CN106215971A - A kind of catalyst of two-step method preparing gasoline by methanol hydrocarbonylation and preparation method thereof - Google Patents

A kind of catalyst of two-step method preparing gasoline by methanol hydrocarbonylation and preparation method thereof Download PDF

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Publication number
CN106215971A
CN106215971A CN201610556441.9A CN201610556441A CN106215971A CN 106215971 A CN106215971 A CN 106215971A CN 201610556441 A CN201610556441 A CN 201610556441A CN 106215971 A CN106215971 A CN 106215971A
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molecular sieve
catalyst
methanol
method preparing
preparing gasoline
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秦如浩
陈忠民
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Henan Bo Jie Energy Engineering Technology Co Ltd
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Henan Bo Jie Energy Engineering Technology Co Ltd
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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
    • B01J29/405—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
    • 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
    • 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
    • C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
    • C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
    • 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
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline
    • 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
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Abstract

The catalyst of a kind of two-step method preparing gasoline by methanol hydrocarbonylation, its percentage by weight consists of: ZSM 5 molecular sieve 35～80%, binding agent 15～60%, active metal auxiliary agent are 20～300 with metal simple-substance content meter 0.5～5%, the silica alumina ratio of ZSM 5 molecular sieve.Its preparation method, comprises the following steps: HZSM 5 molecular sieve is carried out hydrothermal treatment consists；Molecular sieve is carried out pickling, and solid-to-liquid ratio is 1:(1～10), sucking filtration after dipping, washing, sucking filtration, roasting obtains HZSM 5 molecular sieve of pickling；HZSM 5 molecular sieve of pickling is mixed with binding agent, water, is dried after extruded moulding, then roasting 3～5 hours, obtain bar shaped modified ZSM-5 5 molecular sieve；Bar shaped modified ZSM-5 5 molecular sieve is joined in the nitrate containing active metal auxiliary agent, sulfate liquor or ammonium molybdate solution, impregnates, wash, filter, be dried, roasting 3～after 5 hours and get final product.After modified, stability is good for catalyst of the present invention, extends the single pass life of catalyst, improves catalytic capability simultaneously, and gasoline selective is high.

