CN107376987A - Prepared By Dual-template Method synthesizing flokite molecular sieve catalyst and its application in methanol/dimethyl ether carbonylation - Google Patents
Prepared By Dual-template Method synthesizing flokite molecular sieve catalyst and its application in methanol/dimethyl ether carbonylation Download PDFInfo
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- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
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- C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
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Abstract
The present invention discloses Prepared By Dual-template Method synthesizing flokite molecular sieve catalyst and its application in methanol/dimethyl ether carbonylation, using the mordenite molecular sieve with octatomic ring structure as crystal seed, nitrogenous hybrid molecule and tetraethyl ammonium hydroxide are used as composite mould plate agent, is prepared by ageing and crystallization.Compared with prior art, double template has been used during due to synthesis, the catalyst of the present invention can efficiently control the aluminium element distribution of mordenite molecular sieve, enable entering in octatomic ring for aluminium element selectivity, so as to improve the activity of Dimethyl ether carbonylation synthesis of acetic acid methyl esters reaction, while the element silicon loss amount in material liquid reduces, it is readily synthesized the MOR compared with high silica alumina ratio, and there is higher catalytic activity, and it is environmentally friendly, it is pollution-free.
Description
Technical field
The invention belongs to lift the catalysis technique of methanol or Dimethyl ether carbonylation synthesis of acetic acid methyl esters reactivity, more have
Say body, be related to a kind of catalyst for carbonyl synthesis of acetic methyl esters and preparation method thereof.
Background technology
Methyl acetate (methyl acetate, referred to as MA), have the advantages that toxicity is low, biodegradable, and chemistry
Property is active, and solubility property is excellent, is expected to progressively replace acetone, butanone, ethyl acetate, pentamethylene etc. to make solvent, applied to painting
The fields such as material, ink, resin, adhesive.Pass through methyl acetate hydrogenation synthesis ethanol simultaneously, it is possible to achieve by synthesis gas ethanol
Indirect method process route, be advantageous to mitigate dependence of the China to petroleum resources, ensure the great need of China's energy strategy development
Ask.
The synthesis technique of methyl acetate includes acetic acid methanol esterification process, methanol/ethanol dehydrogenation synthetic method, methyl formate homology
Change method, methanol/dimethyl ether carbonylation method etc..Wherein methanol/dimethyl ether carbonyl compound is high into methyl acetate technique Atom economy,
Reaction condition is gentle, meets the requirement of green chemical industry.With the introducing of molecular sieve series catalysts, the advantage of the technique is more prominent
Go out：Avoid the use of halide, catalyst is cheap and easy to get and easy recovery, and the selectivity of methyl acetate is high, has huge
Industrial prospect.
The reaction of the technique is as follows：
2CH3OH+CO→CH3COOCH3+H2O (methanol carbonyl)
CH3OCH3+CO→CH3COOCH3(Dimethyl ether carbonylation)
At present, the document and patent on the catalysts and technical study increase year by year, are born mainly around noble metal
Two catalyst systems of heteropoly acid and molecular sieve of load conduct a research.But consider catalytic reaction Cost Problems, most of scholar
The research of molecular sieve is concentrated on, how modenite (MOR), the ZSM-35 particularly with octatomic ring structure obtain reactivity
Preferably catalyst has attracted the concern of many scholars.
The content of the invention
It is an object of the invention to overcome the deficiencies in the prior art, obtains the reaction of Dimethyl ether carbonylation synthesis of acetic acid methyl esters and lives
Property preferably catalyst, there is provided synthesize the preparation method of MOR molecular sieves, one of which suitable for the double template of the reaction system
Structure inducer (template) is tetraethyl ammonium hydroxide, and another (template) is nitrogen heterocyclic ring organic molecule.In this way
Obtained H-MOR catalyst activities are high, selectivity is good, preparation process is simple, are easy to industrial amplification.
The technical purpose of the present invention is achieved by following technical proposals：
Molecular sieve catalyst based on modenite, has modenite crystalline phase and crystallinity is high, same in preparation process
When use tetraethyl ammonium hydroxide and nitrogen heterocyclic ring molecule as double template so that Al elements are enriched with octatomic ring, increase
B acid quantity in octatomic ring.
