CN103787836A - Cyclopentene hydration method for preparing cyclopentanol - Google Patents

Cyclopentene hydration method for preparing cyclopentanol Download PDF

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CN103787836A
CN103787836A CN201210427679.3A CN201210427679A CN103787836A CN 103787836 A CN103787836 A CN 103787836A CN 201210427679 A CN201210427679 A CN 201210427679A CN 103787836 A CN103787836 A CN 103787836A
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cyclopentenes
reaction
cyclopentene
tio
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CN103787836B (en
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李花伊
霍稳周
吕清林
刘野
魏晓霞
田丹
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
    • C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a cyclopentene hydration method for preparing cyclopentanol. Cyclopentene and water reacts in a fixed bed reactor in the presence of a catalyst of titanium based composite oxide loaded with phosphotungstate rubidium acid salt under the following conditions: reaction temperature of 90-200 DEG C, reaction pressure of 1.0-7.0 MPa, volume space velocity of cyclopentene of 1.5-18 / h, and the molar ratio of cyclopentene and water of 1.0-10:1. The method significantly improves conversion rate of cyclopentene and the selectivity of cyclopentanol, and has the advantages of simple operation, easy separation of subsequent products, low cost, and suitability for industrial application, etc.

Description

A kind of method of Preparation of Cyclopantanol by Hydration of Cyclopentene
Technical field
The present invention relates to a kind of method of Preparation of Cyclopantanol by Hydration of Cyclopentene.
Background technology
Cyclopentanol is a kind of important fine chemical product intermediate, mainly for the preparation of bromocyclopentane, chlorocyclopentane etc., and can be used for manufacturing the medicines such as antibacterial, antianaphylaxis.
Cyclopentanol can make cyclopentanone through high temperature depickling by hexanodioic acid, then by obtaining after hydrogenation reaction, but owing to producing a large amount of pollutents and the restriction that is subject to raw material sources, this preparation method is eliminated gradually.In addition, with the C of petroleum cracking ethylene by-product processed 5in cut, be raw material through separating the cyclopentenes obtaining, also can produce cyclopentanol through hydration reaction.Hydration process mainly contains two kinds of techniques, the one, indirect hydrating process, the 2nd, direct hydration technique.Although hydrating process has the advantage that transformation efficiency is high, selectivity is good indirectly, owing to using sulfuric acid in technological process, high to equipment material requirement, waste is difficult to process, and environmental pollution is comparatively serious.And there are not the problems referred to above in indirect hydration in direct hydration technique, be therefore eco-friendly technological line, the documents and materials of report all adopt this operational path in recent years.
Japanese Patent JP2003212803 proposes to adopt storng-acid cation exchange resin to carry out the method for Preparation of Cyclopantanol by Hydration of Cyclopentene, this patent is under the condition of the molar ratio 1.2～3.0 of cyclopentenes and water, cyclopentenes per pass conversion is 3.5% left and right, selectivity 98% left and right.
Chinese patent CN1676504A has proposed a kind of method by Preparation of Cyclopantanol by Hydration of Cyclopentene, the method is the material fixed-bed reactor as Primary Catalysts by storng-acid cation exchange resin continuously that formed take cyclopentenes, water, solvent phenol and promotor trialkylamine, carry out hydration reaction, volume space velocity is 2～15h -1the mol ratio 0.8～5.0 of cyclopentenes and water, in raw material, cocatalyst concentration is 0.01%～0.2%, the weight ratio of phenol and cyclopentenes is 0.5 ~ 1, temperature of reaction is 130 ℃～180 ℃, and reaction pressure is 1.0MPa～3.0MPa, under these conditions, the transformation efficiency of cyclopentenes is 27% left and right, selectivity 99% left and right of cyclopentanol.
