CN104549225B - Olefin disproportionation catalyst - Google Patents
Olefin disproportionation catalyst Download PDFInfo
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- CN104549225B CN104549225B CN201310512263.6A CN201310512263A CN104549225B CN 104549225 B CN104549225 B CN 104549225B CN 201310512263 A CN201310512263 A CN 201310512263A CN 104549225 B CN104549225 B CN 104549225B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The present invention relates to a kind of olefin disproportionation catalyst, mainly solve the problems, such as that the activity of catalyst disproportionation present in conventional art is low.The present invention passes through to use a kind of olefin disproportionation catalyst, in terms of parts by weight, including following components：A) 1~30 part of wolfram element or its oxide；B) 0.1~5 part of magnesium elements or its oxide；C) 0.001~1 part of at least one element or its oxide being selected from the B races of the periodic table of elements II；D) 64~99 parts of technical schemes of silica, preferably solve the problem, can be used for the industrial production of olefin dismutation reaction.
Description
Technical field
The present invention relates to a kind of olefin disproportionation catalyst.
Background technology
Traditional ethene coproduction and refinery's Propylene recovery method obviously is difficult to meet growing propylene demand, using alkene
Hydrocarbon dismutation technology can digest C while naphtha pyrolysis severity is not reduced4Cut, and can propylene enhancing, thus alkene
The research and development of disproportionation propylene technology processed is not only to the yield of raising propylene, while C low value-added to promotion4The synthesis of cut
Using having great significance, wherein butylene disproportionation production propylene involved in the present invention makes a kind of up-and-coming technique.
Olefin dismutation reaction is also called olefinic double bonds displacement reaction, is that a kind of alkene conversion for finding the sixties in 20th century is existing
As, since then olefin dismutation reaction just turn into alkene conversion a class significant process, using olefin dismutation reaction can by some compared with
For cheap, abundant olefin feedstock is converted into various added values olefin product higher.
The A of CN 102811986 describe to be converted under the condition and catalyst effective for olefin metathesis comprising butylene,
The method of such as all or most of single C4 olefin isomers such as hydrocarbon feed of 1- butylene.Olefin product, particularly propylene are being urged
Formed in the presence of agent, the catalyst is comprising solid carrier and is bonded to the tungsten hydride present in carrier on aluminum oxide.
This causes the expection with the olefin product formation of other carbon numbers and occurs regardless of olefin metathesis reaction mechanism.
A kind of technique that propylene and amylene are obtained by butene-1 and butene-2 disproportionation is proposed in US6271430.Should
Technique uses tank reactor, and catalyst is Re2O7/Al2O3, reaction temperature is 0~150 DEG C, and reaction pressure is 2~200bar.
WO00014038 describes a kind of method of preparing propylene by butene disproportionation.Raw material butylene be butene-1, butene-2 or its
Mixture, catalyst is WO3/SiO2, common reaction temperature is 500-550 DEG C, and reaction pressure is 1atm.
US513891 reports the preparation method of olefin disproportionation catalyst, and its catalyst composition is B2O3-Re2O7/Al2O3/
SiO2, using amorphous silica-alumina as catalyst carrier, the activity of olefin dismutation reaction is greatly improved.
EP0152112 is reported and is modified WO with Ti3/SiO2Catalyst carrier；US5905055 is reported and is modified WO with Nb3/
SiO2 catalyst carriers, olefin(e) disproportionation activity is all improved.
CN 201110032235.5 discloses a kind of while having the olefin(e) disproportionation of mesoporous and macropore combined porous structure with urging
Agent, including selected from the catalytically-active metals and catalyst carrier of at least one of rhenium, molybdenum, the oxide of tungsten, the catalyst
Carrier is the aluminum oxide with mesopore/macropore combined pore passage structure.The catalyst carrier passes through aluminum contained compound and mesoporous mould
Plate agent and macroporous granules template mix, are calcined and prepare.Above-mentioned catalyst solves low-carbon alkene in conventional art
There are problems that catalyst activity is low in disproportionation, inactivate faster.Also disclose the preparation method of the olefin(e) disproportionation catalyst.
CN88107893.X discloses the composition of the catalyst system for being adapted as olefin(e) disproportionation, and it contains and is loaded in oxidation
Molybdenum oxide on aluminium, is the method that catalyst is disproportionated with said composition.
CN95196917.X discloses the silicic acid alumina supporter for catalysts for metahesis reactions, there is provided be supported on alumina silicate
On rhenium oxide, if desired, boron oxide compound, tungsten oxide, molybdenum oxide or barium oxide can be added, it be used for alkene and
The metathesis reaction of the metathesis reaction of functional olefines, particularly carboxylate, and carrier material carries out hydro-thermal process.
CN96108099.X discloses the method that C4 olefine fractions are changed into polyisobutene and propylene using double decomposition.
