CN114054086B - Molecular sieve catalyst, preparation method and application thereof - Google Patents
Molecular sieve catalyst, preparation method and application thereof Download PDFInfo
- Publication number
- CN114054086B CN114054086B CN202010778720.6A CN202010778720A CN114054086B CN 114054086 B CN114054086 B CN 114054086B CN 202010778720 A CN202010778720 A CN 202010778720A CN 114054086 B CN114054086 B CN 114054086B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- dimethyl ether
- catalyst
- mor
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0292—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate
- B01J31/0294—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate by polar or ionic interaction with the substrate, e.g. glass
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
- C07C67/37—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by reaction of ethers with carbon monoxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application discloses a molecular sieve catalyst, a preparation method and application thereof. The active component of the molecular sieve catalyst is a modified H-MOR molecular sieve which is prepared by ion exchange of the H-MOR molecular sieve and an imidazole salt compound. Dimethyl ether and feed gas containing carbon monoxide are fed into a reactor and contacted with the molecular sieve catalyst to react to produce methyl acetate, and the catalyst has high stability and methyl acetate selectivity.
Description
Technical Field
The invention relates to a molecular sieve catalyst, a preparation method and application thereof, belonging to the field of catalysis.
Background
With the sustainable development of society, the contradiction between energy supply and demand is increasingly prominent. As a large energy consumption country in China, the alternative energy needs to be searched urgently to guarantee the energy safety in China. The fuel ethanol is used as a novel high-efficiency clean energy source and gradually becomes a new energy source field, the ethanol can be used as a gasoline additive, the octane number and the oxygen content of gasoline are improved, the full combustion of fuel is promoted, the emission of carbon monoxide and hydrocarbons in automobile exhaust is reduced, and the fuel ethanol is widely applied to the field of pharmaceutical chemicals.
The coal resources in China are very rich, the petroleum and natural gas resources are relatively few, and the energy structure of 'rich coal, lean oil and little gas' determines that China inevitably develops the coal resources vigorously, and actively promotes the efficient and clean conversion of coal, so that the method has important strategic significance for relieving the problem of shortage of petroleum in China and ensuring the energy safety in China. At present, the technical routes for preparing ethanol from coal are mainly divided into two types: firstly, the synthesis gas is directly used for preparing the carbon-containing oxygen-containing compound, and further hydrogenation is carried out to prepare the ethanol, but the process needs noble metal rhodium as a catalyst, and the catalyst cost is higher; secondly, the synthetic gas is used for preparing methanol, and then the acetic acid is used for preparing ethanol, the route is relatively mature, but the used equipment needs corrosion-resistant materials, and meanwhile, the precious metal catalyst is adopted, so that the investment cost and the catalyst cost are high.
US20070238897A1 discloses that molecular sieves having an eight-member ring channel structure, such as MOR, FER and OFF, as ether carbonylation catalysts and eight-member ring channel sizes greater than 0.25X 0.36nm, in the presence of mordenite as the catalyst at 165 ℃ and 1MPa, 0.163-MeOAC (g-Cat. H) is obtained -1 The space-time yield of (a). WO2008132450A1 reports that the MOR catalyst modified by copper and silver has performance obviously superior to that of an unmodified MOR catalyst under the conditions of hydrogen atmosphere and 250-350 ℃. CN102950018A discloses data on the carbonylation reaction of dimethyl ether on rare earth ZSM-35/MOR eutectic molecular sieve, and the results show that the activity and stability of the eutectic molecular sieve are obviously superior to those of ZSM-35 alone, and the stability is obviously superior to that of the MOR catalyst alone.
However, the inventor of the present application finds that the stability of the catalyst for producing methyl acetate by the carbonylation of dimethyl ether is poor, and the catalytic activity is obviously reduced and even inactivated when the catalyst is operated for more than 10 hours.
Disclosure of Invention
In order to overcome the defects in the related art, the invention provides a molecular sieve catalyst which still maintains excellent catalytic activity after stable operation for 30 hours or even more than 100 hours.
The active component of the molecular sieve catalyst provided by the application is a modified H-MOR molecular sieve which is prepared by ion exchange of H-MOR and an imidazole salt compound.
Optionally, the H-MOR molecular sieve has a silicon to aluminum atomic ratio of 6 to 50.
Alternatively, the H-MOR molecular sieve has a lower limit of silicon to aluminum atomic ratio of 6.5, 20, or 30.
Alternatively, the H-MOR molecular sieve has an upper limit on the silicon to aluminum atomic ratio of 20 or 30.
Alternatively, the imidazolium salt compound has structural formula I:
wherein R is 1 、R 2 Is H-, CH 3 -、CH 3 CH 2 -、CH 3 (CH 2 ) n CH 2 Any one of (n =1, 2); x is Cl - 、SO 4 2- 、NO 3 - M is 1 or 2.
Optionally, the imidazole salt compound is any one or more of 1,3-dimethylimidazole hydrochloride, 1,3-dimethylimidazole sulfate, 1-methylimidazole hydrochloride, 1-methylimidazole sulfate, 1-butyl-3-methylimidazole hydrochloride, 1-butyl-3-methylimidazole sulfate, 1,3-dimethylimidazole nitrate and 1-ethylimidazole hydrochloride.
The application also provides a preparation method for preparing the molecular sieve catalyst, which comprises the step of carrying out ion exchange treatment on the H-MOR molecular sieve by using imidazole salt solution at the temperature of 20-100 ℃ for 1-10H.
