CN103787836B - A kind of method of Preparation of Cyclopantanol by Hydration of Cyclopentene - Google Patents

A kind of method of Preparation of Cyclopantanol by Hydration of Cyclopentene Download PDF

Info

Publication number
CN103787836B
CN103787836B CN201210427679.3A CN201210427679A CN103787836B CN 103787836 B CN103787836 B CN 103787836B CN 201210427679 A CN201210427679 A CN 201210427679A CN 103787836 B CN103787836 B CN 103787836B
Authority
CN
China
Prior art keywords
hours
cyclopentenes
composite oxide
reaction
rubidium
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
Application number
CN201210427679.3A
Other languages
Chinese (zh)
Other versions
CN103787836A (en
Inventor
李花伊
霍稳周
吕清林
刘野
魏晓霞
田丹
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Original Assignee
China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Fushun Research Institute of Petroleum and Petrochemicals filed Critical China Petroleum and Chemical Corp
Priority to CN201210427679.3A priority Critical patent/CN103787836B/en
Publication of CN103787836A publication Critical patent/CN103787836A/en
Application granted granted Critical
Publication of CN103787836B publication Critical patent/CN103787836B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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

Landscapes

  • 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 present invention discloses a kind of method of Preparation of Cyclopantanol by Hydration of Cyclopentene, with the Ti-base composite oxide of load phosphotungstic acid rubidium acid salt as catalyst, it it is 90 DEG C～200 DEG C in reaction temperature, reaction pressure is that cyclopentenes and water carry out hydration reaction by fixed bed reactors under conditions of 1.0MPa～7.0MPa, and the volume space velocity of cyclopentenes is 1.5h-1～18h-1, cyclopentenes is 1.0～10:1 with the mol ratio of water.The method is significantly improving the selectivity of the conversion ratio of cyclopentenes and cyclopentanol simultaneously, has that operating process is simple, subsequent product separates easily, low cost, is suitable to the advantages such as commercial Application.

