CN104549295B - Olefin isomerization catalyst - Google Patents
Olefin isomerization catalyst Download PDFInfo
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- CN104549295B CN104549295B CN201310512549.4A CN201310512549A CN104549295B CN 104549295 B CN104549295 B CN 104549295B CN 201310512549 A CN201310512549 A CN 201310512549A CN 104549295 B CN104549295 B CN 104549295B
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Abstract
The present invention relates to a kind of olefin isomerization catalyst, the problem of mainly solving the activity low and poor stability of olefin isomerization catalyst present in conventional art.The present invention is by using a kind of olefin isomerization catalyst, in terms of parts by weight, including following components：A) 77~100 parts of magnesia；B) 0.1~20 part of calcium oxide；C) 0.01~2 part of iron oxide；D) technical scheme of 0~1 part of nickel oxide, preferably solves the problem, the industrial production available for olefin isomerization.
Description
Technical field
The present invention relates to a kind of isomerization catalyst, the particularly isomerization catalyst for olefin dismutation reaction.
Background technology
The transfer of position of double bond in double bond isomerization reaction, that is, olefin(e) compound, can relative worth is relatively low or
Superfluous alkene is converted into more valuable or relatively small number of isomers.
At present, market is just being incrementally increased to the demand of alhpa olefin, such as 1- butylene, 1- hexenes etc..The production of business alhpa olefin is led to
Often produced with substantial amounts of isomers.With industrial C4Exemplified by logistics, except containing 1- butylene, 2- butylene also accounts for significant proportion.
Can be 1- butylene by 2- butencs by double bond isomerization reaction.
On the other hand, in some techniques, double bond isomerization reaction changes the boiling point for making alkene, so as to be conducive to
The separation of product.One example, such as C4In the separation process of hydro carbons, 1- butylene (- 6 DEG C of boiling point) is such as converted into 2- butylene (suitable
4 DEG C of formula, trans 1 DEG C), isobutene (- 7 DEG C of boiling point) will be made from C4Separation in logistics becomes simple and easy to do.
In addition, double bond isomerizing catalyst usually combines to promote disproportionated reaction with disproportionation catalyst.In ethene and butylene
In disproportionation preparation of propene, the addition of isomerization catalyst except by 1- butencs for the 2- butylene needed for reaction, while can
Reactivity is set to be greatly improved.
Alkaline earth oxide, magnesia, calcium oxide etc., it is reported in olefines double bond isomerizing reaction with excellent
Catalytic performance, but in high reaction temperatures, this kind of catalyst surface can be because the reason such as coking be progressively lost its reaction and lived
Property.How the stability of this kind of isomerization catalyst is kept, and the requirement for making it more adapt to commercial Application, researcher makees in this regard
Many work.
United States Patent (USP) US6875901 points out, by using the higher magnesia of purity, butylenes double-bond isomerization can be made anti-
The stability answered is extended.When the sulfur content in magnesia from 2335ppm is down to 74ppm, iron content is down to from 692ppm
After 330ppm, the stability of catalyst extended to 168 hours from 50 hours.
United States Patent (USP) US4127244 reports a kind of renovation process of magnesia isomerization catalyst.By in regeneration gas
O is stepped up in atmosphere2Content, until tail gas in without CO2Produce and be passed through pure oxygen and continue to be calcined, the reaction of catalyst can be made
Activity is improved, while catalyst surface carbon distribution is reduced, catalyst stability is extended.
CN200610029968.2 discloses a kind of method of butylenes double-bond isomerization, and the raw material containing butylene is urged with molecular sieve
Agent is contacted, and reaction generation is containing butene-1 and butene-2 mol ratio close to the effluent of thermodynamic equilibrium value, its molecule used
Screened from pure silicon molecular sieve or silica alumina ratio SiO2/Al2O3For 5~1000 crystal aluminosilicate, crystal aluminosilicate is selected from
At least one of ZSM Series Molecules sieve, modenite or beta-molecular sieve.It is 100 in reaction temperature by fixed bed reactors
~380 DEG C, weight space velocity is 1~30 hour-1, pressure be 0.1~2MPa under conditions of, to butylene carry out double-bond isomerization it is anti-
Should, its purpose product selection better performances, catalyst was checked and rated through 1700 hours, and its feed stock conversion and product yield can be kept not
Become.