Optionally, the concentration of the imidazole salt solution is 0.05-2 mol/L.
Optionally, the lower limit of the concentration of the imidazole salt solution is 0.5, 1.0 or 1.5mol/L.
Optionally, the upper limit of the concentration of the imidazole salt solution is 0.5, 1.0 or 1.5mol/L.
Optionally, the ion exchange temperature is 30-80 ℃ and the time is 2-6 h.
Optionally, the lower limit of the ion exchange temperature is 80 ℃ and the lower limit of the ion exchange treatment time is 6h.
Optionally, the upper limit of the ion exchange temperature is 30 ℃ and the upper limit of the ion exchange treatment time is 2h.
The application also provides a dimethyl ether carbonylation catalyst for producing methyl acetate, which comprises the molecular sieve catalyst or the molecular sieve catalyst prepared according to the method.
The application also provides the molecular sieve catalyst, the molecular sieve catalyst prepared by the method, or the application of the catalyst for producing methyl acetate by carbonylation of dimethyl ether in the production of methyl acetate by carbonylation of dimethyl ether.
Optionally, the reaction temperature for producing the methyl acetate is 150-280 ℃, the reaction pressure is 0.5-25.0 MPa, and the mass space velocity of the dimethyl ether feeding is 0.05-4 h -1 The molar ratio of dimethyl ether to carbon monoxide is 0.1.
Optionally, the reaction temperature for producing the methyl acetate is 160-280 ℃, the reaction pressure is 0.5-20.0 MPa, and the mass space velocity of dimethyl ether feeding is 0.1-3 h -1 The molar ratio of carbon monoxide to dimethyl ether is 0.1.
Optionally, the reaction temperature for producing the methyl acetate is 170-260 ℃, the reaction pressure is 1.0-15.0 MPa, and the mass space velocity of dimethyl ether feeding is 0.2-2.5 h -1 The molar ratio of carbon monoxide to dimethyl ether is 0.2.
Optionally, the reaction temperature is 200-260 ℃, the reaction pressure is 2-15.0 MPa, and the mass space velocity of dimethyl ether feeding is 0.05-0.2 h -1 The molar ratio of the carbon monoxide to the dimethyl ether is 8:1-15.
Alternatively, the lower limit of the reaction temperature for the production of methyl acetate is 150 ℃, 160 ℃, 170 ℃, 200 ℃, 210 ℃, 240 ℃ or 260 ℃, the lower limit of the reaction pressure is 0.5, 1, 2, 6, 10, 15 or 20MPa, and the lower limit of the mass space velocity of the dimethyl ether feed is 0.25, 0.05, 0.1, 0.20, 0.25, 1, 2.5 or 3h -1 The lower limit of the molar ratio of dimethyl ether to carbon monoxide is 5 (i.e. about 0.14).
Alternatively, the upper limit of the reaction temperature for the production of methyl acetate is 160 ℃, 170 ℃, 200 ℃, 210 ℃, 240 ℃, 260 ℃ or 280 ℃, the upper limit of the reaction pressure is 1, 2, 6, 10, 15, 20 or 25MPa, and the upper limit of the mass space velocity of the dimethyl ether feed is 0.05, 0.1, 0.20, 025, 1, 2.5, 3 or 4h -1 The upper limit of the molar ratio of dimethyl ether to carbon monoxide is, 0.2.
Alternatively, the lower limit of the reaction run time to produce methyl acetate is 10, 20, 30, 100, or 500 hours.
Alternatively, the upper limit of the reaction run time to produce methyl acetate is 20, 30, 100, 500, or 3000 hours.
Optionally, the raw material gas further comprises any one or more of hydrogen, nitrogen, argon, carbon dioxide and methane, based on the total volume of the raw material gas, the volume content of carbon monoxide is 15-100%, and the volume content of other gases such as any one or more of hydrogen, nitrogen, argon, carbon dioxide and methane is 0-85%.
Optionally, the lower limit of the volume content of carbon monoxide is 25%, 33.3%, 37%, 50%, 80% or 90% based on the total volume of the feed gas.
Optionally, the upper limit of the volume content of carbon monoxide is 25%, 33%, 37%, 50%, 80%, 90% or 100% based on the total volume of the feed gas.
Optionally, the reactor is a fixed bed reactor.
Benefits of the present application include, but are not limited to:
(1) The invention provides a catalyst for producing methyl acetate by dimethyl ether carbonylation, which has the advantages of high activity, high space-time yield of methyl acetate, good stability, excellent catalytic performance maintained when the reaction is stably operated for more than 100 hours, and the like.
(2) The invention provides a preparation method of a catalyst for producing methyl acetate by carbonylation of dimethyl ether, which adopts organic cations with proper kinetic diameters to selectively poison acid sites of 12-membered ring channels in a mordenite molecular sieve, so that the catalyst realizes directional regulation and control and protection of the internal acidity of the molecular sieve, and a new method is provided for preparing a high-stability molecular sieve catalyst.
(3) The catalyst is applied to the reaction of producing methyl acetate by dimethyl ether carbonylation, not only can ensure high product yield and long service life, but also has wide adjustable range of reaction process conditions, so that the catalyst has universality and extremely wide industrial application range.
Drawings
FIG. 1 is an XRD spectrum of H-MOR molecular sieves before and after modification of examples of the present application.
FIG. 2 is a nuclear magnetic hydrogen spectrum of an H-MOR molecular sieve modified with 1,3-dimethylimidazole hydrochloride according to the examples of the present application.
