CN1760340A - Method for removing metal from hydrocarbon oils through use of homopolymer of carboxylic acid - Google Patents
Method for removing metal from hydrocarbon oils through use of homopolymer of carboxylic acid Download PDFInfo
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- CN1760340A CN1760340A CN 200410083925 CN200410083925A CN1760340A CN 1760340 A CN1760340 A CN 1760340A CN 200410083925 CN200410083925 CN 200410083925 CN 200410083925 A CN200410083925 A CN 200410083925A CN 1760340 A CN1760340 A CN 1760340A
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- carboxylic acid
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Abstract
A process for removing metals (Ca, Fe, etc) from hydrocarbon oil by the homopolymer of carboxylic acid includes such steps as mixing unsaturated said homopolymer or its salt with water, demulsifier and hydrocarbon oil, reaction to generate water-soluble metal matches dissolved in water, and oil-water separation.
Description
Technical field
The present invention relates to from crude oil, heavy hydrocarbon residual oil, solvent-deasphalted oils or from crude oil derived other hydrocarbon-type oil that goes out, remove the method for metal.
Technical background
Along with the development of oil recovery technique, many heavy crude are exploited out in recent years.Metal content in these crude oil, particularly some alkaline-earth metal such as Ca, Mg content increases greatly, and they are processed the influence that brings to crude oil and are subject to people's attention day by day.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 agent poisoning and deactivation appears in the high refinery that contains Ca crude oil of some refinings in recent years, yield of light oil is reduced significantly, but also have influence on downstream residual oil quality, causes the crude oil processing profit of refinery to reduce greatly.
Alkaline-earth metal Ca, Mg etc. in the crude oil, a part exists with forms such as water-soluble salt, slightly soluble salt such as calcium chloride, Calcium hydrogen carbonate, calcium sulfate, lime carbonate, and major part exists with 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 metal salts and organic bound state almost there is not removal effect.This part metal overwhelming majority remains in the vacuum residuum, has influenced further processing and utilization to vacuum residuum.
Relevant crude oil demetalization technology has been carried out more research work both at home and abroad.In U.S. Pat 4,439, in 345, Duke discloses a kind of carboxylic acid or its amine salt of using and has come to strengthen the intermediate phase emulsion of the displacement of reservoir oil product demetalization so that the method for its breakdown of emulsion from tensio-active agent.In U.S. Pat 3,059, in 368, H.Bieber discloses and has a kind ofly made Ni in the oil with mineral acid treatment hydrocarbon ils such as hydrochloric acid, V, and the cohesion of porphyrin metal compounds such as Fe reaches the method that removes the metal purpose thereby separate condensation product then.Disclosed and industrial widely used metal remover can roughly be divided into three major types according to its mechanism of action in the domestic and foreign literature at present: (1) precipitation agent, mainly be phosphoric acid, sulfuric acid or its esters that can generate hydrophilic slightly soluble or indissoluble salt with calcium in the oil, adopt ammonium phosphate to make precipitation agent as CN1054261A, with vitriol, hydrogen hydroxyl phenol is made solid wetting agent; CN1055552A is with H
2SO
4Or its salt makes metal remover, makes precipitating inhibitor with organic phospho acid or its salt.Because the calcium sulfate or the calcium phosphate slightly soluble or water insoluble that generate, and easily carried secretly thereby the decalcification effect of such metal remover is affected by oil phase.(2) inorganic chelator mainly is the polyphosphoric acid or its esters that can generate water soluble chelate compound with Ca, makes sequestrant as the CN1076473A report with Sodium hexametaphosphate 99 or tripoly phosphate sodium STPP.Because the easy hydrolysis on chemical property of polyphosphoric acid or its esters generates ortho-phosphoric acid or its salt, and large usage quantity, thereby can not effectively calcium be removed.(3) organic sequestering agent mainly is the aminocarboxylic acid or its esters that can generate water soluble chelate compound with Ca, di-carboxylic acid or its esters, monocarboxylic acid or its esters, hydroxycarboxylic acid or its esters, organic phospho acid or its esters, as CN8,610,728A, CN1,036,981A, US4,988,433, CN87,105,863, CN1,120,575A, CN1,120, the metal remover of reports such as 575A promptly belongs to this type of.
