CN108097324A - A kind of catalyst for preparing acrylic acid and methyl acrylate and preparation method thereof - Google Patents
A kind of catalyst for preparing acrylic acid and methyl acrylate and preparation method thereof Download PDFInfo
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- CN108097324A CN108097324A CN201611055139.1A CN201611055139A CN108097324A CN 108097324 A CN108097324 A CN 108097324A CN 201611055139 A CN201611055139 A CN 201611055139A CN 108097324 A CN108097324 A CN 108097324A
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols
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Abstract
The present invention relates to a kind of catalyst for preparing acrylic acid and methyl acrylate and preparation method thereof.Its method includes the following steps：(1) there is the molecular sieve of MOR configurations using alkali process, dry, roasting obtains the molecular sieve with MOR configurations of alkali modification；(2) binding agent is added after the molecular sieve with MOR configurations of the alkali modification is washed to neutrality, is molded, roasting；(3) molecular sieve with MOR configurations of the alkali modification in step (2) is handled under the atmosphere containing pyridine and/or pyridine substituent, so as to which the catalyst containing alkali modification MOR molecular sieves be made.
Description
Technical field
The present invention relates to a kind of catalyst for preparing acrylic acid and methyl acrylate and preparation method thereof.
Background technology
Acrylic acid and methyl acrylate are a kind of important industrial chemicals, can be used as coating, flocculant, dispersant and bonding
The uses such as agent are widely used in industries such as building, water process, daily-use chemical industry, soil treatment and leathers, the daily life with people
Work is closely bound up.The industrial most common acrylic acid and the method for methyl acrylate of preparing is propylene two-stage oxidizing method at present, i.e.,
The propylene first step is oxidized to methacrylaldehyde, and further oxidation can obtain acrylic acid.However its raw material propylene belongs to non-from oil
Renewable resource does not meet sustainable development idea.
With the rapid development of C1 chemistry, cause acetic acid and methyl acetate excess capacity.With cheap raw material acetic acid and acetic acid
Methyl esters for raw material prepare acrylic acid and methyl acrylate for it is sustainable prepare acrylic acid and methyl acrylate provide one it is feasible
Route.
Catalyst is mostly basic catalyst or soda acid bifunctional catalysis' agent used by the studies above, preparation process one
As using dipping, ion exchange, co-precipitation the methods of active component is carried on carrier, there is prepare it is cumbersome, influence because
The shortcomings of plain complicated and repeated low and active ingredient is easy to run off, can not meet the needs of industrialization large-scale production.
The content of the invention
An object of the present invention provides a kind of prepares third by the raw material containing carbon monoxide and benzaldehyde compound
The catalyst of olefin(e) acid and/or methyl acrylate, the catalyst contain the molecular sieve with MOR configurations of alkali modification, the first
Aldehyde compound is selected from least one of formaldehyde, dimethoxym ethane, metaformaldehyde.
In a detailed embodiment, the sial atomic ratio in the molecular sieve with MOR configurations of the alkali modification is 3
To 100.
In a detailed embodiment, the sial atom in the molecular sieve with MOR configurations of preferably described alkali modification
Than for 6 to 30.
In a detailed embodiment, the tool of pyridine compounds and their or the alkali modification is contained in the catalyst
Have in the molecular sieve of MOR configurations and contain pyridine compounds and their.
In a detailed embodiment, the pyridines that mass content is 0.01% to 15% are contained in the catalyst
It closes in the molecular sieve with MOR configurations of object or the alkali modification containing the pyridines that mass content is 0.01% to 15%
Compound.
In a detailed embodiment, the pyridines chemical combination that mass content is 1% to 10% is contained in the catalyst
Contain the pyridines chemical combination that mass content is 1% to 10% in the molecular sieve with MOR configurations of object or the alkali modification
Object.
In a detailed embodiment, the pyridines chemical combination that mass content is 3% to 7% is contained in the catalyst
Contain the pyridine compounds and their that mass content is 3% to 7% in the molecular sieve with MOR configurations of object or the alkali modification.
In a detailed embodiment, the pyridines chemical combination that mass content is 4% to 6% is contained in the catalyst
Contain the pyridine compounds and their that mass content is 4% to 6% in the molecular sieve with MOR configurations of object or the alkali modification.
