CN1234811C - Method for removing metal from hydrocarbon oil using acrylic acid - acrylic ester copolymers - Google Patents
Method for removing metal from hydrocarbon oil using acrylic acid - acrylic ester copolymers Download PDFInfo
- Publication number
- CN1234811C CN1234811C CN 03102264 CN03102264A CN1234811C CN 1234811 C CN1234811 C CN 1234811C CN 03102264 CN03102264 CN 03102264 CN 03102264 A CN03102264 A CN 03102264A CN 1234811 C CN1234811 C CN 1234811C
- Authority
- CN
- China
- Prior art keywords
- acrylic acid
- multipolymer
- acrylic
- acrylic ester
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Abstract
The present invention relates to a method for removing metal from hydrocarbon oil by using an acrylic acid-acrylic ester copolymer. The method comprises that: the acrylic acid-acrylic ester copolymer, filled water, demulsifying agents and raw oil are mixed at 30 to 200 DEG C; as a result, the metal in the hydrocarbon oil generates a water-soluble coordination compound; the coordination compound is dissolved in water; the metal in the hydrocarbon oil is removed by separating oil from water. The molecular weight of the acrylic acid-acrylic ester copolymer is from 1000 to 50000; the molar ratio of an acrylic acid structural unit to an acrylic ester structural unit in the copolymer is from 0.1 to 20; the dosage of the copolymer is 0.5 to 5 times of the total mass of calcium in the hydrocarbon oil and is 1.0 to 3.0 times of the optimal mass. When the method of the present invention adopts the acrylic acid-acrylic ester as metal removing agents of the hydrocarbon oil, the method has the characteristics of few dosage and high removing efficiency; the method can be used for any hydrocarbon raw material containing excessive calcium content.
Description
Technical field
The present invention relates to a kind of method that from hydrocarbon ils, removes metal with vinylformic acid-acrylic acid esters co-polymer.
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 CN1054261, with vitriol, hydrogen hydroxyl phenol is made solid wetting agent; CN1055552 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 CN1076473 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 be with the calcium effective elimination.(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, organic phosphine sulfonic compound etc., as CN8,610,728A, CN1,036,981, US4,988,433, CN87,105,863, CN1,120,575, CN1,120,575, CN1, the metal remover of reports such as 221,018 promptly belongs to this type of.In U.S. Pat 5976358, employing crude oil such as Sartori contact the calcium metal that removes in the oil with the resin that is loaded with carboxyl, sulfonic group and the acid groups of seeing.
Summary of the invention
The present invention adopts acrylic acid and acrylic ester copolymers, and to crude oil, residual oil, deasphalted oil or the demetalization of the viscosity breaking wet goods degree of depth, especially Ca, Fe satisfy the requirement of following process to the influence of crude oil deep processing to alleviate alkaline-earth metal and transition metal.
The method that removes metals in hydrocarbon oil with acrylic acid and acrylic ester copolymers provided by the invention comprises: with acrylic acid and acrylic ester copolymers and water filling and emulsion splitter 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.
Studies show that the oil soluble calcium of non-porphyrin form and iron mainly exist with the naphthenate form in the crude oil.By with the acrylic acid and acrylic ester copolymers aqueous solution and crude oil thorough mixing, metal ions such as the calcium that exists with the naphthenate form in acrylic acid and acrylic ester copolymers and the crude oil on water-oil interface, magnesium, iron combine, forming water-soluble complex compound goes forward side by side into water, with oily water separation, thereby remove metal in the crude oil.For the metal that exists with the porphyrin form, almost do not remove effect as ferrous porphyrin, porphyrin vanadium and porphyrin nickel etc.
Vinylformic acid-acrylic acid esters co-polymer can form the different multipolymer of composition, structure and molecular weight according to the difference of polymerization single polymerization monomer, as vinylformic acid-methyl acrylate copolymer, vinylformic acid-Hydroxyethyl acrylate multipolymer, vinylformic acid-hydroxyethyl methylacrylate multipolymer, vinylformic acid-Propylene glycol monoacrylate multipolymer, vinylformic acid-Rocryl 410 multipolymer and vinylformic acid-Propylene glycol monoacrylate-methyl acrylate terpolymer etc.
Said acrylic acid and acrylic ester copolymers molecular weight is at 1000-50000, preferred 2000-40000, and the unitary mol ratio of acrylic acid structure unit and acrylate structural is 1 in the multipolymer: 10-20: 1, preferred 1: 2-10: 1.The consumption of multipolymer is 0.5-5 a times of calcium total mass in the hydrocarbon ils, and the best is 1.0-3.0 times.
