CN1111094C - Process for preparing beta molecular sieve membrane catalyst supported by regular ripple filler for etherification - Google Patents
Process for preparing beta molecular sieve membrane catalyst supported by regular ripple filler for etherification Download PDFInfo
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- CN1111094C CN1111094C CN 01110335 CN01110335A CN1111094C CN 1111094 C CN1111094 C CN 1111094C CN 01110335 CN01110335 CN 01110335 CN 01110335 A CN01110335 A CN 01110335A CN 1111094 C CN1111094 C CN 1111094C
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- molecular sieve
- beta molecular
- sieve membrane
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Abstract
The present invention relates to a process for preparing a beta molecular sieve membrane catalyst supported by regular ripple filler for etherification, which uses ceramic filler as supporting base material. Reaction liquid is composed of a mould plate agent, a silica resource, an aluminum source and a sodium source. A beta molecular sieve membrane is made on the surface of filler by making hydrothermal crystallization reaction in a reactor. A beta molecular sieve membrane catalyst supported by the regular ripple filler is obtained by modifying the beta molecular sieve membrane. The present invention is characterized in that tetraethylammonium bromide is used as the mould plate agent; program is used for transforming reaction temperature, a static flowing state of the reaction liquid and a gravitational field direction of the base material. The method of the present invention has the advantage of low membrane making expenses, and the beta molecular sieve membrane catalyst has the characteristics of high activity, good selection, uniform liquid distribution, little resistance and high mass transfer efficiency.
Description
Technical field
The present invention relates to a kind of etherificate beta molecular sieve membrane catalyst supported technology of preparing of regular corrugation filler, belong to the preparation and the modification technique of carrier supported molecular-sieve film.
Background technology
In the industrial production of synthetic fuel ether, adopt the macropore strong acid cation exchange resin catalysts at present more.Though resin catalyst is active high, its poor heat stability is higher than under 85 ℃ of environment in temperature, and the load sulfonic acid group runs off serious and causes catalysqt deactivation, etching apparatus and polluted product.
Compare with resin catalyst, molecular sieve catalyst then has Heat stability is good, reaction selectivity height, is not subjected to system acidity to influence, be easy to good characteristics such as activating and regenerating.But granular molecular sieve catalyst still has problems: loading and unloading difficulty in the use, easily broken, the volume utilization is lower, the lack of homogeneity of cloth liquid and influence mass-transfer efficiency.
Based on the above-mentioned weak point of particulate molecular sieve catalyst, people's carrier supported molecular-sieve film catalytic agent that begins one's study the eighties.The preparation patent report of at present relevant molecular sieve film catalyst is more, but does not relate to beta molecular sieve membrane catalyst supported preparation.Periodical literature (Chem.Eng.Sci.1999; 54:1413) and periodical literature (Microp.Mesop.Materials1999; the beta molecular sieve membrane catalyst supported preparation of report all is to adopt expensive tetraethyl ammonium hydroxide (TEAOH) to be the template agent 27:95), and prop carrier is the pottery or the stainless steel of granule or tablet sheet.In addition, do not see the report of using hot acid steam decorating molecule sieve membrane as yet.
Summary of the invention
The object of the present invention is to provide a kind of etherificate beta molecular sieve membrane catalyst supported preparation method of regular corrugation filler.This procedure is simple, and system film cost is low, and the molecular sieve rete is even, and its catalytic activity and selectivity height also are easy to regeneration.
For achieving the above object, the present invention is realized by following scheme.Corrugated plating or the whole filling block of ripple network planning with pottery are support base material, after base material being carried out pickling, washing and dry the processing, put it into by template agent, silica gel (SiO
2) and NaAlO
2In the preparation liquid of forming, carry out the hydrothermal crystallizing reaction then, through after washing, drying, roasting, ion-exchange and the hot acid steam treatment, it is beta molecular sieve membrane catalyst supported with regular corrugation filler to obtain etherificate, it is characterized in that again: tetraethylammonium bromide (TEABr) is adopted in the template agent; The mol ratio of system film reaction liquid consists of: TEA
+: SiO
2=0.15～0.5, Na
2O: SiO
2=0.15～0.6, H
2O: SiO
2=8～20, SiO
2: Al
2O
3=20～100; Hydrothermal crystallizing reaction is to finish under the condition of stationary stream state, program transformation base material gravitational field at program transformation reaction temperature, program transformation reactant liquor, the program transformation reaction temperature, be to rise to 140 ℃～150 ℃ and keep constant temperature 5～60h with 0.5 ℃/min～1 ℃/min by 60 ℃～80 ℃, be warming up to 170 ℃～180 ℃ and keep constant temperature 5～60h by 140 ℃～150 ℃ with 0.5 ℃/min～1 ℃/min again, be cooled to 20～30 ℃ then; The stationary stream state of program transformation reactant liquor is in hydrothermal crystallization process, and leaving standstill and flowing of reactant liquor hockets, and at first makes reactant liquor leave standstill 1～10h, and the Modelling of Flow with Recirculation reactant liquor reaches 1～10min then, repeats said process successively and finishes until reaction; Program transformation base material gravitational field is to rotate continuously the direction to 90 ° of base material～180 ° in the time at 0.5～5h, and repeats this process to reaction and finish; Heat treatment is carried out in two steps, and at first the heating rate with 1 ℃/min rises to 550 ℃, constant temperature 3～4h in Muffle furnace, in Muffle furnace, reduce to room temperature naturally, adopting the pH value then is that 1～6 acid vapor carries out dynamic hot acid and handles, and treatment temperature is 300 ℃～450 ℃, and the processing time is 3～4h.
