CN105062548A - Crude oil decalcifying agent - Google Patents
Crude oil decalcifying agent Download PDFInfo
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- CN105062548A CN105062548A CN201510523945.6A CN201510523945A CN105062548A CN 105062548 A CN105062548 A CN 105062548A CN 201510523945 A CN201510523945 A CN 201510523945A CN 105062548 A CN105062548 A CN 105062548A
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- crude oil
- decalcifying agent
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- cationic polyacrylamide
- oil decalcifying
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Abstract
The invention discloses a crude oil decalcifying agent. The crude oil decalcifying agent is an aqueous solution which comprises, by mass, 70%-85% of lactic acid, 2% of sodium lactate, 5%-10% of ammonium sulfate, 0.5%-3% of water-soluble imidazoline amide and 0.1% of cationic polyacrylamide. According to the crude oil decalcifying agent, the preparation technology is simple, calcium ions in crude oil can be effectively removed, and when the calcium ions are removed, other metal ions are removed to some extent; sustained release effect of the water-soluble imidazoline amide can effectively reduce corrosion to refinery equipment in the using process, and the stability of the decalcifying agent is maintained.
Description
Technical field
The present invention relates to crude Treatment technical field, be specifically related to a kind of crude oil decalcifying agent.
Background technology
In recent years along with the development of petroleum industry, the degree of Oil extraction is progressively deepened, no matter be that the sour matterization of domestic or external crude oil is all on the rise, and this certain corresponding relation of metal content matter sour with it ubiquity in crude oil, increase along with the increase of acid number, especially calcium, the calcium contents of part crude oil is up to more than 200mg/L.
Crude oil decalcifying problem is the emphasis and difficulties that must pay close attention in the oil refining process of domestic and international many refineries always, the safe operation of the technological process such as demineralising process, Atmospheric vacuum, catalytic cracking, hydrocracking in it and oil refining process is closely related, directly affects the quality of refined oil product.Such as: in electric desalting process, if the too high meeting of calcium contents makes crude oil specific conductivity increase, desalination electric current is increased, when power consumption increases serious, device can be caused to stop production; In atmospheric and vacuum distillation unit, the calcium salt in crude oil, can cause structure and the etching problem of interchanger and process furnace, reduces the hot lower frequency of interchanger and process furnace, reduces the work-ing life of equipment; In catalytic cracking process, the calcium cpd deposition in stock oil on a catalyst, causes hydrogenation catalyst inactivation, makes granules of catalyst condense into block, thus affect fluidization; In catalytic hydrogenation, except causing catalyst deactivation, more the medium channel of possibility blocking catalyst bed, makes hydrogenator internal drop significantly increase; The existence of Calcium in Crude Oil compound, can make derived product Quality Down.
Decalcification method conventional at present has two kinds, i.e. the decalcification of chelating method and precipitator method decalcification.It is simple to operate, the adjustment of any technique, equipment is not brought to refinery, only water-soluble decalcifying agent fully need be contacted with the metallic compound of stock oil oil-soluble and reacts, utilize strength of electric field, by generate throw out, inner complex etc. water-soluble or be easily distributed to aqueous phase non-oil soluble metal compound be separated, along with electric decontamination water is drained, to reach the object of crude oil decalcifying.
The decalcification efficiency of chelating class decalcifying agent is higher, but its cost is higher, simple organic carboxyl acid or phosphine carboxylic-acid chelating decalcifying agent, in decalcification process, because its draining pH value is lower, electric desalting equipment and water discharge line heavy corrosion can be caused, add larger intractability to the Sewage treatment systems of postorder.
Precipitation class decalcifying agent generally can not cause the corrosion of equipment and pipeline, draining is little on follow-up waste disposal plant impact, but its decalcification effect is not high, this type of decalcifying agent can generate the salt of slightly soluble or insoluble, when limiting water injection rate, be difficult to remove completely, metal removal effect is difficult to be guaranteed.Precipitation class decalcifying agent makes electric desalting equipment and the fouling of water discharge line secondary in addition, and increases the problems such as crude sodium ion, makes it not have the too strong market competitiveness.
In sum, the chelating class that generally uses of current domestic refinery and precipitation class decalcifying agent all also exist respective deficiency.
Summary of the invention
Goal of the invention: the object of the invention is the problem that calcium decreasing ratio is low, decalcifying agent has stronger corrosion to equipment in order to solve decalcifying agent in process refinery oil refining process, a kind of decalcifying agent for the treatment of refinery decalcification process is provided, this decalcifying agent can improve the decreasing ratio of refinery's Calcium in Crude Oil ion, there is obvious slow releasing function to the equipment of refinery simultaneously, effectively can be reduced in the corrosive nature used to equipment in decalcifying agent process.In addition, this decalcifying agent also can part magnesium ion in effective elimination crude oil.
