CN107177369A - A kind of composite type crude oil decalcifying agent - Google Patents
A kind of composite type crude oil decalcifying agent Download PDFInfo
- Publication number
- CN107177369A CN107177369A CN201710541540.4A CN201710541540A CN107177369A CN 107177369 A CN107177369 A CN 107177369A CN 201710541540 A CN201710541540 A CN 201710541540A CN 107177369 A CN107177369 A CN 107177369A
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- Prior art keywords
- crude oil
- decalcifying agent
- composite type
- agent
- calcium
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/20—Organic compounds not containing metal atoms
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1033—Oil well production fluids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a kind of composite type crude oil decalcifying agent, by 90~95% chelating agent, 0.5~2% surfactant, 0.5~2% corrosion inhibiter, mixture is formed 4~6% demulsifier by mass percentage, is mainly used in decalcification and the de-magging of peracid heavy crude.What each group of the present invention was divided asks that, with good compatibility, the corrosivity to equipment is small, is easily mixed with heavy crude, and decalcification rate can reach more than 80%.
Description
Technical field
The invention belongs to crude oil preconditioning technique field, a kind of composite type crude oil decalcifying agent is related generally to.
Background technology
With the continuous heaviness of crude oil and in poor quality, the calcium content in crude oil has the trend substantially risen.In crude oil
Calcium is divided into inorganic calcium and the major class of organic calcium two, and inorganic calcium exists in forms such as calcium chloride, calcium carbonate, calcium sulfate, and organic calcium is with ring
The forms such as alkanoic acid calcium, fatty acid calcium, phenol calcium are present, and wherein calcium is largely with oil-soluble calcium naphthenate, phenol calcium, fatty acid calcium
Form Deng organic calcium is present.
Harm of the calcium to petroleum refining process is very big, is mainly manifested in：(1) catalyst inactivation for causing crude oil processing to use
And equipment scaling, the quiet run of process units is influenceed, the quality of product and the processing benefit of crude oil is reduced.(2) to electro-desalting
The harm of system：Calcium content is too high to make the increase of crude oil electrical conductivity, increases desalination electric current, and power consumption increase is unfavorable for electro-desalting dress
Put desalination/dehydration.(3) atmospheric and vacuum distillation unit tower top condensing system is caused to corrode, heat transmission equipment corrosion and the corruption of high-temperature combustion equipment
Erosion.
Up to the present, the decalcification technic developed both at home and abroad have chelate precipitation, hydrogenation catalyst method, membrane separation process,
CO2Method, resin method, bioanalysis etc..Wherein, because chelate precipitation need not change existing desalinating process, simply by decalcification
Agent is injected into electric desalting apparatus as a kind of auxiliary agent together with demulsifier, small investment, instant effect, thus is obtained in oil plant
Extensive use.Chinese patent CN102485838A, CN 105062548 A, CN1657594A disclose a kind of crude oil decalcifying
Agent, but be all the experimental verification done on static electric desalting apparatus, and the decalcification effect of static electric desalting apparatus takes off with dynamic electric
Salt device has very big difference, and its decalcification rate is apparently higher than dynamic electric desalination processes；Patent CN105733664A describes one
Crude oil electric desalting decalcification process is planted, is the experiment done on dynamic electric desalting apparatus, but the introduction to decalcifying agent is seldom.
The content of the invention
It is an object of the invention to provide a kind of composite type crude oil decalcifying agent, the decalcifying agent is applied to the dynamic of peracid heavy crude
The demetalization processes such as state electro-desalting decalcification, de-magging, the corrosivity to equipment is small, is easily mixed with heavy crude, and decalcification rate can be with
More than 80% is reached, existing industrial electro-desalting/dehydration device is adapted to completely.
Invention realizes that above-mentioned purpose is adopted the technical scheme that：The compound decalcifying agent presses quality percentage by following component
Formed than mixed preparing, 90%~95% chelating agent, 0.5%~2% surfactant, 0.5%~2% corrosion inhibiter, 4~6%
Demulsifier.
Chelating agent of the present invention is made up of acetic acid and 1- hydroxyl propylidene -1,1- di 2 ethylhexyl phosphonic acids.
Surfactant of the present invention is polyacrylamide, one kind in hydroxypropyl acrylate copolymer or several
Kind.
Corrosion inhibiter of the present invention is benzotriazole and its derivative.
Demulsifier of the present invention is water-soluble demulsifier generally in the art, and the present invention selects NS-9906.
Chelating agent mass ratio of the present invention is constituted：1- hydroxyl propylidene -1,1- di 2 ethylhexyl phosphonic acids：Acetic acid=2~4：1.
Compound decalcifying agent of the present invention is before the one-level static mixer of crude electric desalter with the aqueous solution
Form is disposably injected, and the concentration of the described decalcifying agent aqueous solution is 1.8~11%, the addition and crude oil of described decalcifying agent
The weight ratio of middle calcium content is 2~4:1.
