CN106423256A - Catalyst for synthesis of liquid fuel, preparation method and application - Google Patents
Catalyst for synthesis of liquid fuel, preparation method and application Download PDFInfo
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- CN106423256A CN106423256A CN201610835099.6A CN201610835099A CN106423256A CN 106423256 A CN106423256 A CN 106423256A CN 201610835099 A CN201610835099 A CN 201610835099A CN 106423256 A CN106423256 A CN 106423256A
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- 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
- B01J29/40—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
- B01J29/42—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 iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- 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
- B01J29/40—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
- B01J29/48—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 arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A catalyst for synthesis of liquid fuel comprises components of SiO2 and Al2O3 in a molar ratio of 100:(1-5), the grain size is smaller than 600 nm, and the crystallinity is higher than or equal to 93%. The catalyst has the advantages of high catalytic activity and long service life.
Description
Technical field
The invention belongs to a kind of catalyst and preparation method and application are and in particular to a kind of catalyst of synthetic liquid fuel
And preparation method and application.
Background technology
Natural gas, coal, living beings etc. are prepared the process route of clean fuel by chemical reaction, disclosure satisfy that environmental protection will
Ask, alleviate energy supply and demand contradiction, thus favored by everybody, in most of process route, be that these materials are turned first
Chemical conversion synthesis gas (CO+H2), then it is directly or indirectly changed into required product.Indirect coal liquefaction (GTL) technology is one
Bar prepares the process route of clean fuel by chemical reaction, in addition converts synthesis gas into methyl alcohol, then passes through methyl alcohol one
Petroleum chemicals needed for synthesizing with high selectivity under fixed catalytic reaction are also a work preparing clean fuel by chemical reaction
Skill route.
In view of methyl alcohol prepares liquid fuel reaction has important economic worth and strategic value, people are efficient to synthesizing
Methyl alcohol is prepared liquid fuel catalyst and has been carried out substantial amounts of research.M.Firoozi etc. is respectively adopted oil bath crystallization and hydrothermal crystallizing
Method preparation ZSM-5 molecular sieve, within the reaction time of 200h, the methanol conversion of nano-ZSM-5 molecular sieve and product
Selectivity apparently higher than micron ZSM-5 molecular sieve.Uffe V.Mentzel etc. is prepared for ladder with BP-2000 for the second template
Degree hole HZSM-5 and HGa-MFI molecular sieve catalyst, more traditional HZSM-5 life-span brings up to 140h by 57h；XueZhaoteng etc.
It is prepared for the ZSM-5 molecular sieve of graded pore structure using organic-silylation method, its life-span improves.Ali A.Rownaghi
It is prepared for, Deng using single template method, the ZSM-5 molecular sieve that particle diameter is 120nm, to a certain degree improve the propylene in catalysate
Yield with alkylaromatic hydrocarbon.
To sum up, the catalyst of prior art has that catalysis activity is low, the shortcoming of short life.
Content of the invention
It is an object of the invention to provide a kind of catalysis activity is high, the catalyst of synthesis gas synthetic liquid fuel of life-span length and
Its preparation method and application.
The present invention is that through one section of methanolizing reaction, synthesis gas is generated the gaseous mixture containing methyl alcohol, and not separated methyl alcohol enters two
Duan Fanying prepares liquid fuel, simplifies separating methanol flow process it is achieved that synthesis gas successive reaction prepares liquid fuel, is a kind of
The technique that efficient synthesis gas prepares liquid fuel.
The catalyst mole of the present invention consists of SiO2：Al2O3=100：1-5, size of microcrystal be less than 600nm, degree of crystallinity >=
93%.