CN200680012442.1 discloses a kind of for the C4 of butylene containing 1- and 2- butylene to be flowed into preferential conversion into 2- fourths
The method of alkene.This method includes mixing C4 streams with the first hydrogen stream, is formed into stream;In depositing for the first hydroisomerisation catalysts
It is lower by it is described enter stream hydroisomerization so that at least a portion of the 1- butylene changes into 2- butylene, thus produce plus
Hydrogen hydroisomerization effluent;In the still with top and bottom, the hydroisomerization effluent is separated, to be formed
The bottoms of the 1- butene mixtures of upper end, the overhead stream effluent stream containing iso-butane and isobutene and the butylene containing 2-;With
And using the second hydroisomerisation catalysts by the 1- butene mixture hydroisomerizations of the upper end of the post.
CN200680020964.6 discloses one kind in fixed bed hydroisomerization reactor to C4 olefin logistics
Body carries out hydroisomerization, to increase 2- butene concentrations and to minimize 1- butene concentrations, while minimizing butane product
Method and apparatus.In one embodiment, carbon monoxide is introduced into double bond hydroisomerization reaction device together with hydrogen.
In an alternate embodiment, along multiple positions on the double bond hydroisomerization reaction device length direction by hydrogen and optionally
Carbon monoxide introduce.
The problem of there is low catalyst activity or poor stability in the olefin isomerization catalyst of above patent report.
The content of the invention
The technical problems to be solved by the invention are that the activity of olefin isomerization catalyst present in prior art is low and steady
Qualitative poor the problem of, there is provided a kind of new olefin isomerization catalyst.When the isomerization catalyst is used for isomerization reaction, have
Catalyst activity height and the good advantage of stability.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：A kind of olefin isomerization catalyst, with weight
Measure number meter, including following components：A) 77~100 parts of magnesia；B) 0.1~20 part of calcium oxide；C) 0.01~2 part of oxidation
Iron；D) 0~1 part of nickel oxide.
In above-mentioned technical proposal, in terms of olefin isomerization catalyst parts by weight, catalyst is also containing 0.001~1 part
Manganese oxide；In terms of olefin isomerization catalyst parts by weight, the preferred scope of oxidation manganese content is 0.005~0.05 part；With alkene
Hydrocarbon isomerization catalyst weight number meter, nickel oxide content preferred scope is 0.001 ~ 0.01 part；With olefin isomerization catalyst
Parts by weight meter, content of magnesia preferred scope is 80~100 parts；In terms of olefin isomerization catalyst parts by weight, calcium oxide
The preferred scope of content is 0.1~5 part；In terms of olefin isomerization catalyst parts by weight, the more preferably scope of calcium oxide content
For 0.2~1 part；In terms of olefin isomerization catalyst parts by weight, the preferred scope of iron oxide content is 0.01~1.5 part；With
Olefin isomerization catalyst parts by weight meter, the more preferably scope of iron oxide content is 0.05~0.5 part.
Above-mentioned isomerization catalyst is used for the method for 1- butylene disproportionation 2- butylene, in 200~400 DEG C of reaction temperature,
0.1~20h of reaction pressure 1~4Mpa, 1- butylene mass space velocity-1Under conditions of, 1- butylene connects with described isomerization catalyst
Touch reaction generation 2- butylene.
Above-mentioned isomerization catalyst is used for the method that 3- hexenes are disproportionated 1- hexenes processed, in 200~400 DEG C of reaction temperature,
0.1~20h of reaction pressure 1~4Mpa, 3- hexene mass air speed-1Under conditions of, 3- hexenes connect with described isomerization catalyst
Touch reaction generation 1- hexenes.
The preparation method of catalyst can be mixed using dipping, chemisorbed, chemical deposition, ion exchange, physics in the present invention
Prepared by the methods such as conjunction, by being molded in terms of extrusion, spin, tabletting to catalyst.
The preparation method of catalyst in turn includes the following steps：
1) by Ca, Fe and Ni metal institute corresponding salt, alkali or oxide is soluble in water that solution I is made；
2) the corresponding salt of Mg, alkali or oxide are added to solution I and solution II is made；
3) through drying after solution II washing, suction filtration, it is calcined to obtain required catalyst.
In above-mentioned preparation method, step 1）The corresponding salt of middle metal is at least one of nitrate, sulfate and ammonium salt.
The more preferably scheme of above-mentioned preparation method is：Obtained solution I is also corresponding containing Mn metals institute in step (1)
Salt, alkali or oxide.
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, is stirred
Mix kneading and be allowed to Load Balanced, well mixed product is put into extruded moulding in banded extruder, the shape of extruded moulding includes circle
Cylindricality, cloverleaf pattern, mesopore shape, five clover shapes.
