CN1078234C - Compound decalcifying agent for hydrocarbon oil and its application - Google Patents
Compound decalcifying agent for hydrocarbon oil and its application Download PDFInfo
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- CN1078234C CN1078234C CN98117505A CN98117505A CN1078234C CN 1078234 C CN1078234 C CN 1078234C CN 98117505 A CN98117505 A CN 98117505A CN 98117505 A CN98117505 A CN 98117505A CN 1078234 C CN1078234 C CN 1078234C
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Abstract
The present invention relates to a compound decalcifying agent for hydrocarbon oil, and application thereof. The decalcifying agent comprises soluble sulfate or a mixture thereof of 1 to 12 times of Ca and Mg total content in the hydrocarbon oil, a compound or a mixture of two kinds or more than two kinds selected from organic phosphurous carboxylic acid and organic phosphurous sulfonic acid or the soluble salt thereof, which accounts for 1 to 1000 ppm of the hydrocarbon oil, and a demulsifying agent. The decalcifying agent can use the technology of fresh water injection at each grade, and two cutting water drainage when the high calcium hydrocarbon oil of which the Ca and Mg total content is larger than 40 ppm. The decalcifying agent is suitable for the hydrocarbon oil of which the Ca and Mg total content does not exceed 150 ppm. A Ca elimination rate can reach 75 to 99% by the decalcifying agent and the elimination technology.
Description
The invention belongs to hydrocarbon oil refining agent and process for refining, exactly is a kind of compound decalcifying agent that contains acid or acd compound and decalcification technology that is used for hydrocarbon ils.
At present, metallic impurity in the crude oil such as Ni, V, Cu, Fe and Na etc. to the influence of crude oil processing after deliberation comparatively thorough, the corresponding techniques exploitation is also comparatively deep, and the influence of metal pair crude oil such as Ca, Mg processing then is that the eighties causes just that later on people pay attention to.Ca, Mg possible existence form in crude oil has water miscible calcium chloride, Calcium hydrogen carbonate etc., microsolubility lime carbonate, calcium sulfate etc. are arranged, oil-soluble have calcium naphthenate, fatty acid calcium and a phenates etc.Ca, Mg content and existence form have certain difference in the crude oil of different areas.
In recent years, some oil fields had entered the exploitation later stage, and the Ca in the crude oil, Mg have trend of rising day by day.Contain Ca46.7ppm as LIAOHE CRUDE, Central Plains bridge mouth crude oil contains Ca75ppm, Yan'an commingled crude 99.5ppm, huge port crude oil 115ppm.In the crude oil distillation process, Ca, Mg almost all stay in the heavy constituent, thereby secondary processing is threatened, and under such situation, are that the development of metal remover of object is just more urgent and necessary with Ca, Mg.It is pointed out that the content of Mg in crude oil is far smaller than Ca, and generally also produce effect taking off Mg to taking off the resultful metal remover of Ca.
Disclosed and industrial widely used decalcifying agent can be divided into two big classes according to its mechanism of action in the domestic and foreign literature at present: (1) sequestrant mainly is aminocarboxylic acid, di-carboxylic acid, hydroxycarboxylic acid or its esters etc. that can generate water soluble chelate compound with Ca.Metal remover as reports such as CN86107286A, CN1036981A, CN87105863 promptly belongs to this type of.(2) precipitation agent mainly is phosphoric acid, sulfuric acid or its esters that can generate hydrophilic slightly soluble or difficulty soluble salt with the Ca in the oil, and promptly adopting ammonium phosphate as CN1054261A is precipitation agent, with vitriol, oxygen hydroxyl phenol as the solid wetting agent; CN1055552A with sulfuric acid or its salt as metal remover, with organic phospho acid or its salt as precipitating inhibitor.Though it is the above-mentioned metal remover of enumerating has in various degree effect to removing Ca in the crude oil, also unsatisfactory to the removal effect of the crude oil of high Ca content.
