CN102399581A - Recycling method of hydrocarbon oil metal-removing agent - Google Patents
Recycling method of hydrocarbon oil metal-removing agent Download PDFInfo
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Abstract
The invention relates to a recycling method of a hydrocarbon oil metal-removing agent. According to the invention, the hydrocarbon oil metal-removing agent is sufficiently mixed with hydrocarbon oil, and the mixture is processed through a common electrostatic desalting process, such that metal-ion-removed hydrocarbon oil is obtained; a desalting solution containing the metal ions is filtered, and is subject to ion exchange with ion exchange resin filled in a double-layered bed ion exchanger, such that a recycled water solution containing the hydrocarbon oil metal-removing agent is obtained; the recycled water solution containing the hydrocarbon oil metal-removing agent is well mixed with hydrocarbon oil and is reused; the failed ion exchange resin is processed through a regeneration treatment, and is repeatedly used. In prior arts, solid-liquid separation is not sufficiently carried out, part of metal salt slag which is not easily soluble or insoluble in water enters the electrostatic desalting system along with the circulated water solution, such that normal operation of the apparatus is influenced; also, a precipitant is over-dosed, such that apparatus corrosion is caused. With the method provided by the invention, the defects are overcome. The method is advantaged in environment friendliness and high metal removing rate.
Description
Technical field
The present invention relates to a kind of method that recycles that from hydrocarbon ils, removes the metal remover of metal.
Background technology
Along with the oil field gets into the exploitation middle and later periods; The exploitation of the surplus oil that a large amount of heavy oil or first and second recover the oil is because by tertiary oil recovery technologies such as chemical adjuvants; Cause kind and content such as calcium, magnesium, iron, nickel, the vanadium etc. of metals ion in the crude oil to increase greatly, and be continuous ascendant trend.The harm that the existence of above-mentioned metals ion causes crude distillation and secondary processing, as far back as last century the eighties promptly caused insider's concern, and develop the technology that the metals ion to different existing waies removes in succession from hydrocarbon ils.The demetalization Study on Technology that wherein combines with conventional technology of electric de-salting with crude oil and fraction oil demetalization technology, because of it need not change existing technology of electric de-salting, investment is little, easy to operate, the industriallization exploitativeness is the most active by force and.
This type of hydrocarbon ils demetal process generally adopts the electric desalting treatment process, its with metal remover with (or) demetalization assistant agent, emulsion splitter and water is by a certain percentage with after hydrocarbon ils mixes, entering one-level electrical desalter, after profit fully separated, single stage desalting water effluxed; The first class purification oil of separating from the one-level electrical desalter again with composite good metal remover by a certain percentage with (or) demetalization assistant agent, emulsion splitter and water mixes or with do not contain metal remover and (or) demetalization assistant agent, emulsion splitter aqueous solution wash; Get into the secondary electrical desalter then; Under the current field condition of regulation, carry out oily water separation again; Isolated oil is secondary purification oil; And the secondary de-salted water partly returns the notes one-level, and all the other efflux, the metal remover after using simultaneously with (or) demetalization assistant agent, emulsion splitter also efflux with the electric desalting draining.Like CN86107286, CN1036981, CN1267707, CN87105863, CN1054261, CN1055552, CN107673, CN110575, CN221017, CN1221018, CN1245201, CN1693424, CN1657596, CN1431277, CN1454967, CN1982413, CN101085932, CN101067012 etc. all disclosed be above-mentioned metal remover and (or) the disposable hydrocarbon ils demetal process of demetalization assistant agent; Demetalization has effective elimination, advantage easy and simple to handle to this technology to hydrocarbon ils; But exist environmental pollution more serious; Metal remover with (or) waste of demetalization assistant agent, emulsion splitter and water resources, and defectives such as ton hydrocarbon ils tooling cost height that cause thus.CN1454969 discloses a kind of hydrocarbon ils demetalization circulation means; The problems referred to above have well been solved; But exist solid-liquid separation incomplete, be insoluble in water or the water-fast metal-salt slag that do not remove get into the electric desalting system with the aqueous solution that recycles, and influence the normal operation of electric desalting and postorder device; And have the excessive use of precipitation agent, cause defectives such as corrosion of equipment.WO98/14534 has announced a kind of resin decalcification technology; Be with resin make bed by crude oil through or resin is suspended in the crude oil; Calcium in the crude oil is shifted into resin, can crude oil and resin isolation can be obtained decalcification crude oil after the reaction; Used resin usable acid is handled back regeneration, but has that the decalcification cost is high, limited, poor for applicability to compact organic calcium decreasing ratio, resin weak point in work-ing life, be difficult to realize problem such as through engineering approaches.
Summary of the invention
The method that recycles that the purpose of this invention is to provide a kind of hydrocarbon oil metal removal agent; The desalination solution that contains metal-salt that it generates through metal remover and hydrocarbon ils effect; After carrying out IX with ion exchange resin again, make hydrocarbon oil metal removal agent obtain reprocessing cycle and use.This method environmental pollution is few, demetalization efficient is high, can the safety in production of device not impacted.
Technical scheme of the present invention realizes through following measure: with hydrocarbon oil metal removal agent and hydrocarbon ils in needed ratio thorough mixing after; Handle through conventional technology of electric de-salting; Obtain the hydrocarbon ils behind the demetalization ion; And the desalination solution that contains metal-salt carries out IX with ion exchange resin after filtering processing; Obtain containing the recycle-water solution of hydrocarbon ils metal remover, and then the recycle-water solution and the hydrocarbon ils that will contain the hydrocarbon ils metal remover recycle in needed ratio thorough mixing, the ion exchange resin after the inefficacy carries out reusing after the manipulation of regeneration.
Above-mentioned hydrocarbon oil metal removal agent contains 10～99.5% metal remover by weight percentage, 0～90% emulsion splitter, and surplus is a water; The blending ratio of this hydrocarbon oil metal removal agent and hydrocarbon ils is to account for 0.002～5% of hydrocarbon ils weight.
Above-mentioned metal remover is with a kind of in acetic anhydride, second third acid anhydride, succinic anhydride, formic acid, acetate, propionic acid, butyric acid, Phenylsulfonic acid, oxalic acid, Hydrocerol A, EDTA, organic phosphine carboxylic acid, organic phosphine sulfonic, dithiocarbamic acid or its salt or the metal remover that combines of two or more component arbitrarily, and this metal remover can phase trans-substitution; Or/and; Emulsion splitter is with emulsion splitter or other the disclosed emulsion splitter that is applicable to that the hydrocarbon ils breakdown of emulsion is used that the hydrocarbon ils breakdown of emulsion is used that be applicable to of KR-40, LH-12, LH-14, PC-6, GAR-36, SH-1, SH-4, AY-910 or the sale of other manufacturer production, and this emulsion splitter can phase trans-substitution.
