CN104826670B - Remove the method and device of oil pollutant contained by catalyst micro mist in MTO chilling waste water - Google Patents
Remove the method and device of oil pollutant contained by catalyst micro mist in MTO chilling waste water Download PDFInfo
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Abstract
The present invention relates to the method and device for removing oil pollutant contained by catalyst micro mist in MTO chilling waste water, there is provided the method for oil pollutant contained by catalyst micro mist, this method comprise the following steps in a kind of removal MTO chilling waste water：(1) storage regulation and control；(2) hydro-thermal micro-cyclone de is attached；And (3) wet-type peroxide oxidizing.Additionally provide a kind of device of oil pollutant contained by catalyst micro mist in removal MTO chilling waste water.
Description
Technical field
The invention belongs to coal chemical industry and field of Environment Protection, is related to oil-containing catalyst micro mist oil removing in a kind of MTO chillings waste water
Method and apparatus, to realize the target that catalyst is purified, reclaimed from oil-containing catalyst micro mist.Specifically, the present invention provides
A kind of hydro-thermal micro-cyclone de is attached to integrate oil-containing catalyst in coupling technique processing MTO chilling waste water with wet-type peroxide oxidizing
The method and device of micro mist.
Background technology
MTO is the abbreviation of methanol-to-olefins, and its general principle is converted through synthesising gas systeming carbinol, then by methanol from coal
For low-carbon alkenes such as ethene, propylene.MTO technologies representative at present have：UOP, UOP/Hydro, ExxonMobil and big
The even technology of the Chemistry and Physics Institute (DMTO).With increasingly soaring and traditional production line via oil of low-carbon alkene demand
Because of the worsening shortages of petroleum resources, the development of MTO technology and its industrial applications have caused the weight of various aspects
Depending on.
Based on the characteristic of the easy carbon distribution inactivation of MTO catalyst, generally use successive reaction-regeneration follows in MTO industrial productions
Ring fluid bed is reacted.In prolonged fluidized reaction, catalyst can be worn away, catalyst micro mist caused by abrasion because
Size distribution reason can not participate in fluidized reaction again, and reactor is discharged with product effluent.Carry the product row of catalyst micro mist
Go out after stream leaves reactor and enter chilling tower chilling, most of catalyst micro mist enters in water as chilled water (chw) discharges chilling tower.
For catalyst during reactor catalysis reacts and is discharged to chilled water (chw) to outside wearing away, it is dirty that its particle surface can adsorb substantial amounts of oils
Thing (high molecular alkane, aromatic hydrocarbons, ketone, ester etc.) is contaminated, these pollutants can be to human body, animals and plants, air water body ring into environment
Cause high risks in border.For waste catalyst, various countries have formulated a large amount of strict legislationss of environmental protection one after another.U.S. environment is protected
Dead catalyst is classified as danger wastes by shield administration (EPA).Dead catalyst is included in National Hazard in 2008 by Environment Protect in China portion
Waste register, and its hazard property is classified as T levels (poisonous)., should maximum in commercial Application and MTO catalyst price is higher
The consideration of limit recycles, but these pollutants are attached to catalyst micro mist surface, directly affect the recovery of catalyst again
It is raw.Therefore in order to reach the purpose of environmental protection and catalyst recycle, it is necessary to catalyst micro mist contained oil in chilling waste water
Pollutant is removed.
The catalyst micro mist that CN 102658213A are disclosed in a kind of chilling waste water to MTO is concentrated, dried, so as to
The method and apparatus for reclaiming catalyst in solid form.CN 103951098A disclose one kind and use UF membrane and three-phase cyclone
The method and apparatus of the integrated coupling of separator solid oil removing de- to MTO chilled water (chw)s.But invention is simply by catalyst micro mist solid above
Concentrate, separate from chilled water (chw), and oil pollutant of the absorption on catalyst micro mist can not be removed.
The oil-containing catalyst micro mist arranged outside chilled water (chw) belongs to oil containing medium.Hydrothermal desorption method is current processing oil containing medium
A kind of more universal method, and had certain commercial Application basis.But traditional hydrothermal desorption equipment needs larger
Mixing plant hydrothermal desorption is stirred to oily waste, often make processing equipment volume bigger than normal, and handle in this way
Oil containing medium the halfway problem of de-oiling also be present, the presence of these problems limit the application of conventional hydrothermal separating process with
Development.
Wet oxidation process refers at high temperature under high pressure, anti-using oxidation in aqueous by the use of oxygen or air as oxidant
Organic pollution should be handled, is allowed to be degraded to the technology of the inorganic matters such as carbon dioxide, water.This method has that flow is simple, processing is dirty
The advantages that species are more, contaminant degradation is thorough are contaminated, there is certain grind in terms of processing waste water from dyestuff, organism P wastewater
Study carefully and apply.Wet-type peroxide oxidizing method, it is the development to wet oxidation process, its change is to use hydrogen peroxide as liquid
Oxidant, compared to hyperbaric oxygen or compressed air, system stagnation pressure can be reduced to a certain extent, is improved because of caused by high pressure
Equipment corrosion, security problems.Other hydrogen peroxide autoxidation is very competent, can directly by organic pollution or reproducibility without
Organic pollutants aoxidize, and its catabolite is water and oxygen, and new impurity will not be introduced to reaction system, is had a extensive future.
