CN104437525A - Disproportionation catalyst - Google Patents
Disproportionation catalyst Download PDFInfo
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- CN104437525A CN104437525A CN201310435396.8A CN201310435396A CN104437525A CN 104437525 A CN104437525 A CN 104437525A CN 201310435396 A CN201310435396 A CN 201310435396A CN 104437525 A CN104437525 A CN 104437525A
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Abstract
The invention relates to a disproportionation catalyst which is mainly used for solving the problem of low disproportionation activity of the catalysts in the prior art. The disproportionation catalyst comprises the following components in parts by weight: (a) 1-30 parts of molybdenum element or an oxide thereof, (b) 0.0001-2 parts of tungsten element or an oxide thereof, (c) 0.0001-1 part of iron element or an oxide thereof, (d) 0.0001-1 part of alkaline metal element or an oxide thereof, (e) 0-15 parts of alkaline earth metal elements or an oxide thereof, (f) 0.0001-1 part of copper element or oxides thereof, and (g) 50-98 parts of aluminum oxide. According to the technical scheme of the disproportionation catalyst, the problem of low disproportionation activity of the catalysts can be well solved, and the disproportionation catalyst can be used for industrial production of disproportionation reaction of alkenes.
Description
Technical field
The present invention relates to a kind of disproportionation catalyst, especially for the disproportionation catalyst of olefin dismutation reaction.
Background technology
Traditional ethene coproduction and refinery's Propylene recovery method are obviously difficult to meet growing propylene demand, adopt olefin(e) disproportionation technology can digest C while not reducing naphtha pyrolysis 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 displacement reaction, it is a kind of olefin substitute phenomenon found the sixties in 20th century, olefin dismutation reaction just becomes a class significant process of olefin substitute 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(e) disproportionation and catalyst 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 catalyst comprises the tungsten hydride on aluminium oxide that solid carrier and being bonded to exists in carrier.No matter olefin dismutation 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 catalyst is Re
2o
7/ Al
2o
3, 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 is butene-1, butene-2 or its mixture, and catalyst is WO
3/ SiO
2, 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 consists of B
2o
3-Re
2o
7/ Al
2o
3/ SiO
2, using amorphous aluminum silicide as catalyst carrier, the activity of olefin dismutation reaction improves greatly.
EP0152112 reports and modifies WO with Ti
3/ SiO
2catalyst carrier; US5905055 reports and modifies WO with Nb
3/ SiO2 catalyst carrier, olefin(e) disproportionation activity all obtains raising.
CN 201110032235.5 discloses a kind of mesoporous and olefin(e) disproportionation catalyst that is macropore combined porous structure of simultaneously having, comprise catalytically-active metals and the catalyst carrier of at least one in the oxide being selected from rhenium, molybdenum, tungsten, described catalyst carrier is the aluminium oxide with mesopore/macropore combined pore passage structure.Described catalyst carrier is by aluminum contained compound and mesoporous template and the mixing of macroporous granules template, roasting and preparing.Above-mentioned catalyst 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(e) disproportionation catalyst.
CN88107893.X discloses the composition of the catalyst system be suitable for as olefin(e) disproportionation, and it contains the molybdenum oxide be loaded on aluminium oxide, is the method that catalyst carries out disproportionation by said composition.
CN95196917.X discloses the alumina silicate carrier for disproportionation reaction catalyzer, provide the rhenium oxide of load on alumina silicate, if needed, boron oxide compound, tungsten oxide, molybdenum oxide or barium oxide can be added, it is for the disproportionated reaction of alkene and functional olefines, the particularly disproportionated reaction of carboxylate, and carrier material carries out hydrothermal treatment consists.
CN96108099.X discloses the method adopting discrimination method C4 olefine fraction to be changed into polyisobutene and propylene.Described method comprises three steps in succession: 1) selective hydration alkadienes, and simultaneously 1-isomerization of butene becomes 2-butylene, 2) isobutene polymerisation, preextraction isobutene may be comprised, 3) 2-butylene and ethene disproportionation.After the isomerization of C 5 fraction hydrogen, part or all of C 4 fraction can come from the disproportionated reaction of C5 olefine 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 a kind of internal olefin disproportionation under non-equilibrium condition.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 disproportionation catalyst exists and make 2-amylene and ethylene reaction, above-mentioned catalyst 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 disproportionation 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 disproportionation catalyst exists, 2-amylene and ethene are reacted, generate propylene and 1-butylene, d) propylene generated and 1-butylene is separated, e) the 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 disproportionation 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 isobutene, and then butene-2 isomery turns to butene-1, and this butene-1 is namely as the charging of disproportionation.
