CN1318544C - Treating agent for removing metal calcium from crude oil - Google Patents
Treating agent for removing metal calcium from crude oil Download PDFInfo
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- CN1318544C CN1318544C CNB2004100163861A CN200410016386A CN1318544C CN 1318544 C CN1318544 C CN 1318544C CN B2004100163861 A CNB2004100163861 A CN B2004100163861A CN 200410016386 A CN200410016386 A CN 200410016386A CN 1318544 C CN1318544 C CN 1318544C
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- crude oil
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- oil
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- 239000010779 crude oil Substances 0.000 title claims abstract description 77
- 239000011575 calcium Substances 0.000 title claims abstract description 72
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 63
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 62
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 23
- 239000002184 metal Substances 0.000 title claims abstract description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000605 extraction Methods 0.000 claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- 150000004714 phosphonium salts Chemical group 0.000 claims abstract description 13
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000003983 crown ethers Chemical group 0.000 claims abstract description 5
- 239000004094 surface-active agent Substances 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 16
- 239000000839 emulsion Substances 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 12
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 12
- -1 polyoxyethylene Polymers 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 239000013543 active substance Substances 0.000 claims description 9
- 239000000460 chlorine Substances 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical group 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 3
- KOVAQMSVARJMPH-UHFFFAOYSA-N 4-methoxybutan-1-ol Chemical compound COCCCCO KOVAQMSVARJMPH-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 239000003945 anionic surfactant Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims 2
- 239000003921 oil Substances 0.000 abstract description 54
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 16
- 229930195733 hydrocarbon Natural products 0.000 abstract description 16
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 15
- 238000011033 desalting Methods 0.000 abstract description 12
- 238000005516 engineering process Methods 0.000 abstract description 12
- 229920000642 polymer Polymers 0.000 abstract 6
- 150000002009 diols Chemical class 0.000 abstract 3
- 238000005265 energy consumption Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 abstract 1
- 235000011149 sulphuric acid Nutrition 0.000 abstract 1
- 239000001117 sulphuric acid Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 38
- 230000000694 effects Effects 0.000 description 15
- 239000002253 acid Substances 0.000 description 11
- 238000000926 separation method Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- 239000009671 shengli Substances 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 230000005684 electric field Effects 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- 238000009938 salting Methods 0.000 description 6
- 239000012071 phase Substances 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000013058 crude material Substances 0.000 description 3
- 238000004945 emulsification Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
- 235000015320 potassium carbonate Nutrition 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 239000013505 freshwater Substances 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 235000015598 salt intake Nutrition 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- MAZPIOPHRNWBNG-UHFFFAOYSA-N [Cl-].Cl[NH3+].[Na] Chemical compound [Cl-].Cl[NH3+].[Na] MAZPIOPHRNWBNG-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 1
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 235000011132 calcium sulphate Nutrition 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 229940001516 sodium nitrate Drugs 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000011275 tar sand Substances 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Abstract
The present invention relates to a treating agent for removing metal calcium from crude oil. The present invention mainly solves the problems of large electrical energy consumption and a low actual calcium removing rate of the hydrocarbon oil of electric desalting technology in the prior art. The present invention well solves the problems by the technical scheme that the treating agent compounded from single alcohol polymer or a diol polymer, quaternary ammonium salt and quaternary phosphonium salt or crown ether is added into of an extraction agent selected from carbonic acid, sulphuric acid and silicic acid or the salt thereof, and a non-forcible added surface active agent or a demulsifying agent, wherein the single alcohol polymer or the diol polymer contains 1 to 18 carbon atoms, and the average molecular weight of the single alcohol polymer or the diol polymer is from 100 to 4000. The present invention can be used for the industrial production of the calcium removal of the crude oil.
Description
Technical field
The present invention relates to from crude oil, remove the treatment agent of calcium metal.
