CN106674003A - Method for preparing cyclopentanol by hydrating cyclopentene - Google Patents
Method for preparing cyclopentanol by hydrating cyclopentene Download PDFInfo
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- 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
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
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- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
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Abstract
The invention discloses a method for preparing cyclopentanol by hydrating cyclopentene. The method comprises the following steps: (1) performing addition reaction on cyclopentene and acetic acid under the action of modified sulfonic acid group cation exchange resin to produce cyclopentyl acetate, wherein the modified sulfonic acid group cation exchange resin is prepared by soaking the conventional sulfonic acid group cation exchange resin with methylbenzene and methyl isobutyl ketone sequentially; (2) enabling the material obtained in the step (1) to enter a rectifying tower, forming azeotrope with water on the lower part of the rectifying tower, performing hydrolysis reaction on the material and water under the action of a sulfonic acid group cation exchange resin catalyst filling the upper part of the rectifying tower, withdrawing a product cyclopentanol from the top of the tower and withdrawing acetic acid from the bottom of the tower. The method has the advantages of simple technical process, low energy consumption, high conversion rate, high selectivity, high product yield and the like.
Description
Technical field
The present invention relates to a kind of method of Preparation of Cyclopantanol by Hydration of Cyclopentene, relates in particular to one kind under acid cation exchange resin effect, by the method for 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 to manufacture the medicines such as antibacterial, antiallergy.Cyclopentanol can be obtained cyclopentanone by the depickling of adipic acid Jing high temperature, then be obtained after hydrogenation reaction, but due to producing substantial amounts of pollutant and being restricted by raw material sources, this preparation method is gradually eliminated.In addition, with the C of petroleum cracking ethylene by-product5It is raw material through isolated cyclopentene in cut, through hydration reaction cyclopentanol can also be produced.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 high conversion rate, selective good advantage, due to sulfuric acid used in technical process, equipment material is had high demands, discarded object is difficult to process, and environmental pollution is more serious.And direct hydration technique does not have the problems referred to above in indirect hydration, therefore it is eco-friendly technology path, the documents and materials reported in recent years adopt this process route.Such as the method that JP2003212803 propositions carry out Preparation of Cyclopantanol by Hydration of Cyclopentene using storng-acid cation exchange resin, the patent is under conditions of the molar ratio 1.2～3.0 of cyclopentene and water, cyclopentene conversion per pass is 3.50% or so, selective 98% or so.The method is disadvantageous in that reaction conversion ratio is relatively low, and raw material cyclopentene internal circulating load is big.CN1676504A proposes a kind of method by Preparation of Cyclopantanol by Hydration of Cyclopentene, the method is that the material constituted with cyclopentene, water, solvent phenol and co-catalyst trialkylamine continues through fixed bed reactors of the storng-acid cation exchange resin as major catalyst, hydration reaction is carried out, volume space velocity is 2～15h-1, the mol ratio 0.8～5.0 of cyclopentene and water, cocatalyst concentration is 0.01%～0.2% in raw material, 130 DEG C～180 DEG C of reaction temperature, reaction pressure 1.0MPa～3.0MPa, under these conditions, the conversion ratio of cyclopentene is 27% or so, the selectivity 99% or so of cyclopentanol.Although the method improves the conversion ratio of cyclopentene, but C is added in reaction system2～C5Trialkylamine, due to trialkylamine for alkalescence, neutralized the sulfonic acid group in storng-acid cation exchange resin so that storng-acid cation exchange resin activity reduction.A large amount of phenol are also added into system（Phenol is 0.5 ~ 1 with the weight ratio of cyclopentene）So that non-reaction solution occupies larger proportion in reaction system, and the separating difficulty that technical process becomes complicated, follow-up is increased, and energy consumption is of a relatively high.