When above-mentioned metal remover concentration is higher than the metal remover that sets and accounts for the needed ratio of hydrocarbon ils; Replenish the water of the recycle-water solution amount 1%～500% that contains the hydrocarbon ils metal remover, replenish the emulsion splitter of the recycle-water solution amount 0.001%～0.02% that contains the hydrocarbon ils metal remover; Perhaps, when above-mentioned metal remover concentration is lower than the metal remover that sets and accounts for the needed ratio of hydrocarbon ils, replenish the hydrocarbon oil metal removal agent of the recycle-water solution amount 0.001%～5% that contains the hydrocarbon ils metal remover.
The technology of electric de-salting treatment condition of above-mentioned routine are: 50～150 ℃ of desalination temperature, weak electric field intensity 50～500V/cm, the residence time 1～60min; Highfield intensity 500～1500V/cm; The residence time 5～200min; Utilize mixing valve or static mixer or boxshear apparatus or whisking appliance or film reactor with hydrocarbon ils with account for the water of hydrocarbon ils 2%～20% and the hydrocarbon oil metal removal agent of aequum, thorough mixing under 50～150 ℃ of mixing temperatures, 0.02MPa～1.0MPa mixing differential pressure.
Above-mentioned hydrocarbon oil metal removal agent and the thorough mixing of hydrocarbon ils are to mix through mixing valve or static mixer or boxshear apparatus or whisking appliance, and control profit mean particle dia is in 0.1 μ m～50 mu m ranges.
Above-mentioned hydrocarbon oil metal removal agent is to mix through film reactor with the thorough mixing of hydrocarbon ils, and the membrane pore size span of control is between 0.1 μ m～50 μ m, and material of preparing can be selected the polyolefine material film of metallic membrane or mineral membrane or solvent-resisting.
Above-mentioned ion exchange resin with 001 * 7,001 * 8,001 * 10,001 * 11,001 * 2,001 * 4,001 * 13, D001 and (or) other disclosed strongly acidic cationic exchange resin and 111,112 * 1,112 * 4,122, D111, D113 and (or) a kind of in the weakly acidic cation-exchange resin or the ion exchange resin that combines of two or more component arbitrarily, this ion exchange resin can phase trans-substitution.
Above-mentioned ion exchange resin is to be seated in the dual bed ion-exchanger.
The floor height ratio of weakly acidic resin is more than 30% of total bed height in the above-mentioned dual bed ion-exchanger.
The above-mentioned desalination solution that contains metal-salt is through filtration treatment, the desalination solution turbidity＜5mg/L that contains metal-salt behind the controlled filter.
The desalination solution that contains metal-salt after the above-mentioned filtration normal temperature～120 ℃ down with the dual bed ion-exchanger in ion exchange resin carry out ion exchange reaction; 5 minutes～300 minutes residence time, control calcium ion content≤500mg/L in the recycle-water solution that contains the hydrocarbon ils metal remover.The recycle-water solution and the hydrocarbon ils that contain the hydrocarbon ils metal remover recycle by needed mixed.
Behind calcium ion content＞500mg/L, the ion exchange resin that is seated in the dual bed ion-exchanger lost efficacy in the above-mentioned recycle-water solution that contains the hydrocarbon ils metal remover.
The above-mentioned regeneration of ion-exchange resin treatment process that lost efficacy in the dual bed ion-exchanger that is seated in is: counter-current regeneration.
Described counter-current regeneration method and processing condition are: using the desalination solution that contains metal-salt after filtering is under the condition of 10～15m/h at flow velocity; Ion exchange resin is carried out small reverse washing, after the turbidity of drainage water is less than 5mg/L, stop small reverse washing; Open the middle comb valve of ion-exchanger; Till the not water outlet of middle comb, send into pressurized air from dual bed ion-exchanger top then and carry out roof pressure, when the roof pressure working pressure reaches 0.2～0.6kgf/cm
2After, using concentration is that 0.5～5% sulfuric acid or 1～3% aqueous hydrochloric acid are under the condition of 4～6m/h at flow velocity, gets into from dual bed ion-exchanger bottom; Ion exchange resin is regenerated; Recovery time is 40～70min, behind the regeneration ending, closes sulfuric acid or aqueous hydrochloric acid; Continuing to use the desalination solution that contains metal-salt after filtering is under the condition of 4～6m/h at flow velocity; Get into from dual bed ion-exchanger bottom, ion exchange bed carried out replacement operator, until the difference of draining acidity and water inlet acidity less than 5 [H
+] mmol/L, the desalination solution that contains metal-salt after use filtering at last is just to advance to wash under the condition of 8～12m/h at flow velocity, until the difference of draining acidity and water inlet acidity less than 0.5 [H
+] mmol/L, can normally use.
Advantage of the present invention is: utilize ion exchange resin that the metal remover reprocessing cycle is used to remove metals in hydrocarbon oil ionic technology; Having overcome in the existing technology exists solid-liquid separation incomplete; Part is insoluble in water or water-fast metal-salt slag gets into the electric desalting system with the aqueous solution that recycles; Influence the normal operation of device, and have the excessive use of precipitation agent, cause defectives such as corrosion of equipment.Therefore, it is strong that the present invention possesses the through engineering approaches exploitativeness, environmentally friendly, the advantage that demetalization efficient is high.
Embodiment
The desalination solution that contains metal-salt adopts the JX-I type mechanical filter of the huge filtration of Yixing City Science and Technology Ltd. production to carry out filtration treatment.
The mensuration of acidity adopts the method for SS-6-1-84 in the People's Republic of China's power industry aqueous vapor TP rules to analyze in the water.
The mensuration of turbidity adopts the TP of good fortune horse hydrazine turbidity GB/T12151-1989 to analyze in the water.
The TP that the mensuration of calcium ion adopts the water quality calcium contents to survey GB7476-87 in the water is analyzed.
The mensuration of decalcifying agent concentration adopts the TP of GB1628-89 to analyze in the water.