Background technology
Along with the development of oil recovery technique, a large amount of heavy crude are exploited out in recent years.Metal content in these crude oil, particularly the content of some alkaline-earth metal such as Ca increases greatly, and they are subject to people's attention day by day to the influence of crude oil processing.Studies show that Ca content increases in the stock oil, will significantly reduce catalyst molecule sieve and matrix area, directly influence activity of such catalysts.The phenomenon of catalytic cracking catalyst poisoning and deactivation appears in the high refinery that contains Ca crude oil of some refinings in recent years, and yield of light oil is reduced significantly, also has influence on downstream residual oil quality, and the crude oil processing profit of refinery is greatly affected.
Metal parts such as the alkaline-earth metal in the crude oil, particularly Ca exist with forms such as aqueous solution salt, slightly soluble salt such as calcium chloride, Calcium hydrogen carbonate, calcium sulfate and lime carbonate, and another part exists with the form of oil soluble petroleum acid calcium.In the electric desalting process of general refinery, mainly remove most soluble salts, the petroleum acid calcium of various water-fast inorganic salt and organic bound state almost there is not removal effect.This part metal overwhelming majority remains in the vacuum residuum, influences the further processing and the utilization of vacuum residuum.
Relevant crude oil demetalization technology, the research work of U.S. Chervon company are carried out early also morely.Relevant patent comprises two big classes: (1) sequestrant, adopt aminocarboxylic acid, di-carboxylic acid, hydroxycarboxylic acid and its esters and Ca to generate water soluble chelate compound, as CN8610728A, CN1036981A, CN87105863 etc.This type of medicament price is comparatively expensive, is difficult to industrialization.(2) precipitation agent adopts the sour calcium of phosphoric acid, sulfuric acid etc. and oily PetroChina Company Limited. to generate hydrophilic slightly soluble or indissoluble salt, under the solid wetting agent effect, is deposited on water, as CN1055552A and CN1054261A.CN1055552A adopts sulfuric acid and salt thereof to make metal remover, makes precipitating inhibitor with organic phospho acid or its salt, and the calcium sulfate of generation is slightly soluble in water, under the situation of restriction water injection rate, is difficult to remove fully.CN1054261A adopts ammonium phosphate to make precipitation agent, and the calcium phosphate granules of generation is water insoluble, and is easily carried secretly by oil phase, and removal effect is very influenced.Above method is more undesirable to the removal effect of high calcium hydrocarbon ils.
In view of above situation, people consider to use compound decalcifying agent, as having introduced a kind of compound decalcifying agent and application thereof that is used for hydrocarbon ils among the CN1245201A.It is that soluble sulphate and organic phosphine carboxylic acid, organic phosphine sulfonic or its soluble salt and emulsion splitter are composited.But it is only applicable to the crude oil that Ca, Mg total content are no more than 150ppm, is particularly useful for the crude oil that Ca, Mg total content are no more than 120ppm.When this decalcifying agent is handled Ca content and is no more than the hydrocarbon ils of 40ppm, can adopt general one-level electric desalting apparatus, but when Ca content＞40ppm, preferably adopt the secondary technology of electric de-salting, can reach better removal effect.Said secondary technology of electric de-salting comprises:
Compound decalcifying agent and fresh water are mixed, inject the firsts and seconds desalting plant respectively, hydrocarbon ils is injected the single stage desalting device, the water of separating from the single stage desalting device effluxes, the hydrocarbon ils of separating reinjects in the secondary desalting plant, after the oily water separation, will take off back hydrocarbon ils and two and cut water and from the secondary desalting plant, discharge respectively.
