CN105130928B - The method for removing hydrogen peroxide legal system propylene oxide process gaseous mixture micro amount of oxygen - Google Patents
The method for removing hydrogen peroxide legal system propylene oxide process gaseous mixture micro amount of oxygen Download PDFInfo
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- CN105130928B CN105130928B CN201510496036.8A CN201510496036A CN105130928B CN 105130928 B CN105130928 B CN 105130928B CN 201510496036 A CN201510496036 A CN 201510496036A CN 105130928 B CN105130928 B CN 105130928B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
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Abstract
The present invention relates to a kind of method for removing hydrogen peroxide legal system propylene oxide process gaseous mixture micro amount of oxygen, the problem of propylene surge tank in the prior art is easily fired, nitrogen consumption is big is mainly solved.The present invention is by using a kind of method for removing hydrogen peroxide legal system propylene oxide process gaseous mixture micro amount of oxygen, deoxidation reactor is set between circulation propylene compressor and propylene surge tank, technique gaseous mixture and hydrogen enter deoxidation reactor after being mixed through gas mixer, contacted with catalyst, the catalyst can make that oxygen and hydrogen react and propylene and hydrogen do not react, the technical scheme that deoxidation reactor outlet material enters propylene surge tank preferably solves above mentioned problem, in the deoxidation available for hydrogen peroxide legal system propylene oxide process gaseous mixture.
Description
Technical field
The present invention relates to a kind of method for removing hydrogen peroxide legal system propylene oxide process gaseous mixture micro amount of oxygen.
Background technology
Expoxy propane is very important organic compound raw material, is the third-largest propylene for being only second to polypropylene and acrylonitrile
Analog derivative.Expoxy propane has two big main applications, and one is to be used to produce propylene dihydric alcohol, and one is for producing polyalcohol.It is many
First alcohol is the primary raw material for producing polyurethane, and polyurethane material purposes widely, can replace rubber, nylon etc. to be used for a variety of
Occasion, such as insulation material, coating, adhesive, foam, elastomer.And propylene dihydric alcohol is production cosmetics, NMF, prevented
Freeze liquid, lubricate the main material of solution additive.
Hydrogen peroxide legal system expoxy propane (hydrogene peroxide propylene oxide) technique is a kind of new
Synthesis of Propylene Oxide, the technique is using hydrogen peroxide and propylene as raw material, and reaction generation expoxy propane and water are compared
Conventional epoxy oxide production process, hydrogen peroxide legal system propylene oxide process has clean environment firendly, infrastructure few, no coupling product
Advantage, but the technique there is also it is corresponding the problem of.Decomposition can occur for hydrogen peroxide in technical process so that in circulation propylene
It is also easy to produce in the concentration increase of oxygen, propylene surge tank and fires operating mode, and then causes danger classes to raise.
CN201310076350.1 provides a kind of method of deoxidation of coalbed methane containing oxygen, it is characterized in that：By coalbed methane containing oxygen
It is passed through with artificial coal gas in the reactor equipped with catalyst, the carbon monoxide and hydrogen in artificial coal gas is made in the presence of catalyst
Gas carries out reaction generation carbon dioxide and water with the oxygen in coal bed gas and reaches the purpose for removing oxygen.
The industrial method for diluting to solve this problem using nitrogen or discharging torch, the method nitrogen of nitrogen dilution
Consumption is big, and the method propylene of discharge torch is largely wasted, and both of which have impact on economic benefit.Therefore develop suitable de-
Oxygen technique to the circulation propylene carry out deoxidation treatment, to reduction plant energy consumption, increase economic efficiency it is significant.
The content of the invention
The technical problems to be solved by the invention be in the prior art propylene surge tank easily fire, nitrogen consumption asking greatly
Inscribe a kind of method there is provided removing hydrogen peroxide legal system propylene oxide process gaseous mixture micro amount of oxygen newly.This method is used for hydrogen peroxide
In the deoxidation of legal system propylene oxide process gaseous mixture, have the advantages that propylene surge tank is not easy to blast, nitrogen consumption is small.
