CN110437865A - A kind of high viscosity oil decalcifying agent and preparation method thereof - Google Patents
A kind of high viscosity oil decalcifying agent and preparation method thereof Download PDFInfo
- Publication number
- CN110437865A CN110437865A CN201910657479.9A CN201910657479A CN110437865A CN 110437865 A CN110437865 A CN 110437865A CN 201910657479 A CN201910657479 A CN 201910657479A CN 110437865 A CN110437865 A CN 110437865A
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- Prior art keywords
- component
- acid
- high viscosity
- decalcifying agent
- viscosity oil
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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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Abstract
The present invention is a kind of high viscosity oil decalcifying agent and preparation method thereof, the high viscosity oil decalcifying agent contains following component: component A is tetramethyl acetylenic glycols polyoxyethylene ether compound, component B is modified oleic acid base Imidazoline Quatemary-ammonium-salt Corrosion Inhibitor, component C is water-soluble organic acid and its salt, and component D is deionized water；Wherein, the mass percent of component A is 0.1~1%, and the mass percent of component B is 0.3~2%, and the mass percent of component C is 10~99.5%, and surplus is deionized water.High viscosity oil decalcifying agent of the present invention to conveyance conduit and electric desalting apparatus low corrosion, in high viscosity oil lipophilic inorganic calcium salt particle and petroleum acids calcium there is good removal effect.
Description
Technical field
The present invention relates to the oil field chemicals of refinery decompressioning device's crude oil preprocessing technical field, more specifically, being related to
A kind of crude oil decalcifying agent of suitable high viscosity oil.
Background technique
Calcium a part in crude oil exists in the form of water soluble salt, slightly soluble salt, and another part is in the form of petroleum acids calcium
In the presence of.Most water-soluble salt and hydrophilic inorganic calcium salt particle can be generally removed during the electro-desalting of refinery；And
When the viscosity of crude oil is higher for the lipophilic inorganic calcium salt particle and petroleum acids calcium that are present in oily phase then almost without de-
Except effect, and this part metals calcium can produce negative effect to the processing of postorder crude oil, will make to occur in the processing of refinery's crude oil
Catalyst inactivation, coking plant coke product quality decline, influences the quiet run of crude oil production device, increases the processing of crude oil
Cost, reduces the quality of product, to reduce the processing benefit of crude oil.
The step of process that decalcifying agent deviates from organic calcium is a heterogeneous reaction process, reaction are as follows: (1) in oily phase
Calcium compound is diffused at oil-water interfaces；(2) decalcifying agent is reacted with organic calcium at oil-water interfaces, forms chelating object or water-soluble calcium
Salt；(3) the chelating object or water-soluble Ca salt formed is diffused into water phase from oil-water interfaces.And gum asphalt contains in high viscosity oil
Amount is high, and existing decalcifying agent cannot be fully dispersed in oily phase, is unfavorable for lipophilic inorganic calcium salt particle and petroleum acids calcium and takes off
The effective component of calcium agent acts on, and causes decalcifying agent to the removal effect of lipophilic inorganic calcium salt particle and petroleum acids calcium in oily phase
It is poor.
Summary of the invention
It is an object of the invention to overcome lipophilic inorganic calcium salt particle and stone in high viscosity oil of the existing technology
The defect of calcium oleate removal effect difference, the oil-soluble calcium provided in a kind of pair of high viscosity oil have good removal effect, fit
Close the high viscosity oil decalcifying agent of the needs of production of refinery's high viscosity oil.
