CN105669453B - A kind of method for preparing methyl formate co-production dimethyl ether - Google Patents
A kind of method for preparing methyl formate co-production dimethyl ether Download PDFInfo
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Abstract
The application provides a kind of method for preparing methyl formate co-production dimethyl ether, including by being loaded with the reactor generation disproportionated reaction of acid molecular sieve catalyst prepared by the raw material containing dimethoxym ethane into methyl formate co-production dimethyl ether.The purity requirement of raw material dimethoxym ethane is not high in the application method, and catalyst life length, reaction condition is gentle, and Atom economy is high, can continuous production, possess heavy industrialization application potential.
Description
Technical field
The application is related to a kind of preparation method of methyl formate.
Background technology
In C1In chemistry, after methane chemical, syngas chemistry and methanol chemistry, methyl formate due to can economy have
The reasons such as effect ground mass produces, downstream product is more, have been developing progressively as a new C in recent years1The starting of chemicals is former
Material and construction unit.From methyl formate, formic acid, acetic acid, ethylene glycol, methyl propionate, methyl acrylate, ethanol can be prepared
Numerous C such as sour methyl esters, N- N-formyl morpholine Ns, N-METHYLFORMAMIDE, N,N-dimethylformamide1Chemical products.
At present, the technology for synthesizing methyl formate has：Methanol Carbonylation method, methanol oxidation dehydriding, methanol oxydehydro process, two
Carbonoxide is hydrogenated with condensation method, synthesis gas direct synthesis technique etc. with methanol.Wherein Methanol Carbonylation is current industrial production first both at home and abroad
The main method of sour methyl esters.The process catalyst used catalyst is generally sodium methoxide, meets water facile hydrolysis and generates undissolved first
Sour sodium and pollute and block, and the separation of catalyst is more difficult, therefore the technique is in material benzenemethanol and carbon monoxide
The impurity such as water, carbon dioxide, oxygen are very sensitive, and material purity requires very harsh.In view of the foregoing, the process route list
It is general all in 100,000 tons/year to cover production scale, it is more difficult to form scale effect.The other technique is needed by gas making, water-gas
The process such as conversion and pressure-variable adsorption can just obtain carbon monoxide, and investment is very high, be unfavorable for medium-sized and small enterprises use.
The content of the invention
The purpose of the application is to provide a kind of method for preparing methyl formate co-production dimethyl ether.
Therefore, this application provides a kind of method that disproportionated reaction by dimethoxym ethane prepares methyl formate, its feature exists
In dimethoxym ethane CH will be contained3O-CH2-OCH3Raw material by being loaded with the reaction zone of acid molecular sieve catalyst, in reaction temperature
50~200 DEG C, 0.1~10MPa of reaction pressure, dimethoxym ethane mass space velocity be 0.01~15.0h-1Under conditions of reaction prepare product
Methyl formate co-production dimethyl ether, wherein the acid molecular sieve catalyst is solid phase, raw material and product can independently be gas
Phase or/and liquid phase.
Preferably, the acid molecular sieve catalyst is optionally from acid MFI-type molecular sieve catalyst, acid MWW types molecule
Sieve catalyst, acid FER types molecular sieve catalyst, acid MOR types molecular sieve catalyst, acid FAU types molecular sieve catalyst, acid
The one or more of property BEA type molecular sieve catalysts.
Preferably, the acid molecular sieve catalyst is optionally from the acid molecular sieve catalyst without modification, warp
Cross desiliconization modification acid molecular sieve catalyst, by Dealumination handle acid molecular sieve catalyst in one kind or
It is several.
Preferably, the untreated acid molecular sieve catalyst silica alumina ratio is 3:1~150:1.
Preferably, the molecular sieve contained in the acid molecular sieve catalyst, crystal yardstick are micron-scale and/or nanometer
Size.
Preferably, the molecular sieve contained in the acid molecular sieve catalyst has multi-stage artery structure；Further preferably
Ground, there is microcellular structure and/or microporous mesoporous composite construction.
As the embodiment of the application, the acid molecular sieve catalyst can be pure acidic molecular sieve, also may be used
To contain binding agent or other typical additives, such as silica, aluminum oxide.Those skilled in the art can be according to specific raw
The needs of production, the type according to reactor and the requirement to catalyst, select suitable shaping of catalyst mode, common catalysis
Agent molding mode has compression forming methods, extrusion moulding, rotational forming method, spray drying forming method etc..