Said desalting plant is the general device in this area, comprises desalter and coupled emulsor, and the effect of emulsor is to make that hydrocarbon ils and water mix, emulsification, and the effect of desalter is to make emulsion oily water separation under electric field action.Specifically, the decalcification technology that it provides can be carried out as follows: compound decalcifying agent and fresh water filling are mixed, after formation contains the water filling of decalcifying agent, be divided into two-way, wherein a road inject emulsor by the road with crude oil before taking off, mix, emulsification, emulsion injects desalter then, carry out oily water separation, all water of telling efflux, and that tells one takes off crude oil and another road and contain the water filling of decalcifying agent and inject another emulsor simultaneously, mix, emulsification, emulsion injects another desalter and carries out oily water separation, and that tells two cuts water and efflux, and the crude oil of telling is the qualified back crude oil that takes off.Claim according to the document, this compound decalcifying agent and decalcification technology, can make Ca, Mg total content is that the decreasing ratio of the hydrocarbon ils Ca of 5～150ppm reaches 75～99%, but on the one hand must 2 grades of technology of electric de-salting in the document, and under high current status long action time, consume lot of energy, test confirmation through us on the other hand, actual crude oil decalcifying rate is lower, less than 70%, need also have big gap from industry.A kind of method of hydrocarbon oil decalcifying is disclosed among the document CN1267707A.It is to adopt thionamic acid or sulfuric acid to make host, make assistant agent with one of sodium-chlor, ammonium chloride, SODIUMNITRATE or ammonium nitrate or its mixture, and emulsion splitter is formed decalcifying agent.The decalcification rate introduction that its one-level is handled reaches 70～95%, tests discovery through us equally, and the actual decalcification rate of its crude oil is all less than 70%.
Summary of the invention
Technical problem to be solved by this invention is that the technology of electric de-salting consumed power is bigger in the conventional art, and the lower problem of the actual decalcification rate of hydrocarbon ils provides a kind of new treatment agent that removes calcium metal from crude oil.It is low that this treatment agent has a technology of electric de-salting power consumption, the high advantage of technology of electric de-salting decalcification rate.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of treatment agent that removes calcium metal from crude oil comprises following component by weight percentage:
A) 10～90% extraction agent, wherein extraction agent is selected from least a in carbonic acid, sulfuric acid, silicic acid, silicoaluminate and their salt;
B) 10～60% consisting of phase-transferring agent, wherein to be selected from molecular-weight average be 100～4000 to contain at least a in polymkeric substance, organic ammonium salt, organic squama salt and the crown ether of single alcohol of 1～18 carbon atom or glycol to consisting of phase-transferring agent;
C) 0～30% tensio-active agent or emulsion splitter;
Wherein organic ammonium salt has following general formula:
X is selected from halogen or hydroxyl, R in the formula
1, R
2, R
3And R
4Be selected from hydrogen or C respectively
1～C
18Alkyl, aryl, aralkyl or alkaryl, N is nitrogen, wherein R
1, R
2, R
3And R
4In at least one is C
6～C
18Alkyl, aryl, aralkyl or alkaryl; Organic squama salt has following general formula:
Y is selected from halogen or hydroxyl, R in the formula
5, G
6, R
7And R
8Be selected from hydrogen or C respectively
1～C
18Alkyl, aryl, aralkyl or alkaryl, P is phosphorus, wherein R
5, R
6, R
7And R
8In at least one is C
6～C
18Alkyl, aryl, aralkyl or alkaryl.