High viscosity oil decalcifying agent of the present invention using tetramethyl acetylenic glycols polyoxyethylene ether compound as surfactant,
It is set to form new decalcifying agent composition with Imidazoline corrosion inhibitor and organic acid or acylate.The decalcifying agent composition is under
The group of face constituent content is grouped as:
A) with the tetramethyl acetylenic glycols polyoxyethylene ether compound of following structural formula:
Wherein, the value range of m+n is greater than 1 and less than 15, Mn (number-average molecular weight) are as follows: 300~900；
B) modified oleic acid base Imidazoline Quatemary-ammonium-salt Corrosion Inhibitor；
C) water-soluble organic acid and its salt are preferably selected from citric acid, malic acid, tartaric acid, succinic acid, ethylenediamine tetrem
Acid, oxalic acid, lactic acid, hydroxyacetic acid, ethanedioic acid, acetic acid, formic acid, sodium citrate, hexa metaphosphoric acid, sodium polyphosphate, ethylenediamine tetraacetic
In sodium acetate, sodium lactate, TS-639 (Co., Ltd, CNOOC Tianjin Chemical Research & Design Institute) or the hydrochlorate of above-mentioned organic acid
At least one or its several mixture；
D) deionized water；
Wherein, the mass percent of component A is 0.1~1%, and the mass percent of component B is 0.3~2%, component C's
Mass percent is 10~60%, and surplus is deionized water.
The invention also discloses above-mentioned decalcifying agent the preparation method comprises the following steps:
Component C is added in component D at room temperature and is stirred evenly, sequentially adds component B and component A under stiring, mixing is equal
It is made after even.
High viscosity oil decalcifying agent of the present invention, the tetramethyl acetylenic glycols polyoxyethylene ether compound in component are environment-friendly type
Nonionic surface active agent, unique double hydroxyl groups and alkynyl group are had in structure, there is unique surface-active,
There is more excellent performance compared with traditional surfactant, oil water interfacial tension can be significantly reduced, promote oil mixing with water
Degree improves oil water contact area, to promote reacting for decalcifying agent and petroleum acids calcium；Meanwhile polyether group is with good
Hydrophily can promote the reaction product and oleophylic of decalcifying agent and petroleum acids calcium in the higher crude oil of gum asphaltic content
Inorganic calcium particle is diffused into water phase from oil-water interfaces.
The decalcifying agent composition that the present invention designs, another feature are: the tetramethyl acetylenic glycols polyoxyethylene ether contained
Compound and Imidazoline Quatemary-ammonium-salt Corrosion Inhibitor can generate synergistic effect, significantly reduce corrosion inhibiter and fill in conveyance conduit and electro-desalting
The tension on surface is set, the corrosion inhibiter is promoted to form uniform, fine and close and strong adhesive force protective film in refinery equipment, is effectively dropped
Corrosion of the low decalcifying agent to equipment.Therefore, decalcifying agent of the present invention to conveyance conduit and electric desalting apparatus low corrosion, to high viscosity original
Lipophilic inorganic calcium salt particle and petroleum acids calcium in oil have good removal effect.
Specific embodiment
Technical solution of the present invention and technical effect are further described combined with specific embodiments below.
Embodiment 1
The component of high viscosity oil decalcifying agent is as follows:
Embodiment 2
The component of high viscosity oil decalcifying agent is as follows:
Embodiment 3
The component of high viscosity oil decalcifying agent is as follows:
Embodiment 4
The component of high viscosity oil decalcifying agent is as follows:
Comparative example 1
The component of high viscosity oil decalcifying agent is as follows:
Comparative example 2
The component of high viscosity oil decalcifying agent is as follows:
The evaluation of decalcifying agent composition properties is to 316L stainless steel by the decalcification rate and decalcifying agent of crude oil in high temperature and pressure
Under corrosion rate test, as a result, obtaining according to following experiments method:
The eliminating efficiency experimental method of calcium in organic calcium and lipophilic inorganic calcium particle:
1, the inorganic calcium compound in crude oil is removed
The ratio for being 1:1 in grease mass ratio with secondary distilled water extracts crude oil three times, will be inorganic in crude oil
Calcium compound removes, and is allowed to only remaining organic calcium.
2, the test method of calcium eliminating efficiency
A certain amount of decalcifying agent, water and demulsifier are added to crude oil by the crude oil for accurately weighing certain mass extracted
In, after being sufficiently mixed, demulsification divides water at certain temperature and current field condition, the crude oil sample analysis calcium ion after taking water-oil separation
Mass fraction simultaneously calculates decalcification rate.The calculation formula of decalcification rate are as follows:
In terms of X, numerical value is indicated decalcification rate with %:
X=(1-C2/C1)*100
In formula:
Calcium content before C1- decalcification in oil sample, unit ppm；
Calcium content after C2- decalcification in oil sample, unit ppm.
