CN101048347A

CN101048347A - Method and apparatus for removing organic substance from oily water from oilfield

Info

Publication number: CN101048347A
Application number: CN 200580036851
Authority: CN
Inventors: 荒户利昭; 饭塚秀宏; 望月明; 铃木朋子; 本地章夫; 小松茂三郎; 矶上尚志; 佐佐木洋
Original assignee: Hitachi Ltd
Current assignee: Hitachi Ltd
Priority date: 2004-11-05
Filing date: 2005-11-01
Publication date: 2007-10-03

Abstract

A method and an apparatus for removing dissolved organic substances from an oily water obtained as a by-product from an oilfield, characterized in that an oily water obtained as a by-product from an oilfield by separating a crude oil from a crude oil/brine mixture is brought into contact with an adsorbent to adsorptively remove organic substances dissolved in the water containing oil suspended therein and that the adsorbent is regenerated.

Description

Organicly in the oil field oil-containing water remove method and remove device

Technical field

The present invention relates to the treatment process and the treatment unit of the oil field oil-containing water that from crude oil and brinish mixture, separates, produce at field area, particularly effectively remove the method and the device of organism such as oil droplet contained in the oil field oil-containing water and the molten organic compound of depositing.

Background technology

In field area, crude oil extraction and salt solution are the mixture of admixture, separate crude oil and salt solution from this mixture, and generate oil field oil-containing water.Because oil field oil-containing water contains considerable oil droplet and moltenly has an organic compounds, therefore directly being back to then has the risk that produces environmental disruption in sea or the lake.

All the time, in order to separate, remove contained oil content in the oil field oil-containing water that field area is produced, after deliberation the whole bag of tricks.For example, open in the 2003-144805 communique, disclose the oil content in the oil field oil-containing water is carried out emulsification, and add magnetic powder and agglutinant therein, separate by magnetic attraction magnetic flocs unit again to form the magnetic flocs unit the spy.

In addition, " Experience of Produced Water Treatment in the North Sea ", MarinePollution Bulletin, Vol.29, No.6-12, (1994) have been put down in writing use liquid cyclone separator in p.312-316 and have been separated oil droplet.

Yet, even removed the oil droplet in the oil field oil-containing water, owing to moltenly in oil field oil-containing water have considerable organic compound, for example acetate, propionic acid, a valeric acid etc., and Here it is stench and environment produced the destructive reason, so the time removing also of they study.Measuring the index that aforementioned appearance has organic compounds content is the value that is called COD (chemical oxygen demand (COD)).Therefore molten in the aforementioned oil field oil-containing water has organic compounds and is commonly referred to as the COD composition.

Open in the 2004-275884 communique the spy, put down in writing in oil field oil-containing water and added active carbon powder and CO absorption D composition, aggegation isolating active carbon powder again to wherein adding agglutinant.

Open in the 2004-255290 communique the spy, put down in writing and in oil field oil-containing water, added organic polymer coagulant, and further added polymer coagulant and oxygenant, and decomposed oil content thus.Wherein also put down in writing with the remaining oxygenant of charcoal absorption and be removed, and the hypochlorous acid that electrolysis is produced etc. is as oxygenant.

The technology of being put down in writing in above-mentioned each known document, existing problems in these areas, promptly to the oil content in the oil field oil-containing water and the molten suitable processing that has organic compounds that can have problems later on, and to the processing of isolating organic compound.For example, in make the sedimentary method of gac of adsorb organic compound etc. by agglutinant, a large amount of sedimentary processing have produced big problem.Use oxygenant such as hypochlorous acid perhaps can decompose oil content to a certain extent, but that whether it can effectively reduce the molten organic compound of depositing is not clear.

In addition, open in the 2000-93957 communique the spy, the technology that water purification film purifying drinking water by containing zeolite etc. contains a small amount of organic water is disclosed, but this treatment technology that contains the poor-quality water of a large amount of oil contents and organic compound of oil field oil-containing water openly.

Patent documentation 1: the spy opens the 2003-144805 communique

Patent documentation 2: the spy opens the 2004-275884 communique

Patent documentation 3: the spy opens the 2004-255290 communique

Patent documentation 4: the spy opens the 2000-093957 communique

Non-patent literature 1: " Experience of Produced Water Treatment in the North Sea ", Marine Pollution Bulletin, Vol.29, No.6-12, (1994), p.312-316

Summary of the invention

Therefore, wish a kind of effective separation, remove the oil content in the oil field oil-containing water and moltenly have organic compounds, and in its aftertreatment equipment, expense and to the few oil field oil-containing water treatment method and the device of load of environment etc.

The invention provides a kind of oil content and molten method and apparatus that has organic compounds removed, it carries out separating treatment by the oil content in the oil field oil-containing water that separates crude oil in the crude oil that will exploit and the brinish mixture obtain from the oil field, and will adsorb, remove and carry out oil content and remove the sorbent material of the molten organic compound of depositing in the oil field oil-containing water of processing and contact with above-mentioned oil field oil-containing water, effectively remove oil content and moltenly have an organic compounds.

Description of drawings

Fig. 1 represents the summary construction diagram of the oil field oil-containing water treatment system of the embodiment of the invention 1.

Fig. 2 represents the summary construction diagram of the oil field oil-containing water treatment system of other embodiment of the present invention.

Fig. 3 represents the cross-sectional of employed in the present invention adsorption tower topology example.

Fig. 4 is the synoptic diagram of the X-ray diffraction figure of employed sorbent material in the present invention.

Fig. 5 represents the outside drawing according to the adsorption tower structure example of the treatment system of the embodiment of the invention.

Fig. 6 represents the Heating temperature of employed in the present invention sorbent material sorbent material when desorption by heating and breaks away from the graph of a relation of pneumatolytic branch concentration.

Fig. 7 represents the employed in the present invention catalyst-loaded regeneration temperature and the graph of a relation that remains in the carbon concentration on the sorbent material of regeneration back that changes into the sorbent material of branch.

Fig. 8 represents adsorbent reactivation temperature and the COD that adsorbs front and back in embodiments of the present invention _MnThe graph of a relation of value.

Fig. 9 represent catalyzer change into branch Co concentration with use behind the sorbent material support Co, at the graph of a relation of 400 ℃ of following thermal regenerations residual carbon concentration after 1 hour.

Figure 10 represent catalyzer change into branch Mn concentration with use behind the sorbent material support Mn, at the graph of a relation of 400 ℃ of following thermal regenerations residual carbon concentration after 1 hour.

Figure 11 represents the sorbent material use temperature and handles the graph of a relation of the COD decrement of aftertreatment water.

Figure 12 is illustrated among the embodiment 6, replaces potential generator and electrolyzer among Fig. 1 and the sketch chart of the aerator tank structure that disposes.

Nomenclature

1... oil field oil-containing water, 2... former tank, 3... coagulating bath, 4... rotating filter device, 5... rotate through filter membrane, 6... rotational circle cylindrical shell, 7... flocs unit, 8... scraper plate, 10... drain treatment apparatus, 11... equipment for magnetic separation, 13... electric generating unit, 14... electrolyzer, 15... vapor pipe, 16... exhaust combustion tower, 17,19...COD adsorption tank, 18... draining supply-pipe, 20... process furnace, 21... sorbent material, 22... air-heater, 23... rising pipe, 24... valve, 25...2 inferior treating water, 26...COD watch-dog, 27... hopper, 28... blast tube, 29... wet bulb thermometer, 30... conduit, 31... thief hole, 31 ' ... gas-analysis apparatus, 91,92... electrode, 180...2 inferior treating water.

Embodiment

The present invention has removed the oil droplet in the oil field oil-containing water etc., and absorption removed the molten organic compound of depositing in the oil-containing water, and as the method for removing of oil droplet etc., the magneticseparation method is particularly suitable.In addition, though, must be to use the absorption of sorbent material to remove,, also can use electrolytic process etc. as the pre-treatment of adsorption treatment as the molten method of removing that has organic compounds.Hereinafter, relate to the most important absorption of the present invention and remove method, and describe several projects in detail.

(I) the molten content example that has organic compounds: the typical Japan of table 1 expression produces the salt and the molten content that has organic compounds of oily crude water.In addition, the composition and the concentration of table 2 expression typical foreign product oily crude water.The kind of this organic compound, content can produce various variations according to the oil field.Just and/or isopropylformic acid, just and/or isovaleric acid be malodorous cause material.