The mixed proportion of the decalcifying agent aqueous solution and crude oil in injection one-level electrical desalter is to account for crude oil weight 4~10%；
Temperature is 130~140 DEG C in electrical desalter；Electric-field intensity is 500~4000 V/cm and continuously adjustabe.
, will be de- from demineralized water or the desulfurized purified water of refinery when using composite type crude oil decalcifying agent of the present invention
Calcium agent is configured to the aqueous solution that concentration is 1.8%~11%, is then sent to the aqueous solution of decalcifying agent in proportion by measuring pump
Before static mixer, it is sufficiently mixed with the crude oil after preheating, washings and demulsifier in static mixer and mixing valve
And react, mixed finish enters one-level electrical desalter and carries out water-oil separating, oily after taking off to be discharged by tank deck, carries out follow-up
It is changed into water miscible calcium and magnesium salt after organic calcium, magnesium and decalcifying agent reaction in desalination/dehydration, crude oil, is transferred to aqueous phase, is cut with tank bottom
Water is sent to saline sewage processing system together.
Beneficial effects of the present invention are：Decalcifying agent of the present invention is compound, chelating agent energy used and surface
Activating agent, corrosion inhibiter and demulsifier have good compatibility；Surfactant of the present invention and bi-component chelating
Agent can strengthen crude oil（Especially heavy crude）The removing ability of the polyvalent metals such as middle calcium, magnesium.Molecular acid amount is small, offensiveness
By force, but to polyvalent metal ions such as calcium, magnesium there is no sequestering power；1- hydroxyl propylidene -1,1- di 2 ethylhexyl phosphonic acids molecular weight is big, offensiveness
It is weak but very strong to the sequestering power of the polyvalent metal ions such as calcium, magnesium；Described surfactant can reduce oil-water interfaces
The contact probability of power, increase chelating agent and oil phase；Above three component acts synergistically, and is conducive to raising Calcium in Crude Oil, magnesium etc. many
The removal efficiency of valence metal ion.Decalcifying agent of the present invention contains corrosion inhibiter component, it is possible to decrease decalcifying agent is to refinery equipment
Corrosion, and maintain decalcifying agent stable.Decalcifying agent of the present invention does not interfere with the desalting and dewatering effect of electric desalting apparatus.
Embodiment
In order to deepen the understanding of the present invention, below in conjunction with embodiment, the invention will be further described, following to implement
Example is verified that crude oil sample used is Xinjiang mixed crude on dynamic electric desalting test device.
Embodiment 1
Composite type crude oil decalcifying agent of the present invention is configured first, and the mass percent of each component is as follows：By 60% 1- hydroxyls
Propylidene -1,1- di 2 ethylhexyl phosphonic acid, 30% acetic acid, 2% polyacrylamide, 2% BTA and 6% NS-9906 are well mixed,
Then 1.8% aqueous solution is configured to demineralized water；Miscella A calcium contents are 256 μ g/g before de-.
Miscella A is heated to 80~90 DEG C in head tank, is heated up by being delivered to preheating furnace after raw material pump accurately metering
To 130~140 DEG C, by miscella A, washings equivalent to crude quality percentage 6%, equivalent to the μ g/ of crude quality 15~30
G demulsifier, equivalent to the μ g/g of crude quality 512（The mass ratio of decalcifying agent and Calcium in Crude Oil is 2：1）It is quiet that one-level is sent to together
Before state blender, one-level electrical desalter is entered after being sufficiently mixed through one-level static mixer and mixing valve, in the presence of electric field
Water-oil separating is carried out, oil flows out above desalter after the one-level after separation is de-, proceeds follow-up desalting and dewatering, one-level is cut
Water is handled into refinery's saline sewage system.After two grades of desalinations, the decalcification rate of de- rear crude oil is shown in Table 1.
Embodiment 2
Decalcifying agent mass percent is as follows：By 65% 1- hydroxyl propylidene -1,1- di 2 ethylhexyl phosphonic acids, 30% acetic acid, 0.5% polypropylene
Acid amides, 0.5% BTA and 4% NS-9906 are well mixed, and 2% aqueous solution is then configured to desalted water；Before de-
Miscella B calcium contents are 243 μ g/g, and the addition of decalcifying agent is equivalent to the μ g/g of crude quality 486（Decalcifying agent and Calcium in Crude Oil
Mass ratio is 2：1）, other conditions are same as Example 1, after two grades of desalinations, it is de- after the decalcification rate of crude oil be shown in Table 1.
