CN105396615A - Catalyst for preparing low carbon olefins from methanol - Google Patents
Catalyst for preparing low carbon olefins from methanol Download PDFInfo
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- CN105396615A CN105396615A CN201510675516.0A CN201510675516A CN105396615A CN 105396615 A CN105396615 A CN 105396615A CN 201510675516 A CN201510675516 A CN 201510675516A CN 105396615 A CN105396615 A CN 105396615A
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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
- B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
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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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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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
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/82—Phosphates
- C07C2529/84—Aluminophosphates containing other elements, e.g. metals, boron
- C07C2529/85—Silicoaluminophosphates (SAPO compounds)
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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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Abstract
The invention discloses a catalyst for preparing low carbon olefins from methanol. The catalyst (by dry basis) contains 15-60wt% of a silicoaluminophosphate molecular sieve, 5-50wt% of high silica-alumina ratio modified clinoptilolite, 0-40wt% of clay, 5-40wt% of an inorganic oxide binder (by oxide), 0.5-10wt% of a Zn additive (by oxide)and 2-20wt% of a phosphorus additive (by oxide). The catalyst can efficiently convert methanol into low carbon olefins and especially greatly improves the isobutene selectivity when the catalyst is applied in methanol-to-low carbon olefins (C2= ~ C4=).
Description
Technical field
The invention relates to a kind of for the catalyst by preparing low carbon olefinic hydrocarbon with methanol, contain silicoaluminophosphamolecular molecular sieves (SAPO) and high silica alumina ratio modified clinoptilolite and Zn, P additive about one furtherly, can be low-carbon alkene by methanol conversion effectively, the catalyst of especially high selective isobutene.
Background technology
Low-carbon alkene (C
2-C
4) be important Organic Chemicals.The method of current preparing low-carbon olefins is a lot, such as, is that raw material is through steam cracking preparing low-carbon olefins with natural gas; Be that raw material is through catalytic dehydrogenation preparing low-carbon olefins and hydrogen with low-carbon alkanes; With the light petroleum hydrocarbon such as naphtha or diesel oil for raw material is through tubular type thermal cracking process to prepare lower olefine; By heavy petroleum hydrocarbon catalytic pyrolysis or catalytic cracking by-product low-carbon alkene; By low-carbon alcohols preparing low carbon alkene by catalytic conversion etc.Along with day by day rising violently of the day by day deficient of petroleum resources and price, with the coal of low price, natural gas resource for waste methyl alcohol, more more and more demonstrate advantage economically and attraction by the technology path of methanol oxidation preparing low-carbon olefin by conversion.
Propose from Mobil company in 1984, preparing gasoline by methanol technique is improved, for preparing low carbon olefinic hydrocarbon with methanol (MTO) (Chang, C.D etc., J.Catal., SB, 289 (1984)) after, many alumino-silicates or zeolitic material are used as the active component of MTO catalyst.The large pore zeolites such as such as Y zeolite, modenite can be converted into hydrocarbon by catalysis methanol, but
hydrocarbon selective is high, and selectivity of light olefin is low; The pore zeolites such as erionite, T zeolite, chabasie, although can improve olefine selective, because silica alumina ratio is high, coking and deactivation is very fast.Thus more sight concentrates on the mesopore zeolites such as ZSM-5.Such as USP4238631B1, USP4238384B1 and USP4423274B1 etc.The method that it is alkene by methyl alcohol or dimethyl ether conversion that CN1352627A discloses with the P modified ZSM-5 zeolite catalyst that is active component.
In prior art, the another kind of important catalyst being alkene for methanol conversion is for active component with silicoaluminophosphamolecular molecular sieves (SAPO).Silicon is introduced in aluminium phosphate molecular sieve skeleton the early 1980s by UCC company of the U.S., synthesizes silicoaluminophosphamolecular molecular sieves (SAPO) (USP4440871).Silicoaluminophosphamolecular molecular sieves (SAPO) skeleton is made up of phosphorus oxygen tetrahedron, aluminum-oxygen tetrahedron and silicon-oxy tetrahedron, and skeleton is electronegative.Therefore the outer balance cation of skeleton is H
+time, molecular sieve has acidity, can be used in the catalytic reaction of the carbonium ion mechanism such as cracking hydrocarbon, isomerization, alkylation and dehydration of alcohols as solid acid.Disclose many kinds in USP4499327B1 and can be converted into the SAPO molecular sieve of alkene by catalysis methanol, wherein the aperture of preferred molecular sieve is between adsorbs xenon (kinetic diameters 4.0 dust) and repulsion iso-butane (kinetic diameters 5.0 dust), is particularly preferably SAPO-34 molecular sieve.
CN1341584A discloses a kind of wear-resistant catalyst for preparing low carbon olefinic hydrocarbon with methanol, this catalyst comprises the host material of crystal metal SAPO molecules of salt sieve (as SAPO-34), inorganic oxide adhesive and filler, and wherein filler is preferably clay (as kaolin).When molecular sieve content is lower than the anti-wear performance that can significantly improve catalyst during 40 heavy %.
Also other metallic element can be introduced in SAPO framework of molecular sieve.USP4752651B1 discloses and uses the technology that ELAPO and MeAPO molecular sieve catalytic converting methanol is alkene.CN1128676C disclose there is flat crystal structure, empirical formula is (EL
xal
yp
z) O
2metal aluminophosphate molecular sieve.Wherein EL is metallic silicon or magnesium, and x, y and z are the molar fraction of EL, Al and P respectively.As being the catalyst of low-carbon alkene by methanol conversion, product ethylene selectivity is high.
The catalyst that to disclose with Zn-SAPO-34 molecular sieve in CN1704390A be active component, reaction temperature 300 ~ 500 DEG C, normal pressure, the quick 1.0 ~ 10h of methanol weight
-1, water/methanol weight is than under the reaction condition of 0 ~ 5, and propylene, ethylene selectivity are high.
