CN1157258C - Rapid deaminatio activating method of beta-zeolite containing organic ammonium - Google Patents
Rapid deaminatio activating method of beta-zeolite containing organic ammonium Download PDFInfo
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- CN1157258C CN1157258C CNB991135776A CN99113577A CN1157258C CN 1157258 C CN1157258 C CN 1157258C CN B991135776 A CNB991135776 A CN B991135776A CN 99113577 A CN99113577 A CN 99113577A CN 1157258 C CN1157258 C CN 1157258C
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Abstract
The present invention relates to a rapid deamination and activation method of beta zeolite containing organic ammonium, which well mainly solves the problems of long time of removing a template agent in a molecular sieve by high-temperature calcination and complex operation of a deamination process existing in the present document by the method of high temperature rising speed in air flows or/and nitrogen. The method can be used for industrial production.
Description
The present invention relates to contain the rapid deaminatio activating method of organic ammonium β zeolite.
The β zeolite is a kind of crystalline silico-alumino zeolite of three-dimensional twelve-ring macropore, through suitably making catalyst with a certain amount of binding agent mixing, extrusion, roasting after the modification.The catalyst that elements such as VIII family, VA, group vib in β zeolite and various thulium and the periodic table is mixed or flood various oil refineries such as to make suitable alkane dewaxing, isomerization, catalytic pyrolysis, toluene disproportionation or benzene olefin alkylation and petrochemical industry.
The synthetic of β zeolite synthesized as numerous molecular sieves, and the general reaction mixture of being made up of aluminium source, silicon source, sodium source and organic formwork agent carries out the hydrothermal crystallizing prepared in reaction and forms.The β zeolite that contains organic ammonium ion does not have catalytic activity as other zeolite, and specific area is less, and adsorption capacity is low, and becomes amorphous material and lose its exclusive pore passage structure under higher serviceability temperature.Therefore be necessary to take off the amine activation processing to containing organic ammonium β zeolite.Owing to be subjected to the restriction of duct diffusion, need to use higher sintering temperature and sufficiently long time of contact, so that with oxidation operation.Like this, may cause β zeolitic frameworks and duct to be damaged, influence the stability and the absorption property of β zeolite.From the document analysis of having reported, synthetic sodium type β zeolite all be basically directly roasting at high temperature or through the ammonium exchange or/and through after the steam treatment, roasting at high temperature again reaches the template agent of removing in the molecular sieve pore passage, the purpose that improves β zeolite specific area.All adopt 500～600 ℃ of following roastings tens hours as document EP 95304, EP488867, EP94827 and US4554065, reach the template agent purpose that removes in the molecular sieve pore passage.Document CN1105646A adopts three sections constant temperature calcinings to handle.First section low temperature dewatering prevents that when taking off amine, skeleton is deep sealumination modified.They are under 150～250 ℃ of temperature conditions, and residual moisture is sloughed in roasting 2.0～4.0 hours; Warm amine decomposes in second section, and control organic amine decomposition rate makes skeleton structure exempt from destruction, keeps the duct unimpeded.Its under 250～450 ℃ of temperature conditions, roasting 4.0～6.0 hours; The 3rd section pyrolytic.Roasting at high temperature makes organic ammonium decompose the free charcoal that produces and removes, and material is pure white.They are under 450～650 ℃ of temperature conditions, and free charcoal is decomposed in roasting 5.0～15.0 hours, and the β zeolite carbon content after the roasting is less than 0.2% (weight).
US4789656 has reported that a kind of β zeolite of high stability repeatedly takes off the amine method, and its synthetic β zeolite takes off the amine process and comprises following step: 1. in the presence of normal pressure, nitrogen or helium, and 538 ℃ of high-temperature roastings 2 hours, the organic matter in the decomposition β zeolite; 2. incite somebody to action β zeolite 1., under air and normal pressure, carbide residual in the β zeolite was removed in 538 ℃ of roastings in 2 hours.
US5256392 has reported that a kind of ion-exchange high temperature takes off the method for amine.Synthetic β zeolite carries out part NH earlier
4 +Ion-exchange substitutes the Na in the part β zeolite
+Be no less than 1 hour swap time, then at 400～700 ℃ of roasting temperature certain hours, to remove the template agent in the β zeolite, make its specific area reach 2 times of new synthetic β zeolite specific area, carry out the ion-exchange second time afterwards again, make the Na content of β zeolite be lower than 0.04% (weight).Make catalyst through β zeolite after the above-mentioned processing and binding agent mixing extrusion at last.
