CN104437525B - Disproportionation catalyst - Google Patents
Disproportionation catalyst Download PDFInfo
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- CN104437525B CN104437525B CN201310435396.8A CN201310435396A CN104437525B CN 104437525 B CN104437525 B CN 104437525B CN 201310435396 A CN201310435396 A CN 201310435396A CN 104437525 B CN104437525 B CN 104437525B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The present invention relates to a kind of disproportionation catalyst, mainly solve the active low problem of catalyst disproportionation present in conventional art.The present invention is by using a kind of disproportionation catalyst, in terms of parts by weight, including following components: a) 1～30 part of molybdenum element or its oxide；B) 0.0001～2 part of wolfram element or its oxide；C) 0.0001～1 part of ferrum 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) technical scheme of 50～98 parts of aluminium oxidies, preferably solves this problem, can be used for the commercial production of olefin dismutation reaction.
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 ethylene coproduction and refinery's Propylene recovery method are obviously difficult to meet growing propylene demand, use alkene
Hydrocarbon dismutation technology can digest C while not reducing naphtha pyrolysis severity4Fraction, and can propylene enhancing, thus alkene
It is disproportionated the research and development of propylene technology processed not only to improving the yield of propylene, simultaneously to promoting low value-added C4Fraction comprehensive
Utilizing and all have great significance, butylene disproportionation the most involved in the present invention produces propylene and makes a kind of up-and-coming technique.
Olefin dismutation reaction is also called olefinic double bonds displacement reaction, is that a kind of alkene found the sixties in 20th century converts now
As, olefin dismutation reaction just becomes the class significant process that alkene converts since then, utilizes the olefin dismutation reaction can by some relatively
It is converted into the olefin product that multiple added value is higher for olefin feedstock cheap, abundant.
CN 102811986 A describes to convert under the condition being effective to olefin(e) disproportionation and catalyst and comprises butylene, example
Method such as the hydrocarbon feed of all or most of single C4 olefin isomer such as 1-butylene.Olefin product, particularly propylene are in catalysis
Being formed in the presence of agent, described catalyst comprises solid carrier and the tungsten hydride being bonded to present in carrier on aluminium oxide.This
Cause that there is the expection of the olefin product formation of other carbon number regardless of olefin dismutation reaction mechanism and occur.
US6271430 proposes a kind of technique obtaining propylene and amylene by butene-1 and butene-2 disproportionation.Should
Technique uses tank reactor, and catalyst is Re2O7/Al2O3, reaction temperature is 0～150 DEG C, and reaction pressure is 2～200bar.
WO00014038 describes a kind of method of preparing propylene by butene disproportionation.Raw material butylene be butene-1, butene-2 or its
Mixture, catalyst is WO3/SiO2, common reaction temperature is 500-550 DEG C, and reaction pressure is 1atm.
US513891 reports the preparation method of olefin disproportionation catalyst, and its catalyst consists of B2O3-Re2O7/Al2O3/
SiO2, it is greatly improved using amorphous silica-alumina as catalyst carrier, the activity of olefin dismutation reaction.
EP0152112 reports and modifies WO with Ti3/SiO2Catalyst carrier；US5905055 reports and modifies WO with Nb3/
SiO2 catalyst carrier, olefin(e) disproportionation activity all obtains raising.
CN 201110032235.5 discloses a kind of has the olefin(e) disproportionation of mesoporous and macropore combined porous structure with urging simultaneously
Agent, including selected from rhenium, molybdenum, tungsten oxide at least one catalytically-active metals and catalyst carrier, described catalyst
Carrier is the aluminium oxide with mesopore/macropore combined pore passage structure.Described catalyst carrier passes through aluminum contained compound and mesoporous mould
Plate agent and macroporous granules template mixing, roasting and prepare.Above-mentioned catalyst solves low-carbon alkene in conventional art
Disproportionation exists catalyst activity is low, inactivate problem faster.Also disclose the preparation method of described olefin(e) disproportionation catalyst.
CN88107893.X discloses the compositions of the catalyst system being adapted as olefin(e) disproportionation, and it contains and is loaded in oxidation
Molybdenum oxide on aluminum, is the method that catalyst carries out being disproportionated by said composition.
CN95196917.X discloses the aluminium silicate carrier for disproportionation reaction catalyzer, it is provided that be supported on aluminium silicate
Rhenium oxide, the need to, boron oxide compound, tungsten oxide, molybdenum oxide or barium oxide can be added, it be used for alkene and official
The dismutation reaction of the dismutation reaction of alkene, particularly carboxylate can be changed, and carrier material carries out hydrothermal treatment consists.
CN96108099.X discloses the method using discrimination method that C4 olefine fraction is changed into polyisobutylene and propylene.Institute
The method stated includes three steps in succession: 1) selective hydration alkadienes, and 1-butylene is isomerizated into 2-butylene simultaneously, 2) and isobutyl
Alkene is polymerized, and potentially includes preextraction isobutene., 3) 2-butylene is disproportionated with ethylene.After C 5 fraction hydrogen isomerization, partly or entirely
C 4 fraction may be from the dismutation reaction of C5 olefine fraction and ethylene.Application in terms of steamed cracking C4 and C 5 fraction.
CN97193071.6 relates to a kind of method preparing alpha-olefin product, and the method includes making a kind of internal olefin non-flat
It is disproportionated under the conditions of weighing apparatus.Thus generate a kind of more lower boiling internal olefin product that is removed and a kind of higher when being formed
Middle chain internal olefin product, makes the middle chain internal olefin product of higher and contact ethylene subsequently and reacts, generating molecular weight ranges
Narrow alpha-olefin product.
