CN1057075C - Process for producing low carbon alcohol by directly hydrating low carbon olefines - Google Patents
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Abstract
The present invention discloses a technological method for continuously producing C2 to C5 alcohol from C2 to C5 alkene by direct hydration. The method adopts a main reaction vessel and a subsidiary reaction vessel; unreacted alkene discharged from the main reaction vessel and fresh deionized water carry out hydration reaction with a high water/alkene ratio in the subsidiary reaction vessel, a water solution containing the alcohol generated by the reaction is used as the raw material water of the main reaction vessel; thereby, the conversion rate of the alkene raw material is greatly enhanced.
Description
The present invention relates to the method that a kind of low-carbon alkene prepares low-carbon alcohol.
Early stage alkene direct hydration system alcohol adopts raw material olefin once by reactor, carries out hydration reaction in the presence of resin catalyst.As English Patent 1,374,368,1,386,195, the method for this process using big flood/alkene mol ratio obtains higher transformation efficiency.Because this process water amount is big, the energy consumption height, uneconomical, so this technology replaced by little water/alkene mol ratio, hydrocarbon circulation technology gradually, as United States Patent (USP) 4,476,333,4,831,197, all adopts the hydrocarbon circulation technology.This technology has been compared obvious superiority with big flood/alkene than technology, is adopted by present industrial production.Little water/alkene is than hydrocarbon circulation technology, reactor outlet unreacted alkene major part again Returning reactor carry out hydration reaction with fresh feed, keep certain total conversion rate with the method for control hydrocarbon recycle ratio.This method is suitable for total conversion rate less demanding most, and reacted tail gas has the technology of specific purposes; Do not have special purpose for tail gas, require the high technology of total conversion rate just not possess superiority.
English Patent 1,374 in 368, in the presence of acidic cation-exchange resin, adopts greater than water/alkene of 100: 1 and tests than the liquid-phase hydration that carries out n-butene, requires temperature to be higher than 100 ℃, preferably is higher than 130 ℃.A large amount of waters are arranged in the product, contain sec-butyl alcohol in the water, then also can contain a spot of other organism as raw material is impure less than 2.5%.In water/alkene mol ratio is 173: 1, and raw material is under the situation of 100% n-butene, and flooding quantity is 25mol/h, advances the hydrocarbon amount and be 0.14 to 0.15mol/h, reach the peak rate of conversion 70% in giving an example, contain 1.7% (m) sec-butyl alcohol in the product aqueous solution.Water in another example/alkene ratio is 161: 1, and n-butene concentration is 59.5% (m), and other reaction conditions is identical substantially with last example, and transformation efficiency is 38%.Though water/alkene has the high advantage of per pass conversion than big, from technological angle, water/alkene is bigger than big then total quantity of circulating water, and energy consumption increases, and economic benefit descends.
United States Patent (USP) 4,476,333, be in the presence of acidic cation-exchange resin, adopt little water/alkene than the liquid-phase hydration test of carrying out n-butene, its technical process is that fresh deionized water and fresh feed enter reactor from the bottom, and reaction product is discharged aqueous solution of alcohol through the phase separator bottom, and the organic phase that discharge at the top enters pressurizing tower.Thick low-carbon alcohol is discharged in the pressurizing tower bottom, and the unreacting hydrocarbon that contains alkene is discharged at the top, and wherein a part is as the recycle hydrocarbons Returning reactor, and another part discharges (see figure 3) as the tail hydrocarbon via pipeline.In water/alkene molecular ratio is 4: 1, and the n-butene concentration that enters reactor is 78～81% (m), and temperature of reaction is 150 ℃, and reaction pressure is that its transformation efficiency is 52.6% under the condition of 70 crust, and the sec-butyl alcohol space-time yield is 1.6mol/L, h..The total conversion rate of this patent is lower, does not have the situation of specific purposes for reaction end gas, and significant loss is bigger, and is inadvisable economically.
