CN104826670A - Method and apparatus for removing oil pollutants contained in catalyst micro-powder in MTO quenching wastewater - Google Patents
Method and apparatus for removing oil pollutants contained in catalyst micro-powder in MTO quenching wastewater Download PDFInfo
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Abstract
The present invention relates to a method and an apparatus for removing oil pollutants contained in catalyst micro-powder in MTO quenching wastewater, and provides a method for removing oil pollutants contained in catalyst micro-powder in MTO quenching wastewater. The method comprises: (1) storage regulation; (2) hydrothermal micro-cyclone desorption; and (3) wet hydrogen peroxide oxidation. The invention further provides the apparatus for removing oil pollutants contained in catalyst micro-powder in MTO quenching wastewater.
Description
Technical field
The invention belongs to Coal Chemical Industry and field of Environment Protection, relate to the method and apparatus of oil-containing catalyst micro mist oil removing in a kind of MTO chilling waste water, to realize the target purifying, reclaim catalyst from oil-containing catalyst micro mist.Specifically, the invention provides a kind of attached method with oil-containing catalyst micro mist in wet-type peroxide oxidizing integrated coupling technique process MTO chilling waste water of hydro-thermal micro-cyclone de and device.
Background technology
MTO is the abbreviation of methanol-to-olefins, and its general principle is from coal through synthesising gas systeming carbinol, then is the low-carbon alkene such as ethene, propylene by methanol conversion.MTO technology representative at present has: the technology of UOP, UOP/Hydro, ExxonMobil and the Dalian Chemistry and Physics Institute (DMTO).Along with the day by day soaring of low-carbon alkene demand and tradition via the production line of oil because of the worsening shortages of petroleum resources, the development of MTO technology and industrial applications thereof have caused the attention of various aspects.
Based on the characteristic of the easy carbon distribution inactivation of MTO catalyst, the recirculating fluidized bed of successive reaction-regeneration in MTO industrial production, is usually adopted to react.In long fluidized reaction, catalyst can wear away, and the catalyst micro mist that abrasion produce cannot participate in fluidized reaction again because of size distribution reason, discharges reactor with product effluent.Enter quench tower chilling after the product effluent carrying catalyst micro mist leaves reactor, most of catalyst micro mist enters in water along with chilled water (chw) discharges quench tower.Catalyst is discharged in the process of chilled water (chw) in reactor catalysis reaction to abrasion are outer, its particle surface can adsorb a large amount of oil pollutants (high molecular alkane, aromatic hydrocarbons, ketone, ester etc.), and these pollutant entered environments can cause high risks to human body, animals and plants, air water body environment.For waste catalyst, various countries have formulated a large amount of strict legislations of environmental protection one after another.Dead catalyst is classified as danger wastes by Environmental Protection Agency (EPA).In National Hazard refuse register is listed dead catalyst in 2008 by Environment Protect in China portion, and its hazard property is classified as T level (poisonous).And MTO catalyst price is higher, should consider to greatest extent to recycle in commercial Application, but these pollutants are attached to catalyst micro mist surface, directly affect the reclaiming of catalyst.Therefore in order to reach the object of protection of the environment and catalyst recycle, need to remove catalyst micro mist contained oil pollutant in chilling waste water.
CN 102658213A disclose a kind of catalyst micro mist in MTO chilling waste water to be concentrated, dry, thus reclaim the method and apparatus of catalyst in solid form.CN 103951098A discloses and a kind ofly adopts UF membrane and three-phase cyclone separator integrated coupling MTO chilled water (chw) to be taken off to the method and apparatus of solid oil removing.But more than invention just catalyst micro mist solid is concentrated from chilled water (chw), separation, and the oil pollutant be adsorbed on catalyst micro mist cannot be removed.
The oil-containing catalyst micro mist that chilled water (chw) is arranged outward belongs to oil containing medium.Hydrothermal desorption method is a kind of more general method processing oil containing medium at present, and has had certain commercial Application basis.But traditional hydrothermal desorption equipment needs larger mixing plant to carry out stirring hydrothermal desorption to oily waste, often make treatment facility volume bigger than normal, and the oil containing medium processed in this way also exists the halfway problem of de-oiling, the existence of these problems limits the application & development of conventional hydrothermal separating process.
Wet oxidation process refers at high temperature under high pressure, utilizes oxidation reaction process organic pollution in aqueous, make it the technology being degraded to the inorganic matter such as carbon dioxide, water with oxygen or air as oxidant.The method has the advantages such as flow process is simple, process pollutant kind is many, contaminant degradation is thorough, now in dye wastewater treatment, organism P wastewater, has had certain research and apply.Wet-type peroxide oxidizing method, be the development to wet oxidation process, its change utilizes hydrogen peroxide as liquid oxidizer, compared to hyperbaric oxygen or compressed air, system stagnation pressure can be reduced to a certain extent, improve the equipment corrosion, the security problems that cause because of high pressure.Hydrogen peroxide autoxidation is very competent in addition, can directly organic pollution or reducing inorganic pollutant be oxidized, and its catabolite is water and oxygen, can not introduce new impurity, have a extensive future to reaction system.