CN97121426.3 discloses the method preparing propylene and 1-butylene and the method preparing propylene, is included in disproportionation
Make in the presence of catalyst 2-amylene and ethylene reaction, above-mentioned catalyst contain at least one periodic table of elements the VIth b, VII b or
The compound of VIII group 4 transition metal, including: a) in the presence of disproportionation catalyst, make 1-butylene react with 2-butylene, generate
Propylene and 2-amylene, b) then separate propylene and the 2-amylene of generation, c) in the presence of disproportionation catalyst, make 2-amylene and second
Alkene reacts, and generates propylene and 1-butylene, d) separates the propylene generated and 1-butylene, e) sent back to by the 1-butylene of generation
In step a).
CN02807165.4 discloses by butene-1, by the disproportionation of butene-1 and hexene-3 isomery wherein produced
Turn to hexene-1, produce ethylene and hexene-1.Initial feed is mixed butene stream, and wherein butene-1 is isomerized to butene-2, and
Therefrom isolating isobutene., then butene-2 is isomerized to butene-1, and this butene-1 is i.e. as the charging of disproportionation.
CN02137461.9 relates to a kind of fixed bde catalyst for producing propene from butylene by disproportion.Mainly solve literary composition in the past
There is product in offering to separate difficulty, catalyst price height, need consumption of ethylene or reaction temperature high, the problem that energy consumption is high.The present invention
By using with silicon dioxide as carrier, load the fixed bde catalyst of tungsten oxide, and specific surface area of catalyst is 270～550
Rice2/ gram technical scheme preferably solve this problem, can be used in the commercial production of preparing propylene by butene disproportionation.
When for the reaction of ethylene and preparing propylene by butene disproportionation, all there is catalyst activity in the catalyst in document above
Low problem.
Summary of the invention
The technical problem to be solved is the active low problem of catalyst disproportionation present in prior art, it is provided that
A kind of new disproportionation catalyst.This catalyst, when olefin dismutation reaction, has the advantage that catalyst disproportionation activity is high.
For solving above-mentioned technical problem, the technical solution used in the present invention is as follows: a kind of disproportionation catalyst, with parts by weight
Meter, including following components: a) 1～30 part of molybdenum element or its oxide；B) 0.0001～2 part of wolfram element or its oxide；c)
0.0001～1 part of ferrum element or its oxide；D) 0.0001～1 part of alkali metal or its oxide；E) 0～15 part of alkaline earth gold
Belong to element or its oxide；F) 0.0001～1 part of copper or its oxide；G) 50～98 parts of aluminium oxidies.
In technique scheme, in terms of parts by weight, the content of wolfram element or its oxide is 0.001～1 part；Ferrum element
Or the preferred scope of its oxide content is 0.001～0.5 part；The preferred scope of alkali metal or its oxide content is
0.001～0.5 part；The preferred version of alkali metal is potassium；The preferred scope of copper or its oxide content be 0.001～
0.5 part；The preferred scope of alumina content is 60～80 parts；The preferred scope of alkali earth metal or its oxide content is
0.01～10 part, the most preferred range of alkali earth metal or its oxide content is 1～5 part；Alkali earth metal preferred
Scheme 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
Ethylene and preparing propylene by butene disproportionation reaction, with butylene and ethylene as raw material, reaction temperature 200～400 DEG C, reaction pressure 1～
4Mpa, butylene mass space velocity 0.1～20h-1, the mol ratio of ethylene and butylene is reaction generation propylene under conditions of 1～6；By institute
The disproportionation catalyst stated reacts for preparing propylene by butene disproportionation, with butylene as raw material, in reaction temperature 200～400 DEG C, reaction pressure
Power 0～3Mpa, butylene mass space velocity 0.1～10h-1Under conditions of reaction generate propylene；Described disproportionation catalyst is used for 1-fourth
Alkene is disproportionated hexene processed and reacts, with 1-butylene as raw material, in reaction temperature 300～500 DEG C, reaction pressure 0～1Mpa, 1-butylene matter
Amount air speed 2～50h-1Reaction generate hexene；Described disproportionation catalyst is used for preparing tetramethylethylene through isobutene metathesis reaction,
With isobutene. as raw material, at reaction temperature 300～500 DEG C, reaction pressure 0～1Mpa, isobutene. mass space velocity 0.1～10h-1's
Under the conditions of reaction generate tetramethyl-ethylene, in technique scheme, in terms of parts by weight, catalyst also comprises the oxygen of 0.1～1 part
Change indium.
In the present invention, the preparation method of catalyst can use dipping, chemisorbed, chemical deposition, ion exchange, physics to mix
Prepared by the methods such as conjunction, be shaped catalyst by aspects such as extrusion, spin, tablettings.
The preparation method of catalyst in turn includes the following steps: 1) by corresponding for Mo, W, Fe and Cu metal institute salt or oxidation
Thing is soluble in water makes solution I；2) at least one corresponding salt or the oxide selected from alkali metal or alkaline-earth metal is joined
Solution I makes solution II；3) oxide at solution II addition aluminum obtains catalyst precarsor.
In above-mentioned preparation method, the oxide of aluminum is at least one in aluminium glue, Alumina gel, aluminium oxide；Gold in step 1)
The salt belonging to corresponding is at least one in nitrate, sulfate and ammonium salt.