The silicoaluminophosphamolecular molecular sieves of the intergrowth phase comprising at least one AEI and CHA framework structure type molecular sieve is disclosed in CN1525940A.This molecular sieve can be used for the catalyzed conversion of Methanol for alkene.
Disclose in CN101676028A with a kind of silicoaluminophosphamolecular molecular sieves (SRM-4) of diethylamine and the synthesis of di-n-propylamine double template and the catalyst that is active component with SRM-4 molecular sieve.This catalyst catalysis methanol conversion can prepare low-carbon alkene (C effectively
2 =~ C
4 =), and the ratio of ethene and propylene can be regulated neatly.
Methyl tertiary butyl ether (MTBE) octane number is high, and steam forces down, and toxicity is little, is octane number additive effective, clean in commercial gasoline.Isobutene is the basic material preparing methyl tertiary butyl ether (MTBE).But although methanol conversion can be effectively low-carbon alkene by preparing low carbon olefinic hydrocarbon with methanol catalyst of the prior art, it lays particular emphasis on high ethene, Propylene Selectivity, and selective isobutene is very low, generally lower than 10 weight portion %.
Summary of the invention
The object of the invention is to provide on the basis of existing technology a kind of for by preparing low carbon olefinic hydrocarbon with methanol (C
2 =~ C
4 =) catalyst, methanol conversion can not only be low-carbon alkene by this catalyst effectively, can increase substantially the selective of isobutene simultaneously.
In the present invention, with silicoaluminophosphamolecular molecular sieves (SAPO) and high silica alumina ratio modified clinoptilolite for active component, and introduce appropriate Zn additive and P additive further, prepared catalyst application is in low carbon olefin hydrocarbon in methanol conversion, can reach object of the present invention.
Catalyst provided by the present invention is by butt, the phosphorus additive of the clay of the silicoaluminophosphamolecular molecular sieves (SAPO) containing 15 ~ 60 weight portion %, the high silica alumina ratio modified clinoptilolite of 5 ~ 50 weight portion %, 0 ~ 40 weight portion %, the inorganic oxide binder of 5 ~ 40 weight portion %, the Zn additive of 0.5 ~ 10 weight portion % and 2 ~ 20 weight portion %, wherein said inorganic oxide binder, Zn additive and phosphorus additive are all with oxide basis.The skeleton SiO of said high silica alumina ratio modified clinoptilolite
2: Al
2o
3mol ratio is 15 ~ 100.
Catalyst provided by the invention is by butt, and preferably consisting of is the phosphorus additive of the silicoaluminophosphamolecular molecular sieves (SAPO) of 20 ~ 45 weight portion %, the high silica alumina ratio modified clinoptilolite of 10 ~ 30 weight portion %, the clay of 10 ~ 25 weight portion %, the inorganic oxide binder of 10 ~ 20 weight portion %, the Zn additive of 2 ~ 5 weight portion % and 5 ~ 15 weight portion %.In catalyst provided by the invention, said phosphorus additive and content thereof do not comprise the phosphorus in silicoaluminophosphamolecular molecular sieves (SAPO).
Catalyst provided by the invention, the skeleton SiO of wherein said high silica alumina ratio modified clinoptilolite
2: Al
2o
3mol ratio is preferably 25 ~ 75.
Catalyst provided by the invention, wherein said high silica alumina ratio modified clinoptilolite is carried out modification in accordance with the following methods by using natural clinoptilolite mineral and is prepared:
Step (A), using natural clinoptilolite mineral are pulverized, sieved, gets the following fine powder of 200 order, be dispersed into the slurries of solid content 10 ~ 45 weight portion % with deionized water making beating, pump in ball mill and grind, until the particle diameter of solid matter of more than 90% is less than 7 microns in slurries;
Step (B), step (A) gained slurries are warming up to 60 ~ 95 DEG C in enamel reaction still, then add hydrochloric acid, oxalic acid successively, remove the dirts such as Ca, Mg, Al, Fe of institute's association, use H simultaneously
+alkali metal is become H type clinoptilolite with the clinoptilolite ion-exchange of alkaline earth type.Slurries are filtered, washes, obtain H type clinoptilolite solid filter cake;
Step (C), H type clinoptilolite solid filter cake is dispersed in enamel reaction still the slurries of solid content 10 ~ 45 weight portion % with deionized water making beating, be warming up to 40 ~ 70 DEG C, then the mixed acid adding hydrochloric acid and fluosilicic acid carries out aluminium-eliminating and silicon-replenishing, and the modification of H type clinoptilolite is become high silica alumina ratio H type clinoptilolite.Slurries are filtered, washes, obtain high silica alumina ratio H type clinoptilolite solid filter cake.
Catalyst provided by the invention, in wherein said using natural clinoptilolite mineral, the content of clinoptilolite is not less than 50 heavy %, is preferably not less than 65 heavy %.
Catalyst provided by the invention, the clinoptilolite in wherein said using natural clinoptilolite mineral is K type, Na type, Ca type, Mg type or its mixed type clinoptilolite, is preferably K type, Na type or its mixed type clinoptilolite.
Catalyst provided by the invention, solid (butt) described in wherein said step (B) is 1:0.01:0.01 ~ 1:0.20:0.20 with the weight ratio of hydrochloric acid (technical hydrochloric acids of 31 weight portion %), oxalic acid, is preferably 1:0.05:0.05 ~ 1:0.15:0.15.
Catalyst provided by the invention, solid (butt) described in wherein said step (C) is 1:0.01:0.05 ~ 1:0.15:0.25 with the weight ratio of hydrochloric acid (technical hydrochloric acids of 31 weight portion %), fluosilicic acid (the industrial fluosilicic acid of 35 weight portion %), is preferably 1:0.05:0.10 ~ 1:0.10:0.15.