CN 103611567A discloses a kind of renovation process of the MTO catalyst based on wet-type peroxide oxidizing method, the method is by carrying out stripping to decaying catalyst, remove the organic matter carried secretly, again by the further oil removing of oxidation, then filtration is carried out to the catalyst after oil removing and remove impurity and the stable process of mediation, obtain the catalyst of activation recovering.But the method flow process is longer, and technique is loaded down with trivial details, and only for the catalyst of inactivation in MTO fluidized reaction, chilled water (chw) is carried secretly to the catalyst micro mist of outer row, due to reasons such as its particle size features, its deoiling effect is also desirable.
Up to now, this area is not yet developed and is a kind ofly carried out the method for oil removing for catalyst micro mist in MTO chilling waste water.Therefore, the method for oil removing is a kind ofly carried out for catalyst micro mist in MTO chilling waste water in the urgent need to developing in this area.
Summary of the invention
The invention provides method and the device of catalyst micro mist contained oil pollutant in a kind of removal MTO chilling waste water of novelty, overcome the defect existed in prior art.
On the one hand, the invention provides a kind of method removing catalyst micro mist contained oil pollutant in MTO chilling waste water, the method comprises the following steps:
(1) storage regulation and control: store after pre-treatment through concentrated MTO catalyst micro mist slurry, by heating temperature adjustment to 20-180 DEG C in storage process, to reduce the viscosity of the oil pollutant of catalyst micro mist surface attachment;
(2) hydro-thermal micro-cyclone de is attached: carry out the attached pretreatment of hydro-thermal micro-cyclone de, to complete the preliminary desorption of catalyst micro mist surface contaminant to the catalyst micro mist through storage regulation and control obtained in step (1); And
(3) wet-type peroxide oxidizing: by the catalyst micro mist attached through hydro-thermal micro-cyclone de that obtain in step (2) through regulate pH to 0-10, pressure regulation in gauge pressure 0.1-10MPa, temperature adjustment to 20-180 DEG C after, fully mix with hydrogen peroxide, make oil-containing catalyst micro mist, under the oxidation of hydrogen peroxide, wet oxidation reaction occur, the oil pollutant being adsorbed on catalyst micro mist surface is made to be oxidized to inorganic matter or small organic molecule soluble in water, thus be separated from catalyst micro mist surface desorption, complete the final desorption to catalyst micro mist.
In one preferred embodiment, in step (2), water-oil separating is carried out to the oil-containing hot water produced, realize the recovery of oil and recycling of separating obtained water; Carry out eddy flow to the catalyst micro mist of generation and the mixture of water to concentrate, the catalyst micro mist after thickening enters step (3), and the concentrated water taken off recycles in hydro-thermal micro-cyclone de additive process;
In step (3), carry out micro-eddy flow to the mixture of the catalyst micro mist processed and reactant liquor to concentrate, catalyst micro mist after thickening carries out the oven dry of internal return micro mist, and to be removed by the reactant liquor remained in micro mist, the cleaning realizing catalyst micro mist is reclaimed; The concentrated reactant liquor taken off recycles in wet-type peroxide oxidizing process.
Another preferred embodiment in, in the MTO chilling waste water after described pre-treatment, the particle diameter of catalyst micro mist is 0.5-250 μm, and moisture content is 0.01 ~ 100 % by weight, and oil content is 0.01-35 % by weight, and specific area is 1 ~ 2500m
2/ g.
On the other hand, the invention provides a kind of device removing catalyst micro mist contained oil pollutant in MTO chilling waste water, this device comprises:
Storage regulating tank, for storing after pre-treatment through concentrated MTO catalyst micro mist slurry, and controls intermittent take-off, to ensure that the interval of wet-type peroxide oxidizing processing procedure is carried out;
The micro-cyclone de adnexa be connected with the discharging opening of described storage regulating tank, carries out the attached pretreatment of hydro-thermal micro-cyclone de, to complete the preliminary desorption of catalyst micro mist surface contaminant for the catalyst micro mist through storage regulation and control obtained storage regulating tank;
The pH regulating tank be connected with described micro-cyclone de adnexa, for regulating the pH value of catalyst micro mist;
The feed pump be connected with the discharging opening of described pH regulating tank, for catalyst micro mist is pumped to stirred autoclave, and is forced into reaction pressure;
The heat exchanger be connected with described charging delivery side of pump, for the cooling of mixture and the first heating of catalyst micro mist of post catalyst reaction micro mist and reactant liquor;
Another heat exchanger be connected with the outlet of described heat exchanger, for just heating the heating of rear catalyst micro mist, makes it to reach reaction temperature; And
The stirred autoclave be connected with the outlet of described heat exchanger, for by catalyst micro mist and the abundant haptoreaction of hydrogen peroxide in still, makes the oxidized decomposition of oil pollutant, completes the final desorption of catalyst particles surface attachment oil pollutant.