During actually operating, multipolymer can be made into the aqueous solution earlier and join in the hydrocarbon ils, can also directly join in the hydrocarbon ils, contact with the hydrocarbon ils thorough mixing with water filling.Total water injection rate is the 3-50% of hydrocarbon ils volume, preferred 4-20%.Mixing time was generally 0.5 second-60 minutes, and in general, mixing means is different with mixture strength, reaches well-mixed also asynchronism(-nization), for example, adopted the fruit juice agitator of selling on the market can mix in 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 big more, and then mixing temperature is high more, otherwise then can carry out being low to moderate under the room temperature, is generally 30-200 ℃, preferred 60-150 ℃.
Said emulsion splitter can based on crude or the kind of hydrocarbon feed select, can be used as auxiliary products and buy from the producer that sells hydrocarbon ils.Can be single emulsion splitter or composite demulsifying agent, as BP2040, FC9301 etc., consumption be the 1-100ppm of hydrocarbon ils weight, and the effect of emulsion splitter is to promote oily water separation.
Said hydrocarbon ils can be crude oil, heavy hydrocarbon residual oil, solvent-deasphalted oils or from crude oil derived other hydrocarbon-type oil that goes out.
The inventive method can be carried out in the conventional demineralising process of refinery, also can realize on electric desalting apparatus, and decalcification is finished with desalination, dehydration.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 metal remover to relevant carbon steel equipment.
The inventive method adopts vinylformic acid-acrylate to make hydrocarbon oil metal removal agent, has to add the characteristics that dosage is little, removal efficiency is high, can be applicable to contain any hydrocarbon feed of super allowance calcium.
Embodiment
Embodiment 1
Present embodiment vinylformic acid-Propylene glycol monoacrylate multipolymer demetalization calcium and iron.
Getting experiment is that Kelamayi Jiu Qu viscous crude (calcium contents 266ppm), Kelamayi Jiu Qu viscous crude and kerosene are with the vacuum residuum of the mixing oil of 7: 3 mixing oil (calcium contents 154ppm), North SinKiang, Xinjiang crude oil and South Sinkiang crude oil and the mixing oil (calcium contents 87.1ppm) of kerosene with stock oil.Used vinylformic acid-Propylene glycol monoacrylate multipolymer is commercial goods (molecular weight 1000～50000, a monomer ratio 11: 1～1: 2, water quality stabilizer factory of Nanjing Chemical Engineering College produces).
With metal remover, water filling, emulsion splitter by certain agent/calcium mass ratio, injection rate, be made into the aqueous solution, emulsion splitter dosage 50ppm.With the aqueous solution that is made into be preheated to 90～100 ℃ stock oil thorough mixing 20 seconds in commercially available fruit juice agitator, pour the cone-shaped glass desalter then into.Adopt DP-II type electric desalting breakdown of emulsion instrument to carry out oily water separation, electric-force gradient 200v/cm, 80 ℃ of temperature.Get after the oily water separation and take off back crude oil, (ICP/AES) carries out metal content analysis with plasma emission spectroscopy, the results are shown in Table 1.
By table 1 result as can be known, vinylformic acid-Propylene glycol monoacrylate multipolymer has good decalcification effect to different crude oils in agent/calcium mass ratio 1.0-3.0 preferable range.Especially to Kelamayi Jiu Qu viscous crude, agent/calcium mass ratio is low to moderate 1.4 can satisfy the needs that remove the high calcium amount, and when not adding vinylformic acid-Propylene glycol monoacrylate multipolymer, the decalcification rate only is 4.4%; To vacuum residuum, be 2.85 o'clock at agent/calcium mass ratio, can satisfy the needs that remove calcium.The result during calcium, can also remove the part iron in the hydrocarbon feed also as can be known in removing hydrocarbon feed from table 1.
