CN109092348A - Mordenite molecular sieve catalyst and preparation method thereof and its application in carbonylation acetic acid methyl esters - Google Patents
Mordenite molecular sieve catalyst and preparation method thereof and its application in carbonylation acetic acid methyl esters Download PDFInfo
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- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
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Abstract
The present invention provides mordenite molecular sieve catalyst and preparation method thereof and its application in carbonylation acetic acid methyl esters, carries out as steps described below: adding water and stirring ageing into silicon source, silicon source and alkali source and form colloidal sol；One or more of template, cation and crystal seed are added in the colloidal sol that step 1 is prepared, are stirred ageing；It carries out crystallization and Na-MOR molecular sieve is prepared；H-MOR molecular sieve is obtained after ammonia exchange.Under conditions of guaranteeing that silica alumina ratio, specific surface area, pore volume etc. are certain, can quick controllable preparation difference crystal grain modenite, be advantageously selected for the grain size of Dimethyl ether carbonylation methyl acetate, reduce diffusional resistance, reduce catalyst carbon deposition.
Description
Technical field
The present invention relates to the catalysis techniques for promoting methanol or Dimethyl ether carbonylation synthesis of acetic acid methyl esters reactivity, more specifically
Ground, which is said, is related to a kind of mordenite molecular sieve catalyst and preparation method thereof for carbonylation acetic acid methyl esters.
Background technique
Methyl acetate (methyl acetate) also known as methyl acetate have many advantages, such as that toxicity is low, biodegradable, and change
Property is active, and solubility property is excellent.It does not limit the organic pollutant discharge used as one kind, can achieve environmentally friendly mark
Standard gradually makees solvent instead of acetone, butanone, ethyl acetate, pentamethylene etc., can be applied to coating, ink, resin, adhesive
Equal fields.With the popularization of alcohol fuel worldwide, in recent years methyl acetate hydrogenation synthesis ethyl alcohol by academia and
The extensive concern of industrial circle, the synthesis of catalyst and the development of key process technology are expected to open up by the new of synthesis gas ethyl alcohol
Path substantially reduces the domestic degree of dependence to petroleum, therefore its application prospect is boundless.
The synthesis technology of methyl acetate includes acetic acid methanol esterification process, methanol dehydrogenation synthetic method, methanol carbonylation, formic acid
Methyl esters homologization method, Dimethyl ether carbonylation method etc..Wherein Dimethyl ether carbonylation synthesizes methyl acetate as molecular sieve system is catalyzed
The introducing of agent avoids the use of noble metal (Ru etc.), realizes catalyst Halogen, and is demonstrated by good activity at low temperature
And selectivity, both met the requirement of green chemical industry, also there is huge industrial value.The overall reaction of the industry is as follows:
CH3OCH3+CO→CH3COOCH3
The PCT Patent WO2006121778 of entitled " alkylation carbonylation process " is reported with H-MOR and H-FER molecular sieve
Or the molecular sieve catalyst of the Metal Supporteds such as copper, nickel, iridium synthesizes methyl acetate for Dimethyl ether carbonylation.Reaction is in 150-180
DEG C, 5MPa hereinafter, high CO partial pressure under show good activity.
The PCT Patent WO2009081099 A1 of entitled " carbonylation method of production acetic acid and/or methyl acetate " is reported
It is not more than 3 microns modenite (MOR) molecular sieve, especially 0.1-1.5 microns of silk using the crystallite dimension of commercial source
Geolyte (MOR) molecular sieve has preferable catalytic activity.Therefore modenite (MOR) catalysis compared with little crystal grain can be synthesized
Agent, will be of great advantage to the yield for improving dimethyl ether carbonylation reaction.
Summary of the invention
The present invention overcomes deficiency in the prior art, provides a kind of synthesis nano modenite (MOR) and be applicable in
In the catalyst and preparation method thereof of carbonylation acetic acid methyl esters reaction；Shadow is limited by the diffusion during elimination reaction
It rings, improves it in the activity of carbonylation acetic acid methyl esters reaction；By the way of microwave assisted and crystallization process chilling, controllably
Synthesis various grain sizes, especially nanoscale modenite (MOR) molecular sieve improves modenite (MOR) molecular sieve and exists
Activity and selectivity in the reaction of carbonylation acetic acid methyl esters.
The purpose of the present invention is achieved by following technical proposals.
