CN109847789A - The method that bifunctional catalyst and preparation method thereof, toluene and methanol prepare styrene - Google Patents
The method that bifunctional catalyst and preparation method thereof, toluene and methanol prepare styrene Download PDFInfo
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Abstract
The invention discloses the methods that a kind of bifunctional catalyst and preparation method thereof, toluene and methanol prepare styrene.The bifunctional catalyst, the Silicate-1 molecular sieve comprising alkaline molecular sieve and metal ion exchanged；Preparation method is simple.Bifunctional catalyst provided by the present invention is applied in toluene and methanol side chain alkylation reaction process, effectively increases toluene conversion, use ratio of methanol and styrene yield.
Description
Technical field
The present invention relates to the methods that a kind of bifunctional catalyst and preparation method thereof, toluene and methanol prepare styrene, belong to
In catalytic field.
Background technique
Styrene (ST) is a kind of important Organic Chemicals, mainly for the production of polystyrene (PS), acrylic nitrile-butadiene
Diene resin (ABS), expansible polystyrene (EPS), SBR styrene butadiene rubbers (SBR) etc..Currently, industrial traditional
Production of styrene technology is ethylbenzene dehydrogenation method, mainly by Friedel-Craft reaction, catalytic dehydrogenating reaction, finally obtains benzene
Ethylene, a systems such as that there is process routes is long for this method, equipment investment is big, side reaction is more, energy consumption is high, depends on petroleum resources unduly
Column problem.Therefore, new styrene Production has obtained people and has widely paid close attention to.
Japanese researchers Sidorenko in 1967 et al. (Dokl.Akad.NaukSSSR, 1967,173 (1): 132-134)
Methylbenzene methanol side chain alkylation reaction on alkali metal exchange X molecular sieve is reported for the first time, has raw material compared with ethylbenzene dehydrogenation method
From a wealth of sources, omission dehydrogenation step reduces energy consumption, reduces cost and methanol is selected to reduce as alkylating reagent to petroleum money
The dependence in source reduces the advantages such as environmental pollution, has potential application foreground.Turn however, the process route remains toluene
The problems such as rate is low, the serious utilization rate of Methanol Decomposition is low, resultant styrene is selectively low, ethyl-benzene level is higher, hinders toluene
The further industrial application of methanol side chain alkylation technique.
Summary of the invention
According to an aspect of the invention, there is provided a kind of bifunctional catalyst and preparation method thereof, which is being mentioned
While high toluene conversion, use ratio of methanol, styrene yield is improved；Solve current toluene and methanol side chain alkylation
Prepare low-conversion, low selectivity problem present in styrene reaction.
The bifunctional catalyst, which is characterized in that the Silicate-1 comprising alkaline molecular sieve and metal ion exchanged
Molecular sieve；
Wherein, the composition mass ratio of the alkaline molecular sieve and the Silicate-1 molecular sieve of metal ion exchanged is 0.1
~10:1.
Optionally, the composition quality of the alkaline molecular sieve and the Silicate-1 molecular sieve of metal ion exchanged compares the upper limit
Selected from 1:2,1:1,2:1,4:1 or 10:1；Lower limit is selected from 0.1:1,1:2,1:1,2:1 or 4:1.
Optionally, the composition mass ratio of the alkaline molecular sieve and the Silicate-1 molecular sieve of metal ion exchanged is
0.5~4:1.
Optionally, the metal ion be selected from potassium ion, copper ion, cerium ion, manganese ion, magnesium ion, molybdenum ion, zinc from
At least one of son, cesium ion.
Optionally, the alkali molecules exchange at least one of modified FAU structure molecular screen screened from alkali metal ion.
Optionally, the alkali metal ion is selected from least one of potassium ion, rubidium ion, cesium ion；
The FAU structural molecule is screened from least one of X-type molecular sieve, Y type molecular sieve；
The alkali metal ion exchanges in modified FAU structure molecular screen, and alkali metal ion exchange degree is 20~90%.
