CN103755087A - System and method for treatment of methanol aromatized process wastewater - Google Patents
System and method for treatment of methanol aromatized process wastewater Download PDFInfo
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Abstract
A system for treatment of methanol aromatized process wastewater comprises a high-temperature steam stripping device for removing most of organic matters in the wastewater, a carbon medium absorption device for removing organic acids and a part of organic matters in the wastewater of the high-temperature steam stripping device, and an anion exchange system for reducing the amount of the organic acids in the wastewater of the carbon medium absorption device to be trace amount. During treatment, the methanol aromatized process wastewater firstly enters the high-temperature steam stripping device, and a large amount of organic matters and a small amount of organic acids are removed in the high-temperature steam stripping device; then, the organic matters and the organic acids are absorbed and further removed in the carbon medium absorption device; and finally, the wastewater enters the anion exchange system, the organic acids are removed, and the concentration of the organic acids in the discharged wastewater is allowed to be lower than 20 ppm. An alkali liquid is not adopted for neutralization, and therefore, the salt content in the wastewater can be reduced, and subsequent treatment and utilization difficulties are reduced; and the system can greatly shorten the wastewater treatment flow path, reduces investment of wastewater treatment, and besides has the advantages of low energy consumption, easy regeneration of a carbon medium, long service life and low operation cost.
Description
Technical field
The invention belongs to technical field of waste water processing, the System and method for that particularly a kind of aromatization of methanol processing wastewater is processed.
Background technology
Aromatic hydrocarbons is the important foundation raw material in modern chemistry industry, aromatic hydrocarbons is mainly derived from petroleum refining process traditionally, its raw material is mainly petroleum naphtha, use this year oxygenatedchemicals aromatics process processed particularly methyl alcohol dme aromatics process processed reach its maturity, be expected to complete industrial applications between in recent years.
And not yet consider for the system of aromatization of methanol spent process water treatment and reuse process and the report of process aspect at present, and the processing of comparing Methanol aromatic hydrocarbons spent process water with current waste water treatment process has the feature of self:
1. in waste water, have certain petroleum substance and alcohols material, organic content is higher.
2. in waste water, contain certain acid organism.
3. in waste water, ammonia nitrogen amount and phenols content are lower.
At present, in petrochemical complex and Coal Chemical Industry process reaction process, produce a large amount of containing organic acid oily(waste)water, its treatment process generally all adopts conventional treatment process, first through grid and air-floating apparatus, remove the greasy dirt in waste water, then adopt in a large amount of alkali and waste water in organic acid, then further by biological treatment and advanced treatment, reach the reuse effect of sewage, in N-process, can in waste water, generate a large amount of salts substances, can affect waste water in the application in system for meeting, also can suppress the microorganism in biological treatment process in wastewater treatment process simultaneously, bring difficulty to follow-up processing and comprehensive treating process.Generally speaking, this processing mode long flow path, investment is large, and the working cost of processing unit waste water is higher, fluctuation of service.
Summary of the invention
The invention provides the System and method for that a kind of aromatization of methanol processing wastewater is processed, overcome in above-mentioned organic acid treatment of Organic Wastewater process, adopt N-process to produce a large amount of salts substances, give follow-up processing and comprehensive treating process bring difficulty and existing process flow long, investment is large, the working cost of processing unit waste water is higher, the shortcoming of fluctuation of service.
To achieve these goals, the technical solution used in the present invention is:
The system that aromatization of methanol processing wastewater is processed, comprising:
Be used for removing the most of organic high temperature stripper plant 1 of waste water;
Connect described high temperature stripper plant 1, for removing out the waste water organic acid of high temperature stripper plant 1 and the carbon Absorption of Medium device 2 of partial organic substances;
And connect described carbon Absorption of Medium device 2, for the organic acid that goes out the waste water of carbon Absorption of Medium device 2 being reduced to an anion exchange system 3 of trace.
Described high temperature stripper plant 1 is comprised of one or two stripping towers.