The invention has the advantages that preparation process is simple, cost is low.Prepared catalyst is used for the not only active height of reaction of synthetic fuel ether, and selectivity is good, and antipollution is easy to regeneration, be convenient to loading and unloading, and when as catalytic rectification packing, it is big to have a vapour-liquid mass surface area, resistance is little, and the uniform characteristics of cloth liquid can improve the mass-transfer efficiency of reaction zone greatly.
Below the present invention is described in detail.
Method provided by the invention is because to adopt the lower tetraethylammonium bromide of price be template agent and do not use expensive tetraethyl ammonium hydroxide, thereby greatly reduces cost, helps suitability for industrialized production.It is beta molecular sieve membrane catalyst supported to prepare the large scale structured packing according to method provided by the invention, the silicon source can be 60～300 purpose solid silicones with granularity, needn't use Ludox, therefore can reduce the content of water in the reactant liquor, thereby saved template agent consumption, further reduce production cost, and shortened crystallization time.
The mol ratio composition of determining raw material is one of key technology of the present invention.The preparation liquid of forming by above-mentioned mol ratio can guarantee that the molecular screen membrane of making has good selectivity,, high activity, good pollution resistance and stronger film and support base material adhesion.What of silicon, aluminium and sodium content can influence the structure of silica alumina ratio and fenestra in the synthetic liquid, and then have influence on catalytic activity and the selectivity of molecular screen membrane to etherification reaction; What of template agent not only can influence the quality of molecular sieve crystallization, but also influence the firm performance of support membrane.
The present invention is to be support base material with ceramic regulation ripple net filler or corrugated plate packing, and it is big that these structured packings have specific area, and resistance is little, and cloth liquid is even, mass-transfer efficiency height, and advantage easy to loading and unloading in suitability for industrialized production and in using.But because their space body complex geometry, it is quite difficult preparing the uniform molecular screen membrane of thickness in its surface.For this reason, key technology on the other hand provided by the present invention be program transformation reaction temperature, reactant liquor stationary stream state and base material gravitational field direction.Program transformationreation temperature can prevent to form cavity heterogeneous between molecular screen membrane and the base material in the hydrothermal crystallizing course of reaction, can strengthen the fastness that molecular screen membrane combines with substrate surface simultaneously.Leave standstill and the flow regime and timing conversion base material gravitational field direction of program checker reactant liquor not only can guarantee the even distribution of solid silicone in reactant liquor and the relative equilibrium advolution of substrate surface crystallization condition effectively, can farthest reduce of the impact of liquid stream again, thereby make molecular sieve crystal evenly growth fast molecular screen membrane.
For the catalytic performance that improves molecular screen membrane and the durability of use, it also is considerable link that molecular screen membrane is modified processing.It is 1～6 hot acid water vapour that the present invention adopts the pH value, N
2Be carrier gas, molecular screen membrane is carried out post processing, make the catalytic activity of molecular screen membrane and activity stability obviously be better than the molecular screen membrane of modifying with other method.Described hot acid water vapour can be the water vapour of acetate or hydrochloric acid or nitric acid.
Description of drawings
Fig. 1 is the X-ray diffraction spectrogram with the prepared support beta molecular sieve membrane of the present invention.
Fig. 2 is the beta molecular sieve membrane catalyst supported overall structure photo of regular corrugation filler.
Fig. 3 is the electron microscope photo scanning on support base material surface.
Fig. 4～Fig. 6 is the electron microscope photo scanning of the epontic beta molecular sieve membrane of support base material.