The method for preparing catalyst of the present invention, comprises the steps：
(1) weigh silicon source, sodium salt and deionized water to add in synthesis reactor, stir, wherein, silicon source is with SiO2Meter, sodium
Salt is with Na2O counts, and each constitutive molar ratio is Na2O:SiO2：H2O=(15-30)：100：(1000-6000)；
(2) weigh aluminium salt to be dissolved completely in water, add sulfuric acid and stir, wherein aluminium salt is with Al2O3Meter, sulfuric acid with
S04 2-Meter, each constitutive molar ratio is Al2O3:S04 2-:H2O=1：(5-15)：(1000-2400)；
(3) consist of SiO by material molar ratio2：Al2O3=100：1-5, the solution that step (2) is prepared instills step
(1), in the solution prepared, it is stirred at room temperature uniformly；
(4) add template in synthesis reactor, its mol ratio is SiO2：Template=1：(0.1-0.3), in 150-200
DEG C crystallization 2-10 hour, chilling adds H2O2, its consumption is the 2.5-3.5wt% that step (3) prepares solution total amount, adjusts brilliant afterwards
Change temperature and be 100-200 DEG C, continue crystallization 10-100 hour；
(5) after the completion of crystallization, cooling, washing, filtration, 100-120 DEG C of drying, 500-550 DEG C of roasting 4-6 hour, obtain
The NaZSM-5 molecular screen primary powder of nanometer particle size；
(6) by the NaZSM-5 molecular screen primary powder NH of 0.2-1mol/L4NO3Solution stirs 1-5 hour at 60-100 DEG C,
Filter, washing, repeat ammonium exchange step 2-4 time, in 100-120 DEG C of drying, in 500-550 DEG C of roast 4-6h, obtain HZSM-5 and urge
Agent powder；
(7) add the binding agent of 10-50wt% in HZSM-5 catalyst fines, squeezed with the salpeter solution mixing of 1-5v%
Molded, in 100-120 DEG C of drying, 500-550 DEG C of roast 4-6h, obtain HZSM-5 molecular sieve catalyst, be broken for 20-40 mesh
Stand-by.
Silicon source as described in step (1) is sodium metasilicate etc., and sodium salt is sodium sulphate etc.；
Silicon source as described in step (2) is aluminum sulfate etc.；
Template as described in step (4) is TPAOH (TPAOH), n-butylamine or hexamethylene diamine etc.；
Binding agent as described in step (7) is sesbania powder etc..
The application of the present invention comprises the steps：
First synthesis gas is generated, through one section of methanolizing reaction, the gaseous mixture containing methyl alcohol, then the gaseous mixture containing methyl alcohol with this is former
Material gas, is reacted under catalyst action of the present invention, and its reaction pressure is 3.5-5.0MPa, and gaseous mixture air speed is 2500-
4000h-1, reaction temperature be 350 DEG C -500 DEG C.
The catalyst that one section of methanolizing reaction as above uses is Cu/Zr/La/Ti, Cu/Zn/Al, Cu/Zr/Mn/
Ni etc. is applied to the catalyst of synthesis gas methanolizing reaction.
The present invention has advantages below：
The application process of the present invention is that first through one section of methanolizing reaction, synthesis gas is generated the gaseous mixture containing methyl alcohol, Ran Houjin
Enter second-stage reaction and prepare liquid fuel, simplify separating methanol flow process it is achieved that synthesis gas successive reaction prepares liquid fuel, be
The technique that a kind of efficient synthesis gas prepares liquid fuel.
The present invention synthesizes little crystal grain HZSM-5 catalyst using hydrothermal synthesis method, and its particle diameter is less than 600nm, degree of crystallinity
(>=93%).There is higher methanol conversion and liquid hydrocarbon productivity, decreasing deep reaction makes catalyst carbon deposit inactivation slow down,
Catalyst single pass life is more than 480 hours, renewable use, and entire life, more than 5000 hours, is that synthesis gas prepares liquid combustion
Material provides a kind of efficient catalyst.
Specific embodiment
The present invention enters second-stage reaction through the gaseous mixture that one section of methanolizing reaction generates containing methyl alcohol for unstripped gas with synthesis gas
Prepare liquid fuel.
Embodiment 1
(its mol ratio is 25Na to weigh sodium metasilicate, sodium sulphate and deionized water2O:100SiO2：5000H2O.), add not
In rust steel synthesis reactor, it is stirred into sodium silicate solution；Weigh aluminum sulfate to be dissolved completely in water, add sulfuric acid and stir
(its mol ratio is Al to become aluminum sulfate solution2O3:5.5S04 2-:2000H2O.)；300ml aluminum sulfate solution is instilled in reactor
In 450ml sodium silicate solution, it is stirred at room temperature uniformly, is subsequently adding 15.25gTPAOH, chilling adds after 180 DEG C of crystallization 5 hours
23.32gH2O2, adjust crystallization temperature and be 120 DEG C, continue crystallization 45 hours；After the completion of crystallization, cooling, washing, filtration, 100 DEG C
It is dried 12 hours, 550 DEG C of roastings 6 hours, obtain the NaZSM-5 molecular screen primary powder of nanometer particle size, its mole consists of 25Na2O:
100SiO2：1.67Al2O3；By the NaZSM-5 molecular screen primary powder NH of 1mol/L4NO3Solution stirs 3 hours at 65 DEG C, mistake
Filter, washing, repeats ammonium exchange step 2 times.100 DEG C of dryings in an oven, 500 DEG C of roast 6h in Muffle furnace, obtain HZSM-5 and urge
Agent powder, its mole consists of SiO2：Al2O3=100：1.63, size of microcrystal 523nm, degree of crystallinity 94%.Urge in HZSM-5
The sesbania powder binding agent of 12wt% is added, with the salpeter solution mixing extrusion molding of 5v%, 110 DEG C in baking oven in agent powder
It is dried, 540 DEG C of roast 5h in Muffle furnace, obtain HZSM-5 molecular sieve catalyst, be broken for 20-40 mesh stand-by.
