CN105327710A - Method for microwave synthesis of pillar type mesoporous activated clay olefin removal catalyst - Google Patents
Method for microwave synthesis of pillar type mesoporous activated clay olefin removal catalyst Download PDFInfo
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- CN105327710A CN105327710A CN201510880540.8A CN201510880540A CN105327710A CN 105327710 A CN105327710 A CN 105327710A CN 201510880540 A CN201510880540 A CN 201510880540A CN 105327710 A CN105327710 A CN 105327710A
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Abstract
The invention discloses a method for microwave synthesis of a pillar type mesoporous activated clay olefin removal catalyst and mainly relates to synthesis of a pillar type mesoporous activated clay catalyst which contains rich mesoporous structures and Lewis acid loci and is used for removing a trace amount of olefin in reformed aromatic oil. The preparing method mainly comprises the steps of dispersing bentonite in water to obtain preprocessed slurry, slowly adding an aqueous solution of a template agent cetyl trimethyl ammonium bromide (CTAB) at 20-40 DEG C while stirring, regulating pH to be 1-5 by means of inorganic acid, slowly adding tetraethyl orthosilicate (TEOS) and aluminium isopropoxide, conducting microwave processing of a sample for 5-30 min under the power of 300-900 w, conducting washing, filtering and drying, and conducting baking at 350-650 DEG C to remove the template agent so that the corresponding pillar type mesoporous activated clay catalyst can be obtained. The catalyst contains rich mesoporous channels and Lewis acid loci and has high olefin removal activity and long operating life. The microwave synthesis method is adopted in the preparing process, so that energy consumption during production is effectively reduced and production cycle is effectively shortened.
Description
Technical field
The invention discloses the method for the mesoporous activated carclazyte olefinic hydrocarbon expelling catalyzer of the pillared type of a kind of Microwave synthesize, relate generally to synthesis containing enrich mesopore orbit with the mesoporous activated clay catalyst of pillared type of Lewis-acid sites, for removing the alkene of trace in reforming aromatic oil.
Background technology
Aromatic hydrocarbons is the primary raw material producing polyamide, Merlon, polyacetals, polyester, the large high-tech environment-friendly novel general engineering plastic of polyphenylene oxide five.Catalytic reforming is one of Main Means producing aromatic hydrocarbons, and 2012, aromatic hydrocarbons (benzene,toluene,xylene) output that China's catalytic reforming is produced was more than 2,000,000 tons.But all contain a small amount of olefin impurity in the aromatic hydrocarbon product that reforming process is produced, these olefin impurity character are very active, being easy to be polymerized formation colloid affects the quality of aromatic hydrocarbon product and further processing and utilization thereof.In order to obtain qualified industrial chemicals and ensure carrying out smoothly of subsequent technique, trace amounts of olefin hydrocarbon in arene must be removed, to improve the economic benefit of aromatic hydrocarbons processing technology.
Clay-filtered is deolefination technique the most ripe at present, and the clay catalyst wherein adopted is the atlapulgite obtained through acid activation by bentonite.China's bentonite reserves rank first in the world, and atlapulgite is cheap, make clay-filtered operating cost lower; The advantage of these uniquenesses determines the clay-filtered method becoming the topmost reformed arene oil-off olefin of current domestic petroleum chemical enterprise.A small amount of acid more weak L(lewis is there is in atlapulgite) sour site and a large amount of acid stronger B(Bronsted) sour site, they catalyzing aromatic hydrocarbon and alkene generation alkylated reaction can obtain alkylbenzene, thus reach the object removing alkene.The strong acidic site of atlapulgite olefinic hydrocarbon expelling catalyzer easily brings the side reactions such as carbon distribution coking while efficient removal alkene.And the pore passage structure of atlapulgite mostly is micropore, the less (200cm of surface area
2about/g).Catalyst is once carbon distribution coking will cover acid activity position, and the micropore canals of blocking carclazyte, causes catalysqt deactivation, so the operation lifetime of industrial activated bauxite catalyst is shorter.The heat endurance of atlapulgite is not enough in addition, and 350 DEG C of roastings namely can causing hole structure collapses, and catalyst carbon deposition coking cannot be regenerated by high-temperature roasting.The regeneration times of catalyst is limited.
