CN104725230B - The method for preparing polymethoxy dimethyl ether carbonyl compound and methoxy menthyl acetate - Google Patents
The method for preparing polymethoxy dimethyl ether carbonyl compound and methoxy menthyl acetate Download PDFInfo
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Abstract
The present invention provides a kind of method of the polymethoxy dimethyl ether carbonyl compound and/or methoxy menthyl acetate for preparing the intermediate as production ethylene glycol, including by raw material polymethoxy dimethyl ether or dimethoxym ethane together with carbon monoxide and hydrogen by being loaded with the reactor of the modified acid molecular sieve catalyst of desiliconization, reaction prepares corresponding product under the conditions of the appropriate reaction without other solvents, and wherein course of reaction is gas-liquid-solid phase reaction.The high conversion rate of raw material polymethoxy dimethyl ether or dimethoxym ethane in the inventive method, the selectivity of each product is high, and catalyst life is long, it is not necessary to use plus solvent, and reaction condition is gentleer, can continuously produce, and possesses industrial applications potentiality.And, the product for being obtained can produce ethylene glycol by being hydrolyzed after hydrogenation or hydrolyzing back end hydrogenation.
Description
Technical field
The present invention relates to the polymethoxy dimethyl ether carbonyl compound and methoxyl group second of a kind of intermediate as production ethylene glycol
The preparation method of sour methyl esters.
Background technology
Ethylene glycol is the important industrial chemicals of country and strategic materials, for manufacture polyester (can further produce terylene,
PET bottle, film), explosive, glyoxal, and can be used as antifreezing agent, plasticizer, hydraulic fluid and solvent etc..China in 2009
Ethylene glycol import volume is more than 5,800,000 tons, it is contemplated that China's ethylene glycol demand is up to 11,200,000 tons, production capacity about 500 within 2015
Ten thousand tons, insufficiency of supply-demand still up to 6,200,000 tons, therefore, before the development and application of China's ethylene glycol production new technology have good market
Scape.The main ethene using petroleum cracking is oxidized in the world obtains oxirane, and ethylene oxide hydration obtains ethylene glycol.In view of
The energy resources structure of China's " few gas of rich coal oil starvation " maintains the present situations such as run at high level for a long time with crude oil price, and coal-ethylene glycol is new
Moulded coal Chemical Engineering Technology can ensure the energy security of country, and the coal resources of China are taken full advantage of again, be that following Coal Chemical Industry is produced
The most real selection of industry.
At present, the ripe technology of domestic contrast is " the CO gas phase catalytic synthesis developed by Chinese Academy of Sciences's Fujian thing structure
Oxalate and oxalate catalytic hydrogenation synthesizing glycol packaged process." in early December, 2009, what is attracted much industry attention is complete
The first set industrialization demonstration plant of ball-Tongliao, Inner Mongolia gold Coal Chemical Industry company " coal-ethylene glycol project " first stage of the project, annual output 200000
Ton coal-ethylene glycol project smoothly gets through all fronts technological process, produces qualified ethylene glycol product.But technique unit is more, work
The requirement of industry gas purity is high, needs to use noble metal catalyst during oxidative coupling, it is necessary to using latency environment pollution
Economy, the feature of environmental protection, energy saving and the further engineering that oxynitrides etc. can restrict the flow are amplified.
Polymethoxy dimethyl ether (or polymethoxy methylal is, English entitled Polyoxymethylene dimethyl
Ethers molecular formula) is CH3O(CH2O)nCH3, wherein n >=2, commonly abbreviated as DMMn(or PODEn).Preparing polymethoxy
During dimethyl ether, the product irrational distribution of its generation, dimethoxym ethane and DMM2It is higher, and can serve as diesel fuel additives
DMM3~4Selectivity is relatively low, as a result, it is often necessary to the accessory substance in its preparation process is separated repeatedly react again, so
Energy consumption is larger, and economy is poor.Therefore, if can be using as the DMM of accessory substance2Directly it is processed into economic worth product higher
The economy of this process will be improved.
In recent years, the Alexis T.Bell professors seminar of U.S. UC, Berkeley proposes to utilize dimethoxym ethane gas phase carbonyl
Change method prepares methoxy menthyl acetate, and then hydrogenation hydrolyzation obtains a variation route of ethylene glycol, and a step of wherein most critical is
Gas carbonylation.But catalyst life is short, dimethoxym ethane concentration is low in unstripped gas, dimethoxym ethane conversion ratio and methoxyacetic acid first
Ester selectivity it is all not ideal enough, from industrialization also have it is considerably long with a distance from [Angew.Chem.Iht.Ed., 2009,48,4813~
4815；J.Catal., 2010,270,185~195；J.Catal., 2010,274,150~162；WO2010/048300A1].
The content of the invention
It is an object of the invention to provide a kind of poly- methoxy that the intermediate as production ethylene glycol is prepared by being carbonylated
The method of base dimethyl ether carbonyl compound and methoxy menthyl acetate.
Therefore, the invention provides a kind of polymethoxy two that the intermediate as production ethylene glycol is prepared by being carbonylated
The method of methyl ether carbonyl compound, it is characterised in that by raw material polymethoxy dimethyl ether CH3O(CH2O)nCH3Together with carbon monoxide and hydrogen
Gas by being loaded with the reactor of the modified acid molecular sieve catalyst of desiliconization, 60~140 DEG C of reaction temperature, reaction pressure 2~
10MPa, polymethoxy dimethyl ether mass space velocity are 0.2~10.0h-1And prepare product without reaction under conditions of other solvents
Polymethoxy dimethyl ether carbonyl compound, wherein under the cited reaction conditions, the raw material is liquid with least one in the product
Phase, the modified acid molecular sieve catalyst of the desiliconization is solid phase, and carbon monoxide and hydrogen are gas phase so that course of reaction is gas
Liquid solid phase reaction, and the mol ratio of carbon monoxide and the raw material is 2: 1~20: 1, the mol ratio of hydrogen and the raw material
It is 1: 1~5: 1, wherein n >=2 and be integer.