To solve the above problems, the technical solution adopted by the present invention is as follows：One kind removing hydrogen peroxide legal system expoxy propane work
The method of skill gaseous mixture micro amount of oxygen, produces the circulation propylene compressor of expoxy propane commercial plant in peroxide passivation and propylene is buffered
Deoxidation reactor, the technique gaseous mixture and hydrogen of the commercial plant is set to enter deoxidation after being mixed through gas mixer between tank
Reactor, is contacted with catalyst, and deoxidation reactor outlet material enters propylene surge tank；Technique before gas mixer is entered
Oxygen content analyzer is set on gaseous mixture pipeline, and two from three interlocked control, control are formed with the inlet valve on hydrogen pipeline
The aperture of hydrogen inlet valve；Set oxygen content analyzer at the top of deoxidation reactor, and with the torch of setting fire at the top of deoxidation reactor
Control valve formation two from three interlocked control on pipeline, starts at the top of interlocking, deoxidation reactor when oxygen volume content is more than 5%
Gaseous mixture is emitted into torch；On propylene surge tank set oxygen content analyzer, and with the torch pipe of setting fire on propylene surge tank
Control valve formation two from three interlocked control on line, starts interlocking, the mixing of propylene surge tank when oxygen volume content is more than 5%
Gas is emitted into torch；Wherein, the catalyst is Pd/ aluminum oxide, is prepared using the method comprised the following steps：
(1) by NaCl and PdCl2Chlorine palladium acid sodium solution is made between using mol ratio as 1.5~4；
(2) alumina support is added in the sour sodium maceration extract of chlorine palladium, maceration extract is put into ultrasonic oscillation instrument and carried out
Ultrasonic oscillation impregnates；
(3) ultrasonic oscillation impregnates 2~8h, and then sample is aged to >=8h at room temperature；
(4) sample is put into drying box, be dried under >=80 DEG C of temperature conditionss；
(5) by dried sample in high temperature resistance furnace in roasting >=2h at 300~600 DEG C；
(6) prepare sodium formate solution palladium catalyst is reduced, reduction temperature be 70~100 DEG C, the recovery time be >=
2h, the consumption of sodium formate is 3~6 times of Palladium Content in Catalyst；
(7) palladium catalyst after reduction is sufficiently washed after the completion of reducing；
(8) catalyst after washing is dried under the conditions of >=80 DEG C, the Pd/ aluminium oxide catalysts being molded.
In above-mentioned technical proposal, it is preferable that the oxygen content of deoxidation reactor import and outlet is measured, calculating is urged
The DNA vaccine of agent, the DNA vaccine of the catalyst is more than 90%.
In above-mentioned technical proposal, it is preferable that the reaction condition of the deoxidation reactor is：50~100 DEG C；0~0.5MPa.
In above-mentioned technical proposal, it is preferable that the mass ratio of palladium and alumina support is 1 ‰~5 ‰ in the catalyst.
In above-mentioned technical proposal, it is preferable that the oxygen volume content at the top of deoxidation reactor is more than 1% alarm, report
Operating personnel, which need to check hydrogen inlet, reaction temperature and stop 1, after police stays time, and the activity of sampling and testing catalyst.
The present invention can remove the oxygen in gaseous mixture after peroxide passivation production expoxy propane reaction, using effective catalyst
Reduce the oxygen concentration in gaseous mixture so that the inside oxygen content of propylene surge tank is not exceeded in technique, does not form the system of firing,
The safety of effective guarantee device reaction system；Propylene row torch is a large amount of when reducing the consumption and too high oxygen of nitrogen simultaneously
Waste, improve economic benefit, achieve preferable technique effect.
Below by embodiment, the invention will be further elaborated, but is not limited only to the present embodiment.
Embodiment
【Embodiment 1】
A kind of method for removing hydrogen peroxide legal system propylene oxide process gaseous mixture micro amount of oxygen, epoxy third is produced in peroxide passivation
Deoxidation reactor is set between the circulation propylene compressor and propylene surge tank of alkane commercial plant, and the technique of the commercial plant is mixed
Close after gas and hydrogen are mixed through gas mixer and enter deoxidation reactor, contacted with catalyst, the catalyst can make oxygen and
Hydrogen reacts and propylene and hydrogen do not react, and deoxidation reactor outlet material enters propylene surge tank；Wherein, entering
Enter setting oxygen content analyzer on the technique gaseous mixture pipeline before gas mixer, and formed with the inlet valve on hydrogen pipeline
Two from three interlocked control, controls the aperture of hydrogen inlet valve, that is, controls the mol ratio of hydrogen and oxygen；At the top of deoxidation reactor
If oxygen content analyzer, and two from three interlocked control is formed with the control valve put on flare line at the top of deoxidation reactor,
Oxygen volume content at the top of deoxidation reactor more than 1% alarm, after alarm operating personnel need to check hydrogen inlet, it is anti-
Answer temperature and residence time, and the activity of sampling and testing catalyst.Start interlocking when oxygen volume content is more than 5%, deoxidation is anti-
Gaseous mixture at the top of device is answered to be emitted into torch；On propylene surge tank set oxygen content analyzer, and with propylene surge tank
The control valve formation two from three interlocked control on flare line is put, starts interlocking, propylene buffering when oxygen volume content is more than 5%
The gaseous mixture of tank is emitted into torch.