In the technique scheme, extraction agent consumption preferable range is 60～90% by weight percentage, and extraction agent is selected from least a in carbonic acid, sulfuric acid, silicic acid, silicoaluminate and their salt.Consisting of phase-transferring agent consumption preferable range is 10～30% by weight percentage; The polymkeric substance preferred version is the polyoxyethylene glycol of 200～2000 molecular-weight average, and more preferably scheme is the polyoxyethylene glycol of 200～800 molecular-weight average; Organic ammonium salt is for having following general formula:
X is selected from halogen or hydroxyl in the formula, and preferred version is selected from chlorine, bromine or hydroxyl; R
1, R
2, R
3And R
4Be selected from hydrogen or C respectively
1～C
18Alkyl, aryl, aralkyl or alkaryl, R wherein
1, R
2, R
3And R
4In at least one is C
6～C
18Alkyl, aryl, aralkyl or alkaryl, preferred version is R
1, R
2, R
3And R
4In have only one for C
16Alkyl, its excess-three is hydrogen; Or R
1, R
2, R
3And R
4In have only one for C
18Alkyl, its excess-three is hydrogen; Or R
1Or R
2Be ethyl, R
3Be C
7Alkaryl, R
4Be methyl, N is a nitrogen.You Ji phosphonium salt has following general formula:
Y is selected from halogen or hydroxyl in the formula, and preferred version is selected from chlorine, bromine or hydroxyl; P is a phosphorus; R
5, R
6, R
7And R
8Be selected from hydrogen or C respectively
1～C
18Alkyl, aryl, aralkyl or alkaryl, R wherein
5, R
6, R
7And R
8In at least one is C
6～C
18Alkyl, aryl, aralkyl or alkaryl, preferred version is R
5, R
6, R
7And R
8In have only one for C
16Alkyl, its excess-three is hydrogen; Or R
5, R
6, R
7And R
8In have only one for C
18Alkyl, its excess-three is hydrogen; Or R
5Or R
6Be ethyl, R
7Be C
7Alkaryl, R
8Be methyl.The consumption of tensio-active agent or emulsion splitter is 0.5～10% by weight percentage, and tensio-active agent is selected from least a in nonionic surface active agent, anion surfactant, ethylene glycol monomethyl ether and the butyleneglycol methyl ether.
Crude oil described in the present invention can be various stock oils or the product oil in unprocessed crude oil, fraction oil, normal pressure or vacuum residuum, shale oil, tar sand extract, liquefaction coal, the petrochemical complex production, and the mixture of above-mentioned oil product.Before with crude oil and water and emulsion splitter or tensio-active agent mixing, can earlier crude oil be preheating to about 60 ℃, make it easy to stir, for the bigger oil of viscosity, also can add light fraction oil or non-polar solvent and dilute viscosity reduction.
The metal of the add-on of treatment agent in can based on crude be Ca, Mg, Fe content and decide especially, and in general metal content is high more, and the consumption of treatment agent also will strengthen.Treatment agent and weight 5～100% water as hydrocarbon ils can be joined in the crude oil when using, also can earlier treatment agent be made into the aqueous solution of 20～60% (weight), mend then and add water to 5～100% of former weight of oil, increase the meltage that water-content in the crude oil (comprising the aqueous gross weight of institute in the water of independent adding and the decalcifying agent aqueous solution) helps increasing Ca, thus the raising metal removal effect.But when water-oil ratio surpassed 1: 1, the variation of demetallization per was no longer obvious, and therefore suitable water-content is 5～100%, is preferably 5～50%.Selected water is low-hardness water preferably, and as [Ca]+[Mg]≤20ppm, the concentration of decalcifying agent in crude oil is generally 10～1000ppm, and preferable range is 10～500ppm, and more preferably scope is 50～200ppm.
The model of described emulsion splitter or tensio-active agent is to select according to the kind evaluation of crude oil, assessment method is that this area is general, selected emulsion splitter or tensio-active agent also are that this area is general, as nonionic surface active agent, anion surfactant, glycol ether, butanediol ethere, BP2040, TP9603 etc.The mode of oily water separation can be hot standing separation, it also can be conventional electric desalting process, or the counter-current extraction process, velocity of separation is faster under electric field action certainly, and general suitable electric-force gradient is 300～1500 volts/centimetre, no matter be above-mentioned which kind of separate mode, disengaging time fully separately is as the criterion with profit, and separation temperature is 50～200 ℃, under the identical situation of other conditions, temperature is high more, and oily water separation speed is fast more.
