CN106111180A - The catalyst of methanol high-knock rating gasoline blend component and compounding method thereof - Google Patents

The catalyst of methanol high-knock rating gasoline blend component and compounding method thereof Download PDF

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Publication number
CN106111180A
CN106111180A CN201610452966.8A CN201610452966A CN106111180A CN 106111180 A CN106111180 A CN 106111180A CN 201610452966 A CN201610452966 A CN 201610452966A CN 106111180 A CN106111180 A CN 106111180A
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catalyst
molecular sieve
zsm
parts
oxide
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刘贵生
屈新
屈一新
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Compass Aerospace Satellite Application Technology Group Co Ltd
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Compass Aerospace Satellite Application Technology Group 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
    • 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
    • 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
    • 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
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/38—Base treatment
    • 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
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles
    • 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
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)

Abstract

The invention provides catalyst and the compounding method thereof of methanol high-knock rating gasoline blend component, relate to high-knock rating gasoline blend component preparation field.The catalyst that used of methanol high-knock rating gasoline blend component that the present invention provides includes following composition: a) 30～90 parts of modified ZSM-5 5 molecular sieve carriers be loaded in thereon；B) 0.1～20 part of zinc element or its oxide；C) 35～70 parts of binding agents；Wherein, Si0 in ZSM 5 molecular sieve2With A1203Mass ratio be 70～100.Compared with the catalyst used in prior art, it can improve the yield being produced high-knock rating gasoline blend component by methanol, and improve single trip use life-span and the entire life of catalyst, improve the degree of freedom that this catalyst of use is prepared the Scheme Choice of high-knock rating gasoline blend component the most to a certain extent；Improve methanol conversion.

