CN103965006A - Purification method for butylene oxydehydrogenation products - Google Patents
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Abstract
The invention relates to a purification method for butylene oxydehydrogenation products, and mainly solves the problem of removal of oxygen-containing compounds such as organic acids, ketone and aldehyde in the butylene oxydehydrogenation products in the prior art. The method comprises the following steps: a) cooling the butylene oxydehydrogenation products in a reaction product cooling system, and sending the butylene oxydehydrogenation products into an acid washing tower toconduct countercurrent contact with the washing water from the tower top, and sending the acid washing tower top gas with organic acid removed into a generation gas compressor; b) pressurizing the acid washing tower top gas by a compressor, sending the gas into an aldehyde washing tower bottom, conducting countercurrent contact with the washing water from the tower top, and removing aldehyde impurities in the generated gas; and c) sending the tower bottom aldehyde-containing wastewater and wastewater from the acid washing tower into a neutralization tank, adding dilute alkali lye to neutralize organic acid, and sending the wastewater into wastewater treatment after reaching the standard. The scheme well solves the above problem and can be applied to butylene oxydehydrogenation industrial production.
Description
Technical field
The present invention relates to a kind of purifying method of butylene oxidation-dehydrogenation product.
Background technology
Divinyl is the important monomer of synthetic rubber, synthetic resins, is mainly used in synthetic cis-1,4-polybutadiene rubber, styrene-butadiene rubber(SBR), paracril and ABS resin etc.Divinyl is also multiple coating and Organic Chemicals.
At present the mode of production of divinyl mainly contains that C-4-fraction separates and two kinds of synthesis methods (comprising butane dehydrogenation, butylene dehydrogenation, butylene oxidation-dehydrogenation etc.).At present except the U.S., the by-product C-4-fraction (again can be written as C-4-fraction) of countries in the world divinyl during almost all directly from hydrocarbon cracking ethene processed.The source of U.S.'s divinyl, only about half of from butane, butylene dehydrogenation, half is directly from cracking c_4 cut.
While producing ethene taking petroleum naphtha or diesel oil as cracking stock, the C-4-fraction of by-product is generally 8%～10%(quality of material quantity), wherein butadiene content is up to 40%～50%(quality), so separation of butadiene is economic production method from cracking c_4 cut.The industrial method that all adopts extracting rectifying,, by adding acetonitrile, methylformamide equal solvent to increase the relative volatility of divinyl and other carbon four hydrocarbon in cut, obtains divinyl by rectifying separation (seeing that C-4-fraction separates).
Along with the development of China's Rubber Industry, the output of divinyl can not meet the demand of domestic rubber production in recent years.Along with the development of China's chemical industry, national economy will become increasingly conspicuous to the demand contradictory of divinyl, the amount that the amount that petroleum naphtha produces carbon four and divinyl during as cracking stock generates when using carbon two, carbon three and carbon fourth class light constituent as cracking stock, the cracking technology that therefore light constituent is made raw material does not have butadiene extraction unit supporting conventionally.Meanwhile, the technology of this olefin hydrocarbon making by coal of methanol-to-olefins (MTO) does not have divinyl by-product.Therefore develop Oxidative Dehydrogenation of Butene into Butadiene method and there is important practical significance.
Oxidative Dehydrogenation of Butene into Butadiene is under water vapor exists, and utilizes the hydrogen of oxygen in butylene molecule to be combined, and obtains divinyl and constitutionally stable water.This reaction is irreversible reaction substantially.Main reaction equation is as follows:
Other side reaction mainly contains:
As patent CN100494130C, its flow process is the reactor that raw material normal butane enters non-oxidizable catalytic dehydrogenation, obtains the mixture flow that contains normal butane, butylene, divinyl, hydrogen, lower boiling secondary component and steam.This mixture flow and oxygen-containing gas are mixed into oxydehydrogenation region, obtain the product gas flow that contains divinyl, normal butane, butylene, hydrogen, lower boiling secondary component and steam, next from this product gas flow, isolate divinyl.
