CN105777473B - A kind of online washing methods of the water system of methanol-to-olefins device - Google Patents
A kind of online washing methods of the water system of methanol-to-olefins device Download PDFInfo
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- CN105777473B CN105777473B CN201410817891.XA CN201410817891A CN105777473B CN 105777473 B CN105777473 B CN 105777473B CN 201410817891 A CN201410817891 A CN 201410817891A CN 105777473 B CN105777473 B CN 105777473B
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Abstract
The invention discloses a kind of novel methanol-to-olefins (MTO) to produce the washing methods in reaction process to water scrubber.This method uses several organic solvents, is cleaned in two stages to water scrubber, mainly solves in MTO device operational process, the blockage problem that water scrubber is susceptible to.It can be carried out in the case of not parking, while detergent can recycle, and of low cost, be very suitable for the heavy oil by-product that washing MTO reactions generate.This method can be adapted for the sample that heavy oil component is multi-methyl benzene, multi-methylnaphthalene and condensed-nuclei aromatics and wash, operating temperature range is wide, it is easy to operate, have no need to change existing DMTO water scrubbers workflow, washing effect is apparent, the pressure difference that water scrubber can significantly be lowered makes the differential pressure of water wash system maintain device and goes into operation the state at initial stage, ensures DMTO reaction unit trouble-free operations.
Description
Technical field
The present invention relates to coal chemical technologies, are specially washed online for one kind of methanol-to-olefins device water wash system is novel
Wash method.
Background technology
Methanol-to-olefins are the technologies that raw materials for ethylene production and propylene are done with coal or substitute gas oil.Methanol-to-olefins
Device is mainly made of following three parts:Reaction system, residual neat recovering system and water system.Water system is mainly followed including chilling
Loop system, water washing cycles system, stripping system and separation of olefins unit.In device operational process, by reaction system in
Between product through chilling tower, water scrubber removing heat, washing catalyst and by big portion's water condensation after separate, detach water after substance
Downstream olefin separator is sent into for separation and purification.In the reacted water stripper recycling of water that chilling tower and water scrubber condense out
Outer row after the organic oxygen-containing compounds such as a small amount of methanol, dimethyl ether, the methanol of recycling, dimethyl ether are with feeding into reaction system freshening.
It during the long-term operation of methanol-to-olefins device, needs to be cleaned in turn(a)round, the inspection of general device
The period is repaiied to differ in 1~3 year.But in the actual production process, a small amount of oily substance is condensed and is accumulated in water system, this
A little oily substances form greasy filth and wax in water with catalyst, make the equipment such as tower tray, heat exchanger, the air cooler in water system
It blocks speed to be exceedingly fast, flux is caused to reduce, efficiency reduces, and plant energy consumption increases considerably.
To solve the above problems, Shenhua Group Co provides a kind of methanol-to-olefins device water wash system
Online washing methods (CN 10265949A).The concrete measure of this method is in the case where ensureing that device is not parking to water scrubber
Interior injection dimethylbenzene etc. extractants are to extract greasy filth in water scrubber in medium and wax and it forms flowable liquid object
Matter and discharge system.Described in Shenhua Group Co, this method can be good in its Normal production practices
Processing is mixed in greasy filth and wax in medium, due to effectively improve the accumulation attachment because of greasy filth and wax in water system
Caused blocking.It oils the largely accumulation and of mud and wax however, especially washing tower tray floor in the water scrubber
When causing more serious blocking, the effect of this washing methods is unsatisfactory.The methanol system of Ningbo Fu De limited energies company
Olefin hydrocarbon apparatus is gone into operation on January 28th, 2013, occurs the decline of washing water heat-exchange system efficiency by the end of June, and heat exchanger blocks;Go out by the end of June
Existing washing water heat-exchange system efficiency declines, and heat exchanger blocks;Chilled water (chw), washing water- to-water heat exchanger, air-cooled frequent clean;Water at the beginning of 7 months
Wash the slow liter of tower pressure drop;August is quite serious, September shut-down (breakdown) mainteance water scrubber.Water scrubber at the beginning of 10 months blocks again after returning to work
Phenomenon, using Shenhua Group Co provide methanol-to-olefins device water system system after line washing methods not yet
See apparent effect.
