CN105772066A - Catalyst used for preparing double-terminated glycol ether and preparation method thereof - Google Patents
Catalyst used for preparing double-terminated glycol ether and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a catalyst used for preparing double-terminated glycol ether through a reaction of glycol monoether with monohydric alcohol and/or monohydric ether alcohol. The catalyst is characterized by comprising one or more selected from a group consisting of an acidic molecular sieve, an acidic molecular sieve having undergone desilicication and an acidic molecular sieve having undergone dealuminzation. The catalyst has the advantages of high activity, high selectivity, long service life and regenerability, and the performance of the catalyst can be retained after regeneration.
Description
Technical field
The application belongs to chemical field, in particular to a kind of Catalysts and its preparation method preparing double; two end-blocking glycol ether.
Background technology
Double; two end-blocking glycol ethers refer to that the hydrogen on two terminal hydroxy groups of ethylene glycol is replaced the glycol ether of gained by alkyl.Double; two end-blocking glycol ethers do not have active hydrogen, and chemical stability is strong, and pour point is low, it is little, heat-resist to stick temperature change, ph stability strengthens, emulsifying capacity is good, the low lipophile of foam strong, anti-coking is better, have relatively low viscosity and density etc..Therefore, double; two end-blocking polyglycol ethers have a wide range of applications in fields such as high-speed spin finishes, low-foaming detergent, food processing and biofermentations.
The preparation of double; two end-blocking glycol ethers mainly has halogenated hydrocarbons and sodium alkoxide (Williamson synthesis) method and direct etherification method, wherein Williamson synthetic method refers to that halogenated hydrocarbons and sodium alkoxide react generation ether in anhydrous conditions, and it is seriously polluted, operational hazards, economy are relatively low；Direct etherification method refers to spent glycol or ethylene glycol mono-ether and monohydric alcohol or the method for the direct etherificate of unitary alcohol ether, and its catalyst is acidic resins.The yield of catalyst, selectivity and life-span are all not high, and its catalyst is all difficult to regenerate, and are easily formed the by-product such as substantial amounts of Isosorbide-5-Nitrae-dioxane and high boiling many ethylene glycol bis end-blocking ether simultaneously.
Summary of the invention
An aspect according to the application, providing a kind of catalyst for ethylene glycol mono-ether and monohydric alcohol and/or unitary alcohol ether reaction preparation double; two end-blocking glycol ether, after having high activity, high selectivity, life-span length, renewable and regeneration, property can continue to the advantage kept.
Containing acidic molecular sieve in the described catalyst terminating glycol ether for ethylene glycol mono-ether and monohydric alcohol and/or the preparation pair of unitary alcohol ether reaction；Described acidic molecular sieve is one or more in the molecular sieve of MWW, FER, MFI, MOR, FAU, BEA selected from structure type.
Preferably, described ethylene glycol mono-ether is contact passing into reactor containing ethylene glycol mono-ether with the raw material of monohydric alcohol and/or unitary alcohol ether with described catalyst and react with monohydric alcohol and/or unitary alcohol ether reaction, produces double; two end-blocking glycol ether；
Reaction temperature is 50～300 DEG C, and reaction pressure is 0.1～15MPa；
In described raw material, the mass space velocity of ethylene glycol mono-ether is 0.01～15.0h-1；
In described raw material, the mol ratio of monohydric alcohol and/or unitary alcohol ether and ethylene glycol mono-ether is unitary alcohol ether: ethylene glycol mono-ether=1～100:1.
Preferably, described acidic molecular sieve comprises the acidic molecular sieve through desiliconization process and/or the acidic molecular sieve through dealumination treatment.
Preferably, one or more in Hydrogen MCM-22 molecular sieve, Hydrogen ferrierite, Hydrogen ZSM-5 molecular sieve, h-mordenite, Hydrogen Y molecular sieve, the Hydrogen Beta molecular sieve of described acidic molecular sieve.