Preferably, the acid molecular sieve catalyst contains optionally from Hydrogen MCM-22 molecular sieves, Hydrogen ferrierite, hydrogen
One or more in type ZSM-5 molecular sieve, h-mordenite, Hydrogen Y zeolites, Hydrogen Beta molecular sieves.
As the embodiment of the application, the preparation of the acid molecular sieve catalyst by desiliconization modification
Method comprises the steps of：
A) molecular sieve is put into 0.05~6.0mol/L alkaline solution, reacted under 15~95 DEG C of reaction temperature
0.5~24h；
B) after sample obtained by step a) is washed with 0.01~0.5mol/L acid solution and deionized water, by ammonium from
Son is exchanged, filtered, drying and roasting, obtains the acid molecular sieve catalyst of the desiliconization modification.
Preferably, alkaline solution is optionally molten from sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide described in step a)
One or more in liquid, magnesium hydroxide solution, aqua calcis, sodium carbonate liquor, sodium bicarbonate solution；Alkali in step a)
The preferable scope of concentration of property solution is 0.2~1.5mol/L；The preferable scope of reaction temperature is 50~85 DEG C in step a)；Step
It is rapid b) described in acid solution optionally from the one or more in hydrochloric acid solution, salpeter solution, sulfuric acid solution, acetic acid solution.
As one preferred embodiment of the application, the acid molecular sieve catalyst by desiliconization modification
Preparation method comprises the steps of：Acidic molecular sieve is put into 0.05~6.0mol/L, preferably 0.2~1.5mol/L hydroxide
One or more of aqueous solution in sodium, potassium hydroxide, lithium hydroxide, magnesium hydroxide, calcium hydroxide, sodium carbonate or sodium acid carbonate
In, at 15~95 DEG C, 0.5~24h is reacted at preferably 50~85 DEG C, the filter cake after filtering is selected from salt with 0.01~0.5mol/L
Acid, nitric acid, the aqueous solution of sulfuric acid or acetic acid wash and are neutralized to faintly acid, then that salt caused by net neutralize is washed with deionized water is molten
Liquid, then exchange, filter by ammonium ion, drying and calcination, obtaining the acid molecular sieve catalyst that the desiliconization is modified.
It is described by Dealumination handle acidic molecular sieve in, containing by steam treatment Dealumination method or/
The molecular sieve obtained with acid treatment Dealumination method.
Preferably, the steam treatment Dealumination method is that molecular sieve is placed in into the water that temperature is 400~700 DEG C
1~8h is handled in steam；The acid treatment Dealumination method is that molecular sieve is placed in 0.03~3.0mol/L acid solution
In, 1~24h is handled at 15~95 DEG C.
Preferably, the acid solution used in the acid treatment Dealumination method is optionally from hydrochloric acid solution, sulfuric acid solution, nitre
One or more in acid solution, acetum, oxalic acid solution, citric acid solution.
In general, molecular sieve passes through is modified with the desiliconization of alkali process, and microporous molecular sieve volume slightly reduces, but mesoporous body
Product increases considerably, while framework si-al ratio reduces, in catalytic reaction, the diffusivity enhancing of reactant and product molecule,
Side reaction can be inhibited, and carbon distribution speed can decline, and accommodate the ability of carbon distribution and can strengthen.Molecular sieve passes through with acid or hydro-thermal process
Dealumination, can dredge molecular sieve pore passage, silica alumina ratio increase, heat-resisting, resistance to vapor, the enhancing of antiacid ability, be catalyzed
High activity and high stability can be shown in reaction.
Preferably, the molar content of dimethoxym ethane is preferably 20%~100% in the raw material.Can be only i.e. in reaction raw materials
There is dimethoxym ethane, the other components in addition to CO can also be contained.
According to the application embodiment, the raw material can contain optionally from methanol, hydrogen, nitrogen, helium, argon
One or more in gas.
Preferably, preferably 60~150 DEG C of the reaction temperature, reaction pressure preferably 0.1~2MPa, the quality of the raw material
Air speed preferably 0.5~6.0h-1。
Preferably, the reaction zone contains optional self-retaining bed reactor, tank reactor, moving-burden bed reactor, fluidisation
One or more in bed reactor.The reaction zone can contain a single reactor, can also contain and pass through series connection
Or/and the multiple reactors being connected in parallel.