In one preferred embodiment, this device also comprises: the cycling hot water pot be connected with the oil-containing hot water outlet of described micro-cyclone de adnexa, in order to complete the standing water-oil separating of oil-containing hot water, realizes the recovery of hot water circuit utilization and oil;
The circulating hot-water pump be connected with the delivery port of described cycling hot water pot, recycles for circulating hot water being pumped to storage regulating tank;
With the catalyst micro mist enrichment phase of described micro-cyclone de adnexa export be connected, be placed in micro-swirl concentrator between micro-cyclone de adnexa and pH regulating tank, mixture for externally arranging catalyst micro mist and water carries out dehydration decrement, forms catalyst micro mist concentrate feed;
The knockout drum be connected with the discharging opening of described stirred autoclave, for carrying out standing separation to reacted gaseous phase materials and liquid phase material;
The incinerator be connected with the gaseous phase materials discharging opening of described knockout drum, for being oxidized to CO by the pernicious gas produced in course of reaction
2;
The CO be connected with the outlet of described incinerator
2absorption tower, for by burn after CO
2absorb;
The booster pump be connected with the liquid phase material discharging opening of described knockout drum, for being pumped to micro-swirl concentrator by the mixture of catalyst micro mist and reactant liquor;
The micro-swirl concentrator be connected with described supercharging delivery side of pump, for carrying out de-liquid decrement to the mixture of catalyst micro mist and reactant liquor, forms catalyst micro mist concentrate feed;
Export with the catalyst micro mist concentrate feed of described micro-swirl concentrator the internal return drying machine be connected, the final oven dry for catalyst micro mist concentrate feed takes off liquid, realizes the recovery of catalyst micro mist solid.
Another preferred embodiment in, in described storage regulating tank, the ratio of catalyst micro mist and circulating hot water is 1/1000000 to 2/1, by weight; The operating temperature of described storage regulating tank is 20 ~ 180 DEG C, and operating pressure is 0.1 ~ 10MPa, and in gauge pressure, regulating time is 1 ~ 1800s; Described storage regulating tank is selected from dispersed with stirring equipment.
Another preferred embodiment in, the catalyst dust removing efficiency of described micro-swirl concentrator and micro-swirl concentrator is not less than 85%, operation pressure drop be not more than 30mmH
2o; Be selected from hydrocyclone; Composed in parallel by single, two or more micro-eddy flow core pipes.
Another preferred embodiment in, in described pH regulating tank, catalyst micro mist slurry pH value is after adjustment 0 ~ 10; Described pH regulating tank is selected from dispersed with stirring equipment.
Another preferred embodiment in, the concentration of the hydrogenperoxide steam generator added in described stirred autoclave is 0.1 ~ 28 % by weight; The ratio of catalyst micro mist slurry and hydrogenperoxide steam generator is 1/1000000 to 5/1, by weight; The operating temperature of described stirred autoclave is 20 ~ 180 DEG C, and operating pressure is 0.1 ~ 10MPa, and in gauge pressure, regulating time is 1 ~ 1800s.
Another preferred embodiment in, the temperature of described internal return drying machine is not less than 85 DEG C or boiling point higher than reactant liquor; The oil content of the catalyst micro mist after wet-type peroxide oxidizing is brought down below 0.01 ~ 20 % by weight after the drying, with the weighing scale of described outer row's catalyst micro mist.
Accompanying drawing explanation
Fig. 1 is the processing technological flow figure of the MTO chilling waste water oil-containing catalyst micro mist according to an embodiment of the invention.
Detailed description of the invention
Present inventor finds after extensive and deep research:
Arrange in the oil removal treatment of oil-containing catalyst micro mist in chilling waste water outward at MTO, wet-type peroxide oxidizing method has that technique is simple, oil removing feature thoroughly; But consider for economic benefit, be necessary to carry out preliminary oil removing pretreatment to oil-containing catalyst micro mist before wet-type peroxide oxidizing process, the attached method of hydro-thermal micro-cyclone de based on hydrothermal desorption principle is a kind of economy, easy de-oiling preprocess method; Therefore, hydrothermal desorption is coupled with the principle of wet-type peroxide oxidizing is integrated by whole handling process, and make two kinds of principal advantage complementations, whole processing procedure embodies good high efficiency, practicality and economy;
The attached method of hydro-thermal micro-cyclone de is the optimization to conventional hydrothermal desorption method, namely the Osima jacoti, Osima excavata effect in eddy flow field is utilized, a kind of deoiling method of fortified water thermal desorption effect, its process characteristic is very applicable carries out pre-oil removal treatment to oil-containing catalyst micro mist, makes oil pollutant minimizing;
Wet-type peroxide oxidizing method is the organic contamination substance treating method of a kind of advanced person, hydrogen peroxide has strong oxidizing property, in the reaction system of HTHP, by stirring, catalyst micro mist is made to carry out sufficient haptoreaction with hydrogen peroxide, the oil pollutant (high molecular alkane, aromatic hydrocarbons, ketone, ester etc.) being attached to catalyst micro mist surface is oxidized to the inorganic matter such as carbon dioxide, water or small organic molecule soluble in water, thus be separated from catalyst micro mist surface desorption, complete the final desorption to catalyst micro mist; Whole oxidizing process pollutant desorption is thorough, cost is low, it is little to pollute, equipment is relatively simple, has good applicability.
