CN104549225A - Olefin disproportionation catalyst - Google Patents
Olefin disproportionation catalyst Download PDFInfo
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- CN104549225A CN104549225A CN201310512263.6A CN201310512263A CN104549225A CN 104549225 A CN104549225 A CN 104549225A CN 201310512263 A CN201310512263 A CN 201310512263A CN 104549225 A CN104549225 A CN 104549225A
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Abstract
The invention relates to an olefin disproportionation catalyst, which is mainly used for solving the problem of low disproportionation activity of a catalyst in the prior art. The problem is well solved through the adoption of the technical scheme that the olefin disproportionation catalyst comprises the following components in parts by weight: a) 1-30 parts of tungsten or a tungsten oxide; b) 0.1-5 parts of magnesium or a magnesium oxide; c) 0.001-1 part of at least one element in group IIB in the periodic table of elements or an oxide of the IIB element; and d) 64-99 parts of silicon oxide. The olefin disproportionation catalyst can be applied to the industrial production of olefin disproportionation 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 are obviously difficult to meet growing propylene demand, adopt olefin metathesis technology can digest C while not reducing naphtha cracking severity
4cut, and can propylene enhancing, thus the research and development of preparing propylene through olefin disproportionation technology is not only to the output improving propylene, simultaneously to the low value-added C of promotion
4the comprehensive utilization of cut all has great significance, and butylene disproportionation wherein involved in the present invention is produced third and rarely made a kind of up-and-coming technique.
Olefin dismutation reaction is also called olefinic double bonds replacement(metathesis)reaction, it is a kind of conversion of olefines phenomenon found the sixties in 20th century, olefin dismutation reaction just becomes a class significant process of conversion of olefines since then, utilizes olefin dismutation reaction some comparatively cheap, abundant olefin feedstocks can be converted into the higher olefin product of multiple added value.
CN 102811986 A describes to transform under the condition being effective to olefin metathesis and catalyzer and comprises butylene, and such as all or most of single C4 olefin isomer is as the method for the hydrocarbon feed of 1-butylene.Olefin product, particularly propylene is formed in the presence of a catalyst, and described catalyzer comprises the tungsten hydride on aluminum oxide that solid carrier and being bonded to exists in carrier.No matter olefin metathesis reaction mechanism causes expection of the olefin product formation with other carbon number and occurs for this.
A kind of technique being obtained the third rare and amylene by butene-1 and butene-2 disproportionation is proposed in US6271430.This technique adopts tank reactor, and catalyzer is Re
2o
7/ Al
2o
3, temperature of reaction 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 is butene-1, butene-2 or its mixture, and catalyzer is WO
3/ SiO
2, common temperature of reaction is 500-550 DEG C, and reaction pressure is 1atm.
US513891 reports the preparation method of olefin disproportionation catalyst, and its catalyzer consists of B
2o
3-Re
2o
7/ Al
2o
3/ SiO
2, using amorphous aluminum silicide as support of the catalyst, the activity of olefin dismutation reaction improves greatly.
EP0152112 reports and modifies WO with Ti
3/ SiO
2support of the catalyst; US5905055 reports and modifies WO with Nb
3/ SiO2 support of the catalyst, olefin metathesis activity all obtains raising.
CN 201110032235.5 discloses a kind of mesoporous and olefin metathesis catalyzer that is macropore combined porous structure of simultaneously having, comprise catalytically-active metals and the support of the catalyst of at least one in the oxide compound being selected from rhenium, molybdenum, tungsten, described support of the catalyst is the aluminum oxide with mesopore/macropore combined pore passage structure.Described support of the catalyst is by aluminum contained compound and mesoporous template and the mixing of macroporous granules template, roasting and preparing.Above-mentioned catalyzer solves in conventional art exists in low-carbon alkene disproportionation that catalyst activity is low, inactivation problem faster.Also disclose the preparation method of described olefin metathesis catalyzer.
CN88107893.X discloses the composition of the catalyst system be suitable for as olefin metathesis, and it contains the molybdenum oxide be loaded on aluminum oxide, is the method that catalyzer carries out disproportionation by said composition.
CN95196917.X discloses the pure aluminium silicate carrier for catalysts for metahesis reactions, provide the rhenium oxide of load on pure aluminium silicate, if needed, boron oxide compound, tungsten oxide, molybdenum oxide or barium oxide can be added, it is for the replacement(metathesis)reaction of alkene and functional olefines, the particularly replacement(metathesis)reaction of carboxylicesters, and solid support material carries out hydrothermal treatment consists.
CN96108099.X discloses the method adopting double decomposition C4 olefin fraction to be changed into polyisobutene and propylene.Described method comprises three steps in succession: 1) selective hydration diolefine, and simultaneously 1-butylene is isomerizated into 2-butylene, 2) isobutene polymerisation, preextraction iso-butylene may be comprised, 3) 2-butylene and ethene metathesis.After the isomerization of C 5 fraction hydrogen, part or all of C 4 fraction can come from the replacement(metathesis)reaction of C5 olefin fraction and ethene.Application in steamed cracking C4 and C 5 fraction.