Description

The catalyst of methanol high-knock rating gasoline blend component and compounding method thereof
Technical field
The present invention relates to high-knock rating gasoline blend component preparation field, in particular to methanol high-octane rating vapour The catalyst of oil blend component and compounding method thereof.
Background technology
Now with the fast development of industry, crude oil breach is increasing, and China's external crude oil dependency degree has reached 50%- About 60%, serious threat national energy security strategy, aromatic hydrocarbons has become as a kind of trend as new petrochemical material source, is Alleviate China's energy shortage situation, improve comprehensive utilization of resources, kind ambient condition, the effective shortcut preserved the ecological environment.
Material in high-knock rating gasoline blend component, particularly light aromatics BTX (benzene (Benzene), toluene (Toluene) and dimethylbenzene (Xylene)) be important Organic Chemicals, there is high added value.Essentially from petroleum industry And Coal Chemical Industry circuit, it has been widely used at industry tools such as chemical industry, medicine, light industry, weavings.The aromatic hydrocarbons of China is mainly derived from Petroleum resources, and the present situation of China's oil shortage of resources determines the scarcity of aromatic hydrocarbon resource, therefore, finds one and can replace stone The new technique of oil Chemical Manufacture aromatic hydrocarbons is most important.From the direct preparing aromatic hydrocarbon by converting of resourceful methanol, for alleviating aromatic hydrocarbons Shortage, improve the added value of Downstream Products of Methanol, extend Coal Chemical Industry and gas chemical industry's industrial chain, there is important value.
For oil, the coal resources of China are abundanter.In recent years, with coal for raw material production methanol forward Maximization, energy-saving development, methanol output is continuously increased, and production capacity will be far beyond actual demand.Wherein aromatization of methanol system Taking high-knock rating gasoline blend component technology is exactly a good methanol conversion technology, and on the one hand it improve the utilization of methanol Rate, increases its added value, the problem that on the other hand can also solve the shortage of high-knock rating gasoline blend component.
The performance of the catalyst used during methanol structure produces high-knock rating gasoline blend component at present is not Enough good, this directly results in methanol and converts the inefficient of BTX aromatics.
Summary of the invention
It is an object of the invention to provide catalyst and the compounding method thereof of methanol high-knock rating gasoline blend component, with Raising methanol produces the yield during high-knock rating gasoline blend component and the service life of catalyst.
First aspect, embodiments provides the catalyst that methanol high-knock rating gasoline blend component is used, Including following composition:
A) 30～90 parts of modified zsm-5 zeolite carriers and be loaded in thereon；
B) 0.1～20 part of zinc element or its oxide；
C) 35～70 parts of binding agents；
Wherein, Si0 in ZSM-5 molecular sieve2With A1203Mass ratio be 70～100.
Preferably, the oxide of zinc element is following one or more:
Zinc chloride, zinc nitrate, zinc sulfate or zinc acetate.
Preferably, zinc element or its oxide for 4-12 part.
Preferably, binding agent is 1.75～6:1 with the mass ratio of zinc element or its oxide.
Preferably, in zinc element or its oxide, the ratio of zinc chloride, zinc nitrate and zinc sulfate is 4:6:2.
Preferably, Si0 in ZSM-5 molecular sieve2With A1203Mass ratio be 75～81.
Preferably, binding agent is A1203。
Preferably, modified zsm-5 zeolite is 45 parts；Zinc element or its oxide are 11 parts；Binding agent is 62 parts；ZSM- Si0 in 5 molecular sieves2With A1203Mass ratio be 81.
Second aspect, the embodiment of the present invention additionally provides preparation such as the methanol high-knock rating gasoline mediation group of first aspect Divide the compounding method of the catalyst used, comprise the steps:
By fabricated in situ or infusion process, the ZSM-5 molecular sieve obtained adds metal promoter, wherein, metal promoter Including the oxide of one or more of metallic element, Fe, K, Mg, Mn, Cr, W, Co, Ni, Zn, Cd, Ce, V, Zr, Mo unit Element；
ZSM-5 molecular sieve is carried out alkali process, and the ZSM-5 molecular sieve after described alkali is processed and binding agent molding, with Make catalyst carrier；
Zinc element or its oxide are added in catalyst carrier, and makes described methanol Gaoxin through being dried with roasting The catalyst that alkane value gasoline blend component is used.
Preferably, described ZSM-5 molecular sieve is carried out alkali process include:
At 20～80 DEG C, with 0.1～5mol/L aqueous slkali, ZSM-5 molecular sieve is processed one or many, wherein, every time Process 0.1～8 hour；
ZSM-5 molecular sieve is carried out filtration washing；
ZSM-5 molecular sieve is dried under conditions of 100～150 DEG C.
The catalyst that the methanol high-knock rating gasoline blend component that the embodiment of the present invention provides is used, with prior art Used in catalyst compare, it can improve the yield being produced high-knock rating gasoline blend component by methanol, and improves The single trip use life-span of catalyst and entire life, improve this catalyst of use the most to a certain extent and be prepared high-octane rating The degree of freedom of the Scheme Choice of gasoline blend component；Improve methanol conversion.
For making the above-mentioned purpose of the present invention, feature and advantage to become apparent, preferred embodiment cited below particularly, make in detail It is described as follows.
Detailed description of the invention
Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described, Obviously, described embodiment is only a part of embodiment of the present invention rather than whole embodiments.Reality based on the present invention Execute example, the every other embodiment that those skilled in the art are obtained on the premise of not making creative work, broadly fall into The scope of protection of the invention.
