CN1721070A - Catalyst for producing isopropyl benzene - Google Patents
Catalyst for producing isopropyl benzene Download PDFInfo
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- CN1721070A CN1721070A CNA2004100527285A CN200410052728A CN1721070A CN 1721070 A CN1721070 A CN 1721070A CN A2004100527285 A CNA2004100527285 A CN A2004100527285A CN 200410052728 A CN200410052728 A CN 200410052728A CN 1721070 A CN1721070 A CN 1721070A
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- isopropylbenzene
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The present invention relates to catalyst for cumene production to solve the problem that reaction temperature is high, rate of cumene vs. hydrocarbon is high and space velocity of propylene is low. It uses crystal aluminosilicate with characterized diffraction data of 1 XRD as the active main body, and the catalyst has been treated in high temperature water vapor of 200~1000Deg and treated with organic acid. It solves the problem well and fits to practical production.
Description
Technical field
The present invention relates to be used to produce the catalyst of isopropylbenzene.
Background technology
Isopropylbenzene is an important intermediate raw material of producing phenol, acetone and AMS.Phenol more than 90% is to adopt cumene method production in the world at present.The conventional method of industrial production isopropylbenzene has the solid phosphoric acid method (SPA method) of UOP (UOP) and the improvement AlCl of Monsanto/Lummus Crest company
3Method.SPA operating condition harshness, impurity is many, can not improve the productive rate of isopropylbenzene by reverse alkylation.And AlCl
3Though method has the reaction condition that relaxes, and can improve the productive rate of isopropylbenzene by reverse alkylation, this catalytic erosion is strong, pollution is heavy and post processing is numerous and diverse.
Molecular sieve liquid phase alkylation methods because reaction condition mitigations, conversion ratio height, selectivity is good, impurity is few, pollution-free, do not have to corrode; main accessory substance polyisopropylbenzene can change isopropylbenzene into via reverse alkylation; make the isopropylbenzene productive rate up to more than 99%; be each institute of big industrial group company common concern in recent years, and an advanced technology of competitively developmental research, to significant " cleaning procedure " technology of environmental protection.
The isopropylbenzene molecular sieve catalyst of heavy industrialization has the Y zeolite of Uop Inc., the beta-molecular sieve of EniChem company at present.
A kind of steam treatment process of zeolite catalyst being carried out the part dealuminzation is provided among the Chinese patent literature CN1113649; CN1125641 provides a kind of method for preparing the isopropylbenzene zeolite catalyst of high activity, high selectivity, is mainly used in the reaction of bubbling bed, and CN1227770 then adopts mineral acid treatment β zeolite to prepare alkylation catalyst.The common drawback of all above-mentioned catalyst is reaction temperature height, high, low, the poor stability of propylene air speed of benzene hydrocarbon ratio, is difficult to commercial Application.
Summary of the invention
Technical problem to be solved by this invention is that the catalyst that uses in the conventional art exists reaction temperature height, benzene hydrocarbon than the problem high, that the propylene air speed is low, and a kind of new catalyst that is used to produce isopropylbenzene is provided.This catalyst has that reaction temperature is low, benzene hydrocarbon is than characteristics low, that the catalyst regeneration cycle is long.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of catalyst that is used to produce isopropylbenzene comprises following component by weight percentage:
A) 50～80% crystal aluminosilicate;
B) 20～50% binding agent;
Wherein catalyst is handled with organic acid after adopting 200～1000 ℃ of high-temperature water vapors to handle again, and crystal aluminosilicate has following XRD diffraction data:
| The 2 θ angles of diffraction | Diffraction peak intensity (I/I 0×100) |
| 6.5° | 28.8±0.1 |
| 7.2° | 17.3±0.1 |
| 8.8° | 15.4±0.1 |
| 9.7° | 53.8±0.1 |
| 13.5° | 39.4±0.1 |
| 14° | 28.8±0.1 |
| 14.3° | 19.2±0.1 |
| 15.4° | 23.1±0.1 |
| 19.5° | 34.6±0.1 |
| 22.2° | 69.2±0.1 |
| 23.8° | 23.1±0.1 |
| 25.5° | 100±0.1 |
| 26.2° | 65.4±0.1 |
| 27.5° | 46.7±0.1 |
| 31° | 27.9±0.1 |
| 35.8° | 15.4±0.1 |
。
The specific area preferable range of crystal aluminosilicate is 500～600 meters in the technique scheme
2/ gram, pore volume preferable range are 0.45～0.60 milliliter/gram.The binding agent preferable range is selected from aluminium oxide, titanium oxide, zinc oxide, zirconia or its mixture.The catalyst preferred version is 400～700 ℃ for the temperature that adopts high-temperature water vapor to handle, and the processing time is 0.5～20 hour, and the processing time preferable range is 1～5 hour.The organic acid preferred version is selected from citric acid, tartaric acid, oxalic acid or glacial acetic acid, and more preferably scope is selected from oxalic acid; The organic acid concentration preferable range is 0.1～3 mol, and more preferably scope is 0.5～1.5 mol; Organic acid processing time preferable range is 1～72 hour, and more preferably scope is 24～60 hours.