Based on above-mentioned discovery, in conjunction with the integrated thought be coupled of micro-cyclone water thermal desorption and wet-type peroxide oxidizing, the present invention is accomplished.
In a first aspect of the present invention, provide a kind of method removing catalyst micro mist contained oil pollutant in MTO chilling waste water, the method comprises the following steps:
(1) storage regulation and control: store after pre-treatment through concentrated MTO catalyst micro mist slurry, by heating water temperature adjustment in storage process, to reduce the viscosity of the oil pollutant of catalyst micro mist surface attachment, improve oil, the mobility of salt pollutant on catalyst micro mist surface;
(2) hydro-thermal micro-cyclone de is attached: carry out the attached pretreatment of hydro-thermal micro-cyclone de to the catalyst micro mist after regulation and control, utilize the Osima jacoti, Osima excavata effect in eddy flow field to complete the preliminary desorption of catalyst micro mist surface contaminant;
(3) wet-type peroxide oxidizing: by through the attached catalyst micro mist of hydro-thermal micro-cyclone de through regulating pH, pressure regulation, after temperature adjustment, interval feeding is to stirred autoclave, and hydrogen peroxide is also added in the mode of intermittent take-off, by stirring, catalyst micro mist is fully mixed with hydrogen peroxide, whole system reaches optimum reactiveness, wet oxidation reaction is there is in oil-containing catalyst micro mist under the oxidation of hydrogen peroxide, be adsorbed on oil pollutant (the macromolecule alkane on catalyst micro mist surface, aromatic hydrocarbons, ketone, ester etc.) be oxidized to carbon dioxide, the inorganic matters such as water or small organic molecule soluble in water, thus be separated from catalyst micro mist surface desorption, complete the final desorption to catalyst micro mist.
Preferably, in the hydro-thermal micro-cyclone de attached middle school of step (2), water-oil separating is carried out to the oil-containing hot water produced, realize the recovery of oil and recycling of separating obtained water; Carry out eddy flow to the catalyst micro mist of generation and the mixture of water to concentrate, the catalyst micro mist after thickening enters step (3), and the concentrated water taken off recycles in hydro-thermal micro-cyclone de additive process.
Preferably, in step (3) in wet-type peroxide oxidizing process, carry out micro-eddy flow to the mixture of the catalyst micro mist processed and reactant liquor to concentrate, catalyst micro mist after thickening carries out the oven dry of internal return micro mist, the reactant liquor remained in micro mist is removed, the cleaning realizing catalyst micro mist is reclaimed, and the concentrated reactant liquor taken off recycles in wet-type peroxide oxidizing process.
In the present invention, the particle diameter that MTO chilling waste water after described pre-treatment arranges catalyst micro mist is outward 0.5-250 μm, preferably 3 μm, moisture content is 0.01 ~ 100 % by weight, preferably 3 % by weight, oil content is 0.01-35 % by weight, preferably 24.0 % by weight, all with catalyst weight, specific area is 1 ~ 2500m
2/ g, preferred 58m
2/ g, pore volume is preferably 0.019ml/g.