The present invention is also a kind of by the way that the intermediate methoxy menthyl acetate and poly- first that prepare as ethylene glycol is produced is carbonylated
The method of epoxide dimethyl ether carbonyl compound, it is characterised in that by raw material dimethoxym ethane CH3O-CH2-OCH3Together with carbon monoxide and hydrogen
By being loaded with the reactor of the modified acid molecular sieve catalyst of desiliconization, 60~140 DEG C of reaction temperature, reaction pressure 2~
10MPa, dimethoxym ethane mass space velocity are 0.2~10.0h-1And prepare product methoxyl group second without reaction under conditions of other solvents
Sour methyl esters and polymethoxy dimethyl ether carbonyl compound, wherein under the cited reaction conditions, in the raw material and the product at least
One kind is liquid phase, and the modified acid molecular sieve catalyst of the desiliconization is solid phase, and carbon monoxide and hydrogen are gas phase so that reaction
Process is gas-liquid-solid phase reaction, and the mol ratio of carbon monoxide and the raw material is 2: 1~20: 1, hydrogen and the raw material
Mol ratio be 1: 1~5: 1.
In a preferred embodiment, the product polymethoxy dimethyl ether carbonyl compound is in polymethoxy dimethyl ether
CH3O(CH2O)nCH3- the O-CH of strand2Inserted on-O- construction units formed after one or more carbonyls-CO- with-O-
(CO)-CH2- O- or-O-CH2The product of-(CO)-O- construction units, wherein n >=2.
In a preferred embodiment, the polymethoxy dimethyl ether is two polymethoxy dimethyl ether CH3O(CH2O)2CH3。
In a preferred embodiment, the polymethoxy dimethyl ether carbonyl compound be it is following in one or more：
CH3-O-(CO)-CH2-O-CH2-O-CH3,
CH3-O-CH2-(CO)-O-CH2-O-CH3,
CH3-O-(CO)-CH2-O-(CO)-CH2-O-CH3, and
CH3-O-(CO)-CH2-O-CH2-(CO)-O-CH3。
The modified acid molecular sieve catalyst of the desiliconization is prepared via a method which：Acidic molecular sieve is put into 0.05~
The NaOH of 6.0mol/L, preferably 0.2~1.5mol/L, potassium hydroxide, lithium hydroxide, magnesium hydroxide, calcium hydroxide, carbonic acid
In the aqueous solution of one or more in sodium or sodium acid carbonate, at 15~95 DEG C, 0.5~24h, mistake are reacted at preferably 50~85 DEG C
Filter cake after filter is washed selected from hydrochloric acid, nitric acid, sulfuric acid or second aqueous acid with 0.01~0.5mol/L and is neutralized to acidity,
The net salting liquid for neutralizing and producing is washed with deionized water again, then by ammonium ion exchange, filtering, drying and calcination, obtains described
The modified acid molecular sieve catalyst of desiliconization.
In a preferred embodiment, the structure type of the modified acid molecular sieve catalyst of the desiliconization be MWW,
FER, MFI, MOR, FAU or BEA.
In a preferred embodiment, the modified acid molecular sieve catalyst of the desiliconization is MCM-22 molecular sieves, magnesium
One or more in alkali zeolite, ZSM-5 molecular sieve, modenite, Y zeolites or Beta molecular sieves.
In a preferred embodiment, reaction temperature is 60~120 DEG C, and reaction pressure is 4~10MPa, the raw material
Mass space velocity be 0.5~3.0h-1, the mol ratio of carbon monoxide and the raw material is 2: 1~15: 1, hydrogen and the raw material
Mol ratio is 1: 1~3: 1.
In a preferred embodiment, reaction temperature is 60~90 DEG C, and reaction pressure is 5~10MPa, the raw material
Mass space velocity is 0.5~1.5h-1, carbon monoxide is 2: 1~10: 1 with the mol ratio of the raw material, and hydrogen rubs with the raw material
You are than being 1: 1~2: 1.
In a preferred embodiment, the reactor is fixed bed reactors, the still reaction for realizing successive reaction
Device, moving-burden bed reactor or fluidized-bed reactor.
The high conversion rate of raw material polymethoxy dimethyl ether or dimethoxym ethane in the inventive method, the selectivity of each product is high, urges
Agent long lifespan, it is not necessary to use plus solvent, reaction condition is gentleer, can continuously produce, and possesses industrial applications and dives
Power.And, the product for being obtained can produce ethylene glycol by being hydrolyzed after hydrogenation or hydrolyzing back end hydrogenation.
Specific embodiment
The present invention provides a kind of method for preparing polymethoxy dimethyl ether carbonyl compound, it is characterised in that：Poly- methoxy will be contained
Base dimethyl ether CH3O(CH2O)nCH3, carbon monoxide and optional hydrogen the raw material acidic molecular modified by being loaded with desiliconization
The reactor of sieve catalyst, in 60~140 DEG C of reaction temperature, 2~10MPa of reaction pressure, polymethoxy dimethyl ether mass space velocity
It is 0.2~10.0h-1And reacted without under conditions of other solvents, prepare polymethoxy dimethyl ether carbonyl compound；Under reaction condition
It is liquid phase that raw material polymethoxy dimethyl ether is at least one with product polymethoxy dimethyl ether carbonyl compound, and catalyst is solid phase, raw material
Carbon monoxide and hydrogen are gas phase, and course of reaction is gas-liquid-solid phase reaction；In raw material, carbon monoxide and polymethoxy dimethyl ether
Mol ratio be 2: 1~20: 1, the mol ratio of hydrogen and polymethoxy dimethyl ether is 1: 1~5: 1.