Catalyst provided by the invention, wherein said silicoaluminophosphamolecular molecular sieves is the mixture of one or more in the modified product of SAPO-34, SAPO-11, SAPO-22 or its Zn, Fe, Co, Ni, Mn, Cr, is preferably the mixture of one or more in the modified product of SAPO-34 or its Zn, Fe, Co, Ni, Mn, Cr.
Catalyst provided by the invention, wherein said inorganic oxide binder is selected from as one or more in the inorganic oxide of catalyst substrates and binder component, comprise the mixture of one or more in aluminium oxide, silica, amorphous aluminum silicide, zirconia and titanium oxide, be preferably aluminium oxide or silica.
Catalyst provided by the invention, wherein said clay is known to the skilled person, the present invention has no particular limits it, the mixture of one or more in the clay material comprising kaolin, metakaolin, sepiolite, attapulgite, montmorillonite, tired de-stone, diatomite, galapectite, saponite, boron-moisten soil, hydrotalcite can be selected from, or the modified product of above-mentioned clay after peracid treatment.Wherein be preferably the mixture of one or more in kaolin, metakaolin, diatomite, sepiolite, attapulgite, montmorillonite and tired de-stone.
Catalyst provided by the invention can by silicoaluminophosphamolecular molecular sieves (SAPO), high silica alumina ratio modified clinoptilolite, clay and inorganic oxide binder, and Zn compound and phosphorus compound adopt any method comprised in the existing technology of preparing of spray drying forming to prepare, the present invention has no particular limits it.
In catalyst provided by the present invention, described Zn additive exists with the form of their oxide, phosphate, phosphite, subphosphate, acid phosphate.
Catalyst provided by the invention, the Zn compound in its preparation process is selected from one or more in their inorganic compound and organic compound, and can be soluble in water, also can be insoluble in water or water-fast compound.The example of Zn compound comprises the organic compound etc. of the oxide of Zn, hydroxide, chloride, nitrate, sulfate, phosphate, transition metal.Preferred Zn compound is selected from one or more in their chloride, nitrate, sulfate and phosphate.
In slurries, add Zn compound in any step of Zn additive preferably before the spray drying forming of catalyst preparation process and introduce; Can certainly be introduced by roasting after dipping or chemisorbed Zn compound after catalyst spray drying and moulding, comprise and catalyst is carried out flooding or chemisorbed process with containing Zn compound water solution, then Separation of Solid and Liquid (if necessary), dry and roasting is carried out, wherein dry temperature is room temperature to 400 DEG C, preferably 100 ~ 300 DEG C, the temperature of roasting is 400 ~ 700 DEG C, be preferably 450 ~ 650 DEG C, roasting time is 0.5 ~ 100 hour, is preferably 0.5 ~ 10 hour.
Therefore, described Zn additive may reside in any position that may exist of catalyst, duct as may reside in zeolite is inner, the surface of zeolite, may reside in host material, can also be present in the inside, duct of zeolite, the surface of zeolite and described host material simultaneously, preferably be present in host material.
Catalyst provided by the invention, exists with the form of phosphorus compound (oxide, phosphate, phosphite, subphosphate, acid phosphate as phosphorus) phosphorus additive.
Catalyst provided by the invention, can adopt the combination of one of following method or several method to phosphorus additive, but is not limited in these methods introducing catalyst:
1, introduce in by phosphorus compound process high silica alumina ratio modified clinoptilolite, such as adopt phosphoric acid and/or phosphorous acid as sour reagent, or adopt diammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), ammonium phosphate, ammonium phosphite, dihydrogen phosphite ammonium etc. as inorganic ammonium salt process high silica alumina ratio clinoptilolite;
2, phosphorus compound is added going in slurries of catalyst spray drying and moulding;
3, introduce in catalyst by inorganic oxide binder, time in such as inorganic oxide binder containing phosphorus Alumina gel, both brought phosphorus in calcined catalyst, phosphorus Alumina gel serves again the effect of host material and binding agent;
4, after catalyst spray drying and moulding through dipping or chemisorbed phosphorus compound, introduce through Separation of Solid and Liquid, drying and roasting process, the temperature of said drying is room temperature to 400 DEG C, preferably 100 ~ 300 DEG C, the temperature of roasting is 400 ~ 700 DEG C, be preferably 450 ~ 650 DEG C, roasting time is 0.5 ~ 100 hour, is preferably 0.5 ~ 10 hour.
Therefore, phosphorus additive may reside in any position that may exist of catalyst, duct as may reside in molecular sieve is inner, the surface of molecular sieve, may reside in described host material, can also be present in the inside, duct of molecular sieve, the surface of molecular sieve and described host material simultaneously.
Catalyst provided by the invention, in its preparation method, phosphorus compound is selected from one or more in the various inorganic compound of phosphorus and organic compound.Phosphorus compound can be soluble in water, also can be to be insoluble in water or water-fast phosphorus compound.The embodiment of phosphorus compound comprises oxide, phosphoric acid, phosphate, phosphite, hypophosphites, the phosphorous organic compound etc. of phosphorus.Preferred phosphorus compound is selected from one or more in phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate (ADP), diammonium hydrogen phosphate, aluminum phosphate and phosphorus Alumina gel.
Owing to introducing high silica alumina ratio modified clinoptilolite in catalyst provided by the present invention, and introduce appropriate Zn additive and phosphorus additive further, can not only be low-carbon alkene by methanol conversion effectively, the selective of isobutene can be increased substantially simultaneously.
Accompanying drawing explanation
Fig. 1 is natural zeolite raw material XRD thing phasor.
Fig. 2 is XF01 high silica alumina ratio modified clinoptilolite XRD thing phasor.
Fig. 3 is XF02 high silica alumina ratio modified clinoptilolite XRD thing phasor.
Detailed description of the invention
Below in conjunction with drawings and Examples, the present invention is described in further detail.In the present invention, in embodiment and comparative example, element composition is by x-ray fluorescence spectrometry, and molecular sieve crystallinity is measured by XRD diffraction approach.