In the application, the acid MFI-type molecular sieve catalyst, refer in catalyst containing the molecule that structure type is MFI
Sieve, and contain B acid or/and L acid in molecular sieve；The acid MWW types molecular sieve catalyst, refers to and contains structure type in catalyst
For MWW molecular sieve, and contain B or/and L acid in molecular sieve；The acid FER types molecular sieve catalyst, refers in catalyst and contains
There is the molecular sieve that structure type is FER, and contain B acid or/and L acid in molecular sieve；The acid MOR types molecular sieve catalyst,
Refer to containing the molecular sieve that structure type is MOR in catalyst, and contain B acid or/and L acid in molecular sieve；The acid FAU types point
Sub- sieve catalyst, refer to containing the molecular sieve that structure type is FAU in catalyst, and contain B acid or/and L acid in molecular sieve；It is described
Acid BEA types molecular sieve catalyst, refer to containing the molecular sieve that structure type is BEA in catalyst, and contain B acid in molecular sieve
Or/and L acid.
In the application, the hydrogen type molecular sieve catalyst, refer to the catalyst containing hydrogen type molecular sieve.It is public according to this area
Know general knowledge, hydrogen type molecular sieve is usually that molecular sieve through ammonium ion exchange, roasting obtain.
In the application, the alkaline solution or acid solution of concentration are expressed in units of mol/L, it is molten to refer to unit volume (1L)
The amount of the material of all solutes contained in liquid.
Separately illustrate Ru non-, the solvent of various solution described herein is water.
Dimethoxym ethane disproportionated reaction equation is as follows：
2 CH3O-CH2-OCH3=2 CH3OCH3+HCOOCH3
The reaction is the endothermic reaction, without the risk of temperature runaway.If reacted product not with the impurity in raw material (such as
Water) other reactions occur, then the dimethyl ether and the mol ratio of methyl formate produced or carbon mol ratio are 2:1.Raw material dimethoxym ethane
Mainly produced by methanol and formaldehyde catalytic distillation, production technology is highly developed, cheap, and market demand is little, therefore
Supply is easy；And product dimethyl ether is high-quality clean fuel, the huge market demand, mainly produced by methanol dehydration, price ratio
Dimethoxym ethane is slightly expensive.Can also be that methanol or oxidation convert by hydrolysis if other dimethyl ether is sold not as product
For formaldehyde, and then dimethoxym ethane is converted into, such technology is highly developed.The reaction does not produce other accessory substances, formic acid first
Ester separation is easy, can obtain the higher methyl formate of purity.
The beneficial effect of the application includes but is not limited to：
1) raw material is dimethoxym ethane used by the present processes, and the production technology of dimethoxym ethane is highly developed now,
It is easy to be produced by catalytic rectification process by methanol and formaldehyde.Relative to Methanol Carbonylation methyl formate technique, the application institute
It is low to ingredient requirement to state technical scheme, it is not necessary to using purity height and the high raw material of quality, and with cheap methanol azeotropic
Body dimethoxym ethane, by-product dimethoxym ethane etc. are raw material.Relative to Methanol Carbonylation technique, the application need not use carbon monoxide, be not required to
The fixed investment for wanting the gas making, conversion and gas of somewhat expensive to 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 is hydrolyzed or Oxidative inactivation.Molecular sieve catalyst warp used herein
It is easy to separate with raw material and product after crossing industry shaping, it is strong to separate hardly possible, corrosivity in the absence of catalyst in Methanol Carbonylation technique
The problem of.Other molecular sieve catalyst passes through desiliconization or dealumination treatment, and conversion ratio improves, and catalyst single pass life extends.
3) dimethoxym ethane disproportionation products are methyl formate co-production dimethyl ether in the application, are generated without other products, former
Subeconomy is high.Dimethyl ether is huge as clean fuel market demand now, and price is more slightly higher than dimethoxym ethane.Other dimethyl ether is such as
Fruit is sold not as product, can also be that methanol or oxidation are converted into formaldehyde by hydrolysis, and then is converted into dimethoxym ethane,
Such technology is highly developed.Therefore the dimethoxym ethane in the application is disproportionated methyl formate co-production dimethyl ether technique market warp processed
Ji value is high.
