CN103521034A - Improved method for resolving ammonium salt in acrylonitrile non-ammonium-sulfate process - Google Patents
Improved method for resolving ammonium salt in acrylonitrile non-ammonium-sulfate process Download PDFInfo
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- CN103521034A CN103521034A CN201210225884.1A CN201210225884A CN103521034A CN 103521034 A CN103521034 A CN 103521034A CN 201210225884 A CN201210225884 A CN 201210225884A CN 103521034 A CN103521034 A CN 103521034A
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Abstract
The invention relates to an improved method for resolving an ammonium salt in an acrylonitrile non-ammonium-sulfate process and is mainly used for solving the problem that the energy consumption is high during ammonium salt resolving in the prior art. According to the technical scheme, the method comprises the following steps: (1) enabling a reaction gas I and a low-ammonium absorption liquid I to come into contact with unreacted ammonium in a quenching tower so as to obtain a high-ammonium absorption liquid II and a ammonium-free reaction gas II; (2) performing steam stripping on the high-ammonium absorption liquid II in a stripping tower and then performing oil-water separation so as to obtain a high-ammonium absorption liquid III; heating the high-ammonium absorption liquid III in a resolving tower and performing the steam stripping so as to obtain an ammonium gasflow III and an ammonium dihydrogen phosphate crystal IV; dissolving the low-ammonium absorption liquid V; returning the absorption liquid V into the quenching tower for absorbing the unreacted ammonium; and (3) performing rectification separation on the ammonium gasflow III in an ammonium rectification tower so as to obtain ammonium IV with high purity; and returning the ammonium IV into an ammonium oxidation reactor and reacting. Thus, the problem in the prior art is solved well. The method provided by the invention can be applied to an industrial device of acrylonitrile.
Description
Technical field
The present invention relates to a kind of acrylonitrile improving one's methods without the parsing of thiamine process ammonium salt.
Background technology
The unreacted ammonia that has 10% left and right in Acrylonitrile Production need to be absorbed from reaction logistics 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 technology 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, ammonium dihydrogen phosphate (ADP) 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 about 0.7-1.3 with the ratio of phosphate anion, is preferably 1.0-1.2.In order to remove the useless remaining organic matter 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 vapor 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 pollutant contained in ammonium phosphate solution.
In above two patents, for removing contained organic matter 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 acrylonitrile.
Summary of the invention
Technical problem to be solved by this invention is that available technology adopting wet oxidation causes the problem that energy consumption is high, material consumption is high, and a kind of new acrylonitrile improving one's methods without the parsing of thiamine process ammonium salt is provided.The method has advantages of that energy consumption is low, material consumption is low.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: what a kind of acrylonitrile was resolved without thiamine process ammonium salt improves one's methods, 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 stripper is removed to volatile organic component, then carry out separating treatment in an oily-water seperating equipment, remove contained organic matter and high polymer in solution, obtain rich ammonium absorption liquid III; Then in Analytic Tower, heat rich ammonium absorption liquid III, stripping obtains ammonia flow III and ammonium dihydrogen phosphate crystal IV, and ammonium dihydrogen phosphate crystal IV continues to resolve to obtain poor ammonium absorption liquid V after secondary Analytic Tower dissolves, and returns to quench tower for the absorption of unreacted ammonia; (3) the rectifying separation in ammonia rectifying column of ammonia flow III 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, ammonium dihydrogen phosphate (ADP) or its mixture, and the N/P mol ratio of poor ammonium absorption liquid is 0.5-1.5:1, and preferable range is 0.7-1.3:1, and more preferably scope is 0.9-1.2:1.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 oily-water seperating equipment upper outlet is removed light organic component, and the heavy constituent of high polymer and catalyst fines is removed in lower outlet.Analytic Tower temperature is 100-165 ℃, 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 vapour, air or nitrogen.Secondary Analytic Tower temperature is 165-190 ℃
In the inventive method, at rich ammonium absorption liquid, enter before Analytic Tower, without the pressurization of heating, process polymer, do not need to process by wet oxidation operation.And wet oxidation need to be carried out under HTHP, energy consumption is higher, causes production cost to raise; Because operating condition is harsh, to reactor material, require also higher simultaneously.And the further parsing of ammonium dihydrogen phosphate (ADP) can obtain phosphoric acid, and phosphoric acid is more effective than ammonium salt to the assimilation effect of ammonia, the assimilation effect without adding again phosphoric acid enhancing unreacted ammonia, has reduced the consumption of phosphoric acid.So adopt this method can reduce energy consumption, energy consumption, reduce production costs, 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, and 3 is stripper, 4 is light organic component, 5 gaseous components such as be acrylonitrile, and 6 is stripping gas, 7 is light organic component, 8 is separator, 9 attach most importance to organic component and catalyst fineses, and 10 is rich ammonium absorption liquid, 11 is Analytic Tower, 12 is ammonium dihydrogen phosphate crystal, and 13 is thick ammonia, and 14 is ammonia rectifying column, 15 is rectifying still liquid, and 16 is anhydrous ammonia, and 17 is acrylonitrile reactor, 18 is secondary Analytic Tower, and 19 is ammonium dihydrogen phosphate (ADP) absorption liquid, and 20 is thick ammonia.
Below by embodiment, the present invention is further elaborated.