CN 103611567A disclose a kind of renovation process of the MTO catalyst based on wet-type peroxide oxidizing method, should
Method removes the organic matter of entrainment by being stripped to decaying catalyst, then by aoxidizing further oil removing, then to oil removing
Catalyst afterwards carries out filtering off the removal of impurity and the stable processing of mediation, obtains the catalyst of activation recovering.But the method flow compared with
To grow, technique is cumbersome, and only for the catalyst inactivated in MTO fluidized reactions, the catalyst micro mist arranged outside for chilled water (chw) entrainment,
Due to reasons such as its particle size features, its deoiling effect is simultaneously preferable.
So far, a kind of side for being directed to catalyst micro mist in MTO chilling waste water and carrying out oil removing is not yet developed in this area
Method.Therefore, there is an urgent need to develop a kind of method for being directed to catalyst micro mist progress oil removing in MTO chilling waste water for this area.
The content of the invention
The invention provides a kind of method of oil pollutant contained by catalyst micro mist in novel removal MTO chilling waste water
And device, overcome defect present in prior art.
On the one hand, the invention provides a kind of side of oil pollutant contained by catalyst micro mist in removal MTO chilling waste water
Method, this method comprise the following steps：
(1) storage regulation and control：MTO catalyst micro mist slurry after pre-treatment by concentration is stored, in storage process
In by heating temperature adjustment to 20-180 DEG C, to reduce the viscosity of the oil pollutant of catalyst micro mist surface attachment；
(2) hydro-thermal micro-cyclone de is attached：The micro- rotation of hydro-thermal is carried out to the catalyst micro mist through storage regulation and control obtained in step (1)
Stream desorption pretreatment, to complete the preliminary desorption of catalyst micro mist surface contaminant；And
(3) wet-type peroxide oxidizing：By the catalyst micro mist attached through hydro-thermal micro-cyclone de obtained in step (2) through adjusting
PH to 0-10, pressure regulation to the 0.1-10MPa in terms of gauge pressure, temperature adjustment are saved to after 20-180 DEG C, is sufficiently mixed with hydrogen peroxide so that contain
Under the oxidation of hydrogen peroxide wet oxidation reaction occurs for oily catalyst micro mist, makes oils of the absorption on catalyst micro mist surface dirty
Dye thing is oxidized to inorganic matter or small organic molecule soluble in water, so as to be separated from catalyst micro mist surface desorption, completes
To the final desorption of catalyst micro mist.
In one preferred embodiment, in step (2), water-oil separating is carried out to caused oil-containing hot water, realized
The recovery of oil and recycling for separating obtained water；Eddy flow concentration is carried out to the mixture of caused catalyst micro mist and water,
Catalyst micro mist after thickening enters step (3), and the water that concentration takes off recycles during hydro-thermal micro-cyclone de is attached；
In step (3), micro- eddy flow concentration is carried out to the mixture of treated catalyst micro mist and reaction solution, concentration is de-
Catalyst micro mist after water carries out internal return micro mist drying, and the reaction solution remained in micro mist is removed, realizes catalyst micro mist
Clean recovery；The reaction solution that concentration takes off recycles during wet-type peroxide oxidizing.
In another preferred embodiment, the particle diameter of catalyst micro mist in the MTO chilling waste water after the pre-treatment
For 0.5-250 μm, moisture content is 0.01~100 weight %, and oil content is 0.01-35 weight %, specific surface area is 1~
2500m2/g。
On the other hand, the invention provides oil pollutant contained by catalyst micro mist in a kind of removal MTO chilling waste water
Device, the device include：
Storage regulation tank, for the MTO catalyst micro mist slurry after pre-treatment by concentration to be stored, and control room
Have a rest discharging, to ensure that the interval of wet-type peroxide oxidizing processing procedure is carried out；
The micro-cyclone de adnexa being connected with the discharging opening of the storage regulation tank, for being obtained to storage regulation tank through storage
The catalyst micro mist for depositing regulation and control carries out the attached pretreatment of hydro-thermal micro-cyclone de, to complete the preliminary de- of catalyst micro mist surface contaminant
It is attached；
The pH regulation tanks being connected with the micro-cyclone de adnexa, for the pH value of catalyst micro mist to be adjusted；
The feed pump being connected with the discharging opening of pH regulation tanks, for catalyst micro mist to be pumped into stirred autoclave,
And it is forced into reaction pressure；
The heat exchanger that outlet with the feed pump connects, for post catalyst reaction micro mist and the mixture of reaction solution
Cooling and catalyst micro mist first heating；
With another heat exchanger of the outlet connection of the heat exchanger, adding for rear catalyst micro mist is heated for first
Heat, make up to reaction temperature；And
With the stirred autoclave of the outlet connection of the heat exchanger, for by catalyst micro mist and hydrogen peroxide in kettle
Interior abundant haptoreaction, it is oxidized oil pollutant and decomposes, complete catalyst particles surface attachment oil pollutant most
Desorption eventually.
