CN103755087B - The System and method for of a kind of aromatization of methanol processing wastewater process - Google Patents
The System and method for of a kind of aromatization of methanol processing wastewater process Download PDFInfo
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Abstract
The system of a kind of aromatization of methanol processing wastewater process, comprise for remove most of organic high temperature stripper plant in waste water, for remove out high temperature stripper plant waste water in organic acid and the carbon Absorption of Medium device of partial organic substances and an anion exchange system for the organic acid gone out in the waste water of carbon Absorption of Medium device being reduced to trace, during process, first aromatization of methanol processing wastewater enters high temperature stripper plant, removes large amount of organic and a small amount of organic acid wherein; Then in carbon Absorption of Medium device, removing organism and organic acid is further absorbed, last waste water enters anion exchange system and removes organic acid, the organic acid concentration in discharge waste water is made to be less than 20ppm, the present invention does not use alkali lye to neutralize the salts contg that can reduce in waste water, reduces the difficulty of follow-up disposal and utilization; Significantly can shorten the flow process of wastewater treatment, reduce the investment of wastewater treatment, energy consumption is low simultaneously, and carbon medium easily regenerates, and the life-span is long, and running cost is low.
Description
Technical field
The invention belongs to technical field of waste water processing, the System and method for of particularly a kind of aromatization of methanol processing wastewater process.
Background technology
Aromatic hydrocarbons is the important foundation raw material in modern chemical industry, aromatic hydrocarbons is mainly derived from petroleum refining process traditionally, its raw material mainly petroleum naphtha, use this year oxygenatedchemicals aromatics process particularly methyl alcohol dimethyl ether aromatics process reach its maturity, be expected to complete industrial applications between in recent years.
And not yet consider the report of the technology and system aspect for aromatization of methanol spent process water treatment and reuse process at present, and the process of Methanol aromatic hydrocarbons spent process water has the feature of self compared with current waste water treatment process:
1. have certain petroleum substance and alcohols material in waste water, organic content is higher.
2. contain certain Acidic organic matter in waste water.
3. in waste water ammonia nitrogen amount and phenols content lower.
At present, produce a large amount of containing organic acid oily(waste)water in petrochemical complex and Coal Chemical Industry process reaction process, its treatment process generally all adopts conventional treatment process, first the greasy dirt in grid and air-floating apparatus removing waste water, then the organic acid in a large amount of alkali neutralized wastewater is adopted, then the reuse effect of sewage is reached further by biological treatment and advanced treatment, a large amount of salts substances can be generated in waste water in N-process, waste water can be affected and can use the application in system, also can suppress the microorganism in wastewater treatment process in biological treatment process simultaneously, difficulty is brought to follow-up process and comprehensive treating process.Generally speaking, this processing mode long flow path, investment is large, and the working cost of process unit waste water is higher, fluctuation of service.
Summary of the invention
The invention provides the System and method for of a kind of aromatization of methanol processing wastewater process, overcome in above-mentioned organic acid treatment of Organic Wastewater process, N-process is adopted to produce a large amount of salts substances, to follow-up process and comprehensive treating process bring difficulty and existing process flow long, investment is large, the working cost of process unit waste water is higher, the shortcoming of fluctuation of service.
To achieve these goals, the technical solution used in the present invention is:
A system for aromatization of methanol processing wastewater process, comprising:
For removing most of organic high temperature stripper plant 1 in waste water;
Connect described high temperature stripper plant 1, for remove out high temperature stripper plant 1 waste water in the carbon Absorption of Medium device 2 of organic acid and partial organic substances;
And connect described carbon Absorption of Medium device 2, for the organic acid gone out in 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 made up of one or two stripping towers.
Described carbon Absorption of Medium device 2 is made up of one or more carbon dielectric layer, and described carbon medium is one or more in carbon nanotube, Graphene, expanded graphite, carbon fiber and gac.
Described anion exchange system 3 is made up of the fixed bed of two filling anionite-exchange resin in parallel.
Present invention also offers the method for wastewater treatment based on aromatization of methanol Waste Water Treatment described in claim 1, comprise the following steps:
A) first sewage aromatization of methanol processing wastewater enters high temperature stripper plant 1, temperature bottom high temperature stripper plant 1 is 100-120 DEG C, remove a large amount of organism and a small amount of organic acid wherein, COD(Cr) be less than 600, organic acid concentration is less than 200ppm;
B) waste water going out high temperature stripper plant 1 enters carbon Absorption of Medium device 2, absorbs the organism in removing waste water and a part of organic acid, the COD(Cr of its outlet waste water) be less than 200, organic acid concentration is less than 60ppm;
C) waste water going out carbon Absorption of Medium device 2 enters anion exchange system 3 and removes organic acid in waste water, makes the organic acid concentration in discharge waste water be less than 20ppm.