Described carbon Absorption of Medium device 2 is comprised of one or more carbon Absorption of Medium layers, and described carbon medium is one or more in carbon nanotube, Graphene, expanded graphite, carbon fiber and gac.
Described anion exchange system 3 consists of the fixed bed of two filling anionite-exchange resin in parallel.
The present invention also provides the method for wastewater treatment based on aromatization of methanol Waste Water Treatment described in claim 1, comprises the following steps:
A) first sewage aromatization of methanol processing wastewater enters high temperature stripper plant 1, and the temperature of high temperature stripper plant 1 bottom is 100-120 ℃, removes therein a large amount of organism and a small amount of organic acid, COD(Cr) is less than 600, and organic acid concentration is less than 200ppm;
B) waste water that goes out high temperature stripper plant 1 enters carbon Absorption of Medium device 2, absorbs and removes organism and a part of organic acid in waste water, the COD(Cr of its outlet waste water) be less than 200, organic acid concentration is less than 60ppm;
C) waste water that goes out carbon Absorption of Medium device 2 enters anion exchange system 3 and removes the organic acid in waste water, and the organic acid concentration that makes to discharge in waste water is less than 20ppm.
The organic acid in waste water is removed in described anionresin, comprises the steps:
A) from the waste water of carbon Absorption of Medium device 2 by weak base anion exchange system 3 is housed, part organic acid is adsorbed, in anion exchange system 3 water outlets, organic acid content is less than 10ppm;
B) in anion exchange system 3 water outlets, organic acid content is greater than 20ppm, and resin absorption approaches saturated, stops absorption, with air, intrasystem liquid is blown out;
C) to the weak lye that passes into 5-10wt% in saturated ion exchange system 3, carry out desorption;
D) ion exchange system after desorption 3 adopts Air blowing alkali lye.
Described alkali lye comprises ammoniacal liquor, sodium hydroxide, calcium hydroxide.
Described carbon Absorption of Medium device 2 absorbs removes organism and the organic acid in waste water, comprises following steps:
A) organism and the organic acid that from the waste water of high temperature stripper plant 1, by the carbon Absorption of Medium device 2 of carbon material is housed, absorb in waste water, the COD of water outlet is less than 200ppm, and organic acid content is less than 50ppm;
B) COD of the water outlet in carbon Absorption of Medium device 2 approaches 200ppm, and organic acid approaches 60ppm, and carbon material approaches saturated, stops absorption, adopts the liquid of Air blowing device;
C) adopt high-temperature vapor to remove organism and the organic acid that is adsorbed on carbon dielectric surface, further recycle.
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) do not use alkali lye neutralization can reduce the salts contg in waste water, reduce the difficulty of follow-up disposal and utilization;
(2) the method can significantly shorten the flow process of wastewater treatment, reduces the investment of wastewater treatment.
(3) energy consumption of the method processing waste water is low, and carbon medium is easily regenerated, and the life-span is long, and running cost is low.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of embodiment of the present invention.
Embodiment
Below in conjunction with drawings and Examples, describe embodiments of the present invention in detail.
As shown in Figure 1, the system of a kind of aromatization of methanol wastewater treatment of the present invention, comprises for removing the most of organic high temperature stripper plant 1 of waste water, for removing out the waste water organic acid of high temperature stripper plant 1 and the carbon Absorption of Medium device 2 of partial organic substances and for the organic acid that goes out the waste water of carbon Absorption of Medium device 2 being reduced to an anion exchange system 3 of trace.Wherein high temperature stripper plant 1 can be comprised of one or two stripping towers; Carbon Absorption of Medium device 2 can be comprised of one or more carbon Absorption of Medium layers, and carbon medium can be one or more in carbon nanotube, Graphene, expanded graphite, carbon fiber and gac; Anion exchange system 3 can consist of the fixed bed of two filling anionite-exchange resin in parallel.