FIG. 3 is a nuclear magnetic carbon spectrum of an H-MOR molecular sieve modified with 1,3-dimethylimidazole hydrochloride according to the examples herein.
FIG. 4 is an IR spectrum of H-MOR after modification with 1,3-dimethylimidazole hydrochloride, 1-methylimidazole hydrochloride, 1-butyl-3-methylimidazole hydrochloride, and an unmodified HMOR molecular sieve of an example of the present application.
Detailed Description
The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.
The endpoints of the ranges and any values disclosed in the present application are not limited to the precise range or value, and such ranges or values should be understood to include proximity to such ranges or values. For numerical ranges, the endpoints of each of the ranges and the individual points between each may be combined with each other to give one or more new numerical ranges, and these numerical ranges should be considered as specifically disclosed herein.
In the examples of the present application, the raw materials for the preparation of the catalyst (e.g., unmodified H-MOR and the imidazolium compound) and the reaction raw materials for the preparation of methyl acetate (e.g., dimethyl ether and a feed gas comprising CO) were all purchased commercially.
In the examples of the present application, the elemental composition of the H-MOR molecular sieve before and after modification was determined using a Maxix 2424X-ray fluorescence Analyzer (XRF) from Philips, and the ratio of silica to alumina in the mordenite molecular sieve before and after modification was unchanged.
In the examples of the present application, the phases of the H-MOR molecular sieves before and after modification were determined by X-ray powder diffraction phase analysis (XRD); an X' Pert PRO X-ray diffractometer from pananace (PANalytical) of the netherlands, cu target, K α radiation source (λ =0.15418 nm), voltage 40KV, current 40mA were used.
In the examples of the present application, the nuclear magnetic spectrum of the modified H-MOR molecular sieve was determined by a solid nuclear magnetic resonance experiment; using a Bruker Avance III 600 (14.1 Tesla) spectrometer, 13 c and 1 the resonance frequencies of H are 300.13 and 150.9MHz respectively, 13 c MAS NMR employs a high power proton decoupling procedure with a sample delay of 4s and a pulse width of 1.8 μ s for π/4. In that 1 Prior to H MAS NMR experiments, the samples were typically at 300 ℃ 10 -3 Dehydrating under Pa for 20h. 1 The H MAS NMR spectra were recorded with a MAS probe of 4 mm. The pulse width of pi/4 is 2.2 mus, the sampling delay is 4s, and adamantane is used as a chemical shift reference. .
In the examples of the present application, the modified H-MOR molecular sieve was measured by Fourier transform infrared spectroscopy, and the skeleton structure and surface groups of the sample before and after modification were analyzed by a Vertex-70 type infrared spectrometer from Bruker, USA, with a resolution of 4cm -1 The scanning times are 32 times, and the scanning range is 4000-400 cm -1 Firstly, uniformly mixing sample powder and dry potassium bromide according to a certain mass ratio, grinding and tabletting, then placing the mixture into a transmission cell, and recording the infrared spectrogram of the sample in the air.
In the examples of the present application, the reaction raw materials for the preparation of methyl acetate and the resulting products were analyzed on-line by Agilent 7890A gas chromatography (column: HP-PLOT-Q capillary column, porapak-Q packed column; detector: FID, TCD).
In the examples of the present application, the conversion of dimethyl ether, the selectivity of methyl acetate and acetic acid are all calculated based on the carbon moles of dimethyl ether:
dimethyl ether conversion = [ (carbon mole number of dimethyl ether in feed gas) - (carbon mole number of dimethyl ether in product) ]/(carbon mole number of dimethyl ether in feed gas) × (100%);
methyl acetate selectivity = (2/3) × (carbon moles of methyl acetate in product) ÷ [ (carbon moles of dimethyl ether in feed gas) - (carbon moles of dimethyl ether in product) ] × (100%);
acetic acid selectivity =1/2 × (carbon moles of acetic acid in product) ÷ [ (carbon moles of dimethyl ether in feed gas) - (carbon moles of dimethyl ether in product) ] x (100%).
Example 1
Putting 100.0g H-MOR (Si/Al = 10) molecular sieve into 1000ml of 1,3-dimethyl imidazole hydrochloride solution with the concentration of 1.0mol/L, treating for 3h at 80 ℃, filtering, washing and drying at 110 ℃ to obtain the catalyst 1#.
Examples 1 to 1
Putting 100.0g H-MOR (Si/Al = 10) molecular sieve into 1000ml 1,3-dimethyl imidazole hydrochloride solution with concentration of 1.0mol/L, treating for 3h at 20 ℃, 30 ℃ and 100 ℃, filtering, washing, and drying at 110 ℃ to obtain the catalysts 2#, 3#, and 4#.
Examples 1 to 2
Putting 100.0g H-MOR (Si/Al = 10) molecular sieve into 1000ml 1,3-dimethyl imidazole hydrochloride solution with the concentration of 1.0mol/L, treating for 1h, 6h and 10h at the temperature of 80 ℃, filtering, washing and drying at the temperature of 110 ℃ to obtain the catalysts 5#, 6#, and 7#.