Embodiment 3：
Decalcifying agent mass percent is as follows：By 1% 1- hydroxyl propylidene -1,1- di 2 ethylhexyl phosphonic acids, 19% acetic acid, 1% polyacrylamide
+ 1% hydroxypropyl acrylate, 2% BTA and 6% NS-9906 are well mixed, and 8% water is then configured to desalted water
Solution；Miscella C calcium contents are 1538 μ g/g before de-.The addition of decalcifying agent is equivalent to the μ g/g of crude quality 6152（Decalcifying agent
Mass ratio with Calcium in Crude Oil is 4：1）, other conditions are same as Example 1, after two grades of desalinations, the decalcification of crude oil after taking off
Rate is shown in Table 1.
Embodiment 4：
Decalcifying agent mass percent is as follows：By 71% 1- hydroxyl propylidene -1,1- di 2 ethylhexyl phosphonic acids, 20.5% acetic acid, 2% acrylic acid
Hydroxypropyl acrylate, 1.5% BTA and 5% NS-9906 are well mixed, and 2% aqueous solution is then configured to desalted water；It is de-
Preceding miscella A calcium contents are 256 μ g/g, and the addition of decalcifying agent is equivalent to the μ g/g of crude quality 768（Decalcifying agent and Calcium in Crude Oil
Mass ratio be 3：1）, other conditions are same as Example 1, after two grades of desalinations, it is de- after the decalcification rate of crude oil be shown in Table 1.
Embodiment 5：
Decalcifying agent mass percent is as follows：By 60% 1- hydroxyl propylidene -1,1- di 2 ethylhexyl phosphonic acids, 34.5% acetic acid, poly- the third of 0.25%
The hydroxypropyl acrylate of acrylamide+0.25%, 1% BTA and 4% NS-9906 mechanical mixtures are uniform, then use desalted water
It is configured to 6% aqueous solution；Miscella B calcium contents are 243 μ g/g before de-, and the addition of decalcifying agent is equivalent to the μ of crude quality 486
g/g（The mass ratio of decalcifying agent and Calcium in Crude Oil is 2：1）, other conditions are same as Example 1, after two grades of desalinations, after taking off
The decalcification rate of crude oil is shown in Table 1.
Embodiment 6：
Decalcifying agent mass percent is as follows：By 62% 1- hydroxyl propylidene -1,1- di 2 ethylhexyl phosphonic acids, 30% acetic acid, 0.5% polypropylene
The hydroxypropyl acrylate of acid amides+0.5%, 2% BTA and 5% NS-9906 mechanical mixtures are uniform, are then matched somebody with somebody with desalted water
It is set to 5% aqueous solution；Miscella A calcium contents are 256 μ g/g before de-, and the addition of decalcifying agent is equivalent to the μ g/g of crude quality 512
（The mass ratio of decalcifying agent and Calcium in Crude Oil is 2：1）, other conditions are same as Example 1, after two grades of desalinations, crude oil after taking off
Decalcification rate be shown in Table 1.
Embodiment 7：
Decalcifying agent mass percent is as follows：By 61.5% 1- hydroxyl propylidene -1,1- di 2 ethylhexyl phosphonic acids, 30% acetic acid, 2% polypropylene
Acid amides, 0.5% BTA and 6% NS-9906 mechanical mixtures are uniform, and 2% aqueous solution is then configured to desalted water；
Miscella B calcium contents are 243 μ g/g before de-, and the addition of decalcifying agent is equivalent to the μ g/g of crude quality 486（In decalcifying agent and crude oil
The mass ratio of calcium is 2：1）, other conditions are same as Example 1, after two grades of desalinations, it is de- after the decalcification rate of crude oil be shown in Table 1.
Embodiment 8：
Decalcifying agent mass percent is as follows：By 70% 1- hydroxyl propylidene -1,1- di 2 ethylhexyl phosphonic acids, 24% acetic acid, 1% polyacrylamide
Amine, 1% six BTAs and 4% NS-9906 mechanical mixtures are uniform, and 8% aqueous solution is then configured to desalted water；It is de-
Preceding miscella A calcium contents are 256 μ g/g, and the addition of decalcifying agent is equivalent to the μ g/g of crude quality 768（Decalcifying agent and Calcium in Crude Oil
Mass ratio be 3：1）, other conditions are same as Example 1, after two grades of desalinations, it is de- after the decalcification rate of crude oil be shown in Table 1.
| Crude oil | Water injection rate/% | Decalcification agent content/% | Oil calcium content/μ g/g before de- | Oil calcium content/μ g/g after de- | Decalcification efficiency/% | |
| Embodiment 1 | Miscella A | 6 | 2 | 256 | 51 | 80.0 |
| Embodiment 2 | Miscella B | 6 | 2 | 243 | 44 | 81.9 |
| Embodiment 3 | Miscella C | 8 | 8 | 1538 | 58 | 96.2 |
| Embodiment 4 | Miscella A | 6 | 2 | 256 | 37 | 85.5 |
| Embodiment 5 | Miscella B | 6 | 2 | 243 | 43 | 82.3 |
| Embodiment 6 | Miscella A | 6 | 2 | 256 | 46 | 82.0 |
| Embodiment 7 | Miscella B | 6 | 2 | 243 | 45 | 81.4 |
| Embodiment 8 | Miscella A | 6 | 2 | 256 | 35 | 86.3 |
From above-mentioned result of the test, decalcification rate of the decalcifying agent of the present invention on dynamic electric desalting test device reaches
80%, while there is good slow releasing function, the operation feelings of the electrical desalting/dewatering device under commercial process conditions can be simulated completely
Condition.