The treatment agent that removes calcium metal from crude oil provided by the invention, owing to contain extraction agent in the treatment agent, extraction agent and calcium ion have generated extremely insoluble corresponding salt.After introducing consisting of phase-transferring agent and making oily water separation, between oil phase and water, can overcome and differ energy barrier, between oil phase and water, transmit polar material, calcium ion in the oil phase is constantly combined with extraction agent, be dispersed in aqueous phase then, reached calcium concn in the reduction oil phase, improve the effect of decalcification efficient.Use technical scheme of the present invention can reach 85.7% to decalcification rate in the crude oil, to composite hydrocarbon ils is that the decalcification rate of a part of crude oil and a part of aviation kerosene reaches as high as 100%, use technical solution of the present invention an electric desalting can finish in addition, and the electric desalting time is shorter, got final product in general 5～10 minutes, save the consumption of electric energy greatly, obtained better technical effect.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1～6]
This group embodiment adopts actual crude oil sample, routine Liaohe River high acid value heavy crude, proportion 0.92 gram per centimeter
3, colloid 13%, Ca content 46.3ppm; Huge port crude oil (calcium contents 104ppm); Shengli Oil Field crude oil (calcium contents 33.67ppm); Lu Ning manages oil transportation (calcium contents 26.42ppm), Iranian sump oil (calcium contents 69.7ppm), Iranian residual oil (calcium contents 241.1ppm).
With deionized water, 50ppm BP2040 emulsion splitter (production of Mengjin, Luoyang, Henan petrochemical industry impregnating material factory), the extraction agent of different concns and the crown ether of different concns, mix with the crude oil of 70 gram different calcium content, effect is 6 minutes under 60 ℃, 1000 volts/centimetre electric fields, separate crude oil and water then, mensuration is taken off calcium contents in the crude oil of back, and it the results are shown in table 1.
Table 1
| Numbering | Hydrocarbon oil crude material | Crude oil calcium contents ppm | Crown ether consumption ppm | Extraction agent | Water filling volume % | Decalcification rate % | |
| Title | Consumption ppm | ||||||
| Embodiment 1 | Liaohe River high acid value heavy crude | 46.3 | 80 | Silicic acid | 300 | 8 | 84.5 |
| Embodiment 2 | Huge port crude oil | 104 | 150 | Sodium bicarbonate | 600 | 8 | 84.0 |
| Embodiment 3 | Shengli Oil Field crude oil | 33.67 | 50 | Silicoaluminate | 150 | 10 | 84.6 |
| Embodiment 4 | Lu Ning manages oil transportation | 26.42 | 30 | Sulfuric acid | 120 | 10 | 85.7 |
| Embodiment 5 | Iran's sump oil | 69.7 | 100 | Salt of wormwood | 500 | 15 | 84.2 |
| Embodiment 6 | Iran's residual oil | 241.1 | 200 | Yellow soda ash | 1600 | 15 | 80.7 |
[comparative example 1]
Change crude oil and be the mould oil (boiling range that promptly adds different volumes is that 150～240 ℃ virgin kerosene dilution forms) by embodiment among the CN1267707A 1, all the other are all with the embodiment of the invention 1, and its decalcification rate as a result is 100%.
[comparative example 2]
Change crude oil for pressing the mould oil of embodiment 2 among the CN1267707A, all the other are all with the embodiment of the invention 2, and its decalcification rate as a result is 99.8%.
[comparative example 3]
Change crude oil for pressing the mould oil of embodiment 3 among the CN1267707A, all the other are all with the embodiment of the invention 6, and its decalcification rate as a result is 98.7%.
[embodiment 7]
Press each Step By Condition of embodiment 1, just do not add emulsion splitter, its decalcification rate as a result is 84.3%.
[embodiment 8～13]
This group embodiment adopts actual crude oil sample, routine Liaohe River high acid value heavy crude, proportion 0.92 gram per centimeter
3, colloid 13%, Ca content 46.3ppm; Huge port crude oil (calcium contents 104ppm); Shengli Oil Field crude oil (calcium contents 33.67ppm); Lu Ning manages oil transportation (calcium contents 26.42ppm), Iranian sump oil (calcium contents 69.7ppm), Iranian residual oil (calcium contents 241.1ppm).