Example 2
1,3-dimethylimidazole hydrochloride was exchanged for 1-methylimidazole hydrochloride, 1-butyl-3-methylimidazole hydrochloride, 1,3-dimethylimidazole sulfate, 1-methylimidazole sulfate, 1-butyl-3-methylimidazole sulfate, 1,3-dimethylimidazole nitrate, 1-methylimidazole nitrate, 1-butyl-3-methylimidazole nitrate, imidazole hydrochloride, 1-ethylimidazole hydrochloride, 1-propylimidazole hydrochloride, 1-butylimidazole hydrochloride, 3-methylimidazole hydrochloride, 1-methyl-3-propylimidazole hydrochloride, 1-propyl-3-methylimidazole hydrochloride, 1-methyl-3-butylimidazole hydrochloride, 3-methylimidazole sulfate, 1-methyl-3-butylimidazole sulfate, respectively; all preparation procedures are consistent with those of example 1, and catalysts 8#, 9#, 10#, 11#, 12#, 13#, 14#, 15#, 16#, 17#, 18#, 19#, 20#, 21#, 22#, 23#, 24#, and 25# are prepared in sequence.
Example 3
The 1,3-dimethylimidazole hydrochloride concentrations were changed to 0.05, 0.5, 1.5, and 2.0mol/L, and all preparation procedures were kept the same as in example 1, and catalysts 26#, 27#, 28#, and 29# were prepared in this order.
Example 4
When the molar ratio of Si to Al atoms of H-MOR is 6.5, 20, 30 and 50, the other conditions are kept the same as those in example 1, and catalysts 30#, 31#, 32#, and 33# are prepared in sequence.
FIG. 1 shows XRD spectra of H-MOR molecular sieve catalyst modified with 1-methylimidazole hydrochloride, 1,3-dimethylimidazole hydrochloride, and 1-butyl-3-methylimidazole hydrochloride, and unmodified H-MOR molecular sieve catalyst. As can be seen from FIG. 1, the crystal structure of H-MOR remains unchanged before and after modification. Wherein, in FIG. 1, mmiz-MOR represents the H-MOR molecular sieve catalyst modified with 1-methylimidazole hydrochloride, dmim-MOR represents the H-MOR molecular sieve catalyst modified with 1,3-dimethylimidazole hydrochloride, bmim-MOR represents the H-MOR molecular sieve catalyst modified with 1-butyl-3-methylimidazole hydrochloride.
The crystal structure of H-MOR modified with imidazole salt compounds other than those described above also remained unchanged compared to the crystal structure of H-MOR before modification. The XRD patterns of the H-MOR modified with other types of imidazolium compounds are omitted for brevity.
FIG. 2 shows the nuclear magnetic hydrogen spectrum of H-MOR molecular sieve modified with 1,3-dimethylimidazole hydrochloride ( 1 H MAS NMR). The 1H MAS NMR spectrum gave four characteristic peaks, 8.3ppm (H2), 7.2ppm (H4, H5), 3.8ppm (H6), which were assigned to the characteristic peaks of 1,3-dimethylimidazole cation for different hydrogen atoms, and 1.7ppm to the silicon hydroxyl group of the molecular sieve. Indicating that 1,3-dimethylimidazole cation successfully exchanged hydrogen ions in H-MOR.
In addition, FIG. 3 shows the nuclear magnetic carbon spectrum of H-MOR molecular sieve modified with 1,3-dimethylimidazole hydrochloride (C: (R)) 13 C CP/MAS NMR). By 13 The C CP/MAS NMR spectrum gave three characteristic peaks 131ppm (C2), 124ppm (C4, C5), 36ppm (C6) assigned to the different C atoms in 1,3-dimethylimidazolium cation, further demonstrating that 1,3-dimethylimidazolium cation successfully exchanged hydrogen ions in H-MOR.
FIG. 4 showsThe IR spectra of the modified H-MOR molecular sieve and the unmodified H-MOR molecular sieve with 1-methylimidazole hydrochloride, 1,3-dimethylimidazole hydrochloride, and 1-butyl-3-methylimidazole hydrochloride are shown. The infrared spectrum shows that the infrared result is compared with that of an unmodified HMOR sample and is between 2800 and 3000cm -1 And 3100cm -1 And new characteristic peaks appear nearby, which are respectively attributed to the vibration peak of alkyl on imidazole cation and the stretching vibration peak of C-H on imidazole ring, and show that the modified H-MOR molecular sieve catalyst contains alkyl imidazole cation. Specifically, the infrared characteristic peak of 1-methylimidazole hydrochloride is as follows: 3151cm -1 (ii) a 5363 the infrared characteristic peak of 1,3-dimethylimidazole hydrochloride is 3162cm -1 、3105cm -1 、2850cm -1 The infrared characteristic peak of the 1-butyl-3-methylimidazole hydrochloride is 3162cm -1 、3105cm -1 、2935cm -1 、2877cm -1 (ii) a This indicates that the alkylimidazolium cation in 1-methylimidazole hydrochloride, 1,3-dimethylimidazole hydrochloride, 1-butyl-3-methylimidazole hydrochloride successfully exchanged the hydrogen ion in H-MOR.
In addition to the modified H-MOR catalysts described in figures 2 to 4 above, H-MOR molecular sieves modified with other types of imidazolium compounds also successfully achieved the exchange of imidazolium cations with hydrogen ions, with corresponding nuclear magnetic and infrared spectra similar to those of figures 2 to 4. For the sake of brevity, the corresponding drawings and description are omitted.
Example 5
The above catalyst was examined for catalytic activity under the following conditions.