Table 1

Ingredient	Molecular formula	Concentration (mg/L) analytical value
Ingredient	Molecular formula	Concentration (mg/L) analytical value	Sodium-chlor	NaCl	16000
Acetate	CH ₃COOH	1970	Sodium-chlor	NaCl	16000
Acetate	CH ₃COOH	1970	Propionic acid	CH ₃CH ₂COOH	400
Butanic acid	CH ₃(CH ₂) ₂COOH	78	Propionic acid	CH ₃CH ₂COOH	400
Butanic acid	CH ₃(CH ₂) ₂COOH	78	Isopropylformic acid	(CH ₃) ₂CHCOOH	430
Positive valeric acid	CH ₃(CH ₂) ₃COOH	15	Isopropylformic acid	(CH ₃) ₂CHCOOH	430
Positive valeric acid	CH ₃(CH ₂) ₃COOH	15	Isovaleric acid	(CH ₃) ₂CHCH ₂COOH	78
Acetone	CH ₃COCH ₃	2	Isovaleric acid	(CH ₃) ₂CHCH ₂COOH	78
Acetone	CH ₃COCH ₃	2	Phenol	C ₆H ₅OH	12
Cresols	C ₆H ₄(CH ₃)OH	8	Phenol	C ₆H ₅OH	12
Cresols	C ₆H ₄(CH ₃)OH	8	Methylethylketone	(CH ₃) ₂CH ₂CO	0.3
Benzene	C ₆H ₆	0.28	Methylethylketone	(CH ₃) ₂CH ₂CO	0.3
Benzene	C ₆H ₆	0.28	Toluene	C ₆H ₅CH ₃	0.06

Table 2

Ingredient	Molecular formula	Concentration (mg/L) analytical value
Ingredient	Molecular formula	Concentration (mg/L) analytical value	Sodium-chlor	NaCl	21000
Acetate	CH ₃COOH	12000	Sodium-chlor	NaCl	21000
Acetate	CH ₃COOH	12000	Propionic acid	CH ₃CH ₂COOH	2420
Butanic acid	CH ₃(CH ₂) ₂COOH	110	Propionic acid	CH ₃CH ₂COOH	2420
Butanic acid	CH ₃(CH ₂) ₂COOH	110	Isopropylformic acid	(CH ₃) ₂CHCOOH	460
Positive valeric acid	CH ₃(CH ₂) ₃COOH	110	Isopropylformic acid	(CH ₃) ₂CHCOOH	460
Positive valeric acid	CH ₃(CH ₂) ₃COOH	110	Isovaleric acid	(CH ₃) ₂CHCH ₂COOH	1840
Acetone	CH ₃COCH ₃	5	Isovaleric acid	(CH ₃) ₂CHCH ₂COOH	1840
Acetone	CH ₃COCH ₃	5	Phenol	C ₆H ₅OH	14
Cresols	C ₆H ₄(CH ₃)OH	12	Phenol	C ₆H ₅OH	14
Cresols	C ₆H ₄(CH ₃)OH	12	Methylethylketone	(CH ₃) ₂CH ₂CO	0.8
Benzene	C ₆H ₆	1.5	Methylethylketone	(CH ₃) ₂CH ₂CO	0.8
Benzene	C ₆H ₆	1.5	Toluene	C ₆H ₅CH ₃	0.8

(II) the COD facture relatively

Remove in the facture at various COD, during according to its validity of experimental verification, can obtain following result.That is, for other method the method for this easy regeneration type inorganic adsorbent of use zeolite adsorbents used in the present invention, they have problems in actual use as can be known.

(1) activated sludge method: because the halogen influence, biology is suppressed.Treatment time is long.

(2) add clorox: almost do not have COD to reduce effect.

(3) produce hypochlorous acid (electrolysis): almost do not have COD to reduce effect.

(4) Fenton oxidation: almost do not have COD to reduce effect.

(5) concentrating under reduced pressure (distillation): only can separate the material that differs greatly with water boiling point.The processing of concentrated solution also has problems.

(6) gac: can reduce COD, but the regeneration difficulty.Need big carbon content active, so the cost height.

In the present invention, the proterties of the preferred easy regeneration type inorganic adsorbent that uses is as described below.

(a) loading capacity is big.

(b) speed of absorption, desorption is fast.

(c) (along with its regeneration, the consumption of sorbent material is few) can regenerate.

(d) physical strength is enough big.

(e) micropore size of suitable sorbent material.

(f) adsorbent surface character with as the adsorbed material fit of object.

Remove in the embodiment of method at the particularly preferred COD of the present invention, remove method, can bring into play the COD composition characterization of adsorption of synthetic zeolite and remove by being used in combination oily water separation method, electrolytic process and absorption.In addition, though abundant planar water soluble organic compound, and after absorption property descends, absorption property is returned to and use before identical degree, therefore operation is gone up uncomplicatedly, and can reduce the draining processing cost.

In the present invention, wish to use the proton type zeolite as sorbent material.And the special ratio height of wishing to use silica/alumina, mol ratio is the synthetic zeolite more than 5.Because the synthetic zeolite hydrophobicity that the ratio of this silica/alumina is high is outstanding, is suitable for the organic composition in the selective adsorption draining.

The adsorption treatment time of the amount of consideration processed water and the amount of sorbent material and each adsorption tower is waited and manages operation and the utilization that COD removes device, makes treating water COD value for discharging below the benchmark 120mg/L.Remove in the method and apparatus at COD, above-mentioned various data storage in the memory section of control device, as required, are come control method and device based on these data according to embodiment of the present invention.

Oil-containing water treatment unit according to one embodiment of the present invention, it is regardless of the concentration of compositions such as contained organic solvent in the oil field oil-containing water, can carry out height handles, and do not need large-scale equipment etc., and can make the miniaturization of device own, therefore can be with low-cost processes oil field oil-containing water.

As mentioned above, in oil field oil-containing water, dissolve various organic compositions, become the cause material that COD rises.Problem to be solved by this invention is to make the dried up following COD of draining benchmark that is reduced to of this oil content.In addition, also be to provide a kind of process can also keep the COD of adsorption activity, weather resistance to remove system for a long time.

As the sorbent material of from oil field oil-containing water, removing organic solvent by absorption, can realize by carbon class sorbent material (gac) and inorganics class sorbent material.But although the charcoal absorption performance is good, but its existence is not easy such problem of regenerating, and therefore, taking a kind of using method is very important to address this problem.

Typical Japanese petroliferous oil-containing water COD composition is acetone, methylethylketone, acetate, propionic acid, butyric acid, valeric acid, trieline, zellon, benzene, toluene, ethylbenzene, dimethylbenzene, phenol, cresols, xylenol, Perchlorobenzene, dithiocarbonic anhydride, methyl alcohol, ethanol, Succinic Acid, lactic acid etc.

For above-mentioned COD composition, the adsorptivity aspect of synthetic zeolite has specificity.Multiple synthetic zeolite intermingling can be used or and use.Particularly combine by sorbent material with different micropore sizes (pore size), can the organic compound of active adsorption from the small molecular weight to the macromolecule.For example, the organic compound of small molecular weights such as acetate adsorbs with the little sorbent material of micropore size, and the valeric acid of macromolecule or aromatics are by the big adsorbents adsorb of micropore size.Why doing like this, is may remain in the oil-containing water because have the compound of the molecular weight that a kind of sorbent material can't adsorb.Said, a plurality of adsorption towers by will having filled sorbent material are with respect to the flow direction parallel connection or the configured in series of processed water as can be known, the sorbent material that maybe will have different micropore sizes mixes and is filled in 1 adsorption tower, and each sorbent material progressively adsorbs its adsorption component targetedly, can more effectively remove the COD composition thus.

The sorbent material shape is carried out various considerations, as can be known except that powdery, granular, ball shape, bar-shaped, fibrous, molding such as tabular in addition, cellular or Raschig ring shape.Consider that from viewpoints such as economy and environmental protection with used adsorbent reactivation, and use is extremely important repeatedly.Therefore, sorbent material uses with easy regenerated form, or uses by easy regenerated using method.For example, powdery, granular, form that the ball shape is such are isolated from processed water easily, and are carried out manipulation of regeneration, thereby be important.Therefore, these various forms of sorbent materials are placed among mesh or the porous plate etc. and are arranged in the adsorption tower,, and can from processed water, separate simply so that it does not flow out from adsorption tower.Under the situation of other shape, also adopt and consider the regenerated method to set up.

According to the present invention, a kind of treatment unit of oil field oil-containing water is provided, it has that removing swims and is suspended in the oil content in the draining and the oil-water separation tank of non-dissolved particles, decompose electrolyzer by the organic composition molecule in 1 treating water of this oil-water separation tank, remove groove from the absorption of removing organic composition by absorption 2 treating water of this electrolyzer, and will be from remove the burner of isolated organic compound burning and gas-exhausting in the absorption remover of filling the groove in this absorption.