The preparation method of the crystal aluminosilicate that uses in the catalyst of the present invention is as follows:
After silicon source (Ludox, waterglass etc.), aluminium source (sodium aluminate, aluminum sulfate etc.) and organic ammonium (hexamethylene diamine, hexa-methylene imonium), caustic soda, water mixed according to following ratio, under the effect of directed agents organic ammonium,, filter, washing, oven dry obtain finished product SHY in 140～180 ℃ of following crystallization 50～200 hours.Wherein the feed molar proportioning is as follows: (molecular proportion, M refers to organic ammonium)
SiO
2∶Al
2O
3＝20～200
SiO
2∶Na
2O＝100～200
SiO
2∶H
2O＝0.01～0.1
SiO
2∶M＝2～8
The inventory of directed agents is 0.1%～10% of a silicon source weight.
Catalyst of the present invention can prepare as follows:
A) synthetic crystallization alumino-silicate materials SHY according to the method described above;
The crystal aluminosilicate material SHY that b) will newly synthesize exchanges with ammonium salt, and the content that makes alkali metal ion is wherein dried below 0.05% (weight) then;
C) high-temperature water vapor is handled zeolite;
D) organic acid is handled zeolite.
The ammonium salt that is used for treatment S HY can be ammonium salt commonly used, for example ammonium chloride, ammonium nitrate or ammonium phosphate etc.
The present invention is by with handling catalyst with organic acid again behind the steam treatment catalyst, removed the non-framework aluminum of catalyst surface effectively, increased the aperture of catalyst, thereby reduced the oligomerisation reaction of alkene at catalyst surface, make product from the catalyst duct, to spread out apace, suppressed the carbon distribution that reaction mass generates at the catalyst surface dehydrocyclization effectively, thereby improved the reaction stability of catalyst, make that catalyst can be than 100～170 ℃ of low reaction temperatures, low benzene hydrocarbon has been obtained better technical effect than 2～5 times reactions.
Description of drawings
Accompanying drawing 1 is the XRD diffraction pattern of crystal aluminosilicate SHY.
The invention will be further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
1500 gram waterglass (modulus=2.8) are evenly mixed with 500 gram hexamethylene imines, 50 gram sodium aluminates and 25 gram NaOH are evenly mixed in 500 gram water, above-mentioned two kinds of solution are evenly mixed under strong agitation, continue to stir 2 hours, adding 500 gram water stirred 1 hour, above-mentioned mixed good solution is formed jelly at 10 ℃ after aging 100 hours, standby.
[embodiment 2]
25 gram sodium aluminates and the dissolving in 500 gram water of 20 gram NaOH are evenly mixed, adding 500 gram (40% weight) Ludox stirs, adding 800 gram pure water again stirs evenly mixed, colloidal sol 50 grams that add preparation among the embodiment 1, continue to stir after 2 hours and change in the crystallizing kettle, stirred crystallization 100 hours at 165 ℃, filtration washing is to PH=8,150 ℃ of oven dry.The specific area of gained sample is 550 meters
2/ gram, pore volume are 0.5 milliliter/gram, and the XRD diffraction data is as shown in table 1, and the XRD diffraction pattern as shown in Figure 1.
Table 1 XRD diffraction data
| The 2 θ angles of diffraction | Diffraction peak intensity (I/I 0×100) |
| 6.5° | 28.8 |
| 7.3° | 17.2 |
| 8.8° | 15.5 |
| 9.7° | 53.6 |
| 13.5° | 39.5 |
| 14° | 28.8 |
| 14.3° | 19.1 |
| 15.4° | 23.2 |
| 19.5° | 34.6 |
| 22.2° | 69.2 |
| 23.8° | 23.1 |
| 25.5° | 100 |
| 26.2° | 65.3 |
| 27.5° | 46.7 |
| 31° | 27.8 |
| 35.8° | 15.4 |
Get above-mentioned synthetic crystal aluminosilicate material 100 grams, add 0.5 mol ammonium nitrate solution, be warming up to 95 ℃ of exchanges 2 hours, exchange repeatedly 6 times, make alkali metal ion content measured in the crystal aluminosilicate less than 100ppm, crystal aluminosilicate 90 grams that above-mentioned exchange is good and 25 gram aluminium oxide, 10 gram zinc oxide, 15 gram zirconias, 5 gram titanium oxide are evenly mixed, add 200 milliliter of 5% weight nitric acid solution, 5 gram sesbania powder are mediated extruded moulding after 1 hour, with the catalyst of forming 150 ℃ of oven dry, under air atmosphere, be warming up to 580 ℃ of roastings 4 hours then, with above-mentioned product of roasting with 550 ℃ of water vapours with 0.5 hour
-1Handled 2 hours, cooling is placed in the oxalic acid solution of 1 normal concentration 50 ℃ and soaked 48 hours, and distilled water cleans to neutral, and oven dry obtains finished catalyst.