It is preferred that forming method it is as follows：Roller forming in roller-ball devices is put into after Ludox will be added in catalyst precarsor,
Roller forming obtains a diameter of 2-10mm spheric catalyst.
Preferred forming method is as follows：Compression molding in tablet press machine, compression molding will be put into after catalyst precarsor film-making
Obtaining shape includes cylinder, amorphous.
After shaping of catalyst finished catalyst is obtained after drying, roasting.In above-mentioned technical proposal, catalyst sintering temperature
Preferred scope is 500~600 DEG C, and the preferred scope of roasting time is 4~6 hours.
The butylenes double-bond isomerization of the present invention reacts, and reaction condition is：In fixed bed reactors, reaction temperature be 200~
400 DEG C, reaction pressure is 1~4MPa, and 1- butylene weight space velocity is 0.1~20 hour-1Under the conditions of, double-bond isomerism occurs for 1- butylene
Metaplasia is into 2- butylene.
Ethene and the preparing propylene by butene disproportionation reaction of the present invention, the disproportionation catalyst used in reaction is 12 weight %WO3/
SiO2The weight ratio of catalyst, isomerization catalyst and disproportionation catalyst is 5: 1.Reaction condition is：In fixed bed reactors, instead
It is 200~400 DEG C to answer temperature, and reaction pressure is 1~4MPa, and the weight space velocity of butylene is 0.1~20 hour-1Under the conditions of, butylene
Occurs disproportionated reaction generation propylene with ethene.
The hexene double bond isomerization reaction of the present invention, reaction condition is：In fixed bed reactors, reaction temperature be 200~
400 DEG C, reaction pressure is 1~4MPa, and 3- hexenes weight space velocity is 0.1~20 hour-1Under the conditions of, double-bond isomerism occurs for 3- hexenes
Metaplasia is into 1- hexenes.
The present invention using Ca, Fe, Ni by, as the auxiliary agent of isomerization catalyst, passing through Ca, Fe, Ni and main active component Mg
Between interaction, the reactivity of isomerization catalyst can be effectively improved, at the same activity in the equal of molecular sieve carrier surface
Even distribution, is difficult to be covered by carbon deposit during the course of the reaction, so as to effectively improve the life-span of catalyst, between each active component
Synergy substantially, only under conditions of Ca, Fe and Ni these active components are all present, catalyst can just have good discrimination
Change activity；When adding active component Mn, the isomerization activity of catalyst is significantly increased again, stability can improve 10% with
On.It it is 300 DEG C in reaction temperature, reaction pressure is 3MPa, and the weight space velocity of 1- butylene is 0.12 hour-1Space velocities under,
Catalyst of the present invention is used for 1- butylene disproportionation 2- butene reactions or olefin dismutation reaction, good isomery can be obtained
Change the stability of catalyst in activity, its 1- butylene disproportionation 2- butene reaction up to more than 400 hours, contrast existing magnesia
Its stability of catalyst improves more than 20%；And in olefin dismutation reaction the stability of catalyst can reach 500 hours with
On, more than 30% can also be improved by contrasting existing its stability of magnesia catalyst；Achieve unexpected technique effect.
Below by embodiment, the present invention is further elaborated.
Embodiment
【Embodiment 1】
By 18 kilograms of calcium oxide CaO, 10.1 kilograms of ferric nitrate Fe (NO3)3·9H2O, which is dissolved in double centner water, is made solution,
Solution is put into mixer, solution is then heated up to 80 DEG C, stirring adds 80 kilograms of magnesia MgO after 30 minutes, continues
Stirring stops stirring after 2 hours, stands 5 hours, and solution is washed, dried 4 hours at 120 DEG C after suction filtration, then in 550 DEG C of roastings
Catalyst needed for obtaining for 6 hours.
【Embodiment 2】
By 18 kilograms of calcium oxide CaO, 10.1 kilograms of ferric nitrate Fe (NO3)3·9H2O, 3.89 kilograms of nickel nitrate Ni (NO3)2·
6H2O, which is dissolved in double centner water, is made solution, and solution is put into mixer, and solution then is heated up into 80 DEG C, stirs 30 points
80 kilograms of magnesia MgO are added after clock, continues to stop stirring after stirring 2 hours, stands 5 hours, solution is washed, after suction filtration