Respectively loading H-MOR catalysts (1.0 g) modified by different imidazole salts into a fixed bed reactor with the inner diameter of 8mm, heating to 300 ℃ at the speed of 5 ℃/min under the nitrogen atmosphere, keeping for 4 hours, then reducing to the reaction temperature of 200 ℃ under the nitrogen atmosphere, and taking dimethyl ether as the component: CO: n is a radical of 2 The raw material gas of =5 -1 The catalytic reaction was carried out for 30 hours, and the reaction results are shown in Table 1.
TABLE 1 evaluation results of dimethyl ether carbonylation catalysts with different catalysts
The modified catalysts prepared in example 2, which are not listed in the above table, also have excellent catalytic activity, selectivity and stability, and are not listed here for the sake of simplicity.
Example 6
The results of dimethyl ether carbonylation at different reaction temperatures are shown below.
1.0g of No. 1 catalyst is loaded into a fixed bed reactor with the inner diameter of 8mm, the temperature is raised to 300 ℃ at the speed of 5 ℃/min under the nitrogen atmosphere, the temperature is kept for 4 hours, and then the temperature is lowered to the reaction temperature under the nitrogen atmosphere, and the composition of dimethyl ether is as follows: CO: n is a radical of 2 Feed gas of = 5. The reaction temperatures were 150 deg.C, 160 deg.C, 170 deg.C, 210 deg.C, 240 deg.C, 260 deg.C and 280 deg.C, respectively. The mass space velocity of dimethyl ether feeding is 0.23h -1 The results of the catalytic reaction run for 30 hours are shown in table 2.
TABLE 2 reaction results at different reaction temperatures
| Reaction temperature (. Degree. C.) | 150 | 160 | 170 | 200 | 240 | 260 | 280 |
| Conversion ratio of dimethyl ether (%) | 10.3 | 15.8 | 19.6 | 68.8 | 70.3 | 83.8 | 93.5 |
| Methyl acetate selectivity (%) | 98.6 | 97.5 | 96.8 | 99.6 | 98.5 | 96.3 | 92.0 |
| Acetic acid selectivity (%) | 0.8 | 1.5 | 2.1 | 0.4 | 1.1 | 2.9 | 1.4 |
Example 7
The results of dimethyl ether carbonylation at different reaction pressures are shown below.
The catalyst used was sample No. 1, the reaction pressures were 0.5, 1, 6, 10, 15, 20 and 25MPa, the reaction temperature was 200 ℃ and the other conditions were the same as in example 5. The catalytic reaction was run for 30 hours and the results are shown in Table 3.
TABLE 3 results of reactions at different reaction pressures
| Reaction pressure (MPa) | 0.5 | 1 | 6 | 10 | 15 | 20 | 25 |
| Conversion ratio of dimethyl ether (%) | 24.5 | 26.2 | 70.5 | 82.4 | 86.3 | 90.1 | 95.2 |
| Methyl acetate selectivity (%) | 98.7 | 99.2 | 99.6 | 99.6 | 99.6 | 99.7 | 99.6 |
| Acetic acid selectivity (%) | 1.1 | 1.3 | 0.4 | 0.4 | 0.4 | 0.2 | 0.1 |
Example 8
The results of dimethyl ether carbonylation reactions at different mass space velocities of dimethyl ether feed are shown below.
The catalyst used is sample No. 1, and the mass space velocities of dimethyl ether feeding are respectively 0.05, 0.1, 0.20, 1, 2.5, 3 and 4h -1 The reaction temperature was 200 ℃ and the other conditions were the same as in example 6. The catalytic reaction was run for 30 hours and the results are shown in Table 4.
TABLE 4 reaction results at different dimethyl ether feed mass airspeeds
| Mass space velocity (h) of dimethyl ether feed -1 ) | 0.05 | 0.1 | 0.2 | 1 | 2.5 | 3 | 4 |
| Conversion ratio of dimethyl ether (%) | 100 | 100 | 68.2 | 16.5 | 8.6 | 5.8 | 4.9 |
| Methyl acetate selectivity (%) | 98.3 | 98.9 | 99.6 | 98.5 | 98.1 | 98.6 | 98.7 |
| Acetic acid selectivity (%) | 0.4 | 0.3 | 0.4 | 0.6 | 0.7 | 1.0 | 0.3 |
Example 9
The results of dimethyl ether carbonylation reactions at different carbon monoxide to dimethyl ether molar ratios are shown below.
The catalyst used was a sample # 1, and the reaction temperature was 200 ℃ when the molar ratio of carbon monoxide to dimethyl ether was 0.2. The catalytic reaction was run for 30 hours and the results are shown in Table 5.
TABLE 5 reaction results with different dimethyl ether and carbon monoxide gas volume ratios
Example 10
The results of dimethyl ether carbonylation with a feed gas comprising carbon monoxide under inert gas are shown below.
The catalyst used is a 1# sample, and the mass space velocity of dimethyl ether feeding is 0.23h -1 The carbon monoxide feed gas contained the following inert gas, and the molar ratio of carbon monoxide to dimethyl ether at the inlet of the reactor was maintained at 7:1, and the reaction temperature was 200 ℃. The catalytic reaction was run for 30 hours and the results are shown in Table 6.
TABLE 6 reaction results when the carbon monoxide-containing feed gas contains an inert gas
Example 11
The results of dimethyl ether carbonylation at different reaction times are shown below.
The used catalyst is a No. 1 sample, the temperature is raised to 300 ℃ at the speed of 5 ℃/min under the nitrogen atmosphere, the temperature is kept for 4 hours, then the temperature is lowered to 200 ℃ under the nitrogen atmosphere, and the dimethyl ether with the composition is prepared by the following steps: CO: n is a radical of 2 The feed gas of 35 =5 -1 The reaction is respectively operated for 10, 20, 30, 100, 500 and 3000 hours, and the result shows that the catalyst still has better activity and product selectivity after 3000 hours of reaction operation, can meet the requirements of future industrial application, and the results under different catalytic reaction time are shown in Table 7.