Summary of the invention
Outside above-mentioned all methods, we find, adopt homopolymer of carboxylic acid or its esters metal, the especially calcium in can the former wet goods hydrocarbon feed of effective elimination.
The method that removes metal from hydrocarbon ils provided by the invention comprises: with the homopolymer of unsaturated carboxylic acid or its salt as metal remover, with water, emulsion splitter and hydrocarbon ils thorough mixing, make the metal in the hydrocarbon ils generate water miscible title complex, be dissolved in the water, by oily water separation, remove the metal in the hydrocarbon ils.
The metal remover that the present invention adopts is the unsaturated carboxylic acid homopolymer, wherein the preferred C of unsaturated carboxylic acid
3～C
6Unsaturated fatty acids is as vinylformic acid (AA), methacrylic acid (MAA), toxilic acid (maleic anhydride) etc.Said unsaturated carboxylic acid compounds also can be the compound that contains heteroatom groups such as hydroxyl, amino, epoxy group(ing) in the molecule, as aspartic acid, Epoxysuccinic acid etc.Preferred unsaturated carboxylic acid homopolymer has: polyacrylic acid (PAA), polymethyl acrylic acid (PMAA), hydrolytic polymaleic anhydride (HPMA, i.e. polymaleic acid), poly-epoxy succinic acid (PESA), poly aspartic acid etc.Above-mentioned homopolymer is as metal remover, and its relative molecular weight is 200～20000, and preferred 300～15000.
The metal remover that the present invention adopts can also be the salt of unsaturated carboxylic acid homopolymer, as sylvite, sodium salt, ammonium salt etc.
The metal remover that the present invention adopts can be a kind of of above-mentioned homopolymer, also can be the mixture of two or more homopolymer.
Adopt the inventive method, the ratio (being called for short agent calcium mass ratio) of the quality of calcium is 1～10 in the consumption of metal remover and the hydrocarbon ils, and is general 2～8, and the best is 3～7.Metal remover can use in the mode of doing agent (solid), also metal remover can be made into the aqueous solution or organic solution, wherein used organic solvent comprises that all can dissolve the material of metal remover, it generally is small molecule alcohol, as methyl alcohol, ethanol, propyl alcohol, butanols etc., can also be dimethyl formamide, dimethyl sulfoxide (DMSO), methylcarbonate etc.The hybrid mode of metal remover and hydrocarbon ils can have multiple, for example, the aqueous solution of metal remover directly can be mixed with hydrocarbon ils, also the solution of metal remover or metal remover can be mixed then with water filling and mix with hydrocarbon ils with water filling.Total Water in the hydrocarbon ils (comprising the water yield in the water injection rate and the metal remover aqueous solution) is 1～60%, preferred 3～30% of the hydrocarbon ils volume.
The kind of best based on crude of emulsion splitter or hydrocarbon feed is selected, and can be used as auxiliary products and buys from the producer that sells hydrocarbon ils.Can be single emulsion splitter or composite demulsifying agent, the emulsion splitter consumption be 1～100ppm of hydrocarbon ils weight, and the effect of emulsion splitter is to promote oily water separation.Water-soluble demulsifier can directly inject hydrocarbon ils to be mixed with it, also can mix with hydrocarbon ils with water filling; Oil-soluble demulsifier preferably directly injects hydrocarbon ils to be mixed.
The profit mixing time was generally 0.5 second～10 minutes, preferred 1 second～2 minutes.Mixing temperature changes with the density and the viscosity of hydrocarbon ils pan feeding, and density is high more, and viscosity is approximately big, then temperature required high more, otherwise then can carry out being low to moderate under the room temperature, is generally 30～150 ℃, preferred 60～140 ℃.Oily water separation can be adopted any technology that comprises the counter-current extraction method.
Process for demetalizating provided by the invention can carry out in the conventional demineralising process of refinery, can realize on electric desalting apparatus in the actually operating, and decalcification is finished with desalination, dehydration.Generally can in the crude oil electric desalting equipment of routine, realize.
When on electric desalting apparatus, realizing,, tackle electric desalting apparatus before implementing, comprise that injecting pipeline, electrical desalter and internal electrical pole plate etc. carry out rotproofing in order to reduce or to avoid the corrosion of acid to relevant carbon steel equipment.