In one preferred embodiment, the device also includes：With the oil-containing hot water outlet of the micro-cyclone de adnexa
The cycling hot water pot of connection, to complete the standing water-oil separating of oil-containing hot water, realize hot water circuit utilization and the recovery of oil；
The circulating hot-water pump being connected with the delivery port of the cycling hot water pot, for circulating hot water to be pumped into storage regulation
Tank recycles；
With the catalyst micro mist enrichment phase of micro-cyclone de adnexa outlet connection, be placed in micro-cyclone de adnexa and pH tune
Micro- swirl concentrator between tank is saved, the mixture for externally arranging catalyst micro mist and water carries out dehydration decrement, forms catalysis
Agent micro mist concentrate feed；
The knockout drum being connected with the discharging opening of the stirred autoclave, for reacted gaseous phase materials and liquid phase
Material carries out standing separation；
The incinerator being connected with the gaseous phase materials discharging opening of the knockout drum, for having caused in course of reaction
Evil gas is oxidized to CO2；
With the CO of the outlet connection of the incinerator2Absorption tower, for by the CO after burning2Absorbed；
The booster pump being connected with the liquid phase material discharging opening of described knockout drum, for by catalyst micro mist and reaction
The mixture of liquid is pumped to micro- swirl concentrator；
Micro- swirl concentrator that outlet with the booster pump connects, for the mixture to catalyst micro mist and reaction solution
De- liquid decrement is carried out, forms catalyst micro mist concentrate feed；
The internal return drying machine that catalyst micro mist concentrate feed outlet with micro- swirl concentrator connects, for catalyst
The final drying of micro mist concentrate feed takes off liquid, realizes the recovery of catalyst micro mist solid.
In another preferred embodiment, the ratio of catalyst micro mist and circulating hot water is in the storage regulation tank
1/1000000 to 2/1, by weight；It is described storage regulation tank operation temperature be 20~180 DEG C, operating pressure be 0.1~
10MPa, in terms of gauge pressure, regulating time is 1~1800s；The storage regulation tank, which is selected from, is dispersed with stirring equipment.
In another preferred embodiment, the catalyst micro mist point of micro- swirl concentrator and micro- swirl concentrator
It is not less than 85% from efficiency, operation pressure drop is not more than 30mmH2O；Selected from hydrocyclone；Be by it is single, two or more are micro-
Eddy flow core pipe composes in parallel.
In another preferred embodiment, the pH value of catalyst micro mist slurry after adjustment is in the pH regulations tank
0~10；The pH regulations tank, which is selected from, is dispersed with stirring equipment.
In another preferred embodiment, the concentration of the hydrogenperoxide steam generator added in the stirred autoclave is
0.1~28 weight %；The ratio of catalyst micro mist slurry and hydrogenperoxide steam generator is 1/1000000 to 5/1, by weight；Institute
The operation temperature for stating stirred autoclave is 20~180 DEG C, and operating pressure be 0.1~10MPa, in terms of gauge pressure, regulating time for 1~
1800s。
In another preferred embodiment, the temperature of the internal return drying machine is not less than 85 DEG C or higher than reaction solution
Boiling point；The oil content of catalyst micro mist after wet-type peroxide oxidizing is brought down below 0.01~20 weight after the drying
% is measured, in terms of the weight of outer row's catalyst micro mist.
Brief description of the drawings
Fig. 1 is the treatment of process streams according to the MTO chilling waste water oil-containing catalyst micro mists of an embodiment of the invention
Cheng Tu.
Embodiment
Present inventor is by extensive and found after in-depth study：
Arranged outside MTO in chilling waste water in the oil removal treatment of oil-containing catalyst micro mist, wet-type peroxide oxidizing method has
The characteristics of technique is simple, oil removing is thorough；But consider for economic benefit, it is necessary to oil-containing catalyst micro mist in wet type peroxidating
Hydroxide before processing carries out preliminary oil removing pretreatment, the attached method of hydro-thermal micro-cyclone de based on hydrothermal desorption principle be it is a kind of it is economical,
Easy de-oiling preprocess method；Therefore, whole handling process integrates the principle of hydrothermal desorption and wet-type peroxide oxidizing
Coupling, makes two kinds of principal advantage complementations, whole processing procedure embodies preferable high efficiency, practicality and economy；
The attached method of hydro-thermal micro-cyclone de is the optimization to conventional hydrothermal desorption method, i.e., is made using the Osima jacoti, Osima excavata in eddy flow field
With a kind of deoiling method of reinforcing hydrothermal desorption effect, its process characteristic is very suitable for removing oil-containing catalyst micro mist in advance
Oil processing, make oil pollutant minimizing；
Wet-type peroxide oxidizing method is a kind of advanced organic contamination substance treating method, and hydrogen peroxide has Strong oxdiative
Property, in the reaction system of HTHP, by stirring, catalyst micro mist is carried out sufficient haptoreaction with hydrogen peroxide,
Be attached to catalyst micro mist surface oil pollutant (high molecular alkane, aromatic hydrocarbons, ketone, ester etc.) be oxidized to carbon dioxide,
The inorganic matters such as water or small organic molecule soluble in water, so as to be separated from catalyst micro mist surface desorption, complete to catalyst
The final desorption of micro mist；Whole oxidizing process pollutant desorption is thoroughly, cost is low, pollution is small, equipment is relatively easy, has fine
Applicability.
Based on above-mentioned discovery, with reference to micro- eddy flow hydrothermal desorption and the integrated thought coupled of wet-type peroxide oxidizing, this hair
It is bright to be accomplished.
