CN105669453A - Method for preparing methyl formate and coproducing dimethyl ether - Google Patents
Method for preparing methyl formate and coproducing dimethyl ether Download PDFInfo
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- CN105669453A CN105669453A CN201410653147.0A CN201410653147A CN105669453A CN 105669453 A CN105669453 A CN 105669453A CN 201410653147 A CN201410653147 A CN 201410653147A CN 105669453 A CN105669453 A CN 105669453A
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Abstract
The invention provides a method for preparing methyl formate and coproducing dimethyl ether. The method comprises the step of subjecting a methylal containing raw material to a disproportionation reaction in an acidic molecular sieve catalyst loaded reactor, thereby preparing the methyl formate and coproducing the dimethyl ether. According to the method provided by the invention, the requirements on methylal purity of the raw material are not high, the life of a catalyst is long, the reaction conditions are mild, the atom economy is high, and continuous production can be achieved, so that the method has large-scale industrialized application potential.
Description
Technical field
The preparation method that the application relates to a kind of methyl formate.
Background technology
At C1In chemistry, after methane chemical, syngas chemistry and methanol chemistry, methyl formate due to can the reason such as large-scale production cost-effectively, downstream product be many, being developing progressively in recent years is a new C1The initiation material of chemicals and construction unit. From methyl formate, it is possible to prepare numerous C such as formic acid, acetic acid, ethylene glycol, methyl propionate, acrylic acid methyl ester., methyl glycollate, N-N-formyl morpholine N, N-METHYLFORMAMIDE, DMF1Chemical products.
At present, the technology synthesizing methyl formate has: Methanol Carbonylation method, methanol oxidation dehydriding, methanol oxydehydro process, carbon dioxide and methanol hydrogenation condensation method, synthesis gas direct synthesis technique etc. Wherein Methanol Carbonylation is the main method of commercial production methyl formate both at home and abroad at present. This process catalyst used catalyst is generally Feldalat NM, meet water facile hydrolysis to generate undissolved sodium formate and pollute and block, and the separation of catalyst is more difficult, therefore this technique is very sensitive to impurity such as the water in material benzenemethanol and carbon monoxide, carbon dioxide, oxygen, and material purity requires very harsh. In view of the foregoing, this process route list set production scale is general all in 100,000 tons/year, it is more difficult to form scale effect. Additionally this technique requires over gas making, and the process such as Water gas shift/WGS and pressure-variable adsorption just can obtain carbon monoxide, invests very high, is unfavorable for that medium-sized and small enterprises use.
Summary of the invention
The purpose of the application is in that to provide a kind of method preparing methyl formate co-production dimethyl ether.
For this, this application provides a kind of method that dismutation reaction by dimethoxym ethane prepares methyl formate, it is characterised in that will containing dimethoxym ethane CH3O-CH2-OCH3Raw material by being loaded with the reaction zone of acid molecular sieve catalyst, be 0.01～15.0h at reaction temperature 50～200 DEG C, reaction pressure 0.1～10MPa, dimethoxym ethane mass space velocity-1When reaction prepare product formic acid methyl ester co-production dimethyl ether, wherein said acid molecular sieve catalyst is that solid phase, raw material and product can independently be gas phase or/and liquid phase.
Preferably, described acid molecular sieve catalyst optional from acid MFI-type molecular sieve catalyst, acid MWW type molecular sieve catalyst, acid FER type molecular sieve catalyst, acid MOR type molecular sieve catalyst, acid FAU type molecular sieve catalyst, acid BEA type molecular sieve catalyst one or more.
Preferably, described acid molecular sieve catalyst is optional from the acid molecular sieve catalyst without modification, the acid molecular sieve catalyst through desiliconization modification, one or more in the acid molecular sieve catalyst that Dealumination processes.
Preferably, described untreated acid molecular sieve catalyst silica alumina ratio is 3:1～150:1.
Preferably, the molecular sieve contained in described acid molecular sieve catalyst, crystal yardstick is micron-scale and/or nano-scale.