From the above, it is seen that the methanol-to-olefins device water system system that Shenhua Group Co provides exists
Line washing methods is really effective for the device of Shenhua Group Co itself.But other companies are blocked up
Filling in more serious methanol-to-olefins device water wash system, but washing effect is little.Meanwhile it is public according to Shenhua Group Limited Liability
Described in the provided patent specification example of department, the extractant that this method uses needs basis for petroleum chemicals such as dimethylbenzene
Detergent is injected into water scrubber by different blocking positions from different inlets.With the method to Shenhua Group Limited Liability
The total amount that the methanol-to-olefins device water wash system of company oneself completes detergent needed for once washing is 30t or so, it is assumed that its
Using the relatively cheap dimethylbenzene of market at prices, and according to 7,000,000 yuan of calculating of price per ton, then washed using the method, only
One expenditure that will be paid more than 200,000 yuan of detergent raw material, this obviously greatly increases production cost.Therefore, we are urgently
It need to find that a kind of new washability is stronger, it is existing to solve to have universality and easy to operate, lower-cost cleaning method
There is defect present in technology.
Invention content
The present invention is intended to provide a kind of online washing methods of better methanol-to-olefins device water wash system.It is existing to make up
Have method detersive efficiency it is low, do not have universality, it is complicated for operation, washing the higher deficiency of cost.
The present invention is to be injected in two stages by difference into the water system in methanol-to-olefins device operational process
The detergent of density organic solvent composition, makes the detergent in first stage density more than water and with the washing in water scrubber
Water recycles the heavy oil to dissolve in washing water and be attached in water scrubber internal structure together.Wait for that water scrubber pressure difference reaches methanol system
Enter second stage after olefin hydrocarbon apparatus technological requirement, i.e., adjusts the close of detergent in water scrubber by injecting another organic solvent
Degree to less than water and convenient for using oil partition tank detergent being isolated water wash system.
The detergent of the first stage is halogenated aryl hydrocarbon or halogenated alkane.Injection rate is the washing water inventory
0.5%~3%.
The detergent of the second stage be single phenyl ring aromatic hydrocarbons (benzene, toluene or dimethylbenzene) and middle long-chain olefin (hexane,
Heptane or octane) and diesel oil (2), injection rate is 0%~100% of detergent quality used in the first stage, and proportioning is by washing
The different phase washed is adjusted.If after the first stage washs, heavy oil and detergent density, which are less than water, can not implement the
Two-stage needs that density is decreased to less than water by second stage addition detergent, to pass through oil removal if density is more than water
Slot is separated from water out.
Just section, first stage detergent can be followed voluntarily with medium after injecting the water system by detergent injection pump for cleaning
Ring, without realizing cycle by detergent injection pump always such as known method.
The detergent injection port can be one or more, its object is to introduce detergent into washing system, and
Without as having accurate requirement to inlet in known method.
Detergent after oil partition tank is set near the water level line of bottom of tower to realize washing is detached from washing system.
From washing effect, detergent density used by the first stage of the invention is more than water, on washing tower tray floor
Washing medium lower layer can be sunken to when distribution.It is less than the detergent of water, this method first relative to density used in known method
Detergent used by stage can preferably with the jam contacts that are attached on tower tray, therefore can be more efficiently dissolving
Tamper reaches better washing effect so as to realize using mutually less detergent.
From washing cost, detergent amount used in the present invention is total much smaller than detergent used in known method
The constituent of amount, the second stage solvent that this method uses is similar to known method, but the first stage that this method uses
The market price of halogenated alkane in solvent will be far below dimethylbenzene, therefore the average unit price of the detergent of this method use wants small
In the average unit price of the used detergent of known method.Detergent used by this method can be with Jie in water scrubber simultaneously
For matter automatic circulating without borrowing external force, this undoubtedly saves the energy.
From washing process, the present invention need not change the existing equipment of methanol-to-olefins device water wash system.It is washing
Detergent can be voluntarily distributed in water scrubber during washing, without such as known method according to different blocking positions by detergent
It is injected from different positions.This undoubtedly enormously simplifies washing operation, reduces the risk of error of washing process.
