CN103861633B - A kind of heterogeneous catalysis and preparation method thereof and utilize the method for this catalyst preparing 3-M2BOL - Google Patents
A kind of heterogeneous catalysis and preparation method thereof and utilize the method for this catalyst preparing 3-M2BOL Download PDFInfo
- Publication number
- CN103861633B CN103861633B CN201410063025.6A CN201410063025A CN103861633B CN 103861633 B CN103861633 B CN 103861633B CN 201410063025 A CN201410063025 A CN 201410063025A CN 103861633 B CN103861633 B CN 103861633B
- Authority
- CN
- China
- Prior art keywords
- heterogeneous catalysis
- hydrogen
- component
- cam curve
- theoretical cam
- 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.)
- Active
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
Abstract
The invention provides a kind of heterogeneous catalysis and preparation method thereof and utilize the method for this catalyst preparing 3-M2BOL.Described heterogeneous catalysis comprises carrier and is positioned at three kinds of components on carrier, wherein the first component is selected from the one or two or more of palladium, gold, platinum, nickel, chromium and molybdenum, the second component is selected from the one or two or more in III A, IV A and V A race element, and the third component is selected from the one or two or more in lanthanide series.Described preparation method comprises 3-methyl-3-butene-1-alcohol under the effect of described heterogeneous catalysis, obtains 3-M2BOL through reactive distillation process.According to method of the present invention, the yield of 3-M2BOL and selective, raising catalyst stability can be significantly improved, thus reduce production cost.
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 adopting this heterogeneous catalysis to prepare 3-M2BOL in reactive distillation process.
Background technology:
3-M2BOL, i.e. prenol, be 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's deepening continuously to 3-M2BOL synthesis technique, range of application will expand further, and demand also will significantly rise.Therefore, and using value significant to the research of 3-M2BOL synthetic technology is strengthened.
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 under the existence of sodium hydrogen phosphate the mixture generating 3-methyl-3-butene-1-alcohol and 3-M2BOL, then under Pd/C catalyst, enol transposition is become prenol.(2) isoprene method: be that raw material and hcl reaction generate chloroisoamylene with isoprene, the chloro-3-methyl of 1-wherein-3-butylene is 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, and generate acetenyl isopropyl alcohol, then carry out hydrogenation with Pd/C catalyst and obtain methyl butenol, re-isomerization obtains 3-M2BOL.
WO2008037693 describes 3-methyl-3-butene-1-alcohol isomerization on heterogeneous noble metal catalyst in presence of hydrogen and produces 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 the isoamyl alcohol being formed to many 2.5%.
US4117016 describes unsaturated alcohol isomerization in the liquid phase under the homogeneous phase ruthenium of catalytic amount-hydrogen complex exists under part exists, and clearly eliminates the existence of trace oxygen, to guarantee catalyst stability.3-methyl-3-butene-1-alcohol isomery turns to 3-M2BOL and only carries out with low yield under a nitrogen, and this does not have economic interests.
CN101965325 describes 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 the valuable product of 93.4% to multipotency, wherein have the isoamyl olefine aldehydr of a great deal of, accessory substance is more, is separated more difficult.
CN102675048 describes the method utilizing composite catalyst to synthesize 3-M2BOL.With 3-methyl-3-butene-1-alcohol for raw material, adopt the composite catalyst of Raney's nickel and solid super-strong acid composition, 3-methyl-3-butene-1-alcohol isomery is made to 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 prepares 3-M2BOL is balanced reaction, be difficult under normal circumstances make conversion ratio reach 100%, in the patent described, fundamentally do not solve the not high problem of balanced reaction conversion ratio, and the hydrogenation byproduct isoamyl alcohol produced is difficult to be separated, and removing needs higher expense.
In the patent described, utilize loading type Pd/Al
2o
3catalyst carries out isomerization reaction, easy generation hydrogenation byproduct isoamyl alcohol and dewater 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 in the catalyst and suppress hydrogenation, but these two kinds of metal pair catalyst itself have poisoning effect, make catalyst activity reduce.Therefore need selection to have relatively hypotoxic dressing agent, can hydrogenation reaction be suppressed, not reduce catalyst activity again.And the latter has stronger acidity due to alumina catalyst support, impel alcohol to dewater, therefore need to select acid more weak carrier, suppress dehydration of alcohols reaction.