With the extraction agent of deionized water, 50ppm ethylene glycol monomethyl ether, different concns and organic squama salt of different concns, mix with the crude oil of 70 gram different calcium content, effect is 6 minutes under 60 ℃, 1000 volts/centimetre electric fields, separate crude oil and water then, mensuration is taken off calcium contents in the crude oil of back, and it the results are shown in table 2.Wherein You Ji phosphonium salt is C among the embodiment 8
16H
33PH
3Cl, You Ji phosphonium salt is C among the embodiment 9
18H
37PH
3Br, You Ji phosphonium salt is 1 among the embodiment 10,2-2C
2H
5-3-C
7H
7-4-CH
3-PCl, You Ji phosphonium salt is C among the embodiment 11
16H
33PH
3OH, You Ji phosphonium salt is C among the embodiment 12
18H
37PH
3OH, You Ji phosphonium salt is C among the embodiment 13
18H
37PH
3Cl.
Table 2
| Numbering | Hydrocarbon oil crude material | Crude oil calcium contents ppm | Organic squama salt consumption ppm | Extraction agent | Water filling volume % | Decalcification rate % | |
| Title | Consumption ppm | ||||||
| Embodiment 8 | Liaohe River high acid value heavy crude | 46.3 | 80 | Silicic acid | 300 | 8 | 83.9 |
| Embodiment 9 | Huge port crude oil | 104 | 150 | Sodium bicarbonate | 600 | 8 | 83.5 |
| Embodiment 10 | Shengli Oil Field crude oil | 33.67 | 50 | Silicoaluminate | 150 | 10 | 84.2 |
| Embodiment 11 | Lu Ning manages oil transportation | 26.42 | 30 | Sulfuric acid | 120 | 10 | 85.0 |
| Embodiment 12 | Iran's sump oil | 69.7 | 100 | Salt of wormwood | 500 | 15 | 83.9 |
| Embodiment 13 | Iran's residual oil | 241.1 | 200 | Yellow soda ash | 1600 | 15 | 80.4 |
[embodiment 14～19]
This group embodiment adopts actual crude oil sample, routine Liaohe River high acid value heavy crude, proportion 0.92 gram per centimeter
3, colloid 13%, Ca content 46.3ppm; Huge port crude oil (calcium contents 104ppm); Shengli Oil Field crude oil (calcium contents 33.67ppm); Lu Ning manages oil transportation (calcium contents 26.42ppm), Iranian sump oil (calcium contents 69.7ppm), Iranian residual oil (calcium contents 241.1ppm).
With deionized water, 50ppm BP2040 emulsion splitter (production of Mengjin, Luoyang, Henan petrochemical industry impregnating material factory), the extraction agent of different concns and the polyoxyethylene glycol of different concns, mix with the crude oil of 70 gram different calcium content, effect is 6 minutes under 60 ℃, 1000 volts/centimetre electric fields, separate crude oil and water then, mensuration is taken off calcium contents in the crude oil of back, and it the results are shown in table 3.
Table 3
[embodiment 20～25]
This group embodiment adopts actual crude oil sample, routine Liaohe River high acid value heavy crude, proportion 0.92 gram per centimeter
3, colloid 13%, Ca content 46.3ppm; Huge port crude oil (calcium contents 104ppm); Shengli Oil Field crude oil (calcium contents 33.67ppm); Lu Ning manages oil transportation (calcium contents 26.42ppm), Iranian sump oil (calcium contents 69.7ppm), Iranian residual oil (calcium contents 241.1ppm).
With deionized water, 50ppm butyleneglycol methyl ether, the extraction agent of different concns and the organic ammonium salt of different concns, mix with the crude oil of 70 gram different calcium content, effect is 6 minutes under 60 ℃, 1000 volts/centimetre electric fields, separate crude oil and water then, mensuration is taken off calcium contents in the crude oil of back, and it the results are shown in table 4.Wherein organic ammonium salt is C among the embodiment 20
16H
33NH
3Cl, organic ammonium salt is C among the embodiment 21
18H
37NH
3Br, organic ammonium salt is 1 among the embodiment 22,2-2C
2H
5-3-C
7H
7-4-CH
3-NCl, organic ammonium salt is C among the embodiment 23
16H
33NH
3OH, organic ammonium salt is C among the embodiment 24
18H
37NH
3OH, organic ammonium salt is C among the embodiment 25
18H
37NH
3Cl.