Preferably, in described acidic molecular sieve, the atomic ratio of silicon and aluminum is Si/Al=3～180.It is further preferred that the upper limit of the atomic ratio Si/Al of silicon and aluminum is optionally from 180,150,120,100 in described acidic molecular sieve, lower limit is optionally from 3,8,9,10,20,25,30,35,40,50.
Those skilled in the art can select arbitrary shaping of catalyst mode according to actual needs, and typical molding mode is direct compression molding, extruded moulding.
Preferably, possibly together with forming agent in described catalyst；The weight of described forming agent accounts for the 5～50% of described total catalyst weight.
When adopting extruded moulding, those skilled in the art can select suitable forming agent according to the actual requirements.Preferably, by aluminium oxide, silicon oxide, titanium oxide, one or more form described forming agent.
According to further aspect of the application, it is provided that the preparation method of a kind of described acidic molecular sieve processed through desiliconization, including step:
A) described acidic molecular sieve is put in alkaline solution, filter after reacting 0.5～24 hour at reaction temperature 15～95 DEG C；
B) step a) is filtered the solid matter of gained, with the acid solution wash of 0.01～0.5mol/L and be neutralized to pH value and be not more than 7, is then passed through ammonium ion exchange, filtration, dry and roasting, namely obtains the described acidic molecular sieve processed through desiliconization；
Preferably, described alkaline solution is selected from one or more in sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide solution, magnesium hydroxide solution, aqua calcis, sodium carbonate liquor, sodium bicarbonate solution.
Preferably, the concentration of described alkaline solution is 0.05～6.0mol/L.It is further preferred that the concentration of described alkaline solution is 0.2～1.5mol/L.
Preferably, described reaction temperature is 50～85 DEG C.
Another aspect according to the application, it is provided that the preparation method of the described acidic molecular sieve through dealumination treatment, including steam treatment and/or acid treatment.
Preferably, the step of described steam treatment is: processed 1～8 hour in the steam that temperature is 400～700 DEG C by described acidic molecular sieve.It is further preferred that the step of described steam treatment is: described acidic molecular sieve is processed 2～4 hours in the steam that temperature is 500～650 DEG C.
Preferably, the step of described acid treatment is: put in acid solution by described acidic molecular sieve, reacts 1～24 hour at reaction temperature 15～95 DEG C.
Preferably, described acid solution is selected from one or more in hydrochloric acid solution, sulfuric acid solution, salpeter solution, acetum, oxalic acid solution, citric acid solution.
Preferably, the concentration of described acid solution is 0.03～3.0mol/L.It is further preferred that the upper limit of concentration of described acid solution is selected from 3.0mol/L, 1.5mol/L, 1.0mol/L, lower limit is selected from 0.03mol/L, 0.1mol/L, 0.2mol/L, 0.4mol/L.
In the application, described ethylene glycol mono-ether and monohydric alcohol and/or unitary alcohol ether reaction, react including ethylene glycol mono-ether and monohydric alcohol, ethylene glycol mono-ether and unitary alcohol ether reaction, ethylene glycol mono-ether and monohydric alcohol and three kinds of situations of unitary alcohol ether reaction.
In the application, double; two end-blocking glycol ethers refer to that the hydrogen on two hydroxyls of ethylene glycol is all replaced the glycol ether of gained by alkyl.
The beneficial effect that the application can produce includes:
(1) catalyst provided herein, has the advantage of high activity, high selectivity, life-span length.
(2) catalyst provided herein, renewable and regeneration after its performance can continue to keep.
(3) method of modifying of catalyst provided herein, it is possible to improve the activity of catalyst, choosing
Selecting property, life-span.
Detailed description of the invention
If no special instructions, the raw material in embodiment and catalyst are bought each through commercial sources.