CN02137461.9 relates to a kind of fixed bde catalyst for producing propene from butylene by disproportion.Mainly solve in previous literature exist product separation difficulty, catalyst price high, need consumption of ethylene or reaction temperature high, the problem that energy consumption is high.The present invention is the fixed bde catalyst of carrier, load tungsten oxide with silica 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 preparing propylene by butene disproportionation, all there is the problem that catalyst activity is low in the catalyst 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 disproportionation catalyst.When this catalyst 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 disproportionation catalyst, with weight parts, comprises following component: a) 1 ~ 30 part of molybdenum element or its oxide; B) 0.0001 ~ 2 part of W elements or its oxide; C) 0.0001 ~ 1 part of ferro element or its oxide; D) 0.0001 ~ 1 part of alkali metal or its oxide; E) 0 ~ 15 part of alkali earth metal or its oxide; F) 0.0001 ~ 1 part of copper or its oxide; G) 50 ~ 98 parts of aluminium oxide.
In technique scheme, with weight parts, the content of W elements or its oxide is 0.001 ~ 1 part; The preferable range of ferro element or its oxide content is 0.001 ~ 0.5 part; The preferable range of alkali metal or its oxide content is 0.001 ~ 0.5 part; The preferred version of alkali metal is potassium; The preferable range of copper or its oxide content is 0.001 ~ 0.5 part; The preferable range of alumina content is 60 ~ 80 parts; The preferable range of alkali earth metal or its oxide content is 0.01 ~ 10 part, and the most preferred range of alkali earth metal or its oxide content is 1 ~ 5 part; The preferred version of alkali earth metal is at least one in magnesium or calcium, and the most preferably scheme of alkaline earth element is calcium or magnesium; Described disproportionation catalyst is used for ethene and preparing propylene by butene disproportionation reaction, with butylene and ethene for raw material, reaction temperature 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 disproportionation catalyst being used for preparing propylene by butene disproportionation reaction, take butylene as raw material, reaction temperature 200 ~ 400 DEG C, and reaction pressure 0 ~ 3Mpa, butylene mass space velocity 0.1 ~ 10h
-1condition under reaction generate propylene; Described disproportionation catalyst is used for the reaction of 1-preparing hexane by disproportionating butylene, with 1-butylene for raw material, reaction temperature 300 ~ 500 DEG C, and reaction pressure 0 ~ 1Mpa, 1-butylene mass space velocity 2 ~ 50h
-1reaction generate hexene; Described disproportionation catalyst being used for preparing tetramethylethylene through isobutene metathesis reaction, take isobutene as raw material, reaction temperature 300 ~ 500 DEG C, and reaction pressure 0 ~ 1Mpa, isobutene mass space velocity 0.1 ~ 10h
-1condition under reaction generate tetramethyl-ethylene, in technique scheme, with weight parts, catalyst also comprises the indium oxide of 0.1 ~ 1 part.
In the present invention, the preparation method of catalyst can adopt the method such as dipping, chemisorbed, chemical deposition, ion-exchange, physical mixed to prepare, and carries out shaping by aspects such as extrusion, spin, compressing tablets to catalyst.
The preparation method of catalyst in turn includes the following steps: 1) by corresponding for Mo, W, Fe and Cu metal institute salt or oxide solution I of making soluble in water; 2) corresponding at least one being selected from alkali metal or alkaline-earth metal salt or oxide are joined solution I and make solution II; 3) oxide adding aluminium in solution II obtains catalyst precarsor.
In above-mentioned preparation method, the oxide of aluminium is at least one in aluminium glue, Alumina gel, aluminium oxide; The salt that in step 1), metal pair is answered 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, 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 Ludox in catalyst precarsor, put into roller-ball devices roller forming, and roller forming obtains the spheric catalyst that diameter is 2-10mm.
Preferred forming method is as follows: put into tablet press machine compression molding by after catalyst precarsor 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 catalyst sintering temperature is 500 ~ 600 DEG C, and the preferable range of roasting time is 4 ~ 6 hours.
Catalyst prepared by technique scheme is for olefin dismutation reaction, and the embodiment of the present invention is that butylene and ethene disproportionated reaction generate propylene.Reaction condition is as follows: in fixed bed reactors, with butylene and ethene for raw material, reaction temperature 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 conversion ratio of butylene is less than 60%, can think catalysqt deactivation, when ethene and butylene disproportionation reaction propylene processed, evaluation of catalyst activity the conversion ratio of mainly butylene because the selective of target product propylene is more than 98% in reacting, namely the conversion ratio 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 butene-1, butene-2 or butylene, or from the C-4-fraction of steam cracking device.