Description

A kind of method of Preparation of Cyclopantanol by Hydration of Cyclopentene
Technical field
A kind of method that the present invention relates to 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, antiallergic.
Cyclopentanol can be prepared Ketocyclopentane by adipic acid through high temperature deacidification, then obtains by after hydrogenation reaction, but owing to producing substantial amounts of pollutant and being restricted by raw material sources, this preparation method is gradually eliminated.It addition, with the C of petroleum cracking ethylene by-product5In fraction, the cyclopentenes through isolated is raw material, can also produce cyclopentanol through hydration reaction.Hydration process mainly has two kinds of techniques, and one is indirect hydration technique, and two is direct hydration technique.Although indirect hydration technique has the advantage that conversion ratio is high, selectivity is good, but owing to using sulphuric acid in technical process, equipment material is required height, garbage is difficult to process, and environmental pollution is the most serious.And direct hydration technique does not exist the problems referred to above in indirect hydration, being therefore eco-friendly technology path, the documents and materials reported in recent years all use this process route.
The method that Japan Patent JP2003212803 proposes to use storng-acid cation exchange resin to carry out Preparation of Cyclopantanol by Hydration of Cyclopentene, this patent is under conditions of the molar ratio 1.2～3.0 of cyclopentenes and water, cyclopentenes conversion per pass is about 3.5%, selectivity about 98%.
Chinese patent CN1676504A proposes a kind of by the method for Preparation of Cyclopantanol by Hydration of Cyclopentene, the method is that the material formed with cyclopentenes, water, solvent phenol and promoter trialkylamine continues through the storng-acid cation exchange resin fixed bed reactors as major catalyst, carrying out hydration reaction, volume space velocity is 2～15h-1Cyclopentenes and the mol ratio 0.8～5.0 of water, in raw material, cocatalyst concentration is 0.01%～0.2%, phenol is 0.5 ~ 1 with the weight ratio of cyclopentenes, reaction temperature is 130 DEG C～180 DEG C, and reaction pressure is 1.0MPa～3.0MPa, under these conditions, the conversion ratio of cyclopentenes is about 27%, the selectivity about 99% of cyclopentanol.
Chinese patent CN1676505A and CN1676506A all proposes the method for hydration of cyclopentene cyclopentanol, above-mentioned two patents all with strongly acidic cation-exchange as major catalyst, C2～C5Trialkylamine be promoter, the mol ratio 0.8～5.0 of cyclopentenes and water, reaction temperature is 130 DEG C～180 DEG C, and reaction pressure is 1.0MPa～3.0MPa.Above-mentioned two patent differences are, CN1676505A uses intermittent reaction process, and the response time is 1～5 hour, and the consumption of major catalyst is cyclopentenes/major catalyst (weight ratio)=(10～30)/1；Promoter/major catalyst (weight ratio)=(0.1～5)/100.And CN1676506A uses tandem reaction sequence, volume space velocity is 1h-1～10h-1, the consumption of promoter is cyclopentenes/promoter (weight ratio)=100/(0.2～5).
Chinese patent CN1676504A proposes preparation and the process for purification of a kind of cyclopentanol, and this patent is by cyclopentenes, water, phenolic solvent, promoter (C2～C5Trialkylamine) material that forms continues through and carries out hydration reaction in the fixed bed reactors of filling strong-acid cation-exchange resin catalyst and prepare cyclopentanol.It is 2h at volume space velocity-1～15h-1, cyclopentenes and the mol ratio 0.8～5.0:1 of water, solvent phenol is 0.5～1.0 with the weight ratio of cyclopentenes, promoter (C in raw material2～C5Trialkylamine) concentration is 0.01%～0.20%, reaction temperature is 130 DEG C～180 DEG C, and reaction pressure is 1.0MPa～3.0MPa, under conditions of using strong-acid cation-exchange resin as catalyst, the conversion ratio of cyclopentenes reaches about 27%, and the selectivity of cyclopentanol reaches about 99%.
Above-described generally to be there is cyclopentenes conversion ratio by the method for Preparation of Cyclopantanol by Hydration of Cyclopentene low, and device service cycle is short waits deficiency.Though the conversion ratio that improve cyclopentenes the most limited by adding the method for promoter and/or solvent in some technical scheme, its operating process is complicated, cost is high, and it is unfavorable for commercial Application.
Summary of the invention
For the deficiencies in the prior art, the present invention provides a kind of method of Preparation of Cyclopantanol by Hydration of Cyclopentene.The method is significantly improving the selectivity of the conversion ratio of cyclopentenes and cyclopentanol simultaneously, has that operating process is simple, subsequent product separates easily, low cost, is suitable to the advantages such as commercial Application.
A kind of method of Preparation of Cyclopantanol by Hydration of Cyclopentene, with the titanio metal composite oxide of load phosphotungstic acid rubidium acid salt as catalyst, it it is 90 DEG C～200 DEG C in reaction temperature, reaction pressure is that cyclopentenes and water carry out hydration reaction by fixed bed reactors under conditions of 1.0MPa～7.0MPa, and the volume space velocity of cyclopentenes is 1.5h-1～18h-1, cyclopentenes is 1.0～10:1 with the mol ratio of water.
The volume space velocity of the cyclopentenes described in the inventive method is 2.0h-1～6.0h-1, water is 2.5:1～5:1 with the mol ratio of cyclopentenes, reaction temperature 110 DEG C～150 DEG C, reaction pressure 2.0MPa～4.0MPa.