The forming method of catalyst is as follows: put in blender by catalyst precarsor, and adds Ludox and field mountain valley with clumps of trees and bamboo powder, stirs
Mixing kneading and be allowed to Load Balanced, the product of mix homogeneously is put into extruded moulding in banded extruder, the shape of extruded moulding includes circle
Cylindricality, cloverleaf pattern, mesopore shape, Herba Erodii shape.
Preferably forming method is as follows: put into roller forming in roller-ball devices after adding Ludox in catalyst precarsor,
Roller forming obtains the spheric catalyst of a diameter of 2-10mm.
Preferred forming method is as follows: put into compression molding in tablet machine, compression molding by after catalyst precarsor film-making
Obtain shape and include cylinder, amorphous.
After shaping of catalyst through being dried, after roasting finished catalyst.In technique scheme, catalyst sintering temperature
Preferably scope is 500～600 DEG C, and the preferred scope 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 butylene and ethylene disproportionation
Reaction generates propylene.Reaction condition is as follows: in fixed bed reactors, with butylene and ethylene as raw material, in reaction temperature 200～
400 DEG C, reaction pressure 1～4Mpa, butylene mass space velocity 0.1～20h-1, the mol ratio of ethylene and butylene is 1～6, when butylene
When conversion ratio is less than 60%, it is believed that catalysqt deactivation, when ethylene and butylene disproportionation react propylene processed, evaluate catalyst activity
The conversion ratio of mainly butylene because the selectivity of target product propylene is more than 98% in Fan Ying, the conversion ratio height of butylene is
Showing that catalyst disproportionation activity is good, the yield of propylene is high.
In such scheme, butene feedstock can be the mixture of butene-1, butene-2 or butylene, or fills from steam cracking
The C-4-fraction put.
The present invention by using W, Fe, Cu, alkali and alkaline earth metal ions as the auxiliary agent of disproportionation catalyst, by W, Fe, Cu,
Interaction between alkali metal, alkaline-earth metal and main active component Mo, can be effectively improved the reactivity of disproportionation catalyst, with
Time activity being uniformly distributed in molecular sieve supported surface, be difficult to be covered by carbon deposit in course of reaction, urge it is thus possible to be effectively improved
In the life-span of agent, the synergism between each active component is obvious, only W, Fe, Cu, alkali metal, alkaline-earth metal and Mo this
Under conditions of a little active components all exist, catalyst just can have good disproportionation activity；When adding active component indium, catalysis
The disproportionation activity of agent is significantly increased again, and the conversion ratio of butylene can improve more than 4%.It is 300 DEG C in reaction temperature, reaction pressure
It is 3.5 for the mol ratio of 3MPa, ethylene and butylene and is 8 hours at the weight space velocity of butylene-1Space velocities under, by this
Bright described catalyst, for ethylene and the reaction of butylene propylene, under higher space velocities, remains to obtain good disproportionation
Activity, the conversion ratio of its butylene, more than 80%, contrasts MoO3/Al2O3The conversion ratio of its butylene of catalyst can improve more than 20%,
Achieve unexpected technique effect.
Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[embodiment 1]
The sesbania powder mix homogeneously of the Alumina gel of 368 grams (containing the aluminium oxide of 25 weight %) and 1 gram is put in blender,
Add after stirring 12 minutes 0.00013 gram of ammonium metatungstate (containing the tungsten oxide of 80 weight %), 0.0003 gram of ferric nitrate, 0.0001 gram
Potassium oxide, 0.00024 gram of copper nitrate and 9.52 grams of ammonium dimolybdates (containing the molybdenum oxide of 84 weight %), add after being stirred for 5 minutes
250 grams of deionized waters, mediate 2 hours, are dried 4 hours at 100 DEG C after extruded moulding, and under air atmosphere, 550 DEG C of roastings 4 are little
Time prepare catalyst, be designated as SL-1.
The evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, with 2-butylene and ethylene as raw material, by mass fraction
Calculating, raw material is 2-butylene and the ethylene of 99.9% of 99.9%.Reaction is to be 300 DEG C in temperature, and pressure is 3MPa, ethylene and butylene
Mol ratio be 3.5 and the weight space velocity of 2-butylene is 8 hours-1Under conditions of be evaluated, evaluation result is as shown in table 1.