In addition, according to the present invention, a kind of treatment unit of oil field oil-containing water is provided, it has that removing swims and is suspended in the oil content in the draining and the oil-water separation tank of non-dissolved particles, decompose electrolyzer by the organic composition molecule in 1 treating water of this oil-water separation tank, from removing groove by separating the separation of removing organic composition 2 treating water of this electrolyzer, groove is removed in the absorption that organic composition is removed in absorption from 3 treating water removing groove by this separation, and will remove separations removed in the groove organic composition and be removed groove by this absorption and separate the organic composition of removing and mix the also burner of burning and gas-exhausting in this separation.Aforementioned oil-water separation tank is preferably the magneticseparation groove.Aforementioned oil-water separation tank is preferably the magneticseparation groove.In addition, remove absorption remover in the groove, be preferably inorganics class absorption remover as can be used on aforementioned absorption.Aforementioned inorganics class sorbent material is the zeolite with the crystalline structure that contains silicic acid and aluminum oxide, and the existence ratio that is suitable for silicic acid and aluminum oxide is SiO ₂/ Al ₂O ₃Mol ratio is natural zeolite or the synthetic zeolite more than 5.The preferred especially high synthetic zeolite of hydrophobicity.In addition, preferred aforementioned inorganics class sorbent material contains at least a in silicic acid and aluminum oxide and the sodium oxide, and the existence of silicic acid and aluminum oxide ratio is SiO ₂/ Al ₂O ₃Mol ratio is more than 5, contains at least a composition among Pt, Pd, Ru, Rh, Ni, Fe, Cu, Mn, the Co simultaneously in sorbent material.

In addition, preferably the inorganics class after organic composition is removed in heating absorption under 100 ℃-600 ℃ the atmospheric atmosphere is adsorbed remover, thus repeated regeneration and use.

It can be to separate the separation of removing volatile organic compounds and remove groove by aforementioned 1 treating water being carried out aeration that groove is removed in aforementioned separation.

In addition, the invention provides treatment process, it has that removing swims and is suspended in the oil content in the draining and the magneticseparation operation of insoluble particle, the electrowinning process of the oil field oil-containing water that the electrolysis magneticseparation is crossed, from 2 treating water that obtain by aforementioned electrolytic process, separate the separation of removing volatile organic compounds and remove operation, from remove 3 treating water of discharging the groove by aforementioned separation, adsorb the absorption of removing organic composition and remove operation, and to removing the operation that the volatile organic compounds of discharging the groove carries out burning and gas-exhausting from aforementioned the separation together with steam.

According to COD value as the oil field oil-containing water of raw material, be used in combination magnetic separating device, aerator tank, evaporation concentration device, hypochlorous acid reaction unit and/or electrolysis reaction device, and finally the COD composition is removed the mode of discharging the COD value below the benchmark to environment is suitable to the absorption method by using catalysis thinner sorbent material, so is fit at catalysis thinner sorbent material mesolite.Wherein silicon/aluminum oxide is than high, and to have hydrophobic synthetic zeolite be effective especially.

The systematize of comparing of catalysis adsorption treatment method is easy, on the other hand because catalyst life and exchange frequency have much relations with processing cost, so performance of the adsorbent and regenerate all very important easily.

In order to make organic adsorbent reactivations such as having adsorbed organic solvent, by the method that heating method comes the carbon component of oxidizing fire absorption to be removed, just so-called dry type heating method is effective.But, because therefore himself burning of carbon class sorbent material and consume exists restriction when repeated regeneration, and since must have consume composition add pad device etc., thereby have and can't set up efficient COD and remove the such shortcoming of system.In addition, at sea under the situation in oil field, consider, most preferably avoid the additional services sorbent material as far as possible from carrying the cost aspect.

According to the present invention, relate to and from oil field oil-containing water, remove the COD composition, its main being characterised in that can be removed the COD composition as the absorption method of sorbent material by using zeolite, and, recover the reduction of characterization of adsorption by under the atmosphere moderate condition, burn, decomposition etc. according to adsorbed material.

As mentioned above, in zeolite, synthetic zeolite is particularly suitable as the material with feature of the present invention, in addition SiO wherein ₂/ Al ₂O ₃Mol ratio is more than 5, and has that the synthetic zeolite of hydrophobicity proterties is best suited for.ZSM-5 is the sorbent material of special the object of the invention.

If the carbon component from adsorbed organic matter directly remains in adsorbent surface, then adsorbent surface is active descends.Therefore, then must remove carbon component and make activation recovering if adsorbent activity has descended.

The adsorbed organic matter composition remains in the sorbent material as carbon component.Under common atmosphere,, just can't remove carbon component if be not heated to more than 600 ℃.But in the oil field oil-containing water of reality, be dissolved with sodium-chlor with the concentration of seawater same degree.Therefore, because at 600 ℃ of following repeated regenerations, so as the SiO of zeolite principal constituent ₂React at short notice with the Na of sodium-chlor, thereby caused as the function reduction of sorbent material.Thus, wish under than 600 ℃ of low temperature, to heat as far as possible.

By the catalyst-loaded branch that changes into, can be in the temperature below 500 ℃, and top condition is under low temperature such below 400 ℃, decomposes, the organism of oxidizing fire adsorbent surface, and make sorbent material return to original active condition.

According to the present invention, compare the consumption that can prevent sorbent material with conventional art, thereby can reduce the concentration of organic composition in the oil field oil-containing water by cheap running cost.

In addition, in the following areas, the present invention has the advantage above previous methods.That is to say, with the synthetic zeolite is sorbent material, and be supported on the catalytic effect that the lip-deep catalyzer of aforementioned synthetic zeolite changes into branch by coating, can be adsorbed on the organic components of adsorbent surface by oxidizing fire, and identical degree before absorption property can being returned to and using.

Catalyzer changes into branch, except that precious metals such as Pt, Pd, Rh, Au, Ag, even transition metal-types such as Fe, Ni, Mn, Mn, Co also have identical effect.

Because regenerative operation can only be removed treating water under the situation of having filled sorbent material, therefore operation is upward uncomplicated, and considers also to have advantage from the viewpoint that can reduce the draining processing cost.

In order from oil field oil-containing water, to remove the COD composition, oil field oil-containing water is contacted with synthetic zeolite, the result can bring into play absorption property and it is reduced to below the COD concentration below the target draining benchmark.In addition, owing to the long-time sorbent material that causes absorption property to reduce that uses, burn and remove by adding heat-adsorbent from organic carbon component, recover active thus, and like this repeatedly in long-time, thereby effectively remove COD constituents in the oil field oil-containing water.

Particularly,, can keep absorption property, and only under the lesser temps below 500 ℃, heat, get final product the organic composition of oxygenolysis absorption at the catalyst-loaded sorbent material that changes into branch in synthetic zeolite surface, and the oxidizing fire carbon component.

Embodiment

Below, illustrate in greater detail the present invention by embodiment.In addition, in embodiments of the present invention, use following method to carry out performance evaluation.

Absorption property is estimated

Accurate weighing 1.0g sorbent material is also put into the 100mL beaker.Accurate weighing 100mL oil field oil-containing water is also put into wherein.The magnetic stirring apparatus that stirrer is equipped with in use stirs, and carries out the absorption of specified time.After the end, under the situation that can't separate minuteness particle, use centrifuge separator promptly from treating water, to separate minuteness particle, liquid is used for analyzing then.Using centrifuge separator promptly behind separate sorbent and the liquid, liquid is used for COD analyzes.

The mensuration of COD concentration in the draining

The mensuration of COD is by utilizing the chemical oxygen demand (COD) (COD of JIS K 0102 plant drainage test method(s) potassium permanganate _Mn) and carry out.

The quantitative assay of the acetate of draining and propionic acid concentration

The quantitative assay of acetic acid concentration and propionic acid concentration uses the ionic light spectrometry to carry out.

Embodiment 1

Below, based on Fig. 1 one embodiment of the present invention are described.At drain treatment apparatus 10, constitute by the equipment for magnetic separation 11, electrolyzer 14, COD adsorption tank 17 and the exhaust combustion tower 16 that separate oil content in the oil-containing water of oil field as one embodiment of the present invention.

Operation for drain treatment apparatus is described below.At first, oil field oil-containing water 1 is contained in the former tank 2.In oil field oil-containing water, oil content is loose by emulsification.In the oil field oil-containing water, be the mineral ion of representative, also contain atomic little mud, sand and other solid matter except organic composition with sodium.Therefore, oil field oil-containing water 1 is delivered to coagulating bath 3, and use agglutinant and magnet (Fe such as ferric sulfate or polymerize aluminum chloride ₃O ₄), γ-red iron (Fe ₂O ₃) etc. the magnetic particle, make the seston aggegation and the processing of flocculating.

The former water that will contain flocs unit is delivered in the rotating filter device 4, removes oil content and flocs unit.In rotating filter device 4, be equipped with and rotate through filter membrane 5 and rotational circle cylindrical shell 6, these rotational circle cylindrical shell 6 inner not diagrams, but wherein be provided with magnetic field generating unit such as electromagnet.Filter former water by rotating through filter membrane 5, oil content is separated from former water with flocs unit 7.To be deposited in the oil content and the flocs unit that rotate through in the filter membrane 5 by being blown into washing water and 8 scrapings of use scraper plate and from rotational circle cylindrical shell 6, remove, and be expelled to rotating filter device 11 outsides.Again filtered water 90 is delivered in the electrolyzer 14.

