CN106582603B - The preparation and its application of aluminium oxide catalyst for isobutanol dehydration - Google Patents
The preparation and its application of aluminium oxide catalyst for isobutanol dehydration Download PDFInfo
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- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 title claims abstract description 146
- 239000003054 catalyst Substances 0.000 title claims abstract description 68
- 230000018044 dehydration Effects 0.000 title claims abstract description 63
- 238000006297 dehydration reaction Methods 0.000 title claims abstract description 63
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 101
- 238000006243 chemical reaction Methods 0.000 claims abstract description 63
- 238000000034 method Methods 0.000 claims abstract description 55
- 230000032683 aging Effects 0.000 claims abstract description 28
- 239000011959 amorphous silica alumina Substances 0.000 claims abstract description 23
- 229940035429 isobutyl alcohol Drugs 0.000 claims abstract description 23
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 18
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 18
- 238000001125 extrusion Methods 0.000 claims abstract description 14
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 13
- 239000003518 caustics Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000012266 salt solution Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 238000005470 impregnation Methods 0.000 claims abstract description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 24
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 12
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 10
- 150000001298 alcohols Chemical class 0.000 claims description 9
- 238000004448 titration Methods 0.000 claims description 9
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 159000000013 aluminium salts Chemical class 0.000 claims description 3
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 238000010348 incorporation Methods 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- BDRTVPCFKSUHCJ-UHFFFAOYSA-N molecular hydrogen;potassium Chemical compound [K].[H][H] BDRTVPCFKSUHCJ-UHFFFAOYSA-N 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 238000003756 stirring Methods 0.000 description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 14
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 12
- 238000000465 moulding Methods 0.000 description 12
- 239000000428 dust Substances 0.000 description 11
- 239000011575 calcium Substances 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000004411 aluminium Substances 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 9
- 229910021417 amorphous silicon Inorganic materials 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 229910002651 NO3 Inorganic materials 0.000 description 5
- 239000003292 glue Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000002808 molecular sieve Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- -1 isobutyl alkene Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012163 sequencing technique Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of preparation methods of modified alumina catalyst for isobutanol dehydration, the described method comprises the following steps: a) mixing aluminum salt solution and lye；B) mixture for obtaining step a) carries out aging process, obtains boehmite gel；C) the boehmite gel that step b) is obtained is mixed with amorphous silica-alumina, dry, carrier is made in extrusion molding；D) by the obtained carrier impregnation aqueous caustic of step c) and calcium salt soln, then dry, roasting obtains modified alumina catalyst.The catalyst prepared according to the method for the present invention is used for isobutanol dehydration and prepares isobutene, under conditions of isobutyl alcohol conversion improves, selective isobutene is also improved.
Description
Technical field
The present invention relates to a kind of preparation methods of aluminium oxide catalyst, are used for isobutanol dehydration more particularly to one kind
Aluminium oxide catalyst preparation method.The invention further relates to a kind of methods that isobutyl dehydration of alcohols prepares isobutene.
Background technique
Isobutene is the important monomer of a kind of important fine chemical material and synthetic rubber and resin.MTBE (methyl
Tertbutyl ether) cracking is the current production most important method of isobutene, it is abundant with raw material sources, to equipment and material requirements
It is low, the small advantage of environmental pollution.
But the increasingly raised price of crude oil has promoted people to find the production method for substituting petrochemical industry, wherein different
Butanol dehydration increasingly causes to pay close attention to.It the source of isobutanol, can also be raw from Coal Chemical Industry Route in addition to the conventional methods such as carbonylation synthesis
It produces, i.e., by synthesis gas (CO, H2And CO2Mixture) it is raw by being similar to Fischer-Tropsch (Fischer-Tropsch) synthetic method
It produces, obtains the mixture of higher alcohol, wherein about 30% by-product is isobutanol.Since coal has the advantage on reserves, this
Technique has greatly enriched the source of isobutanol.Furthermore in recent years, biomass isobutanol technology is developed rapidly, and has been opened
The method for using micro-organisms long-chain alcohol is issued, becomes the another source of isobutene, has the advantages that raw material is renewable, environmentally friendly.
Isobutanol dehydration produces isobutene, and used catalyst mainly has molecular sieve, aluminium oxide and several classes of modified aluminas,
Middle alumina base catalyst activity is lower, but selective isobutene is higher than molecular sieve.With the improvement of existing catalyst, isobutanol
The conversion ratio of dehydration is increased to 99.5% or more, but the selectivity for being limited to catalyst is difficult to improve, product isobutene
Purity fails to reach chemical grade standard at present.