Organic acid in described anionresin removing waste water, comprises the steps:
A) from the waste water of carbon Absorption of Medium device 2 by being equipped with weak base anion exchange system 3, part organic acid is adsorbed, and 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, close to saturated, stop absorption, blown out by intrasystem liquid with air;
C) weak lye passing into 5-10wt% in saturated ion exchange system 3 carries out desorption;
D) ion exchange system 3 after desorption adopts Air blowing alkali lye.
Described alkali lye comprises ammoniacal liquor, sodium hydroxide, calcium hydroxide.
Organism in described carbon Absorption of Medium device 2 absorption removing waste water and organic acid, comprise following steps:
A) waste water from high temperature stripper plant 1 absorbs organism in waste water and organic acid by the carbon Absorption of Medium device 2 that carbon material is housed, and the COD of water outlet is less than 200ppm, and organic acid content is less than 50ppm;
The COD of the water outlet b) in carbon Absorption of Medium device 2 is close to 200ppm, and organic acid is close to 60ppm, and carbon material, close to saturated, stops absorption, adopts the liquid of Air blowing device;
C) adopt high-temperature vapor to remove the organism and organic acid that are adsorbed on carbon dielectric surface, recycle further.
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) do not use alkali lye to neutralize the salts contg that can reduce in waste water, reduce the difficulty of follow-up disposal and utilization;
(2) the method significantly can shorten the flow process of wastewater treatment, reduces the investment of wastewater treatment.
(3) energy consumption of the method process waste water is low, and carbon medium easily regenerates, 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
Embodiments of the present invention are described in detail below in conjunction with drawings and Examples.
As shown in Figure 1, the system of a kind of aromatization of methanol wastewater treatment of the present invention, comprise for remove most of organic high temperature stripper plant 1 in waste water, for remove out high temperature stripper plant 1 waste water in organic acid and the carbon Absorption of Medium device 2 of partial organic substances and an anion exchange system 3 for the organic acid gone out in the waste water of carbon Absorption of Medium device 2 being reduced to trace.Wherein high temperature stripper plant 1 can be made up of one or two stripping towers; Carbon Absorption of Medium device 2 can be made up of one or more carbon dielectric layer, and carbon medium can be one or more in carbon nanotube, Graphene, expanded graphite, carbon fiber and gac; Anion exchange system 3 can be made up of the fixed bed of two filling anionite-exchange resin in parallel.
The method of wastewater treatment is carried out according to this system, first most of organism is removed by stripping, absorbed by carbon medium (carbon nanotube, carbon fiber or gac) again and remove most of hydro carbons and organic acid, finally by ion-exchange more up hill and dale except disacidify, make the organic acid density loss of final outer draining to below 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) be less than 600, organic acid concentration is less than 200ppm.
B) waste water from high temperature stripper plant 1 enters carbon Absorption of Medium device 2, absorbs the organism in removing waste water and organic acid, the COD(Cr of its outlet waste water) be less than 200, organic acid concentration is less than 60ppm.
C) enter anion exchange system 3 from the waste water of carbon Absorption of Medium device 2 and remove organic acid in organic waste water, make to send the organic acid concentration in waste water to be less than 20ppm.
Adopt the organic acid in anionresin removing waste water, following steps of guaranteeing replacement:
A) from the waste water of carbon Absorption of Medium device 2 by being equipped with weak base anion exchange system 3, organic acid is adsorbed, and 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, close to saturated, stop absorption, blown out by intrasystem liquid with air.
C) weak lye passing into 5-10wt% in saturated ion exchange system 3 carries out desorption.
D) ion exchange system 3 after desorption adopts Air blowing alkali lye.
Adopt the organism in carbon Absorption of Medium device 2 absorption removing waste water and organic acid, comprise following steps:
A) waste water from high temperature stripper plant 1 absorbs organism in waste water and organic acid by the carbon Absorption of Medium device 2 that carbon material is housed, and the COD of water outlet is less than 160ppm, and organic acid content is less than 50ppm.
The COD of the water outlet b) in carbon Absorption of Medium device 2 is close to 200ppm, and organic acid is close to 60ppm, and carbon material, close to saturated, stops absorption, adopts the liquid of Air blowing device.
C) adopt high-temperature vapor to remove the organism and organic acid that are adsorbed on carbon dielectric surface, recycle further.
Below in conjunction with Fig. 1, this explanation technical scheme is further described.
Embodiment 1
First waste water from aromatization of methanol system enter single high temperature stripping tower, and the temperature bottom stripping tower 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 be made up of the absorption tower of two one-level parallel connections, wherein carbon medium is carbon nanotube, absorption tower is made up of 10 layers of carbon nanotube absorption layer, utilize the organism in carbon nanotube absorption removing waste water and organic acid, 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 the regeneration of carbon material in absorption tower is carried out, pass into high-temperature vapor by steam entry and remove the organism and organic acid that are adsorbed on carbon dielectric surface, recycle further.