The demetal process of prior art generally is to adopt the two-stage flow process, be about to hydrocarbon ils and inject the single stage desalting device, metal remover and water inject the secondary desalting plant, two cut water returns the notes one-level, the hydrocarbon ils of separating from the single stage desalting device reinjects in the secondary desalting plant, after oily water separation, from the secondary desalting plant, discharge and take off back crude oil.This technology is rationally with effective when Ca content crude oil is hanged down in processing, but when handling high Ca content hydrocarbon ils, then seem reasonable inadequately, for example, only annotate fresh water at secondary, return and annotate this measure of one-level and can save certain fresh water and save the required energy of preheating one-level water though two cut water, but because two cut the ionic complex that has dissolved a large amount of Ca, Mg in the water, be unfavorable for removing of Ca, Mg in the one-level hydrocarbon ils, all the more so when particularly calcium contents is high in the hydrocarbon ils.
The object of the present invention is to provide a kind of removal efficiency compound decalcifying agent high, that be specially adapted to high Ca hydrocarbon ils.
Another object of the present invention provides a kind of decalcification technology that makes compound decalcifying agent provided by the invention further improve removal efficiency.
The compound decalcifying agent that is used for hydrocarbon ils provided by the invention comprises following component:
(A) soluble sulphate or its mixture of 1～12 times of Ca in the hydrocarbon ils, Mg total content;
(B) account for the compound that is selected from one of organic phosphine carboxylic acid, organic phosphine sulfonic or its soluble salt of hydrocarbon ils 1～1000 ppm or two or more mixture wherein;
(C) emulsion splitter.
Said component (A) is a soluble sulphate, as potassium, sodium, ammonium salt etc., also can be their mixture.This compounds very easily with oil in Ca, Mg generate the wetting ability ionic complex that certain solubility is arranged.The consumption of component (A) is generally Ca in the hydrocarbon ils, Mg total content 1～12 times, preferred 1～8 times.
Said component (B) is organic phosphine carboxylic acid, organic phosphine sulfonic or its soluble salt, and as potassium, sodium, ammonium salt, preferred ammonium salt also can be their mixture.Said organic phosphine carboxylic acid is meant that the hydrogen on one or more carbon atoms is by one or more phosphonate groups (PO (OH) in unit carboxylic acid or the polycarboxylic acid molecule
2) replace the compound that the back forms, as hydroxyl phosphino-acetate (HPAA), 2-phosphono-containing butane-1,2,4 tricarboxylic acid (PBTCA), 1-phosphono-containing butane-1,2,4 tricarboxylic acid, 1,3,3-triphosphine acidic group valeric acid etc., preferred HPAA and PBTCA.The structural formula of above-claimed cpd is:
I hydroxyl phosphino-acetate (HPAA) (OH)
2OP-C (OH) H-COOH
II2-phosphono-containing butane-1,2,4 tricarboxylic acid (PBTCA)
III1-phosphono-containing butane-1,2,4 tricarboxylic acid
IV1,3,3-triphosphine acidic group valeric acid
Said organic phosphine sulfonic is meant that the hydrogen on the nitrogen-atoms is replaced the compound that the back forms by hydroxypropyl sulfonic acid and methyl-phosphorous acid respectively in the polyamines, wherein polyamines can be quadrol, diethylenetriamine etc., as quadrol three methenes phosphonic acids-hydroxypropyl sulfonic acid, quadrol two methene phosphonic acids dihydroxypropyl sulfonic acid, diethylenetriamine tetramethyl fork phosphonic acids-hydroxypropyl sulfonic acid, diethylenetriamine three methene phosphonic acids dihydroxypropyl sulfonic acid, diethylenetriamine two methene phosphonic acids three hydroxypropyl sulfonic acid etc., preferred quadrol three methenes phosphonic acids-hydroxypropyl sulfonic acid, quadrol two methenes phosphonic acids-dihydroxypropyl sulfonic acid.The structural formula of above-claimed cpd is: (I) quadrol three methene phosphonic acids one hydroxypropyl sulfonic acid
(II) quadrol two methene phosphonic acids dihydroxypropyl sulfonic acid
(III) quadrol one methylenephosphonic acid three hydroxypropyl sulfonic acid
(IV) diethylenetriamine tetramethyl fork phosphonic acids one hydroxypropyl sulfonic acid
(V) diethylenetriamine three methene phosphonic acids dihydroxypropyl sulfonic acid
(VI) diethylenetriamine two methene phosphonic acids three hydroxypropyl sulfonic acid
Compound and the Ca in the oil, Mg in the said components (B) have extremely strong complex ability, can generate water-soluble cpds, again component (A) and the ionic complex that Ca, Mg generate are had solublization, make more ionic complex be dissolved in water.Because Ca, Mg in component (B) and the hydrocarbon ils form 1: 1 complex compound, thereby its maximum consumption in hydrocarbon ils equates with the mole number of contained Ca, Mg in the hydrocarbon ils.But the kind of based on crude and with the composite situation of component (A), the consumption of component (B) is that 1 ~ 1000ppm gets final product, and better is 5 ~ 500ppm, preferably 10 ~ 250ppm.