102892729 A of Chinese patent CN discloses a kind of isobutanol while dehydration and skeletal isomerization production alkene
Method, used catalyst are the modified aluminium oxide such as Si-Al molecular sieve, sial phosphorus molecular sieve and titanium, fluorine, and in the comparative example
Provide the dehydration results using aluminium oxide catalyst.Wherein the catalytic activity of molecular sieve is higher, at 350 DEG C of reaction temperature, instead
Answer pressure 2bar, liquid feed air speed 7-21h-1Under conditions of, isobutyl alcohol conversion is greater than 99.5%, selective isobutene 41-
43%；Reaction temperature need to be improved to 380 DEG C when the gama-alumina for using Sasol to produce is as catalyst, but selective isobutene
It is higher, up to 90-94%.
Separately there is document to describe isobutanol and is reacted (Zhang Li under aluminium oxide catalyst effect with very low Feed space velocities
It is beautiful, Gao Junbin, the research of Yao Zhilong biology isobutyl dehydration of alcohols preparing isobutene catalyst, Speciality Petrochemicals [J] .2013,30
(2): 17-20), under conditions of 270 DEG C of reaction temperature, reaction pressure 0.1MPa, isobutyl alcohol conversion and selective isobutene
Respectively 99.46% and 98.76%.
Under the action of existing aluminium oxide catalyst, isobutanol dehydration production isobutene is unable to reach chemical grade isobutyl
The index of alkene can only be used as the raw material of MTBE synthesizer, chemistry need to just can be obtained via MTBE synthesis-cracking process
Grade isobutene, production cost are higher.
Summary of the invention
In view of the above the deficiencies in the prior art, the present invention proposes a kind of preparation method of modified alumina catalyst, by this
Catalyst is applied to isobutanol dehydration, and isobutanol dehydration can effectively be overcome to produce the lower skill of selective isobutene
Art problem.
The present invention also provides a kind of method that isobutyl dehydration of alcohols prepares isobutene, this method obtains high isobutanol conversion
Rate, while also obtaining high selective isobutene.
The present invention provides a kind of preparation method of modified alumina catalyst for isobutanol dehydration, the sides
Method the following steps are included:
A) aluminum salt solution and lye are mixed；
B) mixture for obtaining step a) carries out aging process, obtains boehmite gel；
C) the boehmite gel that step b) is obtained is mixed with amorphous silica-alumina, dry, extrusion molding is made and carries
Body；
D) by the obtained carrier impregnation aqueous caustic of step c) and calcium salt soln, then dry, roasting.
The present invention passes through the composite molding of aluminium oxide catalyst and amorphous silica-alumina and the lye, calcium salt soln and severe
The load of property lye, changes the quantity and intensity of catalyst surface strong acid center, reduces various alkene interconversion reactions, thus
The generation for reducing isobutyl alkene isomer in dehydration, generates more isobutenes, effectively improves the selectivity and work of catalyst
Property.
According to the present invention, in step a), the aluminium salt is preferably selected from least one in aluminum nitrate, aluminium chloride and aluminum sulfate
Kind.Preferably, the concentration of the aluminum salt solution is 0.05-0.5mol/L, preferably 0.1-0.2mol/L.According to the present invention, in step
It is rapid a) in, the lye is preferably selected from ammonium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide and barium hydroxide solution at least
It is a kind of.Preferably, the concentration of the lye is 0.2-1.0mol/L, preferably 0.4-0.6mol/L.Alternatively, the volume of the ammonium hydroxide
Concentration is preferably 1-10%, further preferably 3-6%.
Preferably, in step a), the mixing is carried out by titration, and titration temperature is 30-80 DEG C, preferably 45-65 DEG C；
Titration end-point pH value is 8-9, preferably 8.5-9；Incorporation time is 1-4 hours, preferably 1.5-3 hours.
Preferably, in step b), aging temperature is 65-95 DEG C, preferably 75-90 DEG C；Ageing time is 10-24 hours.
As known to the skilled person, amorphous silica-alumina usually can be total to gluing method system by using silicate and aluminium salt
It is standby to obtain.The amorphous silica-alumina being used in the present invention is amorphous silica-alumina as described above commonly used in the art.