In a detailed embodiment, the pyridine compounds and their includes pyridine and/or substituted pyridines, the substitution pyrrole
One to three H in five H of the pyridine in pyridine ring is independently by selected from F, Cl, Br, I, CH3、CF3、CH3CH2、NO2In
At least one of the compound that is substituted of substituent group.
In a detailed embodiment, the pyridine compounds and their includes monomethyl pyridine, lutidines, trimethyl
Pyridine, ethylpyridine, nitropyridine, fluorine-based pyridine, chloro pyridine, bromo pyridine, iodo pyridine.
In a detailed embodiment, the benzaldehyde compound is at least one in formaldehyde, dimethoxym ethane, metaformaldehyde
Kind.
The second object of the present invention provides a kind of method for the catalyst for preparing one of the object of the invention, and this method includes
Following steps：(1) using alkali process there is the molecular sieve of MOR configurations, obtain the molecular sieve with MOR configurations of alkali modification；(2)
Binding agent is added after the molecular sieve with MOR configurations of the alkali modification is washed to neutrality, is molded, roasting；(3) by step
(2) molecular sieve through ammonium exchange with MOR configurations of the alkali modification in, washing, after dry and roasting, in chemical combination containing pyridines
It is handled under the atmosphere of object, so as to which the catalyst containing alkali modification MOR molecular sieves be made.
In a detailed embodiment, in step (1), by the molecular sieve with MOR configurations in aqueous slkali
1h to 10h is handled at 30 DEG C to 100 DEG C.
In a detailed embodiment, in step (1), by the molecular sieve with MOR configurations in aqueous slkali
2h to 5h is handled in 40 DEG C to 90 DEG C.
In a detailed embodiment, the alkali is sodium hydroxide and/or potassium hydroxide.
In a detailed embodiment, the concentration of the alkali in the solution is 0.05mol/L to 1mol/L；It is it is preferred that described
The concentration of alkali in the solution is 0.1mol/L to 0.7mol/L.
In a detailed embodiment, the binding agent is selected from silica, zirconium oxide, aluminium oxide, magnesia, oxidation
At least one of titanium, boehmite, kaolin, montmorillonite.
In a detailed embodiment, the mass content of preferably described binding agent in the catalyst for 1% to
70%.
In a detailed embodiment, more preferably the mass content of the binding agent in the catalyst for 10% to
50%.
In a detailed embodiment, in step (3), pyridines chemical combination in the atmosphere containing pyridine compounds and their
The volumn concentration of object is 0.01% to 15%.
In a detailed embodiment, in step (3), pyridines chemical combination in the atmosphere containing pyridine compounds and their
The volumn concentration of object is 1% to 10%.
In a detailed embodiment, the pyridine compounds and their includes pyridine and/or substituted pyridines, the substitution pyrrole
One to three H in five H of the pyridine in pyridine ring is independently by selected from F, Cl, Br, I, CH3、CF3、CH3CH2、NO2In
At least one of the compound that is substituted of substituent group.
In a detailed embodiment, the pyridine compounds and their includes monomethyl pyridine, lutidines, trimethyl
Pyridine, ethylpyridine, nitropyridine, fluorine-based pyridine, chloro pyridine, bromo pyridine, iodo pyridine.
In a detailed embodiment, the condition of the roasting independently is in step (2) and (3)：Air atmosphere,
350 DEG C to 680 DEG C, 1h to 10h.
In a detailed embodiment, the condition of preferably described roasting independently is in step (2) and (3)：Air
Atmosphere, 400 DEG C to 600 DEG C, 2h to 6h.
In a detailed embodiment, in step (3), the treatment conditions are：240 DEG C to 400 DEG C, 0.5 it is small when
To 24 it is small when.
In a detailed embodiment, preferably in step (3), the treatment conditions are：250 DEG C to 350 DEG C, 2 is small
When 10 is small.