The component of compound decalcifying agent provided by the invention (C) is an emulsion splitter, and it can be selected according to the kind evaluation of hydrocarbon ils according to this area method in common, also can be used as auxiliary products and buys in the lump from the producer that sells hydrocarbon ils.Said emulsion splitter can be single emulsion splitter, can be composite demulsifying agent also, as BP2040, and TP9603 etc., the consumption in hydrocarbon ils is generally 10 ~ 200ppm.
Compound decalcifying agent provided by the invention is applicable to that Ca, Mg total content are no more than the crude oil of 150ppm, is particularly useful for the crude oil that Ca, Mg total content are no more than 120ppm.
When using decalcifying agent provided by the invention to handle Ca content to be no more than the hydrocarbon ils of 40ppm, can adopt general one-level electric desalting apparatus, but when Ca content＞40ppm, preferably adopt the secondary technology of electric de-salting, can reach better removal effect.Said secondary technology of electric de-salting comprises;
Compound decalcifying agent and fresh water are mixed, inject the firsts and seconds desalting plant respectively, hydrocarbon ils is injected the single stage desalting device, the water of separating from the single stage desalting device effluxes, the hydrocarbon ils of separating reinjects in the secondary desalting plant, after the oily water separation, will take off back hydrocarbon ils and two and cut water and from the secondary desalting plant, discharge respectively.
Said desalting plant is the general device in this area, comprises desalter and coupled emulsor, and the effect of emulsor is to make that hydrocarbon ils and water mix, emulsification, and the effect of desalter is to make emulsion oily water separation under electric field action.Specifically, decalcification technology provided by the invention can be carried out as follows: compound decalcifying agent is mixed with fresh water filling, after formation contains the water filling of decalcifying agent, be divided into two-way, wherein a road inject emulsor 2 by the road with crude oil before taking off, mix, emulsification, emulsion injects desalter 1 then, carry out oily water separation, all water of telling efflux, and that tells one takes off crude oil and another road and contain the water filling of decalcifying agent and inject emulsor 4 simultaneously, mix, emulsification, emulsion injects desalter 3 and carries out oily water separation, and that tells two cuts water and efflux, and the crude oil of telling is the qualified back crude oil that takes off.
The emulsor that the present invention selects for use is the static mixing valve.The pressure drop of mixing valve can be 0.02 ~ 0.16MPa, and preferred 0.03 ~ 0.08MPa, emulsification times can be 0.2 ~ 5 second, preferably 0.5 ~ 2 second.The hydrocarbon ils temperature can be 60 ~ 150 ℃ in the desalter, preferably 90 ~ 140 ℃.The oily water separation time can be 5～50 minutes, preferably 10～30 minutes.In the desalter institute's making alive can be direct current, alternating-current or alternating current-direct current all can, potential gradient can be 150 ~ 3000v/cm.