Described method includes three successive steps:1) selective hydration alkadienes, while 1- isomerization of butene is into 2- butylene, 2) it is different
Butene polymerization, potentially includes preextraction isobutene, 3) 2- butylene and ethene double decomposition.After C 5 fraction hydrogen isomerization, part or
Whole C 4 fractions may be from the metathesis reaction of C5 olefine fractions and ethene.Answering in terms of steamed cracking C4 and C 5 fraction
With.
CN97193071.6 is related to a kind of method for preparing alpha-olefin product, and the method is including making a kind of internal olefin non-flat
Double decomposition under the conditions of weighing apparatus.So as to generate a kind of more lower boiling internal olefin product and a kind of higher that are removed when being formed
Middle chain internal olefin product, then make the middle chain internal olefin product of higher and contact ethylene and react, generate molecular weight model
Enclose narrow alpha-olefin product.
CN97121426.3 discloses the method for preparing the method for propylene and 1- butylene and preparing propylene, is included in subdivision
2- amylenes and ethylene reaction, above-mentioned catalyst is set to contain the VIth b, VII b at least one periodic table of elements in the presence of solution catalyst
Or VIII group 4 transition metal compound, including:A) in the presence of metathesis catalyst, 1- butylene is made to be reacted with 2- butylene,
Generation propylene and 2- amylenes, b) then separate the propylene and 2- amylenes of generation, c) in the presence of metathesis catalyst, make 2- penta
Alkene is reacted with ethene, generates propylene and 1- butylene, d) separates generated propylene and 1- butylene, e) the 1- fourths that will be generated
Alkene is sent back in step a).
It is different by the double decomposition of butene-1 and the hexene -3 for wherein producing CN02807165.4 is disclosed by butene-1
Structure turns to hexene -1, produces ethene and hexene -1.Initial feed is mixed butene stream, and wherein butene-1 is isomerized to butene-2,
And isobutene is therefrom isolated, then butene-2 is isomerized to butene-1, and the butene-1 is as the charging of double decomposition.
CN02137461.9 is related to a kind of fixed bed catalyst for producing propene from butylene by disproportion.Mainly solve text in the past
There is product separation difficulty in offering, catalyst price is high, need consumption of ethylene or reaction temperature high, the problem of high energy consumption.The present invention
By using with silica as carrier, the fixed bed catalyst of tungsten oxide is loaded, and specific surface area of catalyst is 270~550
Rice2/ gram technical scheme preferably solve the problem, can be used in the industrial production of preparing propylene by butene disproportionation.
There is catalyst activity low in the reaction for ethene and butylene propylene in the catalyst in document above
Problem.
The content of the invention
The technical problems to be solved by the invention are the low problems of the activity of catalyst disproportionation present in prior art, there is provided
A kind of new olefin disproportionation catalyst.When the catalyst is used for olefin dismutation reaction, have the advantages that catalyst disproportionation activity is high.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：A kind of olefin disproportionation catalyst, with weight
Number meter, including following components：A) 1~30 part of wolfram element or its oxide；B) 0.1~5 part of magnesium elements or its oxide；c)
0.001~1 part selected from least one element or its oxide in the B races of the periodic table of elements II；D) 64~99 parts of silica.
In above-mentioned technical proposal, in terms of olefin disproportionation catalyst parts by weight, wolfram element or its oxide content it is preferred
Scope is 4~15 parts；In terms of olefin disproportionation catalyst parts by weight, the preferred scope of magnesium elements or its oxide content is 0.5
~2 parts；The more preferably scope of magnesium elements or its oxide content is 1~2 part；In terms of olefin disproportionation catalyst parts by weight, choosing
The preferred scope of at least one element or its oxide content from the B races of the periodic table of elements II is 0.002~0.2 part, is selected from
The preferred scope of at least one element or its oxide content in the B races of the periodic table of elements II is 0.005~0.15 part；With alkene
Disproportionation catalyst parts by weight meter, the preferred scope of silica content is 70~80 parts.
In above-mentioned technical proposal, selected from least one element in the B races of the periodic table of elements II or the preferred side of its oxide
Case is mercury or its oxide.
Described olefin disproportionation catalyst is used for ethene and preparing propylene by butene disproportionation reacts, with butylene and ethene as former
Material, in 200~400 DEG C of reaction temperature, 1~4Mpa of reaction pressure, 0.1~20h of butylene mass space velocity-1, ethene and butylene rub
Your ratio is reaction generation propylene under conditions of 1~6；Described metathesis catalyst is reacted for preparing propylene by butene disproportionation, with
Butylene is raw material, in 200~400 DEG C of reaction temperature, 0~3Mpa of reaction pressure, 0.1~10h of butylene mass space velocity-1Under conditions of
Reaction generation propylene；Described olefin disproportionation catalyst reacts for 1- preparing hexane by disproportionating butylene, with 1- butylene as raw material, anti-
Answer 300~500 DEG C of temperature, 2~50h of reaction pressure 0~1Mpa, 1- butylene mass space velocity-1Reaction generation hexene；Will be described
Olefin disproportionation catalyst for preparing tetramethylethylene through isobutene metathesis react, with isobutene as raw material, reaction temperature 300~
500 DEG C, 0~1Mpa of reaction pressure, 0.1~10h of isobutene mass space velocity-1Under conditions of react generation tetramethyl-ethylene.
