-07-11 | 华东理工大学 | Catalyst used for synthesizing methyl tertiary butyl ether and preparation method thereof |
| CN103433072B (en) * | 2013-09-12 | 2015-07-08 | 凯瑞环保科技股份有限公司 | Catalyst for methyl tert-butyl ether cracking reaction to prepare isobutene and preparation method thereof |
| CN105944754A (en) * | 2016-05-24 | 2016-09-21 | 山东成泰化工有限公司 | Light oil etherification catalyst and preparation method thereof |
| CN106000457A (en) * | 2016-05-24 | 2016-10-12 | 山东成泰化工有限公司 | Composite catalyst used for gasoline etherification and preparation method thereof |
| CN105949039A (en) * | 2016-06-24 | 2016-09-21 | 安庆市泰发能源科技有限公司 | Preparation device capable of enhancing conversion rate of methyl tert-butyl ether |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5081318A (en) * | 1991-03-04 | 1992-01-14 | Texaco Chemical Company | One step synthesis of methyl t-butyl ether from t-butanol using fluorosulfonic acid-modified zeolite catalysts |
| US5220078A (en) * | 1992-07-23 | 1993-06-15 | Texaco Chemical Company | One step synthesis of methyl t-butyl ether from t-butanol using fluorophosphoric acid-modified zeolite catalysts |
| FR2686337A1 (en) * | 1992-01-20 | 1993-07-23 | Inst Francais Du Petrole | Synthesis of tertiary olefins by chemical dehydration of tertiary alcohols |
-
1995
- 1995-07-18 CN CN95107789A patent/CN1048198C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5081318A (en) * | 1991-03-04 | 1992-01-14 | Texaco Chemical Company | One step synthesis of methyl t-butyl ether from t-butanol using fluorosulfonic acid-modified zeolite catalysts |
| FR2686337A1 (en) * | 1992-01-20 | 1993-07-23 | Inst Francais Du Petrole | Synthesis of tertiary olefins by chemical dehydration of tertiary alcohols |
| US5220078A (en) * | 1992-07-23 | 1993-06-15 | Texaco Chemical Company | One step synthesis of methyl t-butyl ether from t-butanol using fluorophosphoric acid-modified zeolite catalysts |
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| Publication number | Publication date |
|---|---|
| CN1140629A (en) | 1997-01-22 |
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