In a detailed embodiment, the reaction condition for preparing acrylic acid and/or methyl acrylate is as follows：Temperature is
180 DEG C to 400 DEG C, pressure is 0.2Mpa to 15.0Mpa, and the combined feed air speed of unstripped gas is 0.05h-1To 10.0h-1。
In a detailed embodiment, the reaction condition for preparing acrylic acid and/or methyl acrylate is as follows：Temperature is
300 DEG C to 350 DEG C, pressure is 0.2Mpa to 5.0Mpa, and the combined feed air speed of unstripped gas is 0.3h-1To 2h-1。
In a detailed embodiment, the ratio of the integral molar quantity of the mole and benzaldehyde compound of the carbon monoxide
For 1:1 to 200:1.
In a detailed embodiment, the ratio of the integral molar quantity of the mole and benzaldehyde compound of the carbon monoxide
For 2:1 to 100:1.
In a detailed embodiment, the ratio of the integral molar quantity of the mole and benzaldehyde compound of the carbon monoxide
For 2:1.
In a detailed embodiment, the benzaldehyde compound is at least one in formaldehyde, dimethoxym ethane, metaformaldehyde
Kind.
In a detailed embodiment, the reactor of the reaction zone is selected from tank reactor, fixed bed reactors, shifting
One kind in dynamic bed reactor and fluidized-bed reactor.
In a detailed embodiment, it can be a reactor, can also be connected by serial or parallel connection mode
Multiple reactors.
Beneficial effects of the present invention include but not limited to：
(1) a kind of catalyst that acrylic acid and methyl acrylate are produced based on dimethoxym ethane and carbon monoxide raw material is prepared for,
It has many advantages, such as that preparation of industrialization is simple, the high selectivity of target product, and catalyst stability is good.It is effectively improved catalysis
The activity and stability of agent reduce the regeneration times of catalyst, simplify dimethoxym ethane production acrylic acid and methyl acrylate
Production technology and catalyst production cost, reduce production operating cost.
(2) catalyst amount of unit product is reduced, reduces investment.
(3) catalyst regeneration, activation and handling frequency are reduced, reduces the discharge of exhaust gas in catalyst regeneration process, together
When reduce production maintenance expense.
Specific embodiment
The present invention is described in detail with reference to embodiment, but the invention is not limited in these embodiments.
Unless otherwise instructed, the raw material in the embodiment of the present invention is bought by commercial sources.
In the present invention, dimethoxym ethane and reaction of carbon monoxide, generation dimethyl ether, acetic acid, methyl acetate, acrylic acid and acrylic acid
The compounds such as methyl esters.By thermodynamics and kinetics factor, control different temperatures and stress reaction condition and different proportion are former
The conditions such as material composition, can be carried out with the generation of oriented control product according to following equation.Under ideal conditions, propylene in product
Total carbon selectivity of acid is 60%, and total carbon selectivity 40% of acetic acid is generated without other by-products.It is if former with single reaction
Expect that dimethoxym ethane calculates selectivity of product, then acrylic acid carbon mole element selectivity is 50%, the carbon molal quantity selectivity of acetic acid
50%.
The present invention raw material and product by agilent company Aligent 7890A gas-chromatographies, using agilent company
FFAP capillary post detections.
A kind of embodiment according to the present invention, selection fixed bed reactors, catalyst filling quality 0.5 to 3.0g, instead
Answer 180 DEG C to 350 DEG C of temperature, reaction pressure 0.1Mpa to 10Mpa.Raw material dimethoxym ethane is by carbon monoxide, in different water-bath temperature
The saturated vapor that dimethoxym ethane is carried under the conditions of degree (0~50 DEG C) is entered in fixed bed reactors, to obtain different volumes content
Dimethoxym ethane unstrpped gas.The computational methods of the saturated vapour pressure of raw material dimethoxym ethane are shown below under condition of different temperatures：
Ln (p1*/p2*)=- Δ vapHm/8.3145 × (1/T1-1/T2)
Wherein p1* and p2* represents the saturated vapour pressure of dimethoxym ethane under different temperatures (T1, T2) respectively.Known dimethoxym ethane rubs
Your vaporization enthalpy Δ vapHm=43.99KJ/mol, boiling point are 42.3 DEG C, can thus calculate the full of dimethoxym ethane under arbitrary temp
And vapour pressure.The amount that raw material dimethoxym ethane substance in reactor is entered in the unit interval can be calculated by saturated vapour pressure.