4) course of reaction of the application is simple, can also be obtained under relatively low reaction temperature, relatively low reaction pressure excellent
Reaction result.Dimethoxym ethane disproportionation is the endothermic reaction, in the absence of the risk of temperature runaway.Catalyst stabilization, it is adapted to extensive continuous raw
Production, overcomes the problem of Methanol Carbonylation technique is not easy large-scale production.The product of generation only has methyl formate and dimethyl ether, because
This product separation investment and energy consumption can all reduce, and be readily obtained the methyl formate of high price high-purity.In a word, dimethoxym ethane disproportionation system
Methyl formate technique fixed investment is not high.
5) dimethoxym ethane is disproportionated methyl formate technique processed and is applicable not only to large scale integration production in the application, is also applied for
Medium-sized and small enterprises scalp small-scale production is few by region and supporting limitation using flexible.
It should be understood that in the range of the herein disclosed technical scheme, above-mentioned each technical characteristic of the application and below
It can be combined with each other between each technical characteristic specifically described in (such as embodiment), so as to form new or preferable technical side
Case.As space is limited, no longer tire out one by one herein and state.
Unless otherwise defined, anticipated known to all specialties used in text and scientific words and one skilled in the art
Justice is identical.In addition, any method similar or impartial to described content and material all can be applied in the application method.Wen Zhong
Described preferable implementation only presents a demonstration with material to be used.
Embodiment
With reference to embodiment, the application is expanded on further.It should be understood that these embodiments be merely to illustrate the application without
For limiting scope of the present application.The experimental method of unreceipted actual conditions in the following example, generally according to normal condition or
According to the condition proposed by manufacturer.
In embodiments herein, dimethoxym ethane conversion ratio and dimethyl ether and methyl formate are selectively all based on carbon mole
Number is calculated:
(the charging of dimethoxym ethane conversion ratio=[(dimethoxym ethane carbon molal quantity in charging)-(dimethoxym ethane carbon molal quantity in discharging)] ÷
Middle dimethoxym ethane carbon molal quantity) × (100%)
[(dimethoxym ethane carbon molal quantity in the charging)-(discharging of dimethyl ether selectivity=(dimethyl ether carbon molal quantity in discharging) ÷
Middle dimethoxym ethane carbon molal quantity)] × (100%)
Methyl formate selectivity=and (methyl formate molal quantity in discharging) ÷ [(dimethoxym ethane carbon molal quantity in charging)-(go out
Dimethoxym ethane carbon molal quantity in material)] × (100%)
Unless otherwise specified, the S.O.P. that embodiment cationic molecular sieve is converted into hydrogen type molecular sieve is：
The dried Cation molecule sieves of 50g are put into 400ml 0.8M NH4NO3In solution, 12h is stirred at 80 DEG C, after filtering
With 800ml distillation water washing.This ion exchange process obtains NH in triplicate4 +The molecular sieve of type.After fully drying, put
In Muffle furnace, it is increased to 550 DEG C with 2 DEG C/min and keeps calcining 4h to obtain hydrogen type molecular sieve.
Embodiment 1
It is 40 by 50g sodium form silica alumina ratio:1 MCM-22 molecular sieves are converted into MCM-22 points of Hydrogen using S.O.P.
Son sieve, is designated as catalyst A, is shown in Table 1.
Embodiment 2
It is 40 by 100g sodium form silica alumina ratio:1 MCM-22 molecular sieves are added to the hydroxide that 500ml concentration is 1.5mol/L
In calcium solution, the stirring reaction 10h at 75 DEG C, after filtering, it is 6 that filter cake washs pH with 0.08ml/L salpeter solution, filtering
Washed repeatedly to neutrality with deionized water afterwards, hydrogen type molecular sieve is converted into by S.O.P. after being dried at 100 DEG C, remembered
For catalyst B, 1 is shown in Table.
Embodiment 3
It is 40 by 100g sodium form silica alumina ratio:1 MCM-22 molecular sieves are passed through steam treatment 4h under the conditions of 550 DEG C, so
Hydrogen type molecular sieve is changed into using S.O.P. afterwards, catalyst C is designated as, is shown in Table 1.