Said compound decalcifying agent can be made into concentration when using and be no more than 25% the aqueous solution, is passed in the water filling with pump, also can directly join in the water filling.Two-stage is all annotated fresh water, and the water yield of each grade is 3 ~ 15% of a hydrocarbon ils weight, and preferred 4 ~ 10%.The softening water, distilled water, industrial water of condensation etc. of water quality for not containing Ca, Mg, Na, Fe.
Decalcification technology provided by the invention is suitable for and does Ca, the Mg total content is the crude oil of 40 ~ 150ppm.
Compound decalcifying agent provided by the invention and decalcification technology also are applicable to various stock oils and the product wet goods hydrocarbon ils in fraction oil, normal pressure or vacuum residuum and the petrochemical complex production.
Compound decalcifying agent provided by the invention makes the effect that has produced synergy between each component owing to adopted special formula.Component (A) generates hydrophilic ionic complex by Ca, Mg in PRECIPITATION MECHANISM and the oil, and component (B) combines with ionic complex by chelating mechanism and generates water-soluble inner complex, thereby the decreasing ratio of Ca, Mg in the high Ca hydrocarbon ils is significantly improved.
Decalcification technology provided by the invention will only be annotated fresh water at secondary in the traditional technology in conjunction with the characteristics of high Ca hydrocarbon ils, and two cut water returns the notes one-level, change two-stage into and all annotate fresh water, two cut water effluxes, thereby has improved the one-level removal effect, and then makes and always take off Ca and lead corresponding raising.
In sum, adopt compound decalcifying agent provided by the invention and decalcification technology, can make Ca, Mg total content is that the decreasing ratio of the hydrocarbon ils Ca of 5 ~ 150ppm reaches 75 ~ 99%.
Fig. 1 is a decalcification process flow sheet provided by the invention.
The invention will be further described below by embodiment.
Example 1
Even this example illustrates compound decalcifying agent provided by the invention and also can reach removal effect preferably in the one-level removing process.
50ppm HPAA (Lin Hua chemical plant, Beijing product), 600ppm ammonium sulfate, 50ppmTP9603 emulsion splitter (chemical plant, ten thousand Fengshun, Tianjin product) are mixed with 6 gram distilled water, promptly obtain the decalcifying agent aqueous solution provided by the invention.This decalcifying agent aqueous solution and 60 gram huge port crude oil (are contained Ca104ppm, Mg1.4ppm) mix, place desalter, effect is 10 minutes under 95 ℃, weak electric field 500v/cm, effect is 20 minutes under highfield 1000v/cm, after the oily water separation, analyze the Ca content take off in the crude oil of back, record that to take off that Ca leads be 85.3%.
Comparative Examples 1
The tripoly phosphate sodium STPP that uses in the prior art is made into the aqueous solution of working concentration as 650ppm, mixes, carry out oily water separation, record and take off Ca and lead 33.7% according to the method for example 1 and 60 gram crude oil.
Table 2
| | 2 | 3 | 4 | 5 | 6 |
| Decalcifying agent and dosage, ppm | Sodium sulfate, 210 LA, 20 | Monoammonium sulfate, 170 LB, 25 | Monoammonium sulfate, the ammonium salt of 250 PBTC, 40 | Vitriolate of tartar, the sodium salt of 200 HPAA, 100 | Ammonium sulfate, the sylvite of 500 LC, 25 |
| Crude oil Ca before taking off, ppm Mg, ppm | 42 1.8 | 64 0.9 | 93 1.2 | 67 5.6 | 104 1.4 |
| Take off back crude oil Ca, ppm Mg, ppm | 3.8 0.2 | 2.3 0 | 6.2 0.3 | 0.8 0.2 | 3.5 0.7 |
| Take off Ca and lead, % | 90.5 | 96.4 | 87.8 | 98.8 | 96.1 |
| Take off Mg and lead, % | 89.7 | 100 | 75.5 | 96.4 | 50.4 |
Annotate: LA is diethylenetriamine tetramethyl fork phosphonic acids one hydroxypropyl sulfonic acid
LB is quadrol three methenes phosphonic acids-hydroxypropyl sulfonic acid
LC is quadrol two methene phosphonic acids dihydroxypropyl sulfonic acid
Example 2 ~ 6
Test conditions according to example 1 handles twice continuously, promptly changes the two-stage demetal process into, and two-stage is all annotated fresh water, every grade of water filling 6%, and decalcifying agent is identical at the dosage of each grade, and emulsion splitter is TP9603, dosage 50ppm, test-results sees Table 2.Selected phosphono and sulfonic is the product of Henan three cyclisation factories.