Titanio metal composite oxide described in the inventive method is Al2O3-TiO2Or ZrO2-TiO2In one or more.Wherein, TiO2Weight content be 25%～85%；It is preferably 35%～65%.
In the titanio metal composite oxide of the load phosphotungstic acid rubidium acid salt described in the inventive method, the weight content of phosphotungstic acid rubidium acid salt is 20%～55%, preferably 30%～40%.
The inventive method use with the titanium-based metal composite oxides of load phosphotungstic acid rubidium acid salt as catalyst, this catalyst has suitable physical property structure, during being applied to the fixed bed reaction 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, improve the mass transfer rate of cyclopentenes.Test result indicate that, the method significantly improves the conversion ratio of cyclopentenes and the service cycle of device, and after operating 1200 hours, the conversion ratio of cyclopentenes is still up to more than 35% and has no downward trend.Additionally, the method also has the plurality of advantages such as easy and simple to handle, low cost, it is the effective ways of a kind of continuous high stability production cyclopentanol.
Detailed description of the invention
Below by specific embodiment, the inventive method is further described.
Embodiment 1～6
Ti-base composite oxide carrier preparation process is as follows:
After preparing titanium tetrachloride and aluminum nitrate mixed solution, titanium tetrachloride and Zirconium tetrachloride. mixed solution, by potassium hydroxide solution by being gradually dropped in above-mentioned mixed solution, the response time is 4 hours～20 hours, obtains white paste precipitation.Through washing, filtration, being dried 6 hours～18 hours at 80 DEG C～120 DEG C, after overmolding, at 400 DEG C～750 DEG C, roasting 4 hours～14 hours, obtain Al2O3-TiO2Or ZrO2-TiO2Composite oxide carrier.
Acid salt (the Rb of carried phospho-tungstic acid rubidium2.1H0.9PW12O40) method for preparing catalyst:
Above-mentioned carrier is dipped in rubidium carbonate (Rb2CO3) in aqueous solution 5 hours～20 hours, sample is dried 3 hours～12 hours at 80 DEG C～150 DEG C, roasting 3 hours～10 hours at 300 DEG C～400 DEG C.
Sample after above-mentioned roasting is dipped in phosphotungstic acid (H3PW12O40) in aqueous solution 5 hours～20 hours, after being dried 5 hours～18 hours at 80 DEG C～160 DEG C, then roasting 4 hours～14 hours at 400 DEG C～600 DEG C, obtain final catalyst.
The acid salt catalyst physical property of Ti-base composite oxide carrier loaded phosphotungstic acid rubidium is as shown in table 1.
Table 1
Sequence number Ti-base composite oxide TiO2/ Ti-base composite oxide (quality %) Active component/catalyst (quality %)
Embodiment 1 Al2O3 -TiO2 25 20
Embodiment 2 Al2O3 -TiO2 45 30
Embodiment 3 Al2O3 -TiO2 50 40
Embodiment 4 ZrO2 -TiO2 65 45
Embodiment 5 ZrO2 -TiO2 35 35
Embodiment 6 ZrO2 -TiO2 20 25
The acid salt catalyst of carried phospho-tungstic acid rubidium embodiment 1～6 prepared is applied in Preparation of Cyclopantanol by Hydration of Cyclopentene course of reaction.Course of reaction uses the fixed bed reactors (material is rustless steel) of Φ 20mm × 1000mm.Reactor is divided into three sections of fillings, and bottom loads a certain amount of quartz sand, and position, stage casing loads 30ml carried phospho-tungstic acid rubidium acid salt catalyst, and top loading quartz sand is till filling up.With the air in the replacement fixed bed reactor of nitrogen, until airtight qualified after, just cyclopentenes and water dosing pump ratio as requested sends into preheater, and reaction mass is preheating to 100 DEG C～200 DEG C.Reaction mass after preheating enters above-mentioned fixed bed reactors and carries out hydration reaction.Recycle unreacted material.Reaction condition and reaction result are as shown in table 2.
Table 2
Sequence number Reaction pressure/MPa Reaction temperature/DEG C Cyclopentenes air speed/h-1 Cyclopentenes/water/mol ratio Cyclopentenes conversion ratio/% Selecting property of cyclopentanol/%
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
Carried phospho-tungstic acid rubidium acid salt catalyst, this catalyst TiO is prepared according to embodiment 1 method2Being 40% with Ti-base composite oxide mass percent, active component phosphotungstic acid rubidium acid salt is 30% with the mass percent of catalyst.
Being 110 DEG C in reaction temperature, reaction pressure is 3.0MPa, and cyclopentenes volume space velocity is 5.5h-1, under the conditions of cyclopentenes/water (mol ratio) is 4.5:1, the long period Activity evaluation operated 1200 hours is as shown in table 3.
Table 3
Sequence number The duration of runs/hour Cyclopentenes conversion ratio/%
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 conversion ratio is basically unchanged, and is always held at about 38%.
Comparative example 1～4 is different one-component oxide carrier load phosphotungstic acid rubidium acid salt catalyst preparation and Activity evaluation.
Comparative example 1
Prepare titanium dioxide carrier load phosphotungstic acid caesium acid salt catalyst: with a certain amount of rubidium carbonate solution impregnation TiO28 hours, then it is dried 10 hours at 110 DEG C, at 450 DEG C after roasting 8 hours, impregnate 6 hours with a certain amount of Salkowski's solution again, then it is dried 8 hours at 110 DEG C, roasting 10 hours at 500 DEG C, obtains titania oxide supported phosphotungstic acid rubidium acid salt catalyst.Evaluating catalyst method is with embodiment 1, and catalyst physical property is as shown in table 4, and reaction condition and reaction result are as shown in table 5.