Public affairs of the invention use several organic solvents, are cleaned in two stages to water scrubber, mainly solve MTO devices fortune
During row, blockage problem that water scrubber is susceptible to.It can be carried out in the case of not parking, while detergent can recycle
It utilizes, and of low cost, is very suitable for the heavy oil by-product that washing MTO reactions generate.This method can be adapted for heavy oil component
It is washed for the sample of multi-methyl benzene, multi-methylnaphthalene and condensed-nuclei aromatics, operating temperature range is wide, easy to operate, haves no need to change
Existing DMTO water scrubbers workflow, washing effect is apparent, can significantly lower the pressure difference of water scrubber, make the difference of water wash system
Pressure maintains device and goes into operation the state at initial stage, ensures DMTO reaction unit trouble-free operations.
Relative to existing washing methods, the present invention also has as follows in addition to it can meet or exceed its corresponding cleaning ability
Advantage:
1. cleaning agent agent dosage is less.
2. the cleaning agent cost of unit quantity is lower and cleaning efficiency higher.
3. the clean range of cleaning agent is wider.
4. cleaning agent is more friendly to environment and live operator.
Description of the drawings
The work of water scrubber (18 layers of valve water scrubber structural schematic diagram) is shown in methanol-to-olefins device in Fig. 1 present invention
It is intended to;
Recirculated water can be recycled after being handled by water treatment system.Detergent, which washs after heavy oil density is less than water, to be led to
It crosses oil partition tank and is separated water scrubber.Wherein water inlet can be 2 or multiple.2 are only illustrated in figure.
In figure, it is 1. washing water for water treatment system, 2., is 3. oil partition tank, the washing water that 4. bottom of tower is accumulated, is 5. mass transfer
Rear washing water, be 6. reaction gas after washing, be 7. reaction gas, wherein 6. with 7. between pressure difference should be less than technological parameter
Setting value.Oil partition tank is the attachment of water scrubber, and effect is to the oil removing from water, and structure and working principle is due to supply
The difference of quotient is also not quite similar, and simplest oil partition tank is separated except washing using nature floating method by grease difference in specific gravity
In water can oil slick and the finely divided oil in part.
Specific implementation mode
Fully to compare the washing effect of the present invention and known washing methods, we simulate methanol alkene in the lab
The working condition of water scrubber in hydrocarbon device water wash system is used in combination from Ningbo Fu De limited energies company methanol-to-olefins device and is washed
The tamper taken out in system water scrubber has carried out different degrees of plugging handling to simulation water scrubber.Here is respectively with known
The practical operation result that method and the present invention wash the simulation water scrubber of different chocking-up degrees.
Embodiment 1
It will be uniformly applied on the tower tray of simulation water scrubber after the heating melting of above-mentioned tamper, make whole disk hole portions of tower tray
Divide and blocks (aperture of disk hole reduces because of tamper).When using this simulation water scrubber simulation water-washing process in this case,
Air inlet and the pressure difference of gas outlet rise to 19kPa by the 13.2kPa of normal condition.Being handled using method of the present invention should
Simulate water scrubber.
1, the dichloroethanes of washing water inventory 2% is injected into simulation water scrubber.
2, simulation water scrubber air inlet and the pressure difference of gas outlet were gradually reduced after dichloropropane injection, by 12 minutes or so
Pressure difference is down to normal condition.
3, in the normal backward simulation water scrubber of pressure difference injection washing water inventory 1.5% diesel oil, will be dissolved with by oil partition tank
The cleaning composition of obturator separates simulation water scrubber, lasts 6 minutes.
4, stop simulation water-washing process, observation washing tower tray floor after washing, tamper cleans up completely.
To sum up, the detergent of washing water inventory 3.5% is shared according to the method for the invention, takes 18 minutes
It completes to complete washing to the simulation water scrubber of such chocking-up degree.
Comparative example 1
As the mode in embodiment 1 handles simulation water scrubber, and air inlet and gas outlet when being adjusted to simulation water-washing process
Pressure be 19kPa.The simulation water scrubber is handled using known washing methods.
1, from washing water inlet, into simulation water scrubber, the dimethylbenzene of water inventory 7% is washed in injection.
2, diformazan benzo is constantly extracted out by it again from washing water inlet injection from simulation water scrubber lower part by oil partition tank
Simulate water scrubber.
