CN107641069A - The processing method of methanol-to-olefins product gas - Google Patents
The processing method of methanol-to-olefins product gas Download PDFInfo
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- CN107641069A CN107641069A CN201710884116.XA CN201710884116A CN107641069A CN 107641069 A CN107641069 A CN 107641069A CN 201710884116 A CN201710884116 A CN 201710884116A CN 107641069 A CN107641069 A CN 107641069A
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- acetaldehyde
- methanol
- product gas
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- bisulfite solution
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Abstract
This application provides a kind of processing method of methanol-to-olefins product gas.The processing method includes：Step S1, the acetaldehyde in methanol-to-olefins product gas is removed using bisulfite solution；Step S2, alkali washing process is carried out to the methanol-to-olefins product gas after step S1 processing, with acetaldehyde addition reaction occurs for the bisulfites in bisulfites absorption bottle, acetaldehyde is removed, and then avoid acetaldehyde from being reacted in alkaline cleaning procedure with alkali lye and generate butter, so as to ensure that alkaline cleaner is well smoothly run.
Description
Technical field
The application is related to chemical field, in particular to a kind of processing method of methanol-to-olefins product gas.
Background technology
Shenhua packet header coal chemical industry is national coal-to-olefin demonstrative project.Methanol-to-olefins (MTO) are contact methanol technics
With the tie of Olefin Separation Technology.The accessory substance such as some side reactions, generation carbon dioxide is also occurred that while methanol-to-olefins.
To reduce influence of the carbon dioxide to product and equipment, alkaline cleaner is specially provided with the device of methanol-to-olefins.But
It can produce in the process of running " butter ", caustic wash tower pressure difference is increased, cause the reduction of alkali cleaning efficiency, influence the load of caustic wash tower；
Handled for follow-up salkali waste, also result in very big influence.
Therefore, find it is a kind of solve the problems, such as the method for butter, it is significant to device even running.
The content of the invention
The main purpose of the application is to provide a kind of processing method of methanol-to-olefins product gas, to solve prior art
In alkaline cleaner in butter the problem of causing itself and follow up device cisco unity malfunction.
To achieve these goals, this application provides a kind of processing method of methanol-to-olefins product gas, the processing side
Method includes：Step S1, the acetaldehyde in methanol-to-olefins product gas is removed using bisulfite solution；Step S2, to by upper
State the above-mentioned methanol-to-olefins product gas after step S1 processing and carry out alkali washing process.
Further, above-mentioned steps S1 includes continuous n times using the above-mentioned methanol alkene of above-mentioned bisulfite solution removal
The process of acetaldehyde in hydrocarbon product gas, the above-mentioned bisulfite solution that X time uses during removing above-mentioned acetaldehyde is X
Bisulfite solution, the above-mentioned sulfurous used during+1 acetaldehyde removed in above-mentioned methanol-to-olefins product gas of X
Sour hydrogen salt solution is the bisulfite solution of X+1, and the concentration of the bisulfites in X bisulfite solution is A, X+
The concentration of bisulfites in 1 bisulfite solution is B, and B>A, and X ＜ N, N >=2.
Further, above-mentioned steps S1 includes：Step S11, methanol-to-olefins are removed using the first bisulfite solution
Acetaldehyde in product gas, obtain the first product gas；Step S12, above-mentioned first product is removed using the second bisulfite solution
Acetaldehyde in gas, obtain the second product gas；Step S13, removed using the 3rd bisulfite solution in above-mentioned second product gas
Acetaldehyde.
Further, in above-mentioned first bisulfite solution, the mass concentration of above-mentioned bisulfites is 5%.
Further, in above-mentioned second bisulfite solution, the mass concentration of above-mentioned bisulfites is 10%.
Further, in above-mentioned 3rd bisulfite solution, the mass concentration of above-mentioned bisulfites is 20%.
Further, in above-mentioned steps S1, in the above-mentioned bisulfite solution of use, the matter of above-mentioned bisulfites
Concentration is measured between 5~30%.
Further, above-mentioned bisulfite solution is selected from solution of sodium bisulfite and/or bisulfite potassium solution.