In prior art, the catalyst that methanol high-knock rating gasoline blend component is used, its service life is short, uses The yield that high-knock rating gasoline blend component prepared by this catalyst is relatively low.In view of this, this application provides methanol higher octane The catalyst of value gasoline blend component and compounding method thereof.
Illustrate that methanol high-knock rating gasoline blend component provided herein is made with different embodiments below Catalyst.
Embodiment 1
As a example by 65 parts of catalyst of preparation, according to mass fraction meter, including 30 parts of modified zsm-5 zeolite carriers be loaded in Thereon, 0.5 part of zinc element or its oxide and 34 parts of binding agents, wherein, Si0 in ZSM-5 molecular sieve2With A1203Mass ratio It is 70.
Embodiment 2
As a example by 175 parts of catalyst of preparation, according to mass fraction meter, including 88 parts of modified zsm-5 zeolite carriers and load Thereon, 20 parts of zinc element or its oxide and 67 parts of binding agents, wherein, Si0 in ZSM-5 molecular sieve2With A1203Quality Ratio is 100.
Embodiment 3
As a example by 120 parts of catalyst of preparation, according to mass fraction meter, including 60 parts of modified zsm-5 zeolite carriers and load Thereon, 10 parts of zinc element or its oxide and 50 parts of binding agents, wherein, Si0 in ZSM-5 molecular sieve2With A1203Quality Ratio is 86.
Embodiment 4
As a example by 118 parts of catalyst of preparation, according to mass fraction meter, including 45 parts of modified zsm-5 zeolite carriers and load Thereon, 11 parts of zinc element or its oxide and 62 parts of binding agents, wherein, Si0 in ZSM-5 molecular sieve2With A1203Quality Ratio is 81, and binding agent is 1.8:1 with the mass ratio of zinc element or its oxide.
Embodiment 5
As a example by 133 parts of catalyst of preparation, according to mass fraction meter, including 85 parts of modified zsm-5 zeolite carriers and load Thereon, 9 parts of zinc element or its oxide and 39 parts of binding agents, wherein, Si0 in ZSM-5 molecular sieve2With A1203Mass ratio Being 76, binding agent is 4.2:1 with the mass ratio of zinc element or its oxide.
Embodiment 6
As a example by 134 parts of catalyst of preparation, according to mass fraction meter, including 69 parts of modified zsm-5 zeolite carriers and load Thereon, 4 parts of zinc element or its oxide and 61 parts of binding agents, wherein, Si0 in ZSM-5 molecular sieve2With A1203Mass ratio Being 93, binding agent is 5.5:1 with the mass ratio of zinc element or its oxide.
Provide below under same experimental conditions, used the catalyst of different component provided by the present invention to carry out higher octane Experimental result prepared by value gasoline blend component (is shown in Table 1, i.e. uses methanol to prepare the experiment knot of high-knock rating gasoline blend component Fruit and condition, wherein, under same experimental conditions that 2-7 row are the most corresponding, use the catalyst obtained in embodiment 1-6 to carry out Concrete outcome prepared by high-knock rating gasoline blend component).
Table 1
Illustrate in correlation technique with different comparative examples below, the methanol high-knock rating gasoline blend component provided The catalyst used.
Comparative example 1
As a example by 43.7 parts of catalyst of preparation, according to mass fraction meter, including 20 parts of molecular sieve carriers be loaded in thereon, 0.8 part of lanthanum element or its oxide, 0.9 part of P elements or its oxide and 22 parts of binding agents, wherein, molecular sieve is by 10 parts HZSM-5 molecular sieve and 10 parts of HZSM-11 molecular sieve compositions.
Comparative example 2
As a example by 170 parts of catalyst of preparation, according to mass fraction meter, including 75 parts of molecular sieve carriers be loaded in thereon, 11 parts of lanthanum elements or its oxide, 9 parts of P elements or its oxide and 75 parts of binding agents, wherein, molecular sieve is by 30 parts of HZSM-5 Molecular sieve and 35 parts of HZSM-11 molecular sieve compositions.
Comparative example 3
As a example by 122 parts of catalyst of preparation, according to mass fraction meter, including 60 parts of molecular sieve carriers be loaded in thereon, 6.5 parts of lanthanum elements or its oxide, 5.5 parts of P elements or its oxide and 50 parts of binding agents, wherein, molecular sieve is by 20 parts HZSM-5 molecular sieve and 30 parts of HZSM-11 molecular sieve compositions.
Comparative example 4
As a example by 119 parts of catalyst of preparation, according to mass fraction meter, including 38 parts of molecular sieve carriers be loaded in thereon, 8.5 parts of lanthanum elements or its oxide, 6.5 parts of P elements or its oxide and 66 parts of binding agents, wherein, molecular sieve is by 33 parts HZSM-5 molecular sieve and 33 parts of HZSM-11 molecular sieve compositions.
Comparative example 5
As a example by 97 parts of catalyst of preparation, according to mass fraction meter, including 55 parts of molecular sieve carriers be loaded in thereon, 3 Part lanthanum element or its oxide, 4 parts of P elements or its oxide and 35 parts of binding agents, wherein, molecular sieve is divided by 20 parts of HZSM-5 Son sieve and 15 parts of HZSM-11 molecular sieve compositions.
Comparative example 6
As a example by 71 parts of catalyst of preparation, according to mass fraction meter, including 29 parts of molecular sieve carriers be loaded in thereon, 11 Part lanthanum element or its oxide, 2 parts of P elements or its oxide and 29 parts of binding agents, wherein, molecular sieve is divided by 15 parts of HZSM-5 Son sieve and 14 parts of HZSM-11 molecular sieve compositions.
Below, give under same experimental conditions, use traditional catalyst to carry out high-knock rating gasoline blend component The experimental result (being shown in Table 2) of preparation.
