CN103145520B - Method for removing dimethyl ether from C4 material flow - Google Patents
Method for removing dimethyl ether from C4 material flow Download PDFInfo
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- CN103145520B CN103145520B CN201110300450.9A CN201110300450A CN103145520B CN 103145520 B CN103145520 B CN 103145520B CN 201110300450 A CN201110300450 A CN 201110300450A CN 103145520 B CN103145520 B CN 103145520B
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- logistics
- dme
- material flow
- hydrogenation
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Abstract
The invention relates to a method for removing dimethyl ether from a C4 hydrogenation material flow, mainly to solve problems of difficulty for removing trace dimethyl ether in the C4 material flow, heavy loss of C4, and complex technological processes in the prior art. The method for removing dimethyl ether from the C4 hydrogenation material flow provided by the invention comprises the following steps: a) providing an olefin material flow I containing C4 and dimethyl ether; b) feeding the material flow I into a separation column A, and dividing into a material flow III and a material flow IV after washing with a methanol stream II; c) feeding the material flow III into a separation column B, and dividing into a material flow VI and a material flow VII after washing with a water-containing material flow; d) feeding the material flow VI into a dryer C, and obtaining a material flow VIII after dehydration, wherein the material flow VIII contains C4 , methanol, and dimethyl ether; and e) feeding the material flow VIII into an adsorption vessel D, and obtaining a material flow IX after dimethyl ether is adsorbed, wherein the material flow IX and H2 are fed into a hydrogenation reactor E, and X is a material flow after hydrogenation. The method provided by the invention solves the problems better and can be used for industrial production of the C4 hydrogenation material flow.
Description
Technical field
The present invention relates to a kind of C
4the removal methods of dme in logistics.
Background technology
The a large amount of C4 hydro carbons of by-product in refining of petroleum and petrochemical production process, how fully these by-product resources of Appropriate application, carry out the exploitation of deep processed product, have caused the extensive concern of people.
The comprehensive utilization of C4 mainly comprises: ethylene cracking material, C4 preparing propylene through olefin disproportionation, C4 hydro carbons freshening increasing output of ethylene and propylene are made in hydrofining, oxidation of isobutane method produces propylene oxide and the coproduction trimethyl carbinol and MTBE alkylate oil machinery etc.
Containing the 1,3-butadiene of the 1.5 ~ 2wt% that has an appointment in C4, further OCC or OMT process is carried out to C4 logistics, all need to carry out selective hydrogenation.But because of the dme containing 2000 ~ 3000ppm in C4, if C4 selective hydrogenation catalyst has comparatively severe specifications requirement to oxygenatedchemicals, then shortening could be carried out further after needing to remove dme.C4 logistics, by means of only rectifying separation or absorbing process, is difficult to the dme removal effect obtained, and C4 loss is larger.
Such as, patent US4,474,647 disclose dme can affect the oligomeric of some alkene.That patent describes and utilize distillation from C
4and/or C
5the method of dme is removed in olefin stream.Logistics is distilled and is separated into tower top and tower base stream.This top gaseous phase logistics is after cooling, then gas-liquid separation, can isolate the logistics containing dme, water; Tower base stream contains the C of purification
4and/or C
5alkene.But the method dme maximum processing capability is only 800ppm, and C at the bottom of tower
4and/or C
5in alkene, dme content is still higher than the requirement of hydrogenation.
EP0229994 discloses from liquid C
3~ C
5the method of dme is removed in alkene.Make the liquefied olefines of monoolefine, 100 ~ 20000wppm diolefine and the 1 ~ 5000wppm dme that there are 3 ~ 5 carbon atoms containing 5 ~ 50% with liquid state by molecules sieve adsorbant.Described zeolite has faujusite structure, comprises Y zeolite, X zeolite and LZ-210 zeolite.Preferred described olefin stream is the C of mixing
4~ C
5hydrocarbon stream, from fluid catalystic cracking (FCC) device, in this alkene, contained iso-butylene/or isopentene great majority have been reacted by FCC olefin product and methyl alcohol and have generated MTBE or TAME and remove.Described adsorption system can be fixed bed, moving-bed, simulation moving-bed or fluidised bed system, but is preferably fixed bed system.Dme content can be dropped to below 1000wppm by the method, but still can not meet the requirement of hydrogenation.