Patent CN102728394A and CN103861644A describes SO respectively
4 2-the clay olefinic hydrocarbon expelling catalyzer of load and the clay olefinic hydrocarbon expelling catalyzer of heteropoly acid modification.Though this type of acidity of catalyst site increases to some extent, aperture is still less, and specific area is also very low.Though therefore the initial activity of catalyst is higher, its operation lifetime is still partially short.
Patent CN102658196A describes a kind of modified argil method for preparing catalyst, just simple by atlapulgite, lewis acid catalyst, molecular sieve, rare earth chloride mixing.There is dispersion uneven, and not activation, active component such as can not to play one's part to the full at the problem.
Extend the operation lifetime of atlapulgite, increase the emphasis that its regeneration times is the application study of current activated bauxite catalyst technology.The current study on the modification to atlapulgite mainly concentrates on and improves acid strength, increase Surface acidity, although its alkylation activity can be improved, but also improve the activity of the side reactions such as aromatic hydrocarbons polymerization simultaneously, its deolefination operation lifetime can not be solved short, unrenewable problem.
Summary of the invention
For the weak point of existing modification technology, the object of the invention is by pillared containing aluminium mesopore molecular sieve between bentonite bed, more how weak L acid site will be introduced in aluminium site, and the mesopore molecular sieve that interlayer is pillared simultaneously improves the specific area of activated bauxite catalyst.Increase the generation that weak L acid site can suppress the side reactions such as carbon distribution coking while improving catalyst initial activity; And mesopore orbit and bigger serface can avoid duct to block on the one hand, improve the mass-and heat-transfer efficiency of reaction, the heat endurance of atlapulgite can be improved on the other hand, catalyst regeneration number of times is increased.
The present invention is achieved through the following technical solutions above-mentioned purpose:
1. a method for the mesoporous activated carclazyte olefinic hydrocarbon expelling catalyzer of the pillared type of Microwave synthesize, comprises the steps:
(1) bentonite original soil ball milling is sieved, obtain the pretreated bentonite of 100-200 order, and be scattered in water according to the mass ratio of 2-5wt%, obtain pretreated bentonite slurry;
(2) 2-5g softex kw (CTAB) solution will be got in water, slowly drop in the pretreated bentonite slurry of step (1) under 40-60 DEG C of stirring condition, pH=1-5 is regulated and controled with inorganic acid (hydrobromic acid or hydrochloric acid), stir 15min, slowly add silicon source tetraethyl orthosilicate (TEOS) and aluminium source aluminium isopropoxide again, control silica alumina ratio is 30-70:1, stirs 1-3h, obtains the presoma of the mesoporous activated carclazyte olefinic hydrocarbon expelling catalyzer of pillared type;
(3) catalyst precursor that obtains of microwave treatment step (2), controlling power in Microwave synthesize process is 300-900W, time is 5-30min, wash again, filter, dry reacted sample, finally obtain the mesoporous activated carclazyte olefinic hydrocarbon expelling catalyzer of corresponding pillared type at 450-650 DEG C of roasting removing template.
2. according to above scheme, the temperature range of the mesoporous activated clay catalyst precursor synthesis of the pillared type described in step (2) is 20-40 DEG C, and regulating and controlling its pH with inorganic acid (hydrobromic acid or hydrochloric acid) is 1-5, and generated time is 1-3h.
3., according to above scheme, the template described in step (2) is softex kw (CTAB), and its inventory is 2-5g.
4., according to above scheme, post silicon source described in step (3) and aluminium source molar ratio are 30-70:1.
5., according to above scheme, controlling power in Microwave synthesize process described in step (3) is 300-900W, and the microwave time is 5-30min.
