CN1298813C - Process for treating oil by alkali washing - Google Patents
Process for treating oil by alkali washing Download PDFInfo
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- CN1298813C CN1298813C CNB2005100116564A CN200510011656A CN1298813C CN 1298813 C CN1298813 C CN 1298813C CN B2005100116564 A CNB2005100116564 A CN B2005100116564A CN 200510011656 A CN200510011656 A CN 200510011656A CN 1298813 C CN1298813 C CN 1298813C
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- petroleum
- dispersion medium
- caustic soda
- alkali washing
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- 239000003513 alkali Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000005406 washing Methods 0.000 title claims abstract description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 131
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 51
- 239000002612 dispersion medium Substances 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 229910001220 stainless steel Inorganic materials 0.000 claims description 10
- 239000010935 stainless steel Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 7
- 238000010612 desalination reaction Methods 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 5
- 238000005260 corrosion Methods 0.000 claims description 4
- 230000007797 corrosion Effects 0.000 claims description 4
- 239000002609 medium Substances 0.000 claims description 3
- 238000001471 micro-filtration Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 abstract description 38
- 239000003208 petroleum Substances 0.000 abstract description 16
- 229910021645 metal ion Inorganic materials 0.000 abstract description 8
- 238000004945 emulsification Methods 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 6
- 150000003839 salts Chemical class 0.000 abstract description 5
- 239000007864 aqueous solution Substances 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract 6
- 239000003209 petroleum derivative Substances 0.000 abstract 6
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 34
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 13
- 239000010779 crude oil Substances 0.000 description 12
- 230000035484 reaction time Effects 0.000 description 7
- 230000003247 decreasing effect Effects 0.000 description 6
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 5
- 230000001476 alcoholic effect Effects 0.000 description 5
- 229910001424 calcium ion Inorganic materials 0.000 description 5
- 229910001453 nickel ion Inorganic materials 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 239000002283 diesel fuel Substances 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000011033 desalting Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- -1 metals ion Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention provides a method for alkali washing of petroleum products, which belongs to the technical field of petroleum product pretreatment in petrochemical industry, particularly relates to a technology for removing petroleum acid, salt or metal ions from the petroleum products. The present invention is characterized in that the alkali washing process is carried out in a mixer, and the used alkali liquid is the alcohol aqueous solution of sodium hydroxide. The mixer is divided into an upper layer and a lower layer by a dispersing medium, wherein the alcohol aqueous solution of the sodium hydroxide flows into the upper layer, and petroleum liquid to be washed flows into the lower layer. The alkali liquid in the upper layer flows across the dispersing medium, and is dispersed into micro liquid drops to react with the petroleum liquid in the lower layer. The mixed liquid flows out from an outlet at the lower side, and then is separated to obtain the deacidified, desalted and demetallized petroleum products. The present invention has the advantages of high deacidifying rate, low operation energy consumption, high transmission speed, short stay time and emulsification avoidance. Two phases can be naturally precipitated and separated without adding a demulsifying agent, high-voltage field, etc. Additionally, partial metal ions are removed during deacidification. The acid value and the metal ion concentration of the petroleum products can be effectively lowered, and the treatment cost of the petroleum products can be saved.
Description
Technical field
The invention belongs to petrochemical complex oil product preconditioning technique field, the technology that removes of particularly oil product PetroChina Company Limited. acid, salt or metal ion.
Background technology
In the preprocessing process of oil product, need carry out alkali cleaning and washing usually, to remove petroleum acid, metal and the water-soluble salt in the oil product.For processed oil such as gasoline, diesel oil etc., petroleum acid wherein has corrosive nature to metal, makes the equipment early failure; Reduce the stability of oil product, make oil product oxidation in storage process generate colloid, sediment; Acidity is excessive, and the petroleum acid in crude oil also causes emulsification of crude oil easily, so it is refining to carry out depickling in the course of processing; For crude oil, except petroleum acid, also contain certain density metal ion such as calcium, magnesium and nickel etc., therefore their existence causes the fouling and the corrosion of equipment in the carried of crude oil process easily, must carry out removing of salt and metal in the oil product.
