CN103664694A - Method for lowering content of organic matters in absorption liquid in ammonium sulfate-free acrylonitrile technology - Google Patents
Method for lowering content of organic matters in absorption liquid in ammonium sulfate-free acrylonitrile technology Download PDFInfo
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- CN103664694A CN103664694A CN201210325053.1A CN201210325053A CN103664694A CN 103664694 A CN103664694 A CN 103664694A CN 201210325053 A CN201210325053 A CN 201210325053A CN 103664694 A CN103664694 A CN 103664694A
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Abstract
The invention relates to a method for lowering the content of organic matters in an absorption liquid in ammonia sulfate-free acrylonitrile technology, which mainly solves problems that the energy consumption is high and the removal efficiency of organic impurities in the absorption liquid is low in the prior art. The method comprises the steps of allowing reaction gas I and ammonia-poor absorption liquid I to contact with unreacted ammonia so as to obtain ammonia-rich absorption liquid II and ammonia-free reaction gas II not containing ammonia; (2) steam stripping the absorption liquid II rich in ammonia in a steam stripping tower, adding acid for regulating pH value, then carrying out oil-water separation so as to obtain ammonia-rich absorption liquid III; then heating up the ammonia-rich absorption liquid III in a resolution tower, carrying out steam stripping so as to obtain ammonia gas flow III and ammonia-poor absorption liquid IV, and returning the ammonia-poor absorption liquid IV back to a quench tower for absorbing unreacted ammonia; and (3) rectifying and separating the ammonia gas flow III in an ammonia rectification tower so as to obtain high-purity ammonia IV, and returning the high-purity ammonia IV back to an ammonia oxidation reactor for reaction. The method adopting the technical scheme well solves the problems and can be used by an industrial device of acrylonitrile.
Description
Technical field
The present invention relates to a kind of vinyl cyanide without the method that reduces organic content in absorption liquid in thiamine process.
Background technology
The unreacted ammonia that has 10% left and right in Acrylonitrile Production need to be absorbed from reactant flow to be separated.Although have technology can reduce the content of reactor outlet ammonia, still have the existence of a large amount of unreacted ammonia.Thereby production technique is mainly to absorb unreacted ammonia by sulfuric acid scrubbing at present, amine wastewater of sulphuric acid directly injects deep-well to be processed, or reclaims crystallization sulphur ammonium through sulphur ammonium recycle section, or SO is made in the burning of sulphur ammonium
3, then through absorption, make sulfuric acid and return systemic circulation use.Also there is partial monopoly to pass through in phosphoric acid, primary ammonium phosphate or the two mixture and reclaim unreacted ammonia.
Patent CN1204620A discloses a kind of method for recovery unreacted ammonia in from producing reactor that alkene nitrile or methacrylonitrile reaction zone obtain and flowing out, with the above-mentioned reactor effluent of ammonium phosphate solution quenching, wherein, ammonium ion in described solution is approximately 0.7 ~ 1.3 with the ratio of phosphate anion, is preferably 1.0 ~ 1.2.In order to remove the useless remaining organism in absorption liquid, in method, added wet oxidation unit, wet oxidation reaction carries out under the pressure of the temperature of approximately 200 ℃ ~ 650 ℃ and 600 ~ 3000 pounds/square inch.
Patent CN101027252A discloses a kind of recovery from vapour stream and the modification method of circulation ammonia, and the method is included at least two stages the aqueous solution quench reactor effluent with ammonium phosphate, thereby catches the ammonia components in effluent.By heated phosphoric aqueous ammonium, can reclaim the ammonia of catching in year, then by this ammonium phosphate solution circulation.Before circulation, by wet oxidation, can remove pollutent contained in ammonium phosphate solution.
In above two patents, for removing contained organism in the aqueous solution, be provided with wet oxidation operation, wet oxidation needs higher temperature and pressure, and energy consumption is high, and production cost is high.In patent CN101027252A, adopt two-part to absorb unreacted ammonia, the ammonium ion of a section is 1.3 ~ 2 with the ratio of phosphate anion in fact, acidity a little less than, in absorption liquid, organic polymer is serious, can reduce the productive rate of target product vinyl cyanide.