According to the present invention, in step c), by the boehmite gel be 100 parts by weight in terms of, it is described amorphous
Sial dosage is 1~10 parts by weight, preferably 2~6 parts by weight.Alternatively, amorphous silica-alumina quality contains in the carrier
Amount is preferably 1-9%, further preferably 2-5%.In the present invention, amorphous silica-alumina is added in aluminium oxide catalyst,
Especially within the scope of usage amount as described above, the specific surface area and surface acidity of aluminium oxide catalyst can be improved, be more advantageous to
Combine with catalyst at subsequent solid alkali center.It is assumed that this may be derived from that amorphous silica-alumina has higher acid and
Biggish specific surface area.
In preferred embodiments, the carrier that the step c) is obtained can be further dried, roast, wherein drying temperature
It is 90-150 DEG C, preferably 100-120 DEG C.
In preferred embodiments, in step c), boehmite gel mixed with amorphous silica-alumina after through filtering
Re-dry afterwards.
According to the present invention, in the step d), the aqueous caustic is preferably selected from potassium hydroxide and/or sodium hydroxide is molten
Liquid.
Preferably, the aqueous caustic concentration is 0.1-5mol/L, also preferably 1-3mol/L, further preferably 1.5-
2.5mol/L.Alternatively, the mass concentration of the aqueous caustic is preferably 5-20%, further preferably 10-15%.
In the present invention, it is not particularly limited in the sequencing that step d), the aqueous caustic and calcium salt soln impregnate,
It such as can first be impregnated in aqueous caustic and be impregnated in calcium salt soln again, can also first be impregnated in calcium salt soln and be impregnated in causticity again
Lye solution.
According to the present invention, the calcium salt is preferably selected from least one of calcium nitrate, calcium sulfate and calcium chloride.
Preferably, the concentration of the calcium salt soln is 0.1-3mol/L, preferably 0.2-1.0mol/L, preferably 0.3-
0.6mol/L.Alternatively, the mass concentration of the calcium salt soln is preferably 1-20%, further preferably 5-10%.
In preferred embodiments, in step d), the drying temperature is 90-150 DEG C, preferably 100-120 DEG C；Roasting
Burning temperature is 300-600 DEG C, preferably 400-500 DEG C.
The present invention also provides a kind of obtained modified alumina catalyst prepared according to the methods of the invention, specific surface areas
For 180-240m2/ g, Kong Rongwei 0.3-0.7ml/g.It can be seen that aluminium oxide catalyst provided by the invention can load more
Solid base center, it is more to improve catalyst surface acidity, better catalytic stability is kept in dehydration, is realized more
High catalysis selects effect.
Further, the present invention also provides a kind of methods that isobutyl dehydration of alcohols prepares isobutene, including isobutanol is made to exist
Dehydration is carried out in the presence of the modified alumina catalyst that the method provided according to the present invention is prepared, and obtains isobutene
Product.
In a specific embodiment, the method that the isobutyl dehydration of alcohols prepares isobutene include it is according to the present invention such as
Upper the method prepares modified alumina catalyst, places it in dehydration reactor, and isobutanol is then passed through the dehydration
In reactor, dehydration is carried out under dehydration conditions.
Wherein, it is 260-330 DEG C, preferably 280-310 DEG C that dehydration conditions, which include: dehydration temperature,；Dehydration pressure
For 0.1-0.5MPa, preferably 0.2-0.3MPa；Isobutanol Feed space velocities 0.5-1h-1, preferably 0.6-0.7h-1。
The method provided according to the present invention implements isobutyl dehydration of alcohols and prepares isobutene reaction, and isobutyl alcohol conversion can reach
99.5%, selective isobutene can reach 99.3%.This is a kind of significant effect promoting for industrial production.
In a preferred embodiment, when the method that the isobutyl dehydration of alcohols prepares isobutene is included in reaction beginning,
Water is passed through in dehydration reactor, and stops water inlet when isobutyl alcohol conversion is reduced to setting value.According to the present invention, described to set
Definite value is preferably 96-98.8%, further preferred 97.5-98.3%.
As known to the skilled person, by detecting the isobutanol for entering reactor and the isobutanol for leaving reactor
Content, would know that the conversion ratio of isobutanol.In the present invention, the situation of change of the amount of isobutanol and isobutene can be by online
Analysis instrument real time monitoring, or be monitored by the measurement of artificial timing sampling.It should be noted that being surveyed by manual sampling
The normal time for determining the amount of isobutanol and then acquisition conversion ratio can't generate substantial effect to the control effect of water inlet.
In terms of being 100 parts by weight by the isobutanol, the water consumption is 5-20 parts by weight, preferably 10-15 weight
Number.By the method, the selectivity of isobutene can reach 99.4% or more.