120 DEG C of dryings 4 hours, then 550 DEG C of roastings 6 hours needed for catalyst.
【Embodiment 3】
By 18 kilograms of calcium oxide CaO, 10.1 kilograms of ferric nitrate Fe (NO3)3·9H2O, 3.89 grams of nickel nitrate Ni (NO3)2·
6H2O, which is dissolved in double centner water, is made solution, and solution is put into mixer, and solution then is heated up into 80 DEG C, stirs 30 points
80 kilograms of magnesia MgO are added after clock, continues to stop stirring after stirring 2 hours, stands 5 hours, solution is washed, after suction filtration
120 DEG C of dryings 4 hours, then 550 DEG C of roastings 6 hours needed for catalyst.
【Embodiment 4】
By 18 kilograms of calcium oxide CaO, 10.1 kilograms of ferric nitrate Fe (NO3)3·9H2O, 389 grams of nickel nitrate Ni (NO3)2·
6H2O, which is dissolved in double centner water, is made solution, and solution is put into mixer, and solution then is heated up into 80 DEG C, stirs 30 points
80 kilograms of magnesia MgO are added after clock, continues to stop stirring after stirring 2 hours, stands 5 hours, solution is washed, after suction filtration
120 DEG C of dryings 4 hours, then 550 DEG C of roastings 6 hours needed for catalyst.
【Embodiment 5】
By 18 kilograms of calcium oxide CaO, 10.1 kilograms of ferric nitrate Fe (NO3)3·9H2O, 3.52 grams of manganese nitrate Mn (NO3)2·
4H2O, which is dissolved in double centner water, is made solution, and solution is put into mixer, and solution then is heated up into 80 DEG C, stirs 30 points
80 kilograms of magnesia MgO are added after clock, continues to stop stirring after stirring 2 hours, stands 5 hours, solution is washed, after suction filtration
120 DEG C of dryings 4 hours, then 550 DEG C of roastings 6 hours needed for catalyst.
【Embodiment 6】
By 18 kilograms of calcium oxide CaO, 10.1 kilograms of ferric nitrate Fe (NO3)3·9H2O, 3.52 kilograms of manganese nitrate Mn (NO3)2·
4H2O, which is dissolved in double centner water, is made solution, and solution is put into mixer, and solution then is heated up into 80 DEG C, stirs 30 points
80 kilograms of magnesia MgO are added after clock, continues to stop stirring after stirring 2 hours, stands 5 hours, solution is washed, after suction filtration
120 DEG C of dryings 4 hours, then 550 DEG C of roastings 6 hours needed for catalyst.
【Embodiment 7】
By 18 kilograms of calcium oxide CaO, 10.1 kilograms of ferric nitrate Fe (NO3)3·9H2O, 17.6 grams of manganese nitrate Mn (NO3)2·
4H2O, which is dissolved in double centner water, is made solution, and solution is put into mixer, and solution then is heated up into 80 DEG C, stirs 30 points
80 kilograms of magnesia MgO are added after clock, continues to stop stirring after stirring 2 hours, stands 5 hours, solution is washed, after suction filtration
120 DEG C of dryings 4 hours, then 550 DEG C of roastings 6 hours needed for catalyst.
【Embodiment 8】
By 18 kilograms of calcium oxide CaO, 10.1 kilograms of ferric nitrate Fe (NO3)3·9H2O, 176 grams of manganese nitrate Mn (NO3)2·
4H2O, which is dissolved in double centner water, is made solution, and solution is put into mixer, and solution then is heated up into 80 DEG C, stirs 30 points
80 kilograms of magnesia MgO are added after clock, continues to stop stirring after stirring 2 hours, stands 5 hours, solution is washed, after suction filtration
120 DEG C of dryings 4 hours, then 550 DEG C of roastings 6 hours needed for catalyst.
【Embodiment 9】
By 18 kilograms of calcium oxide CaO, 10.1 kilograms of ferric nitrate Fe (NO3)3·9H2O, 389 grams of nickel nitrate Ni (NO3)2·
6H2O, 176 grams of manganese nitrate Mn (NO3)2·4H2O, which is dissolved in double centner water, is made solution, solution is put into mixer, then
Solution is heated up to 80 DEG C, stirring adds 80 kilograms of magnesia MgO after 30 minutes, continues to stop stirring after stirring 2 hours, stand
5 hour, solution is washed, dried 4 hours at 120 DEG C after suction filtration, then 550 DEG C of roastings 6 hours needed for catalyst.
【Embodiment 10】
By 18 kilograms of calcium oxide CaO, 5.05 kilograms of ferric nitrate Fe (NO3)3·9H2O, 3.89 kilograms of nickel nitrate Ni (NO3)2·
6H2O, 3.52 grams of manganese nitrate Mn (NO3)2·4H2O, which is dissolved in double centner water, is made solution, solution is put into mixer, so
Solution is heated up to 80 DEG C afterwards, stirring adds 80 kilograms of magnesia MgO after 30 minutes, continues to stop stirring after stirring 2 hours, it is quiet
Put 5 hours, solution washed, dried 4 hours at 120 DEG C after suction filtration, then 550 DEG C of roastings 6 hours needed for catalyst.