Table 1
| The crude oil place of production and type | The emulsion splitter type | Agent/calcium mass ratio | Take off the back metal content, ppm | Decalcification rate/% | ||
| Ca | Fe | Ca | Fe | |||
| Kelamayi, Xinjiang Jiu Qu viscous crude and kerosene were with 7: 3 mixed (calcium contents 154ppm, iron level 17.1ppm) | FC9301 | 0.73 | 60.1 | 16.7 | 61.0 | 2.3 |
| 1.17 | 22.8 | 14.9 | 85.2 | 12.8 | ||
| 1.21 | 16.6 | 11.8 | 89.2 | 30.4 | ||
| 1.31 | 14.9 | 12.8 | 90.3 | 24.3 | ||
| 1.41 | 8.3 | 11.9 | 94.6 | 30.4 | ||
| Kelamayi Jiu Qu viscous crude (calcium contents 266ppm, iron level 23.7ppm) | FC9301 | 0 | 254.3 | - | 4.4 | - |
| 0.85 | 146.3 | - | 45.0 | - | ||
| 1.13 | 102.1 | - | 61.6 | - | ||
| 1.41 | 12.5 | 6.8 | 95.3 | 71.3 | ||
Embodiment 2
Present embodiment removes calcium metal and iron in the crude oil with vinylformic acid-methyl acrylate copolymer (molecular weight 3000～20000, monomer ratio 4: 1～5: 1), vinylformic acid-Hydroxyethyl acrylate multipolymer (molecular weight 3000～5000, monomer ratio 4: 1～6: 1).
Test method is identical with embodiment 1, and used crude oil is that Kelamayi, Xinjiang Jiu Qu viscous crude and kerosene form with 7: 3 mixed, calcium contents 154ppm wherein, iron level 17.1ppm.The results are shown in Table 2.
By table 2 result as can be known, when agent/calcium compared for 1.5-2, vinylformic acid-methyl acrylate and vinylformic acid-Hydroxyethyl acrylate multipolymer all had good decalcification effect.
Embodiment 3
Present embodiment removes the calcium in the crude oil with vinylformic acid-Propylene glycol monoacrylate-methyl acrylate terpolymer
Test oil is that blue refining vacuum residuum and kerosene were with 4: 1 mixed (calcium contents 87.1ppm, iron level 9.3), vinylformic acid-Propylene glycol monoacrylate-methyl acrylate terpolymer is the water conditioner NC-309 of a U.S. Nacol company commodity, and test method and embodiment 1 are together.Test-results sees Table 3.
By result in the table 3 as can be known, vinylformic acid-Propylene glycol monoacrylate-methyl acrylate terpolymer has good metal removal effect equally.
Table 2
| Polymer type | The emulsion splitter type | Agent/calcium mass ratio | Take off the back metal content, ppm | Decalcification rate/% | ||
| Ca | Fe | Ca | Fe | |||
| Vinylformic acid-methyl acrylate | FC9301 | 0.75 | 57.75 | 16.5 | 62.5 | 3.1 |
| 1.50 | 15.1 | 12.8 | 90.2 | 25.4 | ||
| 1.85 | 8.3 | 11.0 | 94.6 | 35.4 | ||
| Vinylformic acid-Hydroxyethyl acrylate | FC9301 | 0.80 | 64.4 | 16.3 | 58.2 | 4.3 |
| 1.60 | 21.3 | 14.4 | 86.2 | 15.8 | ||
| 1.95 | 10.3 | 13.6 | 93.3 | 20.3 | ||
Table 3
| The emulsion splitter type | Agent/calcium mass ratio | Take off the back metal content, ppm | Decalcification rate/% | ||
| Ca | Fe | Ca | Fe | ||
| NS9906 | 1.43 | 23.3 | 5.9 | 73.2 | 36.6 |
| 2.86 | 3.0 | 5.6 | 96.5 | 39.9 | |
Claims (10)
1. remove the method for metals in hydrocarbon oil with acrylic acid and acrylic ester copolymers, comprise: acrylic acid and acrylic ester copolymers is contacted at 30-200 ℃ of thorough mixing with emulsion splitter with water filling, 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, wherein the consumption of multipolymer be calcium total mass in the hydrocarbon ils 0.5-5 doubly.
2. in accordance with the method for claim 1, it is characterized in that said acrylic acid and acrylic ester copolymers is selected from vinylformic acid-methyl acrylate copolymer, vinylformic acid-Hydroxyethyl acrylate multipolymer, vinylformic acid-hydroxyethyl methylacrylate multipolymer, vinylformic acid-Propylene glycol monoacrylate multipolymer, vinylformic acid-Rocryl 410 multipolymer and vinylformic acid-Propylene glycol monoacrylate-methyl acrylate terpolymer.
3. in accordance with the method for claim 1, it is characterized in that said acrylic acid and acrylic ester copolymers molecular weight is 1000-50000.
4. according to claim 1 or 3 described methods, it is characterized in that said acrylic acid and acrylic ester copolymers molecular weight is 2000-40000.
5. in accordance with the method for claim 1, it is characterized in that the unitary mol ratio of acrylic acid structure unit and acrylate structural is 1 in the multipolymer: 10-20: 1.