TABLE 7 reaction results at different catalytic reaction times
| Reaction time/h | Conversion ratio of dimethyl ether (%) | Methyl acetate selectivity (%) | Acetic acid selectivity (%) |
| 10 | 63.1 | 99.5 | 0.3 |
| 20 | 65.2 | 99.5 | 0.2 |
| 30 | 68.8 | 99.6 | 0.4 |
| 100 | 68.6 | 99.8 | 0.2 |
| 500 | 69.4 | 99.8 | 0.2 |
| 3000 | 69.2 | 99.8 | 0.1 |
Comparative example
The catalyst used was an unmodified H-MOR sample, heated to 300 ℃ at 5 ℃/min under nitrogen atmosphere, held for 4 hours, then lowered to a reaction temperature of 200 ℃ under nitrogen atmosphere, and the composition was dimethyl ether: CO: n is a radical of 2 The feed gas of 35 =5 -1 The reactions were run for 10, 20, 30, 100, 500 and 3000 hours, respectively, and the results showed that the reactions were rapidly deactivated in a shorter time, the modified samples showed superior catalytic performance compared to them, and the results at different catalytic reaction times are shown in table 8.
TABLE 8 reaction results at different catalytic reaction times
Example 12
The catalyst used was sample No. 10, heated to 300 ℃ at 5 ℃/min under nitrogen atmosphere, held for 4 hours, then lowered to reaction temperature 200 ℃ under nitrogen atmosphere, and the composition was dimethyl ether: CO: n is a radical of 2 The feed gas of 35 =5 -1 The reaction is respectively operated for 10, 20, 30, 100, 500 and 3000 hours, and the result shows that the catalyst still has better activity and product selectivity after 3000 hours of reaction operation, can meet the requirements of future industrial application, and the results under different catalytic reaction time are shown in Table 9.
TABLE 9 reaction results at different catalytic reaction times
| Reaction time/h | Conversion ratio of dimethyl ether (%) | Methyl acetate selectivity (%) | Acetic acid selectivity (%) |
| 10 | 62.9 | 98.7 | 0.5 |
| 20 | 65.2 | 99.1 | 0.4 |
| 30 | 67.6 | 99.3 | 0.4 |
| 100 | 67.5 | 99.3 | 0.3 |
| 500 | 66.2 | 99.2 | 0.4 |
| 3000 | 65.2 | 99.3 | 0.3 |
Example 13
The catalyst used was 13# sample, which was heated to 300 ℃ at 5 ℃/min under nitrogen atmosphere for 4 hours, then lowered to a reaction temperature of 200 ℃ under nitrogen atmosphere to obtain a mixture of dimethyl ether: CO: n is a radical of 2 The feed gas of 35 =5 -1 The reaction is respectively operated for 10, 20, 30, 100, 500 and 3000 hours, and the result shows that the catalyst still has better activity and product selectivity after 3000 hours of reaction operation, can meet the requirements of future industrial application, and the results under different catalytic reaction time are shown in table 10.
TABLE 10 reaction results at different catalytic reaction times
| Reaction time/h | Conversion ratio of dimethyl ether (%) | Methyl acetate selectivity (%) | Acetic acid selectivity (%) |
| 10 | 65.3 | 98.9 | 0.5 |
| 20 | 66.9 | 99.3 | 0.4 |
| 30 | 68.5 | 99.5 | 0.4 |
| 100 | 68.1 | 99.4 | 0.3 |
| 500 | 67.8 | 99.4 | 0.3 |
| 3000 | 68.0 | 99.3 | 0.3 |
Example 14
The catalyst used was sample No. 17, which was heated to 300 ℃ at 5 ℃/min under nitrogen atmosphere for 4 hours, then lowered to a reaction temperature of 200 ℃ under nitrogen atmosphere to form dimethyl ether: CO: n is a radical of 2 The feed gas of 35 =5 -1 The reaction is respectively operated for 10, 20, 30, 100, 500 and 3000 hours, and the result shows that the catalyst still has better activity and product selectivity after 3000 hours of reaction operation, can meet the requirements of future industrial application, and the results under different catalytic reaction time are shown in Table 11.
TABLE 11 reaction results at different catalytic reaction times
| Reaction time/h | Conversion ratio of dimethyl ether (%) | Methyl acetate selectivity (%) | Acetic acid selectivity (%) |
| 10 | 62.1 | 98.1 | 0.5 |
| 20 | 63.5 | 98.6 | 0.7 |
| 30 | 65.4 | 98.8 | 0.6 |
| 100 | 65.0 | 99.1 | 0.5 |
| 500 | 64.3 | 98.8 | 0.4 |
| 3000 | 64.1 | 99.0 | 0.4 |
In the process of catalyzing the carbonylation reaction of dimethyl ether by the mordenite molecular sieve, the acid sites B in different pore channels of the mordenite have different catalytic effects on the carbonylation reaction of the dimethyl ether, wherein the acid sites in 8-membered ring pore channels are main active sites of the carbonylation reaction, and the B acid sites in 12-membered ring pore channels can cause side reactions, so that carbon deposit is generated quickly, and the catalyst is inactivated. In the existing patents, pyridine derivatives, pyridine-like substances and other basic molecules with proper sizes are mostly adopted, and are selectively adsorbed on acid sites of 12-membered ring channels in an acid-base neutralization mode (namely, adsorbed on a B acid center through electron pair coordination), so that the purpose of eliminating the acid sites of the 12-membered ring channels in the mordenite is achieved. In the patent, imidazole organic cations with a proper kinetic diameter are creatively adopted to selectively exchange hydrogen ions on the B acid sites in the 12-membered ring channels into the imidazole organic cations (namely, the imidazole cations occupy hydrogen ions in the 12-membered ring channels) in an ion exchange mode, so that the aim of directionally eliminating the acid sites in the 12-membered ring is fulfilled, the B acid sites in the 8-membered ring are well maintained, the generation rate of carbon deposit is effectively slowed down, the utilization rate of the active sites of the molecular sieve is obviously improved, and the activity and the stability of the catalyst are comprehensively improved.