In a word, though more than two class technology separately advantage is arranged, all have the low shortcoming of transformation efficiency, and one also exist the energy consumption height, also there is the bigger problem of significant loss in another one.
At the above existing in prior technology weak point, it is not high to the objective of the invention is to propose a kind of energy consumption, the method for the low-carbon alkene direct hydration continuous production low-carbon alcohol that total conversion rate is high.
The objective of the invention is to be achieved through the following technical solutions: adopt two reactors of major-minor to carry out hydration reaction, auxiliary reactor, carry out one time hydration reaction again, thereby improve the total conversion rate of raw material from the unreacted alkene that main reactor comes out.
By method of the present invention, the raw material hydrocarbon that contains low-carbon alkene is mixed with the aqueous solution of alcohol that comes from auxiliary reactor with by the recycle hydrocarbons that tripping device comes, and enters main reactor together.Reaction product is discharged from main reactor, divides water outlet through tripping device then, product low-carbon alcohol, by-product low-carbon (LC) ether and contain the hydrocarbon component of low-carbon alkene.A hydrocarbon component part that contains low-carbon alkene loops back main reactor, another part with enter auxiliary reactor after fresh deionized water mixes, reaction product is after phase separator separates, hydrocarbon phase is discharged, and contains pure water and loops back main reactor.With technology in the past (as United States Patent (USP) 4,476,333) contrast, the present invention adopted an auxiliary reactor in the past the discharge hydrocarbon in the technology carry out hydration reaction with fresh deionized water, the tail hydrocarbon is discharged the fresh water that send fuel system, water directly to enter in the alternative technology in the past of main reactor and is carried out hydration reaction.
According to method of the present invention, unreacted low-carbon alkene also can not loop back main reactor in main reactor, directly all with after deionized water mixes, enters auxiliary reactor and carries out hydration reaction.
The raw material hydrocarbon that enters main reactor is the raw material hydrocarbon of C2～C5 normal olefine of containing 80m%～90m%, and it is 0.5m%～2m% that the aqueous solution of alcohol that is generated by auxiliary reactor contains C2～C5 alcohol.
Recycle hydrocarbons of separating after the reaction of fresh low-carbon alkene raw material and main reactor and the aqueous solution of alcohol separated through auxiliary reactor are that 1～20: 1 mixed enters main reactor by water/alkene ratio, with the liquid water is external phase, reacts in the reactor of strong acid cation exchange resin catalyst is housed.70～200 ℃ of temperature of reaction, reaction pressure 1～12Mpa.Main reactor come out material cooling, step-down after enter separation system, separate water outlet, product low-carbon alcohol, by-product low-carbon (LC) ether and contain the hydrocarbon component of low-carbon alkene.Contain a low-carbon alkene component part and loop back main reactor, another part mixes with fresh deionized water, enter and carry out hydration reaction in the auxiliary reactor, water/alkene molecular ratio is 62～300: 1, the used catalyzer of auxiliary reactor also is the strongly acidic cation-exchange catalyzer, and its kind can be identical with main reactor.Reaction product is isolated hydrocarbon phase through phase separator and is discharged, and water enters main reactor.
The reaction mass of main reactor is to enter from the bottom, and product is discharged from top, and external phase is water in the reactor; The reaction raw materials of auxiliary reactor enters from top, and product is discharged from the bottom, and the external phase in the reactor is overcritical or the hydrocarbon of subcritical state.
The temperature of reaction of main reactor is preferably at 120～160 ℃, and reaction pressure is preferably at 4～8Mpa, and water alkene molecular ratio is preferably 1～16: 1.
The temperature of reaction of auxiliary reactor is preferably at 120～160 ℃, and reaction pressure is preferably at 4～8Mpa, and water alkene molecular ratio is preferably 100～200: 1.
The reaction mass that enters major and minor reactor preferably reacts under overcritical or suberathem state.