Optionally, the alkali metal ion exchange degree upper limit be selected from 23.1%, 29.8%, 51.3%, 56.1%,
58.8%, 60.9%, 62.3%, 63.2%, 63.3%, 68.7% or 90%；Lower limit be selected from 20%, 23.1%, 29.8%,
51.3%, 56.1%, 58.8%, 60.9%, 62.3%, 63.2%, 63.3% or 68.7%.
Optionally, the FAU structural molecule is screened from least one of NaX molecular sieve, NaY molecular sieve.
Optionally, the atom silica alumina ratio Si/Al of the FAU structure molecular screen is 1~10.
Optionally, the upper limit of the atom silica alumina ratio Si/Al of the FAU structure molecular screen be selected from 1.17,2.89,4.53,
5.54,8.98,9.79 or 10；Lower limit is selected from 1,1.17,2.89,4.53,5.54,8.98 or 9.79.
Optionally, the bifunctional catalyst prepares the reaction of styrene for toluene and methanol.
Another aspect of the present invention provides the preparation method of the bifunctional catalyst, which is characterized in that at least wrap
Include following steps:
(a) alkaline molecular sieve is obtained；
(b) the Silicate-1 molecular sieve of metal ion exchanged is obtained；
(c) by the mixture containing alkaline molecular sieve and the Silicate-1 molecular sieve of metal ion exchanged, ball milling 2~20
Hour, then carry out shaping of catalyst；Or
Alkaline molecular sieve and the Silicate-1 molecular sieve of metal ion exchanged are distinguished ball milling 2~20 hours, mixing is equal
Shaping of catalyst is carried out after even.
Optionally, the preparation method of alkaline molecular sieve described in step (a) include: using alkali metal precursor solution to point
After son sieve carries out ion exchange, it is separated by solid-liquid separation, washs, dries, roasts, obtain the alkaline molecular sieve；
The preparation method of the Silicate-1 molecular sieve of metal ion exchanged described in step (b) include: using metal from
After sub- precursor solution carries out ion exchange to molecular sieve, it is separated by solid-liquid separation, washs, dries, roasts, obtain the metal ion
The Silicate-1 molecular sieve of exchange.
Optionally, the preparation method of alkaline molecular sieve described in step (a) includes: using 0.2~0.6mol/L alkali metal
Precursor solution carries out ion exchange to molecular sieve, and solid-to-liquid ratio exchanges 4h at 80 DEG C when being 10:1, after filtering, wash, being dry
Obtained solid roasts 6h in Muffle furnace at 550 DEG C, be then repeated 2 times the process to get the alkaline molecular sieve is arrived.
Optionally, the upper limit of concentration of the alkali metal precursor solution is selected from 0.3mol/L, 0.4mol/L or 0.6mol/L；
Lower limit is selected from 0.2mol/L, 0.3mol/L or 0.4mol/L.
Wherein, the solid-to-liquid ratio in the ion exchange process, the temperature-time of exchange, the condition of roasting, duplicate number
Deng can be can be adjusted as needed by those skilled in the art.
As a kind of specific embodiment, the preparation method of alkaline molecular sieve described in step (a) includes: certain mass
X molecular sieve and/or Y molecular sieve, the precursor solutions pair such as 0.2~0.6mol/L potassium nitrate, rubidium nitrate, cesium nitrate are respectively adopted
Molecular sieve carries out ion exchange, and solid-to-liquid ratio exchanges 4h at 80 DEG C when being 10:1, and obtained solid is in horse after filtering, wash, being dry
6h is not roasted in furnace at 550 DEG C, then the process is repeated 2 times, obtains alkaline molecular sieve.