According to this system, carry out the method for wastewater treatment, first by stripping, remove most of organism, by carbon medium (carbon nanotube, carbon fiber or gac), absorb and remove most of hydro carbons and organic acid again, finally by ion-exchange, remove more up hill and dale disacidify, make the organic acid density loss of final outer draining to 20ppm, COD(Cr) drop to below 200ppm.
The treatment process of the aromatization of methanol processing wastewater that the present invention adopts comprises following steps:
A) first sewage aromatization of methanol processing wastewater enters high temperature stripper plant 1, and the temperature of bottom of device is 100-120oC, removes a large amount of organism and a small amount of organic acid, COD(Cr) is less than 600, and organic acid concentration is less than 200ppm.
B) waste water from high temperature stripper plant 1 enters carbon Absorption of Medium device 2, absorbs and removes organism and the organic acid in waste water, the COD(Cr of its outlet waste water) be less than 200, organic acid concentration is less than 60ppm.
C) from the waste water of carbon Absorption of Medium device 2, enter anion exchange system 3 and remove the organic acid in organic waste water, make to send the organic acid concentration in waste water to be less than 20ppm.
Adopt anionresin to remove the organic acid in waste water, the following steps of guaranteeing replacement:
A) from the waste water of carbon Absorption of Medium device 2 by weak base anion exchange system 3 is housed, organic acid is adsorbed, in anion exchange system 3 water outlets, organic acid content is less than 10ppm.
B) in anion exchange system 3 water outlets, organic acid content is greater than 20ppm, and resin absorption approaches saturated, stops absorption, with air, intrasystem liquid is blown out.
C) to the weak lye that passes into 5-10wt% in saturated ion exchange system 3, carry out desorption.
D) ion exchange system after desorption 3 adopts Air blowing alkali lye.
Adopt carbon Absorption of Medium device 2 to absorb and remove organism and the organic acid in waste water, comprise following steps:
A) organism and the organic acid that from the waste water of high temperature stripper plant 1, by the carbon Absorption of Medium device 2 of carbon material is housed, absorb in waste water, the COD of water outlet is less than 160ppm, and organic acid content is less than 50ppm.
B) COD of the water outlet in carbon Absorption of Medium device 2 approaches 200ppm, and organic acid approaches 60ppm, and carbon material approaches saturated, stops absorption, adopts the liquid of Air blowing device.
C) adopt high-temperature vapor to remove organism and the organic acid that is adsorbed on carbon dielectric surface, further recycle.
Below in conjunction with Fig. 1, this explanation technical scheme is further described.
First waste water from aromatization of methanol system enter single high temperature stripping tower, and the temperature of stripping tower bottom is 120oC, removes a large amount of organism and a small amount of organic acid, the COD(Cr of water outlet) be 500, organic acid concentration is 200ppm.
The waste water of stripping tower enters the carbon Absorption of Medium device 2 that the absorption tower by two one-level parallel connections forms, wherein carbon medium is carbon nanotube, absorption tower is comprised of 10 layers of carbon nanotube absorption layer, utilize carbon nanotube to absorb and remove organism and the organic acid in waste water, the COD(Cr of its outlet waste water) be 160, organic acid concentration is 50ppm.In the outlet waste water of carbon Absorption of Medium device COD concentration higher than 200ppm or organic acid concentration higher than 60ppm after, switch absorption tower, then carry out the regeneration of carbon material in absorption tower, by steam entry, pass into high-temperature vapor and remove organism and the organic acid that is adsorbed on carbon dielectric surface, further recycle.
From the waste water of carbon Absorption of Medium device 2, enter by two anionite-exchange resin in parallel and remove the organic acid in organic waste water as the anion exchange system 3 of filler fixed bed, the organic acid concentration that makes to discharge in waste water is 10ppm.Organic acid concentration in discharging waste water is 20ppm, anionite-exchange resin adsorb gradually saturated after, fixed bed in parallel is switched, and the ammoniacal liquor of use 10% is regenerated, and regenerated liquid is arranged outward, when the exit concentration of ammoniacal liquor reaches 95% when above of entrance concentration, show holomorphosis of resin, stop regeneration, adopt the intrasystem alkali lye of air scavenging, complete reproduction operation, can further switch use.