Embodiment 1:
Hydrocarbon oil metal removal agent: 10% metal remover+90% emulsion splitter;
Atmosphere 3rd side cut fraction oil: calcium 41.3mg/L, magnesium 2.98mg/L, sodium 18.8mg/L, vanadium 13.1mg/L, sulphur 1310mg/L;
With the hydrocarbon oil metal removal agent that accounts for atmosphere 3rd side cut fraction oil 0.002%, 5% water and atmosphere 3rd side cut fraction oil in 100 ℃, with static mixer thorough mixing 2min under 0.5MPa mixing pressure reduction; Control profit mean particle dia is in 0.1 μ m～50 mu m ranges; Place electrical desalter; Be respectively under the 1500/100v/cm condition at 100 ℃ of desalination temperature, strong and weak electric field and act on 20/10min; After the oily water separation, calcium contents/the decalcification rate is 2.0mg/L/95.2% to analyze self-cleaning oil, and Mg content/demagnesium rate is that 0.189mg/L/93.7%, sodium content 0.7mg/L/96.3%, content of vanadium/vanadium removal rate are that 0.41mg/L/96.9%, sulphur content are 1300mg/L.Adopting GB7476-87 TP (the water quality calcium contents is measured the EDTA volumetry) to record calcium contents the isolated desalination solution that contains metal-salt is 0.36%; The desalination solution that contains metal-salt is through after the filtration treatment; Through detecting turbidity is 2.8mg/L; Under normal temperature condition, from the dual bed ion-exchanger that ion exchange resin is housed, flow through from top to bottom, flow out after 5 minutes, be the recycle-water solution that contains the hydrocarbon ils metal remover; Through detecting metal remover concentration is 1.4%, and calcium ion content is 0mg/L.Method as described above; The satisfactory recycle-water solution that contains the hydrocarbon ils metal remover with accounting for atmosphere 3rd side cut fraction weight of oil 1.5% mixes with atmosphere 3rd side cut fraction oil; The mensuration of metal content in its hybrid mode, electric desalting parameter, the self-cleaning oil; Contain desalination solution and the ion exchange resin of metal-salt exchanged form, contain calcium ion content and turbidity measurement in the desalination solution of metal-salt, the mensuration that contains metal remover concentration and calcium ion content in the recycle-water solution of hydrocarbon ils metal remover etc. all adopts the aforesaid method condition; Recycle the 2nd time～the 60th time, in the recycle-water solution that contains the hydrocarbon ils metal remover calcium ion content greater than 500mg/L till.Following table is the effect that recycles of the recycle-water solution that contains the hydrocarbon ils metal remover that reclaims.
Visible by last table, after replenishing hydrocarbon oil metal removal agent or moisturizing, emulsion splitter, the hydrocarbon oil metal removal agent aqueous solution does not influence atmosphere 3rd side cut fraction oil metal removal effect.
Metal remover in the last table can be with a kind of in acetic anhydride, second third acid anhydride, succinic anhydride, formic acid, acetate, propionic acid, butyric acid, Phenylsulfonic acid, oxalic acid, Hydrocerol A, EDTA, organic phosphine carboxylic acid, organic phosphine sulfonic, dithiocarbamic acid or its salt or the metal remover that combines of two or more component arbitrarily, but this metal remover phase trans-substitution; Emulsion splitter can openly be applicable to the emulsion splitter that the hydrocarbon ils breakdown of emulsion is used with being applicable to of selling of KR-40, LH-12, LH-14, PC-6, GAR-36, SH-1, SH-4, AY-910 or other manufacturer production of the gram petro-chemical corporation production and sales emulsion splitter that the hydrocarbon ils breakdown of emulsion is used or other, but this emulsion splitter phase trans-substitution.
The weak-acid ion exchange resin floor height accounts for 35% of bed total height in the above-mentioned dual bed ion-exchanger.
Above-mentioned ion exchange resin with 001 * 7,001 * 8,001 * 10,001 * 11,001 * 2,001 * 4,001 * 13, D001 and (or) other disclosed strongly acidic cationic exchange resin and 111,112 * 1,112 * 4,122, D111, D113 and (or) a kind of in other disclosed weakly acidic cation-exchange resin ion exchange resin or the ion exchange resin that combines of two or more component arbitrarily, this ion exchange resin can phase trans-substitution.
Calcium ion content is 600mg/L in the recycle-water solution that contains the hydrocarbon ils metal remover after in the last table the 60th time recycles, shows that the ion exchange resin that is filled in the dual bed ion-exchanger lost efficacy.
Adopt following method that the ion exchange resin after losing efficacy is regenerated.Use the desalination solution that contains metal-salt after filtering under the condition of flow velocity as 10m/h, comb gets in the middle of the ion-exchanger, and comb flows out from ion-exchanger top; Ion exchange resin is carried out small reverse washing, after the turbidity of drainage water is less than 5mg/L, stop into water; Open the middle comb valve of ion-exchanger then, till the not water outlet of middle comb, small reverse washing finishes; Send into pressurized air from dual bed ion-exchanger top then, when the roof pressure working pressure reaches 0.2kgf/cm
2After, use concentration be 0.5% aqueous sulfuric acid under the condition of flow velocity as 4m/h, get into from dual bed ion-exchanger bottom; Ion exchange resin is regenerated, and the recovery time is 70min, behind the regeneration ending; Close aqueous sulfuric acid, continue to use the desalination solution that contains metal-salt after filtering under the condition of flow velocity, from the entering of dual bed ion-exchanger bottom as 4m/h; Ion exchange bed is carried out replacement operator, until draining acidity with the water inlet acidity difference less than 5 [H
+] mmol/L, use the desalination solution that contains metal-salt after filtering under the condition of flow velocity, just to advance to wash at last as 8m/h, until the difference of draining acidity and water inlet acidity less than 0.5 [H
+] mmol/L, the ion exchange resin regeneration success.
Embodiment 2:
Hydrocarbon oil metal removal agent: 50% metal remover+50% emulsion splitter;
Crude oil: calcium 265mg/L, magnesium 1.54mg/L, sodium 5.8mg/L, vanadium 2.6mg/L, iron 7.6mg/L;
With the hydrocarbon oil metal removal agent that accounts for crude oil 0.8%, 10% water and crude oil under 60 ℃, 0.1MPa with whisking appliance thorough mixing 30min; Place electrical desalter; Be respectively 1000/500v/cm effect 60/20min at 50 ℃ of desalination temperature, strong and weak electric field; After the oily water separation; Analyze that calcium contents/decalcification rate is 27.8mg/L/89.5% in the self-cleaning oil, Mg content/demagnesium rate is that 0.412mg/L/73.2%, sodium content 3.3mg/L/43.1%, content of vanadium/vanadium removal rate are that 0.342mg/L/86.8%, iron level are 5.60mg/L/26.3%.Adopt GB7476-87 TP (the water quality calcium contents is measured the EDTA volumetry) to record that calcium contents is 0.35% in the water the isolated desalination solution that contains metal-salt; The desalination solution that contains metal-salt is through after the filtration treatment; Through detecting turbidity is 3.9mg/L; Under 120 ℃ of conditions, from be filled with the good ion exchange resin dual bed ion-exchanger of embodiment 1 regeneration, flow through from top to bottom, flow out after 300 minutes, be the recycle-water solution that contains the hydrocarbon ils metal remover; Through detecting metal remover concentration is 2.1%, and calcium ion content is 0mg/L.
