CN105198688A - Alkali washing method for methanol to olefin (MTO) gas - Google Patents
Alkali washing method for methanol to olefin (MTO) gas Download PDFInfo
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- CN105198688A CN105198688A CN201410273141.0A CN201410273141A CN105198688A CN 105198688 A CN105198688 A CN 105198688A CN 201410273141 A CN201410273141 A CN 201410273141A CN 105198688 A CN105198688 A CN 105198688A
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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
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- 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
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Abstract
The invention relates to the technical field of methanol to olefin (MTO), in particular to an alkali washing method for MTO gas. The alkali washing method for the MTO gas includes the steps that a NaOH solution and an alkali washing addition agent (an amine mixture or an aqueous solution of the amine mixture) are used for conducting alkali washing treatment on the MTO gas including carbon dioxide first; the MTO gas which is subjected to alkali washing enters in the follow-up process to be treated continuously, a liquid phase which is subjected to alkali washing is discharged for airtight oil separating treatment, and accordingly discharged MTO waste lye can be obtained; the COD of the discharged MTO waste lye is 3000 mg/L-15000 mg/L, and the organic nitrogen content is 200 mg/L-1200 mg/L. The alkali washing method for the MTO gas is stable in effect, the NaOH consumption is low, and the obtained MTO waste lye is suitable for being further treated according to removal of organic nitrogen.
Description
Technical field
The present invention relates to methanol-to-olefins (MTO) technical field, is a kind of separation method of MTO alkene gas specifically.Espespecially a kind of alkali washing method of MTO alkene gas.
Background technology
The low-carbon alkene such as ethene, propylene is important Organic Chemicals, has a very important role in modern petroleum and chemical industry.The cracking of the source of ethene and propylene mainly hydrocarbon vapours traditionally, cracking stock is petroleum naphtha mainly.In the last few years, oxygenatedchemicals alkene (OTO) technique reached its maturity, and especially methanol-to-olefins (MTO) technique starts large-scale application.
In typical MTO reactive system, often generate carbonic acid gas by side reaction, and the existence of carbonic acid gas can bring disadvantageous effect to the further separation of alkene gas and processing, therefore, from alkene gas, reduce or remove carbonic acid gas being very important.
Chinese patent CN101072742B discloses a kind of method removing carbonic acid gas from the effluent stream of OTO reactive system.The method comprises the following step: a, provide described effluent stream from OTO technique, and wherein said effluent stream comprises the carbonic acid gas being greater than 100vppm; B, in the first CO2 removal region, effective remove from described effluent stream first part's carbonic acid gas and formed containing 0.5-200vppm carbonic acid gas the first carbonic acid gas depleted stream condition under, make described effluent stream and the first CO2 removal medium contact; C, in the second CO2 removal region, remove under second section carbonic acid gas and formation comprises the condition of the second carbonic acid gas depleted stream being less than about 0.5vppm carbonic acid gas from described first carbonic acid gas depleted stream effective, make described first carbonic acid gas depleted stream and the second CO2 removal medium contact.This patent lays particular emphasis on the carbonic acid gas absorbed with caustic alkali in alkene gas, especially lays particular emphasis on the removal effect of carbonic acid gas in alkene gas, and does not substantially relate to the stability of alkaline cleaning procedure itself and the characteristic of outer waste discharge alkali lye.
Chinese patent CN102372568A discloses a kind of method of biological ethane alkali cleaning, and the method comprises the following step: a, soda-wash tower are at least made up of epimere and hypomere two sections, has dividing plate and external placed type riser in the middle of epimere and hypomere.Epimere is column plate type structure or the filler of 1 ~ 10 block of theoretical tray, hypomere is the spray structure containing inner member, wherein spray structure is positioned at below dividing plate, above inner member, it is characterized in that inner member pattern is circle for being circular, internal passages by 1 ~ 12 outside, equilateral triangle, rectangle or square filler unit form, or be made up of 3 ~ 36 shape of a saddle solid filler units; The reactor effluent of b, acid gas-containing and biological ethane enters the bottom of soda-wash tower, and the alkali lye sprayed in spray mode with nozzle contacts soda-wash tower hypomere is reverse.The alkali lye absorbing sour gas flows out from soda-wash tower bottom, is sent to wastewater treatment equipment; Gas phase enters soda-wash tower epimere by external placed type riser, and after contacting with fresh water, the gaseous effluent at soda-wash tower top carries out subsequent disposal, and wash water carries out wastewater treatment.This patent utilization NaOH solution absorbs the carbonic acid gas in alkene gas, and improves from the angle of soda-wash tower inner member alkali cleaning operation, although the stability of alkaline cleaning procedure obtains raising to a certain extent, still needs to strengthen; In addition, the characteristic of the external waste discharge alkali lye of this patent does not also relate to.
