CN102344331A - 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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- CN102344331A CN102344331A CN2011101836271A CN201110183627A CN102344331A CN 102344331 A CN102344331 A CN 102344331A CN 2011101836271 A CN2011101836271 A CN 2011101836271A CN 201110183627 A CN201110183627 A CN 201110183627A CN 102344331 A CN102344331 A CN 102344331A
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- extraction tower
- moisture eliminator
- propylene
- oxide compound
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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 coal-based methanol system of the present invention relates to propylene technology more particularly, is a kind of method of controlling propylene product water-content in the coal-based methanol system propylene technology, makes resulting propylene product reach the standard of polymerization-grade propylene.
Background technology
The propylene of one of low-carbon alkene is a basic Organic Chemicals important in the chemical industry, and the source of propylene mainly relies on the naphtha cracking technology both at home and abroad for a long time.Over past 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 the propylene industrial expansion largely.So it is the novel method of raw material production propylene that researchers more both domestic and external strive to find with the non-oil resource.Along with reaching its maturity of methanol device suitability for industrialized production technology, the production route of producing propylene with coal or natural gas source generation methyl alcohol again more and more receives people's attention.
As 500,000 tons of/year coal-based propylene units of the first cover in the world, the industrial applications of MTP Technology is to attempt first.The device startup procedure does not have similar experience to use for reference, and propylene product each item index is except water-content exceeds standard device during driving, and other index all reaches even is better than the requirement of polymerization-grade propylene product specification.But water-content exceeds standard and causes MTP device propylene product can't directly be used for polypropylene plant in the product.
The problem that exceeds standard for water-content in the propylene product; Analysis mainly contains following reason at 2: (1) is because oxide compound extraction tower liquid level control difficulty; The outlet water-content exceeds standard, and the liquid hydrocarbon component that has a large amount of free-waters gets into moisture eliminator, makes the saturated inefficacy of molecular sieve adsorption in the moisture eliminator soon.The liquid hydrocarbon that water-content exceeds standard gets into debutanizing tower, at debutylize cat head, gas phase C
4Following component is carried the water that exceeds standard secretly and is got into depropanizing tower again.Containing the depropanizing cat head gas phase C of excessive water
3Following component gets into deethanizing column, and excessive water continues to remain in C at the bottom of the deethanizing column
3Get into propylene tower in the liquid phase, cause that water-content exceeds standard in the propylene product.(2) by behind the liquid hydrocarbon product entering liquid hydrocarbon moisture eliminator that comes out at the bottom of four sections outlet separating tanks of hydrocarbon compressor jar, contain C
6The heavy hydrocarbon that component is above, because the existence of heavy hydrocarbon causes the molecular sieve water-retaining capacity to descend rapidly, and the restriction owing to regeneration temperature is difficult for regeneration fully behind the molecular sieve surface adsorption heavy hydrocarbon, influences soaking effect.
In order to address the above problem, need transform the relevant technical process of coal-based methanol system propylene, so that the water-content of resulting propylene product can meet the standard of polymerization-grade propylene.
Summary of the invention
The objective of the invention is to: a kind of method that can effectively control propylene product water-content in the coal-based methanol system propylene technology is provided, so that resulting propylene product reaches the standard of polymerization-grade propylene.
A kind of method of controlling propylene product water-content in the coal-based methanol system propylene technology, this method comprises:
-adjustment oxide compound extraction tower charging the water yield, the liquid level of extraction tower is controlled at-the 15%-15% scope in;
-at the top of oxide compound extraction tower or middle part and/or oxide compound extraction tower set up fluid collection device between the drying unit;
The length-to-diameter ratio of molecular sieve bed in the-raising moisture eliminator;
-increase moisture eliminator quantity, and make between each moisture eliminator and connect with the parallel connection and serial connection mode of combining.
The method of propylene product water-content in the following further explain control provided by the present invention coal-based methanol system propylene technology.
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 satisfy the requirement of polymerization-grade propylene for water-content.But it will be understood by those skilled in the art that between the above-mentioned measures and do not have sequencing.