3, it is recycled in water scrubber with dimethylbenzene, the pressure difference for simulating water scrubber air inlet and gas outlet is gradually reduced, and is passed through
Pressure difference is down to normal condition within 22 minutes or so.
4, the dimethylbenzene dissolved with tamper is extracted out by oil partition tank after pressure difference is normal, lasts 5 minutes.To sum up, according to
Known washing methods shares the detergent of washing water inventory 7%, takes 27 minutes simulation waters that can be completed to such chocking-up degree
It washes tower and completes washing.
Embodiment 2
The tamper being derived from Ningbo Fu De limited energies company methanol-to-olefins device water wash system water scrubber is heated
It is uniformly applied on the tower tray of simulation water scrubber after melting, keeps on tower tray 50% disk hole completely plugged, remaining 50% disk hole
Partial Blocking.When using this simulation water scrubber simulation water-washing process in this case, the pressure difference of air inlet and gas outlet is by just
The 13.2kPa of normal state rises to 32kPa.The simulation water scrubber is handled using method of the present invention.
1, the dichloroethanes of washing water inventory 2.7% is injected into simulation water scrubber.
2, simulation water scrubber air inlet and the pressure difference of gas outlet were gradually reduced after dichloropropane injection, by 33 minutes or so
Pressure difference is down to normal condition.
3, in the normal backward simulation water scrubber of pressure difference injection washing water inventory 2.3% diesel oil, will be dissolved with by oil partition tank
The cleaning composition of obturator separates simulation water scrubber, lasts 7 minutes.
4, stop simulation water-washing process, observation washing tower tray floor after washing, tamper cleans up completely.
To sum up, the detergent of washing water inventory 5% is shared according to the method for the invention, taking 40 minutes can be complete
The simulation water scrubber of pairs of such chocking-up degree completes washing.
Comparative example 2
As the mode in embodiment 2 handles simulation water scrubber, and air inlet and gas outlet when being adjusted to simulation water-washing process
Pressure be 32kPa.The simulation water scrubber is handled using known washing methods.
1, from washing water inlet, into simulation water scrubber, the dimethylbenzene of water inventory 10% is washed in injection.
2, diformazan benzo is constantly extracted out by it again from washing water inlet injection from simulation water scrubber lower part by oil partition tank
Simulate water scrubber.
3, it is recycled in water scrubber with dimethylbenzene, the pressure difference for simulating water scrubber air inlet and gas outlet is gradually reduced, and is passed through
Pressure difference is down to 27kPa within 16 minutes or so.
4, it is continued cycling through in water scrubber with dimethylbenzene, pressure difference changes rate and slows down.Pressure difference is down to after about 2 hours
25kPa, after this pressure difference hardly change over time.
To sum up, it is known that washing methods is limited to the simulation water scrubber cleaning ability of such chocking-up degree.
Claims (12)
1. a kind of online washing methods of the water system of methanol-to-olefins device, in methanol-to-olefins device operational process, to
The detergent being made of different densities organic solvent is injected in the water system in two stages;
First stage washs:The detergent that density is more than water is set to be recycled together with the washing water in water scrubber to dissolve in washing water
And it is attached to the heavy oil in water scrubber internal structure;Wait for that water scrubber pressure difference reaches the pressure difference required by methanol-to-olefins device technique
Enter second stage after range to wash;
Second stage is washed:The detergent for being less than water by injecting another density in the washing water into water scrubber adjusts washing
Dissolved with density to less than the water of the detergent of heavy oil and convenient for detergent is isolated water wash system using oil partition tank in tower.
2. online washing methods according to claim 1, it is characterised in that:
If after the first stage washs, second stage washing can not be implemented less than water dissolved with the detergent density of heavy oil, directly
It connects and detergent is isolated into water wash system using oil partition tank;
If or, after the first stage washs, it is more than water dissolved with the detergent density of heavy oil, then needs to be added by second stage
Detergent density dissolved with heavy oil in water scrubber is decreased to less than water by the detergent that density is less than water, to be washed by oil partition tank
It washs agent to be separated from water out, detergent is isolated into water wash system.
3. online washing methods according to claim 1, it is characterised in that:
The online washing methods of water system to the group deposited in the water wash system of methanol-to-olefins device for being divided into more methyl
One or two or more kinds of heavy oil in benzene, multi-methylnaphthalene and condensed-nuclei aromatics are handled.