Carrying out the most typical of processed oil depickling desalination is caustic washing electric refining technology, adds concentrated base and carry out entering in the high voltage electric desalting plant after the depickling and wash in steel basin or static mixer, finishes separating of alkaline residue (mainly being the aqueous solution of salt and alkali) and oil product.The crude oil upgrading technology is also very immature at present, only in electric desalting apparatus the small amounts of inorganic salt in the crude oil is separated with water usually, and can't effectively remove for a large amount of oil soluble metal ionic complexs and petroleum acid.Because the complicacy of crude oil system, adopt the alkali cleaning method and apparatus of present processed oil depickling to remove the emulsification that petroleum acid in the crude oil and metal ion very easily cause crude oil, under high-voltage electric field, separate after needing to add emulsion splitter, consumed a large amount of electric energy, the adding of emulsion splitter has also increased extra-pay.And in steel basin or static mixer, carry out alkali cleaning, need mixing for a long time and the mixing of alkali lye in oil product inhomogeneous, so just cause acid removal rate not high, substantially below 80%.For this reason, a kind of depickling simultaneously, desalination or metal efficiently of exploitation and to avoid the emulsive novel method be a major issue in the treating oil by alkali washing technology.
Summary of the invention
The objective of the invention is long, easily emulsification and need shortcoming such as high-voltage electric field desalination and a kind of method that realizes high efficient mixed depickling simultaneously, desalination or metal ion is provided of, residence time low at deacidification efficiency in the prior art.
The invention is characterized in: described alkaline cleaning procedure carries out in a mixing tank, used alkali lye is the alcohol solution of caustic soda, described mixing tank is divided into two-layer up and down by dispersion medium, wherein the upper strata flows into the alcohol solution of described caustic soda, and lower floor flows into fluid to be washed, and the alkaline stream on described upper strata is through dispersion medium, be dispersed into fine droplet, react with the fluid of lower floor, mixed solution is flowed out by the outlet of described mixing tank lower floor, obtains the oil product of depickling, desalination or metal after separating.
The volumetric molar concentration of caustic soda is 0.1mol/L～5mol/L in the alcohol solution of described caustic soda, and the volume content of alcohol is 10%～50%.Alcohol in the alcohol solution of described caustic soda is methyl alcohol or ethanol.Described dispersion medium is tabular or the tubular stainless steel microfiltration membrane or the porous filter medium of anti-naphthenic acid corrosion, and the aperture is 2 μ m～50 μ m.The flow velocity of described lower floor mixed solution is 0.3m/s～3m/s.The volume flow ratio of the fluid that the alcohol solution of the caustic soda that described upper strata flows into and lower floor flow into is 1: 3～1: 100.
The invention has the beneficial effects as follows that the novel method that the present invention proposes compares with existent method in the experimental study with industrial production, have the acid removal rate height, operation energy consumption is low, transmission speed is fast, the residence time is short, avoid emulsification, advantages such as emulsion splitter and high-voltage electric field be separated, be need not to add to two-phase can natural subsidence, and in depickling, removed the part metals ion effectively, for the acid number, concentration of metal ions and the saving oil product processing cost that effectively reduce oil product have been created condition.
Description of drawings
Fig. 1 Hi-mixer is used for schematic flow sheet of the present invention.
Embodiment
Below in conjunction with drawings and Examples the present invention is further specified.