Further, above-mentioned bisulfite solution is solution of sodium bisulfite.
Using the technical scheme of the application, the bisulfites and acetaldehyde generation addition in bisulfites absorption bottle are anti-
Should：
Alpha-hydroxy sulfonate is generated, i.e., the acetaldehyde in methanol-to-olefins product gas can be removed using disulfate solution,
And then avoid acetaldehyde from being reacted in alkaline cleaning procedure with alkali lye and generate butter, so as to ensure that alkaline cleaner is well smoothly transported
OK.
Brief description of the drawings
The Figure of description for forming the part of the application is used for providing further understanding of the present application, and the application's shows
Meaning property embodiment and its illustrate be used for explain the application, do not form the improper restriction to the application.In the accompanying drawings：
Fig. 1 shows the processing side of the methanol-to-olefins product gas provided according to a kind of typical embodiment of the application
The schematic flow sheet of method；
Fig. 2 shows that the methanol-to-olefins product gas before removing technique to acetaldehyde using lowox chromatogram column techniques is divided
Analyse obtained chromatogram；
Fig. 3 shows that the methanol-to-olefins product gas before removing technique to acetaldehyde using Plot Q chromatogram column techniques is divided
Analyse obtained chromatogram；
Fig. 4 shows the chromatogram of the gas after acetaldehyde removes technique in embodiment 1；
Fig. 5 shows the chromatogram of the gas after acetaldehyde three times removes technique in embodiment 2；
Fig. 6 shows the chromatogram of the gas after acetaldehyde three times removes technique in embodiment 3；And
Fig. 7 shows the chromatogram to methanol to olefins reaction gas after washing process in comparative example.
Embodiment
It is noted that described further below is all exemplary, it is intended to provides further instruction to the application.It is unless another
Indicate, all technologies used herein and scientific terminology are with usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe embodiment, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singulative
It is also intended to include plural form, additionally, it should be understood that, when in this manual using term "comprising" and/or " bag
Include " when, it indicates existing characteristics, step, operation, device, component and/or combinations thereof.
As background technology is introduced, the butter in alkaline cleaner of the prior art causes itself and follow up device not
Energy normal work, in order to solve technical problem as above, present applicant proposes a kind of processing method of methanol-to-olefins product gas.
Methanol-to-olefins product gas is carried out analysis and draws gas componant therein, and the machine according to caused by butter by applicant
Reason understands that the source gas of butter should be oxygen-containing gas, so by the corresponding oxygen-containing gas in methanol-to-olefins product gas
Found with alkaline reaction, only acetaldehyde and alkaline reaction generation oily precipitation, therefore, the butter in methanol-to-olefins product gas comes
Source thing is acetaldehyde, so, just must be by the methanol-to-olefins product gas before alkali cleaning in order to avoid substantial amounts of butter produces
Acetaldehyde removes.
In a kind of typical embodiment of the application, there is provided a kind of processing method of methanol-to-olefins product gas, such as
Shown in Fig. 1, the processing method includes：Step S1, the acetaldehyde in methanol-to-olefins product gas is removed using bisulfite solution；
Step S2, alkali washing process is carried out to the above-mentioned methanol-to-olefins product gas after above-mentioned steps S1 processing.
In above-mentioned processing method, with acetaldehyde addition reaction occurs for the bisulfites in bisulfites absorption bottle：
Alpha-hydroxy sulfonate is generated, i.e., the acetaldehyde in methanol-to-olefins product gas can be removed using disulfate solution,
And then avoid acetaldehyde from being reacted in alkaline cleaning procedure with alkali lye and generate butter, so as to ensure that alkaline cleaner is well smoothly transported
OK.
