CN105502433A - Preparation method of methanol-to-gasoline catalyst nano Zn-ZSM-5 - Google Patents
Preparation method of methanol-to-gasoline catalyst nano Zn-ZSM-5 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
- C01B39/40—Type ZSM-5 using at least one organic template directing agent
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention provides a preparation method of a methanol-to-gasoline catalyst nano Zn-ZSM-5, and relates to deep processing of methanol. The method comprises the steps that 1, a mixed solution of an aluminum source, a templating agent and an alkali solution is prepared; 2, a silicon source and zinc salt are added to the mixed solution, stirring is conducted to be uniform, refluxing is conducted, centrifugal separation, drying and calcination are conducted on an obtained turbid solution, and a nano Zn-ZSM-5 molecular sieve is obtained; 3, ion exchange, centrifugal separation, drying and calcination are conducted on the nano Zn-ZSM-5 molecular sieve obtained in the second step, and the methanol-to-gasoline catalyst nano Zn-ZSM-5 is obtained. The methanol-to-gasoline catalyst nano Zn-ZSM-5 can be applied in methanol to gasoline and can show good performance in a methanol-to-gasoline reaction. On the premise of ensuring the catalytic activity, the catalyst stability is greatly improved; compared with commercial ZSM-5, the service life is greatly prolonged, the single-pass service life of the catalyst nano Zn-ZSM-5 is 20 times that of the commercial ZSM-5, and a good application prospect is achieved.
Description
Technical field
The present invention relates to methanol derivatives, especially relate to the preparation method of a kind of preparing gasoline by methanol catalyst nano Zn-ZSM-5.
Background technology
Molecular sieve is a kind of silico-aluminate compound with cubic(al)grating.Molecular sieve has uniform microvoid structure, its hole diameter is even, these holes can the inside of the molecular adsorption less than its diameter to vestibule, and to polar molecule and unsaturated molecule, there is Preferential adsorption ability, thus can polarity degree is different, that degree of saturation is different, molecular size is different and boiling point is different molecular separation come, the field such as be widely used in catalysis, ion-exchange and be separated.Molecular sieve is of a great variety, and wherein ZSM-5 molecular sieve is a kind of molecular sieve with important use invented by Mobil company the seventies in last century, has MFI type topological framework, belongs to the zeolite molecular sieve of high silicon five-element circular type.
ZSM-5 molecular sieve has larger specific surface area, usually at 300m
2/ more than g, and there is good ion-exchange capacity, be a kind of good support of the catalyst; Because this molecular sieve has unique microvoid structure, the intersection two-dimensional channel of its uniqueness is not only shape selective catalysis and provides space constraint effect, provides abundant access way for reactant and product simultaneously yet, therefore can be used as conventional shape-selective catalyst; Again because it has strongly-acid, also can be used as acid catalyst.These character of ZSM-5 make it may be used for numerous catalyzed reactions such as alkylation, aromizing, catalytic cracking, hydrocracking, polymerization, reformation, disproportionation, selective oxidation.
From current existing research report, improve the stability of catalyzer mainly through the modification to ZSM-5 catalyzer and the optimization to reaction conditions.Describe in patent CN1530322A with the larger ZSM-5 structural zeolite of alkaline solution treatment particle diameter, the ZSM-5 obtained after process has larger specific surface area.
Describe priority alkaline solution in patent CN102464336A, acid solution processes ZSM-5 molecular sieve, obtain modified ZSM-5 zeolite finally by separation, washing and drying, specific surface area and aperture all increase
Describe in patent CN1240193 with n-Butyl Amine 99, water glass, Tai-Ace S 150, sodium hydroxide, sodium-chlor, water as raw material, carried out the grain-size of Molecular regulator sieve by the amount changing crystallization time, temperature and an alkali metal salt, and solve the problem of the separation difficulty of ZSM-5 and mother liquor.
The catalyzer that aforesaid method is obtained, the catalytic life for preparing gasoline by methanol reaction is not all very desirable, and the stability therefore improving catalyzer is the current problem demanding prompt solution of preparing gasoline by methanol catalyzer.
Summary of the invention
The object of the invention is to the above-mentioned deficiency for prior art, the preparation method of a kind of preparing gasoline by methanol catalyst nano Zn-ZSM-5 is provided.