The preparation method of catalyst can be mixed using dipping, chemisorbed, chemical deposition, ion exchange, physics in the present invention
Prepared by the methods such as conjunction, catalyst is molded by aspects such as extrusion, spin, compressing tablets.
The preparation method of catalyst in turn includes the following steps：1) by W, selected from least in the B races of the periodic table of elements II
The corresponding salt of kind of element institute or oxide is soluble in water is made solution (I)；2) the corresponding salt of magnesium or oxide are added to solution
(I) it is made solution (II)；4) oxide for adding silicon in solution (II) obtains catalyst precarsor.
In above-mentioned preparation method, the oxide of silicon is at least one in silica gel, Ludox, chromatographic silica gel, molecular sieve, point
Son screening is from MCM series, SBA is serial, HMS is serial, at least one of MSU Series Molecules sieve；Step 1）The corresponding salt of middle metal
It is at least one in nitrate, sulfate and ammonium salt.
The forming method of catalyst is as follows：Catalyst precarsor is put into mixer, and adds Ludox and field mountain valley with clumps of trees and bamboo powder, stirred
Mix kneading and be allowed to Load Balanced, well mixed product is put into extruded moulding in banded extruder, the shape of extruded moulding includes circle
Cylindricality, cloverleaf pattern, mesopore shape, five clover shapes.
Preferred forming method is as follows：Roller forming in roller-ball devices is put into after Ludox will be added in catalyst precarsor,
Roller forming obtains the spheric catalyst of a diameter of 2-10mm.
Preferred forming method is as follows：Compression molding, compression molding in tablet press machine will be put into after catalyst precarsor film-making
Obtaining shape includes cylinder, amorphous.
After shaping of catalyst finished catalyst is obtained after drying, roasting.In above-mentioned technical proposal, catalyst sintering temperature
Preferred scope is 500~600 DEG C, and the preferred scope of roasting time is 4~6 hours.
Catalyst prepared by above-mentioned technical proposal is used for olefin dismutation reaction, and the embodiment of the present invention is that butylene and ethene are disproportionated
Reaction generation propylene.Reaction condition is as follows：In fixed bed reactors, with butylene and ethene as raw material, reaction temperature 200~
400 DEG C, 1~4Mpa of reaction pressure, 0.1~20h of butylene mass space velocity-1, the mol ratio of ethene and butylene is 1~6, when butylene
When conversion ratio is less than 60%, it is believed that catalyst is inactivated, when ethene and butylene disproportionation react propylene processed, catalyst activity is evaluated
Mainly butylene conversion ratio because the selectivity of target product propylene is more than 98% in reaction, the high conversion rate of butylene is
Show that catalyst disproportionation activity is good, the high income of propylene.
Butene feedstock can be the mixture of 1- butylene, 2- butylene or butylene in such scheme, or from steam cracking dress
The C-4-fraction put.
The present invention is by using Mg, selected from least one element the helping as disproportionation catalyst in the B races of the periodic table of elements II
Agent, by Mg, selected from the interaction between at least one element and main active component W in the B races of the periodic table of elements II, can have
Effect improves the reactivity of disproportionation catalyst, while activity being uniformly distributed on molecular sieve carrier surface, during the course of the reaction not
Easily covered by carbon deposit, so as to effectively improve the life-span of catalyst, the synergy between each active component is obvious, as W, Mg
Under conditions of existing selected from least one element in the B races of the periodic table of elements II, catalyst can just have good disproportionation activity.
It it is 300 DEG C in reaction temperature, reaction pressure is 3MPa, the mol ratio of ethene and butylene is 3.5 and the weight space velocity in butylene
It is 8 hours-1Space velocities under, by catalyst of the present invention be used for ethene and butylene propylene reaction, in sky higher
Under the conditions of speed, remain to obtain good disproportionation activity, the conversion ratio of its butylene contrasts WO more than 80%3/SiO2Catalyst its fourth
The conversion ratio of alkene can improve more than 20%, achieve unexpected technique effect.
Below by embodiment, the present invention is further elaborated.
