CN103861633A - Heterogeneous catalyst and preparation method thereof as well as method for preparing 3-methyl-2-butene-1-ol in presence of catalyst - Google Patents
Heterogeneous catalyst and preparation method thereof as well as method for preparing 3-methyl-2-butene-1-ol in presence of catalyst Download PDFInfo
- Publication number
- CN103861633A CN103861633A CN201410063025.6A CN201410063025A CN103861633A CN 103861633 A CN103861633 A CN 103861633A CN 201410063025 A CN201410063025 A CN 201410063025A CN 103861633 A CN103861633 A CN 103861633A
- Authority
- CN
- China
- Prior art keywords
- heterogeneous catalysis
- hydrogen
- catalyst
- methyl
- butene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a heterogeneous catalyst and a preparation method thereof as well as a method for preparing 3-methyl-2-butene-1-ol in the presence of the catalyst. The heterogeneous catalyst comprises a carrier and three components on the carrier, wherein the first component is selected from one or two or several in palladium, gold, platinum, nickel, chromium and molybdenum; the second component is selected from one or two or several in elements of groups IIIA, IVA and VA; the third component is selected from one or two or several in lanthanide elements. The preparation method comprises the step of performing a reactive distillation process on 3-methyl-3-butene-1-ol to prepare the 3-methyl-2-butene-1-ol in the presence of the heterogeneous catalyst. According to the method provided by the invention, the yield and selectivity of the 3-methyl-2-butene-1-ol can be obviously improved, and the stability of the catalyst is improved, so that the production cost is reduced.
Description
Technical field:
The present invention relates to a kind of 3-methyl-3-butene-1-alcohol (different prenol) isomerization and prepare the heterogeneous catalysis of 3-M2BOL (prenol) and the preparation method of this catalyst, also relate to a kind of method that adopts this heterogeneous catalysis to prepare 3-M2BOL in reactive distillation process.
Background technology:
3-M2BOL, i.e. prenol, is mainly used in the important presomas of product such as synthesising complex E, vitamin A, fragrance product citral, higher effective and lower toxic pesticide pyrethroid insecticides.Along with people are to the deepening continuously of 3-M2BOL synthesis technique, range of application will further expand, and demand also will significantly rise.Therefore, strengthen to the research of 3-M2BOL synthetic technology significant and using value.
According to the difference of reaction raw materials, the synthetic route of 3-M2BOL mainly can be divided into following 3 classes: (1) Pu Linsi (Prins) method: isobutene and polyformaldehyde are reacted to the mixture that generates 3-methyl-3-butene-1-alcohol and 3-M2BOL under the existence of sodium hydrogen phosphate, then under Pd/C catalyst, enol transposition is become to prenol.(2) isoprene method: taking isoprene as raw material and hcl reaction generate chloroisoamylene, the chloro-3-methyl-3-of 1-butylene is wherein 1,3,2-CMB through transposition, generate corresponding acetate with sodium acetate again, then hydrolysis obtains 3-M2BOL.(3) methyl butenol isomerate process: under alkali condition, acetone and acetylene carry out ethynylation, generates acetenyl isopropyl alcohol, then carries out hydrogenation with Pd/C catalyst and obtains methyl butenol, and re-isomerization makes 3-M2BOL.
WO2008037693 has described 3-methyl-3-butene-1-alcohol isomerization on heterogeneous noble metal catalyst under hydrogen exists and has produced 3-M2BOL.This metallic catalyst is made up of immobilized Pd, Se and Te on silica.In addition, the excessive hydrogenation in hydrogen atmosphere causes being formed to many 2.5% isoamyl alcohol.
US4117016 has described the isomerization of unsaturated alcohol in liquid phase under the existence of the homogeneous phase ruthenium at catalytic amount-hydrogen complex under part exists, and has clearly got rid of the existence of trace oxygen, to guarantee catalyst stability.Under nitrogen, 3-methyl-3-butene-1-alcohol isomery turns to 3-M2BOL and only carries out with low yield, and this does not have economic interests.
CN101965325 has described containing in oxygen atmosphere, utilizes Pd/C catalyst to make the method for olefinic unsaturated alcohol isomery.The example that this patent is mentioned generates 93.4% valuable product to multipotency, wherein have the isoamyl olefine aldehydr of a great deal of, and accessory substance is more, separates more difficult.
CN102675048 has described the method for utilizing the synthetic 3-M2BOL of composite catalyst.Taking 3-methyl-3-butene-1-alcohol as raw material, adopt the composite catalyst of Raney's nickel and solid super-strong acid composition, make 3-methyl-3-butene-1-alcohol isomery turn to 3-M2BOL, selectivity of product at the most 95% in this invention example, feed stock conversion is at most 68.5%, and yield is at most 65.1%.