The present invention includes following steps:
1) mixed solution of aluminium source, template and alkaline solution is prepared;
2) in mixed solution, add silicon source, zinc salt, reflux after stirring, the turbid solution centrifugation obtained, drying, roasting, obtain nanometer Zn-ZSM-5 molecular sieve;
3) by step 2) nanometer Zn-ZSM-5 molecular sieve of obtaining is through ion-exchange, centrifugation, drying, and roasting, obtains preparing gasoline by methanol catalyst nano Zn-ZSM-5.
In step 1) in, described aluminium source can be selected from the one in aluminum nitrate, Tai-Ace S 150, aluminum chloride, sodium metaaluminate, aluminum isopropylate etc.; Described template can be selected from the one in TPAOH, 4-propyl bromide, quadrol, normal hexyl Amine etc.; One in described alkaline solution selected from sodium hydroxide solution, potassium hydroxide solution, ammoniacal liquor, aqua calcis etc.;
Alkaline solution is added, Keep agitation, until evenly after aluminium source can mix with template by the mixed solution of described preparation aluminium source, template and alkaline solution; The time of described Keep agitation can be 10 ~ 60min.
In step 2) in, described silicon source can be selected from the one in silicon sol, Silica hydrogel, gas-phase silica, tetraethoxy etc.; Described zinc salt is the one in zinc sulfate, zinc nitrate, zinc chloride etc.;
The time of described stirring can be 12 ~ 30h; The temperature of described backflow can be 80 ~ 110 DEG C, and the time of backflow can be 24 ~ 50h;
In step 1) and 2) in, the mol ratio of described aluminium source, template, alkaline solution, silicon source, zinc salt can be: (0.2 ~ 0.5): (3 ~ 6): (1.5 ~ 3): 25: (800 ~ 1500).
In step 3) in, described ion-exchange can exchange at ammonium salt solution intermediate ion, and the volumetric molar concentration of ammonium salt solution can be 0.2 ~ 1mol/L, and the temperature of ion-exchange can be 60 ~ 90 DEG C, and the time of each ion-exchange can be 2 ~ 6h; The rotating speed of described centrifugation can be 6000 ~ 10000r/min; The temperature of described drying can be 80 ~ 110 DEG C, and the dry time can be 8 ~ 20h; The temperature of described roasting can be 450 ~ 600 DEG C, and the time of roasting can be 4 ~ 8h; Described by step 2) nanometer Zn-ZSM-5 molecular sieve of obtaining is through ion-exchange, centrifugation, drying preferably in triplicate.
Described preparing gasoline by methanol catalyst nano Zn-ZSM-5 can apply in preparing gasoline by methanol.
The reaction conditions of described preparing gasoline by methanol catalyst nano Zn-ZSM-5 in preparing gasoline by methanol is: temperature of reaction is 370 ~ 460 DEG C, N
2flow velocity is 15 ~ 30ml/min, and air speed is 1 ~ 13h
-1.
Beneficial effect of the present invention is as follows:
Preparing gasoline by methanol catalyst nano Zn-ZSM-5 prepared by the present invention shows good performance in preparing gasoline by methanol reaction.Under the prerequisite guaranteeing catalytic activity, drastically increase the stability of catalyzer, compared with commodity ZSM-5, the life-span significantly improves, and single pass life is its 20 times, has good application prospect.
Accompanying drawing explanation
Fig. 1 is the high resolution scanning Electronic Speculum figure of nanometer Zn-ZSM-5 molecular sieve prepared by embodiment 1.
Fig. 2 is the XRD figure of nanometer Zn-ZSM-5 molecular sieve prepared by embodiment 1,2,3 and 9.In fig. 2, curve a is embodiment 1, b be embodiment 2, c be embodiment 3, d is embodiment 9.
Fig. 3 is the optionally estimation of stability result of embodiment 4 ~ 8 prepared catalyst.
Fig. 4 is activity and the optionally estimation of stability result of catalyst A and D.
Embodiment
Following examples will the present invention is further illustrated by reference to the accompanying drawings.