Specific embodiment
【Embodiment 1】
52 grams of chromatographic silica gel, 100 grams of Ludox (silica containing 40 weight %) and 2 grams of sesbania powder are well mixed
It is put into mixer, stirring adds 0.1 gram of magnesia, 0.004 gram of zinc nitrate Zn (NO after 20 minutes3)2·6H2O and 10 gram of inclined tungsten
Sour ammonium (tungsten oxide containing 80 weight %), adds 250 grams of deionized waters after being stirred for 5 minutes, mediate 2 hours, after extruded moulding
Dried 4 hours at 100 DEG C, 550 DEG C of roastings, 4 hours prepared catalyst, are designated as SL-1 under air atmosphere.
The evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, with 2- butylene and ethene as raw material, by mass fraction
Calculate, raw material is 99.9% 2- butylene and 99.9% ethene.Reaction be temperature be 300 DEG C, pressure is 3MPa, ethene and butylene
Mol ratio be 3.5 and the weight space velocity of 2- butylene be 8 hours-1Under conditions of evaluated, evaluation result is as shown in table 1.
【Embodiment 2】
52 grams of chromatographic silica gel, 100 grams of Ludox (silica containing 40 weight %) and 2 grams of sesbania powder are well mixed
It is put into mixer, stirring adds 5 grams of magnesia, 0.004 gram of zinc nitrate Zn (NO after 20 minutes3)2·6H2O and 10 gram of metatungstic acid
Ammonium (tungsten oxide containing 80 weight %), adds 250 grams of deionized waters after being stirred for 5 minutes, mediate 2 hours, after extruded moulding
Dried 4 hours at 100 DEG C, 550 DEG C of roastings, 4 hours prepared catalyst, are designated as SL-2 under air atmosphere.
The evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, with 2- butylene and ethene as raw material, by mass fraction
Calculate, raw material is 99.9% 2- butylene and 99.9% ethene.Reaction be temperature be 300 DEG C, pressure is 3MPa, ethene and butylene
Mol ratio be 3.5 and the weight space velocity of 2- butylene be 8 hours-1Under conditions of evaluated, evaluation result is as shown in table 1.
【Embodiment 3】
52 grams of chromatographic silica gel, 100 grams of Ludox (silica containing 40 weight %) and 2 grams of sesbania powder are well mixed
It is put into mixer, stirring adds 0.5 gram of magnesia, 0.004 gram of zinc nitrate Zn (NO after 20 minutes3)2·6H2O and 10 gram of inclined tungsten
Sour ammonium (tungsten oxide containing 80 weight %), adds 250 grams of deionized waters after being stirred for 5 minutes, mediate 2 hours, after extruded moulding
Dried 4 hours at 100 DEG C, 550 DEG C of roastings, 4 hours prepared catalyst, are designated as SL-3 under air atmosphere.
The evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, with 2- butylene and ethene as raw material, by mass fraction
Calculate, raw material is 99.9% 2- butylene and 99.9% ethene.Reaction be temperature be 300 DEG C, pressure is 3MPa, ethene and butylene
Mol ratio be 3.5 and the weight space velocity of 2- butylene be 8 hours-1Under conditions of evaluated, evaluation result is as shown in table 1.
【Embodiment 4】
52 grams of chromatographic silica gel, 100 grams of Ludox (silica containing 40 weight %) and 2 grams of sesbania powder are well mixed
It is put into mixer, stirring adds 2 grams of magnesia, 0.004 gram of zinc nitrate Zn (NO after 20 minutes3)2·6H2O and 10 gram of metatungstic acid
Ammonium (tungsten oxide containing 80 weight %), adds 250 grams of deionized waters after being stirred for 5 minutes, mediate 2 hours, after extruded moulding
Dried 4 hours at 100 DEG C, 550 DEG C of roastings, 4 hours prepared catalyst, are designated as SL-4 under air atmosphere.
The evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, with 2- butylene and ethene as raw material, by mass fraction
Calculate, raw material is 99.9% 2- butylene and 99.9% ethene.Reaction be temperature be 300 DEG C, pressure is 3MPa, ethene and butylene
Mol ratio be 3.5 and the weight space velocity of 2- butylene be 8 hours-1Under conditions of evaluated, evaluation result is as shown in table 1.
【Embodiment 5】
52 grams of chromatographic silica gel, 100 grams of Ludox (silica containing 40 weight %) and 2 grams of sesbania powder are well mixed
It is put into mixer, stirring adds 1 gram of magnesia, 0.004 gram of zinc nitrate Zn (NO after 20 minutes3)2·6H2O and 10 gram of metatungstic acid
Ammonium (tungsten oxide containing 80 weight %), adds 250 grams of deionized waters after being stirred for 5 minutes, mediate 2 hours, after extruded moulding
Dried 4 hours at 100 DEG C, 550 DEG C of roastings, 4 hours prepared catalyst, are designated as SL-5 under air atmosphere.
The evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, with 2- butylene and ethene as raw material, by mass fraction
Calculate, raw material is 99.9% 2- butylene and 99.9% ethene.Reaction be temperature be 300 DEG C, pressure is 3MPa, ethene and butylene
Mol ratio be 3.5 and the weight space velocity of 2- butylene be 8 hours-1Under conditions of evaluated, evaluation result is as shown in table 1.
【Embodiment 6】
52 grams of chromatographic silica gel, 100 grams of Ludox (silica containing 40 weight %) and 2 grams of sesbania powder are well mixed
It is put into mixer, stirring adds 0.1 gram of magnesia, 3.654 grams of zinc nitrate Zn (NO after 20 minutes3)2·6H2O and 10 gram of inclined tungsten
Sour ammonium (tungsten oxide containing 80 weight %), adds 250 grams of deionized waters after being stirred for 5 minutes, mediate 2 hours, after extruded moulding
Dried 4 hours at 100 DEG C, 550 DEG C of roastings, 4 hours prepared catalyst, are designated as SL-6 under air atmosphere.
The evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, with 2- butylene and ethene as raw material, by mass fraction
Calculate, raw material is 99.9% 2- butylene and 99.9% ethene.Reaction be temperature be 300 DEG C, pressure is 3MPa, ethene and butylene
Mol ratio be 3.5 and the weight space velocity of 2- butylene be 8 hours-1Under conditions of evaluated, evaluation result is as shown in table 1.
【Embodiment 7】
52 grams of chromatographic silica gel, 100 grams of Ludox (silica containing 40 weight %) and 2 grams of sesbania powder are well mixed
It is put into mixer, stirring adds 0.1 gram of magnesia, 0.007 gram of zinc nitrate Zn (NO after 20 minutes3)2·6H2O and 10 gram of inclined tungsten
Sour ammonium (tungsten oxide containing 80 weight %), adds 250 grams of deionized waters after being stirred for 5 minutes, mediate 2 hours, after extruded moulding
Dried 4 hours at 100 DEG C, 550 DEG C of roastings, 4 hours prepared catalyst, are designated as SL-7 under air atmosphere.
The evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, with 2- butylene and ethene as raw material, by mass fraction
Calculate, raw material is 99.9% 2- butylene and 99.9% ethene.Reaction be temperature be 300 DEG C, pressure is 3MPa, ethene and butylene
Mol ratio be 3.5 and the weight space velocity of 2- butylene be 8 hours-1Under conditions of evaluated, evaluation result is as shown in table 1.
【Embodiment 8】
52 grams of chromatographic silica gel, 100 grams of Ludox (silica containing 40 weight %) and 2 grams of sesbania powder are well mixed
It is put into mixer, stirring adds 0.1 gram of magnesia, 0.73 gram of zinc nitrate Zn (NO after 20 minutes3)2·6H2O and 10 gram of inclined tungsten
Sour ammonium (tungsten oxide containing 80 weight %), adds 250 grams of deionized waters after being stirred for 5 minutes, mediate 2 hours, after extruded moulding
Dried 4 hours at 100 DEG C, 550 DEG C of roastings, 4 hours prepared catalyst, are designated as SL-8 under air atmosphere.
The evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, with 2- butylene and ethene as raw material, by mass fraction
Calculate, raw material is 99.9% 2- butylene and 99.9% ethene.Reaction be temperature be 300 DEG C, pressure is 3MPa, ethene and butylene
Mol ratio be 3.5 and the weight space velocity of 2- butylene be 8 hours-1Under conditions of evaluated, evaluation result is as shown in table 1.
【Embodiment 9】
52 grams of chromatographic silica gel, 100 grams of Ludox (silica containing 40 weight %) and 2 grams of sesbania powder are well mixed
It is put into mixer, stirring adds 0.1 gram of magnesia, 0.018 gram of zinc nitrate Zn (NO after 20 minutes3)2·6H2O and 10 gram of inclined tungsten
Sour ammonium (tungsten oxide containing 80 weight %), adds 250 grams of deionized waters after being stirred for 5 minutes, mediate 2 hours, after extruded moulding
Dried 4 hours at 100 DEG C, 550 DEG C of roastings, 4 hours prepared catalyst, are designated as SL-9 under air atmosphere.
The evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, with 2- butylene and ethene as raw material, by mass fraction
Calculate, raw material is 99.9% 2- butylene and 99.9% ethene.Reaction be temperature be 300 DEG C, pressure is 3MPa, ethene and butylene
Mol ratio be 3.5 and the weight space velocity of 2- butylene be 8 hours-1Under conditions of evaluated, evaluation result is as shown in table 1.
The appreciation condition of catalyst is with embodiment 1, and evaluation result is as shown in table 1.