Preferably, the molecular sieve contained in described acid molecular sieve catalyst has multi-stage artery structure; It is further preferred that have microcellular structure and/or microporous mesoporous composite construction.
As an embodiment of the application, described acid molecular sieve catalyst can be pure acidic molecular sieve, it is also possible to containing binding agent or other typical additives, such as silicon oxide, aluminium oxide etc. Those skilled in the art can according to the concrete needs produced, type according to reactor and the requirement to catalyst, selecting suitable shaping of catalyst mode, common shaping of catalyst mode has compression forming method, extrusion moulding, rotational forming method, spray drying forming method etc.
Preferably, described acid molecular sieve catalyst contains one or more in Hydrogen MCM-22 molecular sieve, Hydrogen ferrierite, Hydrogen ZSM-5 molecular sieve, h-mordenite, Hydrogen Y zeolite, Hydrogen Beta molecular sieve optional.
As an embodiment of the application, the described preparation method through the acid molecular sieve catalyst of desiliconization modification comprises the steps of
A) molecular sieve is put in the alkaline solution of 0.05～6.0mol/L, under the reaction temperature of 15～95 DEG C, react 0.5～24h;
B) after step a) the gained sample acid solution with 0.01～0.5mol/L and deionized water wash, through ammonium ion exchange, filtration, dry and roasting, the acid molecular sieve catalyst of described desiliconization modification will be obtained.
Preferably, optionally one or more in sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide solution, magnesium hydroxide solution, aqua calcis, sodium carbonate liquor, sodium bicarbonate solution of alkaline solution described in step a); The concentration of step a) neutral and alkali solution preferably ranges for 0.2～1.5mol/L; In step a), reaction temperature preferably ranges for 50～85 DEG C; Optionally one or more in hydrochloric acid solution, salpeter solution, sulfuric acid solution, acetic acid solution of acid solution described in step b).
As the application one preferred embodiment, the described preparation method through the acid molecular sieve catalyst of desiliconization modification comprises the steps of puts into 0.05～6.0mol/L by acidic molecular sieve, the preferably sodium hydroxide of 0.2～1.5mol/L, potassium hydroxide, Lithium hydrate, magnesium hydroxide, calcium hydroxide, in the aqueous solution of one or more in sodium carbonate or sodium bicarbonate, at 15～95 DEG C, preferably reaction 0.5～24h at 50～85 DEG C, filter cake after filtration is selected from hydrochloric acid with 0.01～0.5mol/L's, nitric acid, the solution washing of sulphuric acid or acetic acid is also neutralized to faintly acid, clean with deionized water again and neutralize the saline solution produced, it is then passed through ammonium ion exchange, filter, dry and calcining, obtain the acid molecular sieve catalyst that described desiliconization is modified.
Described in the acidic molecular sieve that Dealumination processes, containing through steam treatment Dealumination method or/and the molecular sieve that obtains of acid treatment Dealumination method.
Preferably, described steam treatment Dealumination method is, is placed in by molecular sieve in the steam that temperature is 400～700 DEG C and processes 1～8h; Described acid treatment Dealumination method is be placed in the acid solution of 0.03～3.0mol/L by molecular sieve, processes 1～24h at 15～95 DEG C.
Preferably, acid solution optionally one or more in hydrochloric acid solution, sulfuric acid solution, salpeter solution, acetum, oxalic acid solution, citric acid solution adopted in described acid treatment Dealumination method.
In general, molecular sieve modifiies through the desiliconization processed with alkali, microporous molecular sieve volume slightly reduces, but mesopore volume increases considerably, framework si-al ratio reduces simultaneously, in catalytic reaction, the diffusivity of reactant and product molecule strengthens, side reaction can be inhibited, and carbon distribution speed can decline, and the ability holding carbon distribution can strengthen. The Dealumination of the acid of molecular sieve process or hydrothermal treatment consists, it is possible to dredging molecular sieve pore passage, silica alumina ratio increases, and steam heat-resisting, resistance to, antiacid ability strengthen, and can show high activity and high stability in catalytic reaction.