The defect that prior art exists:
(1) single transformation rate is not high, and the single transformation rate 60-70% at the most mentioned in existing patent, target selectivity is at most 95%, and too high conversion ratio causes target product selectivity to decline, and 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, the generation of the accessory substance such as isoamyl alcohol, isoprene can be suppressed, thus improve the conversion ratio of raw material and the selective of product.
Another object of the present invention is the preparation method providing above-mentioned heterogeneous catalysis, and preparation method is simple.
Another object of the present invention is to provide a kind of reactive distillation process method adopting this heterogeneous catalysis to prepare 3-M2BOL, pass through the method, the balance restriction of isomerization reaction can be broken, and water is removed in time from system, improve conversion per pass, reduce energy consumption and production costs.
For reaching above object, the present invention adopts following technical scheme:
The invention provides a kind of heterogeneous catalysis, 3-M2BOL is prepared 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, preferred palladium, the second component is selected from III A, one or two or more in IV A and V A race element, preferred 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, preferred lanthanum, one or two or more in cerium and praseodymium, more preferably praseodymium.
Carrier of the present invention is selected from the ZSM-5 molecular sieve that silica alumina ratio is 200 ~ 300.
In heterogeneous catalysis of the present invention, three kinds of component gross weights account for the 0.1wt% ~ 10wt% of heterogeneous catalysis gross weight, preferred 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 three components 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 the soluble metallic salt of respective metal in three kinds of components or oxide, as palladium bichloride, germanium chloride, praseodymium chloride etc., join in deionized water in proportion and be mixed with the aqueous solution, the carrier of corresponding proportion is added in this aqueous solution, stir, then aging 10 ~ 12 hours are left standstill, after super-dry, at 150 ~ 500 DEG C, preferably roasting obtains catalyst precarsor in 2 ~ 3 hours at 200 ~ 300 DEG C, then 100 ~ 200g catalyst precarsor uses 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, described heterogeneous catalysis can be obtained.
The second component of heterogeneous catalysis, Main Function is for modify the first component, suppress the hydrogenation activity of the first component to a certain extent, especially germanium and/or arsenic, while the first component hydrogenation activity of suppression, ensure that the heterogeneous activity of the first component, thus reach the object of the generation reducing hydrogenation byproduct isoamyl alcohol preferably.
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 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 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 pieces, 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 load 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, tower top water knockout drum extraction side reaction produce water, remaining gas and low-boiling-point substance emptying from emptying system.
Advantage of the present invention:
(1) prepared a kind of heterogeneous catalysis, the isoamyl alcohol of the water that can effectively suppress side reaction to produce and isoprene and hydrogenation side reaction generation, improves the selective of prenol.
(2) improve the stability of catalyst, reduce the impact of water on catalyst.
(3) by adopt reactive distillation process, enable isomerization reaction conversion ratio reach more than 95.5%, preferably close to 100%, improve the conversion ratio of reaction, product prenol selective >=96%.
Accompanying drawing illustrates:
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: SHIMADZUGC-2010Plus.Chromatographic column is TR-5 chromatographic column, temperature of vaporization chamber 280 DEG C, fid detector temperature 280 DEG C, split ratio is 40:1, and bypass flow is 60mL/min, temperature programming: first 50 DEG C keep 1 minute, then 10 ° of C/min keep 10 minutes to 240 DEG C, and running time is 30 minutes.
Reagent source: PdCl
2, GeCl
4, As
2o
3, PrCl
3, CeCl
3be analysis pure, Ke Miou reagent
Catalyst preparing
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, the ZSM-5 molecular sieve that 100g particle size is 2-3mm is added 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 identical preparation process, 500mL deionized water, 100gZSM-5 molecular sieve carrier, hydrogen reducing temperature 150 DEG C with embodiment 1, all the other parameters prepare 2 ~ 10# catalyst respectively according to table 1.
