CN101112685A - Process for preparation of high activity W-based catalysts and uses thereof - Google Patents
Process for preparation of high activity W-based catalysts and uses thereof Download PDFInfo
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- CN101112685A CN101112685A CNA2006100889425A CN200610088942A CN101112685A CN 101112685 A CN101112685 A CN 101112685A CN A2006100889425 A CNA2006100889425 A CN A2006100889425A CN 200610088942 A CN200610088942 A CN 200610088942A CN 101112685 A CN101112685 A CN 101112685A
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- molecular sieve
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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
Abstract
A W-based catalyst preparing the propylene with the ethane and butylene disproportionation takes the Y molecular sieve as the carrier which bears the active component of tungsten oxide solid powder; the bearing quantity of the active component ranges from 5 percent to 16 percent of the catalyst weight; the carrier is the mixture carrier added with inertia component, wherein, hydrogen-typed Y molecular sieve weight at least occupies 50 percent of the mixture carrier weight. The preparation method is that the hydrogen-typed Y molecular sieve, the tungsten trioxide and the inertia mechanism are mixed and are roasted in dry or steam-contained flow air for 0.5 hour through 24 hours under the temperature ranging from 400 DEG C to 750 DEG C, and the W-based catalyst is prepared. The catalyst of the invention is used for the reaction of preparing the propylene with the ethane and butylene disproportionation on a fixed bed reactor, and has the advantages of high selection, high rate of conversion and good stability.
Description
Technical field
It is catalyst based to the present invention relates to a kind of W.
The invention still further relates to above-mentioned Preparation of catalysts method.
The invention still further relates to the application of above-mentioned catalyst in ethene and preparing propylene by butene disproportionation reaction.
Background technology
Propylene is one of important foundation raw material of development petrochemical industry, also is the petrochemical industry product that demand growth is the fastest in the world, and world's propylene demand from 1,800 ten thousand tons of nearly 5,000 ten thousand tons of increasing to 2000 in 1980, expects 2010 and will reach 75,000,000 tons.It with ethene and butene reaction system propylene one of method that increases propone output, because supply exceed demand for butylene at present, especially 2-butylene shortage is effectively utilized approach, so suit measures to local conditions to adopt this course of reaction can reasonably regulate the product layout of ethene, propylene and butylene.There is part to contain the crude ethylene of methane, ethane and small quantity of hydrogen in addition in the product of heavy oil catalytic pyrolysis, itself and butene reaction are made propylene, both can improve the output of propylene, can reduce the energy consumption of cryogenic separation again.This is a process with practicality and novelty, and it is succeeded in developing and can produce remarkable economic efficiency and social benefit.
United States Patent (USP) (USP5,120,894) reported the catalyst of ethene and preparing propylene by butene disproportionation, this catalyst is that Mo, W and Re are compound loaded on carriers such as aluminium oxide, silica, alkali metal oxide and alkaline earth oxide, reaction temperature at 274～343 ℃, pressure at 2.4～3.5MPa.But above-mentioned catalyst is used for the reaction by ethene and butylene system propylene, and its selectivity is relatively poor.
Chinese patent (application number is 01104355.5) has been reported the catalyst of ethene and preparing propylene by butene disproportionation, and this catalyst is that Mo, W and Re are compound loaded on molecular sieve carrier, and molecular sieve comprises Y, Beta, SAPO series, ZSM series and MCM series.Be reflected in fixed bed or the fluidized-bed reactor and carry out, 0～300 ℃ of reaction temperature; Weight space velocity: 0.01～3h
-1C in the reactor feed gas
2H
4/ C
4H
8Than being 0.2～4; Reaction pressure is 0.1～2.0MPa.
Chinese patent (application number CN200610003585.8) has reported that a kind of W that is used for ethene and preparing propylene by butene disproportionation is catalyst based, and is by conventional infusion process that W is compound loaded on hydrothermal treatment consists, inorganic acid dealuminzation modified Y molecular sieve.Be reflected in the fixed bed reactors and carry out, reaction temperature is 120～280 ℃, and reaction pressure is 0.1～2.3MPa, ethylene/butylene mol ratio 0.5～3.5, and weight space velocity is 0.1-3.0h
-1
Summary of the invention
The object of the present invention is to provide a kind of W catalyst based.
It is the method that the tungsten source prepares above-mentioned catalyst that another purpose of the present invention is to provide with the tungstic acid pressed powder.
For achieving the above object, the W that is used for ethene and preparing propylene by butene disproportionation provided by the invention is catalyst based, and carrier is the mixture that the Hydrogen Y molecular sieve adds inert component, and wherein Hydrogen Y molecular sieve weight accounts for 50% of vehicle weight at least, and all the other are inert component; The active component that supports on the carrier is the oxide of tungsten, and the loading of active component is 5～16% of a vehicle weight.