Conversion ratio, selectivity calculate as follows in the embodiment of the present invention：
Dimethoxym ethane conversion ratio=[(dimethoxym ethane molal quantity in charging)-(dimethoxym ethane molal quantity in discharging)] ÷ (first in charging
Acetal molal quantity) × (100%)
Acrylic acid selectivity=2/3 (the carbon molal quantity of acrylic acid in discharging) ÷ [(carbon mole of dimethoxym ethane in charging
Number)-(the carbon molal quantity of dimethoxym ethane in discharging)] × (100%)
Methyl acrylate selectively=3/4 (the carbon molal quantity of methyl acrylate in discharging) ÷ [(carbon of dimethoxym ethane in charging
Molal quantity)-(the carbon molal quantity of dimethoxym ethane in discharging)] × (100%)
Acetic acid selectivity=1/2 (the carbon molal quantity of acetic acid in discharging) ÷ [(the carbon molal quantity of dimethoxym ethane in charging)-(go out
The carbon molal quantity of dimethoxym ethane in material)] × (100%)
Methyl acetate selectively=2/3 (the carbon molal quantity of methyl acetate in discharging) ÷ [(carbon mole of dimethoxym ethane in charging
Number)-(the carbon molal quantity of dimethoxym ethane in discharging)] × (100%).
Analysis of Organic Substances in catalyst/molecular sieve, operating process are as follows：
100mg catalyst samples are weighed, are fitted into the polytetrafluoroethylene (PTFE) bottle of tool lid；The hydrofluoric acid for adding in 1ml 20% is water-soluble
Liquid, vibration stand 1h and so that molecular sieve catalyst dissolving is complete after shaking up；1ml dichloromethane is added in solution upon dissolution
(CH2Cl2) extraction organic phase, it vibrates and stratification in the separatory funnel of polytetrafluoro piston is transferred to after shaking up, release lower floor's oily
Liquid；It is analyzed using Agilent gas chromatograph-mass spectrometer (GC-MS) (Agilent 7890A/5975C GC/MSD).To dichloromethane
Chlorobenzene or carbon trichloride are added in solution as internal standard compound (1 μ l C6H5Cl/100ml CH2Cl2Or 10ppm C2Cl6).Point
Using HP-5MS chromatographic columns, starting post case temperature is 35 DEG C, rises to 300 DEG C with 5 DEG C/min and keeps 10min for analysis.
Embodiment 1
100 grams of MOR (Si/Al=6.5) molecular sieves are put into the NaOH solution that 1000mL concentration is 0.5mol/L 80
DEG C processing 2 it is small when, filtration washing to neutrality.Take out the MOR molecular sieves after 80g alkali process, 28g boehmites and 10% dilute nitre
Acid extruded moulding after mixing, when 550 DEG C of roastings 4 are small after, exchange when small (2/time) three times with 0.5mol/L ammonium nitrate, spend
Ion water washing, dry, when 550 DEG C of roastings 4 are small, sample obtained contains the pyridine of 7.5% volume at 300 DEG C in gas phase
When processing 2 is small under atmosphere, catalyst 1# is made.Content through the pyridine in analysis of catalyst 1# is 6%.
Embodiment 2
The MOR molecular sieves that 100 grams of Si/Al are respectively 5,25,50,100 are respectively put into 1000ml concentration as 0.5mol/L
KOH solution in 80 DEG C processing 2 it is small when, filtration washing to neutrality.The MOR molecular sieves after 80g alkali process are taken out, 28g intends thin
Diaspore and 10% dust technology extruded moulding after mixing, when 550 DEG C of roastings 4 are small after, exchange three with 0.5mol/L ammonium nitrate
Secondary when small (2/time), are washed with deionized, dry, when 550 DEG C of roastings 4 are small, sample are made and contains in 300 DEG C, gas phase
When processing 2 is small under the pyridine atmosphere of 10% volume, dimethoxym ethane reforming catalyst 2#, 3#, 4#, 5# is made.Through analysis of catalyst 2#
In pyridine content be 5.8%；The content of pyridine in catalyst 3# is 5.9%；The content of pyridine in catalyst 4# is
6.0%；The content of pyridine in catalyst 5# is 5.8%.