In the method for control propylene product water-content provided by the present invention, need content according to the water in the oxide compound extraction tower outlet material, methyl alcohol, dme, the adjustment oxide compound extraction tower charging water yield, the liquid level of extraction tower is controlled at-the 15%-15% scope in; Preferably, liquid level be controlled at-the 10%-10% scope in; Further preferably, liquid level be controlled at-the 5%-5% scope in.Concrete control method is identical with this area ordinary method, for example, according to the material analyzing data that the oxide compound extraction tower is imported and exported, adjusts the water hydrocarbon 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 in the material is low, suitably increase the material input; When if oxide content is higher in the material, suitably reduce the material input; Material input scope is controlled in the 43.50%-72.12% scope of tower capacity.
In the present invention, preferably, the liquid level of oxide compound extraction tower is controlled through setting up the realization of long-range interfacial meter and liquidometer.Simultaneously, interfacial meter is carried out adjustment, with the control control effect consistent in reaching with on-site operational data.Take into account level gauge journey scope through adjustment oxide compound extraction tower interface, and adjustment liquid level control height, the water-content that tower top outlet is carried secretly reduced.
In the method for control propylene product water-content provided by the present invention; Need between oxide compound extraction tower and/or oxide compound extraction tower to moisture eliminator, to set up fluid collection device; Like coalescer or/and water knockout; Make liquid hydrocarbon in the oxide compound extraction tower; Isolate a large amount of free-waters through coalescer and water knockout, to guarantee the stable operation of downstream unit.
Described fluid collection device can be arranged on the top or the middle part of oxide compound extraction tower, also can be arranged on the downstream of oxide compound extraction tower, also can be provided with simultaneously at the top of oxide compound extraction tower and the downstream of oxide compound extraction tower.In concrete technological transformation process, can be according to the characteristics of isolating 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 cat head of oxide compound extraction tower, and water knockout can be arranged on the oxide compound extraction tower and be exported between the downstream unit.
In the method for the invention, said coalescer can be selected any one in the coalescer that is suitable for liquid-liquid separation for use, adopts the coalescence filter core, removes solid impurity, and minimum water droplets coalescence is become the bigger globule.The globule after the overwhelming majority coalescence can lean on deadweight from oil, to separate and remove, be deposited in the water leg.
In the method for control propylene product water-content provided by the present invention, need to improve drying effect through improving the length-to-diameter ratio of molecular sieve bed in the liquid hydrocarbon moisture eliminator.Preferably, the length-to-diameter ratio of molecular sieve bed is 1-5 in the said liquid hydrocarbon moisture eliminator, further is preferably 1.2-4, further is preferably 2-3.Can adopt any this area conventional means to improve the length-to-diameter ratio of molecular sieve bed in the 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 between each moisture eliminator and connect with the parallel connection and serial connection mode of combining.Generally, the design regeneration period of liquid hydrocarbon moisture eliminator and hydrocarbon gas moisture eliminator is 48 hours.By water saturated moisture eliminator, the recovery time of moisture eliminator needs 41 hours usually for.Before moisture eliminator regeneration, the material returned of moisture eliminator also needs 6-8 hour with displacement; After regeneration was accomplished, moisture eliminator is carried out filling also needed 5-8 hour.Therefore, exceed standard for fear of the propylene product water-content, 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, under the prerequisite that increases moisture eliminator quantity, make between each moisture eliminator to connect with the parallel connection and serial connection mode of combining.Like this, both can guarantee that drying process and regenerative process are successfully switched carries out, and also can make hydrocarbon material that enough residence time are arranged in moisture eliminator.Those skilled in the art can calculate definite required moisture eliminator quantity and concrete set-up mode thereof through common process according to concrete processing requirement.For example, four moisture eliminators can be set, per two placed in-line moisture eliminators are one group, and two groups of moisture eliminators are connected in parallel, to make things convenient for blocked operation.
According to the preferred embodiment of the present invention, also can adjust position from the liquid hydrocarbon moisture eliminator of four sections outlet separating tank bottoms of compressor.Owing to contain C in the liquid hydrocarbon that comes out at the bottom of four sections outlet separating tanks of hydrocarbon compressor jar
6The heavy hydrocarbon of above component, and heavy hydrocarbon can cause the molecular sieve water-retaining capacity to descend rapidly.Preferably, arrange and the pipe arrangement trend according to existing equipment, adjustment liquid hydrocarbon moisture eliminator position, thus the soaking effect of molecular sieve can be brought into play well, also can prolong the activity cycle of moisture eliminator simultaneously.Concrete adjustment mode is following: the liquid hydrocarbon moisture eliminator in four sections outlet separating tanks of compressor downstream is adjusted on the gas-phase feed line that the depropanizing tower overhead condenser removes deethanizing column.