The key difference of the present invention and existing technology is that the present invention has set up an auxiliary reactor, and the low-carbon alkene tail hydrocarbon that contains of prior art is carried out the hydration reaction second time, further utilizes the low-carbon alkene in the discharging hydrocarbon.Wherein the raw water of main reactor is the aqueous solution of alcohol of auxiliary reactor, and the raw water of auxiliary reactor is fresh deionized water.
The advantage that present method is outstanding is the total conversion rate height, can reach more than 90% (mol), has improved utilization ratio of raw materials and production efficiency widely.In addition, the shared cover product separation device of present method main reactor and auxiliary reactor compared with prior art only increases an auxiliary reactor, does not increase the unit consumption of energy of production low-carbon alcohol.
Fig. 1: be schema I of the present invention.
Fig. 2: be schema II of the present invention.
Fig. 3: the general flow chart that is prior art (United States Patent (USP) 4,476,333).
Process flow sheet such as Fig. 1, new hydrocarbon reaches from the laggard reactor A of becoming owner of of the aqueous solution that contains low-carbon alcohol 0.5～2m% of pipeline 12 by the recycle hydrocarbons of pipeline 1 with pipeline 8, from bottom to top pass through the resin catalyst bed, carry out hydration reaction, all material is discharged by reactor head, enter crude product separation system C via pipeline 2 and separate water outlet along pipeline 6 discharges, the reaction product low-carbon alcohol is discharged along pipeline 4 along pipeline 3 and low-carbon (LC) ether, unreacting hydrocarbon enters auxiliary reactor B along pipeline 5 parts by pipeline 7, and all the other return main reactor A along pipeline 8.Auxiliary reactor B advances deionized water by pipeline 9, mixes from top to down by auxiliary reactor B with unreacting hydrocarbon from pipeline 7, carries out hydration reaction.Reacted whole material enters phase separator D along pipeline 10, discharges the tail hydrocarbon by the top of phase separator D along pipeline 11, and the aqueous solution of alcohol that discharge the phase separator bottom enters main reactor A along pipeline 12.
Main reactor A is the stainless steel tube of internal diameter 25mm, virtual height 3m, interior dress strong acid cation exchange resin catalyst 1L, this resin catalyst consist of SDVB copolymer comprised 42.5m%, bromine accounts for 36.5m%, sulfonic acid group accounts for 20.9m%.Auxiliary reactor B is the stainless steel tube of internal diameter 25mm, virtual height 1m, the resin catalyst 108ml that interior dress is identical with main reactor.Main reactor advances new hydrocarbon 72.5g/h (containing n-butene 92.0m%), advance recycle hydrocarbons 794g/h (containing n-butene 70.0m%), auxiliary reactor advances the hydrocarbon component that contains unreacting olefin (the containing n-butene 70.0m%) 19.1g/h that comes out at crude product separation system top, advance fresh deionized water 700g/h, temperature of reaction in the main side effect device is 155 ℃, reaction pressure 8.0Mpa.Under these conditions, the total conversion rate of n-butene is 90% (mol), and the sec-butyl alcohol productive rate is 71.6g/l.h.
Example 2
Identical with example 1 technical process, catalyst system therefor and feedstock property are identical.Main reactor apparatus with catalyst inside 1L, auxiliary reactor dress catalyzer 126ml.In main reactor, advance new hydrocarbon 85.1g/h (containing n-butene 92.0% (m)), advance recycle hydrocarbons 955g/h (containing n-butene 70.0% (m)).Auxiliary reactor advances the hydrocarbon component that contains unreacting olefin (the containing n-butene 70.0m%) 22.5g/h that comes out at crude product separation system top, advances fresh deionized water 700g/h.155 ℃ of major and minor reactor interior reaction temperatures, reaction pressure 8.0MPa.The n-butene total conversion rate is 90% (mol), and the sec-butyl alcohol productive rate is 81.9g/L.h, and by-product di-secondary butyl ether productive rate is 0.8g/L.h.