In the first aspect of the present invention, there is provided one kind removes oil pollution contained by catalyst micro mist in MTO chilling waste water
The method of thing, this method comprise the following steps：
(1) storage regulation and control：MTO catalyst micro mist slurry after pre-treatment by concentration is stored, in storage process
In by heating water temperature adjustment, to reduce the viscosity of the oil pollutant of catalyst micro mist surface attachment, improve oil, salt pollutant exists
The mobility on catalyst micro mist surface；
(2) hydro-thermal micro-cyclone de is attached：The attached pretreatment of hydro-thermal micro-cyclone de is carried out to the catalyst micro mist after regulation and control, utilizes rotation
The preliminary desorption of catalyst micro mist surface contaminant is completed in Osima jacoti, Osima excavata effect in flow field；
(3) wet-type peroxide oxidizing：Will by the attached adjusted pH of catalyst micro mist of hydro-thermal micro-cyclone de, pressure regulation,
Interval feeding is also added to stirred autoclave, and by hydrogen peroxide in a manner of intermittent take-off after temperature adjustment, by stirring, makes catalysis
Agent micro mist with hydrogen peroxide is sufficiently mixed, whole system reaches optimum reactiveness, oil-containing catalyst micro mist is in peroxidating
Wet oxidation reaction occurs under the oxidation of hydrogen, adsorb catalyst micro mist surface oil pollutant (macromolecule alkane, aromatic hydrocarbons,
Ketone, ester etc.) inorganic matters such as carbon dioxide, water or small organic molecule soluble in water are oxidized to, so as to from catalyst micro mist
Surface desorption separates, and completes the final desorption to catalyst micro mist.
It is preferred that in the hydro-thermal micro-cyclone de attached middle school of step (2), water-oil separating is carried out to caused oil-containing hot water, realized
The recovery of oil and recycling for separating obtained water；Eddy flow concentration is carried out to the mixture of caused catalyst micro mist and water,
Catalyst micro mist after thickening enters step (3), and the water that concentration takes off recycles during hydro-thermal micro-cyclone de is attached.
It is preferred that in step (3) during wet-type peroxide oxidizing, to treated catalyst micro mist and reaction solution
Mixture carry out micro- eddy flow concentration, the catalyst micro mist after thickening carries out internal return micro mist drying, will be remained in micro mist
Reaction solution removing, realize the clean recovery of catalyst micro mist, concentration it is de- reaction solution in wet-type peroxide oxidizing process
Middle recycling.
In the present invention, the particle diameter that catalyst micro mist is arranged outside the MTO chillings waste water after the pre-treatment is 0.5-250 μm,
It is preferred that 3 μm, moisture content is 0.01~100 weight %, preferably 3 weight %, and oil content is 0.01-35 weight %, preferably 24.0 weights
% is measured, with catalyst weight, specific surface area is 1~2500m2/ g, preferably 58m2/ g, pore volume are preferably 0.019ml/g.
In the second aspect of the present invention, there is provided one kind removes oil pollution contained by catalyst micro mist in MTO chilling waste water
The device of thing, the device include：
Storage regulation tank, for storage to be adjusted to the MTO chilling waste water catalyst micro mist slurries after concentration, and is controlled
Intermittent take-off, to ensure that the interval of wet-type peroxide oxidizing processing procedure is carried out；
The micro-cyclone de adnexa being connected with the discharging opening of the storage regulation tank, for being cut by the flowing in rotational flow field
Shear force realizes the preliminary desorption of catalyst micro mist surface attachment oil pollutant；
The cycling hot water pot being connected with the oil-containing hot water outlet of the micro-cyclone de adnexa, to complete the quiet of oil-containing hot water
Water-oil separating is put, realizes hot water circuit utilization and the recovery of oil；
The circulating hot-water pump being connected with the delivery port of the cycling hot water pot, for circulating hot water to be pumped into storage regulation
Tank recycles；
With micro- swirl concentrator of the catalyst micro mist enrichment phase outlet connection of the micro-cyclone de adnexa, arranged for external
Catalyst micro mist/aqueous mixtures carry out dehydration decrement, form catalyst micro mist concentrate feed；
Tank is adjusted with the pH of the catalyst micro mist concentrate feed outlet connection of micro- swirl concentrator, for micro- to catalyst
The pH value of powder concentrate feed is adjusted；
The feed pump being connected with the discharging opening of pH regulation tanks, it is anti-for being pumped to stirring to catalyst micro mist concentrate feed
Kettle is answered, and is forced into reaction pressure；
The heat exchanger that outlet with the feed pump connects, for post catalyst reaction micro mist/reaction liquid mixture
Cooling and the first heating of catalyst differential concentrate feed；
With another heat exchanger of the outlet connection of the heat exchanger, rear catalyst micro mist concentrate feed is heated for first
Heating, make up to reaction temperature；
With the stirred autoclave of the outlet connection of the heat exchanger, for by catalyst micro mist and hydrogen peroxide in kettle
Interior abundant haptoreaction, it is oxidized oil pollutant and decomposes, complete catalyst particles surface attachment oil pollutant most
Desorption eventually；
The knockout drum being connected with the discharging opening of the stirred autoclave, for reacted gaseous phase materials and liquid phase
Material carries out standing separation；
The incinerator being connected with the gaseous phase materials discharging opening of the knockout drum, for by caused CO in course of reaction
CO is oxidized to Deng pernicious gas2Deng gas；
With the CO of the outlet connection of the incinerator2Absorption tower, for by the CO after burning2Absorbed Deng gas；
The booster pump being connected with the liquid phase material discharging opening of described knockout drum, for by catalyst micro mist/reaction
Liquid mixture is pumped to micro- swirl concentrator；
Micro- swirl concentrator that outlet with the booster pump connects, for entering to catalyst micro mist/reaction liquid mixture
The de- liquid decrement of row, forms catalyst micro mist concentrate feed；
The internal return drying machine that catalyst micro mist concentrate feed outlet with micro- swirl concentrator connects, for catalyst
The final drying of micro mist concentrate feed takes off liquid, realizes the recovery of catalyst micro mist solid.