The A of CN 102399133 propose a kind of method of preparing cyclopentanol from cyclopentene through indirect hydration method, including：Cyclopentene carries out addition reaction and generates cyclopentyl acetate with liquid phase with acetic acid by fixed bde catalyst, and catalyst is sulfonic group cation exchange resin, and the mass exchange capacity of resin is 3～5.5mmol/g；Addition reaction product carries out rectifying separation, obtains refined cyclopentyl acetate；The refined vinegar of acetic acid ring penta carries out vinegar exchange reaction in the presence of catalyst Ca0 and generates cyclopentanol and methyl acetate with methyl alcohol, and the methyl acetate of generation is removed in course of reaction；Rectifying separation is carried out after product of transesterification reaction Filtration of catalyst, product cyclopentanol is obtained.The method has compared with prior art higher conversion ratio and selectivity, and whole course of reaction does not have the high material of acid strong, corrosivity.
Need to be separated through addition reaction, refined intermediate products, ester exchange, filtration, rectifying in prior art, can just obtain product cyclopentanol.Therefore complex technical process, high energy consumption, product yield is low.
The content of the invention
For the deficiencies in the prior art, the present invention provides a kind of method that cyclopentene prepares cyclopentanol.The method has technical process simple, and energy consumption is low, the advantages of conversion ratio, selectivity and high product yield.
A kind of method of Preparation of Cyclopantanol by Hydration of Cyclopentene, including procedure below：
（1）Cyclopentene carries out addition reaction in the presence of modified sulfonic group cation exchange resin and generates cyclopentyl acetate with acetic acid, and cyclopentene is 1 with the molar ratio of acetic acid：(1～10), cyclopentene liquid quality air speed is 0.5h-1～3.5h-1, reaction temperature is 50 DEG C～150 DEG C, and reaction pressure is 0.1MPa～2.0MPa, and modified sulfonic group cation exchange resin soaks successively conventional sulfonic group cation exchange resin and is obtained by toluene, methyl iso-butyl ketone (MIBK)；
（2）Step（1）The material for obtaining enters rectifying column, azeotropic mixture is formed in rectifying column bottom and water, in the presence of the sulfonic group cation exchange resin catalyst for filling in rectifier, cyclopentyl acetate and water in the azeotropic mixture of rectifying column bottom is hydrolyzed reaction, overhead extraction product cyclopentanol, bottom of towe produces acetic acid, and water is with the mol ratio of cyclopentyl acetate（1～25）：1, the liquid quality air speed of cyclopentyl acetate is 0.5h-1～2.5h-1。
The inventive method step（1）In, described cyclopentene is preferably 1 with the molar ratio of acetic acid：(1～8), it is most preferably 1：(1～5)；Liquid quality air speed is preferably 0.5h-1～2.0h-1, be most preferably 0.5h-1～1.0h-1；Reaction temperature is preferably 60 DEG C～150 DEG C, is most preferably 70 DEG C～120 DEG C；Reaction pressure is preferably 0.1MPa～1.5MPa, is most preferably 0.1MPa～1.0MPa.
The inventive method step（1）In, the concrete modifying process of the sulfonic group cation exchange resin that is modified is as follows：First conventional sulfonic group cation exchange resin toluene is invaded into bubble 8h～48h at a temperature of 40 DEG C～150 DEG C, it is preferred that 40 DEG C～120 DEG C are invaded bubble 10h～28h, then invaded at a temperature of 40 DEG C～100 DEG C with methyl iso-butyl ketone (MIBK) again and steep 24h～48h, bubble 28h～40h is preferably invaded at a temperature of 50 DEG C～80 DEG C.Toluene or methyl iso-butyl ketone (MIBK) are with the volume ratio of sulfonic group cation exchange resin（5～50）：1；Preferably（10～40）：1st, it is most preferably（10～30）:1.
The inventive method step（2）In, water is preferably with the mol ratio of cyclopentyl acetate（1～20）：1st, it is most preferably（1～15）：1；The liquid quality air speed of cyclopentyl acetate is preferably 0.5h-1～2.0h-1, be most preferably 0.5h-1～1.5h-1.Rectifying column tower top temperature is 70 DEG C～150 DEG C, preferably 70 DEG C～130 DEG C, most preferably 70 DEG C～110 DEG C；Tower bottom of rectifying tower is 100 DEG C～250 DEG C, preferably 100 DEG C～230 DEG C, most preferably 150 DEG C～230 DEG C；Reaction pressure is preferably normal pressure；The reflux ratio of tower top is 5～50, preferably 5～40, is most preferably 10～30.