Using natural clinoptilolite raw mineral materials from Henan five river process Materials Co., Ltd, its chemical composition, zeolite content, skeleton SiO
2/ Al
2o
3mol ratio is in table 1.
Table 1 using natural clinoptilolite mineral chemical composition
SAPO-34 molecular sieve is the industrial products that Catalyst Factory, Nankai Univ is produced, its relative crystallinity 95 heavy %, Al
2o
3content 40.93 heavy %, SiO
2content 10.32% weight portion %, P
2o
5the heavy % of content 48.08.
High silica alumina ratio ZSM-5 zeolite is the industrial products that Catalyst Factory, Nankai Univ is produced, specific surface 360m
2/ g, relative crystallinity 90 weight portion %, SiO
2/ Al
2o
3mol ratio 800.
Alumina gel is PetroChina Company Limited.'s Lanzhou catalyst plant industrial products, Al
2o
3content is 21.5 weight portion %.
Technical hydrochloric acid, concentration 31 weight portion %, Hunan chemical reagent work of coal science research institute produces.Oxalic acid, analyzes pure, China Drug Co.'s Beijing Company.
Industry fluosilicic acid, the heavy % of concentration 35, Tianjin Jin Wei Chemical Co., Ltd. produces.
Kaolin is the special kaolin of Cracking catalyst that Kaolin of Suzhou company produces, solid content 78 weight portion %.
Boehmite raw material is Shandong Aluminum Plant's manufacture product, solid content 62 weight portion %.
Acidic silicasol is the industrial products that Xinhua's chemical reagent factory is produced, SiO
2content is 30.5 weight portion %.
Zn (NO
3)
26H
2o, chemical pure, Beijing Xinhua chemical reagent factory is produced.SPA, chemical pure, the heavy % of concentration 98.5, Hunan chemical reagent work of coal science research institute produces.
Embodiment 1 ~ 2 illustrates the preparation of high silica alumina ratio modified clinoptilolite.
embodiment 1
Using natural clinoptilolite mineral are pulverized, sieved, get the slurries that the making beating of the following fine powder of 200 order 200 kilograms deionized water is dispersed into solid content 25 weight portion %, pump in ball mill and grind, until the particle diameter of solid matter of more than 90% is less than 5.5 microns in slurries, for subsequent use.Fig. 1 is shown in by the XRD thing phase collection of illustrative plates of the using natural clinoptilolite slurries after grinding.
The using natural clinoptilolite slurries after 5.0 kilograms of decationizing water and 20 kilograms of grindings are dropped in enamel stirred tank, 65 DEG C are warming up under stirring, add hydrochloric acid (concentration is the technical hydrochloric acid of 31 weight portion %) 250 grams, stir 60 minutes, add oxalic acid 250 grams again, continue stirring 60 minutes, vacuum filtration also uses decationizing flush cake, obtain the clinoptilolite removing metal impurities, be designated as XF-A.
15.0 kilograms of decationizing water and XF-A is dropped in enamel stirred tank, 50 DEG C are warming up under stirring, add hydrochloric acid (concentration is the technical hydrochloric acid of 31 weight portion %) 200 grams and fluosilicic acid 400 grams, continue stirring 60 minutes, vacuum filtration also uses decationizing flush cake, obtain high silica alumina ratio modified clinoptilolite, be designated as XF01.Its chemical composition, zeolite content, skeleton SiO
2/ Al
2o
3mol ratio is in table 1.Fig. 2 is shown in by the XRD thing phase collection of illustrative plates of XF01 high silica alumina ratio modified clinoptilolite.
embodiment 2
The using natural clinoptilolite slurries after 5.0 kilograms of decationizing water and 20 kilograms of grindings are dropped in enamel stirred tank, 65 DEG C are warming up under stirring, add hydrochloric acid (concentration is the technical hydrochloric acid of 31 weight portion %) 400 grams, stir 60 minutes, add oxalic acid 400 grams again, continue stirring 60 minutes, vacuum filtration also uses decationizing flush cake, obtain the clinoptilolite removing metal impurities, be designated as XF-B.
15.0 kilograms of decationizing water and XF-B is dropped in enamel stirred tank, 50 DEG C are warming up under stirring, add hydrochloric acid (concentration is the technical hydrochloric acid of 31 weight portion %) 400 grams and fluosilicic acid 600 grams, continue stirring 60 minutes, vacuum filtration also uses decationizing flush cake, obtain high silica alumina ratio modified clinoptilolite, be designated as XF02.Its chemical composition, zeolite content, skeleton SiO
2/ Al
2o
3mol ratio is in table 1.Fig. 3 is shown in by the XRD thing phase collection of illustrative plates of XF02 high silica alumina ratio modified clinoptilolite.
Embodiment 3 ~ 9 illustrates the preparation of preparing low-carbon olefin by using methanol catalyst provided by the invention.
embodiment 3
18 kilograms of decationized Y sieve water, 1.64 kilograms of acidic silicasols, 4 kilograms of (butt) SAPO-34 molecular sieves, 1 kilogram of (butt) XF01,2.5 kilograms of (butt) kaolin, 0.2 kilogram of (butt) Zn (NO are dropped into successively in stirred tank
3)
26H
2o and 1 kilogram of (butt) boehmite, after making beating dispersion 120 points of kinds, then adds 1.3 kilograms of SPAs, continues making beating 60 minutes; Then by the slurries that obtain inlet temperature 500 DEG C, carry out spraying dry under the condition that exhaust temperature is 180 DEG C, obtained containing 40 weight portion %SAPO-34,10 weight portion %XF01,25 weight portion % kaolin, 10 weight portion %Al
2o
3, 5 weight portion %SiO
2, 2 weight portion %Zn additives (in ZnO) and 8 weight portion % phosphorus additives are (with P
2o
5meter) catalyst, i.e. C
1.
Acidic silicasol selects Xinhua's chemical reagent factory to produce, SiO
2content is 30.5 weight portion %.