Described polymethoxy dimethyl ether is one-component or mixture, and molecular formula is CH3O(CH2O)nCH3, wherein n >=2
And be integer, preferably n=2, i.e. CH3O(CH2O)2CH3。
In a preferred embodiment, course of reaction is gas-liquid-solid phase reaction, and reaction temperature is 60~120 DEG C, instead
Pressure is answered for 4~10MPa, polymethoxy dimethyl ether mass space velocity is 0.5~3.0h-1, carbon monoxide and polymethoxy dimethyl ether
Mol ratio for the mol ratio of 2: 1~15: 1 preferred hydrogen and polymethoxy dimethyl ether be 1: 1~3: 1.
In a preferred embodiment, course of reaction is gas-liquid-solid phase reaction, and reaction temperature is 60~90 DEG C, reaction
Pressure is 5~10MPa, and polymethoxy dimethyl ether mass space velocity is 0.5~1.5h-1, carbon monoxide and polymethoxy dimethyl ether
Mol ratio is 2: 1~10: 1, preferred hydrogen is 1: 1~2: 1 with the mol ratio of polymethoxy dimethyl ether.
In some embodiments of the invention, the conversion ratio of polymethoxy dimethyl ether and polymethoxy dimethyl ether carbonyl compound
Selectivity is all based on polymethoxy dimethyl ether carbon molal quantity and is calculated：
Polymethoxy dimethyl ether conversion ratio=[(polymethoxy dimethyl ether carbon molal quantity in charging)-(polymethoxy in discharging
Dimethyl ether carbon molal quantity)] ÷ (polymethoxy dimethyl ether carbon molal quantity in charging) × (100%)
Polymethoxy dimethyl ether carbonyl compound selectivity=(polymethoxy dimethyl ether carbonyl compound removes the carbon after carbonyl in discharging
Molal quantity) ÷ [(polymethoxy dimethyl ether carbon molal quantity in charging)-(polymethoxy dimethyl ether carbon molal quantity in discharging)] ×
(100%)
The present invention also provides the preparation method of a kind of methoxy menthyl acetate and polymethoxy dimethyl ether carbonyl compound, its feature
It is that will contain dimethoxym ethane CH3O-CH2-OCH3, carbon monoxide and hydrogen the raw material acidic molecular modified by being loaded with desiliconization
The reactor of sieve catalyst, 60~140 DEG C of reaction temperature, reaction pressure 2~10MPa dimethoxym ethanes mass space velocity be 0.2~
10.0h-1And reacted without under conditions of other solvents, prepare methoxy menthyl acetate and polymethoxy dimethyl ether carbonyl compound；
It is liquid phase that raw material dimethoxym ethane is at least one with product methoxy menthyl acetate and polymethoxy dimethyl ether carbonyl compound under reaction condition,
Catalyst is solid phase, and raw material carbon monoxide and hydrogen are gas phase, and course of reaction is gas-liquid-solid phase reaction；In raw material, an oxidation
Carbon is 2: 1~20: 1 with the mol ratio of dimethoxym ethane, and hydrogen is 1: 1~5: 1 with the mol ratio of dimethoxym ethane.
In a preferred embodiment, course of reaction is gas-liquid-solid phase reaction, and reaction temperature is 60~120 DEG C, instead
Pressure is answered for 4~10MPa, dimethoxym ethane mass space velocity is 0.5~3.0h-1, carbon monoxide is 2: 1~15 with the mol ratio of dimethoxym ethane
: 1 preferred hydrogen is 1: 1~3: 1 with the mol ratio of dimethoxym ethane.
In a preferred embodiment, course of reaction is gas-liquid-solid phase reaction, and reaction temperature is 60~90 DEG C, reaction
Pressure is 5~10MPa, and dimethoxym ethane mass space velocity is 0.5~1.5h-1, carbon monoxide is 2: 1~10 with the mol ratio of dimethoxym ethane:
1, preferred hydrogen is 1: 1~2: 1 with the mol ratio of dimethoxym ethane.
In certain embodiments, the conversion ratio of dimethoxym ethane and the selectivity of product are all based on dimethoxym ethane carbon molal quantity and are counted
Calculate：
Dimethoxym ethane conversion ratio=[(dimethoxym ethane carbon molal quantity in charging)-(dimethoxym ethane carbon molal quantity in discharging)] ÷ is (in charging
Dimethoxym ethane carbon molal quantity) × (100%)
Methoxy menthyl acetate selectivity=(methoxy menthyl acetate removes the carbon molal quantity after carbonyl in discharging) ÷ [(enters
Dimethoxym ethane carbon molal quantity in material)-(dimethoxym ethane carbon molal quantity in discharging)] × (100%)
Polymethoxy dimethyl ether carbonyl compound selectivity=(polymethoxy dimethyl ether carbonyl compound removes the carbon after carbonyl in discharging
Molal quantity) ÷ [(dimethoxym ethane carbon molal quantity in charging)-(dimethoxym ethane carbon molal quantity in discharging)] × (100%)
The preparation method of the modified acid molecular sieve catalyst of the desiliconization includes for molecular sieve being put into optional 0.05~
The NaOH of 6.0mol/L, preferably 0.2~1.5mol/L, potassium hydroxide, lithium hydroxide, magnesium hydroxide, calcium hydroxide, carbonic acid
In one or more mixed solutions of sodium or sodium acid carbonate, at 15~95 DEG C, 0.5~24h, filtering are reacted at preferably 50~85 DEG C
Filter cake afterwards is washed with the hydrochloric acid of 0.01~0.5mol/L, nitric acid, sulfuric acid or acetic acid solution, and it is acid to neutralize filter cake, then spend from
Sub- water cleans the salting liquid for neutralizing generation, then obtains desiliconization by conventional ammonium ion exchange, filtering, dry, calcination procedure
Modified acid molecular sieve catalyst.