Description

A kind of catalyst of two-step method preparing gasoline by methanol hydrocarbonylation and preparation method thereof
Technical field
The invention belongs to catalyst technical field, be specifically related to a kind of two-step method preparing gasoline by methanol hydrocarbonylation catalyst and Its preparation method.
Background technology
Methanol is the major products of coal chemical technology.In recent years, along with the development of China's coal chemical industry, China's methanol produces Industry development is very fast, the many first-selected methanol of starting project of various places Development of Coal chemical industry, makes methanol production capacity increase sharply.2011 extremely 2015, newly-increased production capacity reached 53,300,000 tons；The production capacity of methanol is considerably beyond actual demand, therefore, it is necessary to active development Carry out the downstream product of methanol, increase new methanol application, improve the production technology level of existing Downstream Products of Methanol, right The development of methanol industry has highly important meaning.
United States Patent (USP) US3931349A and US4579999 disclose methanol and convert the technology of hydro carbons processed, have attracted industry Boundary and the huge concern of academia.This technology uses two sections of conversion process of fixed bed, and wherein first paragraph reaction is methanol dewatered Dimethyl ether, the outlet material of a section enters second stage reactor, generates gasoline and low-carbon (LC) hydro carbons under the effect of molecular sieve catalyst. Chinese patent CN1923366A discloses molecular sieve catalyst of a kind of methanol by one-step method synthetic gasoline and preparation method thereof, should Method has obtained LaZSM-5 molecular sieve catalyst by fabricated in situ means, and this catalyst has higher gasoline selective, And stability and the selectivity of product of catalyst can be improved under certain condition by the acidic character of modulation molecular sieve.At present, Although the technology of preparing gasoline by methanol has obtained quick development, but ZSM-5 molecular sieve catalyst still easily inactivates because of carbon distribution, The single pass life making catalyst is shorter, selectivity is low.
Summary of the invention
Present invention aim at providing the catalyst of a kind of two-step method preparing gasoline by methanol hydrocarbonylation, corresponding system is provided simultaneously Preparation Method is another goal of the invention of the present invention.
Based on above-mentioned purpose, the present invention takes techniques below scheme:
The catalyst of a kind of two-step method preparing gasoline by methanol hydrocarbonylation, the percentage by weight of described catalyst consists of: ZSM-5 molecule Sieve 35～80%, binding agent 15～60%, active metal auxiliary agent with metal simple-substance content meter 0.5～5%, described ZSM-5 molecular sieve Silica alumina ratio is 20～300.
Described active metal auxiliary agent one, two kinds and above mixture in ammonium molybdate, nitrate and sulfate.
Described active metal auxiliary agent is selected from ammonium molybdate, copper nitrate, nickel nitrate, Ganite (Fujisawa)., ferric nitrate, zinc nitrate Kind, two kinds and above mixture.
Described binding agent one in activated alumina, silicon oxide, aluminum phosphate and boehmite, two kinds and more than Mixture.
The preparation method of the catalyst of two-step method preparing gasoline by methanol hydrocarbonylation, comprises the following steps:
1), after the HZSM-5 molecular sieve that silica alumina ratio is 20～300 being carried out hydrothermal treatment consists at 400～650 DEG C, it is cooled to Room temperature；
2), at 80～100 DEG C, it is that 0.1～1mol/L acid solution carries out acid by step 1) gained molecular sieve addition molar concentration Washing, solid-to-liquid ratio is 1:(1～10), after impregnating 3～5 hours, sucking filtration, washing, sucking filtration, at 400～650 DEG C, roasting obtains pickling HZSM-5 molecular sieve；
3) by step 2) the HZSM-5 molecular sieve of gained pickling mixes with binding agent, water, is dried, in 400～650 after extruded moulding DEG C roasting 3～5 hours, obtain bar shaped modified zsm-5 zeolite；
4) being joined by step 3) gained bar shaped modified zsm-5 zeolite in the aqueous solution of active metal auxiliary agent, solid-to-liquid ratio is 1: (1～10), at 80～100 DEG C, sucking filtration after impregnating 3～10 hours, repeated impregnations, wash, filter, be dried, 400～650 Roasting 3～after 5 hours and get final product at DEG C.
HZSM-5 molecular sieve described in step 1) by silica alumina ratio be 20～300, particle diameter be 20～200nm NaZSM- 5 molecular sieves carry out ammonium exchange, and after washing is dried, at 500～800 DEG C, roasting 4～6 hours prepare；Dry temperature be 100～ 120℃。
The ammonium salt of described ammonium clearing house is ammonium sulfate, ammonium phosphate, ammonium chloride or ammonium nitrate.
In step 1), the time of hydrothermal treatment consists is 3～8h, and the liquid phase quality air speed of water is 1h-1。
Step 2) described in acid selected from nitric acid, phosphoric acid and molybdic acid.
Repeated impregnations number of times described in step 4) is 1～5 time.
Compared with prior art, the method have the advantages that
1) after ZSM-5 molecular sieve is modified by the present invention by hydrothermal treatment consists, acid modification and supported active metals, catalysis The stability of agent is good, extends the single pass life of catalyst, improves catalytic capability simultaneously, and gasoline selective is high.
2) catalyst processed through molybdenum element (molybdic acid and ammonium molybdate), the molybdenum that there is trace is modified, and ZSM-5 divides Molybdenum and the aluminum atom of son sieve outer surface enrichment the most all can migrate to inner surfaces of pores, and the migration of Mo adds in duct The quantity of L acid position and intensity, the migration of Al adds the quantity of B-acid position in duct, strengthens B-acid-L acid center Cooperative effect, and newly-increased L acid center promotes electron cloud to offset, and exacerbates the mobility of proton in the heart in neighbouring B-acid, thus Adding the intensity at Bronsted acid center, catalyst in MTG react the content of aromatic hydrocarbons modified through permolybdic acid and ammonium molybdate carries Height will by about one time, and then improves the octane number of component.
Detailed description of the invention
In conjunction with specific embodiments, the present invention is described in further details:
Embodiment 1