In order to further remove acetaldehyde, above-mentioned steps S1 is included continuous n times and removed using above-mentioned bisulfite solution
State the process of the acetaldehyde in methanol-to-olefins product gas, the above-mentioned bisulfite that X time uses during removing above-mentioned acetaldehyde
Salting liquid is X bisulfite solution, is used during+1 acetaldehyde removed in above-mentioned methanol-to-olefins product gas of X
Above-mentioned bisulfite solution be the bisulfite solution of X+1, the bisulfites in X bisulfite solution it is dense
Spend for A, the concentration of the bisulfites in the bisulfite solution of X+1 is B, and B>A, and X ＜ N, N >=2.Concentration is gradually passed
Increase, bisulfites and acetaldehyde reaction in gas are more complete, can effectively remove acetaldehyde materials in gas.
It should be noted that " concentration " in the application refers both to mass concentration in the case of no specified otherwise.
In a kind of embodiment of the application, above-mentioned steps S1 includes：Step S11, gone using the first bisulfite solution
Except the acetaldehyde in methanol-to-olefins product gas, the first product gas is obtained；Step S12, removed using the second bisulfite solution
Acetaldehyde in above-mentioned first product gas, obtains the second product gas；And step S13, removed using the 3rd bisulfite solution
Acetaldehyde in above-mentioned second product gas.More acetaldehyde in methanol-to-olefins product gas can so be removed, avoided a large amount of
The generation of butter.
It is above-mentioned in above-mentioned first bisulfite solution in a kind of embodiment of the application in order to remove more acetaldehyde
The mass concentration of bisulfites is 5%.
In another embodiment of the application, in above-mentioned second bisulfite solution, the quality of above-mentioned bisulfites
Concentration is 10%.
In order to more remove acetaldehyde for the third time, in a kind of embodiment of the application, above-mentioned 3rd bisulfites is molten
In liquid, the mass concentration of above-mentioned bisulfites is 20%.
It is above-mentioned in the above-mentioned bisulfite solution of use in above-mentioned steps S1 in the another embodiment of the application
The mass concentration of bisulfites is between 5~30%.Such concentration can not only effectively remove methanol-to-olefins product gas
In acetaldehyde, additionally it is possible to avoid the waste of alkali lye.
In a kind of embodiment in the application, above-mentioned bisulfite solution is selected from solution of sodium bisulfite and/or sulfurous
Potassium hydrogen phthalate solution, such bisulfite solution can not only remove acetaldehyde well, moreover it is possible to avoid and methanol-to-olefins
Other gases in reaction gas react.
But above-mentioned bisulfite solution is not limited to above-mentioned two kinds, those skilled in the art can be according to reality
Border situation selects suitable bisulfite solution.
In another embodiment of the application, above-mentioned bisulfite solution is solution of sodium bisulfite, and the solution can
Reacted with acetaldehyde, meanwhile, not with other gas reactions in methanol-to-olefins product gas, ensure that in methanol-to-olefins product gas
Other gas componants it is unaffected.
In order that the technical scheme of the application can clearly be understood by obtaining those skilled in the art, below with reference to tool
The embodiment of body illustrates the technical scheme of the application.
Embodiment 1
In the processing procedure of methanol-to-olefins product gas, concentration is first used as 5% solution of sodium bisulfite and product gas
10min is reacted, reacted gas is entered back into alkali washing process.
Embodiment 2
Pending methanol-to-olefins product gas is identical with embodiment, and the difference of the technique and embodiment 1 of processing is, first
First, concentration is used as 5% bisulfites sodium solution and methanol-to-olefins product solid/liquid/gas reactions 10min；Then, use concentration for
10% bisulfites sodium solution and methanol-to-olefins product solid/liquid/gas reactions 10min；Finally, concentration is used as 20% bisulfites
Sodium solution and methanol-to-olefins product solid/liquid/gas reactions 10min.Reacted gas is entered back into alkali washing process.
Embodiment 3
Pending methanol-to-olefins product gas is identical with embodiment, and the difference of the technique and embodiment 1 of processing is, first
First, concentration is used as 20% bisulfites sodium solution and methanol-to-olefins product solid/liquid/gas reactions 10min；Then, use concentration for
10% bisulfites sodium solution and methanol-to-olefins product solid/liquid/gas reactions 10min；Finally, concentration is used as 5% bisulfites
Sodium solution and methanol-to-olefins product solid/liquid/gas reactions 10min.Reacted gas is entered back into alkali washing process.