In sum, the existing MTO alkene gas alkali washing method problem that still existence and stability is poor, in addition, the characteristic of MTO alkene gas alkaline cleaning procedure China and foreign countries' waste discharge alkali lye does not cause the concern of people yet.
Summary of the invention
For the defect existed in prior art, the object of the present invention is to provide a kind of alkali washing method of MTO alkene gas, by adding alkali cleaning auxiliary agent in NaOH solution, the by product produced in remarkable minimizing alkaline cleaning procedure, the obvious blockage improving soda-wash tower, alkali cleaning is operated can continuous and steady operation, reduces the consumption of NaOH simultaneously; For the further process of outer row MTO waste lye specifies direction.
For reaching above object, the technical scheme that the present invention takes is:
An alkali washing method for MTO alkene gas, is characterized in that, specifically comprise the steps:
The first step, alkali cleaning process: under alkali cleaning auxiliary agent existent condition, carry out alkali cleaning process to the MTO alkene gas containing carbonic acid gas, and the MTO alkene gas after alkali cleaning process enters subsequent handling and proceeds process, and the liquid phase after alkali cleaning process is discharged;
Second step, oil removal process: carry out airtight oil removal process to the liquid phase that alkali cleaning is discharged, the oil slick obtained is disposed according to a conventional method further, the liquid phase after removing oil slick, namely outer row MTO waste lye, need carry out subsequent disposal according to specific requirement.
On the basis of technique scheme, in the first step alkali cleaning process, alkali cleaning uses NaOH solution, and its mass concentration is 5% ~ 10%.
On the basis of technique scheme, the mass concentration of NaOH solution is 6% ~ 8%.
On the basis of technique scheme, the alkali cleaning auxiliary agent in the first step alkali cleaning process is the aqueous solution of amine mixture or amine mixture.
On the basis of technique scheme, the mixture of amine mixture preferred fat amine and aromatic amine, in amine mixture, the mass concentration of N element is 10% ~ 20%.
On the basis of technique scheme, in the first step alkali cleaning process, in amine mixture, add-on and the MTO alkene gas mass ratio of alkali cleaning auxiliary agent are 25ppm ~ 250ppm.
On the basis of technique scheme, in amine mixture, add-on and the MTO alkene gas mass ratio of alkali cleaning auxiliary agent are 50ppm ~ 200ppm.
On the basis of technique scheme, the airtight oil removal process of second step is carried out in airtight oil partition tank, and the residence time of liquid phase in airtight oil partition tank that alkali cleaning is discharged is more than 2h.
On the basis of technique scheme, the residence time of liquid phase in airtight oil partition tank that alkali cleaning is discharged is 6h ~ 36h.
On the basis of technique scheme, after oil removal process, the outer of gained arranges the mainly composed as follows of MTO waste lye: COD is 3000mg/L ~ 15000mg/L, and organic nitrogen content is 200mg/L ~ 1200mg/L.
The alkali washing method of MTO alkene gas of the present invention, its beneficial effect is:
(1) by adding alkali cleaning auxiliary agent in NaOH solution, can significantly reduce the by product produced in alkaline cleaning procedure, as hydrocarbon polymer and aldol condensation product etc., thus obviously improve the blockage of soda-wash tower, alkali cleaning is operated can continuous and steady operation, reduces the consumption of NaOH simultaneously;
(2) the key composition of outer row MTO waste lye is obtained by alkali washing method of the present invention, especially specify that the impact of alkali cleaning auxiliary agent, for the further process of outer row MTO waste lye specifies direction, the MTO waste lye obtained should carry out further process for removing of organonitrogen.