In a second aspect of the present invention, provide a kind of device removing catalyst micro mist contained oil pollutant in MTO chilling waste water, this device comprises:
Storage regulating tank, stores for carrying out to the MTO chilling waste water catalyst micro mist slurry after concentrated adjustments, and controls intermittent take-off, to ensure that the interval of wet-type peroxide oxidizing processing procedure is carried out;
The micro-cyclone de adnexa be connected with the discharging opening of described storage regulating tank, for realizing the preliminary desorption of catalyst micro mist surface attachment oil pollutant by the Osima jacoti, Osima excavata in rotational flow field;
The cycling hot water pot be connected with the oil-containing hot water outlet of described micro-cyclone de adnexa, in order to complete the standing water-oil separating of oil-containing hot water, realizes the recovery of hot water circuit utilization and oil;
The circulating hot-water pump be connected with the delivery port of described cycling hot water pot, recycles for circulating hot water being pumped to storage regulating tank;
Exporting with the catalyst micro mist enrichment phase of described micro-cyclone de adnexa the micro-swirl concentrator be connected, carrying out dehydration decrement for externally arranging catalyst micro mist/aqueous mixtures, form catalyst micro mist concentrate feed;
The pH regulating tank be connected is exported, for regulating the pH value of catalyst micro mist concentrate feed with the catalyst micro mist concentrate feed of described micro-swirl concentrator;
The feed pump be connected with the discharging opening of described pH regulating tank, for being pumped to stirred autoclave to catalyst micro mist concentrate feed, and is forced into reaction pressure;
The heat exchanger be connected with described charging delivery side of pump, for the cooling of post catalyst reaction micro mist/reactant liquor mixture and the first heating of catalyst differential concentrate feed;
Another heat exchanger be connected with the outlet of described heat exchanger, for just heating the heating of rear catalyst micro mist concentrate feed, makes it to reach reaction temperature;
The stirred autoclave be connected with the outlet of described heat exchanger, for by catalyst micro mist and the abundant haptoreaction of hydrogen peroxide in still, makes the oxidized decomposition of oil pollutant, completes the final desorption of catalyst particles surface attachment oil pollutant;
The knockout drum be connected with the discharging opening of described stirred autoclave, for carrying out standing separation to reacted gaseous phase materials and liquid phase material;
The incinerator be connected with the gaseous phase materials discharging opening of described knockout drum, for being oxidized to CO by pernicious gases such as the CO produced in course of reaction
2deng gas;
The CO be connected with the outlet of described incinerator
2absorption tower, for by burn after CO
2absorb Deng gas;
The booster pump be connected with the liquid phase material discharging opening of described knockout drum, for being pumped to micro-swirl concentrator by catalyst micro mist/reactant liquor mixture;
The micro-swirl concentrator be connected with described supercharging delivery side of pump, for carrying out de-liquid decrement to catalyst micro mist/reactant liquor mixture, forms catalyst micro mist concentrate feed;
Export with the catalyst micro mist concentrate feed of described micro-swirl concentrator the internal return drying machine be connected, the final oven dry for catalyst micro mist concentrate feed takes off liquid, realizes the recovery of catalyst micro mist solid.
Preferably, in described storage regulating tank, the ratio of catalyst micro mist and circulating hot water is 1/1000000 to 2/1, preferably 1/100, by weight; The operating temperature of described storage regulating tank is 20 ~ 180 DEG C, preferably 95 DEG C, and operating pressure is 0.1 ~ 10MPa, preferred 0.3MPa, and in gauge pressure, regulating time is 1 ~ 1800s, preferred 600s.
Preferably, the catalyst dust removing efficiency of described micro-swirl concentrator is not less than 85%, and operation pressure drop is not more than 30mmH
2o; Described swirl concentrator is selected from hydrocyclone; Described micro-swirl concentrator by single, two or more micro-eddy flow core pipe composes in parallel.
Preferably, in described pH regulating tank, catalyst micro mist slurry pH value is after adjustment 0 ~ 10, preferably 3.0.
Preferably, the concentration of the hydrogenperoxide steam generator added in described stirred autoclave is 0.1 ~ 28 % by weight, preferably 28 % by weight; The ratio of catalyst micro mist slurry and hydrogenperoxide steam generator is 1/1000000 to 5/1, preferably 100/1, by weight; The operating temperature of described stirred autoclave is 20 ~ 180 DEG C, preferably 95 DEG C, and operating pressure is 0.1 ~ 10MPa, preferred 0.3MPa, and in gauge pressure, regulating time is 1 ~ 1800s, preferred 300s.
In the present invention, the oil content of the catalyst micro mist after wet-type peroxide oxidizing is down to weight less than 0.01 ~ 20% after the drying, and preferably less than 8.2 % by weight, with the weighing scale of described outer row's catalyst.
Preferably, the temperature of described internal return drying machine is not less than 85 DEG C or boiling point higher than reactant liquor.
Preferably, described storage regulating tank is selected from dispersed with stirring equipment, guarantees that the temperature adjusting of whole system is even by dispersed with stirring.
In the present invention, described adjustment hold-up tank, by sealing gland controlled atmosphere control device interior pressure, so that produce suitable vapour pressure, ensures, when circulating hot water is superheated water, extensive gasification to occur.
Preferably, described pH regulating tank is selected from dispersed with stirring equipment, guarantees that the pH value regulation and control of catalyst micro mist slurry are consistent by dispersed with stirring.
Preferably, method and apparatus of the present invention also can be applicable to the oil removal treatment of oil-containing catalyst micro mist in the chilling waste water of MTP (preparing propylene from methanol) and OTO (oxygenatedchemicals producing olefinic hydrocarbons) technique.
Below referring to accompanying drawing.