4. online washing methods according to claim 1, it is characterised in that:
Wait for that the pressure differential range that water scrubber pressure difference reaches required by methanol-to-olefins device technique refers to:Water scrubber air inlet and outlet
Pressure difference when pressure difference between mouthful reaches the initial launch for the first time of methanol-to-olefins device between water scrubber air inlet and gas outlet.
5. online washing methods according to claim 4, it is characterised in that:
Refer to when the initial launch for the first time in washing water, first when water scrubber internal part and water scrubber internal face are without attachment heavy oil
When alcohol olefin hydrocarbon apparatus is run.
6. online washing methods according to claim 1, it is characterised in that:The detergent of the first stage is halogenated virtue
One or two or more kinds in hydrocarbon or halogenated alkane, injection rate are the 0.5%~3% of the washing water quality;It is described halogenated
Aromatic hydrocarbons is room temperature lower density and boiling point is more than water, and is the halogenated aryl hydrocarbon of liquid under room temperature, and the halogenated alkane is close under room temperature
Degree and boiling point are more than water, and are the halogenated aryl hydrocarbon of liquid under room temperature.
7. online washing methods according to claim 6, it is characterised in that:The halogenated aryl hydrocarbon is room temperature lower density and boiling
Point is more than water, and be the halogenated aryl hydrocarbon of liquid under room temperature is bromobenzene, and the halogenated alkane is room temperature lower density and boiling point more than water,
And be the halogenated aryl hydrocarbon of liquid under room temperature it is dichloropropane.
8. online washing methods according to claim 1, it is characterised in that:Second stage detergent be single phenyl ring aromatic hydrocarbons or
One or two or more kinds in diesel oil;Its injection rate is 0%~100% of detergent quality used in the first stage, when not implementing
It is 0% when second stage is washed, injection rate is 1%~100% of detergent quality used in the first stage;Single phenyl ring aromatic hydrocarbons is
Benzene, toluene or dimethylbenzene.
9. online washing methods according to claim 1, it is characterised in that:
Second stage detergent is hexane, heptane or octane.
10. online washing methods according to claim 1, it is characterised in that:
The water scrubber lower part is equipped with the air inlet entered for reaction gas, and top is equipped with for the reaction gas outflow after water washed
Gas outlet, bottom is equipped with the water outlet for the washing water outflow after mass transfer, washing water is respectively equipped in top and middle part
Water inlet;
Oil partition tank is equipped at the water level line of bottom of tower inside water scrubber, detergent is detached from washing body after being washed with realization
System.
11. the online washing methods according to claim 1 or 10, it is characterised in that:
The oil partition tank is the attachment of water scrubber, and effect is to the oil removing from water, and oil partition tank is adopted by grease difference in specific gravity
Separated with natural floating method remove in washing water can oil slick and the finely divided oil in part.
12. online washing methods according to claim 1, it is characterised in that:
The first stage detergent can be not necessarily to after injecting the water system by detergent injection pump voluntarily with medium circulation
Always cycle is realized by detergent injection pump;It cleans and carries out with the first stage, pressure difference reduces, the injection of this time-division 2-3 times the
Two-stage detergent is to adjust detergent density, until when washing finishes, the density of detergent should be less than water;First section detergent density
More than water, and the detergent density in water scrubber is gradually adjusted to be less than water by back segment.
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Families Citing this family (4)
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CN106643276A (en) * | 2016-12-13 | 2017-05-10 | 天津市瑞德赛恩新材料开发有限公司 | Method for solid removal of MTO quenched water and online cleaning of water scrubber |
CN108295894A (en) * | 2018-01-24 | 2018-07-20 | 正大能源材料(大连)有限公司 | A kind of preparation method and catalyst of hud typed wear-resistant catalyst |
CN109115022A (en) * | 2018-06-14 | 2019-01-01 | 何志颖 | A kind of on-line cleaning system of methanol-to-olefins heat exchanger |
CN116174372A (en) * | 2022-10-31 | 2023-05-30 | 中安联合煤化有限责任公司 | Online chemical cleaning method for tower packing on ammonia absorption tower |
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