Be provided with

electrode

91 and 92 in the electrolyzer 14.Electrode 91 is connected with potential generating device 13 with 92.After in entering electrolyzer 14, decompose organism in the filtered water 90 by carrying out electrolysis continuously, and form the organism of small molecular weight.Owing in oil field oil-containing water, dissolved the sodium-chlor of high density, therefore helped the carrying out of electrolytic reaction.Using gas analyzer 31 ' is analyzed the exhaust gas composition of electrolyzer 14.

In electrolyzer 14, because the formation reaction that energising has also produced hydrocarbon produces volatile organic component.Therefore, carry out exhaust on electrolyzer 14 tops by the vapor pipe 15 that reclaims volatile organic component.At vapor pipe 15 front ends, the exhaust combustion tower 16 that being provided with is used to burn removes volatile organic component, and by conduit 30 burning and gas-exhausting is discarded in the atmosphere.

According to analysis, the deflated volatile organic component is saturated hydrocarbons such as ethane, ethene, cyclopropane from electrolyzer 14.In electrolyzer 14, be used for electrolytic electrode materials and be suitably for Fe, Ni, Al, Au, Pt, SUS etc.If can obtain the electrode materials of high current density, then produce 2 molecular weight carboxylic acids and 2 protons in conjunction with the also main reaction that generates hydrocarbon.Therefore, wish the condition of high current density, and discover in above-mentioned electrode materials, Pt or be particularly suitable with the material that form of film applies Pt through the present inventor.

In electrolyzer 14, need not to finish electrolytic reaction, so filtered water 90 can flow into continuously in the electrolyzer 14.Undecomposed organic composition or the organic composition that decomposes halfway are sent among

COD adsorption tank

17 or 19 some by draining supply-pipe 18 as the composition in 2 treating water 180 in electrolyzer 14.

The COD adsorption tank is made up of 1COD adsorption tank 17 and 2COD adsorption tank 19.Usually during operation, use 1COD adsorption tank 17, and 2COD adsorption tank 19 is set to standby, and be used alternatingly the 1st and the 2nd adsorption tower.Therefore, the structure of 1COD adsorption tank and 2COD adsorption tank is identical.Below describe based on 17 pairs of adsorption tank one-piece constructions of 1COD adsorption tank.

In the present embodiment, have 2 COD adsorption tanks, but also can have more a plurality of adsorption tanks.Filled the ZSM-5 particle in sorbent material 21, this ZSM-5 particle is a kind of in the synthetic zeolite.Support catalyzer in the ZSM-5 particle in advance and changed into branch.Under the situation of present embodiment, the Ni composition that supports is scaled 0.5wt% by the ZSM-5 of per unit weight.As sorbent material 21 compositions, except that ZSM-5, mordenite also has the absorption property of same degree.

The COD adsorption tank container of present embodiment is the drum of SUS304 system.The material of adsorption tank container is not limited to SUS304.COD adsorption tank 17 is configured in the inside of process furnace 20, and each COD adsorption tank 17 all is the structure that can add heat-adsorbent 21.In COD adsorption tank 17, be provided with air-heater 22 and rising pipe 23.Rising pipe 23 and flowing water Valve 24 are all in the adsorption tank bottom.

When the adsorbents adsorb performance reduces, the processed water stream is switched to adsorption tower 19, open the flowing water Valve 24 of adsorption tower 17, extract the water in the COD adsorption tank 17 out.Then, operation air-heater 22 is blown into the hot blast about 100-120 ℃ in the COD adsorption tank 17, makes the sorbent material drying.And wish a kind of from top air-supply, from COD adsorption tank bottom water outlet deflated structure simultaneously.

By about 30 minutes of use air-heater 22 air-supplies, and the water ratio of all sorbent materials 21 in the COD adsorption tank 17 is reduced to below 10%.The time of blowing in addition changes according to the flute length and the wind pushing temperature of COD adsorption tank 17, and it is not limited by present embodiment.

For the water ratio of control and management sorbent material, preferably in the blast tube 28 of adsorption tank bottom, wet bulb thermometer 29 is set.2 treating water 25 of process COD adsorption tank 17 carry out draining 28 after storing in interim hopper 27.Be provided with COD watch-dog 26 before and after the hopper, it is used in particular for the management (COD≤120mg/L) of draining COD value.

Also can use air-heater to replace above-mentioned process furnace 20 that temperature is warming up to uniform temp.In this case, wish that hot blast atmosphere is Atmospheric components.

Fig. 3 represents the structure example of adsorption tower used in the embodiment of the present invention.Fig. 3 (a) is provided with the structure of electric furnace or microwave oven 61 around the adsorption tower of having filled the COD sorbent material.Supply with former water (containing COD) 62 from the adsorption tower below, become treating water 63, and from adsorption tower, discharge.When adsorption tower is regenerated, discharge residuary water 67 in the tower, supply with combustion air 64 from the adsorption tower below, and burning and gas-exhausting (containing CO2, CO, CH) 65 is directed in the burner 66 burns.

Fig. 3 (b) and Fig. 3 (a) are roughly the same, but process furnace is not set around the adsorption tower, and (T≤600 ℃) 68 of supplying with high temperature air or high-temperature gas from the adsorption tower below.Burning and gas-exhausting 69 is directed in the burner 66.

Fig. 3 (c) is from adsorption tower top supply combustion turbine exhaustion 70, to supply with combustion air 68 from the adsorption tower below, and discharge burning and gas-exhausting 69.The structure of these adsorption towers is demonstration, and it is also applicable to the situation outside the above-mentioned embodiment.

Embodiment 2

Embodiment 2 is to use an example of the test-results of embodiment 1 shown device.

COD in table 3 expression electrolytic process and the adsorption process _MnThe measurement result of value.

Table 3

	Contents processing	COD _Mn	Acetate	Propionic acid	Methyl alcohol
	Contents processing	COD _Mn	Acetate	Propionic acid	Methyl alcohol		1 treating water	Oily water separation	386	1740	390	-
2 treating water	Electrolysis	270	1200	222	150		1 treating water	Oily water separation	386	1740	390	-
2 treating water	Electrolysis	270	1200	222	150	3 treating water	Adsorption treatment		110	410	90	70

Unit: mg/L

1 treating water is the analytical results of taking a sample in 1 treating water thief hole 31 of Fig. 1 in the table 3.Use electric field bringing device 13 in being arranged at electrolyzer electrolyzer 14 electrode 91 and electrode 92 between produce electric field, handle treating water thus 2 times.Though do not have souvenir at Fig. 1, can from draining supply-pipe 18 ways, take analytic sample, and the analytical results of 2 treating water 180 that obtain taking.

By electrolyzer the time, COD _MnReduced 116mg/L.Acetic acid concentration has reduced 540mg/L, and propionic acid concentration has reduced about 170mg/L.On the contrary, produced methyl alcohol, and methanol concentration is 150mg/L.In the output water of this oil field, add electric field, carried out the Kolbe reaction and organic acid concentration changes in the output water of oil field result is shown.

COD why _MnValue reduces because of electrolysis, is because acetate produces C by the reaction of the Kolbe shown in (1) formula ₂H ₆, and form gas, thus be disposed in the atmosphere by 2 treating water.

2CH ₃COO ^-+2(+)→CH ₃CH ₃+2CO ₂ (1)

Herein, (+) expression proton.

Result by set Gas Analyzers 31 in the middle of the vapor pipe 15 that is arranged at electrolyzer (14) top is analyzed can confirm that ethane concentration has risen.

The result who produces methyl alcohol in the above embodiment of the present invention represents to have carried out the reaction by shown in (2) formula.

CH ₃COO ^-+OH ^-+2(+)→CH ₃OH+CO ₂ (2)

Used electrode

91 and 92 material are Pt (platinum) among the present invention, all are Pt but do not need all electrode materialss.Use is showing that SUS, the Fe, Al, the Ti etc. that apply Pt also can obtain same result.The method that applies Pt on surfaces such as SUS, Fe, Al, Ti has methods such as ion plating, evaporation or sputter, wherein anyly all can effectively form electrode materials.

Then, sorbent material 21 is described.As the feature of sorbent material 21, by the following as can be known content of present inventor's experimental result.As the sorbent material composition, its SiO ₂/ Al ₂O ₃Mol ratio is to get final product more than 5, particularly, for the water soluble organic substance in the active adsorption oil field oil-containing water more, more wishes SiO ₂/ Al ₂O ₃Mol ratio is more than 80.Under the situation that organic kind compares to adsorbate, if the organism carbonatoms increases, therefore the tendency that then exists adsorptive capacity to descend in identical sorbent material is wished that the aperture of the micropore that is used to adsorb is 0.5-0.6nm, and is wished that the micropore that is used to adsorb forms 3 dimension structures.