CN101333144A discloses a kind of method removing dme from olefin stream, and the method is first from C
2/ C
3segmentation H
2, methane, ethene, ethane, propylene, propane, C
4 +with dme logistics, more respectively from C
1/ C
2and C
3/ C
4segmentation, isolated C
2and C
3distillation operation is carried out again after hydrogenator.The method flow process is comparatively complicated, can remove alkene C
4the dme of part in logistics, but the requirement of hydrogenation can not be met.
The technique of current various published solution washing is all comparatively complicated, and causes C
4logistics loss too much, though simple absorbing process can remove portion dme, can not meet the requirement of hydrogenation technique.
Summary of the invention
Technical problem to be solved by this invention is C in prior art
4in logistics micro-dme be difficult to remove, C
4the problem that loss is large, technical process is complicated, provides a kind of C
4the removal methods of dme in hydrogenation logistics, the method has that dme decreasing ratio is high, C
4loss less, the simple advantage of flow process.
In order to solve the problems of the technologies described above, technical solution of the present invention is as follows: a kind of C
4the removal methods of dme in hydrogenation logistics, comprising:
A) olefin stream I containing Trimethylmethane, iso-butylene, 1-butylene, 1,3-butadiene, normal butane, Trans-2-butene, n-2-butylene and dme is provided;
B) stream I enters knockout tower A, and after washing containing methanol stream II, be divided into stream I II and stream I V, wherein stream I II contains C
4, methyl alcohol and dme, stream I V contains methyl alcohol and dme;
C) stream I II enters knockout tower B, is divided into logistics VI and logistics VII after aqueous stream V washes, and wherein contains C in logistics VI
4, methyl alcohol, water and dme, containing water, methyl alcohol and dme in logistics VII;
D) logistics VI enters moisture eliminator C, obtains logistics VIII after dehydration, and logistics VIII contains C
4, methyl alcohol and dme;
E) logistics VIII enters contactor D, after dme is adsorbed, obtains dme content and is less than 100wppb stream I X;
F) stream I X and H
2go hydrogenator E to react, obtain logistics X after hydrogenation.
In such scheme, in stream I, dme content preferable range is 10 ~ 4000wppm, and more preferably scope is 100 ~ 3000wppm, and in stream I, olefin(e) centent preferable range is for being at least 50%.The operational condition of methanol wash column tower A is: tower top pressure preferable range is 0.2 ~ 1.0MPag, and more preferably scope is 0.3 ~ 0.6MPag; Methyl alcohol and C
4logistics quality throughput ratio preferable range is 0.1 ~ 1.0wt, more preferably scope 0.2 ~ 0.6; The operational condition of water wash column B: tower top pressure preferable range is 0.2 ~ 1.0MPag, more preferably scope 0.3 ~ 0.6MPag, water and C
4logistics quality throughput ratio preferable range is 0.1 ~ 10.0wt, more preferably scope 2.0 ~ 8.0.
In preferred technical scheme moisture eliminator C, siccative is at least one in the physics such as calcium chloride, soda-lime, Vanadium Pentoxide in FLAKES, silicic acid, silica-gel drier, clay desiccant, molecular sieve desiccant, mineral agent, fiber desiccant or chemical drier.In moisture eliminator C outlet streams VIII, water-content preferable range is for being less than 500wppb, and more preferably scope is for being less than 50wppb.Contactor D outlet streams IX dme content preferable range is for being less than 100wppb, and more preferably scope is for being less than 10wppb.