In the prior art, the water generated in bed blending reaction can reduce isobutyl alcohol conversion and isobutene in dehydration
Selectivity, it is necessary in advance removal raw material in water simultaneously remove product water in time during reaction.However, of the invention
Inventor in experiments it is found that, when using catalyst of the present invention in isobutanol dehydration, be added in initial reaction stage appropriate
Water be conducive to instead reaction progress, obtain preferable conversion ratio and selection sexual balance.
In the present invention, the dehydration reactor can be fixed bed reactors or moving-burden bed reactor.Due to according to this
It invents the catalyst being prepared and has good stability, therefore dehydration can be continuous in two reactors in parallel
Ground carries out, wherein another reactor carries out catalyst regeneration when a reactor is run.Catalyst of the invention can also be with
Regeneration.
It is possible to further be separated by conventional method to the product that dehydration obtains, with remove isobutanol and
Light dydrocarbon, and then the isobutene that purity is 99.4% can be obtained.
It prepares in isobutene reaction in isobutyl dehydration of alcohols using catalyst of the present invention, can save from raw material and production
The equipment and technique of middle water removal, substantially reduce production cost.
The present invention provides a kind of preparation methods of modified alumina catalyst, and the catalyst according to made from the method is used
In isobutanol dehydration production isobutene, on the basis of isobutyl alcohol conversion 99.5%, selective isobutene can reach
99.3%, MTBE synthesis-cracking process must be passed through for crude product to reach chemical grade isobutene in the prior art by eliminating,
Realize efficient, production energy-saving chemical grade isobutene effect.
Specific embodiment
Although the present invention has been described in detail, it will be understood by those skilled in the art that in spirit and scope of the invention
Modification will be apparent.However, it should be understood that various aspects, different specific embodiment that the present invention records
Each section and the various features enumerated can be combined or all or part of exchange.In above-mentioned each specific embodiment, that
A little embodiments with reference to another embodiment can be combined suitably with other embodiment, this is will be by this field skill
Art personnel are to understand.In addition, it will be understood to those of skill in the art that the description of front is only exemplary mode, not purport
In the limitation present invention.
Embodiment 1
It weighs 37.51g (0.1mol) aluminum nitrate to be dissolved in 55 DEG C of 500ml of hot water, 0.6mol/L ammonia spirit is added dropwise extremely
PH=8.5 continues stirring 2 hours, then hydrothermal aging 24 hours at 80 DEG C.The gel of generation is cooled to after aging
It is spare after room temperature.
It weighs 0.6g amorphous silicon aluminium powder and appropriate above-mentioned gel (amorphous silica-alumina weight: boehmite gel is added
Weight=6:100) in, it stirs 1 hour at room temperature, with extrusion after 5% dust technology mixing at cylindrical type, circle after filtering drying
Column diameter is 2mm.3 hours dry through 100 DEG C after molding, 500 DEG C are prepared into carrier after roasting 4 hours.
The KOH solution for preparing 20ml 12% (2mol/L) impregnates above-mentioned carrier 1 hour, then prepares 8% (0.5mol/L)
Ca (NO3)2Solution 20ml impregnates above-mentioned carrier 2 hours, 3 hours dry in 120 DEG C, and 500 DEG C are prepared into after roasting 4 hours and urge
Agent.
The progress isobutanol dehydration on fixed bed catalyst, loaded catalyst 30ml, 290 DEG C of reaction temperature,
Reaction pressure 0.1MPa, Feed space velocities 0.7h-1.Isobutyl alcohol conversion and selective isobutene the results are shown in Table 1.
Embodiment 2
It weighs 37.51g (0.1mol) aluminum nitrate to be dissolved in 55 DEG C of 500ml of hot water, 0.6mol/L ammonia spirit is added dropwise extremely
PH=8.5 continues stirring 2 hours, then hydrothermal aging 24 hours at 80 DEG C.The gel of generation is cooled to after aging
It is spare after room temperature.
It weighs 0.4g amorphous silicon aluminium powder and is added in appropriate above-mentioned gel that (amorphous silica-alumina weight: boehmite is solidifying
Glue weight=4:100) in, stir 1 hour at room temperature, after being mixed after filtering drying with 5% dust technology extrusion at cylindrical type,
Body diameter is 2mm.3 hours dry through 100 DEG C after molding, 500 DEG C are prepared into carrier after roasting 4 hours.