Method through propylene product water-content in the control coal-based methanol system propylene technology provided by the present invention has solved the problem that water-content exceeds standard in the propylene product effectively.The water-content of resulting propylene product can satisfy the standard of polymerization-grade propylene below 5ppm.In addition, process modification provided by the present invention is easy to implement, and the plant modification cost is low.
Description of drawings
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 explain method provided by the present invention, but therefore the present invention does not receive any restriction.
As shown in Figure 1, get into quenching system from the product gas of MTP reactor through heat recovery system and cool off, cooled product gas gets into the compression separating unit, isolates hydrocarbon gas (C
4Following component) and liquid hydrocarbon (C
4And C
4Above component).Hydrocarbon gas gets into depropanizing tower after drying, make C
3And C
3Following component and C
4And C
4Above component and be separated as the methyl alcohol of sorbent material, dme etc.Hydrocarbon gas (the C at depropanizing tower top
3And C
3Following component), drying unit according to the invention gets into deethanizing column after carrying out drying.In deethanizing column, separation of C
2And C
3Component.Resulting C
3Component is sent into C
3The component knockout tower is to realize separating of propylene and propane.And the isolated liquid hydrocarbon (C of compression separating unit
4And C
4Above component), behind the superoxide extraction tower, get into follow-up debutanizing tower and handle.
Can find out that through above-mentioned description the logistics that gets into drying unit according to the invention is C for improved MTP technical process
4Following lighter hydrocarbons.Therefore, the soaking effect of molecular sieve can be brought into play well, to guarantee at the bottom of deethanizing column, getting into C
3The C of component knockout tower
3The component water content does not exceed standard, thereby obtains qualified polymerization-grade propylene product fully.
As shown in Figure 2, be provided with fluid collection device 2 in the primary oxide extraction tower 1, for example, can adopt the coalescer of stainless steel, its effect is the foam of removing in the material, and minimum water droplets coalescence is become the bigger globule.The globule of most coalescences leans on the self gravitation effect to separate, and is deposited in the water leg.In the present invention, the 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, set up the 3rd fluid collection device 3 in the downstream section of oxide compound extraction tower 1; Further preferably, said the 3rd fluid collection device 3 is a water knockout.
As shown in Figure 3, former drying unit comprises first moisture eliminator 4 and second moisture eliminator 5 that is connected in parallel.The present invention sets up the 3rd moisture eliminator 6 on the basis of former drying unit, and changes the mode of connection between the moisture eliminator, makes these three moisture eliminators connect in twos, and is parallelly connected with the 3rd, and two open one is equipped with.For example, first moisture eliminator 4 is connected with the 3rd newly-increased moisture eliminator 6, to improve drying efficiency; When first moisture eliminator 4 needed regeneration, switch valve made second moisture eliminator 5 connect with the 3rd newly-increased moisture eliminator 6, and to 4 roasting regenerations of first moisture eliminator.The set-up mode of drying unit according to the invention is not limited to form shown in Figure 3.Fig. 3 only is used to illustrate drying unit according to the invention.Drying unit according to the invention is arranged on the gas-phase feed pipeline of depropanizing tower overhead condenser to deethanizing column.
Further set forth the present invention through embodiment and Comparative Examples below, but therefore the present invention does not receive any restriction.
Embodiment 1-4
According to oxide compound extraction tower outlet oxide compound index, the adjustment 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 the gas phase, methanol content 0.009wt%.At this moment, control material input is 63.80% of a tower capacity.As shown in table 1, level gauge journey scope is taken into account at adjustment oxide compound extraction tower interface, and adjustment liquid level control height, to reduce the water-content that tower top outlet is carried secretly.Karl Fischer appearance (model DL-31, U.S.'s plum Teller-Tuo benefit group) is installed in oxide compound extraction tower inlet and the outlet of oxide compound extraction tower, to record trace water contained in the hydrocarbon product.
Table 1
Embodiment 5-9
To the transformation of oxide compound extraction tower, increase fluid collection device, like coalescer or/and water knockout.Concrete technological transformation situation sees table 2 for details.Wherein, the coalescer that is adopted 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
Before oxide compound extraction tower outlet back and moisture eliminator, set up water knockout in the workshop section.