【Embodiment 10】
By 200 grams of calcium oxide CaO, 2.5 grams of ferric nitrate Fe (NO3)3·9H2O and 35.2 gram of manganese nitrate Mn (NO3)2·4H2O
It is soluble in water that solution is made, solution is heated up to 80 DEG C, stirring adds 770 grams of magnesia MgO after 40 minutes, continues stirring 2 small
When after stop stirring, stand 4 hours, solution washed, dried 5 hours at 80 DEG C after suction filtration, then in 550 DEG C of roastings 4 hours
Required catalyst.
【Embodiment 11】
By 0.1 kilogram of calcium oxide CaO, 10.1 kilograms of ferric nitrate Fe (NO3)3·9H2O, 3.89 kilograms of nickel nitrate Ni
(NO3)2·6H2O, which is dissolved in double centner water, is made solution, and solution is put into mixer, solution then is heated up into 80 DEG C, stirred
80 kilograms of magnesia MgO of addition after 30 minutes are mixed, continues to stop stirring after stirring 2 hours, stands 5 hours, solution is washed, taken out
Dried 4 hours at 120 DEG C after filter, then the catalyst needed for 550 DEG C of roastings are obtained for 6 hours.
【Embodiment 12】
By 5 kilograms of calcium oxide CaO, 10.1 kilograms of ferric nitrate Fe (NO3)3·9H2O, 3.89 kilograms of nickel nitrate Ni (NO3)2·
6H2O, which is dissolved in double centner water, is made solution, and solution is put into mixer, and solution then is heated up into 80 DEG C, stirs 30 points
80 kilograms of magnesia MgO are added after clock, continues to stop stirring after stirring 2 hours, stands 5 hours, solution is washed, after suction filtration
120 DEG C of dryings 4 hours, then 550 DEG C of roastings 6 hours needed for catalyst.
【Embodiment 13】
By 0.2 kilogram of calcium oxide CaO, 10.1 kilograms of ferric nitrate Fe (NO3)3·9H2O, 3.89 kilograms of nickel nitrate Ni
(NO3)2·6H2O, which is dissolved in double centner water, is made solution, and solution is put into mixer, solution then is heated up into 80 DEG C, stirred
80 kilograms of magnesia MgO of addition after 30 minutes are mixed, continues to stop stirring after stirring 2 hours, stands 5 hours, solution is washed, taken out
Dried 4 hours at 120 DEG C after filter, then the catalyst needed for 550 DEG C of roastings are obtained for 6 hours.
【Embodiment 14】
By 1 kilogram of calcium oxide CaO, 10.1 kilograms of ferric nitrate Fe (NO3)3·9H2O, 3.89 kilograms of nickel nitrate Ni (NO3)2·
6H2O, which is dissolved in double centner water, is made solution, and solution is put into mixer, and solution then is heated up into 80 DEG C, stirs 30 points
80 kilograms of magnesia MgO are added after clock, continues to stop stirring after stirring 2 hours, stands 5 hours, solution is washed, after suction filtration
120 DEG C of dryings 4 hours, then 550 DEG C of roastings 6 hours needed for catalyst.
【Embodiment 15】
By 18 kilograms of calcium oxide CaO, 50.5 grams of ferric nitrate Fe (NO3)3·9H2O, 3.89 kilograms of nickel nitrate Ni (NO3)2·
6H2O, which is dissolved in double centner water, is made solution, and solution is put into mixer, and solution then is heated up into 80 DEG C, stirs 30 points
80 kilograms of magnesia MgO are added after clock, continues to stop stirring after stirring 2 hours, stands 5 hours, solution is washed, after suction filtration
120 DEG C of dryings 4 hours, then 550 DEG C of roastings 6 hours needed for catalyst.
【Embodiment 16】
By 18 kilograms of calcium oxide CaO, 7.57 kilograms of ferric nitrate Fe (NO3)3·9H2O, 3.89 kilograms of nickel nitrate Ni (NO3)2·
6H2O, which is dissolved in double centner water, is made solution, and solution is put into mixer, and solution then is heated up into 80 DEG C, stirs 30 points
80 kilograms of magnesia MgO are added after clock, continues to stop stirring after stirring 2 hours, stands 5 hours, solution is washed, after suction filtration