The structure type of described acid molecular sieve catalyst is MWW, FER, MFI, MOR, FAU or BEA.Preferably, institute
The acid molecular sieve catalyst stated is MCM-22 molecular sieves, ferrierite, ZSM-5 molecular sieve, modenite, Y zeolites or Beta
Any one in molecular sieve or any several mixing, sial atomic ratio is 3: 1~150: 1.
In a specific embodiment, Cation molecule sieve is converted into the S.O.P. of acidic molecular sieve and is：Will
The dried Cation molecule sieves of 50g are put into the 0.8M NH of 400ml4NO3In solution, 12h is stirred at 80 DEG C, used after filtering
The distillation water washing of 800ml.This ion exchange process obtains NH in triplicate4 +The molecular sieve of type.After fully drying, it is placed in
In Muffle furnace, it is increased to 550 DEG C with 2 DEG C/min and keeps calcining 4h to obtain acidic molecular sieve.
Described polymethoxy dimethyl ether carbonyl compound is in polymethoxy dimethyl ether strand-O-CH2- O- construction units
Formed after upper insertion carbonyl-CO- with-O- (CO)-CH2- O- or-O-CH2The product of-(CO)-O- construction units, poly- methoxy
Base dimethyl ether carbonyl compound contains one or more carbonyls.
In embodiment produce polymethoxy dimethyl ether carbonyl compound can be it is following in one or more：
CH3-O-(CO)-CH2-O-CH2-O-CH3Referred to as C5-1,
CH3-O-CH2-(CO)-O-CH2-O-CH3Referred to as C5-2,
CH3-O-(CO)-CH2-O-(CO)-CH2-O-CH3Referred to as C6-1,
CH3-O-(CO)-CH2-O-CH2-(CO)-O-CH3Referred to as C6-2.
Product methoxy menthyl acetate of the invention or polymethoxy dimethyl ether carbonyl compound can by hydrolysis after hydrogenation or
Hydrolysis back end hydrogenation obtains ethylene glycol, additionally, the product is also used as vapour, diesel fuel additives.For example, with two polymethoxies two
Methyl ether (DMM2)CH3O(CH2O)2CH3As a example by profile up to generation ethylene glycol course of reaction be：
In a preferred embodiment, the reactor is fixed bed reactors, tank reactor, the shifting of continuous flowing
Dynamic bed reactor or fluidized-bed reactor.
Below by embodiment in detail the present invention is described in detail, but the invention is not limited in these embodiments.
Embodiment 1
By 50g sodium form silica alumina ratio for 40: 1 MCM-22 molecular sieves are converted into acidic molecular sieve using S.O.P.,
Catalyst A is designated as, 1 is shown in Table.
Embodiment 2
By 100g sodium form silica alumina ratio for 40: 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 the salpeter solution of 0.08ml/L, filtering
Afterwards with deionized water cyclic washing to neutrality, acidic molecular sieve is converted into by S.O.P. after being dried at 100 DEG C, remembered
It is catalyst B, is shown in Table 1.
Embodiment 3
By 50g sodium form silica alumina ratio for 10: 1 ferrierite is converted into acidic molecular sieve using S.O.P., it is designated as
Catalyst C, is shown in Table 1.
Embodiment 4
By 100g sodium form silica alumina ratio for 10: 1 ferrierite is added to 500ml concentration for the magnesium hydroxide of 0.2mol/L is molten
In liquid, the stirring reaction 24h at 50 DEG C, after filtering, it is 6 that filter cake washs pH with the hydrochloric acid solution of 0.1ml/L, is spent after filtering
Ionized water cyclic washing is converted into acidic molecular sieve after being dried at 100 DEG C to neutrality by S.O.P., is designated as catalysis
Agent D, is shown in Table 1.
Embodiment 5
By 50g sodium form silica alumina ratio for 150: 1 ZSM-5 molecular sieve is converted into acidic molecular sieve using S.O.P.,
Catalyst E is designated as, 1 is shown in Table.
Embodiment 6
By 100g sodium form silica alumina ratio for 150: 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 the hydrochloric acid solution of 0.2ml/L, after filtering
With deionized water cyclic washing to neutrality, acidic molecular sieve is converted into by S.O.P. after being dried at 100 DEG C, be designated as
Catalyst F, is shown in Table 1.
Embodiment 7
By 50g sodium form silica alumina ratio for 3: 1 modenite is converted into acidic molecular sieve using S.O.P., it is designated as urging
Agent G, is shown in Table 1.
Embodiment 8
By 100g sodium form silica alumina ratio for 3: 1 modenite is added to 500ml concentration for the lithium hydroxide of 1.0mol/L is molten
In liquid, the stirring reaction 0.5h at 95 DEG C, after filtering, it is 6 that filter cake washs pH with the acetum of 0.5ml/L, is used after filtering
Deionized water cyclic washing is converted into acidic molecular sieve after being dried at 100 DEG C to neutrality by S.O.P., is designated as urging
Agent H, is shown in Table 1.