Preferably, in described raw material, the molar content of dimethoxym ethane is preferably 20%～100%. Namely reaction raw materials can only have dimethoxym ethane, it is also possible to containing other components except CO.
An embodiment according to the application, described raw material can contain one or more in methanol, hydrogen, nitrogen, helium, argon optional.
Preferably, described reaction temperature preferably 60～150 DEG C, reaction pressure is 0.1～2MPa preferably, the mass space velocity of described raw material preferably 0.5～6.0h-1。
Preferably, one or more in optional self-retaining bed bioreactor, tank reactor, moving-burden bed reactor, fluidized-bed reactor are contained in described reaction zone. An independent reactor can be contained in described reaction zone, it is also possible to containing by connecting or/and the multiple reactors being connected in parallel.
In the application, described acid MFI-type molecular sieve catalyst, refer in catalyst containing structure type be the molecular sieve of MFI, and in molecular sieve containing B-acid or/and L acid; Described acid MWW type molecular sieve catalyst, refers in catalyst containing structure type be the molecular sieve of MWW, and in molecular sieve containing B or/and L acid; Described acid FER type molecular sieve catalyst, refers in catalyst containing structure type be the molecular sieve of FER, and in molecular sieve containing B-acid or/and L acid; Described acid MOR type molecular sieve catalyst, refers in catalyst containing structure type be the molecular sieve of MOR, and in molecular sieve containing B-acid or/and L acid; Described acid FAU type molecular sieve catalyst, refers in catalyst containing structure type be the molecular sieve of FAU, and in molecular sieve containing B-acid or/and L acid; Described acid BEA type molecular sieve catalyst, refers in catalyst containing structure type be the molecular sieve of BEA, and in molecular sieve containing B-acid or/and L acid.
In the application, described hydrogen type molecular sieve catalyst, refer to the catalyst containing hydrogen type molecular sieve. According to general knowledge known in this field, hydrogen type molecular sieve is generally the exchange of molecular sieve through ammonium ion, roasting obtains.
In the application, in units of mol/L, express described alkaline solution or the acid solution of concentration, refer to the amount of substance of all solutes contained in unit volume (1L) solution.
Illustrating separately as non-, the solvent of various solution described herein is water.
Dimethoxym ethane dismutation reaction equation is as follows:
2CH3O-CH2-OCH3=2CH3OCH3+HCOOCH3
This reaction is the endothermic reaction, it does not have the risk of temperature runaway. If reacted product does not occur other to react with the impurity (such as water) in raw material, then mol ratio or the carbon mol ratio of the dimethyl ether produced and methyl formate are 2:1. Raw material dimethoxym ethane produces with formaldehyde catalytic distillation mainly through methanol, and production technology is highly developed, low price, and market demand is little, and therefore supply is easily;And product dimethyl ether is high-quality cleaning fuel, the huge market demand, produce mainly through methanol dehydration, price is slightly more expensive than dimethoxym ethane. If additionally dimethyl ether is sold not as product, it is also possible to being methanol by hydrolysis or oxidation is converted into formaldehyde, and then be converted into dimethoxym ethane, this type of technology is highly developed. This reaction does not produce other by-product, and methyl formate separates easily, it is possible to obtain the methyl formate that purity is higher.
The beneficial effect of the application includes but not limited to:
1) raw material that the present processes adopts is dimethoxym ethane, and the production technology of dimethoxym ethane is highly developed now, it is easy to produced through catalytic rectification process by methanol and formaldehyde. Relative to Methanol Carbonylation methyl formate technique, herein described technical scheme is low to ingredient requirement, it is not necessary to use the raw material that purity is high and quality is high, and with low-cost methanol azeotropic body dimethoxym ethane, by-product dimethoxym ethane etc. for raw material. Relative to Methanol Carbonylation technique, the application need not use carbon monoxide, it is not necessary to the fixed investment that the gas making of somewhat expensive, conversion and gas separate.