120 DEG C of dryings 4 hours, then 550 DEG C of roastings 6 hours needed for catalyst.
【Embodiment 17】
By 18 kilograms of calcium oxide CaO, 0.26 kilogram of ferric nitrate Fe (NO3)3·9H2O, 3.89 kilograms of nickel nitrate Ni (NO3)2·
6H2O, which is dissolved in double centner water, is made solution, and solution is put into mixer, and solution then is heated up into 80 DEG C, stirs 30 points
80 kilograms of magnesia MgO are added after clock, continues to stop stirring after stirring 2 hours, stands 5 hours, solution is washed, after suction filtration
120 DEG C of dryings 4 hours, then 550 DEG C of roastings 6 hours needed for catalyst.
【Embodiment 18】
By 18 kilograms of calcium oxide CaO, 2.52 kilograms of ferric nitrate Fe (NO3)3·9H2O, 3.89 kilograms of nickel nitrate Ni (NO3)2·
6H2O, which is dissolved in double centner water, is made solution, and solution is put into mixer, and solution then is heated up into 80 DEG C, stirs 30 points
80 kilograms of magnesia MgO are added after clock, continues to stop stirring after stirring 2 hours, stands 5 hours, solution is washed, after suction filtration
120 DEG C of dryings 4 hours, then 550 DEG C of roastings 6 hours needed for catalyst.
【Embodiment 19】
By 20 kilograms of calcium oxide CaO, 10.1 kilograms of ferric nitrate Fe (NO3)3·9H2O, 3.89 kilograms of nickel nitrate Ni (NO3)2·
6H2O, which is dissolved in double centner water, is made solution, and solution is put into mixer, and solution then is heated up into 80 DEG C, stirs 30 points
77 kilograms of magnesia MgO are added after clock, continues to stop stirring after stirring 2 hours, stands 5 hours, solution is washed, after suction filtration
120 DEG C of dryings 4 hours, then 550 DEG C of roastings 6 hours needed for catalyst.
【Embodiment 20】
By 0.1 kilogram of calcium oxide CaO, 50.5 grams of ferric nitrate Fe (NO3)3·9H2O, which is dissolved in double centner water, is made solution,
Solution is put into mixer, solution is then heated up to 80 DEG C, stirring adds double centner magnesia MgO after 30 minutes, continues
Stirring stops stirring after 2 hours, stands 5 hours, and solution is washed, dried 4 hours at 120 DEG C after suction filtration, then in 550 DEG C of roastings
Catalyst needed for obtaining for 6 hours.
【Comparative example 1】
Isomerization catalyst is made according to embodiment 2 in patent CN200610029981.8.
MgO hydrolysis and drying
50 grams of commodity MgO are weighed, 300 ml deionized waters are added, obtained white opacity solution is in 60 DEG C of heating water baths
Stirring stands 3 hours again after 2 hours, moisture in suction filtration solution, and product is dried 12 hours at 80 DEG C, then small in 500 DEG C of roastings 6.5
When be calcined after sample.
【Comparative example 2】
By 18 kilograms of calcium oxide CaO, 10.1 kilograms of ferric nitrate Fe (NO3)3·9H2O, 7.78 kilograms of nickel nitrate Ni (NO3)2·
6H2O, which is dissolved in double centner water, is made solution, and solution is put into mixer, and solution then is heated up into 80 DEG C, stirs 30 points
80 kilograms of magnesia MgO are added after clock, continues to stop stirring after stirring 2 hours, stands 5 hours, solution is washed, after suction filtration
120 DEG C of dryings 4 hours, then 550 DEG C of roastings 6 hours needed for catalyst.
【Comparative example 3】
By 25 kilograms of calcium oxide CaO, 10.1 kilograms of ferric nitrate Fe (NO3)3·9H2O, which is dissolved in double centner water, is made solution,
Solution is put into mixer, solution is then heated up to 80 DEG C, stirring adds 80 kilograms of magnesia MgO after 30 minutes, continues
Stirring stops stirring after 2 hours, stands 5 hours, and solution is washed, dried 4 hours at 120 DEG C after suction filtration, then in 550 DEG C of roastings
Catalyst needed for obtaining for 6 hours.
【Comparative example 4】
By 18 kilograms of calcium oxide CaO, 15.1 kilograms of ferric nitrate Fe (NO3)3·9H2O, which is dissolved in double centner water, is made solution,
Solution is put into mixer, solution is then heated up to 80 DEG C, stirring adds 80 kilograms of magnesia MgO after 30 minutes, continues
Stirring stops stirring after 2 hours, stands 5 hours, and solution is washed, dried 4 hours at 120 DEG C after suction filtration, then in 550 DEG C of roastings
Catalyst needed for obtaining for 6 hours.