Waste water from carbon Absorption of Medium device 2 enters the organic acid removed as the anion exchange system 3 of filler fixed bed by two anionite-exchange resin in parallel in organic waste water, makes the organic acid concentration in discharge waste water be 10ppm.When the organic acid concentration in discharge waste water is 20ppm, anionite-exchange resin adsorb gradually saturated after, switched by the fixed bed of parallel connection, use the ammoniacal liquor of 10% to regenerate, regenerated liquid is arranged outward, when the exit concentration of ammoniacal liquor reaches more than 95% of entrance concentration, show resin holomorphosis, stop regeneration, adopt the intrasystem alkali lye of air scavenging, complete reproduction operation, switching can be carried out further and use.
Embodiment 2
First waste water from aromatization of methanol system enter single high temperature stripping tower, and the temperature bottom stripping tower 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 be made up of two absorption towers in parallel, wherein carbon medium is Graphene, absorption tower is made up of 10 layer graphene absorption layers, utilize the organism in Graphene absorption removing waste water and organic acid, 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 the regeneration of carbon material in absorption tower is carried out, pass into high-temperature vapor by steam entry and remove the organism and organic acid that are adsorbed on carbon dielectric surface, recycle further.
Waste water from carbon Absorption of Medium device 2 enters the organic acid removed as the anion exchange system 3 of filler fixed bed by two anionite-exchange resin in parallel in organic waste water, makes the organic acid concentration in discharge waste water be 10ppm.When the organic acid concentration in discharge waste water is 20ppm, anionite-exchange resin adsorb gradually saturated after, switched by the fixed bed of parallel connection, use the sodium hydroxide of 5% to regenerate, regenerated liquid is arranged outward, when the exit concentration of sodium hydroxide reaches more than 95% of entrance concentration, show resin holomorphosis, stop regeneration, adopt the intrasystem alkali lye of air scavenging, complete reproduction operation, switching can be carried out further and use.
Embodiment 3
First waste water from aromatization of methanol system enter single high temperature stripping tower, and the temperature bottom stripping tower 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 be made up of two absorption towers in parallel, wherein carbon medium is expanded graphite, its absorption tower is made up of 5 layers of expanded graphite absorption layer, utilize the organism in expanded graphite absorption removing waste water and organic acid, 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 the regeneration of carbon material in absorption tower is carried out, pass into high-temperature vapor by steam entry and remove the organism and organic acid that are adsorbed on carbon dielectric surface, recycle further.
Waste water from carbon Absorption of Medium device 2 enters the organic acid removed as the anion exchange system 3 of filler fixed bed by two anionite-exchange resin in parallel in organic waste water, makes the organic acid concentration in discharge waste water be 8ppm.When the organic acid concentration in discharge waste water is 20ppm, anionite-exchange resin adsorb gradually saturated after, switched by the fixed bed of parallel connection, use the calcium hydroxide of 5% to regenerate, regenerated liquid is arranged outward, when the exit concentration of calcium hydroxide reaches more than 95% of entrance concentration, show resin holomorphosis, stop regeneration, adopt the intrasystem alkali lye of air scavenging, complete reproduction operation, switching can be carried out further and use.
Embodiment 4
First waste water from aromatization of methanol system enter single high temperature stripping tower, and the temperature bottom stripping tower 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 be made up of two absorption towers in parallel, wherein carbon medium is carbon fiber, its absorption tower is made up of 20 layers of carbon fiber absorption layer, utilize the organism in carbon fiber absorption removing waste water and organic acid, 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 the regeneration of carbon material in absorption tower is carried out, pass into high-temperature vapor by steam entry and remove the organism and organic acid that are adsorbed on carbon dielectric surface, recycle further.
Waste water from carbon Absorption of Medium device 2 enters the organic acid removed as the anion exchange system 3 of filler fixed bed by two anionite-exchange resin in parallel in organic waste water, makes the organic acid concentration in discharge waste water be 5ppm.When the organic acid concentration in discharge waste water is 20ppm, anionite-exchange resin adsorb gradually saturated after, switched by the fixed bed of parallel connection, use the ammoniacal liquor of 5% to regenerate, regenerated liquid is arranged outward, when the exit concentration of ammoniacal liquor reaches more than 95% of entrance concentration, show resin holomorphosis, stop regeneration, adopt the intrasystem alkali lye of air scavenging, complete reproduction operation, switching can be carried out further and use.
Embodiment 5
First waste water from aromatization of methanol system enter single high temperature stripping tower, and the temperature bottom stripping tower 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 be made up of two absorption towers in parallel, wherein carbon medium is gac, its absorption tower is made up of 30 layers of gac absorption layer, utilize the organism in gac absorption removing waste water and organic acid, 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 the regeneration of carbon material in absorption tower is carried out, pass into high-temperature vapor by steam entry and remove the organism and organic acid that are adsorbed on carbon dielectric surface, recycle further.