Similarly also has patent CN100447117C, different from patent CN100494130C is, after removing hydrogen, lower boiling secondary species and steam, the product gas in autoxidation dehydrogenation region is divided into two portions by extracting rectifying, the logistics that a part mainly comprises normal butane and butylene loops back non-oxide dehydrogenation region, and another part mainly comprises butadiene stream.
Patent CN101367702 discloses a kind of method of preparing butadiene with butylene oxo-dehydrogenation of axially-located bed, its flow process is for adopting two sections of axial restraint bed bioreactors, butene feedstock, water vapor and air segmenting enter, reactor outlet is by heating steam and cooling, enters next section of reactor after reaching next section of reactor inlet temperature.
Patent CN102675027A discloses a kind of preparing butadiene with butylene oxo-dehydrogenation technique, adopts thermal insulation radial fixed-bed by preparing butadiene with butylene oxo-dehydrogenation, and radial adiabatic fixed bed forms by three sections.
Above-mentioned patented technology all utilizes butylene and oxygen to react under catalyst action, generate divinyl, in reaction process due to the existence of oxygen, inevitably can generate acetic acid, the aldehydes such as acetaldehyde, formic acid, the organic acids such as acetic acid, the oxygenatedchemicalss such as ketone and furans such as acetone, general, the yield of divinyl is 60% ~ 80%, reflect in implication oxygenates level below 1%, though oxygenates level is little, but for the compression that generates gas, oil absorption extraction and Butadiene Extraction are all harmful to very much, also can produce corrosion to equipment containing oxygen organic acid, the easy autohemagglutination occluding device of unsaturated aldehyde, therefore, in butylene oxidation-dehydrogenation technique, the effective elimination of oxygenatedchemicals has great significance for the enforcement of technique.
Summary of the invention
Technical problem to be solved by this invention is the problem that removes of the oxygenatedchemicalss such as the organic acid that carries in butylene oxidation-dehydrogenation product, ketone, aldehyde, the invention provides a kind of purifying method of butylene oxidation-dehydrogenation product, the method has that the oxygenatedchemicals decreasing ratiies such as the organic acid that carries in butylene oxidation-dehydrogenation product, ketone, aldehyde are high, waste water is few, tractable advantage.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of purifying method of butylene oxidation-dehydrogenation product, comprises following step:
A) butylene oxidation-dehydrogenation product is first passed through to reaction product cooling system cooling, enter again and wash the washing water counter current contact that acid tower and tower top get off and wash away organic acid, remove organic acid and wash sour overhead gas and enter generation air compressor, wash acid tower tower reactor waste water and send into neutralization tank;
B) wash sour overhead gas after generating air compressor pressurization, enter and wash aldehyde tower tower reactor, with the washing water counter current contact that tower top comes, remove the aldehyde type impurities generating in gas, enter follow-up workshop section;
C) wash aldehyde tower tower reactor aldehyde-containing sewage and send into neutralization tank, in neutralization tank, add sig water to neutralize organic acid wherein, rear waste water up to standard is sent into sewage disposal.
In technique scheme, the butylene oxidation-dehydrogenation product described in step a) refers to taking butylene as raw material, under catalyzer existence condition, and the reacted resultant of oxygen-containing gas, in resultant except containing butylene, divinyl, oxygen, N
2, CO, CO
2, beyond water, also contain the oxygenatedchemicals of aldehydes, organic acid, ketone and heterocyclic.Preferred technical scheme is that oxygenatedchemicals comprises formaldehyde, acetaldehyde, formic acid, acetic acid, acetone or furans.