CN97193071.6 relates to a kind of method preparing alpha-olefin product, and the method comprises makes the metathesis under non-equilibrium condition of a kind of internal olefin.Thus the medium chain internal olefin product of a kind of more lower boiling internal olefin product be removed when being created on formation and a kind of higher, make the medium chain internal olefin product of higher and contact ethylene subsequently and react, generating the alpha-olefin product that molecular weight ranges is narrow.
CN97121426.3 discloses the method preparing propylene and 1-butylene and the method preparing propylene, be included under metathesis catalyst exists and make 2-amylene and ethylene reaction, above-mentioned catalyzer contains the VIth b at least one periodic table of elements, the compound of VII b or VIII group 4 transition metal, comprise: a) under metathesis catalyst exists, 1-butylene and 2-butylene are reacted, generate propylene and 2-amylene, b) propylene and the 2-amylene of generation is then separated, c) under metathesis catalyst exists, 2-amylene and ethene are reacted, generate propylene and 1-butylene, d) propylene generated and 1-butylene is separated, e) 1-butylene of generation is sent back to step a) in.
CN02807165.4 discloses by butene-1, turns to hexene-1, produce ethene and hexene-1 by the metathesis of butene-1 and hexene-3 isomery that wherein produces.Initial feed is mixed butene stream, and wherein butene-1 isomery turns to butene-2, and therefrom isolates iso-butylene, and then butene-2 isomery turns to butene-1, and this butene-1 is namely as metathetic charging.
CN02137461.9 relates to a kind of fixed bed catalyst for producing propene from butylene by disproportion.Mainly solve in previous literature exist product separation difficulty, catalyzer price high, need consumption of ethylene or temperature of reaction high, the problem that energy consumption is high.The present invention is the fixed bed catalyst of carrier, load Tungsten oxide 99.999 with silicon-dioxide by employing, and specific surface area of catalyst is 270 ~ 550 meters
2/ gram technical scheme solve this problem preferably, can be used in the industrial production of preparing propylene by butene disproportionation.
When the reaction for ethene and butylene propylene, all there is the problem that catalyst activity is low in the catalyzer in above document.
Summary of the invention
Technical problem to be solved by this invention is the active low problem of catalyst disproportionation existed in prior art, provides a kind of new olefin disproportionation catalyst.When this catalyzer is used for olefin dismutation reaction, there is the active high advantage of catalyst disproportionation.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of olefin disproportionation catalyst, with weight parts, comprises following component: a) 1 ~ 30 part of W elements or its oxide compound; B) 0.1 ~ 5 part of magnesium elements or its oxide compound; C) 0.001 ~ 1 part is selected from least one element in the periodic table of elements II B race or its oxide compound; D) 64 ~ 99 parts of silicon oxide.
In technique scheme, with olefin disproportionation catalyst weight parts, the preferable range of W elements or its oxide content is 4 ~ 15 parts; With olefin disproportionation catalyst weight parts, the preferable range of magnesium elements or its oxide content is 0.5 ~ 2 part; More preferably the scope of magnesium elements or its oxide content is 1 ~ 2 part; With olefin disproportionation catalyst weight parts, the preferable range being selected from least one element in the periodic table of elements II B race or its oxide content is 0.002 ~ 0.2 part, and the preferable range being selected from least one element in the periodic table of elements II B race or its oxide content is 0.005 ~ 0.15 part; With olefin disproportionation catalyst weight parts, the preferable range of silica content is 70 ~ 80 parts.
In technique scheme, the preferred version being selected from least one element in the periodic table of elements II B race or its oxide compound is mercury or its oxide compound.
Described olefin disproportionation catalyst is used for ethene and preparing propylene by butene disproportionation reaction, with butylene and ethene for raw material, temperature of reaction 200 ~ 400 DEG C, reaction pressure 1 ~ 4Mpa, butylene mass space velocity 0.1 ~ 20h
-1, the mol ratio of ethene and butylene is that under the condition of 1 ~ 6, reaction generates propylene; Described metathesis catalyst being used for preparing propylene by butene disproportionation reaction, take butylene as raw material, temperature of reaction 200 ~ 400 DEG C, and reaction pressure 0 ~ 3Mpa, butylene mass space velocity 0.1 ~ 10h
-1condition under reaction generate propylene; Described olefin disproportionation catalyst is used for the reaction of 1-butylene disproportionation hexene, take 1-butylene as raw material, temperature of reaction 300 ~ 500 DEG C, and reaction pressure 0 ~ 1Mpa, 1-butylene mass space velocity 2 ~ 50h
-1reaction generate hexene; Described olefin disproportionation catalyst being used for preparing tetramethylethylene through isobutene metathesis reaction, take iso-butylene as raw material, temperature of reaction 300 ~ 500 DEG C, and reaction pressure 0 ~ 1Mpa, iso-butylene mass space velocity 0.1 ~ 10h
-1condition under reaction generate tetramethyl-ethylene.
In the present invention, the preparation method of catalyzer can adopt the method such as dipping, chemisorption, electroless plating, ion-exchange, physical mixed to prepare, and carries out shaping by aspects such as extrusion, spin, compressing tablets to catalyzer.
The preparation method of catalyzer in turn includes the following steps: 1) by W, at least one element institute salt or the oxide compound solution (I) of making soluble in water be accordingly selected from the periodic table of elements II B race; 2) corresponding for magnesium salt or oxide compound are joined solution (I) and make solution (II); 4) oxide compound adding silicon at solution (II) obtains catalyst precursor.