Chinese patent CN1676505A and CN1676506A have all proposed the method for hydration of cyclopentene cyclopentanol processed, and above-mentioned two patents are all take strongly acidic cation-exchange as Primary Catalysts, C 2～C 5trialkylamine be promotor, the mol ratio 0.8～5.0 of cyclopentenes and water, temperature of reaction is 130 ℃～180 ℃, reaction pressure is 1.0MPa～3.0MPa.Above-mentioned two patent differences are, CN1676505A employing intermittent reaction process, and the reaction times is 1～5 hour, the consumption of Primary Catalysts is cyclopentenes/Primary Catalysts (weight ratio)=(10～30)/1; Promotor/Primary Catalysts (weight ratio)=(0.1～5)/100.And CN1676506A adopts tandem reaction sequence, volume space velocity is 1 h -1～10h -1, the consumption of promotor is cyclopentenes/promotor (weight ratio)=100/(0.2～5).
Chinese patent CN1676504A has proposed a kind of preparation and process for purification of cyclopentanol, and this patent is by cyclopentenes, water, phenolic solvent, promotor (C 2～C 5trialkylamine) material of composition carries out hydration reaction and prepares cyclopentanol in the fixed-bed reactor by filling strong-acid cation-exchange resin catalyst continuously.Be 2 h at volume space velocity -1～15h -1, the mol ratio 0.8～5.0:1 of cyclopentenes and water, the weight ratio of solvent phenol and cyclopentenes is 0.5～1.0, promotor (C in raw material 2～C 5trialkylamine) concentration is 0.01%～0.20%, temperature of reaction is 130 ℃～180 ℃, and reaction pressure is 1.0MPa～3.0MPa, adopts under the condition of strong-acid cation-exchange resin as catalyzer, the transformation efficiency of cyclopentenes reaches 27% left and right, and the selectivity of cyclopentanol reaches 99% left and right.
The above-described method ubiquity by Preparation of Cyclopantanol by Hydration of Cyclopentene cyclopentenes low conversion rate, the device short deficiency that waits running period.Although the method by adding promotor and/or solvent in some technical scheme to a certain extent limited raising the transformation efficiency of cyclopentenes, its operating process complexity, cost are high, and are unfavorable for industrial application.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of method of Preparation of Cyclopantanol by Hydration of Cyclopentene.The method is obviously improving the transformation efficiency of cyclopentenes and the selectivity of cyclopentanol simultaneously, has that operating process is simple, subsequent product separates easily, cost is low, is suitable for the advantages such as industrial application.
A kind of method of Preparation of Cyclopantanol by Hydration of Cyclopentene, take the titanium based composite metal oxidate of load phosphotungstic acid rubidium acid salt as catalyzer, it is 90 ℃～200 ℃ in temperature of reaction, reaction pressure is that under the condition of 1.0MPa～7.0MPa, cyclopentenes and water carry out hydration reaction by fixed-bed reactor, and the volume space velocity of cyclopentenes is 1.5h -1～18h -1, the mol ratio of cyclopentenes and water is 1.0～10:1.
The volume space velocity of the cyclopentenes described in the inventive method is 2.0h -1～6.0h -1, the mol ratio of water and cyclopentenes is 2.5:1～5:1,110 ℃～150 ℃ of temperature of reaction, reaction pressure 2.0MPa～4.0MPa.
Titanium based composite metal oxidate described in the inventive method is Al 2o 3-TiO 2or ZrO 2-TiO 2in one or more.Wherein, TiO 2weight content be 25%～85%; Be preferably 35%～65%.
In the titanium based composite metal oxidate of the load phosphotungstic acid rubidium acid salt described in the inventive method, the weight content of phospho-wolframic acid rubidium acid salt is 20%～55%, is preferably 30%～40%.
In the inventive method, employing is take the titanium-based metal composite oxides of load phosphotungstic acid rubidium acid salt as catalyzer, this catalyzer has suitable physical property structure, be applied in the fixed bed reaction process of Preparation of Cyclopantanol by Hydration of Cyclopentene, match with fixed bed reaction technique, improve the absorption of cyclopentenes and the desorption rate of cyclopentanol, improved the rate of mass transfer of cyclopentenes.Experimental result shows, the method has obviously improved the running period of transformation efficiency and the device of cyclopentenes, at the transformation efficiency of running cyclopentenes after 1200 hours still up to more than 35% and have no downtrending.In addition, the method also has the plurality of advantages such as easy and simple to handle, cost is low, is the effective ways that a kind of continuous high stability is produced cyclopentanol.