Embodiment 3
It is respectively 0.05mol/L, 0.1mol/L, 0.7mol/L, 1mol/ that 100 grams of MOR molecular sieves are put into 1000mL concentration
In the NaOH solution of L when 80 DEG C of processing 2 are small, other conditions are consistent with embodiment 1, obtained dimethoxym ethane reforming catalyst 6#, 7#,
8#、9#.Content through the pyridine in analysis of catalyst 6# is 6.1%；The content of pyridine in catalyst 7# is 6.0%；Catalysis
The content of pyridine in agent 8# is 5.9%；The content of pyridine in catalyst 9# is 6.0%.
Embodiment 4
By 100 grams of MOR molecular sieves be put into the NaOH solution that 1000mL concentration is respectively 0.5mol/L respectively 30 DEG C, 40
DEG C, 70,90 DEG C of processing 2 it is small when, other conditions and embodiment 1 are consistent, be made dimethoxym ethane carbonylation reforming catalyst 10#, 11#,
12#、13#、14#.Content through the pyridine in analysis of catalyst 10# is 6.0%；The content of pyridine in catalyst 11# is
5.9%；The content of pyridine in catalyst 12# is 5.8%；The content of pyridine in catalyst 13# is 5.8%；Catalyst 14#
In pyridine content be 6.1%.
Embodiment 5
The weight content that binding agent intends thin water aluminium is 10%, 30% and 50%, and other conditions are consistent with embodiment, is made and urges
Agent 15#, 16#, 17#.Content through the pyridine in analysis of catalyst 15# is 5.0%；The content of pyridine in catalyst 16#
For 4.2%；The content of pyridine in catalyst 17# is 3.5%.
Binding agent intends thin water aluminium respectively by silica, titanium oxide, silica and aluminium oxide, silica and oxidation
Titanium, aluminium oxide and titanium oxide are replaced, weight of binder content 20%, and other conditions are consistent with embodiment 1, and dimethoxym ethane is made and turns
Change catalyst 18#, 19#, 20#, 21#, 22#.Content through the pyridine in analysis of catalyst 18# is 4.5%；In catalyst 19#
Pyridine content be 4.9%；The content of pyridine in catalyst 20# is 4.3%；The content of pyridine in catalyst 21# is
4.5%；The content of pyridine in catalyst 22# is 4.5%.
Embodiment 6
By 100 grams of MOR molecular sieves be put into 1000mL concentration be 0.5mol/L NaOH solution in 80 DEG C respectively processing 1,
6th, 10 it is small when, other conditions and embodiment 1 are consistent, and dimethoxym ethane reforming catalyst 23#, 24#, 25# is made.Through analysis of catalyst
The content of pyridine in 23# is 6.1%；The content of pyridine in catalyst 24# is 6.0%；Pyridine in catalyst 25# contains
It measures as 6.1%.
Embodiment 7
100 grams of MOR molecular sieves are put into the NaOH solution that 1000mL concentration is 0.5mol/L when 80 DEG C of processing 2 are small,
Filtration washing is to neutrality.The MOR molecular sieves after 80g alkali process are taken out, 28g boehmites and 10% dust technology are after mixing
Extruded moulding, when 550 DEG C of roastings 4 are small after, exchange when small (2/time) three times with 0.5mol/L ammonium nitrate, be washed with deionized,
Dry, respectively when 400,500,650 DEG C of roastings 4 are small, gained sample is in 300 DEG C, gas phase under the pyridine atmosphere containing 1% volume
Handle 2 it is small when, dimethoxym ethane reforming catalyst 26#, 27#, 28# is made.Content through the pyridine in analysis of catalyst 26# is
4.1%；The content of pyridine in catalyst 27# is 4.2%；The content of pyridine in catalyst 28# is 4.0%.
Embodiment 8
100 grams of MOR molecular sieves are put into the NaOH solution that 1000mL concentration is 0.5mol/L when 80 DEG C of processing 2 are small,
Filtration washing is to neutrality.The MOR molecular sieves after 80g alkali process are taken out, 28g boehmites and 10% dust technology are after mixing
Extruded moulding, when 550 DEG C of roastings 4 are small after, exchange when small (2/time) three times with 0.5mol/L ammonium nitrate, be washed with deionized,
Dry, respectively when 550 DEG C of roastings 2,6,10 are small, gained sample is in 300 DEG C, gas phase under the pyridine atmosphere containing 15% volume
Manage 2 it is small when, dimethoxym ethane reforming catalyst 29#, 30#, 31# is made.Content through the pyridine in analysis of catalyst 29# is 4.0%；
The content of pyridine in catalyst 30# is 4.1%；The content of pyridine in catalyst 31# is 4.2%.