Comparative example 2
With a certain amount of rubidium carbonate solution impregnation SiO2Carrier, other conditions, with comparative example 1, prepare silica support load phosphotungstic acid rubidium acid salt catalyst, and evaluating catalyst method is with embodiment 1, and catalyst physical property is as shown in table 4, and reaction condition and reaction result are as shown in table 5.
Comparative example 3
With a certain amount of rubidium carbonate solution impregnation Al2O3Carrier, other conditions, with comparative example 1, prepare alumina support load phosphotungstic acid rubidium acid salt catalyst, and evaluating catalyst method is with embodiment 1, and catalyst physical property is as shown in table 4, and reaction condition and reaction result are as shown in table 5.
Comparative example 4
With a certain amount of rubidium carbonate solution impregnation ZrO2Carrier, other conditions, with comparative example 1, prepare Zirconia carrier load phosphotungstic acid rubidium acid salt catalyst, and evaluating catalyst method is with embodiment 1, and catalyst physical property is as shown in table 4, and reaction condition and reaction result are as shown in table 5.
Table 4
Sequence number Oxide carrier Active component/catalyst (quality %)
Comparative example 1 TiO2 40
Comparative example 2 SiO2 30
Comparative example 3 Al2O3 35
Comparative example 4 ZrO2 45
Table 5
Sequence number Reaction pressure/MPa Reaction temperature/DEG C 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
Using comparative example 2 catalyst (Tricesium dodecatungstophosphate acid salt loads on the alumina support) is 110 DEG C in reaction temperature, and reaction pressure is 3.0MPa, and cyclopentenes volume space velocity is 5.5h-1Under the conditions of cyclopentenes/water (mol ratio) is 4.5:1, operate and carried out long period activity rating in 1200 hours, its result shows, when reaction starts, cyclopentenes conversion ratio is 22.4%, after operating 600 hours, cyclopentenes conversion ratio drops to 10.2%, after operating 1200 hours, reaction temperature improves 30 DEG C, and cyclopentenes conversion ratio only has 5.8%.
Comparative example 5～10 is the heteropoly acid outside Ti-base composite oxide carrier loaded dephosphorization wolframic acid rubidium acid salt or the catalyst preparation process of its acid salt and Activity evaluation.
Comparative example 5
By the titanium oxide of embodiment 2 and aluminium oxide (Al2O3-TiO2) composite oxide carrier is dipped in phosphorus molybdenum acid solution, dip time is 10 hours, is dried 8 hours at 100 DEG C, then roasting 10 hours at 400 DEG C, prepares catalyst, and catalyst composition is shown in Table 6, and reaction result is shown in Table 7.
Comparative example 6
Titanium oxide and aluminium oxide (Al2O3-TiO2) composite oxide carrier is dipped in silicomolybdic acid solution, other conditions are identical with comparative example 5, and catalyst composition is shown in Table 6, and reaction result is shown in Table 7.
Comparative example 7
Titanium oxide and aluminium oxide (Al2O3-TiO2) composite oxide carrier is dipped in arsenowolframic acid solution, other conditions are identical with comparative example 5, and catalyst composition is shown in Table 6, and reaction result is shown in Table 7.
Comparative example 8
Titanium oxide and zirconium oxide (ZrO2-TiO2) composite oxide carrier is dipped in silico-tungstic acid solution, other condition is shown in Table 6 with comparative example 5, catalyst composition, and reaction result is shown in Table 7.
Comparative example 9
Titanium oxide and zirconium oxide (ZrO2-TiO2) composite oxide carrier is dipped in Salkowski's solution, other condition is shown in Table 6 with comparative example 5, catalyst composition, and reaction result is shown in Table 7.
Comparative example 10
Titanium oxide and zirconium oxide (ZrO2-TiO2) composite oxide carrier is dipped in germanotungstic acid solution, other condition is shown in Table 6 with comparative example 5, catalyst composition, and reaction result is shown in Table 7.
Table 6
Sequence number Ti-base composite oxide carrier TiO2/ Ti-base composite oxide (quality %) Active component Active component/catalyst (quality %)
Comparative example 5 Al2O3-TiO2 20 Phosphomolybdic acid 35
Comparative example 6 Al2O -TiO2 40 Silicomolybdic acid 20
Comparative example 7 Al2O -TiO2 50 Arsenowolframic acid 25
Comparative example 8 ZrO2- TiO2 30 Silico-tungstic acid 45
Comparative example 9 ZrO2 -TiO2 35 Phosphotungstic acid 30
Comparative example 10 ZrO2 -TiO2 35 Germanotungstic acid 15
Table 7
Sequence number Reaction pressure/MPa Reaction temperature/DEG C Cyclopentenes air speed/h-1 Cyclopentenes/water/mol ratio Cyclopentenes conversion ratio/% 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
Use comparative example 9 catalyst, be 110 DEG C in reaction temperature, reaction pressure be 3.0MPa cyclopentenes volume space velocity be 5.5h-1Under the conditions of cyclopentenes/water (mol ratio) is 4.5:1, operate and carried out long period activity rating in 1200 hours, its result shows (see Table 8), and when reaction starts, cyclopentenes conversion ratio is 23.5%, after operating 600 hours, cyclopentenes conversion ratio drops to 13.8%, after operating 1200 hours, reaction temperature improves 30 DEG C, and cyclopentenes conversion ratio only has 5.3%.
Table 8
Sequence number Operation time/h Cyclopentenes conversion ratio/%
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 (7)