Waste water from carbon Absorption of Medium device 2 enters the organic acid removed as the anion exchange system 3 of filler fixed bed by two anionite-exchange resin in parallel in organic waste water, makes the organic acid concentration in discharge waste water be 5ppm.When the organic acid concentration in discharge waste water is 20ppm, anionite-exchange resin adsorb gradually saturated after, switched by the fixed bed of parallel connection, use the ammoniacal liquor of 5% to regenerate, regenerated liquid is arranged outward, when the exit concentration of ammoniacal liquor reaches more than 95% of entrance concentration, show resin holomorphosis, stop regeneration, adopt the intrasystem alkali lye of air scavenging, complete reproduction operation, switching can be carried out further and use.
Claims (7)
1. a system for aromatization of methanol processing wastewater process, is characterized in that, comprising:
For removing most of organic high temperature stripper plant (1) in waste water;
Connect described high temperature stripper plant (1), for remove out high temperature stripper plant (1) waste water in the carbon Absorption of Medium device (2) of organic acid and partial organic substances, described carbon Absorption of Medium device (2) is made up of one or more carbon dielectric layer, and described carbon medium is one or more in carbon nanotube, Graphene, expanded graphite and carbon fiber;
And connect described carbon Absorption of Medium device (2), for the organic acid gone out in the waste water of carbon Absorption of Medium device (2) being reduced to an anion exchange system (3) of trace.
2. the system of aromatization of methanol processing wastewater according to claim 1 process, is characterized in that, described high temperature stripper plant (1) is made up of one or two stripping towers.
3. the system of aromatization of methanol processing wastewater according to claim 1 process, is characterized in that, described anion exchange system (3) is made up of the fixed bed of two filling anionite-exchange resin in parallel.
4., based on the method for wastewater treatment of aromatization of methanol Waste Water Treatment described in claim 1, it is characterized in that, comprise 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 DEG C, remove a large amount of organism and a small amount of organic acid wherein, COD (Cr) is less than 600ppm, and organic acid concentration is less than 200ppm;
B) waste water going out high temperature stripper plant (1) enters carbon Absorption of Medium device (2), absorb the organism in removing waste water and a part of organic acid, the COD (Cr) of its outlet waste water is less than 200ppm, and organic acid concentration is less than 60ppm;
C) waste water going out carbon Absorption of Medium device (2) enters the organic acid in anion exchange system (3) removing waste water, makes the organic acid concentration in discharge waste water be less than 20ppm.
5. the treatment process of aromatization of methanol processing wastewater according to claim 4, is characterized in that, the organic acid in described anionresin removing waste water, comprises the steps:
A) from the waste water of carbon Absorption of Medium device (2) by being equipped with weak base anion exchange system (3), part organic acid is adsorbed, and 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, close to saturated, stop absorption, blown out by intrasystem liquid with air;
C) weak lye passing into 5-10wt% in saturated ion exchange system (3) carries out desorption;
D) ion exchange system (3) after desorption adopts Air blowing alkali lye.
6. the treatment process of aromatization of methanol processing wastewater according to claim 5, it is characterized in that, described alkali lye comprises ammoniacal liquor, sodium hydroxide, calcium hydroxide.
7. the treatment process of aromatization of methanol processing wastewater according to claim 5, is characterized in that, described carbon Absorption of Medium device (2) absorbs organism in removing waste water and organic acid, comprises following steps:
A) waste water from high temperature stripper plant (1) absorbs organism in waste water and organic acid by the carbon Absorption of Medium device (2) that carbon material is housed, and the COD of water outlet is less than 200ppm, and organic acid content is less than 50ppm;
The COD of the water outlet b) in carbon Absorption of Medium device (2) is close to 200ppm, and organic acid is close to 60ppm, and carbon material, close to saturated, stops absorption, adopts the liquid of Air blowing device;
C) adopt high-temperature vapor to remove the organism and organic acid that are adsorbed on carbon dielectric surface, recycle further.
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| CN115215489B (en) * | 2022-09-20 | 2022-11-18 | 山东新和成维生素有限公司 | Method for recovering iodine element from aromatization wastewater |
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| ITMI20081035A1 (en) * | 2008-06-06 | 2009-12-07 | Eni Spa | PROCESS FOR THE TREATMENT OF THE AQUEOUS CURRENT COMING FROM THE REACTION OF FISCHER-TROPSCH BY MEANS OF IONIC EXCHANGE RESINS |
| CN102040303B (en) * | 2009-10-23 | 2012-07-18 | 中国石油化工股份有限公司 | Method for recovering organic matters in wastewater generated in process for preparing olefin from methanol |
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