[embodiment 3]
The catalyst powder of preparation among the embodiment 2 is broken into 20～60 purpose particles, gets 1.0 gram catalyst and carry out propylene liquid-phase alkylation reaction in fixed bed reactors, reaction condition is, propylene air speed=1.7 hour
-1, reaction temperature=150 ℃, reaction pressure=2.6MPa, product is an isopropylbenzene, propylene conversion=100%, selectivity of product 99.3%, total benzene/olefin molar ratio is 2.1, reacts and does not observe the catalyst activity loss in 2000 hours, and outlet isopropylbenzene concentration reaches 44%.
[embodiment 4]
25 gram sodium aluminates and the dissolving in 500 gram water of 20 gram NaOH are evenly mixed, adding 800 gram (40% weight) Ludox stirs, adding 800 gram pure water again stirs evenly mixed, colloidal sol 30 grams that add preparation among the embodiment 1, continue stirring and change in the crystallizing kettle after 2 hours, stirred crystallization 130 hours at 165 ℃, filtration washing is to PH=7,150 ℃ of oven dry, the specific area of gained sample is 520 meters
2/ gram, pore volume are 0.48 milliliter/gram.Get above-mentioned synthetic crystal aluminosilicate 100 grams, add 1 mol ammonium chloride solution, be warming up to 95 ℃ of exchanges 2 hours, exchange repeatedly 6 times, alkali metal ion content measured in the gained crystal aluminosilicate is less than 150ppm, crystal aluminosilicate 90 grams that above-mentioned exchange is good and 25 gram aluminium oxide, 10 gram zinc oxide, 15 gram zirconias, 5 gram titanium oxide are evenly mixed, add 200 milliliter of 5% weight nitric acid solution, 5 gram sesbania powder are mediated extruded moulding after 3 hours, the catalyst of forming is being warming up to 580 ℃ of roastings 4 hours under air atmosphere after 150 ℃ of oven dry, with above-mentioned product of roasting with 450 ℃ of water vapours with 1.0 hours
-1Handled 5 hours, cooling is placed in the oxalic acid solution of 1 normal concentration 50 ℃ and soaked 48 hours, and distilled water cleans to neutral, and oven dry obtains finished catalyst.
[embodiment 5]
The catalyst powder of preparation among the embodiment 4 is broken into 20～60 purpose particles, gets 1.0 gram catalyst and carry out propylene liquid-phase alkylation reaction in fixed bed reactors, reaction condition is, propylene air speed=2.5 hour
-1, reaction temperature=155 ℃, reaction pressure=2.8MPa, product is an isopropylbenzene, propylene conversion=100%, selectivity of product 99.4%, total benzene/olefin molar ratio is 2.5, reacts and does not observe the catalyst activity loss in 2500 hours, and outlet isopropylbenzene concentration is 37.3%.
[comparative example 1]
To be ground into 20～60 purpose particles with the Y zeolite catalyst of same procedure preparation, and get 1.0 gram catalyst and carry out the propylene liquid-phase alkylation reaction in fixed bed reactors, reaction condition is, propylene air speed=0.3 hour
-1, reaction temperature=190 ℃, reaction pressure=3.0MPa, product is an isopropylbenzene, initial propylene conversion=100%, selectivity of product 99.2%, total benzene/olefin molar ratio is 5.0, react after 1500 hours propylene conversion and reduces to 95%, and exporting isopropylbenzene concentration is 25%.
[comparative example 2]
To be ground into 20～60 purpose particles with the beta-zeolite catalyst of same procedure preparation, and get 1.0 gram catalyst and carry out the propylene liquid-phase alkylation reaction in fixed bed reactors, reaction condition is, propylene air speed=0.75 hour
-1, reaction temperature=170 ℃, reaction pressure=2.8MPa, product is an isopropylbenzene, initial propylene conversion=100%, selectivity of product is greater than 99.3%, total benzene/olefin molar ratio is 3.0, react after 1500 hours propylene conversion and reduces to 98%, and exporting isopropylbenzene concentration is 31.8%.