6., according to above scheme, the sintering temperature except catalysts template agent described in step (3) is: 450-650 DEG C.
Compared with prior art, the invention has the beneficial effects as follows:
1. the present invention is pillared containing aluminium mesopore molecular sieve between bentonite soil layer, and the aluminium in framework of molecular sieve will provide a large amount of acid more weak L acid site.Acid more weak L acid site can not only remove alkene in reforming aromatic oil by efficient catalytic, and can not bring the side reactions such as carbon distribution coking, and this reduces the possibility of the inactivation of catalyst from source;
Have a large amount of mesopore orbit to be uniformly distributed between bentonite bed in 2 mesoporous bentonite catalysts of pillared type involved in the present invention, compare with traditional activated clay catalyst, the mesoporous bentonite catalyst borehole enlargement of pillared type is to 2-5nm, and specific surface is increased to 500cm
2/ g.Specific area increase is beneficial to reactant and acid activity position haptoreaction, and borehole enlargement is beneficial to reaction mass transfer heat transfer, can effectively avoid carbon distribution coking, thus the operation lifetime of extending catalyst;
3. the mesoporous bentonite catalyst of pillared type involved in the present invention still can keep original pore passage structure through 600 DEG C of roastings, illustrates that catalyst has good heat endurance, and this will effectively improve the regeneration times of catalyst, avoids catalyst roasting inactivation;
4. have employed microwave synthesis method in preparation technology, effectively reduce energy consumption and production cycle.
specific embodiment
embodiment 1:
A method for the mesoporous activated carclazyte olefinic hydrocarbon expelling catalyzer of the pillared type of Microwave synthesize, comprises the steps:
(1) bentonite original soil ball milling is sieved, obtain the pretreated bentonite of 200 order, and be scattered in water according to the mass ratio of 5wt%, obtain pretreated bentonite slurry;
(2) 2g softex kw (CTAB) solution will be got in water, slowly drop in the pretreated bentonite slurry of step (1) under 40 DEG C of stirring conditions, pH=2 is regulated and controled with hydrobromic acid, stir 15min, slowly add silicon source tetraethyl orthosilicate (TEOS) and aluminium source aluminium isopropoxide again, control silica alumina ratio is 30:1, stirs 2h, obtains the presoma of the mesoporous activated carclazyte olefinic hydrocarbon expelling catalyzer of pillared type;
(3) catalyst precursor that obtains of microwave treatment step (2), controlling power in Microwave synthesize process is 400w, time is 15min, wash again, filter, dry reacted sample, finally obtain the mesoporous activated carclazyte olefinic hydrocarbon expelling catalyzer of corresponding pillared type at 500 DEG C of roasting removing templates.
embodiment 2
A method for the mesoporous activated carclazyte olefinic hydrocarbon expelling catalyzer of the pillared type of Microwave synthesize, comprises the steps:
(1) bentonite original soil ball milling is sieved, obtain the pretreated bentonite of 200 order, and be scattered in water according to the mass ratio of 5wt%, obtain pretreated bentonite slurry;
(2) 3.5g softex kw (CTAB) solution will be got in water, slowly drop in the pretreated bentonite slurry of step (1) under 50 DEG C of stirring conditions, pH=1 is regulated and controled with hydrochloric acid, stir 15min, slowly add silicon source tetraethyl orthosilicate (TEOS) and aluminium source aluminium isopropoxide again, control silica alumina ratio is 40:1, stirs 2h, obtains the presoma of the mesoporous activated carclazyte olefinic hydrocarbon expelling catalyzer of pillared type;
(3) catalyst precursor that obtains of microwave treatment step (2), controlling power in Microwave synthesize process is 600W, time is 10min, wash again, filter, dry reacted sample, finally obtain the mesoporous activated carclazyte olefinic hydrocarbon expelling catalyzer of corresponding pillared type at 500 DEG C of roasting removing templates.