Embodiment 9
100 grams of MOR molecular sieves are put into the NaOH solution that 1000mL concentration is 0.5mol/L when 80 DEG C of processing 2 are small,
Filtration washing is to neutrality.The MOR molecular sieves after 80g alkali process are taken out, 28g boehmites and 10% dust technology are after mixing
Extruded moulding after roasting, exchanges when small (2/time) three times with 0.5mol/L ammonium nitrate, is washed with deionized, dry, exists respectively
When 550 DEG C of roastings 4 are small, gained sample contains in 240,280,350,400 DEG C, gas phase respectively to be handled under 0.01% pyridine atmosphere
2 it is small when, dimethoxym ethane reforming catalyst 32#, 33#, 34#, 35# is made.Content through the pyridine in analysis of catalyst 32# is
3.8%；The content of pyridine in catalyst 33# is 3.9%；The content of pyridine in catalyst 34# is 3.8%；Catalyst 35#
In pyridine content be 3.7%.
Embodiment 10
100 grams of MOR molecular sieves are put into the NaOH solution that 1000mL concentration is 0.5mol/L when 80 DEG C of processing 2 are small,
Filtration washing is to neutrality.The MOR molecular sieves after 80g alkali process are taken out, 28g boehmites and 10% dust technology are after mixing
Extruded moulding after roasting, exchanges when small (2/time) three times with 0.5mol/L ammonium nitrate, is washed with deionized, dry, exists respectively
After when 550 DEG C of roastings 4 are small, gained sample contains monomethyl pyridine, the dimethyl pyrazole of 7.5% volume in 300 DEG C of difference in the gas phase
It is handled under pyridine, trimethylpyridine, ethylpyridine, nitropyridine, fluorine-based pyridine, chloro pyridine, bromo pyridine, iodo pyridine atmosphere
2 it is small when, dimethoxym ethane reforming catalyst 36#, 37#, 38#, 39#, 40#, 41#, 42#, 43#, 44# is made.Through analysis of catalyst 36#
In pyridine compounds and their content be 3.9%；The content of pyridine compounds and their in catalyst 37# is 4.0%；Catalyst
The content of pyridine compounds and their in 38# is 4.1%；The content of pyridine compounds and their in catalyst 39# is 3.9%；Catalysis
The content of pyridine compounds and their in agent 40# is 3.8%；The content of pyridine compounds and their in catalyst 41# is 4.1%；It urges
The content of pyridine compounds and their in agent 42# is 4.2%；The content of pyridine compounds and their in catalyst 43# is 4.2%；
The content of pyridine compounds and their in catalyst 44# is 4.0%.
Embodiment 11
100 grams of MOR molecular sieves are put into the NaOH solution that 1000mL concentration is 0.5mol/L when 80 DEG C of processing 2 are small,
Filtration washing is to neutrality.The MOR molecular sieves after 80g alkali process are taken out, 28g boehmites and 10% dust technology are after mixing
Extruded moulding after roasting, exchanges when small (2/time) three times with 0.5mol/L ammonium nitrate, is washed with deionized, dry, exists respectively
After when 550 DEG C of roastings 4 are small, gained sample contains the pyridine gas of 0.01%, 2%, 8%, 15% volume in 300 DEG C of difference in the gas phase
When processing 2 is small under atmosphere, dimethoxym ethane reforming catalyst 45#, 46#, 47#, 48# is made.Through containing for the pyridine in analysis of catalyst 45#
It measures as 0.1%；The content of pyridine in catalyst 46# is 1.0%；The content of pyridine in catalyst 47# is 6.0%；Catalysis
The content of pyridine in agent 48# is 10.2%.
