CN1247503C - Method for continuously producing lower alcohol - Google Patents

Method for continuously producing lower alcohol Download PDF

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Publication number
CN1247503C
CN1247503C CN 200410001113 CN200410001113A CN1247503C CN 1247503 C CN1247503 C CN 1247503C CN 200410001113 CN200410001113 CN 200410001113 CN 200410001113 A CN200410001113 A CN 200410001113A CN 1247503 C CN1247503 C CN 1247503C
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reaction
reactor
catalyst
water
alcohol
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CN1648116A (en
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刘中民
朱书魁
许磊
王�华
吕志辉
李铭芝
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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Abstract

The present invention relates to a method for continuously producing lower alcohol containing 2 to 5 carbon atoms. In the method, lower-carbon alkene containing 2 to 5 carbon atoms is catalyzed and hydrated to form lower alcohol at a reaction temperature of 100 to 200 DEG C and reaction pressure of 4.0 to 20.0MPa under the action of a solid acid catalyst. The present invention is characterized in that water used as a raw material of a hydrating reaction is oxygen-free deionized water whose oxygen dissolving concentration is smaller than 50 mug/l.

Description

A kind of method of continuous production lower alcohol
Technical field
The present invention relates to a kind of continuous production and contain the method for the lower alcohol of 2 to 5 carbon atoms.This method is at 100~200 ℃ of temperature of reaction, reaction pressure 4.0~20.0MPa, and under the effect of solid acid catalyst, the direct catalytic hydration of low-carbon alkene that will contain 2 to 5 carbon atoms obtains containing the lower alcohol of 2 to 5 carbon atoms.
Background technology
The low-carbon alkene direct hydration technology that with the solid acid is catalyzer be with raw material olefin with after reaction process water mixes, be preheated to 100~200 ℃ and enter the direct hydration catalyticreactor and react, reaction pressure is 4.0~20.0MPa.Several sections beds are set in the reactor, and reactant is by each section of catalyzer bed in the catalyticreactor, and the product of generation contains and separates after pure material is derived reactor.Aqueous phase also contains the various ions and the impurity that produce in the reaction process except that containing trace alcohol, cause disadvantageous effect in order to prevent various ions and impurity to the corrosion of equipment or to reaction, needs through purifying treatment before process water loops back reactor.
Under the solid acid catalyst effect, low-carbon alkene can generate corresponding low-carbon alcohol by the catalytic effect of proton.Because low-carbon alkene and water dissolve each other hardly, therefore reaction is to carry out under three-phase (solid catalyst phase, liquid phase water gas phase, low-carbon alkene phase) condition.
The catalyzer that reaction is used also can be zeolite catalyst such as beta-zeolite, ZSM-5, Y-zeolite etc. as the heatproof strong-acid ion exchange resin of modification, and the characteristics of above catalyzer are the reactive behavior height, heat resistance is good, corrosion is little, pollution is light.
The reaction process that various hydration reaction processes adopt in the industrial production because the reaction process the when low-carbon alkene that contains 2 to 5 carbon atoms carries out hydration and mechanism do not coexist is different.For example the butylene direct hydration adopts, and what be that bubbling style three-phase fixed-bed reactor propylene direct hydration then adopts is the three phase trickle flow bed.But the problem that exists in its reaction process and the industrial production is similar substantially.
In solid acid catalysis propylene direct hydration process, propylene and water enter catalyticreactor through after the preheating, hydration reaction takes place form Virahol.Be reflected at gas phase or liquid phase and carry out, reaction pressure 2.0~20.0MPa, 100~200 ℃ of temperature of reaction.The catalyzer of canonical process is Zeo-karb or molecular sieve, and the per pass conversion of gas-liquid phase propylene hydration reaction propylene is at 60~70mol%.
The propylene hydration reaction product is sent into water wash column, and unreacted propylene loops back reactor after separating with Virahol.Anhydrous isopropyl alcohol or 87% Virahol then separate aqueous Virahol with water through 3~6 distillation towers with a small amount of other weight component if desired.Benzene, diisopropyl ether or C6 alkane are used as the entrainment reagent of water in sepn process.
In solid acid catalysis n-butene direct hydration process, butylene and water enter catalyticreactor through after the preheating, hydration reaction takes place generate sec-butyl alcohol, reaction pressure 2.0~25.0MPa, 100~200 ℃ of temperature of reaction.The catalyzer of canonical process is a Zeo-karb, and the per pass conversion of the n-butene of gas-liquid phase reaction is at 6~7mol%.
Resultant of reaction is flowed through from reactor head and is divided behind the heat exchanger water-yielding stratum to enter the liquid liquid separator to take off C 4Tower 4, water loop back reactive system after treatment.Take off C 4Column overhead distilled butylene-butane cut major part is circulated back to reactive system, and the small part discharging is to avoid the accumulation of inertia butane.The crude secbutyl alcohol that the tower still obtains contains a small amount of C 4Impurity such as hydrocarbon, di-secondary butyl ether, not moisture substantially.The purification system of the crude secbutyl alcohol distillation system with the indirect hydration method of sulfuric acid basically is identical, and the purity of the back sec-butyl alcohol of purifying can reach 99.9%.
In German Patent 2233967 and 2429770 specification sheetss, obtain together describing with other method in the aforesaid method.These methods are applied in the production of the sec-butyl alcohol (SBA) and the trimethyl carbinol (TBA) especially at Virahol (IPA).
Method described in German patent DE 2429770 specification sheetss, the n-butylene hydration that carries out has adopted the water cycle technology, is increasing gradually through 200-400 hour the operation post-reactor bottom and the pressure reduction at top.Along with the continuity of operating time, tangible compression shock can take place.These vibrations can make reaction process shut down, for eliminating this influence and must washing by water.
In the drip process described in the Deutsches Reichs-Patent DE2233967 specification sheets, there is the liquid material distribution problem, this shows how needs research makes the distribution of reactant better, particularly the time marquis of the industrial reactor entry into service that has refilled live catalyst, observed some focuses and generated, the generation of these focuses makes the distillatory Virahol that a kind of special smell be arranged.This can be assumed in the process of entry into service, be accompanied by local bad water distribution, run off in a large number and caused the cinder of burning fully of catalyzer and formed agglomerate at the activity of such catalysts group, and adopt ion exchange resin treatment round-robin water of productive use can not solve about reducing this problem of pressure reduction.
In Chinese patent CN86102121, mention and used cats product to reduce reactor bed resistance problem in the low-carbon alkene direct hydration process, make reactant be distributed in the surface of catalyzer better, reduced the pressure reduction problem that exists in the reaction process, this method has been widely used in propylene direct hydration, the butylene direct hydration reaction process.Yet the life-time service tensio-active agent can bring pollution problem to environment.