embodiment 3
A method for the mesoporous activated carclazyte olefinic hydrocarbon expelling catalyzer of the pillared type of Microwave synthesize, comprises the steps:
(1) bentonite original soil ball milling is sieved, obtain the pretreated bentonite of 200 order, and be scattered in water according to the mass ratio of 5wt%, obtain pretreated bentonite slurry;
(2) 5g softex kw (CTAB) solution will be got in water, slowly drop in the pretreated bentonite slurry of step (1) under 20-60 DEG C of stirring condition, pH=3 is regulated and controled with hydrochloric acid, stir 15min, slowly add silicon source tetraethyl orthosilicate (TEOS) and aluminium source aluminium isopropoxide again, control silica alumina ratio is 50:1, stirs 2h, obtains the presoma of the mesoporous activated carclazyte olefinic hydrocarbon expelling catalyzer of pillared type;
(3) catalyst precursor that obtains of microwave treatment step (2), controlling power in Microwave synthesize process is 900W, time is 5min, wash again, filter, dry reacted sample, finally obtain the mesoporous activated carclazyte olefinic hydrocarbon expelling catalyzer of corresponding pillared type at 500 DEG C of roasting removing templates.
Each raw material cited by the present invention can realize the present invention, and bound value and its interval value of each raw material can realize the present invention, do not enumerate embodiment at this.
The catalytic performance of the mesoporous activated carclazyte olefinic hydrocarbon expelling catalyzer of pillared type prepared by above different process will be tested by the following method:
(1) reaction is carried out in fixed bed reactors, and reaction temperature is 160 DEG C, and once, reaction pressure is 0.9Mpa in per sampling half an hour;
(2) by the bromine number of aromatic naphtha after iodimetric titration measured reaction, with the activity of evaluate catalysts.Using 60% of olefin removal rate as the standard judging catalysqt deactivation.Regenerate 4 hours 400 DEG C of air oxidations after inactivation, terminate rear nitrogen and purge, remove the polymer, poisonous substance etc. that catalyst hide active component, then reuse, accumulation measures the operation lifetime of catalyst;
(3) the olefin removal rate of formulae discovery aromatic naphtha is below utilized:
Olefin removal rate=(after feedstock oil bromine number-reaction aromatic naphtha bromine number)/feedstock oil bromine number × 100%;
(4) specific area of catalyst is by N
2adsorption desorption instrument is measured.
accompanying drawing illustrates:
Fig. 1 is the specific area of example prepared catalyst, deolefination efficiency and operation lifetime figure.
Claims (6)
1. a method for the mesoporous activated carclazyte olefinic hydrocarbon expelling catalyzer of the pillared type of Microwave synthesize, is characterized in that comprising the steps:
(1) bentonite original soil ball milling is sieved, obtain the pretreated bentonite of 100-200 order, and be scattered in water according to the mass ratio of 2-5wt%, obtain pretreated bentonite slurry;
(2) 2-5g softex kw (CTAB) solution will be got in water, slowly drop in the pretreated bentonite slurry of step (1) under 20-60 DEG C of stirring condition, pH=1-5 is regulated and controled with inorganic acid (hydrobromic acid or hydrochloric acid), stir 15min, slowly add silicon source tetraethyl orthosilicate (TEOS) and aluminium source aluminium isopropoxide again, control silica alumina ratio is 30-70:1, stirs 1-3h, obtains the presoma of the mesoporous activated carclazyte olefinic hydrocarbon expelling catalyzer of pillared type;
(3) catalyst precursor that obtains of microwave treatment step (2), controlling power in Microwave synthesize process is 300-900W, time is 5-30min, wash again, filter, dry reacted sample, finally obtain the mesoporous activated carclazyte olefinic hydrocarbon expelling catalyzer of corresponding pillared type at 450-650 DEG C of roasting removing template.
