OA16414A - Additive and method for removal of calcium from crude oils containing calcium napthenate. - Google Patents
Additive and method for removal of calcium from crude oils containing calcium napthenate. Download PDFInfo
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- OA16414A OA16414A OA1201300205 OA16414A OA 16414 A OA16414 A OA 16414A OA 1201300205 OA1201300205 OA 1201300205 OA 16414 A OA16414 A OA 16414A
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- Prior art keywords
- crude oil
- additive
- calcium
- acid
- wash water
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- 239000000654 additive Substances 0.000 title claims abstract description 98
- 239000011575 calcium Substances 0.000 title claims abstract description 97
- 239000010779 crude oil Substances 0.000 title claims abstract description 92
- 230000000996 additive Effects 0.000 title claims abstract description 70
- OYPRJOBELJOOCE-UHFFFAOYSA-N calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 66
- 239000000203 mixture Substances 0.000 claims abstract description 50
- LKVLGPGMWVYUQI-UHFFFAOYSA-L calcium;naphthalene-2-carboxylate Chemical compound [Ca+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 LKVLGPGMWVYUQI-UHFFFAOYSA-L 0.000 claims abstract description 39
- HHLFWLYXYJOTON-UHFFFAOYSA-N Glyoxylic acid Natural products OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 claims description 111
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 60
- 239000002253 acid Substances 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 21
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 18
- 229910052717 sulfur Inorganic materials 0.000 claims description 18
- 239000011593 sulfur Substances 0.000 claims description 18
- VHUUQVKOLVNVRT-UHFFFAOYSA-N ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 15
- 239000000908 ammonium hydroxide Substances 0.000 claims description 13
- 150000002830 nitrogen compounds Chemical class 0.000 claims description 13
- 150000007514 bases Chemical class 0.000 claims description 12
- 125000004432 carbon atoms Chemical group C* 0.000 claims 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 48
- BJEPYKJPYRNKOW-UHFFFAOYSA-N Malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 31
- 239000001630 malic acid Substances 0.000 description 30
- 235000011090 malic acid Nutrition 0.000 description 30
- 229940099690 malic acid Drugs 0.000 description 30
- 239000010410 layer Substances 0.000 description 26
- 238000010979 pH adjustment Methods 0.000 description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 9
- 235000012208 gluconic acid Nutrition 0.000 description 9
- 229950006191 gluconic acid Drugs 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N Maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 6
- 229940044600 Maleic Anhydride Drugs 0.000 description 5
- 229960004275 glycolic acid Drugs 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- IFQUWYZCAGRUJN-UHFFFAOYSA-N 2-[2-(carboxymethylamino)ethylamino]acetic acid Chemical compound OC(=O)CNCCNCC(O)=O IFQUWYZCAGRUJN-UHFFFAOYSA-N 0.000 description 2
- 210000002381 Plasma Anatomy 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000008186 active pharmaceutical agent Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- -1 amine compounds Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 125000001145 hydrido group Chemical group *[H] 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003068 static Effects 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Abstract
There is provided an additive and method for removal of calcium from crude oil or its blends containing calcium naphthenate at low pH as well as at high pH. Particularly, there is also provided an additive and method for removal of calcium from crude oil or its blends containing calcium naphthenate under basic or alkaline conditions and at low pH as well as at high pH varying from about 5 to 11.
Description
Title of the Invention:Additive and method for removal of calcium from crude oils containing calcium naphthenate.
Field of the Invention:5 The présent invention relates to an additive and method for removal of calcium from crude oils containing calcium naphthenate, wherein the additive is effective to remove the calcium not only at low pH but also at high pH of the wash water for the desalter used in the crude oil processing System.
In particular, the présent invention relates to an additive and method for removal of calcium from crude oils containing calcium naphthenate, wherein the additive is effective to remove the calcium under basic or alkaline conditions and having a pH varying from about 5 to 11, preferably from about 6 to 11, more preferably from about 7 to 11, even more preferably from about 9 to 11 of the wash water for the desalter used in the crude oil processing System.
Background ofthe Invention:15 The DOBA is a high acid crude oil originating from the Chad région of West Africa. The
DOBA is known to contain calcium naphthenate and the amount of calcium naphthenate varies over a range from about 150 to about 700 ppm. In a typically supplied DOBA crude oil, the amount of calcium naphthenate may vary from about 250 - about 300 ppm.
The DOBA is a heavy high acid crude oil with Total Acid Number [TAN] ranging upwards 20 of 4.0 mg KOH/gm of sample and the API gravity is about 19. The sulfur content in DOBA is very low to nil.