The preparation method of the catalyst of a kind of two-step method preparing gasoline by methanol hydrocarbonylation, comprises the following steps:
1) the NaZSM-5 molecular sieve that silica alumina ratio is 100 is joined in 0.2mol/L ammonium chloride solution, stir, Gu Liquor ratio is 1:10, and at 90 DEG C, ammonium exchanges 2 hours, and through washing, after being dried 5 hours at 120 DEG C, at 650 DEG C, roasting 6 is little Time, preparing HZSM-5 molecular sieve, after then carrying out hydrothermal treatment consists 3h at 400 DEG C, be cooled to room temperature, the liquid phase quality of water is empty Speed is 1h-1；
2) at 80 DEG C, being to carry out pickling in 1mol/L acid solution by step 1) gained molecular sieve addition molar concentration, solid-to-liquid ratio is 1:10, after impregnating 4 hours, sucking filtration, deionized water wash, sucking filtration, roasting 4h at 600 DEG C, obtain the HZSM-5 molecule of pickling Sieve；
3) by step 2) the HZSM-5 molecular sieve of gained pickling mixes with aluminium oxide, water, after extruded moulding, is dried at 120 DEG C 5h, roasting 4 hours at 600 DEG C, obtain bar shaped modified zsm-5 zeolite, binding agent quality accounts for bar shaped modified zsm-5 zeolite The 20% of quality；
4) joining step 3) gained bar shaped modified zsm-5 zeolite containing in 0.1mol/L zinc nitrate solution, solid-to-liquid ratio is 1:10, at 80 DEG C, sucking filtration after impregnating 10 hours, repeated impregnations 3 times, after washing, filtering, at 120 DEG C, it is dried 5h, 600 At DEG C after roasting 4 hours, broken, the granule of screening 20～40 mesh and get final product.
Embodiment 2-4
Embodiment 2-4 respectively is containing the solution of active metal auxiliary agent in step 4): the iron nitrate solution of same concentrations, Ammonium molybdate solution, nickel nitrate solution, other are with reference to embodiment 1.
Embodiment 5-6
Step 2 in embodiment 5-6) in acid solution respectively be the nitric acid of 1mol/L, molybdic acid, other are with reference to embodiments 1.
Embodiment 7-8
In embodiment 7-8, in step 3), binding agent respectively is aluminum phosphate, boehmite, and other are with reference to embodiment 1.
Embodiment 9-10
The solution carrying out ammonium exchange in embodiment 9-10 in step 1) respectively is ammonium nitrate solution, ammonium sulfate, other With reference to embodiment 1.
Embodiment 11-17
In embodiment 11 silica alumina ratio of step 1) NaZSM-5 molecular sieve respectively be 80,50,20,290,240,200, 150, other are with reference to embodiment 1.
Embodiment 18 hydrothermal treatment consists and the pickling impact on HZSM-5 molecular sieve structure
The HZSM-5 sieve sample that in embodiment 1, step 1) prepares is divided into sample 1, sample 2, sample 3, sample 4 and sample 5 five Part, sample 1 is the sample not carrying out hydrothermal treatment consists；Sample 2 is gained sample after hydrothermal treatment consists 3h at 500 DEG C；Sample 3 be Hydrothermal treatment consists 3h gained sample at 600 DEG C；Sample 4 is hydrothermal treatment consists 3h gained sample at 650 DEG C；Sample 5 is hydro-thermal at 600 DEG C Process 3h, hydrogen nitrate dipping 3h gained sample, use N2Physical absorption-desorption characterizes sample 1, sample 2, sample 3, sample 4 and sample The pore property of product 5, the results are shown in Table 1.
As shown in Table 1, the HZSM-5 molecular sieve specific surface area after hydrothermal treatment consists all reduces, but is as the liter of hydrothermal treatment consists temperature Height, the specific surface area of sample is in slightly rising trend；Through nitric acid acidwashing after hydrothermal treatment consists, the specific surface area of sample increases, and nitric acid is described Pickling, really eliminates the non-skeleton compound in Partial Blocking duct, has dredged the duct of molecular sieve, thus illustrated, molecular sieve Pickling is favorably improved the gasoline selective of catalyst.
The reactivity worth evaluation of embodiment 19 catalyst
With the methanol aqueous solution of identical water content as raw material, the catalyst sample obtained by embodiment 1-17 normal pressure, 380 DEG C, Under the conditions of the mass space velocity of identical methanol aqueous solution, carrying out MTG reaction, product cools down through ice-water bath, is separated into gas phase lower carbon number hydrocarbons Product and liquid product, liquid product is divided into oil phase and aqueous phase through separatory funnel again, and gas-phase product uses gas phase TCD to analyze and produces Thing forms, and aqueous phase uses FID detection assay products composition, calculates gained methanol conversion and yield of gasoline, is shown in Table 2.
As shown in Table 2, molecular sieve, after metal-modified, improves yield of gasoline in MTG reaction.And through molybdenum element (molybdenum Acid and ammonium molybdate) catalyst that processed, the molybdenum that there is trace is modified, and molybdenum and the aluminum of the enrichment of ZSM-5 molecular sieve outer surface are former Son the most all can migrate to inner surfaces of pores, and the migration of Mo adds quantity and intensity, the Al of the L acid position in duct Migration add the quantity of B-acid position in duct, strengthen the cooperative effect at B-acid-L acid center, and in newly-increased L acid The heart promotes electron cloud to offset, and exacerbates the mobility of proton in the heart in neighbouring B-acid, thus adds the intensity at Bronsted acid center, Improving through catalyst content of aromatic hydrocarbons in MTG reacts that permolybdic acid and ammonium molybdate are modified will by about one time, and then improves group The octane number divided.
The life assessment of embodiment 20 catalyst
By sample obtained by embodiment 1 normal pressure, at 370 DEG C, the mass space velocity of methanol feedstock be 1.0h-1Under to carry out MTG anti- Should, in methanol feedstock, water content is 20wt%, and product cools down through ice-water bath, is separated into gas-phase product and liquid product, and liquid phase is produced Thing is separated into oil phase and aqueous phase through separatory funnel again, and oil-phase product uses gas phase TCD assay products composition, and water-phase product uses FID detection assay products composition.In MTG reaction, methanol conversion and yield of gasoline situation over time are shown in Table 3.
As shown in Table 3, in reaction 1180h, the catalyst sample MTG methanol of reaction conversion ratio obtained by embodiment 1 is still protected Holding more than 98%, yield of gasoline is maintained at more than 80%, it follows that catalyst is through modified, its stability is good, extends In the life-span of catalyst, improve catalytic capability simultaneously.