Compared with prior art, essential distinction of the present invention is:
The first, in NaOH solution, with the addition of alkali cleaning auxiliary agent, can significantly reduce the by product produced in alkaline cleaning procedure, such as hydrocarbon polymer and aldol condensation product etc., thus obviously can improve the blockage of soda-wash tower, be conducive to the continuous and steady operation realizing alkali cleaning operation.
The understanding of the second, alkali cleaning auxiliary agent externally being arranged to the impact of MTO waste lye characteristic has had breakthrough.When carrying out alkali cleaning to traditional cracking ethylene gas in the past, because sulfide is very high to the contribution proportion of waste lye COD, investigator is caused all main attention to be placed on removing of sulfide, pay close attention to the auxiliary agent in waste lye there are no people, also do not see the play-by-play about alkali cleaning auxiliary agent in waste lye.Inventor herein, on the basis of extensive work, makes public for the first time the relevant information of auxiliary agent.
Inventor herein finds through research, and arrange in MTO waste lye outside, the impact of alkali cleaning auxiliary agent is in particular in three aspects:
(1) arrange the organonitrogen containing high level in MTO waste lye outward, be approximately 200 ~ 1000mg/L, substantially contributed by alkali cleaning auxiliary agent;
(2) COD arranging MTO waste lye is outward 3000 ~ 15000mg/L, and wherein more than 80% is contributed by alkali cleaning auxiliary agent;
(3) owing to there is the organonitrogen of high level in outer row MTO waste lye, the organism in outer row MTO waste lye is caused to be difficult to biological degradation.
Accompanying drawing explanation
The present invention has following accompanying drawing:
Fig. 1 process flow sheet of the present invention.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in further detail.
As shown in Figure 1, the alkali washing method of MTO alkene gas of the present invention, specifically comprises the steps:
The first step, alkali cleaning process: under alkali cleaning auxiliary agent existent condition, alkali cleaning process is carried out to the MTO alkene gas containing carbonic acid gas, carbon dioxide content in MTO alkene gas is reduced to below 5ppm, MTO alkene gas after alkali cleaning process enters subsequent handling and proceeds process, and the liquid phase after alkali cleaning process is discharged;
Second step, oil removal process: airtight oil removal (gravity oil removal) process is carried out to the liquid phase that alkali cleaning is discharged, the oil slick obtained according to a conventional method (such as recovery or burning etc.) is disposed further, liquid phase after removing oil slick, namely outer row MTO waste lye, need carry out subsequent disposal according to specific requirement.
Alkali cleaning auxiliary agent is used to be the negative effect brought to reduce alkali cleaning during the gas alkali cleaning of MTO alkene, especially in order to reduce the generation of hydrocarbon polymer and aldol condensation product etc.
On the basis of such scheme, in the first step alkali cleaning process, alkali cleaning uses fresh NaOH solution, and its mass concentration is 5% ~ 10%, is preferably 6% ~ 8%.Fresh NaOH solution described herein refers to that NaOH solution fills into continuously in alkali cleaning treating processes.
On the basis of such scheme, alkali cleaning auxiliary agent in the first step alkali cleaning process is the aqueous solution of amine mixture or amine mixture, the wherein mixture (proportioning is any) of amine mixture preferred fat amine and aromatic amine, in amine mixture, the mass concentration of N element is 10% ~ 20%.
On the basis of such scheme, in the first step alkali cleaning process, in amine mixture, add-on and the MTO alkene gas mass ratio of alkali cleaning auxiliary agent are 25ppm ~ 250ppm, preferred 50ppm ~ 200ppm.
On the basis of such scheme, the airtight oil removal process of second step is carried out in airtight oil partition tank, and the residence time of liquid phase in airtight oil partition tank that alkali cleaning is discharged is more than 2h, preferred 6h ~ 36h.