Method as described above; The satisfactory recycle-water solution 90% (accounting for former weight of oil) that contains the hydrocarbon ils metal remover is mixed with crude oil; The mensuration of metal content in its hybrid mode, electric desalting parameter, the self-cleaning oil; Contain the exchanged form of calcium ion content and turbidity measurement in the desalination solution of metal-salt, the desalination solution that contains metal-salt and ion exchange resin, the mensuration that contains metal remover concentration and calcium ion content in the recycle-water solution of hydrocarbon ils metal remover etc. and all adopt the aforesaid method condition; Recycle the 2nd time～the 40th time, following table is the effect that recycles of the recycle-water solution that contains the hydrocarbon ils metal remover that reclaims.
Visible by last table, after replenishing hydrocarbon oil metal removal agent or moisturizing, emulsion splitter, hydrocarbon oil metal removal agent does not influence the crude oil metal removal effect in 40 processes of circulation.
Metal remover in the last table can be with a kind of in acetic anhydride, second third acid anhydride, succinic anhydride, formic acid, acetate, propionic acid, butyric acid, Phenylsulfonic acid, oxalic acid, Hydrocerol A, EDTA, organic phosphine carboxylic acid, organic phosphine sulfonic, dithiocarbamic acid or its salt or the metal remover that combines of two or more component arbitrarily, but this metal remover phase trans-substitution; Emulsion splitter can openly be applicable to the emulsion splitter that the hydrocarbon ils breakdown of emulsion is used with being applicable to of selling of KR-40, LH-12, LH-14, PC-6, GAR-36, SH-1, SH-4, AY-910 or other manufacturer production of the gram petro-chemical corporation production and sales emulsion splitter that the hydrocarbon ils breakdown of emulsion is used or other, but this emulsion splitter phase trans-substitution.
The weak-acid ion exchange resin floor height accounts for 50% of bed total height in the above-mentioned dual bed ion-exchanger.
Above-mentioned ion exchange resin with 001 * 7,001 * 8,001 * 10,001 * 11,001 * 2,001 * 4,001 * 13, D001 and (or) other disclosed strongly acidic cationic exchange resin and 111,112 * 1,112 * 4,122, D111, D113 and (or) a kind of in other disclosed weakly acidic cation-exchange resin ion exchange resin or the ion exchange resin that combines of two or more component arbitrarily, this ion exchange resin can phase trans-substitution.
Calcium ion content is 550mg/L in the recycle-water solution that contains the hydrocarbon ils metal remover after in the last table the 40th time recycles, shows that the ion exchange resin that is filled in the dual bed ion-exchanger lost efficacy.
Adopt following method that the ion exchange resin after losing efficacy is regenerated.Use the desalination solution that contains metal-salt after filtering under the condition of flow velocity as 15m/h, comb gets in the middle of the ion-exchanger, and comb flows out from ion-exchanger top; Ion exchange resin is carried out small reverse washing, after the turbidity of drainage water is less than 5mg/L, stop into water; Open the middle comb valve of ion-exchanger then, till the not water outlet of middle comb, small reverse washing finishes; Send into pressurized air from dual bed ion-exchanger top then, when the roof pressure working pressure reaches 0.6kgf/cm
2After, use concentration be 5% aqueous sulfuric acid under the condition of flow velocity as 6m/h, get into from dual bed ion-exchanger bottom; Ion exchange resin is regenerated, and the recovery time is 40min, behind the regeneration ending; Close aqueous sulfuric acid, continue to use the desalination solution that contains metal-salt after filtering under the condition of flow velocity, from the entering of dual bed ion-exchanger bottom as 6m/h; Ion exchange bed is carried out replacement operator, until draining acidity with the water inlet acidity difference less than 5 [H
+] mmol/L, use the desalination solution that contains metal-salt after filtering under the condition of flow velocity, just to advance to wash at last as 12m/h, until the difference of draining acidity and water inlet acidity less than 0.5 [H
+] mmol/L, the ion exchange resin regeneration success.
Embodiment 3:
Hydrocarbon oil metal removal agent: 99.5% metal remover+0% emulsion splitter+0.5% water
Crude oil: calcium 680mg/L, magnesium 5.02mg/L, iron 20.6mg/L, sodium 45mg/L, vanadium 3.10mg/L
Is that 50 ℃, pressure are to be trimmed to the profit mean particle dia in 0.1 μ m～50 mu m ranges with boxshear apparatus under the condition of 0.5Mpa with the hydrocarbon oil metal removal agent that accounts for crude oil 2%, 20% water and crude oil in temperature; Place electrical desalter; Be respectively 500/50v/cm effect 200/60min at 150 ℃ of desalination temperature, strong and weak electric field; After the oily water separation; Analyze that calcium contents/decalcification rate is 45.0mg/L/93.4% in the self-cleaning oil, Mg content/demagnesium rate is that 0.61mg/L/87.8%, sodium content 2.3mg/L/94.9%, content of vanadium/vanadium removal rate are that 0.25mg/L/91.9%, iron level are 5.1mg/L/75.2%.Adopt GB7476-87 TP (the water quality calcium contents is measured the EDTA volumetry) to record that calcium ion content is 4.2% in the water the isolated desalination solution that contains metal-salt; The desalination solution that contains metal-salt is through after the filtration treatment; Through detecting turbidity is 3.3mg/L; Under 80 ℃ of conditions, from be filled with the good ion exchange resin dual bed ion-exchanger of embodiment 2 regeneration, flow through from top to bottom, flow out after 100 minutes, be the recycle-water solution that contains the hydrocarbon ils metal remover; Through detecting metal remover concentration is 3.8%, and calcium ion content is 0mg/L.
Method as described above; The satisfactory recycle-water solution that contains the hydrocarbon ils metal remover that accounts for former weight of oil 55% is mixed with crude oil; The mensuration of its hybrid mode, electric desalting parameter, self-cleaning oil metal content; Contain the exchanged form of calcium ion content and turbidity measurement in the desalination solution of metal-salt, the desalination solution that contains metal-salt and ion exchange resin, the mensuration that contains metal remover concentration and calcium ion content in the recycle-water solution of hydrocarbon ils metal remover etc. and all adopt the aforesaid method condition; Recycle the 2nd time～the 30th time, following table is the effect that recycles of the recycle-water solution that contains the hydrocarbon ils metal remover that reclaims.