Nitrogen heterocyclic ring molecule (Nitrogenous Heterocyclic Compounds, be abbreviated as NHC) is pyrrolidines, pyrrole
Pyridine, piperidines, 1,1- diethyls phenylpiperidines, cycloheximide or cycloheptyl imines.
During in progress in use, using tetraethyl ammonium hydroxide as main body, tetraethyl ammonium hydroxide and nitrogen heterocyclic ring molecule
Mol ratio is (2-25)：1, preferably (5-25)：1.
Carrying out in use, during using nitrogen heterocyclic ring molecule as main body, nitrogen heterocyclic ring molecule and tetraethyl ammonium hydroxide rub
Your ratio is (3-30)：1, preferably (10-30)：1.
The method of Prepared By Dual-template Method synthesizing flokite molecular sieve catalyst, is carried out as steps described below：
Step 1, silicon source, silicon source and alkali source are well mixed and form colloidal sol
In step 1, the silicon source is Ludox, tetraethyl orthosilicate or silica, and silicon source is sodium metaaluminate
(NaAlO2), alkali source is sodium hydroxide (NaOH), and when forming colloidal sol, selection is added water and is stirred, so that mixing is fully equal
It is even.
In step 1, stirring uses mechanical agitation, or magnetic agitation, and speed is 100-00 turn per minute, and stirring 1~
6h, preferably 3~5h.
Step 2, after nitrogen heterocyclic ring molecule and tetraethyl ammonium hydroxide (TEAOH) being well mixed, it is added to step 1 and prepares
Colloidal sol in and be aged and crystallization, nitrogen heterocyclic ring molecule, tetraethyl ammonium hydroxide are being added to colloidal sol prepared by step 1
In after, in the mixed system of formation, in terms of mole Billy, silica：Sodium metaaluminate：Sodium hydroxide：Tetraethyl hydroxide
Ammonium：Nitrogen heterocyclic ring molecule：Water=1：(0.01~0.2)：(0.1~0.4)：(being more than zero and less than or equal to 0.45)：(be more than zero and
Less than or equal to 0.5)：(10~25), i.e. 1.0SiO2:aNaAlO2:bNaOH:cTEAOH：dNHC：eH2O, wherein a=0.01~
0.2, b=0.1~0.4, c are more than 0 and are more than 0 less than or equal to 0.45, d and are less than or equal to 0.5, e=10~25
In step 2, persistently it is stirred when being aged, stirring uses the mechanical agitation, or magnetic agitation, speed to be
100-00 turn per minute, Aging Temperature is 20-25 degrees Celsius of room temperature, and digestion time is more than zero and is less than or equal to 48h, preferably
4~24h.
In step 2, crystallization temperature is 140~200 DEG C, and preferably 160~180 DEG C, crystallization time is 24~120h, preferably
48~72h.
In step 2, nitrogen heterocyclic ring molecule (Nitrogenous Heterocyclic Compounds, be abbreviated as NHC)
For pyrrolidines, pyridine, piperidines, 1,1- diethyls phenylpiperidines, cycloheximide or cycloheptyl imines.
Due to adding water in step 1 to form colloidal sol, in addition Ludox (mass percent of silica be 15-
30%) contain water, calculate water mole when need simultaneously consider Ludox reclaimed water and addition water so that water dosage meet will
Ask；Silicon source is Ludox, tetraethyl orthosilicate or silica simultaneously, carries out molar ratio with the silica after conversion
Computing, such as need to calculate mole of silica in Ludox according to the mass percent of silica during selection Ludox
Quantity, require to carry out feeding further according to molar ratio；Select to need the silica that can be generated according to it during tetraethyl orthosilicate
Molal quantity calculate tetraethyl orthosilicate dosage.
Step 3, pH will be washed to after the sample filtering after crystallization<10, dry after with 1-5 DEG C/min heating rate from
20-25 degrees Celsius of room temperature is warming up to 450~550 DEG C, keeps 4-6h, drops 20-25 degrees Celsius of room temperature processed naturally, that is, obtains Na
Type MOR；
In step 3, pH is washed to as after 7-8,4-8h is dried under 100-120 degrees Celsius.