SAPO-34 molecular screening Catalyst Factory, Nankai Univ is produced, relative crystallinity 95 weight portion %, Al
2o
3content 40.93 weight portion %, SiO
2content 10.32% weight portion %, P
2o
5content 48.08 weight portion %.
The special kaolin of Cracking catalyst that kaolin selects Kaolin of Suzhou company to produce, solid content 78 weight portion %.
Zn (NO
3)
26H
2o is chemical pure, selects Beijing Xinhua chemical reagent factory to produce.
Boehmite is technical grade, selects Shandong Aluminum Plant to produce, solid content 62 weight portion %.
SPA is chemical pure, concentration 98.5 weight portion %, and Hunan chemical reagent work of coal science research institute produces.
embodiment 4
18 kilograms of decationized Y sieve water, 1.64 kilograms of acidic silicasols, 4 kilograms of (butt) SAPO-34 molecular sieves, 0.8 kilogram of (butt) XF02,2.4 kilograms of (butt) kaolin, 0.8 kilogram of (butt) Zn (NO are dropped into successively in stirred tank
3)
26H
2o and 1 kilogram of (butt) boehmite, after making beating dispersion 120 points of kinds, then adds 0.81 kilogram of SPA, continues making beating 60 minutes; Then by the slurries that obtain inlet temperature 500 DEG C, carry out spraying dry under the condition that exhaust temperature is 180 DEG C, obtained containing 40 weight portion %SAPO-34,8 weight portion %XF02,24 weight portion % kaolin, 10 weight portion %Al
2o
3, 5 weight portion %SiO
2, 8 weight portion %Zn additives (in ZnO) and 5 weight portion % phosphorus additives are (with P
2o
5meter) catalyst, i.e. C
2.
embodiment 5
18 kilograms of decationized Y sieve water, 1.64 kilograms of acidic silicasols, 3 kilograms of (butt) SAPO-34 molecular sieves, 1.5 kilograms of (butt) XF01,2.5 kilograms of (butt) kaolin, 0.5 kilogram of (butt) Zn (NO are dropped into successively in stirred tank
3)
26H
2o and 1 kilogram of (butt) boehmite, after making beating dispersion 120 points of kinds, then adds 1.62 kilograms of SPAs, continues making beating 60 minutes; Then by the slurries that obtain inlet temperature 500 DEG C, carry out spraying dry under the condition that exhaust temperature is 180 DEG C, obtained containing 30 weight portion %SAPO-34,15 weight portion %XF01,25 weight portion % kaolin, 10 weight portion %Al
2o
3, 5 weight portion %SiO
2, 5 weight portion %Zn additives (in ZnO) and 10 weight portion % phosphorus additives are (with P
2o
5meter) catalyst, i.e. C
3.
embodiment 6
18 kilograms of decationized Y sieve water, 1.64 kilograms of acidic silicasols, 2 kilograms of (butt) SAPO-34 molecular sieves, 3.5 kilograms of (butt) XF02,1.6 kilograms of (butt) kaolin, 0.4 kilogram of (butt) Zn (NO are dropped into successively in stirred tank
3)
26H
2o and 1 kilogram of (butt) boehmite, after making beating dispersion 120 points of kinds, then adds 1.62 kilograms of SPAs, continues making beating 60 minutes; Then by the slurries that obtain inlet temperature 500 DEG C, carry out spraying dry under the condition that exhaust temperature is 180 DEG C, obtained containing 20 weight portion %SAPO-34,35 weight portion %XF01,16 weight portion % kaolin, 10 weight portion %Al
2o
3, 5 weight portion %SiO
2, 4 weight portion %Zn additives (in ZnO) and 10 weight portion % phosphorus additives are (with P
2o
5meter) catalyst, i.e. C
4.
embodiment 7
18 kilograms of decationized Y sieve water, 1.64 kilograms of acidic silicasols, 1.5 kilograms of (butt) SAPO-34 molecular sieves, 4 kilograms of (butt) XF01,1.7 kilograms of (butt) kaolin, 0.5 kilogram of (butt) Zn (NO are dropped into successively in stirred tank
3)
26H
2o and 1 kilogram of (butt) boehmite, after making beating dispersion 120 points of kinds, then adds 1.3 kilograms of SPAs, continues making beating 60 minutes; Then by the slurries that obtain inlet temperature 500 DEG C, carry out spraying dry under the condition that exhaust temperature is 180 DEG C, obtained containing 15 weight portion %SAPO-34,40 weight portion %XF01,17 weight portion % kaolin, 10 weight portion %Al
2o
3, 5 weight portion %SiO
2, 5 weight portion %Zn additives (in ZnO) and 8 weight portion % phosphorus additives are (with P
2o
5meter) catalyst, i.e. C
5.
embodiment 8
18 kilograms of decationized Y sieve water, 1.64 kilograms of acidic silicasols, 4.5 kilograms of (butt) SAPO-34 molecular sieves, 1.0 kilograms of (butt) XF02,1.6 kilograms of (butt) kaolin, 0.4 kilogram of (butt) Zn (NO are dropped into successively in stirred tank
3)
26H
2o and 1 kilogram of (butt) boehmite, after making beating dispersion 120 points of kinds, then adds 1.62 kilograms of SPAs, continues making beating 60 minutes; Then by the slurries that obtain inlet temperature 500 DEG C, carry out spraying dry under the condition that exhaust temperature is 180 DEG C, obtained containing 45 weight portion %SAPO-34,10 weight portion %XF02,16 weight portion % kaolin, 10 weight portion %Al
2o
3, 5 weight portion %SiO
2, 4 weight portion %Zn additives (in ZnO) and 10 weight portion % phosphorus additives are (with P
2o
5meter) catalyst, i.e. C
6.