Impurity in reaction process recirculated water, particularly organic impurity be the major cause that produces pressure reduction in the reactor of olefin hydration production low-carbon alcohol, and these impurity gather with the continuous circulation of reaction water.The continuous increase of impurity not only can make reactor pressure reduction up and down increase gradually, also can compete the activity of such catalysts center and side reaction takes place with reactant.
Summary of the invention
The objective of the invention is to adopt a kind of more economical, more effective and nonpolluting method, the reactor bed pressure reduction that makes low-carbon alkene directly carry out the hydration reaction process is stabilized in a lower level, has guaranteed that olefin hydration stable production process ground carries out.Simultaneously since enforcement of the present invention can reduce side reaction generation, reduce the problem that bed layer pressure that focus that the beds of reaction process exists and reaction process exist increases.Owing to the focus that exists in generation that has suppressed side reaction effectively and the beds.Therefore also prolonged the work-ing life of catalyzer.
To achieve these goals, the present invention proposes to adopt in reaction process the method for the deionized water of removing trace dissolved oxygen to solve the above-mentioned method of putting forward.The method of removing micro amount of oxygen in the deionized water can realize by deaeration in condenser or the method by catalytic deoxidation.
Specifically, a kind of continuous production of the present invention contains the method for the lower alcohol of 2 to 5 carbon atoms, be at 100~200 ℃ of temperature of reaction, reaction pressure 4.0~20.0MPa, under the effect of solid acid catalyst, the low-carbon alkene catalytic hydration that will contain 2 to 5 carbon atoms becomes low-carbon alcohol, and the raw water that it is characterized in that being used for hydration reaction is the anaerobic deionized water of the concentration of ordinary dissolution<50 μ g/l of oxygen.
In above-mentioned method, can use cation resin catalyzing agent, molecular sieve catalyst or phosphoric acid infusorial earth catalyst, reactor can be used fixed-bed reactor, at least a component is passed fixed bed catalyst for one section from reactor in reaction process, reaction back mixture shifts out from the reactor the other end, the alcohol that obtains generating by separation.
Embodiment
Simultaneous test 1
This simultaneous test is to carry out on 160 * 3000mm single tube trickle bed adiabatic reactor in a Φ, and the reactor external thermal insulation adopts adiabatic control.40 liters of cation exchange resin catalyst (commercial catalysts of filling in the reactor, the chemical plant produces in the Ji, Cangzhou, the trade mark is D008) catalyzer divides equally three sections fillings, be respectively equipped with cold water pipe to solve the problem of taking out reaction heat in two, three sections beds are annotated, the pressure reduction of whole reactor is measured by differential manometer.The charging density of propylene is greater than 95.0m%, and reaction water is that specific conductivity is the deionized water of ∠ 5 μ s/cm.Reacted product obtains reacting thick product after by decompression separation, analyzes the yield that product is formed and obtained to the gas, liquid product.Reaction conditions: pressure 8.0MPa, 135 ℃ of temperature of reaction.
Raw material input and output material such as following table:
3 hours material balances
Component Charging (g) Discharging (g)
Propylene propane butylene butane water isopropyl alcohol diisopropyl ether 2, the loss of 3-dimethyl dibutene 3-methyl cinene adds up to 11287 528 82000 93815 2533 528 79202 10287 805 41 72 347 93815
Pressure reduction is as follows in operating process:
Operating time, hour Pressure reduction, Mpa The Virahol yield, Grams Per Hour
24 0.08 3429
48 0.10 3311
72 0.13 3056
96 0.16 2910
Simultaneous test 2
A Φ is used in this test In28 * 3000mm bubbling sheet pipe reactor.Filling 1 liter of cation exchange resin catalyst (commercial catalyst, H in the reactor +The chemical plant produces in the Ji, type Cangzhou, and the trade mark is D008), the pressure reduction of whole reactor is measured by differential manometer, and the reaction process synoptic diagram is shown in figure two.Mix the n-butene raw material and enter reactor along the feed olefin pipeline, this mixture contains 85% n-butene, and water enters reactor along the feed water pipeline, and reacted product obtains thick product after by decompression separation, analyzes to obtain product and form.Reaction conditions is 160 ℃ of reaction pressure 6.0MPa, temperature of reaction.300.3g/hr the n-butene mixture and the deionized water of 300.3g/hr enter reactor from reactor bottom, reaction product obtains reacting thick product after by decompression separation, analyzes the yield that product is formed and obtained to the gas, liquid product.
Pressure reduction is as follows in operating process:
Operating time, hour Pressure reduction, MPa The sec-butyl alcohol yield, Grams Per Hour
24 0.12 231
48 0.15 220
72 0.17 216
96 0.19 203
Embodiment 1
Present embodiment adopts reaction unit and the catalyzer identical with simultaneous test 1.The concentration of charging propylene is greater than 95%, and reaction process water is that oxygen level is that ∠ 50 μ g/l, specific conductivity are ∠ 5 μ s/cm anaerobic deionized waters.Reacted product is analyzed the yield that product is formed and obtained to the gas, liquid product by arriving the thick product of reaction after the decompression separation.Reaction conditions is reaction pressure 8.0MPa, 135 ℃ of temperature of reaction.
Raw material input and output material such as following table:
3 hours material balances
Component Charging (g) Discharging (g)
Propylene propane water isopropyl alcohol diisopropyl ether 2, the loss of 3-dimethyl dibutene 3-methyl cinene adds up to 11287 528 82000 93815 2489 528 79241 10465 798 30 46 218 93815
Pressure reduction is as follows in operating process:
Operating time (hour) Pressure reduction, MPa The Virahol yield, Grams Per Hour
24 0.08 3488
48 0.10 3426
72 0.13 3433
96 0.16 3479
Embodiment 2
Present embodiment uses reaction unit and the catalyzer identical with simultaneous test 2.Filling 1 liter of cation exchange resin catalyst (commercial catalyst, H in the reactor +Type), the pressure reduction of whole reactor is measured by differential manometer.The mixture of n-butene enters reactor along the feed olefin pipeline, and this mixture contains 85% n-butene, and reaction water enters reactor along the feed water pipeline.Reacted product obtains reacting thick product by after the decompression separation, analyzes to obtain the product composition.Reaction conditions: reaction pressure 6.0MPa, 160 ℃ of temperature of reaction, the charging of n-butene mixture is 300.3g/hr, the charging of reaction process water is 300.3g/hr, reaction process water be dissolved oxygen amount be ∠ 50 μ g/l,, specific conductivity is ∠ 5 μ s/cm anaerobic deionized waters.
Pressure reduction is as follows in operating process:
Operating time, hour Pressure reduction, MPa The sec-butyl alcohol yield, Grams Per Hour
24 0.10 231
48 0.11 233
72 0.12 230
96 0.11 229
Result by the foregoing description and contrast experiment can see, when the deionized water that adopts dissolved oxygen amount ∠ 50 μ g/l reacts when making the low-carbon alkene catalytic hydration become lower alcohol, reactor bed pressure reduction is stabilized in a lower level, has guaranteed that olefin hydration stable production process ground carries out.