It is preferred that the ratio of catalyst micro mist and circulating hot water is 1/1000000 to 2/1 in the storage regulation tank, it is excellent
1/100 is selected, by weight；It is described storage regulation tank operation temperature be 20~180 DEG C, preferably 95 DEG C, operating pressure be 0.1~
10MPa, preferably 0.3MPa, in terms of gauge pressure, regulating time is 1~1800s, preferably 600s.
It is preferred that the catalyst dust removing efficiency of micro- swirl concentrator is not less than 85%, operation pressure drop is not more than
30mmH2O；The swirl concentrator is selected from hydrocyclone；Micro- swirl concentrator be by it is single, two or more
What micro- eddy flow core pipe composed in parallel.
It is preferred that the pH value of catalyst micro mist slurry after adjustment is 0~10, preferably 3.0 in the pH regulations tank.
It is preferred that the concentration of the hydrogenperoxide steam generator added in the stirred autoclave is 0.1~28 weight %, preferably 28
Weight %；The ratio of catalyst micro mist slurry and hydrogenperoxide steam generator is 1/1000000 to 5/1, preferably 100/1, by weight；
The operation temperature of the stirred autoclave is 20~180 DEG C, and preferably 95 DEG C, operating pressure is 0.1~10MPa, preferably 0.3MPa,
In terms of gauge pressure, regulating time is 1~1800s, preferably 300s.
In the present invention, the oil content of the catalyst micro mist after wet-type peroxide oxidizing is down to weight after the drying
Less than 0.01~20%, preferably below 8.2 weight %, in terms of the weight of outer row's catalyst.
It is preferred that the temperature of the internal return drying machine is not less than 85 DEG C or the boiling point higher than reaction solution.
It is preferred that the storage regulation tank is selected from and is dispersed with stirring equipment, the temperature of whole system is ensured by being dispersed with stirring
Regulation and control are uniform.
In the present invention, the regulation hold-up tank is suitable in order to produce by sealing gland controlled atmosphere control device interior pressure
Vapour pressure, ensure to occur to gasify on a large scale when circulating hot water is superheated water.
It is preferred that the pH regulations tank is selected from and is dispersed with stirring equipment, catalyst micro mist slurry is ensured by being dispersed with stirring
PH value regulation and control are consistent.
It is preferred that methods and apparatus of the present invention can also be applied to MTP (preparing propylene from methanol) and OTO (oxygenatedchemicals systems
Take alkene) oil removal treatment of oil-containing catalyst micro mist in the chilling waste water of technique.
Below referring to accompanying drawing.
Fig. 1 is the treatment of process streams according to the MTO chilling waste water oil-containing catalyst micro mists of an embodiment of the invention
Cheng Tu.As shown in figure 1, the oil-containing catalyst micro mist slurry after pre-treatment is stored in storage regulation tank 1, while by circulating hot water
Pump 5 is quantitatively pumped into hot water to storage regulation tank 1, and is stirred, regulating and controlling temperature；Oil-containing catalyst micro mist and circulating hot water
In mixture press-in micro-cyclone de adnexa 2, catalyst micro mist adsorption oil is realized by the Osima jacoti, Osima excavata in rotational flow field
Micro-cyclone de Fufen from；The attached separating obtained oil-containing hot water of micro-cyclone de, which enters in cycling hot water pot 4, to carry out standing profit point
From that realizes hot water recycles and be desorbed the recovery of oil, and maintains water in tank by moisturizing；It is attached by micro-cyclone de
Catalyst micro mist enter in swirl concentrator 3 in a subtle way to carry out thickening, be dehydrated point and to enter in cycling hot water pot 4；After concentration
Catalyst micro mist slurry enter in pH regulation tanks 6, adjust to wet-type peroxide oxidizing and react suitable pH value；After regulation
Catalyst micro mist slurry is forced into reaction pressure in a manner of intermittent feeding through feed pump 7, is heated in heat exchanger 8,9 anti-
Temperature is answered, subsequently into stirred autoclave 10；Hydrogen peroxide is added in stirred autoclave 10 also through the mode of intermittent feeding；
In stirred autoclave 10, under the oxidation of hydrogen peroxide wet oxidation reaction occurs for oil-containing catalyst micro mist, adsorbs and is being catalyzed
The oil pollutant (macromolecule alkane, aromatic hydrocarbons, ketone, ester etc.) on agent micro mist surface be oxidized to the inorganic matters such as carbon dioxide, water or
Small organic molecule soluble in water, so as to be separated from catalyst micro mist surface desorption；Catalyst micro mist after desorption is the same as reaction
Liquid cools down into heat exchanger 8 together, while heats the catalyst micro mist slurry into reactor；Catalyst after cooling is micro-
Powder/reaction liquid mixture enters knockout drum 11, the gas, liquid product standing separation in tank；The gas-phase products such as CO, which enter, to be burnt
It is CO to burn stove 12 to burn rear oxidation2Deng gas；CO2CO is passed through Deng gas2Absorbed in absorption tower 13；Catalyst micro mist/reaction solution
Mixture pressurizes through booster pump 14 to carry out eddy flow in laggard swirl concentrator in a subtle way 15 and takes off liquid, and the de- liquid of institute enters in pH regulation tanks 6；
Catalyst micro mist after concentration is dried into internal return drying machine 16, and dried catalyst micro mist is all reclaimed.