embodiment 9
18 kilograms of decationized Y sieve water, 1.64 kilograms of acidic silicasols, 5.0 kilograms of (butt) SAPO-34 molecular sieves, 0.5 kilogram of (butt) XF02,1.7 kilograms of (butt) kaolin, 0.5 kilogram of (butt) Zn (NO are dropped into successively in stirred tank
3)
26H
2o and 1 kilogram of (butt) boehmite, after making beating dispersion 120 points of kinds, then adds 1.3 kilograms of SPAs, continues making beating 60 minutes; Then by the slurries that obtain inlet temperature 500 DEG C, carry out spraying dry under the condition that exhaust temperature is 180 DEG C, obtained containing 45 weight portion %SAPO-34,10 weight portion %XF01,16 weight portion % kaolin, 10 weight portion %Al
2o
3, 5 weight portion %SiO
2, 5 weight portion %Zn additives (in ZnO) and 8 weight portion % phosphorus additives are (with P
2o
5meter) catalyst, i.e. C
7.
embodiment 10
18 kilograms of decationized Y sieve water, 1.64 kilograms of acidic silicasols, 4.0 kilograms of (butt) SAPO-34 molecular sieves, 2.0 kilograms of (butt) XF02,1.6 kilograms of (butt) kaolin, 0.4 kilogram of (butt) Zn (NO are dropped into successively in stirred tank
3)
26H
2o and 1 kilogram of (butt) boehmite, after making beating dispersion 120 points of kinds, then adds 0.81 kilogram of SPA, continues making beating 60 minutes; Then by the slurries that obtain inlet temperature 500 DEG C, carry out spraying dry under the condition that exhaust temperature is 180 DEG C, obtained containing 40 weight portion %SAPO-34,20 weight portion %XF02,16 weight portion % kaolin, 10 weight portion %Al
2o
3, 5 weight portion %SiO
2, 4 weight portion %Zn additives (in ZnO) and 5 weight portion % phosphorus additives are (with P
2o
5meter) catalyst, i.e. C
8.
embodiment 11
18 kilograms of decationized Y sieve water, 1.64 kilograms of acidic silicasols, 4 kilograms of (butt) SAPO-34 molecular sieves, 1.0 kilograms of (butt) XF02,1.9 kilograms of (butt) kaolin, 0.4 kilogram of (butt) Zn (NO are dropped into successively in stirred tank
3)
26H
2o and 1 kilogram of (butt) boehmite, after making beating dispersion 120 points of kinds, then adds 1.95 kilograms of SPAs, continues making beating 60 minutes; Then by the slurries that obtain inlet temperature 500 DEG C, carry out spraying dry under the condition that exhaust temperature is 180 DEG C, obtained containing 40 weight portion %SAPO-34,10 weight portion %XF02,19 weight portion % kaolin, 10 weight portion %Al
2o
3, 5 weight portion %SiO
2, 4 weight portion %Zn additives (in ZnO) and 12 weight portion % phosphorus additives are (with P
2o
5meter) catalyst, i.e. C
9.
embodiment 12
18 kilograms of decationized Y sieve water, 1.64 kilograms of acidic silicasols, 4 kilograms of (butt) SAPO-34 molecular sieves, 1.0 kilograms of (butt) XF01,1.6 kilograms of (butt) kaolin, 0.4 kilogram of (butt) Zn (NO are dropped into successively in stirred tank
3)
26H
2o and 1 kilogram of (butt) boehmite, after making beating dispersion 120 points of kinds, then adds 2.44 kilograms of SPAs, continues making beating 60 minutes; Then by the slurries that obtain inlet temperature 500 DEG C, carry out spraying dry under the condition that exhaust temperature is 180 DEG C, obtained containing 40 weight portion %SAPO-34,10 weight portion %XF01,16 weight portion % kaolin, 10 weight portion %Al
2o
3, 5 weight portion %SiO
2, 4 weight portion %Zn additives (in ZnO) and 15 weight portion % phosphorus additives are (with P
2o
5meter) catalyst, i.e. C
10.
comparative example 1
Comparative example 1 illustrates that conveniently technology prepares reference preparing low-carbon olefin by using methanol catalyst.
18 kilograms of decationized Y sieve water, 1.64 kilograms of acidic silicasols, 4 kilograms of (butt) SAPO-34 molecular sieves, 4.0 kilograms of (butt) kaolin and 1 kilogram of (butt) boehmite are dropped into successively in stirred tank, after making beating dispersion 90 points of kinds, add 182ml hydrochloric acid, continue making beating 45 points of kinds; Then add 2.33 kilograms of Alumina gel to pull an oar 60 minutes; Then by the slurries that obtain inlet temperature 500 DEG C, carry out spraying dry under the condition that exhaust temperature is 180 DEG C, obtained containing 40 weight portion %SAPO-34,40 weight portion % kaolin, 15 weight portion %Al
2o
3, and 5 weight portion %SiO
2, (with P
2o
5meter) catalyst, i.e. CB
1.
Hydrochloric acid is technical-grade hydrochloric acid, concentration 31 weight portion %, and Hunan chemical reagent work of coal science research institute produces.
Alumina gel selects Lanzhou catalyst plant to produce, solid content 21.5 weight portion %.
comparative example 2
Comparative example 2 illustrates containing Zn additive and phosphorus additive, but not containing the preparation of the reference preparing low-carbon olefin by using methanol catalyst of high silica alumina ratio modified clinoptilolite.
18 kilograms of decationized Y sieve water, 1.64 kilograms of acidic silicasols, 4 kilograms of (butt) SAPO-34 molecular sieves, 2.7 kilograms of (butt) kaolin, 0.8 kilogram of (butt) Zn (NO are dropped into successively in stirred tank
3)
26H
2o and 1 kilogram of (butt) boehmite, after making beating dispersion 120 points of kinds, then adds 1.62 kilograms of SPAs, continues making beating 60 minutes; Then by the slurries that obtain inlet temperature 500 DEG C, carry out spraying dry under the condition that exhaust temperature is 180 DEG C, obtained containing 40 weight portion %SAPO-34,27 weight portion % kaolin, 10 weight portion %Al
2o
3, 5 weight portion %SiO
2, 8 weight portion %Zn additives (in ZnO) and 10 weight portion % phosphorus additives are (with P
2o
5meter) catalyst, i.e. CB
2.
comparative example 3
Comparative example 3 illustrates containing conventional clinoptilolite, does not contain the preparation of Zn additive and phosphorus additive reference preparing low-carbon olefin by using methanol catalyst.