See Fig. 1, this method has adopted new alkali lye system, and caustic soda is joined in a certain proportion of pure water mixed solution, as the used alkali lye for the treatment of oil by alkali washing, to solve emulsification problem, carries out when realizing alkali cleaning and washing; Hi-mixer is used for this technological process, fixing dispersion medium 3 in mixing tank 4, alkali lye and pending oil product in dispersion medium 3 both sides respectively with volume flow ratio 1: flow (3-100) enters mixing tank 4, form pressure difference in both sides, the alcohol solution of caustic soda enters in the mixing tank 4 from the aqueous solution import 2 at dispersion medium 3 upsides, and dispersion medium 3 only contacts with the alcohol solution of caustic soda in this side; Under action of pressure, alkali lye passes dispersion medium 3 with certain flow, be dispersed into fine droplet, be injected into dispersion medium 3 opposite sides, contact with 1 oil product that enters that enters the mouth from oil phase, and oil product along the dispersion medium surface with in the flowing of certain flow, the realization two-phase is mixed, and together along the dispersion medium surface flow, carry out neutralization reaction, two-phase mixing back is 0.3-3m/s along the velocity of flow on dispersion medium surface, and mixing time is 0.1-3s, and concrete mixing time is mixed the back by two-phase and regulated and control along the velocity of flow on dispersion medium 3 surfaces with along the mobile distance of dielectric surface 3.Mixed mixed solution flows out in the phase separator and can natural subsidence separate, and the complete disengaging time of two-phase is at 2-15min.Dispersion medium adopts can be by the tabular of naphthenic acid corrosion or tubular stainless steel microfiltration membrane or porous filter medium, and the aperture is 2-50 μ m.The volumetric molar concentration of caustic soda is 0.1-5mol/L in the alcohol solution of caustic soda, and used alcohol is ethanol or methyl alcohol, and content is at 10%-50% (volume fraction).The oil product of handling can be oil product system of different nature, comprises gasoline, diesel oil and high viscosity viscous crude, has contained the oil product system that needs alkali cleaning to handle substantially.
Embodiment is as follows:
Embodiment one
Using the aperture is that the stainless steel filtering membrane of 20 μ m is dispersion medium, is 1.84mgKOH.g with the acid number
-1Gasoline be pending oil product system, concentration is that the caustic soda alcohol solution of 3mol/L is the alkali lye system, and wherein the alcoholic acid volume fraction is 10%, and the volume flow ratio of alkali lye and oil product is 1: 100, velocity of flow along the dispersion medium surface after two-phase is mixed is 1m/s, and the reaction times is 0.5s; The complete disengaging time of two-phase is 2min in phase separator; Remaining petroleum acid concentration in the gasoline after the mensuration phase-splitting, trying to achieve acid removal rate is 95.5%, the alkali lye utilization ratio is 79%;
Embodiment two
Using the aperture is that the stainless steel plate type film of 10 μ m is dispersion medium, is 1.84mgKOH.g with the acid number
-1Gasoline be pending oil product system, concentration is that the caustic soda alcohol solution of 0.8mol/L is the alkali lye system, and wherein the alcoholic acid volume fraction is 30%, and the volume flow ratio of alkali lye and gasoline is 1: 25, velocity of flow along the dispersion medium surface after two-phase is mixed is 0.3m/s, and the reaction times is 1.67s; The complete disengaging time of two-phase is 2min in phase separator; Remaining petroleum acid concentration in the gasoline after the mensuration phase-splitting, trying to achieve acid removal rate is 98%, the alkali lye utilization ratio is 76%;
Embodiment three
Using the aperture is that the stainless steel plate type film of 2 μ m is dispersion medium, is 1.84mgKOH.g with the acid number