Table 1 catalyst preparing parameter
Note: catalyst composition=composition weight/heterogeneous catalysis gross weight * 100%
Comparative example 1
Be the Pd/Al of 1.0wt% by Φ 2 ~ 3mm, Pd load capacity
2o
3catalyst 100mL mix with Φ 2mm θ ring filler 100mL and be filled in conversion zone, conversion zone theoretical cam curve is 30 pieces, and rectifying section and stripping section respectively load the triangle helical packing 150mL of Φ 2mm, and theoretical cam curve is respectively 30 pieces.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 space velocity is 200hr
-1, tower top setting infinite reflux, hydrogen nitrogen mixed gas and low-boiling-point substance are discharged from emptying system, and reaction is produced a small amount of water and separated by water knockout drum, and product is from the continuous extraction of tower reactor.Product carries out gas chromatographic analysis, different prenol conversion ratio 90.5%, prenol selective 92.0%, and isoamyl alcohol is selective is 4.0%, and isoprene is selective is 1.5%, and other is selective 2.5% years old.
Embodiment 11
Mixed with the triangle helical packing of 100mL Φ 2mm by 100mL1# catalyst and be filled in conversion zone, conversion zone theoretical cam curve is 30 pieces, and rectifying section and stripping section respectively load the triangle helical packing 150mL of Φ 2mm, and theoretical cam curve is respectively 30 pieces.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 space velocity is 200hr
-1, tower top setting infinite reflux, hydrogen nitrogen mixed gas and low-boiling-point substance are discharged from emptying system, and reaction is produced a small amount of water and separated by water knockout drum, and product is from the continuous extraction of tower reactor.Product carries out gas chromatographic analysis, different prenol conversion ratio 95.5%, prenol selective 96.0%, and isoamyl alcohol is selective is 3.0%, and isoprene is selective is 0.9%, and other is selective 0.1% years old.
Embodiment 12
Mixed with the triangle helical packing of 100mL Φ 2mm by 100mL2# catalyst and be filled in conversion zone, conversion zone theoretical cam curve is 30 pieces, and rectifying section and stripping section respectively load the triangle helical packing 150mL of Φ 2mm, and theoretical cam curve is respectively 30 pieces.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 space velocity is 200hr
-1, tower top setting infinite reflux, hydrogen nitrogen mixed gas and low-boiling-point substance are discharged from emptying system, and reaction is produced a small amount of water and separated by water knockout drum, and product is from the continuous extraction of tower reactor.Product carries out gas chromatographic analysis, different prenol conversion ratio 99.5%, prenol selective 98.0%, and isoamyl alcohol is selective is 1.0%, and isoprene is selective is 0.9%, and other is selective 0.1% years old.
Embodiment 13
Mixed with the triangle helical packing of 100mL Φ 2mm by 100mL3# catalyst and be filled in conversion zone, conversion zone theoretical cam curve is 30 pieces, and rectifying section and stripping section respectively load the triangle helical packing 150mL of Φ 2mm, and theoretical cam curve is respectively 30 pieces.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 setting infinite reflux, hydrogen and low-boiling-point substance are discharged from emptying system, and reaction is produced a small amount of water and separated by water knockout drum, and product is from the continuous extraction of tower reactor.Product is by gas chromatographic analysis, and different prenol conversion ratio 98.5%, prenol selective 99.0%, isoamyl alcohol is selective is 0.5%, and isoprene is selective is 0.4%, and other is selective 0.1% years old.
Embodiment 14
Mixed with the triangle helical packing of 100mL Φ 2mm by 100mL4# catalyst and be filled in conversion zone, conversion zone theoretical cam curve is 30 pieces, and rectifying section and stripping section respectively load the triangle helical packing 150mL of Φ 2mm, and theoretical cam curve is respectively 30 pieces.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 space velocity is 150hr
-1, tower top setting infinite reflux, hydrogen nitrogen mixed gas and low-boiling-point substance are discharged from emptying system, and reaction is produced a small amount of water and separated by water knockout drum, and product is from the continuous extraction of tower reactor.Product is by gas chromatographic analysis, and different prenol conversion ratio 99.5%, prenol selective 99.2%, isoamyl alcohol is selective is 0.3%, and isoprene is selective is 0.4%, and other is selective 0.1% years old.