The reaction that 3-methyl-3-butene-1-alcohol is prepared 3-M2BOL is balanced reaction, be difficult under normal circumstances make conversion ratio reach 100%, in the patent of having described, fundamentally do not solve the problem that balanced reaction conversion ratio is not high, and produce hydrogenation byproduct isoamyl alcohol be difficult to separate, remove need to be higher expense.
In the patent of having described, utilize loading type Pd/Al
2o
3catalyst carries out isomerization reaction, easily generate hydrogenation byproduct isoamyl alcohol and dehydration accessory substance isoprene and water, the former is because the hydrogenation of Pd generates, there is patent to propose to add dressing agent Se, Te to suppress hydrogenation in catalyst, but these two kinds of metal pair catalyst itself have poisoning effect, catalyst activity is reduced.Therefore need to select to there is relatively hypotoxic dressing agent, can suppress hydrogenation reaction, do not reduce again catalyst activity.And the latter has stronger acidity due to alumina catalyst support, impel alcohol to dewater, therefore need to select acid weak carrier, suppress dehydration of alcohols reaction.
The defect that prior art exists:
(1) single conversion ratio is not high, the single conversion ratio 60-70% at the most mentioning in existing patent, and target selection is at most 95%, and too high conversion ratio causes target product selectivity to decline, accessory substance increases.
(2) accessory substance is more, is mainly isoamyl alcohol, isoprene, water, and this makes separation of products difficulty, and energy consumption increases.
Summary of the invention
The object of the present invention is to provide a kind of heterogeneous catalysis, can suppress the generation of the accessory substance such as isoamyl alcohol, isoprene, thereby the conversion ratio of raising raw material and product is selective.
Another object of the present invention is to provide the preparation method of above-mentioned heterogeneous catalysis, and preparation method is simple.
A further object of the present invention is to provide a kind of reactive distillation process method that adopts this heterogeneous catalysis to prepare 3-M2BOL, pass through the method, can break the equilibrium-limited of isomerization reaction, and water is removed in time from system, improve conversion per pass, reduced energy consumption and production costs.
For reaching above object, the present invention adopts following technical scheme:
The invention provides a kind of heterogeneous catalysis, prepare 3-M2BOL for the isomerization of catalysis 3-methyl-3-butene-1-alcohol, this heterogeneous catalysis comprises carrier and is positioned at three kinds of components on carrier, wherein the first component is selected from palladium, gold, platinum, nickel, the one or two or more of chromium and molybdenum, preferably palladium, the second component is selected from III A, one or two or more in IV A and V A family element, preferably gallium, the one or two or more of germanium and arsenic, more preferably one or both of germanium and arsenic, the third component is selected from the one or two or more in lanthanide series, preferably lanthanum, one or two or more in cerium and praseodymium, more preferably praseodymium.
It is 200～300 ZSM-5 molecular sieve that carrier of the present invention is selected from silica alumina ratio.
In heterogeneous catalysis of the present invention, three kinds of component gross weights account for the 0.1wt%～10wt% of heterogeneous catalysis gross weight, preferably 0.3wt%～5wt%, more preferably 0.5wt%～2wt%; Surplus is carrier; The weight ratio of the first component and second component is 50:1～20:1; The weight ratio of the first component and the 3rd component is 50:1～20:1.
The particle diameter of heterogeneous catalysis of the present invention is 0.5～10mm, preferably 1～5mm.
Heterogeneous catalysis preparation method of the present invention, comprise the following steps: by soluble metallic salt or the oxide of respective metal in three kinds of components, as palladium bichloride, germanium chloride, praseodymium chloride etc., join in proportion and in deionized water, be mixed with the aqueous solution, to the carrier that adds corresponding proportion in this aqueous solution, stir, then leave standstill aging 10～12 hours, after super-dry, at 150～500 DEG C, preferably roasting obtains catalyst precarsor for 2～3 hours at 200～300 DEG C, then 100～200g catalyst precarsor is used hydrogen reducing 0.5～5 hour at 150 DEG C, preferably 1～3 hour, hydrogen flowing quantity is 30～300mL/min, preferably 50～100mL/min, can obtain described heterogeneous catalysis.
The second component of heterogeneous catalysis, Main Function is for to modify the first component, suppress to a certain extent the hydrogenation activity of the first component, especially germanium and/or arsenic, in suppressing the first component hydrogenation activity, ensure the heterogeneous activity of the first component, thereby reached preferably the object of the generation that reduces hydrogenation byproduct isoamyl alcohol.
Lanthanum in the third component, cerium, praseodymium, especially praseodymium, play the effect of stabilizing agent, can reduce the impact of water on the first composition activity in catalyst, improves catalyst stability.
ZSM-5 molecular sieve has less acidic site center and larger specific area, can reduce the generation of water and isoprene.