The inventive method step（2）In, it is preferred to use modified sulfonic group cation exchange resin, the sulfonic group cation exchange resin that is modified passes through oxygen content≤5mg/L, most preferably preferred oxygen content≤3mg/L, oxygen content≤1mg/L（In terms of under the conditions of 20 DEG C, 100kPa）The conventional sulfonic group cation exchange resin of distilled water immersion be obtained.Modified concrete modifying process is as follows：Sulfonic group cation exchange resin is placed in the distilled water of oxygen content≤5mg/L, a point three phases are processed：First stage treatment conditions are pressure 0.5MPa～0.8MPa；Bubble 8h～24h is invaded at temperature 60 C～75 DEG C, inert gas is passed through while invading bubble, the flow velocity of inert gas is 20m3/ h～25m3/h；Second stage treatment conditions are pressure 0.9MPa～1.1MPa；Bubble 12h～24h is invaded at 85 DEG C～100 DEG C of temperature, inert gas is passed through while invading bubble, the flow velocity of inert gas is 10m3/ h～15m3/h；Phase III treatment conditions are pressure 1.3MPa～1.5MPa；Bubble 12h～48h is invaded at 120 DEG C～150 DEG C of temperature, inert gas is passed through while invading bubble, the flow velocity of inert gas is 5m3/ h～8m3/ h, process carries out washing drying and is obtained for the catalyst of cyclopentyl acetate hydrolysis after terminating.
In the inventive method, commercial goods, the type sulfonic group cation exchange resins of D005- II or DZH type sulfonic group cation exchange resins of commercial goods such as Dandong Mingzhu Special Type Resin Co., Ltd.'s production can be made or be adopted to conventional sulfonic group cation exchange resin by oneself according to prior art.
In the inventive method, cyclopentene first carries out addition reaction with acetic acid and generates cyclopentyl acetate, because the catalyst for adopting is to pass sequentially through toluene（It is nonpolar）, methyl iso-butyl ketone (MIBK)（Polarity）The modified sulfonic group cation exchange tree of immersion, therefore, the conversion ratio of cyclopentene can reach 100%, and the material containing cyclopentyl acetate for then generating is hydrolyzed reaction in rectifying column with water, obtains cyclopentanol and acetic acid.Cyclopentyl acetate steam in the water rising of rectifier bottoms and tower, and form azeotropic mixture, the azeotropic mixture for being formed rises to the catalyst of the top filling of reactive distillation column, the reaction that is hydrolyzed generates cyclopentanol and acetic acid, simultaneously further gasification is separated cyclopentanol with liquid-phase acetic acid, finally by overhead extraction, and liquid-phase acetic acid is used after extraction by separating the bottom for returning to catalytic rectifying tower through concentrate Posterior circle.
The whole course of reaction technological process of the inventive method is simple, cyclopentene conversion ratio and selectively height, and rectifying is completed simultaneously with hydrolysis in a rectifying column, simple to operate, and accessory substance is few, and product yield height can reach more than 90%.Unreacted acetic acid can be with recycled through concentrate thickness, therefore whole technical process is environmental protection technique.
Specific embodiment
The process and advantage of the inventive method are further illustrated with reference to embodiment and comparative example, but following examples are not construed as limiting the invention.The type sulfonic group cation exchange resins of D005- II and DZH type sulfonic group cation exchange resins that the conventional sulfonic group cation exchange resin adopted in the inventive method is produced for Dandong Mingzhu Special Type Resin Co., Ltd., specific nature is shown in Table 1.
