CN101554591B - Mo/mordenite-aluminum oxide catalyst for butylene disproportionation and preparation method and application thereof - Google Patents
Mo/mordenite-aluminum oxide catalyst for butylene disproportionation and preparation method and application thereof Download PDFInfo
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- CN101554591B CN101554591B CN2008100109456A CN200810010945A CN101554591B CN 101554591 B CN101554591 B CN 101554591B CN 2008100109456 A CN2008100109456 A CN 2008100109456A CN 200810010945 A CN200810010945 A CN 200810010945A CN 101554591 B CN101554591 B CN 101554591B
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- mordenite
- aluminum oxide
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- butylene
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- 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 invention provides a Mo/mordenite-aluminum oxide catalyst for butylene disproportionation and a preparation method and application thereof. The catalyst takes the mixture of mordenite-aluminum oxide as a carrier, and the supported active component is an oxide of molybdenum; the mordenite is evenly mixed with a certain proportion of aluminum oxide and water, then molded by extrusion, dried and roasted to be put in ammonium solution for exchange to be prepared into an H-type mixture carrier; and the mixture carrier is dipped in the solution containing molybdenum element, theload of the metal molybdenum is 2-30 percent, and the mixture carrier is prepared into the Mo/mordenite-aluminum oxide catalyst after being dried and roasted. The provided catalyst is used in reactionof propylene and amylene prepared by 1-butylene disproportionation and can prepare propylene and amylene with high transformation ratio, high selectivity and high stability.
Description
Technical field
The present invention relates to a kind of Mo/ mordenite-aluminum oxide catalyst, its preparation and application that is used for butylene disproportionation, this catalyst is used for the 1-butylene disproportionation and prepares propylene and amylene reaction, specifically, be to be carried on the method that improves 1-butylene disproportionation reactivity worth on the mordenite-aluminum oxide complex carrier by molybdenum.
Background technology
Along with the sustainable growth of world wide inner propene demand, technology for Increasing Propylene Yield has become a research focus of petrochemical industry.World's propylene demand is from 1,800 ten thousand tons of 6,710 ten thousand tons of increasing to 2005 in 1980, global propylene demand will continue to increase with 4.9%/year speed in 2008～2015 years, the Asia will become maximum in the world propylene demand area in 2015, and the Middle East then can become the fastest-rising area of consumption.Low-carbon alkene disproportionation technology can also be regulated the distribution of olefin product according to the market demand in propylene enhancing, and can realize coproduction with technologies such as steam cracking, methanol-to-olefins, is a kind of technology for Increasing Propylene Yield that has a extensive future.The 1-butylene from the disproportionation route can increasing output of ethylene, propylene, realize C
4The deep processing and utilization of alkene has important practical significance.This technology can be utilized the 1-butylene resource of China than horn of plenty, does not consume same ethene resource in short supply simultaneously.This is a process with practicality and novelty, and it is succeeded in developing and can produce remarkable economic efficiency and social benefit.
WO 00014038 has introduced a kind of method of preparing propylene by butene disproportionation.The raw material butylene is butene-1, butene-2 or its mixture, and catalyst is WO
3/ SiO
2Or Cs
+, PO
4 3-WO Deng modification
3/ SiO
2, common reaction temperature is 500～550 ℃, pressure is 1atm.
US6271430 has reported a kind of technology for preparing propylene and amylene by butene-1 and butene-2 disproportionated reaction.The catalyst of this process using is Re
2O
7/ Al
2O
3
CN1490289A has reported the catalyst of preparing propylene by butene disproportionation, and this catalyst is WO
3/ SiO
2The raw material butylene is butene-1, butene-2 or its mixture, and reaction temperature is 250～450 ℃.
CN101121627A has introduced a kind of method of preparing propylene by butene disproportionation.The raw material butylene is the mixture of butene-1 and butene-2, and catalyst is WO
3/ SiO
2, reaction temperature is 250～500 ℃.
Summary of the invention
The purpose of this invention is to provide a kind of Mo/ mordenite-aluminum oxide catalyst, its preparation and application that is used for butylene disproportionation.
The invention provides a kind of Mo/ mordenite-aluminum oxide catalyst that is used for butylene disproportionation, this catalyst is a carrier with the mordenite-aluminum oxide mixture, and the active component that supports is the oxide of molybdenum.