The present invention also provides a kind of method of preparing 3-M2BOL, is included in reactive distillation column, uses heterogeneous catalysis of the present invention, and 3-methyl-3-butene-1-alcohol is carried out to isomerization reaction under hydrogen and optional inert gas exist.
Reactive distillation column of the present invention comprises tower reactor, stripping section, conversion zone, rectifying section, tower top, wherein tower top has reflux condenser, water knockout drum and emptying system, tower reactor has reboiler, and reactive distillation column theoretical cam curve is 30～150, and preferably 50～100, wherein rectifying section theoretical cam curve is 10～60, preferably 20～50, conversion zone theoretical cam curve is 10～50, preferably 20～40, stripping section theoretical cam curve is 8～40, preferably 10～30.
Heterogeneous catalysis of the present invention mixes with inert filler to be loaded in distillation column reactor section, volume ratio is 1:5～5:1, rectifying section and stripping section are loaded inert filler, described inert filler particle size is 1～10mm, preferably 2～3mm, inert filler is selected from the one or two or more in Raschig ring, θ ring and triangle helical packing etc., more preferably triangle helical packing.
The pressure of reaction of the present invention is absolute pressure 30～760mmHg, preferably 50～760mmHg; The temperature of described reaction is 40～150 DEG C, preferably 50～140 DEG C; The weight (hourly) space velocity (WHSV) of 3-methyl-3-butene-1-alcohol is 2.0～9.0hr
-1, be preferably 3.0～6.0hr
-1, the volume space velocity of hydrogen and optional inert gas is 10～300hr
-1, preferably 100～200hr
-1; The volume ratio of inert gas and hydrogen is 0～99:1, preferably 1～19:1.Described inert gas is selected from the one or two or more in nitrogen, argon gas and helium, preferred nitrogen.
3-methyl-3-butene-1-alcohol of the present invention is from conversion zone its top feed, hydrogen and optional inert gas are from tower reactor air inlet, tower top is infinite reflux, the continuous extraction 3-M2BOL of tower reactor, the water that tower top water knockout drum extraction side reaction produces, remaining gas and low-boiling-point substance are emptying from emptying system.
Advantage of the present invention:
(1) prepare a kind of heterogeneous catalysis, can effectively suppress the water of side reaction generation and the isoamyl alcohol of isoprene and hydrogenation side reaction generation, improved the selective of prenol.
(2) improve the stability of catalyst, reduced the impact of water on catalyst.
(3) by adopting reactive distillation process, isomerization reaction conversion ratio can be reached more than 95.5%, preferably approaches 100%, improved the conversion ratio of reaction, product prenol selective >=96%.
Brief description of the drawings:
Fig. 1 is the reactive distillation column schematic diagram that the present invention uses, and wherein 1 is emptying system, and 2 is condenser, and 3 is water knockout drum, and 4 is rectifying section, and 5 is conversion zone, and 6 is stripping section, and 7 is reboiler, and 8 is product extraction, and 9 is raw material, and 10 is hydrogen and optional inert gas.
Detailed description of the invention:
Analytical instrument: SHIMADZU GC-2010Plus.Chromatographic column is TR-5 chromatographic column, 280 DEG C of temperature of vaporization chamber, 280 DEG C of fid detector temperature, split ratio is 40:1, and bypass flow is 60mL/min, temperature programming: first 50 DEG C keep 1 minute, then 10 ° C/min to 240 DEG C keeps 10 minutes, and be 30 minutes running time.
Reagent source: PdCl
2, GeCl
4, As
2o
3, PrCl
3, CeCl
3be analysis pure, Ke Miou reagent
Catalyst preparation
Embodiment 1
0.83g palladium bichloride, 0.03g germanium chloride, 0.045g praseodymium chloride are joined in the deionized water of 500mL and be mixed with the aqueous solution, be the ZSM-5 molecular sieve of 2-3mm to adding 100g particle size in this aqueous solution, stir, then leave standstill aging 12 hours, obtain catalyst precarsor.Catalyst precarsor is after super-dry, and roasting 2h at 200 DEG C then uses hydrogen reducing 2h at 150 DEG C, and hydrogen flowing quantity is 50mL/min, can obtain 1# catalyst.
Embodiment 2-10
Adopt 150 DEG C of identical preparation processes, 500mL deionized water, 100gZSM-5 molecular sieve carrier, hydrogen reducing temperature with embodiment 1, all the other parameters are prepared respectively 2～10# catalyst according to table 1.