Claims (6)
1. a kind of composite type crude oil decalcifying agent, it is characterised in that：Described crude oil decalcifying agent by following component by mass percentage
Mixture is formed, 90%~95% chelating agent, 0.5%~2% surfactant, 0.5%~2% corrosion inhibiter, 4%~6% demulsification
Agent.
2. composite type crude oil decalcifying agent according to claim 1, it is characterised in that：Described chelating agent is by acetic acid and 1- hydroxyls
Base propylidene -1,1- di 2 ethylhexyl phosphonic acids are constituted.
3. composite type crude oil decalcifying agent according to claim 1, it is characterised in that：Described surfactant is polypropylene
One or more in acid amides, hydroxypropyl acrylate copolymer.
4. composite type crude oil decalcifying agent according to claim 1, it is characterised in that：Described corrosion inhibiter is BTA
And its derivative.
5. composite type crude oil decalcifying agent according to claim 1 or 2, it is characterised in that：Described chelating agent has quality hundred
Divide than being 1- hydroxyl propylidene -1,1- di 2 ethylhexyl phosphonic acids：Acetic acid=2~4：1.
6. composite type crude oil decalcifying agent according to claim 1, it is characterised in that：The addition of described decalcifying agent and original
The weight ratio of calcium content is 2~4 in oil:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201710541540.4A CN107177369A (en) | 2017-07-05 | 2017-07-05 | A kind of composite type crude oil decalcifying agent |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710541540.4A CN107177369A (en) | 2017-07-05 | 2017-07-05 | A kind of composite type crude oil decalcifying agent |
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| CN107177369A true CN107177369A (en) | 2017-09-19 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109762537A (en) * | 2019-02-27 | 2019-05-17 | 郑州智锦电子科技有限公司 | A kind of preparation method of environment universality Multi-effect oilfield additive |
| CN109796942A (en) * | 2019-02-27 | 2019-05-24 | 郑州智锦电子科技有限公司 | A kind of environment universality Multi-effect oilfield additive |
| CN110964556A (en) * | 2018-09-28 | 2020-04-07 | 广东粤首新科技有限公司 | Crude oil decalcifying agent and preparation method and application thereof |
| CN112552952A (en) * | 2020-12-07 | 2021-03-26 | 深圳市广昌达石油添加剂有限公司 | Crude oil decalcifying agent and preparation method and application thereof |
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| WO2008007847A1 (en) * | 2006-07-10 | 2008-01-17 | Sk Energy Co., Ltd. | Method of removing the calcium from hydrocarbonaceous oil using maleic acid or its derivatives |
| CN103215064A (en) * | 2013-05-10 | 2013-07-24 | 中国海洋石油总公司 | Method for removing metal in high-acid heavy crude oil |
| CN103242891A (en) * | 2013-05-10 | 2013-08-14 | 中国海洋石油总公司 | Decalcifying agent for high-acid heavy crude oil |
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2017
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| WO2008007847A1 (en) * | 2006-07-10 | 2008-01-17 | Sk Energy Co., Ltd. | Method of removing the calcium from hydrocarbonaceous oil using maleic acid or its derivatives |
| CN103215064A (en) * | 2013-05-10 | 2013-07-24 | 中国海洋石油总公司 | Method for removing metal in high-acid heavy crude oil |
| CN103242891A (en) * | 2013-05-10 | 2013-08-14 | 中国海洋石油总公司 | Decalcifying agent for high-acid heavy crude oil |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110964556A (en) * | 2018-09-28 | 2020-04-07 | 广东粤首新科技有限公司 | Crude oil decalcifying agent and preparation method and application thereof |
| CN109762537A (en) * | 2019-02-27 | 2019-05-17 | 郑州智锦电子科技有限公司 | A kind of preparation method of environment universality Multi-effect oilfield additive |
| CN109796942A (en) * | 2019-02-27 | 2019-05-24 | 郑州智锦电子科技有限公司 | A kind of environment universality Multi-effect oilfield additive |
| CN112552952A (en) * | 2020-12-07 | 2021-03-26 | 深圳市广昌达石油添加剂有限公司 | Crude oil decalcifying agent and preparation method and application thereof |
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Application publication date: 20170919 |