First waste water from aromatization of methanol system enter single high temperature stripping tower, and the temperature of stripping tower bottom is 100oC, removes a large amount of organism and a small amount of organic acid, the COD(Cr of water outlet) be 600, organic acid concentration is 200ppm.
The waste water of stripping tower enters the carbon Absorption of Medium device 2 being comprised of two absorption towers in parallel, wherein carbon medium is Graphene, absorption tower is comprised of 10 layer graphene absorption layers, utilize Graphene to absorb and remove organism and the organic acid in waste water, the COD(Cr of its outlet waste water) be 140, organic acid concentration is 40ppm.In the outlet waste water of carbon Absorption of Medium device COD concentration higher than 200ppm or organic acid concentration higher than 60ppm after, switch absorption tower, then carry out the regeneration of carbon material in absorption tower, by steam entry, pass into high-temperature vapor and remove organism and the organic acid that is adsorbed on carbon dielectric surface, further recycle.
From the waste water of carbon Absorption of Medium device 2, enter by two anionite-exchange resin in parallel and remove the organic acid in organic waste water as the anion exchange system 3 of filler fixed bed, the organic acid concentration that makes to discharge in waste water is 10ppm.Organic acid concentration in discharging waste water is 20ppm, anionite-exchange resin adsorb gradually saturated after, fixed bed in parallel is switched, and the sodium hydroxide of use 5% is regenerated, and regenerated liquid is arranged outward, when the exit concentration of sodium hydroxide reaches 95% when above of entrance concentration, show holomorphosis of resin, stop regeneration, adopt the intrasystem alkali lye of air scavenging, complete reproduction operation, can further switch use.
First waste water from aromatization of methanol system enter single high temperature stripping tower, and the temperature of stripping tower bottom is 110oC, removes a large amount of organism and a small amount of organic acid, the COD(Cr of water outlet) be 600, organic acid concentration is 200ppm.
The waste water of stripping tower enters the carbon Absorption of Medium device 2 being comprised of two absorption towers in parallel, wherein carbon medium is expanded graphite, its absorption tower is comprised of 5 layers of expanded graphite absorption layer, utilize expanded graphite to absorb and remove organism and the organic acid in waste water, the COD(Cr of its outlet waste water) be 130, organic acid concentration is 45ppm.In the outlet waste water of carbon Absorption of Medium device COD concentration higher than 200ppm or organic acid concentration higher than 60ppm after, switch absorption tower, then carry out the regeneration of carbon material in absorption tower, by steam entry, pass into high-temperature vapor and remove organism and the organic acid that is adsorbed on carbon dielectric surface, further recycle.
From the waste water of carbon Absorption of Medium device 2, enter by two anionite-exchange resin in parallel and remove the organic acid in organic waste water as the anion exchange system 3 of filler fixed bed, the organic acid concentration that makes to discharge in waste water is 8ppm.Organic acid concentration in discharging waste water is 20ppm, anionite-exchange resin adsorb gradually saturated after, fixed bed in parallel is switched, and the calcium hydroxide of use 5% is regenerated, and regenerated liquid is arranged outward, when the exit concentration of calcium hydroxide reaches 95% when above of entrance concentration, show holomorphosis of resin, stop regeneration, adopt the intrasystem alkali lye of air scavenging, complete reproduction operation, can further switch use.
Embodiment 4
First waste water from aromatization of methanol system enter single high temperature stripping tower, and the temperature of stripping tower bottom is 120oC, removes a large amount of organism and a small amount of organic acid, the COD(Cr of water outlet) be 500, organic acid concentration is 150ppm.