2) catalyst used herein is molecular sieve. Relative to the sodium methoxide catalyst used in Methanol Carbonylation technique, the catalyst stability of the application is high, it is not easy to be hydrolyzed or Oxidative inactivation. Molecular sieve catalyst used herein is easy to separate with raw material and product after industry molding, the problem that to be absent from Methanol Carbonylation technique catalyst separation difficult, corrosivity is strong. Additionally molecular sieve catalyst is through desiliconization or dealumination treatment, and conversion ratio improves, and catalyst single pass life extends.
3) in the application, dimethoxym ethane disproportionation products is methyl formate co-production dimethyl ether, it does not have other product generates, and Atom economy is high. Dimethyl ether is huge as cleaning fuel market demand now, and price is more slightly higher than dimethoxym ethane. If additionally dimethyl ether is sold not as product, it is also possible to being methanol by hydrolysis or oxidation is converted into formaldehyde, and then be converted into dimethoxym ethane, this type of technology is highly developed. Therefore the dimethoxym ethane disproportionation methyl formate co-production dimethyl ether technique market economy in the application is worth height.
4) course of reaction of the application is simple, also can obtain the reaction result of excellence under relatively low reaction temperature, relatively low reaction pressure. Dimethoxym ethane disproportionation is the endothermic reaction, is absent from the risk of temperature runaway. Catalyst stabilization, is suitable for large-scale continuous production, the problem overcoming the not easily large-scale production of Methanol Carbonylation technique. The product generated only has methyl formate and dimethyl ether, and therefore product separates to invest and all can reduce with energy consumption, it is easy to obtain the highly purified methyl formate of high price. In a word, the technique fixed investment of dimethoxym ethane disproportionation methyl formate is not high.
5) in the application, dimethoxym ethane disproportionation methyl formate technique is applicable not only to large scale integration and produces, and is also applied for medium-sized and small enterprises scalp small-scale production, and applying flexible is few by region and supporting restriction.
Should be understood that within the scope of herein disclosed technical scheme, above-mentioned each technical characteristic of the application and can combining mutually between specifically described each technical characteristic in below (eg embodiment), thus constituting new or preferred technical scheme. As space is limited, tired no longer one by one state at this.
Unless otherwise defined, the same meaning that all specialties used in literary composition are familiar with one skilled in the art with scientific words. Additionally, any method similar or impartial to described content and material all can be applicable in the application method.The use that preferably implementation described in literary composition and material only present a demonstration.
Detailed description of the invention
Below in conjunction with 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. The experimental technique of unreceipted actual conditions in the following example, generally conventionally condition or according to manufacturer it is proposed that condition.
In embodiments herein, dimethoxym ethane conversion ratio and dimethyl ether and methyl formate selectivity are all based on carbon molal quantity and are calculated:
Dimethoxym ethane conversion ratio=[(in charging dimethoxym ethane carbon molal quantity)-(in discharging dimethoxym ethane carbon molal quantity)] ÷ (in charging dimethoxym ethane carbon molal quantity) × (100%)
Dimethyl ether selectivity=(in discharging dimethyl ether carbon molal quantity) ÷ [(in charging dimethoxym ethane carbon molal quantity)-(in discharging dimethoxym ethane carbon molal quantity)] × (100%)
Methyl formate selectivity=(in discharging methyl formate molal quantity) ÷ [(in charging dimethoxym ethane carbon molal quantity)-(in discharging dimethoxym ethane carbon molal quantity)] × (100%)
Unless otherwise specified, embodiment cationic molecular sieve converts the S.O.P. of hydrogen type molecular sieve to and is: dried for 50g Cation molecule sieve is put into the 0.8MNH of 400ml4NO3In solution, at 80 DEG C, stir 12h, with the distilled water wash of 800ml 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.
Embodiment 1
Utilize S.O.P. to convert Hydrogen MCM-22 molecular sieve in the MCM-22 molecular sieve that 50g sodium form silica alumina ratio is 40:1, be designated as catalyst A, in Table 1.