[embodiment 2]
The sesbania powder mix homogeneously of the Alumina gel of 368 grams (containing the aluminium oxide of 25 weight %) and 1 gram is put in blender,
0.0013 gram of ammonium metatungstate (containing the tungsten oxide of 80 weight %), 0.0003 gram of ferric nitrate, 0.0001 gram of oxygen is added after stirring 12 minutes
Change potassium, 0.00024 gram of copper nitrate and 9.52 grams of ammonium dimolybdates (containing the molybdenum oxide of 84 weight %), after being stirred for 5 minutes, add 250
Gram deionized water, mediates 2 hours, is dried 4 hours at 100 DEG C after extruded moulding, 550 DEG C of roastings 4 hours under air atmosphere
Prepare catalyst, be 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 mix homogeneously of the Alumina gel of 364 grams (containing the aluminium oxide of 25 weight %) and 1 gram is put in blender,
1.25 grams of ammonium metatungstates (containing the tungsten oxide of 80 weight %), 0.0003 gram of ferric nitrate, 0.0001 gram of oxidation are added after stirring 12 minutes
Potassium, 0.00024 gram of copper nitrate and 9.52 grams of ammonium dimolybdates (containing the molybdenum oxide of 84 weight %), add 250 grams after being stirred for 5 minutes
Deionized water, mediates 2 hours, is dried 4 hours at 100 DEG C after extruded moulding, 4 hours systems of 550 DEG C of roastings under air atmosphere
Obtain catalyst, be 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 mix homogeneously of the Alumina gel of 360 grams (containing the aluminium oxide of 25 weight %) and 1 gram is put in blender,
2.5 grams of ammonium metatungstates (containing the tungsten oxide of 80 weight %), 0.0003 gram of ferric nitrate, 0.0001 gram of oxidation are added after stirring 12 minutes
Potassium, 0.00024 gram of copper nitrate and 9.52 grams of ammonium dimolybdates (containing the molybdenum oxide of 84 weight %), add 250 grams after being stirred for 5 minutes
Deionized water, mediates 2 hours, is dried 4 hours at 100 DEG C after extruded moulding, 4 hours systems of 550 DEG C of roastings under air atmosphere
Obtain catalyst, be 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 mix homogeneously of the Alumina gel of 368 grams (containing the aluminium oxide of 25 weight %) and 1 gram is put in blender,
0.00013 gram of ammonium metatungstate (containing the tungsten oxide of 80 weight %), 0.003 gram of ferric nitrate, 0.0001 gram of oxygen is added after stirring 12 minutes
Change potassium, 0.00024 gram of copper nitrate and 9.52 grams of ammonium dimolybdates (containing the molybdenum oxide of 84 weight %), after being stirred for 5 minutes, add 250
Gram deionized water, mediates 2 hours, is dried 4 hours at 100 DEG C after extruded moulding, 550 DEG C of roastings 4 hours under air atmosphere
Prepare catalyst, be 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 mix homogeneously of the Alumina gel of 366 grams (containing the aluminium oxide of 25 weight %) and 1 gram is put in blender,
0.00013 gram of ammonium metatungstate (containing the tungsten oxide of 80 weight %), 1.5 grams of ferric nitrates, 0.0001 gram of oxidation are added after stirring 12 minutes
Potassium, 0.00024 gram of copper nitrate and 9.52 grams of ammonium dimolybdates (containing the molybdenum oxide of 84 weight %), add 250 grams after being stirred for 5 minutes
Deionized water, mediates 2 hours, is dried 4 hours at 100 DEG C after extruded moulding, 4 hours systems of 550 DEG C of roastings under air atmosphere
Obtain catalyst, be 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 mix homogeneously of the Alumina gel of 364 grams (containing the aluminium oxide of 25 weight %) and 1 gram is put in blender,
0.00013 gram of ammonium metatungstate (containing the tungsten oxide of 80 weight %), 3.025 grams of ferric nitrates, 0.0001 gram of oxygen are added after stirring 12 minutes
Change potassium, 0.00024 gram of copper nitrate and 9.52 grams of ammonium dimolybdates (containing the molybdenum oxide of 84 weight %), after being stirred for 5 minutes, add 250
Gram deionized water, mediates 2 hours, is dried 4 hours at 100 DEG C after extruded moulding, 550 DEG C of roastings 4 hours under air atmosphere
Prepare catalyst, be 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 mix homogeneously of the Alumina gel of 368 grams (containing the aluminium oxide of 25 weight %) and 1 gram is put in blender,
0.00013 gram of ammonium metatungstate (containing the tungsten oxide of 80 weight %), 0.0003 gram of ferric nitrate, 0.001 gram of oxygen is added after stirring 12 minutes
Change potassium, 0.00024 gram of copper nitrate and 9.52 grams of ammonium dimolybdates (containing the molybdenum oxide of 84 weight %), after being stirred for 5 minutes, add 250
Gram deionized water, mediates 2 hours, is dried 4 hours at 100 DEG C after extruded moulding, 550 DEG C of roastings 4 hours under air atmosphere
Prepare catalyst, be 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 mix homogeneously of the Alumina gel of 366 grams (containing the aluminium oxide of 25 weight %) and 1 gram is put in blender,
0.00013 gram of ammonium metatungstate (containing the tungsten oxide of 80 weight %), 0.0003 gram of ferric nitrate, 0.5 gram of oxidation is added after stirring 12 minutes
Potassium, 0.00024 gram of copper nitrate and 9.52 grams of ammonium dimolybdates (containing the molybdenum oxide of 84 weight %), add 250 grams after being stirred for 5 minutes
Deionized water, mediates 2 hours, is dried 4 hours at 100 DEG C after extruded moulding, 4 hours systems of 550 DEG C of roastings under air atmosphere