[embodiment 6]
In 200 ml waters, dissolve 80 gram sodium aluminates and 14 gram NaOH evenly mixed, adding 600 gram (40% weight) Ludox stirs, adding 600 gram pure water again stirs evenly mixed, add 200 gram hexamethylene imines, add colloidal sol 50 grams of preparation among the embodiment 1, continue stirring and change in the crystallizing kettle after 2 hours, stirred crystallization 120 hours at 155 ℃, filtration washing is to PH=9,150 ℃ of oven dry.Get above-mentioned synthetic crystal aluminosilicate 100 grams, add 1 mol ammonium nitrate solution, be warming up to 95 ℃ of exchanges 2 hours, exchange repeatedly 6 times, alkali metal ion content measured in the gained crystal aluminosilicate is less than 100ppm, crystal aluminosilicate 90 grams that above-mentioned exchange is good and 25 gram aluminium oxide, 10 gram zinc oxide, 15 gram zirconias, 5 gram titanium oxide are evenly mixed, add 200 milliliter of 5% salpeter solution, 5 gram sesbania powder are mediated extruded moulding after 3 hours, the catalyst of forming is being warming up to 580 ℃ of roastings 4 hours under air atmosphere after 150 ℃ of oven dry, with above-mentioned product of roasting with 600 ℃ of water vapours with 0.2 hour
-1Handled 2 hours, cooling was placed in the oxalic acid solution of 1.0 normal concentrations soak at room temperature 48 hours, and distilled water cleans to neutral, and oven dry obtains finished catalyst.
[embodiment 7]
The catalyst powder of preparation among the embodiment 6 is broken into 20～60 purpose particles, gets 1.0 gram catalyst and carry out the ethene liquid phase alkylation reaction in fixed bed reactors, reaction condition is, propylene air speed=2.5 hour
-1, reaction temperature=155 ℃, reaction pressure=2.7MPa, product is an isopropylbenzene, propylene conversion=100%, selectivity of product 99.5%, total benzene/olefin molar ratio is 2.5, reacts not detect propylene in the product in 2500 hours, reactor outlet isopropylbenzene concentration 37.8%.
Claims (7)
1, a kind of catalyst that is used to produce isopropylbenzene comprises following component by weight percentage:
A) 50～80% crystal aluminosilicate;
B) 20～50% binding agent;
Wherein catalyst is handled with organic acid after adopting 200～1000 ℃ of high-temperature water vapors to handle again, and crystal aluminosilicate has following XRD diffraction data:
The 2 θ angles of diffraction Diffraction peak intensity (I/I
0×100)
6.5° 28.8±0.1
7.2° 17.3±0.1
8.8° 15.4±0.1
9.7° 53.8±0.1
13.5° 39.4±0.1
14° 28.8±0.1
14.3° 19.2±0.1
15.4° 23.1±0.1
19.5° 34.6±0.1
22.2° 69.2±0.1
23.8° 23.1±0.1
25.5° 100±0.1
26.2° 65.4±0.1
27.5° 46.7±0.1
31° 27.9±0.1
35.8° 15.4±0.1
。
2, according to the described catalyst that is used to produce isopropylbenzene of claim 1, the specific area that it is characterized in that crystal aluminosilicate is 500～600 meters
2/ gram, pore volume are 0.45～0.60 milliliter/gram.
3,, it is characterized in that binding agent is selected from aluminium oxide, titanium oxide, zinc oxide, zirconia or its mixture according to the described catalyst that is used to produce isopropylbenzene of claim 1.
4, according to the described catalyst that is used to produce isopropylbenzene of claim 1, it is characterized in that the temperature that catalyst adopts high-temperature water vapor to handle is 400～700 ℃, the processing time is 0.5～20 hour.
5,, it is characterized in that the time that catalyst is handled with high-temperature water vapor is 1～5 hour according to the described catalyst that is used to produce isopropylbenzene of claim 4.
6, according to the described catalyst that is used to produce isopropylbenzene of claim 1, it is characterized in that organic acid is selected from citric acid, tartaric acid, oxalic acid or glacial acetic acid, organic acid concentration is 0.1～3 mol, the organic acid processing time is 1～72 hour.
7, according to the described catalyst that is used to produce isopropylbenzene of claim 6, it is characterized in that organic acid is selected from oxalic acid, organic acid concentration is 0.5～1.5 mol, and the organic acid processing time is 24～60 hours.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100527285A CN1293939C (en) | 2004-07-12 | 2004-07-12 | Catalyst for producing isopropyl benzene |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100527285A CN1293939C (en) | 2004-07-12 | 2004-07-12 | Catalyst for producing isopropyl benzene |
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| Publication Number | Publication Date |
|---|---|
| CN1721070A true CN1721070A (en) | 2006-01-18 |
| CN1293939C CN1293939C (en) | 2007-01-10 |
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|---|---|---|---|
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Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1500765A (en) * | 1918-06-11 | 1924-07-08 | Perfect Window Regulator Compa | Electrically-operated raising and lowering mechanism for windows |
| US5192727A (en) * | 1991-08-19 | 1993-03-09 | Uop | Process for modifying the pore system of zeolite LZ-202 |
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