What US4916097 had reported the protection of a kind of favorable environment contains the organic formwork agent deaminatio activating method.Contain organic ammonium zeolite (as the β zeolite), in the presence of 260～593 ℃ of water vapours, decomposing organic matter 2～24 hours, and then roasting 2～10 hours under 398～593 ℃ of air are at last with ethene in the product and C
4Product such as hydrocarbon and hydrogen-containing compound is by washing spray, and flush away hydrogen-containing compound, lighter hydrocarbons tail gas are converted into CO containing in the presence of Cu, Ni, the W equimolecular sieve catalyst
2
In sum, be not difficult to find that the β zeolite that these documents relate to takes off the problem that there is the following aspects in the amine method: 1. roasting time is generally longer, reach tens hours even longer; 2. under short roasting time situation, often comprise the activation process of more complicated, as steam treatment, give after roasting, the part ion exchange roasting again and ion-exchange etc. again; In addition, all do not mention the heating rate problem in these documents.
The objective of the invention is to exist roasting time long in order to overcome in the above-mentioned document, the shortcoming of complicated operating process provides a kind of new rapid deaminatio activating method that contains organic ammonium β zeolite.This method can reach quickly and effectively and remove template agent in the molecular sieve pore passage, improves β zeolite specific area.
The objective of the invention is to realize: a kind of rapid deaminatio activating method that contains organic ammonium ion β zeolite by following technical scheme, at first with aluminium source, sodium source, tetraethylammonium cation, silica gel or/and Ludox and water are raw material, the feed molar of reaction system is formed and to be counted with oxide: aNa
2ObA1
2O
3C (TEA)
2OdSiO
2EH
2O, d/b=10～100 wherein, a/d=0.04～0.25, c/d=0.01～0.06, e/d=2～6, TEA is a tetraethylammonium cation, reaction raw materials crystallization 40～80 hours under 130～170 ℃ of conditions, synthetic Na β zeolite, under 60～100 ℃ of conditions, carry out ion-exchange with ammonium salt solution again and become ammonium type β zeolite, after drying, be air or/and nitrogen at activation phenomenon, flow is 40～100 ml/min, heating rate is under 15～60 ℃ of/minute conditions, be warming up to 500～650 ℃, constant temperature calcining is 0.5～6 hour under this temperature, obtains H β zeolite.
In the technique scheme, the preferable range of heating rate is 20～40 ℃/minute; The activation phenomenon preferred version is an air; Heating rate mode preferred version is that average rate heats up or temperature programming.
Among the present invention, owing to adopt high heating rate, make in the air oxygen content less relatively, make tetraethyl ammonium be difficult to abundant oxidation, thereby cause the Hofmann degradation reaction to account for leading factor; Flow down at nitrogen, taking off the amine decomposition is exactly in fact that three grades of Hofmann degradation reactions have taken place, and has created condition for shortening roasting time greatly; Owing to adopt high heating rate, shortened the time that rises to sintering temperature greatly in addition, general needs nearly 0.5 hour, so just makes the whole amine process time that takes off shorten greatly, is no more than 7.0 hours at most.Whole heating rate can adopt average rate, also can adopt not average rate, but is good with average rate.Because roasting at high temperature carries out, therefore, can save the energy of high-temperature roasting greatly, simultaneously, take off through the present invention that carbonaceous residue has reached and taken off the clean purpose of amine less than 0.1% (weight) in the H β zeolite that the amine method obtains, obtained effect preferably.
Under air draught, from the DSC spectrum that contains organic ammonium β zeolite, learn, the β zeolite that contains organic ammonium under high heating rate (as 20 ℃/minute, average rate heats up), there has not been endothermic peak later at 500 ℃, shown that the template agent removes, hanged down under the heating rate (as 3 ℃/minute, average rate heats up), still there is exothermic peak later at 500 ℃.
The present invention is further elaborated below by embodiment.
[embodiment 1]
By the reaction mixture that aluminium source, sodium source, tetraethyl ammonium hydroxide are formed, satisfy following proportioning (mol ratio):
Na
2O/SiO
2＝0.04～0.25，SiO
2/Al
2O
3＝10～100，H
2O/SiO
2＝2～6，(TEA)
2O/SiO
2＝0.01～0.06。By weight, get 4.95 parts of sodium aluminates, 0.25 part in NaOH after mixing, joins in the solution of 45.3 parts of tetraethyl ammonium hydroxides (2.0 mol concentration).Stir after the dissolving, join in 49.5 parts of solid silicones, stir, change in the crystallizing kettle, 150 ℃ of crystallization 60 hours are isolated solid product, washing, 120 ℃ of dryings 2 hours Na β zeolite finished product.
The sodium type β zeolite (butt) of getting above-mentioned preparation adds the salpeter solution of 10% (weight), liquid/(Gu w/w)=4: 1, exchange is 4 hours under 95 ℃ of stirrings, reduce temperature to 30～40 ℃, centrifugal filtration, filter cake carries out second, third, exchanges for the 4th time, and sodium content meets the requirements in filter cake.