Comparative example
Pending methanol-to-olefins product gas is identical with embodiment, and the difference of the technique and embodiment 1 of processing is：In first
In the processing procedure of alcohol olefin product gas, advanced row washing process, then the gas after washing process directly use alkali
Wash PROCESS FOR TREATMENT methanol-to-olefins product gas.
Sulfurous is passed through into embodiment 3 to pending methanol-to-olefins product gas, to embodiment 1 using gas chromatograph
Gas in gas and comparative example after sour hydrogen sodium solution processing after washing process carries out chromatography.Also, obtain
Fig. 2 to Fig. 7.For Fig. 2 into Fig. 7, abscissa represents retention time, unit min, and ordinate represents to respond the big of voltage
Small, unit is μ V × 103.Specifically use lowox chromatogram column techniques or Plot Q chromatogram column techniques.Wherein, Fig. 2, Fig. 4 and Fig. 7 are
The gas chromatograph figure obtained using lowox chromatogram column techniques, Fig. 3, Fig. 5 and Fig. 6 are obtained using Plot Q chromatogram column techniques.These
In figure, the chromatogram peak position of acetaldehyde is embodied in retention time, the gas chromatograph figure obtained for lowox chromatogram column techniques, second
Aldehyde peak is in 4.8min or so, and the gas chromatograph figure obtained for Plot Q chromatogram column techniques, acetaldehyde peak is in 14.4min or so.
By Fig. 4, Fig. 5, Fig. 6 respectively compared with Fig. 3, by Fig. 7 compared with Fig. 2, by relatively, in 4.8min in Fig. 7
When, it is big with ordinates of the Fig. 5 and Fig. 6 in 14.4min although the value of ordinate is smaller than Fig. 2, that is to say, that contrast
Though the washing process of example can remove part acetaldehyde, removal effect is poor, and embodiment 1 uses bisulfite into embodiment 3
Sodium solution can remove most acetaldehyde.Also, Fig. 4, Fig. 5, Fig. 6 are understood compared with Fig. 3 respectively, using sodium hydrogensulfite
In reaction gas before and after solution absorption acetaldehyde, hydrocarbon component changes, and only acetaldehyde is greatly reduced has with methanol
A small amount of to reduce, also further demonstrated that solution of sodium bisulfite absorbs does not influence for the hydrocarbon component in reaction gas, also,
Peakedness ratio Fig. 4's and Fig. 6 of acetaldehyde in Fig. 5 is small, i.e., acetaldehyde and bisulfite are repeatedly removed using bisulfite solution
Salting liquid gradually increases, and the removal effect of obtained acetaldehyde is more preferable.
The sulfite hydrogen sodium solution of embodiment 1 has been obtained using gas chromatography analysis and has absorbed front and rear gas component, reality
Apply the gas component before and after solution of sodium bisulfite absorbs three times in example 2 and solution of sodium bisulfite absorption three times in embodiment 3
Front and rear gas component, 1 is specifically shown in Table to table 3.
Table 1
Table 2
| Composition | MTO reaction gases before absorption | MTO reaction gases after absorption |
| Permanent gases (%) | 5.16 | 5.16 |
| Methane (%) | 4.57 | 4.58 |
| Ethene (%) | 45.80 | 45.93 |
| Ethane (%) | 0.78 | 0.78 |
| Propylene (%) | 31.38 | 31.48 |
| Propane (%) | 2.08 | 2.08 |
| Dimethyl ether (ppm) | 172 | 161 |
| Methanol (ppm) | 288 | 19 |
| C4 (%) | 7.41 | 7.40 |
| C5+ (%) | 2.55 | 2.56 |
| Acetaldehyde (ppm) | 2219 | 1 |
| Acetylene (ppm) | 4 | 4 |
Table 3
By the data of upper table 1, front and rear reaction gas ratio of components is absorbed compared with after absorption by solution of sodium bisulfite
Reaction gas key reaction product ethylene and the content of propylene all increase, on the contrary, acetaldehyde is dropped by 2087ppm before absorbing
For 136ppm after absorption, acetaldehyde absorptivity has reached 93.48%, and methanol is also decreased due to the presence content of water.By above-mentioned
The data of table 2 are understood, by upper table it is known that absorbing front and rear reaction gas ratio of components compared with suction by solution of sodium bisulfite
The content of reaction gas key reaction product ethylene and propylene after receipts all increases, on the contrary, before acetaldehyde is by absorbing
2219ppm is reduced to 1ppm after absorption, and acetaldehyde absorptivity has reached 99.9%, and methanol is also decreased due to the presence content of water.