Table 1 catalyst preparation parameter
Note: catalyst composition=composition weight/heterogeneous catalysis gross weight * 100%
Comparative example 1
By Φ 2～3mm, the Pd/Al that Pd load capacity is 1.0wt%
2o
3catalyst 100mL mix and be filled in conversion zone with Φ 2mm θ ring filler 100mL, conversion zone theoretical cam curve is 30, rectifying section and stripping section are respectively loaded the triangle helical packing 150mL of Φ 2mm, theoretical cam curve is respectively 30.System pressure 50mmHg, reaction temperature is 60 DEG C, and different prenol is from conversion zone its top feed, and weight (hourly) space velocity (WHSV) is 3.0hr
-1, hydrogen 20%(volume ratio) and hydrogen nitrogen mixed gas is from stripping section bottom feed, and gaseous mixture volume air speed is 200hr
-1, tower top is set infinite reflux, and hydrogen nitrogen mixed gas and low-boiling-point substance are discharged from emptying system, and reaction produces a small amount of water and separates by water knockout drum, and product is from the continuous extraction of tower reactor.Product is carried out gas chromatographic analysis, different prenol conversion ratio 90.5%, and prenol is selective 92.0%, and isoamyl alcohol is selectively 4.0%, and isoprene is selectively 1.5%, and other is selective 2.5% years old.
Embodiment 11
100mL1# catalyst is mixed and is filled in conversion zone with the triangle helical packing of 100mL Φ 2mm, and conversion zone theoretical cam curve is 30, and rectifying section and stripping section are respectively loaded the triangle helical packing 150mL of Φ 2mm, and theoretical cam curve is respectively 30.System pressure 50mmHg, reaction temperature is 60 DEG C, and different prenol is from conversion zone its top feed, and weight (hourly) space velocity (WHSV) is 3.0hr
-1, hydrogen 20%(volume ratio) and hydrogen nitrogen mixed gas is from stripping section bottom feed, and gaseous mixture volume air speed is 200hr
-1, tower top is set infinite reflux, and hydrogen nitrogen mixed gas and low-boiling-point substance are discharged from emptying system, and reaction produces a small amount of water and separates by water knockout drum, and product is from the continuous extraction of tower reactor.Product is carried out gas chromatographic analysis, different prenol conversion ratio 95.5%, and prenol is selective 96.0%, and isoamyl alcohol is selectively 3.0%, and isoprene is selectively 0.9%, and other is selective 0.1% years old.
Embodiment 12
100mL2# catalyst is mixed and is filled in conversion zone with the triangle helical packing of 100mL Φ 2mm, and conversion zone theoretical cam curve is 30, and rectifying section and stripping section are respectively loaded the triangle helical packing 150mL of Φ 2mm, and theoretical cam curve is respectively 30.System pressure 150mmHg, reaction temperature is 80 DEG C, and different prenol is from conversion zone its top feed, and weight (hourly) space velocity (WHSV) is 6.0hr
-1, hydrogen 10%(volume ratio) and hydrogen nitrogen mixed gas is from stripping section bottom feed, and gaseous mixture gas air speed is 200hr
-1, tower top is set infinite reflux, and hydrogen nitrogen mixed gas and low-boiling-point substance are discharged from emptying system, and reaction produces a small amount of water and separates by water knockout drum, and product is from the continuous extraction of tower reactor.Product is carried out gas chromatographic analysis, different prenol conversion ratio 99.5%, and prenol is selective 98.0%, and isoamyl alcohol is selectively 1.0%, and isoprene is selectively 0.9%, and other is selective 0.1% years old.
Embodiment 13
100mL3# catalyst is mixed and is filled in conversion zone with the triangle helical packing of 100mL Φ 2mm, and conversion zone theoretical cam curve is 30, and rectifying section and stripping section are respectively loaded the triangle helical packing 150mL of Φ 2mm, and theoretical cam curve is respectively 30.System pressure 50mmHg, reaction temperature is 60 DEG C, and different prenol is from conversion zone its top feed, and weight (hourly) space velocity (WHSV) is 3.0hr
-1, hydrogen is from stripping section bottom feed, and hydrogen volume air speed is 100hr
-1, tower top is set infinite reflux, and hydrogen and low-boiling-point substance are discharged from emptying system, and reaction produces a small amount of water and separates by water knockout drum, and product is from the continuous extraction of tower reactor.Product is by gas chromatographic analysis, different prenol conversion ratio 98.5%, and prenol is selective 99.0%, and isoamyl alcohol is selectively 0.5%, and isoprene is selectively 0.4%, and other is selective 0.1% years old.
Embodiment 14
100mL4# catalyst is mixed and is filled in conversion zone with the triangle helical packing of 100mL Φ 2mm, and conversion zone theoretical cam curve is 30, and rectifying section and stripping section are respectively loaded the triangle helical packing 150mL of Φ 2mm, and theoretical cam curve is respectively 30.System pressure 150mmHg, reaction temperature is 80 DEG C, and different prenol is from conversion zone its top feed, and weight (hourly) space velocity (WHSV) is 5.0hr
-1, hydrogen 20%(volume ratio) and hydrogen nitrogen mixed gas is from stripping section bottom feed, and gaseous mixture volume air speed is 150hr
-1, tower top is set infinite reflux, and hydrogen nitrogen mixed gas and low-boiling-point substance are discharged from emptying system, and reaction produces a small amount of water and separates by water knockout drum, and product is from the continuous extraction of tower reactor.Product is by gas chromatographic analysis, different prenol conversion ratio 99.5%, and prenol is selective 99.2%, and isoamyl alcohol is selectively 0.3%, and isoprene is selectively 0.4%, and other is selective 0.1% years old.