In above-mentioned preparation method, the oxide compound of silicon is at least one in silica gel, silicon sol, chromatographic silica gel, molecular sieve, and molecular screening is serial from MCM, SBA is serial, HMS is serial, at least one of MSU Series Molecules sieve; The salt that in step 1), metal pair is answered is at least one in nitrate, vitriol and ammonium salt.
The forming method of catalyzer is as follows: catalyst precursor is put into stirrer, and adds silicon sol and field mountain valley with clumps of trees and bamboo powder, stirs kneading and makes it Load Balanced, the product mixed is put into banded extruder extruded moulding, and the shape of extruded moulding comprises cylindrical, cloverleaf pattern, middle hole shape, five leaf grass shapes.
Preferred forming method is as follows: after adding silicon sol in catalyst precursor, put into roller-ball devices roller forming, and roller forming obtains the spherical catalyst that diameter is 2-10mm.
Preferred forming method is as follows: put into tabletting machine compression molding by after catalyst precursor film-making, and compression molding obtains shape and comprises cylindrical, amorphous.
After drying, roasting, finished catalyst is obtained after shaping of catalyst.In technique scheme, the preferable range of catalyzer maturing temperature is 500 ~ 600 DEG C, and the preferable range of roasting time is 4 ~ 6 hours.
Catalyzer prepared by technique scheme is for olefin dismutation reaction, and the embodiment of the present invention is that butylene and ethene disproportionation reaction generate propylene.Reaction conditions is as follows: in fixed-bed reactor, with butylene and ethene for raw material, temperature of reaction 200 ~ 400 DEG C, and reaction pressure 1 ~ 4Mpa, butylene mass space velocity 0.1 ~ 20h
-1the mol ratio of ethene and butylene is 1 ~ 6, when the transformation efficiency of butylene is less than 60%, can think catalyst deactivation, when ethene and butylene disproportionation reaction propylene processed, evaluation of catalyst activity the transformation efficiency of mainly butylene because the selectivity of target product propylene is more than 98% in reacting, namely the transformation efficiency height of butylene shows that catalyst disproportionation activity is good, and the yield of propylene is high.
In such scheme, butene feedstock can be the mixture of 1-butylene, 2-butylene or butylene, or from the C-4-fraction of steam cracking device.
The present invention passes through Mg, be selected from the auxiliary agent of at least one element in the periodic table of elements II B race as disproportionation catalyst, pass through Mg, be selected from the interaction between at least one element in the periodic table of elements II B race and main active ingredient W, effectively can improve the reactive behavior of disproportionation catalyst, active being uniformly distributed in molecular sieve supported surface simultaneously, not easily covered by carbon deposit in reaction process, thus effectively can improve the life-span of catalyzer, synergy between each active ingredient is obvious, work as W, Mg is with under at least one element existent condition be selected from the periodic table of elements II B race, catalyzer just can have good disproportionation active.Be 300 DEG C in temperature of reaction, reaction pressure is 3MPa, and the mol ratio of ethene and butylene is 3.5 and is 8 hours at the weight space velocity of butylene
-1space velocities under, catalyzer of the present invention is used for ethene and the reaction of butylene propylene, under higher space velocities, still can obtains good disproportionation active, the transformation efficiency of its butylene more than 80%, contrast WO
3/ SiO
2the transformation efficiency of its butylene of catalyzer can improve more than 20%, achieves unexpected technique effect.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
The sesbania powder of the chromatographic silica gel of 52 grams, 100 grams of silicon sol (silicon oxide containing 40 % by weight) and 2 grams is mixed and puts into stirrer, stir after 20 minutes and add 0.1 gram of magnesium oxide, 0.004 gram of zinc nitrate Zn (NO
3)
26H
2o and 10 gram ammonium metawolframate (Tungsten oxide 99.999s containing 80 % by weight), 250 grams of deionized waters are added after stirring 5 minutes again, mediate 2 hours, after extruded moulding at 100 DEG C dry 4 hours, under air atmosphere, 550 DEG C of roastings, 4 hours obtained catalyzer, are designated as SL-1.
The evaluation of catalyzer is carried out on olefin metathesis evaluating apparatus, and with 2-butylene and ethene for raw material, calculate by massfraction, raw material is the 2-butylene of 99.9% and the ethene of 99.9%.Reaction is 300 DEG C in temperature, and pressure is 3MPa, the mol ratio of ethene and butylene be 3.5 and the weight space velocity of 2-butylene be 8 hours
-1condition under evaluate, evaluation result is as shown in table 1.
[embodiment 2]
The sesbania powder of the chromatographic silica gel of 52 grams, 100 grams of silicon sol (silicon oxide containing 40 % by weight) and 2 grams is mixed and puts into stirrer, stir after 20 minutes and add 5 grams of magnesium oxide, 0.004 gram of zinc nitrate Zn (NO
3)
26H
2o and 10 gram ammonium metawolframate (Tungsten oxide 99.999s containing 80 % by weight), 250 grams of deionized waters are added after stirring 5 minutes again, mediate 2 hours, after extruded moulding at 100 DEG C dry 4 hours, under air atmosphere, 550 DEG C of roastings, 4 hours obtained catalyzer, are designated as SL-2.