The DOBA is typically a crude oil with a lot of residue in it and for proper blending, typically internationally, refiners biend it with very light crude oil or condensâtes to increase the API of the resulted biend to more than 30. Such blending with light crude oil or condensâtes 25 helps to create suffirent light ends to help achieve product yields for the crude distillation unit.
The most of light crude oil or condensâtes thus selected generally have very little to nil sulfur contents, which means the overall sulfur content still remains very low. Further, the H2S being oil soluble is not présent in relatively higherquantities in these types of blends.
The inventor of présent invention has observed that if solution of calcium naphthenate in an organic solvent, for example toluène having concentration of Ca of about 2247 ppm is treated with equal weight of water by heating to about 130 degree C, that is, being equal to a crude oil having very little to nil sulfur contents or say in absence of sulfur compound in a Parr autoclave under autogenous pressure, and separated into organic and aqueous layers in a separating funnel, no black layer is formed at the interface in presence of water or say in presence of very little to nil sulfur contents, being less than 0.2%. When organic layer, as separated, was dried by evaporating toluene, its acid value was found to be very low - about 48.36 (mg KOH per gm). The low Acid Value indicates that calcium naphthenate does not * :
hydrolyze appreciably merely in presence of water or say in presence of very little to nil sulfur contents, being less than 0.2%.
The inventer of présent invention has observed that when DOBA or its blend containing calcium naphthenate with no sulfur or sulfur contents being very little [less than 0.2%] is treated with additives as known in the art, for example with glycolic acid it does not hamper removal of metals including calcium from such DOBA crude oil or its blend.
However, the inventer has experimentally found that even with very little to nil sulfur contents, the efficiency of glycolic acid to remove calcium from crude oils containing calcium naphthenate is very low, which surprisingly reduces further if the pH of the crude oil increases te about 6 or to about 11 due te presence of ammonium hydroxide or ammonia or other nitrogen compounds in wash water ter desalter.
The inventer of présent invention has also observed that when DOBA or its blend containing calcium naphthenate with no sulfur or sulfur contents being very little [less than 0.2%J is treated with additives as known in the art, for example with malic acid, it does not hamper removal of metals including calcium from such DOBA crude oil or its blend.
However, the inventer has experimentally also found that even with very little to nil sulfur contents, the efficiency of malic acid to remove calcium from crude oils containing calcium naphthenate is very low, which surprisingly reduces further if the pH of the crude oil increases to about 6 or to about 9 or to about 11 due to presence of ammonium hydroxide or ammonia or other nitrogen compounds in wash water for desalter.
Inventor’s above findings confîrm that prior art additives - glycolic acid and malic acid are effective to remove calcium from DOBA crude oil, but with very low efficiency, and this efficiency, surprisingly, reduces further if pH of the crude oil or wash water increase to about 6 or to about 9 or to about 11.
The inventer has also found that efficiency of prior art additives - maleic anhydride, citric acid, D-gluconic acid to remove calcium from DOBA crude oil is very low particularly when pH of the crude oil or wash water increase to about 6 or preferably te about 9 or te about 11.
Accordingly, the industry processing DOBA or its blends containing calcium naphthenate even with very little to nil sulfur contents faces serious problème in removing calcium from such oil or its blends at pH varying from about 6 to about 11 of the wash water for desalter.
Problem to be solved by the Invention:
Therefore, the problem to be solved by présent invention is to provide an additive and method for removal of calcium from crude oils or its blends containing calcium naphthenate, which should be effective to remove the calcium from crude oil or its blends not only at low pH but also at high pH, particularly under basic or alkaline conditions of the wash water for the desalter used in the crude oil processing System.
With above aim, the inventer has tried to solve the above described industrial problem with known additives - glycolic acid (the mono basic hydroxyl acid) and malic acid (the dibasic t
hydroxy! acid), and maleic anhydride, D-gluconic acid, and found that when solution of calcium naphthenate in toluene was treated with equal weight of water containing the additive - glycolic acid or malic acid or maleic anhydride, or or D-gluconic acid, the efficiency of these acids to remove calcium from the crude oils containing calcium naphthenate is very low, which 5 surprisingly reduces further if the pH of the crude oil (of the wash water for desalter) increases to about 6 or to about 9 or to about 11.
It is understood from the foregoing description that the prior art additives, which may be effective to remove calcium from DOBA crude oil, but with very low efficiency, and this efficiency to remove calcium reduces further if pH of the crude oil or wash water increases to about 6 or to 10 about 9 or to about 11.