-1Gasoline be pending oil product system, concentration is that the caustic soda alcohol solution of 0.1mol/L is the alkali lye system, and wherein the alcoholic acid volume fraction is 50%, and the volume flow ratio of alkali lye and gasoline is 1: 3, velocity of flow along the dispersion medium surface after two-phase is mixed is 2m/s, and the reaction times is 0.25s; The complete disengaging time of two-phase is 2min in phase separator; Remaining petroleum acid concentration in the gasoline after the mensuration phase-splitting, trying to achieve acid removal rate is 97%, the alkali lye utilization ratio is 73%;
Embodiment four
Using the aperture is that the stainless steel plate type film of 10 μ m is dispersion medium, is 3.2mgKOH.g with the acid number
-1Diesel oil be pending oil product system, concentration is that the caustic soda alcohol solution of 2.5mol/L is the alkali lye system, and wherein the volume fraction of methyl alcohol is 10%, and the volume flow ratio of alkali lye and gasoline is 1: 50, velocity of flow along the dispersion medium surface after two-phase is mixed is 1.38m/s, and the reaction times is 0.36s; The complete disengaging time of two-phase is 4min in phase separator; Remaining petroleum acid concentration in the diesel oil after the mensuration phase-splitting, trying to achieve acid removal rate is 95%, the alkali lye utilization ratio is 87%;
Embodiment five
Using the aperture is that the stainless steel filtering membrane of 50 μ m is dispersion medium, is 8.95mgKOH.g with the acid number
-1The viscous crude of calcium ion concn 95.5 μ g/g and nickel ion concentration 34.5 μ g/g is pending oil product system, concentration is that the caustic soda alcohol solution of 5mol/L is the alkali lye system, wherein the alcoholic acid volume fraction is 20%, the volume flow ratio of alkali lye and gasoline is 1: 30, velocity of flow along the dispersion medium surface after two-phase is mixed is 1.5m/s, 80 ℃ of temperature of reaction, and the reaction times is 0.33s; The complete disengaging time of two-phase is 10min in phase separator; Measure after the phase-splitting remaining petroleum acid concentration, calcium ion concn and nickel ion concentration in the crude oil, trying to achieve acid removal rate is 84%, and the calcium decreasing ratio is 55.5% simultaneously, and the nickel decreasing ratio is 46.1%, and the alkali lye utilization ratio is 75%;
Embodiment six
Using the aperture is that the stainless steel plate type film of 5 μ m is dispersion medium, is 8.95mg KOH.g with the acid number
-1, calcium ion concn 95.5 μ g/g and nickel ion concentration 34.5 μ g/g viscous crude be pending oil product system, concentration is that the caustic soda alcohol solution of 5mol/L is the alkali lye system, wherein the alcoholic acid volume fraction is 40%, the volume flow ratio of alkali lye and gasoline is 1: 30, velocity of flow along the dispersion medium surface after two-phase is mixed is 3m/s, 80 ℃ of temperature of reaction, the reaction times is 0.17s, the complete disengaging time of two-phase is 12min in phase separator; Measure after the phase-splitting remaining petroleum acid concentration, calcium ion concn and nickel ion concentration in the crude oil, trying to achieve acid removal rate is 95%, and the calcium decreasing ratio is 49% simultaneously, and the nickel decreasing ratio is 47%, and the alkali lye utilization ratio is 84%;
Embodiment seven
Using the aperture is that the stainless steel plate type film of 2 μ m is dispersion medium, is 8.95mg KOH.g with the acid number
-1Viscous crude be pending oil product system, concentration is that the caustic soda alcohol solution of 2mol/L is the alkali lye system, wherein the volume fraction of methyl alcohol is 10%, the volume flow ratio of alkali lye and gasoline is 1: 10, velocity of flow along the dispersion medium surface after two-phase is mixed is 1.5m/s, 70 ℃ of temperature of reaction, the reaction times is 0.33s, the complete disengaging time of two-phase is 15min in phase separator; Measure after the phase-splitting remaining petroleum acid concentration, calcium ion concn and nickel ion concentration in the crude oil, trying to achieve acid removal rate is 98%, and the calcium decreasing ratio is 53% simultaneously, and the nickel decreasing ratio is 51%, and the alkali lye utilization ratio is 73%.