Preferred technical scheme is that in butylene oxidation-dehydrogenation product, organic acid weight content is 1 ~ 5000ppm, and aldehydes content is 1 ~ 5000ppm.To be butylene oxidation-dehydrogenation reaction product be cooled to 50 ~ 200 DEG C through cooling system to preferred technical scheme enters and wash acid tower; Preferred technical scheme is 5 ~ 50 DEG C for washing acid tower tower top temperature, and tower reactor temperature is 5 ~ 80 DEG C, and working pressure is 0 ~ 1.0MpG, and washing acid tower is tray column, packing tower or sieve-tray tower.Preferred technical scheme be step a) and b) in washing water used be at least one of de-salted water, recirculated water, tower reactor washing rear section reuse water.Preferred technical scheme is: step b) is washed acid tower overhead gas and is forced into 0.5 ~ 2.0MPaG through compressor, and compressor is screw, the pattern such as reciprocating, centrifugal; In step b), follow-up workshop section is reactant gases condensation, washing, oil absorption and butadiene extraction rectifying.Preferred technical scheme is 5 ~ 40 DEG C for washing aldehyde column overhead temperature, and tower reactor temperature is 5 ~ 60 DEG C, and working pressure is 0.5 ~ 2.0MpaG, and washing aldehyde tower is tray column, packing tower or sieve-tray tower.At least one that the added alkali lye of neutralization tank in step b) contains sodium hydroxide, potassium hydroxide, sodium carbonate, the weight concentration of alkali lye is 1 ~ 50%; In step b), the injection rate of alkali lye is to make the pH value of waste water be more than or equal to 7.
The present invention enters oxidative dehydrogenation reactor after butylene and air, water vapor after overheated are mixed, and carries out oxidative dehydrogenation under Fe-series catalyst effect, generates the by products such as divinyl, C4 alkynes and furans, aldehyde, acid, CO2, CO.Resultant of reaction is through steam generator recovery waste heat, generating gas is cooled to 50～200 DEG C and enters and wash the washing water counter current contact that acid tower and tower top get off, under condition of normal pressure, wash away organic acid and the part aldehyde in reaction gas by low temperature or normal-temperature water, ketone, because organic acid Henry'S coefficient is very little, being very easy to water under normal pressure washes away, can save the consumption of washing water by water at low temperature, but the Henry'S coefficient of aldehyde and furans is very large, under normal pressure, can only be dissolved on a small quantity water, therefore the present invention adopts the method for pressurization, remove the oxygenatedchemicals such as aldehyde and furans after deacidification with the water of suitable temp, so-called suitable temp, refer to excess Temperature, the solubility with temperature of aldehyde in water raises and reduces, affect the removal effect of aldehyde, temperature is too low, can lose butylene, the raw materials such as divinyl and product.Adopt the inventive method, the oxygenatedchemicalss such as the organic acid that carries in can effective elimination butylene oxidation-dehydrogenation product, ketone, aldehyde, decreasing ratio is high, waste water is few, energy consumption is low and waste water is easily processed, and has obtained good technique effect.
Brief description of the drawings
Fig. 1 is the process flow diagram that butylene oxidation-dehydrogenation product of the present invention purifies.
In Fig. 1,1 is butylene oxidation-dehydrogenation product, and 2 is washing water, 3 for washing sour waste water, and 4 for washing the rear reaction gas of acid, and 5 is reaction gas after compression, 6 is washing water, and 7 for washing aldehyde waste water, and 8 is purification gas, 9 is composite waste, and 10 is alkali lye, and 11 is waste water after neutralization, I is for washing acid tower, and II is compressor, and III is for washing aldehyde tower, IV is neutralization tank, and V is Sewage treatment systems.
In Fig. 1, butylene oxidation-dehydrogenation product 1 enters washes acid tower I, washing water 2 counter current contact with tower top, slough organic acid and part aldehyde ketone in butylene oxidation-dehydrogenation product, after tower top is washed acid, reaction gas 4 enters compressor II and compresses, after compression, reaction gas 5 enters and washes aldehyde tower III, washing water 6 counter current contact with tower top, slough remaining aldehyde and ketone in butylene oxidation-dehydrogenation product, tower top is purified reaction gas 8 and enters follow-up refining system, wash aldehyde waste water 7 and wash the mixed logistics 9 of sour waste water and enter neutralization tank IV, with in alkali lye 10 and waste water ph to 7, after neutralization, waste water 11 send the processing of Sewage treatment systems V.
Below by specific embodiment, invention is further elaborated.