Need of the Invention:
The mechanism of reduced efficiency of glycolic acid, malic acid, maleic anhydride, and D-gluconic acid to remove calcium from crude oil containing calcium naphthenate, particularly of further reduced efficiency of glycolic acid, malic acid, maleic anhydride, and D-gluconic acid to 15 remove calcium from crude oil containing calcium naphthenate under basic or alkaline conditions of wash water for desalter and at pH varying from about 5 to about 11, preferably from about 6 to 11, more preferably from about 7 to 11, even more preferably from about 9 to 11 could not be visualized at présent. However, the problem to remove calcium from crude oil or its blends containing calcium naohthenate under basic or alkaline conditions of the wash water of 20 desalter still remains unresolved.
Therefore, there is a need to hâve an additive and method for removal of calcium from crude oils or its blends containing calcium naphthenate which is effective in removing the calcium under basic or alkaline conditions of wash water for desalter and at a pH varying from about 5 to about 11, preferably from about 6 to 11, more preferably from about 7 to 11, even 25 more preferably from about 9 to 11 of the wash water for the desalter used in the crude oil processing System.
Objects and Advantages of the Invention:Accordingly, the main object of the présent invention is to provide an additive and method of its use which is effective for removal of calcium from crude oils or its blends 30 containing calcium naphthenate not only at low pH but also at high pH of the wash water for the desalter used in the crude oil processing System.
In particular, the main object of the présent invention is to provide an additive and method of its use which is effective for removal of calcium from crude oils or its blends containing calcium naphthenate under basic or alkaline conditions of wash water for desalter 35 and at a pH varying from about 5 to about 11.
In another particular embodiment, the object of the présent invention is to provide an additive and method of its use which is effective for removal of calcium from crude oils or its blends containing calcium naphthenate under basic or alkaline conditions of wash water for
I *<
r desalter, which may be due to presence of a compound selected from the group comprising ammonium hydroxide, ammonia, nitrogen compounds, basic compounds and alkaline compounds and at a pH varying from about 5 to about 11, preferabiy from about 6 to 11, more preferabiy from about 7 to 11, even more preferabiy from about 9 to 11.
Other objects and advantages of the présent invention will become more apparent when the foilowing description is read in conjunction with foilowing examples and accompanying figures, which are not intended to limit the scope of présent invention.
Description and Preferred Embodiments of the Inventîon:With aim to solve above-described industrial problem of the prior art, the inventor of présent invention has found that when glyoxylic acid is employed as an additive in processing of crude oils or its blends containing calcium naphthenate in presence of water, it not only removes the calcium from the crude oil or its blends at low pH, but, surprisingly and effectively, it also removes calcium from the crude oil or its blends at high pH of about 6 to about 11, partîcularly of pH of about 7 to about 11, more partîcularly of pH of about 9 to about 11 of the wash water for the desalter used in the crude oil processing System, and that's too without causing any problem.
Accordingly, the présent invention relates to an additive for removing calcium from crude oil or its blends containing calcium naphthenate at low pH as well as at high pH, wherein the additive is glyoxylic acid.
In another embodiment, the présent invention relates to a method for removing calcium from crude oil or its blends containing calcium naphthenate at low pH as well as at high pH, wherein the additive added to crude oil or its blend or the wash water for the desalter is glyoxylic acid.
In yet another embodiment, the présent invention relates to use of glyoxylic acid for removal of calcium from crude oil or its blends containing calcium naphthenate at low pH as well as at high pH.
In accordance with one of the embodiments of the présent invention, the glyoxylic acid may be added to or mixed with crude oil or its blend or the wash water for the desalter.
It may be noted that the inventor has partîcularly found that even with very little to nil sulfur contents, the efficiency of additives known in the prior art to remove calcium from crude oils containing calcium naphthenate is very low, which surprisingly reduces further if the pH of the crude oil increases upto about 7 or upto about 9 or upto about 11 due to basic or alkaline conditions, which may be due to the presence of a compound selected from the group comprising ammonium hydroxide, ammonia, nitrogen compounds, basic compounds and alkaline compounds in wash water for desalter.