The preparation of embodiment 1 nanometer Zn-ZSM-5 molecular sieve
(1) 1mol/L sodium hydroxide solution 25mL is added after being mixed with 20ml 4-propyl bromide by 1g aluminum nitrate, Keep agitation, until evenly;
(2) in above-mentioned mixed solution, add silicon sol 20g, zinc nitrate 0.2g, stir, until solution mixes, then container is transferred to, backflow, by the turbid solution that obtains through centrifugation, 100 DEG C of dry 8h, 550 DEG C of roasting 4h, obtains nanometer Zn-ZSM-5 molecular sieve;
(3) by described nanometer Zn-ZSM-5 molecular sieve 60 DEG C of ion-exchange 6h, centrifugation, 100 DEG C of dry 8h in 0.2mol/L ammonium nitrate solution, repeat 3 times, 550 DEG C of roasting 4h, namely obtain Hydrogen nanometer Zn-ZSM-5 molecular sieve catalyzer.As shown in Figure 1, nanometer Zn-ZSM-5 molecular sieve is evenly regular for its high resolution scanning Electronic Speculum figure, and crystalline form is spherical, and surface is more smooth, and relative to commodity ZSM-5 molecular sieve, grain-size is less, is about about 100nm, and its X-ray collection of illustrative plates is as shown in curve a in Fig. 2.
Embodiment 2
Prepare the method for nanometer Zn-ZSM-5 with embodiment 1, difference is, aluminium source in step (1) is changed to Tai-Ace S 150, and other condition is constant, and obtained nanometer Zn-ZSM-5 molecular sieve, its X-ray collection of illustrative plates is as shown in curve b in Fig. 2.
Embodiment 3
Prepare the method for nanometer Zn-ZSM-5 with embodiment 1, difference is, template in step (1) is changed to TPAOH, and other condition is constant, and obtained nanometer Zn-ZSM-5 molecular sieve, its X-ray collection of illustrative plates is as shown in curve c in Fig. 2.
Embodiment 4
Prepare the method for nanometer Zn-ZSM-5 with embodiment 1, difference is, the concentration of sodium hydroxide solution in step (1) is replaced by 2mol/L, and other condition is constant, obtained nanometer Zn-ZSM-5 molecular sieve.
Embodiment 5
Prepare the method for nanometer Zn-ZSM-5 with embodiment 1, difference is, the amount of silicon sol in step (2) is replaced by 30g, and other condition is constant, obtained nanometer Zn-ZSM-5 molecular sieve.
Embodiment 6
Prepare the method for nanometer Zn-ZSM-5 with embodiment 1, difference is, the amount of 4-propyl bromide in step (1) is replaced by 45ml, silicon sol in step (2) is replaced by tetraethyl orthosilicate, other condition is constant, obtained nanometer Zn-ZSM-5 molecular sieve.
Embodiment 7
Prepare the method for nanometer Zn-ZSM-5 with embodiment 1, difference is, the amount of aluminum nitrate in step (1) is replaced by 3g, and the amount of zinc nitrate in step (2) is replaced by 0.5g, and other condition is constant, obtained nanometer Zn-ZSM-5 molecular sieve.
Embodiment 8
Prepare the method for nanometer Zn-ZSM-5 with embodiment 1, difference is, aluminum nitrate in step (1) is replaced by aluminum isopropylate, and the concentration of ammonium nitrate in step (3) is replaced by 1mol/L, other condition is constant, obtained nanometer Zn-ZSM-5 molecular sieve.
Embodiment 9
Take HZSM-5 molecular sieve (X-ray collection of illustrative plates is as shown in curve d in Fig. 2) each 3g that described in embodiment 1, embodiment 2, embodiment 3, nanometer Zn-ZSM-5 molecular sieve and commodity silica alumina ratio are 50, through compressing tablet, pulverize, sieve (20 ~ 40 order), obtained catalyzer, is designated as A, B, C, D respectively.By the following method the preparing gasoline by methanol reaction preference of catalyzer is evaluated.
The catalyst loading prepared by 0.5g enters in fixed-bed reactor, in a nitrogen atmosphere with the ramp to 370 of 3K/min DEG C, then carries out material benzenemethanol injecting reactor reacting that (reaction pressure is normal pressure, and air speed is 13h with micro pump
-1).Product is by GC9560 type gas chromatograph (PONA packed column, hydrogen flame ionization detector) on-line analysis, and result is as shown in table 1.