Visible by last table, after replenishing hydrocarbon oil metal removal agent or moisturizing, emulsion splitter, the hydrocarbon oil metal removal agent aqueous solution does not influence high metal content crude oil metal removal effect in 30 processes of circulation.
Metal remover in the last table can be with a kind of in acetic anhydride, second third acid anhydride, succinic anhydride, formic acid, acetate, propionic acid, butyric acid, Phenylsulfonic acid, oxalic acid, Hydrocerol A, EDTA, organic phosphine carboxylic acid, organic phosphine sulfonic, dithiocarbamic acid or its salt or the metal remover that combines of two or more component arbitrarily, but this metal remover phase trans-substitution; Emulsion splitter can openly be applicable to the emulsion splitter that the hydrocarbon ils breakdown of emulsion is used with being applicable to of selling of KR-40, LH-12, LH-14, PC-6, GAR-36, SH-1, SH-4, AY-910 or other manufacturer production that gram petro-chemical corporation the produces emulsion splitter that the hydrocarbon ils breakdown of emulsion is used or other, but this emulsion splitter phase trans-substitution.
The weak-acid ion exchange resin floor height accounts for 80% of bed total height in the above-mentioned dual bed ion-exchanger.
Above-mentioned ion exchange resin with 001 * 7,001 * 8,001 * 10,001 * 11,001 * 2,001 * 4,001 * 13, D001 and (or) other disclosed strongly acidic cationic exchange resin and 111,112 * 1,112 * 4,122, D111, D113 and (or) a kind of in other disclosed weakly acidic cation-exchange resin ion exchange resin or the ion exchange resin that combines of two or more component arbitrarily, this ion exchange resin can phase trans-substitution.
Calcium ion content is 596mg/L in the recycle-water solution that contains the hydrocarbon ils metal remover after in the last table the 30th time recycles, shows that the ion exchange resin that is filled in the dual bed ion-exchanger lost efficacy.
Adopt following method that the ion exchange resin after losing efficacy is regenerated.Use the desalination solution that contains metal-salt after filtering under the condition of flow velocity as 12m/h, comb gets in the middle of the ion-exchanger, and comb flows out from ion-exchanger top; Ion exchange resin is carried out small reverse washing, after the turbidity of drainage water is less than 5mg/L, stop into water; Open the middle comb valve of ion-exchanger then, till the not water outlet of middle comb, small reverse washing finishes; Send into pressurized air from dual bed ion-exchanger top then, when the roof pressure working pressure reaches 0.4kgf/cm
2After, use concentration be 3% aqueous sulfuric acid under the condition of flow velocity as 5m/h, get into from dual bed ion-exchanger bottom; Ion exchange resin is regenerated, and the recovery time is 50min, behind the regeneration ending; Close aqueous sulfuric acid, continue to use the desalination solution that contains metal-salt after filtering under the condition of flow velocity, from the entering of dual bed ion-exchanger bottom as 5m/h; Ion exchange bed is carried out replacement operator, until draining acidity with the water inlet acidity difference less than 5 [H
+] mmol/L, use the desalination solution that contains metal-salt after filtering under the condition of flow velocity, just to advance to wash at last as 10m/h, until the difference of draining acidity and water inlet acidity less than 0.5 [H
+] mmol/L, the ion exchange resin regeneration success.
Embodiment 4:
Hydrocarbon oil metal removal agent: 75% metal remover+25% emulsion splitter;
Crude oil: calcium 980mg/L, magnesium 6.32mg/L, iron 45.3mg/L, sodium 120mg/L, vanadium 7.44mg/L;
Under 125 ℃, 0.3MPa, adopt membrane pore size between 0.1 μ m～50 μ m the hydrocarbon oil metal removal agent that accounts for crude oil 5%, 15% water and crude oil; Metallic membrane is that the film reactor of material of preparing mixes; Place electrical desalter; Be respectively 1200/400v/cm effect 5/1min at 125 ℃ of desalination temperature, strong and weak electric field; After the oily water separation, analyze that calcium contents/decalcification rate is 47.8mg/L/95.1% in the self-cleaning oil, Mg content/demagnesium rate is that 0.98mg/L/84.5%, sodium content 2.3mg/L/98.1%, content of vanadium/vanadium removal rate are that 1.51mg/L/79.7%, iron level are 9.1mg/L/79.9%.Adopting GB7476-87 TP (the water quality calcium contents is measured the EDTA volumetry) to record calcium ion content the isolated desalination solution that contains metal-salt is 5.8%; The desalination solution that contains metal-salt is after filtering processing; Through detecting turbidity is 1.6mg/L; Under 60 ℃ of conditions, from be filled with the good ion exchange resin dual bed ion-exchanger of embodiment 3 regeneration, flow through from top to bottom, flow out after 50 minutes, be the recycle-water solution that contains the hydrocarbon ils metal remover; Through detecting metal remover concentration is 6.86%, and calcium ion content is 0mg/L.
Method as described above; The satisfactory recycle-water solution that contains the hydrocarbon ils metal remover that accounts for former weight of oil 55% is mixed with crude oil; The mensuration of its hybrid mode, electric desalting parameter, self-cleaning oil metal content; Contain the exchanged form of calcium ion content and turbidity measurement in the desalination solution of metal-salt, the desalination solution that contains metal-salt and ion exchange resin, the mensuration that contains metal remover concentration and calcium ion content in the recycle-water solution of hydrocarbon ils metal remover etc. and all adopt the aforesaid method condition; Recycle the 2nd time～the 20th time, following table is the effect that recycles of the recycle-water solution that contains the hydrocarbon ils metal remover that reclaims.
Visible by last table, after replenishing hydrocarbon oil metal removal agent or moisturizing, emulsion splitter, the hydrocarbon oil metal removal agent aqueous solution does not influence high metal content crude oil metal removal effect in working cycle.
Metal remover in the last table can be with a kind of in acetic anhydride, second third acid anhydride, succinic anhydride, formic acid, acetate, propionic acid, butyric acid, Phenylsulfonic acid, oxalic acid, Hydrocerol A, EDTA, organic phosphine carboxylic acid, organic phosphine sulfonic, dithiocarbamic acid or its salt or the metal remover that combines of two or more component arbitrarily, but this metal remover phase trans-substitution; Emulsion splitter can openly be applicable to the emulsion splitter that the hydrocarbon ils breakdown of emulsion is used with being applicable to of selling of KR-40, LH-12, LH-14, PC-6, GAR-36, SH-1, SH-4, AY-910 or other manufacturer production of the gram petro-chemical corporation production and sales emulsion splitter that the hydrocarbon ils breakdown of emulsion is used or other, but this emulsion splitter phase trans-substitution.