The major advantage of methods and apparatus of the present invention is：
(1) MTO chilling waste water is contained by the integrated coupling of the attached method of hydro-thermal micro-cyclone de and wet-type peroxide oxidizing method
The processing of oily catalyst micro mist, embodies preferable high efficiency, practicality, economy.
(2) the attached method of hydro-thermal micro-cyclone de utilizes the Osima jacoti, Osima excavata effect in eddy flow field to complete catalyst micro mist surface contamination
The preliminary desorption of thing, as the preprocessing process of wet-type peroxide oxidizing, economy, efficiently realize oil pollutant decrement
Change is handled.
(3) wet-type peroxide oxidizing method utilizes the strong oxidizing property of hydrogen peroxide, on the basis of hydro-thermal micro-cyclone de is attached,
Thoroughly oxidation Decomposition is carried out to the pollutant of catalyst micro mist surface attachment in stirred autoclave, completes absorption oil pollution
The final desorption of thing, and hydrogen peroxide is decomposed into oxygen and water and environment will not be impacted.Flow operations equipment is simple, can
Realize the thorough desorption to oil pollutant.
Embodiment
The present invention is expanded on further with reference to specific embodiment.It should be appreciated, however, that these embodiments are only used for
It is bright the present invention and be not meant to limit the scope of the invention.The test method of unreceipted actual conditions in the following example, generally
According to normal condition, or according to the condition proposed by manufacturer.Unless otherwise indicated, all percentage and number be by weight
Meter.
Embodiment 1：
In 600,000 tons/year of MTO devices, according to the method for the present invention to containing in the MTO chilling waste water of pre-treatment
Oily catalyst micro mist slurry carries out oil removal treatment, and its specific implementation process and deoiling effect are described as follows：
1. oil-containing catalyst micro mist slurry properties：
In MTO device normal course of operation, it is (dry for 10.08 tons that oil-containing catalyst micro mist slurry produces weekly total amount
Base), wherein 2.42 tons of oil-containing.
The particle diameter of catalyst micro mist is 3 μm, and moisture content is 3 weight %, and oil content is 24.0 weight % (with catalyst weight
Gauge)；Specific surface area is 58m2/ g, pore volume 0.019ml/g.
The oil pollutant that catalyst micro mist is adsorbed is mainly high molecular alkane, aromatic hydrocarbons, ketone, ester etc..
2. implementation process：
Referring to Fig. 1.Specific implementation step with reference to the present invention is as follows：
(1) oil-containing catalyst pulp in the MTO chilling waste water of pre-treatment is stored in storage regulation tank, intermittently to go out
The mode of material is transported to micro-cyclone de adnexa, and the amount of each intermittent take-off is 1000kg, and discharging speed is 15000kg/ hours；
(2) circulating hot water being pumped into from circulating hot-water pump to cycling hot water pot, circulating hot water flow is 10000kg/ hours, and
It is stirred, regulating and controlling temperature is to 85 DEG C；
(3) catalyst micro mist/hot water mixture is pressed into micro-cyclone de adnexa with 0.3MPa pressure, carries out the micro- rotation of hydro-thermal
Stream desorption separation；
(4) during hydro-thermal micro-cyclone de is attached, the oil-containing hot water of gained enters cycling hot with the flow of 3000kg/ hours
Standing water-oil separating is carried out in water pot, realize circulating hot water recycle and oil recovery；It is attached to complete hydro-thermal micro-cyclone de
Catalyst micro mist afterwards is still scattered in circulating hot water, with the shape of catalyst micro mist slurry after micro- swirl concentrator dehydration decrement
Formula is discharged into pH regulation tanks, and flow is 2000kg/ hours；
(5) in pH adjusts tank, the pH value of catalyst micro mist slurry is adjusted to 3.5 using hydrochloric acid/sodium hydroxide；
(6) adjust the catalyst micro mist slurry after pH value and be forced into 0.3MPa through feed pump, then add through two heat exchangers
Stirred autoclave is sent into after hot to 130 DEG C, and the hydrogen peroxide 2.5kg that concentration is 28 weight % is added into kettle, carries out wet type
Hydrogen peroxide oxidation reacts；
(7) reacted catalyst micro mist/reaction liquid mixture is delivered to gas-liquid point after heat exchanger is cooled to 50 DEG C
Gas-liquid separation is carried out from tank, gas-phase product is sent into CO after burning2Absorption tower absorbs；
(8) catalyst micro mist/reaction liquid mixture of liquid phase carries out de- liquid decrement into micro- swirl concentrator, gained it is anti-
Answer liquid to be returned with the flow of 1200kg/ hours in pH regulation tanks, complete recycling for reaction solution.