The present invention also provides a kind of preparation method who is used for the Mo/ mordenite-aluminum oxide catalyst of butylene disproportionation, and concrete steps are:
(1) modenite and a certain proportion of aluminium oxide and water are mixed, mix the back extruded moulding, 60-120 ℃ dry 2-4 hour down, in the air atmosphere 450-550 ℃ roasting 1-4 hour;
(2) to place concentration be the ammonium salt solution of 0.3～1.0M to the product that step (1) is obtained, and stirs 1-12h in 45～100 ℃ of following air bubblings, filtration washing, and 100～120 ℃ of oven dry, 500～550 ℃ are burnt ammoniums, Na
2O content≤0.5wt% makes H-type silk zeolite-alumina support;
(3) the H-type mordenite-aluminum oxide carrier that step (2) is obtained is prepared into 16-40 purpose mixture carrier with conventional method;
(4) product that step (3) is obtained floods in containing the solution of molybdenum element, and the load capacity of metal molybdenum is 2～30%, and is dry and in 400～800 ℃ of roastings 1～4 hour in the air atmosphere then, makes the Mo/ mordenite-aluminum oxide catalyst.
The preparation method who is used for the Mo/ mordenite-aluminum oxide catalyst of butylene disproportionation provided by the invention, the SiO of described modenite
2/ Al
2O
3Mol ratio is 8～20, Na
2O content≤0.5wt%.
The preparation method who is used for the Mo/ mordenite-aluminum oxide catalyst of butylene disproportionation provided by the invention, the mixture carrier in the described step (2), wherein modenite weight accounts for 10% of mixture carrier weight at least, is preferably 30～80%; All the other are aluminium oxide.
The preparation method who is used for the Mo/ mordenite-aluminum oxide catalyst of butylene disproportionation provided by the invention, the loading of the metal molybdenum in the described step (3) is 2～30% of a catalyst weight, is preferably 3～12%.
The preparation method who is used for the Mo/ mordenite-aluminum oxide catalyst of butylene disproportionation provided by the invention, the sintering temperature in the described step (3) is preferably 450～700 ℃.
The Mo/ mordenite-aluminum oxide catalyst that is used for butylene disproportionation provided by the invention is used for the 1-butylene disproportionation and prepares propylene and amylene reaction, reaction condition is: reaction temperature is 60～300 ℃, reaction pressure is 0.1～3.0MPa, and the weight space velocity of 1-butylene is 0.1～4.0h
-1
Catalyst provided by the invention can high conversion, high selectivity and high stability be used for 1-producing propene from butylene by disproportion and amylene.
The specific embodiment
The following examples will give further instruction to the present invention, but not thereby limiting the invention.
Embodiment 1
Take by weighing Mordenit molecular sieve 75.3g (butt), SiO
2/ Al
2O
3Mol ratio is 10, adds 40.32g aluminium oxide (butt), is 15% salpeter solution moulding and with the orifice plate extruded moulding of Φ 2.0mm with weight concentration, dried 24 hours for 120 ℃, under moving air through 520 ℃ of roastings 2 hours.In concentration is 100 ℃ of exchanges in the ammonium nitrate solution of 0.8mol/L, exchanges 2 hours at every turn, repeats 2 times, and filtration washing 120 ℃ of oven dry, makes Na
2O content≤0.5wt%; 550 ℃ are burnt ammonium, make 70HM-30Al
2O
3(HM represents the modenite of Hydrogen, 70 and 30 expression weight ratios) mixed carrier.Get the 5g pulverizing and be granularity 20～40 purpose 70HM-30Al
2O
3Carrier is put into the vacuum impregnation jar, vacuumizes under 25 ℃, vacuum＞700mmHg, in 30 minutes pumpdown times, the ammonium molybdate solution 5ml of adding weight concentration 0.1104g/ml 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, 4 ℃/min of programming rate under moving air, be warmed up to 600 ℃ of roastings 2 hours, promptly making Mo content after the cooling is the A catalyst of 6wt%.
Embodiment 2
Prepare carrier 70HM-30Al according to the process of describing among the embodiment 1
2O
3, dipping, calcination steps are also with embodiment 1 subsequently, and just the weight concentration of ammonium molybdate solution becomes 0.0552g/ml, and obtaining Mo content at last is the B catalyst of 3wt%.
Embodiment 3
Prepare carrier 70HM-30Al according to the process of describing among the embodiment 1
2O
3, dipping, calcination steps are also with embodiment 1 subsequently, and just the weight concentration of ammonium molybdate solution becomes 0.3312g/ml, and obtaining Mo content at last is the C catalyst of 18wt%.