Embodiment 12
100 grams of MOR molecular sieves are put into the NaOH solution that 1000mL concentration is 0.5mol/L when 80 DEG C of processing 2 are small,
Filtration washing is to neutrality.The MOR molecular sieves after 80g alkali process are taken out, 28g boehmites and 10% dust technology are after mixing
Extruded moulding after roasting, exchanges when small (2/time) three times with 0.5mol/L ammonium nitrate, is washed with deionized, dry, exists respectively
When 550 DEG C of roastings 4 are small, processing 0.5,2,4,10,20,24 is small under 300 DEG C, the pyridine atmosphere containing 7.5% respectively for gained sample
When, dimethoxym ethane reforming catalyst 49#, 50#, 51#, 52#, 53#, 54# is made.Content through the pyridine in analysis of catalyst 49#
For 1.8%；The content of pyridine in catalyst 50# is 3.9%；The content of pyridine in catalyst 51# is 5.2%；Catalyst
The content of pyridine in 52# is 6.1%；The content of pyridine in catalyst 53# is 6.2%；Pyridine in catalyst 54# contains
It measures as 6.5%.
The preparation of 1 Cs base catalyst of comparative example
(1) cesium acetate 82.9g, zirconium nitrate 5.5g, cerous nitrate 5.0g are weighed and adds 120mL deionized water dissolvings, is made into water-soluble
Liquid；
(2) silica 1 70g, magnesia 28g are weighed, the solution that step (1) is prepared is added in after mixing and is pinched
It closes, extruded moulding, the dry 4h at 120 DEG C, when roasting 4 is small at 400 DEG C, you can obtain metal oxide catalyst, be denoted as sample
D0#。
Comparative example 2
Containing the atom silica alumina ratio in embodiment 1 be 6.5 non-modified MOR molecular sieves catalyst number be D1#.
Comparative example 3
It is respectively the catalysis of 5,25,50,100 non-modified MOR molecular sieves containing the atom silica alumina ratio in embodiment 2
Agent number is D2#, D3#, D4#, D5#.
The evaluation of 13 catalyst of embodiment
Catalyst sample 10g obtained is packed into the stainless steel fixed bed reaction pipe that internal diameter is 8.5mm, is passed through an oxidation
Reaction system is boosted to 5MPa by carbon；Then according to reaction velocity WHSV=3000h-1, open under conditions of 240 DEG C of reaction temperature
Open up dimethoxym ethane and the research of carbon monoxide carbonylation conversion.Raw material and products obtained therefrom Agilent 7890A gas-chromatography (chromatographies
Column：HP-PLOT-Q capillary columns, Porapak-Q packed columns；Detector：FID, TCD) carry out on-line analysis, reaction condition and result
Table 1 is listed in, wherein, the reaction pressure of test number 2,3,4,5 is respectively 0.2Mpa, 4Mpa, 5Mpa, 15Mpa, remaining is tested
Reaction pressure is 3Mpa..
Table 1
Technical scheme is compared with the technical solution of comparative example it can be seen from 1 data of table, acrylic acid and propylene
The selectivity of sour methyl esters has significantly high；Test number 1 especially in table 1 compared with test number 56 and 58, urge by comparative example
Agent D1#With the extension in reaction time, conversion ratio and selectivity decline quickly, and catalysis prepared by technical scheme
Agent 1#Conversion ratio and selectivity are still very high after 1500h is reacted, and the service life is much larger than the catalyst D1 of comparative example 2#, also much larger than
The catalyst D0 of comparative example 1#。
The above is only several embodiments of the present invention, any type of limitation is not done to the present invention, although this hair
It is bright to be disclosed as above with preferred embodiment, however not to limit the present invention, any person skilled in the art is not taking off
In the range of technical solution of the present invention, make a little variation using the technology contents of the disclosure above or modification is equal to
Case study on implementation is imitated, is belonged in the range of technical solution.
Claims (10)
1. a kind of catalysis that acrylic acid and/or methyl acrylate are prepared by the raw material containing carbon monoxide and benzaldehyde compound
Agent, which is characterized in that the catalyst contains the molecular sieve with MOR configurations of alkali modification, and the benzaldehyde compound is selected from
At least one of formaldehyde, dimethoxym ethane, metaformaldehyde.
2. catalyst according to claim 1, which is characterized in that in the molecular sieve with MOR configurations of the alkali modification
Sial atomic ratio be 3 to 100；
It is preferred that the sial atomic ratio in the molecular sieve with MOR configurations of the alkali modification is 6 to 30.