Mordenite molecular sieve catalyst and preparation method thereof carries out as steps described below:
Step 1, ageing is added water and stirred into silicon source, silicon source and alkali source form colloidal sol；
In step 1, silicon source be silica solution, sodium metasilicate, silica or ethyl orthosilicate, silicon source be sodium metaaluminate or
Person's aluminium oxide, alkali source are sodium hydroxide or ammonium hydroxide, wherein the molar ratio of Si and Al is (5-25) in silicon source and silicon source: 1, alkali
OH in source and silicon source-Molar ratio with Al is (2-8): 1, preferably (3-6): 1, the molar ratio of water and Si in silicon source is (0-10):
1, and do not include 0:1 and 10:1；
In step 1, stirring is 1-24h using mechanical stirring either magnetic agitation, stirring digestion time；
Step 2, template, cation and crystal seed are added in the colloidal sol that step 1 is prepared, are stirred ageing；
In step 2, template is that perhaps tetraethylammonium bromide cation is ammonium nitrate or chlorine to tetraethyl ammonium hydroxide
Change ammonium, wherein the molar ratio of Si is (0.1-0.4) in template and silicon source: 1, the molar ratio of cation and Si in silicon source is
(0.03-0.1): 1, preferably (0.05-0.09): 1, the additional amount of crystal seed is the 1-10wt% of silicon source quality；
In step 2, using mechanical stirring either magnetic agitation, digestion time is to be less than or equal to greater than zero for 24 hours for stirring,
It is preferred that 4-24h；
Step 3, sample step 2 being prepared is added in autoclave, and microwave high pressure reaction is put into after sealing
First time crystallization is carried out in system, and autoclave is taken out into fast cooling to 20-25 DEG C of room temperature after first time crystallization 0.1-48h
Afterwards, autoclave is placed into microwave high pressure reaction system again and carries out second of crystallization, so that total crystallization time is 3-9
It, after the completion of second of crystallization, the product in autoclave is taken out, and being washed to PH is that 6.5-7.5 is obtained after drying, roasting
To Na-MOR molecular sieve；
Wherein, the reaction condition of microwave high pressure reaction system: crystallization temperature is 150-200 DEG C, preferably 150-170 DEG C, brilliant
Change pressure is 1-10MPa, and preferably 5-7MPa, first time crystallization time is 0.1-3.0h, preferably 0.5-2.5h, and total crystallization time is
1-9h, preferably 4-5h；
Wherein, the reaction condition of hydro-thermal reaction system: crystallization temperature be 150-200 DEG C, preferably 150-170 DEG C, crystallization pressure
Power is 1-10MPa, preferably 5-7MPa, and first time crystallization time is 0.1-48h, and preferably 3-24h, total crystallization time is 3-9 days, excellent
It selects 4-6 days；
Wherein, drying temperature is 100-150 DEG C, drying time 5-10h, and maturing temperature is 500-600 DEG C, calcining time
For 2-6h；
Step 4, the Na-MOR molecular sieve that step 3 is prepared is uniformly dispersed in ammonium nitrate or ammonium chloride liquid
Ammonia exchange is carried out, after ammonia exchanges 2-3 times, after drying, roasting, obtains H-MOR molecular sieve；
Wherein, the concentration of ammonium nitrate solution either ammonium chloride solution is 0.1-1mol/L, preferably 0.4-0.6mol/L, ammonia
The condition of exchange: swap time 5-7h, preferably 5.5-6.5h, exchange temperature are 50-70 DEG C, preferably 55-65 DEG C, Na-MOR points
Son sieve and the solid-to-liquid ratio of ammonium nitrate solution either ammonium chloride solution are 1:(8-12), preferably 1:(9-11)；
Wherein, drying temperature is 100-150 DEG C, drying time 5-10h, and maturing temperature is 400-600 DEG C, calcining time
For 1-5h.
The H-MOR molecular sieve that the step 4 is prepared uses ion-exchange, infusion process, ammonia still process method or solid
Single active metal or double activated metal component are loaded on H-MOR molecular sieve by ion-exchange, it is described list active metal be copper,
Perhaps any one of nickel double activated metal component is any two kinds in copper, silver, iron, cobalt or nickel for silver, iron, cobalt.
Mordenite molecular sieve catalyst and its application in carbonylation acetic acid methyl esters, wherein reaction condition is original
The molar ratio of material is n (CH3OCH3): n (CO)=1:(5-60), reaction temperature is 180-220 DEG C, reaction pressure 1-
3MPa, gas air speed are 1000-4000h-1。
The invention has the benefit that under conditions of guaranteeing that silica alumina ratio, specific surface area, pore volume etc. are certain, it can be fast
The modenite of fast controllable preparation difference crystal grain is advantageously selected for the grain size of Dimethyl ether carbonylation methyl acetate, reduces
Diffusional resistance reduces catalyst carbon deposition.Catalyst of the present invention is environmentally friendly, pollution-free；Catalyst manufacturing process has used micro-
Wave reaction system, substantially reduces the nucleation time of molecular sieve, while reducing molecular sieve partial size, promotes the boiling of nanoscale mercerising
The synthesis of stone (MOR) molecular sieve；Reaction system is easy to operate, quick, has saved catalyst Production Time.
Detailed description of the invention
Fig. 1 is the XRD diagram for the nanoscale mordenite molecular sieve that embodiment 1-5 is prepared in the present invention, wherein 1 is
It is embodiment 3,4 be embodiment 4,5 is embodiment 5 that embodiment 1,2, which is embodiment 2,3,；
Fig. 2 is the XRD diagram for the nanoscale mordenite molecular sieve that comparative example 1-5 is prepared in the present invention, wherein 1 is
It is comparative example 3,4 be comparative example 4,5 is comparative example 5 that comparative example 1,2, which is comparative example 2,3,；
Specific embodiment
Below by specific embodiment, further description of the technical solution of the present invention.
Embodiment 1
Weigh 24g silica solution (silica quality percentage is 30wt%), 0.656g sodium metaaluminate, 1.28g hydroxide
Sodium is mixed uniformly in plastic beaker, 1h is stirred at room temperature, and mixes well to gelled, stirring ageing 4h.
Weigh tetraethyl ammonium hydroxide 16g (tetraethyl ammonium hydroxide mass percent is 25wt%), crystal seed 0.07g is added
In above-mentioned gel, stirring ageing 4h after be packed into microwave high pressure reaction kettle, be put into microwave high pressure reaction system, pressure be 6MPa,
It is 5h that reaction temperature, which carries out total crystallization time of microwave crystallization reaction under conditions of being 170 DEG C,.
After first time crystallization 0.5h, it is put into after reaction kettle taking-up fast cooling to room temperature (20-25 DEG C), then by reaction kettle
Microwave reaction system carries out second of crystallization, and second of crystallization time is 4.5h, and it is 6.5- that product, which is washed with deionized water to PH,
After 7.5,8h is dried under the conditions of 120 DEG C, is then placed on Muffle kiln roasting 4h, maturing temperature is 550 DEG C, with removing
Template in Na-MOR obtains Na-MOR molecular sieve.
Na-MOR molecular sieve is placed in a beaker again, the ammonium nitrate solution of 0.5mol/L is added into beaker in 60 DEG C of conditions
Under, it carries out ammonium ion and exchanges 6h, wherein the solid-to-liquid ratio of Na-MOR molecular sieve and ammonium nitrate solution is 1:10, repeats ammonium ion and hands over
After changing twice, after 120 DEG C of dry 8h, places it in and roast 3h in 500 DEG C of Muffle furnace, H-MOR molecular sieve is made.
By H-MOR molecular sieve obtained, tabletting, sieving measures the 40-60 mesh H-MOR loading fixed bed reactors of 2mL
It is interior, first use N2It pre-processes 4h in situ under the conditions of 450 DEG C to be reacted, unstripped gas proportion is DME/Ar/CO=1/2/47, gas
Air speed is 3000h-1, 200 DEG C of reaction temperature, reaction pressure 1.5MPa carries out activity rating.
Embodiment 2-5
Under conditions of other conditions are identical with embodiment 1, only change first time crystallization time, respectively 1h is (real
Apply example 2), 1.5h (embodiment 3), 2h (embodiment 4), after 2.5h (embodiment 5), reaction kettle is taken out into fast cooling to room temperature
After (20-25 DEG C), second of crystallization is carried out, after the completion of crystallization, after removed template method, ammonium ion exchange, dry, roasting, is obtained
To H-MOR molecular sieve.
The H-MOR of 1 microwave crystallization difference chilling period of table is catalyzed Dimethyl ether carbonylation methyl acetate reaction result
The results show that in the case where total crystallization time is certain, the chilling of different time, available grain size difference
H-MOR, while crystal grain it is smaller be more conducive to catalyst activity raising.
Embodiment 6-10
Under conditions of other conditions are identical with embodiment 5, silica solution is changed to sodium metasilicate, and water supplement (is implemented
Example 6), fumed silica (embodiment 7), tetraethyl ammonium hydroxide is changed to tetraethylammonium bromide, and water supplement (embodiment
8) sodium hydroxide, is changed to potassium hydroxide (embodiment 9), seed load is changed to 0.2g (embodiment 10).
Embodiment 11-12
Under conditions of other conditions are identical with embodiment 10, after adding template tetraethyl ammonium hydroxide,
It adds 0.5g ammonium nitrate (embodiment 11), the additional amount of sodium metaaluminate is changed to 0.492g (embodiment 12).
Influence of the 2 microwave crystallization source material of table to H-MOR catalysis Dimethyl ether carbonylation methyl acetate reaction
The results show that optimal raw material is sodium hydroxide, silica solution, sodium metaaluminate and tetraethyl ammonium hydroxide, addition is brilliant
Kind can reduce crystallite dimension, improve catalyst activity, and increasing silica alumina ratio can reduce crystallite dimension, but reduce activity.
Embodiment 13-16
Under conditions of other conditions are identical with embodiment 10, total crystallization time is changed to 4h (embodiment 13), it will
Crystallization temperature is changed to 150 DEG C (embodiments 14), and crystallization pressure is changed to 5MPa (embodiment 15), digestion time is changed to (real for 24 hours
Apply example 16).
Influence of the 3 microwave crystallization condition of table to H-MOR catalysis Dimethyl ether carbonylation methyl acetate reaction
The results show that optimal crystallization condition be crystallization time be 5h, crystallization temperature is 170 DEG C, crystallization pressure 6MPa,
Extending digestion time then can reduce crystallite dimension, improve catalyst activity.
Comparative example 1
Under conditions of other conditions are identical with embodiment 16, crystal pattern is changed to hydro-thermal method by microwave method, always
Crystallization time is 5 days.
Comparative example 2-5
Under conditions of other conditions are identical with embodiment 16, during hydrothermal synthesis, first time crystallization time is
Reaction kettle is taken out fast cooling to room temperature by 3h (comparative example 2), 6h (comparative example 3), 12h (comparative example 4), for 24 hours (comparative example 5)
After (20-25 DEG C), second of crystallization is carried out, after the completion of crystallization, after removed template method, ammonium ion exchange, dry, roasting, is obtained
To H-MOR molecular sieve.
The H-MOR of 4 hydrothermal synthesis difference chilling period of table is catalyzed Dimethyl ether carbonylation methyl acetate reaction result
The results show that the H-MOR crystal grain that hydrothermal synthesis obtains is larger, and catalyst performance is poor compared with microwave crystallization.
Embodiment 17
Under conditions of other conditions are identical with embodiment 16, H-MOR molecular sieve that embodiment 16 is prepared
Copper modified catalyst is prepared using exchange process, is used for dimethyl ether carbonylation reaction.Copper modified catalyst is the preparation method is as follows: weigh
0.76gCu(NO3)2·3H2O is configured to 100mL aqueous solution, and the H-MOR molecular sieve that 10g is prepared is added into above-mentioned solution
After exchanging 2h, suction filtration at 80 DEG C, drying for 24 hours, then places it in 500 DEG C of Muffle furnaces roasting 4h at 110 DEG C.
Embodiment 18
Under conditions of other conditions are identical with embodiment 16, H-MOR molecular sieve that embodiment 16 is prepared
Copper modified catalyst is prepared using infusion process, is used for dimethyl ether carbonylation reaction.Copper modified catalyst is the preparation method is as follows: weigh
0.76gCu(NO3)2·3H2O is configured to 100mL ethanol solution, and the H-MOR molecule that 10g is prepared is added into above-mentioned solution
After sieve impregnates 4h, suction filtration at 40 DEG C, drying for 24 hours, then places it in 500 DEG C of Muffle furnaces roasting 4h at 110 DEG C.
Embodiment 19
Under conditions of other conditions are identical with embodiment 16, H-MOR molecular sieve that embodiment 16 is prepared
Copper modified catalyst is prepared using cuprammonium process, is used for dimethyl ether carbonylation reaction.Copper modified catalyst is the preparation method is as follows: weigh
0.76gCu(NO3)2·3H2O is configured to 100mL copper ammon solution, and the pH of copper ammon solution is adjusted to 11, is added into above-mentioned solution
A small amount of ammonium hydroxide is added thereto again after the H-MOR molecular sieve that 10g is prepared, and the pH of aforesaid liquid is adjusted to 11, at 40 DEG C
Under the conditions of keep 2h, after suction filtration, at 110 DEG C it is dry for 24 hours, then place it in 500 DEG C of Muffle furnaces roasting 4h.
Embodiment 20
Under conditions of other conditions are identical with embodiment 16, H-MOR molecular sieve that embodiment 16 is prepared
Copper modified catalyst is prepared using ammonia still process method, is used for dimethyl ether carbonylation reaction.Copper modified catalyst is the preparation method is as follows: take Cu
(NO3)2·3H2O 0.76g configures 100mL copper ammon solution, and adjusting pH is about 11, and the H-MOR molecular sieve that 10g is prepared is added
It adds a small amount of ammonium hydroxide thereto again afterwards, the pH of aforesaid liquid is adjusted to 11, keep 3h under the conditions of 40 DEG C, be warming up to 80 DEG C of steamings
After ammonia 2h, suction filtration, drying for 24 hours, then places it in 500 DEG C of Muffle furnaces roasting 4h at 110 DEG C.
The H-MOR of 5 different Cu upload method of table is catalyzed Dimethyl ether carbonylation methyl acetate reaction result
| Catalyst sample | DME conversion ratio (%) | MA selectivity (%) | MA space-time yield (mg/L.h) |
| Embodiment 17 | 80 | 99 | 276 |
| Embodiment 18 | 79 | 99 | 273 |
| Embodiment 19 | 88 | 99 | 304 |
| Embodiment 20 | 83 | 99 | 287 |
The results show that upper copper-loaded H-MOR increases the active site of dimethyl ether carbonylation reaction, it is living to improve catalyst
Property.Meanwhile the Cu/H-MOR activity that cuprammonium process obtains is optimal.
Embodiment 21
Under conditions of other conditions are identical with embodiment 17, metal precursor copper nitrate is changed to silver nitrate, is used
In dimethyl ether carbonylation reaction.Specifically the preparation method is as follows: weighing 1.40gAgNO3It is configured to 100mL aqueous solution, in no ring of light
Under border, after the H-MOR molecular sieve that addition 10g is prepared into above-mentioned solution exchanges 2h, suction filtration at room temperature, at 110 DEG C
Drying for 24 hours, then places it in 500 DEG C of Muffle furnaces roasting 4h.
Embodiment 22
Under conditions of 17 is identical, metallic precursor copper nitrate is changed to cobalt nitrate, is used for dimethyl ether carbonylation reaction.
Specifically the preparation method is as follows: weighing 1.18Co (NO3)2·6H2O is configured to 100mL aqueous solution, and 10g system is added into above-mentioned solution
After standby obtained H-MOR molecular sieve exchanges 2h, suction filtration at room temperature, drying for 24 hours, then places it in 500 DEG C of horses at 110 DEG C
Not furnace roasts 4h.
| Catalyst sample | DME conversion ratio (%) | MA selectivity (%) | MA space-time yield (mg/Lh) |
| Embodiment 21 | 80 | 99 | 275 |
| Embodiment 22 | 81 | 99 | 279 |
All metal component mass contents 0.5~10%, preferably 2%~5%.
Illustrative description has been done to the present invention above, it should explanation, the case where not departing from core of the invention
Under, any simple deformation, modification or other skilled in the art can not spend the equivalent replacement of creative work equal
Fall into protection scope of the present invention.
Claims (10)
1. the preparation method of mordenite molecular sieve catalyst, it is characterised in that: carry out as steps described below:
Step 1, ageing is added water and stirred into silicon source, silicon source and alkali source form colloidal sol；
Wherein, silicon source is silica solution, sodium metasilicate, silica or ethyl orthosilicate, and silicon source is sodium metaaluminate or aluminium oxide, alkali
Source is sodium hydroxide or ammonium hydroxide；
Stirring is 1-24h using mechanical stirring either magnetic agitation, stirring digestion time；
Step 2, template, cation and crystal seed are added in the colloidal sol that step 1 is prepared, are stirred ageing；
Wherein, template is that perhaps tetraethylammonium bromide cation is ammonium nitrate or ammonium chloride to tetraethyl ammonium hydroxide；
In step 2, stirring is to be less than or equal to for 24 hours, preferably greater than zero using mechanical stirring either magnetic agitation, digestion time
4-24h；
Step 3, sample step 2 being prepared is added in autoclave, and microwave high pressure reaction system is put into after sealing
Autoclave is taken out fast cooling to after 20-25 DEG C of room temperature after first time crystallization 0.1-48h by middle progress first time crystallization,
Autoclave is placed into microwave high pressure reaction system again and carries out second of crystallization, so that total crystallization time is 3-9 days,
After the completion of second of crystallization, the product in autoclave is taken out, being washed to PH is that 6.5-7.5 is obtained after drying, roasting
Na-MOR molecular sieve；
Wherein, drying temperature is 100-150 DEG C, drying time 5-10h, and maturing temperature is 500-600 DEG C, calcining time 2-
6h；
Step 4, the Na-MOR molecular sieve that step 3 is prepared is uniformly dispersed in ammonium nitrate or ammonium chloride liquid and is carried out
Ammonia exchange after ammonia exchanges 2-3 times, after drying, roasting, obtains H-MOR molecular sieve；
Wherein, the concentration of ammonium nitrate solution either ammonium chloride solution is 0.1-1mol/L, and the condition of ammonia exchange: swap time is
5-7h, exchange temperature are 50-70 DEG C, and the solid-to-liquid ratio of Na-MOR molecular sieve and ammonium nitrate solution either ammonium chloride solution is 1:
(8-12)；
Wherein, drying temperature is 100-150 DEG C, drying time 5-10h, and maturing temperature is 400-600 DEG C, calcining time 1-
5h。
2. the preparation method of mordenite molecular sieve catalyst according to claim 1, it is characterised in that: in the step
In 1, the molar ratio of Si and Al is (5-25) in silicon source and silicon source: 1, OH in alkali source and silicon source-Molar ratio with Al is (2-8):
1, preferably (3-6): 1, the molar ratio of Si is (0-10) in water and silicon source: 1, and do not include 0:1 and 10:1.
3. the preparation method of mordenite molecular sieve catalyst according to claim 1, it is characterised in that: in the step
In 2, the molar ratio of Si is (0.1-0.4) in template and silicon source: 1, the cationic molar ratio with Si in silicon source is (0.03-
0.1): 1, preferably (0.05-0.09): 1, the additional amount of crystal seed is the 1-10wt% of silicon source quality.
4. the preparation method of mordenite molecular sieve catalyst according to claim 1, it is characterised in that: in the step
In 3, the reaction condition of microwave high pressure reaction system: crystallization temperature be 150-200 DEG C, preferably 150-170 DEG C, crystallization pressure 1-
10MPa, preferably 5-7MPa, first time crystallization time are 0.1-3.0h, and preferably 0.5-2.5h, total crystallization time is 1-9h, preferably
4-5h。
5. the preparation method of mordenite molecular sieve catalyst according to claim 1, it is characterised in that: in the step
In 3, the reaction condition of hydro-thermal reaction system: crystallization temperature be 150-200 DEG C, preferably 150-170 DEG C, crystallization pressure 1-
10MPa, preferably 5-7MPa, first time crystallization time are 3-24h, and total crystallization time is 4-6 days.
6. the preparation method of mordenite molecular sieve catalyst according to claim 1, it is characterised in that: in the step
In 4, the concentration of ammonium nitrate solution either ammonium chloride solution is 0.4-0.6mol/L, in the step 4, the item of ammonia exchange
Part: swap time 5.5-6.5h, exchange temperature are 55-65 DEG C, Na-MOR molecular sieve and ammonium nitrate solution either ammonium chloride
The solid-to-liquid ratio of solution is 1:(9-11).
7. the preparation method of mordenite molecular sieve catalyst according to claim 1, it is characterised in that: by the step
The 4 H-MOR molecular sieves being prepared will single activity using ion-exchange, infusion process, ammonia still process method or Solid-state Ion-exchange method
Metal or double activated metal component are loaded on H-MOR molecular sieve, and the list active metal is in copper, silver, iron, cobalt or nickel
Any, the double activated metal component is any two kinds in copper, silver, iron, cobalt or nickel.
8. the silk being prepared using the preparation method of the mordenite molecular sieve catalyst any in claim 1 to 7
Geolyte molecular sieve catalyst.
9. the modenite molecule that the preparation method of mordenite molecular sieve catalyst according to claim 1 is prepared
The application of sieve catalyst or mordenite molecular sieve catalyst according to any one of claims 8 in carbonylation acetic acid methyl esters.
10. mordenite molecular sieve catalyst according to claim 9 and its answering in carbonylation acetic acid methyl esters
With, it is characterised in that: reaction condition: the molar ratio of raw material is n (CH3OCH3): n (CO)=1:(5-60), reaction temperature is
180-220 DEG C, reaction pressure 1-3MPa, gas air speed is 1000-4000h-1。
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