Embodiment
[embodiment 1]
Certain 100,000 tons/year of Oxidative Dehydrogenation of Butene into Butadiene device, adopt the Technology of Fig. 1, cooled butylene oxidation-dehydrogenation product flow is 79000 kgs/hour, 90 DEG C of temperature, pressure 0.1MPa, composition is in table 1, wherein oxygenatedchemicals total amount is 1200ppm, this butylene oxidation-dehydrogenation product enters washes acid tower tower reactor, it is the industrial circulating water of 30 DEG C that tower top passes into temperature, 10 tons/hour of recirculated water consumptions, washing acid tower is tray column, stage number 8, tower reactor is for washing sour waste water, 35 DEG C of overhead gas temperature enter compressor, compressor is reciprocation compressor, be compressed to after 1.0MPa and enter and wash aldehyde tower, washing aldehyde tower is that stage number is 10 tray column, it is the low temperature de-salted water of 5 DEG C that tower top passes into temperature, 4 tons/hour of de-salted water consumptions, overhead gas removes follow-up refining system, tower reactor is washed aldehyde waste water and is washed the sour waste water of washing of acid tower tower reactor and mix, after mixing, waste water ph is 4, enter neutralization tank, with in 10% sodium carbonate solution and waste water to pH value be 7, after neutralization, waste water send Sewage treatment systems processing.
In butylene oxidation-dehydrogenation product after purification, organic acid, aldehyde, ketone content are less than 1ppm, 44 tons/hour of wastewater flow rates, 150 kilograms of mark oil/ton divinyl of purification system energy consumption.
Table 1
| Component | Oxydehydrogenation product composition (wt%) |
| N2 | 32.28 |
| CO | 0.17 |
| O2 | 0.28 |
| CO2 | 4.13 |
| Butylene | 5.10 |
| Divinyl | 16.16 |
| Butane | 3.01 |
| Furans | 0.01 |
| Propenal | 0.001 |
| Acetaldehyde | 0.06 |
| Formic acid | 0.001 |
| Acetic acid | 0.02 |
| Acetone | 0.03 |
| Methyl vinyl ketone | 0.001 |
| Water | 38.75 |
[embodiment 2]
Certain 100,000 tons/year of Oxidative Dehydrogenation of Butene into Butadiene device, adopt the Technology of Fig. 1, cooled butylene oxidation-dehydrogenation product flow is 79000 kgs/hour, 90 DEG C of temperature, pressure 0.1MPa, composition is in table 1, wherein oxygenatedchemicals total amount is 1200ppm, this butylene oxidation-dehydrogenation product enters washes acid tower tower reactor, it is the low temperature de-salted water of 5 DEG C that tower top passes into temperature, 6 tons/hour of low temperature de-salted water consumptions, washing acid tower is tray column, stage number 8, tower reactor is for washing sour waste water, 7 DEG C of overhead gas temperature enter compressor, compressor is reciprocation compressor, be compressed to after 1.0MPa and enter and wash aldehyde tower, washing aldehyde tower is that stage number is 10 tray column, it is the low temperature de-salted water of 5 DEG C that tower top passes into temperature, 4 tons/hour of de-salted water consumptions, overhead gas removes follow-up refining system, tower reactor is washed aldehyde waste water and is washed the sour waste water of washing of acid tower tower reactor and mix, after mixing, waste water ph is 4, enter neutralization tank, with in 10% sodium carbonate solution and waste water to pH value be 7, after neutralization, waste water send Sewage treatment systems processing.
In butylene oxidation-dehydrogenation product after purification, organic acid, aldehyde, ketone content are less than 1ppm, 39 tons/hour of wastewater flow rates, 130 kilograms of mark oil/ton divinyl of purification system energy consumption.
[embodiment 3]
Certain 100,000 tons/year of Oxidative Dehydrogenation of Butene into Butadiene device, adopt the Technology of Fig. 1, cooled butylene oxidation-dehydrogenation product flow is 79000 kgs/hour, 90 DEG C of temperature, pressure 0.1MPa, composition is in table 1, wherein oxygenatedchemicals total amount is 1200ppm, this butylene oxidation-dehydrogenation product enters washes acid tower tower reactor, it is the low temperature de-salted water of 5 DEG C that tower top passes into temperature, 6 tons/hour of low temperature de-salted water consumptions, washing acid tower is tray column, stage number 8, tower reactor is for washing sour waste water, 7 DEG C of overhead gas temperature enter compressor, compressor is reciprocation compressor, be compressed to after 1.3MPa and enter and wash aldehyde tower, washing aldehyde tower is that stage number is 10 tray column, it is the low temperature de-salted water of 5 DEG C that tower top passes into temperature, 2 tons/hour of de-salted water consumptions, overhead gas removes follow-up refining system, tower reactor is washed aldehyde waste water and is washed the sour waste water of washing of acid tower tower reactor and mix, after mixing, waste water ph is 4, enter neutralization tank, with in 10% sodium carbonate solution and waste water to pH value be 7, after neutralization, waste water send Sewage treatment systems processing.