Embodiment 15
Mixed with the triangle helical packing of 100mL Φ 2mm by 100mL5# catalyst and be filled in conversion zone, conversion zone theoretical cam curve is 30 pieces, and rectifying section and stripping section respectively load the triangle helical packing 150mL of Φ 2mm, and theoretical cam curve is respectively 30 pieces.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 space velocity is 150hr
-1, tower top setting infinite reflux, hydrogen nitrogen mixed gas and low-boiling-point substance are discharged from emptying system, and reaction is produced a small amount of water and separated by water knockout drum, and product is from the continuous extraction of tower reactor.Product is by gas chromatographic analysis, and different prenol conversion ratio 96.5%, prenol selective 96.5%, isoamyl alcohol is selective is 2.3%, and isoprene is selective is 1.0%, and other is selective 0.2% years old.
Embodiment 16
Mixed with the triangle helical packing of 100mL Φ 2mm by 100mL6# catalyst and be filled in conversion zone, conversion zone theoretical cam curve is 30 pieces, and rectifying section and stripping section respectively load the triangle helical packing 150mL of Φ 2mm, and theoretical cam curve is respectively 30 pieces.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 space velocity is 150hr
-1, tower top setting infinite reflux, hydrogen nitrogen mixed gas and low-boiling-point substance are discharged from emptying system, and reaction is produced a small amount of water and separated by water knockout drum, and product is from the continuous extraction of tower reactor.Product is by gas chromatographic analysis, and different prenol conversion ratio 99.5%, prenol selective 98.0%, isoamyl alcohol is selective is 1.0%, and isoprene is selective is 0.9%, and other is selective 0.1% years old.。
Embodiment 17
Mixed with the triangle helical packing of 100mL Φ 2mm by 100mL7# catalyst and be filled in conversion zone, conversion zone theoretical cam curve is 30 pieces, and rectifying section and stripping section respectively load the triangle helical packing 150mL of Φ 2mm, and theoretical cam curve is respectively 30 pieces.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 setting infinite reflux, hydrogen nitrogen mixed gas and low-boiling-point substance are discharged from emptying system, and reaction is produced a small amount of water and separated by water knockout drum, and product is from the continuous extraction of tower reactor.Product is by gas chromatographic analysis, and different prenol conversion ratio 97.5%, prenol selective 97.1%, isoamyl alcohol is selective is 2.0%, and isoprene is selective is 0.7%, and other is selective 0.2% years old.
Embodiment 18
Mixed with the triangle helical packing of 100mL Φ 2mm by 100mL8# catalyst and be filled in conversion zone, conversion zone theoretical cam curve is 30 pieces, and upper-lower section respectively loads the triangle helical packing 150mL of Φ 2mm, and rectifying section and stripping section theoretical cam curve are 30 pieces.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 space velocity is 200hr
-1, tower top setting infinite reflux, hydrogen nitrogen mixed gas and low-boiling-point substance are discharged from emptying system, and reaction is produced a small amount of water and separated by water knockout drum, and product is from the continuous extraction of tower reactor.Product is by gas chromatographic analysis, and different prenol conversion ratio 98.2%, prenol selective 99.0%, isoamyl alcohol is selective is 0.1%, and isoprene is selective is 0.8%, and other is selective 0.1% years old.
Embodiment 19
Mixed with the triangle helical packing of 100mL Φ 2mm by 100mL9# catalyst and be filled in conversion zone, conversion zone theoretical cam curve is 30 pieces, and upper-lower section respectively loads the triangle helical packing 150mL of Φ 2mm, and rectifying section and stripping section theoretical cam curve are 30 pieces.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 space velocity is 200hr
-1, tower top setting infinite reflux, hydrogen nitrogen mixed gas and low-boiling-point substance are discharged from emptying system, and reaction is produced a small amount of water and separated by water knockout drum, and product is from the continuous extraction of tower reactor.Product is by gas chromatographic analysis, and different prenol conversion ratio 98.5%, prenol selective 97.8%, isoamyl alcohol is selective is 1.6%, and isoprene is selective is 0.5%, and other is selective 0.1% years old.