The present invention adopts the unsaturated carboxylic acid homopolymer to do hydrocarbon oil metal removal agent, to removing metals such as the calcium that exists with the naphthenate form in the hydrocarbon ils, iron, especially calcium is effective especially, has the advantages that consumption is little, removal efficiency is high, and is applicable to the hydrocarbon ils that contains super allowance calcium.
Embodiment
Illustrate experimental procedure of the present invention and result below, purpose is that the invention will be further described, and unrestricted its use range.
Embodiment 1: remove metal in the crude oil with polyacrylic acid (PAA)
Getting experiment is huge port crude oil with crude oil, density 0.89g/cm
3, the crude oil calcium contents is 18.4ppm, iron level 5.4.Used commercially available prod polyacrylic acid is a relative molecular weight 2000～5000, and solid content is not less than 30% the aqueous solution, and actual add-on is calculated with solid content.Polyacrylic acid, water filling are mixed by required dose of calcium mass ratio, injection rate, commercially available emulsion splitter HG952 dosage 50ppm, in agitator, pour the aqueous solution and crude oil, the emulsion splitter that are made into into desalter behind the thorough mixing, adopt DP-II type electric desalting breakdown of emulsion instrument to carry out oily water separation, electric-force gradient 200v/cm, 80 ℃ of temperature were taken out after 1 hour, carried out metal content analysis to taking off the back crude oil sampling with plasma emission spectroscopy.The decalcification result is as shown in table 1.
Table 1
| Agent calcium mass ratio | Injection rate, % | Take off the back calcium contents, ppm | Take off the back iron level, ppm | The decalcification rate, % | The deferrization rate, % |
| 3.0 | 10 | 2.4 | 3.3 | 87.0 | 38.8 |
| 4.0 | 10 | 2.3 | 2.7 | 87.5 | 50.0 |
| 5.0 | 10 | 1.7 | 2.3 | 90.8 | 57.4 |
By result in the table 1 as can be known, polyacrylic acid has good decalcification effect in the preferable range of agent calcium mass ratio 3～6.Simultaneously iron also had removal effect.
Embodiment 2: (HPMA) remove calcium in the crude oil with hydrolyzed polymaleic anhydride (acid anhydride)
Hydrolytic polymaleic anhydride (HPMA) is commercially available water conditioner product, relative molecular weight 300～1500, and solid content is not less than 48%, and actual add-on is calculated with solid content.Experiment condition and step and embodiment 1 are together.The result is as shown in table 2.
Table 2
| Agent calcium mass ratio | Injection rate, % | Take off the back calcium contents, ppm | Take off the back iron level, ppm | The decalcification rate, % | The deferrization rate, % |
| 3.0 | 10 | 4.6 | 5.1 | 75.0 | 5.5 |
| 4.0 | 10 | 2.0 | 2.5 | 89.1 | 53.7 |
| 6.0 | 10 | 1.5 | 1.6 | 91.8 | 70.4 |
By result in the table 2 as can be known, hydrolytic polymaleic anhydride can satisfy the needs that remove calcium in the preferable range of agent calcium mass ratio 3～6, has the good effect that removes iron in the crude oil simultaneously.
Embodiment 3: remove calcium in the crude oil with poly-epoxy succinic acid (PESA) and poly aspartic acid (PASP)
Poly-epoxy succinic acid (PESA) relative molecular weight 400～800, solid is provided by the Beijing Lianzhong Dadi Technology Co., Ltd; Poly aspartic acid (PASP) molecular weight 4000～5000, solid is provided by normal luxuriant biochemicals company.Respectively poly-epoxy succinic acid and poly aspartic acid are dissolved in ethanol and add the hydrocarbon ils mixing, other experiment condition and step are with embodiment 1.The result is as shown in table 3.
Table 3
| The metal remover type | Agent calcium mass ratio | Injection rate, % | Take off the back calcium contents, ppm | The decalcification rate, % |
| Poly-epoxy succinic acid | 2.5 | 10 | 8.0 | 56.5 |
| 3.5 | 10 | 3.6 | 80.5 | |
| Poly aspartic acid | 3.5 | 10 | 4.5 | 75.6 |
By result in the table 3 as can be known, poly-epoxy succinic acid, poly aspartic acid are to the equal tool of calcium in crude oil removal effect preferably, and greater than 3.5 o'clock, the decalcification rate reached more than 80% at agent calcium mass ratio.
