CN101020134B - W-base catalyst and its preparation and application - Google Patents
W-base catalyst and its preparation and application Download PDFInfo
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- CN101020134B CN101020134B CN2006100035858A CN200610003585A CN101020134B CN 101020134 B CN101020134 B CN 101020134B CN 2006100035858 A CN2006100035858 A CN 2006100035858A CN 200610003585 A CN200610003585 A CN 200610003585A CN 101020134 B CN101020134 B CN 101020134B
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Abstract
The W-base catalyst for disproportionating ethylene and butylene to prepare propylene has modified Y-molecular sieve comprising Y-molecular sieve in 50 wt% and added inertial component as the carrier, and oxide of W in the supported amount of 3-24 wt% of catalyst as the active component. The preparation process of the catalyst includes the following steps: 1. treating NaY molecular sieve through ammonium exchange, hydrothermal treatment and inorganic acid dealuminizing to obtain modified Y-molecular sieve; and 2. soaking the modified Y-molecular sieve in W containing solution, drying and baking at 400-750 deg.c for 1-4 hr to obtain the W-base catalyst. The catalyst is used for disproportionating ethylene and butylene to prepare propylene and has the features of high selectivity, high conversion rate and high 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 0.1～2.0M Pa.
Summary of the invention
The object of the present invention is to provide a kind of W catalyst based.
Another purpose of the present invention is to provide above-mentioned Preparation of catalysts method.
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, is carrier with the modified Y molecular sieve, and the active component that supports is the oxide of tungsten, and the loading of active component is 3～24% of a catalyst weight.
Described W is catalyst based, wherein the SiO of modified Y molecular sieve
2/ Al
2O
3Mol ratio is 5～18, 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 5～20% of a catalyst weight.
Described W is catalyst based, wherein carrier is the mixture carrier that is added with inert component, wherein modified Y molecular sieve weight accounts for 50% of mixture carrier weight at least, and all the other are inert component, and described inert component is one or more in aluminium oxide, silica and the clay.
The present invention prepares the catalyst based method of above-mentioned W:
A), obtain the support modification Y molecular sieve with NaY molecular sieve through ammonium exchange, hydrothermal treatment consists, inorganic acid dealuminzation;
B) modified Y molecular sieve that step a obtained floods with the solution that contains W elements, and is dry and in 400～750 ℃ of roastings 1～4 hour, and it is catalyst based to make W.
Described preparation method, wherein the modified Y molecular sieve that step a is obtained mixes with inert component, and after 100～120 ℃ of dryings, 500～550 ℃ of roastings are 1～4 hour under the atmosphere that flows, and make mixture carrier, continue step b again; Wherein modified Y molecular sieve weight accounts for 50% of mixture carrier weight at least.
Among the described preparation method, the Modified Zeolite Y among the step a is NaY (SiO
2/ Al
2O
3Mol ratio is 4～5), 90～100 ℃ of exchanges, exchange 1～3 hour by ammonium salt at every turn, repeated exchanged 2～3 times, filtration washing 100～120 ℃ of oven dry, obtains NH
4The NaY molecular sieve, relative crystallinity 〉=95%, SiO
2/ Al
2O
3Mol ratio is 4～5, and cell parameter is 2.460～2.470nm, Na
2O content 2.0～2.6%.Then with NH
4NaY carries out the super steady processing of hydro-thermal 1～3 hour at 500～650 ℃, exchanges 1 time 1～3 hour by ammonium salt at 90～100 ℃ again, and filtration washing 100～120 ℃ of oven dry, obtains modification USY molecular sieve, relative crystallinity 〉=90%, SiO
2/ Al
2O
3Mol ratio is 5.2～7, and cell parameter is 2.450～2.465nm, Na
2O content 0.1～0.5%.
Among the described preparation method, the Modified Zeolite Y among the step a can also be NaY (SiO
2/ Al
2O
3Mol ratio is 4～5), 90～100 ℃ of exchanges, exchange 1～3 hour by ammonium salt at every turn, repeated exchanged 2～3 times, filtration washing 100～120 ℃ of oven dry, obtains NH
4The NaY molecular sieve, relative crystallinity 〉=95%, SiO
2/ Al
2O
3Mol ratio is 4～5, and cell parameter is 2.460～2.470nm, Na
2O content 2.0～2.6%.Then with NH
4NaY is placed in the pressure vessel of sealing, utilizes the water and the NH that himself contain
3, 500～650 ℃ of temperature, hydrothermal treatment consists is 1～4 hour under pressure 0.05～0.11MPa.Y zeolite after the above-mentioned hydrothermal treatment consists was handled reprocessing 2～3 times, filtration washing 1～4 hour with ammonium salt and inorganic acid down at 90～100 ℃, 100～120 ℃ of oven dry, obtain modification DHY molecular sieve, relative crystallinity 〉=90%, cell parameter is 2.430～2.460nm, SiO
2/ Al
2O
3Mol ratio is 8～6, Na
2O content 0.1～0.5%.