Table 4
| Numbering | Hydrocarbon oil crude material | Crude oil calcium contents ppm | Organic ammonium salt consumption ppm | Extraction agent | Water filling volume % | Decalcification rate % | |
| Title | Consumption ppm | ||||||
| Embodiment 20 | Liaohe River high acid value heavy crude | 46.3 | 80 | Silicic acid | 300 | 8 | 84.6 |
| Embodiment 21 | Huge port crude oil | 104 | 150 | Sodium bicarbonate | 600 | 8 | 84.1 |
| Embodiment 22 | Shengli Oil Field crude oil | 33.67 | 50 | Silicoaluminate | 150 | 10 | 84.7 |
| Embodiment 23 | Lu Ning manages oil transportation | 26.42 | 50 | Sulfuric acid | 120 | 10 | 85.6 |
| Embodiment 24 | Iran's sump oil | 69.7 | 100 | Salt of wormwood | 500 | 15 | 84.5 |
| Embodiment 25 | Iran's residual oil | 241.1 | 200 | Yellow soda ash | 1600 | 15 | 80.9 |
Claims (9)
1, a kind of treatment agent that removes calcium metal from crude oil comprises following component by weight percentage:
A) 10～90% extraction agent, wherein extraction agent is selected from least a in carbonic acid, sulfuric acid, silicic acid, silicoaluminate and their salt;
B) 10～60% consisting of phase-transferring agent, wherein to be selected from molecular-weight average be 100～4000 to contain at least a in polymkeric substance, organic ammonium salt, You Ji phosphonium salt and the crown ether of single alcohol of 1～18 carbon atom or glycol to consisting of phase-transferring agent;
C) 0～30% tensio-active agent or emulsion splitter;
Wherein organic ammonium salt has following general formula:
X is selected from halogen or hydroxyl, R in the formula
1, R
2, R
3And R
4Be selected from hydrogen or C respectively
1～C
18Alkyl, aryl, aralkyl or alkaryl, N is nitrogen, wherein R
1, R
2, R
3And R
4In at least one is C
6～C
18Alkyl, aryl, aralkyl or alkaryl; You Ji phosphonium salt has following general formula:
Y is selected from halogen or hydroxyl, R in the formula
5, R
6, R
7And R
8Be selected from hydrogen or C respectively
1～C
18Alkyl, aryl, aralkyl or alkaryl, P is phosphorus, wherein R
5, R
6, R
7And R
8In at least one is C
6～C
18Alkyl, aryl, aralkyl or alkaryl.
2,, it is characterized in that the consumption of extraction agent is 60～90% by weight percentage according to the described treatment agent that from crude oil, removes calcium metal of claim 1.
3,, it is characterized in that the consumption of consisting of phase-transferring agent is 10～30% by weight percentage according to the described treatment agent that from crude oil, removes calcium metal of claim 1.
4,, it is characterized in that polymkeric substance is the polyoxyethylene glycol of 200～2000 molecular-weight average according to the described treatment agent that from crude oil, removes calcium metal of claim 1.
5, according to the described treatment agent that from crude oil, removes calcium metal of claim 1, it is characterized in that X is selected from chlorine, bromine or hydroxyl, R in the organic ammonium salt
1, R
2, R
3And R
4In have only one for C
16Alkyl, its excess-three is hydrogen; Y is selected from chlorine, bromine or hydroxyl, R in the You Ji phosphonium salt
5, R
6, R
7And R
8In have only one for C
16Alkyl, its excess-three is hydrogen.