Claims (4)

1, a kind of continuous production contains the method for the lower alcohol of 2 to 5 carbon atoms, be at 100~200 ℃ of temperature of reaction, reaction pressure 4.0~20.0MPa, under the effect of solid acid catalyst, the low-carbon alkene catalytic hydration that will contain 2 to 5 carbon atoms becomes low-carbon alcohol, and the raw water that it is characterized in that being used for hydration reaction is the anaerobic deionized water of the concentration of ordinary dissolution<50 μ g/l of oxygen.
2,, it is characterized in that solid acid catalyst is cation resin catalyzing agent, molecular sieve catalyst or phosphoric acid infusorial earth catalyst according to the described method of claim 1.
3,, it is characterized in that reactor is fixed-bed reactor according to the described method of claim 1.
4, according to claim 1,2 or 3 described methods, it is characterized in that at least a component passes fixed bed catalyst for one section from reactor, reaction back mixture shifts out from the reactor the other end, the alcohol that obtains generating by separation.
CN 200410001113 2004-01-19 2004-01-19 Method for continuously producing lower alcohol Expired - Lifetime CN1247503C (en)

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CN1247503C true CN1247503C (en) 2006-03-29

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Assignee: ZHEJIANG XINHUA CHEMICAL Co.,Ltd.

Assignor: Dalian Institute of Chemical Physics, Chinese Academy of Sciences

Contract record no.: 2011330001362

Denomination of invention: Method for continuously producing lower alcohol

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