The specific embodiment
[embodiment 1～6]
Embodiment 1-6 presses flow operations shown in Fig. 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 light organic component 7 and catalyst through stripping gas 5 strippings to entering particular oils water separation device 8 after light organic component 4 at stripper 3, the heavy constituents such as polymer 9 obtain rich ammonium absorption liquid 10, and then enter Analytic Tower 11 and resolve and obtain thick ammonia flow 13 and ammonium dihydrogen phosphate crystal 12, ammonium dihydrogen phosphate crystal enters secondary Analytic Tower 18 and is dissolved in ammonia rectifying tower bottoms 15 and obtains diammonium hydrogen phosphate absorption liquid, further resolve and obtain the poor ammonium absorption liquid 19 of thick ammonia flow 20, turn back to quench tower 1 for absorbing unreacted ammonia.Thick ammonia flow 13 obtains anhydrous ammonia 16 at rectifying column 14 and returns to acrylonitrile reactor 17 and carry out ammoxidation reaction after rectifying.Concrete technology condition is as following table:
The embodiment being undertaken by above process conditions all can effectively absorb and can realize recycling of ammonia the unreacted ammonia in acrylonitrile reactor gas.
[comparative example 1-4]
Comparative example 1-4 is by the requirement method operation of patent CN1204620A institute, and concrete technology condition is as following table.
Comparative example 1-4 process conditions are identical with embodiment 1-4 respectively, but the too low desired temperature of wet oxidation reaction that do not reach of temperature, organic matter cannot effectively be removed, and finally cannot realize the recovery of unreacted ammonia.
Claims (9)
1. what an acrylonitrile was resolved without thiamine process ammonium salt improves one's methods, and 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 stripper is removed to volatile organic component, then carry out separating treatment in an oily-water seperating equipment, remove contained organic matter and high polymer in solution, obtain rich ammonium absorption liquid III; Then in Analytic Tower, heat rich ammonium absorption liquid III, stripping obtains ammonia flow III and ammonium dihydrogen phosphate crystal IV, and ammonium dihydrogen phosphate crystal IV continues to resolve to obtain poor ammonium absorption liquid V after secondary Analytic Tower dissolves, and returns to quench tower for the absorption of unreacted ammonia;
(3) the rectifying separation in ammonia rectifying column of ammonia flow III obtains highly purified ammonia IV, returns to ammonia oxidation reactor and reacts.
2. what acrylonitrile according to claim 1 was resolved without thiamine process ammonium salt improves one's methods, and it is characterized in that oily-water seperating equipment upper outlet removes light organic component, and the heavy constituent of high polymer and catalyst fines is removed in lower outlet.
3. what acrylonitrile according to claim 1 was resolved without thiamine process ammonium salt improves one's methods, it is characterized in that poor ammonium absorption liquid I and V are phosphoric acid, ammonium dihydrogen phosphate (ADP) or its mixture, N/P mol ratio in poor ammonium absorption liquid I is 0.5-1.5:1, and pH value is 2-6.5, and temperature is 50-85 ℃.
4. what acrylonitrile according to claim 3 was resolved without thiamine process ammonium salt improves one's methods, it is characterized in that, and the N/P mol ratio 0.7-1.3:1 in poor ammonium absorption liquid I and V, pH value is 2.5-4.
5. what acrylonitrile according to claim 4 was resolved without thiamine process ammonium salt improves one's methods, and it is characterized in that the N/P mol ratio in poor ammonium absorption liquid I is 0.9-1.2:1.
6. what acrylonitrile according to claim 1 was resolved without thiamine process ammonium salt improves one's methods, and it is characterized in that in Analytic Tower that stripping gas used is for being the gas of inertia to stripping thing.
7. what acrylonitrile according to claim 6 was resolved without thiamine process ammonium salt improves one's methods, and it is characterized in that in Analytic Tower, stripping gas used is water vapour, air or nitrogen.
8. what acrylonitrile according to claim 1 was resolved without thiamine process ammonium salt improves one's methods, and it is characterized in that Analytic Tower temperature is 100-165 ℃, and pressure is the saturated vapor pressure of the solution under relevant temperature.
9. what acrylonitrile according to claim 1 was resolved without thiamine process ammonium salt improves one's methods, and the temperature that it is characterized in that secondary Analytic Tower is 165-190 ℃.
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| CN201210225884.1A CN103521034A (en) | 2012-07-03 | 2012-07-03 | Improved method for resolving ammonium salt in acrylonitrile non-ammonium-sulfate process |
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| CN201210225884.1A CN103521034A (en) | 2012-07-03 | 2012-07-03 | Improved method for resolving ammonium salt in acrylonitrile non-ammonium-sulfate process |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105664683A (en) * | 2014-11-20 | 2016-06-15 | 中国石油化工股份有限公司 | Method for processing of ammonia nitrogen in acrylonitrile reaction device by catalytic wet oxidation |
| 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 |
| CN106955564A (en) * | 2017-04-24 | 2017-07-18 | 中国石油化工股份有限公司 | The handling process of the stream containing dicyanogen in acrylonitrile installation |
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 |
| US20010006614A1 (en) * | 1998-12-23 | 2001-07-05 | Nero Linda L. | 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
- 2012-07-03 CN CN201210225884.1A patent/CN103521034A/en active Pending
Patent 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 |
| US20010006614A1 (en) * | 1998-12-23 | 2001-07-05 | Nero Linda L. | 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 |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105664683A (en) * | 2014-11-20 | 2016-06-15 | 中国石油化工股份有限公司 | Method for processing of ammonia nitrogen in acrylonitrile reaction device by catalytic wet oxidation |
| CN105664683B (en) * | 2014-11-20 | 2018-01-09 | 中国石油化工股份有限公司 | The method of CWO processing ammonia nitrogen in acrylonitrile reactor device |
| 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 |
| CN106955564A (en) * | 2017-04-24 | 2017-07-18 | 中国石油化工股份有限公司 | The handling process of the stream containing dicyanogen in acrylonitrile installation |
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Application publication date: 20140122 |