Embodiment 2
The MCM-22 molecular sieve that 100g sodium form silica alumina ratio is 40:1 is joined in the aqua calcis that 500ml concentration is 1.5mol/L, stirring reaction 10h 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 type molecular sieve to through S.O.P. after drying at 100 DEG C, be designated as catalyst B, in Table 1.
Embodiment 3
The MCM-22 molecular sieve that 100g sodium form silica alumina ratio is 40:1 is passed into steam treatment 4h under 550 DEG C of conditions, then utilizes S.O.P. to change into hydrogen type molecular sieve, be designated as catalyst C, in Table 1.
Embodiment 4
The MCM-22 molecular sieve that 100g sodium form silica alumina ratio is 40:1 is processed 1h under 60 DEG C of conditions in the 0.1mol/L hydrochloric acid solution of 500ml, then utilizes S.O.P. to change into hydrogen type molecular sieve, be designated as catalyst D, in Table 1.
Embodiment 5
Utilize S.O.P. to convert hydrogen type molecular sieve to the ferrierite that 50g sodium form silica alumina ratio is 10:1, be designated as catalyst E, in Table 1.
Embodiment 6
The ferrierite that 100g sodium form silica alumina ratio is 10:1 is joined in the magnesium hydroxide solution that 500ml 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 type molecular sieve to through S.O.P. after drying at 100 DEG C, be designated as catalyst F, in Table 1.
Embodiment 7
The ferrierite that 100g sodium form silica alumina ratio is 10:1 is passed into steam treatment 1h under 700 DEG C of conditions, then utilizes S.O.P. to change into hydrogen type molecular sieve, be designated as catalyst G, in Table 1.
Embodiment 8
The ferrierite that 100g sodium form silica alumina ratio is 10:1 is processed 4h under 80 DEG C of conditions in the 0.4mol/L sulfuric acid solution of 500ml, then utilizes S.O.P. to change into hydrogen type molecular sieve, be designated as catalyst H, in Table 1.
Embodiment 9
Utilize S.O.P. to convert hydrogen type molecular sieve to the ZSM-5 molecular sieve that 50g sodium form silica alumina ratio is 150:1, be designated as catalyst I, in Table 1.
Embodiment 10
The ZSM-5 molecular sieve that 100g sodium form silica alumina ratio is 150:1 is joined in the sodium bicarbonate solution that 500ml 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 type molecular sieve to through S.O.P. after drying at 100 DEG C, be designated as catalyst J, in Table 1.
Embodiment 11
The ZSM-5 molecular sieve that 100g sodium form silica alumina ratio is 150:1 is passed into steam treatment 8h under 400 DEG C of conditions, then utilizes S.O.P. to change into hydrogen type molecular sieve, be designated as catalyst K, in Table 1.
Embodiment 12
The ZSM-5 molecular sieve that 100g sodium form silica alumina ratio is 150:1 is processed 8h under 75 DEG C of conditions in the 1.0mol/L acetum of 500ml, then utilizes S.O.P. to change into hydrogen type molecular sieve, be designated as catalyst L, in Table 1.
Embodiment 13
Utilize S.O.P. to convert hydrogen type molecular sieve to the modenite that 50g sodium form silica alumina ratio is 3:1, be designated as catalyst M, in Table 1.
Embodiment 14
The modenite that 100g sodium form silica alumina ratio is 3:1 is joined in the lithium hydroxide solution that 500ml 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, convert hydrogen type molecular sieve to through S.O.P. after drying at 100 DEG C, be designated as catalyst n, in Table 1.
Embodiment 15
The modenite that 100g sodium form silica alumina ratio is 3:1 is passed into steam treatment 3h under 650 DEG C of conditions, then utilizes S.O.P. to change into hydrogen type molecular sieve, be designated as catalyst O, in Table 1.
Embodiment 16
The modenite that 100g sodium form silica alumina ratio is 3:1 is processed 12h under 60 DEG C of conditions in the 3.0mol/L citric acid solution of 500ml, then utilizes S.O.P. to change into hydrogen type molecular sieve, be designated as catalyst P, in Table 1.