Embodiment 4
Prepare carrier 70HM-30Al according to the process of describing among the embodiment 1
2O
3, dipping, calcination steps are also with embodiment 1 subsequently, and just the weight concentration of ammonium molybdate solution becomes 0.552g/ml, and obtaining Mo content at last is the D catalyst of 30wt%.
Embodiment 5
Taking by weighing the modenite 25g (butt) among the embodiment 1, add aluminium oxide 25g (butt), is 15% salpeter solution moulding and with the orifice plate extruded moulding of Φ 2.0mm with weight concentration, dried 24 hours for 120 ℃, under moving air through 520 ℃ of roastings 2 hours.Concentration be in the ammonium nitrate solution of 0.8mol/l 100 ℃ of exchanges, exchange 2 hours at every turn, repeat 2 times, filtration washing 120 ℃ of oven dry, makes Na
2O content≤0.5wt%; 550 ℃ are burnt ammonium, make 50HM-50Al
2O
3Carrier.The dipping of molybdenum element and calcination steps are with embodiment 1, and making the Mo weight percentage is the E catalyst of 6wt%.
Embodiment 6
Take by weighing the modenite 30.3g (butt) among the embodiment 1, add aluminium oxide 4.03g (butt), with weight concentration is 15% salpeter solution moulding and with the orifice plate extruded moulding of Φ 2.0mm, 120 ℃ of oven dry 24 hours, under moving air through 520 ℃ of roastings 2 hours.Concentration be in the ammonium nitrate solution of 0.8mol/L 100 ℃ of exchanges, exchange 2 hours at every turn, repeat 2 times, filtration washing 120 ℃ of oven dry, makes Na
2O content≤0.5wt%; 550 ℃ are burnt ammonium, make 10HM-90Al
2O
3Carrier.The dipping of molybdenum element and calcination steps are with embodiment 1, and making the Mo weight percentage is the F catalyst of 6wt%.
Embodiment 7
70HM-30Al
2O
3The preparation of carrier and impregnation steps are with embodiment 1, and just the sintering temperature of catalyst is 400 ℃, and roasting time is 4 hours, and obtaining Mo content at last is the G catalyst of 6wt%.
Embodiment 8
70HM-30Al
2O
3The preparation of carrier and impregnation steps are with embodiment 1, and just the sintering temperature of catalyst is 700 ℃, and roasting time is 1 hour, and obtaining Mo content at last is the H catalyst of 6wt%.
Embodiment 9
Prepare carrier 70HM-30Al according to the process of describing among the embodiment 1
2O
3, the SiO of modenite wherein just
2/ Al
2O
3Mol ratio is 16.Dipping, calcination steps are also with embodiment 1 subsequently, and obtaining Mo content at last is the I catalyst of 6wt%.
Comparative Examples 1
Taking by weighing 10g aluminium oxide (butt), is 15% salpeter solution moulding and the orifice plate extruded moulding of using Ф 2.0mm with weight concentration, dried 24 hours, and through 520 ℃ of roastings 2 hours, made Al under moving air for 120 ℃
2O
3Carrier.Dipping subsequently, calcination steps are with embodiment 1, and obtaining Mo content is the J catalyst of 6wt%.
Embodiment 1～9 and Comparative Examples 1 reaction evaluating
The reactivity worth evaluation of catalyst is carried out on conventional fixed bed reactors, tube inner diameter 10mm, length 30cm, catalyst loading amount 3g.The reaction procatalyst is at N
2The following 500 ℃ of preliminary treatment 1h of atmosphere are then at N
2Cool to reaction temperature under the atmosphere, switch N
2For unstripped gas 1-butylene reacts.Begin sample analysis behind the disproportionated reaction 20min.Product and unstripped gas all adopt the analysis of Varian3800 gas chromatography system to form, with the ethene in PONA post (column length 50m) assay products, propylene, 1-butylene (isobutene), anti--the 2-butylene, suitable-the 2-butylene, amylene, hexene and C7
+Product, fid detector detects.Analysis result normalization obtains the molar yield of product.The 1-butylene disproportionation reactivity worth of A-I catalyst and comparative catalyst J is listed in table 1.Can find, under identical reaction condition, obtain higher propylene selectivity on the A-I catalyst.Illustrate that the load catalyst with base of molybdenum has disproportionation activity preferably on the mordenite-aluminum oxide complex carrier.