The specific embodiment
Embodiment one
With overall dimensions is the YC-3 type sial pottery corrugated regular filler base material (SiO of Φ 100 * 150mm
2/ Al
2O
3=72, Zhuzhou space dragon ceramics factory) with the HCl aqueous solution reflow treatment 30min of 0.1M, use deionized water rinsing, dry 2h under 110 ℃.In above-mentioned treated base material is packed reactor into.Take by weighing 160g TEABr (the emerging good fortune fine chemistry in Beijing research institute) and be dissolved in the 400ml deionized water, in above-mentioned solution, add 220ml NaOH solution (5.74M, self-control) and 50ml NaAlO successively again
2Solution (Al
3+Concentration is 3.73M, self-control), strong agitation 30min makes and mixes, and slowly adds 156g SiO more while stirring
2(80～100 orders, Haiyang Chemical Plant, Qingdao).In the reactor of going into to be equipped with base material, sealed reactor carries out crystallization by the heating schedule of setting with above-mentioned mixed liquor.Temperature conditions is: by 80 ℃～140 ℃, heating rate is 0.5 ℃/mim, 140 ℃ of constant temperature 30h; From 140 ℃～170 ℃, heating rate is 0.5 ℃/mim; 170 ℃ of constant temperature 30h reduce to 30 ℃ by the rate of temperature fall of 0.5 ℃/mim again.Take out filler from reactor, spend deionised water, 100 ℃ of following dry 4h put into Muffle furnace, rise to 550 ℃ by the heating rate of 1 ℃/mim, at 550 ℃ of following roasting 3h, reduce to 25 ℃ naturally in Muffle furnace, handle 15min with ultrasonic wave.At the substrate surface even and firm beta molecular sieve membrane of one deck of growing.The XRD spectra that characterizes molecular screen membrane thing phase is seen Fig. 1, the pattern when substrate surface is not grown molecular screen membrane such as Fig. 3, substrate surface pattern such as Fig. 4 behind the molecular screen membrane that grown, the beta molecular sieve membrane catalyst supported structure of structured packing such as Fig. 2.Record the SiO of the molecular sieve powder that scrapes from rete
2/ Al
2O
3Be 30.5.The amount that contains molecular sieve on the regular catalyst is 2.96wt%.Repeat as stated above to synthesize for the second time and synthesize for the third time, handle 15min with ultrasonic wave again.Pattern through three synthetic back substrate surface molecular screen membranes is seen Fig. 5.With the beta molecular sieve membrane catalyst supported NH that makes at 1M
4The 4h that refluxes in the Cl aqueous solution spends deionised water to there not being Cl
-(use AgNO
3Detect), carry out temperature-programmed calcination, its heating rate is 1 ℃/mim, at 550 ℃ of constant temperature 3h, reduces to 30 ℃ naturally in Muffle furnace.Use the acetic acid steam of 0.1M again, N
2For dynamic hot acid steam treatment, N are carried out in carrier gas
2Flow is 20ml/min, and treatment temperature is 350 ℃, and the processing time is 4h, just obtains etherificate with beta molecular sieve membrane catalyst supported.Carry out the reaction of methyl alcohol and isobutene synthesize methyl tert-butyl ether (MTBE) with above-mentioned catalyst in recirculation reactor, its condition is: 85 ℃ of temperature, pressure 1.5MPa, alfin ratio 4, cycle rate 25ml/min.Take a sample behind the reaction 1h, form with SQ-206 gas chromatograph analytic sample, the result is that isobutene conversion is 92.44%.
Embodiment two
Press the synthetic beta molecular sieve membrane that supports of method of embodiment one, different is: with the acetic acid steam of 0.5M, N
2For dynamic hydrothermal treatment consists is carried out in carrier gas, treatment temperature is 450 ℃, and the processing time is 3h.Carry out the reaction of the synthetic ethyl tert-butyl ether (ETBE) (ETBE) of ethanol and isobutene with this catalyst in recirculation reactor, its condition is: 85 ℃ of temperature, pressure 1.5MPa, alfin ratio are 3.5, cycle rate 25ml/min.Take a sample behind the reaction 2h, form with SQ-206 gas chromatograph analytic sample, the result is that isobutene conversion is 84.03%.