Claims (5)
1, a kind of method that is used for treating oil by alkali washing, it is characterized in that, described alkaline cleaning procedure carries out in a mixing tank, used alkali lye is the alcohol solution of caustic soda, wherein the volumetric molar concentration of caustic soda is 0.1mol/L～5mol/L, the volume content of alcohol is 10%～50%, described mixing tank is divided into two-layer up and down by dispersion medium, the aperture of described dispersion medium is 2 μ m～50 μ m, wherein the upper strata flows into the alcohol solution of described caustic soda, lower floor flows into fluid to be washed, the alkaline stream on described upper strata is dispersed into fine droplet through dispersion medium, reacts with the fluid of lower floor, mixed solution is flowed out by the outlet of described mixing tank lower floor, obtains depickling after separating, the oil product of desalination or metal.
2, the method that is used for treating oil by alkali washing as claimed in claim 1 is characterized in that, the alcohol in the alcohol solution of described caustic soda is methyl alcohol or ethanol.
3, the method that is used for treating oil by alkali washing as claimed in claim 1 is characterized in that, described dispersion medium is tabular or the tubular stainless steel microfiltration membrane or the porous filter medium of anti-naphthenic acid corrosion.
4, the method that is used for treating oil by alkali washing as claimed in claim 1 is characterized in that, the flow velocity of described lower floor mixed solution is 0.3m/s～3m/s.
5, the method that is used for treating oil by alkali washing as claimed in claim 1 is characterized in that, the volume flow ratio of the fluid that the alcohol solution of the caustic soda that described upper strata flows into and lower floor flow into is 1: 3～1: 100.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100116564A CN1298813C (en) | 2005-04-29 | 2005-04-29 | Process for treating oil by alkali washing |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100116564A CN1298813C (en) | 2005-04-29 | 2005-04-29 | Process for treating oil by alkali washing |
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| Publication Number | Publication Date |
|---|---|
| CN1693423A CN1693423A (en) | 2005-11-09 |
| CN1298813C true CN1298813C (en) | 2007-02-07 |
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| CNB2005100116564A Active CN1298813C (en) | 2005-04-29 | 2005-04-29 | Process for treating oil by alkali washing |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101200653B (en) * | 2006-12-12 | 2011-10-05 | 中国石油天然气股份有限公司 | Method for removing petroleum acid in hydrocarbon oil by using membrane dispersion extractor |
| CN106554809B (en) * | 2015-09-30 | 2018-09-28 | 中国石油化工股份有限公司 | Lighter hydrocarbons sulfur method and device |
| CN106554801B (en) * | 2015-09-30 | 2018-07-31 | 中国石油化工股份有限公司 | A kind of method of lighter hydrocarbons deep desulfuration |
| CN106947522B (en) * | 2016-01-06 | 2018-11-06 | 中国石油化工股份有限公司 | A kind of start-up method of the hydrocracking unit containing two class site catalysts |
| CN106978207B (en) * | 2016-01-15 | 2019-02-01 | 中国石油化工股份有限公司 | A kind of method of sulfur-bearing lighter hydrocarbons deep desulfuration |
| CN106978208B (en) * | 2016-01-15 | 2019-03-22 | 中国石油化工股份有限公司 | A kind of method of lighter hydrocarbons desulfurization |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4992210A (en) * | 1989-03-09 | 1991-02-12 | Betz Laboratories, Inc. | Crude oil desalting process |
| CN1295607A (en) * | 1998-03-27 | 2001-05-16 | 埃克森研究工程公司 | Removal of naphthenic acids in crude oils and distillates |
-
2005
- 2005-04-29 CN CNB2005100116564A patent/CN1298813C/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4992210A (en) * | 1989-03-09 | 1991-02-12 | Betz Laboratories, Inc. | Crude oil desalting process |
| CN1295607A (en) * | 1998-03-27 | 2001-05-16 | 埃克森研究工程公司 | Removal of naphthenic acids in crude oils and distillates |
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