Optionally, the preparation method of the Silicate-1 molecular sieve of metal ion exchanged described in step (b) includes: certain
Quality Silicate-1 molecular sieve carries out ion exchange, solid-liquid to it using 0.1~0.5mol/L metal ion precursor solution
Than filtering to be exchanged for 4h when 10:1 at 80 DEG C, washing, it is dry after by obtained solid in Muffle furnace 550 DEG C of roasting 6h, so
Process is repeated 2 times afterwards, obtains the Silicate-1 molecular sieve of metal ion exchanged.
Optionally, the upper limit of concentration of the metal ion precursor solution is selected from 0.2mol/L, 0.3mol/L, 0.4mol/L
Or 0.5mol/L；Lower limit is selected from 0.1mol/L, 0.2mol/L, 0.3mol/L or 0.4mol/L.
As a kind of specific embodiment, the Silicate-1 molecular sieve of metal ion exchanged described in step (b)
Preparation method includes: certain mass Silicate-1 molecular sieve, using 0.1~0.5mol/L metal nitrate or chloride forerunner
Liquid solution carries out ion exchange to it, and solid-to-liquid ratio is exchanged for 4h at 80 DEG C when being 10:1, by gained after filtering, wash, being dry
Process, is then repeated 2 times, obtains the Silicate-1 molecule of metal ion exchanged by solid 550 DEG C of roasting 6h in Muffle furnace
Sieve.
Optionally, the alkali metal presoma is selected from least one of alkali metal salt；
The metal ion presoma is selected from least one of the corresponding nitrate of metal, chloride.
As a kind of preparation method of bifunctional catalyst described in specific embodiment, follow the steps below:
(1) alkaline molecular sieve prepare: the X molecular sieve and/or Y molecular sieve of certain mass, be respectively adopted 0.2~0.6mol/L potassium nitrate,
The precursor solutions such as rubidium nitrate, cesium nitrate carry out ion exchange to molecular sieve, and solid-to-liquid ratio exchanges 4h when being 10:1 at 80 DEG C, take out
Obtained solid roasts 6h in Muffle furnace after filter, washing, drying at 550 DEG C, is then repeated 2 times the process, obtains alkalinity point
Son sieve.
(2) the Silicate-1 system with molecular sieve for preparing of metal ion exchanged is standby: certain mass Silicate-1 molecular sieve, uses
0.1~0.5mol/L metal nitrate or chloride precursor solution carry out ion exchange to it, 80 when solid-to-liquid ratio is 10:1
Be exchanged for 4h at DEG C, filter, washing, it is dry after by obtained solid in Muffle furnace 550 DEG C of roasting 6h, then by process repetition 2
It is secondary, obtain the Silicate-1 molecular sieve of metal ion exchanged.
(3) by alkaline molecular sieve and the Silicate-1 molecular sieve of metal ion exchanged according to following two mode wherein
Bifunctional catalyst is prepared in one kind:
Mode (1): by alkaline molecular sieve and the Silicate-1 molecular sieve of ion exchange the ball milling 2- on ball mill respectively
It 20 hours, remixes and uniformly carries out shaping of catalyst；
Mode (2): after alkaline molecular sieve is mixed with the Silicate-1 molecular sieve of ion exchange, the ball milling on ball mill
Shaping of catalyst is carried out again within 2-20 hours.
Another aspect of the present invention provides a kind of method that toluene and methanol prepare styrene, which is characterized in that at least
The following steps are included: by the gaseous mixture containing methanol and toluene by the reactor containing catalyst, reaction obtains the benzene second
Alkene；
Wherein, the catalyst is selected from the bifunctional catalyst and/or is prepared according to the method double
At least one of function catalyst.
Optionally, the molar ratio of the toluene and methanol is 0.2~9:1；
The condition of the reaction are as follows: reaction temperature is 350~500 DEG C, and reaction pressure is 0.1~2MPa, toluene and methanol
Gross mass air speed is 0.2~5h-1。
Optionally, the reactor is fixed bed reactors.
Optionally, the molar ratio upper limit of the toluene and methanol is selected from 1:3,1:1,3:1,6:1 or 9:1；Lower limit is selected from 1:
3,1:1,3:1,6:1 or 9:1.