Embodiment is analyzed method and conversion ratio, selective calculation as follows:
The composition that the Agilent7890 gas chromatograph with gas automatic sampling device, fid detector and FFAP capillary column carries out gas/liquid phase component is utilized to automatically analyze.
In embodiments herein, ethylene glycol mono-ether conversion ratio and product double; two end-blocking glycol ether and by-product selectivity are all based on quality and are calculated:
Ethylene glycol mono-ether conversion ratio=[(in charging ethylene glycol mono-ether quality)-(in discharging ethylene glycol mono-ether quality)] ÷ (in charging ethylene glycol mono-ether quality) × (100%)
Double; two end-blocking glycol ether selectivitys=(in discharging double; two end-blocking glycol ether quality) ÷ [(in discharging all ethylene glycol derivative quality)-(in discharging the complete ethylene glycol mono-ether quality of unreacted)] × (100%)
By-product selectivity=(in discharging by-product quality) ÷ [(in discharging all ethylene glycol derivative quality)-(in discharging the complete ethylene glycol mono-ether quality of unreacted)] × (100%)
Above-mentioned all ethylene glycol derivatives refer to containing in molecular formula containing-O-CH2-CH2The material of-O-structure, mainly includes the complete ethylene glycol mono-ether of double; two end-blocking glycol ether, Isosorbide-5-Nitrae-dioxane, unreacted, double; two end-blocking diethylene glycol ether, diethylene glycol monoether and ethylene glycol.
The ammonium ion exchange operating procedure of molecular sieve:
In one detailed description of the invention of the application, Cation molecule sieve converts the S.O.P. of hydrogen type molecular sieve to and is: dried for 2Kg Cation molecule sieve is put into the NH of the 0.8mol/L of 5L4NO3In solution, at 80 DEG C, stir 12h, with the distilled water wash of 5L after filtration.This ion exchange process obtains NH in triplicate4 +The molecular sieve of type.Through fully dried, it is placed in Muffle furnace, is increased to 550 DEG C with 2 DEG C/min and keeps calcining 4h to obtain hydrogen type molecular sieve.
Silica alumina ratio: the silica alumina ratio in the application is the atomic ratio of the silicon in molecular sieve and aluminum.
Below in conjunction with specific embodiment, the application is expanded on further.Should be understood that these embodiments are merely to illustrate the application rather than restriction scope of the present application.
Embodiment 1
Convert, by ammonium ion exchange, the MCM-22 molecular sieve that 2Kg sodium form silica alumina ratio is 45:1 to Hydrogen MCM-22 molecular sieve, be designated as molecular sieve-4 A, in Table 1.
Embodiment 2
The MCM-22 molecular sieve that 3Kg sodium form silica alumina ratio is 45:1 is joined in the aqua calcis that 5L concentration is 1.5mol/L, stirring reaction 10 hours (being abbreviated as h) at 75 DEG C, after filtration, it is 6 that the salpeter solution of filter cake 0.08ml/L washs pH, with deionized water cyclic washing to neutral after filtration, convert Hydrogen MCM-22 molecular sieve to by ammonium ion exchange after drying at 100 DEG C, be designated as molecular sieve B, in Table 1.
Embodiment 3
The MCM-22 molecular sieve that 3Kg sodium form silica alumina ratio is 45:1 is passed at 550 DEG C the steam treatment 4h of 550 DEG C, then passes through ammonium ion exchange and convert Hydrogen MCM-22 molecular sieve to, be designated as molecular sieve C, in Table 1.
Embodiment 4
The MCM-22 molecular sieve that 3Kg sodium form silica alumina ratio is 45:1 is processed 1h under 60 DEG C of conditions in the 0.1mol/L hydrochloric acid solution of 5L, then passes through ammonium ion exchange and convert Hydrogen MCM-22 molecular sieve to, be designated as molecular sieve D, in Table 1.
Embodiment 5
Convert, by ammonium ion exchange, the ferrierite that 2Kg sodium form silica alumina ratio is 15:1 to Hydrogen ferrierite, be designated as molecular sieve E, in Table 1.