Technical scheme: a kind of crude oil decalcifying agent of the present invention, it is be the lactic acid of 70-85%, the Sodium.alpha.-hydroxypropionate of 2% containing massfraction, the ammonium sulfate of 5-10%, 0.5-3% water-soluble imidazoline amide and 0.1% the aqueous solution of cationic polyacrylamide.
Further preferred as the present invention, a kind of crude oil decalcifying agent, its be contain massfraction be 85% lactic acid, 2% Sodium.alpha.-hydroxypropionate, 10% ammonium sulfate, 1% water-soluble imidazoline amide and 0.1% the aqueous solution of cationic polyacrylamide.
Further, the number-average molecular weight of described water-soluble imidazoline amide is 1000-3000.
Further, the electric density of described cationic polyacrylamide is 20-50%, and molecular weight is 600-1200 ten thousand, and solid content is greater than 40%.
The present invention also provides a kind of preparation method of crude oil decalcifying agent, step is: first by Sodium.alpha.-hydroxypropionate and lactic acid dissolution in water, then ammonium sulfate is added, be stirred to and dissolve completely, add water-soluble imidazoline amide again, finally add cationic polyacrylamide, be stirred to the aqueous solution reaching complete homogeneous phase.
Crude oil decalcifying agent of the present invention, the wherein lactic acid of proper ratio, Sodium.alpha.-hydroxypropionate and ammonium sulfate, there is good compatibility synergy, with the use of time to have Calcium in Crude Oil ion and outstanding remove effect, cationic polyacrylamide can better help water miscible calcium ion and other metal ions in crude oil to separate from crude oil.
Crude oil decalcifying agent of the present invention, wherein water-soluble imidazoline amide, have good sustained release performance, Heat stability is good, and chemical stability is good, and low toxicity, free from extraneous odour should not cause oil-water emulsion, have no side effect to oil product following process.In this crude oil decalcifying agent, add appropriate water-soluble imidazoline amide can obviously reduce in use to the corrosive nature of equipment, and the decalcifying agent stable in properties containing water-soluble imidazoline amide.
Beneficial effect: the crude oil decalcifying agent preparation technology prepared by the present invention is simple, effectively can remove the calcium ion in crude oil, also certain removing is had to other metal ions while removing calcium ion, and the slow releasing function of water-soluble imidazoline amide in use effectively can reduce the corrosion to refinery equipment, and maintain the stable of decalcifying agent.
Embodiment
In order to deepen the understanding of the present invention, below in conjunction with embodiment, the invention will be further described, and these embodiments only for explaining the present invention, do not form limiting the scope of the present invention.
Embodiment 1
First by 2% Sodium.alpha.-hydroxypropionate and 70% lactic acid dissolution in water, then add 5% ammonium sulfate, be stirred to and dissolve completely, add 0.5% water-soluble imidazoline amide again, finally slowly add 0.1% cationic polyacrylamide, be stirred to the aqueous solution reaching complete homogeneous phase, namely obtain crude oil decalcifying agent.
Embodiment 2
First by 2% Sodium.alpha.-hydroxypropionate and 85% lactic acid dissolution in water, then add 5% ammonium sulfate, be stirred to and dissolve completely, add 0.5% water-soluble imidazoline amide again, finally slowly add 0.1% cationic polyacrylamide, be stirred to the aqueous solution reaching complete homogeneous phase, namely obtain crude oil decalcifying agent.
Embodiment 3
First by 2% Sodium.alpha.-hydroxypropionate and 70% lactic acid dissolution in water, then add 10% ammonium sulfate, be stirred to and dissolve completely, add 0.5% water-soluble imidazoline amide again, finally slowly add 0.1% cationic polyacrylamide, be stirred to the aqueous solution reaching complete homogeneous phase, namely obtain crude oil decalcifying agent.
Embodiment 4
First by 2% Sodium.alpha.-hydroxypropionate and 85% lactic acid dissolution in water, then add 10% ammonium sulfate, be stirred to and dissolve completely, add 1% water-soluble imidazoline amide again, finally slowly add 0.1% cationic polyacrylamide, be stirred to the aqueous solution reaching complete homogeneous phase, namely obtain crude oil decalcifying agent.
Embodiment 5
First by 2% Sodium.alpha.-hydroxypropionate and 70% lactic acid dissolution in water, then add 5% ammonium sulfate, be stirred to and dissolve completely, add 3% water-soluble imidazoline amide again, finally slowly add 0.1% cationic polyacrylamide, be stirred to the aqueous solution reaching complete homogeneous phase, namely obtain crude oil decalcifying agent.