Embodiment 17
Utilize S.O.P. to convert hydrogen type molecular sieve to the Y molecular sieve that 50g sodium form silica alumina ratio is 20:1, be designated as catalyst Q, in Table 1.
Embodiment 18
The Y molecular sieve that 100g sodium form silica alumina ratio is 20:1 is joined in the sodium hydroxide solution that 500ml 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 type molecular sieve to through S.O.P. after drying at 100 DEG C, be designated as catalyst R, in Table 1.
Embodiment 19
The Y molecular sieve that 100g sodium form silica alumina ratio is 20:1 is passed into steam treatment 2h under 500 DEG C of conditions, then utilizes S.O.P. to change into hydrogen type molecular sieve, be designated as catalyst S, in Table 1.
Embodiment 20
The Y molecular sieve that 100g sodium form silica alumina ratio is 20:1 is processed 5h under 95 DEG C of conditions in the 1.5mol/L oxalic acid solution of 500ml, then utilizes S.O.P. to change into hydrogen type molecular sieve, be designated as catalyst T, in Table 1.
Embodiment 21
Utilize S.O.P. to convert hydrogen type molecular sieve in the Beta molecular sieve that 50g sodium form silica alumina ratio is 15:1, be designated as catalyst U, in Table 1.
Embodiment 22
The Beta molecular sieve that 100g sodium form silica alumina ratio is 15:1 is joined sodium carbonate that 500ml 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 type molecular sieve to through S.O.P. after drying at 100 DEG C, be designated as catalyst V, in Table 1.
Embodiment 23
The Beta molecular sieve that 100g sodium form silica alumina ratio is 15:1 is passed into steam treatment 4h under 600 DEG C of conditions, then utilizes S.O.P. to change into hydrogen type molecular sieve, be designated as catalyst W, in Table 1.
Embodiment 24
The Beta molecular sieve that 100g sodium form silica alumina ratio is 15:1 is processed 24h under 15 DEG C of conditions in the 0.03mol/L salpeter solution of 500ml, then utilizes S.O.P. to change into hydrogen type molecular sieve, be designated as catalyst X, in Table 1.
Method for preparing catalyst in table 1 embodiment 1～24
Embodiment 25
By 50g catalyst A pressed powder pellet, it is ground into 20～40 orders, for active testing. Weigh sample 10g, load in the stainless steel reaction pipe that internal diameter is 8.5mm, normal pressure, at 550 DEG C with nitrogen activation 4 hours, then reaction temperature (T)=90 DEG C is dropped to, what pass into raw material mole consists of 100% dimethoxym ethane, reaction pressure (P)=0.1MPa, dimethoxym ethane mass space velocity (WHSV)=3h-1, to use gas chromatographic analysis product, after stable reaction, calculate the conversion ratio of dimethoxym ethane and the selectivity of product, reaction result is in Table 2.
Embodiment 26
Catalyst in embodiment 25 is changed to catalyst B, and all the other experimental procedures are consistent with embodiment 25, and reaction result is in Table 2.
Embodiment 27
Catalyst in embodiment 25 is changed to catalyst C, and all the other experimental procedures are consistent with embodiment 25, and reaction result is in Table 2.
Embodiment 28
Catalyst in embodiment 25 is changed to catalyst D, and all the other experimental procedures are consistent with embodiment 25, and reaction result is in Table 2.
Embodiment 29
Change the catalyst in embodiment 25 into catalyst E, T=150 DEG C, P=2MPa, WHSV=0.5h-1, all the other experimental procedures are consistent with embodiment 25, and reaction result is in Table 2.
Embodiment 30
Changing the catalyst in embodiment 29 into catalyst F, all the other experimental procedures are consistent with embodiment 29, and reaction result is in Table 2.
Embodiment 31
Changing the catalyst in embodiment 29 into catalyst G, all the other experimental procedures are consistent with embodiment 29, and reaction result is in Table 2.
Embodiment 32
Changing the catalyst in embodiment 29 into catalyst H, all the other experimental procedures are consistent with embodiment 29, and reaction result is in Table 2.