Example 3
Identical with example 1 technical process, catalyst system therefor and raw material hydrocarbon character are identical.Main reactor apparatus with catalyst inside 1L, auxiliary reactor dress catalyzer 120ml.Main reactor advances new hydrocarbon 85g/h (containing n-butene 92.0% (m)), advances recycle hydrocarbons 971g/h (containing n-butene 68.6% (m)); Auxiliary reactor advances the hydrocarbon component that contains unreacting olefin (the containing n-butene 68.6m%) 21.7g/h that comes out at crude product separation system top, advances fresh deionized water 700g/h.155 ℃ of the temperature of reaction of main side effect device, reaction pressure 8.0MPa.N-butene total conversion rate 90.5mol%, sec-butyl alcohol productive rate 82.1g/L.h, by-product di-secondary butyl ether 1.3g/L.h.
Example 4
Technical process is identical with example 1, the used resin catalyst of main side effect device consist of SDVB copolymer comprised 42.1m%, bromine accounts for 38.6m%, sulfonic acid group accounts for 19.3m%.Raw material n-butene content is 88m%.Main reactor dress catalyzer 1L, auxiliary reactor dress catalyzer 111ml.Main reactor advances new hydrocarbon 74.9g/h (containing n-butene 88.0% (m)), recycle hydrocarbons 1135g/h (containing n-butene 60.0% (m)); Auxiliary reactor advances the hydrocarbon component that contains unreacting olefin (the containing n-butene 60.0m%) 23.2g/h that comes out at crude product separation system top, advances fresh deionized water 700g/h.The temperature of reaction of major and minor reactor: 155 ℃, reaction pressure: 8.0MPa.The n-butene total conversion rate is 90mol%, and the sec-butyl alcohol productive rate is 72.6g/L.h, and by-product di-secondary butyl ether productive rate is 1.1g/L.h.
Example 5
Technical process and catalyzer are identical with example 4, and raw material hydrocarbon n-butene content is 80m%.Main reactor dress catalyzer 1L, auxiliary reactor dress catalyzer 185ml.Main reactor advances new hydrocarbon 95.6g/h (containing n-butene 80.0% (m)), advances recycle hydrocarbons 1225g/h (containing n-butene 54.5% (m)); Auxiliary reactor advances the hydrocarbon component that contains unreacting olefin (the containing n-butene 54.5m%) 42.1g/h that comes out at crude product separation system top, advances fresh deionized water 1000g/h.The temperature of reaction of major and minor reactor: 155 ℃, reaction pressure: 8.0MPa.The n-butene total conversion rate is 85mol%, sec-butyl alcohol productive rate 71.6g/L.h, and by-product di-secondary butyl ether productive rate is 1.0g/L.h.
Example 6
Technical process, raw material hydrocarbon are all identical with example 1, and catalyzer is identical with example 4.Main reactor dress catalyzer 1L, auxiliary reactor dress catalyzer 235ml.Main reactor advances new hydrocarbon 83g/h (containing n-butene 92.0% (m)), advance recycle hydrocarbons 1109g/h (containing n-butene 68.6% (m)), auxiliary reactor advances the hydrocarbon component that contains unreacting olefin (the containing n-butene 68.6m%) 21.2g/h that comes out at crude product separation system top, advances fresh deionized water 600g/h.The temperature of reaction of major and minor reactor: 155 ℃, reaction pressure: 6.0MPa.N-butene total conversion rate 91.6mol%, sec-butyl alcohol productive rate are 72.9g/L.h, by-product di-secondary butyl ether 2.3g/L.h.
Example 7
Technical process, raw material hydrocarbon are all identical with example 1, and catalyzer is identical with example 4.Main reactor dress catalyzer 1L, auxiliary reactor dress catalyzer 79ml.In main reactor, advance new hydrocarbon 71.2g/h (containing n-butene 92.0% (m)), recycle hydrocarbons 1136g/h (containing n-butene 63.2% (m)); Auxiliary reactor advances the hydrocarbon component that contains unreacting olefin (the containing n-butene 63.2m%) 15.5g/h that comes out at crude product separation system top, advances fresh deionized water 600g/h.The temperature of reaction of major and minor reactor: 155 ℃, reaction pressure: 8.0MPa.The n-butene total conversion rate is 92.5mol%, and the sec-butyl alcohol productive rate is 71.9g/L.h, and by-product di-secondary butyl ether productive rate is 2.2g/L.h.