If be filled in sorbent material in the adsorption tower and be particle shape, the shape with above-mentioned absorption property such as Powdered, just no problem, but under pulverous situation, the stream when having water flowing is the dispersive risk not, and is closely related with the crushing rising in the thermal regeneration process.Therefore, wish Powdered sorbent material is configured as the particle shape in advance, or Powdered sorbent material is supported on cellular etc. the carrier, and it is arranged on COD absorption removes in the groove.

The adsorption tower concrete example of embodiment of the present invention is illustrated among Fig. 5.In the drawings, a plurality of COD adsorption towers 70 are with respect to the mobile configured in series of oil-containing water 85, and treating water 90 is discharged from the head of last adsorption tower.Each adsorption tower 70 is equipped with the process furnace 75 that is used for adsorbent reactivation.In addition, in each adsorption tower, be equipped with sorbent material exsiccant air-heater system 80 when being used to regenerate.

Embodiment 3 Fig. 6 represent the result of adsorbent reactivation of the present invention.The CO that produces by sorbent material when just representing repeated regeneration ₂, the generation of CO and hydrocarbon and Heating temperature the figure of relation.

As shown in Figure 6, use and support the sorbent material that various concentration catalyzer change into branch, carry out the absorption of the same terms, and the ablation experiment that heats up under the same conditions, and compare CO ₂And/or the gas of CO generation peak temperature, can determine that thus optimal catalyzer changes into branch kind and concentration range.

Result's the test conditions that is used to obtain Fig. 6 is as described below.In synthetic zeolite ZSM-5, use SiO ₂/ Al ₂O ₃Than being that 90 zeolite is as sorbent material.At first the above-mentioned sorbent material of 5.0g is put into the 200mL beaker, put into 2 treating water of 50mL oil field oil-containing water again and stirred 10 minutes.This operation is equivalent to adsorption process.Then, use centrifuge separator etc. carries out the solid-liquid separation operation, and only collects sorbent material.About 100 ℃ are heated this sorbent material and dry down in atmosphere.

In Fig. 7 and Fig. 8, use following method to carry out the absorption property evaluation.Measure 300mL oil field oil-containing water, put into beaker, in beaker, drop into the sorbent material of accurate weighing again.After lid was tight, the vibration by the specified time mixed or uses the rotation of agitator to mix to react fully and carry out.After reaction finishes, Filtration Adsorption agent and it is separated from treating water rapidly.In the time can't separating minuteness particle, use centrifuge separator that minuteness particle is separated from treating water.The liquid that obtains as mentioned above is used for analyzing.

Then, in Fig. 7, expression is heated with the heat-up rate of 10 ℃ of per minutes and is when heating in atmospheric atmosphere, remains in the carbon concentration on the sorbent material and the absorption property of regenerated sorbent material.

Sorbent material is to be the material that 0.2wt% supports Pt and catalysis thinner by the zeolite weight ratio.Zeolite is that the diameter for preparing by the extrusion molding method is that 3mm, length are the ZSM-5 particle of 5-20mm.Pt is a raw material with dinitrobenzene diamines Pt (II) salpeter solution, and above-mentioned ZSM-5 particle is immersed in the water-reducible Pt aqueous solution of use purifying to form above-mentioned concentration.

With all particles are whole adhere to and soak into Pt solution after, at 120 ℃ of following transpiring moistures, after moisture evaporates fully, heating 1 hour in atmosphere under 600 ℃.

Use catalysis thinner sorbent material, and it is contacted with oil field oil-containing water in beaker, stirred 10 minutes by method for preparing.The COD value of the oil field oil-containing water before putting into beaker is 600mg/L.Affirmation is determined churning time after 10 minutes COD values with the water after the aftertreatment almost do not change.After stirring end, separating treatment water and sorbent material with the dry sorbent material of air-heater, and heated 1 hour the carbon concentration after the quantitative analysis heating in the sorbent material under 300-550 ℃ temperature.

The transverse axis of Fig. 7 is the regeneration Heating temperature of catalysis thinner sorbent material, and it is equivalent to the regeneration temperature of sorbent material of the present invention.The value of the longitudinal axis is the concentration of residual carbon in the sorbent material.If regeneration temperature is below 400 ℃, then residual C concentration is more than the 0.1wt%.On the contrary, if be more than 400 ℃, then residual C concentration is below the 0.1wt%.COD according to oily muddy water _MnThe variation of value is sought the influence which kind of degree this residual C produces to absorption property, as shown in Figure 8.The longitudinal axis of Fig. 8 carries out the COD value of the treating water after 10 absorption reactions and the 10 times regeneration for oil field oil-containing water.Former water COD _MnValue is 600mg/L, though by the absorption at the ZSM-5 of 300 ℃ and 350 ℃ following repeated regenerations particle sorbent material the COD value has been reduced, does not also satisfy the COD as environmental benchmark value _MnValue≤120mg/L.If regeneration temperature is 400 ℃ and 500 ℃, then influent density 600mg/L is reduced to 105-110mg/L, and it satisfies environmental benchmark value.This is speculated as, since the regeneration under 350 ℃ of following temperature, the carbon concentration height of residues of combustion on adsorbent surface, therefore the COD composition in the former water becomes and is difficult to absorption, thus absorption property descends.As shown in Figure 8, by under the temperature about 380 ℃, regenerating, can become the regeneration of satisfying environmental criteria.

The above-mentioned embodiment according to the present invention owing in the COD composition, have the step for regeneration of keeping the adsorbents adsorb performance in using adsorbents adsorb oil field oil-containing water, therefore can be removed the COD composition in long-time.

Embodiment 4

Fig. 9 represents to change into/one Co for the catalyzer as sorbent material, the result when determining the most suitable content of Co.

Sorbent material is the material that supports Co and catalysis thinner by zeolite weight ratio maximum to 3wt%.Zeolite is that the diameter for preparing by the extrusion molding method is that 3mm, length are the ZSM-5 particle of 5-20mm.Co is a raw material with the aqueous solution of Cobalt(II) nitrate hexahydrate, and above-mentioned ZSM-5 particle is immersed in the water-reducible Co aqueous solution of use purifying to form above-mentioned concentration.

With all particles are whole adhere to and soak into Co solution after, at 100-120 ℃ down behind the complete transpiring moisture, heating 1 hour in atmosphere under 600 ℃.

Use Co dipping sorbent material, and it is contacted with oil field oil-containing water in beaker, and stirred 10 minutes by method for preparing.The COD value of the oil field oil-containing water before putting into beaker is 450mg/L.According to the reason identical with embodiment, churning time is 10 minutes.After stirring end, separating treatment water and sorbent material, dry sorbent material in thermostatic drier heated 1 hour in atmosphere under 400 ℃ then, and residual carbon concentration in the sorbent material of quantitative analysis heating back.

The transverse axis of Fig. 9 represents to be supported on the Co concentration on the ZSM-5 carrier.The longitudinal axis represents to remain in C concentration in the sorbent material with the ratio form.What be equivalent to the residual C concentration ratio of longitudinal axis denominator is to use the residual C concentration in sorbent material (ZSM-5 particle) absorption, drying and the sorbent material after 400 ℃ are heated 1 hour down that does not contain catalyzer and change into branch Co.

Clear as can be known by Fig. 9, represent as the most effective concentration range of catalyst component when residual C concentration ratio is minimum.Hence one can see that, and in order to support the Co as catalyst component on the ZSM-5 particle, the about 1-2wt% of Co loading is only.

When catalyst component is Mn, the same with the result of Co, can confirm to make the existence of the minimum Mn concentration range of residual C concentration.Under the situation of Mn, the most suitable concentration range of reproducing adsorbent is 0.3-0.6wt%.

Embodiment 5

For the embodiment that in the oil field oil-containing water treatment of Oil extraction well, uses disintegrating system in waste pipe of the present invention, use Fig. 2 to describe.But the present invention is not limited thereto.In the oil field oil-containing water treatment system that Fig. 2 represents, oil field oil-containing water 100 is contained in the former tank 106.In oil field oil-containing water, oil content is loose by emulsification.In the oil field oil-containing water, except organic composition and sodium, also contain atomic little mud, sand and other solid matter.Therefore, will deliver to coagulating bath 107, and use agglutinant and magnet (Fe such as ferric sulfate or polymerize aluminum chloride as the former water of oil field oil-containing water ₃O ₄), γ-red iron (Fe ₂O ₃) etc. the magnetic particle, make the seston aggegation and the processing of flocculating.The former water that will contain flocs unit is delivered in the rotating filter device 108, removes oil content and flocs unit.