In butylene oxidation-dehydrogenation product after purification, organic acid, aldehyde, ketone content are less than 1ppm, 42 tons/hour of wastewater flow rates, purification system energy consumption 120 kg mark oil/ton divinyl.
[embodiment 4]
Certain 100,000 tons/year of Oxidative Dehydrogenation of Butene into Butadiene device, adopt the Technology of Fig. 1, cooled butylene oxidation-dehydrogenation product flow is 79000 kgs/hour, 90 DEG C of temperature, pressure 0.1MPa, composition is in table 1, wherein oxygenatedchemicals total amount is 1200ppm, this butylene oxidation-dehydrogenation product enters washes acid tower tower reactor, it is the low temperature de-salted water of 5 DEG C that tower top passes into temperature, 6 tons/hour of low temperature de-salted water consumptions, washing acid tower is packing tower, 3 meters of packed heights, tower reactor is for washing sour waste water, 7 DEG C of overhead gas temperature enter compressor, compressor is reciprocation compressor, be compressed to after 1.0MPa and enter and wash aldehyde tower, washing aldehyde tower is sieve-tray tower, stage number is 10, it is the low temperature de-salted water of 5 DEG C that tower top passes into temperature, 4 tons/hour of de-salted water consumptions, overhead gas removes follow-up refining system, tower reactor is washed aldehyde waste water and is washed the sour waste water of washing of acid tower tower reactor and mix, after mixing, waste water ph is 4, enter neutralization tank, with in 10% sodium carbonate solution and waste water to pH value be 7, after neutralization, waste water send Sewage treatment systems processing.
In butylene oxidation-dehydrogenation product after purification, organic acid, aldehyde, ketone content are less than 1ppm, 44 tons/hour of wastewater flow rates, 150 kilograms of mark oil/ton divinyl of purification system energy consumption.
[embodiment 5]
Certain 100,000 tons/year of Oxidative Dehydrogenation of Butene into Butadiene device, adopt the Technology of Fig. 1, cooled butylene oxidation-dehydrogenation product flow is 79000 kgs/hour, 90 DEG C of temperature, pressure 0.1MPa, composition is in table 1, wherein oxygenatedchemicals total amount is 1200ppm, this butylene oxidation-dehydrogenation product enters washes acid tower tower reactor, it is the low temperature de-salted water of 5 DEG C that tower top passes into temperature, 6 tons/hour of low temperature de-salted water consumptions, washing acid tower is tray column, stage number 8, tower reactor is for washing sour waste water, 7 DEG C of overhead gas temperature enter compressor, compressor is reciprocation compressor, be compressed to after 1.0MPa and enter and wash aldehyde tower, washing aldehyde tower is that stage number is 10 tray column, it is the low temperature de-salted water of 5 DEG C that tower top passes into temperature, 4 tons/hour of de-salted water consumptions, overhead gas removes follow-up refining system, tower reactor is washed aldehyde waste water and is washed the sour waste water of washing of acid tower tower reactor and mix, after mixing, waste water ph is 4, enter neutralization tank, with in 10% sodium hydroxide solution and waste water to pH value be 7, after neutralization, waste water send Sewage treatment systems processing.
In butylene oxidation-dehydrogenation product after purification, organic acid, aldehyde, ketone content are less than 1ppm, 44 tons/hour of wastewater flow rates, 150 kilograms of mark oil/ton divinyl of purification system energy consumption.