Summary of the invention
Technical problem to be solved by this invention is that available technology adopting wet oxidation causes the low problem of organic impurity removal effect in the high and absorption liquid of energy consumption, provides a kind of new vinyl cyanide without the method that reduces organic content in absorption liquid in thiamine process.The method has that energy consumption is low, organic impurity removal effect is good, the advantage that circulation fluid is clean.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of vinyl cyanide is without the method that reduces organic content in absorption liquid in thiamine process, comprise the following steps: (1) reaction gas I out from ammonia oxidation reactor contacts unreacted ammonia in absorption reaction gas with poor ammonium absorption liquid I in quench tower, obtain rich ammonium absorption liquid II and not containing the reaction gas II of ammonia; (2) rich ammonium absorption liquid II stripping in stripping tower is removed to volatile organic constituent, add acid or alkali to regulate pH value, then in an oily-water seperating equipment, carry out separating treatment, remove contained organism and superpolymer in solution, obtain rich ammonium absorption liquid III; Then in Analytic Tower, heat rich ammonium absorption liquid III, stripping obtains ammonia flow III and poor ammonium absorption liquid IV, and poor ammonium absorption liquid IV is returned to quench tower for the absorption of unreacted ammonia; (3) ammonia flow III rectifying separation in ammonia rectifying tower obtains highly purified ammonia IV, returns to ammonia oxidation reactor and reacts.
In technique scheme, poor ammonium absorption liquid I or III are phosphoric acid, primary ammonium phosphate or its mixture, and the N/P mol ratio of poor ammonium absorption liquid is 0.5 ~ 1.5, and preferable range is 0.7 ~ 1.3, and more preferably scope is 0.9 ~ 1.2.The temperature of poor ammonium absorption liquid I is 50 ~ 85 ℃.The pH value of poor ammonium absorption liquid I is 2 ~ 6.5, and preferable range is 2.5 ~ 4.Wherein in rich ammonium absorption liquid, acid adding or alkali regulate pH value, and its scope is 3 ~ 5.Oily-water seperating equipment upper outlet is removed light organic constituent, and the heavy constituent of superpolymer and catalyst fines is removed in lower outlet.Analytic Tower temperature is 150 ~ 250 ℃, and pressure is the saturated vapor pressure of the solution under relevant temperature.In Analytic Tower, stripping gas used is for being the gas of inertia to stripping thing, and preferred version is for being selected from water vapor, air or nitrogen.Ammonia rectifying tower also can unite two into one with Analytic Tower, becomes combination unit.
In the inventive method, at rich ammonium absorption liquid, enter before Analytic Tower, without the pressurization of heating, process polymkeric substance, do not need to process by wet oxidation operation.And wet oxidation need to be carried out under High Temperature High Pressure, energy consumption is higher, causes production cost to raise; Because operational condition is harsh, to reactor material, require also higher simultaneously.So adopt present method can reduce energy consumption, reduce production costs.And add acid or alkali to regulate the pH value of rich ammonium absorption liquid, can be by the organic impurity polymerization in absorption liquid, in oily-water seperating equipment, remove, prevent from entering Analytic Tower post polymerization and stop up column plate, thereby improved the removal effect of organic impurity and the clean and cycle of operation of Analytic Tower, obtained good technique effect.
Accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention.