Embodiment 20
Mixed with the triangle helical packing of 100mL Φ 2mm by 100mL10# catalyst and be filled in conversion zone, conversion zone theoretical cam curve is 30 pieces, and upper-lower section respectively loads the triangle helical packing 150mL of Φ 2mm, and rectifying section and stripping section theoretical cam curve are 30 pieces.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 space velocity is 200hr
-1, tower top setting infinite reflux, hydrogen nitrogen mixed gas and low-boiling-point substance are discharged from emptying system, and reaction is produced a small amount of water and separated by water knockout drum, and product is from the continuous extraction of tower reactor.Product is by gas chromatographic analysis, and different prenol conversion ratio 97.0%, prenol selective 99.2%, isoamyl alcohol is selective is 0.1%, and isoprene is selective is 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, on the other hand by adopting reactive distillation process, enabling isomerization reaction conversion ratio reach more than 95.5%, preferably close to 100%, improve the conversion ratio of reaction.The isoprene that can effectively suppress side reaction to produce is 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 change according to technical scheme provided by the invention, these changes all should belong to protection scope of the present invention.
Claims (15)
1. a heterogeneous catalysis, 3-M2BOL is prepared 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, first component is selected from one or more of palladium, gold, platinum, nickel, chromium and molybdenum, the second component is selected from one or both of germanium and arsenic, the third component be selected from lanthanum, cerium and praseodymium one or more; Described three kinds of component gross weights account for the 0.1wt% ~ 10wt% of described heterogeneous catalysis gross weight; First component and second component weight ratio are 50:1 ~ 20:1, and the first component and three components weight ratio are 50:1 ~ 20:1.
2. heterogeneous catalysis according to claim 1, is characterized in that, described three kinds of component gross weights account for the 0.3wt% ~ 5wt% of described heterogeneous catalysis gross weight.
3. heterogeneous catalysis according to claim 2, is characterized in that, described three kinds of component gross weights account for the 0.5wt% ~ 2wt% of described heterogeneous catalysis gross weight.
4. the heterogeneous catalysis according to any one of claim 1-3, is characterized in that, described carrier is selected from the ZSM-5 molecular sieve that silica alumina ratio is 200 ~ 300.
5. heterogeneous catalysis according to claim 4, is characterized in that, described heterogeneous catalysis particle diameter is 0.5 ~ 10mm.
6. heterogeneous catalysis according to claim 5, is characterized in that, described heterogeneous catalysis particle diameter is 1 ~ 5mm.
7. prepare the method for the heterogeneous catalysis described in any one of claim 1-6 for one kind, comprise the following steps: by the soluble metallic salt of respective metal in three kinds of components or oxide, join in deionized water in proportion and be mixed with the aqueous solution, the carrier of corresponding proportion is added in this aqueous solution, stir, then aging 10 ~ 12 hours are left standstill, after super-dry, at 150 ~ 500 DEG C, roasting obtains catalyst precarsor in 2 ~ 3 hours, then 100 ~ 200g catalyst precarsor uses hydrogen reducing 0.5 ~ 5 hour at 150 DEG C, and hydrogen flowing quantity is 30 ~ 300mL/min.
8. method according to claim 7, is characterized in that, sintering temperature is 200 ~ 300 DEG C, hydrogen reducing 1 ~ 3 hour, and hydrogen flowing quantity is 50 ~ 100mL/min.
9. the heterogeneous catalysis utilizing the heterogeneous catalysis described in any one of claim 1-6 or the method described in claim 7 or 8 to prepare prepares 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 isomerization reaction under hydrogen and optional inert gas exist.
10. method according to claim 9, it 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 wherein rectifying section theoretical cam curve is 10 ~ 60, conversion zone theoretical cam curve is 10 ~ 50, and stripping section theoretical cam curve is 8 ~ 40.
11. methods according to claim 10, is characterized in that, described reactive distillation column theoretical cam curve is 50 ~ 100, and wherein rectifying section theoretical cam curve is 20 ~ 50, and conversion zone theoretical cam curve is 20 ~ 40, and stripping section theoretical cam curve is 10 ~ 30.