Table 3
Embodiment 11-12
Adopt to change molecular sieve in the moisture eliminator type of feed, increase moisture eliminator quantity, change means such as mode of connection and adjustment liquid hydrocarbon moisture eliminator position between the moisture eliminator, drying unit is transformed.
Drying unit before transforming:
Former liquid hydrocarbon moisture eliminator bottom is provided with grid, and molecular sieve begins 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 opens one is equipped with;
Liquid hydrocarbon moisture eliminator position: be positioned at oxide compound extraction tower cat head liquid phase outlet next unit.
Improved drying unit:
Grid cancellation with former liquid hydrocarbon moisture eliminator bottom; From begin to load certain porcelain ball (Jiangxi Pingxiang Huangguan Chemical Industry Co., Ltd.) earlier in the bottom a little more than the undercutting line; Directly load molecular sieve (Jiangxi Pingxiang City Daxing chemical filler company limited of production firm then; Model 3A molecular sieve); To increase the loading height of molecular sieve, the 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 in twos, and parallelly connected with the 3rd moisture eliminator, two open one is equipped with;
Liquid hydrocarbon moisture eliminator position: the depropanizing tower overhead condenser goes on the gas-phase feed line of deethanizing column.
Table 4
Embodiment 13
The exceed standard method of problem of water-content in the propylene product is to be made up of according to the Measures of technical that connect and progressively strengthen each other a series of in the solution coal-based methanol system propylene technology provided by the present invention.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 table 5.
Table 5
Claims (10)
1. method of controlling propylene product water-content in the coal-based methanol system propylene technology is characterized in that this method comprises:
-adjustment oxide compound extraction tower charging the water yield, the liquid level of extraction tower is controlled at-the 15%-15% scope in;
-at the top of oxide compound extraction tower or middle part and/or oxide compound extraction tower set up fluid collection device between the drying unit;
The length-to-diameter ratio of molecular sieve bed in the-raising moisture eliminator;
-increase moisture eliminator quantity, and make between each moisture eliminator and connect with the parallel connection and serial connection mode of combining.
2. method according to claim 1 is characterized in that, the liquid level of said extraction tower is controlled at-the 10%-10% scope in.
3. method according to claim 2 is characterized in that, the liquid level of said extraction tower is controlled at-the 5%-5% scope in.
4. method according to claim 1 is characterized in that, realizes the control to said extraction tower liquid level through setting up long-range interfacial meter and liquidometer.
5. method according to claim 1 is characterized in that, said fluid collection device is coalescer or water knockout.
6. method according to claim 5 is characterized in that, at the cat head of oxide compound extraction tower coalescer is set, and is exported at the oxide compound extraction tower water knockout is set between the drying unit.
7. method according to claim 1 is characterized in that, the length-to-diameter ratio of molecular sieve bed is 1-5 in the said moisture eliminator.
8. method according to claim 7 is characterized in that, the length-to-diameter ratio of molecular sieve bed is 1.2-4 in the said moisture eliminator.
9. method according to claim 8 is characterized in that, the length-to-diameter ratio of molecular sieve bed is 2-3 in the said moisture eliminator.
10. method according to claim 9 is characterized in that, said drying unit is arranged on the gas-phase feed pipeline of depropanizing tower overhead condenser to deethanizing column.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105503497A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Method for removal of water from oxygen-containing compound to propylene reaction product |
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| WO2005030811A1 (en) * | 2003-09-26 | 2005-04-07 | Statoil Asa | Process |
| CN101080373A (en) * | 2004-11-02 | 2007-11-28 | 卢吉股份公司 | Method and device for producing lower olefins from oxygenates |
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2011
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0448000B1 (en) * | 1990-03-23 | 1994-05-25 | Süd-Chemie Ag | Process for preparing lower olefins |
| WO2005030811A1 (en) * | 2003-09-26 | 2005-04-07 | Statoil Asa | Process |
| CN101080373A (en) * | 2004-11-02 | 2007-11-28 | 卢吉股份公司 | Method and device for producing lower olefins from oxygenates |
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Non-Patent Citations (1)
| Title |
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| CN105503497A (en) * | 2014-09-25 | 2016-04-20 | 中国石油化工股份有限公司 | Method for removal of water from oxygen-containing compound to propylene reaction product |
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