Embodiment 4
It is 40 by 100g sodium form silica alumina ratio:1 MCM-22 molecular sieves 500ml 0.1mol/L hydrochloric acid under the conditions of 60 DEG C is molten
1h is handled in liquid, then changes into hydrogen type molecular sieve using S.O.P., catalyst D is designated as, is shown in Table 1.
Embodiment 5
It is 10 by 50g sodium form silica alumina ratio:1 ferrierite is converted into hydrogen type molecular sieve using S.O.P., is designated as
Catalyst E, is shown in Table 1.
Embodiment 6
It is 10 by 100g sodium form silica alumina ratio:It is molten that 1 ferrierite is added to the magnesium hydroxide that 500ml concentration is 0.2mol/L
In liquid, the stirring reaction 24h at 50 DEG C, after filtering, it is 6 that filter cake washs pH with 0.1ml/L hydrochloric acid solution, is spent after filtering
Ionized water washs to neutrality repeatedly, is converted into hydrogen type molecular sieve by S.O.P. after being dried at 100 DEG C, is designated as being catalyzed
Agent F, is shown in Table 1.
Embodiment 7
It is 10 by 100g sodium form silica alumina ratio:1 ferrierite is passed through steam treatment 1h, Ran Houli under the conditions of 700 DEG C
Hydrogen type molecular sieve is changed into S.O.P., catalyst G is designated as, is shown in Table 1.
Embodiment 8
It is 10 by 100g sodium form silica alumina ratio:1 ferrierite is under the conditions of 80 DEG C in 500ml 0.4mol/L sulfuric acid solutions
4h is handled, then hydrogen type molecular sieve is changed into using S.O.P., is designated as catalyst H, is shown in Table 1.
Embodiment 9
It is 150 by 50g sodium form silica alumina ratio:1 ZSM-5 molecular sieve is converted into hydrogen type molecular sieve using S.O.P.,
Catalyst I is designated as, is shown in Table 1.
Embodiment 10
It is 150 by 100g sodium form silica alumina ratio:1 ZSM-5 molecular sieve is added to the bicarbonate that 500ml concentration is 6.0mol/L
In sodium solution, the stirring reaction 12h at 85 DEG C, after filtering, it is 6 that filter cake washs pH with 0.2ml/L hydrochloric acid solution, after filtering
Washed repeatedly to neutrality with deionized water, be converted into hydrogen type molecular sieve by S.O.P. after being dried at 100 DEG C, be designated as
Catalyst J, is shown in Table 1.
Embodiment 11
It is 150 by 100g sodium form silica alumina ratio:1 ZSM-5 molecular sieve is passed through steam treatment 8h under the conditions of 400 DEG C, so
Hydrogen type molecular sieve is changed into using S.O.P. afterwards, catalyst K is designated as, is shown in Table 1.
Embodiment 12
It is 150 by 100g sodium form silica alumina ratio:1 ZSM-5 molecular sieve 500ml 1.0mol/L acetic acid under the conditions of 75 DEG C is molten
8h is handled in liquid, then changes into hydrogen type molecular sieve using S.O.P., catalyst L is designated as, is shown in Table 1.
Embodiment 13
It is 3 by 50g sodium form silica alumina ratio:1 modenite is converted into hydrogen type molecular sieve using S.O.P., is designated as urging
Agent M, is shown in Table 1.
Embodiment 14
It is 3 by 100g sodium form silica alumina ratio:It is molten that 1 modenite is added to the lithium hydroxide that 500ml concentration is 1.0mol/L
In liquid, the stirring reaction 0.5h at 95 DEG C, after filtering, it is 6 that filter cake washs pH with 0.5ml/L acetum, is used after filtering
Deionized water is washed to neutrality repeatedly, is converted into hydrogen type molecular sieve by S.O.P. after being dried at 100 DEG C, is designated as urging
Agent N, is shown in Table 1.
Embodiment 15
It is 3 by 100g sodium form silica alumina ratio:1 modenite is passed through steam treatment 3h under the conditions of 650 DEG C, then utilizes
S.O.P. changes into hydrogen type molecular sieve, is designated as catalyst O, is shown in Table 1.
Embodiment 16
It is 3 by 100g sodium form silica alumina ratio:1 modenite 500ml under the conditions of 60 DEG C 3.0mol/L citric acid solutions
Middle processing 12h, then changes into hydrogen type molecular sieve using S.O.P., is designated as catalyst P, is shown in Table 1.