Table 1
Embodiment 1
The type sulfonic group cation exchange resin toluene of D005- II that commercially available Dandong Mingzhu Special Type Resin Co., Ltd. produces is invaded into bubble 28h at 40 DEG C, invaded at a temperature of 50 DEG C with methyl iso-butyl ketone (MIBK) again after filtration and steep 40h, Jing washings, dry prepared addition reaction catalyst after filtration, toluene or methyl iso-butyl ketone (MIBK) are 10 with the volume ratio of sulfonic group cation exchange resin：1.Take above-mentioned addition reaction catalyst to be fitted into the stainless steel reactor of Φ 18mm × 1200mm, reactor head and bottom are respectively charged into the quartz sand of a diameter of Φ 0.5mm～1.2mm, after reactor is installed, with nitrogen displacement three times, and air seal test is qualified.Being passed through cyclopentene and acetic acid carries out addition reaction, and addition reaction condition is shown in Table 2, and addition reaction the results are shown in Table 4.Above-mentioned addition reaction product and water are hydrolyzed reaction into rectifying column, rectifier loads the DZH type sulfonic group cation exchange resins of 500ml Dandong Mingzhu Special Type Resin Co., Ltd. production, catalytic rectifying tower bottom loads the θ filler 500ml of 3m × 3m, rectifying column operating condition is shown in Table 3, and reaction result is shown in Table 4.
Embodiment 2
The DZH type sulfonic group cation exchange resin toluene that commercially available Dandong Mingzhu Special Type Resin Co., Ltd. produces is invaded into bubble 10h at 120 DEG C, invaded at a temperature of 80 DEG C with methyl iso-butyl ketone (MIBK) again after filtration and steep 28h, Jing washings, dry prepared addition reaction catalyst after filtration, toluene or methyl iso-butyl ketone (MIBK) are 30 with the volume ratio of sulfonic group cation exchange resin：1.Take above-mentioned addition reaction catalyst to be fitted into the stainless steel reactor of Φ 18mm × 1200mm, reactor head and bottom are respectively charged into the quartz sand of a diameter of Φ 0.5mm～1.2mm, after reactor is installed, with nitrogen displacement three times, and air seal test is qualified.Being passed through cyclopentene and acetic acid carries out addition reaction, and addition reaction condition is shown in Table 2, and addition reaction the results are shown in Table 4.Above-mentioned addition reaction product and water are hydrolyzed reaction into rectifying column, rectifier loads the DZH type sulfonic group cation exchange resins of 500ml Dandong Mingzhu Special Type Resin Co., Ltd. production, catalytic rectifying tower bottom loads the θ filler 500ml of 3m × 3m, rectifying column operating condition is shown in Table 3, and reaction result is shown in Table 4.
Embodiment 3
The type sulfonic group cation exchange resin toluene of D005- II that commercially available Dandong Mingzhu Special Type Resin Co., Ltd. produces is invaded into bubble 15h at 100 DEG C, invaded at a temperature of 70 DEG C with methyl iso-butyl ketone (MIBK) again after filtration and steep 35h, Jing washings, dry prepared addition reaction catalyst after filtration, toluene or methyl iso-butyl ketone (MIBK) are 20 with the volume ratio of sulfonic group cation exchange resin：1.Take above-mentioned addition reaction catalyst to be fitted into the stainless steel reactor of Φ 18mm × 1200mm, reactor head and bottom are respectively charged into the quartz sand of a diameter of Φ 0.5mm～1.2mm, after reactor is installed, with nitrogen displacement three times, and air seal test is qualified.Being passed through cyclopentene and acetic acid carries out addition reaction, and addition reaction condition is shown in Table 2, and addition reaction the results are shown in Table 4.Above-mentioned addition reaction product and water are hydrolyzed reaction into rectifying column, rectifier loads the type sulfonic group cation exchange resins of D005- II of 500ml Dandong Mingzhu Special Type Resin Co., Ltd. production, catalytic rectifying tower bottom loads the θ filler 500ml of 3m × 3m, rectifying column operating condition is shown in Table 3, and reaction result is shown in Table 4.
Embodiment 4
With embodiment 1, difference is that the DZH type sulfonic group cation exchange resins loaded in rectifying column are adopted and processed with the following method：DZH type sulfonic group cation exchange resin catalyst 500ml are taken, is placed in the deoxygenated water for 4mg/L, with 20m per hour3Flow velocity enters nitrogen, and bubble 16h is invaded at pressure 0.6MPa, 65 DEG C of temperature；Then nitrogen flow rate is adjusted into 15m3/ h, by pressure 1.0MPa is upgraded to, and temperature invades bubble 18h at being upgraded to 90 DEG C；Again nitrogen flow rate is adjusted into 5m3/ h, by pressure 1.5MPa is upgraded to, and temperature invades bubble 24h at being upgraded to 140 DEG C, process carries out washing and is dried prepared hydrolyst after terminating.