2. the method for the mesoporous activated carclazyte olefinic hydrocarbon expelling catalyzer of the pillared type of a kind of Microwave synthesize according to claim 1, the temperature range that it is characterized in that the mesoporous activated clay catalyst precursor synthesis of pillared type described in step (2) is 40-60 DEG C, regulating and controlling its pH with inorganic acid (hydrobromic acid or hydrochloric acid) is 1-5, and the time is 1-3h.
3. the method for the mesoporous activated carclazyte olefinic hydrocarbon expelling catalyzer of the pillared type of a kind of Microwave synthesize according to claim 1, it is characterized in that the template described in step (2) is softex kw (CTAB), its inventory is 2-5g.
4. the method for the mesoporous activated carclazyte olefinic hydrocarbon expelling catalyzer of the pillared type of a kind of Microwave synthesize according to claim 1, is characterized in that post silicon source described in step (3) and aluminium source molar ratio are 30-70:1.
5. the method for the mesoporous activated carclazyte olefinic hydrocarbon expelling catalyzer of the pillared type of a kind of Microwave synthesize according to claim 1, it is characterized in that controlling power in Microwave synthesize process described in step (3) is 300-900W, the microwave time is 5-30min.
6. the method for the mesoporous activated carclazyte olefinic hydrocarbon expelling catalyzer of the pillared type of a kind of Microwave synthesize according to claim 1, is characterized in that the sintering temperature except catalysts template agent described in step (3) is: 450-650 DEG C.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106311200A (en) * | 2016-07-27 | 2017-01-11 | 湖南大学 | AlSi composite pillared clay catalyst used for bisphenol F synthesis |
| CN107876070A (en) * | 2017-10-20 | 2018-04-06 | 淮阴工学院 | The acid pillared atlapulgite olefinic hydrocarbon expelling catalyzer of Mesoporous zirconium phosphate |
| CN114471704A (en) * | 2020-10-23 | 2022-05-13 | 华东理工大学 | Preparation of montmorillonite nanosheet loaded trifluoromethanesulfonic acid material and application of montmorillonite nanosheet loaded trifluoromethanesulfonic acid material in removal of trace olefins in aromatic hydrocarbons |
| CN115254088A (en) * | 2022-08-30 | 2022-11-01 | 华东理工大学 | Catalyst for producing alkyl diphenylamine and preparation method and application thereof |
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| CN103805273A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Method for olefin removal of reformate |
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| CN101239323A (en) * | 2007-02-09 | 2008-08-13 | 中国石油化工股份有限公司 | Method for preparing bedded clay/molecular sieve composite material |
| CN102407117A (en) * | 2011-11-14 | 2012-04-11 | 江苏星晨环保集团有限公司 | Photocatalysis water-treating material as well as preparation method and application thereof |
| CN103805273A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Method for olefin removal of reformate |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106311200A (en) * | 2016-07-27 | 2017-01-11 | 湖南大学 | AlSi composite pillared clay catalyst used for bisphenol F synthesis |
| CN107876070A (en) * | 2017-10-20 | 2018-04-06 | 淮阴工学院 | The acid pillared atlapulgite olefinic hydrocarbon expelling catalyzer of Mesoporous zirconium phosphate |
| CN107876070B (en) * | 2017-10-20 | 2020-04-24 | 淮阴工学院 | Acid mesoporous zirconium phosphate column-supported active clay olefin-removing catalyst |
| CN114471704A (en) * | 2020-10-23 | 2022-05-13 | 华东理工大学 | Preparation of montmorillonite nanosheet loaded trifluoromethanesulfonic acid material and application of montmorillonite nanosheet loaded trifluoromethanesulfonic acid material in removal of trace olefins in aromatic hydrocarbons |
| CN115254088A (en) * | 2022-08-30 | 2022-11-01 | 华东理工大学 | Catalyst for producing alkyl diphenylamine and preparation method and application thereof |
| CN115254088B (en) * | 2022-08-30 | 2023-11-21 | 华东理工大学 | Catalyst for producing alkyl diphenylamine and preparation method and application thereof |
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