W of the present invention is catalyst based can be used for than under the low reaction temperatures (120～280 ℃) by ethene and preparing propylene by butene disproportionation, use catalyst provided by the invention can high conversion, high selectivity and high stability ground produces propylene.Reaction condition is: 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
The specific embodiment
Below in conjunction with embodiment the present invention is further elaborated, but the present invention is not produced any restriction.
Comparative Examples 1
Take by weighing 120g NaY molecular sieve (the synthetic factory of big fluidization thing produces), SiO
2/ Al
2O
3Mol ratio 4.3 adds 1200 milliliters of 0.8N concentration aqueous ammonium nitrate solutions, 90 ℃ of exchanges 2 hours, and repeated exchanged twice, filtration washing was dried 24 hours down at 120 ℃ then, made NH
4NaY, relative crystallinity 96%, cell parameter 2.465nm, Na
2O weight content 2.60%.Take by weighing NH
4NaY molecular sieve 35g (butt), add 15g aluminium oxide (butt), with weight concentration is 15% salpeter solution moulding and the orifice plate extruded moulding of using Φ 2.0mm, dried 24 hours for 120 ℃, under moving air through 520 ℃ of roastings 2 hours, be cooled to room temperature and obtain the HNaY-A carrier, then put into the vacuum impregnation jar, under 25 ℃, vacuumize vacuum＞700mmHg, 30 minutes pumpdown times, add 50 milliliters of weight concentration 0.125g/ml ammonium metatungstate aqueous solutions, flooded 30 minutes, and put subsequently, be blown into 120 ℃ dry 6 hours of hot-air to normal pressure, then above-mentioned sample is put into muffle furnace, 4 ℃/min of programming rate under moving air is warmed up to 600 ℃ of roastings 2 hours, promptly makes the A catalyst of W content 10w% after the cooling.
Embodiment 1
NH
4The preparation of NaY is with Comparative Examples 1.NH with gained
4NaY puts into the high-temperature roasting stove, and at 600 ℃, 100% steam 0.1MPa handled 2 hours down, and the gained molecular sieve repeats above ammonium exchange again and washing step obtains super steady USY molecular sieve, SiO
2/ Al
2O
3Mol ratio is 6.2, and cell parameter is 2.456nm, Na
2O content 0.15wt%, relative crystallinity 94%.With the USY molecular sieve 35g (butt) of gained, add 15g Al
2O
3(butt) is that 15% aqueous solution of nitric acid mixes and to pinch agglomerating (need to prove with weight concentration, inert component of the present invention is not limited only to aluminium oxide, also can adopt as: the mixture of one or several in silica, clay and the diatomite), orifice plate extruded moulding with Φ 2.0mm, dried 24 hours for 120 ℃, under moving air,, be cooled to room temperature, obtain carrier HUSY-A through 520 ℃ of roastings 2 hours.The dipping of W elements and calcination steps be with comparative example 1, makes the W weight percentage and be 10% B catalyst.
Embodiment 2
NH
4The preparation of NaY is with comparative example 1.With NH
4NaY puts into the stainless steel airtight container, and 5 ℃/min of programming rate is warming up to 590 ℃, utilizes NH
4The pressure that NaY self produces, the system that keeps constant 3.5 hours, reduces to room temperature under 0.11MPa (gauge pressure) pressure.Take by weighing the molecular sieve after the above-mentioned hydrothermal treatment consists of 100g, add 800 milliliters of 2.0N concentration aqueous ammonium nitrate solutions, add HNO again
3Weight concentration is that 30% aqueous solution 77g exchanges under 90 ℃ and handled 2 hours, and repeated exchanged handles twice, filtration washing, 120 ℃ of dryings 24 hours, DHY1, relative crystallinity 93%, cell parameter 2.453nm, SiO
2/ Al
2O
3Mol ratio 10, Na
2O weight content 0.15%.With 35g DHY1 (butt), add 15gAl
2O
3(butt) is that 15% aqueous solution of nitric acid mixes and to pinch agglomeratingly with weight concentration, and with the orifice plate extruded moulding of Φ 2.0mm, 120 ℃ of oven dry 24 hours through 520 ℃ of roastings 2 hours, are cooled to room temperature and obtain the DHY1 carrier under moving air.The dipping of W elements and calcination steps be with comparative example 1, makes the W weight percentage and be 10% C catalyst.