Fig. 1 is the processing technological flow figure of the MTO chilling waste water oil-containing catalyst micro mist according to an embodiment of the invention.As shown in Figure 1, the oil-containing catalyst micro mist slurry after pre-treatment is stored in storage regulating tank 1, pumps into hot water quantitatively simultaneously, and be uniformly mixed, regulating and controlling temperature by circulating hot-water pump 5 to storage regulating tank 1; In the mixture press-in micro-cyclone de adnexa 2 of oil-containing catalyst micro mist and circulating hot water, the micro-cyclone de Fufen being realized catalyst micro mist adsorption oil by the Osima jacoti, Osima excavata in rotational flow field from; The attached separating obtained oil-containing hot water of micro-cyclone de enters in cycling hot water pot 4 and carries out standing water-oil separating, realizes the recovery with desorption oil that recycles of hot water, and maintains the water yield in tank by moisturizing; Enter in micro-swirl concentrator 3 through the catalyst micro mist that micro-cyclone de is attached and carry out thickening, dewater and point enter in circulating hot water tank 4; Catalyst micro mist slurry after concentrated enters in pH regulating tank 6, is adjusted to the pH value that wet-type peroxide oxidizing reaction is suitable; Catalyst micro mist slurry after adjustment is forced into reaction pressure in the mode of intermittent feeding through feed pump 7, in heat exchanger 8,9, be heated to reaction temperature, then enters in stirred autoclave 10; Hydrogen peroxide also adds in stirred autoclave 10 by the mode of intermittent feeding; In stirred autoclave 10, wet oxidation reaction is there is in oil-containing catalyst micro mist under the oxidation of hydrogen peroxide, the oil pollutant (macromolecule alkane, aromatic hydrocarbons, ketone, ester etc.) being adsorbed on catalyst micro mist surface is oxidized to the inorganic matter such as carbon dioxide, water or small organic molecule soluble in water, thus is separated from catalyst micro mist surface desorption; Catalyst micro mist after desorption enters heat exchanger 8 together with reactant liquor and cools, and heating simultaneously enters the catalyst micro mist slurry of reactor; Cooled catalyst micro mist/reactant liquor mixture enters knockout drum 11, gas, liquid product standing separation in tank; The gas-phase products such as CO enter incinerator 12, and to burn rear oxidation be CO
2deng gas; CO
2cO is passed into Deng gas
2absorbed in absorption tower 13; Catalyst micro mist/reactant liquor mixture carries out eddy flow and takes off liquid in booster pump 14 pressurizes laggard swirl concentrator in a subtle way 15, and de-liquid enters in pH regulating tank 6; Catalyst micro mist after concentrated enters internal return drying machine 16 and carries out drying, and dried catalyst micro mist is all reclaimed.
The major advantage of method and apparatus of the present invention is:
(1) by the integrated coupling of the attached method of hydro-thermal micro-cyclone de and wet-type peroxide oxidizing method to the process of MTO chilling waste water oil-containing catalyst micro mist, embody good 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 the preliminary desorption of catalyst micro mist surface contaminant, as the preprocessing process of wet-type peroxide oxidizing, economical, achieve oil pollutant minimizing process efficiently.
(3) wet-type peroxide oxidizing method utilizes the strong oxidizing property of hydrogen peroxide, on the basis that hydro-thermal micro-cyclone de is attached, in stirred autoclave, oxidation Decomposition is thoroughly carried out to the pollutant of catalyst micro mist surface attachment, complete the final desorption of adsorbed oil pollutant, and peroxide decomposition is oxygen and water can not impact environment.Flow operations equipment is simple, can realize the thorough desorption to oil pollutant.
embodiment
The present invention is set forth further below in conjunction with specific embodiment.But, should be understood that these embodiments only do not form limitation of the scope of the invention for illustration of the present invention.The test method of unreceipted actual conditions in the following example, usually conveniently condition, or according to the condition that manufacturer advises.Except as otherwise noted, all percentage and number are by weight.
embodiment 1:
In 600,000 tons/year of MTO devices, carry out oil removal treatment according to method of the present invention to oil-containing catalyst micro mist slurry in the MTO chilling waste water of pre-treatment, its specific implementation process and deoiling effect are described below:
1. oil-containing catalyst micro mist slurry properties:
In MTO device normal course of operation, it is 10.08 tons (butts) that oil-containing catalyst micro mist slurry produces weekly total amount, wherein oil-containing 2.42 tons.
The particle diameter of catalyst micro mist is 3 μm, and moisture content is 3 % by weight, and oil content is 24.0 % by weight (all with catalyst weight); Specific area is 58m
2/ g, pore volume is 0.019ml/g.
The oil pollutant that catalyst micro mist adsorbs is mainly high molecular alkane, aromatic hydrocarbons, ketone, ester etc.