The evaluation of catalyzer is carried out on olefin metathesis evaluating apparatus, and with 2-butylene and ethene for raw material, calculate by massfraction, raw material is the 2-butylene of 99.9% and the ethene of 99.9%.Reaction is 300 DEG C in temperature, and pressure is 3MPa, the mol ratio of ethene and butylene be 3.5 and the weight space velocity of 2-butylene be 8 hours
-1condition under evaluate, evaluation result is as shown in table 1.
[embodiment 3]
The sesbania powder of the chromatographic silica gel of 52 grams, 100 grams of silicon sol (silicon oxide containing 40 % by weight) and 2 grams is mixed and puts into stirrer, stir after 20 minutes and add 0.5 gram of magnesium oxide, 0.004 gram of zinc nitrate Zn (NO
3)
26H
2o and 10 gram ammonium metawolframate (Tungsten oxide 99.999s containing 80 % by weight), 250 grams of deionized waters are added after stirring 5 minutes again, mediate 2 hours, after extruded moulding at 100 DEG C dry 4 hours, under air atmosphere, 550 DEG C of roastings, 4 hours obtained catalyzer, are designated as SL-3.
The evaluation of catalyzer is carried out on olefin metathesis evaluating apparatus, and with 2-butylene and ethene for raw material, calculate by massfraction, raw material is the 2-butylene of 99.9% and the ethene of 99.9%.Reaction is 300 DEG C in temperature, and pressure is 3MPa, the mol ratio of ethene and butylene be 3.5 and the weight space velocity of 2-butylene be 8 hours
-1condition under evaluate, evaluation result is as shown in table 1.
[embodiment 4]
The sesbania powder of the chromatographic silica gel of 52 grams, 100 grams of silicon sol (silicon oxide containing 40 % by weight) and 2 grams is mixed and puts into stirrer, stir after 20 minutes and add 2 grams of magnesium oxide, 0.004 gram of zinc nitrate Zn (NO
3)
26H
2o and 10 gram ammonium metawolframate (Tungsten oxide 99.999s containing 80 % by weight), 250 grams of deionized waters are added after stirring 5 minutes again, mediate 2 hours, after extruded moulding at 100 DEG C dry 4 hours, under air atmosphere, 550 DEG C of roastings, 4 hours obtained catalyzer, are designated as SL-4.
The evaluation of catalyzer is carried out on olefin metathesis evaluating apparatus, and with 2-butylene and ethene for raw material, calculate by massfraction, raw material is the 2-butylene of 99.9% and the ethene of 99.9%.Reaction is 300 DEG C in temperature, and pressure is 3MPa, the mol ratio of ethene and butylene be 3.5 and the weight space velocity of 2-butylene be 8 hours
-1condition under evaluate, evaluation result is as shown in table 1.
[embodiment 5]
The sesbania powder of the chromatographic silica gel of 52 grams, 100 grams of silicon sol (silicon oxide containing 40 % by weight) and 2 grams is mixed and puts into stirrer, stir after 20 minutes and add 1 gram of magnesium oxide, 0.004 gram of zinc nitrate Zn (NO
3)
26H
2o and 10 gram ammonium metawolframate (Tungsten oxide 99.999s containing 80 % by weight), 250 grams of deionized waters are added after stirring 5 minutes again, mediate 2 hours, after extruded moulding at 100 DEG C dry 4 hours, under air atmosphere, 550 DEG C of roastings, 4 hours obtained catalyzer, are designated as SL-5.
The evaluation of catalyzer is carried out on olefin metathesis evaluating apparatus, and with 2-butylene and ethene for raw material, calculate by massfraction, raw material is the 2-butylene of 99.9% and the ethene of 99.9%.Reaction is 300 DEG C in temperature, and pressure is 3MPa, the mol ratio of ethene and butylene be 3.5 and the weight space velocity of 2-butylene be 8 hours
-1condition under evaluate, evaluation result is as shown in table 1.
[embodiment 6]
The sesbania powder of the chromatographic silica gel of 52 grams, 100 grams of silicon sol (silicon oxide containing 40 % by weight) and 2 grams is mixed and puts into stirrer, stir after 20 minutes and add 0.1 gram of magnesium oxide, 3.654 grams of zinc nitrate Zn (NO
3)
26H
2o and 10 gram ammonium metawolframate (Tungsten oxide 99.999s containing 80 % by weight), 250 grams of deionized waters are added after stirring 5 minutes again, mediate 2 hours, after extruded moulding at 100 DEG C dry 4 hours, under air atmosphere, 550 DEG C of roastings, 4 hours obtained catalyzer, are designated as SL-6.
The evaluation of catalyzer is carried out on olefin metathesis evaluating apparatus, and with 2-butylene and ethene for raw material, calculate by massfraction, raw material is the 2-butylene of 99.9% and the ethene of 99.9%.Reaction is 300 DEG C in temperature, and pressure is 3MPa, the mol ratio of ethene and butylene be 3.5 and the weight space velocity of 2-butylene be 8 hours
-1condition under evaluate, evaluation result is as shown in table 1.