Embodiment 33
Changing the catalyst in embodiment 25 into catalyst I, T=60 DEG C, feed molar composition is changed to 20% dimethoxym ethane and 80% nitrogen mixture, P=1MPa, WHSV=0.01h-1, all the other experimental procedures are consistent with embodiment 25, and reaction result is in Table 2.
Embodiment 34
Changing the catalyst in embodiment 33 into catalyst J, all the other experimental procedures are consistent with embodiment 33, and reaction result is in Table 2.
Embodiment 35
Changing the catalyst in embodiment 33 into catalyst K, all the other experimental procedures are consistent with embodiment 33, and reaction result is in Table 2.
Embodiment 36
Changing the catalyst in embodiment 33 into catalyst L, all the other experimental procedures are consistent with embodiment 33, and reaction result is in Table 2.
Embodiment 37
Changing the catalyst in embodiment 25 into catalyst M, T=200 DEG C, feed molar composition is changed to 10% dimethoxym ethane and 90% ar mixture, P=10MPa, WHSV=15h-1, all the other experimental procedures are consistent with embodiment 25, and reaction result is in Table 2.
Embodiment 38
Changing the catalyst in embodiment 37 into catalyst n, all the other experimental procedures are consistent with embodiment 37, and reaction result is in Table 2.
Embodiment 39
Changing the catalyst in embodiment 37 into catalyst O, all the other experimental procedures are consistent with embodiment 37, and reaction result is in Table 2.
Embodiment 40
Changing the catalyst in embodiment 37 into catalyst P, all the other experimental procedures are consistent with embodiment 37, and reaction result is in Table 2.
Embodiment 41
Changing the catalyst in embodiment 25 into catalyst Q, T=50 DEG C, feed molar composition is changed to 70% dimethoxym ethane, 20% hydrogen and 10% helium mix thing, P=5MPa, WHSV=6h-1, all the other experimental procedures are consistent with embodiment 25, and reaction result is in Table 2.
Embodiment 42
Changing the catalyst in embodiment 41 into catalyst R, all the other experimental procedures are consistent with embodiment 41, and reaction result is in Table 2.
Embodiment 43
Changing the catalyst in embodiment 41 into catalyst S, all the other experimental procedures are consistent with embodiment 41, and reaction result is in Table 2.
Embodiment 44
Changing the catalyst in embodiment 41 into catalyst T, all the other experimental procedures are consistent with embodiment 41, and reaction result is in Table 2.
Embodiment 45
Changing the catalyst in embodiment 25 into catalyst U, T=120 DEG C, feed molar composition is changed to 90% dimethoxym ethane and 10% carbinol mixture, P=0.5MPa, WHSV=1.5h-1, all the other experimental procedures are consistent with embodiment 25, and reaction result is in Table 2.
Embodiment 46
Changing the catalyst in embodiment 45 into catalyst V, all the other experimental procedures are consistent with embodiment 45, and reaction result is in Table 2.
Embodiment 47
Changing the catalyst in embodiment 45 into catalyst W, all the other experimental procedures are consistent with embodiment 45, and reaction result is in Table 2.
Embodiment 48
Changing the catalyst in embodiment 45 into catalyst X, all the other experimental procedures are consistent with embodiment 45, and reaction result is in Table 2.
The catalytic reaction result of table 2 embodiment 25～48
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 method preparing methyl formate co-production dimethyl ether by dimethoxym ethane dismutation reaction, it is characterized in that, by the raw material containing dimethoxym ethane by being loaded with the reaction zone of acid molecular sieve catalyst, in reaction temperature 50～200 DEG C, reaction pressure 0.1～10MPa, raw material, dimethoxym ethane mass space velocity is 0.01～15.0h-1When reaction prepare product formic acid methyl ester and dimethyl ether; Described raw material and product can independently be gas phase or/and liquid phase.