The present invention passes through W, Fe, Cu, alkali and alkaline earth metal ions is as the auxiliary agent of disproportionation catalyst, pass through W, Fe, Cu, alkali metal, interaction between alkaline-earth metal and main active component Mo, effectively can improve the reactivity of disproportionation catalyst, active being uniformly distributed in molecular sieve supported surface simultaneously, not easily covered by carbon deposit in course of reaction, thus effectively can improve the life-span of catalyst, synergy between each active component is obvious, only at W, Fe, Cu, alkali metal, alkaline-earth metal and these active components of Mo are all under existent condition, catalyst just can have good disproportionation active, when adding active component indium again, the disproportionation activity of catalyst is significantly increased again, and the conversion ratio of butylene can improve more than 4%.Be 300 DEG C in reaction temperature, 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, catalyst 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 conversion ratio of its butylene more than 80%, contrast MoO
3/ Al
2o
3the conversion ratio of its butylene of catalyst can improve more than 20%, achieves unexpected technique effect.
Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[embodiment 1]
The sesbania powder of the Alumina gel of 368 grams (aluminium oxide containing 25 % by weight) and 1 gram is mixed and puts into mixer, stir after 12 minutes and add 0.00013 gram of ammonium metatungstate (tungsten oxides containing 80 % by weight), 0.0003 gram of ferric nitrate, 0.0001 gram of potassium oxide, 0.00024 gram of copper nitrate and 9.52 grams of ammonium dimolybdates (molybdenum oxides containing 84 % 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 catalyst, are designated as SL-1.
The evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, and with 2-butylene and ethene for raw material, calculate by mass fraction, 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 Alumina gel of 368 grams (aluminium oxide containing 25 % by weight) and 1 gram is mixed and puts into mixer, stir after 12 minutes and add 0.0013 gram of ammonium metatungstate (tungsten oxides containing 80 % by weight), 0.0003 gram of ferric nitrate, 0.0001 gram of potassium oxide, 0.00024 gram of copper nitrate and 9.52 grams of ammonium dimolybdates (molybdenum oxides containing 84 % 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 catalyst, are designated as SL-2.
The appreciation condition of catalyst is with embodiment 1, and evaluation result is as shown in table 1.
[embodiment 3]
The sesbania powder of the Alumina gel of 364 grams (aluminium oxide containing 25 % by weight) and 1 gram is mixed and puts into mixer, stir after 12 minutes and add 1.25 grams of ammonium metatungstates (tungsten oxides containing 80 % by weight), 0.0003 gram of ferric nitrate, 0.0001 gram of potassium oxide, 0.00024 gram of copper nitrate and 9.52 grams of ammonium dimolybdates (molybdenum oxides containing 84 % 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 catalyst, are designated as SL-3.
The appreciation condition of catalyst is with embodiment 1, and evaluation result is as shown in table 1.
[embodiment 4]
The sesbania powder of the Alumina gel of 360 grams (aluminium oxide containing 25 % by weight) and 1 gram is mixed and puts into mixer, stir after 12 minutes and add 2.5 grams of ammonium metatungstates (tungsten oxides containing 80 % by weight), 0.0003 gram of ferric nitrate, 0.0001 gram of potassium oxide, 0.00024 gram of copper nitrate and 9.52 grams of ammonium dimolybdates (molybdenum oxides containing 84 % 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 catalyst, are designated as SL-4.
The appreciation condition of catalyst is with embodiment 1, and evaluation result is as shown in table 1.
[embodiment 5]
The sesbania powder of the Alumina gel of 368 grams (aluminium oxide containing 25 % by weight) and 1 gram is mixed and puts into mixer, stir after 12 minutes and add 0.00013 gram of ammonium metatungstate (tungsten oxides containing 80 % by weight), 0.003 gram of ferric nitrate, 0.0001 gram of potassium oxide, 0.00024 gram of copper nitrate and 9.52 grams of ammonium dimolybdates (molybdenum oxides containing 84 % 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 catalyst, are designated as SL-5.
The appreciation condition of catalyst is with embodiment 1, and evaluation result is as shown in table 1.
[embodiment 6]
The sesbania powder of the Alumina gel of 366 grams (aluminium oxide containing 25 % by weight) and 1 gram is mixed and puts into mixer, stir after 12 minutes and add 0.00013 gram of ammonium metatungstate (tungsten oxides containing 80 % by weight), 1.5 grams of ferric nitrates, 0.0001 gram of potassium oxide, 0.00024 gram of copper nitrate and 9.52 grams of ammonium dimolybdates (molybdenum oxides containing 84 % 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 catalyst, are designated as SL-6.