[embodiment 7]
The sesbania powder of the chromatographic silica gel of 52 grams, 100 grams of silicon sol (silicon oxide containing 40 % by weight) and 2 grams is mixed and puts into stirrer, stir after 20 minutes and add 0.1 gram of magnesium oxide, 0.007 gram of zinc nitrate Zn (NO
3)
26H
2o and 10 gram ammonium metawolframate (Tungsten oxide 99.999s containing 80 % by weight), 250 grams of deionized waters are added after stirring 5 minutes again, mediate 2 hours, after extruded moulding at 100 DEG C dry 4 hours, under air atmosphere, 550 DEG C of roastings, 4 hours obtained catalyzer, are designated as SL-7.
The evaluation of catalyzer is carried out on olefin metathesis evaluating apparatus, and with 2-butylene and ethene for raw material, calculate by massfraction, raw material is the 2-butylene of 99.9% and the ethene of 99.9%.Reaction is 300 DEG C in temperature, and pressure is 3MPa, the mol ratio of ethene and butylene be 3.5 and the weight space velocity of 2-butylene be 8 hours
-1condition under evaluate, evaluation result is as shown in table 1.
[embodiment 8]
The sesbania powder of the chromatographic silica gel of 52 grams, 100 grams of silicon sol (silicon oxide containing 40 % by weight) and 2 grams is mixed and puts into stirrer, stir after 20 minutes and add 0.1 gram of magnesium oxide, 0.73 gram of zinc nitrate Zn (NO
3)
26H
2o and 10 gram ammonium metawolframate (Tungsten oxide 99.999s containing 80 % by weight), 250 grams of deionized waters are added after stirring 5 minutes again, mediate 2 hours, after extruded moulding at 100 DEG C dry 4 hours, under air atmosphere, 550 DEG C of roastings, 4 hours obtained catalyzer, are designated as SL-8.
The evaluation of catalyzer is carried out on olefin metathesis evaluating apparatus, and with 2-butylene and ethene for raw material, calculate by massfraction, raw material is the 2-butylene of 99.9% and the ethene of 99.9%.Reaction is 300 DEG C in temperature, and pressure is 3MPa, the mol ratio of ethene and butylene be 3.5 and the weight space velocity of 2-butylene be 8 hours
-1condition under evaluate, evaluation result is as shown in table 1.
[embodiment 9]
The sesbania powder of the chromatographic silica gel of 52 grams, 100 grams of silicon sol (silicon oxide containing 40 % by weight) and 2 grams is mixed and puts into stirrer, stir after 20 minutes and add 0.1 gram of magnesium oxide, 0.018 gram of zinc nitrate Zn (NO
3)
26H
2o and 10 gram ammonium metawolframate (Tungsten oxide 99.999s containing 80 % by weight), 250 grams of deionized waters are added after stirring 5 minutes again, mediate 2 hours, after extruded moulding at 100 DEG C dry 4 hours, under air atmosphere, 550 DEG C of roastings, 4 hours obtained catalyzer, are designated as SL-9.
The evaluation of catalyzer is carried out on olefin metathesis evaluating apparatus, and with 2-butylene and ethene for raw material, calculate by massfraction, raw material is the 2-butylene of 99.9% and the ethene of 99.9%.Reaction is 300 DEG C in temperature, and pressure is 3MPa, the mol ratio of ethene and butylene be 3.5 and the weight space velocity of 2-butylene be 8 hours
-1condition under evaluate, evaluation result is as shown in table 1.
The appreciation condition of catalyzer is with embodiment 1, and evaluation result is as shown in table 1.
[embodiment 10]
The sesbania powder of the chromatographic silica gel of 52 grams, 100 grams of silicon sol (silicon oxide containing 40 % by weight) and 2 grams is mixed and puts into stirrer, stir after 20 minutes and add 0.1 gram of magnesium oxide, 0.548 gram of zinc nitrate Zn (NO
3)
26H
2o and 10 gram ammonium metawolframate (Tungsten oxide 99.999s containing 80 % by weight), 250 grams of deionized waters are added after stirring 5 minutes again, mediate 2 hours, after extruded moulding at 100 DEG C dry 4 hours, under air atmosphere, 550 DEG C of roastings, 4 hours obtained catalyzer, are designated as SL-10.
The evaluation of catalyzer is carried out on olefin metathesis evaluating apparatus, and with 2-butylene and ethene for raw material, calculate by massfraction, raw material is the 2-butylene of 99.9% and the ethene of 99.9%.Reaction is 300 DEG C in temperature, and pressure is 3MPa, the mol ratio of ethene and butylene be 3.5 and the weight space velocity of 2-butylene be 8 hours
-1condition under evaluate, evaluation result is as shown in table 1.
[embodiment 11]
The sesbania powder of the chromatographic silica gel of 52 grams, 100 grams of silicon sol (silicon oxide containing 40 % by weight) and 2 grams is mixed and puts into stirrer, stir after 20 minutes and add 0.1 gram of magnesium oxide, 0.008 gram of Mercury pernitrate Hg (NO
3)
2with 10 grams of ammonium metawolframates (Tungsten oxide 99.999s containing 80 % by weight), 250 grams of deionized waters are added after stirring 5 minutes again, mediate 2 hours, after extruded moulding at 100 DEG C dry 4 hours, under air atmosphere, 550 DEG C of roastings, 4 hours obtained catalyzer, are designated as SL-11.