The waste water of stripping tower enters the carbon Absorption of Medium device 2 being comprised of two absorption towers in parallel, wherein carbon medium is carbon fiber, its absorption tower absorbs layer by 20 layers of carbon fiber and forms, utilize carbon fiber to absorb and remove organism and the organic acid in waste water, the COD(Cr of its outlet waste water) be 120, organic acid concentration is 40ppm.In the outlet waste water of carbon Absorption of Medium device COD concentration higher than 200ppm or organic acid concentration higher than 60ppm after, switch absorption tower, then carry out the regeneration of carbon material in absorption tower, by steam entry, pass into high-temperature vapor and remove organism and the organic acid that is adsorbed on carbon dielectric surface, further recycle.
From the waste water of carbon Absorption of Medium device 2, enter by two anionite-exchange resin in parallel and remove the organic acid in organic waste water as the anion exchange system 3 of filler fixed bed, the organic acid concentration that makes to discharge in waste water is 5ppm.Organic acid concentration in discharging waste water is 20ppm, anionite-exchange resin adsorb gradually saturated after, fixed bed in parallel is switched, and the ammoniacal liquor of use 5% is regenerated, and regenerated liquid is arranged outward, when the exit concentration of ammoniacal liquor reaches 95% when above of entrance concentration, show holomorphosis of resin, stop regeneration, adopt the intrasystem alkali lye of air scavenging, complete reproduction operation, can further switch use.
Embodiment 5
First waste water from aromatization of methanol system enter single high temperature stripping tower, and the temperature of stripping tower bottom is 120oC, removes a large amount of organism and organic acid, the COD(Cr of water outlet) be 500, organic acid concentration is 150ppm.
The waste water of stripping tower enters the carbon Absorption of Medium device 2 being comprised of two absorption towers in parallel, wherein carbon medium is gac, its absorption tower is comprised of 30 layers of gac absorption layer, utilize gac to absorb and remove organism and the organic acid in waste water, the COD(Cr of its outlet waste water) be 120, organic acid concentration is 40ppm.In the outlet waste water of carbon Absorption of Medium device COD concentration higher than 200ppm or organic acid concentration higher than 60ppm after, switch absorption tower, then carry out the regeneration of carbon material in absorption tower, by steam entry, pass into high-temperature vapor and remove organism and the organic acid that is adsorbed on carbon dielectric surface, further recycle.
From the waste water of carbon Absorption of Medium device 2, enter by two anionite-exchange resin in parallel and remove the organic acid in organic waste water as the anion exchange system 3 of filler fixed bed, the organic acid concentration that makes to discharge in waste water is 5ppm.Organic acid concentration in discharging waste water is 20ppm, anionite-exchange resin adsorb gradually saturated after, fixed bed in parallel is switched, and the ammoniacal liquor of use 5% is regenerated, and regenerated liquid is arranged outward, when the exit concentration of ammoniacal liquor reaches 95% when above of entrance concentration, show holomorphosis of resin, stop regeneration, adopt the intrasystem alkali lye of air scavenging, complete reproduction operation, can further switch use.
Claims (8)
1. the system that aromatization of methanol processing wastewater is processed, is characterized in that, comprising:
Be used for removing the most of organic high temperature stripper plant of waste water (1);
Connect described high temperature stripper plant (1), for removing out the waste water organic acid of high temperature stripper plant (1) and the carbon Absorption of Medium device (2) of partial organic substances;
And connect described carbon Absorption of Medium device (2), for the organic acid that goes out the waste water of carbon Absorption of Medium device (2) being reduced to an anion exchange system (3) of trace.
2. the System and method for that aromatization of methanol processing wastewater according to claim 1 is processed, is characterized in that, described high temperature stripper plant (1) is comprised of one or two stripping towers.
3. the System and method for that aromatization of methanol processing wastewater according to claim 1 is processed, it is characterized in that, described carbon Absorption of Medium device (2) is comprised of one or more carbon Absorption of Medium layers, and described carbon medium is one or more in carbon nanotube, Graphene, expanded graphite, carbon fiber and gac.