C containing Trimethylmethane, iso-butylene, 1-butylene, 1,3-butadiene, normal butane, Trans-2-butene, n-2-butylene and dme in the olefin stream provided in such scheme
4logistics, usually this C
4logistics can from any Common sources.For the C containing dme
4logistics, if do not carry out effective elimination, then can affect the final performance of follow-up hydrogenation process catalyst and the effect of polymerization.The present invention is for from C
4micro-dme successful is removed in logistics.This programme first carries out methanol wash column to stream I, though C
4logistics has a small amount of loss, but removes C
4most of dme in logistics; Stream I II is washed, C
4logistics has insubstantial loss, can by C
4in logistics, dme is down to below 10ppm; After drying and absorption are carried out to stream I V, C
4logistics water content can be down to below 1ppm, and dme content is down to below 10wppb.The dme removing process that this programme provides, C
4total loss is less than 4%.
Accompanying drawing explanation
Fig. 1 is the process flow diagram that the present invention program is separated.
In Fig. 1,26 is C
4stream I, 27 is methanol stream II, and 28 is methanol wash column tower A, 29 is methanol wash column tower A overhead extraction stream I II, and 30 is distillation tower A tower reactor extraction IV, and 32 is water wash column B, 31 is water logistics V, and 33 is water wash column B overhead extraction logistics VI, and 34 is extraction logistics VII at the bottom of water wash column B tower, 35 is moisture eliminator C, 36 is moisture eliminator effluent stream VIII, and 37 is contactor, and 38 is contactor effluent stream IX, 39 for adding hydrogen tank E, and 40 is logistics X after hydrogenation.
In Fig. 1, C
4logistics 26 enters methanol wash column tower A, after washing from tower top methanol stream 27, and the C after methanol wash column
4logistics 29 from tower A top flow out laggard enter water wash column B, extraction methyl alcohol at the bottom of tower and dme mixture flow 30.In water wash column B, C
4the logistics 33 of logistics after washing from overhead water logistics 31 removes moisture eliminator C, recovered water, methyl alcohol and dme mixture flow 34 at the bottom of tower.In moisture eliminator C, logistics 33 drying anhydrate after logistics 36 remove contactor D, in contactor D, dme is removed hydrogenator E by the logistics 38 after adsorbent, and after hydrogenation, logistics is 40.
Below by example, this programme is further set forth.
Embodiment
[embodiment 1]
Adopt present invention process flow process, the olefin stream I containing Trimethylmethane, iso-butylene, 1-butylene, 1,3-butadiene, normal butane, Trans-2-butene, n-2-butylene and dme is provided; Stream I enters knockout tower A, and after washing containing methanol stream II, be divided into stream I II and stream I V, wherein stream I II contains C
4, methyl alcohol and dme, stream I V contains methyl alcohol and dme; Stream I II enters knockout tower B, is divided into logistics VI and logistics VII after aqueous stream V washes, and wherein contains C in logistics VI
4, methyl alcohol, water and dme, containing water, methyl alcohol and dme in logistics VII; Logistics VI enters moisture eliminator C, obtains logistics VIII after dehydration, and logistics VIII contains C
4, methyl alcohol and dme; Logistics VIII enters contactor D, after dme is adsorbed, obtains stream I X, stream I X and H
2remove hydrogenator E, X is logistics after hydrogenation.
C
4the working pressure of logistics dme content 2000ppm, A is 0.36MPag, methyl alcohol and C
4the ratio of logistics flux is 0.5 (wt); The working pressure of B is 0.34MPag, water and C
4the ratio of logistics flux is 5.0 (wt).Moisture eliminator service temperature is 40 DEG C, and contactor service temperature is 20 DEG C, washing, drying effect and C
4logistics loss is as table 1.