Claims (11)
1. from hydrocarbon ils, remove the method for metal with homopolymer of carboxylic acid, comprise: with the homopolymer of unsaturated carboxylic acid or its salt as metal remover, with water, emulsion splitter and hydrocarbon ils thorough mixing, again with oily water separation, wherein the ratio of the quality of calcium is 1～10 in the consumption of metal remover and the hydrocarbon ils.
2. in accordance with the method for claim 1, it is characterized in that unsaturated carboxylic acid is C
3～C
6Unsaturated fatty acids.
3. in accordance with the method for claim 1, it is characterized in that, contain the heteroatom group that is selected from hydroxyl, amino, epoxy group(ing) in the unsaturated carboxylic acid.
4. in accordance with the method for claim 1, it is characterized in that the homopolymer of unsaturated carboxylic acid is polyacrylic acid, polymethyl acrylic acid, polymaleic acid, poly-epoxy succinic acid, poly aspartic acid.
5. in accordance with the method for claim 1, it is characterized in that the relative molecular weight of unsaturated carboxylic acid homopolymer is 200～20000.
6. in accordance with the method for claim 5, it is characterized in that the relative molecular weight of unsaturated carboxylic acid homopolymer is 300～15000.
7. in accordance with the method for claim 1, it is characterized in that said metal remover is sylvite, sodium salt, the ammonium salt of unsaturated carboxylic acid homopolymer.
8. in accordance with the method for claim 1, it is characterized in that said metal remover is a kind of of unsaturated carboxylic acid homopolymer, or two or more mixture wherein.
9. in accordance with the method for claim 1, it is characterized in that the ratio of the quality of calcium is 2～8 in the consumption of metal remover and the hydrocarbon ils, the Total Water in the hydrocarbon ils is 1～60% of a hydrocarbon ils volume.
10. according to claim 9 described method, it is characterized in that the ratio of the quality of calcium is 3～7 in the consumption of metal remover and the hydrocarbon ils, the Total Water in the hydrocarbon ils is 3～30% of a hydrocarbon ils volume.
11. in accordance with the method for claim 1, it is characterized in that the profit mixing time was generally 0.5 second～10 minutes, mixing temperature is 30～150 ℃.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101314728B (en) * | 2007-05-31 | 2012-08-01 | 中国石油化工股份有限公司 | Deferrization method for hydrocarbons raw oil |
| CN110387257A (en) * | 2018-04-19 | 2019-10-29 | 中国石油化工股份有限公司 | Suitable for clear tank oil demetalization metal remover and combinations thereof and clear tank oil treatment process |
| CN110753741A (en) * | 2017-06-19 | 2020-02-04 | Bp北美公司 | Calcium removal optimization |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1205309C (en) * | 2002-01-10 | 2005-06-08 | 中国石油化工股份有限公司 | Method for removing metal from hydrocarbon oil by using by product generated in producing fatty acid through oxidizing paraffin |
| CN1234811C (en) * | 2003-01-30 | 2006-01-04 | 中国石油化工股份有限公司 | Method for removing metal from hydrocarbon oil using acrylic acid - acrylic ester copolymers |
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2004
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101314728B (en) * | 2007-05-31 | 2012-08-01 | 中国石油化工股份有限公司 | Deferrization method for hydrocarbons raw oil |
| CN110753741A (en) * | 2017-06-19 | 2020-02-04 | Bp北美公司 | Calcium removal optimization |
| US11242491B2 (en) | 2017-06-19 | 2022-02-08 | Bp Corporation North America Inc. | Calcium removal optimisation |
| CN110753741B (en) * | 2017-06-19 | 2022-07-15 | Bp北美公司 | Calcium removal optimization |
| CN110387257A (en) * | 2018-04-19 | 2019-10-29 | 中国石油化工股份有限公司 | Suitable for clear tank oil demetalization metal remover and combinations thereof and clear tank oil treatment process |
| CN110387257B (en) * | 2018-04-19 | 2021-08-06 | 中国石油化工股份有限公司 | Demetallizing agent suitable for demetallizing clear tank oil, composition thereof and method for treating clear tank oil |
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