Embodiment 15
100mL5# catalyst is mixed and is filled in conversion zone with the triangle helical packing of 100mL Φ 2mm, and conversion zone theoretical cam curve is 30, and rectifying section and stripping section are respectively loaded the triangle helical packing 150mL of Φ 2mm, and theoretical cam curve is respectively 30.System pressure 50mmHg, reaction temperature is 150 DEG C, and different prenol is from conversion zone its top feed, and weight (hourly) space velocity (WHSV) is 3.0hr
-1, hydrogen 5%(volume ratio) and hydrogen nitrogen mixed gas enters reactor from gas distributor, and gaseous mixture volume air speed is 150hr
-1, tower top is set infinite reflux, and hydrogen nitrogen mixed gas and low-boiling-point substance are discharged from emptying system, and reaction produces a small amount of water and separates by water knockout drum, and product is from the continuous extraction of tower reactor.Product is by gas chromatographic analysis, different prenol conversion ratio 96.5%, and prenol is selective 96.5%, and isoamyl alcohol is selectively 2.3%, and isoprene is selectively 1.0%, and other is selective 0.2% years old.
Embodiment 16
100mL6# catalyst is mixed and is filled in conversion zone with the triangle helical packing of 100mL Φ 2mm, and conversion zone theoretical cam curve is 30, and rectifying section and stripping section are respectively loaded the triangle helical packing 150mL of Φ 2mm, and theoretical cam curve is respectively 30.System pressure 150mmHg, reaction temperature is 80 DEG C, and different prenol is from conversion zone its top feed, and weight (hourly) space velocity (WHSV) is 5.0hr
-1, hydrogen 10%(volume ratio) and hydrogen nitrogen mixed gas is from stripping section bottom feed, and gaseous mixture volume air speed is 150hr
-1, tower top is set infinite reflux, and hydrogen nitrogen mixed gas and low-boiling-point substance are discharged from emptying system, and reaction produces a small amount of water and separates by water knockout drum, and product is from the continuous extraction of tower reactor.Product is by gas chromatographic analysis, different prenol conversion ratio 99.5%, and prenol is selective 98.0%, and isoamyl alcohol is selectively 1.0%, and isoprene is selectively 0.9%, and other is selective 0.1% years old.。
Embodiment 17
100mL7# catalyst is mixed and is filled in conversion zone with the triangle helical packing of 100mL Φ 2mm, and conversion zone theoretical cam curve is 30, and rectifying section and stripping section are respectively loaded the triangle helical packing 150mL of Φ 2mm, and theoretical cam curve is respectively 30.System pressure 150mmHg, reaction temperature is 80 DEG C, and different prenol is from conversion zone its top feed, and weight (hourly) space velocity (WHSV) is 5.0hr
-1, hydrogen 20%(volume ratio) and hydrogen nitrogen mixed gas is from stripping section bottom feed, and gaseous mixture hydrogen gas space velocity is 100hr
-1, tower top is set infinite reflux, and hydrogen nitrogen mixed gas and low-boiling-point substance are discharged from emptying system, and reaction produces a small amount of water and separates by water knockout drum, and product is from the continuous extraction of tower reactor.Product is by gas chromatographic analysis, different prenol conversion ratio 97.5%, and prenol is selective 97.1%, and isoamyl alcohol is selectively 2.0%, and isoprene is selectively 0.7%, and other is selective 0.2% years old.
Embodiment 18
100mL8# catalyst is mixed and is filled in conversion zone with the triangle helical packing of 100mL Φ 2mm, and conversion zone theoretical cam curve is 30, and upper-lower section is respectively loaded the triangle helical packing 150mL of Φ 2mm, and rectifying section and stripping section theoretical cam curve are 30.System pressure 50mmHg, reaction temperature is 60 DEG C, and different prenol is from conversion zone its top feed, and weight (hourly) space velocity (WHSV) is 5.0hr
-1, hydrogen 10%(volume ratio) and hydrogen nitrogen mixed gas is from stripping section bottom feed, and gaseous mixture gas air speed is 200hr
-1, tower top is set infinite reflux, and hydrogen nitrogen mixed gas and low-boiling-point substance are discharged from emptying system, and reaction produces a small amount of water and separates by water knockout drum, and product is from the continuous extraction of tower reactor.Product is by gas chromatographic analysis, different prenol conversion ratio 98.2%, and prenol is selective 99.0%, and isoamyl alcohol is selectively 0.1%, and isoprene is selectively 0.8%, and other is selective 0.1% years old.