The appreciation condition of catalyst is with embodiment 1, and evaluation result is as shown in table 1.
[embodiment 7]
The sesbania powder of the Alumina gel of 364 grams (aluminium oxide containing 25 % by weight) and 1 gram is mixed and puts into mixer, stir after 12 minutes and add 0.00013 gram of ammonium metatungstate (tungsten oxides containing 80 % by weight), 3.025 grams of ferric nitrates, 0.0001 gram of potassium oxide, 0.00024 gram of copper nitrate and 9.52 grams of ammonium dimolybdates (molybdenum oxides containing 84 % 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 catalyst, are designated as SL-7.
The appreciation condition of catalyst is with embodiment 1, and evaluation result is as shown in table 1.
[embodiment 8]
The sesbania powder of the Alumina gel of 368 grams (aluminium oxide containing 25 % by weight) and 1 gram is mixed and puts into mixer, stir after 12 minutes and add 0.00013 gram of ammonium metatungstate (tungsten oxides containing 80 % by weight), 0.0003 gram of ferric nitrate, 0.001 gram of potassium oxide, 0.00024 gram of copper nitrate and 9.52 grams of ammonium dimolybdates (molybdenum oxides containing 84 % 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 catalyst, are designated as SL-8.
The appreciation condition of catalyst is with embodiment 1, and evaluation result is as shown in table 1.
[embodiment 9]
The sesbania powder of the Alumina gel of 366 grams (aluminium oxide containing 25 % by weight) and 1 gram is mixed and puts into mixer, stir after 12 minutes and add 0.00013 gram of ammonium metatungstate (tungsten oxides containing 80 % by weight), 0.0003 gram of ferric nitrate, 0.5 gram of potassium oxide, 0.00024 gram of copper nitrate and 9.52 grams of ammonium dimolybdates (molybdenum oxides containing 84 % 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 catalyst, are designated as SL-9.
The appreciation condition of catalyst is with embodiment 1, and evaluation result is as shown in table 1.
[embodiment 10]
The sesbania powder of the Alumina gel of 364 grams (aluminium oxide containing 25 % by weight) and 1 gram is mixed and puts into mixer, stir after 12 minutes and add 0.00013 gram of ammonium metatungstate (tungsten oxides containing 80 % by weight), 0.0003 gram of ferric nitrate, 1 gram of potassium oxide, 0.00024 gram of copper nitrate and 9.52 grams of ammonium dimolybdates (molybdenum oxides containing 84 % 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 catalyst, are designated as SL-10.
The appreciation condition of catalyst is with embodiment 1, and evaluation result is as shown in table 1.
[embodiment 11]
The sesbania powder of the Alumina gel of 368 grams (aluminium oxide containing 25 % by weight) and 1 gram is mixed and puts into mixer, stir after 12 minutes and add 0.00013 gram of ammonium metatungstate (tungsten oxides containing 80 % by weight), 0.0003 gram of ferric nitrate, 0.0001 gram of potassium oxide, 0.0024 gram of copper nitrate and 9.52 grams of ammonium dimolybdates (molybdenum oxides containing 84 % 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 catalyst, are designated as SL-11.
The appreciation condition of catalyst is with embodiment 1, and evaluation result is as shown in table 1.
[embodiment 12]
The sesbania powder of the Alumina gel of 366 grams (aluminium oxide containing 25 % by weight) and 1 gram is mixed and puts into mixer, stir after 12 minutes and add 0.00013 gram of ammonium metatungstate (tungsten oxides containing 80 % by weight), 0.0003 gram of ferric nitrate, 0.0001 gram of potassium oxide, 1.175 grams of copper nitrates and 9.52 grams of ammonium dimolybdates (molybdenum oxides containing 84 % 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 catalyst, are designated as SL-12.
The appreciation condition of catalyst is with embodiment 1, and evaluation result is as shown in table 1.
[embodiment 13]
The sesbania powder of the Alumina gel of 364 grams (aluminium oxide containing 25 % by weight) and 1 gram is mixed and puts into mixer, stir after 12 minutes and add 0.00013 gram of ammonium metatungstate (tungsten oxides containing 80 % by weight), 0.0003 gram of ferric nitrate, 0.0001 gram of potassium oxide, 2.35 grams of copper nitrates and 9.52 grams of ammonium dimolybdates (molybdenum oxides containing 84 % 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 catalyst, are designated as SL-13.
The appreciation condition of catalyst is with embodiment 1, and evaluation result is as shown in table 1.