Described W is catalyst based, wherein the SiO of Hydrogen Y molecular sieve
2/ Al
2O
3Mol ratio is 5～12, Na
2O weight content≤0.5w%, cell parameter is 2.430～2.470nm.
Described W is catalyst based, and wherein the loading of active component is 6～14% of a catalyst weight.
Described W is catalyst based, and wherein inert component is one or more in alchlor, silica and the clay.
The present invention prepares the catalyst based method of above-mentioned W: with the solid tungsten trioxide powder is the tungsten source, and the method for disperseing by heat on the Hydrogen Y molecular sieve, makes high activity, catalyst optionally with tungsten load.Its key step is:
A) Hydrogen Y molecular sieve, tungstic acid and inert component powder is even, fully grind; Wherein Hydrogen Y molecular sieve weight accounts for 50% of vehicle weight at least; The loading of active component tungstic acid is 5～16% of a vehicle weight;
B) step a obtains powder 400～750 ℃ of roastings 0.5 hour to 24 hours, with gained mixture compression molding, be crushed to 20～40 orders, W is catalyst based.
Among the described preparation method, can be with step a gained powder (2000～9000h in moving air atmosphere
-1) in 450～700 ℃ of roastings 14～24 hours, gained mixture compression molding was ground into 20～40 orders.
Among the described preparation method, also step a gained powder can contained the moving air atmosphere (air 2000～9000h of a certain amount of water vapour
-1Water vapour/air=0.1～0.5 (v/v)) in 450～700 ℃ of roastings 0.5 hour to 12 hours, gained mixture compression molding, pulverizing, it is standby to get 20～40 orders.
W of the present invention is catalyst based can be used for than under the low reaction temperatures by ethene and preparing propylene by butene disproportionation, have the characteristics of high conversion, high selectivity and better stability.Reaction condition is: reaction temperature is 120～200 ℃, and reaction pressure is 0.1～1.2MPa, ethylene/butylene mol ratio 0.7～1.5, and weight space velocity is 0.1-3.0h
-1
The specific embodiment
The present invention is further elaborated below in conjunction with embodiment, but the present invention is not produced any restriction.
Comparative Examples 1
(the synthetic factory of big fluidization thing produces relative crystallinity 93%, cell parameter 2.453nm, SiO to take by weighing 35g Hydrogen Y molecular sieve
2/ Al
2O
3Mol ratio 10, Na
2O weight content 0.15%), adding 15g alchlor (butt), is 15% salpeter solution moulding and the orifice plate extruded moulding of using Φ 2.0mm with weight concentration, dries 24 hours for 120 ℃, at moving air (7200h
-1) under through 520 ℃ of roastings 2 hours, be cooled to room temperature and obtain the HY-A carrier, then put into the vacuum impregnation jar, under 25 ℃, vacuumize, vacuum＞700mmHg, 30 minutes pumpdown times added 50 milliliters of weight concentration 0.125g/ml ammonium metatungstate aqueous solutions, flooded 30 minutes, put subsequently to normal pressure, be blown into 120 ℃ dry 6 hours of hot-air, then above-mentioned sample put into muffle furnace, at moving air (7200h
-1) following 4 ℃/min of programming rate, be warmed up to 600 ℃ of roastings 2 hours, promptly make the A catalyst of W weight loading 10% after the cooling.
Embodiment 1
Take by weighing 30g Hydrogen Y molecular sieve (with Comparative Examples 1), add 20g alchlor (butt) and 5.5g solid WO
3Powder mixes the back and ground 10 minutes, gets 10g.Bubbling air (7200h simultaneously subsequently
-1) and water vapour (water vapour/air=0.31 (v/v)), be warmed up to 590 ℃ of roastings 3 hours with 5 ℃/min.Gained mixture compression molding, pulverizing obtain 20～40 order W weight loadings and are 10% B catalyst at last.(adopting alchlor also can be silica or clay, below each embodiment all identical therewith.)
Embodiment 2
Prepare Hydrogen Y molecular sieve, WO according to the process of describing among the embodiment 1
3With the powder of alchlor, get 10g.Bubbling air (8500h simultaneously subsequently
-1) and water vapour (water vapour/air=0.15 (v/v)), be warmed up to 680 ℃ of roastings 1 hour with 8 ℃/min, obtain W weight loading at last and be 8.8% C catalyst.