The KOH solution for preparing 20ml 12% (2mol/L) impregnates above-mentioned carrier 1 hour, then prepares 8% (0.5mol/L)
Ca (NO3)2Solution 20ml impregnates above-mentioned carrier 2 hours, 3 hours dry in 120 DEG C, and 500 DEG C are prepared into after roasting 4 hours and urge
Agent.
The progress isobutanol dehydration on fixed bed catalyst, loaded catalyst 30ml, 302 DEG C of reaction temperature,
Reaction pressure 0.1MPa, Feed space velocities 0.7h-1.Isobutyl alcohol conversion and selective isobutene the results are shown in Table 1.
Embodiment 3
It weighs 37.51g (0.1mol) aluminum nitrate to be dissolved in 55 DEG C of 500ml of hot water, 0.6mol/L ammonia spirit is added dropwise extremely
PH=8.5 continues stirring 2 hours, then hydrothermal aging 24 hours at 80 DEG C.The gel of generation is cooled to after aging
It is spare after room temperature.
It weighs 0.6g amorphous silicon aluminium powder and is added in appropriate above-mentioned gel that (amorphous silica-alumina weight: boehmite is solidifying
Glue weight=6:100) in, stir 1 hour at room temperature, after being mixed after filtering drying with 5% dust technology extrusion at cylindrical type,
Body diameter is 2mm.3 hours dry through 100 DEG C after molding, 500 DEG C are prepared into carrier after roasting 4 hours.
The KOH solution for preparing 20ml 16% (2.8mol/L) impregnates above-mentioned carrier 1 hour, then prepares 10%
Ca (the NO of (0.6mol/L)3)2Solution 20ml impregnates above-mentioned carrier 2 hours, 3 hours dry in 120 DEG C, and 500 DEG C roast 4 hours
After be prepared into catalyst.
The progress isobutanol dehydration on fixed bed catalyst, loaded catalyst 30ml, 302 DEG C of reaction temperature,
Reaction pressure 0.1MPa, Feed space velocities 0.7h-1.Isobutyl alcohol conversion and selective isobutene the results are shown in Table 1.
Embodiment 4
It weighs 37.51g (0.1mol) aluminum nitrate to be dissolved in 55 DEG C of 500ml of hot water, 0.6mol/L ammonia spirit is added dropwise extremely
PH=8.5 continues stirring 2 hours, then hydrothermal aging 24 hours at 80 DEG C.The gel of generation is cooled to after aging
It is spare after room temperature.
It weighs 0.4g amorphous silicon aluminium powder and is added in appropriate above-mentioned gel that (amorphous silica-alumina weight: boehmite is solidifying
Glue weight=4:100) in, stir 1 hour at room temperature, after being mixed after filtering drying with 5% dust technology extrusion at cylindrical type,
Body diameter is 2mm.3 hours dry through 100 DEG C after molding, 500 DEG C are prepared into carrier after roasting 4 hours.
The KOH solution for preparing 20ml 12% (2mol/L) impregnates above-mentioned carrier 1 hour, then prepares 8% (0.5mol/L)
Ca (NO3)2Solution 20ml impregnates above-mentioned carrier 2 hours, 3 hours dry in 120 DEG C, and 500 DEG C are prepared into after roasting 4 hours and urge
Agent.
The progress isobutanol dehydration on fixed bed catalyst, loaded catalyst 30ml, 320 DEG C of reaction temperature,
Reaction pressure 0.1MPa, Feed space velocities 1.0h-1.Isobutyl alcohol conversion and selective isobutene the results are shown in Table 1.
Embodiment 5
It weighs 37.51g (0.1mol) aluminum nitrate to be dissolved in 45 DEG C of 500ml of hot water, be added dropwise 0.5mol/L Ca (OH)2It is molten
Liquid continues stirring 2 hours, then hydrothermal aging 24 hours at 70 DEG C to pH=8.It is after aging that the gel of generation is cooling
It is spare after to room temperature.
It weighs 1.0g amorphous silicon aluminium powder and is added in appropriate above-mentioned gel that (amorphous silica-alumina weight: boehmite is solidifying
Glue weight=10:100) in, it stirs 1 hour at room temperature, with extrusion after 5% dust technology mixing at cylinder after filtering drying
Type, body diameter 2mm.3 hours dry through 100 DEG C after molding, 400 DEG C are prepared into carrier after roasting 4 hours.
The KOH solution for preparing 20ml 6% (1mol/L) impregnates above-mentioned carrier 1 hour, then prepares 6% (0.4mol/L)
CaSO4Solution 20ml impregnates above-mentioned carrier 2 hours, 3 hours dry in 120 DEG C, and 400 DEG C are prepared into catalysis after roasting 4 hours
Agent.