Table 1
Four kinds of catalyst A, B, C and D are in preparing gasoline by methanol reaction, during reaction 1h, interior methanol conversion is 100%, as can be seen from Table 1, the aromatic hydrocarbons initial selectivity of various product is suitable, wherein the aromatic hydrocarbons initial selectivity of catalyzer D commodity HZSM-5 molecular sieve is slightly higher, be 51.8%, the aromatic hydrocarbons initial selectivity of catalyst A is 49.4..
Embodiment 10
By the evaluation method of embodiment 9, evaluate the optionally stability of embodiment 4 ~ 8 prepared catalyst, result as shown in Figure 3.In reaction times 24h, the methanol conversion of all catalyzer is 100%, and along with the reaction times extends, arenes selectivity slowly declines gradually, still keeps more than 35% after reaction 24h.Along with the reaction times extends, the arenes selectivity of embodiment 4 controlling catalysts declines slower.
Embodiment 11
By the evaluation method of embodiment 9, to catalyst A and D activity (methanol conversion) and optionally stability investigate, result is as shown in Figure 4.Under the same reaction conditions, the activity of catalyst A of the present invention and the stability of gasoline selective are significantly better than commodity ZSM-5 catalyzer D.After catalyst A reaction 24h of the present invention, methanol conversion still keeps 100%, and selectivity slowly drops to 35% by initial 49%, illustrates that this catalyzer carbon accumulation resisting ability is strong.Commodity ZSM-5 molecular sieve D reacts after 1h and namely starts fast deactivation, complete deactivation during 4h.
The invention provides the preparation method of a kind of nanometer Zn-ZSM-5 molecular sieve catalyzer, catalyzer adopts the preparation of clear liquid backflow single stage method, not only reduce the step of traditional method load Zn, and be convenient to form uniform particle diameter, constitutionally stable nano molecular sieve, thus improve the coking resistivity of catalyzer, extend the life-span of catalyzer.Under the same conditions, the single pass life in the reaction of fixed bed preparing gasoline by methanol of the catalyzer prepared by the present invention is about 20 times of commodity ZSM-5 molecular sieve.
Claims (10)
1. a preparation method of preparing gasoline by methanol catalyst nano Zn-ZSM-5, is characterized in that comprising the following steps:
1) mixed solution of aluminium source, template and alkaline solution is prepared;
2) in mixed solution, add silicon source, zinc salt, reflux after stirring, the turbid solution centrifugation obtained, drying, roasting, obtain nanometer Zn-ZSM-5 molecular sieve;
3) by step 2) nanometer Zn-ZSM-5 molecular sieve of obtaining is through ion-exchange, centrifugation, drying, and roasting, obtains preparing gasoline by methanol catalyst nano Zn-ZSM-5.
2. the preparation method of a kind of preparing gasoline by methanol catalyst nano Zn-ZSM-5 as claimed in claim 1, is characterized in that in step 1) in, described aluminium source is selected from the one in aluminum nitrate, Tai-Ace S 150, aluminum chloride, sodium metaaluminate, aluminum isopropylate.
3. the preparation method of a kind of preparing gasoline by methanol catalyst nano Zn-ZSM-5 as claimed in claim 1, is characterized in that in step 1) in, described template is selected from the one in TPAOH, 4-propyl bromide, quadrol, normal hexyl Amine.
4. the preparation method of a kind of preparing gasoline by methanol catalyst nano Zn-ZSM-5 as claimed in claim 1, is characterized in that in step 1) in, described alkaline solution is selected from the one in sodium hydroxide solution, potassium hydroxide solution, ammoniacal liquor, aqua calcis.
5. the preparation method of a kind of preparing gasoline by methanol catalyst nano Zn-ZSM-5 as claimed in claim 1, it is characterized in that in step 1) in, the mixed solution of described preparation aluminium source, template and alkaline solution adds alkaline solution, Keep agitation, until evenly after being mixed with template in aluminium source; The time of described Keep agitation can be 10 ~ 60min.
6. the preparation method of a kind of preparing gasoline by methanol catalyst nano Zn-ZSM-5 as claimed in claim 1, is characterized in that in step 2) in, described silicon source is selected from the one in silicon sol, Silica hydrogel, gas-phase silica, tetraethoxy; Described zinc salt is the one in zinc sulfate, zinc nitrate, zinc chloride; The time of described stirring can be 12 ~ 30h; The temperature of described backflow can be 80 ~ 110 DEG C, and the time of backflow can be 24 ~ 50h.