Embodiment 3
NH
4The preparation process of NaY is with embodiment 1, but NH
4NO
3And HNO
3The number of times of common dealumination treatment is 3 times, obtains the DHY2 molecular sieve at last, relative crystallinity 90%, cell parameter 2.443nm, SiO
2/ Al
2O
3Mol ratio 16, Na
2O weight content 0.1%.In 35g DHY2 (butt), add 15gAl
2O
3(butt) is that 15% aqueous solution of nitric acid mixes and to pinch agglomeratingly with weight concentration, and with the orifice plate extruded moulding of Φ 2.0mm, 120 ℃ of oven dry 24 hours through 540 ℃ of roastings 1.5 hours, are cooled to room temperature and obtain the DHY2-A carrier under moving air.The dipping of W elements and calcination steps be with comparative example 1, makes the W weight percentage and be 10% D catalyst.
Embodiment 4
Take by weighing DHY1 molecular sieve 25g (butt) among the embodiment 2, add clay 25g (butt), with weight concentration be 15% aqueous solution of nitric acid mix pinch agglomerating, orifice plate extruded moulding with Φ 2.0mm, dried 24 hours for 120 ℃, under moving air,, be cooled to room temperature and obtain the DHY-50A carrier through 510 ℃ of roastings 3 hours.The dipping of W elements and calcination steps be with comparative example 1, makes the W weight percentage and be 5% E catalyst.
Embodiment 5
Prepare carrier DHY1 according to the process of describing among the embodiment 2, dipping, calcination steps are also with embodiment 3 subsequently, and just the weight concentration of ammonium metatungstate solution becomes 0.062g/ml, and obtaining W content at last is the F catalyst of 5wt%.
Embodiment 6
Prepare carrier DHY1 according to the process of describing among the embodiment 2, dipping, calcination steps are also with embodiment 3 subsequently, and just the concentration of ammonium metatungstate solution becomes 0.25g/ml, and obtaining W content at last is the G catalyst of 20wt%.
Embodiment 7
The preparation of DHY1 carrier and impregnation steps are with embodiment 2, and just the sintering temperature of catalyst is 450 ℃, and roasting time is 6 hours, and obtaining W content at last is the H catalyst of 10wt%.
Embodiment 8
The preparation of DHY2 carrier and impregnation steps are with embodiment 3, and just the sintering temperature of catalyst is 700 ℃, and roasting time is 1.5 hours, and obtaining W content at last is the I catalyst of 10wt%.
Embodiment and comparative example 9
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, and through the super steady Y molecular sieve prepared catalyst B that obtains that handles of hydro-thermal, the disproportionation activity obviously is better than untreated A activity of such catalysts; Super steady processing of process hydro-thermal and/or the modification of inorganic acid dealuminzation are handled the prepared catalyst C-I of Y molecular sieve that obtains and are all shown as the good reactivity energy.
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
Claims (8)
1. the catalyst based preparation method of W who is used for ethene and preparing propylene by butene disproportionation is a carrier with the modified Y molecular sieve, and the active component that supports is the oxide of tungsten, and the loading of active component is 3～24% of a catalyst weight, and main preparation methods is:
A), obtain the support modification Y molecular sieve with NaY molecular sieve through ammonium exchange, hydrothermal treatment consists and inorganic acid dealuminzation;
B) modified Y molecular sieve that step a obtained floods with the solution that contains W elements, and is dry and in 400～750 ℃ of roastings 1～4 hour, and it is catalyst based to make W.
2. according to the described preparation method of claim 1, it is characterized in that the modified Y molecular sieve that step a is obtained mixes with inert component, after 100～120 ℃ of dryings, 500～550 ℃ of roastings are 1～4 hour under the atmosphere that flows, and make mixture carrier, continue step b again; Wherein modified Y molecular sieve weight accounts for 50% of mixture carrier weight at least.