Optionally, the upper limit of the reaction temperature is selected from 380 DEG C, 420 DEG C, 460 DEG C or 500 DEG C；Lower limit be selected from 350 DEG C,
380 DEG C, 420 DEG C or 460 DEG C.
Optionally, the reaction pressure upper limit is selected from 0.5MPa, 1.0MPa or 2.0MPa；Lower limit be selected from 0.1MPa,
0.5MPa or 1.0MPa.
Optionally, the toluene and the methanol gross mass air speed upper limit are selected from 0.5h-1、1h-1、2h-1、3h-1Or 5h-1；Lower limit
Selected from 0.2h-1、0.5h-1、1h-1、2h-1Or 3h-1。
As a kind of specific embodiment, the method that the toluene and methanol prepare styrene includes at least following step
Rapid: the reaction that the toluene and methanol prepare styrene carries out in fixed bed reactors, and step is summarized as follows: taking aequum
Above-mentioned bifunctional catalyst be put into the flat-temperature zone of reactor, after quartz sand is loaded at both ends, by catalyst in helium atmosphere, 400
1~2h is activated at a temperature of~650 DEG C, then under set temperature and pressure, by the toluene prepared in proportion and carbinol mixture
Preheater is injected with micro pump, reactor is entered after mixing with carrier gas, with bifunctional catalyst bed haptoreaction, reaction product is adopted
It is analyzed with gas-chromatography.
Bifunctional catalyst of the present invention, using the Silicate-1 molecule of alkaline molecular sieve catalyst and ion exchange
Compound preparation is sieved, the reaction rate that methanol dehydrogenation generates formaldehyde process not only can be improved, inhibits Methanol Decomposition side reaction
Generation, improve the utilization rate of methanol, and gained formaldehyde is reacted as the higher alkylating reagent of activity with toluene, can be into one
Step accelerates side chain alkylation reaction, improves toluene conversion, increases side chain alkylation yield, i.e. styrene yield；Meanwhile alkalinity
The Silicate-1 molecular sieve of metal ion exchanged is added in molecular sieve, effectively inhibits the alkylation of the phenyl ring of toluene and methanol anti-
It answers, reduces the generation of the by-products such as dimethylbenzene and more toluene.
In the present invention, partial size unit " mesh " refers to that per inch is apart from interior eyelet number on the sieve for sieving different-grain diameter
Mesh.Such as 20 mesh just refer to that the eyelet on per inch is 20 sieves, 20~40 mesh are the sieves referred to through 20 mesh
The partial size retained by the sieve of 40 mesh.
The beneficial effect that the present invention can generate includes:
(1) bifunctional catalyst provided by the present invention prepares styrene reaction for toluene and methanol, first can be improved
Selectivity of styrene in benzene conversion ratio, use ratio of methanol and product；
(2) bifunctional catalyst provided by the present invention has preferable stability, continuous to transport on fixed bed reactors
Row 500h's there are no apparent deactivation phenomenom；
(3) method that toluene provided by the present invention and methanol prepare styrene, it is easy to operate, meet industrial application and wants
It asks, is convenient for large-scale industrial production.
Specific embodiment
The present invention is described in detail below with reference to embodiment, but the invention is not limited to these embodiments.
Unless otherwise instructed, the raw material in the embodiment of the present invention and catalyst are bought by commercial sources.
In embodiment, toluene and methanol are prepared in styrene reaction, toluene conversion, use ratio of methanol and styrene yield
It is calculated according to following formula:
Embodiment 1: the preparation of alkaline molecular sieve
Molecular sieve employed in embodiment is all from commercially available.