Embodiment 5
With embodiment 2, difference is that the DZH type sulfonic group cation exchange resins loaded in rectifying column are adopted and processed with the following method：DZH type sulfonic group cation exchange resin catalyst 500ml are taken, is placed in the deoxygenated water for 3mg/L, with 20m per hour3Flow velocity enters nitrogen, and bubble 16h is invaded under pressure 0.8MPa, temperature 70 C；Then nitrogen flow rate is adjusted into 10m3/ h, by pressure 1.0MPa is upgraded to, and temperature invades bubble 15h at being upgraded to 90 DEG C；Again nitrogen flow rate is adjusted into 8m3/ h, by pressure 1.3MPa is upgraded to, and temperature invades bubble 15h at being upgraded to 120 DEG C, process carries out washing and is dried prepared hydrolyst after terminating.
Embodiment 6
With embodiment 3, difference is that the sulfonic group cation exchange resins of D005- II loaded in rectifying column are adopted and processed with the following method：DZH type sulfonic group cation exchange resin catalyst 500ml are taken, is placed in the deoxygenated water for 0.01mg/L, with 25m per hour3Flow velocity enters nitrogen, and bubble 12h is invaded at pressure 0.8MPa, 100 DEG C of temperature；Then nitrogen flow rate is adjusted into 15m3/ h, by pressure 1.0MPa is upgraded to, and temperature invades bubble 15h at being upgraded to 90 DEG C；Again nitrogen flow rate is adjusted into 5m3/ h, by pressure 1.5MPa is upgraded to, and temperature invades bubble 12h at being upgraded to 150 DEG C, process carries out washing and is dried prepared hydrolyst after terminating.
Comparative example 1
It is that DZH type sulfonic groups cation exchange tree only invades bubble 28h at 40 DEG C with toluene with the difference of embodiment 2, Jing washings, dry prepared addition reaction catalyst after filtration.
Table 2
Table 3
The reaction result of table 4
Claims (15)
1. a kind of method of Preparation of Cyclopantanol by Hydration of Cyclopentene, it is characterised in that：Including procedure below：
（1）Cyclopentene carries out addition reaction in the presence of modified sulfonic group cation exchange resin and generates cyclopentyl acetate with acetic acid, and cyclopentene is 1 with the molar ratio of acetic acid：1～10, cyclopentene liquid quality air speed is 0.5h-1～3.5h-1, reaction temperature is 50 DEG C～150 DEG C, and reaction pressure is 0.1MPa～2.0MPa, and modified sulfonic group cation exchange resin soaks successively conventional sulfonic group cation exchange resin and is obtained by toluene, methyl iso-butyl ketone (MIBK)；
（2）Step（1）The material for obtaining enters rectifying column, azeotropic mixture is formed in rectifying column bottom and water, in the presence of the conventional sulfonic group cation exchange resin catalyst for filling in rectifier, cyclopentyl acetate and water in the azeotropic mixture of rectifying column bottom is hydrolyzed reaction, overhead extraction product cyclopentanol, bottom of towe produces acetic acid, and water is 1～25 with the mol ratio of cyclopentyl acetate：1, the liquid quality air speed of cyclopentyl acetate is 0.5h-1～2.5h-1。
2. method according to claim 1, it is characterised in that：Step（1）Middle cyclopentene is 1 with the molar ratio of acetic acid：1～8；Liquid quality air speed is 0.5h-1～2.0h-1；Reaction temperature is 60 DEG C～150 DEG C；Reaction pressure is 0.1MPa～1.5MPa.
3. method according to claim 2, it is characterised in that：Step（1）Middle cyclopentene is 1 with the molar ratio of acetic acid：1～5；Liquid quality air speed is 0.5h-1～1.0h-1；Reaction temperature is 70 DEG C～120 DEG C；Reaction pressure is 0.1MPa～1.0MPa.