3. according to the described preparation method of claim 1, it is characterized in that the NaY molecular sieve among the step a 90～100 ℃ of exchanges, exchanges 1～3 hour by ammonium salt at every turn, repeated exchanged 2～3 times, filtration washing 100～120 ℃ of oven dry, obtains NH
4The NaY molecular sieve, Na
2O content is 2.0～2.6%; With NH
4The NaY molecular sieve carries out the super steady processing of hydro-thermal 1～3 hour at 500～650 ℃, exchanges 1～3 hour by ammonium salt and inorganic acid at 90～100 ℃ again, and filtration washing 100～120 ℃ of oven dry, obtains modification USY molecular sieve, Na
2O content 0.1～0.5%.
4. according to the described preparation method of claim 1, it is characterized in that the NaY molecular sieve among the step a 90～100 ℃ of exchanges, exchanges 1～3 hour by ammonium salt at every turn, repeated exchanged 2～3 times, filtration washing 100～120 ℃ of oven dry, obtains NH
4The NaY molecular sieve, Na
2O content is 2,0～2.6%; With NH
4The NaY molecular sieve is placed in the pressure vessel of sealing, utilizes the water and the NH that himself contain
3, in 500～650 ℃, hydrothermal treatment consists is 1～4 hour under 0.05～0.11MPa; Y zeolite after the above-mentioned hydrothermal treatment consists was handled 1～4 hour down at 90～100 ℃ with ammonium salt and inorganic acid, reprocessing 2～3 times, filtration washing 100～120 ℃ of oven dry, obtains modification DHY molecular sieve, Na
2O content 0.1～0.5%.
5. according to the described preparation method of claim 1, it is characterized in that the SiO of described modified Y molecular sieve
2/ Al
2O
3Mol ratio is 5～18, Na
2O weight content≤0.5w%, cell parameter is 2.430～2.470nm.
6. according to the described preparation method of claim 1, it is characterized in that the loading of active component is 5～20% of a catalyst weight.
7. according to the described preparation method of claim 1, it is characterized in that carrier is the mixture carrier that is added with inert component, wherein modified Y molecular sieve weight accounts for 50% of mixture carrier weight at least, and all the other are inert component.
8. according to the described preparation method of claim 1, it is characterized in that inert component is one or more in aluminium oxide, silica and the clay.
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|---|---|---|---|
| CN2006100035858A CN101020134B (en) | 2006-02-15 | 2006-02-15 | W-base catalyst and its preparation and application |
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|---|---|---|---|
| CN2006100035858A CN101020134B (en) | 2006-02-15 | 2006-02-15 | W-base catalyst and its preparation and application |
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| CN101020134B true CN101020134B (en) | 2010-09-08 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103265978B (en) * | 2013-05-31 | 2014-07-30 | 陕西煤业化工技术研究院有限责任公司 | Integrated system and method for catalytic cracking and dust removal of medium-and-low temperature dry distillation coal gas |
| CN109847790B (en) * | 2017-11-30 | 2020-09-04 | 中国科学院大连化学物理研究所 | Catalyst, preparation method thereof and application of catalyst in ethylene-butylene disproportionation reaction |
| CN111013644A (en) * | 2018-10-09 | 2020-04-17 | 中国石油化工股份有限公司 | Heteroatom W- β molecular sieve and preparation method and application thereof |
| CN113351206B (en) * | 2020-03-06 | 2023-04-07 | 中国科学院大连化学物理研究所 | Olefin disproportionation catalyst and preparation method thereof |
| CN112675902B (en) * | 2020-12-22 | 2023-06-06 | 中国华能集团有限公司 | Catalyst for preparing propylene by inverse disproportionation of ethylene and butene and preparation method thereof |
| CN114062550B (en) * | 2021-11-16 | 2024-02-02 | 西南石油大学 | Natural gas full-component analysis device and method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1373007A (en) * | 2001-02-28 | 2002-10-09 | 中国科学院大连化学物理研究所 | Catalyst for preparing propylene by dismutation reaction and its preparing process and application |
-
2006
- 2006-02-15 CN CN2006100035858A patent/CN101020134B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1373007A (en) * | 2001-02-28 | 2002-10-09 | 中国科学院大连化学物理研究所 | Catalyst for preparing propylene by dismutation reaction and its preparing process and application |
Non-Patent Citations (1)
| Title |
|---|
| Shengjun Huang et.al..Metathesis of ethene and 2-butene to propene on W/Al2O3-HY catalysts with different HY contents.Journal of Molecular Catalysis A: Chemical 226.2004,(226),61-68. * |
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