The progress isobutanol dehydration on fixed bed catalyst, loaded catalyst 30ml, 302 DEG C of reaction temperature,
Reaction pressure 0.1MPa, Feed space velocities 0.7h-1.Isobutyl alcohol conversion and selective isobutene the results are shown in Table 1.
Embodiment 6
It weighs 37.51g (0.1mol) aluminum nitrate to be dissolved in 65 DEG C of 500ml of hot water, be added dropwise 0.8mol/L Ca (OH)2It is molten
Liquid continues stirring 2 hours, then hydrothermal aging 24 hours at 85 DEG C to pH=8.5.It is after aging that the gel of generation is cold
But to spare after room temperature.
It weighs 1.0g amorphous silicon aluminium powder and is added in appropriate above-mentioned gel that (amorphous silica-alumina weight: boehmite is solidifying
Glue weight=10:100) in, it stirs 1 hour at room temperature, with extrusion after 5% dust technology mixing at cylinder after filtering drying
Type, body diameter 2mm.3 hours dry through 100 DEG C after molding, 500 DEG C are prepared into carrier after roasting 4 hours.
The KOH solution for preparing 20ml 18% (3mol/L) impregnates above-mentioned carrier 1 hour, then prepares 16% (1mol/L)
CaCl2Solution 20ml impregnates above-mentioned carrier 2 hours, 3 hours dry in 120 DEG C, and 500 DEG C are prepared into catalysis after roasting 4 hours
Agent.
The progress isobutanol dehydration on fixed bed catalyst, loaded catalyst 30ml, 302 DEG C of reaction temperature,
Reaction pressure 0.2MPa, Feed space velocities 0.7h-1.Isobutyl alcohol conversion and selective isobutene the results are shown in Table 1.
Embodiment 7
It weighs 37.51g (0.1mol) aluminum nitrate to be dissolved in 75 DEG C of 500ml of hot water, be added dropwise 0.3mol/L Ca (OH)2It is molten
Liquid continues stirring 2 hours, then hydrothermal aging 24 hours at 95 DEG C to pH=9.It is after aging that the gel of generation is cooling
It is spare after to room temperature.
It weighs amorphous silicon aluminium powder in 0.2g and (amorphous silica-alumina weight: boehmite in appropriate above-mentioned gel is added
Gel weight=2:100), stir 1 hour at room temperature, after being mixed after filtering drying with 5% dust technology extrusion at cylindrical type,
Body diameter is 2mm.3 hours dry through 100 DEG C after molding, 600 DEG C are prepared into carrier after roasting 4 hours.
The KOH solution for preparing 20ml 18% (3mol/L) impregnates above-mentioned carrier 1 hour, then prepares 16% (1mol/L)
CaCl2Solution 20ml impregnates above-mentioned carrier 2 hours, 3 hours dry in 150 DEG C, and 600 DEG C are prepared into catalysis after roasting 4 hours
Agent.
The progress isobutanol dehydration on fixed bed catalyst, loaded catalyst 30ml, 320 DEG C of reaction temperature,
Reaction pressure 0.2MPa, Feed space velocities 0.7h-1.Isobutyl alcohol conversion and selective isobutene the results are shown in Table 1.
Embodiment 8
It weighs 37.51g (0.1mol) aluminum nitrate to be dissolved in 55 DEG C of 500ml of hot water, 0.6mol/L ammonia spirit is added dropwise extremely
PH=8.5 continues stirring 2 hours, then hydrothermal aging 24 hours at 80 DEG C.The gel of generation is cooled to after aging
It is spare after room temperature.
It weighs 0.6g amorphous silicon aluminium powder and appropriate above-mentioned gel (amorphous silica-alumina weight: boehmite gel is added
Weight=6:100) in, it stirs 1 hour at room temperature, with extrusion after 5% dust technology mixing at cylindrical type, circle after filtering drying
Column diameter is 2mm.3 hours dry through 100 DEG C after molding, 500 DEG C are prepared into carrier after roasting 4 hours.
The KOH solution for preparing 20ml 12% (2mol/L) impregnates above-mentioned carrier 1 hour, then prepares 8% (0.5mol/L)
Ca (NO3)2Solution 20ml impregnates above-mentioned carrier 2 hours, 3 hours dry in 120 DEG C, and 500 DEG C are prepared into after roasting 4 hours and urge
Agent.