The evaluation of catalyst is carried out in fixed bed reactors, and unstripped gas composition is shown in Table 1, unstripped gas air speed 3000h-1, reaction
Condition T=380 DEG C, P=5.0MPa, catalyst single pass life 523 hours, 7845 hours entire lives.Methanol conversion 100%,
Liquid hydrocarbon yield 32.43%, oil-phase product composition is shown in Table 4.
Unstripped gas be use catalyst be Cu/Zr/La/Ti, its mol ratio Cu：Zr：La：Ti=53:51:7.5:
9.8, its reaction condition is reaction pressure 5MPa, synthesis gas H2/ CO=2 (mol ratio), air speed 10000h-1, 250 DEG C of reaction temperature
Under the conditions of preparation.
Table 1 feed gas molar forms (mol%)
| H2 | CO | CH4 | CO2 | CH3OH | (CH3)2O | H2O |
| 59.4227 | 29.0663 | 0.2580 | 0.6128 | 9.8475 | 0.0093 | 0.7834 |
Embodiment 2
(its mol ratio is 18.18Na to weigh Ludox, sodium sulphate and deionized water2O:100SiO2:2018H2O.), add
In stainless steel synthesis reactor, it is stirred into silicon sol solution；Weigh aluminum sulfate to be dissolved in water, add sulfuric acid and stir
(its mol ratio is Al2O3:7.2S04 2-:1009H2O.) become aluminum sulfate solution；400ml aluminum sulfate solution is instilled in reactor
In 400ml silicon sol solution, it is stirred at room temperature and is uniformly subsequently adding 16.09g n-butylamine, chilling adds after 160 DEG C of crystallization 6 hours
29.14gH2O2, adjust crystallization temperature and be 100 DEG C, continue crystallization 55 hours；After the completion of crystallization, cooling, washing, filter, 120 DEG C
It is dried 12 hours, 540 DEG C of roastings 6 hours, obtain the NaZSM-5 molecular screen primary powder of nanometer particle size, its mole consists of
18.18Na2O:100SiO2：2Al2O3；By the NaZSM-5 molecular screen primary powder NH of 0.5mol/L4NO3Solution stirs 2 at 80 DEG C
Hour, filter, washing, repeat ammonium exchange step 3 times.120 DEG C of dryings in an oven, in Muffle furnace, 550 DEG C of roast 5h, obtain
HZSM-5 catalyst raw powder, its mole consists of SiO2：Al2O3=100：1.97, size of microcrystal 487nm, degree of crystallinity 96%.?
The sesbania powder binding agent of 20wt% is added, with the salpeter solution mixing extrusion molding of 2v%, in baking in HZSM-5 catalyst fines
120 DEG C of dryings in case, 550 DEG C of roast 4h in Muffle furnace, obtain HZSM-5 molecular sieve catalyst, be broken for 20-40 mesh stand-by.
The evaluation of catalyst is carried out in fixed bed reactors, and unstripped gas composition is shown in Table 2, unstripped gas air speed 2500h-1, reaction
Condition T=420 DEG C, P=4.0MPa, catalyst single pass life 624 hours, 8112 hours entire lives.Methanol conversion 100%,
Liquid hydrocarbon yield 28.18%, oil-phase product composition is shown in Table 4.
Unstripped gas be use catalyst be Cu/Zn/Al, its mol ratio Cu：Zn：Al=6:3:1, its reaction condition is
Reaction pressure 4MPa, synthesis gas H2/ CO=2 (mol ratio), air speed 6000h-1, preparation under the conditions of 230 DEG C of reaction temperature.