4. method according to claim 1, it is characterised in that：Step（1）In be modified sulfonic group cation exchange resin concrete modifying process it is as follows：First conventional sulfonic group cation exchange resin toluene is invaded into bubble 8h～48h at a temperature of 40 DEG C～150 DEG C, then invaded at a temperature of 40 DEG C～100 DEG C with methyl iso-butyl ketone (MIBK) again and steep 24h～48h, toluene or methyl iso-butyl ketone (MIBK) are 5～50 with the volume ratio of sulfonic group cation exchange resin：1.
5. method according to claim 4, it is characterised in that：Step（1）In be modified sulfonic group cation exchange resin concrete modifying process it is as follows：First conventional sulfonic group cation exchange resin toluene is invaded into bubble 10h～28h at 40 DEG C～120 DEG C, then invaded at a temperature of 50 DEG C～80 DEG C with methyl iso-butyl ketone (MIBK) again and steep 28h～40h, toluene or methyl iso-butyl ketone (MIBK) are 10～30 with the volume ratio of sulfonic group cation exchange resin：1.
6. method according to claim 1, it is characterised in that：Step（2）The mol ratio 1～20 of middle water and cyclopentyl acetate：1；The liquid quality air speed of cyclopentyl acetate is preferably 0.5h-1～2.0h-1。
7. method according to claim 6, it is characterised in that：Step（2）Middle water is 1～15 with the mol ratio of cyclopentyl acetate：1；The liquid quality air speed of cyclopentyl acetate is 0.5h-1～1.5h-1。
8. method according to claim 1, it is characterised in that：Step（2）Middle rectifying column tower top temperature is 70 DEG C～150 DEG C；Tower bottom of rectifying tower is 100 DEG C～250 DEG C；Reaction pressure is normal pressure；The reflux ratio of tower top is 5～50.
9. method according to claim 8, it is characterised in that：Step（2）Middle rectifying column tower top temperature is 70 DEG C～130 DEG C；Tower bottom of rectifying tower is 100 DEG C～230 DEG C；The reflux ratio of tower top is 5～40.
10. method according to claim 9, it is characterised in that：Step（2）Middle rectifying column tower top temperature is 70 DEG C～110 DEG C；Tower bottom of rectifying tower is 150 DEG C～230 DEG C；The reflux ratio of tower top is 10～30.
11. methods according to claim 1, it is characterised in that：Step（2）The sulfonic group cation exchange resin of the middle distilled water immersion routine for passing through oxygen content≤5mg/L using modified sulfonic group cation exchange resin, the sulfonic group cation exchange resin that is modified is obtained.
12. methods according to claim 11, it is characterised in that：Modified sulfonic group cation exchange resin is obtained by the conventional sulfonic group cation exchange resin of the distilled water immersion of oxygen content≤3mg/L.
13. methods according to claim 12, it is characterised in that：Modified sulfonic group cation exchange resin is obtained by the conventional sulfonic group cation exchange resin of the distilled water immersion of oxygen content≤1mg/L.
14. methods according to claim 11, it is characterised in that：Three phases are divided to carry out immersion treatment：First stage treatment conditions are pressure 0.5MPa～0.8MPa；Bubble 8h～24h is invaded at temperature 60 C～75 DEG C, inert gas is passed through while invading bubble, the flow velocity of inert gas is 20m3/ h～25m3/h；Second stage treatment conditions are pressure 0.9MPa～1.1MPa；Bubble 12h～24h is invaded at 85 DEG C～100 DEG C of temperature, inert gas is passed through while invading bubble, the flow velocity of inert gas is 10m3/ h～15m3/h；Phase III treatment conditions are pressure 1.3MPa～1.5MPa；Bubble 12h～48h is invaded at 120 DEG C～150 DEG C of temperature, inert gas is passed through while invading bubble, the flow velocity of inert gas is 5m3/ h～8m3/ h,.
15. methods according to claim 1, it is characterised in that：Conventional sulfonic group cation exchange resin is to make or adopt commercial goods by oneself according to prior art.
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| CN111606780A (en) * | 2020-06-19 | 2020-09-01 | 凯瑞环保科技股份有限公司 | Device and method for synthesizing cyclopentanol from cyclopentene |
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