[embodiment 14]
The sesbania powder of the Alumina gel of 368 grams (aluminium oxide containing 25 % by weight) and 1 gram is mixed and puts into mixer, stir after 12 minutes and add 0.00013 gram of ammonium metatungstate (tungsten oxides containing 80 % by weight), 0.0003 gram of ferric nitrate, 0.0001 gram of potassium oxide, 0.01 gram of magnesia, 0.00024 gram of copper nitrate and 9.52 grams of ammonium dimolybdates (molybdenum oxides containing 84 % 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, 550 DEG C of roastings, 4 hours obtained catalyst under air atmosphere, be designated as SL-14.
The appreciation condition of catalyst is with embodiment 1, and evaluation result is as shown in table 1.
[embodiment 15]
The sesbania powder of the Alumina gel of 364 grams (aluminium oxide containing 25 % by weight) and 1 gram is mixed and puts into mixer, stir after 12 minutes and add 0.00013 gram of ammonium metatungstate (tungsten oxides containing 80 % by weight), 0.0003 gram of ferric nitrate, 0.0001 gram of potassium oxide, 1 gram of magnesia, 0.00024 gram of copper nitrate and 9.52 grams of ammonium dimolybdates (molybdenum oxides containing 84 % 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, 550 DEG C of roastings, 4 hours obtained catalyst under air atmosphere, be designated as SL-15.
The appreciation condition of catalyst is with embodiment 1, and evaluation result is as shown in table 1.
[embodiment 16]
The sesbania powder of the Alumina gel of 348 grams (aluminium oxide containing 25 % by weight) and 1 gram is mixed and puts into mixer, stir after 12 minutes and add 0.00013 gram of ammonium metatungstate (tungsten oxides containing 80 % by weight), 0.0003 gram of ferric nitrate, 0.0001 gram of potassium oxide, 5 grams of magnesia, 0.00024 gram of copper nitrate and 9.52 grams of ammonium dimolybdates (molybdenum oxides containing 84 % 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, 550 DEG C of roastings, 4 hours obtained catalyst under air atmosphere, be designated as SL-16.
The appreciation condition of catalyst is with embodiment 1, and evaluation result is as shown in table 1.
[embodiment 17]
The sesbania powder of the Alumina gel of 328 grams (aluminium oxide containing 25 % by weight) and 1 gram is mixed and puts into mixer, stir after 12 minutes and add 0.00013 gram of ammonium metatungstate (tungsten oxides containing 80 % by weight), 0.0003 gram of ferric nitrate, 0.0001 gram of potassium oxide, 10 grams of magnesia, 0.00024 gram of copper nitrate and 9.52 grams of ammonium dimolybdates (molybdenum oxides containing 84 % 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, 550 DEG C of roastings, 4 hours obtained catalyst under air atmosphere, be designated as SL-17.
The appreciation condition of catalyst is with embodiment 1, and evaluation result is as shown in table 1.
[embodiment 18]
The sesbania powder of the Alumina gel of 308 grams (aluminium oxide containing 25 % by weight) and 1 gram is mixed and puts into mixer, stir after 12 minutes and add 0.00013 gram of ammonium metatungstate (tungsten oxides containing 80 % by weight), 0.0003 gram of ferric nitrate, 0.0001 gram of potassium oxide, 15 grams of magnesia, 0.00024 gram of copper nitrate and 9.52 grams of ammonium dimolybdates (molybdenum oxides containing 84 % 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, 550 DEG C of roastings, 4 hours obtained catalyst under air atmosphere, be designated as SL-18.
The appreciation condition of catalyst is with embodiment 1, and evaluation result is as shown in table 1.
[embodiment 19]
The sesbania powder of the Alumina gel of 368 grams (aluminium oxide containing 25 % by weight) and 1 gram is mixed and puts into mixer, stir after 12 minutes and add 0.0013 gram of ammonium metatungstate (tungsten oxides containing 80 % by weight), 0.003 gram of ferric nitrate, 0.001 gram of potassium oxide, 0.01 gram of magnesia, 0.0024 gram of copper nitrate and 9.52 grams of ammonium dimolybdates (molybdenum oxides containing 84 % 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, 550 DEG C of roastings, 4 hours obtained catalyst under air atmosphere, be designated as SL-19.
The appreciation condition of catalyst is with embodiment 1, and evaluation result is as shown in table 1.
[embodiment 20]
The sesbania powder of the Alumina gel of 358 grams (aluminium oxide containing 25 % by weight) and 1 gram is mixed and puts into mixer, stir after 12 minutes and add 1.25 grams of ammonium metatungstates (tungsten oxides containing 80 % by weight), 1.5 grams of ferric nitrates, 0.5 gram of potassium oxide, 1.175 grams of copper nitrates and 9.52 grams of ammonium dimolybdates (molybdenum oxides containing 84 % 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 catalyst, are designated as SL-20.