1. the method for a Preparation of Cyclopantanol by Hydration of Cyclopentene, it is characterized in that: the method is with the titanio metal composite oxide of load phosphotungstic acid rubidium acid salt as catalyst, it it is 90 DEG C～200 DEG C in reaction temperature, under conditions of reaction pressure is 1.0MPa～7.0MPa, cyclopentenes and water carry out hydration reaction by fixed bed reactors, and the volume space velocity of cyclopentenes is 1.5h-1～18h-1, cyclopentenes is 1.0～10:1 with the mol ratio of water, and described titanio metal composite oxide is Al2O3-TiO2Or ZrO2-TiO2, TiO2Weight content in titanio metal composite oxide is 25%～85%, and in the titanio metal composite oxide of load phosphotungstic acid rubidium acid salt, the weight content of phosphotungstic acid rubidium acid salt is 20%～55%.
Method the most according to claim 1, it is characterised in that: the volume space velocity of described cyclopentenes is 2.0h-1～6.0h-1, cyclopentenes is 2.5:1～5:1 with the mol ratio of water, reaction temperature 110 DEG C～150 DEG C, reaction pressure 2.0MPa～4.0MPa.
Method the most according to claim 1, it is characterised in that: TiO2Weight content in titanio metal composite oxide is 35%～65%.
Method the most according to claim 1, it is characterised in that: in the titanio metal composite oxide of load phosphotungstic acid rubidium acid salt, the weight content of phosphotungstic acid rubidium acid salt is 30%～40%.
Method the most according to claim 1, it is characterised in that: titanio metal composite oxide uses coprecipitation to prepare, and the co-precipitation time is 4 hours～20 hours；Baking temperature is 80 DEG C～120 DEG C；Drying time is 6 hours～18 hours；Sintering temperature is 400 DEG C～750 DEG C；Roasting time is 6 hours～20 hours.
Method the most according to claim 1, it is characterised in that: the acid salt loading process of phosphotungstic acid rubidium uses step impregnation method, and first dipping rubidium carbonate solution, then impregnates Salkowski's solution.
Method the most according to claim 6, it is characterised in that: the dip time of dipping rubidium carbonate solution is 5 hours～20 hours, is then dried 5 hours～20 hours at 80 DEG C～150 DEG C, roasting 3 hours～12 hours at 300 DEG C～400 DEG C；The dip time of dipping Salkowski's solution is 4 hours～18 hours, is then dried 5 hours～18 hours at 80 DEG C～160 DEG C and roasting 4 hours～14 hours at 400 DEG C～600 DEG C, obtains final catalyst.
CN201210427679.3A 2012-11-01 2012-11-01 A kind of method of Preparation of Cyclopantanol by Hydration of Cyclopentene Active CN103787836B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201210427679.3A CN103787836B (en) 2012-11-01 2012-11-01 A kind of method of Preparation of Cyclopantanol by Hydration of Cyclopentene