Embodiment 19
100mL9# catalyst is mixed and is filled in conversion zone with the triangle helical packing of 100mL Φ 2mm, and conversion zone theoretical cam curve is 30, and upper-lower section is respectively loaded the triangle helical packing 150mL of Φ 2mm, and rectifying section and stripping section theoretical cam curve are 30.System pressure 50mmHg, reaction temperature is 60 DEG C, and different prenol is from conversion zone its top feed, and weight (hourly) space velocity (WHSV) is 5.0hr
-1, hydrogen 10%(volume ratio) and hydrogen nitrogen mixed gas is from stripping section bottom feed, and gaseous mixture gas air speed is 200hr
-1, tower top is set infinite reflux, and hydrogen nitrogen mixed gas and low-boiling-point substance are discharged from emptying system, and reaction produces a small amount of water and separates by water knockout drum, and product is from the continuous extraction of tower reactor.Product is by gas chromatographic analysis, different prenol conversion ratio 98.5%, and prenol is selective 97.8%, and isoamyl alcohol is selectively 1.6%, and isoprene is selectively 0.5%, and other is selective 0.1% years old.
Embodiment 20
100mL10# catalyst is mixed and is filled in conversion zone with the triangle helical packing of 100mL Φ 2mm, and conversion zone theoretical cam curve is 30, and upper-lower section is respectively loaded the triangle helical packing 150mL of Φ 2mm, and rectifying section and stripping section theoretical cam curve are 30.System pressure 50mmHg, reaction temperature is 60 DEG C, and different prenol is from conversion zone its top feed, and weight (hourly) space velocity (WHSV) is 5.0hr
-1, hydrogen 10%(volume ratio) and hydrogen nitrogen mixed gas is from stripping section bottom feed, and gaseous mixture gas air speed is 200hr
-1, tower top is set infinite reflux, and hydrogen nitrogen mixed gas and low-boiling-point substance are discharged from emptying system, and reaction produces a small amount of water and separates by water knockout drum, and product is from the continuous extraction of tower reactor.Product is by gas chromatographic analysis, different prenol conversion ratio 97.0%, and prenol is selective 99.2%, and isoamyl alcohol is selectively 0.1%, and isoprene is selectively 0.6%, and other is selective 0.1% years old.
In the above-described embodiments, on the one hand by the effect of heterogeneous catalysis, by adopting reactive distillation process, isomerization reaction conversion ratio can be reached more than 95.5% on the other hand, preferably approach 100%, improved the conversion ratio of reaction.Can effectively suppress the isoprene that side reaction produces selective≤1%, the isoamyl alcohol that hydrogenation side reaction produces selective≤3%, prenol selective >=96%.
The above description of this invention is not limited to scope of the present invention.For the person of ordinary skill of the art, can make various corresponding changes according to technical scheme provided by the invention, these change all should belong to protection scope of the present invention.
Claims (10)
1. a heterogeneous catalysis, prepare 3-M2BOL for the isomerization of catalysis 3-methyl-3-butene-1-alcohol, it is characterized in that, described heterogeneous catalysis comprises carrier and is positioned at three kinds of components on carrier, the first component is selected from palladium, gold, platinum, nickel, the one or two or more of chromium and molybdenum, preferably palladium, the second component is selected from III A, one or two or more in IV A and V A family element, preferably gallium, the one or two or more of germanium and arsenic, more preferably one or both of germanium and arsenic, the third component is selected from the one or two or more in lanthanide series, preferably lanthanum, one or two or more in cerium and praseodymium, more preferably praseodymium.
2. heterogeneous catalysis according to claim 1, is characterized in that, it is 200～300 ZSM-5 molecular sieve that described carrier is selected from silica alumina ratio.
3. heterogeneous catalysis according to claim 1 and 2, is characterized in that, described three kinds of component gross weights account for the 0.1wt%～10wt% of described heterogeneous catalysis gross weight, preferably 0.3wt%～5wt%, more preferably 0.5wt%～2wt%; The first component and second component weight ratio are 50:1～20:1, and the first component and the 3rd components by weight are 50:1～20:1.
4. according to the heterogeneous catalysis described in claim 1-3 any one, it is characterized in that, described heterogeneous catalysis particle diameter is 0.5～10mm, preferably 1～5mm.
5. prepare the method for the heterogeneous catalysis described in claim 1-4 any one for one kind, comprise the following steps: by soluble metallic salt or the oxide of respective metal in three kinds of components, join in proportion and in deionized water, be mixed with the aqueous solution, to the carrier that adds corresponding proportion in this aqueous solution, stir, then leave standstill aging 10～12 hours, after super-dry, at 150～500 DEG C, preferably roasting obtains catalyst precarsor for 2～3 hours at 200～300 DEG C, then 100～200g catalyst precarsor is used hydrogen reducing 0.5～5 hour at 150 DEG C, preferably 1～3 hour, hydrogen flowing quantity is 30～300mL/min, preferably 50～100mL/min.