Embodiment 17
It is 20 by 50g sodium form silica alumina ratio:1 Y molecular sieve is converted into hydrogen type molecular sieve using S.O.P., is designated as urging
Agent Q, is shown in Table 1.
Embodiment 18
It is 20 by 100g sodium form silica alumina ratio:It is molten that 1 Y molecular sieve is added to the sodium hydroxide that 500ml concentration is 0.5mol/L
In liquid, the stirring reaction 4h at 80 DEG C, after filtering, it is 6 that filter cake washs pH with 0.1ml/L salpeter solution, is spent after filtering
Ionized water washs to neutrality repeatedly, is converted into hydrogen type molecular sieve by S.O.P. after being dried at 100 DEG C, is designated as being catalyzed
Agent R, is shown in Table 1.
Embodiment 19
It is 20 by 100g sodium form silica alumina ratio:1 Y molecular sieve is passed through steam treatment 2h under the conditions of 500 DEG C, then utilizes
S.O.P. changes into hydrogen type molecular sieve, is designated as catalyst S, is shown in Table 1.
Embodiment 20
It is 20 by 100g sodium form silica alumina ratio:1 Y molecular sieve is under the conditions of 95 DEG C in 500ml 1.5mol/L oxalic acid solutions
5h is handled, then hydrogen type molecular sieve is changed into using S.O.P., is designated as catalyst T, is shown in Table 1.
Embodiment 21
It is 15 by 50g sodium form silica alumina ratio:1 Beta molecular sieves are converted into hydrogen type molecular sieve using S.O.P., note
For catalyst U, 1 is shown in Table.
Embodiment 22
It is 15 by 100g sodium form silica alumina ratio:1 Beta molecular sieves be added to 500ml concentration be 3.5mol/L sodium carbonate with
In 0.05mol/L potassium hydroxide mixed solution, the stirring reaction 12h at 15 DEG C, after filtering, filter cake 0.01ml/L sulfuric acid
Solution washing is 6 to pH, is washed repeatedly to neutrality with deionized water after filtering, by standard operation journey after being dried at 100 DEG C
Sequence is converted into hydrogen type molecular sieve, is designated as catalyst V, is shown in Table 1.
Embodiment 23
It is 15 by 100g sodium form silica alumina ratio:1 Beta molecular sieves are passed through steam treatment 4h under the conditions of 600 DEG C, then
Hydrogen type molecular sieve is changed into using S.O.P., catalyst W is designated as, is shown in Table 1.
Embodiment 24
It is 15 by 100g sodium form silica alumina ratio:1 Beta molecular sieves 500ml 0.03mol/L nitric acid under the conditions of 15 DEG C is molten
24h is handled in liquid, then changes into hydrogen type molecular sieve using S.O.P., catalyst X is designated as, is shown in Table 1.
Method for preparing catalyst in the embodiment 1~24 of table 1
Embodiment 25
By 50g catalyst A pressed powder pellets, 20~40 mesh are ground into, for active testing.Sample 10g is weighed, is loaded
Internal diameter is in 8.5mm stainless steel reaction pipe, nitrogen activation is used at normal pressure, 550 DEG C 4 hours, then drops to reaction temperature (T)
=90 DEG C, mole composition for being passed through raw material is 100% dimethoxym ethane, reaction pressure (P)=0.1MPa, dimethoxym ethane mass space velocity
(WHSV)=3h-1, with gas chromatographic analysis product, after stable reaction, the conversion ratio of dimethoxym ethane and the selectivity of product are calculated, instead
2 should be the results are shown in Table.
Embodiment 26
Catalyst in embodiment 25 is changed to catalyst B, remaining experimental procedure is consistent with embodiment 25, and reaction result is shown in
Table 2.
Embodiment 27
Catalyst in embodiment 25 is changed to catalyst C, remaining experimental procedure is consistent with embodiment 25, and reaction result is shown in
Table 2.
Embodiment 28
Catalyst in embodiment 25 is changed to catalyst D, remaining experimental procedure is consistent with embodiment 25, and reaction result is shown in
Table 2.