The weak-acid ion exchange resin floor height accounts for 70% of bed total height in the above-mentioned dual bed ion-exchanger.
Above-mentioned ion exchange resin with 001 * 7,001 * 8,001 * 10,001 * 11,001 * 2,001 * 4,001 * 13, D001 and (or) other disclosed strongly acidic cationic exchange resin and 111,112 * 1,112 * 4,122, D111, D113 and (or) a kind of in other disclosed weakly acidic cation-exchange resin ion exchange resin or the ion exchange resin that combines of two or more component arbitrarily, this ion exchange resin can phase trans-substitution.
Calcium ion content is 528mg/L in the recycle-water solution that contains the hydrocarbon ils metal remover after in the last table the 24th time recycles, shows that the ion exchange resin that is filled in the dual bed ion-exchanger lost efficacy.
Adopt following method that the ion exchange resin after losing efficacy is regenerated.Use the desalination solution that contains metal-salt after filtering under the condition of flow velocity as 11m/h, comb gets in the middle of the ion-exchanger, and comb flows out from ion-exchanger top; Ion exchange resin is carried out small reverse washing, after the turbidity of drainage water is less than 5mg/L, stop into water; Open the middle comb valve of ion-exchanger then, till the not water outlet of middle comb, small reverse washing finishes; Send into pressurized air from dual bed ion-exchanger top then, when the roof pressure working pressure reaches 0.4kgf/cm
2After, using concentration is that 1% aqueous hydrochloric acid is under the condition of flow velocity as 4.5m/h, from the entering of dual bed ion-exchanger bottom; Ion exchange resin is regenerated, and the recovery time is 60min, behind the regeneration ending; Close aqueous hydrochloric acid, continue to use the desalination solution that contains metal-salt after filtering under the condition of flow velocity, from the entering of dual bed ion-exchanger bottom as 4.5m/h; Ion exchange bed is carried out replacement operator, until draining acidity with the water inlet acidity difference less than 5 [H
+] mmol/L, use the desalination solution that contains metal-salt after filtering under the condition of flow velocity, just to advance to wash at last as 9m/h, until the difference of draining acidity and water inlet acidity less than 0.5 [H
+] mmol/L, the ion exchange resin regeneration success.
Embodiment 5:
Hydrocarbon oil metal removal agent: 80% metal remover+10% emulsion splitter+10% water;
Diesel oil: calcium contents 27.3mg/L, magnesium 0.38mg/L, sodium 6.8mg/L, vanadium 0.6mg/L;
With the hydrocarbon oil metal removal agent that accounts for diesel oil 0.002%, 2% water and diesel oil under 50 ℃, the condition of 0.02Mpa with whisking appliance thorough mixing 15min; Place electrical desalter; Be respectively 800/80v/cm effect 40/5min at 50 ℃ of desalination temperature, strong and weak electric field; After profit fully separates, analyze that calcium contents/decalcification rate is 1.5mg/L/94.5% in the self-cleaning oil, Mg content less than 0.2mg/L, sodium content less than 0.5mg/L, content of vanadium less than 0.2mg/L.Adopting GB7476-87 TP (the water quality calcium contents is measured the EDTA volumetry) to record calcium ion content the isolated desalination solution that contains metal-salt is 0.02%; The desalination solution that contains metal-salt is through after the filtration treatment; Through detecting turbidity is 3.6mg/L; Under 50 ℃ of conditions, from be filled with the good ion exchange resin dual bed ion-exchanger of embodiment 4 regeneration, flow through from top to bottom, flow out after 10 minutes, be the recycle-water solution that contains the hydrocarbon ils metal remover; Through detecting metal remover concentration is 0.4%, and calcium ion content is 0mg/L.
Method as described above; The 0.2% satisfactory hydrocarbon ils metal remover that contains that accounts for diesel oil weight is mixed with diesel oil; The mensuration of its hybrid mode, electric desalting parameter, self-cleaning oil metal content; Contain the exchanged form of calcium ion content and turbidity measurement in the desalination solution of metal-salt, the desalination solution that contains metal-salt and ion exchange resin, the mensuration that contains metal remover concentration and calcium ion content in the recycle-water solution of hydrocarbon ils metal remover etc. and all adopt the aforesaid method condition; Recycle the 2nd time to the 60th time, following table is the effect that recycles of the recycle-water solution that contains the hydrocarbon ils metal remover that reclaims.
Visible by last table, after replenishing hydrocarbon oil metal removal agent or moisturizing, emulsion splitter, the hydrocarbon oil metal removal agent aqueous solution does not influence the diesel oil metal removal effect in 60 processes of circulation.
Metal remover in the last table can be with a kind of in acetic anhydride, second third acid anhydride, succinic anhydride, formic acid, acetate, propionic acid, butyric acid, Phenylsulfonic acid, oxalic acid, Hydrocerol A, EDTA, organic phosphine carboxylic acid, organic phosphine sulfonic, dithiocarbamic acid or its salt or the metal remover that combines of two or more component arbitrarily, but this metal remover phase trans-substitution; Emulsion splitter can openly be applicable to the emulsion splitter that the hydrocarbon ils breakdown of emulsion is used with being applicable to of selling of KR-40, LH-12, LH-14, PC-6, GAR-36, SH-1, SH-4, AY-910 or other manufacturer production of the gram petro-chemical corporation production and sales emulsion splitter that the hydrocarbon ils breakdown of emulsion is used or other, but this emulsion splitter phase trans-substitution.
The weak-acid ion exchange resin floor height accounts for 60% of bed total height in the above-mentioned dual bed ion-exchanger.
Above-mentioned ion exchange resin with 001 * 7,001 * 8,001 * 10,001 * 11,001 * 2,001 * 4,001 * 13, D001 and (or) other disclosed strongly acidic cationic exchange resin and 111,112 * 1,112 * 4,122, D111, D113 and (or) a kind of in other disclosed weakly acidic cation-exchange resin ion exchange resin or the ion exchange resin that combines of two or more component arbitrarily, this ion exchange resin can phase trans-substitution.
Calcium ion content is 578mg/L in the recycle-water solution that contains the hydrocarbon ils metal remover after in the last table the 70th time recycles, shows that the ion exchange resin that is filled in the dual bed ion-exchanger lost efficacy.