The progress isobutanol dehydration on fixed bed catalyst, loaded catalyst 30ml, 290 DEG C of reaction temperature,
Reaction pressure 0.1MPa, Feed space velocities 0.7h-1, the water flowing (water weight: isobutanol weight=8:100) when reacting beginning, and
It detects and stops water inlet when isobutyl alcohol conversion is down to 98.5% or less.Isobutyl alcohol conversion and selective isobutene the results are shown in Table
1。
Embodiment 9
It weighs 37.51g (0.1mol) aluminum nitrate to be dissolved in 55 DEG C of 500ml of hot water, 0.6mol/L ammonia spirit is added dropwise extremely
PH=8.5 continues stirring 2 hours, then hydrothermal aging 24 hours at 80 DEG C.The gel of generation is cooled to after aging
It is spare after room temperature.
It weighs 0.6g amorphous silicon aluminium powder and appropriate above-mentioned gel (amorphous silica-alumina weight: boehmite gel is added
Weight=6:100) in, it stirs 1 hour at room temperature, with extrusion after 5% dust technology mixing at cylindrical type, circle after filtering drying
Column diameter is 2mm.3 hours dry through 100 DEG C after molding, 500 DEG C are prepared into carrier after roasting 4 hours.
The KOH solution for preparing 20ml 12% (2mol/L) impregnates above-mentioned carrier 1 hour, then prepares 8% (0.5mol/L)
Ca (NO3)2Solution 20ml impregnates above-mentioned carrier 2 hours, 3 hours dry in 120 DEG C, and 500 DEG C are prepared into after roasting 4 hours and urge
Agent.
The progress isobutanol dehydration on fixed bed catalyst, loaded catalyst 30ml, 290 DEG C of reaction temperature,
Reaction pressure 0.1MPa, Feed space velocities 0.7h-1, the water flowing (water weight: isobutanol weight=16:100) when reacting beginning, and
It detects and stops water inlet when isobutyl alcohol conversion is down to 97.8% or less.Isobutyl alcohol conversion and selective isobutene the results are shown in Table
1。
Comparative example 1
It weighs 37.51g (0.1mol) aluminum nitrate to be dissolved in 55 DEG C of 500ml of hot water, 0.6mol/L ammonia spirit is added dropwise extremely
PH=8.5 continues stirring 2 hours, then hydrothermal aging 24 hours at 80 DEG C.Aging terminates to be filtered, and washing is used after drying
5% dust technology is concocted and extrusion is at cylindrical type, body diameter 2mm.It is 3 hours dry through 100 DEG C after molding, 500 DEG C of roastings 4
Catalyst is prepared into after hour.
The progress isobutanol dehydration on fixed bed catalyst, loaded catalyst 30ml, 325 DEG C of reaction temperature,
Reaction pressure 0.1MPa, Feed space velocities 0.7h-1.Isobutyl alcohol conversion and selective isobutene the results are shown in Table 1.
Comparative example 2
50g amorphous silica-alumina is weighed, with extrusion after 5% dust technology blending at cylindrical type, body diameter 2mm.Molding
3 hours dry by 100 DEG C, 500 DEG C are prepared into carrier after roasting 4 hours.
The KOH solution for preparing 100ml 12% (2mol/L) impregnates above-mentioned carrier 1 hour, then prepares 8% (0.5mol/
L Ca (NO)3)2Solution 100ml impregnates above-mentioned carrier 2 hours, 3 hours dry in 120 DEG C, and 500 DEG C are prepared into after roasting 4 hours
Catalyst.
The progress isobutanol dehydration on fixed bed catalyst, loaded catalyst 30ml, 261 DEG C of reaction temperature,
Reaction pressure 0.1MPa, Feed space velocities 0.7h-1.Isobutyl alcohol conversion and selective isobutene the results are shown in Table 1.
Table 1
Above embodiments and comparative example explanation, the catalyst prepared using the method for the invention, in isobutyl alcohol conversion
Under conditions of 99.5%, selective isobutene is up to 99.3%.Further, it is properly joined into water in the reaction, can protect
Demonstrate,prove the unobvious decline of isobutyl alcohol conversion in the case where, be improved the selectivity of isobutene, for example, reach 99.4% or with
On.The present invention can directly produce chemical grade isobutene by isobutanol dewatering process, synthesize-split by MTBE to eliminate
The process of solution greatly reduces the production cost of chemical grade isobutene.