3. catalyst according to claim 1, which is characterized in that contain in the catalyst pyridine compounds and their or
Contain pyridine compounds and their in the molecular sieve with MOR configurations of the alkali modification；
Preferably, change in the catalyst containing the pyridine compounds and their or the alkali that mass content is 0.01% to 15%
Property the molecular sieve with MOR configurations in contain mass content be 0.01% to 15% pyridine compounds and their；
It is further preferred that contain the pyridine compounds and their or the alkali that mass content is 4% to 6% in the catalyst
Contain the pyridine compounds and their that mass content is 4% to 6% in the modified molecular sieve with MOR configurations；
The pyridine compounds and their includes pyridine and/or substituted pyridines, in five H of the substituted pyridines in pyridine ring
One to three H is independently by selected from F, Cl, Br, I, CH3、CF3、CH3CH2、NO2In the compound that is substituted of substituent group in
It is at least one.
4. a kind of method for preparing catalyst described in any one in claim 1-3, this method comprises the following steps：
(1) using alkali process there is the molecular sieve of MOR configurations, obtain the molecular sieve with MOR configurations of alkali modification；
(2) binding agent is added after the molecular sieve with MOR configurations of the alkali modification is washed to neutrality, is molded, roasting；
(3) by the molecular sieve through ammonium exchange with MOR configurations of the alkali modification in step (2), wash, after dry and roasting,
It is handled under the atmosphere containing pyridine compounds and their, so as to which the catalyst containing alkali modification MOR molecular sieves be made.
5. according to the method described in claim 4, it is characterized in that, in step (1), by the molecule with MOR configurations
Sieve handles 1h to 10h in aqueous slkali at 30 DEG C to 100 DEG C；It is preferred that in step (1), by point with MOR configurations
Son sieve handles 2h to 5h in aqueous slkali in 40 DEG C to 90 DEG C.
6. according to the method described in claim 4, it is characterized in that, the alkali is sodium hydroxide and/or potassium hydroxide；
It is preferred that the concentration of the alkali in the solution is 0.05mol/L to 1mol/L；The more preferable concentration of the alkali in the solution is
0.1mol/L to 0.7mol/L.
7. according to the method described in claim 4, it is characterized in that, the binding agent selects silica, zirconium oxide, aluminium oxide, oxygen
Change at least one of magnesium, titanium oxide, boehmite, kaolin, montmorillonite；
It is preferred that the mass content of the binding agent in the catalyst is 1% to 70%；
The mass content of the more preferable binding agent in the catalyst is 10% to 50%.
8. according to the method described in claim 4, it is characterized in that, in step (3), the atmosphere containing pyridine compounds and their
The volumn concentration of middle pyridine compounds and their is 0.01% to 15%；
It is preferred that in step (3), the volumn concentration of pyridine compounds and their is 1% in the atmosphere containing pyridine compounds and their
To 10%；
The pyridine compounds and their includes pyridine and/or substituted pyridines, in five H of the substituted pyridines in pyridine ring
One to three H is independently by selected from F, Cl, Br, I, CH3、CF3、CH3CH2、NO2In the compound that is substituted of substituent group in
It is at least one.
9. according to the method described in claim 4, it is characterized in that, the condition of the roasting in step (2) and (3) independently
For：Air atmosphere, 350 DEG C to 680 DEG C, 1h to 10h；
It is preferred that the condition of the roasting independently is in step (2) and (3)：Air atmosphere, 400 DEG C to 600 DEG C, 2h to 6h；
More in step (3), the treatment conditions are：240 DEG C to 400 DEG C, 0.5 hour to 24 it is small when；
Most preferably in step (3), the treatment conditions are：250 DEG C to 350 DEG C, 2 hours to 10 it is small when.
10. according to the method described in claim 4, it is characterized in that, prepare the reaction condition of acrylic acid and/or methyl acrylate
It is as follows：
Temperature is 180 DEG C to 400 DEG C, and pressure is 0.2Mpa to 15.0Mpa, and the combined feed air speed of unstripped gas is 0.05h-1Extremely
10.0h-1；
Preferable temperature is 300 DEG C to 350 DEG C, and pressure is 0.2Mpa to 5.0Mpa, and the combined feed air speed of unstripped gas is 0.3h-1Extremely
2h-1。
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