CN1431276A - Method for removing metal from hydrocarbon oil by using inorganic acid - Google Patents
Method for removing metal from hydrocarbon oil by using inorganic acid Download PDFInfo
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- CN1431276A CN1431276A CN 02100235 CN02100235A CN1431276A CN 1431276 A CN1431276 A CN 1431276A CN 02100235 CN02100235 CN 02100235 CN 02100235 A CN02100235 A CN 02100235A CN 1431276 A CN1431276 A CN 1431276A
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Abstract
A process for removing metals existing in the mode of nophthenate, especially calcium, from hydrocarbon oil includes mixing hydrocarbon oil with the aqueous solution of hydrochloric acid or nitric acid, water and demulsifier, emulsifying to change the metals into water-soluble ionic compound, and water-oil separation. Its advantages are low dosage of additive and high efficiency.
Description
Technical field
The present invention relates to a kind of method that from hydrocarbon ils, removes metal with mineral acid.
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 be 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 US4,988,433, CN1,120, the metal remover of reports such as 575A promptly belongs to this type of.
Above-mentioned decalcification technology all has certain removal effect to the calcium in the crude oil, but removal efficiency is not high, especially high to calcium content crude oil exists to be unfavorable for industrialization such as the metal remover consumption is big, cost is too high or removal efficiency is low thereby can not satisfy the especially problems such as requirement of catalytic cracking and heavy oil hydrogenation process of oil refining process.
Summary of the invention
The objective of the invention is provides a kind of more efficient, cheap demetallated method on the basis of existing hydrocarbon ils demetalization technology, this method can alleviate alkaline-earth metal and transition metal, and especially Ca, Fe satisfy the requirement of following process to the influence of crude oil deep processing.
The method that removes genus from hydrocarbon ils provided by the invention is with hydrocarbon ils and hydrochloric acid or aqueous nitric acid, water filling and emulsion splitter thorough mixing, emulsification, makes metal in the hydrocarbon ils form the water soluble ions compound and goes forward side by side into water, removes by oily water separation.
Hydrochloric acid is the monobasic inorganic acid, and the another name spirit of salt is the aqueous solution of HCl.HCl molecular weight 36.5, ionization is H fully in dilute aqueous soln
+And Cl
-Ion.Cl
-Metal is had very strong complex ability,, having inhibiter to have the clean-out system that is used as scale removal such as metal-derusting and boiler under the situation industrial.
Nitric acid is another monobasic inorganic acid, and molecular formula is HNO
3, molecular weight 63.Industrially also make clean-out system with the nitric acid dilute solution.
When using as metal remover, the consumption of hydrochloric acid or nitric acid is 0.5～3 times of total calcium mole number in the hydrocarbon ils, and the best is 1.5～2.5 times.Earlier hydrochloric acid or nitric acid are made into the aqueous solution, total water injection rate is 3～50% of a hydrocarbon ils volume, preferred 4～20%.Regulating the pH value with ammoniacal liquor is 2～7, be preferably in 4～7, by volume pump this aqueous solution, emulsion splitter are injected hydrocarbon ils at the same time or separately again, fully stirring makes it to mix, and service temperature changes with the density and the viscosity of hydrocarbon ils pan feeding, density is high more, viscosity is approximately big, and then service temperature is high more, otherwise then can carry out being low to moderate under the room temperature, be generally 20～140 ℃, preferred 60～130 ℃.
Emulsion splitter can be selected according to the kind of hydrocarbon ils, can be used as auxiliary products and buys from the producer that sells hydrocarbon ils.Can be single emulsion splitter or composite demulsifying agent, as BP2040, FC9301 etc., consumption be 1～100ppm of hydrocarbon ils weight, and the effect of emulsion splitter is to promote oily water separation.
The inventive method can be carried 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.
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 hydrochloric acid or rare nitric acid to do metal remover, and is effective especially to removing metal, especially calcium such as the calcium that exists with the naphthenate form, iron; Almost do not remove effect for the metal that exists with the porphyrin form.
The present invention adopts hydrochloric acid or rare nitric acid to do metal remover, has the characteristics that dosage is little, removal efficiency is high that add.
When the present invention adopts hydrochloric acid or rare nitric acid to do metal remover, generate water-soluble compound with the metal in the crude oil, when having avoided use sulfuric acid or phosphoric acid and its esters to do decalcifying agent and calcium generate water-fast calcium precipitation, these precipitations become entrained in the oil and are not easy to remove.