The catalyst is Pd/ aluminum oxide, is prepared using the method comprised the following steps：
(1) by NaCl and PdCl2Using mol ratio as 2:1 is made into chlorine palladium acid sodium solution；
(2) alumina support is added in the sour sodium maceration extract of chlorine palladium, maceration extract is put into ultrasonic oscillation instrument and carried out
Ultrasonic oscillation impregnates；
(3) ultrasonic oscillation dipping 2h, is then aged 10h at room temperature by sample；
(4) sample is put into drying box, be dried under 80 DEG C of temperature conditionss；
(5) by dried sample in high temperature resistance furnace in being calcined 3h at 300 DEG C；
(6) prepare sodium formate solution to reduce palladium catalyst, reduction temperature is 70 DEG C, and the recovery time is 3h, formic acid
The consumption of sodium is 3 times of Palladium Content in Catalyst；
(7) palladium catalyst after reduction is sufficiently washed after the completion of reducing；
(8) catalyst after washing is dried under the conditions of 80 DEG C, the Pd/ aluminium oxide catalysts being molded.
As a result show, the DNA vaccine of catalyst reaches 95%.
【Embodiment 2】
In accordance with the method for claim 1, the catalyst is Pd/ aluminum oxide, using the method comprised the following steps
Prepare：
(1) by NaCl and PdCl2Using mol ratio as 2:1 is made into chlorine palladium acid sodium solution；
(2) alumina support is added in the sour sodium maceration extract of chlorine palladium, maceration extract is put into ultrasonic oscillation instrument and carried out
Ultrasonic oscillation impregnates；
(3) ultrasonic oscillation dipping 8h, is then aged 9h at room temperature by sample；
(4) sample is put into drying box, be dried under 100 DEG C of temperature conditionss；
(5) by dried sample in high temperature resistance furnace in being calcined 2h at 600 DEG C；
(6) prepare sodium formate solution to reduce palladium catalyst, reduction temperature is 100 DEG C, and the recovery time is 2h, formic acid
The consumption of sodium is 6 times of Palladium Content in Catalyst；
(7) palladium catalyst after reduction is sufficiently washed after the completion of reducing；
(8) catalyst after washing is dried under the conditions of 100 DEG C, the Pd/ aluminium oxide catalysts being molded.
As a result show, the DNA vaccine of catalyst reaches 93%.
【Embodiment 3】
In accordance with the method for claim 1, the catalyst is Pd/ aluminum oxide, using the method comprised the following steps
Prepare：
(1) by NaCl and PdCl2Using mol ratio as 3:1 is made into chlorine palladium acid sodium solution；
(2) alumina support is added in the sour sodium maceration extract of chlorine palladium, maceration extract is put into ultrasonic oscillation instrument and carried out
Ultrasonic oscillation impregnates；
(3) ultrasonic oscillation dipping 5h, is then aged 12h at room temperature by sample；
(4) sample is put into drying box, be dried under 100 DEG C of temperature conditionss；
(5) by dried sample in high temperature resistance furnace in being calcined 5h at 500 DEG C；
(6) prepare sodium formate solution to reduce palladium catalyst, reduction temperature is 90 DEG C, and the recovery time is 5h, formic acid
The consumption of sodium is 4 times of Palladium Content in Catalyst；
(7) palladium catalyst after reduction is sufficiently washed after the completion of reducing；
(8) catalyst after washing is dried under the conditions of 100 DEG C, the Pd/ aluminium oxide catalysts being molded.
As a result show, the DNA vaccine of catalyst reaches 96%.
Obviously, method of the invention can remove the oxygen in peroxide passivation production expoxy propane tail gas, using efficiently urging
Oxygen concentration in agent reduction gaseous mixture so that the inside oxygen content of propylene surge tank is not exceeded in technique, is not formed and fired
System, the safety of effective guarantee device reaction system；Propylene row torch when reducing the consumption and too high oxygen of nitrogen simultaneously
A large amount of wastes, improve economic benefit.