Embodiment three
With overall dimensions is the YC-3 type sial pottery corrugated plate regular packing base material (SiO of Φ 100 * 50mm
2/ Al
2O
3=60, Zhuzhou space dragon ceramics factory) with the HCl aqueous solution reflow treatment 30min of 0.1M, use deionized water rinsing, dry 2h under 110 ℃.120g TEABr (the emerging good fortune fine chemistry in Beijing research institute) is dissolved in the 400ml deionized water, adds 200ml NaOH solution (5.74M, self-control) and 50mlNaAlO more successively
2Solution (Al
3+Concentration is 3.73M, self-control), strong agitation 30min makes and mixes, and slowly adds 100g SiO more while stirring
2(80～100 orders, Haiyang Chemical Plant, Qingdao) obtains preparation liquid.Above-mentioned preparation liquid and ceramic base material are put into reactor simultaneously, carry out crystallization by the heating schedule of setting.Temperature conditions is: by 80 ℃～140 ℃, heating rate is 1 ℃/mim; 140 ℃ of constant temperature 40h; From 140 ℃～170 ℃, heating rate is 1 ℃/mim; 170 ℃ of constant temperature 40h; Be cooled to 30 ℃ by 1 ℃/mim again, the result has obtained even and firm beta molecular sieve membrane equally on base material.Record the SiO of molecular sieve rete
2/ Al
2O
3Be 20.2.Repeat as stated above to synthesize for the second time, handle 15min with ultrasonic wave then.Pattern through the synthetic back of secondary substrate surface molecular screen membrane is seen Fig. 6.With the beta molecular sieve membrane catalyst supported NH that makes at 1M
4The 4h that refluxes in the Cl aqueous solution spends deionised water, carries out temperature-programmed calcination, and its heating rate is 1 ℃/mim, at 550 ℃ of constant temperature 4h, is cooled to 30 ℃ naturally then in Muffle furnace.With the acetic acid steam of 0.05M, N
2For dynamic hot acid steam treatment, N are carried out in carrier gas
2Flow is 20ml/min, and treatment temperature is 300 ℃, and the processing time is 4h, also can obtain etherificate with beta molecular sieve membrane catalyst supported.Carry out the reaction of methyl alcohol and the synthetic MTBE of isobutene with above-mentioned catalyst in recirculation reactor, its condition is: 80 ℃ of temperature, pressure 1.2MPa, alfin ratio 3.5, cycle rate 25ml/min.Take a sample behind the reaction 1h, the result is that isobutene conversion is 71.58%.
Claims (1)
1. an etherificate is with the beta molecular sieve membrane catalyst supported preparation method of regular corrugation filler, and this method is a support base material with the ceramic regulation filler, after base material is carried out preliminary treatment, puts it into by template agent, silica gel (SiO
2) and NaAlO
2In the preparation liquid of forming, carry out the hydrothermal crystallizing reaction then, pass through ion-exchange and heat treatment again after, it is beta molecular sieve membrane catalyst supported with regular corrugation filler to obtain etherificate, it is characterized in that: tetraethylammonium bromide (TEABr) is adopted in the template agent; The template agent consists of with the mol ratio of system film reaction liquid: TEA
+: SiO
2=0.15～0.5, Na
2O: SiO
2=0.15～0.6, H
2O: SiO
2=8～20, SiO
2: Al
2O
3=20～100; Reaction temperature is, rise to 140 ℃～150 ℃ and keep constant temperature 5～60h by 60 ℃～80 ℃ with 0.5 ℃/min～1 ℃/min, be warming up to 170 ℃～180 ℃ and keep constant temperature 5～60h by 140 ℃～150 ℃ with 0.5 ℃/min～1 ℃/min again, be cooled to 20～30 ℃ then; In the hydrothermal crystallization process, leaving standstill and flowing of reactant liquor hockets, and at first makes reactant liquor leave standstill 1～10h, and the Modelling of Flow with Recirculation reactant liquor reaches 1～10min then, repeats said process successively and finishes until reaction; In the hydrothermal crystallization process, program transformation base material gravitational field rotates continuously the direction to 90 ° of base material～180 ° at 0.5～5h in the time, and repeats this process to reaction and finish; Heat treatment is carried out in two steps, and at first the heating rate with 1 ℃/min rises to 550 ℃, constant temperature 3～4h in Muffle furnace, in Muffle furnace, reduce to room temperature naturally, adopting the pH value then is that 1～6 acid vapor carries out dynamic hot acid and handles, and treatment temperature is 300 ℃～450 ℃, and the processing time is 3～4h.
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Families Citing this family (6)
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| CN100341783C (en) * | 2005-04-07 | 2007-10-10 | 中国科学院大连化学物理研究所 | Method for preparing molecular sieve membrane on porous ceramic carrier by utilizing hydrothermal synthesis |
| JP5449823B2 (en) * | 2008-04-04 | 2014-03-19 | 花王株式会社 | Method for producing film catalyst |
| CN101862602B (en) * | 2010-05-24 | 2012-08-22 | 江西师范大学 | Preparation method and application of Ti-Beta molecular sieve membrane in separating organic matters |
| CN107918720B (en) * | 2017-11-16 | 2021-07-23 | 中国石油大学(华东) | Method for quantitatively analyzing force field parameters of n-pentane/isopentane separation in molecular sieve |
| CN111359564B (en) * | 2020-03-30 | 2021-06-08 | 黄山学院 | Method for synthesizing high-quality inorganic membrane by microwave heating |
| CN111876210A (en) * | 2020-07-15 | 2020-11-03 | 中石化南京化工研究院有限公司 | Improve COS, CS in natural gas2Method for removing rate |
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