Embodiment
Embodiment 1
Present embodiment adopts the hydrochloric acid decalcification.
Experiment crude oil:
A: Kelamayi Jiu Qu viscous crude (calcic 240ppm) and 7: 3 mixing oil of kerosene (calcic 179ppm);
B: the North SinKiang crude oil in Xinjiang (calcic 110ppm);
C: North SinKiang crude oil and 7: 3 mixing oil of South Sinkiang crude oil (calcic 40.7ppm).
Hydrochloric acid, water filling, emulsion splitter are made into the aqueous solution by agent shown in the table 1/calcium mol ratio and injection rate, emulsion splitter dosage 50ppm, in agitator, pour the aqueous solution and the crude oil that are made into into the cone-shaped glass 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, respectively to taking off preceding and taking off the back crude oil sampling and carry out the calcium contents analysis.The results are shown in Table 1.
Table 1
| The crude oil type | Agent/calcium mol ratio | The emulsion splitter type | Injection rate, % | The crude oil calcium contents, ppm | The decalcification rate, % | |
| Before taking off | After taking off | |||||
| ????A | ????1.5 | ?FC9301 | ????10 | ????179 | ????40.0 | ????77.7 |
| ????2.0 | ?FC9301 | ????10 | ????179 | ????3.4 | ????98.1 | |
| ????2.4 | ?FC9301 | ????10 | ????179 | ????4.9 | ????97.3 | |
| ????B | ????2.2 | ?NS-9906 | ????10 | ????110 | ????3.8 | ????96.5 |
| ????C | ????2.2 | ?NS-9906 | ????10 | ????40.7 | ????3.5 | ????91.5 |
By result in the table as can be known, hydrochloric acid has good decalcification effect to the crude oil of different calcium content in agent/calcium mol ratio 1.5～2.5 scopes.To Kelamayi Jiu Qu viscous crude and kerosene (7: 3) mixing oil, agent/calcium mol ratio is low to moderate 2.0 can satisfy the needs that remove the high calcium amount; To the mixing oil of North SinKiang and North SinKiang crude oil and South Sinkiang crude oil (7: 3), agent/calcium can satisfy the needs that remove the high calcium amount than being low to moderate 2.2.
Embodiment 2
Present embodiment hydrochloric acid deferrization.
Experiment is Kelamayi Jiu Qu viscous crude and kerosene with 7: 3 mixing oil with crude oil, iron level 17.6ppm in the crude oil, and iron experimental procedure and embodiment 1 are same in the crude oil, the results are shown in Table 2.
Table 2
| The crude oil type | Agent/iron mol ratio | The emulsion splitter type | Injection rate, % | The crude oil iron level, ppm | The deferrization rate, % | |
| Before taking off | After taking off | |||||
| Kelamayi Jiu Qu viscous crude: kerosene (7: 3) | ????1.5 | ?FC9301 | ????10 | ????17.6 | ????4.6 | ????76.5 |
| ????2.5 | ?FC9301 | ????10 | ????17.6 | ????2.0 | ????88.6 | |
| ????4.0 | ?FC9301 | ????10 | ????17.6 | ????1.5 | ????91.2 | |
By result in the table as can be known, hydrochloric acid reagent/iron mol ratio is low to moderate 2.5 can satisfy the needs that remove iron level.
Embodiment 3
Present embodiment nitric acid decalcification.
Experimental procedure is with embodiment 1,60 ℃ of breakdown of emulsion temperature.The result is as shown in table 3.
Table 3
| The crude oil type | Agent/calcium mol ratio | The emulsion splitter type | Injection rate, % | The crude oil calcium contents, ppm | The decalcification rate, % | |
| Before the decalcification | After the decalcification | |||||
| ????B | ????2.0 | ?NS-9906 | ????10 | ????110 | ????14.8 | ????86.5 |
| ????C | ????2.0 | ?NS-9906 | ????10 | ????42.8 | ????8.9 | ????89.5 |
By result in the table as can be known, nitric acid is to the removal effect preferably of calcium tool in the crude oil, and the decalcification rate reaches more than 85%.
Claims (9)
1. removing the method for genus from hydrocarbon ils with mineral acid, is with hydrocarbon ils and hydrochloric acid or aqueous nitric acid, water filling and emulsion splitter thorough mixing, emulsification, makes metal in the hydrocarbon ils form the water soluble ions compound and goes forward side by side into water, removes by oily water separation.