[embodiment 6]
Certain 100,000 tons/year of Oxidative Dehydrogenation of Butene into Butadiene device, adopt the Technology of Fig. 1, cooled butylene oxidation-dehydrogenation product flow is 79000 kgs/hour, 150 DEG C of temperature, pressure 0.15MPa, composition is in table 1, wherein oxygenatedchemicals total amount is 1200ppm, this butylene oxidation-dehydrogenation product enters washes acid tower tower reactor, it is the industrial circulating water of 30 DEG C that tower top passes into temperature, 15 tons/hour of recirculated water consumptions, washing acid tower is tray column, stage number 8, tower reactor is for washing sour waste water, overhead gas temperature 60 C enters compressor, compressor is reciprocation compressor, be compressed to after 1.0MPa and enter and wash aldehyde tower, washing aldehyde tower is that stage number is 10 tray column, it is the low temperature de-salted water of 5 DEG C that tower top passes into temperature, 4 tons/hour of de-salted water consumptions, overhead gas removes follow-up refining system, tower reactor is washed aldehyde waste water and is washed the sour waste water of washing of acid tower tower reactor and mix, after mixing, waste water ph is 4, enter neutralization tank, with in 10% sodium carbonate solution and waste water to pH value be 7, after neutralization, waste water send Sewage treatment systems processing.
In butylene oxidation-dehydrogenation product after purification, organic acid, aldehyde, ketone content are less than 1ppm, 49 tons/hour of wastewater flow rates, 190 kilograms of mark oil/ton divinyl of purification system energy consumption.
[embodiment 7]
Certain 100,000 tons/year of Oxidative Dehydrogenation of Butene into Butadiene device, adopt the Technology of Fig. 1, cooled butylene oxidation-dehydrogenation product flow is 82900 kgs/hour, 105 DEG C of temperature, pressure 0.11MPa, composition is in table 2, wherein oxygenatedchemicals total amount is 1700ppm, this butylene oxidation-dehydrogenation product enters washes acid tower tower reactor, it is the water at low temperature of 5 DEG C that tower top passes into temperature, 10 tons/hour of water at low temperature consumptions, washing acid tower is tray column, stage number 10, tower reactor is for washing sour waste water, 40 DEG C of overhead gas temperature enter compressor, compressor is reciprocation compressor, be compressed to after 1.5MPa and enter and wash aldehyde tower, washing aldehyde tower is that stage number is 8 tray column, it is the low temperature de-salted water of 5 DEG C that tower top passes into temperature, 3 tons/hour of de-salted water consumptions, overhead gas removes follow-up refining system, tower reactor is washed aldehyde waste water and is washed the sour waste water of washing of acid tower tower reactor and mix, after mixing, waste water ph is 3, enter neutralization tank, with in 10% sodium carbonate solution and waste water to pH value be 7, after neutralization, waste water send Sewage treatment systems processing.
In butylene oxidation-dehydrogenation product after purification, organic acid, aldehyde, ketone content are less than 1ppm, 46 tons/hour of wastewater flow rates, 160 kilograms of mark oil/ton divinyl of purification system energy consumption.
Table 2
| Component | Oxydehydrogenation product composition (wt%) |
| N2 | 30.82 |
| CO | 0.19 |
| O2 | 0.32 |
| CO2 | 4.52 |
| Butylene | 4.95 |
| Divinyl | 15.4 |
| Butane | 3.52 |
| Furans | 0.01 |
| Propenal | 0.002 |
| Acetaldehyde | 0.08 |
| Formic acid | 0.002 |
| Acetic acid | 0.03 |
| Acetone | 0.04 |
| Methyl vinyl ketone | 0.002 |
| Water | 40.11 |
Claims (10)
1. a purifying method for butylene oxidation-dehydrogenation product, comprises following step:
A) butylene oxidation-dehydrogenation product is first passed through to reaction product cooling system cooling, enter again and wash the washing water counter current contact that acid tower and tower top get off and wash away organic acid, remove organic acid and wash sour overhead gas and enter generation air compressor, wash acid tower tower reactor waste water and send into neutralization tank;
B) wash sour overhead gas after generating air compressor pressurization, enter and wash aldehyde tower tower reactor, the washing water counter current contact with tower top comes, removes after the aldehyde type impurities in gas, enters follow-up workshop section;
C) wash aldehyde tower tower reactor aldehyde-containing sewage and send into neutralization tank, in neutralization tank, add alkali lye to neutralize organic acid wherein, rear waste water up to standard is sent into sewage disposal.