3, the experimental method of corrosion test:
The accurate 500ml decalcifying agent stoste that measures is added in the autoclave of 1L, and test piece is fixed in a kettle, will
Kettle installs, and after being heated to 125 DEG C, pressure 10kpa, constant temperature and pressure 3 hours, test piece is taken out.Coupon results evaluation executes industry
Standard JB/T 7901-1999 Uniform Corrosion Method of Laboratory Immersion Test method.
The decalcifying agent of embodiment 1-4 and comparative example 1-2, decalcification rate and high temperature pressure corrosion rate evaluation result are listed in table 1.
The removing evaluation result of organic calcium and lipophilic inorganic calcium particle in 1 high viscosity oil of table
Claims (3)
1. a kind of high viscosity oil decalcifying agent, which is characterized in that including following component:
A) there is the tetramethyl acetylenic glycols polyoxyethylene ether compound of following structural formula, are as follows:
Wherein, Mn is 300~900；
B a kind of) the oleic acid base Imidazoline Quatemary-ammonium-salt Corrosion Inhibitor of modification；
C) water-soluble organic acid or acylate；
D) deionized water
Wherein, the mass percent of component A is 0.2~1%, and the mass percent of component B is 0.3~2%, the quality of component C
Percentage is 10~99.5%, and surplus is deionized water.
2. high viscosity oil decalcifying agent according to claim 1, which is characterized in that the water-soluble organic acid or organic
Hydrochlorate is selected from citric acid, malic acid, tartaric acid, succinic acid, ethylenediamine tetra-acetic acid, oxalic acid, lactic acid, hydroxyacetic acid, ethanedioic acid, second
At least one of acid, formic acid, sodium citrate, sodium ethylene diamine tetracetate, sodium lactate, TS-639 or its several mixture.
3. a kind of preparation method of high viscosity oil decalcifying agent described in claim 1 characterized by comprising
1) component C is added into component D at room temperature and is stirred evenly；
2) component B and component A are sequentially added under stiring, are made after mixing.
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| CN201910657479.9A CN110437865A (en) | 2019-07-19 | 2019-07-19 | A kind of high viscosity oil decalcifying agent and preparation method thereof |
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| CN201910657479.9A CN110437865A (en) | 2019-07-19 | 2019-07-19 | A kind of high viscosity oil decalcifying agent and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103965461A (en) * | 2014-05-19 | 2014-08-06 | 上海多纶化工有限公司 | Method for synthesizing acetylene alcohol polyoxyethylene ether |
| CN106433745A (en) * | 2016-09-14 | 2017-02-22 | 中国海洋石油总公司 | High-adaptability low-corrosion decalcifying agent of crude oil |
| CN107829095A (en) * | 2017-11-06 | 2018-03-23 | 陕西盛迈石油有限公司 | The preparation method of modified imidazoline quaternary ammonium salt corrosion inhibitor |
-
2019
- 2019-07-19 CN CN201910657479.9A patent/CN110437865A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103965461A (en) * | 2014-05-19 | 2014-08-06 | 上海多纶化工有限公司 | Method for synthesizing acetylene alcohol polyoxyethylene ether |
| CN106433745A (en) * | 2016-09-14 | 2017-02-22 | 中国海洋石油总公司 | High-adaptability low-corrosion decalcifying agent of crude oil |
| CN107829095A (en) * | 2017-11-06 | 2018-03-23 | 陕西盛迈石油有限公司 | The preparation method of modified imidazoline quaternary ammonium salt corrosion inhibitor |
Non-Patent Citations (1)
| Title |
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| 丁涓等: "松香改性油酸基咪唑啉季铵盐的缓蚀性能", 《南京工业大学学报(自然科学版)》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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