2. implementation process:
See Fig. 1.As follows with reference to specific embodiment of the invention step:
(1) be stored in by oil-containing catalyst pulp in the MTO chilling waste water of pre-treatment in storage regulating tank, be transported to micro-cyclone de adnexa in the mode of intermittent take-off, the amount of each intermittent take-off is 1000kg, and discharging speed is 15000kg/ hour;
(2) pump into circulating hot water by circulating hot-water pump to cycling hot water pot, circulating hot water flow is 10000kg/ hour, and be uniformly mixed, regulating and controlling temperature to 85 DEG C;
(3) catalyst micro mist/hot water mixture is with in the pressure of 0.3MPa press-in micro-cyclone de adnexa, carry out hydro-thermal micro-cyclone de Fufen from;
(4) in hydro-thermal micro-cyclone de additive process, the oil-containing hot water of gained enters in cycling hot water pot with the flow of 3000kg/ hour and carries out standing water-oil separating, realizes recycling and the recovery of oil of circulating hot water; The catalyst micro mist completing hydro-thermal micro-cyclone de attached is still scattered in circulating hot water, and enter in pH regulating tank with the form of catalyst micro mist slurry after micro-swirl concentrator dehydration decrement, flow is 2000kg/ hour;
(5) in pH regulating tank, utilize hydrochloric acid/NaOH that the pH value of catalyst micro mist slurry is adjusted to 3.5;
(6) the catalyst micro mist slurry after adjust ph is forced into 0.3MPa through feed pump, stirred autoclave is sent into again after two heat exchanger heats to 130 DEG C, and in still, add the hydrogen peroxide 2.5kg that concentration is 28 % by weight, carry out wet-type peroxide oxidizing reaction;
(7) reacted catalyst micro mist/reactant liquor mixture is after cools down to 50 DEG C, is delivered to knockout drum and carries out gas-liquid separation, and gas-phase product sends into CO after burning
2absorption tower absorbs;
(8) the catalyst micro mist/reactant liquor mixture of liquid phase enters micro-swirl concentrator and carries out de-liquid decrement, and the reactant liquor of gained returns in pH regulating tank with the flow of 1200kg/ hour, completes recycling of reactant liquor.
3. interpretation of result:
After each step is implemented, shown in the material table 1 composed as follows of catalyst micro mist:
The material composition of oil-containing catalyst pulp after each step is implemented in table 1:MTO chilling waste water
Wherein, the yield of wet oxidation-attached oil of hydro-thermal micro-cyclone de is 379.2kg, and the whole oil mass ratios accounted in catalyst micro mist are 79.17%.
The all documents mentioned in the present invention are quoted as a reference all in this application, are just quoted separately as a reference as each section of document.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after having read above-mentioned instruction content of the present invention.
Claims (10)
1. remove a method for catalyst micro mist contained oil pollutant in MTO chilling waste water, the method comprises the following steps:
(1) storage regulation and control: store after pre-treatment through concentrated MTO catalyst micro mist slurry, by heating temperature adjustment to 20-180 DEG C in storage process, to reduce the viscosity of the oil pollutant of catalyst micro mist surface attachment;
(2) hydro-thermal micro-cyclone de is attached: carry out the attached pretreatment of hydro-thermal micro-cyclone de, to complete the preliminary desorption of catalyst micro mist surface contaminant to the catalyst micro mist through storage regulation and control obtained in step (1); And
(3) wet-type peroxide oxidizing: by the catalyst micro mist attached through hydro-thermal micro-cyclone de that obtain in step (2) through regulate pH to 0-10, pressure regulation in gauge pressure 0.1-10MPa, temperature adjustment to 20-180 DEG C after, fully mix with hydrogen peroxide, make oil-containing catalyst micro mist, under the oxidation of hydrogen peroxide, wet oxidation reaction occur, the oil pollutant being adsorbed on catalyst micro mist surface is made to be oxidized to inorganic matter or small organic molecule soluble in water, thus be separated from catalyst micro mist surface desorption, complete the final desorption to catalyst micro mist.
2. the method for claim 1, is characterized in that, in step (2), carries out water-oil separating to the oil-containing hot water produced, and realizes the recovery of oil and recycling of separating obtained water; Carry out eddy flow to the catalyst micro mist of generation and the mixture of water to concentrate, the catalyst micro mist after thickening enters step (3), and the concentrated water taken off recycles in hydro-thermal micro-cyclone de additive process;
In step (3), carry out micro-eddy flow to the mixture of the catalyst micro mist processed and reactant liquor to concentrate, catalyst micro mist after thickening carries out the oven dry of internal return micro mist, and to be removed by the reactant liquor remained in micro mist, the cleaning realizing catalyst micro mist is reclaimed; The concentrated reactant liquor taken off recycles in wet-type peroxide oxidizing process.
3. method as claimed in claim 1 or 2, it is characterized in that, in the MTO chilling waste water after described pre-treatment, the particle diameter of catalyst micro mist is 0.5-250 μm, and moisture content is 0.01 ~ 100 % by weight, and oil content is 0.01-35 % by weight, and specific area is 1 ~ 2500m
2/ g.