Data in table 3 understand that the content of reaction gas key reaction product ethylene and propylene after absorption all increases, on the contrary, second
Aldehyde is reduced to 80ppm after absorption by 2219ppm before absorbing, and acetaldehyde absorptivity has reached 96.39%, and by table 1, table 2 with
The contrast of table 3 finds that embodiment 2 is handled reaction gas with embodiment 3 due to solution of sodium bisulfite is employed many times so that second
The removal effect of aldehyde is more preferable, and embodiment 2 increases due to the concentration for the solution of sodium bisulfite being employed many times successively, and it is to second
The removal effect of aldehyde is more preferable.
As can be seen from the above description, the application the above embodiments realize following technique effect：
In the processing method of the application, with acetaldehyde addition reaction occurs for the bisulfites in bisulfites absorption bottle：
Alpha-hydroxy sulfonate is generated, i.e., the acetaldehyde in methanol-to-olefins product gas can be removed using disulfate solution,
And then avoid acetaldehyde from being reacted in alkaline cleaning procedure with alkali lye and generate butter, so as to ensure that alkaline cleaner is well smoothly transported
OK.
The preferred embodiment of the application is the foregoing is only, is not limited to the application, for the skill of this area
For art personnel, the application can have various modifications and variations.It is all within spirit herein and principle, made any repair
Change, equivalent substitution, improvement etc., should be included within the protection domain of the application.
Claims (9)
1. a kind of processing method of methanol-to-olefins product gas, it is characterised in that the treating method comprises：
Step S1, the acetaldehyde in methanol-to-olefins product gas is removed using bisulfite solution；And
Step S2, alkali washing process is carried out to the methanol-to-olefins product gas after step S1 processing.
2. processing method according to claim 1, it is characterised in that the step S1 uses the Asia including continuous n times
Disulfate solution removes the process of the acetaldehyde in the methanol-to-olefins product gas, during X time removes the acetaldehyde
For X bisulfite solution, X removes in the methanol-to-olefins product gas for+1 time the bisulfite solution used
Acetaldehyde during the bisulfite solution that uses for the bisulfite solution of X+1, X bisulfite solution
In the concentration of bisulfites be A, the concentration of the bisulfites in the bisulfite solution of X+1 is B, and B>A, and X
＜ N, N >=2.
3. processing method according to claim 1, it is characterised in that the step S1 includes：
Step S11, the acetaldehyde in methanol-to-olefins product gas is removed using the first bisulfite solution, obtains the first product
Gas；
Step S12, the acetaldehyde in first product gas is removed using the second bisulfite solution, obtains the second product gas；
And
Step S13, the acetaldehyde in second product gas is removed using the 3rd bisulfite solution.
4. processing method according to claim 3, it is characterised in that in first bisulfite solution, the Asia
The mass concentration of disulfate is 5%.
5. processing method according to claim 3, it is characterised in that in second bisulfite solution, the Asia
The mass concentration of disulfate is 10%.
6. processing method according to claim 3, it is characterised in that in the 3rd bisulfite solution, the Asia
The mass concentration of disulfate is 20%.
7. processing method according to claim 1, it is characterised in that in the step S1, the sulfurous acid of use
In hydrogen salt solution, the mass concentration of the bisulfites is between 5~30%.
8. processing method according to claim 1, it is characterised in that the bisulfite solution is selected from sodium hydrogensulfite
Solution and/or bisulfite potassium solution.
9. processing method according to claim 1, it is characterised in that the bisulfite solution is that sodium hydrogensulfite is molten
Liquid.
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Cited By (1)
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