6. a heterogeneous catalysis that utilizes heterogeneous catalysis described in claim 1-4 any one or method claimed in claim 5 to prepare is prepared the method for 3-M2BOL, it is characterized in that, in reactive distillation column, use described heterogeneous catalysis, 3-methyl-3-butene-1-alcohol is carried out to isomerization reaction under hydrogen and optional inert gas exist.
7. method according to claim 6, is characterized in that, described reactive distillation column comprises tower reactor, stripping section, conversion zone, rectifying section, tower top, wherein tower top has reflux condenser, water knockout drum and emptying system, tower reactor has reboiler, and reactive distillation column theoretical cam curve is 30～150, and preferably 50～100, wherein rectifying section theoretical cam curve is 10～60, preferably 20～50, conversion zone theoretical cam curve is 10～50, preferably 20～40, stripping section theoretical cam curve is 8～40, preferably 10～30.
8. according to the method described in claim 6 or 7, it is characterized in that: the pressure of described reaction is absolute pressure 30～760mmHg, preferably 50～760mmHg; The temperature of described reaction is 40～150 DEG C, preferably 50～140 DEG C; The weight (hourly) space velocity (WHSV) of 3-methyl-3-butene-1-alcohol is 2.0～9.0hr
-1, be preferably 3.0～6.0hr
-1, the volume space velocity of hydrogen and optional inert gas is 10～300hr
-1, preferably 100～200hr
-1; The volume ratio of inert gas and hydrogen is 0～99:1, preferably 1～19:1.
9. according to the method described in claim 6-8 any one, it is characterized in that: described heterogeneous catalysis mixes with inert filler to be loaded in distillation column reactor section, and volume ratio is 1:5～5:1, rectifying section and stripping section are loaded inert filler.
10. according to the method described in claim 6-9 any one, it is characterized in that: 3-methyl-3-butene-1-alcohol is from conversion zone its top feed, hydrogen and optional inert gas are from tower reactor air inlet, tower top is infinite reflux, the continuous extraction 3-M2BOL of tower reactor, the water that tower top water knockout drum extraction side reaction produces, remaining gas and low-boiling-point substance are emptying from emptying system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410063025.6A CN103861633B (en) | 2014-02-24 | 2014-02-24 | A kind of heterogeneous catalysis and preparation method thereof and utilize the method for this catalyst preparing 3-M2BOL |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410063025.6A CN103861633B (en) | 2014-02-24 | 2014-02-24 | A kind of heterogeneous catalysis and preparation method thereof and utilize the method for this catalyst preparing 3-M2BOL |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103861633A true CN103861633A (en) | 2014-06-18 |
| CN103861633B CN103861633B (en) | 2015-11-25 |
Family
ID=50900996
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410063025.6A Active CN103861633B (en) | 2014-02-24 | 2014-02-24 | A kind of heterogeneous catalysis and preparation method thereof and utilize the method for this catalyst preparing 3-M2BOL |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103861633B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107754790A (en) * | 2017-11-07 | 2018-03-06 | 万华化学集团股份有限公司 | Prepare linalool catalyst and preparation method thereof, the method for preparing linalool |
| CN112121848A (en) * | 2020-10-30 | 2020-12-25 | 万华化学集团股份有限公司 | Modified hierarchical pore molecular sieve catalyst, preparation method thereof and production method of 3-methyl-2-butene-1-ol |
| WO2021142938A1 (en) * | 2020-01-17 | 2021-07-22 | 浙江新和成股份有限公司 | Ceramic corrugated plate catalyst coated with metal oxide, preparation therefor, and use thereof in preparing key intermediate of citral |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008037693A1 (en) * | 2006-09-26 | 2008-04-03 | Basf Se | Continuous method for producing citral |
| CN101940928A (en) * | 2009-07-06 | 2011-01-12 | 中国石油化工股份有限公司上海石油化工研究院 | Nickel-based catalyst for hydroisomerization of n-butene for preparing butene-2 or butene-1 |
| CN101965325A (en) * | 2008-02-28 | 2011-02-02 | 巴斯夫欧洲公司 | Method for isomerizing olefinically unsaturated alcohols |
| CN102675048A (en) * | 2012-04-20 | 2012-09-19 | 山东新和成药业有限公司 | Method for synthesizing prenol by composite catalyst |
-
2014
- 2014-02-24 CN CN201410063025.6A patent/CN103861633B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008037693A1 (en) * | 2006-09-26 | 2008-04-03 | Basf Se | Continuous method for producing citral |