The evaluation of catalyzer is carried out on olefin metathesis evaluating apparatus, and with 2-butylene and ethene for raw material, calculate by massfraction, raw material is the 2-butylene of 99.9% and the ethene of 99.9%.Reaction is 300 DEG C in temperature, and pressure is 3MPa, the mol ratio of ethene and butylene be 3.5 and the weight space velocity of 2-butylene be 8 hours
-1condition under evaluate, evaluation result is as shown in table 1.
[embodiment 12]
The sesbania powder of the chromatographic silica gel of 52 grams, 100 grams of silicon sol (silicon oxide containing 40 % by weight) and 2 grams is mixed and puts into stirrer, stir after 20 minutes and add 0.1 gram of magnesium oxide, 0.22 gram of Mercury pernitrate Hg (NO
3)
2with 10 grams of ammonium metawolframates (Tungsten oxide 99.999s containing 80 % by weight), 250 grams of deionized waters are added after stirring 5 minutes again, mediate 2 hours, after extruded moulding at 100 DEG C dry 4 hours, under air atmosphere, 550 DEG C of roastings, 4 hours obtained catalyzer, are designated as SL-12.
The evaluation of catalyzer is carried out on olefin metathesis evaluating apparatus, and with 2-butylene and ethene for raw material, calculate by massfraction, raw material is the 2-butylene of 99.9% and the ethene of 99.9%.Reaction is 300 DEG C in temperature, and pressure is 3MPa, the mol ratio of ethene and butylene be 3.5 and the weight space velocity of 2-butylene be 8 hours
-1condition under evaluate, evaluation result is as shown in table 1.
[embodiment 13]
The sesbania powder of the chromatographic silica gel of 59 grams, 100 grams of silicon sol (silicon oxide containing 40 % by weight) and 4 grams is mixed and puts into stirrer, stir after 30 minutes and add 0.1 gram of magnesium oxide, 0.004 gram of zinc nitrate Zn (NO
3)
26H
2o and 1.25 gram ammonium metawolframate (Tungsten oxide 99.999s containing 80 % by weight), 250 grams of deionized waters are added after stirring 5 minutes again, mediate 2 hours, after extruded moulding at 120 DEG C dry 4 hours, under air atmosphere, 580 DEG C of roastings, 3 hours obtained catalyzer, are designated as SL-13.
The evaluation of catalyzer is carried out on olefin metathesis evaluating apparatus, and with 2-butylene and ethene for raw material, calculate by massfraction, raw material is the 2-butylene of 99.9% and the ethene of 99.9%.Reaction is 300 DEG C in temperature, and pressure is 3MPa, the mol ratio of ethene and butylene be 3.5 and the weight space velocity of 2-butylene be 8 hours
-1condition under evaluate, evaluation result is as shown in table 1.
[embodiment 14]
The sesbania powder of the chromatographic silica gel of 28 grams, 100 grams of silicon sol (silicon oxide containing 40 % by weight) and 2 grams is mixed and puts into stirrer, stir after 20 minutes and add 1.5 grams of magnesium oxide, 1.827 grams of zinc nitrate Zn (NO
3)
26H
2o and 37.5 gram ammonium metawolframate (Tungsten oxide 99.999s containing 80 % by weight), 250 grams of deionized waters are added after stirring 5 minutes again, mediate 2 hours, after extruded moulding at 100 DEG C dry 4 hours, under air atmosphere, 550 DEG C of roastings, 4 hours obtained catalyzer, are designated as SL-14.
The evaluation of catalyzer is carried out on olefin metathesis evaluating apparatus, and with 2-butylene and ethene for raw material, calculate by massfraction, raw material is the 2-butylene of 99.9% and the ethene of 99.9%.Reaction is 300 DEG C in temperature, and pressure is 3MPa, the mol ratio of ethene and butylene be 3.5 and the weight space velocity of 2-butylene be 8 hours
-1condition under evaluate, evaluation result is as shown in table 1.
[embodiment 15]
The sesbania powder of the chromatographic silica gel of 30 grams, 100 grams of silicon sol (silicon oxide containing 40 % by weight) and 2 grams is mixed and puts into stirrer, stir after 20 minutes and add 5 grams of magnesium oxide, 3.654 grams of zinc nitrate Zn (NO
3)
26H
2o and 5 gram ammonium metawolframate (Tungsten oxide 99.999s containing 80 % by weight), 250 grams of deionized waters are added after stirring 5 minutes again, mediate 2 hours, after extruded moulding at 100 DEG C dry 4 hours, under air atmosphere, 550 DEG C of roastings, 4 hours obtained catalyzer, are designated as SL-15.
The evaluation of catalyzer is carried out on olefin metathesis evaluating apparatus, and with 2-butylene and ethene for raw material, calculate by massfraction, raw material is the 2-butylene of 99.9% and the ethene of 99.9%.Reaction is 300 DEG C in temperature, and pressure is 3MPa, the mol ratio of ethene and butylene be 3.5 and the weight space velocity of 2-butylene be 8 hours
-1condition under evaluate, evaluation result is as shown in table 1.