【Embodiment 21】
Disproportionation preparation of propene
The isomerization catalyst of embodiment 1~20 and comparative example 1 ~ 4 is used for disproportionation preparation of propene, the shaping of catalyst
Using pressed disc method, after 2.0MPa tablettings, ground with mortar, 20~40 mesh samples of screening are stand-by.
It it is 110 centimetres in length, internal diameter is that 2.5 centimetres of reactor lower curtate addition volume is 110 centimetres3, granularity is
10~20 mesh glass marble fillers；The disproportionation catalyst and 20 grams of isomerization catalysts of 4 grams of formings are added into reactor, disproportionation is urged
Agent is 12 weight %WO3/SiO2, the weight ratio of disproportionation catalyst and isomerization catalyst is 1: 5, and upper end adds 60 centimetres3,
Granularity is 10~20 mesh glass marble fillers.Reactor is warming up to 550 DEG C in the case where being passed through the air conditionses of 100 ml/mins, and
After being kept for 4 hours at this temperature, N is then used2Purging 8 hours, is down to 300 DEG C of reaction temperatures.
Reactor stops being passed through nitrogen, and is passed through 99.5 weight %1- butene feedstocks and 99.9 weight % from reactor upper end
Ethylene raw, butylene：Ethylene molar ratio is 1：2, liquid quality air speed is 0.12 hour-1, reaction system pressure goes out by reactor
The governor valve control of mouth, Stress control is in 3.0MPa.Reaction product is by gas-chromatography on-line analysis after release, and evaluation result is shown in
Table 2.
【Embodiment 22】
1- Isomerization of butene
The isomerization catalyst of embodiment 1~20 and comparative example 1~4 is used for 1- Isomerization of butene, catalyst
Shaping uses pressed disc method, after 2.0MPa tablettings, is ground with mortar, and 20~40 mesh samples of screening are stand-by.
It it is 110 centimetres in length, internal diameter is that 2.5 centimetres of reactor bottom addition volume is 110 centimetres3, granularity is
10~20 mesh glass marble fillers；The isomerization catalyst of 20 grams of formings is added into reactor, catalyst upper end adds 60 lis
Rice3, granularity is 10~20 mesh glass marble fillers.Reactor is warming up to 550 DEG C in the case where being passed through 10 ls/h of air conditionses,
And after being kept for 2 hours at this temperature, then use N2Purging 1 hour, is down to 300 DEG C of reaction temperatures.
Reactor stops being passed through nitrogen, and is passed through 99.5 weight %1- butene feedstocks, liquid quality air speed from reactor upper end
For 0.12 hour-1, reaction system pressure is by the governor valve control of reactor outlet, and Stress control is in 3.0MPa.Reaction product exists
By gas-chromatography on-line analysis after release, evaluation result is shown in Table 2.
【Embodiment 20】
1- Isomerization of butene
By 200 grams of calcium oxide CaO, 101 grams of ferric nitrate Fe (NO3)3·9H2O and 35.2 gram of manganese nitrate Mn (NO3)2·4H2O
It is soluble in water that solution is made, solution is heated up to 80 DEG C, stirring adds 770 grams of magnesia MgO after 40 minutes, continues stirring 2 small
When after stop stirring, stand 4 hours, solution washed, dried 5 hours at 80 DEG C after suction filtration, then in 550 DEG C of roastings 4 hours
Isomerization catalyst, the shaping of catalyst uses pressed disc method, after 2.0MPa tablettings, is ground with mortar, screens 20~40 mesh samples
It is stand-by.
Isomerization catalyst obtained above is used for 1- Isomerization of butene, is 110 centimetres in length, internal diameter is
It is 110 centimetres that 2.5 centimetres of reactor bottom, which adds volume,3, granularity is 10~20 mesh glass marble fillers；By 20 grams of formings
Isomerization catalyst add reactor, catalyst upper end adds 60 centimetres3, granularity is 10~20 mesh glass marble fillers.
Reactor is warming up to 550 DEG C in the case where being passed through 10 ls/h of air conditionses, and after being kept for 2 hours at this temperature, then uses N2
Purging 1 hour, is down to 300 DEG C of reaction temperatures.
Reactor stops being passed through nitrogen, and is passed through 99.5 weight %1- butene feedstocks from reactor upper end, reaction condition and comments
Valency the results are shown in Table 3.