Embodiment
Below by specific embodiment, the inventive method is further described.
Embodiment 1 ～6
Ti-base composite oxide carrier preparation process is as follows:
After preparation titanium tetrachloride and aluminum nitrate mixing solutions, titanium tetrachloride and zirconium tetrachloride mixing solutions, by potassium hydroxide solution, by splashing into gradually in above-mentioned mixing solutions, the reaction times is 4 hours～20 hours, obtains white pasty state precipitation.Through washing, filter, be dried 6 hours～18 hours at 80 ℃～120 ℃, after overmolding, at 400 ℃～750 ℃, roasting 4 hours～14 hours, obtains Al 2o 3-TiO 2or ZrO 2-TiO 2composite oxide carrier.
Acid salt (the Rb of carried phospho-tungstic acid rubidium 2.1h 0.9pW 12o 40) method for preparing catalyst:
Above-mentioned carrier is dipped in to rubidium carbonate (R b2cO 3) in the aqueous solution 5 hours～20 hours, sample at 80 ℃～150 ℃ dry 3 hours～12 hours, roasting 3 hours～10 hours at 300 ℃～400 ℃.
Sample after above-mentioned roasting is dipped in to phospho-wolframic acid (H 3pW 12o 40) in the aqueous solution 5 hours～20 hours, dry after 5 hours～18 hours at 80 ℃～160 ℃, then roasting 4 hours～14 hours at 400 ℃～600 ℃, final catalyzer obtained.
The acid salt catalyzer physical property of the carrier loaded phospho-wolframic acid rubidium of Ti-base composite oxide is as shown in table 1.
Table 1
Sequence number Ti-base composite oxide TiO 2/ Ti-base composite oxide (quality %) Active ingredient/catalyzer (quality %)
Embodiment 1 Al 2O 3 -TiO 2 25 20
Embodiment 2 Al 2O 3 -TiO 2 45 30
Embodiment 3 Al 2O 3 -TiO 2 50 40
Embodiment 4 ZrO 2 -TiO 2 65 45
Embodiment 5 ZrO 2 -TiO 2 35 35
Embodiment 6 ZrO 2 -TiO 2 20 25
The acid salt catalyzer of the carried phospho-tungstic acid rubidium of embodiment 1～6 preparation is applied in Preparation of Cyclopantanol by Hydration of Cyclopentene reaction process.Reaction process adopts the fixed-bed reactor (material is stainless steel) of Φ 20mm × 1000mm.Reactor is divided into three sections of fillings, and a certain amount of quartz sand is loaded in bottom, and 30ml carried phospho-tungstic acid rubidium acid salt catalyzer is loaded at position, stage casing, and top loading quartz sand is until fill up.With the air in nitrogen replacement fixed-bed reactor, until airtight qualified after, just cyclopentenes and water are sent into preheater by volume pump ratio as requested, and reaction mass is preheating to 100 ℃～200 ℃.Reaction mass after preheating enters above-mentioned fixed-bed reactor and carries out hydration reaction.Recycle unreacted material.Reaction conditions and reaction result are as shown in table 2.
Table 2
Sequence number Reaction pressure/MPa Temperature of reaction/℃ Cyclopentenes air speed/h -1 Cyclopentenes/water/mol ratio Cyclopentenes transformation efficiency/% Cyclopentanol selecting property/%
Embodiment 1 1.0 90 2.5 2.0 31.1 99.1
Embodiment 2 3.0 110 5.5 4.5 39.3 98.2
Embodiment 3 5.0 130 7.0 6.5 40.1 98.6
Embodiment 4 7.0 150 5.0 3.5 37.8 98.9
Embodiment 5 2.0 120 10.0 8.0 35.4 98.5
Embodiment 6 4.0 140 3.0 10.0 32.5 98.1
Embodiment 7
Prepare carried phospho-tungstic acid rubidium acid salt catalyzer, this catalyzer TiO according to embodiment 1 method 2with Ti-base composite oxide mass percent be 40%, the mass percent of active ingredient phospho-wolframic acid rubidium acid salt and catalyzer is 30%.