The present invention has been described in detail above, but the present invention is not limited to the specific embodiments described herein. It will be understood by those skilled in the art that other modifications and variations may be made without departing from the scope of the invention. The scope of the invention is defined by the appended claims.
Claims (11)
1. The application of the molecular sieve catalyst in the production of methyl acetate by dimethyl ether carbonylation is characterized in that the active component of the molecular sieve catalyst is a modified H-MOR molecular sieve, and the modified H-MOR molecular sieve is prepared by ion exchange of H-MOR and an imidazole salt compound;
the application comprises the following steps:
introducing dimethyl ether and a feed gas comprising carbon monoxide into a reactor and contacting with the molecular sieve catalyst to react to produce methyl acetate;
the silicon-aluminum atomic ratio of the H-MOR molecular sieve is 6-50;
the structural formula of the imidazole salt compound is shown as formula I:
Wherein R is 1 、R 2 Independently H, CH 3 -、CH 3 CH 2 -、CH 3 (CH 2 )CH 2 -、CH 3 (CH 2 ) 2 CH 2 Any one of the above-mentioned; x is Cl - 、SO 4 2- 、NO 3 - M is 1 or 2.
2. The use according to claim 1, wherein the imidazole salt compound is any one or more of 1,3-dimethylimidazole hydrochloride, 1,3-dimethylimidazole sulfate, 1-methylimidazole hydrochloride, 1-methylimidazole sulfate, 1-butyl-3-methylimidazole hydrochloride, 1-butyl-3-methylimidazole sulfate, 1,3-dimethylimidazole nitrate and 1-ethylimidazole hydrochloride.
3. The application of claim 1, wherein the reaction temperature for producing the methyl acetate is 150-280 ℃, the reaction pressure is 0.5-25.0 MPa, and the mass space velocity of the dimethyl ether feeding is 0.05-4 h -1 The molar ratio of dimethyl ether to carbon monoxide is 0.1 to 1.
4. The application of claim 1, wherein the reaction temperature is 160-280 ℃, the reaction pressure is 0.5-20.0 MPa, and the mass space velocity of dimethyl ether feeding is 0.1-3h -1 The molar ratio of carbon monoxide to dimethyl ether is 0.1 to 20.
5. The application of claim 1, wherein the reaction temperature is 170-260 ℃, the reaction pressure is 1.0-15.0 MPa, and the mass space velocity of dimethyl ether feeding is 0.2-2.5 h -1 The molar ratio of carbon monoxide to dimethyl ether is 0.2 to 1.
6. The application of claim 1, wherein the reaction temperature is 200-260 ℃, the reaction pressure is 2-15.0 MPa, and the mass space velocity of dimethyl ether feeding is 0.05-0.2h -1 The molar ratio of carbon monoxide to dimethyl ether is 8 to 1.
7. The use according to claim 1, wherein the feed gas further comprises any one or more of hydrogen, nitrogen, argon, carbon dioxide and methane; based on the total volume of the raw material gas, the volume content of the carbon monoxide is 15-100%.
8. A method of making the molecular sieve catalyst of any of claims 1 to 7, characterized in that the method comprises: performing ion exchange treatment on the H-MOR molecular sieve by using an imidazole salt solution at the temperature of 20-100 ℃ for 1-10h, and filtering, washing and drying to obtain the molecular sieve catalyst.