Obtain catalyst, be 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 mix homogeneously of the Alumina gel of 364 grams (containing the aluminium oxide of 25 weight %) and 1 gram is put in blender,
0.00013 gram of ammonium metatungstate (containing the tungsten oxide of 80 weight %), 0.0003 gram of ferric nitrate, 1 gram of oxidation is added after stirring 12 minutes
Potassium, 0.00024 gram of copper nitrate and 9.52 grams of ammonium dimolybdates (containing the molybdenum oxide of 84 weight %), add 250 grams after being stirred for 5 minutes
Deionized water, mediates 2 hours, is dried 4 hours at 100 DEG C after extruded moulding, 4 hours systems of 550 DEG C of roastings under air atmosphere
Obtain catalyst, be 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 mix homogeneously of the Alumina gel of 368 grams (containing the aluminium oxide of 25 weight %) and 1 gram is put in blender,
Add after stirring 12 minutes 0.00013 gram of ammonium metatungstate (containing the tungsten oxide of 80 weight %), 0.0003 gram of ferric nitrate, 0.0001 gram
Potassium oxide, 0.0024 gram of copper nitrate and 9.52 grams of ammonium dimolybdates (containing the molybdenum oxide of 84 weight %), add 250 after being stirred for 5 minutes
Gram deionized water, mediates 2 hours, is dried 4 hours at 100 DEG C after extruded moulding, 550 DEG C of roastings 4 hours under air atmosphere
Prepare catalyst, be 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 mix homogeneously of the Alumina gel of 366 grams (containing the aluminium oxide of 25 weight %) and 1 gram is put in blender,
Add after stirring 12 minutes 0.00013 gram of ammonium metatungstate (containing the tungsten oxide of 80 weight %), 0.0003 gram of ferric nitrate, 0.0001 gram
Potassium oxide, 1.175 grams of copper nitrates and 9.52 grams of ammonium dimolybdates (containing the molybdenum oxide of 84 weight %), add 250 after being stirred for 5 minutes
Gram deionized water, mediates 2 hours, is dried 4 hours at 100 DEG C after extruded moulding, 550 DEG C of roastings 4 hours under air atmosphere
Prepare catalyst, be 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 mix homogeneously of the Alumina gel of 364 grams (containing the aluminium oxide of 25 weight %) and 1 gram is put in blender,
Add after stirring 12 minutes 0.00013 gram of ammonium metatungstate (containing the tungsten oxide of 80 weight %), 0.0003 gram of ferric nitrate, 0.0001 gram
Potassium oxide, 2.35 grams of copper nitrates and 9.52 grams of ammonium dimolybdates (containing the molybdenum oxide of 84 weight %), add 250 grams after being stirred for 5 minutes
Deionized water, mediates 2 hours, is dried 4 hours at 100 DEG C after extruded moulding, 4 hours systems of 550 DEG C of roastings under air atmosphere
Obtain catalyst, be 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 mix homogeneously of the Alumina gel of 368 grams (containing the aluminium oxide of 25 weight %) and 1 gram is put in blender,
Add after stirring 12 minutes 0.00013 gram of ammonium metatungstate (containing the tungsten oxide of 80 weight %), 0.0003 gram of ferric nitrate, 0.0001 gram
Potassium oxide, 0.01 gram of magnesium oxide, 0.00024 gram of copper nitrate and 9.52 grams of ammonium dimolybdates (containing the molybdenum oxide of 84 weight %), be stirred for
Add 250 grams of deionized waters after 5 minutes, mediates 2 hours, after extruded moulding at 100 DEG C dry 4 hours, under air atmosphere
4 hours prepared catalyst of 550 DEG C of roastings, are 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 mix homogeneously of the Alumina gel of 364 grams (containing the aluminium oxide of 25 weight %) and 1 gram is put in blender,
Add after stirring 12 minutes 0.00013 gram of ammonium metatungstate (containing the tungsten oxide of 80 weight %), 0.0003 gram of ferric nitrate, 0.0001 gram
Potassium oxide, 1 gram of magnesium oxide, 0.00024 gram of copper nitrate and 9.52 grams of ammonium dimolybdates (containing the molybdenum oxide of 84 weight %), be stirred for 5 points
Add 250 grams of deionized waters after clock, mediates 2 hours, after extruded moulding at 100 DEG C dry 4 hours, under air atmosphere 550
DEG C 4 hours prepared catalyst of roasting, are 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 mix homogeneously of the Alumina gel of 348 grams (containing the aluminium oxide of 25 weight %) and 1 gram is put in blender,
Add after stirring 12 minutes 0.00013 gram of ammonium metatungstate (containing the tungsten oxide of 80 weight %), 0.0003 gram of ferric nitrate, 0.0001 gram
Potassium oxide, 5 grams of magnesium oxide, 0.00024 gram of copper nitrate and 9.52 grams of ammonium dimolybdates (containing the molybdenum oxide of 84 weight %), be stirred for 5 points
Add 250 grams of deionized waters after clock, mediates 2 hours, after extruded moulding at 100 DEG C dry 4 hours, under air atmosphere 550
DEG C 4 hours prepared catalyst of roasting, are 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 mix homogeneously of the Alumina gel of 328 grams (containing the aluminium oxide of 25 weight %) and 1 gram is put in blender,
Add after stirring 12 minutes 0.00013 gram of ammonium metatungstate (containing the tungsten oxide of 80 weight %), 0.0003 gram of ferric nitrate, 0.0001 gram
Potassium oxide, 10 grams of magnesium oxide, 0.00024 gram of copper nitrate and 9.52 grams of ammonium dimolybdates (containing the molybdenum oxide of 84 weight %), be stirred for 5
Add 250 grams of deionized waters after minute, mediates 2 hours, after extruded moulding at 100 DEG C dry 4 hours, under air atmosphere
4 hours prepared catalyst of 550 DEG C of roastings, are 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 mix homogeneously of the Alumina gel of 308 grams (containing the aluminium oxide of 25 weight %) and 1 gram is put in blender,