3. interpretation of result：
After each step is implemented, the material composition of catalyst micro mist is as shown in table 1 below：
Table 1：Material composition of the oil-containing catalyst pulp after the implementation of each step in MTO chilling waste water
Wherein, the attached oily yield of wet oxidation-hydro-thermal micro-cyclone de is 379.2kg, the whole accounted in catalyst micro mist
Oil mass ratio is 79.17%.
All it is incorporated as referring in this application in all documents that the present invention refers to, it is independent just as each document
It is incorporated as with reference to such.In addition, it is to be understood that after the above-mentioned instruction content of the present invention has been read, those skilled in the art can
To be made various changes or modifications to the present invention, these equivalent form of values equally fall within the model that the application appended claims are limited
Enclose.
Claims (10)
1. the method for oil pollutant contained by catalyst micro mist, this method comprise the following steps in a kind of removal MTO chilling waste water：
(1) storage regulation and control：MTO catalyst micro mist slurry after pre-treatment by concentration is stored, led in storage process
Heating temperature adjustment is crossed to 20-180 DEG C, to reduce the viscosity of the oil pollutant of catalyst micro mist surface attachment；
(2) hydro-thermal micro-cyclone de is attached：Hydro-thermal micro-cyclone de is carried out to the catalyst micro mist through storage regulation and control obtained in step (1)
Attached pretreatment, to complete the preliminary desorption of catalyst micro mist surface contaminant；And
(3) wet-type peroxide oxidizing：The catalyst micro mist adjusted pH attached through hydro-thermal micro-cyclone de that will be obtained in step (2)
To 0-10, pressure regulation to the 0.1-10MPa in terms of gauge pressure, temperature adjustment to after 20-180 DEG C, it is sufficiently mixed with hydrogen peroxide so that oil-containing is urged
Under the oxidation of hydrogen peroxide wet oxidation reaction occurs for agent micro mist, makes absorption in the oil pollutant on catalyst micro mist surface
Inorganic matter or small organic molecule soluble in water are oxidized to, so as to be separated from catalyst micro mist surface desorption, is completed to urging
The final desorption of agent micro mist.
2. the method as described in claim 1, it is characterised in that in step (2), profit point is carried out to caused oil-containing hot water
From the recovery and separating obtained water for realizing oil recycle；The mixture of caused catalyst micro mist and water is revolved
Stream concentration, the catalyst micro mist after thickening enter step (3), and the water that concentration takes off follows during hydro-thermal micro-cyclone de is attached
Ring uses；
In step (3), micro- eddy flow concentration is carried out to the mixture of treated catalyst micro mist and reaction solution, after thickening
Catalyst micro mist carry out internal return micro mist drying, by the reaction solution remained in micro mist remove, realize the clean of catalyst micro mist
Net recovery；The reaction solution that concentration takes off recycles during wet-type peroxide oxidizing.
3. method as claimed in claim 1 or 2, it is characterised in that the MTO catalyst micro mist after the pre-treatment by concentration
The particle diameter of catalyst micro mist is 0.5-250 μm in slurry, the moisture content of slurry for 0.01~be less than 100 weight %, oil content is
0.01-35 weight %, specific surface area are 1~2500m2/g。
4. the device of oil pollutant contained by catalyst micro mist, the device include in a kind of removal MTO chilling waste water：
Storage regulation tank (1), for the MTO catalyst micro mist slurry after pre-treatment by concentration to be stored, and control room
Have a rest discharging, to ensure that the interval of wet-type peroxide oxidizing processing procedure is carried out；
The micro-cyclone de adnexa (2) being connected with the discharging opening of the storage regulation tank (1), for being obtained in storage regulation tank (1)
The catalyst micro mist through storage regulation and control arrived carries out the attached pretreatment of hydro-thermal micro-cyclone de, to complete catalyst micro mist surface contaminant
Preliminary desorption；
The pH regulation tanks (6) being connected with the micro-cyclone de adnexa (2), for the pH value of catalyst micro mist to be adjusted；
The feed pump (7) being connected with the discharging opening of pH regulation tanks (6), for catalyst micro mist to be pumped into stirred autoclave
(10), and it is forced into reaction pressure；
With the heat exchanger (8) of the outlet connection of the feed pump (7), the mixing for post catalyst reaction micro mist and reaction solution
The cooling of thing and the first heating of catalyst micro mist；
With another heat exchanger (9) of the outlet connection of the heat exchanger (8), adding for rear catalyst micro mist is heated for first
Heat, make up to reaction temperature；And
The stirred autoclave (10) that outlet with the heat exchanger (9) connects, for passing through catalyst micro mist and hydrogen peroxide
Abundant haptoreaction in kettle, it is oxidized oil pollutant and decomposes, complete catalyst particles surface attachment oil pollutant
Final desorption.