In Fig. 1,1 is quench tower, and 2 is rich ammonium absorption liquid, 3 is stripping tower, and 4 is light organic constituent, 5 gaseous components such as be vinyl cyanide, 6 is stripping gas, and 7 is light organic constituent, and 8 is tripping device, 9 attach most importance to organic constituent and catalyst fineses, 10 is rich ammonium absorption liquid, 11 is Analytic Tower, 12 is poor ammonium absorption liquid, and 13 is thick ammonia, and 14 is ammonia rectifying tower, 15 is rectifying still liquid, and 16 is anhydrous ammonia, and 17 is acrylonitrile reactor.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1 ~ 6]
Embodiment presses flow operations shown in Fig. 1, as shown in Figure 1, acrylonitrile reactor gas contacts with poor ammonium absorption liquid 12 at quench tower 1 and absorbs reaction gas 5 and the rich ammonium absorption liquid 2 that unreacted ammonia obtains not containing ammonia, rich ammonium absorption liquid 2 is removed the heavy constituents 9 such as light organic constituent 7 and catalyzer, polymkeric substance and is obtained rich ammonium absorption liquid 10 to entering particular oils water separation device 8 after light organic constituent 4 through stripping gas 5 strippings at stripping tower 3, and then enter Analytic Tower 11 and resolve and obtain thick ammonia flow 13 and poor ammonium absorption liquid 12, poor ammonium absorption liquid 12 turns back to quench tower for absorbing unreacted ammonia.Thick ammonia flow 13 obtains anhydrous ammonia 16 at rectifying tower 14 and returns to acrylonitrile reactor 17 and carry out oxidative ammonolysis after rectifying.Concrete technology condition is as following table:
The embodiment being undertaken by above processing condition all can effectively absorb and can realize the recycle of ammonia to the unreacted ammonia in acrylonitrile reactor gas.
[comparative example 1 ~ 3]
Comparative example 1 ~ 3 is by the requirement method operation of patent CN1204620A institute, and concrete technology condition is as following table.
Comparative example 1, comparative example 2 processing condition are identical with embodiment 3,4 respectively, but the too low desired temperature of wet oxidation reaction that do not reach of temperature, organism cannot effectively be removed, and finally cannot realize the recovery of unreacted ammonia.Comparative example 3 has been realized the recycling of ammonia, but the rate of recovery of unreacted ammonia is lower than the embodiment 2 of same process condition; Comparative example 4 has reached the recovering effect identical with embodiment, but temperature is temperature required higher than embodiment far away, and absorption liquid enters organic content before Analytic Tower far away higher than embodiment, is unfavorable for the long-term operation of Analytic Tower.
Claims (10)
1. vinyl cyanide, without a method that reduces organic content in absorption liquid in thiamine process, comprises the following steps:
(1) from ammonia oxidation reactor, reaction gas I out contacts unreacted ammonia in absorption reaction gas with poor ammonium absorption liquid I in quench tower, obtains rich ammonium absorption liquid II and not containing the reaction gas II of ammonia;
(2) rich ammonium absorption liquid II stripping in stripping tower is removed to volatile organic constituent, add acid or alkali to regulate pH value, then in an oily-water seperating equipment, carry out separating treatment, remove contained organism and superpolymer in solution, obtain rich ammonium absorption liquid III; Then in Analytic Tower, heat rich ammonium absorption liquid III, stripping obtains ammonia flow III and poor ammonium absorption liquid IV, and poor ammonium absorption liquid IV is returned to quench tower for the absorption of unreacted ammonia;
(3) ammonia flow III rectifying separation in ammonia rectifying tower obtains highly purified ammonia IV, returns to ammonia oxidation reactor and reacts.
2. vinyl cyanide according to claim 1 is without the method that reduces organic content in absorption liquid in thiamine process, it is characterized in that oily-water seperating equipment upper outlet removes light organic constituent, and the heavy constituent of superpolymer and catalyst fines is removed in lower outlet.
3. vinyl cyanide according to claim 1 is without the method that reduces organic content in absorption liquid in thiamine process, it is characterized in that in rich ammonium absorption liquid it is 3 ~ 5 that acid adding or alkali regulate pH value.
4. vinyl cyanide according to claim 1 is without the method that reduces organic content in absorption liquid in thiamine process, it is characterized in that poor ammonium absorption liquid I and III are phosphoric acid, primary ammonium phosphate or its mixture, the N/P mol ratio in poor ammonium absorption liquid I and III is 0.5 ~ 1.5.
5. vinyl cyanide according to claim 4, without the method that reduces organic content in absorption liquid in thiamine process, is characterized in that the N/P mol ratio 0.7 ~ 1.3 in poor ammonium absorption liquid I and III.
6. vinyl cyanide according to claim 5, without the method that reduces organic content in absorption liquid in thiamine process, is characterized in that the N/P mol ratio in poor ammonium absorption liquid I and III is 0.9 ~ 1.2.