Embodiment 29
Change the catalyst in embodiment 25 into catalyst E, T=150 DEG C, P=2MPa, WHSV=0.5h-1, remaining experiment
Step is consistent with embodiment 25, and reaction result is shown in Table 2.
Embodiment 30
Change the catalyst in embodiment 29 into catalyst F, remaining experimental procedure is consistent with embodiment 29, and reaction result is shown in
Table 2.
Embodiment 31
Change the catalyst in embodiment 29 into catalyst G, remaining experimental procedure is consistent with embodiment 29, and reaction result is shown in
Table 2.
Embodiment 32
Change the catalyst in embodiment 29 into catalyst H, remaining experimental procedure is consistent with embodiment 29, and reaction result is shown in
Table 2.
Embodiment 33
Change the catalyst in embodiment 25 into catalyst I, T=60 DEG C, feed molar composition be changed to 20% dimethoxym ethane and
80% nitrogen mixture, P=1MPa, WHSV=0.01h-1, remaining experimental procedure is consistent with embodiment 25, and reaction result is shown in Table 2.
Embodiment 34
Change the catalyst in embodiment 33 into catalyst J, remaining experimental procedure is consistent with embodiment 33, and reaction result is shown in
Table 2.
Embodiment 35
Change the catalyst in embodiment 33 into catalyst K, remaining experimental procedure is consistent with embodiment 33, and reaction result is shown in
Table 2.
Embodiment 36
Change the catalyst in embodiment 33 into catalyst L, remaining experimental procedure is consistent with embodiment 33, and reaction result is shown in
Table 2.
Embodiment 37
Change the catalyst in embodiment 25 into catalyst M, T=200 DEG C, feed molar composition be changed to 10% dimethoxym ethane and
90% ar mixture, P=10MPa, WHSV=15h-1, remaining experimental procedure is consistent with embodiment 25, and reaction result is shown in Table 2.
Embodiment 38
Change the catalyst in embodiment 37 into catalyst n, remaining experimental procedure is consistent with embodiment 37, and reaction result is shown in
Table 2.
Embodiment 39
Change the catalyst in embodiment 37 into catalyst O, remaining experimental procedure is consistent with embodiment 37, and reaction result is shown in
Table 2.
Embodiment 40
Change the catalyst in embodiment 37 into catalyst P, remaining experimental procedure is consistent with embodiment 37, and reaction result is shown in
Table 2.
Embodiment 41
Change the catalyst in embodiment 25 into catalyst Q, T=50 DEG C, feed molar composition be changed to 70% dimethoxym ethane,
20% hydrogen and 10% helium mixture, P=5MPa, WHSV=6h-1, remaining experimental procedure is consistent with embodiment 25, reaction knot
Fruit is shown in Table 2.
Embodiment 42
Change the catalyst in embodiment 41 into catalyst R, remaining experimental procedure is consistent with embodiment 41, and reaction result is shown in
Table 2.
Embodiment 43
Change the catalyst in embodiment 41 into catalyst S, remaining experimental procedure is consistent with embodiment 41, and reaction result is shown in
Table 2.
Embodiment 44
Change the catalyst in embodiment 41 into catalyst T, remaining experimental procedure is consistent with embodiment 41, and reaction result is shown in
Table 2.
Embodiment 45
Change the catalyst in embodiment 25 into catalyst U, T=120 DEG C, feed molar composition be changed to 90% dimethoxym ethane and
10% carbinol mixture, P=0.5MPa, WHSV=1.5h-1, remaining experimental procedure is consistent with embodiment 25, and reaction result is shown in Table
2。
Embodiment 46
Change the catalyst in embodiment 45 into catalyst V, remaining experimental procedure is consistent with embodiment 45, and reaction result is shown in
Table 2.
Embodiment 47
Change the catalyst in embodiment 45 into catalyst W, remaining experimental procedure is consistent with embodiment 45, and reaction result is shown in
Table 2.
Embodiment 48
Change the catalyst in embodiment 45 into catalyst X, remaining experimental procedure is consistent with embodiment 45, and reaction result is shown in
Table 2.
The catalytic reaction result of the embodiment 25~48 of table 2
It is described above, only it is several embodiments of the application, any type of limitation is not done to the application, although this Shen
Please with preferred embodiment disclose as above, but and be not used to limit the application, any person skilled in the art, do not taking off
In the range of technical scheme, make a little variation using the technology contents of the disclosure above or modification is equal to
Case study on implementation is imitated, is belonged in the range of technical scheme.