Table 1
| Moisture eliminator C inlet water content (wt%) | 0.003 |
| Moisture eliminator C exports water-content (wt%) | 50ppb |
| Contactor D entrance dme content (wt%) | 3ppm |
| Contactor D outlet dimethyl ether content (wt%) | 10ppb |
| Contactor D exports C 4Logistics loss amount (wt%) | 2.96％ |
[embodiment 2]
The operational condition changing tower A and B is constant, and the working pressure of A is 0.62MPag, methyl alcohol and C
4the ratio of logistics flux is 0.2 (wt); The working pressure of B is 0.56MPag, water and C
4the ratio of logistics flux is 5.5 (wt).Moisture eliminator service temperature is 40 DEG C, and contactor service temperature is 20 DEG C, and acquired results is as shown in table 2.As can be seen from the table, when operational condition changes, gained C
4in logistics, dme content is all less than 10wppb, and purity all reaches hydrogenation requirements, C
4logistics loss amount is little.
[embodiment 3]
According to embodiment 1 method, changing dme content in stream I is 100ppm and 3000ppm, obtains the results are shown in Table 3.
Table 2
| Moisture eliminator C inlet water content (wt%) | 0.003 |
| Moisture eliminator C exports water-content (wt%) | 40ppb |
| Contactor D entrance dme content (wt%) | 80ppb |
| Contactor D outlet dimethyl ether content (wt%) | 9ppb |
| Contactor D exports C 4Logistics loss amount (wt%) | 3.45 |
table 3
| Dme content in stream I | 100ppm | 3000ppm |
| Moisture eliminator C inlet water content (wt%) | 0.003 | 0.003 |
| Moisture eliminator C exports water-content (wt%) | 50ppb | 50ppb |
| Contactor D entrance dme content (wt%) | 3ppm | 3ppm |
| Contactor D outlet dimethyl ether content (wt%) | 1ppb | 15ppb |
| Contactor D exports C 4Logistics loss amount (wt%) | 1.96％ | 3.26％ |
[embodiment 4]
According to [embodiment 2] method, when in stream I, dme content is respectively 100ppm and 3000ppm, obtain the results are shown in Table 4.
Table 4
| Dme content in stream I | 100ppm | 3000ppm |
| Moisture eliminator C inlet water content (wt%) | 0.003 | 0.003 |
| Moisture eliminator C exports water-content (wt%) | 40ppb | 40ppb |
| Contactor D entrance dme content (wt%) | 80ppb | 80ppb |
| Contactor D outlet dimethyl ether content (wt%) | ＜1ppb | 10ppb |
| Contactor D exports C 4Logistics loss amount (wt%) | 2.45 | 3.65 |
[comparative example 1]
By adsorption scheme described in patent US4474647, through operations such as rectifying, condensation, gas-liquid separators, dme content is down to 20ppm by 800ppm, higher than hydrogenation technique requirement, C
4logistics loss is greater than 5%.
Claims (8)
1. a C
4the removal methods of dme in hydrogenation logistics, comprises following several step:
A) olefin stream I containing Trimethylmethane, iso-butylene, 1-butylene, 1,3-butadiene, normal butane, Trans-2-butene, n-2-butylene and dme is provided;
B) logistics I enters knockout tower A, after washing containing methanol stream II, be divided into logistics III and logistics IV, and wherein logistics III is containing C
4, methyl alcohol and dme, logistics IV is containing methyl alcohol and dme;
C) logistics III enters knockout tower B, is divided into logistics VI and logistics VII after aqueous stream V is washed, and wherein contains C in logistics VI
4, methyl alcohol, water and dme, containing water, methyl alcohol and dme in logistics VII;
D) logistics VI enters moisture eliminator C, obtains logistics VIII after dehydration, and logistics VIII is containing C
4, methyl alcohol and dme;
E) logistics VIII enters contactor D, after dme is adsorbed, obtains the logistics Ⅸ that dme content is less than 100wppb;
F) logistics Ⅸ and H2 go hydrogenator E to react, and obtain logistics Ⅹ after hydrogenation.