7. vinyl cyanide according to claim 1 is without the method that reduces organic content in absorption liquid in thiamine process, and the temperature that it is characterized in that poor ammonium absorption liquid I is 50 ~ 85 ℃, and the pH value of poor ammonium absorption liquid I is 2 ~ 6.5.
8. vinyl cyanide according to claim 7 is without the method that reduces organic content in absorption liquid in thiamine process, and the pH value that it is characterized in that poor ammonium absorption liquid I is 2.5 ~ 4.
9. vinyl cyanide according to claim 1, without the method that reduces organic content in absorption liquid in thiamine process, is characterized in that in Analytic Tower that stripping gas used is for being the gas of inertia to stripping thing; Analytic Tower temperature is 150 ~ 250 ℃, and pressure is the saturated vapor pressure of the solution under relevant temperature.
10. vinyl cyanide according to claim 9, without the method that reduces organic content in absorption liquid in thiamine process, is characterized in that in Analytic Tower, stripping gas used is water vapor, air or nitrogen.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210325053.1A CN103664694A (en) | 2012-09-05 | 2012-09-05 | Method for lowering content of organic matters in absorption liquid in ammonium sulfate-free acrylonitrile technology |
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| CN201210325053.1A CN103664694A (en) | 2012-09-05 | 2012-09-05 | Method for lowering content of organic matters in absorption liquid in ammonium sulfate-free acrylonitrile technology |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106430245A (en) * | 2015-08-12 | 2017-02-22 | 中国石油化工股份有限公司 | Improvement method for ammonium-sulfate-free process in acrylonitrile reaction apparatus |
| CN106565538A (en) * | 2016-11-07 | 2017-04-19 | 上海东化环境工程有限公司 | Purification technology for acrylonitrile reaction gas |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1204620A (en) * | 1997-07-04 | 1999-01-13 | 标准石油公司 | Process for recovery and recycle of ammonia from acrylonitrile reactor efflvent stream using ammonium phosphate quench system |
| US5895635A (en) * | 1996-04-30 | 1999-04-20 | The Standard Oil Company | Process for recovery and recycle of ammonia from an acrylonitrile reactor effluent stream using an ammonium phosphate quench system |
| CN101027252A (en) * | 2004-07-22 | 2007-08-29 | 伊内奥斯美国公司 | Process for recovery and recycle of ammonia from a vapor stream |
| CN102452955A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | Method for recovering and recycling unreacted ammonia in acrylonitrile reaction device |
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2012
- 2012-09-05 CN CN201210325053.1A patent/CN103664694A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5895635A (en) * | 1996-04-30 | 1999-04-20 | The Standard Oil Company | Process for recovery and recycle of ammonia from an acrylonitrile reactor effluent stream using an ammonium phosphate quench system |
| CN1204620A (en) * | 1997-07-04 | 1999-01-13 | 标准石油公司 | Process for recovery and recycle of ammonia from acrylonitrile reactor efflvent stream using ammonium phosphate quench system |
| CN101027252A (en) * | 2004-07-22 | 2007-08-29 | 伊内奥斯美国公司 | Process for recovery and recycle of ammonia from a vapor stream |
| CN102452955A (en) * | 2010-10-21 | 2012-05-16 | 中国石油化工股份有限公司 | Method for recovering and recycling unreacted ammonia in acrylonitrile reaction device |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106430245A (en) * | 2015-08-12 | 2017-02-22 | 中国石油化工股份有限公司 | Improvement method for ammonium-sulfate-free process in acrylonitrile reaction apparatus |
| CN106430245B (en) * | 2015-08-12 | 2018-10-23 | 中国石油化工股份有限公司 | Improved method without thiamine process in acrylonitrile reactor device |
| CN106565538A (en) * | 2016-11-07 | 2017-04-19 | 上海东化环境工程有限公司 | Purification technology for acrylonitrile reaction gas |
| CN106565538B (en) * | 2016-11-07 | 2019-03-15 | 上海东化环境工程有限公司 | A kind of purification process of acrylonitrile reactor gas |
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Application publication date: 20140326 |