Table 2 feed gas molar forms (mol%)
| H2 | CO | CH4 | CO2 | CH3OH | (CH3)2O | H2O |
| 55.2226 | 25.8214 | 0.4717 | 1.1336 | 17.3508 | 0.0257 | 2.2503 |
Embodiment 3
(its mol ratio is 20Na to weigh Ludox, sodium sulphate and deionized water2O:100SiO2：:2000H2O.), add not
In rust steel synthesis reactor, it is stirred into silicon sol solution；Weigh aluminum sulfate to be dissolved completely in water, add sulfuric acid and stir
(its mol ratio is Al2O3:11.8S04 2-：1000H2O).Become aluminum sulfate solution；360ml aluminum sulfate solution is instilled in reactor
360ml silicon sol solution in, be stirred at room temperature uniformly, be subsequently adding 34.86g hexamethylene diamine, chilling after 190 DEG C of crystallization 3 hours
Add 20.48gH2O2, adjust crystallization temperature and be 150 DEG C, continue crystallization 48 hours；After the completion of crystallization, cool down, wash, filtering,
120 DEG C of dryings 12 hours, 540 DEG C of roastings 6 hours, obtain the NaZSM-5 molecular screen primary powder of nanometer particle size, its mole consists of
20Na2O:100SiO2：2.5Al2O3:；By the NaZSM-5 molecular screen primary powder NH of .0.2mol/L4NO3Solution stirs at 90 DEG C
4 hours, filter, washing, repeat ammonium exchange step 4 times.110 DEG C of dryings in an oven, in Muffle furnace, 500 DEG C of roast 4h, obtain
HZSM-5 catalyst fines, its mole consists of SiO2：Al2O3=100：2.43, size of microcrystal 572nm, degree of crystallinity 95%.?
The sesbania powder binding agent of 30wt% is added, with the salpeter solution mixing extrusion molding of 1v%, in baking in HZSM-5 catalyst fines
100 DEG C of dryings in case, 540 DEG C of roast 6h in Muffle furnace, obtain HZSM-5 molecular sieve catalyst, be broken for 20-40 mesh stand-by.
The evaluation of catalyst is carried out in fixed bed reactors, and unstripped gas composition is shown in Table 3, unstripped gas air speed 3500h-1, reaction
Condition T=480 DEG C, P=3.5MPa.Catalyst single pass life 504 hours, 5512 hours entire lives.Methanol conversion 100%,
Liquid hydrocarbon yield 41.13%, oil-phase product composition is shown in Table 4.
Unstripped gas be use catalyst be Cu/Zr/Mn/Ni, its mol ratio Cu：Zr：Mn：Ni=27:54:14:5,
Its reaction condition is reaction pressure 8MPa, synthesis gas H2/ CO=2 (mol ratio), air speed 4000h-1, 280 DEG C of conditions of reaction temperature
Lower preparation.
Table 3 feed gas molar forms (mol%)
| H2 | CO | CH4 | CO2 | CH3OH | (CH3)2O | H2O |
| 57.4796 | 26.8767 | 0.4910 | 1.1799 | 13.9729 | 0.0207 | 1.8122 |
Table 4 embodiment oil-phase product forms
Claims (9)
1. a kind of catalyst of synthetic liquid fuel is it is characterised in that catalyst mole consists of SiO2： Al2O3=100：1-5,
Size of microcrystal is less than 600nm, degree of crystallinity >=93%.
2. as claimed in claim 1 a kind of preparation method of the catalyst of synthetic liquid fuel it is characterised in that include as follows
Step：
（1）Weigh silicon source, sodium salt and deionized water to add in synthesis reactor, stir, wherein, silicon source is with SiO2Meter, sodium salt with
Na2O counts, and each constitutive molar ratio is Na2O: SiO2： H2O=15-30：100：1000-6000；
（2）Weigh aluminium salt to be dissolved completely in water, add sulfuric acid and stir, wherein aluminium salt is with Al2O3Meter, sulfuric acid is with S04 2-
Meter, each constitutive molar ratio is Al2O3: S04 2-:H2O= 1：5-15：1000-2400；
（3）Consist of SiO by material molar ratio2：Al2O3=100：1-5, the solution that step 2 is prepared instills step（1）Prepare
In solution, it is stirred at room temperature uniformly；
（4）Add template in synthesis reactor, its mol ratio is SiO2：Template=1：0.1-0.3, in 150-200 DEG C of crystallization 2-
10 hours, chilling added H2O2, its consumption is step（3）Prepare the 2.5-3.5wt% of solution total amount, adjustment crystallization temperature is afterwards
100-200 DEG C, continue crystallization 10-100 hour；
（5）After the completion of crystallization, cooling, washing, filtration, 100-120 DEG C of drying, 500-550 DEG C of roasting 4-6 hour, obtain nanometer
The NaZSM-5 molecular screen primary powder of particle diameter；
（6）By the NaZSM-5 molecular screen primary powder NH of 0.2-1 mol/L4NO3Solution stirs 1-5 hour, mistake at 60-100 DEG C
Filter, washing, repeats ammonium exchange step 2-4 time, in 100-120 DEG C of drying, in 500-550 DEG C of roast 4-6h, obtains HZSM-5 catalysis
Agent powder；
（7）Add the binding agent of 10-50wt% in HZSM-5 catalyst fines, be squeezed into the salpeter solution mixing of 1-5v%
Type, in 100-120 DEG C of drying, 500-550 DEG C of roast 4-6 h, obtains HZSM-5 molecular sieve catalyst, is broken for 20-40 mesh and treats
With.