On the basis of such scheme, after oil removal process, the outer of gained arranges the mainly composed as follows of MTO waste lye: COD is 3000mg/L ~ 15000mg/L, and organic nitrogen content is 200mg/L ~ 1200mg/L.
Be below some specific embodiments.
Embodiment 1
Using the aqueous solution of amine mixture as alkali cleaning auxiliary agent, wherein N element content accounts for the mass ratio (mass concentration of N element) of amine mixture is 15%.8% fresh NaOH solution is utilized to carry out alkali cleaning process to the MTO alkene gas containing carbonic acid gas, alkali cleaning auxiliary agent (in amine mixture) add-on and MTO alkene gas mass ratio are 120ppm, alkali cleaning operation can continuous and steady operation, in alkene gas after alkali cleaning process, carbon dioxide content is 2ppm, enter subsequent handling and proceed process, the liquid phase after alkali cleaning process is discharged;
The liquid phase of alkali cleaning discharge is carried out to the airtight oil removal process of 6h, the oil slick obtained is disposed according to a conventional method further, the liquid phase after removing oil slick, i.e. outer row MTO waste lye, and it consists of: COD is 3000mg/L, organic nitrogen content is 200mg/L.
Embodiment 2
Using the aqueous solution of amine mixture as alkali cleaning auxiliary agent, wherein N element content accounts for the mass ratio (mass concentration of N element) of amine mixture is 20%.10% fresh NaOH solution is utilized to carry out alkali cleaning process to the MTO alkene gas containing carbonic acid gas, alkali cleaning auxiliary agent (in amine mixture) add-on and MTO alkene gas mass ratio are 250ppm, alkali cleaning operation can continuous and steady operation, in alkene gas after alkali cleaning process, carbon dioxide content is 3ppm, enter subsequent handling and proceed process, the liquid phase after alkali cleaning process is discharged;
The liquid phase of alkali cleaning discharge is carried out to the airtight oil removal process of 2h, the oil slick obtained is disposed according to a conventional method further, the liquid phase after removing oil slick, i.e. outer row MTO waste lye, and it consists of: COD is 15000mg/L, organic nitrogen content is 1200mg/L.
Embodiment 3
Using amine mixture as alkali cleaning auxiliary agent, wherein N element content accounts for the mass ratio (mass concentration of N element) of amine mixture is 10%.5% fresh NaOH solution is utilized to carry out alkali cleaning process to the MTO alkene gas containing carbonic acid gas, alkali cleaning auxiliary agent (in amine mixture) add-on and MTO alkene gas mass ratio are 25ppm, alkali cleaning operation can continuous and steady operation, in alkene gas after alkali cleaning process, carbon dioxide content is 5ppm, enter subsequent handling and proceed process, the liquid phase after alkali cleaning process is discharged;
The liquid phase of alkali cleaning discharge is carried out to the airtight oil removal process of 36h, the oil slick obtained is disposed according to a conventional method further, the liquid phase after removing oil slick, i.e. outer row MTO waste lye, and it consists of: COD is 6800mg/L, organic nitrogen content is 520mg/L.
The content be not described in detail in this specification sheets belongs to the known prior art of professional and technical personnel in the field.
Claims (10)
1. an alkali washing method for MTO alkene gas, is characterized in that, specifically comprises the steps:
The first step, alkali cleaning process: under alkali cleaning auxiliary agent existent condition, carry out alkali cleaning process to the MTO alkene gas containing carbonic acid gas, and the MTO alkene gas after alkali cleaning process enters subsequent handling and proceeds process, and the liquid phase after alkali cleaning process is discharged;
Second step, oil removal process: carry out airtight oil removal process to the liquid phase that alkali cleaning is discharged, the oil slick obtained is disposed according to a conventional method further, the liquid phase after removing oil slick, namely outer row MTO waste lye, need carry out subsequent disposal according to specific requirement.
2. the alkali washing method of MTO alkene gas as claimed in claim 1, it is characterized in that, in the first step alkali cleaning process, alkali cleaning uses NaOH solution, and its mass concentration is 5% ~ 10%.
3. the alkali washing method of MTO alkene gas as claimed in claim 2, it is characterized in that, the mass concentration of NaOH solution is 6% ~ 8%.