| CN101965325A (en) * | 2008-02-28 | 2011-02-02 | 巴斯夫欧洲公司 | Method for isomerizing olefinically unsaturated alcohols |
| CN101940928A (en) * | 2009-07-06 | 2011-01-12 | 中国石油化工股份有限公司上海石油化工研究院 | Nickel-based catalyst for hydroisomerization of n-butene for preparing butene-2 or butene-1 |
| CN102675048A (en) * | 2012-04-20 | 2012-09-19 | 山东新和成药业有限公司 | Method for synthesizing prenol by composite catalyst |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107754790A (en) * | 2017-11-07 | 2018-03-06 | 万华化学集团股份有限公司 | Prepare linalool catalyst and preparation method thereof, the method for preparing linalool |
| CN107754790B (en) * | 2017-11-07 | 2021-02-02 | 万华化学集团股份有限公司 | Catalyst for preparing linalool, preparation method of catalyst and method for preparing linalool |
| WO2021142938A1 (en) * | 2020-01-17 | 2021-07-22 | 浙江新和成股份有限公司 | Ceramic corrugated plate catalyst coated with metal oxide, preparation therefor, and use thereof in preparing key intermediate of citral |
| CN112121848A (en) * | 2020-10-30 | 2020-12-25 | 万华化学集团股份有限公司 | Modified hierarchical pore molecular sieve catalyst, preparation method thereof and production method of 3-methyl-2-butene-1-ol |
| CN112121848B (en) * | 2020-10-30 | 2022-08-05 | 万华化学集团股份有限公司 | Modified hierarchical pore molecular sieve catalyst, preparation method thereof and production method of 3-methyl-2-butene-1-ol |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103861633B (en) | 2015-11-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Bienholz et al. | Selective hydrogenolysis of glycerol over copper catalysts both in liquid and vapour phase: Correlation between the copper surface area and the catalyst's activity | |
| CN105263621A (en) | Process for the production of 1,3-butadiene | |
| CN101745389A (en) | A kind of egg-shell catalyst that is used for preparation of ethylene through selective hydrogenation of acetylene | |
| CN101544538B (en) | Method for preparing isopentenol from 3-methyl-3-butenol | |
| CN103275096B (en) | A kind of method preparing Isosorbide based on Mierocrystalline cellulose | |
| CN103861633B (en) | A kind of heterogeneous catalysis and preparation method thereof and utilize the method for this catalyst preparing 3-M2BOL | |
| CN100503534C (en) | Method for synthesis of isopropanol | |
| KR101325457B1 (en) | Method for producing olefin | |
| CN105435779B (en) | Carbon monoxide vapor- phase synthesis oxalate catalyst | |
| CN103127945A (en) | Method for preparing catalyst used for preparing acetaldehyde through direct dehydrogenation of ethanol and application of catalyst | |
| CN104193606A (en) | Technique for preparing acetone from synthetic gas | |
| CN101209415B (en) | Catalyst for preparing linalyl acetate by hydrogenation of dehydrogenated linalyl acetate | |
| CN103130625B (en) | Method for preparing acetaldehyde and co-producing acetal by using ethanol | |
| CN103787810B (en) | Dehydrogenation method of mixed light alkane | |
| CN103497093A (en) | Method for preparing benzaldehyde through low-temperature gas-phase selective catalytic oxidation of benzyl alcohol | |
| CN110981698B (en) | Preparation method of 3-methyl-2-butenol | |
| CN101747138B (en) | One-step catalytic isomerization preparation method of terpinolene | |
| CN101209966A (en) | Method for preparing dehydrolinalyl acetate from dehydrolinalool | |
| CN107754790B (en) | Catalyst for preparing linalool, preparation method of catalyst and method for preparing linalool | |
| CN103787816B (en) | Cyclohexene preparation process by partial hydrogenation of benzene | |
| CN108554405B (en) | Barium ion modified noble metal loaded zirconium-magnesium composite oxide catalyst and preparation method and application thereof | |
| CN101289376A (en) | Process for synthesizing 3,3-dimethyl-2-butanone | |
| CN105709777A (en) | Catalyst for preparing ethanol through acetic acid hydrogenation, preparation method of catalyst and method for preparing ethanol through acetic acid hydrogenation | |
| CN109809973A (en) | A method of preparing 2- ethyl hexanal | |
| CN101209967A (en) | Method for preparing linalyl acetate from dehydrolinalool |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee | ||
| CP02 | Change in the address of a patent holder |
Address after: 264002 Yantai economic and Technological Development Zone, Shandong, Tian Shan Road, No. 17 Patentee after: Wanhua Chemical Group Co., Ltd. Patentee after: Wanhua Chemical (Ningbo) Co., Ltd. Address before: 264002 Yantai City, Shandong province Zhifu District No. 7 Patentee before: Wanhua Chemical Group Co., Ltd. Patentee before: Wanhua Chemical (Ningbo) Co., Ltd. |