【Embodiment 10】
52 grams of chromatographic silica gel, 100 grams of Ludox (silica containing 40 weight %) and 2 grams of sesbania powder are well mixed
It is put into mixer, stirring adds 0.1 gram of magnesia, 0.548 gram of zinc nitrate Zn (NO after 20 minutes3)2·6H2O and 10 gram of inclined tungsten
Sour ammonium (tungsten oxide containing 80 weight %), adds 250 grams of deionized waters after being stirred for 5 minutes, mediate 2 hours, after extruded moulding
Dried 4 hours at 100 DEG C, 550 DEG C of roastings, 4 hours prepared catalyst, are designated as SL-10 under air atmosphere.
The evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, with 2- butylene and ethene as raw material, by mass fraction
Calculate, raw material is 99.9% 2- butylene and 99.9% ethene.Reaction be temperature be 300 DEG C, pressure is 3MPa, ethene and butylene
Mol ratio be 3.5 and the weight space velocity of 2- butylene be 8 hours-1Under conditions of evaluated, evaluation result is as shown in table 1.
【Embodiment 11】
52 grams of chromatographic silica gel, 100 grams of Ludox (silica containing 40 weight %) and 2 grams of sesbania powder are well mixed
It is put into mixer, stirring adds 0.1 gram of magnesia, 0.008 gram of mercuric nitrate Hg (NO after 20 minutes3)2With 10 grams of ammonium metatungstates
(tungsten oxide containing 80 weight %), adds 250 grams of deionized waters, 100 after kneading 2 hours, extruded moulding after being stirred for 5 minutes
Dried 4 hours at DEG C, 550 DEG C of roastings, 4 hours prepared catalyst, are designated as SL-11 under air atmosphere.
The evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, with 2- butylene and ethene as raw material, by mass fraction
Calculate, raw material is 99.9% 2- butylene and 99.9% ethene.Reaction be temperature be 300 DEG C, pressure is 3MPa, ethene and butylene
Mol ratio be 3.5 and the weight space velocity of 2- butylene be 8 hours-1Under conditions of evaluated, evaluation result is as shown in table 1.
【Embodiment 12】
52 grams of chromatographic silica gel, 100 grams of Ludox (silica containing 40 weight %) and 2 grams of sesbania powder are well mixed
It is put into mixer, stirring adds 0.1 gram of magnesia, 0.22 gram of mercuric nitrate Hg (NO after 20 minutes3)2(contain with 10 grams of ammonium metatungstates
The tungsten oxide of 80 weight %), 250 grams of deionized waters are added after being stirred for 5 minutes, after kneading 2 hours, extruded moulding at 100 DEG C
Dry 4 hours, 550 DEG C of roastings, 4 hours prepared catalyst, are designated as SL-12 under air atmosphere.
The evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, with 2- butylene and ethene as raw material, by mass fraction
Calculate, raw material is 99.9% 2- butylene and 99.9% ethene.Reaction be temperature be 300 DEG C, pressure is 3MPa, ethene and butylene
Mol ratio be 3.5 and the weight space velocity of 2- butylene be 8 hours-1Under conditions of evaluated, evaluation result is as shown in table 1.
【Embodiment 13】
59 grams of chromatographic silica gel, 100 grams of Ludox (silica containing 40 weight %) and 4 grams of sesbania powder are well mixed
It is put into mixer, stirring adds 0.1 gram of magnesia, 0.004 gram of zinc nitrate Zn (NO after 30 minutes3)2·6H2O and 1.25 gram partially
Ammonium tungstate (tungsten oxide containing 80 weight %), adds 250 grams of deionized waters, after kneading 2 hours, extruded moulding after being stirred for 5 minutes
Dried 4 hours at 120 DEG C, 580 DEG C of roastings, 3 hours prepared catalyst, are designated as SL-13 under air atmosphere.
The evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, with 2- butylene and ethene as raw material, by mass fraction
Calculate, raw material is 99.9% 2- butylene and 99.9% ethene.Reaction be temperature be 300 DEG C, pressure is 3MPa, ethene and butylene
Mol ratio be 3.5 and the weight space velocity of 2- butylene be 8 hours-1Under conditions of evaluated, evaluation result is as shown in table 1.
【Embodiment 14】
28 grams of chromatographic silica gel, 100 grams of Ludox (silica containing 40 weight %) and 2 grams of sesbania powder are well mixed
It is put into mixer, stirring adds 1.5 grams of magnesia, 1.827 grams of zinc nitrate Zn (NO after 20 minutes3)2·6H2O and 37.5 gram partially
Ammonium tungstate (tungsten oxide containing 80 weight %), adds 250 grams of deionized waters, after kneading 2 hours, extruded moulding after being stirred for 5 minutes
Dried 4 hours at 100 DEG C, 550 DEG C of roastings, 4 hours prepared catalyst, are designated as SL-14 under air atmosphere.
The evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, with 2- butylene and ethene as raw material, by mass fraction
Calculate, raw material is 99.9% 2- butylene and 99.9% ethene.Reaction be temperature be 300 DEG C, pressure is 3MPa, ethene and butylene
Mol ratio be 3.5 and the weight space velocity of 2- butylene be 8 hours-1Under conditions of evaluated, evaluation result is as shown in table 1.
【Embodiment 15】
30 grams of chromatographic silica gel, 100 grams of Ludox (silica containing 40 weight %) and 2 grams of sesbania powder are well mixed
It is put into mixer, stirring adds 5 grams of magnesia, 3.654 grams of zinc nitrate Zn (NO after 20 minutes3)2·6H2O and 5 gram of metatungstic acid
Ammonium (tungsten oxide containing 80 weight %), adds 250 grams of deionized waters after being stirred for 5 minutes, mediate 2 hours, after extruded moulding
Dried 4 hours at 100 DEG C, 550 DEG C of roastings, 4 hours prepared catalyst, are designated as SL-15 under air atmosphere.
The evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, with 2- butylene and ethene as raw material, by mass fraction
Calculate, raw material is 99.9% 2- butylene and 99.9% ethene.Reaction be temperature be 300 DEG C, pressure is 3MPa, ethene and butylene
Mol ratio be 3.5 and the weight space velocity of 2- butylene be 8 hours-1Under conditions of evaluated, evaluation result is as shown in table 1.
【Embodiment 16】
40 grams of chromatographic silica gel, 100 grams of Ludox (silica containing 40 weight %) and 2 grams of sesbania powder are well mixed
It is put into mixer, stirring adds 4 grams of magnesia, 3.654 grams of zinc nitrate Zn (NO after 20 minutes3)2·6H2O and 18.75 gram partially
Ammonium tungstate (tungsten oxide containing 80 weight %), adds 250 grams of deionized waters, after kneading 2 hours, extruded moulding after being stirred for 5 minutes
Dried 4 hours at 100 DEG C, 550 DEG C of roastings, 4 hours prepared catalyst, are designated as SL-16 under air atmosphere.
The evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, with 2- butylene and ethene as raw material, by mass fraction
Calculate, raw material is 99.9% 2- butylene and 99.9% ethene.Reaction be temperature be 300 DEG C, pressure is 3MPa, ethene and butylene
Mol ratio be 3.5 and the weight space velocity of 2- butylene be 8 hours-1Under conditions of evaluated, evaluation result is as shown in table 1.
【Embodiment 17~20】
With SL-1 as catalyst is evaluated, the evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, with 2- butylene and second
Alkene is raw material, is calculated by mass fraction, and raw material is 99.9% 2- butylene and 99.9% ethene.Reaction condition and evaluation result such as table
Shown in 2.
【Comparative example 1】
52 grams of chromatographic silica gel, 100 grams of Ludox (silica containing 40 weight %) and 2 grams of sesbania powder are well mixed
It is put into mixer, stirring adds 0.004 gram of zinc nitrate Zn (NO after 20 minutes3)2·6H2O and 10 gram of ammonium metatungstate (contains 80 weights
Measure the tungsten oxide of %), 250 grams of deionized waters are added after being stirred for 5 minutes, dried at 100 DEG C after kneading 2 hours, extruded moulding
4 hours, 550 DEG C of roastings, 4 hours prepared catalyst, were designated as BJL-1 under air atmosphere.
The evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, with 2- butylene and ethene as raw material, by mass fraction
Calculate, raw material is 99.9% 2- butylene and 99.9% ethene.Reaction be temperature be 300 DEG C, pressure is 3MPa, ethene and butylene
Mol ratio be 3.5 and the weight space velocity of 2- butylene be 8 hours-1Under conditions of evaluated, evaluation result is as shown in table 1.
【Comparative example 2】
52 grams of chromatographic silica gel, 100 grams of Ludox (silica containing 40 weight %) and 2 grams of sesbania powder are well mixed
It is put into mixer, stirring adds 0.1 gram of magnesia and 10 grams of ammonium metatungstates (tungsten oxide containing 80 weight %) after 20 minutes, then
Stirring adds 250 grams of deionized waters after 5 minutes, dried 4 hours at 100 DEG C after kneading 2 hours, extruded moulding, in air atmosphere
4 hours prepared catalyst of lower 550 DEG C of roastings are enclosed, BJL-2 is designated as.
The evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, with 2- butylene and ethene as raw material, by mass fraction
Calculate, raw material is 99.9% 2- butylene and 99.9% ethene.Reaction be temperature be 300 DEG C, pressure is 3MPa, ethene and butylene
Mol ratio be 3.5 and the weight space velocity of 2- butylene be 8 hours-1Under conditions of evaluated, evaluation result is as shown in table 1.