The preparation of alkali metal ion modified X molecular sieve and Y molecular sieve:
20g NaX or NaY molecular sieve are taken, respectively with presomas such as 0.2~0.6mol/L potassium nitrate, rubidium nitrate, cesium nitrates
Solution carries out ion exchange to molecular sieve, and solid-to-liquid ratio exchanges 4h at 80 DEG C when being 10:1, and gained is solid after filtering, wash, being dry
Body roasts 6h in Muffle furnace at 550 DEG C, be then repeated 2 times the process, obtains alkali metal ion modified X molecular sieve and Y
Molecular sieve, it is Q-1 that sample is numbered respectively#~Q-10#。
Gained sample number into spectrum, precursor solution type and concentration and exchange degree are as shown in table 1.Using XRF elemental analysis
Instrument (the Axios 2.4KW type of PANAbalytical company) carries out elemental analysis to acquired sample, and ion-exchange degree is according to friendship
The sodium content for changing front and back sample is calculated, calculation formula are as follows:
Ion-exchange degree=100% × (in the preceding molecular sieve of exchange after molar content-exchange of Na element in molecular sieve
The molar content of Na element)/exchange before in molecular sieve Na element molar content.
Table 1
| Sample number into spectrum | Molecular sieve | Precursor solution and concentration | Ion-exchange degree/% |
| Q-1# | NaX (Si/Al=1.17) | 0.4mol/L potassium nitrate | 62.3 |
| Q-2# | NaX (Si/Al=1.17) | 0.4mol/L rubidium nitrate | 56.1 |
| Q-3# | NaX (Si/Al=1.17) | 0.4mol/L cesium nitrate | 51.3 |
| Q-4# | NaY (Si/Al=2.89) | 0.4mol/L potassium nitrate | 68.7 |
| Q-5# | NaY (Si/Al=2.89) | 0.4mol/L rubidium nitrate | 63.2 |
| Q-6# | NaY (Si/Al=2.89) | 0.4mol/L cesium nitrate | 58.8 |
| Q-7# | NaX (Si/Al=4.53) | 0.2mol/L rubidium nitrate | 23.1 |
| Q-8# | NaX (Si/Al=8.98) | 0.6mol/L cesium nitrate | 60.9 |
| Q-9# | NaY (Si/Al=5.54) | 0.2mol/L rubidium nitrate | 29.8 |
| Q-10# | NaY (Si/Al=9.79) | 0.6mol/L cesium nitrate | 63.3 |
Embodiment 2: the preparation of the Silicate-1 molecular sieve of ion exchange
In the Silicate-1 molecular sieve of metal ion exchanged, metal ion is selected from potassium ion, copper ion, cerium ion, manganese
At least one of ion, magnesium ion, molybdenum ion, zinc ion, cesium ion.
5g Silicate-1 molecular sieve is taken, is respectively forerunner with 0.1~0.5mol/L metal nitrate or/and chloride
Liquid solution carries out ion exchange to molecular sieve, and solid-to-liquid ratio is exchanged for 4h at 80 DEG C when being 10:1, will after filtering, wash, being dry
Process, is then repeated 2 times, obtains the Silicate-1 of metal ion exchanged by obtained solid 550 DEG C of roasting 6h in Muffle furnace
Molecular sieve, gained sample number into spectrum are A-1#~A-17#。
Gained sample number into spectrum, precursor solution type, precursor solution concentration and mixed proportion are as shown in table 2.