Claims (10)

1. the catalyst of a two-step method preparing gasoline by methanol hydrocarbonylation, it is characterised in that the percentage by weight group of described catalyst Become: ZSM-5 molecular sieve 35～80%, binding agent 15～60%, active metal auxiliary agent are with metal simple-substance content meter 0.5～5%, institute The silica alumina ratio stating ZSM-5 molecular sieve is 20～300.
2. the catalyst of two-step method preparing gasoline by methanol hydrocarbonylation as claimed in claim 1, it is characterised in that described active metal helps Agent one, two kinds and above mixture in ammonium molybdate, nitrate and sulfate.
3. the catalyst of two-step method preparing gasoline by methanol hydrocarbonylation as claimed in claim 2, it is characterised in that described active metal helps Agent one, two kinds and above mixture in ammonium molybdate, copper nitrate, nickel nitrate, Ganite (Fujisawa)., ferric nitrate, zinc nitrate.
4. the catalyst of two-step method preparing gasoline by methanol hydrocarbonylation as claimed in claim 1, it is characterised in that described binding agent is selected from One, two kinds and above mixture in activated alumina, silicon oxide, aluminum phosphate and boehmite.
5. the preparation method of the catalyst of two-step method preparing gasoline by methanol hydrocarbonylation as claimed in claim 1, it is characterised in that bag Include following steps:
1), after the HZSM-5 molecular sieve that silica alumina ratio is 20～300 being carried out hydrothermal treatment consists at 400～650 DEG C, it is cooled to Room temperature；
2), at 80～100 DEG C, it is that 0.1～1mol/L acid solution carries out acid by step 1) gained molecular sieve addition molar concentration Washing, solid-to-liquid ratio is 1:(1～10), after impregnating 3～5 hours, sucking filtration, washing, sucking filtration, at 400～650 DEG C, roasting obtains pickling HZSM-5 molecular sieve；
3) by step 2) the HZSM-5 molecular sieve of gained pickling mixes with binding agent, water, is dried, in 400～650 after extruded moulding DEG C roasting 3～5 hours, obtain bar shaped modified zsm-5 zeolite；
4) being joined by step 3) gained bar shaped modified zsm-5 zeolite in the aqueous solution of active metal auxiliary agent, solid-to-liquid ratio is 1: (1～10), at 80～100 DEG C, sucking filtration after impregnating 3～10 hours, repeated impregnations, wash, filter, be dried, 400～650 Roasting 3～after 5 hours and get final product at DEG C.
6. the preparation method of the catalyst of two-step method preparing gasoline by methanol hydrocarbonylation as claimed in claim 5, it is characterised in that step Rapid 1) HZSM-5 molecular sieve described in by silica alumina ratio be 20～300, particle diameter be 20～200nm NaZSM-5 molecular sieve enter Row ammonium exchanges, and after washing is dried, at 500～800 DEG C, roasting 4～6 hours prepare；Drying temperature is 100～120 DEG C.
7. the preparation method of the catalyst of two-step method preparing gasoline by methanol hydrocarbonylation as claimed in claim 6, it is characterised in that institute The ammonium salt stating ammonium clearing house is ammonium sulfate, ammonium phosphate, ammonium chloride or ammonium nitrate.
8. the preparation method of the catalyst of two-step method preparing gasoline by methanol hydrocarbonylation as claimed in claim 5, it is characterised in that step Rapid 1) in, the time of hydrothermal treatment consists is 3～8h, and the liquid phase quality air speed of water is 1h-1。
9. the preparation method of the catalyst of two-step method preparing gasoline by methanol hydrocarbonylation as claimed in claim 5, it is characterised in that step Rapid 2) described in, acid is selected from nitric acid, phosphoric acid and molybdic acid.
10. the preparation method of the catalyst of two-step method preparing gasoline by methanol hydrocarbonylation as claimed in claim 5, it is characterised in that Repeated impregnations number of times described in step 4) is 1～5 time.
CN201610556441.9A 2016-07-15 2016-07-15 A kind of catalyst of two-step method preparing gasoline by methanol hydrocarbonylation and preparation method thereof Pending CN106215971A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106582789A (en) * 2016-12-27 2017-04-26 上海卓悦化工科技有限公司 Preparation method and application of modified HZSM-5 molecular sieve catalyst
CN108392950A (en) * 2018-01-23 2018-08-14 湖南大学 Application of the oxide-molecular sieve catalyst in being catalyzed carbon dioxide