Table 2 sets forth and use the traditional catalyst of different component to carry out methanol and prepare high-knock rating gasoline mediation group The experimental data divided.Wherein, under same experimental conditions that 2-7 row are the most corresponding, the catalyst obtained in comparative example 1-6 is used Carry out concrete outcome prepared by high-knock rating gasoline blend component).
Table 2
Methanol flow (g/h) 13.74 13.74 13.74 13.74 13.74 13.74
Discharge (g/h) 2.4 2.4 2.4 2.4 2.4 2.4
Gas speed (h-1) 1444 1444 1444 1444 1444 1444
Methanol weight air speed (WHSV) (h-1) 2.0 2.0 2.0 2.0 2.0 2.0
Temperature (DEG C) 380 380 380 380 380 380
Pressure (MPa) 1.2 1.2 1.2 1.2 1.2 1.2
Methanol conversion (%) 98.92 97.79 96.82 96.63 95.77 96.52
Gas phase yield (wt%) 16.60 11.35 15.24 15.12 14.32 11.65
C5 ratio (wt%) in the gas phase 12.52 12.22 10.15 15.42 16.21 12.04
Liquid yield (wt%) 83.56 98.54 89.11 75.34 82.25 82.13
Aromatics yield (wt%) 22.34 25.2 25.96 28.51 31.78 22.44
Benzene, toluene and xylol yield (wt%) 9.63 8.35 9.15 9.25 8.32 6.85
Visible, under the reaction condition of 380 DEG C of methanol weight air speeds 1.5～2.5h-1 and pressure 1.2MPa, with methanol For raw material, using catalyst provided herein, aromatics yield is up to 40-43%, relative to using traditional catalyst, virtue Hydrocarbon yield can only achieve 28-32%, and therefore, catalysis provided by the present invention achieves preferable technique effect.Preparation experiment In result, olefin(e) centent ＜ 8%, benzene content ＜ 0.3%；Methanol conversion: 100%；Catalyst single pass life: 20～25d, urges Agent entire life: >=1 year.
Above, it is that the component to catalyst provided herein illustrates, below the preparation method of this catalyst is entered Row explanation:
The complete preparation flow of catalyst provided by the present invention is as follows:
1, by fabricated in situ or infusion process, the ZSM-5 molecular sieve obtained adds metal promoter, wherein, metal promoted Agent includes the oxide of one or more of metallic element, Fe, K, Mg, Mn, Cr, W, Co, Ni, Zn, Cd, Ce, V, Zr, Mo unit Element；
2, ZSM-5 molecular sieve is carried out alkali process, and by the ZSM-5 molecular sieve after the process of described alkali and binding agent molding, To make catalyst carrier；
3, zinc element or its oxide are added in catalyst carrier, and makes described methanol system height through being dried with roasting The catalyst that octane rating gasoline blend component is used.
In step 2, ZSM-5 molecular sieve is carried out alkali process and comprises the steps:
At 20～80 DEG C, with 0.1～5mol/L aqueous slkali, ZSM-5 molecular sieve is processed one or many, wherein, every time Process 0.1～8 hour；
ZSM-5 molecular sieve is carried out filtration washing；
ZSM-5 molecular sieve is dried under conditions of 100～150 DEG C.
Wherein, aqueous slkali and ZSM-5 molecular sieve solid-liquid mass ratio are 1:3～1:50.
The aqueous slkali used can be following one or more:
Sodium hydroxide, sodium carbonate, ammonia, organic amino one or more, sodium hydroxide or ammonia are preferably used.
Metal promoter used in step 1 is preferably ammonium molybdate and iron content, the nitrate of zinc element, sulfate, carbon One or more in hydrochlorate and oxalates；Preferred metal promoter is ammonium molybdate, ferric nitrate and zinc nitrate.Wherein, metal The content of auxiliary agent, in terms of metal ingredient, the content of metal promoter accounts for the 0.5～5% (more preferably 2.3-of catalyst quality 2.5%).
Through inventor's experiment test, used using methanol high-knock rating gasoline blend component provided herein Catalyst before, preferably to catalyst use acid water thermal process process, the non-framework aluminum in Removal of catalyst duct, make Coming out in partially acidic center, so that aromatic hydrocarbons increases (but benzene content is little, less than 0.3%) in oil product product, alkene reduces, weight Constituent content reduces, and the stability of catalyst also obtains bigger improvement simultaneously.It is prepared as the catalyst of finished product, its activation condition For: use air and the coking carbon deposit of nitrogen mixed gas burn off catalyst surface of 500-800 DEG C of high temperature.
It is prepared as the modified zsm-5 zeolite (catalysis that i.e. methanol high-knock rating gasoline blend component is used of finished product Agent), a kind of metallic element is evenly distributed on the surface of ZSM-5 molecular sieve.
Concrete, modified zsm-5 zeolite, profile is that hollow pipe is cylindrical, internal diameter 1-2mm, external diameter 5-10mm, length 5- 10mm。
The binding agent used, except aluminium oxide, it is also possible to use hydrated alumina, Alumina gel, Ludox, sial to coagulate One or more in glue, silicon-aluminum sol and their precursor.
Research is thought, during methanol directly converts high-knock rating gasoline blend component (referring in particular to aromatic hydrocarbons) processed, long-pending Carbon first occurs at the outer surface acidity center of molecular sieve, and when carbon deposition quantity reaches to a certain degree, the metal center of outer surface Also carbon distribution inactivates simultaneously, and carbon distribution spreads toward the cross point of molecular sieve pore passage further subsequently, finally results in molecular sieve part duct Blocking so that catalyst loses activity further.Methanol provided by the present invention directly converts high-knock rating gasoline processed and adjusts With the catalyst of component, by molecular sieve is carried out alkali process, eliminate the partially acidic center of molecular sieve outer surface, it is suppressed that The speed of carbon distribution, is processed by alkali simultaneously and dredges molecular sieve pore passage, enhance the appearance carbon ability of molecular sieve, thus improve The stability of catalyst.
The above, the only detailed description of the invention of the present invention, but protection scope of the present invention is not limited thereto, and any Those familiar with the art, in the technical scope that the invention discloses, can readily occur in change or replace, should contain Cover within protection scope of the present invention.Therefore, protection scope of the present invention should described be as the criterion with scope of the claims.