Add after stirring 12 minutes 0.00013 gram of ammonium metatungstate (containing the tungsten oxide of 80 weight %), 0.0003 gram of ferric nitrate, 0.0001 gram
Potassium oxide, 15 grams of magnesium oxide, 0.00024 gram of copper nitrate and 9.52 grams of ammonium dimolybdates (containing the molybdenum oxide of 84 weight %), be stirred for 5
Add 250 grams of deionized waters after minute, mediates 2 hours, after extruded moulding at 100 DEG C dry 4 hours, under air atmosphere
4 hours prepared catalyst of 550 DEG C of roastings, are 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 mix homogeneously of the Alumina gel of 368 grams (containing the aluminium oxide of 25 weight %) and 1 gram is put in blender,
0.0013 gram of ammonium metatungstate (containing the tungsten oxide of 80 weight %), 0.003 gram of ferric nitrate, 0.001 gram of oxidation is added after stirring 12 minutes
Potassium, 0.01 gram of magnesium oxide, 0.0024 gram of copper nitrate and 9.52 grams of ammonium dimolybdates (containing the molybdenum oxide of 84 weight %), be stirred for 5 minutes
250 grams of deionized waters of rear addition, mediate 2 hours, are dried 4 hours at 100 DEG C after extruded moulding, under air atmosphere 550 DEG C
4 hours prepared catalyst of roasting, are 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 mix homogeneously of the Alumina gel of 358 grams (containing the aluminium oxide of 25 weight %) and 1 gram is put in blender,
Add after stirring 12 minutes 1.25 grams of ammonium metatungstates (containing the tungsten oxide of 80 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 (containing the molybdenum oxide of 84 weight %), add 250 grams of deionizations after being stirred for 5 minutes
Water, mediates 2 hours, is dried 4 hours at 100 DEG C after extruded moulding, and under air atmosphere, 550 DEG C of roastings prepare catalysis in 4 hours
Agent, is 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 mix homogeneously of the Alumina gel of 348 grams (containing the aluminium oxide of 25 weight %) and 1 gram is put in blender,
Add after stirring 12 minutes 2.5 grams of ammonium metatungstates (containing the tungsten oxide of 80 weight %), 3.025 grams of ferric nitrates, 1 gram of potassium oxide, 2.35
Gram copper nitrate and 9.52 grams of ammonium dimolybdates (containing the molybdenum oxide of 84 weight %), add 250 grams of deionized waters, pinch after being stirred for 5 minutes
Close 2 hours, be dried 4 hours at 100 DEG C after extruded moulding, 4 hours prepared catalyst of 550 DEG C of roastings under air atmosphere, note
For 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 mix homogeneously of the Alumina gel of 376 grams (containing the aluminium oxide of 25 weight %) and 1 gram is put in blender,
Add after stirring 12 minutes 1.25 grams of ammonium metatungstates (containing the tungsten oxide of 80 weight %), 3.025 grams of ferric nitrates, 1 gram of sodium oxide, 1 gram
Calcium oxide, 2.35 grams of copper nitrates and 1.19 grams of ammonium dimolybdates (containing the molybdenum oxide of 84 weight %), add 250 grams after being stirred for 5 minutes
Deionized water, mediates 2 hours, is dried 4 hours at 100 DEG C after extruded moulding, 4 hours systems of 550 DEG C of roastings under air atmosphere
Obtain catalyst, be 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 mix homogeneously of the Alumina gel of 240 grams (containing the aluminium oxide of 25 weight %) and 1 gram is put in blender,
Add after stirring 12 minutes 2.5 grams of ammonium metatungstates (containing the tungsten oxide of 80 weight %), 3.025 grams of ferric nitrates, 1 gram of rubidium oxide, 5 grams
Barium monoxide, 2.35 grams of copper nitrates and 35.7 grams of ammonium dimolybdates (containing the molybdenum oxide of 84 weight %), add 250 grams after being stirred for 5 minutes
Deionized water, mediates 2 hours, is dried 4 hours at 100 DEG C after extruded moulding, 4 hours systems of 550 DEG C of roastings under air atmosphere
Obtain catalyst, be designated as SL-23.
The evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, with butylene as raw material, calculates by mass fraction, and raw material is
The 1-butylene of 50% and the 2-butylene of 50%.Reaction is to be 400 DEG C in temperature, and pressure is 3Mpa, and the weight space velocity of butylene is 10 little
Time-1Under conditions of be evaluated, evaluation result is as shown in table 1.
[embodiment 24]
The sesbania powder mix homogeneously of the Alumina gel of 300 grams (containing the aluminium oxide of 25 weight %) and 1 gram is put in blender,
Add after stirring 12 minutes 1.25 grams of ammonium metatungstates (containing the tungsten oxide of 80 weight %), 3.025 grams of ferric nitrates, 1 gram of rubidium oxide, 1 gram
Strontium oxide, 2.35 grams of copper nitrates and 23.8 grams of ammonium dimolybdates (containing the molybdenum oxide of 84 weight %), add 250 grams after being stirred for 5 minutes
Deionized water, mediates 2 hours, is dried 4 hours at 100 DEG C after extruded moulding, 4 hours systems of 550 DEG C of roastings under air atmosphere
Obtain catalyst, be designated as SL-24.
The evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, with butylene as raw material, calculates by mass fraction, and raw material is
The 1-butylene of 50% and the 2-butylene of 50%.Reaction is to be 200 DEG C in temperature, and pressure is normal pressure, and the weight space velocity of butylene is 0.1 little
Time-1Under conditions of be evaluated, evaluation result is as shown in table 1.