4. the alkali washing method of MTO alkene gas as claimed in claim 1, it is characterized in that, the alkali cleaning auxiliary agent in the first step alkali cleaning process is the aqueous solution of amine mixture or amine mixture.
5. the alkali washing method of MTO alkene gas as claimed in claim 4, it is characterized in that, the mixture of amine mixture preferred fat amine and aromatic amine, in amine mixture, the mass concentration of N element is 10% ~ 20%.
6. the alkali washing method of MTO alkene gas as claimed in claim 4, it is characterized in that, in the first step alkali cleaning process, in amine mixture, add-on and the MTO alkene gas mass ratio of alkali cleaning auxiliary agent are 25ppm ~ 250ppm.
7. the alkali washing method of MTO alkene gas as claimed in claim 6, it is characterized in that, in amine mixture, add-on and the MTO alkene gas mass ratio of alkali cleaning auxiliary agent are 50ppm ~ 200ppm.
8. the alkali washing method of MTO alkene gas as claimed in claim 1, it is characterized in that, the airtight oil removal process of second step is carried out in airtight oil partition tank, and the residence time of liquid phase in airtight oil partition tank that alkali cleaning is discharged is more than 2h.
9. the alkali washing method of MTO alkene gas as claimed in claim 8, is characterized in that, the residence time of liquid phase in airtight oil partition tank that alkali cleaning is discharged is 6h ~ 36h.
10. the alkali washing method of MTO alkene gas as claimed in claim 1, is characterized in that, after oil removal process, the outer of gained arranges the mainly composed as follows of MTO waste lye: COD is 3000mg/L ~ 15000mg/L, and organic nitrogen content is 200mg/L ~ 1200mg/L.
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| CN201410273141.0A CN105198688A (en) | 2014-06-18 | 2014-06-18 | Alkali washing method for methanol to olefin (MTO) gas |
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| CN201410273141.0A CN105198688A (en) | 2014-06-18 | 2014-06-18 | Alkali washing method for methanol to olefin (MTO) gas |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105674299A (en) * | 2016-03-11 | 2016-06-15 | 中国神华能源股份有限公司 | Method for processing waste lye generated in olefin separating unit alkali washing system |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101072742A (en) * | 2004-12-06 | 2007-11-14 | 埃克森美孚化学专利公司 | Removing carbon dioxide from an oxygenate to olefins reaction effluent |
| CN101092576A (en) * | 2006-06-23 | 2007-12-26 | 中国石油化工股份有限公司 | Method for removing acid gases in cracked gas |
| CN102442744A (en) * | 2010-09-30 | 2012-05-09 | 中国石油化工股份有限公司 | Treatment method of high-concentration process waste water during methanol-to-olefin process |
| CN103833171A (en) * | 2013-12-05 | 2014-06-04 | 武汉纺织大学 | Method for treating ultrahigh-concentration organic waste water produced by preparation of olefin from methanol |
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2014
- 2014-06-18 CN CN201410273141.0A patent/CN105198688A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101072742A (en) * | 2004-12-06 | 2007-11-14 | 埃克森美孚化学专利公司 | Removing carbon dioxide from an oxygenate to olefins reaction effluent |
| CN101092576A (en) * | 2006-06-23 | 2007-12-26 | 中国石油化工股份有限公司 | Method for removing acid gases in cracked gas |
| CN102442744A (en) * | 2010-09-30 | 2012-05-09 | 中国石油化工股份有限公司 | Treatment method of high-concentration process waste water during methanol-to-olefin process |
| CN103833171A (en) * | 2013-12-05 | 2014-06-04 | 武汉纺织大学 | Method for treating ultrahigh-concentration organic waste water produced by preparation of olefin from methanol |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105674299A (en) * | 2016-03-11 | 2016-06-15 | 中国神华能源股份有限公司 | Method for processing waste lye generated in olefin separating unit alkali washing system |
| CN105674299B (en) * | 2016-03-11 | 2018-04-06 | 中国神华能源股份有限公司 | The processing method of caused spent lye in a kind of olefin separation caustic washing system |
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Application publication date: 20151230 |