2. the purifying method of butylene oxidation-dehydrogenation product according to claim 1, it is characterized in that the butylene oxidation-dehydrogenation product described in step a) refers to taking butylene as raw material, under catalyzer existence condition, with the reacted resultant of oxygen-containing gas, in described resultant, remove and contain butylene, divinyl, oxygen, N
2, CO, CO
2, beyond water, also contain the oxygenatedchemicals of aldehydes, organic acid, ketone and heterocyclic.
3. the purifying method of butylene oxidation-dehydrogenation product according to claim 2, is characterized in that oxygenatedchemicals comprises formaldehyde, acetaldehyde, formic acid, acetic acid, acetone or furans.
4. the purifying method of butylene oxidation-dehydrogenation product according to claim 1, is characterized in that in butylene oxidation-dehydrogenation product, organic acid weight content is 1 ~ 5000ppm, and aldehydes content is 1 ~ 5000ppm.
5. the purifying method of butylene oxidation-dehydrogenation product according to claim 1, is characterized in that butylene oxidation-dehydrogenation reaction product is cooled to 50 ~ 200 DEG C through cooling system and enters and wash acid tower.
6. the purifying method of butylene oxidation-dehydrogenation product according to claim 1, it is characterized in that washing acid tower tower top temperature is 5 ~ 50 DEG C, and tower reactor temperature is 5 ~ 80 DEG C, and working pressure is 0 ~ 1.0MpG, and washing acid tower is tray column, packing tower or sieve-tray tower.
7. the purifying method of butylene oxidation-dehydrogenation product according to claim 1, it is characterized in that step a) and b) in washing water used be at least one of de-salted water, recirculated water, tower reactor washing rear section reuse water.
8. the purifying method of butylene oxidation-dehydrogenation product according to claim 1, is characterized in that step b) washes acid tower overhead gas and be forced into 0.5 ~ 2.0MPa through compressor, and compressor is screw, the pattern such as reciprocating, centrifugal; In step b), follow-up workshop section is reactant gases condensation, washing, oil absorption and butadiene extraction rectifying.
9. the purifying method of butylene oxidation-dehydrogenation product according to claim 1, it is characterized in that washing aldehyde column overhead temperature is 5 ~ 40 DEG C, and tower reactor temperature is 5 ~ 60 DEG C, and working pressure is 0.5 ~ 2.0MpaG, and washing aldehyde tower is tray column, packing tower or sieve-tray tower.
10. the purifying method of butylene oxidation-dehydrogenation product according to claim 1, is characterized in that at least one that the added alkali lye of neutralization tank in step b) contains sodium hydroxide, potassium hydroxide, sodium carbonate, and the weight concentration of alkali lye is 1 ~ 50%; In step b), the injection rate of alkali lye is to make the pH value of waste water be more than or equal to 7.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107459441A (en) * | 2017-09-12 | 2017-12-12 | 惠生工程（中国）有限公司 | A kind of generation gas disposal technique of Oxidative Dehydrogenation of Butene into Butadiene |
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| CN102826950A (en) * | 2012-09-06 | 2012-12-19 | 湖南百利工程科技股份有限公司 | Process method for circularly utilizing waste water produced by butadiene preparation through butene oxidative dehydrogenation |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102826950A (en) * | 2012-09-06 | 2012-12-19 | 湖南百利工程科技股份有限公司 | Process method for circularly utilizing waste water produced by butadiene preparation through butene oxidative dehydrogenation |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107459441A (en) * | 2017-09-12 | 2017-12-12 | 惠生工程（中国）有限公司 | A kind of generation gas disposal technique of Oxidative Dehydrogenation of Butene into Butadiene |
| CN107459441B (en) * | 2017-09-12 | 2020-11-06 | 惠生工程（中国）有限公司 | Treatment process of generated gas for preparing butadiene through oxidative dehydrogenation of butylene |
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Application publication date: 20140806 |