The appreciation condition of catalyst is with embodiment 1, and evaluation result is as shown in table 1.
[embodiment 21]
The sesbania powder of the Alumina gel of 348 grams (aluminium oxide containing 25 % by weight) and 1 gram is mixed and puts into mixer, stir after 12 minutes and add 2.5 grams of ammonium metatungstates (tungsten oxides containing 80 % by weight), 3.025 grams of ferric nitrates, 1 gram of potassium oxide, 2.35 grams of copper nitrates and 9.52 grams of ammonium dimolybdates (molybdenum oxides containing 84 % 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 catalyst, are designated as SL-21.
The appreciation condition of catalyst is with embodiment 1, and evaluation result is as shown in table 1.
[embodiment 22]
The sesbania powder of the Alumina gel of 376 grams (aluminium oxide containing 25 % by weight) and 1 gram is mixed and puts into mixer, stir after 12 minutes and add 1.25 grams of ammonium metatungstates (tungsten oxides containing 80 % by weight), 3.025 grams of ferric nitrates, 1 gram of sodium oxide molybdena, 1 gram of calcium oxide, 2.35 grams of copper nitrates and 1.19 grams of ammonium dimolybdates (molybdenum oxides containing 84 % 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 catalyst, are designated as SL-22.
The appreciation condition of catalyst is with embodiment 1, and evaluation result is as shown in table 1.
[embodiment 23]
The sesbania powder of the Alumina gel of 240 grams (aluminium oxide containing 25 % by weight) and 1 gram is mixed and puts into mixer, stir after 12 minutes and add 2.5 grams of ammonium metatungstates (tungsten oxides containing 80 % by weight), 3.025 grams of ferric nitrates, 1 gram of rubidium oxide, 5 grams of barium monoxide, 2.35 grams of copper nitrates and 35.7 grams of ammonium dimolybdates (molybdenum oxides containing 84 % 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 catalyst, are designated as SL-23.
The evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, take butylene as raw material, and calculate by mass fraction, raw material is the 1-butylene of 50% and the 2-butylene of 50%.Reaction is 400 DEG C in temperature, and pressure is 3Mpa, and the weight space velocity of butylene is 10 hours
-1condition under evaluate, evaluation result is as shown in table 1.
[embodiment 24]
The sesbania powder of the Alumina gel of 300 grams (aluminium oxide containing 25 % by weight) and 1 gram is mixed and puts into mixer, stir after 12 minutes and add 1.25 grams of ammonium metatungstates (tungsten oxides containing 80 % by weight), 3.025 grams of ferric nitrates, 1 gram of rubidium oxide, 1 gram of strontium oxide strontia, 2.35 grams of copper nitrates and 23.8 grams of ammonium dimolybdates (molybdenum oxides containing 84 % 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 catalyst, are designated as SL-24.
The evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, take butylene as raw material, and calculate by mass fraction, raw material is the 1-butylene of 50% and the 2-butylene of 50%.Reaction is 200 DEG C in temperature, and pressure is normal pressure, and the weight space velocity of butylene is 0.1 hour
-1condition under evaluate, evaluation result is as shown in table 1.
[embodiment 25]
The sesbania powder of the Alumina gel of 348 grams (aluminium oxide containing 25 % by weight) and 3 grams is mixed and puts into mixer, stir after 20 minutes and add 1.25 grams of ammonium metatungstates (tungsten oxides containing 80 % by weight), 3.025 grams of ferric nitrates, 1 gram of potassium oxide, 1 gram of magnesia, 2.35 grams of copper nitrates and 9.52 grams of ammonium dimolybdates (molybdenum oxides containing 84 % by weight), 300 grams of deionized waters are added after stirring 5 minutes again, mediate 3 hours, after extruded moulding at 120 DEG C dry 3 hours, under air atmosphere, 600 DEG C of roastings, 3 hours obtained catalyst, are designated as SL-25.
The evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, and calculate by mass fraction, raw material is the 2-butylene of 99.9% and the ethene of 99.9%.Reaction is 200 DEG C in temperature, and pressure is 4MPa, the mol ratio of ethene and butylene be 6 and the weight space velocity of 2-butylene be 20 hours
-1condition under evaluate, evaluation result is as shown in table 1.