Embodiment 9
By 50g sodium form silica alumina ratio for 20: 1 Y molecular sieve is converted into acidic molecular sieve using S.O.P., it is designated as urging
Agent I, is shown in Table 1.
Embodiment 10
By 100g sodium form silica alumina ratio for 20: 1 Y molecular sieve is added to 500ml concentration for the NaOH of 0.5mol/L is molten
In liquid, the stirring reaction 4h at 80 DEG C, after filtering, it is 6 that filter cake washs pH with the salpeter solution of 0.1ml/L, is spent after filtering
Ionized water cyclic washing is converted into acidic molecular sieve after being dried at 100 DEG C to neutrality by S.O.P., is designated as catalysis
Agent J, is shown in Table 1.
Embodiment 11
By 50g sodium form silica alumina ratio for 15: 1 Beta molecular sieves are converted into acidic molecular sieve using S.O.P., remember
It is catalyst K, is shown in Table 1.
Embodiment 12
By 100g sodium form silica alumina ratio for 15: 1 Beta molecular sieves be added to 500ml concentration be 3.5mol/L sodium carbonate with
In the potassium hydroxide mixed solution of 0.05mol/L, the stirring reaction 12h at 15 DEG C, after filtering, the filter cake sulfuric acid of 0.01ml/L
Solution washing is 6 to pH, and deionized water cyclic washing to neutrality is used after filtering, by standard operation journey after being dried at 100 DEG C
Sequence is converted into acidic molecular sieve, is designated as catalyst L, is shown in Table 1.
Method for preparing catalyst in the embodiment 1~12 of table 1
Embodiment 13
Catalyst A sample compressing tablet, 20~40 mesh are ground into, for active testing.Catalyst A10g is weighed, loads internal diameter
In the stainless steel reaction pipe of 8.5mm, nitrogen activation to be used 4 hours at normal pressure, 550 DEG C, reaction temperature (T)=90 is then dropped to
DEG C, it is passed through carbon monoxide: two polymethoxy dimethyl ethers: hydrogen (CO: DMM2∶H2)=7: 1: 1, slowly boost to reaction pressure (P)=
10MPa, two polymethoxy dimethyl ether mass space velocities (WHSV)=0.2h-1, gas chromatographic analysis product is used, after reacting basicly stable,
The conversion ratio of two polymethoxy dimethyl ethers and the selectivity of polymethoxy dimethyl ether carbonyl compound are calculated, reaction result is shown in Table 2.
Embodiment 14
Change the catalyst in embodiment 13 into catalyst B, remaining experimental procedure is consistent with embodiment 13, and reaction result is shown in
Table 2.
Embodiment 15
Change the catalyst in embodiment 13 into catalyst C, T=60 DEG C, CO: DMM2∶H2=13: 1: 3, P=4MPa, WHSV=
1.5h-1, remaining experimental procedure is consistent with embodiment 13, and reaction result is shown in Table 2.
Embodiment 16
Change the catalyst in embodiment 15 into catalyst D, remaining experimental procedure is consistent with embodiment 15, and reaction result is shown in
Table 2.
Embodiment 17
Change the catalyst in embodiment 13 into catalyst E, reaction condition is changed to：T=140 DEG C, CO: DMM2∶H2=2: 1: 5,
P=6.5MPa, WHSV=3.0h-1, remaining experimental procedure is consistent with embodiment 13, and reaction result is shown in Table 2.
Embodiment 18
Change the catalyst in embodiment 17 into catalyst F, remaining experimental procedure is consistent with embodiment 17, and reaction result is shown in
Table 2.
Embodiment 19
Change the catalyst in embodiment 13 into catalyst G, reaction condition is changed to：T=105 DEG C, CO: DMM2∶H2=20∶1∶
1, P=5.0MPa, WHSV=1.0h-1, remaining experimental procedure is consistent with embodiment 13, and reaction result is shown in Table 2.
Embodiment 20
Change the catalyst in embodiment 19 into catalyst H, remaining experimental procedure is consistent with embodiment 19, and reaction result is shown in
Table 2.
Embodiment 21
Change the catalyst in embodiment 13 into catalyst I, reaction condition is changed to：T=73 DEG C, CO: DMM2∶H2=10: 1: 2,
P=2MPa, WHSV=10.0h-1, remaining experimental procedure is consistent with embodiment 13, and reaction result is shown in Table 2.
Embodiment 22
Change the catalyst in embodiment 21 into catalyst J, remaining experimental procedure is consistent with embodiment 21, and reaction result is shown in
Table 2.
Embodiment 23
Change the catalyst in embodiment 13 into catalyst K, reaction condition is changed to：T=120 DEG C, CO: DMM2∶H2=15∶1∶
4, P=4.7MPa, WHSV=0.5h-1, remaining experimental procedure is consistent with embodiment 13, and reaction result is shown in Table 2.
Embodiment 24
Change the catalyst in embodiment 23 into catalyst L, remaining experimental procedure is consistent with embodiment 23, and reaction result is shown in
Table 2.