1-butylene disproportionation reactivity worth on table 1 different carriers Mo is catalyst based
Claims (4)
1. Mo/ mordenite-aluminum oxide catalyst that is used for butylene disproportionation, it is characterized in that: this catalyst is a carrier with the mordenite-aluminum oxide mixture, the active component that supports is the oxide of molybdenum; Wherein, the SiO of described modenite
2/ Al
2O
3Mol ratio is 8～20, Na
2O content≤0.5wt%; The loading of metal molybdenum is 2～30% of a catalyst weight;
Concrete preparation process is as follows:
(1) modenite and a certain proportion of aluminium oxide and water are mixed, mix the back extruded moulding, 60-120 ℃ dry 2-4 hour down, in the air atmosphere 450-550 ℃ roasting 1-4 hour;
(2) to place concentration be the ammonium salt solution of 0.3～1.0M to the product that step (1) is obtained, and stirs 1-12h in 45～100 ℃ of following air bubblings, filtration washing, and 100～120 ℃ of oven dry, 500～550 ℃ are burnt ammoniums, Na
2O content≤0.5wt% makes H-type mordenite-aluminum oxide carrier;
(3) the H-type mordenite-aluminum oxide carrier that step (2) is obtained is prepared into 16-40 purpose mixture carrier with conventional method;
(4) product that step (3) is obtained floods in containing the solution of molybdenum element, and the load capacity of metal molybdenum is 2～30%, and is dry and in 400～800 ℃ of roastings 1～4 hour in the air atmosphere then, makes the Mo/ mordenite-aluminum oxide catalyst.
2. according to the described preparation method who is used for the Mo/ mordenite-aluminum oxide catalyst of butylene disproportionation of claim 1, it is characterized in that: the mixture carrier in the described step (3), wherein modenite weight accounts for 10% of mixture carrier weight at least, and all the other are aluminium oxide.
3. according to the described preparation method who is used for the Mo/ mordenite-aluminum oxide catalyst of butylene disproportionation of claim 1, it is characterized in that: the loading of the metal molybdenum in the described step (4) is 3～12% of a catalyst weight.
4. according to the described preparation method who is used for the Mo/ mordenite-aluminum oxide catalyst of butylene disproportionation of claim 1, it is characterized in that: the sintering temperature in the described step (4) is 450～700 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100109456A CN101554591B (en) | 2008-04-08 | 2008-04-08 | Mo/mordenite-aluminum oxide catalyst for butylene disproportionation and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100109456A CN101554591B (en) | 2008-04-08 | 2008-04-08 | Mo/mordenite-aluminum oxide catalyst for butylene disproportionation and preparation method and application thereof |
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| Publication Number | Publication Date |
|---|---|
| CN101554591A CN101554591A (en) | 2009-10-14 |
| CN101554591B true CN101554591B (en) | 2011-08-31 |
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| CN2008100109456A Expired - Fee Related CN101554591B (en) | 2008-04-08 | 2008-04-08 | Mo/mordenite-aluminum oxide catalyst for butylene disproportionation and preparation method and application thereof |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108786903B (en) * | 2017-05-02 | 2020-09-11 | 中国石油化工股份有限公司 | Olefin disproportionation catalyst and preparation method thereof |
| CN109847791A (en) * | 2017-11-30 | 2019-06-07 | 中国科学院大连化学物理研究所 | A kind of catalyst, preparation method and the application in butylene disproportionation reaction |
| CN111250153B (en) * | 2018-11-30 | 2021-08-10 | 中国科学院大连化学物理研究所 | Al (aluminum)2O3Preparation method of Mo-loaded catalytic material of hierarchical pore molecular sieve and application of Mo-loaded catalytic material in preparation of propylene through disproportionation |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3798154A (en) * | 1972-03-01 | 1974-03-19 | Standard Oil Co | Reforming with a non-noble-metal-mordenite catalyst |
| SU467763A1 (en) * | 1973-07-26 | 1975-04-25 | Предприятие П/Я Р-6913 | Hydrocracking catalyst |
| CN1352230A (en) * | 2000-11-15 | 2002-06-05 | 中国石油化工股份有限公司 | Disproportionation and transalkylation process of toluene and C9 and heavier aromatic hydrocarbons |
-
2008
- 2008-04-08 CN CN2008100109456A patent/CN101554591B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3798154A (en) * | 1972-03-01 | 1974-03-19 | Standard Oil Co | Reforming with a non-noble-metal-mordenite catalyst |
| SU467763A1 (en) * | 1973-07-26 | 1975-04-25 | Предприятие П/Я Р-6913 | Hydrocracking catalyst |
| CN1352230A (en) * | 2000-11-15 | 2002-06-05 | 中国石油化工股份有限公司 | Disproportionation and transalkylation process of toluene and C9 and heavier aromatic hydrocarbons |
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