【Comparative example 3】
52 grams of chromatographic silica gel, 100 grams of Ludox (silica containing 40 weight %) and 2 grams of sesbania powder are well mixed
It is put into mixer, stirring adds 0.1 gram of magnesia, 7.3 grams of zinc nitrate Zn (NO after 20 minutes3)2·6H2O and 10 gram of metatungstic acid
Ammonium (tungsten oxide containing 80 weight %), adds 250 grams of deionized waters after being stirred for 5 minutes, mediate 2 hours, after extruded moulding
Dried 4 hours at 100 DEG C, 550 DEG C of roastings, 4 hours prepared catalyst, are designated as BJL-3 under air atmosphere.
The evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, with 2- butylene and ethene as raw material, by mass fraction
Calculate, raw material is 99.9% 2- butylene and 99.9% ethene.Reaction be temperature be 300 DEG C, pressure is 3MPa, ethene and butylene
Mol ratio be 3.5 and the weight space velocity of 2- butylene be 8 hours-1Under conditions of evaluated, evaluation result is as shown in table 1.
【Comparative example 4】
52 grams of chromatographic silica gel, 100 grams of Ludox (silica containing 40 weight %) and 2 grams of sesbania powder are well mixed
It is put into mixer, stirring adds 10 grams of ammonium metatungstates (tungsten oxide containing 80 weight %) after 20 minutes, add after being stirred for 5 minutes
Enter 250 grams of deionized waters, dried 4 hours at 100 DEG C after kneading 2 hours, extruded moulding, 550 DEG C of roastings 4 under air atmosphere
Hour prepared catalyst, is designated as BJL-4.
The evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, with 2- butylene and ethene as raw material, by mass fraction
Calculate, raw material is 99.9% 2- butylene and 99.9% ethene.Reaction be temperature be 300 DEG C, pressure is 3MPa, ethene and butylene
Mol ratio be 3.5 and the weight space velocity of 2- butylene be 8 hours-1Under conditions of evaluated, evaluation result is as shown in table 1.
Table 1
Note：Component c in table 1 is the oxide selected from element in the B races of the periodic table of elements II
Table 2
Claims (8)
1. a kind of olefin disproportionation catalyst, in terms of parts by weight, including following components：
A) 8~30 parts of oxides of tungsten；
B) 0.1~0.5 part of magnesium elements or its oxide；
C) 0.001~0.2 part of at least one element or its oxide being selected from the B races of the periodic table of elements II；
D) 64~99 parts of silica.
2. olefin disproportionation catalyst according to claim 1, it is characterised in that in terms of parts by weight, olefin disproportionation catalyst
The content of the oxide of middle tungsten is 8~15 parts.
3. olefin disproportionation catalyst according to claim 1, it is characterised in that in terms of parts by weight, olefin disproportionation catalyst
In selected from least one element or the content of its oxide in the B races of the periodic table of elements II be 0.002~0.2 part.
4. olefin disproportionation catalyst according to claim 3, it is characterised in that in terms of parts by weight, olefin disproportionation catalyst
In selected from least one element or the content of its oxide in the B races of the periodic table of elements II be 0.005~0.15 part.
5. olefin disproportionation catalyst according to claim 1, it is characterised in that the content of silica is 70~80 parts.
6. the olefin disproportionation catalyst described in any one of Claims 1 to 5 is used for ethene and butylene propylene reacts, with butylene
It is raw material with ethene, in 200~400 DEG C of reaction temperature, 1~4Mpa of reaction pressure, 0.1~20h of butylene mass space velocity-1, ethene
With the mol ratio of butylene to react generation propylene under conditions of 1~6.
7. the olefin disproportionation catalyst described in any one of Claims 1 to 5 is reacted for preparing propylene by butene disproportionation, be with butylene
Raw material, in 200~400 DEG C of reaction temperature, 0~3Mpa of reaction pressure, 0.1~10h of butylene mass space velocity-1Under conditions of react life
Into propylene.
8. the olefin disproportionation catalyst described in any one of Claims 1 to 5 is reacted for preparing tetramethylethylene through isobutene metathesis,
With isobutene as raw material, in 300~500 DEG C of reaction temperature, 0~1Mpa of reaction pressure, 0.1~10h of isobutene mass space velocity-1's
Under the conditions of react generation tetramethyl-ethylene.
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| US4575575A (en) * | 1984-04-05 | 1986-03-11 | Phillips Petroleum Company | Catalysts and process for olefin conversion |
| US4754098A (en) * | 1986-02-24 | 1988-06-28 | Phillips Petroleum Company | Catalyst compositions useful for olefin isomerization and disproportionation |
| CN1490289A (en) * | 2002-10-16 | 2004-04-21 | 中国石油化工股份有限公司 | Method for preparing propylene by butene disproportionation |
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