[embodiment 25]
The sesbania powder mix homogeneously of the Alumina gel of 348 grams (containing the aluminium oxide of 25 weight %) and 3 grams is put in blender,
Add after stirring 20 minutes 1.25 grams of ammonium metatungstates (containing the tungsten oxide of 80 weight %), 3.025 grams of ferric nitrates, 1 gram of potassium oxide, 1 gram
Magnesium oxide, 2.35 grams of copper nitrates and 9.52 grams of ammonium dimolybdates (containing the molybdenum oxide of 84 weight %), add 300 grams after being stirred for 5 minutes
Deionized water, mediates 3 hours, is dried 3 hours at 120 DEG C after extruded moulding, 3 hours systems of 600 DEG C of roastings under air atmosphere
Obtain catalyst, be designated as SL-25.
The evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, calculates by mass fraction, and raw material is the 2-butylene of 99.9%
With 99.9% ethylene.Reaction is to be 200 DEG C in temperature, pressure be the mol ratio of 4MPa, ethylene and butylene be 6 and 2-butylene
Weight space velocity be 20 hours-1Under conditions of be evaluated, evaluation result is as shown in table 1.
[embodiment 26]
The sesbania powder mix homogeneously of the Alumina gel of 348 grams (containing the aluminium oxide of 25 weight %) and 5 grams is put in blender,
Add after stirring 20 minutes 1.25 grams of ammonium metatungstates (containing the tungsten oxide of 80 weight %), 3.025 grams of ferric nitrates, 1 gram of potassium oxide, 1 gram
Magnesium oxide, 2.35 grams of copper nitrates, 0.2 gram of nickel nitrate and 9.52 grams of ammonium dimolybdates (containing the molybdenum oxide of 84 weight %), be stirred for 5 points
Add 200 grams of deionized waters after clock, mediates 3 hours, after extruded moulding at 110 DEG C dry 5 hours, under air atmosphere 580
DEG C 4 hours prepared catalyst of roasting, are designated as SL-26.
The evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, calculates by mass fraction, and raw material is the 2-butylene of 99.9%
With 99.9% ethylene.Reaction is to be 400 DEG C in temperature, pressure be the mol ratio of 1MPa, ethylene and butylene be 1 and 2-butylene
Weight space velocity be 0.1 hour-1Under conditions of be evaluated, evaluation result is as shown in table 1.
[embodiment 27]
The sesbania powder mix homogeneously of the Alumina gel of 368 grams (containing the aluminium oxide of 25 weight %) and 1 gram is put in blender,
Add after stirring 12 minutes 0.00013 gram of ammonium metatungstate (containing the tungsten oxide of 80 weight %), 0.0003 gram of ferric nitrate, 0.0001 gram
Potassium oxide, 0.00024 gram of copper nitrate, 0.21 gram of indium nitrate and 9.52 grams of ammonium dimolybdates (containing the molybdenum oxide of 84 weight %), be stirred for
Add 250 grams of deionized waters after 5 minutes, mediates 2 hours, after extruded moulding at 100 DEG C dry 4 hours, under air atmosphere
4 hours prepared catalyst of 550 DEG C of roastings, are 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 mix homogeneously of the Alumina gel of 368 grams (containing the aluminium oxide of 25 weight %) and 1 gram is put in blender,
Add after stirring 12 minutes 0.00013 gram of ammonium metatungstate (containing the tungsten oxide of 80 weight %), 0.0003 gram of ferric nitrate, 0.0001 gram
Potassium oxide, 0.00024 gram of copper nitrate, 2.17 grams of indium nitrates and 9.52 grams of ammonium dimolybdates (containing the molybdenum oxide of 84 weight %), be stirred for
Add 250 grams of deionized waters after 5 minutes, mediates 2 hours, after extruded moulding at 100 DEG C dry 4 hours, under air atmosphere
4 hours prepared catalyst of 550 DEG C of roastings, are 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 mix homogeneously of the Alumina gel of 368 grams (containing the aluminium oxide of 25 weight %) and 1 gram is put in blender,
Add after stirring 12 minutes 0.00013 gram of ammonium metatungstate (containing the tungsten oxide of 80 weight %), 0.0003 gram of ferric nitrate, 0.0001 gram
Potassium oxide, 0.01 gram of magnesium oxide, 0.00024 gram of copper nitrate, 0.21 gram of indium nitrate and 9.52 grams of ammonium dimolybdates are (containing 84 weight %
Molybdenum oxide), add 250 grams of deionized waters after being stirred for 5 minutes, mediates 2 hours, dry 4 little at 100 DEG C after extruded moulding
Time, under air atmosphere, 4 hours prepared catalyst of 550 DEG C of roastings, are 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 mix homogeneously of the Alumina gel of 368 grams (containing the aluminium oxide of 25 weight %) and 1 gram is put in blender,
Add after stirring 12 minutes 0.00013 gram of ammonium metatungstate (containing the tungsten oxide of 80 weight %), 0.0003 gram of ferric nitrate, 0.0001 gram
Potassium oxide, 0.01 gram of magnesium oxide, 0.00024 gram of copper nitrate, 2.17 grams of indium nitrates and 9.52 grams of ammonium dimolybdates are (containing 84 weight %
Molybdenum oxide), add 250 grams of deionized waters after being stirred for 5 minutes, mediates 2 hours, dry 4 little at 100 DEG C after extruded moulding
Time, under air atmosphere, 4 hours prepared catalyst of 550 DEG C of roastings, are 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]
With SL-1 for evaluating catalyst, the evaluation of catalyst is carried out on olefin(e) disproportionation evaluating apparatus, with 2-butylene and second
Alkene is raw material, calculates by mass fraction, and raw material is 2-butylene and the ethylene of 99.9% of 99.9%.Reaction condition and evaluation result such as table
Shown in 2.