Claims (9)
- A kind of 1. method that methyl formate co-production dimethyl ether is prepared by dimethoxym ethane disproportionated reaction, it is characterised in that will contain The raw material of dimethoxym ethane is by being loaded with the reaction zone of acid molecular sieve catalyst, in 50~200 DEG C of reaction temperature, reaction pressure 0.1 Dimethoxym ethane mass space velocity is 0.01~15.0h in~10MPa, raw material-1Under conditions of reaction prepare product formic acid methyl esters and diformazan Ether；The raw material and product can independently be gas phase or/and liquid phase；The acid molecular sieve catalyst is optionally from the acid molecular sieve catalyst Jing Guo desiliconization modification, by Dealumination One or more in the acid molecular sieve catalyst of processing；Wherein, the silica alumina ratio of the acid molecular sieve catalyst before modification is 3:1~150:1；Carbon monoxide is free of in the raw material.
- 2. according to the method for claim 1, it is characterised in that the acid molecular sieve catalyst is optionally from acid MFI type Molecular sieve catalyst, acid MWW types molecular sieve catalyst, acid FER types molecular sieve catalyst, acid MOR types molecular sieve catalytic Agent, acid FAU types molecular sieve catalyst, the one or more of acid BEA types molecular sieve catalyst；Preferably, in the raw material The molar content of dimethoxym ethane is 20%~100%；Preferably, in the raw material containing optionally from methanol, hydrogen, nitrogen, helium, One or more in argon gas；Preferably, the reaction temperature is 60~150 DEG C, and reaction pressure is 0.1~2MPa, in raw material The mass space velocity of dimethoxym ethane is 0.5~6.0h-1；Preferably, reaction zone contain optional self-retaining bed reactor, tank reactor, One or more in moving-burden bed reactor, fluidized-bed reactor.
- 3. according to the method for claim 1, it is characterised in that the acid molecular sieve catalyst contains optionally from Hydrogen MCM-22 molecular sieves, Hydrogen ferrierite, Hydrogen ZSM-5 molecular sieve, h-mordenite, Hydrogen Y zeolites, Hydrogen Beta molecules One or more in sieve.
- 4. according to the method for claim 1, it is characterised in that the acidic molecular sieve catalysis by desiliconization modification The preparation method of agent comprises the steps of：A) molecular sieve is put into 0.05~6.0mol/L alkaline solution, under 15~95 DEG C of reaction temperature react 0.5~ 24h；B) after sample obtained by step a) is washed with 0.01~0.5mol/L acid solution and deionized water, handed over by ammonium ion Change, filter, drying and being calcined, obtaining the acid molecular sieve catalyst of the desiliconization modification.
- 5. according to the method for claim 4, it is characterised in that alkaline solution is optionally molten from sodium hydroxide described in step a) Liquid, potassium hydroxide solution, lithium hydroxide solution, magnesium hydroxide solution, aqua calcis, sodium carbonate liquor, sodium acid carbonate are molten One or more in liquid；Acid solution is optionally molten from hydrochloric acid solution, salpeter solution, sulfuric acid solution, acetic acid described in step b) One or more in liquid.
- 6. according to the method for claim 4, it is characterised in that the concentration of step a) neutral and alkali solution is 0.2~1.5mol/ L；Reaction temperature is 50~85 DEG C in step a).
- 7. according to the method for claim 1, it is characterised in that the acidic molecular sieve handled by Dealumination is catalyzed In agent, contain the molecular sieve obtained by steam treatment Dealumination method or/and acid treatment Dealumination method.
- 8. according to the method for claim 7, it is characterised in that the steam treatment Dealumination method is, by molecule Sieve is placed in the vapor that temperature is 400~700 DEG C and handles 1~8h；The acid treatment Dealumination method is to put molecular sieve In 0.03~3.0mol/L acid solution, 1~24h is handled at 15~95 DEG C.
- 9. according to the method for claim 8, it is characterised in that the acid solution used in the acid treatment Dealumination method Optionally from a kind of or more in hydrochloric acid solution, sulfuric acid solution, salpeter solution, acetum, oxalic acid solution, citric acid solution Kind.
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