Example 7
This example is commerical test.A year treatment capacity be to carry out on 1,500,000 tons the electric desalting apparatus, compound decalcifying agent is made in advance 20% the aqueous solution, inject water, water injection rate is every grade 5.5%, the fresh water that contains decalcifying agent be divided into two-way respectively with take off before crude oil and one take off crude oil and mix by the static mixing valve, mixing valve pressure drop 0.05Mpa, emulsification times 0.8s enters the firsts and seconds desalter then respectively.The compound decalcifying agent of selecting for use is identical with example 6 with crude oil.Back crude oil is taken off in analysis, records and takes off Ca and lead 78%, takes off Mg and leads 82%.
Comparative Examples 2
On the device of example 7, handle identical crude oil with identical compound decalcifying agent, different is that the fresh water that contains decalcifying agent only injects the secondary desalter by the static mixing valve, and the back water that takes off after the oily water separation of secondary desalter returns the notes one-level again, as single stage desalting jar water.Back crude oil is taken off in analysis, records and takes off Ca and lead 48.7%, takes off Mg and leads 76%.
Claims (10)
1. compound decalcifying agent that is used for hydrocarbon ils is characterized in that comprising following component:
(A) soluble sulphate or its mixture of 1～12 times of Ca in the hydrocarbon ils, Mg total content;
What (B) account for hydrocarbon ils 1～1000ppm is selected from organic phosphine carboxylic acid, organic phosphine sulfonic or its soluble salt
One of compound or two or more mixture wherein;
(C) emulsion splitter.
2. according to the described decalcifying agent of claim 1, it is characterized in that said component (A) is selected from one of vitriolate of tartar, sodium sulfate, ammonium sulfate or its mixture.
3. according to the described decalcifying agent of claim 1, the content that it is characterized in that said component (A) is Ca in the hydrocarbon ils, Mg total content 1～8 times.
4. according to the described decalcifying agent of claim 1, it is characterized in that said organic phosphine carboxylic acid is that the hydrogen on one or more carbon atoms is replaced the compound that the back forms by one or more phosphonate groups in unit carboxylic acid or the polycarboxylic acid molecule.
5. according to claim 1 or 4 described decalcifying agents, it is characterized in that said organic phosphine carboxylic acid is selected from hydroxyl phosphino-acetate, 2-phosphono-containing butane-1,2,4 tricarboxylic acid, 1-phosphono-containing butane-1,2,4 tricarboxylic acid, 1,3, one of 3-triphosphine acidic group valeric acid or its mixture.
6. according to the described decalcifying agent of claim 1, it is characterized in that said organic phosphine sulfonic is that the hydrogen on the nitrogen-atoms is replaced the compound that the back forms by hydroxypropyl sulfonic acid and methyl-phosphorous acid respectively in the polyamines.
7. according to claim 1 or 6 described decalcifying agents, it is characterized in that said organic phosphine sulfonic is selected from one of quadrol three methenes phosphonic acids-hydroxypropyl sulfonic acid, quadrol two methene phosphonic acids dihydroxypropyl sulfonic acid, diethylenetriamine tetramethyl fork phosphonic acids-hydroxypropyl sulfonic acid, diethylenetriamine three methene phosphonic acids dihydroxypropyl sulfonic acid, diethylenetriamine two methene phosphonic acids three hydroxypropyl sulfonic acid or its mixture.