Table 2
| Sample number into spectrum | Precursor solution | Precursor solution concentration (mol/L) | Mixed proportion |
| A-1# | KNO3 | 0.1 | -- |
| A-2# | Cu(NO3)2 | 0.1 | -- |
| A-3# | Ce(NO3)3 | 0.2 | -- |
| A-4# | Mn(NO3)2 | 0.2 | -- |
| A-5# | Mg(NO3)2 | 0.4 | -- |
| A-6# | Mo(NO3)3 | 0.4 | -- |
| A-7# | Zn(NO3)2 | 0.5 | -- |
| A-8# | CsNO3 | 0.5 | -- |
| A-9# | KCl | 0.1 | -- |
| A-10# | KNO3 | 0.2 | -- |
| A-11# | KNO3 | 0.5 | -- |
| A-12# | KNO3+Mn(NO3)2 | 0.2 | 1:1 |
| A-13# | KCl+MnCl2 | 0.2 | 1:1 |
| A-14# | KNO3+MnCl2 | 0.2 | 1:1 |
| A-15# | KNO3+Mn(NO3)2 | 0.3 | 2:1 |
| A-16# | KNO3+Cu(NO3)2+Mn(NO3)2 | 0.3 | 1:1:1 |
| A-17# | KNO3+Cu(NO3)2+Mg(NO3)2 | 0.3 | 2:1:1 |
Embodiment 3: bifunctional catalyst preparation
The alkaline molecular sieve Q-1 that embodiment 1 is prepared#~Q-6#At least one of and the obtained metal of embodiment 2
The Silicate-1 molecular sieve-4 A -1 of ion exchange#~A-17#At least one of mixing, molding is broken, screening is 20~40 mesh,
Obtained bifunctional catalyst number is D-1#~D-30#.Wherein D-1#~D-15#For alkaline molecular sieve and metal ion exchanged
The Silicate-1 molecular sieve ball milling 10h (D-1 on ball mill respectively#~D-5#)、15h(D-6#~D-10#)、20h(D-11#
~D-15#), by evenly mixing after, then formed；D-16#~D-30#For alkaline molecular sieve and metal ion exchanged
Silicate-1 molecular sieve after mixing, the ball milling 10h (D-16 on ball mill#~D-20#)、15h(D-21#~D-25#)、
20h(D-25#~D-30#) formed again.
Acquired bifunctional catalyst number and its contained alkaline molecular sieve and the Silicate-1 of metal ion exchanged points
Son sieve type, the relationship of composite quality ratio are as shown in table 3.
Table 3
1 catalyst preparation of comparative example
The Q-3 obtained by embodiment 1#And Q-8#Alkaline molecular sieve is directly used as comparative catalyst, is crushed, sieves after molding
For 20~40 mesh, number E-1#、E-2#。
4 catalyst preparation of embodiment
The Q-3 that will be obtained without the Silicate-1 molecular sieve of metal ion exchanged and by embodiment 1#Respectively in ball milling
Ball milling 15h on machine is used as comparative catalyst afterwards by evenly mixing.Being crushed, sieving after molding is 20~40 mesh, number E-3#。
5 catalyst preparation of embodiment
The ZSM-5 molecular sieve that commercially available silica alumina ratio is 25 and 50 is passed through into 0.4mol/L Cu (NO respectively3)2Before
Molecular sieve and Q-3 after driving liquid solution ion exchange#The ball milling 15h on ball mill respectively is urged with comparing afterwards by evenly mixing
Agent.Being crushed, sieving after molding is 20~40 mesh, number E-4#And E-5#。
Embodiment 6: evaluating catalyst
Respectively by 1g embodiment 3 prepares bifunctional catalyst and prepared by comparative example 1, comparative example 2 and comparative example 3 catalyst
It is fitted into small fixed reactor, catalyst both ends load quartz sand.Catalyst is first in the He atmosphere of 40mL/min flow velocity
Lower 550 DEG C of activation 1h, is then cooled to reaction temperature, with micro feed pump be passed through raw material toluene and methanol contact with catalyst into
Row reaction, toluene and Methanol Molar charge ratio, air speed, reaction pressure, reaction temperature are shown in Table 4.Product by gas chromatograph into
Row analysis, reaction result are listed in table 4.
Table 4
It can be seen that bifunctional catalyst provided by the present invention by above embodiments result, be used for toluene and methanol system
When the reaction of standby styrene, toluene conversion, use ratio of methanol, styrene yield in product can be improved.