3. as claimed in claim 1 a kind of preparation method of the catalyst of synthetic liquid fuel it is characterised in that step（1）Institute
The silicon source stated is sodium metasilicate.
4. as claimed in claim 1 a kind of preparation method of the catalyst of synthetic liquid fuel it is characterised in that step（1）Institute
The sodium salt stated is sodium sulphate.
5. as claimed in claim 1 a kind of preparation method of the catalyst of synthetic liquid fuel it is characterised in that step（2）Institute
The silicon source stated is aluminum sulfate.
6. as claimed in claim 1 a kind of preparation method of the catalyst of synthetic liquid fuel it is characterised in that step（4）Institute
The template stated is TPAOH（TPAOH）, n-butylamine or hexamethylene diamine.
7. as claimed in claim 1 a kind of preparation method of the catalyst of synthetic liquid fuel it is characterised in that step（7）Institute
The binding agent stated is sesbania powder.
8. a kind of application of the catalyst of synthetic liquid fuel as described in any one of claim 1-7 is it is characterised in that include
Following steps：
First synthesis gas through methanolization reaction is generated the gaseous mixture containing methyl alcohol, then the gaseous mixture of methyl alcohol is contained as unstripped gas with this,
Reacted under catalyst action, its reaction pressure is 3.5-5.0MPa, gaseous mixture air speed is 2500-4000h-1, reaction temperature
For 350 DEG C -500 DEG C.
9. as claimed in claim 8 a kind of application of catalyst of synthetic liquid fuel it is characterised in that described methanolizing
The catalyst of reaction is applied to the catalysis of synthesis gas methanolizing reaction for Cu/Zr/La/Ti, Cu/Zn/Al or Cu/Zr/Mn/Ni
Agent.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3931349A (en) * | 1974-09-23 | 1976-01-06 | Mobil Oil Corporation | Conversion of methanol to gasoline components |
| CN1868593A (en) * | 2006-06-09 | 2006-11-29 | 中国科学院山西煤炭化学研究所 | Method for preparing FeZrZSM-5 molecular and application |
| CN1923366A (en) * | 2006-09-15 | 2007-03-07 | 中国科学院山西煤炭化学研究所 | Preparation of hydrocarbon molecular sieve catalyst by methanol transformation |
| CN102642847A (en) * | 2012-05-09 | 2012-08-22 | 浙江大学 | Synthesizing method of template-free high-dispersion submicron ZSM-5 zeolite molecular sieve |
| CN103007983A (en) * | 2012-10-08 | 2013-04-03 | 太原理工大学 | HZSM-5 molecular sieve based catalyst for producing gasoline from methanol, and preparation method and application thereof |
| CN103183359A (en) * | 2013-03-20 | 2013-07-03 | 中国科学院青岛生物能源与过程研究所 | Nanoscale FeZSM-5 molecular sieve, and preparation method and application thereof |
-
2016
- 2016-09-19 CN CN201610835099.6A patent/CN106423256A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3931349A (en) * | 1974-09-23 | 1976-01-06 | Mobil Oil Corporation | Conversion of methanol to gasoline components |
| CN1868593A (en) * | 2006-06-09 | 2006-11-29 | 中国科学院山西煤炭化学研究所 | Method for preparing FeZrZSM-5 molecular and application |
| CN1923366A (en) * | 2006-09-15 | 2007-03-07 | 中国科学院山西煤炭化学研究所 | Preparation of hydrocarbon molecular sieve catalyst by methanol transformation |
| CN102642847A (en) * | 2012-05-09 | 2012-08-22 | 浙江大学 | Synthesizing method of template-free high-dispersion submicron ZSM-5 zeolite molecular sieve |
| CN103007983A (en) * | 2012-10-08 | 2013-04-03 | 太原理工大学 | HZSM-5 molecular sieve based catalyst for producing gasoline from methanol, and preparation method and application thereof |
| CN103183359A (en) * | 2013-03-20 | 2013-07-03 | 中国科学院青岛生物能源与过程研究所 | Nanoscale FeZSM-5 molecular sieve, and preparation method and application thereof |
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Application publication date: 20170222 |