Embodiment 6
The ferrierite that 3Kg sodium form silica alumina ratio is 15:1 is joined in the magnesium hydroxide solution that 5L concentration is 0.2mol/L, stirring reaction 24h at 50 DEG C, after filtration, it is 6 that the hydrochloric acid solution of filter cake 0.1ml/L washs pH, with deionized water cyclic washing to neutral after filtration, convert Hydrogen ferrierite to by ammonium ion exchange after drying at 100 DEG C, be designated as molecular sieve F, in Table 1.
Embodiment 7
The ferrierite that 3Kg sodium form silica alumina ratio is 15:1 is passed under 700 DEG C of conditions the steam treatment 1h of 700 DEG C, then passes through ammonium ion exchange and convert Hydrogen ferrierite to, be designated as molecular sieve G, in Table 1.
Embodiment 8
The ferrierite that 3Kg sodium form silica alumina ratio is 15:1 is processed 4h under 80 DEG C of conditions in the 0.4mol/L sulfuric acid solution of 5L, then passes through ammonium ion exchange and convert Hydrogen ferrierite to, be designated as molecular sieve H, in Table 1.
Embodiment 9
Convert, by ammonium ion exchange, the ZSM-5 molecular sieve that 2Kg sodium form silica alumina ratio is 140:1 to Hydrogen ZSM-5 molecular sieve, be designated as molecular sieve I, in Table 1.
Embodiment 10
The ZSM-5 molecular sieve that 3Kg sodium form silica alumina ratio is 140:1 is joined in the sodium bicarbonate solution that 5L concentration is 6.0mol/L, stirring reaction 12h at 85 DEG C, after filtration, it is 6 that the hydrochloric acid solution of filter cake 0.2ml/L washs pH, with deionized water cyclic washing to neutral after filtration, convert Hydrogen ZSM-5 molecular sieve to by ammonium ion exchange after drying at 100 DEG C, be designated as molecular sieve J, in Table 1.
Embodiment 11
The ZSM-5 molecular sieve that 3Kg sodium form silica alumina ratio is 140:1 is passed under 400 DEG C of conditions the steam treatment 8h of 400 DEG C, then passes through ammonium ion exchange and convert Hydrogen ZSM-5 molecular sieve to, be designated as molecular sieve K, in Table 1.
Embodiment 12
The ZSM-5 molecular sieve that 3Kg sodium form silica alumina ratio is 140:1 is processed 8h under 75 DEG C of conditions in the 1.0mol/L acetum of 5L, then passes through ammonium ion exchange and convert Hydrogen ZSM-5 molecular sieve to, be designated as molecular sieve L, in Table 1.
Embodiment 13
Convert, by ammonium ion exchange, the modenite that 2Kg sodium form silica alumina ratio is 4:1 to h-mordenite, be designated as molecular sieve M, in Table 1.
Embodiment 14
The modenite that 3Kg sodium form silica alumina ratio is 4:1 is joined in the lithium hydroxide solution that 5L concentration is 1.0mol/L, stirring reaction 0.5h at 95 DEG C, after filtration, it is 6 that the acetum of filter cake 0.5ml/L washs pH, with deionized water cyclic washing to neutral after filtration, through converting h-mordenite to by ammonium ion exchange after drying at 100 DEG C, it is designated as molecular sieve N, in Table 1.
Embodiment 15
The modenite that 3Kg sodium form silica alumina ratio is 4:1 is passed under 650 DEG C of conditions the steam treatment 3h of 650 DEG C, then passes through ammonium ion exchange and convert h-mordenite to, be designated as molecular sieve O, in Table 1.
Embodiment 16
The modenite that 3Kg sodium form silica alumina ratio is 4:1 is processed 12h under 60 DEG C of conditions in the 3.0mol/L citric acid solution of 5L, then passes through ammonium ion exchange and convert h-mordenite to, be designated as molecular sieve P, in Table 1.
Embodiment 17
Convert, by ammonium ion exchange, the Y molecular sieve that 2Kg sodium form silica alumina ratio is 25:1 to Hydrogen Y molecular sieve, be designated as molecular sieve Q, in Table 1.
Embodiment 18
The Y molecular sieve that 3Kg sodium form silica alumina ratio is 25:1 is joined in the sodium hydroxide solution that 5L concentration is 0.5mol/L, stirring reaction 4h at 80 DEG C, after filtration, it is 6 that the salpeter solution of filter cake 0.1ml/L washs pH, with deionized water cyclic washing to neutral after filtration, convert Hydrogen Y molecular sieve to by ammonium ion exchange after drying at 100 DEG C, be designated as molecular sieve R, in Table 1.
Embodiment 19
The Y molecular sieve that 3Kg sodium form silica alumina ratio is 25:1 is passed under 500 DEG C of conditions the steam treatment 2h of 500 DEG C, then passes through ammonium ion exchange and convert Hydrogen Y molecular sieve to, be designated as molecular sieve S, in Table 1.
Embodiment 20
The Y molecular sieve that 3Kg sodium form silica alumina ratio is 25:1 is processed 5h under 95 DEG C of conditions in the 1.5mol/L oxalic acid solution of 5L, then passes through ammonium ion exchange and convert Hydrogen Y molecular sieve to, be designated as molecular sieve T, in Table 1.
Embodiment 21
Convert, by ammonium ion exchange, the Beta molecular sieve that 2Kg sodium form silica alumina ratio is 20:1 to Hydrogen Beta molecular sieve, be designated as molecular sieve U, in Table 1.
Embodiment 22
The Beta molecular sieve that 3Kg sodium form silica alumina ratio is 20:1 is joined sodium carbonate that 5L concentration is 3.5mol/L with in the potassium hydroxide mixed solution of 0.05mol/L, stirring reaction 12h at 15 DEG C, after filtration, it is 6 that the sulfuric acid solution of filter cake 0.01ml/L washs pH, with deionized water cyclic washing to neutral after filtration, convert Hydrogen Beta molecular sieve to by ammonium ion exchange after drying at 100 DEG C, be designated as molecular sieve V, in Table 1.
Embodiment 23
The Beta molecular sieve that 3Kg sodium form silica alumina ratio is 20:1 is passed under 600 DEG C of conditions the steam treatment 4h of 600 DEG C, then passes through ammonium ion exchange and convert Hydrogen Beta molecular sieve to, be designated as molecular sieve W, in Table 1.
Embodiment 24
The Beta molecular sieve that 3Kg sodium form silica alumina ratio is 20:1 is processed 24h under 15 DEG C of conditions in the 0.03mol/L salpeter solution of 5L, then passes through ammonium ion exchange and convert Hydrogen Beta molecular sieve to, be designated as molecular sieve X, in Table 1.
The processing method of table 1 embodiment 1～24 Middle molecule sieve
Embodiment 25
Using 1Kg molecular sieve-4 A aluminium oxide as binding agent extruded moulding, 550 DEG C of roastings 5 hours under the air atmosphere of Muffle furnace, obtaining diameter is 1.5mm, and length is 1.5mm, and quality of alumina content is the bar-shaped preformed catalyst of 15%.Take this catalyst 500g and load in the stainless steel reaction pipe that internal diameter is 25mm, normal pressure, at 550 DEG C with nitrogen activation 4 hours, then drop to reaction temperature (being abbreviated as T)=50 DEG C, pass into raw material and mol ratio is CH3OCH3:CH3OCH2CH2OH=1:1, reaction pressure (is abbreviated as P)=0.1MPa, and ethylene glycol mono-ether mass space velocity (is abbreviated as WHSV)=0.01h-1, no carrier gas, to use gas chromatographic analysis product, after stable reaction, calculate the selectivity of ethylene glycol mono-ether conversion ratio and product, reaction condition and result are in Table 2.
Embodiment 26
Molecular sieve-4 A in catalyst in embodiment 25 is changed to molecular sieve B, and all the other experimental procedures are consistent with embodiment 25, and reaction condition and result are in Table 2.
Embodiment 27
Molecular sieve-4 A in catalyst in embodiment 25 is changed to molecular sieve C, and all the other experimental procedures are consistent with embodiment 25, and reaction condition and result are in Table 2.
Embodiment 28
Molecular sieve-4 A in catalyst in embodiment 25 is changed to molecular sieve D, and all the other experimental procedures are consistent with embodiment 25, and reaction condition and result are in Table 2.
Embodiment 29
Using 1Kg molecular sieve E silicon oxide as binding agent extruded moulding, 550 DEG C of roastings 5 hours under the air atmosphere of Muffle furnace, obtaining diameter is 1.5mm, and length is 1.5mm, and siliconoxide mass content is the bar-shaped preformed catalyst of 5%.Take this catalyst 500g and load in the stainless steel reaction pipe that internal diameter is 25mm, normal pressure, at 550 DEG C with nitrogen activation 4 hours, then drop to reaction temperature T=300 DEG C, P=15MPa, passes into raw material and mol ratio is CH3OH:CH3OCH2CH2OH=100:1, WHSV=15h-1, carrier gas is nitrogen, GHSV=10000h-1, all the other experimental procedures are consistent with embodiment 1, and all the other experimental procedures are consistent with embodiment 25, and reaction condition and result are in Table 2.
Embodiment 30
Molecular sieve E in catalyst in embodiment 29 is changed to molecular sieve F, and all the other experimental procedures are consistent with embodiment 29, and reaction condition and result are in Table 2.
Embodiment 31
Molecular sieve E in catalyst in embodiment 29 is changed to molecular sieve G, and all the other experimental procedures are consistent with embodiment 29, and reaction condition and result are in Table 2.
Embodiment 32
Molecular sieve E in catalyst in embodiment 29 is changed to molecular sieve H, and all the other experimental procedures are consistent with embodiment 29, and reaction condition and result are in Table 2.
Embodiment 33
Using 1Kg molecular sieve I silicon oxide as binding agent extruded moulding, 550 DEG C of roastings 5 hours under the air atmosphere of Muffle furnace, obtaining diameter is 1.5mm, and length is 1.5mm, and siliconoxide mass content is the bar-shaped preformed catalyst of 5%.Take this catalyst 500g and load in the stainless steel reaction pipe that internal diameter is 25mm, normal pressure, at 550 DEG C with nitrogen activation 4 hours, then drop to reaction temperature T=100 DEG C, P=3.5MPa, passes into raw material and mol ratio is
CH3CH2OCH2CH3:CH3CH2OCH2CH2OH=3:1, WHSV=0.5h-1, all the other experimental procedures are consistent with embodiment 25, and reaction condition and result are in Table 2.
Embodiment 34
Molecular sieve I in catalyst in embodiment 33 is changed to molecular sieve J, and all the other experimental procedures are consistent with embodiment 33, and reaction condition and result are in Table 2.
Embodiment 35
Molecular sieve I in catalyst in embodiment 33 is changed to molecular sieve K, and all the other experimental procedures are consistent with embodiment 33, and reaction condition and result are in Table 2.
Embodiment 36
Molecular sieve I in catalyst in embodiment 33 is changed to molecular sieve L, and all the other experimental procedures are consistent with embodiment 33, and reaction condition and result are in Table 2.