Embodiment 3
Take by weighing 37g Hydrogen Y molecular sieve (with Comparative Examples 1), add 11g alchlor (butt), 2g silica (butt) and 8.3g solid WO
3Powder mixes the back and ground 10 minutes, and the gained powder is got 10g.Bubbling air (2400h simultaneously subsequently
-1) and water vapour (water vapour/air=0.45 (v/v)), be warmed up to 620 ℃ of roastings 10 hours with 6 ℃/min, obtain W weight loading at last and be 13.3% D catalyst.
Embodiment 4
(the synthetic factory of big fluidization thing produces SiO to take by weighing 35g Hydrogen Y molecular sieve
2/ Al
2O
3Mol ratio is 5.6, and cell parameter is 2.456nm, Na
2O content 0.15wt%, relative crystallinity 94%), add 14g alchlor (butt), 1g clay (butt) and 6.3g solid WO
3Powder mixes the back and ground 10 minutes.Get 10g, calcination atmosphere subsequently and temperature be with embodiment 1, obtains W weight loading at last and be 10% E catalyst.
Embodiment 5
Take by weighing 35g Hydrogen Y molecular sieve (with Comparative Examples 1), add 15g alchlor (butt) and 6.3g solid WO
3Powder mixes the back and ground 10 minutes, and the gained powder is (3000h under the dry air atmosphere that flows
-1) 4 ℃/min of programming rate, be warmed up to 600 ℃ of roastings 19 hours.20～40 orders are got in gained mixture compression molding, pulverizing, make W weight loading and be 10% F catalyst.
Embodiment 6
Take by weighing 37g Hydrogen Y molecular sieve (with Comparative Examples 1), add 13g alchlor (butt) and 8g solid WO
3Powder mixes the back and ground 10 minutes, and the gained powder is got 10g (8200h under the dry air atmosphere that flows
-1), be warmed up to 710 ℃ of roastings 16 hours.Make W weight loading and be 12.8% G catalyst.
Embodiment 7
Take by weighing 30g Hydrogen Y molecular sieve (with Comparative Examples 1), add 20g alchlor (butt) and 4.3g solid WO
3Powder mixes the back and ground 10 minutes, and the gained powder is got 10g (5000h under moving air atmosphere
-1), be warmed up to 500 ℃ of roastings 23 hours, make W weight loading and be 6.9% H catalyst.
Embodiment and comparative example 8
Is in the stainless steel fixed bed reactors of 10mm, at N with 5g by the catalyst of above-mentioned Comparative Examples and the embodiment method preparation internal diameter of packing into
2Be warmed up to 550 ℃ and kept 1 hour in the atmosphere, then at N
2After atmosphere drops to the reaction temperature that needs, switch ethene and butylene and carry out disproportionated reaction, the products therefrom use is furnished with 100 meters PONA capillary column Varian3800 chromatograms and analyzes fid detector.The gained experimental result is as shown in table 1, all has disproportionated reaction performance preferably containing the catalyst B-H for preparing under the moving air atmosphere; The value that all prepares the A catalyst in the selectivity that contains B catalyst stability, butene conversion and propylene under the moving air atmosphere of water vapour above conventional dipping method.
The foregoing description is the part preferred embodiment, is not the present invention is limited.In fact can realize the present invention so long as meet the condition that summary of the invention partly sets forth, therefore, protection domain of the present invention is as the criterion with the claim of application.
The catalyst based performance that goes up ethene and butylene system propylene of table 1:W
| Catalyst | Reaction condition | Butene conversion (%) | Propylene selectivity (%) | |||||
| Temperature (℃) | Pressure (MPa) | Weight space velocity (h -1) | The ethylene/butylene mol ratio | Reaction time (h) | ||||
| Comparative Examples 1 | A | 180 | 0.1 | 1.5 | 1.0 | 1 | 63.0 | 88.0 |
| 3 | 60.9 | 87.0 | ||||||
| 7 | 53.0 | 82.1 | ||||||
| 12 | 39.6 | 75.0 | ||||||
| Embodiment 1 | B | 180 | 0.1 | 1.5 | 1.0 | 1 | 63.1 | 88.5 |
| 3 | 62.4 | 88.3 | ||||||
| 7 | 62.5 | 88.0 | ||||||
| 12 | 62.0 | 88.0 | ||||||
| Embodiment 2 | C | 145 | 0.1 | 1.5 | 0.8 | 1 | 43.4 | 83.6 |
| 3 | 41.8 | 82.6 | ||||||
| Embodiment 3 | D | 175 | 0.8 | 1.4 | 1.1 | 1 | 66.2 | 90.6 |
| 4 | 63.6 | 89.0 | ||||||
| 7 | 61.0 | 87.6 | ||||||
| Embodiment 4 | E | 185 | 1.1 | 2.7 | 1.3 | 1 | 65.5 | 88.6 |
| Embodiment 5 | F | 180 | 0.1 | 1.5 | 1.1 | 1 | 64.0 | 89.0 |
| 4 | 53.1 | 82.5 | ||||||
| Embodiment 6 | G | 190 | 0.5 | 0.5 | 1.0 | 1 | 62.5 | 87.9 |
| Embodiment 7 | H | 160 | 0.1 | 0.3 | 1.0 | 1 | 59.0 | 83.0 |
Claims (10)
1. a W who is used for ethene and preparing propylene by butene disproportionation is catalyst based, and carrier adds the mixture of inert component for the Hydrogen Y molecular sieve, and wherein Hydrogen Y molecular sieve weight accounts for 50% of vehicle weight at least, and all the other are inert component; The active component that supports on the carrier is the oxide of tungsten, and the loading of active component is 5～16% of a vehicle weight.