In step 3,500~550 DEG C are warming up to for 20-25 degrees Celsius from room temperature with 1-3 DEG C/min heating rate, protected
4-5h is held, drops 20-25 degrees Celsius of room temperature processed naturally.
Step 4, Na-MOR molecular sieves prepared by step 3 are dispersed in aqueous ammonium nitrate solution, carry out ammonia exchange
In step 4, in aqueous ammonium nitrate solution, the concentration of ammonium nitrate is 0.1~1mol/L, preferably 0.2~0.5mol/
L。
In step 4, when carrying out ammonia exchange, add excessive aqueous ammonium nitrate solution and carry out, temperature is 20~80 DEG C, is continued
2-12h is stirred, preferably 40-60 degrees Celsius, persistently stirs 5-10h.
Step 5, after the molecular sieve drying that will be exchanged by step 4 ammonia, with 1~2 DEG C/min programming rates from room temperature 20-
25 degrees Celsius are warming up to 450~550 DEG C, keep 2~6h, are down to 20-25 degrees Celsius of room temperature naturally, obtain H types modenite point
Son sieve, labeled as H-MOR.
In steps of 5, the molecular sieve exchanged by step 4 ammonia carries out filtering washing, dry 1 at 100~120 DEG C~
6h, naturally cool to 20-25 degrees Celsius of room temperature.
In steps of 5,500~550 DEG C are warming up to, keeps 3~4h.
Application of the above-mentioned molecular sieve catalyst in methyl acetate is prepared, methanol carbonyl is carried out with methanol and carbon monoxide
Reaction, or carried out with dimethyl ether (abbreviation DME) and carbon monoxide in dimethyl ether carbonylation reaction.Reaction temperature is 150~250
DEG C, preferably 160-200 degrees Celsius；Reaction pressure is 1.0~3.5MPa, preferably 2-3Mpa；Material benzenemethanol and carbon monoxide
Raw materials components mole ratio is 1:7~1:100, preferably 1：30—1：80, more preferred 1：50—1：60；Using N2, He or Ar etc. dry
Inert gas is pretreatment gas, and the total air speed of gaseous mixture (feedstock) is 1000h-1~10000h-1, preferably 2000-8000h-1, more preferred 3000-6000h-1。
Compared with prior art, the advantage of the invention is that prepared mordenite molecular sieve catalyst (can from Fig. 1
To find out that the molecular sieve for using double template synthesis has typical modenite crystalline phase and maintains higher crystallinity, be free of
Have amorphous substance or other dephasigns), due to synthesis during used double template, can compared with traditional H types catalyst
The aluminium element distribution of mordenite molecular sieve is efficiently controlled, enables entering in octatomic ring for aluminium element selectivity, so as to
The activity of Dimethyl ether carbonylation synthesis of acetic acid methyl esters reaction is improved, wherein methyl acetate space-time yield is up to 500mgg-1 cath-1
More than.On the other hand, the more simple tetraethyl ammonium hydroxide of this method is the sample of template synthesis, the element silicon in its material liquid
Loss amount is low, is readily synthesized the MOR compared with high silica alumina ratio, and has higher catalytic activity, therefore economic benefit improves.Moreover
The use of double template, more only make template synthesis MOR with nitrogenous organic heterocyclic molecule, molecular sieve crystallinity is high, nucleation rate
It hurry up, save the catalyst preparation cycle.In addition, catalyst of the present invention is environmentally friendly, it is pollution-free.
Brief description of the drawings
Fig. 1 is the XRD spectra of the mordenite molecular sieve obtained using double template in the present invention.
Fig. 2 is the mordenite molecular sieve catalytic performance figure obtained using double template in the present invention.
Fig. 3 is the mordenite molecular sieve obtained using double template in the present invention27Al NMR spectra.
Fig. 4 is the NH of the mordenite molecular sieve obtained using double template in the present invention3- TPD schemes.
Fig. 5 is the pyridine adsorption figure of the mordenite molecular sieve obtained using double template in the present invention.