[embodiment 26]
The sesbania powder of the Alumina gel of 348 grams (aluminium oxide containing 25 % by weight) and 5 grams is mixed and puts into mixer, stir after 20 minutes and add 1.25 grams of ammonium metatungstates (tungsten oxides containing 80 % by weight), 3.025 gram ferric nitrate, 1 gram of potassium oxide, 1 gram of magnesia, 2.35 gram copper nitrate, 0.2 gram of nickel nitrate and 9.52 grams of ammonium dimolybdates (molybdenum oxides containing 84 % by weight), 200 grams of deionized waters are added after stirring 5 minutes again, mediate 3 hours, after extruded moulding at 110 DEG C dry 5 hours, 580 DEG C of roastings, 4 hours obtained catalyst under air atmosphere, be designated as SL-26.
The evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, and calculate by mass fraction, raw material is the 2-butylene of 99.9% and the ethene of 99.9%.Reaction is 400 DEG C in temperature, and pressure is 1MPa, the mol ratio of ethene and butylene be 1 and the weight space velocity of 2-butylene be 0.1 hour
-1condition under evaluate, evaluation result is as shown in table 1.
[embodiment 27]
The sesbania powder of the Alumina gel of 368 grams (aluminium oxide containing 25 % by weight) and 1 gram is mixed and puts into mixer, stir after 12 minutes and add 0.00013 gram of ammonium metatungstate (tungsten oxides containing 80 % by weight), 0.0003 gram of ferric nitrate, 0.0001 gram of potassium oxide, 0.00024 gram of copper nitrate, 0.21 gram of indium nitrate and 9.52 grams of ammonium dimolybdates (molybdenum oxides containing 84 % 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, 550 DEG C of roastings, 4 hours obtained catalyst under air atmosphere, be designated as SL-27.
The appreciation condition of catalyst is with embodiment 1, and evaluation result is as shown in table 1.
[embodiment 28]
The sesbania powder of the Alumina gel of 368 grams (aluminium oxide containing 25 % by weight) and 1 gram is mixed and puts into mixer, stir after 12 minutes and add 0.00013 gram of ammonium metatungstate (tungsten oxides containing 80 % by weight), 0.0003 gram of ferric nitrate, 0.0001 gram of potassium oxide, 0.00024 gram of copper nitrate, 2.17 grams of indium nitrates and 9.52 grams of ammonium dimolybdates (molybdenum oxides containing 84 % 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, 550 DEG C of roastings, 4 hours obtained catalyst under air atmosphere, be designated as SL-28.
The appreciation condition of catalyst is with embodiment 1, and evaluation result is as shown in table 1.
[embodiment 29]
The sesbania powder of the Alumina gel of 368 grams (aluminium oxide containing 25 % by weight) and 1 gram is mixed and puts into mixer, stir after 12 minutes and add 0.00013 gram of ammonium metatungstate (tungsten oxides containing 80 % by weight), 0.0003 gram of ferric nitrate, 0.0001 gram of potassium oxide, 0.01 gram of magnesia, 0.00024 gram of copper nitrate, 0.21 gram of indium nitrate and 9.52 grams of ammonium dimolybdates (molybdenum oxides containing 84 % 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, 550 DEG C of roastings, 4 hours obtained catalyst under air atmosphere, be designated as SL-29.
The appreciation condition of catalyst is with embodiment 1, and evaluation result is as shown in table 1.
[embodiment 30]
The sesbania powder of the Alumina gel of 368 grams (aluminium oxide containing 25 % by weight) and 1 gram is mixed and puts into mixer, stir after 12 minutes and add 0.00013 gram of ammonium metatungstate (tungsten oxides containing 80 % by weight), 0.0003 gram of ferric nitrate, 0.0001 gram of potassium oxide, 0.01 gram of magnesia, 0.00024 gram of copper nitrate, 2.17 grams of indium nitrates and 9.52 grams of ammonium dimolybdates (molybdenum oxides containing 84 % 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, 550 DEG C of roastings, 4 hours obtained catalyst under air atmosphere, be designated as SL-30.
The appreciation condition of catalyst is with embodiment 1, and evaluation result is as shown in table 1.
[embodiment 31 ~ 34]
Take SL-1 as evaluate catalysts, the evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, and with 2-butylene and ethene for raw material, calculate by mass fraction, raw material is the 2-butylene of 99.9% and the ethene of 99.9%.Reaction condition and evaluation result as shown in table 2.
[comparative example 1]
The sesbania powder of the Alumina gel of 368 grams (aluminium oxide containing 25 % by weight) and 1 gram is mixed and puts into mixer, stir after 12 minutes and add 0.0003 gram of ferric nitrate, 0.0001 gram of potassium oxide, 0.01 gram of magnesia, 0.00024 gram of copper nitrate and 9.52 grams of ammonium dimolybdates (molybdenum oxides containing 84 % 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 catalyst, are designated as BJL-1.
The appreciation condition of catalyst is with embodiment 1, and evaluation result is as shown in table 1.