Be 110 ℃ in temperature of reaction, reaction pressure is 3.0MPa, and cyclopentenes volume space velocity is 5.5h -1, cyclopentenes/water (mol ratio) is under 4.5:1 condition, the long period activity rating result turning round 1200 hours is as shown in table 3.
Table 3
Sequence number Runtime/hour Cyclopentenes transformation efficiency/%
1 50 39.3
2 100 38.4
3 150 39.5
4 200 37.5
5 250 39.4
6 300 38.8
7 350 39.1
8 400 38.9
9 450 39.5
10 500 38.8
11 550 39.0
12 600 37.9
13 650 39.6
14 700 38.8
15 750 39.1
16 800 38.9
17 850 39.0
18 900 38.2
19 950 39.1
20 1000 38.2
20 1050 38.6
20 1100 37.9
20 1150 38.3
20 1200 38.1
This catalyst runs is after 1200 hours, and cyclopentenes transformation efficiency is substantially constant, remains on 38% left and right always.
Comparative example 1～4 is different single-component oxide carrier load phosphotungstic acid rubidium acid salt catalyzer preparations and activity rating result.
Comparative example 1
Prepare titanium dioxide carrier load phosphotungstic acid caesium acid salt catalyzer: with a certain amount of rubidium carbonate solution impregnation TiO 28 hours, then at 110 ℃, be dried 10 hours, at 450 ℃, roasting is after 8 hours, flood 6 hours with a certain amount of Salkowski's solution again, then at 110 ℃, be dried 8 hours, roasting 10 hours at 500 ℃, obtains titania oxide supported phospho-wolframic acid rubidium acid salt catalyzer.Evaluating catalyst method is with embodiment 1, and catalyzer physical property is as shown in table 4, and reaction conditions and reaction result are as shown in table 5.
Comparative example 2
With a certain amount of rubidium carbonate solution impregnation SiO 2carrier, other conditions, with comparative example 1, are prepared silica support load phosphotungstic acid rubidium acid salt catalyzer, and evaluating catalyst method is with embodiment 1, and catalyzer physical property is as shown in table 4, and reaction conditions and reaction result are as shown in table 5.
Comparative example 3
With a certain amount of rubidium carbonate solution impregnation Al 2o 3carrier, other conditions, with comparative example 1, are prepared alumina supporter load phosphotungstic acid rubidium acid salt catalyzer, and evaluating catalyst method is with embodiment 1, and catalyzer physical property is as shown in table 4, and reaction conditions and reaction result are as shown in table 5.
Comparative example 4
With a certain amount of rubidium carbonate solution impregnation ZrO 2carrier, other conditions, with comparative example 1, are prepared Zirconia carrier load phosphotungstic acid rubidium acid salt catalyzer, and evaluating catalyst method is with embodiment 1, and catalyzer physical property is as shown in table 4, and reaction conditions and reaction result are as shown in table 5.
Table 4
Sequence number Oxide carrier Active ingredient/catalyzer (quality %)
Comparative example 1 TiO 2 40
Comparative example 2 SiO 2 30
Comparative example 3 Al 2O 3 35
Comparative example 4 ZrO 2 45
Table 5
Sequence number Reaction pressure/MPa Temperature of reaction/℃ Cyclopentenes air speed/h -1 Cyclopentenes/water/mol ratio Cyclopentenes rate of rotation/% Cyclopentanol selectivity/%
Comparative example 1 5.0 100 3.5 2.0 20.1 97.2
Comparative example 2 3.0 110 5.5 4.5 22.4 96.1
Comparative example 3 7.0 140 2.0 5.5 23.5 98.6
Comparative example 4 2.0 120 4.0 3.0 22.8 97.2
Adopting comparative example 2 catalyzer (Tricesium dodecatungstophosphate acid salt loads on alumina supporter) is 110 ℃ in temperature of reaction, and reaction pressure is 3.0MPa, and cyclopentenes volume space velocity is 5.5h -1cyclopentenes/water (mol ratio) is under 4.5:1 condition, turn round and within 1200 hours, carried out long period activity rating, its result shows, when reaction starts, cyclopentenes transformation efficiency is 22.4%, turns round after 600 hours, cyclopentenes transformation efficiency drops to 10.2%, turn round after 1200 hours, temperature of reaction improves 30 ℃, and cyclopentenes transformation efficiency only has 5.8%.