4. remove a device for catalyst micro mist contained oil pollutant in MTO chilling waste water, this device comprises:
Storage regulating tank (1), for storing after pre-treatment through concentrated MTO catalyst micro mist slurry, and controls intermittent take-off, to ensure that the interval of wet-type peroxide oxidizing processing procedure is carried out;
The micro-cyclone de adnexa (2) be connected with the discharging opening of described storage regulating tank (1), for carrying out the attached pretreatment of hydro-thermal micro-cyclone de, to complete the preliminary desorption of catalyst micro mist surface contaminant to the catalyst micro mist through storage regulation and control obtained in storage regulating tank (1);
The pH regulating tank (6) be connected with described micro-cyclone de adnexa (2), for regulating the pH value of catalyst micro mist;
The feed pump (7) be connected with the discharging opening of described pH regulating tank (6), for catalyst micro mist is pumped to stirred autoclave (10), and is forced into reaction pressure;
The heat exchanger (8) be connected with the outlet of described feed pump (7), for the cooling of mixture and the first heating of catalyst micro mist of post catalyst reaction micro mist and reactant liquor;
Another heat exchanger (9) be connected with the outlet of described heat exchanger (8), for just heating the heating of rear catalyst micro mist, makes it to reach reaction temperature; And
The stirred autoclave (10) be connected with the outlet of described heat exchanger (9), for passing through catalyst micro mist and the abundant haptoreaction of hydrogen peroxide in still, make the oxidized decomposition of oil pollutant, complete the final desorption of catalyst particles surface attachment oil pollutant.
5. device as claimed in claim 4, it is characterized in that, this device also comprises: the cycling hot water pot (4) be connected with the oil-containing hot water outlet of described micro-cyclone de adnexa (2), in order to complete the standing water-oil separating of oil-containing hot water, realize the recovery of hot water circuit utilization and oil;
The circulating hot-water pump (5) be connected with the delivery port of described cycling hot water pot (4), recycles for circulating hot water being pumped to storage regulating tank (1);
With the catalyst micro mist enrichment phase of described micro-cyclone de adnexa (2) export be connected, be placed in micro-swirl concentrator (3) between micro-cyclone de adnexa (2) and pH regulating tank (6), mixture for externally arranging catalyst micro mist and water carries out dehydration decrement, forms catalyst micro mist concentrate feed;
The knockout drum (11) be connected with the discharging opening of described stirred autoclave (10), for carrying out standing separation to reacted gaseous phase materials and liquid phase material;
The incinerator (12) be connected with the gaseous phase materials discharging opening of described knockout drum (11), for being oxidized to CO by the pernicious gas produced in course of reaction
2;
The CO be connected with the outlet of described incinerator (12)
2absorption tower (13), for by burn after CO
2absorb;
The booster pump (14) be connected with the liquid phase material discharging opening of described knockout drum (11), for being pumped to micro-swirl concentrator (15) by the mixture of catalyst micro mist and reactant liquor;
The micro-swirl concentrator (15) be connected with the outlet of described booster pump (14), for carrying out de-liquid decrement to the mixture of catalyst micro mist and reactant liquor, forms catalyst micro mist concentrate feed;
Export with the catalyst micro mist concentrate feed of described micro-swirl concentrator (15) the internal return drying machine (16) be connected, the final oven dry for catalyst 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, is characterized in that, in described storage regulating tank (1), the ratio of catalyst micro mist and circulating hot water is 1/1000000 to 2/1, by weight; The operating temperature of described storage regulating tank (1) is 20 ~ 180 DEG C, and operating pressure is 0.1 ~ 10MPa, and in gauge pressure, regulating time is 1 ~ 1800s; Described storage regulating tank (1) is selected from dispersed with stirring equipment.
7. device as claimed in claim 5, it is characterized in that, the catalyst dust removing efficiency of described micro-swirl concentrator (3) and micro-swirl concentrator (15) is not less than 85%, and operation pressure drop is not more than 30mmH
2o; Be selected from hydrocyclone; Composed in parallel by single, two or more micro-eddy flow core pipes.
8. the device as described in claim 4 or 5, is characterized in that, in described pH regulating tank (6), catalyst micro mist slurry pH value is after adjustment 0 ~ 10; Described pH regulating tank is selected from dispersed with stirring equipment.
9. the device as described in claim 4 or 5, the concentration of the hydrogenperoxide steam generator added in described stirred autoclave (10) is 0.1 ~ 28 % by weight; The ratio of catalyst micro mist slurry and hydrogenperoxide steam generator is 1/1000000 to 5/1, by weight; The operating temperature of described stirred autoclave (10) is 20 ~ 180 DEG C, and operating pressure is 0.1 ~ 10MPa, and in gauge pressure, regulating time is 1 ~ 1800s.
10. device as claimed in claim 5, is characterized in that, the temperature of described internal return drying machine (16) is not less than 85 DEG C or boiling point higher than reactant liquor; The oil content of the catalyst micro mist after wet-type peroxide oxidizing is brought down below 0.01 ~ 20 % by weight after the drying, with the weighing scale of described outer row's catalyst micro mist.
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