Claims (2)
1. a kind of method for removing hydrogen peroxide legal system propylene oxide process gaseous mixture micro amount of oxygen, expoxy propane is produced in peroxide passivation
Deoxidation reactor, the technique mixing of the commercial plant are set between the circulation propylene compressor and propylene surge tank of commercial plant
Gas and hydrogen enter deoxidation reactor after being mixed through gas mixer, are contacted with catalyst, and deoxidation reactor outlet material enters
Propylene surge tank；Oxygen content analyzer, and and hydrogen pipe are set on the technique gaseous mixture pipeline before entering gas mixer
Inlet valve formation two from three interlocked control on road, controls the aperture of hydrogen inlet valve；Oxygen is set at the top of deoxidation reactor to contain
Analyzer is measured, and two from three interlocked control is formed with the control valve put on flare line at the top of deoxidation reactor, when oxysome product
Start gaseous mixture at the top of interlocking, deoxidation reactor when content is more than 5% and be emitted into torch；Oxygen is set to contain on propylene surge tank
Analyzer is measured, and two from three interlocked control is formed with the control valve put on flare line on propylene surge tank, when oxysome product contains
Start interlocking when amount is more than 5% (volume ratio), the gaseous mixture of propylene surge tank is emitted into torch；Wherein, the catalyst is Pd/
Aluminum oxide, is prepared using the method comprised the following steps：
(1) by NaCl and PdCl2Chlorine palladium acid sodium solution is made between using mol ratio as 1.5~4；
(2) alumina support is added in the sour sodium maceration extract of chlorine palladium, maceration extract is put into ultrasonic oscillation instrument and carries out ultrasound
Ripple concussion dipping；
(3) ultrasonic oscillation impregnates 2~8h, and then sample is aged to >=8h at room temperature；
(4) sample is put into drying box, be dried under >=80 DEG C of temperature conditionss；
(5) by dried sample in high temperature resistance furnace in roasting >=2h at 300~600 DEG C；
(6) prepare sodium formate solution to reduce palladium catalyst, reduction temperature is 70~100 DEG C, the recovery time is >=2h, first
The consumption of sour sodium is 3~6 times of Palladium Content in Catalyst；
(7) palladium catalyst after reduction is sufficiently washed after the completion of reducing；
(8) catalyst after washing is dried under the conditions of >=80 DEG C, the Pd/ aluminium oxide catalysts being molded；
The reaction condition of the deoxidation reactor is：50~100 DEG C；0~0.5MPa；Palladium and alumina support in the catalyst
Mass ratio be 1 ‰~5 ‰；The oxygen content of deoxidation reactor import and outlet is measured, the deoxidation of catalyst is calculated
Rate, the DNA vaccine of the catalyst is more than 90%.
2. a kind of method for removing hydrogen peroxide legal system propylene oxide process gaseous mixture micro amount of oxygen according to claim 1, it is special
The oxygen volume content being at the top of deoxidation reactor is levied more than 1% alarm, operating personnel need to check that hydrogen enters after alarm
Enter amount, reaction temperature and residence time, and the activity of sampling and testing catalyst.
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| CN109748888B (en) * | 2017-11-08 | 2020-12-25 | 中国石油化工股份有限公司 | Method for removing oxygen in HPPO process recycle gas |
| WO2019175700A1 (en) * | 2018-03-13 | 2019-09-19 | Sabic Global Technologies B.V. | Photochemical deoxygenation systems and methods for the storage of liquid that generates peroxide |
| CN110389602B (en) * | 2018-04-19 | 2022-09-23 | 中国石油化工股份有限公司 | Method for controlling content of specific gas in target container |
| CN115888354B (en) * | 2021-08-19 | 2024-10-22 | 中国石油化工股份有限公司 | Device and method for removing oxygen in tail gas of epichlorohydrin process |
| CN113856407A (en) * | 2021-10-28 | 2021-12-31 | 山东新龙集团有限公司 | Method for treating tail gas in process of preparing epoxy chloropropane by oxidation method |
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| US4943650A (en) * | 1989-01-30 | 1990-07-24 | The Boc Group, Inc. | Process for the production of nitriles |
| CN101223152A (en) * | 2005-06-29 | 2008-07-16 | 巴斯福股份公司 | Process for producing propylene oxide |
| CN102103368A (en) * | 2010-10-27 | 2011-06-22 | 中国石油化工股份有限公司 | Method for monitoring and controlling reactor oxygen concentration in epichlorohydrin production process |
| CN102459213A (en) * | 2009-05-12 | 2012-05-16 | 巴斯夫欧洲公司 | Process for preparing propylene oxide |
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2015
- 2015-08-13 CN CN201510496036.8A patent/CN105130928B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4943650A (en) * | 1989-01-30 | 1990-07-24 | The Boc Group, Inc. | Process for the production of nitriles |
| CN101223152A (en) * | 2005-06-29 | 2008-07-16 | 巴斯福股份公司 | Process for producing propylene oxide |
| CN102459213A (en) * | 2009-05-12 | 2012-05-16 | 巴斯夫欧洲公司 | Process for preparing propylene oxide |
| CN102103368A (en) * | 2010-10-27 | 2011-06-22 | 中国石油化工股份有限公司 | Method for monitoring and controlling reactor oxygen concentration in epichlorohydrin production process |
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