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011059674A2 (en) * 2009-11-13 2011-05-19 Chevron U.S.A. Inc. Method for making mfi-type molecular sieves
CN103433067A (en) * 2013-09-09 2013-12-11 中国科学院上海高等研究院 Catalyst for preparing gasoline from methyl alcohol as well as preparation and application of catalyst
CN103506150A (en) * 2013-10-18 2014-01-15 中国科学院上海高等研究院 Water vapor modified catalyst for preparing gasoline from methanol, and preparation method and application of water vapor modified catalyst
CN105502433A (en) * 2015-12-16 2016-04-20 上海英保能源化工科技有限公司 Preparation method of methanol-to-gasoline catalyst nano Zn-ZSM-5

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011059674A2 (en) * 2009-11-13 2011-05-19 Chevron U.S.A. Inc. Method for making mfi-type molecular sieves
CN103433067A (en) * 2013-09-09 2013-12-11 中国科学院上海高等研究院 Catalyst for preparing gasoline from methyl alcohol as well as preparation and application of catalyst
CN103506150A (en) * 2013-10-18 2014-01-15 中国科学院上海高等研究院 Water vapor modified catalyst for preparing gasoline from methanol, and preparation method and application of water vapor modified catalyst
CN105502433A (en) * 2015-12-16 2016-04-20 上海英保能源化工科技有限公司 Preparation method of methanol-to-gasoline catalyst nano Zn-ZSM-5

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
朱建华: "MoCl5在HZSM-5和APO-5上的负载及调变作用", 《催化学报》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106582789A (en) * 2016-12-27 2017-04-26 上海卓悦化工科技有限公司 Preparation method and application of modified HZSM-5 molecular sieve catalyst
CN106582789B (en) * 2016-12-27 2019-05-10 卓悦环保新材料（上海）有限公司 A kind of preparation method and application of Modified HZSM-5 Zeolite Catalyst
CN108392950A (en) * 2018-01-23 2018-08-14 湖南大学 Application of the oxide-molecular sieve catalyst in being catalyzed carbon dioxide

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