7. the preparation method of a kind of preparing gasoline by methanol catalyst nano Zn-ZSM-5 as claimed in claim 1, it is characterized in that in step 1) and 2) in, the mol ratio of described aluminium source, template, alkaline solution, silicon source, zinc salt is: (0.2 ~ 0.5): (3 ~ 6): (1.5 ~ 3): 25: (800 ~ 1500).
8. the preparation method of a kind of preparing gasoline by methanol catalyst nano Zn-ZSM-5 as claimed in claim 1, it is characterized in that in step 3) in, described ion-exchange exchanges at ammonium salt solution intermediate ion, the volumetric molar concentration of ammonium salt solution can be 0.2 ~ 1mol/L, the temperature of ion-exchange can be 60 ~ 90 DEG C, and the time of each ion-exchange can be 2 ~ 6h; The rotating speed of described centrifugation can be 6000 ~ 10000r/min.
9. the preparation method of a kind of preparing gasoline by methanol catalyst nano Zn-ZSM-5 as claimed in claim 1, is characterized in that in step 3) in, the temperature of described drying is 80 ~ 110 DEG C, and the dry time is 8 ~ 20h; The temperature of described roasting is 450 ~ 600 DEG C, and the time of roasting is 4 ~ 8h.
10. the preparation method of a kind of preparing gasoline by methanol catalyst nano Zn-ZSM-5 as claimed in claim 1, it is characterized in that in step 3) in, described by step 2) nanometer Zn-ZSM-5 molecular sieve of obtaining through ion-exchange, centrifugation, drying, repeat 3 times.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105907417A (en) * | 2016-06-21 | 2016-08-31 | 北斗航天软件（北京）有限公司 | Method for preparing high-octane-value gasoline blending components from methyl alcohol |
| CN106219493A (en) * | 2016-07-14 | 2016-12-14 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of efficient storage oxygen sieves composite and preparation method rich in the metallic molecule of delocalized electron |
| CN106215971A (en) * | 2016-07-15 | 2016-12-14 | 河南博洁能源工程技术有限公司 | A kind of catalyst of two-step method preparing gasoline by methanol hydrocarbonylation and preparation method thereof |
| CN106582797A (en) * | 2016-11-25 | 2017-04-26 | 厦门大学 | Preparation method for HZSM-5 methanol aromatization molecular sieve catalyst with skeleton containing molybdenum |
| CN107983402A (en) * | 2017-12-06 | 2018-05-04 | 中国科学院山西煤炭化学研究所 | A kind of propane aromatization catalyst and preparation method and application |
| CN108435235A (en) * | 2018-03-26 | 2018-08-24 | 福州大学 | A kind of mesoporous Zn-ZSM-5 molecular sieves and low cost preparation method |
| CN113896665A (en) * | 2021-09-14 | 2022-01-07 | 湖北工程学院 | Preparation method of 2-chloro-1-methyl-4- (methylsulfonyl) benzene |
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| CN105907417A (en) * | 2016-06-21 | 2016-08-31 | 北斗航天软件（北京）有限公司 | Method for preparing high-octane-value gasoline blending components from methyl alcohol |
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| CN106582797A (en) * | 2016-11-25 | 2017-04-26 | 厦门大学 | Preparation method for HZSM-5 methanol aromatization molecular sieve catalyst with skeleton containing molybdenum |
| CN107983402A (en) * | 2017-12-06 | 2018-05-04 | 中国科学院山西煤炭化学研究所 | A kind of propane aromatization catalyst and preparation method and application |
| CN107983402B (en) * | 2017-12-06 | 2020-12-25 | 中国科学院山西煤炭化学研究所 | Propane aromatization catalyst and preparation method and application thereof |
| CN108435235A (en) * | 2018-03-26 | 2018-08-24 | 福州大学 | A kind of mesoporous Zn-ZSM-5 molecular sieves and low cost preparation method |
| CN113896665A (en) * | 2021-09-14 | 2022-01-07 | 湖北工程学院 | Preparation method of 2-chloro-1-methyl-4- (methylsulfonyl) benzene |
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