Embodiment
Technical scheme is further illustrated with reference to specific embodiment.Entered in embodiment using following steps
Row is prepared (basically identical with Summary)：
(1) preparation of Na types molecular sieve：Choose suitable silicon source, silicon source, alkali source presoma and add water and be mixed
It is even, 1~6h is stirred, preferably 3~5h, above colloidal sol is sufficiently mixed uniformly, then weighs appropriate double template (one of which is
Tetraethyl ammonium hydroxide, another kind are the nitrogenous organic heterocyclic molecule such as pyrrolidines, pyridine, piperidines, cycloheximide) it is well mixed after
Add in above-mentioned mixed sols, continue 0.5~3h of stirring, preferably 1~2h, fill kettle, start crystallization, crystallization temperature is 140~190
DEG C, preferably 160~180 DEG C, crystallization time is 24~120h, preferably 48~72h.The sample that above-mentioned crystallization is completed was passed through
Filter, be washed to pH<10, it is dried overnight, with 1 DEG C/min heating rate to 550 DEG C, keeps 5h, is down to room temperature taking-up naturally, i.e.,
Na type molecular sieves are obtained, labeled as NaM.
(2) preparation of H types molecular sieve：Ammonium nitrate solution is prepared, 0.1~1M of concentration, preferably 0.2~0.5M, is weighed above-mentioned
The NaM molecular sieves being calcined after template, the above-mentioned ammonium nitrate solution prepared is mixed with NaM molecular sieves, at 80 DEG C, stirring
6h, after sample drops to room temperature, filtering is washed, and 4~6h is dried at 100~120 DEG C, is repeated twice.Sample is transferred to Muffle
In stove, 2 DEG C/min is warming up to 500 DEG C, keeps 4h, is down to room temperature naturally, finally gives the H type modenites of double template synthesis
Molecular sieve.
【Embodiment 1】
Weigh 24g Ludox (silica quality percentage is 20wt%), 0.82g sodium metaaluminates, 0.96g sodium hydroxides
In plastic beaker, it is mixed uniformly, 4h is stirred at room temperature, obtains uniform colloidal sol.
Weigh cycloheximide and tetraethyl ammonium hydroxide does double template so that the mol ratio of cycloheximide and silica
For 0.05, the mol ratio of tetraethyl ammonium hydroxide and silica is 0.23, and above-mentioned colloidal sol is added after it is sufficiently mixed uniformly
In, continue stirring 1.5h under 25 degrees Celsius of room temperature and be aged, fill kettle, start crystallization, crystallization temperature is 180 degrees Celsius, crystallization
Time is 48h.After the completion for the treatment of crystallization, filter, be washed to pH<10th, 5h is calcined under 550 DEG C of air atmospheres and removes template, 0.2M
Ammonium nitrate solution under repeated exchanged 2 times, 500 DEG C of air atmospheres roasting 4h remove deammoniation.H-mordenite is obtained labeled as 1
Number sample.
The catalyst sample (40~60 mesh) after 0.5g tablettings screening is taken at 1.5MPa, 200 DEG C, material molar ratio DME/
CO=1:49, the total air speed 6000h- of gas1Under reacted in fixed bed reactors, before reaction, catalyst original position High Purity Nitrogen
4h is swept in air-blowing.Product tail gas is incubated into gas phase on-line chromatograph analysis result.
【Embodiment 2~4】
Under conditions of other conditions are identical with embodiment 1, only change the input amount of cycloheximide so that hexamethylene is sub-
The mol ratio of amine and silica is 0.01 (embodiment 2), 0.12 (embodiment 3), 0.35 (embodiment 4), treats that it is sufficiently mixed
Added after uniformly in above-mentioned colloidal sol, continue to stir 1.5h, fill kettle, start crystallization.After the completion for the treatment of crystallization, filter, wash, being calcined,
Ammonia exchanges, roasting.
【Comparative example 1】
Sample in the comparative example 1 is that cycloheximide is not added with embodiment 1, only using tetraethyl ammonium hydroxide as template
Agent, and with sample that the mol ratio of silica is 0.23.
From activity as can be seen that compared with individually using tetraethyl ammonium hydroxide as template, when with tetraethyl hydroxide
When ammonium is main template, a small amount of cycloheximide is added, is advantageous to catalyst activity raising.
The different amounts cycloheximide H-MOR of table 1 is catalyzed Dimethyl ether carbonylation synthesis of acetic acid methyl esters reaction result
【Embodiment 5~7】
Under conditions of other conditions are identical with embodiment 1, the mol ratio of cycloheximide and silica is 0.3,
And change the input amount of tetraethyl ammonium hydroxide so that the mol ratio of tetraethyl ammonium hydroxide and silica is 0.01 (implementation
Example 5), 0.03 (embodiment 6), 0.10 (embodiment 7).Added after it is sufficiently mixed uniformly in above-mentioned colloidal sol, continue to stir
1.5h, kettle is filled, start crystallization.After the completion for the treatment of crystallization, filtering, washing, roasting, ammonia are exchanged, are calcined.
【Comparative example 2】
Sample in the comparative example 1 is that tetraethyl ammonium hydroxide is not added with embodiment 1, only using cycloheximide as template
Agent, and with sample that the mol ratio of silica is 0.3.The XRD of synthetic sample is shown in accompanying drawing 1, and all samples are the pure crystalline substances of MOR
Phase.
Activity Results can be seen that compared with individually using cycloheximide as template, when using cycloheximide as main mould
During plate agent, a small amount of tetraethyl ammonium hydroxide is added, is advantageous to catalyst activity raising.
The different amounts tetraethyl ammonium hydroxide H-MOR of table 2 is catalyzed Dimethyl ether carbonylation synthesis of acetic acid methyl esters reaction result
【Embodiment 8~11】
In the case where other experiment conditions are identical with embodiment 1, cycloheximide is changed to pyrrolidines (embodiment
8), pyridine (embodiment 9), piperidines (embodiment 10), cycloheptyl imines (embodiment 11) etc., mole of its addition and silica
Than for 0.01.Comparatively speaking, influence of other nitrogen heterocyclic ring molecules to MOR activity be not very notable, but a small amount of second mould
The use of plate agent, the synthesis yield of MOR molecular sieves is improved, reduce the loss of silica, advantageously reduce urging for the reaction
Agent cost.
H-MOR Dimethyl ether carbonylation synthesis of acetic acid methyl esters reaction result of the table 2 using different nitrogen heterocyclic ring molecules as template
【Embodiment 12~14】
In the case where other experiment conditions are identical with embodiment 8, only by the addition and silica of pyrrolidines
Mol ratio be changed to 0.05 (embodiment 12), 0.12 (embodiment 13), 0.23 (embodiment 14).By active testing, can see
Go out, the suitable addition of nitrogen heterocyclic ring template is related to species.In addition, excessive pyrrolidines also results in molecular sieve crystallinity
Decline and the generation (embodiment 13,14) of stray crystal.
The different amounts pyrrolidines H-MOR of table 3 is catalyzed Dimethyl ether carbonylation synthesis of acetic acid methyl esters reaction result
【Embodiment 15~17】
In the case where other experiment conditions are identical with embodiment 6, reaction temperature is only changed to 190 DEG C of (embodiments
15), 210 DEG C (embodiments 16), 220 DEG C (embodiments 17).By active testing as can be seen that temperature is to the activity influence of reaction
Very big, it is methyl acetate that high temperature, which is advantageous to dimethyl ether conversion, and but then, high temperature also causes rapid catalyst deactivation.
H-MOR is catalyzed Dimethyl ether carbonylation synthesis of acetic acid methyl esters reaction result at a temperature of the differential responses of table 4
【Embodiment 18~20】
In the case where other experiment conditions are identical with embodiment 6, only dimethyl ether and CO mol ratio are changed to
DME/CO=1:34 (embodiments 18), 1:29 (embodiments 19) and 1:19 (embodiments 20).By active testing as can be seen that compared with
High CO concentration is advantageous to improve the yield of methyl acetate.
The lower H-MOR catalysis Dimethyl ether carbonylation synthesis of acetic acid methyl esters reaction results of the different material gas of table 5 composition
【Embodiment 21~24】
In the case where other experiment conditions are identical with embodiment 6, reaction pressure is only changed to 1.0MPa (embodiments
21), 2.0MPa (embodiment 22), 2.5MPa (embodiment 23) and 3.0MPa (embodiment 24).By active testing as can be seen that
It is methyl acetate that low pressure, which is unfavorable for dimethyl ether conversion, and after 1.5MPa, pressure increase is on activity substantially without influence.
H-MOR is catalyzed Dimethyl ether carbonylation synthesis of acetic acid methyl esters reaction result under the differential responses pressure of table 5
【Embodiment 25~26】
In the case where other experiment conditions are identical with embodiment 6, it is (real that catalyst grain size is only changed to 10~20 mesh
Apply example 25) and 20~40 mesh (embodiment 26).By active testing it can be seen that under the reaction conditions, catalyst particle size
Do not have influence substantially on reactivity.
The different meshes H-MOR of table 6 is catalyzed Dimethyl ether carbonylation synthesis of acetic acid methyl esters reaction result
【Embodiment 27~29】
In the case where other experiment conditions are identical with embodiment 6, gas space velocity is only changed to 4500h-1(implement
Example 27), 9000h-1(embodiment 28) and 11000h-1(embodiment 29).By active testing it can be seen that in the range of investigation,
Air speed only influences the conversion ratio of dimethyl ether, and the selectivity and yield on methyl acetate are substantially without influence.
The different meshes H-MOR of table 6 is catalyzed Dimethyl ether carbonylation synthesis of acetic acid methyl esters reaction result
In order to clear and definite double template synthesis MOR molecular sieves in the reaction advantageous reason (such as the institute of accompanying drawing 1-5
Show, by taking catalyst prepared by embodiment 6 as an example), pass through Al content (Virian companies, the model of ICP-OES sign molecular sieves
VISTA-MPX),27Al NMR (Varian companies of the U.S., the type NMRs of Infinityplus 300) characterize framework of molecular sieve
Al and non-skeleton Al ratio (Microporous and Mesoporous Materials, 226,251-259), in accompanying drawing 3
Peak area near 0ppm represents non-skeleton Al content, and the peak area near 50~60ppm represents skeleton Al content, thus may be used
To calculate skeleton Al content.Using NH3- TPD (Micromeritics companies of the U.S., Atuochem II 2920) is characterized
The total acid content of molecular sieve, specific procedure are to be cooled to 150 DEG C after 1h is pre-processed under 200 DEG C, Ar gas atmosphere, pulse note NH3Extremely
Adsorption saturation, 1h is purged under Ar gas atmosphere to remove the NH of physical absorption3, 50 DEG C are then cooled to, after baseline stability, with
10 DEG C/min speed is warming up to 730 DEG C, and thermal conductivity detector (TCD) records out peak-to-peak signal (see accompanying drawing 4).To NH3- TPD carries out swarming plan
Correction is closed, passes through the calculated by peak area at high temperature peakContent (the Microporous Mesoporous of acid (B acid)
Materials,2001,47:293-301).The numerical value is consistent with skeleton Al content, it was demonstrated that the reliability of result.Then pass through
Content (U.S. Thermo Fisher Scientific, the type of B acid in pyridine adsorption infrared analysis MOR molecular sieve twelve-rings
Number Nicolet 6700).Specific procedure is：Vacuum pre-treatment 30min, cooling at 450 DEG C by sample in pond are transmitted in the original location
To 150 DEG C of scanning background spectrograms, about 30min is vacuumized after excess pyridine steam Static Adsorption 30min and sloughs gaseous state and physics suction
Attached Pyridine Molecules, scanning times 32 times, resolution ratio 4cm-1Acquisition sample spectrogram.Can by the peak area at peak at 1540cm-1
The B acid for calculating twelve-ring measures (see accompanying drawing 5) (Applied Catalysis A:General 417–418(2012)236–
242).Finally, the two is subtracted each other to the content for obtaining octatomic ring B acid, thus respectively obtain the B acid amount of twelve-ring and octatomic ring with
And ratio.Wherein comparative example 3,4 is that (comparative example 3 is bought in Yangzhou and Co., Ltd of petrochemical industry research institute, comparative example for different manufacturers
4 buy in Tianjin Nan Hua catalyst Co., Ltd) purchase Si/Al be 8~9 sample.According to the literature, typically synthesize
Octatomic ring accounts for 55% or so (i.e. 50~60%) of total B acid amount.And ring-type alkali molecules in Hydrothermal Synthesiss because molecular dimension
Limitation, which can preferentially occupy twelve-ring duct, causes Al atoms to be easier to insert octatomic ring.But individually with ring-type alkaline molecular sieve
For template when, although the content B acid amounts of octatomic ring are also of a relatively high, the active force of its structure directing is again weaker, influences molecule
The generated time and crystallinity of sieve.Therefore, it is used in mixed way using two kinds of templates, higher crystallization can be reached in a short time
Degree, and can control dropping place of the Al atoms in octatomic ring, cause Al elements to be enriched with octatomic ring, increase the B acid in octatomic ring
Quantity, it is final to obtain the catalyst for being more conducive to dimethyl ether/methanol carbonylation.
Table 7 synthesizes the B acid position content of MOR molecular sieves octatomic ring and twelve-ring
The scheme recorded according to Summary in the present invention carries out the adjustment of technological parameter, can prepare the present invention's
Catalyst, after being tested using above-mentioned characterization method, substantially show the structure and performance consistent with embodiment.
Exemplary description has been done to the present invention above, it should explanation, in the situation for the core for not departing from the present invention
Under, any simple deformation, modification or other skilled in the art can not spend the equivalent substitution of creative work equal
Fall into protection scope of the present invention.
Claims (10)
1. the molecular sieve catalyst based on modenite, it is characterised in that there is modenite crystalline phase and crystallinity is high, preparing
During use tetraethyl ammonium hydroxide and nitrogen heterocyclic ring molecule simultaneously as double template so that Al elements richness in octatomic ring
Collection, increases the B acid quantity in octatomic ring, and the nitrogen heterocyclic ring molecule is pyrrolidines, pyridine, piperidines, 1,1- diethyls phenylpiperidines, ring
Own imines or cycloheptyl imines；Carrying out in use, during using tetraethyl ammonium hydroxide as main body, tetraethyl ammonium hydroxide with it is nitrogenous
The mol ratio of heterocyclic molecular is (2-25)：1；During using nitrogen heterocyclic ring molecule as main body, nitrogen heterocyclic ring molecule and tetraethyl hydroxide
The mol ratio of ammonium is (3-30)：1.
2. the molecular sieve catalyst according to claim 1 based on modenite, it is characterised in that carry out in use,
During using tetraethyl ammonium hydroxide as main body, the mol ratio of tetraethyl ammonium hydroxide and nitrogen heterocyclic ring molecule is (5-25)：1；With containing
When azacyclic molecules are main body, the mol ratio of nitrogen heterocyclic ring molecule and tetraethyl ammonium hydroxide is (10-30)：1.
3. the method for Prepared By Dual-template Method synthesizing flokite molecular sieve catalyst, it is characterised in that carry out as steps described below：
Step 1, silicon source, silicon source and alkali source are well mixed and form colloidal sol；The silicon source be Ludox, tetraethyl orthosilicate or
Silica, silicon source are sodium metaaluminate, and alkali source is sodium hydroxide, and addition water is selected when forming colloidal sol and is stirred, so that
Mix full and uniform；
Step 2, after nitrogen heterocyclic ring molecule and tetraethyl ammonium hydroxide being well mixed, it is added in the colloidal sol of step 1 preparation simultaneously
It is aged and crystallization, after being added to nitrogen heterocyclic ring molecule, tetraethyl ammonium hydroxide in colloidal sol prepared by step 1, in shape
Into mixed system in, in terms of mole Billy, silica：Sodium metaaluminate：Sodium hydroxide：Tetraethyl ammonium hydroxide：Nitrogen-containing hetero
Toroidal molecule：Water=1：(0.01~0.2)：(0.1~0.4)：(being more than zero and less than or equal to 0.45)：(it is more than zero and is less than or equal to
0.5)：(10~25), persistently it is stirred when being aged, Aging Temperature is room temperature, and digestion time is more than zero and is less than
Equal to 48h, crystallization temperature is 140~200 DEG C, and crystallization time is 24~120h, and nitrogen heterocyclic ring molecule is pyrrolidines, pyridine, piperazine
Pyridine, 1,1- diethyls phenylpiperidines, cycloheximide or cycloheptyl imines；During in progress in use, using tetraethyl ammonium hydroxide as main body,
The mol ratio of tetraethyl ammonium hydroxide and nitrogen heterocyclic ring molecule is (2-25)：1；During using nitrogen heterocyclic ring molecule as main body, nitrogen-containing hetero
The mol ratio of toroidal molecule and tetraethyl ammonium hydroxide is (3-30)：1；
Step 3, pH will be washed to after the sample filtering after crystallization<10, after drying with 1-5 DEG C/min heating rate from room temperature
20-25 degrees Celsius are warming up to 450~550 DEG C, keep 4-6h, drop 20-25 degrees Celsius of room temperature processed naturally, that is, obtain Na types
MOR；
Step 4, Na-MOR molecular sieves prepared by step 3 are dispersed in aqueous ammonium nitrate solution, carry out ammonia exchange；
Step 5, after the molecular sieve drying that will be exchanged by step 4 ammonia, taken the photograph with 1~2 DEG C/min programming rates from room temperature 20-25
Family name's degree is warming up to 450~550 DEG C, keeps 2~6h, is down to 20-25 degrees Celsius of room temperature naturally, obtains H type modenite molecules
Sieve, labeled as H-MOR.
4. the method for Prepared By Dual-template Method synthesizing flokite molecular sieve catalyst according to claim 3, it is characterised in that
In step 1, stirring use mechanical agitation, or magnetic agitation, and speed is 100-00 turn per minute, stirring 1~6h, and preferably 3
~5h.
5. the method for Prepared By Dual-template Method synthesizing flokite molecular sieve catalyst according to claim 3, it is characterised in that
In step 2, persistently it is stirred when being aged, stirring uses mechanical agitation, or magnetic agitation, and speed is per minute
100-00 turn, Aging Temperature is 20-25 degrees Celsius, and digestion time is 4~24h；Crystallization temperature is 160~180 DEG C, during crystallization
Between be 48~72h.
6. the method for Prepared By Dual-template Method synthesizing flokite molecular sieve catalyst according to claim 3, it is characterised in that
In step 3, pH is washed to as after 7-8,4-8h is dried under 100-120 degrees Celsius；With 1-3 DEG C/min heating rate
From room temperature, 20-25 degrees Celsius are warming up to 500~550 DEG C, keep 4-5h, drop 20-25 degrees Celsius of room temperature processed naturally.
7. the method for Prepared By Dual-template Method synthesizing flokite molecular sieve catalyst according to claim 3, it is characterised in that
In step 4, in aqueous ammonium nitrate solution, the concentration of ammonium nitrate is 0.1~1mol/L, preferably 0.2~0.5mol/L；Carry out ammonia
During exchange, add excessive aqueous ammonium nitrate solution and carry out, temperature is 20~80 DEG C, persistently stirs 2-12h, preferably 40-60 take the photograph
Family name's degree, persistently stir 5-10h.
8. the method for Prepared By Dual-template Method synthesizing flokite molecular sieve catalyst according to claim 3, it is characterised in that
In steps of 5, the molecular sieve exchanged by step 4 ammonia carries out filtering washing, and 1~6h is dried at 100~120 DEG C, naturally cold
But to 20-25 degrees Celsius of room temperature；In steps of 5,500~550 DEG C are warming up to, keeps 3~4h.
9. the molecular sieve catalyst based on modenite as described in claim 1 or 2, or the side according to claim 3
The application of catalyst prepared by method in methyl acetate is prepared, it is characterised in that methanol carbonyl is carried out with methanol and carbon monoxide
Change reaction, or dimethyl ether carbonylation reaction is carried out with dimethyl ether and carbon monoxide.
10. application according to claim 9, it is characterised in that reaction temperature is 150~250 DEG C, and preferably 160-200 take the photograph
Family name's degree；Reaction pressure is 1.0~3.5MPa, preferably 2-3Mpa；The raw materials components mole ratio of material benzenemethanol and carbon monoxide is 1:7~
1:100, preferably 1：30—1：80, more preferred 1：50—1：60；Using N2, the dry inert gas such as He or Ar be pretreatment gas
Body, the total air speed of gaseous mixture are 1000h-1~10000h-1, preferably 2000-8000h-1, more preferred 3000-6000h-1。
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