Example 8
Technical process, raw material hydrocarbon are all identical with example 1, the used resin catalyst of major and minor reactor consist of SDVB copolymer comprised 45.4m%, bromine accounts for 35.7m%, sulfonic acid group accounts for 18.9m%.。Main reactor dress catalyzer 1L, auxiliary reactor dress catalyzer 125ml, main reactor advances new hydrocarbon 83.9g/h (containing n-butene 92.0% (m)), recycle hydrocarbons 957g/h (containing n-butene 70.0% (m)); Auxiliary reactor advances the hydrocarbon component that contains unreacting olefin (the containing n-butene 70.0m%) 22.2g/h that comes out at crude product separation system top, advances fresh deionized water 700g/h.Major and minor reactor interior reaction temperature is: 155 ℃, reaction pressure: 6.0MPa.The n-butene total conversion rate is 90mol%, sec-butyl alcohol productive rate 80.3g/L.h, by-product di-secondary butyl ether 1.2g/L.h.
Example 9
Technical process, raw material hydrocarbon are all identical with example 1, and catalyzer is identical with example 8.Main reactor dress catalyzer 1L, auxiliary reactor dress catalyzer 114ml, main reactor advances new hydrocarbon 76.8g/h (containing n-butene 92.0% (m)), recycle hydrocarbons 966g/h (containing n-butene 70.0% (m)); Auxiliary reactor advances the hydrocarbon component that contains unreacting olefin (the containing n-butene 70.0m%) 20.3g/h that comes out at crude product separation system top, advances fresh deionized water 700g/h.Major and minor reactor interior reaction temperature: 155 ℃, reaction pressure: 4.0MPa.The n-butene total conversion rate is 90mol%, sec-butyl alcohol productive rate 73.4g/L.h, by-product di-secondary butyl ether 1.1g/L.h.
Example 10
Technical process, raw material hydrocarbon are all identical with example 1, and catalyzer is identical with example 8.Main reactor dress catalyzer 1L, auxiliary reactor dress catalyzer 56ml, main reactor advances new hydrocarbon 71g/h (containing n-butene 97.0% (m)), recycle hydrocarbons 721.3g/h (containing n-butene 76.4% (m)); Auxiliary reactor advances the hydrocarbon component that contains unreacting olefin (the containing n-butene 76.4m%) 9.0g/h that comes out at crude product separation system top, advances fresh deionized water 500g/h.Main reactor interior reaction temperature: 155 ℃, reaction pressure: 8.0MPa; Auxiliary reactor interior reaction temperature: 155 ℃, reaction pressure: 6.0MPa.The n-butene total conversion rate is 95mol%, sec-butyl alcohol productive rate 80.2g/L.h, by-product di-secondary butyl ether 1.6g/L.h.
Example 11
Technical process such as Fig. 2, new hydrocarbon is by pipeline 1 and from the laggard reactor A of becoming owner of of the aqueous solution that contains low-carbon alcohol 0.5m～2m% of pipeline 12, from top to down is by the resin catalyst bed, carry out hydration reaction, all material is discharged by reactor bottom, enter the isolated water of crude product separation system C via pipeline 2 and discharge along pipeline 6, the reaction product low-carbon alcohol is discharged along pipeline 4 along pipeline 3 and low-carbon (LC) ether, and unreacting hydrocarbon enters auxiliary reactor B along pipeline 5 by pipeline 7.The deionized water that pipeline 9 is advanced mixes from top to down by auxiliary reactor B with unreacting hydrocarbon from pipeline 7, carries out hydration reaction.Reacted whole material enters phase separator D along pipeline 10, discharges the tail hydrocarbon by the top of phase separator D along pipeline 11, and the aqueous solution of alcohol that discharge the phase separator bottom enters main reactor along pipeline 12.