The above is only several examples of the invention, not does any type of limitation to the present invention, although of the invention
It is disclosed as above, however is not intended to limit the invention, any person skilled in the art with preferred embodiments, do not departing from this
In the range of inventive technique scheme, a little variation or modification are made using the technology contents of the disclosure above and is equal to equivalent reality
Scheme is applied, is belonged within the scope of technical solution of the present invention.
Claims (10)
1. a kind of bifunctional catalyst, which is characterized in that the Silicate-1 comprising alkaline molecular sieve and metal ion exchanged points
Son sieve；
Wherein, the composition mass ratio of the alkaline molecular sieve and the Silicate-1 molecular sieve of metal ion exchanged is 0.1~10:
1。
2. bifunctional catalyst according to claim 1, which is characterized in that the alkaline molecular sieve and metal ion exchanged
Silicate-1 molecular sieve composition mass ratio be 0.5~4:1.
3. bifunctional catalyst according to claim 2, which is characterized in that the metal ion be selected from potassium ion, copper from
At least one of son, cerium ion, manganese ion, magnesium ion, molybdenum ion, zinc ion, cesium ion.
4. bifunctional catalyst according to claim 1, which is characterized in that the alkali molecules are screened from alkali metal ion
Exchange at least one of modified FAU structure molecular screen.
5. bifunctional catalyst according to claim 4, which is characterized in that the alkali metal ion is selected from potassium ion, rubidium
At least one of ion, cesium ion；
The FAU structural molecule is screened from least one of X-type molecular sieve, Y type molecular sieve；
The alkali metal ion exchanges in modified FAU structure molecular screen, and alkali metal ion exchange degree is 20~90%.
6. the preparation method of bifunctional catalyst described in any one of claim 1 to 5, which is characterized in that include at least following
Step:
(a) alkaline molecular sieve is obtained；
(b) the Silicate-1 molecular sieve of metal ion exchanged is obtained；
(c) by the mixture containing alkaline molecular sieve and the Silicate-1 molecular sieve of metal ion exchanged, ball milling 2~20 is small
When, then carry out shaping of catalyst；Or
By alkaline molecular sieve and the Silicate-1 molecular sieve of metal ion exchanged difference ball milling 2~20 hours, after mixing
Carry out shaping of catalyst.
7. the preparation method of bifunctional catalyst according to claim 6, which is characterized in that alkalinity described in step (a)
The preparation method of molecular sieve includes: after carrying out ion exchange to molecular sieve using alkali metal precursor solution, to be separated by solid-liquid separation, washed
It washs, dry, roast, obtain the alkaline molecular sieve；
The preparation method of the Silicate-1 molecular sieve of metal ion exchanged described in step (b) includes: using before metal ion
After liquid solution is driven to molecular sieve progress ion exchange, it is separated by solid-liquid separation, washs, dries, roasts, obtain the metal ion exchanged
Silicate-1 molecular sieve.
8. the preparation method of bifunctional catalyst according to claim 7, which is characterized in that the alkali metal presoma choosing
From at least one of alkali metal salt；
The metal ion presoma is selected from least one of the corresponding nitrate of metal, chloride.
9. a kind of method that toluene and methanol prepare styrene, which is characterized in that at least include the following steps: will containing methanol and
The gaseous mixture of toluene obtains the styrene by the reactor containing catalyst, reaction；
Wherein, the catalyst is selected from bifunctional catalyst described in any one of claim 1 to 5 and/or according to claim 6
At least one of the bifunctional catalyst being prepared to 8 described in any item methods.
10. the method that toluene according to claim 9 and methanol prepare styrene, which is characterized in that the toluene and first
The molar ratio of alcohol is 0.2~9:1；
The condition of the reaction are as follows: reaction temperature is 350~500 DEG C, and reaction pressure is 0.1~2MPa, toluene and the total matter of methanol
Amount air speed is 0.2~5h-1。
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| CN116328752A (en) * | 2022-12-13 | 2023-06-27 | 中国科学院大连化学物理研究所 | Catalyst, preparation method and application of catalyst in preparation of propylene carbonate |
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