[embodiment 16]
The sesbania powder of the chromatographic silica gel of 40 grams, 100 grams of silicon sol (silicon oxide containing 40 % by weight) and 2 grams is mixed and puts into stirrer, stir after 20 minutes and add 4 grams of magnesium oxide, 3.654 grams of zinc nitrate Zn (NO
3)
26H
2o and 18.75 gram ammonium metawolframate (Tungsten oxide 99.999s containing 80 % by weight), 250 grams of deionized waters are added after stirring 5 minutes again, mediate 2 hours, after extruded moulding at 100 DEG C dry 4 hours, under air atmosphere, 550 DEG C of roastings, 4 hours obtained catalyzer, are designated as SL-16.
The evaluation of catalyzer is carried out on olefin metathesis evaluating apparatus, and with 2-butylene and ethene for raw material, calculate by massfraction, raw material is the 2-butylene of 99.9% and the ethene of 99.9%.Reaction is 300 DEG C in temperature, and pressure is 3MPa, the mol ratio of ethene and butylene be 3.5 and the weight space velocity of 2-butylene be 8 hours
-1condition under evaluate, evaluation result is as shown in table 1.
[embodiment 17 ~ 20]
Take SL-1 as evaluate catalysts, the evaluation of catalyzer is carried out on olefin metathesis evaluating apparatus, and with 2-butylene and ethene for raw material, calculate by massfraction, raw material is the 2-butylene of 99.9% and the ethene of 99.9%.Reaction conditions and evaluation result as shown in table 2.
[comparative example 1]
The sesbania powder of the chromatographic silica gel of 52 grams, 100 grams of silicon sol (silicon oxide containing 40 % by weight) and 2 grams is mixed and puts into stirrer, stir after 20 minutes and add 0.004 gram of zinc nitrate Zn (NO
3)
26H
2o and 10 gram ammonium metawolframate (Tungsten oxide 99.999s containing 80 % by weight), 250 grams of deionized waters are added after stirring 5 minutes again, mediate 2 hours, after extruded moulding at 100 DEG C dry 4 hours, under air atmosphere, 550 DEG C of roastings, 4 hours obtained catalyzer, are designated as BJL-1.
The evaluation of catalyzer is carried out on olefin metathesis evaluating apparatus, and with 2-butylene and ethene for raw material, calculate by massfraction, raw material is the 2-butylene of 99.9% and the ethene of 99.9%.Reaction is 300 DEG C in temperature, and pressure is 3MPa, the mol ratio of ethene and butylene be 3.5 and the weight space velocity of 2-butylene be 8 hours
-1condition under evaluate, evaluation result is as shown in table 1.
[comparative example 2]
The sesbania powder of the chromatographic silica gel of 52 grams, 100 grams of silicon sol (silicon oxide containing 40 % by weight) and 2 grams is mixed and puts into stirrer, stir after 20 minutes and add 0.1 gram of magnesium oxide and 10 grams of ammonium metawolframates (Tungsten oxide 99.999s containing 80 % by weight), 250 grams of deionized waters are added after stirring 5 minutes again, mediate 2 hours, after extruded moulding at 100 DEG C dry 4 hours, under air atmosphere, 550 DEG C of roastings, 4 hours obtained catalyzer, are designated as BJL-2.
The evaluation of catalyzer is carried out on olefin metathesis evaluating apparatus, and with 2-butylene and ethene for raw material, calculate by massfraction, raw material is the 2-butylene of 99.9% and the ethene of 99.9%.Reaction is 300 DEG C in temperature, and pressure is 3MPa, the mol ratio of ethene and butylene be 3.5 and the weight space velocity of 2-butylene be 8 hours
-1condition under evaluate, evaluation result is as shown in table 1.
[comparative example 3]
The sesbania powder of the chromatographic silica gel of 52 grams, 100 grams of silicon sol (silicon oxide containing 40 % by weight) and 2 grams is mixed and puts into stirrer, stir after 20 minutes and add 0.1 gram of magnesium oxide, 7.3 grams of zinc nitrate Zn (NO
3)
26H
2o and 10 gram ammonium metawolframate (Tungsten oxide 99.999s containing 80 % by weight), 250 grams of deionized waters are added after stirring 5 minutes again, mediate 2 hours, after extruded moulding at 100 DEG C dry 4 hours, under air atmosphere, 550 DEG C of roastings, 4 hours obtained catalyzer, are designated as BJL-3.
The evaluation of catalyzer is carried out on olefin metathesis evaluating apparatus, and with 2-butylene and ethene for raw material, calculate by massfraction, raw material is the 2-butylene of 99.9% and the ethene of 99.9%.Reaction is 300 DEG C in temperature, and pressure is 3MPa, the mol ratio of ethene and butylene be 3.5 and the weight space velocity of 2-butylene be 8 hours
-1condition under evaluate, evaluation result is as shown in table 1.
[comparative example 4]
The sesbania powder of the chromatographic silica gel of 52 grams, 100 grams of silicon sol (silicon oxide containing 40 % by weight) and 2 grams is mixed and puts into stirrer, stir after 20 minutes and add 10 grams of ammonium metawolframates (Tungsten oxide 99.999s containing 80 % by weight), 250 grams of deionized waters are added after stirring 5 minutes again, mediate 2 hours, after extruded moulding at 100 DEG C dry 4 hours, under air atmosphere, 550 DEG C of roastings, 4 hours obtained catalyzer, are designated as BJL-4.