Embodiment 6
First by 2% Sodium.alpha.-hydroxypropionate and 85% lactic acid dissolution in water, then add 10% ammonium sulfate, be stirred to and dissolve completely, add 3% water-soluble imidazoline amide again, finally slowly add 0.1% cationic polyacrylamide, be stirred to the aqueous solution reaching complete homogeneous phase, namely obtain crude oil decalcifying agent.
The using method of crude oil decalcifying agent of the present invention is that crude oil decalcifying agent is added pending crude oil with emulsion splitter in refinery's electric desalting process simultaneously, and then through technology of electric de-salting process, the metal ion in crude oil can be removed.
The present invention carries out decalcifying agent decalcity evaluation experimental based on the commingled crude of Zhenghai crude oil, the metal content of crude oil: Ca content is 68.0ppm, Mg content be 13.1ppm, Fe content be 6.7ppm, Ni content is 12.4ppm.In crude oil, inject the massfraction accounting for total mass is the water of 6%, then fully stir, then electrical desalter is placed in, add the emulsion splitter of 10ppm and the decalcifying agent of 50ppm, electric desalting test conditions is: the electric desalting temperature of 135 DEG C, and highfield is 800V/cm, the residence time is 2min, weak electric field is 300V/cm, and the residence time is 3min, and the settling time is 15min.After oily water separation, de-rear crude oil in power taking desalter carries out metal content analysis, in de-rear crude oil, the analytical procedure of metal content is with reference to the 124-90 method in " Petrochemical Engineering Analysis method ", pre-treatment is carried out with dry ashing, then analyze with inductively coupled plasma atomic emission spectrometer, carry out simultaneous test with the existing decalcifying agent NS-726 of Jinpu New Material Co., Ltd., record result as shown in the table.
By the mensuration-rotary hanging plate method of product of the present invention with reference to GB/T18175-2014 water conditioner corrosion inhibition, carry out corrosion inhibition evaluation experimental, concrete outcome is as shown in the table.
| Embodiment | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Add dosage, ppm | 50 | 50 | 50 | 50 | 50 | 50 |
| Slowly-releasing rate % | 94.6 | 91.7 | 94.3 | 95.2 | 97.4 | 95.5 |
From above-mentioned experimental result, the calcium decreasing ratio of decalcifying agent of the present invention, up to 90%, has good slow releasing function simultaneously.
Claims (6)
1. a crude oil decalcifying agent, is characterized in that, it is be the lactic acid of 70-85%, the Sodium.alpha.-hydroxypropionate of 2% containing massfraction, the ammonium sulfate of 5-10%, 0.5-3% water-soluble imidazoline amide and 0.1% the aqueous solution of cationic polyacrylamide.
2. crude oil decalcifying agent according to claim 1, is characterized in that, its be containing massfraction be 85% lactic acid, 2% Sodium.alpha.-hydroxypropionate, 10% ammonium sulfate, 1% water-soluble imidazoline amide and 0.1% the aqueous solution of cationic polyacrylamide.
3. crude oil decalcifying agent according to claim 1 and 2, is characterized in that, the number-average molecular weight of described water-soluble imidazoline amide is 1000-3000.
4. crude oil decalcifying agent according to claim 1 and 2, is characterized in that, the electric density of described cationic polyacrylamide is 20-50%, and molecular weight is 600-1200 ten thousand, and solid content is greater than 40%.
5. crude oil decalcifying agent according to claim 3, is characterized in that, the electric density of described cationic polyacrylamide is 20-50%, and molecular weight is 600-1200 ten thousand, and solid content is greater than 40%.
6. the preparation method of the crude oil decalcifying agent as described in claim 1-5 any one, it is characterized in that, step is: first by Sodium.alpha.-hydroxypropionate and lactic acid dissolution in water, then ammonium sulfate is added, be stirred to and dissolve completely, add water-soluble imidazoline amide again, finally add cationic polyacrylamide, be stirred to the aqueous solution reaching complete homogeneous phase.
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Cited By (2)
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103146417A (en) * | 2011-12-07 | 2013-06-12 | 中国石油化工股份有限公司 | Composite demetalization agent and preparation method thereof |
| CN104370819A (en) * | 2014-10-22 | 2015-02-25 | 金浦新材料股份有限公司 | Preparation method and application of water-soluble imidazoline amide corrosion inhibitor |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103146417A (en) * | 2011-12-07 | 2013-06-12 | 中国石油化工股份有限公司 | Composite demetalization agent and preparation method thereof |
| CN104370819A (en) * | 2014-10-22 | 2015-02-25 | 金浦新材料股份有限公司 | Preparation method and application of water-soluble imidazoline amide corrosion inhibitor |
Cited By (2)
| 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 |
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| CN105062548B (en) | 2017-08-18 |
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