Catalyzer is identical with example 8, and olefin feedstock is a propylene.Main reactor dress catalyzer 1L, auxiliary reactor dress catalyzer 100ml, main reactor advances new hydrocarbon 222g/h (containing propylene 95.0% (m)), no recycle hydrocarbons; Auxiliary reactor advances the hydrocarbon component that contains unreacting olefin (the containing propylene 77.8m%) 50g/h that comes out at crude product separation system top, advances fresh deionized water 1400g/h.Major and minor reactor interior reaction temperature: 135 ℃, reaction pressure: 6.0MPa.The propylene total conversion rate is 98mol%, Virahol productive rate 179g/L.h, by-product diisopropyl ether 7.4g/L.h.
Example 12
Technical process such as Fig. 2, catalyzer is identical with example 8, and raw material hydrocarbon is identical with example 11.Main reactor dress catalyzer 1L, auxiliary reactor dress catalyzer 56ml, main reactor advances new hydrocarbon 222g/h (containing propylene 99.0% (m)), no recycle hydrocarbons; Auxiliary reactor advances the hydrocarbon component 40.1g/h that contains unreacting olefin (containing propylene 94.5% (m)) that comes out at crude product separation system top, advances fresh deionized water 1000g/h.Main reactor interior reaction temperature: 135 ℃, reaction pressure: 8.0MPa; Auxiliary reactor interior reaction temperature: 135 ℃, reaction pressure: 6.0MPa.The propylene total conversion rate is 99mol%, Virahol productive rate 201g/L.h, by-product diisopropyl ether 4.2g/L.h.
Comparative example 1
Fig. 3 is seen in technical process.New hydrocarbon mixes after pipeline 3 ' enters reactor A with the recycle hydrocarbons that pipeline 8 ' comes by pipeline 1 '.The fresh deionized water that pipeline 2 ' comes mixes the laggard reactor A of becoming owner of with phase separator D bottom of device through the water that pipeline 10 ' comes.Hydro carbons and water carry out hydration reaction from bottom to up by the resin catalyst bed, and all materials are discharged by reactor head, enter phase separator D via pipeline 4 ' and separate water outlet and discharge and enter reactor A after fresh deionized water mixes along pipeline 10 '.The isolated hydro carbons of phase separator D enters pressurizing tower C ' through pipeline 5 ', and the reaction product sec-butyl alcohol is discharged along pipeline 9 ', and by pipeline 7 ' discharging, all the other all return main reactor A along pipeline 8 ' to unreacting hydrocarbon along pipeline a 6 ' part.
Catalyzer, raw material hydrocarbon are identical with example 1, with the difference of example 1 only be not have the auxiliary reactor system, do not reclaim the low-carbon alkene in the discharging hydrocarbon.Raw material hydrocarbon and deionized water are entered by reactor bottom, carry out hydration reaction through beds, reaction back all material is discharged by reactor head, enter separation system, in tripping device, isolate low-carbon alcohol, low-carbon (LC) ether and water, unreacted low-carbon alkene major part is as recycle hydrocarbons Returning reactor A, and wherein sub-fraction is discharged system as the discharging hydrocarbon.
Reactor dress catalyzer 1L advances new hydrocarbon 72.5g/h (wherein containing n-butene 92% (m)) by reactor lower part, advances recycle hydrocarbons 794g/h (wherein containing n-butene 70.0% (m)) and advances deionized water 700g/h.Discharging tail hydrocarbon 19.1g/h (containing n-butene 70.0% (m)).145 ℃ of temperature of reaction, reaction pressure 8.0MPa.N-butene total conversion rate 80mol%, sec-butyl alcohol productive rate 70.5g/L.h.