6. according to claim 1 or 5 described methods, it is characterized in that the unitary mol ratio of acrylic acid structure unit and acrylate structural is 1 in the multipolymer: 2-10: 1.
7. in accordance with the method for claim 1, it is characterized in that total water injection rate is the 3-50% of hydrocarbon ils volume.
8. in accordance with the method for claim 7, it is characterized in that total water injection rate is the 4-20% of hydrocarbon ils volume.
9. in accordance with the method for claim 1, it is characterized in that the consumption of multipolymer is 1.0～3.0 times of calcium total mass in the hydrocarbon ils.
10. in accordance with the method for claim 1, it is characterized in that the profit mixing time is 1 second-2 minutes, mixing temperature is 60-150 ℃, and the consumption of emulsion splitter is the 1-100ppm of hydrocarbon ils weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03102264 CN1234811C (en) | 2003-01-30 | 2003-01-30 | Method for removing metal from hydrocarbon oil using acrylic acid - acrylic ester copolymers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03102264 CN1234811C (en) | 2003-01-30 | 2003-01-30 | Method for removing metal from hydrocarbon oil using acrylic acid - acrylic ester copolymers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1521237A CN1521237A (en) | 2004-08-18 |
| CN1234811C true CN1234811C (en) | 2006-01-04 |
Family
ID=34281650
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03102264 Expired - Lifetime CN1234811C (en) | 2003-01-30 | 2003-01-30 | Method for removing metal from hydrocarbon oil using acrylic acid - acrylic ester copolymers |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1234811C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1323138C (en) * | 2004-10-13 | 2007-06-27 | 中国石油化工股份有限公司 | Method for removing metal from hydrocarbon oils through use of homopolymer of carboxylic acid |
| CN107384471B (en) * | 2016-05-17 | 2018-12-11 | 中国石化扬子石油化工有限公司 | A kind of without phosphorus crude oil metal removal agent |
-
2003
- 2003-01-30 CN CN 03102264 patent/CN1234811C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1521237A (en) | 2004-08-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1234810C (en) | Method for removing metal from hydrocarbon oil using copolymers or its salts containing acrylic acid and sulfonic acid | |
| CN1255512C (en) | Composition for removing metal from hydrocarbon oil | |
| CN1191326C (en) | Demetallization agent for hy drocarbon oil and its operation method | |
| CN1205308C (en) | Method for removing metal from hydrocarbon oil by using inorganic acid | |
| CN1234811C (en) | Method for removing metal from hydrocarbon oil using acrylic acid - acrylic ester copolymers | |
| CN103242891A (en) | Decalcifying agent for high-acid heavy crude oil | |
| CN1295303C (en) | Process for demetalizating of hydrocarbon oil | |
| CN1055552A (en) | Remove metal in the hydrocarbon feed with the salt of sulfuric acid and it | |
| CN1078234C (en) | Compound decalcifying agent for hydrocarbon oil and its application | |
| CN1255511C (en) | Decalcification agent for crude oil | |
| CN1323138C (en) | Method for removing metal from hydrocarbon oils through use of homopolymer of carboxylic acid | |
| CN1865403A (en) | Chemical precipitation method for hydrocarbon decalcification | |
| CN1760341A (en) | Method for removing metal from soldering paste by using polymers of carboxylic acid | |
| CN1285708C (en) | Method for decalcifying hydrocarbon oil raw material using quaternary ammonium salt | |
| CN1285709C (en) | Method for decalcifying hydrocarbon oil raw material using quaternary alkyl phosphonium salt | |
| CN1112424C (en) | Hydrocarbon oil decalcifying process | |
| CN102876352B (en) | Composite additive for reducing metal ion content of vacuum residues and application of composite additive | |
| CN1252218C (en) | Method for decalcifying hydrocarbon oil | |
| CN1318544C (en) | Treating agent for removing metal calcium from crude oil | |
| CN103571523A (en) | Crude oil complex decalcifying agent composition and application thereof | |
| CN1277905C (en) | Method for removing metals from hydrocarbon oil | |
| CN1205309C (en) | Method for removing metal from hydrocarbon oil by using by product generated in producing fatty acid through oxidizing paraffin | |
| CN101392184B (en) | Method for removing metal from hydrocarbon oil by using phytic acid | |
| CN1246423C (en) | Method for decalcifying hydro carbon oil | |
| CN104449811B (en) | A kind of Demetalization method by hydrocarbon oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term |
Granted publication date: 20060104 |
|
| CX01 | Expiry of patent term |