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201210427679.3A CN103787836B (en) 2012-11-01 2012-11-01 A kind of method of Preparation of Cyclopantanol by Hydration of Cyclopentene

Publications (2)

Publication Number Publication Date
CN103787836A CN103787836A (en) 2014-05-14
CN103787836B true CN103787836B (en) 2016-08-03

Family

ID=50663953

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210427679.3A Active CN103787836B (en) 2012-11-01 2012-11-01 A kind of method of Preparation of Cyclopantanol by Hydration of Cyclopentene

Country Status (1)

Country Link
CN (1) CN103787836B (en)

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

Also Published As

Publication number Publication date
CN103787836A (en) 2014-05-14

Similar Documents

Publication Publication Date Title
US9162954B2 (en) Catalyst and process for preparing acrolein and/or acrylic acid by dehydration reaction of glycerin
TWI612031B (en) Method and device for co-production of cyclohexanol and alkanol
CN104370692B (en) Polyol preparation method through glucose hydrogenolysis
CN102059116B (en) 1,3-propanediol catalyst prepared by directly hydrotreating glycerol and preparation method thereof
CN103785388B (en) A kind of containing V propane dehydrogenation catalyst and preparation method thereof
WO2013018752A2 (en) Catalyst for manufacture of acrolein and acrylic acid by means of dehydration of glycerin, and manufacturing method for same
EP2488298A1 (en) Process for preparing catalyst used in production of unsaturated aldehyde and/or unsaturated carboxylic acid by dehydration reaction of glycerin, and catalyst obtained
CN105709829A (en) Heteropoly acid catalyst and preparation method thereof
CN102040505A (en) Method for preparing unsaturated acid by oxidation of unsaturated aldehyde
WO2013008279A1 (en) Process for preparing catalyst used in production of acrolein and/or acrylic acid and process for preparing acrolein and/or acrylic acid by dehydration reaction of glycerin
CN103664587B (en) Method for preparing cyclohexyl acetate and method for preparing cyclohexanol ethanol
CN103418401A (en) Catalyst for preparing acrolein by propylene oxidation method and preparation method thereof
WO2018146978A1 (en) Catalyst for reduction reaction of 3,4-dihydroxytetrahydrofuran, and method for producing 3,4-dihydroxytetrahydrofuran reduced product
CN103787836B (en) A kind of method of Preparation of Cyclopantanol by Hydration of Cyclopentene
CN103664586B (en) Method for preparing cyclohexyl acetate and method for preparing cyclohexanol ethanol
CN1463960A (en) Process for preparing ethandiol by catalyzing epoxyethane hydration
JP2013040179A (en) Catalyst and method for producing acrolein and/or acrylic acid by dehydration reaction of glycerin
CN110721732A (en) Method for producing p-tert-butylphenol
CN101703944A (en) Molecular sieve modified catalyst, preparation method and application thereof to preparation of acrylic ester
CN110026191B (en) Catalyst and method for preparing 1, 3-propylene glycol by hydrogenolysis of glycerol
JP2013216623A (en) Method for producing propanediol
CN101176850A (en) Catalyzer for preparing ethylene by ethanol dehydration as well as preparation method and usage
CN105709786A (en) Catalyst for selective hydrogenation of butadiene and isomerization of 1-butylene, and preparation method and application thereof
CN109647472B (en) Hydrogenation catalyst, preparation method thereof and preparation method of tetrahydrofurfuryl alcohol
CN102909042B (en) Composite carrier loaded heteropoly acid catalyst and application thereof

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