Claims (25)
1. a kind of preparation method of the modified alumina catalyst for isobutanol dehydration, the method includes following steps
It is rapid:
A) aluminum salt solution and lye are mixed；
B) mixture for obtaining step a) carries out aging process, obtains boehmite gel；
C) the boehmite gel that step b) is obtained is mixed with amorphous silica-alumina, dry, carrier is made in extrusion molding；
D) by the obtained carrier impregnation aqueous caustic of step c) and calcium salt soln, then dry, roasting.
2. the method according to claim 1, wherein the mixing is carried out by titration, titration in step a)
Temperature is 30-80 DEG C；Titration end-point pH value is 8-9；Incorporation time is 1-4 hours.
3. the method according to claim 1, wherein the mixing is carried out by titration, titration in step a)
Temperature is 45-65 DEG C；Titration end-point pH value is 8.5-9；Incorporation time is 1.5-3 hours.
4. the method according to claim 1, wherein aging temperature is 65-95 DEG C in step b)；When aging
Between be 10-24 hours.
5. according to the method described in claim 4, it is characterized in that, aging temperature is 75-90 DEG C.
6. the method according to claim 1, wherein the concentration of the aluminum salt solution is 0.05-0.5mol/L；Institute
The concentration for stating lye is 0.2-1.0mol/L.
7. the method according to claim 1, wherein the concentration of the aluminum salt solution is 0.1-0.2mol/L；Institute
The concentration for stating lye is 0.4-0.6mol/L.
8. the method according to claim 1, wherein the aluminium salt is in aluminum nitrate, aluminium chloride and aluminum sulfate
At least one；The lye in ammonium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide and barium hydroxide solution at least
It is a kind of.
9. the method according to claim 1, wherein in step c), with the boehmite gel for 100
Parts by weight meter, the amorphous silica-alumina dosage are 1~10 parts by weight.
10. according to the method described in claim 9, it is characterized in that, the amorphous silica-alumina dosage is 2~6 parts by weight.
11. method according to claim 1 to 10, which is characterized in that in step d), the aqueous caustic
Concentration is 0.1-5mol/L；The concentration of the calcium salt soln is 0.1-3mol/L.
12. according to the method for claim 11, which is characterized in that the aqueous caustic concentration is 1.5-2.5mol/L；Institute
The concentration for stating calcium salt soln is 0.3-0.6mol/L.
13. according to the method for claim 11, which is characterized in that the aqueous caustic is selected from potassium hydroxide and/or hydrogen-oxygen
Change sodium solution；The calcium salt is selected from least one of calcium nitrate, calcium sulfate and calcium chloride.
14. according to the method for claim 11, which is characterized in that in step d), maturing temperature is 300-600 DEG C.
15. according to the method for claim 14, which is characterized in that maturing temperature is 400-500 DEG C.
16. a kind of modified alumina catalyst that method described in any one of -15 is prepared according to claim 1,
Specific surface area is 180-240m2/ g, Kong Rongwei 0.3-0.7ml/g.
17. a kind of method that isobutyl dehydration of alcohols prepares isobutene, including keep isobutanol any one according to claim 1-15
Dehydration is carried out in the presence of the modified alumina catalyst that method described in is prepared, obtains isobutyl ene product.
18. according to the method for claim 17, which is characterized in that the described method includes: appointing in -15 according to claim 1
Method described in meaning one prepares modified alumina catalyst, places it in dehydration reactor, isobutanol is then passed through institute
It states in dehydration reactor, dehydration is carried out under dehydration conditions, obtain isobutyl ene product.
19. according to the method for claim 18, which is characterized in that the dehydration conditions include: that the temperature of dehydration is
260-330℃；And/or the pressure of dehydration is 0.1-0.5MPa；And/or isobutanol Feed space velocities 0.5-1h-1。
20. according to the method for claim 18, which is characterized in that the dehydration conditions include: that the temperature of dehydration is
280-310℃；And/or the pressure of dehydration is 0.2-0.3MPa；And/or isobutanol Feed space velocities 0.6-0.7h-1。
21. method described in any one of 8-20 according to claim 1, which is characterized in that when reacting beginning, water is passed through de-
In water reactor, and stop water inlet when isobutyl alcohol conversion is reduced to setting value.
22. according to the method for claim 21, which is characterized in that the setting value is 96-98.8%.
23. according to the method for claim 21, which is characterized in that the setting value is 97.5-98.3%.
24. according to the method for claim 21, which is characterized in that by the isobutanol be 100 parts by weight in terms of, the water
Dosage is 5~20 parts by weight.
25. according to the method for claim 24, which is characterized in that the water consumption is 10~15 parts by weight.
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