Embodiment 37
Using 1Kg molecular sieve M titanium oxide as binding agent extruded moulding, 550 DEG C of roastings 5 hours under the air atmosphere of Muffle furnace, obtaining diameter is 1.5mm, and length is 1.5mm, and titanium oxide mass content is the bar-shaped preformed catalyst of 50%.Take this catalyst 500g and load in the stainless steel reaction pipe that internal diameter is 25mm, normal pressure, at 550 DEG C with nitrogen activation 4 hours, then drop to reaction temperature T=200 DEG C, P=8MPa, passes into raw material and mol ratio is CH3CH2OH:CH3CH2OCH2CH2OH=5:1, WHSV=5h-1, carrier gas is helium, GHSV=2000h-1, all the other experimental procedures are consistent with embodiment 25, and reaction condition and result are in Table 2.
Embodiment 38
Molecular sieve M in catalyst in embodiment 37 is changed to molecular sieve N, and all the other experimental procedures are consistent with embodiment 37, and reaction condition and result are in Table 2.
Embodiment 39
Molecular sieve M in catalyst in embodiment 37 is changed to molecular sieve O, and all the other experimental procedures are consistent with embodiment 37, and reaction condition and result are in Table 2.
Embodiment 40
Molecular sieve M in catalyst in embodiment 37 is changed to molecular sieve P, and all the other experimental procedures are consistent with embodiment 37, and reaction condition and result are in Table 2.
Embodiment 41
Using 1Kg molecular sieve Q aluminium oxide as binding agent extruded moulding, 550 DEG C of roastings 5 hours under the air atmosphere of Muffle furnace, obtaining diameter is 1.5mm, and length is 1.5mm, and titanium oxide mass content is the bar-shaped preformed catalyst of 30%.Take this catalyst 500g and load in the stainless steel reaction pipe that internal diameter is 25mm, normal pressure, at 550 DEG C with nitrogen activation 4 hours, then drop to reaction temperature T=130 DEG C, P=5MPa, passes into raw material and mol ratio is CH3OCH3:CH3OH:CH3OCH2CH2OH=2:1:1, WHSV=2h-1, no carrier gas, all the other experimental procedures are consistent with embodiment 25, and reaction condition and result are in Table 2.
Embodiment 42
Molecular sieve Q in catalyst in embodiment 41 is changed to molecular sieve R, and all the other experimental procedures are consistent with embodiment 41, and reaction condition and result are in Table 2.
Embodiment 43
Molecular sieve Q in catalyst in embodiment 41 is changed to molecular sieve S, and all the other experimental procedures are consistent with embodiment 41, and reaction condition and result are in Table 2.
Embodiment 44
Molecular sieve Q in catalyst in embodiment 41 is changed to molecular sieve T, and all the other experimental procedures are consistent with embodiment 41, and reaction condition and result are in Table 2.
Embodiment 45
Using 1Kg molecular sieve U silicon oxide as binding agent extruded moulding, 550 DEG C of roastings 5 hours under the air atmosphere of Muffle furnace, obtaining diameter is 1.5mm, and length is 1.5mm, and titanium oxide mass content is the bar-shaped preformed catalyst of 20%.Take this catalyst 500g and load in the stainless steel reaction pipe that internal diameter is 25mm, normal pressure, at 550 DEG C with nitrogen activation 4 hours, then drop to reaction temperature T=230 DEG C, P=2MPa, passes into raw material and mol ratio is CH3OCH3:CH3OCH2CH2OH=15:1, WHSV=9h-1, carrier gas is nitrogen, GHSV=3000h-1, all the other experimental procedures are consistent with embodiment 25, and reaction condition and result are in Table 2.
Embodiment 46
Molecular sieve U in catalyst in embodiment 45 is changed to molecular sieve V, and all the other experimental procedures are consistent with embodiment 45, and reaction condition and result are in Table 2.
Embodiment 47
Molecular sieve U in catalyst in embodiment 45 is changed to molecular sieve W, and all the other experimental procedures are consistent with embodiment 45, and reaction condition and result are in Table 2.