Claims (10)

1. the catalyst of methanol high-knock rating gasoline blend component, it is characterised in that including:
A) 30～90 parts of modified zsm-5 zeolite carriers and be loaded in thereon；
B) 0.1～20 part of zinc element or its oxide；
C) 35～70 parts of binding agents；
Wherein, Si0 in ZSM-5 molecular sieve2With A1203Mass ratio be 70～100.
Catalyst the most according to claim 1, it is characterised in that
The oxide of zinc element is following one or more:
Zinc chloride, zinc nitrate, zinc sulfate or zinc acetate.
Catalyst the most according to claim 1, it is characterised in that
Zinc element or its oxide for 4-12 part.
Catalyst the most according to claim 1, it is characterised in that
Binding agent is 1.75～6:1 with the mass ratio of zinc element or its oxide.
Catalyst the most according to claim 1, it is characterised in that
In zinc element or its oxide, the ratio of zinc chloride, zinc nitrate and zinc sulfate is 4:6:2.
Catalyst the most according to claim 1, it is characterised in that
Si0 in ZSM-5 molecular sieve2With A1203Mass ratio be 75～81.
Catalyst the most according to claim 1, it is characterised in that binding agent is A1203。
Catalyst the most according to claim 5, it is characterised in that modified zsm-5 zeolite is 45 parts；Zinc element or its oxygen Compound is 11 parts；Binding agent is 62 parts；In ZSM-5 molecular sieve, the mass ratio of Si02 Yu A1203 is 81.
9. preparing the compounding method of the catalyst of methanol high-knock rating gasoline blend component as claimed in claim 1, it is special Levy and be, comprise the steps:
By fabricated in situ or infusion process, adding metal promoter in the ZSM-5 molecular sieve obtained, wherein, metal promoter includes The oxide of one or more of metallic element, Fe, K, Mg, Mn, Cr, W, Co, Ni, Zn, Cd, Ce, V, Zr, Mo element；
ZSM-5 molecular sieve is carried out alkali process, and by the ZSM-5 molecular sieve after the process of described alkali and binding agent molding, to make Catalyst carrier；
Zinc element or its oxide are added in catalyst carrier, and makes described methanol high-octane rating through being dried with roasting The catalyst that gasoline blend component is used.
Method the most according to claim 9, it is characterised in that described ZSM-5 molecular sieve is carried out alkali process include:
At 20～80 DEG C, with 0.1～5mol/L aqueous slkali, ZSM-5 molecular sieve is processed one or many, wherein, process every time 0.1～8 hour；
ZSM-5 molecular sieve is carried out filtration washing；
ZSM-5 molecular sieve is dried under conditions of 100～150 DEG C.
CN201610452966.8A 2016-06-21 2016-06-21 The catalyst of methanol high-knock rating gasoline blend component and compounding method thereof Pending CN106111180A (en)

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Citations (4)

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Application publication date: 20161116