2. in accordance with the method for claim 1, it is characterized in that, is 2～7 with hydrochloric acid or aqueous nitric acid with ammoniacal liquor adjusting pH value.
3. in accordance with the method for claim 3, it is characterized in that, the pH value of hydrochloric acid or aqueous nitric acid is adjusted to 4～7.
4. in accordance with the method for claim 1, it is characterized in that service temperature is 20～140 ℃.
5. in accordance with the method for claim 4, it is characterized in that service temperature is 60～130 ℃.
6. in accordance with the method for claim 1, it is characterized in that water injection rate is 3～50% of a hydrocarbon ils volume.
7. in accordance with the method for claim 6, it is characterized in that water injection rate is 4～20% of a hydrocarbon ils volume.
8. in accordance with the method for claim 1, it is characterized in that the consumption of hydrochloric acid or nitric acid is 0.5～3 times of total calcium mole number in the hydrocarbon ils.
9. according to claim 1 or 8 described methods, it is characterized in that the consumption of hydrochloric acid or nitric acid is 1.5～2.5 times of total calcium mole number in the hydrocarbon ils.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02100235 CN1205308C (en) | 2002-01-10 | 2002-01-10 | Method for removing metal from hydrocarbon oil by using inorganic acid |
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|---|---|---|---|
| CN 02100235 CN1205308C (en) | 2002-01-10 | 2002-01-10 | Method for removing metal from hydrocarbon oil by using inorganic acid |
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| CN1431276A true CN1431276A (en) | 2003-07-23 |
| CN1205308C CN1205308C (en) | 2005-06-08 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100386409C (en) * | 2005-05-20 | 2008-05-07 | 中国石油天然气股份有限公司 | Chemical precipitation method for hydrocarbon decalcification |
| CN101392184B (en) * | 2007-09-20 | 2012-09-12 | 中国石油化工股份有限公司 | Method for removing metal from hydrocarbon oil by using phytic acid |
| CN105001903A (en) * | 2015-06-17 | 2015-10-28 | 成都高普石油工程技术有限公司 | Processing technology for crude oil |
| CN105273734A (en) * | 2015-06-24 | 2016-01-27 | 刘毅 | Carbon black raw material, method for utilizing direct coal liquefaction residue for producing the carbon black raw material |
| US9260601B2 (en) | 2012-09-26 | 2016-02-16 | General Electric Company | Single drum oil and aqueous products and methods of use |
| CN106010621A (en) * | 2016-05-09 | 2016-10-12 | 天津大学 | Separating and recycling method and system for heavy oil deposit rich in carbonate |
| US11629296B2 (en) | 2012-09-26 | 2023-04-18 | Bl Technologies, Inc. | Demulsifying compositions and methods of use |
-
2002
- 2002-01-10 CN CN 02100235 patent/CN1205308C/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100386409C (en) * | 2005-05-20 | 2008-05-07 | 中国石油天然气股份有限公司 | Chemical precipitation method for hydrocarbon decalcification |
| CN101392184B (en) * | 2007-09-20 | 2012-09-12 | 中国石油化工股份有限公司 | Method for removing metal from hydrocarbon oil by using phytic acid |
| US9260601B2 (en) | 2012-09-26 | 2016-02-16 | General Electric Company | Single drum oil and aqueous products and methods of use |
| US11629296B2 (en) | 2012-09-26 | 2023-04-18 | Bl Technologies, Inc. | Demulsifying compositions and methods of use |
| CN105001903A (en) * | 2015-06-17 | 2015-10-28 | 成都高普石油工程技术有限公司 | Processing technology for crude oil |
| CN105273734A (en) * | 2015-06-24 | 2016-01-27 | 刘毅 | Carbon black raw material, method for utilizing direct coal liquefaction residue for producing the carbon black raw material |
| CN106010621A (en) * | 2016-05-09 | 2016-10-12 | 天津大学 | Separating and recycling method and system for heavy oil deposit rich in carbonate |
| CN106010621B (en) * | 2016-05-09 | 2018-01-19 | 天津大学 | A kind of separation and recovery method and system rich in carbonate heavy oil field |
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|---|---|
| CN1205308C (en) | 2005-06-08 |
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