Embodiment 48
Molecular sieve U in catalyst in embodiment 45 is changed to molecular sieve X, and all the other experimental procedures are consistent with embodiment 45, and reaction condition and result are in Table 2.
The catalytic reaction condition of table 2 embodiment 25～48 and result
Embodiment 49
Respectively the catalyst after one way reaction inactivation in embodiment 45,46,47,48 being taken out regeneration, regeneration condition is the lower 550 DEG C of roastings of air atmosphere 4 hours, and the catalyst after regeneration repeats reaction according to the reaction condition of former embodiment respectively.Reaction result is in Table 3.
Reaction result contrast before and after catalytic regeneration in table 3 embodiment
The above, it is only several embodiments of the application, not the application is done any type of restriction, although the application discloses as above with preferred embodiment, but and be not used to restriction the application, any those skilled in the art, without departing from the scope of technical scheme, the technology contents utilizing the disclosure above makes a little variation or modification is all equal to equivalence case study on implementation, belongs within the scope of technical scheme.
Claims (10)
1. the catalyst for ethylene glycol mono-ether with monohydric alcohol and/or unitary alcohol ether reaction preparation double; two end-blocking glycol ether, it is characterised in that containing acidic molecular sieve in described catalyst；
Described acidic molecular sieve is one or more in the molecular sieve of MWW, FER, MFI, MOR, FAU, BEA selected from structure type.
2. catalyst according to claim 1, it is characterised in that described acidic molecular sieve comprises the acidic molecular sieve through desiliconization process and/or the acidic molecular sieve through dealumination treatment.
3. catalyst according to claim 1, it is characterised in that in described acidic molecular sieve, the atomic ratio of silicon and aluminum is Si/Al=3～180.
4. catalyst according to claim 1, it is characterised in that possibly together with forming agent in described catalyst；The weight of described forming agent accounts for the 5～50% of described total catalyst weight.
5. catalyst according to claim 4, it is characterised in that one or more form described forming agent by aluminium oxide, silicon oxide, titanium oxide.
6. the preparation method of the acidic molecular sieve processed through desiliconization described in claim 2, including step:
A) acidic molecular sieve is put in alkaline solution, filter after reacting 0.5～24 hour at reaction temperature 15～95 DEG C；
B) step a) is filtered the solid matter of gained, with the acid solution wash of 0.01～0.5mol/L and be neutralized to pH value and be not more than 7, is then passed through ammonium ion exchange, filtration, dry and roasting, namely obtains the described acidic molecular sieve processed through desiliconization；
Described alkaline solution is selected from one or more in sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide solution, magnesium hydroxide solution, aqua calcis, sodium carbonate liquor, sodium bicarbonate solution；
The concentration of described alkaline solution is 0.05～6.0mol/L.
7. method according to claim 6, it is characterised in that described reaction temperature is 50～85 DEG C；The concentration of described alkaline solution is 0.2～1.5mol/L.
8. through the preparation method of the acidic molecular sieve of dealumination treatment described in claim 2, including steam treatment and/or acid treatment.
9. method according to claim 8, it is characterised in that the step of described steam treatment is: described acidic molecular sieve is processed 1～8 hour in the steam that temperature is 400～700 DEG C.
10. method according to claim 8, it is characterised in that the step of described acid treatment is: put in acid solution by described acidic molecular sieve, processes 1～24 hour at reaction temperature 15～95 DEG C；
Described acid solution is selected from one or more in hydrochloric acid solution, sulfuric acid solution, salpeter solution, acetum, oxalic acid solution, citric acid solution；
The concentration of described acid solution is 0.03～3.0mol/L.
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| CN102757815A (en) * | 2011-04-29 | 2012-10-31 | 中国石油化工股份有限公司 | Method for reducing benzene content in reformed oil |
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| CN1907932A (en) * | 2005-08-04 | 2007-02-07 | 中国科学院大连化学物理研究所 | Method for preparing dimethyl ether from methanol |
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