2. method according to claim 1, it is characterized in that, described acid molecular sieve catalyst optional from acid MFI-type molecular sieve catalyst, acid MWW type molecular sieve catalyst, acid FER type molecular sieve catalyst, acid MOR type molecular sieve catalyst, acid FAU type molecular sieve catalyst, acid BEA type molecular sieve catalyst one or more;Preferably, in described raw material, the molar content of dimethoxym ethane is 20%～100%; Preferably, containing one or more in methanol, hydrogen, nitrogen, helium, argon optional in described raw material; Preferably, described reaction temperature is 60～150 DEG C, and reaction pressure is 0.1～2MPa, and in raw material, the mass space velocity of dimethoxym ethane is 0.5～6.0h-1; Preferably, one or more in optional self-retaining bed bioreactor, tank reactor, moving-burden bed reactor, fluidized-bed reactor are contained in reaction zone.
3. method according to claim 1, it is characterized in that, described acid molecular sieve catalyst contains one or more in Hydrogen MCM-22 molecular sieve, Hydrogen ferrierite, Hydrogen ZSM-5 molecular sieve, h-mordenite, Hydrogen Y zeolite, Hydrogen Beta molecular sieve optional.
4. the method according to any one of claim 1-3, it is characterized in that, described acid molecular sieve catalyst is optional from the acid molecular sieve catalyst without modification, the acid molecular sieve catalyst through desiliconization modification, one or more in the acid molecular sieve catalyst that Dealumination processes.
5. method according to claim 4, it is characterised in that the described preparation method through the acid molecular sieve catalyst of desiliconization modification comprises the steps of
A) molecular sieve is put in the alkaline solution of 0.05～6.0mol/L, under the reaction temperature of 15～95 DEG C, react 0.5～24h;
B) after step a) the gained sample acid solution with 0.01～0.5mol/L and deionized water wash, through ammonium ion exchange, filtration, dry and roasting, the acid molecular sieve catalyst of described desiliconization modification will be obtained.
6. method according to claim 5, it is characterized in that, alkaline solution described in step a) is one or more in sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide solution, magnesium hydroxide solution, aqua calcis, sodium carbonate liquor, sodium bicarbonate solution optionally; Optionally one or more in hydrochloric acid solution, salpeter solution, sulfuric acid solution, acetic acid solution of acid solution described in step b).
7. method according to claim 5, it is characterised in that the concentration of step a) neutral and alkali solution is 0.2～1.5mol/L; In step a), reaction temperature is 50～85 DEG C.
8. method according to claim 4, it is characterised in that described in the acid molecular sieve catalyst that Dealumination processes, containing through steam treatment Dealumination method or/and the molecular sieve that obtains of acid treatment Dealumination method.
9. method according to claim 8, it is characterised in that described steam treatment Dealumination method is, is placed in molecular sieve in the steam that temperature is 400～700 DEG C and processes 1～8h; Described acid treatment Dealumination method is be placed in the acid solution of 0.03～3.0mol/L by molecular sieve, processes 1～24h at 15～95 DEG C.
10. method according to claim 9, it is characterised in that acid solution optionally one or more in hydrochloric acid solution, sulfuric acid solution, salpeter solution, acetum, oxalic acid solution, citric acid solution adopted in described acid treatment Dealumination method.
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| CN109835915A (en) * | 2017-11-28 | 2019-06-04 | 中国科学院大连化学物理研究所 | A method of preparing rich aluminium multistage porous molecular sieve |
| CN111514926A (en) * | 2019-02-02 | 2020-08-11 | 中国科学院大连化学物理研究所 | Molecular sieve catalyst, and preparation method and application thereof |
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| CN109835915A (en) * | 2017-11-28 | 2019-06-04 | 中国科学院大连化学物理研究所 | A method of preparing rich aluminium multistage porous molecular sieve |
| CN111514926A (en) * | 2019-02-02 | 2020-08-11 | 中国科学院大连化学物理研究所 | Molecular sieve catalyst, and preparation method and application thereof |
| CN111514926B (en) * | 2019-02-02 | 2021-06-08 | 中国科学院大连化学物理研究所 | Molecular sieve catalyst, and preparation method and application thereof |
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