Embodiment 25
Catalyst E samples compressing tablet, 20~40 mesh are ground into, for active testing.Catalyst sample 10g is weighed, loads interior
Footpath in the stainless steel reaction pipe of 8.5mm, with nitrogen activation 4 hours at normal pressure, 550 DEG C, then drop to reaction temperature (T)=
88 DEG C, it is passed through raw material carbon monoxide: polymethoxy dimethyl ether: hydrogen (CO: DMMn∶H2)=8: 1: 1, wherein DMMnThe matter of each component
Measuring ratio is：DMM2∶DMM3∶DMM4∶DMM5∶DMM6=51.2: 26.6: 12.8: 6.5: 2.9, slowly boost to reaction pressure (P)=
8MPa, polymethoxy dimethyl ether mass space velocity (WHSV)=1.5h-1, use gas chromatographic analysis product, reaction result to be shown in Table 2.
Embodiment 26
Change the catalyst in embodiment 25 into catalyst F, other conditions are constant, and reaction result is shown in Table 2.
Embodiment 27
Catalyst I samples compressing tablet, 20~40 mesh are ground into, for active testing.Catalyst sample 10g is weighed, loads interior
Footpath in the stainless steel reaction pipe of 8.5mm, with nitrogen activation 4 hours at normal pressure, 550 DEG C, then drop to reaction temperature (T)=
95 DEG C, it is passed through raw material carbon monoxide: polymethoxy dimethyl ether: hydrogen (CO: DMMn∶H2)=10: 1: 1, wherein DMMnEach component
Mass ratio is：DMM2∶DMM3∶DMM4∶DMM5∶DMM6=47.7: 26.9: 14.0: 7.8: 3.6, slowly boost to reaction pressure (P)=
7MPa, polymethoxy dimethyl ether mass space velocity (WHSV)=2.0h-1, gas chromatographic analysis product is used, after reacting basicly stable, instead
2 should be the results are shown in Table.
Embodiment 28
Change the catalyst in embodiment 27 into catalyst J, other conditions are constant, and reaction result is shown in Table 2.
Comparative example 1
Change the gas ratio in embodiment 20 into CO: DMM2∶H2=20: 1: 0, remaining experimental procedure and embodiment 20 1
Cause, reaction result is shown in Table 2.
Comparative example 2
Change the gas ratio in embodiment 22 into CO: DMM2∶H2=10: 1: 0, remaining experimental procedure and embodiment 22 1
Cause, reaction result is shown in Table 2.
Embodiment 29
Catalyst A sample compressing tablet, 20~40 mesh are ground into, for active testing.Catalyst A10g is weighed, loads internal diameter
In the stainless steel reaction pipe of 8.5mm, nitrogen activation to be used 4 hours at normal pressure, 550 DEG C, reaction temperature (T)=90 is then dropped to
DEG C, it is passed through carbon monoxide: dimethoxym ethane: hydrogen (CO: DMM: H2)=7: 1: 1, slowly boost to reaction pressure (P)=10MPa, control first
Acetal mass space velocity (WHSV)=0.2h-1, gas chromatographic analysis product is used, after reacting basicly stable, calculate the conversion ratio of dimethoxym ethane
With the selectivity of product, reaction result is shown in Table 3.
Embodiment 30
Change the catalyst in embodiment 29 into catalyst B, remaining experimental procedure is consistent with embodiment 29, and reaction result is shown in
Table 3.
Embodiment 31
Change the catalyst in embodiment 29 into catalyst C, T=60 DEG C, CO: DMM: H2=13: 1: 3, P=4MPa, WHSV=
1.5h-1, remaining experimental procedure is consistent with embodiment 29, and reaction result is shown in Table 3.
Embodiment 32
Change the catalyst in embodiment 31 into catalyst D, remaining experimental procedure is consistent with embodiment 31, and reaction result is shown in
Table 3.
Embodiment 33
Change the catalyst in embodiment 29 into catalyst E, reaction condition is changed to：T=140 DEG C, CO: DMM: H2=2: 1: 5,
P=6.5MPa, WHSV=3.0h-1, remaining experimental procedure is consistent with embodiment 29, and reaction result is shown in Table 3.
Embodiment 34
Change the catalyst in embodiment 33 into catalyst F, remaining experimental procedure is consistent with embodiment 33, and reaction result is shown in
Table 3.
Embodiment 35
Change the catalyst in embodiment 29 into catalyst G, reaction condition is changed to：T=105 DEG C, CO: DMM: H2=20∶1∶
1, P=5.0MPa, WHSV=1.0h-1, remaining experimental procedure is consistent with embodiment 29, and reaction result is shown in Table 3.
Embodiment 36
Change the catalyst in embodiment 35 into catalyst H, remaining experimental procedure is consistent with embodiment 35, and reaction result is shown in
Table 3.
Embodiment 37
Change the catalyst in embodiment 29 into catalyst I, reaction condition is changed to：T=73 DEG C, CO: DMM: H2=10: 1: 2,
P=2MPa, WHSV=10.0h-1, remaining experimental procedure is consistent with embodiment 29, and reaction result is shown in Table 3.
Embodiment 38
Change the catalyst in embodiment 37 into catalyst J, remaining experimental procedure is consistent with embodiment 37, and reaction result is shown in
Table 3.
Embodiment 39
Change the catalyst in embodiment 29 into catalyst K, reaction condition is changed to：T=120 DEG C, CO: DMM: H2=15∶1∶
4, P=4.7MPa, WHSV=0.5h-1, remaining experimental procedure is consistent with embodiment 29, and reaction result is shown in Table 3.
Embodiment 40
Change the catalyst in embodiment 39 into catalyst L, remaining experimental procedure is consistent with embodiment 39, and reaction result is shown in
Table 3.
Comparative example 3
Gas ratio in embodiment 36 is changed to CO: DMM: H2=20: 1: 0, remaining experimental procedure and embodiment 36 1
Cause, reaction result is shown in Table 3.