Comparative example 2
Technical process, catalyzer, raw material hydrocarbon are identical with comparative example 1.Reactor dress catalyzer 1L advances new hydrocarbon 85.1g/h (containing n-butene 92.0% (m)), advances recycle hydrocarbons 955g/h (containing n-butene 70.0% (m)), advances deionized water 700g/h.Discharging tail hydrocarbon 22.5g/h (containing n-butene 70.0%).Temperature of reaction: 155 ℃, reaction pressure: 8.0MPa.N-butene total conversion rate 80mol%, sec-butyl alcohol productive rate 81.9g/L.h, secondary butyl ether productive rate 0.8g/L.h.
Comparative example 3
Technical process, catalyzer, raw material hydrocarbon are identical with comparative example 1.Reactor dress catalyzer 1L advances new hydrocarbon 85g/h (containing n-butene 92.0% (m)) by reactor lower part, advances recycle hydrocarbons 971g/h (containing n-butene 68.6% (m)), and discharging tail hydrocarbon 21.7g/h (containing n-butene 68.6% (m)) advances deionized water 700g/h.Temperature of reaction: 155 ℃, reaction pressure 8.0MPa.N-butene total conversion rate: 81mol%, sec-butyl alcohol productive rate 83.7g/L.h, the secondary butyl ether 1.3g/L.h of by-product.
Claims (14)
1, a kind of processing method of low-carbon alkene direct hydration continuous production low-carbon alcohol, in the presence of the strongly acidic cation-exchange catalyzer, the raw material hydrocarbon that contains low-carbon alkene is with after raw water and recycle hydrocarbons mix, enter main reactor, enter the crude product tripping device then, it is characterized in that behind the crude product tripping device, also being provided with auxiliary reactor and phase separator, return main reactor by the unreacted hydrocarbon component part that contains low-carbon alkene in main reactor that the crude product tripping device comes out as recycle hydrocarbons, another part is with after deionized water mixes, enter and further carry out hydration reaction in the auxiliary reactor, reaction product enters in the phase separator separates, isolated aqueous solution of alcohol, raw water as main reactor enters main reactor, isolating hydrocarbon phase discharger, water in the wherein said main reactor/alkene mol ratio is 1～20: 1, and water in the described auxiliary reactor/alkene mol ratio is 62～300: 1.
2, press the processing method of the described low-carbon alkene direct hydration of claim 1 continuous production low-carbon alcohol, it is characterized in that the described unreacted hydrocarbon component that contains low-carbon alkene in main reactor of being come out by the crude product tripping device all mixes with deionized water, enter then and further carry out hydration reaction in the auxiliary reactor, reaction product enters in the phase separator separates, isolated aqueous solution of alcohol, raw water as main reactor enters main reactor, isolating hydrocarbon phase discharger.
3,, it is characterized in that the described raw material hydrocarbon that contains low-carbon alkene is that to contain mass percent concentration be 80%～99% C by the processing method of claim 1 or 2 described low-carbon alkene direct hydration continuous production low-carbon alcohol
2～C
5The raw material hydrocarbon of normal olefine.
4,, it is characterized in that described aqueous solution of alcohol is the C that contains by the auxiliary reactor generation by the processing method of claim 1 or 2 described low-carbon alkene direct hydration continuous production low-carbon alcohol
2～C
5The mass percent concentration of alcohol is 0.5%～2% the aqueous solution.
5, by the processing method of claim 1 or 2 described low-carbon alkene direct hydration continuous production low-carbon alcohol, the reaction raw materials that it is characterized in that described main reactor is to pass through beds from bottom to top, and liquid water is an external phase.
6, by the processing method of claim 1 or 2 described low-carbon alkene direct hydration continuous production low-carbon alcohol, the reaction raw materials that it is characterized in that described auxiliary reactor is to pass through beds from top to bottom, and the above-critical state hydrocarbon is an external phase.
7, by the processing method of claim 1 or 2 described low-carbon alkene direct hydration continuous production low-carbon alcohol, it is characterized in that the temperature of reaction in the described main reactor is 70～200 ℃, reaction pressure is 1～12Mpa.