5. device as claimed in claim 4, it is characterised in that the device also includes：With containing for micro-cyclone de adnexa (2)
The cycling hot water pot (4) of oily hot water outlet connection, to complete the standing water-oil separating of oil-containing hot water, realize that hot water circuit utilizes
And the recovery of oil；
The circulating hot-water pump (5) being connected with the delivery port of the cycling hot water pot (4), adjusted for circulating hot water to be pumped into storage
Tank (1) is saved to recycle；
With the catalyst micro mist enrichment phase of the micro-cyclone de adnexa (2) outlet connection, be placed in micro-cyclone de adnexa (2) and pH
Micro- swirl concentrator (3) between tank (6) is adjusted, the mixture for externally arranging catalyst micro mist and water carries out dehydration decrement,
Form catalyst micro mist concentrate feed；
The knockout drum (11) being connected with the discharging opening of the stirred autoclave (10), for reacted gaseous phase materials and
Liquid phase material carries out standing separation；
The incinerator (12) being connected with the gaseous phase materials discharging opening of the knockout drum (11), for will be produced in course of reaction
Pernicious gas be oxidized to CO2；
With the CO of the outlet connection of the incinerator (12)2Absorption tower (13), for by the CO after burning2Absorbed；
The booster pump (14) being connected with the liquid phase material discharging opening of described knockout drum (11), for by catalyst micro mist and
The mixture of reaction solution is pumped to micro- swirl concentrator (15)；
Micro- swirl concentrator (15) that outlet with the booster pump (14) connects, for being mixed to catalyst micro mist and reaction solution
Compound carries out de- liquid decrement, forms catalyst micro mist concentrate feed；
The internal return drying machine (16) that catalyst micro mist concentrate feed outlet with micro- swirl concentrator (15) connects, for urging
The final drying of agent micro mist concentrate feed takes off liquid, realizes the recovery of catalyst micro mist solid.
6. the device as described in claim 4 or 5, it is characterised in that catalyst micro mist and circulation in the storage regulation tank (1)
The ratio of hot water is 1/1000000 to 2/1, by weight；The operation temperature of the storage regulation tank (1) is 20~180 DEG C, behaviour
It is 0.1~10MPa to make pressure, and in terms of gauge pressure, regulating time is 1~1800s；The storage regulation tank (1), which is selected from, to be dispersed with stirring
Equipment.
7. device as claimed in claim 5, it is characterised in that micro- swirl concentrator (3) and micro- swirl concentrator (15)
Catalyst dust removing efficiency be not less than 85%, operation pressure drop be not more than 30mmH2O；Selected from hydrocyclone；Be by it is single,
What two or more micro- eddy flow core pipes composed in parallel.
8. the device as described in claim 4 or 5, it is characterised in that catalyst micro mist slurry is being adjusted in the pH regulation tanks (6)
PH value after section is 0~10；The pH regulations tank, which is selected from, is dispersed with stirring equipment.
9. the device as described in claim 4 or 5, the concentration of the middle hydrogenperoxide steam generator added of the stirred autoclave (10) are
0.1~28 weight %；The ratio of catalyst micro mist slurry and hydrogenperoxide steam generator is 1/1000000 to 5/1, by weight；Institute
The operation temperature for stating stirred autoclave (10) is 20~180 DEG C, and operating pressure is 0.1~10MPa, in terms of gauge pressure, regulating time
For 1~1800s.
10. device as claimed in claim 5, it is characterised in that the temperature of the internal return drying machine (16) is not less than 85 DEG C
Or the boiling point higher than reaction solution；The oil content of catalyst micro mist after wet-type peroxide oxidizing is brought down below 20 after the drying
Weight %, in terms of the weight of outer row's catalyst micro mist.
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| RU2748501C1 (en) * | 2017-09-13 | 2021-05-26 | Шанхай Хуачан Энвайронментал Протекшн Ко., Лтд | Method and apparatus for treatment, sorting and recycling of oil-containing discharged catalyst |
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| US4661265A (en) * | 1985-09-30 | 1987-04-28 | Amoco Corporation | Catalyst deoiling process |
| CN101352620A (en) * | 2008-09-09 | 2009-01-28 | 上海华畅环保设备发展有限公司 | Method and apparatus for micro hydrocyclone separation of MTO quench water and water of water-washing factory, and for concentration of fine catalyst in the same |
| CN101353187B (en) * | 2008-09-10 | 2013-01-23 | 华东理工大学 | MTO prewhirl flow type reaction waste vapor stripping purifying method and apparatus |
| CN101352621A (en) * | 2008-09-10 | 2009-01-28 | 华东理工大学 | Micro hydrocyclone separation and solid removal method and apparatus of MTO quench water and water of water-washing factory |
| CN102658213A (en) * | 2012-05-04 | 2012-09-12 | 上海华畅环保设备发展有限公司 | Method and device for concentrating and coupled-drying catalyst in quenched wastewater in process of using methanol to prepare olefin |
| CN102698818B (en) * | 2012-06-21 | 2014-05-28 | 上海华畅环保设备发展有限公司 | Processing method and processing device for graded desorption of residue hydrotreating excretion catalyst in ebullated bed |
| CN103611567A (en) * | 2013-12-04 | 2014-03-05 | 天津工业大学 | Regeneration method of methanol-to-olefin catalyst |
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