8. according to the described decalcifying agent of claim 1, the content that it is characterized in that said component (B) is for accounting for hydrocarbon ils 5～500ppm.
9. according to claim 1 or 8 described decalcifying agents, the content that it is characterized in that said component (B) is for accounting for hydrocarbon ils 10～250ppm.
10. hydrocarbon oil decalcifying technology, be on the two-stage electric desalting apparatus, to carry out, it is characterized in that described compound decalcifying agent of claim 1 and fresh water are mixed, inject the firsts and seconds desalting plant respectively, hydrocarbon ils is injected the single stage desalting device, and the water of separating from the single stage desalting device effluxes, and the hydrocarbon ils of separating reinjects in the secondary desalting plant, after the oily water separation, will take off back hydrocarbon ils and two and cut water and from the secondary desalting plant, discharge respectively.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98117505A CN1078234C (en) | 1998-08-18 | 1998-08-18 | Compound decalcifying agent for hydrocarbon oil and its application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98117505A CN1078234C (en) | 1998-08-18 | 1998-08-18 | Compound decalcifying agent for hydrocarbon oil and its application |
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| Publication Number | Publication Date |
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| CN1245201A CN1245201A (en) | 2000-02-23 |
| CN1078234C true CN1078234C (en) | 2002-01-23 |
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| CN98117505A Expired - Lifetime CN1078234C (en) | 1998-08-18 | 1998-08-18 | Compound decalcifying agent for hydrocarbon oil and its application |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004106464A1 (en) * | 2003-06-03 | 2004-12-09 | Karamay Jinshan Petrochemical Limited Company | A demetalizing agent for hydrocarbon oil and its preparation and use |
| US9375004B2 (en) | 2010-11-15 | 2016-06-28 | Bayer Intellectual Property Gmbh | 5-halogenopyrazolecarboxamides |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1318544C (en) * | 2004-02-18 | 2007-05-30 | 中国石油化工股份有限公司<Del/> | Treating agent for removing metal calcium from crude oil |
| CN102260524B (en) * | 2010-05-24 | 2013-11-06 | 中国石油天然气股份有限公司 | Chemical precipitation method for removing calcium from crude oil |
| CN102876352B (en) * | 2012-09-27 | 2014-06-18 | 岳阳宇翔科技有限公司 | Composite additive for reducing metal ion content of vacuum residues and application of composite additive |
| CN107216910B (en) * | 2017-07-13 | 2019-08-23 | 深圳市广昌达石油添加剂有限公司 | A kind of crude oil load decalcifying agent, crude oil decalcifying device and its application method |
| CN112195038A (en) * | 2020-11-03 | 2021-01-08 | 四川润和催化新材料股份有限公司 | Crude oil treating agent and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1054261A (en) * | 1991-02-06 | 1991-09-04 | 中国石油化工总公司 | From hydrocarbon feed, remove metal with recombiner |
| CN1055552A (en) * | 1990-04-04 | 1991-10-23 | 切夫里昂研究公司 | Remove metal in the hydrocarbon feed with the salt of sulfuric acid and it |
-
1998
- 1998-08-18 CN CN98117505A patent/CN1078234C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1055552A (en) * | 1990-04-04 | 1991-10-23 | 切夫里昂研究公司 | Remove metal in the hydrocarbon feed with the salt of sulfuric acid and it |
| CN1054261A (en) * | 1991-02-06 | 1991-09-04 | 中国石油化工总公司 | From hydrocarbon feed, remove metal with recombiner |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004106464A1 (en) * | 2003-06-03 | 2004-12-09 | Karamay Jinshan Petrochemical Limited Company | A demetalizing agent for hydrocarbon oil and its preparation and use |
| US9375004B2 (en) | 2010-11-15 | 2016-06-28 | Bayer Intellectual Property Gmbh | 5-halogenopyrazolecarboxamides |
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| CN1245201A (en) | 2000-02-23 |
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