Wherein, in logistics I, dme content is 10 ~ 4000wppm; In logistics I, olefin(e) centent is at least 50%.
2. C according to claim 1
4the removal methods of dme in hydrogenation logistics, is characterized in that in logistics I, dme content is 100 ~ 3000wppm.
3. C according to claim 1
4the removal methods of dme in hydrogenation logistics, is characterized in that the operational condition of methanol wash column tower A is: tower top pressure is 0.2 ~ 1.0MPag, methyl alcohol and C
4logistics quality throughput ratio is 0.1 ~ 1.0; The operational condition of water wash column B: tower top pressure is 0.2 ~ 1.0MPag, water and C
4logistics quality throughput ratio is 0.1 ~ 10.0.
4. C according to claim 1
4the removal methods of dme in hydrogenation logistics, is characterized in that the operational condition of methanol wash column tower A is: tower top pressure is 0.3 ~ 0.6MPag, methyl alcohol and C
4logistics quality throughput ratio is 0.2 ~ 0.6; The operational condition of water wash column B: tower top pressure is 0.3 ~ 0.6MPag, water and C
4logistics quality throughput ratio is 2.0 ~ 8.0.
5. C according to claim 1
4the removal methods of dme in hydrogenation logistics, is characterized in that in moisture eliminator C, siccative is at least one in calcium chloride, soda-lime, Vanadium Pentoxide in FLAKES, silicic acid, silica-gel drier, clay desiccant, molecular sieve desiccant, mineral agent, fiber desiccant.
6. C according to claim 1
4the removal methods of dme in hydrogenation logistics, is characterized in that in moisture eliminator C outlet streams VIII, water-content is less than 500wppb.
7. C according to claim 1
4the removal methods of dme in hydrogenation logistics, is characterized in that in moisture eliminator C outlet streams VIII, water-content is less than 50wppb.
8. C according to claim 1
4the removal methods of dme in hydrogenation logistics, is characterized in that in contactor D, sorbent material is porous molecular screen, and contactor D outlet streams Ⅸ dme content is less than 10wppb.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110300450.9A CN103145520B (en) | 2011-09-29 | 2011-09-29 | Method for removing dimethyl ether from C4 material flow |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110300450.9A CN103145520B (en) | 2011-09-29 | 2011-09-29 | Method for removing dimethyl ether from C4 material flow |
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| CN103145520B true CN103145520B (en) | 2015-01-07 |
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| CN105152840B (en) * | 2015-09-14 | 2017-05-10 | 中国成达工程有限公司 | Process for refining C-4 hydrocarbon fluid |
| CN106748619B (en) * | 2016-12-15 | 2019-08-09 | 惠生工程（中国）有限公司 | A kind of technique refining propane from the feed stream comprising propane and dimethyl ether |
| CN108083968B (en) * | 2017-12-29 | 2020-10-23 | 黄河三角洲京博化工研究院有限公司 | Method for strengthening separation of dimethyl ether in crude isobutene |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1549802A (en) * | 2001-08-31 | 2004-11-24 | ����ɭ���ڻ�ѧר����˾ | Process of removing contaminants from an olefin stream using extractive distillation |
| CN101885656A (en) * | 2009-05-13 | 2010-11-17 | 中国石油化工股份有限公司 | Adsorption purification method for hydrocarbon stream |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1549802A (en) * | 2001-08-31 | 2004-11-24 | ����ɭ���ڻ�ѧר����˾ | Process of removing contaminants from an olefin stream using extractive distillation |
| CN101885656A (en) * | 2009-05-13 | 2010-11-17 | 中国石油化工股份有限公司 | Adsorption purification method for hydrocarbon stream |
Non-Patent Citations (1)
| Title |
|---|
| MTBE合成装置醚后C4中甲醇和二甲醚含量高的原因分析及对策;王华槟等;《石油炼制与化工》;20101231;第41卷(第4期);6-11 * |
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