Comparative example 5～10 is the carrier loaded heteropolyacid except phospho-wolframic acid rubidium acid salt of Ti-base composite oxide or catalyst preparation process and the activity rating result of its acid salt.
Comparative example 5
By the titanium oxide of embodiment 2 and aluminum oxide (Al 2o 3-TiO 2) composite oxide carrier is dipped in phosphorus molybdenum acid solution, dipping time is 10 hours, at 100 ℃ dry 8 hours, then roasting 10 hours at 400 ℃, making catalyzer, catalyzer forms in table 6, and reaction result is in table 7.
Comparative example 6
Titanium oxide and aluminum oxide (Al 2o 3-TiO 2) composite oxide carrier is dipped in silicomolybdic acid solution, other conditions are identical with comparative example 5, and catalyzer forms in table 6, and reaction result is in table 7.
Comparative example 7
Titanium oxide and aluminum oxide (Al 2o 3-TiO 2) composite oxide carrier is dipped in arsenowolframic acid solution, other conditions are identical with comparative example 5, and catalyzer forms in table 6, and reaction result is in table 7.
Comparative example 8
Titanium oxide and zirconium white (ZrO 2-TiO 2) composite oxide carrier is dipped in silicotungstic acid solution, other condition is with comparative example 5, and catalyzer forms in table 6, and reaction result is in table 7.
Comparative example 9
Titanium oxide and zirconium white (ZrO 2-TiO 2) composite oxide carrier is dipped in Salkowski's solution, other condition is with comparative example 5, and catalyzer forms in table 6, and reaction result is in table 7.
Comparative example 10
Titanium oxide and zirconium white (ZrO 2-TiO 2) composite oxide carrier is dipped in germanotungstic acid solution, other condition is with comparative example 5, and catalyzer forms in table 6, and reaction result is in table 7.
Table 6
Sequence number Ti-base composite oxide carrier TiO 2/ Ti-base composite oxide (quality %) Active ingredient Active ingredient/catalyzer (quality %)
Comparative example 5 Al 2O 3-TiO 2 20 Phospho-molybdic acid 35
Comparative example 6 Al 2O -TiO 2 40 Silicomolybdic acid 20
Comparative example 7 Al 2O -TiO 2 50 Arsenowolframic acid 25
Comparative example 8 ZrO 2- TiO 2 30 Silicotungstic acid 45
Comparative example 9 ZrO 2 -TiO 2 35 Phospho-wolframic acid 30
Comparative example 10 ZrO 2 -TiO 2 35 Germanotungstic acid 15
Table 7
Sequence number Reaction pressure/MPa Temperature of reaction/℃ Cyclopentenes air speed/h -1 Cyclopentenes/water/mol ratio Cyclopentenes transformation efficiency/% Cyclopentanol selectivity/%
Comparative example 5 4.0 120 2.0 5.5 24.1 96.6
Comparative example 6 5.0 130 3.0 4.0 25.4 97.2
Comparative example 7 2.0 100 6.0 3.5 23.1 97.1
Comparative example 8 4.5 140 1.5 1.5 24.8 96.2
Comparative example 9 3.0 110 5.5 4.5 23.5 97.4
Comparative example 10 5.5 90 3.5 2.0 22.8 98.3
Adopting comparative example 9 catalyzer, is 110 ℃ in temperature of reaction, and reaction pressure is that 3.0MPa cyclopentenes volume space velocity is 5.5h -1cyclopentenes/water (mol ratio) is under 4.5:1 condition, turn round and within 1200 hours, carried out long period activity rating, its result shows (in table 8), and when reaction starts, cyclopentenes transformation efficiency is 23.5%, turns round after 600 hours, cyclopentenes transformation efficiency drops to 13.8%, turn round after 1200 hours, temperature of reaction improves 30 ℃, and cyclopentenes transformation efficiency only has 5.3%.