2. catalyst based according to the described W of claim 1, it is characterized in that the SiO of described Hydrogen Y molecular sieve
2/ Al
2O
3Mol ratio is 5～12, Na
2O weight content≤0.5w%, cell parameter is 2.430～2.470nm.
3. catalyst based according to the described W of claim 1, it is characterized in that the loading of active component is 6～14% of a vehicle weight.
4. catalyst based according to the described W of claim 1, it is characterized in that inert component is one or more in alchlor, silica and the clay.
5. the catalyst based preparation method of the described W of claim 1 is:
A) Hydrogen Y molecular sieve, tungstic acid and inert component powder is even, fully grind; Wherein Hydrogen Y molecular sieve weight accounts for 50% of vehicle weight at least; The loading of active component tungstic acid is 5～16% of a vehicle weight;
B) step a obtains powder 400～750 ℃ of roastings 0.5 hour to 24 hours, with gained mixture compression molding, be crushed to 20～40 orders, W is catalyst based.
6. according to the described preparation method of claim 5, it is characterized in that Hydrogen Y molecular sieve, WO that step a is obtained
3With the inert component mixed-powder, 450～700 ℃ of roastings are 14～24 hours under the dry, flowable air atmosphere, make mixture; Compression molding, be crushed to 20～40 orders.
7. according to the described preparation method of claim 6, it is characterized in that the amount of leading to of moving air is 2000～9000h
-1
8. according to the described preparation method of claim 5, it is characterized in that Hydrogen Y molecular sieve, WO that step a is obtained
3With the inert component mixed-powder,, make mixture containing under the moving air atmosphere of water vapour 450～700 ℃ of roastings 0.5 hour to 12 hours; Compression molding, pulverizing are used to 20～40 orders.
9. preparation method according to claim 8 is characterized in that, the moving air atmosphere that contains water vapour is: air 2000～9000h
-1Water vapour/air=0.1～0.5 (v/v).
10. the catalyst based application in the reaction of ethene and preparing propylene by butene disproportionation on fixed bed reactors of each described W of claim 1-4, reaction condition is: reaction temperature is 120～200 ℃, reaction pressure is 0.1～1.2MPa, ethylene/butylene mol ratio 0.7～1.5, and weight space velocity is 0.1-3.0h
-1
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016519681A (en) * | 2013-04-03 | 2016-07-07 | エスシージー ケミカルズ カンパニー，リミテッド | Process for converting paraffin to olefin and catalyst for use therein |
| CN107913595A (en) * | 2016-10-09 | 2018-04-17 | 中国石油化工股份有限公司 | The treatment by catalytic oxidation of HCN-containing gases |
| CN114062550A (en) * | 2021-11-16 | 2022-02-18 | 西南石油大学 | Natural gas all-component analysis device and method |
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2006
- 2006-07-27 CN CN2006100889425A patent/CN101112685B/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016519681A (en) * | 2013-04-03 | 2016-07-07 | エスシージー ケミカルズ カンパニー，リミテッド | Process for converting paraffin to olefin and catalyst for use therein |
| CN108404903A (en) * | 2013-04-03 | 2018-08-17 | Scg化学有限公司 | Method and the catalyst that wherein uses of the paraffin conversion at alkene |
| CN107913595A (en) * | 2016-10-09 | 2018-04-17 | 中国石油化工股份有限公司 | The treatment by catalytic oxidation of HCN-containing gases |
| CN107913595B (en) * | 2016-10-09 | 2019-12-10 | 中国石油化工股份有限公司 | Catalytic oxidation treatment method of cyanogen-containing waste gas |
| CN114062550A (en) * | 2021-11-16 | 2022-02-18 | 西南石油大学 | Natural gas all-component analysis device and method |
| CN114062550B (en) * | 2021-11-16 | 2024-02-02 | 西南石油大学 | Natural gas full-component analysis device and method |
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