9. The method according to claim 8, wherein the concentration of the imidazole salt solution is 0.05 to 2mol/L.
10. The method according to claim 8, wherein the ion exchange temperature is 30 to 80 ℃ and the time is 2 to 6h.
11. A catalyst for the carbonylation of dimethyl ether to produce methyl acetate, wherein the catalyst comprises a molecular sieve catalyst according to any one of claims 1 to 7 or a molecular sieve catalyst prepared by a process according to any one of claims 8 to 10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010778720.6A CN114054086B (en) | 2020-08-05 | 2020-08-05 | Molecular sieve catalyst, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010778720.6A CN114054086B (en) | 2020-08-05 | 2020-08-05 | Molecular sieve catalyst, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114054086A CN114054086A (en) | 2022-02-18 |
| CN114054086B true CN114054086B (en) | 2023-04-07 |
Family
ID=80232142
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010778720.6A Active CN114054086B (en) | 2020-08-05 | 2020-08-05 | Molecular sieve catalyst, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114054086B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1561262A (en) * | 2001-10-02 | 2005-01-05 | 贝尔法斯特皇后大学 | Process of utilising zeolites as catalysts/catalyst precursors |
| CN101613274A (en) * | 2008-06-25 | 2009-12-30 | 中国科学院大连化学物理研究所 | A kind of method of preparing methyl acetate by carbonylating dimethyl ether |
| CN106964396A (en) * | 2017-04-14 | 2017-07-21 | 中触媒新材料股份有限公司 | RTH type topological structure molecular sieve catalysts for dimethyl ether carbonylation reaction and its preparation method and application |
| CN108299166A (en) * | 2018-02-07 | 2018-07-20 | 中国科学院兰州化学物理研究所 | A kind of method that load-type ion liquid catalyzes and synthesizes polymethoxy dimethyl ether |
| CN108558666A (en) * | 2018-05-14 | 2018-09-21 | 沈阳化工大学 | A kind of solid acid catalyst alkali modification synthesis dimerization methyl glycollate method |
| CN110876923A (en) * | 2018-09-05 | 2020-03-13 | 中国科学院大连化学物理研究所 | Adsorbent and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB201705882D0 (en) * | 2017-04-12 | 2017-05-24 | Bp Chem Int Ltd | Process |
-
2020
- 2020-08-05 CN CN202010778720.6A patent/CN114054086B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1561262A (en) * | 2001-10-02 | 2005-01-05 | 贝尔法斯特皇后大学 | Process of utilising zeolites as catalysts/catalyst precursors |
| CN101613274A (en) * | 2008-06-25 | 2009-12-30 | 中国科学院大连化学物理研究所 | A kind of method of preparing methyl acetate by carbonylating dimethyl ether |
| CN106964396A (en) * | 2017-04-14 | 2017-07-21 | 中触媒新材料股份有限公司 | RTH type topological structure molecular sieve catalysts for dimethyl ether carbonylation reaction and its preparation method and application |
| CN108299166A (en) * | 2018-02-07 | 2018-07-20 | 中国科学院兰州化学物理研究所 | A kind of method that load-type ion liquid catalyzes and synthesizes polymethoxy dimethyl ether |
| CN108558666A (en) * | 2018-05-14 | 2018-09-21 | 沈阳化工大学 | A kind of solid acid catalyst alkali modification synthesis dimerization methyl glycollate method |
| CN110876923A (en) * | 2018-09-05 | 2020-03-13 | 中国科学院大连化学物理研究所 | Adsorbent and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| Identifying and controlling the acid site distributions in mordenite zeolite for dimethyl ether carbonylation reaction by means of selective ion-exchange;Shiping Liu 等;《Catalysis Science & Technology》;20200605;第10卷;第4663–4672页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114054086A (en) | 2022-02-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Hu et al. | Fe/ZSM-5 catalysts for ammonia decomposition to COx-free hydrogen: Effect of SiO2/Al2O3 ratio | |
| CN103896769B (en) | A kind of method of preparing methyl acetate by carbonylating dimethyl ether | |
| AU2014218628B2 (en) | Carbon dioxide conversion to fuels and chemicals | |
| CN103896766B (en) | A kind of method of producing methyl acetate | |
| CN106890668A (en) | A kind of catalyst for producing methyl acetate, its preparation method and application | |
| CN111514926B (en) | Molecular sieve catalyst, and preparation method and application thereof | |
| CN111792994B (en) | Method for producing methyl acetate by dimethyl ether carbonylation | |
| Cui et al. | CO2 methanation via amino alcohol relay molecules employing a ruthenium nanoparticle/metal organic framework catalyst | |
| Zhang et al. | Catalytic hydrogenation of levulinic acid into gamma-valerolactone over Ni/HZSM-5 catalysts | |
| CN106890671A (en) | A kind of catalyst for producing methyl acetate, its preparation method and application | |
| US20220144748A1 (en) | Method for producing methyl acetate by means of carbonylation of dimethyl ether | |
| EP3827898A1 (en) | Catalyst for preparing ethylbenzene from ethanol and benzene, preparation therefor and use thereof | |
| CN101920199A (en) | Fischer-Tropsch synthesis cobalt-based catalyst using modified silica gel as carrier and preparation method thereof | |
| CN112958133B (en) | Palladium carbon catalyst and method for preparing N-ethyl-2, 6-methylpiperidine by using same | |
| CN111215131B (en) | Preparation method of shape selective isomerism catalyst based on MTW type structure molecular sieve | |
| CN114054086B (en) | Molecular sieve catalyst, preparation method and application thereof | |
| CN108246313B (en) | High-dispersion heavy hydrocarbon Fischer-Tropsch synthesis catalyst based on carbonization treatment method and preparation method thereof | |
| An et al. | Heterogeneous Ru/TiO 2 for hydroaminomethylation of olefins: multicomponent synthesis of amines | |
| US20210163300A1 (en) | Light hydrocarbon partial oxidation catalyst and carbon monoxide production method using same | |
| CN114054079B (en) | Preparation method and application of catalyst for preparing acetaldehyde by ethanol dehydrogenation | |
| CN111517955A (en) | Method for producing methyl acetate by dimethyl ether carbonylation | |
| US12036538B2 (en) | Molecular sieve catalyst, preparation method therefor, and application thereof | |
| US20190135726A1 (en) | Process For The Sustainable Production Of Acrylic Acid | |
| Lv et al. | Supplementary mechanism for oxycarbonylation of methanol over CuY catalyst: origin of the oxygen atom in methoxyl and formation of by-products | |
| KR101391571B1 (en) | Catalyst for direct synthesis of methyl acetate by carbonylation of dimethyl ether and preparation thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |