CN102344331B - Method for controlling water content of propylene product in coal-based methanol propylene production process - Google Patents
Method for controlling water content of propylene product in coal-based methanol propylene production process Download PDFInfo
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- CN102344331B CN102344331B CN201110183627.1A CN201110183627A CN102344331B CN 102344331 B CN102344331 B CN 102344331B CN 201110183627 A CN201110183627 A CN 201110183627A CN 102344331 B CN102344331 B CN 102344331B
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- extraction tower
- moisture eliminator
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Abstract
The invention relates to a method for controlling the water content of a propylene product in a coal-based methanol propylene production process, which comprises the following measures: adjusting the water intake quantity of an oxide extraction tower, so that the liquid level of the extraction tower is controlled to range between -15% and 15%; additionally arranging liquid collecting devices at the top or middle of the oxide extraction tower and/or in the space between the oxide extraction tower and driers; enlarging the length-diameter ratio of a molecular sieve bed in each drier; and increasing the quantity of the driers, and connecting all the driers in a parallel connection and series connection combined mode. The method makes only a small change on the original process flow, and is easy to implement; and the water content of the resulting propylene product can satisfy the standard of polymer grade propylene.
Description
Technical field
The present invention relates to process of preparing propylene from coal-based methanol, more particularly, is a kind of method of controlling water content of propylene product in coal-based methanol propylene production process, makes resulting propylene product reach the standard of polymerization-grade propylene.
Background technology
The propylene of one of low-carbon alkene is basic organic chemical industry raw material important in chemical industry, and the source of propylene mainly relies on naphtha cracking technology both at home and abroad for a long time.Nearly ten years, along with minimizing gradually, the International Crude Oil of petroleum resources rises steadily, the production cost of propylene constantly raises, and has restricted largely propylene industrial expansion.So researchers more both domestic and external strive to find take the novel method of non-oil resource as raw material production propylene.Along with reaching its maturity of methanol device Industrialized processing technique, with coal or natural gas source methanol again the production line of preparing propone more and more receive people's concern.
As 500,000 tons/year of coal-based propylene units of the first cover in the world, the industrial applications of MTP Technology is to attempt first.Device startup procedure does not have similar experience to use for reference, and during driving, propylene product indices is except water-content exceeds standard device, and other index all reaches and is even better than the requirement of polymerization-grade propylene product specification.But in product, water-content exceeds standard and causes MTP device propylene product cannot be directly used in polypropylene plant.
The problem exceeding standard for water-content in propylene product, analysis mainly contains the reason of following 2: (1) is because oxide compound extraction tower liquid level is controlled difficulty, outlet water-content exceeds standard, liquid hydrocarbon component with a large amount of free-waters enters moisture eliminator, makes soon the saturated inefficacy of molecular sieve adsorption in moisture eliminator.The liquid hydrocarbon that water-content exceeds standard enters debutanizing tower, at debutylize tower top, gas phase C
4following component is carried the water exceeding standard secretly and is entered again depropanizing tower.The depropanizing top gaseous phase C that is containing excessive water
3following component enters deethanizing column, and excessive water continues to remain in C at the bottom of deethanizing column
3in liquid phase, enter propylene tower, cause water-content in propylene product to exceed standard.(2) by liquid hydrocarbon product out at the bottom of four sections of outlet separating tank tanks of hydrocarbon compressor, entered after liquid hydrocarbon moisture eliminator, contain C
6heavy hydrocarbon more than component, because the existence of heavy hydrocarbon causes molecular sieve water-retaining capacity to decline rapidly, and after molecular sieve surface adsorption heavy hydrocarbon, the restriction due to regeneration temperature is difficult for regeneration completely, affects soaking effect.
In order to address the above problem, need to transform the relevant technological flow process of preparing propylene by coal-based methanol, so that the water-content of resulting propylene product can meet the standard of polymerization-grade propylene.
Summary of the invention
The object of the invention is to: provide a kind of method that can effectively control water content of propylene product in coal-based methanol propylene production process, so that resulting propylene product reaches the standard of polymerization-grade propylene.
A method of controlling water content of propylene product in coal-based methanol propylene production process, the method comprises:
-adjust the oxide compound extraction tower charging water yield, the liquid level of extraction tower is controlled at-15%-15% within the scope of;
-at the top of oxide compound extraction tower or middle part and/or oxide compound extraction tower between drying unit, set up fluid collection device;
The length-to-diameter ratio of molecular sieve bed in-raising moisture eliminator;
-increase moisture eliminator quantity, and make in the parallel connection and serial connection mode of combining, to connect between each moisture eliminator.
Further describe the method for control water content of propylene product in coal-based methanol propylene production process provided by the present invention below.
The method of control propylene product water-content provided by the present invention mainly comprises the technical measures of above-mentioned several respects.Under the acting in conjunction of above-mentioned measure, resulting propylene product can meet polymerization-grade propylene for the requirement of water-content.But it will be understood by those skilled in the art that between above-mentioned measures and there is no sequencing.
In the method for control propylene product water-content provided by the present invention, need be according to the content of the water in oxide compound extraction tower outlet material, methyl alcohol, dme, adjust the oxide compound extraction tower charging water yield, the liquid level of extraction tower is controlled at-15%-15% within the scope of; Preferably, within the scope of be controlled at-10%-10% of liquid level; Further preferably, within the scope of be controlled at-5%-5% of liquid level.Concrete control method is identical with this area ordinary method, for example, according to the material analyzing data of oxide compound extraction tower import and export, adjusts the Shui Ting circle position of oxide compound extraction tower, adjusts the amount (for example, design washing water yield 12t/h) of charging washing water simultaneously.When oxide content is lower in material, suitably increase material input; When if oxide content is higher in material, suitably reduce material input; Material input scope control is within the scope of the 43.50%-72.12% of tower capacity.
In the present invention, preferably, the liquid level of oxide compound extraction tower is controlled and realized by setting up long-range interfacial meter and liquidometer.Meanwhile, interfacial meter is carried out to adjustment, to reach the middle control control effect consistent with on-site operational data.By adjusting oxide compound extraction tower interface, take into account level gauge journey scope, and adjust liquid level and control height, reduce the water-content that tower top outlet is carried secretly.
In the method for control propylene product water-content provided by the present invention, need between moisture eliminator, set up fluid collection device at oxide compound extraction tower and/or oxide compound extraction tower, as coalescer or/and water knockout, make the liquid hydrocarbon in oxide compound extraction tower, through coalescer and water knockout, isolate a large amount of free-waters, to guarantee the stable operation of downstream unit.
Described fluid collection device can be arranged on top or the middle part of oxide compound extraction tower, also can be arranged on the downstream of oxide compound extraction tower, also can arrange at the top of oxide compound extraction tower and the downstream of oxide compound extraction tower simultaneously.In concrete technology transformation process, can be according to the feature of separated product, selecting increases water coalescer or water knockout, or increases by two kinds of fluid collection devices simultaneously.According to the preferred embodiment of the invention, coalescer can be arranged on the tower top of oxide compound extraction tower, and water knockout can be arranged on oxide compound extraction tower and be exported between downstream unit.
In the method for the invention, described coalescer can be selected any one in the coalescer that is suitable for liquid-liquid separation, adopts Coalescence filter core, removes solid impurity, and minimum water droplets coalescence is become to the larger globule.The globule after the overwhelming majority is coalescent can be removed by deadweight separation from oil, is deposited in water leg.
In the method for control propylene product water-content provided by the present invention, need, by improving the length-to-diameter ratio of molecular sieve bed in liquid hydrocarbon moisture eliminator, to improve drying effect.Preferably, in described liquid hydrocarbon moisture eliminator, the length-to-diameter ratio of molecular sieve bed is 1-5, and more preferably 1.2-4, is further preferably 2-3.Can adopt any this area conventional means to improve the length-to-diameter ratio of molecular sieve bed in liquid hydrocarbon moisture eliminator, for example, increase molecular sieve amount of fill or filling porcelain ball etc. and all can.
In the method for control propylene product water-content provided by the present invention, also can increase moisture eliminator quantity, and make in the parallel connection and serial connection mode of combining, to connect between each moisture eliminator.Generally, the design regeneration period of liquid hydrocarbon moisture eliminator and hydrocarbon gas moisture eliminator is 48 hours.For, by water saturated moisture eliminator, the recovery time of moisture eliminator needs 41 hours conventionally.Before moisture eliminator regeneration, the material returned of moisture eliminator and displacement also need 6-8 hour; After having regenerated, moisture eliminator is carried out to filling also needs 5-8 hour.Therefore, for fear of propylene product water-content, exceed standard, the moisture eliminator that sufficient amount is set is very important.In order to reach better drying effect, need guarantee the residence time sufficiently long of hydrocarbon product in adsorbent of molecular sieve.Therefore,, increasing under the prerequisite of moisture eliminator quantity, make in the parallel connection and serial connection mode of combining, to connect between each moisture eliminator.Like this, both can guarantee that drying process and regenerative process are successfully switched carries out, and also can make hydrocarbon material in moisture eliminator, have enough residence time.Those skilled in the art can be according to concrete technology requirement, by the required moisture eliminator quantity of common process calculative determination and concrete set-up mode thereof.For example, four moisture eliminators can be set, the moisture eliminator of every two series connection is one group, and two groups of moisture eliminators are connected in parallel, to facilitate blocked operation.
According to the preferred embodiment of the present invention, go back capable of regulating from the position of the liquid hydrocarbon moisture eliminator of four sections of outlet separating tank bottoms of compressor.Owing to containing C in liquid hydrocarbon out at the bottom of four sections of outlet separating tank tanks of hydrocarbon compressor
6the heavy hydrocarbon of above component, and heavy hydrocarbon can cause molecular sieve water-retaining capacity to decline rapidly.Preferably, according to existing equipment, arrange and pipe arrangement trend, adjust liquid hydrocarbon moisture eliminator position, thereby the soaking effect of molecular sieve can be brought into play well, also can extend the activity cycle of moisture eliminator simultaneously.Concrete adjustment mode is as follows: the liquid hydrocarbon moisture eliminator in four sections of outlet separating tank downstreams of compressor is adjusted on the gas-phase feed line that depropanizing tower overhead condenser removes deethanizing column.
By the method for control water content of propylene product in coal-based methanol propylene production process provided by the present invention, effectively solved the problem that in propylene product, water-content exceeds standard.The water-content of resulting propylene product, below 5ppm, can meet the standard of polymerization-grade propylene.In addition, process modification provided by the present invention is easy to implement, and plant modification cost is low.
Accompanying drawing explanation
Fig. 1 is the principle flow chart of MTP technological process involved in the present invention;
Fig. 2 is the schematic flow sheet of the oxide compound extraction tower of one of preferred embodiment for the present invention;
Fig. 3 is the schematic flow sheet of the drying unit of one of preferred embodiment for the present invention.
Embodiment
Below in conjunction with accompanying drawing, further describe method provided by the present invention, but the present invention is not therefore subject to any restriction.
As shown in Figure 1, enter quenching system carry out coolingly from the gas product of MTP reactor through heat recovery system, cooled gas product enters compression separating unit, isolates hydrocarbon gas (C
4following component) and liquid hydrocarbon (C
4and C
4above component).Hydrocarbon gas enters depropanizing tower after drying, makes C
3and C
3following component and C
4and C
4above component and being separated as the methyl alcohol of sorbent material, dme etc.Hydrocarbon gas (the C at depropanizing tower top
3and C
3following component) after being dried, drying unit of the present invention enters deethanizing column.In deethanizing column, separation of C
2and C
3component.Resulting C
3component is sent into C
3component knockout tower, to realize the separated of propylene and propane.And the isolated liquid hydrocarbon (C of compression separating unit
4and C
4above component), after superoxide extraction tower, enter follow-up debutanizing tower and process.
By the above-mentioned description for improved MTP technical process, can find out, the logistics that enters drying unit of the present invention is C
4following lighter hydrocarbons.Therefore, the soaking effect of molecular sieve can be brought into play well, to guarantee entering C at the bottom of deethanizing column
3the C of component knockout tower
3component water content does not exceed standard, thereby obtains qualified polymerization-grade propylene product completely.
As shown in Figure 2, be provided with fluid collection device 2 in primary oxide extraction tower 1, for example, can adopt the coalescer of stainless steel, its effect is the foam of removing in material, and minimum water droplets coalescence is become to the larger globule.Most coalescent globules are separated by self gravitation effect, are deposited in water leg.In the present invention, oxide compound extraction tower is transformed, below primary liquid collection device 2, set up second layer fluid collection device 2 '.In addition,, as the preferred embodiment of the present invention, in the downstream section of oxide compound extraction tower 1, set up the 3rd fluid collection device 3; Further preferably, described the 3rd fluid collection device 3 is water knockout.
As shown in Figure 3, former drying unit comprises the first moisture eliminator 4 and the second moisture eliminator 5 being connected in parallel.The present invention, on the basis of former drying unit, sets up the 3rd moisture eliminator 6, and changes the mode of connection between moisture eliminator, and these three moisture eliminators are connected between two, in parallel with the 3rd, two open one standby.For example, the first moisture eliminator 4 is connected with the 3rd newly-increased moisture eliminator 6, to improve drying efficiency; When the first moisture eliminator 4 need to be regenerated, switch valve, makes the second moisture eliminator 5 connect with the 3rd newly-increased moisture eliminator 6, and to the first moisture eliminator 4 roasting regenerations.The set-up mode of drying unit of the present invention is not limited to form shown in Fig. 3.Fig. 3 is only for illustrating drying unit of the present invention.Drying unit of the present invention is arranged at depropanizing tower overhead condenser to the gas-phase feed pipeline of deethanizing column.
Below by embodiment and comparative example, further set forth the present invention, but the present invention is not therefore subject to any restriction.
Embodiment 1-4
According to oxide compound extraction tower outlet oxide compound index, adjust the oxide compound extraction tower charging water yield, and as shown in table 1, the liquid level of control extraction tower.Dme content 0.248wt% in the liquid phase of oxide compound extraction tower, methanol content 0.005wt%; Dme content 0.312wt% in gas phase, methanol content 0.009wt%.Now, controlling material input is 63.80% of tower capacity.As shown in table 1, adjust oxide compound extraction tower interface and take into account level gauge journey scope, and adjust liquid level and control height, the water-content of carrying secretly to reduce tower top outlet.Karl Fischer instrument (model DL-31, U.S. plum Teller-Tuo benefit group) is installed in oxide compound extraction tower entrance and the outlet of oxide compound extraction tower, to record trace water contained in hydrocarbon product.
Table 1
Embodiment 5-9
Transformation to oxide compound extraction tower, increases fluid collection device, as coalescer or/and water knockout.Concrete technology transformation situation refers to table 2.Wherein, the coalescer adopting is Beijing million Hua Xianquan technological development company limiteds, and model is BZTC-JJX-150 * 1500.The manufacturer of water knockout is Beijing million Hua Xianquan technological development company limiteds, 2400mm, capacity 34m
3.
Table 2
Embodiment 10
After the outlet of oxide compound extraction tower and before moisture eliminator, in workshop section, set up water knockout.
Table 3
Embodiment 11-12
In employing change moisture eliminator, the means such as mode of connection and adjustment liquid hydrocarbon moisture eliminator position between the type of feed of molecular sieve, increase moisture eliminator quantity, change moisture eliminator, transform drying unit.
drying unit before transformation:
Former liquid hydrocarbon moisture eliminator bottom is provided with grid, and molecular sieve starts from grid top to load;
The length-to-diameter ratio of molecular sieve bed: 1.1;
Moisture eliminator quantity and mode of connection: two moisture eliminators, take to be connected in parallel, one open one standby;
Liquid hydrocarbon moisture eliminator position: be positioned at oxide compound extraction tower tower top liquid-phase outlet next unit.
improved drying unit:
The grid of former liquid hydrocarbon moisture eliminator bottom is cancelled, from start first to load certain porcelain ball (Pingxiang Jiangxi city yellow hat worn by a Taoist priest Chemical Co., Ltd.) a little more than undercutting line in bottom, then directly load molecular sieve (Daxing, production firm Pingxiang Jiangxi city chemical filler company limited, model 3A molecular sieve), to increase the loading height of molecular sieve, bed length-to-diameter ratio increases;
The length-to-diameter ratio of molecular sieve bed: 1.8;
Moisture eliminator quantity and mode of connection: three moisture eliminators, series connection, and in parallel with the 3rd moisture eliminator between two, two open one standby;
Liquid hydrocarbon moisture eliminator position: depropanizing tower overhead condenser goes on the gas-phase feed line of deethanizing column.
Table 4
Embodiment 13
In solution process of preparing propylene from coal-based methanol provided by the present invention, the exceed standard method of problem of water-content in propylene product, is mutually according to the Measures of technical that connect and progressively strengthen, to consist of a series of.The disappearance of any a part of technical reform scheme, will exert an influence to downstream process product water content's index.In order further to embody the beneficial effect of method provided by the present invention, related embodiment is summarized in to table 5.
Table 5
Claims (10)
1. a method of controlling water content of propylene product in coal-based methanol propylene production process, is characterized in that, the method comprises:
-adjust the oxide compound extraction tower charging water yield, the liquid level of extraction tower is controlled at-15%-15% within the scope of;
-at the top of oxide compound extraction tower or middle part and/or oxide compound extraction tower between drying unit, set up fluid collection device;
The length-to-diameter ratio of molecular sieve bed in-raising moisture eliminator; With
-increase moisture eliminator quantity, and make in the parallel connection and serial connection mode of combining, to connect between each moisture eliminator.
2. method according to claim 1, is characterized in that, within the scope of be controlled at-10%-10% of the liquid level of described extraction tower.
3. method according to claim 2, is characterized in that, within the scope of be controlled at-5%-5% of the liquid level of described extraction tower.
4. method according to claim 1, is characterized in that, by setting up long-range interfacial meter and liquidometer, realizes the control to described extraction tower liquid level.
5. method according to claim 1, is characterized in that, described fluid collection device is coalescer or water knockout.
6. method according to claim 5, is characterized in that, at the tower top of oxide compound extraction tower, coalescer is set, and is exported to water knockout is set between drying unit at oxide compound extraction tower.
7. method according to claim 1, is characterized in that, in described moisture eliminator, the length-to-diameter ratio of molecular sieve bed is 1-5.
8. method according to claim 7, is characterized in that, in described moisture eliminator, the length-to-diameter ratio of molecular sieve bed is 1.2-4.
9. method according to claim 8, is characterized in that, in described moisture eliminator, the length-to-diameter ratio of molecular sieve bed is 2-3.
10. method according to claim 9, is characterized in that, described drying unit is arranged at depropanizing tower overhead condenser to the gas-phase feed pipeline of deethanizing column.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0448000B1 (en) * | 1990-03-23 | 1994-05-25 | Süd-Chemie Ag | Process for preparing lower olefins |
| CN101080373A (en) * | 2004-11-02 | 2007-11-28 | 卢吉股份公司 | Method and device for producing lower olefins from oxygenates |
| CN101381270A (en) * | 2008-10-15 | 2009-03-11 | 上海惠生化工工程有限公司 | Separation method of MTO/MTP reaction mixture |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0322648D0 (en) * | 2003-09-26 | 2003-10-29 | Statoil Asa | Process |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0448000B1 (en) * | 1990-03-23 | 1994-05-25 | Süd-Chemie Ag | Process for preparing lower olefins |
| CN101080373A (en) * | 2004-11-02 | 2007-11-28 | 卢吉股份公司 | Method and device for producing lower olefins from oxygenates |
| CN101381270A (en) * | 2008-10-15 | 2009-03-11 | 上海惠生化工工程有限公司 | Separation method of MTO/MTP reaction mixture |
Non-Patent Citations (2)
| Title |
|---|
| MTO/MTP技术的研发现状及应用前景;陈腊山;《化肥设计》;20080229;第46卷(第1期);第3-6页 * |
| 陈腊山.MTO/MTP技术的研发现状及应用前景.《化肥设计》.2008,第46卷(第1期),第3-6页. |
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