18 kilograms of decationized Y sieve water, 1.64 kilograms of acidic silicasols, 4 kilograms of (butt) SAPO-34 molecular sieves, 1.5 kilograms of (butt) XF-A, 2.5 kilograms of (butt) kaolin and 1 kilogram of (butt) boehmite are dropped into successively in stirred tank, after making beating dispersion 90 points of kinds, add 182ml hydrochloric acid, continue making beating 45 points of kinds; Then add 2.33 kilograms of Alumina gel to pull an oar 60 minutes; Then by the slurries that obtain inlet temperature 500 DEG C, carry out spraying dry under the condition that exhaust temperature is 180 DEG C, obtained containing 40 weight portion %SAPO-34,15 weight portion %XF-A, 25 weight portion % kaolin, 15 weight portion %Al
2o
3, and 5 weight portion %SiO
2, (with P
2o
5meter) catalyst, i.e. CB
3.
comparative example 4
Comparative example 4 illustrates containing Zn additive and phosphorus additive, containing the preparation of the reference preparing low-carbon olefin by using methanol catalyst of conventional clinoptilolite.
18 kilograms of decationized Y sieve water, 1.64 kilograms of acidic silicasols, 4 kilograms of (butt) SAPO-34 molecular sieves, 1.5 kilograms of (butt) XF-A, 1.8 kilograms of (butt) kaolin, 0.4 kilogram of (butt) Zn (NO are dropped into successively in stirred tank
3)
26H
2o and 1.0 kilogram of (butt) boehmite, after making beating dispersion 120 points of kinds, then adds 1.3 kilograms of SPAs, continues making beating 60 minutes; Then by the slurries that obtain inlet temperature 500 DEG C, carry out spraying dry under the condition that exhaust temperature is 180 DEG C, obtained containing 40 weight portion %SAPO-34,15 weight portion %XF-A, 18 weight portion % kaolin, 10 weight portion %Al
2o
3, 4 weight portion %SiO
2, 8 weight portion %Zn additives (in ZnO) and 10 weight portion % phosphorus additives are (with P
2o
5meter) catalyst, i.e. CB
4.
embodiment 13 ~ 22
Embodiment 13 ~ 22, for fixed fluidized-bed reactor, illustrates the effect that catalyst provided by the invention reacts for MTO.
Respectively by the C of 50 grams
1~ C
10(embodiment 3 to embodiment 12 obtained product) 600 DEG C, carry out the burin-in process of 2 hours under 100% steam atmosphere condition; At every turn by 20 grams of C after burin-in process
1~ C
10catalyst loads in the reactor of fixed fluidized bed reaction unit, at normal pressure, and reaction temperature 450 DEG C, regeneration temperature 620 DEG C, with 100% methanol steam for raw material, charging methyl alcohol weight (hourly) space velocity (WHSV) (WHSV) 2.5h
-1reaction condition carry out MTO reaction.With gas chromatograph on-line analysis methyl alcohol and non-water product assay.Catalyst carbon deposit is by O
2regeneration burn rear infrared determine charcoal instrument mensuration CO
xnong Du And calculates green coke amount.Product light olefin selective presentation is the mass percent that detailed hydrocarbon accounts in total hydrocarbon products.Evaluation result is shown in Table 2.
comparative example 5 ~ 8
Comparative example 5 ~ 8, for fixed fluidized-bed reactor, illustrates that reference catalyst is used for the effect of MTO reaction.
By the method in embodiment 13 ~ 22, MTO reaction is carried out to same feedstock oil, be respectively CB unlike used catalyst
1~ CB
4.Evaluation result is shown in Table 2.
As can be seen from Table 2, compared with reference catalyst, methanol conversion can not only be low-carbon alkene by catalyst provided by the invention effectively, can increase substantially the productive rate of isobutene and selective simultaneously.
The results of property of table 2 different catalysts
Claims (10)
1. the catalyst for preparing low-carbon olefin by using methanol, it is characterized in that: this catalyst is by butt, the phosphorus additive of the high silica alumina ratio modified clinoptilolite of the silicoaluminophosphamolecular molecular sieves containing 15 ~ 60 heavy %, 5 ~ 50 heavy %, the clay of 0 ~ 40 heavy %, the inorganic oxide binder of 5 ~ 40 heavy %, the Zn additive of 0.5 ~ 10 heavy % and 2 ~ 20 heavy %, wherein said inorganic oxide binder, Zn additive and phosphorus additive are all with oxide basis; The skeleton SiO of said high silica alumina ratio modified clinoptilolite
2: Al
2o
3mol ratio is 15 ~ 100;
Described silicoaluminophosphamolecular molecular sieves is the mixture of one or more in the modified product of SAPO-34, SAPO-11, SAPO-22 or its Zn, Fe, Co, Ni, Mn, Cr, is preferably the mixture of one or more in the modified product of SAPO-34 or its Zn, Fe, Co, Ni, Mn, Cr.
2. according to the catalyst for preparing low-carbon olefin by using methanol described in claim 1, it is characterized in that: this catalyst is by butt, and the high silica alumina ratio modified clinoptilolite of the silicoaluminophosphamolecular molecular sieves containing 20 ~ 45 heavy %, 10 ~ 30 heavy %, the clay of 10 ~ 25 heavy %, the inorganic oxide binder of 10 ~ 20 heavy %, the Zn additive of 2 ~ 5 heavy % and 5 ~ 15 weigh the phosphorus additive of %.
3. according to the catalyst for preparing low-carbon olefin by using methanol described in claim 1, it is characterized in that: the skeleton SiO of high silica alumina ratio modified clinoptilolite
2: Al
2o
3mol ratio is 25 ~ 75.