Adopt following method that the ion exchange resin after losing efficacy is regenerated.Use the desalination solution that contains metal-salt after filtering under the condition of flow velocity as 13m/h, comb gets in the middle of the ion-exchanger, and comb flows out from ion-exchanger top; Ion exchange resin is carried out small reverse washing, after the turbidity of drainage water is less than 5mg/L, stop into water; Open the middle comb valve of ion-exchanger then, till the not water outlet of middle comb, small reverse washing finishes; Send into pressurized air from dual bed ion-exchanger top then, when the roof pressure working pressure reaches 0.5kgf/cm
2After, using concentration is that 3% aqueous hydrochloric acid is under the condition of flow velocity as 6m/h, from the entering of dual bed ion-exchanger bottom; Ion exchange resin is regenerated, and the recovery time is 50min, behind the regeneration ending; Close aqueous hydrochloric acid, continue to use the desalination solution that contains metal-salt after filtering under the condition of flow velocity, from the entering of dual bed ion-exchanger bottom as 6m/h; Ion exchange bed is carried out replacement operator, until draining acidity with the water inlet acidity difference less than 5 [H
+] mmol/L, use the desalination solution that contains metal-salt after filtering under the condition of flow velocity, just to advance to wash at last as 11m/h, until the difference of draining acidity and water inlet acidity less than 0.5 [H
+] mmol/L, the ion exchange resin regeneration success.
Embodiment 6:
Hydrocarbon oil metal removal agent: 90% metal remover+5% emulsion splitter+5% water;
Crude oil: calcium 260mg/L, magnesium 1.64mg/L, sodium 4.8mg/L, vanadium 1.6mg/L, iron 8.6mg/L;
Adopt static mixer under 130 ℃, 0.08MPa pressure reduction, to mix 10min the hydrocarbon oil metal removal agent that accounts for former weight of oil 2%, 12% water and crude oil; Control profit mean particle dia is at 0.1～50um; Place electrical desalter; Be respectively 900/300v/cm effect 100/40min at 90 ℃ of desalination temperature, strong and weak electric field; After the oily water separation, analyze that calcium contents/decalcification rate is 29.9mg/L/88.5% in the self-cleaning oil, Mg content/demagnesium rate is that 0.36mg/L/78.1%, sodium content 1.7mg/L/64.6%, content of vanadium/vanadium removal rate are that 0.42mg/L/73.8%, iron level are 3.5mg/L/59.3%.Adopting GB7476-87 TP (the water quality calcium contents is measured the EDTA volumetry) to record calcium contents the isolated desalination solution that contains metal-salt is 0.39%; The desalination solution that contains metal-salt is through after the filtration treatment; Through detecting turbidity is 2.7mg/L; Under 100 ℃ of conditions, from be filled with the good ion exchange resin dual bed ion-exchanger of embodiment 5 regeneration, flow through from top to bottom, flow out after 70 minutes, be the recycle-water solution that contains the hydrocarbon ils metal remover; Through detecting metal remover concentration is 1.9%, and calcium ion content is 0mg/L.
Following table be contain the hydrocarbon ils metal remover recycle-water solution recycle effect.
Visible by table, after replenishing hydrocarbon oil metal removal agent or moisturizing, emulsion splitter, the hydrocarbon oil metal removal agent aqueous solution does not influence the crude oil metal removal effect in working cycle.
Metal remover in the last table can be with a kind of in acetic anhydride, second third acid anhydride, succinic anhydride, formic acid, acetate, propionic acid, butyric acid, Phenylsulfonic acid, oxalic acid, Hydrocerol A, EDTA, organic phosphine carboxylic acid, organic phosphine sulfonic, dithiocarbamic acid or its salt or the metal remover that combines of two or more component arbitrarily, but this metal remover phase trans-substitution; Emulsion splitter can openly be applicable to the emulsion splitter that the hydrocarbon ils breakdown of emulsion is used with being applicable to of selling of KR-40, LH-12, LH-14, PC-6, GAR-36, SH-1, SH-4, AY-910 or other manufacturer production of the gram petro-chemical corporation production and sales emulsion splitter that the hydrocarbon ils breakdown of emulsion is used or other, but this emulsion splitter phase trans-substitution.
The weak-acid ion exchange resin floor height accounts for 65% of bed total height in the above-mentioned dual bed ion-exchanger.
Above-mentioned ion exchange resin with 001 * 7,001 * 8,001 * 10,001 * 11,001 * 2,001 * 4,001 * 13, D001 and (or) other disclosed strongly acidic cationic exchange resin and 111,112 * 1,112 * 4,122, D111, D113 and (or) a kind of in other disclosed weakly acidic cation-exchange resin ion exchange resin or the ion exchange resin that combines of two or more component arbitrarily, this ion exchange resin can phase trans-substitution.
Calcium ion content is 530mg/L in the recycle-water solution that contains the hydrocarbon ils metal remover after in the last table the 45th time recycles, shows that the ion exchange resin that is filled in the dual bed ion-exchanger lost efficacy.
Adopt following method that the ion exchange resin after losing efficacy is regenerated.Use the desalination solution that contains metal-salt after filtering under the condition of flow velocity as 13m/h, comb gets in the middle of the ion-exchanger, and comb flows out from ion-exchanger top; Ion exchange resin is carried out small reverse washing, after the turbidity of drainage water is less than 5mg/L, stop into water; Open the middle comb valve of ion-exchanger then, till the not water outlet of middle comb, small reverse washing finishes; Send into pressurized air from dual bed ion-exchanger top then, when the roof pressure working pressure reaches 0.3kgf/cm
2After, using concentration is that 2% aqueous hydrochloric acid is under the condition of flow velocity as 4m/h, from the entering of dual bed ion-exchanger bottom; Ion exchange resin is regenerated, and the recovery time is 70min, behind the regeneration ending; Close aqueous hydrochloric acid, continue to use the desalination solution that contains metal-salt after filtering under the condition of flow velocity, from the entering of dual bed ion-exchanger bottom as 4m/h; Ion exchange bed is carried out replacement operator, until draining acidity with the water inlet acidity difference less than 5 [H
+] mmol/L, use the desalination solution that contains metal-salt after filtering under the condition of flow velocity, just to advance to wash at last as 12m/h, until the difference of draining acidity and water inlet acidity less than 0.5 [H
+] mmol/L, the ion exchange resin regeneration success.