[comparative example 2]
The sesbania powder of the Alumina gel of 368 grams (aluminium oxide containing 25 % by weight) and 1 gram is mixed and puts into mixer, stir after 12 minutes and add 0.00013 gram of ammonium metatungstate (tungsten oxides containing 80 % by weight), 0.0001 gram of potassium oxide, 0.01 gram of magnesia, 0.00024 gram of copper nitrate and 9.52 grams of ammonium dimolybdates (molybdenum oxides containing 84 % 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 catalyst, are designated as BJL-2.
The appreciation condition of catalyst is with embodiment 1, and evaluation result is as shown in table 1.
[comparative example 3]
The sesbania powder of the Alumina gel of 368 grams (aluminium oxide containing 25 % by weight) and 1 gram is mixed and puts into mixer, stir after 12 minutes and add 0.00013 gram of ammonium metatungstate (tungsten oxides containing 80 % by weight), 0.0003 gram of ferric nitrate, 0.01 gram of magnesia, 0.00024 gram of copper nitrate and 9.52 grams of ammonium dimolybdates (molybdenum oxides containing 84 % 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 catalyst, are designated as BJL-3.
The appreciation condition of catalyst is with embodiment 1, and evaluation result is as shown in table 1.
[comparative example 4]
The sesbania powder of the Alumina gel of 368 grams (aluminium oxide containing 25 % by weight) and 1 gram is mixed and puts into mixer, stir after 12 minutes and add 0.00013 gram of ammonium metatungstate (tungsten oxides containing 80 % by weight), 0.0003 gram of ferric nitrate, 0.0001 gram of potassium oxide, 0.01 gram of magnesia and 9.52 grams of ammonium dimolybdates (molybdenum oxides containing 84 % 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 catalyst, are designated as BJL-4.
The appreciation condition of catalyst is with embodiment 1, and evaluation result is as shown in table 1.
[comparative example 5]
The sesbania powder of the Alumina gel of 368 grams (aluminium oxide containing 25 % by weight) and 1 gram is mixed and puts into mixer, stir after 12 minutes and add 0.00013 gram of ammonium metatungstate (tungsten oxides containing 80 % by weight), 0.0003 gram of ferric nitrate, 0.0001 gram of potassium oxide and 9.52 grams of ammonium dimolybdates (molybdenum oxides containing 84 % 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 catalyst, are designated as BJL-5.
The appreciation condition of catalyst is with embodiment 1, and evaluation result is as shown in table 1.
Table 1
Note: SL-27 and SL-29 is containing 0.1 part of indium oxide; SL-28 and SL-30 is containing 1 part of indium oxide
Table 2
Claims (10)
1. a disproportionation catalyst, with weight parts, comprises following component:
A) 1 ~ 30 part of molybdenum element or its oxide;
B) 0.0001 ~ 2 part of W elements or its oxide;
C) 0.0001 ~ 1 part of ferro element or its oxide;
D) 0.0001 ~ 1 part of alkali metal or its oxide;
E) 0 ~ 15 part of alkali earth metal or its oxide;
F) 0.0001 ~ 1 part of copper or its oxide;
G) 50 ~ 98 parts of aluminium oxide.
2. disproportionation catalyst according to claim 1, is characterized in that the content of W elements or its oxide is 0.001 ~ 1 part.
3. disproportionation catalyst according to claim 1, is characterized in that the content of ferro element or its oxide is 0.001 ~ 0.5 part.
4. disproportionation catalyst according to claim 1, is characterized in that the content of alkali metal or its oxide is 0.001 ~ 0.5 part.
5. disproportionation catalyst according to claim 1, is characterized in that the content of copper or its oxide is 0.001 ~ 0.5 part.
6. disproportionation catalyst according to claim 1, is characterized in that the content of aluminium oxide is 60 ~ 80 parts.
7. disproportionation catalyst according to claim 1, is characterized in that the content of alkali earth metal or its oxide is 0.01 ~ 10 part.
8. disproportionation catalyst according to claim 7, is characterized in that the content of alkali earth metal or its oxide is 1 ~ 5 part.
9. the disproportionation catalyst described in any one of claim 1 ~ 8 is used for ethene and preparing propylene by butene disproportionation reaction, with butylene and ethene for raw material, reaction temperature 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.
10. the disproportionation catalyst described in any one of claim 1 ~ 8 being used for preparing propylene by butene disproportionation reaction, take butylene as raw material, reaction temperature 200 ~ 400 DEG C, and reaction pressure 0 ~ 3Mpa, butylene mass space velocity 0.1 ~ 10h
-1condition under reaction generate propylene.
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