【Embodiment 23】
3- hexene isomerization reactions
By 200 grams of calcium oxide CaO, 101 grams of ferric nitrate Fe (NO3)3·9H2O and 35.2 gram of manganese nitrate Mn (NO3)2·4H2O
It is soluble in water that solution is made, solution is heated up to 80 DEG C, stirring adds 770 grams of magnesia MgO after 40 minutes, continues stirring 2 small
When after stop stirring, stand 4 hours, solution washed, dried 5 hours at 80 DEG C after suction filtration, then in 550 DEG C of roastings 4 hours
Isomerization catalyst, the shaping of catalyst uses pressed disc method, after 2.0MPa tablettings, is ground with mortar, screens 20~40 mesh samples
It is stand-by.
Isomerization catalyst obtained above is used for 3- hexene isomerization reactions, is 110 centimetres in length, internal diameter is
It is 110 centimetres that 2.5 centimetres of reactor bottom, which adds volume,3, granularity is 10~20 mesh glass marble fillers；By 20 grams of formings
Isomerization catalyst add reactor, catalyst upper end adds 60 centimetres3, granularity is 10~20 mesh glass marble fillers.
Reactor is warming up to 550 DEG C in the case where being passed through 10 ls/h of air conditionses, and after being kept for 2 hours at this temperature, then uses N2
Purging 1 hour, is down to 300 DEG C of reaction temperatures.
Reactor stops being passed through nitrogen, and is passed through 99.9 weight %3- hexene feeds from reactor upper end, reaction condition and comments
Valency the results are shown in Table 4.
Table 1
Table 2
Table 3
| Temperature (DEG C) | Pressure (MPa) | Weight space velocity (hour-1) | 2- butylene/1- butylene | Stability (hour) |
| 200 | 0 | 0.1 | 4.56 | 400 |
| 300 | 2 | 5 | 4.58 | 410 |
| 350 | 3 | 10 | 4.84 | 430 |
| 400 | 4 | 20 | 4.70 | 420 |
| 300 | 1 | 8 | 4.63 | 420 |
Table 4
| Temperature (DEG C) | Pressure (MPa) | Weight space velocity (hour-1) | 3- hexenes/1- hexenes | Stability (hour) |
| 200 | 0 | 0.1 | 5.61 | 410 |
| 300 | 2 | 5 | 6.42 | 420 |
| 350 | 3 | 10 | 7.02 | 410 |
| 400 | 4 | 20 | 6.03 | 420 |
| 300 | 1 | 8 | 5.33 | 430 |
Claims (9)
1. a kind of olefin isomerization catalyst, composed of the following components in terms of parts by weight：
A) 77~100 parts of magnesia；
B) 0.1~20 part of calcium oxide；
C) 0.01~2 part of iron oxide；
D) 0.001~1 part of nickel oxide；
E) 0.001~1 part of manganese oxide.
2. olefin isomerization catalyst according to claim 1, it is characterised in that with olefin isomerization catalyst parts by weight
Number meter, the content of manganese oxide is 0.005~0.05 part.
3. olefin isomerization catalyst according to claim 1, it is characterised in that with olefin isomerization catalyst parts by weight
Number meter, the content of nickel oxide is 0.001~0.01 part.
4. olefin isomerization catalyst according to claim 1, it is characterised in that with olefin isomerization catalyst parts by weight
Number meter, the content of magnesia is 80~100 parts.
5. olefin isomerization catalyst according to claim 1, it is characterised in that with olefin isomerization catalyst parts by weight
Number meter, the content of calcium oxide is 0.1~5 part.
6. olefin isomerization catalyst according to claim 5, it is characterised in that with olefin isomerization catalyst parts by weight
Number meter, the content of calcium oxide is 0.2~1 part.
7. olefin isomerization catalyst according to claim 1, it is characterised in that with olefin isomerization catalyst parts by weight
Number meter, the content of iron oxide is 0.01~1.5 part.
8. olefin isomerization catalyst according to claim 7, it is characterised in that with olefin isomerization catalyst parts by weight
Number meter, the content of iron oxide is 0.05~0.5 part.
9. a kind of method of 1- butylene disproportionations 2- butylene, in 200~400 DEG C of reaction temperature, reaction pressure 1~4Mpa, 1- fourth
0.1~20h of alkene mass space velocity-1Under conditions of, 1- butylene is contacted with the isomerization catalyst described in any one of claim 1~8
Reaction generation 2- butylene.
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| CN103028388A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Alkene double-bond isomerization catalyst and preparation method thereof |
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| CN103028388A (en) * | 2011-09-29 | 2013-04-10 | 中国石油化工股份有限公司 | Alkene double-bond isomerization catalyst and preparation method thereof |
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