Be equipped with in rotating filter device 108 and rotate through filter membrane 109 and rotational circle cylindrical shell 111, the inside of this rotational circle cylindrical shell 111 is diagram not, but wherein is provided with magnetic field generating unit such as electromagnet.Filter former water by rotating through filter membrane 109, and from former water, separate oil content and flocs unit.Filtered water 110 is delivered in the disintegrating system in waste pipe of the present invention described later.To be deposited in the oil content and the flocs unit that rotate through in the filter membrane 109 by being blown into washing water and 8 scrapings of use scraper plate and from rotational circle cylindrical shell 111, remove, and be expelled to rotating filter device 108 outsides.

Filtered water 110 by draining supply-pipe 114 be sent to

adsorption tower

115a or 115b in one among.In the present embodiment, have 2 adsorption towers, but also can have more a plurality of adsorption towers.Under situation with 2 adsorption towers, handle in order to carry out draining continuously, in the time of can in an adsorption tower, carrying out adsorption treatment, in another adsorption tower, carry out manipulation of regeneration.The switching of adsorption tower is undertaken by opening-closing valve 117a,

117b.In adsorption tower

115a, 115b, difference content inorganic filling class sorbent material 116a, 116b.In order to make the adsorbents adsorb surface-area become big, wish with particulate as raw material.Because particulate self is mobile owing to flowing water produces, so its management trouble, but after it is configured as definite shape and sintering, then use easily.The shape of molding can be column, tabular, cylindric, cellular or netted.Also sorbent particles can be supported on the various molding carriers.As cellular or mesh carrier,, therefore wish to use inorganics or metal owing to need stand repeated regeneration.

In draining supply-pipe 104, be connected with the analytical equipment 130 that is used for analyzing the draining na concn, in addition, in the treating water vent pipe 121,122 of adsorption tower outlet, be connected with the analytical equipment 140a, the 140b that are used for analyzing and processing water na concn.

In

adsorption tower

115a, 115b, be equipped with the heating unit 118a, the 118b that are used to add heat-adsorbent, and

air blast tube

120a, 120b be installed by valve.The air blast tube is connected to not shown air feeder.This heating unit and air blast tube use when the sorbent material of regeneration in the adsorption tower.That is to say that if sorbent material organic composition absorption quantitative change is many, adsorptive power reduces, then temporarily stop adsorption operations, and in adsorption tower, send into air by the air blast tube, and use heating unit at high temperature to add heat-adsorbent, the organic composition that is adsorbed on the sorbent material is removed in burning thus.Because therefore the easy more vitrifying of carrying out sorbent material of high temperature of Heating temperature of this moment removes the scope of organic composition in order to form to burn, low temperature is better.Specifically be that temperature below 500 ℃ is better, and be preferably especially below 400 ℃.When carrying out the adsorbent reactivation processing, the valve 119a or the valve 119b that are arranged at the adsorption tower outlet side that carries out this operation are in closing condition.

In analytical equipment 130,140a, 140b, carry out the na concn analysis continuously or with timed interval arbitrarily, and utilize communication link that this analytical data is sent to data acquisition unit 151.Data acquisition unit 151 collected data are sent in the machine unit 152.In machine unit 152, the data of the data of relative analytic apparatus 130 and

analytical equipment

140a, 140b, if they form predefined prescribed condition, judge that then sorbent material poisons because of sodium and cause end-of-life, and send that to close the valve that just carries out the adsorption operations adsorption tower be any signal among 117a, the 117b.An example of the condition when valve-

off

117a, 117b is the na concn measured in

analytical equipment

140a, 140b has surpassed the na concn of measuring in analytical equipment 130 a situation, perhaps, the na concn of measuring in

analytical equipment

140a, 140b can form the situation of requirement ratio with respect to the na concn of measuring in analytical equipment 130.In addition, in analytical equipment 130,140a, 140b, can use extinction photometer, chromatography of ions or NITRATE BY FLAME ATOMIC absorption spectrometric apparatus etc.

If send the signal of valve-off 117a or valve 117b by control device 150, and stop supplying with to the draining of adsorption tower, then exchange is filled in the sorbent material in the adsorption tower, the processing that perhaps is used to remove sodium.The function of operation can be moved by reading in the program with this function in control device 150.In addition, this program is recorded in the recording medium, and it is read in to control device, also can move this function.

Then, various experimental results are described.

Experiment 1 is packed 300 milliliters of oil field oil-containing water in the polyethylene reagent bottle into, and to wherein dropping into sorbent material and sealing, about 30 minutes of vibration reagent bottle mixes oil field oil-containing water and sorbent material again.Then, use filter paper separate sorbent and moisture, divide the decrement of COD composition in the bleed.Carry out the mensuration of COD decrement by the COD analytical method of utilizing JIS K 0102 plant drainage test method(s) potassium permanganate.In sorbent material, 8 kinds of synthetic zeolites of No.1～8 that the mol ratio of the silica/alumina shown in the use table 5 and specific surface area are different.In addition, as oil field oil-containing water, use the 1st stoste and two kinds of the 2nd stoste shown in the table 4.In these oil field oil-containing water, contain acetate, propionic acid, butyric acid, valeric acid, Succinic Acid, lactic acid, acetone, methylethylketone, trieline, zellon, benzene, toluene, ethylbenzene, dimethylbenzene, phenol, cresols, xylenol, Perchlorobenzene, dithiocarbonic anhydride etc., each all is the major cause that improves COD.The COD reduction for the treatment of water is represented at table 4.The reduction of COD composition is high more, and the organic composition amount that then is adsorbed on the sorbent material is many more, and contained organic composition amount is few more in the draining after handling.

Table 4

	The 1st stoste	The 2nd stoste
	The 1st stoste	The 2nd stoste	Composition	Concentration (mg/L)	Concentration (mg/L)
NaCl	36000	16000	Composition	Concentration (mg/L)	Concentration (mg/L)
NaCl	36000	16000	Acetate	2000	120
Propionic acid	500	40	Acetate	2000	120
Propionic acid	500	40	Ketone	3	10
Phenol	30	60	Ketone	3	10
Phenol	30	60	The benzene class	＜1.0	＜1.0
COD _Cr	7500	1980	The benzene class	＜1.0	＜1.0

Table 5

Zeolites	COD decrement (%)		Silica/alumina (mol ratio)	Specific surface area (m ²/g)
	COD decrement (%)				The 1st stoste	The 2nd stoste
	No.1	34.4			The 1st stoste	The 2nd stoste	47.4	6	550
No.2	No.1	34.4	12.5	31.6	6	230	47.4	6	550
No.2	No.3	7.8	12.5	31.6	6	230	31.6	17	360
No.4	No.3	7.8	32.8	62.6	18	170	31.6	17	360
No.4	No.5	12.5	32.8	62.6	18	170	26.3	40	330
No.6	No.5	12.5	31.3	86.3	200	400	26.3	40	330
No.6	No.7	42.1	31.3	86.3	200	400	81.1	240	420
No.8	No.7	42.1	28.1	64.2	510	750	81.1	240	420

In the zeolite of No.1～8, No.6 and No.7 zeolite be any with respect in the 1st stoste and the 2nd stoste no matter, all expresses high COD decrement.The mol ratio of silica/alumina and specific surface area do not have to produce big influence like that with respect to the COD decrement.

Experiment 2

Synthetic zeolite shown in the No.7 of the 2nd stoste shown in the table 4 and table 5 is put into reagent bottle mix stirring 1 hour.Then, stirred 1 hour with new fluid exchange the 2nd stoste and remix, change stoste 5 times repeatedly after, from reagent bottle, take out sorbent material, and heating at high temperature.As described in 4, Heating temperature is changed in 120-170 ℃ scope.Then, measure the carbon content and the specific surface area of sorbent material.Carbon content is measured by the high-frequency combustion infrared absorption, and specific surface area is measured by the BET method.Measurement result is represented in table 6.

Table 6

Sample	Raw material	After the use	After the use	After the use	After the use
Sample	Raw material	After the use	After the use	After the use	After the use	Heating temperature (℃)	-	120	300	500	700
C content (wt%)	0	0.30	0.28	＜0.01	＜0.01	Heating temperature (℃)	-	120	300	500	700
C content (wt%)	0	0.30	0.28	＜0.01	＜0.01	Specific surface area (m ²/g)	390	385	390	395	390

In table 6, the state before the content that is expressed as raw material is meant and is used to test, and be meant repeatedly the state behind the absorption regeneration after so-called the use 5 times.When Heating temperature was 500 ℃ and 700 ℃, the carbon content that remains on the sorbent material was few, its become and use before state about the same.On the other hand, when Heating temperature was 120 ℃ and 300 ℃, it is many that carbon content becomes, and organic composition is imperfect combustion intact, and its residual ratio uprises.The result in order to make the organic composition active combustion, wishes to be heated to more than 500 ℃ as can be known thus.But, if Heating temperature uprises, the then easy vitrifying of sorbent material, therefore preferred Heating temperature is low as far as possible, and wish by catalyst-loaded change into branchs and under the temperature below 400 ℃, heat make the organic composition can active combustion.Wish most to be below 500 ℃, be specially 400-450 ℃ scope.