Table 8
Sequence number Working time/h Cyclopentenes transformation efficiency/%
1 50 23.5
2 100 22.1
3 150 20.7
4 200 20.0
5 250 19.5
6 300 19.0
7 350 18.4
8 400 17.6
9 450 16.8
10 500 15.7
11 550 14.6
12 600 13.8
13 650 12.4
14 700 11.8
15 750 11.0
16 800 10.5
17 850 9.2
18 900 8.5
19 950 7.2
20 1000 6.3
21 1050 5.4
22 1100 4.8
23 1150 4.2
24 1200 5.3

Claims (10)

1. the method for a Preparation of Cyclopantanol by Hydration of Cyclopentene, it is characterized in that: the method is take the titanium based composite metal oxidate of load phosphotungstic acid rubidium acid salt as catalyzer, it is 90 ℃～200 ℃ in temperature of reaction, reaction pressure is under the condition of 1.0MPa～7.0MPa, cyclopentenes and water carry out hydration reaction by fixed-bed reactor, and the volume space velocity of cyclopentenes is 1.5h -1～18h -1, the mol ratio of cyclopentenes and water is 1.0～10:1.
2. method according to claim 1, is characterized in that: the volume space velocity of described cyclopentenes is 2.0h -1～6.0h -1, the mol ratio of water and cyclopentenes is 2.5:1～5:1,110 ℃～150 ℃ of temperature of reaction, reaction pressure 2.0MPa～4.0MPa.
3. method according to claim 1, is characterized in that: described titanium based composite metal oxidate is Al 2o 3-TiO 2or ZrO 2-TiO 2.
4. according to the method described in claim 1 or 3, it is characterized in that: TiO 2weight content in titanium based composite metal oxidate is 25%～85%.
5. method according to claim 4, is characterized in that: TiO 2weight content in titanium based composite metal oxidate is 35%～65%.
6. method according to claim 1, is characterized in that: in the titanium based composite metal oxidate of load phosphotungstic acid rubidium acid salt, the weight content of phospho-wolframic acid rubidium acid salt is 20%～55%.
7. method according to claim 6, is characterized in that: in the titanium based composite metal oxidate of load phosphotungstic acid rubidium acid salt, the weight content of phospho-wolframic acid rubidium acid salt is 30%～40%.
8. method according to claim 1, is characterized in that: titanium based composite metal oxidate adopts coprecipitation method preparation, and the co-precipitation time is 4 hours～20 hours; Drying temperature is 80 ℃～120 ℃; Be 6 hours～18 hours time of drying; Maturing temperature is 400 ℃～750 ℃; Roasting time is 6 hours～20 hours.
9. method according to claim 1, is characterized in that: the acid salt loading process of phospho-wolframic acid rubidium adopts step impregnation method, first floods cesium carbonate solution, then floods Salkowski's solution.
10. method according to claim 9, is characterized in that: the dipping time of dipping cesium carbonate solution is 5 hours～20 hours, then at 80 ℃～150 ℃, is dried 5 hours～20 hours, roasting 3 hours～12 hours at 300 ℃～400 ℃; The dipping time of dipping Salkowski's solution is 4 hours～18 hours, and then dry 5 hours～18 hours and roasting 4 hours～14 hours at 400 ℃～600 ℃ at 80 ℃～160 ℃, obtains final catalyzer.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1037502A (en) * 1988-05-02 1989-11-29 罗纳·布朗克化学公司 Process for preparing cyclohexanol
CN1231276A (en) * 1998-03-25 1999-10-13 英国石油化学品有限公司 Olefines hydrating process
CN101805244A (en) * 2010-04-08 2010-08-18 华东理工大学 Cyclohexene hydrating process

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1037502A (en) * 1988-05-02 1989-11-29 罗纳·布朗克化学公司 Process for preparing cyclohexanol
CN1231276A (en) * 1998-03-25 1999-10-13 英国石油化学品有限公司 Olefines hydrating process
CN101805244A (en) * 2010-04-08 2010-08-18 华东理工大学 Cyclohexene hydrating process

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