Claims (8)
1. the method that recycles of a hydrocarbon oil metal removal agent; It is characterized in that: undertaken: behind hydrocarbon oil metal removal agent and hydrocarbon ils thorough mixing by following step; Handle through conventional technology of electric de-salting; Obtain the hydrocarbon ils behind the demetalization ion, and the desalination solution that contains metal-salt carries out IX through filtering the ion exchange resin of handling the back and being seated in the dual bed ion-exchanger, obtains containing the recycle-water solution of hydrocarbon ils metal remover; And then the recycle-water solution and the hydrocarbon ils thorough mixing that will contain the hydrocarbon ils metal remover recycle, and the ion exchange resin after the inefficacy carries out reusing after the manipulation of regeneration;
For the desalination solution that contains metal-salt is after elder generation becomes turbidity＜5mg/L with its filtration treatment; Normal temperature～120 ℃ down with the dual bed ion-exchanger in ion exchange resin carry out ion exchange reaction; 5 minutes～300 minutes residence time; Calcium ion content≤500mg/L in the recycle-water solution that contains the hydrocarbon ils metal remover of discharging after the process ion exchange resin treatment; The recycle-water solution and the hydrocarbon ils mixed cycle that contain the hydrocarbon ils metal remover are used; During calcium ion content in through the recycle-water solution that contains the hydrocarbon ils metal remover of discharging after the ion exchange resin treatment＞500mg/L, the ion exchange resin that is seated in the dual bed ion-exchanger lost efficacy, and needed carry out manipulation of regeneration to the ion exchange resin after losing efficacy.
2. the method that recycles of a kind of hydrocarbon oil metal removal agent according to claim 1, the regeneration of ion-exchange resin treatment process that it is characterized in that being seated in the inefficacy in the dual bed ion-exchanger is: counter-current regeneration.
3. the method that recycles of a kind of hydrocarbon oil metal removal agent according to claim 2; It is characterized in that described counter-current regeneration method and processing condition are: using the desalination solution that contains metal-salt after filtering is under the condition of 10～15m/h at flow velocity; Ion exchange resin is carried out small reverse washing, after the turbidity of drainage water is less than 5mg/L, stop small reverse washing; Open the middle comb valve of ion-exchanger; Till the not water outlet of middle comb, send into pressurized air from dual bed ion-exchanger top then and carry out roof pressure, when the roof pressure working pressure reaches 0.2～0.6kgf/cm
2After, using concentration is that 0.5～5% sulfuric acid or 1～3% aqueous hydrochloric acid are under the condition of 4～6m/h at flow velocity, gets into from dual bed ion-exchanger bottom; Ion exchange resin is regenerated; Recovery time is 40～70min, behind the regeneration ending, closes sulfuric acid or aqueous hydrochloric acid; Continuing to use the desalination solution that contains metal-salt after filtering is under the condition of 4～6m/h at flow velocity; Get into from dual bed ion-exchanger bottom, ion exchange bed carried out replacement operator, until the difference of draining acidity and water inlet acidity less than 5 [H
+] mmol/L, the desalination solution that contains metal-salt after use filtering at last is just to advance to wash under the condition of 8～12m/h at flow velocity, until the difference of draining acidity and water inlet acidity less than 0.5 [H
+] mmol/L, can normally use.
4. according to the method that recycles of claim 1 or 3 described a kind of hydrocarbon oil metal removal agents; It is characterized in that ion exchange resin with 001 * 7,001 * 8,001 * 10,001 * 11,001 * 2,001 * 4,001 * 13, D001, other disclosed strongly acidic cationic exchange resin, 111,112 * 1,112 * 4,122, D111, D113, other disclosed weakly acidic cation-exchange resin a kind of or the ion exchange resin that combines of two or more component arbitrarily, this ion exchange resin can phase trans-substitution.
5. the method that recycles of a kind of hydrocarbon oil metal removal agent according to claim 1 is characterized in that described hydrocarbon oil metal removal agent contains 10～99.5% metal remover by weight percentage, 0～90% emulsion splitter, and surplus is a water; The blending ratio of this hydrocarbon oil metal removal agent and hydrocarbon ils is to account for 0.002%～5% of hydrocarbon ils weight.
6. the method that recycles of a kind of hydrocarbon oil metal removal agent according to claim 1 is characterized in that described metal remover is with a kind of in acetic anhydride, second third acid anhydride, succinic anhydride, formic acid, acetate, propionic acid, butyric acid, Phenylsulfonic acid, oxalic acid, Hydrocerol A, EDTA, organic phosphine carboxylic acid, organic phosphine sulfonic, dithiocarbamic acid or its salt or the metal remover that combines of two or more component arbitrarily; Or/and emulsion splitter is with emulsion splitter or other the disclosed emulsion splitter that is applicable to that the hydrocarbon ils breakdown of emulsion is used that the hydrocarbon ils breakdown of emulsion is used that be applicable to of KR-40, LH-12, LH-14, PC-6, GAR-36, SH-1, SH-4, AY-910 or the sale of other manufacturer production.
7. the method that recycles of a kind of hydrocarbon oil metal removal agent according to claim 1; When it is characterized in that in the recycle-water solution of described hydrocarbon oil metal removal agent that metal remover concentration is higher than the metal remover that sets and accounts for the needed ratio of hydrocarbon ils; Replenish the water of the recycle-water solution amount 1～500% that contains the hydrocarbon ils metal remover, replenish the emulsion splitter of the recycle-water solution amount 0.001～0.02% that contains the hydrocarbon ils metal remover; Perhaps, when above-mentioned metal remover concentration is lower than the metal remover that sets and accounts for the needed ratio of hydrocarbon ils, replenish the hydrocarbon oil metal removal agent of the recycle-water solution amount 0.001～5% that contains the hydrocarbon ils metal remover.
8. the method that recycles of a kind of hydrocarbon oil metal removal agent according to claim 1 is characterized in that described technology of electric de-salting treatment condition are: 50～150 ℃ of desalination temperature, weak electric field intensity 50～500V/cm, the residence time 1～60min; Highfield intensity 500～1500V/cm; The residence time 5～200min; Utilize mixing valve or static mixer or boxshear apparatus or whisking appliance or film reactor with hydrocarbon ils with account for the water of hydrocarbon ils 2%～20% and the hydrocarbon oil metal removal agent of aequum; Mix thorough mixing under the differential pressure at 50～150 ℃ of mixing temperatures, 0.02MPa～1.0MPa, make mixed profit mean particle dia in 0.1 μ m～50 mu m ranges.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106319563A (en) * | 2016-09-13 | 2017-01-11 | 广沣金源（北京）科技有限公司 | Electrolytic copper and method for producing electrolytic copper from concentrated nitric acid copper-containing wastewater |
| CN114479912A (en) * | 2020-11-11 | 2022-05-13 | 中石油克拉玛依石化有限责任公司 | Pretreatment method of crude oil containing organic sodium |
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| CN1208434C (en) * | 2003-06-03 | 2005-06-29 | 克拉玛依市金山石油化工有限公司 | Hydrocarbon oil demetalizing agent, and preparing method and use method thereof |
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| CN114479912B (en) * | 2020-11-11 | 2023-12-22 | 中石油克拉玛依石化有限责任公司 | Pretreatment method of crude oil containing organic sodium |
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