12. methods according to claim 9, is characterized in that: the pressure of described reaction is absolute pressure 30 ~ 760mmHg; The temperature of described reaction is 40 ~ 150 DEG C; The weight (hourly) space velocity (WHSV) of 3-methyl-3-butene-1-alcohol is 2.0 ~ 9.0hr
-1, the volume space velocity of hydrogen and optional inert gas is 10 ~ 300hr
-1; The volume ratio of inert gas and hydrogen is 0 ~ 99:1.
13. methods according to claim 12, is characterized in that: the pressure of described reaction is absolute pressure 50 ~ 760mmHg; The temperature of described reaction is 50 ~ 140 DEG C; The weight (hourly) space velocity (WHSV) of 3-methyl-3-butene-1-alcohol is 3.0 ~ 6.0hr
-1, the volume space velocity of hydrogen and optional inert gas is 100 ~ 200hr
-1; The volume ratio of inert gas and hydrogen is 1 ~ 19:1.
14. methods according to any one of claim 10-13, 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, and rectifying section and stripping section load inert filler.
15. methods according to claim 14, 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, tower top water knockout drum extraction side reaction produce water, remaining gas and low-boiling-point substance 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 CN103861633A (en) | 2014-06-18 |
| CN103861633B true 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) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN111167471B (en) * | 2020-01-17 | 2020-10-02 | 浙江新和成股份有限公司 | Metal oxide coated ceramic corrugated plate catalyst, preparation and application thereof in preparation of citral key intermediate |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008037693A1 (en) * | 2006-09-26 | 2008-04-03 | Basf Se | Continuous method for producing citral |
-
2014
- 2014-02-24 CN CN201410063025.6A patent/CN103861633B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103861633A (en) | 2014-06-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106824259B (en) | The molecular sieve catalyst of yttrium containing zinc, preparation method and the application method of 1,3- butadiene are prepared for ethyl alcohol conversion | |
| CN102489315B (en) | Ruthenium catalyst, preparation method and application in synthesizing tetrahydrofurfuryl alcohol | |
| CN109806883B (en) | Catalyst, method for preparing 3-aminopropanol by using catalyst and system used by method | |
| 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 | |
| CN103861633B (en) | A kind of heterogeneous catalysis and preparation method thereof and utilize the method for this catalyst preparing 3-M2BOL | |
| CN106164028A (en) | Composite metal catalyst compositions and use it to be used for the method and apparatus preparing 1,4 cyclohexanedimethanols | |
| CN101544538A (en) | Method for preparing isopentenol from 3-methyl-3-butenol | |
| CN100503534C (en) | Method for synthesis of isopropanol | |
| CN103275096A (en) | Method for preparing isosorbide based on cellulose | |
| CN101618335A (en) | Method for preparing catalyst for compounding p-diethylbenzene by alkylation reaction of ethylbenzene and ethane or alcohol | |
| CN101018755A (en) | Process for the preparation of saturated aliphatic ketones | |
| CN101209415B (en) | Catalyst for preparing linalyl acetate by hydrogenation of dehydrogenated linalyl acetate | |
| CN103497093A (en) | Method for preparing benzaldehyde through low-temperature gas-phase selective catalytic oxidation of benzyl alcohol | |
| CN103787810B (en) | Dehydrogenation method of mixed light alkane | |
| CN103664457A (en) | Selective hydrogenation method of crude isopentene | |
| CN101289376B (en) | Process for synthesizing 3,3-dimethyl-2-butanone | |
| CN101747138B (en) | One-step catalytic isomerization preparation method of terpinolene | |
| CN103357427A (en) | Nano-metal/solid alkali composite catalyst, preparation method and applications | |
| CN107754790B (en) | Catalyst for preparing linalool, preparation method of catalyst and method for preparing linalool | |
| CN107970927A (en) | Selective hydrogenation of pyrolysis gas catalyst, preparation method and method of hydrotreating | |
| CN110981698A (en) | Preparation method of 3-methyl-2-butenol | |
| CN114671750B (en) | Four-ring aerospace fuel, precursor thereof and preparation method thereof | |
| CN109369329A (en) | A kind of method that isoamyl olefine aldehydr selective hydration prepares prenol | |
| CN103071536A (en) | Hydrogenation catalyst with special element distribution |
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. |