4. according to the catalyst for preparing low-carbon olefin by using methanol described in claim 1, it is characterized in that: high silica alumina ratio modified clinoptilolite is carried out modification in accordance with the following methods by using natural clinoptilolite mineral and prepared;
Step (A), using natural clinoptilolite mineral are pulverized, sieved, gets the following fine powder of 200 order, be dispersed into the slurries of solid content 10 ~ 45 weight portion % with deionized water making beating, pump in ball mill and grind, until the particle diameter of solid matter of more than 90% is less than 7 microns in slurries;
Step (B), step (A) gained slurries are warming up to 60 ~ 95 DEG C in enamel reaction still, then add hydrochloric acid, oxalic acid successively, remove the dirts such as Ca, Mg, Al, Fe of institute's association, use H simultaneously
+alkali metal is become H type clinoptilolite with the clinoptilolite ion-exchange of alkaline earth type.Slurries are filtered, washes, obtain H type clinoptilolite solid filter cake;
Step (C), H type clinoptilolite solid filter cake is dispersed in enamel reaction still the slurries of solid content 10 ~ 45 weight portion % with deionized water making beating, be warming up to 40 ~ 70 DEG C, then the mixed acid adding hydrochloric acid and fluosilicic acid carries out aluminium-eliminating and silicon-replenishing, and the modification of H type clinoptilolite is become high silica alumina ratio H type clinoptilolite.Slurries are filtered, washes, obtain high silica alumina ratio H type clinoptilolite solid filter cake.
5. according to the catalyst of claim 4, it is characterized in that: in described using natural clinoptilolite mineral, the content of clinoptilolite is not less than 50 heavy %, is preferably not less than 65 weight fraction %.
6. according to the catalyst of claim 4, it is characterized in that: the clinoptilolite in described using natural clinoptilolite mineral is K type, Na type, Ca type, Mg type or its mixed type clinoptilolite, be preferably K type, Na type or its mixed type clinoptilolite.
7. according to the catalyst of claim 4, it is characterized in that: in step (B), solid (butt) is 1:0.01:0.01 ~ 1:0.20:0.20 with the weight ratio of hydrochloric acid, oxalic acid, be preferably 1:0.05:0.05 ~ 1:0.15:0.15.
8. according to the catalyst of claim 4, it is characterized in that: in step (C), solid (butt) is 1:0.01:0.05 ~ 1:0.15:0.25 with the weight ratio of hydrochloric acid, fluosilicic acid, be preferably 1:0.05:0.10 ~ 1:0.10:0.15.
9. according to the catalyst for preparing low-carbon olefin by using methanol described in claim 1, it is characterized in that: described inorganic oxide binder is selected from the mixture of one or more in aluminium oxide, silica, amorphous aluminum silicide, zirconia and titanium oxide, be preferably aluminium oxide or silica.
10. according to the catalyst for preparing low-carbon olefin by using methanol described in claim 1, it is characterized in that: described clay is selected from the mixture of one or more in kaolin, metakaolin, sepiolite, attapulgite, montmorillonite, tired de-stone, diatomite, galapectite, saponite, boron-moisten soil, hydrotalcite, or the modified product of above-mentioned clay after peracid treatment, be preferably kaolin.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107626345A (en) * | 2016-07-18 | 2018-01-26 | 任丘市华北石油科林环保有限公司 | A kind of high ethylene selectivity preparing low-carbon olefin by using methanol catalyst |
| CN108358740A (en) * | 2018-02-09 | 2018-08-03 | 安徽海德化工科技有限公司 | A kind of auxiliary agent preparing isobutene for isobutyl dehydration of alcohols |
| CN108906119A (en) * | 2018-05-29 | 2018-11-30 | 河南师范大学 | A kind of preparation method of SAPO-34 composite molecular screen |
| CN110721739A (en) * | 2019-10-24 | 2020-01-24 | 杜成荣 | Preparation method of olefin catalyst prepared from methanol |
| CN112264024A (en) * | 2020-11-12 | 2021-01-26 | 西南化工研究设计院有限公司 | Environment-friendly fluidized bed alkane dehydrogenation catalyst and preparation method thereof |
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| CN1341584A (en) * | 2000-07-13 | 2002-03-27 | 环球油品公司 | Abrasion-resisting catalyst for producing light olefin |
| CN1683079A (en) * | 2004-04-16 | 2005-10-19 | 中国石油化工股份有限公司 | Catalyst for reaction to produce olefine with methanol |
| CN101745414A (en) * | 2008-12-12 | 2010-06-23 | 北京化工大学 | Catalyst for producing light olefins through methanol and preparation method thereof |
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| CN1341584A (en) * | 2000-07-13 | 2002-03-27 | 环球油品公司 | Abrasion-resisting catalyst for producing light olefin |
| CN1683079A (en) * | 2004-04-16 | 2005-10-19 | 中国石油化工股份有限公司 | Catalyst for reaction to produce olefine with methanol |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107626345A (en) * | 2016-07-18 | 2018-01-26 | 任丘市华北石油科林环保有限公司 | A kind of high ethylene selectivity preparing low-carbon olefin by using methanol catalyst |
| CN108358740A (en) * | 2018-02-09 | 2018-08-03 | 安徽海德化工科技有限公司 | A kind of auxiliary agent preparing isobutene for isobutyl dehydration of alcohols |
| CN108906119A (en) * | 2018-05-29 | 2018-11-30 | 河南师范大学 | A kind of preparation method of SAPO-34 composite molecular screen |
| CN110721739A (en) * | 2019-10-24 | 2020-01-24 | 杜成荣 | Preparation method of olefin catalyst prepared from methanol |
| CN112264024A (en) * | 2020-11-12 | 2021-01-26 | 西南化工研究设计院有限公司 | Environment-friendly fluidized bed alkane dehydrogenation catalyst and preparation method thereof |
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