Get above-mentioned NH through the ammonium exchange
4The β zeolite, after drying, earlier in air mass flow 40 ml/min, heating rate is under 20 ℃ of/minute conditions, is warming up to 550 ℃; Constant temperature calcining 5 hours under this temperature then, H β zeolite.The specific area of measuring H β zeolite is 636 meters
2/ gram, the carbon residue is 0.05% (weight).
[embodiment 2]
Press each Step By Condition of embodiment 1, just changing air mass flow is 100 ml/min, and heating rate is 60 ℃/minute, is warming up to 650 ℃; Constant temperature 3 hours under this temperature then, H β zeolite.The specific area of measuring H β zeolite is 629 meters
2/ gram, the carbon residue is 0.09% (weight).
[embodiment 3]
Press each Step By Condition of embodiment 1, just changing heating rate is 40 ℃/minute, is warming up to 550 ℃; Constant temperature calcining 4 hours under this temperature then, H β zeolite.The specific area of measuring H β zeolite is 634 meters
2/ gram, the carbon residue is 0.06% (weight).
[comparative example 1]
Press each Step By Condition of embodiment 1, just changing heating rate is 3 ℃/minute, is warming up to 550 ℃; Constant temperature calcining 15 hours under this temperature then, H β zeolite.The specific area of measuring H β zeolite is 635.7 meters
2/ gram, the carbon residue is 0.16% (weight).Learn from the DSC collection of illustrative plates, still have exothermic peak after 500 ℃, illustrate in the time of 500 ℃, organic formwork agent does not take off to the greatest extent as yet.
[comparative example 2]
Press each Step By Condition of embodiment 1, make NH earlier
4The β zeolite.Then by taking off the amine method among the CN1105646A with dried NH
4The β zeolite is put into muffle furnace and is rapidly heated to 250 ℃, and constant temperature 2 hours continues to be rapidly heated to 400 ℃ then, and constant temperature is 4 hours again, rises to 550 ℃ at last, constant temperature 10 hours, and material all turns white.The specific area of measuring H β zeolite is 636.0 meters
2/ gram, the carbon residue is 0.11% (weight).
Can find out that from the foregoing description and comparative example the amine method of taking off fast of the present invention has reached equally the template agent is removed clean purpose from molecular sieve.
Claims (4)
1, a kind of rapid deaminatio activating method that contains organic ammonium ion β zeolite, at first with aluminium source, sodium source, tetraethylammonium cation, silica gel or/and Ludox and water are raw material, the feed molar of reaction system is formed and to be counted with oxide: aNa
2ObAl
2O
3C (TEA)
2OdSiO
2EH
2O, d/b=10～100 wherein, a/d=0.04～0.25, c/d=0.01～0.06, e/d=2～6, TEA is a tetraethylammonium cation, reaction raw materials crystallization 40～80 hours under 130～170 ℃ of conditions, synthetic Na β zeolite carries out ion-exchange with ammonium salt solution again and becomes ammonium type β zeolite under 60～100 ℃ of conditions, after drying, at activation phenomenon is air or/and nitrogen, and flow is 40～100 ml/min, and heating rate is to be warming up to 500～650 ℃ under 15～60 ℃ of/minute conditions, constant temperature calcining is 0.5～6 hour under this temperature, gets H β zeolite.
2, according to the described β zeolite of claim 1 take off the amine method fast, it is characterized in that heating rate is 20～40 ℃/minute.
3, according to the described β zeolite of claim 1 take off the amine method fast, it is characterized in that activation phenomenon is an air.
4, according to the described β zeolite of claim 1 take off the amine method fast, it is characterized in that the heating rate mode is that average rate heats up or temperature programming.
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|---|---|---|---|
| CNB991135776A CN1157258C (en) | 1999-03-30 | 1999-03-30 | Rapid deaminatio activating method of beta-zeolite containing organic ammonium |
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|---|---|---|---|
| CNB991135776A CN1157258C (en) | 1999-03-30 | 1999-03-30 | Rapid deaminatio activating method of beta-zeolite containing organic ammonium |
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| CN1268403A CN1268403A (en) | 2000-10-04 |
| CN1157258C true CN1157258C (en) | 2004-07-14 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10112186B2 (en) | 2013-11-26 | 2018-10-30 | China Petroleum & Chemical Corporation | Beta molecular sieve, preparation method therefor and hydrogenation catalyst containing same |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101643216B (en) * | 2008-08-07 | 2011-04-13 | 郑州富龙新材料科技有限公司 | Method for reducing falling powder degree of molecular sieve |
| CN102616800B (en) * | 2011-01-27 | 2014-04-30 | 中国石油化工股份有限公司 | Method for removing organic amine template in molecular sieve |
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1999
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10112186B2 (en) | 2013-11-26 | 2018-10-30 | China Petroleum & Chemical Corporation | Beta molecular sieve, preparation method therefor and hydrogenation catalyst containing same |
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