The evaluation of catalyzer is carried out on olefin metathesis evaluating apparatus, and with 2-butylene and ethene for raw material, calculate by massfraction, raw material is the 2-butylene of 99.9% and the ethene of 99.9%.Reaction is 300 DEG C in temperature, and pressure is 3MPa, the mol ratio of ethene and butylene be 3.5 and the weight space velocity of 2-butylene be 8 hours
-1condition under evaluate, evaluation result is as shown in table 1.
Table 1
Note: the amount of component b in table 1 is the oxide compound being selected from element in the periodic table of elements II B race
Table 2
Claims (10)
1. an olefin disproportionation catalyst, with weight parts, comprises following component:
A) 1 ~ 30 part of W elements or its oxide compound;
B) 0.1 ~ 5 part of magnesium elements or its oxide compound;
C) 0.001 ~ 1 part is selected from least one element in the periodic table of elements II B race or its oxide compound;
D) 64 ~ 99 parts of silicon oxide.
2. olefin disproportionation catalyst according to claim 1, is characterized in that with weight parts, and in olefin disproportionation catalyst, the content of W elements or its oxide compound is 4 ~ 15 parts.
3. olefin disproportionation catalyst according to claim 1, is characterized in that with weight parts, and in olefin disproportionation catalyst, the content of magnesium elements or its oxide compound is 0.5 ~ 2 part.
4. olefin disproportionation catalyst according to claim 3, is characterized in that with weight parts, and in olefin disproportionation catalyst, the content of magnesium elements or its oxide compound is 1 ~ 2 part.
5. olefin disproportionation catalyst according to claim 1, is characterized in that with weight parts, and the content being selected from least one element in the periodic table of elements II B race or its oxide compound in olefin disproportionation catalyst is 0.002 ~ 0.2 part.
6. olefin disproportionation catalyst according to claim 5, is characterized in that with weight parts, and the content being selected from least one element in the periodic table of elements II B race or its oxide compound in olefin disproportionation catalyst is 0.005 ~ 0.15 part.
7. olefin disproportionation catalyst according to claim 1, is characterized in that the content of silicon oxide is 70 ~ 80 parts.
8. the olefin disproportionation catalyst described in any one of claim 1 ~ 7 is used for ethene and the reaction of butylene propylene, with butylene and ethene for raw material, temperature of reaction 200 ~ 400 DEG C, reaction pressure 1 ~ 4Mpa, butylene mass space velocity 0.1 ~ 20h
-1, the mol ratio of ethene and butylene is that under the condition of 1 ~ 6, reaction generates propylene.
9. the olefin disproportionation catalyst described in any one of claim 1 ~ 7 being used for preparing propylene by butene disproportionation reaction, take butylene as raw material, temperature of reaction 200 ~ 400 DEG C, and reaction pressure 0 ~ 3Mpa, butylene mass space velocity 0.1 ~ 10h
-1condition under reaction generate propylene.
10., by the olefin disproportionation catalyst preparing tetramethylethylene through isobutene metathesis reaction described in any one of claim 1 ~ 7, take iso-butylene as raw material, temperature of reaction 300 ~ 500 DEG C, reaction pressure 0 ~ 1Mpa, iso-butylene mass space velocity 0.1 ~ 10h
-1condition under reaction generate tetramethyl-ethylene.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105080535A (en) * | 2014-05-14 | 2015-11-25 | 中国石油化工股份有限公司 | Butene disproportionation catalyst |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101304963A (en) * | 2005-11-14 | 2008-11-12 | 三井化学株式会社 | Method of producing propylene containing biomass-origin carbon |
| CN101675015A (en) * | 2007-04-27 | 2010-03-17 | 三井化学株式会社 | Process for producing olefin |
| CN102143929A (en) * | 2008-09-04 | 2011-08-03 | 鲁姆斯科技公司 | Olefin isomerization and metathesis catalyst |
| CN102372575A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Method for preparing tetramethylethylene through isobutene metathesis |
| CN103030495A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Method for manufacturing propylene by butene and ethylene disproportionation |
-
2013
- 2013-10-28 CN CN201310512263.6A patent/CN104549225B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101304963A (en) * | 2005-11-14 | 2008-11-12 | 三井化学株式会社 | Method of producing propylene containing biomass-origin carbon |
| CN101675015A (en) * | 2007-04-27 | 2010-03-17 | 三井化学株式会社 | Process for producing olefin |
| CN102143929A (en) * | 2008-09-04 | 2011-08-03 | 鲁姆斯科技公司 | Olefin isomerization and metathesis catalyst |
| CN102372575A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Method for preparing tetramethylethylene through isobutene metathesis |
| CN103030495A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Method for manufacturing propylene by butene and ethylene disproportionation |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105080535A (en) * | 2014-05-14 | 2015-11-25 | 中国石油化工股份有限公司 | Butene disproportionation catalyst |
| CN105080535B (en) * | 2014-05-14 | 2018-04-06 | 中国石油化工股份有限公司 | Catalyst for butylene disproportionation |
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