8, by the processing method of claim 1 or 2 described low-carbon alkene direct hydration continuous production low-carbon alcohol, it is characterized in that the temperature of reaction in the described auxiliary reactor is 70～200 ℃, reaction pressure is 1～12MPa.
9, by the processing method of claim 1 or 2 described low-carbon alkene direct hydration continuous production low-carbon alcohol, it is characterized in that the temperature of reaction in the described main reactor is 120～160 ℃, reaction pressure is 4～8Mpa.
10, by the processing method of claim 1 or 2 described low-carbon alkene direct hydration continuous production low-carbon alcohol, it is characterized in that the temperature of reaction in the described auxiliary reactor is 120～160 ℃, reaction pressure is 4～8Mpa.
11, by the processing method of claim 1 or 2 described low-carbon alkene direct hydration continuous production low-carbon alcohol, it is characterized in that water alkene mol ratio is 1～16 in the described main reactor: 1.
12, by the processing method of claim 1 or 2 described low-carbon alkene direct hydration continuous production low-carbon alcohol, it is characterized in that water alkene mol ratio is 100～200 in the described auxiliary reactor: 1.
13,, it is characterized in that the reaction mass in the described main reactor reacts under overcritical or subcritical state by the processing method of claim 1 or 2 described low-carbon alkene direct hydration continuous production low-carbon alcohol.
14,, it is characterized in that the reaction mass in the described auxiliary reactor reacts under overcritical or subcritical state by the processing method of claim 1 or 2 described low-carbon alkene direct hydration continuous production low-carbon alcohol.
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| CN1326820C (en) * | 2005-05-31 | 2007-07-18 | 中国科学院大连化学物理研究所 | Method for producing lower alcohol continuously |
| CN101481296B (en) * | 2008-01-11 | 2013-05-01 | 山东科技大学 | Production process for preparing sec-butyl alcohol by mixed C4 reaction distillation method |
| US8558036B2 (en) | 2010-11-15 | 2013-10-15 | Saudi Arabian Oil Company | Dual phase catalysts system for mixed olefin hydrations |
| CN102659514A (en) * | 2012-04-26 | 2012-09-12 | 凯瑞化工股份有限公司 | Method for producing sec-butyl alcohol |
| CN104591961B (en) * | 2013-11-01 | 2016-08-17 | 中国石油化工股份有限公司 | A kind of low-carbon alkene hydrating process |
| CN106631688A (en) * | 2017-01-11 | 2017-05-10 | 王艺霖 | Method for preparing sec-butyl alcohol through butylene hydration |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0051164A1 (en) * | 1980-10-31 | 1982-05-12 | Deutsche Texaco Aktiengesellschaft | Process for the continuous production of sec. butanol |
| EP3512518A1 (en) * | 2016-09-13 | 2019-07-24 | Alar Pharmaceuticals Inc. | Sustained-release buprenorphine formulations background of invention |
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1997
- 1997-09-10 CN CN97116406A patent/CN1057075C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0051164A1 (en) * | 1980-10-31 | 1982-05-12 | Deutsche Texaco Aktiengesellschaft | Process for the continuous production of sec. butanol |
| EP3512518A1 (en) * | 2016-09-13 | 2019-07-24 | Alar Pharmaceuticals Inc. | Sustained-release buprenorphine formulations background of invention |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1210847A (en) | 1999-03-17 |
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Owner name: CHINA PETROCHEMICAL CORPORATION; CHINA PETROLEUM & Free format text: FORMER NAME OR ADDRESS: CHINA PETRO-CHEMICAL CORP.; FUSHUN PETROCHEMICAL INSTITUTE., CHINA PETROCHEMICAL CORP. |
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Patentee after: China Petrochemical Group Corp. Patentee after: Sinopec Group Fushun Research Institute of Petroleum and Petrochemicals Patentee before: China Petrochemical Corporation Patentee before: Fushun Research Inst. of Petroleum Processing, China Petro-chem. Corp. |
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