In Heating temperature was 120-700 ℃ scope, specific surface area changes hardly, and was less in this temperature range internal heating Temperature Influence.

Experiment 3

As shown in Figure 4, use diffraction peak intensity had 2 θ=22.98 ° situation before adsorbing in X-ray diffractogram synthetic zeolite, and adsorb the experiment with thermal regeneration repeatedly as sorbent material.With the reagent bottle of packing into of the 1st stoste shown in sorbent material and the table 3, mix 1 hour after, take out sorbent material and at 600 ℃ of following thermal regenerations, again sorbent material and the 1st new stoste are packed in the reagent bottle, then, same repeatedly operation, and experimentize by this method.Sorbent material before Fig. 4 represents to be used to adsorb is a novel sorbents, the sorbent material when adsorbing with thermal regeneration each 20 times, and adsorb and the X-ray diffraction peak of the sorbent material 50 times time of regenerate respectively.The mensuration of X-ray diffractogram is undertaken by powder X-ray diffractometry.In Fig. 4, the peak position of 2 θ=22.98 ° represents that this sorbent material contains SiO ₂If adsorb repeatedly and regenerate, then ° to locate also the peak can occur in 2 θ=21.68, the intensity of this position is many and become big along with the change of absorption regeneration number of times.Sodium is represented to exist in this position, that is to say to have produced vitrifying.As shown in Figure 4, vitrified degree along with increasing the change of absorption regeneration number of times more.

The COD decrement of back draining and the situation that na concn changes are handled in the increase of seeing when expression is used along with sorbent material in Figure 11.In addition, the arrow among the figure is meant that numerical value uprises on its direction, and for example Na concentration uprises in the draining.The chances are 10 hours at the interval of measuring point.In fact, just regenerate, therefore between 10 hours, carried out each absorption and regeneration of 10 times owing to whenever carry out absorption in 1 hour.Known COD decrement reduces along with the increase of duration of service, and on the other hand, na concn uprises along with the increase of duration of service in the draining.Confirmed thus,, along with the increase of duration of service, in sorbent material, put aside sodium, so the absorption rate of removing of organic composition has reduced even adsorb repeatedly and regenerate.Therefore, measure contact with sorbent material before with contact draining afterwards in na concn, very effective on the life-span at the judgement sorbent material.

Embodiment 6

Below, based on Figure 12 and Fig. 1 other embodiment of the present invention is described.In the present embodiment, different with Fig. 1, as shown in figure 12, do not carry out the electrolysis of processed water, and be by blower air supply 114 from 113 times direction aerator tanks 12 of weighting agent of filling.Because others are identical with Fig. 1, therefore use identical symbol to describe.As the drain treatment apparatus 10 of one embodiment of the present invention, constitute by the equipment for magnetic separation 11, aerator tank 12, COD composition adsorption tank 17 and the exhaust combustion tower 16 that separate oil content in the oil-containing water of oil field.

Below the operation of drain treatment apparatus 10 is described.At first, oil field oil-containing water 1 is contained in the former tank 2.In oil field oil-containing water, oil content is loose by emulsification.In the oil field oil-containing water, except organic composition and sodium, also contain atomic little mud, sand and other solid matter.Therefore, oil field oil-containing water 1 is delivered to coagulating bath 3, and use agglutinant and magnet (Fe such as ferric sulfate or polymerize aluminum chloride ₃O ₄), γ-red iron (Fe ₂O ₃) etc. the magnetic particle, make the seston aggegation and the processing of flocculating.The former water that will contain flocs unit is delivered in the rotating filter device 4, and removes oil content and flocs unit.In rotating filter device 4, be equipped with and rotate through filter membrane 5 and rotational circle cylindrical shell 6, these rotational circle cylindrical shell 6 inner not diagrams, but wherein be provided with magnetic field generating unit such as electromagnet.Filter former water by rotating through filter membrane 5, and from former water, separate oil content and flocs unit 7.To be deposited in the oil content and the flocs unit that rotate through in the filter membrane 5 by being blown into washing water and 8 scrapings of use scraper plate and from rotational circle cylindrical shell 6, remove, and be expelled to rotating filter device 11 outsides.

Filtered water 90 is delivered in the aerator tank 12.In aerator tank 12, weighting agent 113 is filled in the tower, and is provided with the blower that to send into air from the weighting agent bottom.Filtered water 90 is after immersing aerator tank 12, and its volatile organic component is discharged from the vapor pipe 15 that is arranged at tower top.On vapor pipe 15 tops, the exhaust combustion tower 16 that being provided with is used to burn removes volatile organic component.According to analysis, the volatile organic component of discharging from aerator tank 12 is ketone and benzene classes such as acetone.

Among any that is difficult in the filtered water 90 that the evaporable composition delivers to 1COD adsorption tank 17 or the 2COD adsorption tank 19 by draining supply-pipe 18 as aeration treating water 180 from the bottom of aerator tank 12.This aeration treating water 180 is 2 treating water.The COD adsorption tank is made up of 1COD adsorption tank 17 and 2COD adsorption tank 19.When moving usually, use 1COD adsorption tank 17, and be set to 2COD adsorption tank 19 standby.Therefore, the structure of 1COD adsorption tank and 2COD adsorption tank is identical.Below describe based on 17 pairs of adsorption tank one-piece constructions of 1COD adsorption tank.2 COD adsorption tanks are arranged in the present embodiment, but also more a plurality of adsorption tanks can be arranged.

Filled the ZSM-5 particle in sorbent material 21, this ZSM-5 particle is a kind of synthetic zeolite.Support catalyzer in the ZSM-5 particle in advance and changed into branch.Under the situation of present embodiment, the Pt composition that supports is scaled 0.2wt% by the ZSM-5 of per unit weight.As sorbent material 21 compositions, except that ZSM-5, mordenite also has the absorption property of same degree.

When the adsorbents adsorb performance reduces, open flowing water Valve 24, extract the water in the COD adsorption tank 17 out.Then, make COD adsorption tank 17 dryings.Operation air-heater 22 is blown into the hot blast about 100-120 ℃ in COD adsorption tank 17, make sorbent material 21 dryings.And wish a kind of from top air-supply, from COD adsorption tank bottom water outlet deflated structure simultaneously.

For the water ratio of control and management sorbent material, preferably in the blast tube 28 of adsorption tank bottom, wet bulb thermometer 29 is set.

The treating water 25 of process COD adsorption tank 17 carries out draining 28 after storing in interim hopper 27.Be provided with COD watch-dog 26 before and after the hopper, it is used in particular for the management (COD≤120mg/L) of draining COD value.

Though in above-mentioned drain treatment apparatus 10, used aerator tank,, also can use underpressure distillation device or electrolyzer or hypochlorous acid reactor to replace aerator tank 12 according to the character of former water.

In addition, the leading portion at the aerator tank 12 of removing device as separation can be provided with electrolyzer.At this moment, also can blower 114 be set, make electrolyzer 14 and aerator tank 12 integrated at the downstream part of electrolyzer electrode 91,92.In addition, also can aerator tank be set, electrolyzer be set at back segment at leading portion.

According to the present invention,, therefore can in long-time, remove owing in using adsorbents adsorb oil field oil-containing water, in the COD composition, have the regenerative process that is used to keep the adsorbents adsorb performance.

Industrial applicibility

The present invention can be used for the harmless treatment of oil field oil-containing water, and described oil field oil-containing water reclaims crude oil and obtains from the mixture of the crude oil of exploitation oil field etc. and salt solution, and it is processed water and can satisfy environment and discharge benchmark.

Claims

1. moltenly in the oil field oil-containing water deposit the organic method of removing, it is characterized in that, the oil field oil-containing water that separates crude oil and obtain from crude oil and saline mixture is contacted with sorbent material, the molten organism of depositing in the oil field oil-containing water is removed in absorption, and makes adsorbent reactivation by this sorbent material desorption adsorbate.

2. moltenly in the oil field oil-containing water according to claim 1 deposit the organic method of removing, it is characterized in that, with before sorbent material contacts, oil field oil-containing water is carried out oily water separation at oil field oil-containing water.

3. moltenly in the oil field oil-containing water according to claim 1 deposit the organic method of removing, it is characterized in that, separate oil droplet in the oil-containing water of oil field by oil field oil-containing water being carried out magneticseparation.

4. moltenly in the oil field oil-containing water according to claim 1 deposit the organic method of removing, it is characterized in that, sorbent material is granular, ball shape, bar-shaped, fibrous, tabular, molding or their combination.