Comparative example 4
Gas ratio in embodiment 38 is changed to CO: DMM: H2=10: 1: 0, remaining experimental procedure and embodiment 38 1
Cause, reaction result is shown in Table 3.
Beneficial effects of the present invention are included but is not limited to：The acid that the catalyst that the method for the present invention is used is modified for desiliconization
Property molecular sieve catalyst, raw material is polymethoxy dimethyl ether or dimethoxym ethane together with carbon monoxide and the gaseous mixture of hydrogen.In this hair
Under bright reaction condition, raw material by catalyst can stability and high efficiency produce as produce ethylene glycol intermediate the poly- first of product
Epoxide dimethyl ether carbonyl compound or methoxy menthyl acetate, course of reaction are gas-liquid-solid phase reaction.Methoxyl group dimethyl ether or first contract
Aldehyde carbonyl groupsization reaction is strong exothermal reaction, in the present invention reaction temperature than relatively low, along with liquid phase thermal capacitance greatly and latent heat of phase change, energy
Enough fine controlling reaction temperatures, prevent the problem of temperature runaway in industrial processes.The gas-liquid-solid three-phase that the present invention is used simultaneously is anti-
Should be able to be operated under polymethoxy dimethyl ether high or dimethoxym ethane concentration, improve one way reaction production capacity in industrial production, reduced
Energy consumption in compression, circulation and separation process, improves economic performance.
The high conversion rate of raw material polymethoxy dimethyl ether or dimethoxym ethane in the present invention, product polymethoxy dimethyl ether carbonyl compound
Or methoxy menthyl acetate selectivity is high, catalyst single pass life is long.Additionally, in the methods of the invention, liquid phase feed reactant
Or product inherently fine solvent, it is not necessary to use plus solvent.Other liquid phase reactor thing or product can catalytic dissolution it is anti-
Pre- carbon distribution material during answering, is conducive to improving the activity and stability of catalyst, and reaction condition is gentleer, can be continuous
Production, possesses industrial applications potentiality.
And, carbonylation uses the gaseous mixture of carbon monoxide and hydrogen as gas phase in the present invention, relative to existing
Coal Chemical Industry production ethylene glycol technology needs high-purity carbon monooxide, and the present invention does not need high-purity carbon monooxide, can be significantly
Synthesis gas separating energy consumption is reduced, the economy in production process is improved.Hydrogen is added in other reaction gas can also improve poly- first
Epoxide dimethyl ether or dimethoxym ethane conversion ratio and polymethoxy dimethyl ether carbonyl compound or methoxy menthyl acetate selectivity, extension catalysis
Agent single pass life.
Molecular sieve desiliconization method of modifying in the present invention is simple to operation, is adapted to industrial mass production, changes by desiliconization
The enough single pass lifes by catalyst of performance extend 5~10 times, effectively reduce the number of times that annual catalyst is lived again, favorably
In improve annual capacity, reduce wastage of material, reduce waste gas discharge of wastewater, reduce catalyst because pressure release and burn carbon distribution and caused by
Loss, extends production equipment usage cycles, improves economic performance.
Additionally, the polymethoxy dimethyl ether carbonyl compound or methoxy menthyl acetate that are produced in the present invention can be by being hydrogenated with water
Solution or hydrolysis back end hydrogenation production ethylene glycol.
Below to the present invention have been described in detail, but the invention is not limited in specific embodiment party described herein
Formula.It will be appreciated by those skilled in the art that in the case without departing from the scope of the present invention, other changes can be made and deformed.This hair
Bright scope is defined by the following claims.
Claims (10)
1. a kind of by the way that the method for preparing the polymethoxy dimethyl ether carbonyl compound as the intermediate for producing ethylene glycol is carbonylated, its
It is characterised by, by raw material polymethoxy dimethyl ether CH3O(CH2O)nCH3It is modified by being loaded with desiliconization together with carbon monoxide and hydrogen
Acid molecular sieve catalyst reactor, in 60~140 DEG C of reaction temperature, 2~10MPa of reaction pressure, polymethoxy diformazan
Ether mass space velocity is 0.2~10.0h-1And prepare product polymethoxy dimethyl ether carbonylation without reaction under conditions of other solvents
Thing, wherein under the cited reaction conditions, the raw material is liquid phase, the modified acid of the desiliconization with least one in the product
Property molecular sieve catalyst be solid phase, carbon monoxide and hydrogen are gas phase so that course of reaction is gas-liquid-solid phase reaction, and one
Carbonoxide is 2: 1~20: 1 with the mol ratio of the raw material, and hydrogen is 1: 1~5: 1, wherein n >=2 with the mol ratio of the raw material
And be integer, the modified acid molecular sieve catalyst of the desiliconization is prepared via a method which：Acidic molecular sieve is put into 0.05
In the NaOH of~6.0mol/L, potassium hydroxide, lithium hydroxide, magnesium hydroxide, calcium hydroxide, sodium carbonate or sodium acid carbonate
In the aqueous solution of one or more, 0.5~24h are reacted at 15~95 DEG C, the choosing of 0.01~0.5mol/L of filter cake after filtering
Washed from hydrochloric acid, nitric acid, sulfuric acid or second aqueous acid and be neutralized to acidity, then be washed with deionized water that net to neutralize the salt for producing molten
Liquid, then by ammonium ion exchange, filtering, drying and calcination, obtains the modified acid molecular sieve catalyst of the desiliconization.