6, according to the described treatment agent that from crude oil, removes calcium metal of claim 1, it is characterized in that R in the organic ammonium salt
1, R
2, R
3And R
4In have only one for C
18Alkyl, its excess-three is hydrogen; R in the You Ji phosphonium salt
5, R
6, R
7And R
8In have only one for C
18Alkyl, its excess-three is hydrogen.
7, according to the described treatment agent that from crude oil, removes calcium metal of claim 1, it is characterized in that R in the organic ammonium salt
1Or R
2Be ethyl, R
3Be C
7Alkaryl, R
4Be methyl; R in the You Ji phosphonium salt
5Or R
6Be ethyl, R
7Be C
7Alkaryl, R
8Be methyl.
8,, it is characterized in that polymkeric substance is the polyoxyethylene glycol of 200～800 molecular-weight average according to the described treatment agent that from crude oil, removes calcium metal of claim 4.
9, according to the described treatment agent that from crude oil, removes calcium metal of claim 1, the consumption that it is characterized in that tensio-active agent by weight percentage or emulsion splitter is 0.5～10%, and tensio-active agent is selected from least a in nonionic surface active agent, anion surfactant, ethylene glycol monomethyl ether and the butyleneglycol methyl ether.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100163861A CN1318544C (en) | 2004-02-18 | 2004-02-18 | Treating agent for removing metal calcium from crude oil |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100163861A CN1318544C (en) | 2004-02-18 | 2004-02-18 | Treating agent for removing metal calcium from crude oil |
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| CN1318544C true CN1318544C (en) | 2007-05-30 |
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| CN103937530B (en) * | 2013-01-21 | 2016-08-03 | 中国石油化工股份有限公司 | A kind of weight oil treatment process |
| CN108929714B (en) * | 2018-08-03 | 2021-12-28 | 洛阳融惠化工科技有限公司 | Sodium removing agent suitable for organic sodium salt in crude oil |
| CN114540071B (en) * | 2020-11-26 | 2023-07-25 | 中国石油天然气股份有限公司 | Demetallizing agent, method and device for removing metal in crude oil |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1055552A (en) * | 1990-04-04 | 1991-10-23 | 切夫里昂研究公司 | Remove metal in the hydrocarbon feed with the salt of sulfuric acid and it |
| US5154857A (en) * | 1987-01-16 | 1992-10-13 | Compagnie De Raffinage Et De Distribution Total France | Demulsifying and antifouling agent suitable for separating possibly emulsified water/hydrocarbon mixtures |
| CN1245201A (en) * | 1998-08-18 | 2000-02-23 | 中国石油化工集团公司 | Compound decalcifying agent for hydrocarbon oil and its application |
| WO2000052114A1 (en) * | 1999-03-05 | 2000-09-08 | Baker Hughes Incorporated | Metal phase transfer additive composition and method |
| CN1330698A (en) * | 1998-12-18 | 2002-01-09 | 埃克森美孚研究工程公司 | Method for decreasing methods contents of petroleum streams |
-
2004
- 2004-02-18 CN CNB2004100163861A patent/CN1318544C/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5154857A (en) * | 1987-01-16 | 1992-10-13 | Compagnie De Raffinage Et De Distribution Total France | Demulsifying and antifouling agent suitable for separating possibly emulsified water/hydrocarbon mixtures |
| CN1055552A (en) * | 1990-04-04 | 1991-10-23 | 切夫里昂研究公司 | Remove metal in the hydrocarbon feed with the salt of sulfuric acid and it |
| CN1245201A (en) * | 1998-08-18 | 2000-02-23 | 中国石油化工集团公司 | Compound decalcifying agent for hydrocarbon oil and its application |
| CN1330698A (en) * | 1998-12-18 | 2002-01-09 | 埃克森美孚研究工程公司 | Method for decreasing methods contents of petroleum streams |
| WO2000052114A1 (en) * | 1999-03-05 | 2000-09-08 | Baker Hughes Incorporated | Metal phase transfer additive composition and method |
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