5. moltenly in the oil field oil-containing water according to claim 1 deposit the organic method of removing, it is characterized in that, sorbent material is remained in certain zone in the oil field oil-containing water, and remain isolating state from oil field oil-containing water easily.

6. moltenly in the oil field oil-containing water according to claim 5 deposit the organic method of removing, it is characterized in that, sorbent material is powdery, ball shape, bar-shaped or their combination, and its median size is 1-10mm.

7. moltenly in the oil field oil-containing water according to claim 6 deposit the organic method of removing, it is characterized in that sorbent material is with SiO ₂-Al ₂O ₃Or SiO ₂-Al ₂O ₃-Na ₂O is the inorganic adsorbent of principal constituent.

8. moltenly in the oil field oil-containing water according to claim 7 deposit the organic method of removing, it is characterized in that described inorganic adsorbent has supported other metallic element.

9. moltenly in the oil field oil-containing water according to claim 1 deposit the organic method of removing, it is characterized in that sorbent material is a gac.

10. moltenly in the oil field oil-containing water according to claim 1 deposit the organic method of removing, it is characterized in that, sorbent material is different at least 2 kinds of emptying aperture size.

11. moltenly in the oil field oil-containing water according to claim 10 deposit the organic method of removing, it is characterized in that sorbent material is that the emptying aperture size is about the following sorbent material peace treaty of 7 dusts 2 kinds greater than the sorbent material of 7 dusts.

12. moltenly in the oil field oil-containing water according to claim 1 deposit the organic method of removing, it is characterized in that, make sorbent material desorption, regeneration by in oxidizing atmosphere, adding heat-adsorbent.

13. moltenly in the oil field oil-containing water according to claim 1 deposit the organic method of removing, it is characterized in that, the desorption thing that adds heat-adsorbent decompose or the desorption thing that burns in organism.

14. moltenly in the oil field oil-containing water according to claim 1 deposit the organic method of removing, it is characterized in that air supply carries out desorption in adsorbent layer.

15. moltenly in the oil field oil-containing water according to claim 1 deposit the organic method of removing, it is characterized in that, sorbent material contact with oil field oil-containing water handle before, have the step of in oil field oil-containing water, adding agglutinant and removing seston.

16. moltenly in the oil field oil-containing water according to claim 1 deposit the organic method of removing, it is characterized in that, sorbent material contacts processing with oil field oil-containing water before, have oil field oil-containing water is flow through adding between the electrode of electric field, and decompose the molten step that has the machine molecule in the oil field oil-containing water.

17. moltenly in the oil field oil-containing water according to claim 1 deposit the organic method of removing, it is for removing the drainage processing method of organic composition in the described draining by the draining that contains organic composition and sodium is contacted with inorganics class sorbent material, it is characterized in that na concn judges whether to use described inorganics class sorbent material continuation draining processing based on na concn in the draining before contacting with described inorganics class sorbent material and in the draining after contact.

18. moltenly in the oil field oil-containing water according to claim 7 deposit the organic method of removing, it is characterized in that described sorbent material is the proton type zeolite.

19. moltenly in the oil field oil-containing water according to claim 17 deposit the organic method of removing, it is characterized in that, carry out to the adsorption process of described inorganics class adsorbents adsorb organic composition repeatedly and make the desorption process that is adsorbed on the organic composition desorption on the described inorganics class sorbent material, handle draining simultaneously, and in this process, measure with draining before described inorganics class sorbent material contacts in na concn with contact draining afterwards with described inorganics class sorbent material in na concn, and based on both observed value and determine whether to make draining to contact with described inorganics class sorbent material.

20. moltenly in the oil field oil-containing water deposit the organic method of removing, it is characterized in that having:

Removing swims is suspended in the oil content in the oil field oil-containing water and the oily water separation operation of non-dissolved particles;

Electrolysis is deposited organic electrowinning process by molten in the treating water of this oily water separation operation;

From 2 treating water that obtain by electrowinning process, separate the separation of removing organic composition and remove operation;

From 3 treating water removing operation by this separation, adsorb the absorption of removing organic composition and remove operation; And

To remove separation is removed in the operation organic composition and remove operation by this absorption and separate the organic composition of removing and lump together the burning operation of carrying out burning and gas-exhausting in this separation.

21. moltenly in the oil field oil-containing water according to claim 20 deposit the organic method of removing, it is characterized in that, remove in the operation in described absorption and to use inorganics class absorption remover, and under 380-600 ℃ atmospheric atmosphere, carry out desorption, regeneration and use repeatedly by absorption being removed described inorganics class absorption remover behind the organic composition.

22. moltenly in the oil field oil-containing water deposit the organic device of removing, it is characterized in that having:

From crude oil and brinish mixture, separate crude oil and generate the equipment of oil field oil-containing water;

Maintenance is deposited the equipment that organism has the sorbent material of adsorptivity to oil field oil-containing is water-soluble;

Make described oil field oil-containing water and the contacted equipment of described sorbent material; And

Make and adsorbed the described molten equipment of depositing organic adsorbent reactivation.

23. moltenly in the oil field oil-containing water according to claim 22 deposit the organic device of removing, it is characterized in that described contact arrangement is a plurality of adsorption towers of having filled sorbent material.

24. moltenly in the oil field oil-containing water according to claim 23 deposit the organic device of removing, it is characterized in that described a plurality of adsorption towers dispose with parallel connection with respect to the flow direction of oil field oil-containing water to be processed.

25. moltenly in the oil field oil-containing water according to claim 22 deposit the organic device of removing, it is characterized in that different types of sorbent material disposes with serial or parallel connection with respect to the flow direction of processed oil field oil-containing water.

26. moltenly in the oil field oil-containing water according to claim 22 deposit the organic device of removing, it is characterized in that described sorbent material has the microwave heating installation that is used to add heat-adsorbent.

27. moltenly in the oil field oil-containing water according to claim 22 deposit the organic device of removing, it is characterized in that, have to crude oil and and crude oil salt solution together carry out the equipment of magneticseparation.

28. moltenly in the oil field oil-containing water according to claim 22 deposit the organic system of removing, it is characterized in that having the test set that detects salt concn in the salt solution, and the signal that sends based on this test set and control the described operating device of removing device.

29. moltenly in the oil field oil-containing water deposit the organic system of removing, it is for removing the molten disintegrating system in waste pipe that has the machine composition contained in the draining by the draining that contains organic composition and sodium is contacted with inorganics class sorbent material, it is characterized in that having the control device that stops to supply with draining based on na concn in the draining that contacts with described inorganics class sorbent material and the draining of from described inorganics class sorbent material, discharging to described inorganics class sorbent material.

30. moltenly in the oil field oil-containing water according to claim 29 deposit the organic system of removing, it is characterized in that, have: to taking a sample with the part of the contacted draining of described inorganics class sorbent material and analyzing the analytical equipment of na concn and the analytical equipment of analyzing na concn in the draining of from described inorganics class sorbent material, discharging.

31. moltenly in the oil field oil-containing water according to claim 30 deposit the organic system of removing, it is characterized in that, described control device has the data acquisition unit that is collected in the analytical data of measuring in 2 described analytical equipments, and sends the signal of draining is supplied with in machine unit from termination to described inorganics class sorbent material based on the data that accumulate in described data acquisition unit.

32. moltenly in the oil field oil-containing water deposit the organic system of removing, it is characterized in that having:

Removing swims is suspended in the oil content in the draining and the oil-water separation tank of non-dissolved particles;

Electrolysis is by the electrolyzer of the organic composition in the draining of this oil-water separation tank;

From removing groove by separating the separation of removing organic composition 2 treating water of this electrolyzer;

To remove organic composition in 3 treating water of groove by this separation is adsorbed on the absorption of removing on the inorganics class sorbent material and removes groove; And

To remove separation is removed in the groove organic composition and remove groove by this absorption and separate the organic composition of removing and lump together the burner that carries out burning and gas-exhausting in this separation.

33. moltenly in the oil field oil-containing water according to claim 32 deposit the organic system of removing, it is characterized in that, after organic composition is removed in absorption, described inorganics class sorbent material is heated, regenerates under 380-600 ℃ atmospheric atmosphere and use repeatedly.

34. moltenly in the oil field oil-containing water according to claim 32 deposit the organic system of removing, it is characterized in that described oil-water separation tank double as magneticseparation groove and electrolyzer.

35. moltenly in the oil field oil-containing water according to claim 32 deposit the organic system of removing, it is characterized in that described inorganics class absorption remover contains silicic acid and aluminum oxide, and the existence of silicic acid and aluminum oxide ratio is SiO ₂/ Al ₂O ₃Mol ratio be more than 5, and absorption micropore have 3 the dimension structures.

36. moltenly in the oil field oil-containing water according to claim 32 deposit the organic system of removing, it is characterized in that it is to separate the separation of removing volatile organic compounds and remove groove by described 2 treating water being carried out aeration that groove is removed in described separation.