2. a kind of by the way that the intermediate methoxy menthyl acetate and polymethoxy dimethyl ether that prepare as production ethylene glycol is carbonylated
The method of carbonyl compound, it is characterised in that by raw material dimethoxym ethane CH3O-CH2-OCH3It is de- by being loaded with together with carbon monoxide and hydrogen
The reactor of the acid molecular sieve catalyst of Si modification, in 60~140 DEG C of reaction temperature, 2~10MPa of reaction pressure, dimethoxym ethane
Mass space velocity is 0.2~10.0h-1And prepare product methoxy menthyl acetate and poly- first without reaction under conditions of other solvents
Epoxide dimethyl ether carbonyl compound, wherein under the cited reaction conditions, the raw material is liquid phase, institute with least one in the product
It is solid phase to state the modified acid molecular sieve catalyst of desiliconization, and carbon monoxide and hydrogen are gas phase so that course of reaction is gas-liquid-solid three
Phase reaction, and carbon monoxide and the mol ratio of the raw material are 2: 1~20: 1, and hydrogen is 1: 1 with the mol ratio of the raw material
~5: 1, wherein the modified acid molecular sieve catalyst of the desiliconization is prepared via a method which：Acidic molecular sieve is put into 0.05
In the NaOH of~6.0mol/L, potassium hydroxide, lithium hydroxide, magnesium hydroxide, calcium hydroxide, sodium carbonate or sodium acid carbonate
In the aqueous solution of one or more, 0.5~24h are reacted at 15~95 DEG C, the choosing of 0.01~0.5mol/L of filter cake after filtering
Washed from hydrochloric acid, nitric acid, sulfuric acid or second aqueous acid and be neutralized to acidity, then be washed with deionized water that net to neutralize the salt for producing molten
Liquid, then by ammonium ion exchange, filtering, drying and calcination, obtains the modified acid molecular sieve catalyst of the desiliconization.
3. method according to claim 1 and 2, it is characterised in that the product polymethoxy dimethyl ether carbonyl compound be
Polymethoxy dimethyl ether CH3O(CH2O)nCH3- the O-CH of strand2After one or more carbonyls-CO- is inserted in-O- construction units
Formed with-O- (CO)-CH2- O- or-O-CH2The product of-(CO)-O- construction units, wherein n >=2.
4. method according to claim 1, it is characterised in that the polymethoxy dimethyl ether is two polymethoxy dimethyl ethers
CH3O(CH2O)2CH3。
5. method according to claim 1 and 2, it is characterised in that the polymethoxy dimethyl ether carbonyl compound is in following
One or more：
CH3-O-(CO)-CH2-O-CH2-O-CH3,
CH3-O-CH2-(CO)-O-CH2-O-CH3,
CH3-O-(CO)-CH2-O-(CO)-CH2-O-CH3, and
CH3-O-(CO)-CH2-O-CH2-(CO)-O-CH3。
6. method according to claim 1 and 2, it is characterised in that the modified acid molecular sieve catalyst of the desiliconization
Structure type is MWW, FER, MFI, MOR, FAU or BEA.
7. method according to claim 6, it is characterised in that the modified acid molecular sieve catalyst of the desiliconization is MCM-
One or more in 22 molecular sieves, ferrierite, ZSM-5 molecular sieve, modenite, Y zeolites or Beta molecular sieves.
8. method according to claim 1 and 2, it is characterised in that reaction temperature is 60~120 DEG C, reaction pressure is 4~
10MPa, the mass space velocity of the raw material is 0.5~3.0h-1, carbon monoxide is 2: 1~15: 1, hydrogen with the mol ratio of the raw material
Gas is 1: 1~3: 1 with the mol ratio of the raw material.
9. method according to claim 1 and 2, it is characterised in that reaction temperature is 60~90 DEG C, reaction pressure is 5~
10MPa, the mass space velocity of the raw material is 0.5~1.5h-1, carbon monoxide is 2: 1~10: 1, hydrogen with the mol ratio of the raw material
Gas is 1: 1~2: 1 with the mol ratio of the raw material.
10. method according to claim 1 and 2, it is characterised in that the reactor is the fixed bed for realizing successive reaction
Reactor, tank reactor, moving-burden bed reactor or fluidized-bed reactor.
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| CN106365995B (en) * | 2015-07-20 | 2018-06-05 | 中国科学院大连化学物理研究所 | A kind of production method of methyl acetate |
| CN106365994B (en) * | 2015-07-20 | 2019-01-01 | 中国科学院大连化学物理研究所 | A kind of production method of lower aliphatic carboxylic acid's Arrcostab |
| CN108097324B (en) * | 2016-11-25 | 2020-03-31 | 中国科学院大连化学物理研究所 | Catalyst for preparing acrylic acid and methyl acrylate and preparation method thereof |
| CN107321686B (en) * | 2017-06-05 | 2021-03-23 | 深圳市航盛新材料技术有限公司 | Cleaning method and cleaning solution for aluminum-air battery catalyst |
| CN107497473B (en) * | 2017-07-20 | 2020-06-23 | 沈阳化工大学 | Preparation method of Y molecular sieve catalyst with cordierite as carrier |
| CN107497479B (en) * | 2017-07-20 | 2020-06-23 | 沈阳化工大学 | Method for preparing methoxy methyl acetate by using cordierite as carrier to synthesize β molecular sieve |
| CN108043169A (en) * | 2017-12-15 | 2018-05-18 | 山东佳星环保科技有限公司 | A kind of oxygenation purification plant |
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| CN102421740A (en) * | 2009-05-14 | 2012-04-18 | 英国石油化学品有限公司 | Carbonylation process |
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