[comparative example 1]
The sesbania powder mix homogeneously of the Alumina gel of 368 grams (containing the aluminium oxide of 25 weight %) and 1 gram is put in blender,
After stirring 12 minutes add 0.0003 gram of ferric nitrate, 0.0001 gram of potassium oxide, 0.01 gram of magnesium oxide, 0.00024 gram of copper nitrate and
9.52 grams of ammonium dimolybdates (containing the molybdenum oxide of 84 weight %), add 250 grams of deionized waters after being stirred for 5 minutes, mediate 2 hours, squeeze
Being dried 4 hours at 100 DEG C after bar molding, under air atmosphere, 4 hours prepared catalyst of 550 DEG C of roastings, 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 mix homogeneously of the Alumina gel of 368 grams (containing the aluminium oxide of 25 weight %) and 1 gram is put in blender,
0.00013 gram of ammonium metatungstate (containing the tungsten oxide of 80 weight %), 0.0001 gram of potassium oxide, 0.01 gram of oxygen is added after stirring 12 minutes
Change magnesium, 0.00024 gram of copper nitrate and 9.52 grams of ammonium dimolybdates (containing the molybdenum oxide of 84 weight %), after being stirred for 5 minutes, add 250
Gram deionized water, mediates 2 hours, is dried 4 hours at 100 DEG C after extruded moulding, 550 DEG C of roastings 4 hours under air atmosphere
Prepare catalyst, be 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 mix homogeneously of the Alumina gel of 368 grams (containing the aluminium oxide of 25 weight %) and 1 gram is put in blender,
0.00013 gram of ammonium metatungstate (containing the tungsten oxide of 80 weight %), 0.0003 gram of ferric nitrate, 0.01 gram of oxygen is added after stirring 12 minutes
Change magnesium, 0.00024 gram of copper nitrate and 9.52 grams of ammonium dimolybdates (containing the molybdenum oxide of 84 weight %), after being stirred for 5 minutes, add 250
Gram deionized water, mediates 2 hours, is dried 4 hours at 100 DEG C after extruded moulding, 550 DEG C of roastings 4 hours under air atmosphere
Prepare catalyst, be 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 mix homogeneously of the Alumina gel of 368 grams (containing the aluminium oxide of 25 weight %) and 1 gram is put in blender,
Add after stirring 12 minutes 0.00013 gram of ammonium metatungstate (containing the tungsten oxide of 80 weight %), 0.0003 gram of ferric nitrate, 0.0001 gram
Potassium oxide, 0.01 gram of magnesium oxide and 9.52 grams of ammonium dimolybdates (containing the molybdenum oxide of 84 weight %), add 250 grams after being stirred for 5 minutes
Deionized water, mediates 2 hours, is dried 4 hours at 100 DEG C after extruded moulding, 4 hours systems of 550 DEG C of roastings under air atmosphere
Obtain catalyst, be 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 mix homogeneously of the Alumina gel of 368 grams (containing the aluminium oxide of 25 weight %) and 1 gram is put in blender,
Add after stirring 12 minutes 0.00013 gram of ammonium metatungstate (containing the tungsten oxide of 80 weight %), 0.0003 gram of ferric nitrate, 0.0001 gram
Potassium oxide and 9.52 grams of ammonium dimolybdates (containing the molybdenum oxide of 84 weight %), add 250 grams of deionized waters, mediate after being stirred for 5 minutes
2 hours, be dried 4 hours at 100 DEG C after extruded moulding, under air atmosphere, 4 hours prepared catalyst of 550 DEG C of roastings, 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 contains 0.1 part of Indium sesquioxide.；SL-28 and SL-30 contains 1 part of Indium sesquioxide.
Table 2
Claims (10)
1. a disproportionation catalyst, in terms of parts by weight, including following components:
A) 1～30 part of molybdenum element or its oxide；
B) 0.0001～2 part of wolfram element or its oxide；
C) 0.0001～1 part of ferrum 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 oxidies.
Disproportionation catalyst the most according to claim 1, it is characterised in that the content of wolfram element or its oxide be 0.001～
1 part.
Disproportionation catalyst the most according to claim 1, it is characterised in that the content of ferrum element or its oxide be 0.001～
0.5 part.
Disproportionation catalyst the most according to claim 1, it is characterised in that the content of alkali metal or its oxide is
0.001～0.5 part.
Disproportionation catalyst the most according to claim 1, it is characterised in that the content of copper or its oxide be 0.001～
0.5 part.
Disproportionation catalyst the most according to claim 1, it is characterised in that the content of aluminium oxide is 60～80 parts.
Disproportionation catalyst the most according to claim 1, it is characterised in that the content of alkali earth metal or its oxide is
0.01～10 part.
Disproportionation catalyst the most according to claim 7, it is characterised in that the content of alkali earth metal or its oxide is 1
～5 parts.
9. the disproportionation catalyst described in any one of claim 1～8 is used for ethylene and preparing propylene by butene disproportionation reaction, with butylene
It is raw material with ethylene, at reaction temperature 200～400 DEG C, reaction pressure 1～4Mpa, butylene mass space velocity 0.1～20h-1, ethylene
It is that reaction generates propylene under conditions of 1～6 with the mol ratio of butylene.
10. the disproportionation catalyst described in any one of claim 1～8 is used for preparing propylene by butene disproportionation reaction, is former with butylene
Material, at reaction temperature 200～400 DEG C, reaction pressure 0～3Mpa, butylene mass space velocity 0.1～10h-1Under conditions of reaction generate
Propylene.
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