4. the System and method for that aromatization of methanol processing wastewater according to claim 1 is processed, is characterized in that, described anion exchange system (3) consists of the fixed bed of two filling anionite-exchange resin in parallel.
5. the method for wastewater treatment based on aromatization of methanol Waste Water Treatment described in claim 1, is characterized in that, comprises the following steps:
A) first sewage aromatization of methanol processing wastewater enters high temperature stripper plant (1), the temperature of high temperature stripper plant (1) bottom is 100-120 ℃, remove therein a large amount of organism and a small amount of organic acid, COD(Cr) be less than 600, organic acid concentration is less than 200ppm;
B) waste water that goes out high temperature stripper plant (1) enters carbon Absorption of Medium device (2), absorbs and removes organism and a part of organic acid in waste water, the COD(Cr of its outlet waste water) be less than 200, organic acid concentration is less than 60ppm;
C) waste water that goes out carbon Absorption of Medium device (2) enters anion exchange system (3) and removes the organic acid in waste water, and the organic acid concentration that makes to discharge in waste water is less than 20ppm.
6. the treatment process of aromatization of methanol processing wastewater according to claim 5, is characterized in that, the organic acid in waste water is removed in described anionresin, comprises the steps:
A) from the waste water of carbon Absorption of Medium device (2) by weak base anion exchange system (3) is housed, part organic acid is adsorbed, in anion exchange system (3) water outlet, organic acid content is less than 10ppm;
B) in anion exchange system (3) water outlet, organic acid content is greater than 20ppm, and resin absorption approaches saturated, stops absorption, with air, intrasystem liquid is blown out;
C) to the weak lye that passes into 5-10wt% in saturated ion exchange system (3), carry out desorption;
D) ion exchange system after desorption (3) adopts Air blowing alkali lye.
7. the treatment process of aromatization of methanol processing wastewater according to claim 6, is characterized in that, described alkali lye comprises ammoniacal liquor, sodium hydroxide, calcium hydroxide.
8. the treatment process of aromatization of methanol processing wastewater according to claim 6, is characterized in that, described carbon Absorption of Medium device (2) absorbs removes organism and the organic acid in waste water, comprises following steps:
A) waste water from high temperature stripper plant (1) absorbs organism and the organic acid in waste water by the carbon Absorption of Medium device (2) of carbon material is housed, and the COD of water outlet is less than 200ppm, and organic acid content is less than 50ppm;
B) COD of the water outlet in carbon Absorption of Medium device (2) approaches 200ppm, and organic acid approaches 60ppm, and carbon material approaches saturated, stops absorption, adopts the liquid of Air blowing device;
C) adopt high-temperature vapor to remove organism and the organic acid that is adsorbed on carbon dielectric surface, further recycle.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108101312A (en) * | 2017-12-30 | 2018-06-01 | 华电煤业集团有限公司 | A kind of system of the wastewater treatment containing aromatic hydrocarbons |
| CN113683261A (en) * | 2021-08-27 | 2021-11-23 | 江苏南大华兴环保科技股份公司 | Treatment method of high-concentration high-salinity methanol organic wastewater |
| CN115215489A (en) * | 2022-09-20 | 2022-10-21 | 山东新和成维生素有限公司 | Method for recovering iodine element from aromatization wastewater |
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| US6462097B1 (en) * | 2000-03-31 | 2002-10-08 | Institut Francais Du Petrole | Process for the production of purified water and hydrocarbons from fossil resources |
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| CN108101312A (en) * | 2017-12-30 | 2018-06-01 | 华电煤业集团有限公司 | A kind of system of the wastewater treatment containing aromatic hydrocarbons |
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| CN113683261B (en) * | 2021-08-27 | 2023-08-29 | 江苏南大华兴环保科技股份公司 | Treatment method of high-concentration high-salt methanol organic wastewater |
| CN115215489A (en) * | 2022-09-20 | 2022-10-21 | 山东新和成维生素有限公司 | Method for recovering iodine element from aromatization wastewater |
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