With aim to solve above industrial problem of the prior art, the inventor of présent invention has found that when glyoxylic acid is employed as an additive in processing of crude oils or its blends containing calcium naphthenate in presence of water and under basic or f
alkaline conditions, which may be due to the presence of a compound selected from the group comprising ammonium hydroxîde, ammonia, nitrogen compounds, basic compounds and alkaline compounds in wash water for desalter, it, surprisingly and unexpectedly, removes the calcium from the crude oil or its blends even if the pH of the crude oil processing mixture has 5 increased upto about 7 or upto about 9 or upto about 11 under basic or alkaline conditions, which may be due to the presence of ammonium hydroxîde, ammonia, nitrogen compounds, basic compounds and alkaline compounds in wash water for desalter, and that's too without causing any problem.
Accordingly, in preferred embodiment, the présent invention relates to an additive for 10 removing calcium from crude oil or its blends containing calcium naphthenate under basic or alkaline conditions and having a pH varying from about 5 to 11, wherein the additive is glyoxylic acid.
In accordance with one of the preferred embodiments of the présent invention, the basic or alkaline conditions of crude processing System (crude oil or its blends or wash water) are due 15 to presence of one or more compounds selected from the group comprising ammonium hydroxîde, ammonia, nitrogen compounds, basic compounds and alkaline compounds.
In accordance with one of the preferred embodiments of the présent invention, the pH varies from about 6 to about 11.
In accordance with one of the preferred embodiments of the présent invention, the pH 20 more particularly varies from about 7 to about 11.
In accordance with one of the preferred embodiments of the présent invention, the pH even more particularly varies from about 9 to about 11.
In accordance with one of the preferred embodiments of the présent invention, the pH referred is of wash water for desalter used in the crude oil processing System.
In another embodiment, the présent invention also relates to a method for removing calcium from crude oil or its blends containing calcium naphthenate under basic or alkaline conditions and having a pH varying from about 5 to 11, wherein the additive added to crude oil or its blend or wash water for the desalter is glyoxylic acid.
In accordance with one of the preferred embodiments of the présent invention, the basic or alkaline conditions of crude processing System (crude oil or its blends or wash water) are due to presence of one or more compounds selected from the group comprising ammonium hydroxîde, ammonia, nitrogen compounds, basic compounds and alkaline compounds.
In accordance with one of the preferred embodiments of the présent invention, the pH varies from about 6 to about 11.
In accordance with one of the preferred embodiments of the présent invention, the pH more particularly varies from about 7 to about 11.
In accordance with one of the preferred embodiments of the présent invention, the pH even more particularly varies from about 9 to about 11.
I
In accordance with one of the preferred embodiments of the présent invention, the pH referred is of wash water for desalter used in the crude oil processing System,
In accordance with one of the preferred embodiments of the présent invention, the additive is added in the crude oil phase or wash water for the desalter.
In yet another embodiment, the présent invention also relates to use of glyoxylic acid for removal of calcium from crude oil or its blends containing calcium naphthenate under basic or alkaline conditions and having a pH varying from about 5 to 11.
In accordance with one of the preferred embodiments of the présent invention, the basic or alkaline conditions of crude processing System (crude oil or its blends or wash water) are due 10 to presence of one or more compounds selected from the group comprising ammonium hydroxide, ammonia, nitrogen compounds, basic compounds and alkaline compounds.
In accordance with one of the preferred embodiments of the présent invention, the pH varies from about 6 to about 11.
In accordance with one of the preferred embodiments of the présent invention, the pH 15 more particularly varies from about 7 to about 11.
In accordance with one of the preferred embodiments of the présent invention, the pH even more particularly varies from about 9 to about 11.
In accordance with one of the preferred embodiments of the présent invention, the pH referred is of wash water for desalter used in the crude oil processing System.
In accordance with one of the preferred embodiments of the présent invention, the additive is added in the crude oil phase or wash water for the desalter.
In accordance with one of the preferred embodiments of the présent invention, the glyoxylic acid is identifiable by cas no. 298-12-4.
In accordance with one of the preferred embodiments of the présent invention, the glyoxylic acid is taken in an amount varying from about 1:1 to 1:3 mole ratio of calcium to giyoxylic acid.
In accordance with one of the preferred embodiments of the présent invention, the glyoxylic acid is taken in an amount varying from about about 1 to about 2000 ppm in the crude oil or its blends or wash water for desalter.
The inventer has found that even small amount of one or more compounds selected from the group comprising ammonium hydroxide, ammonia, nitrogen compounds, basic compounds and alkaline compounds varying upto about 500 ppm in-activates other acids, but, surprisingly and unexpectedly, does not in-activate (deactivate) effects of glyoxylic acid (présent additive).
Accordingly, in accordance with one of the more preferred embodiments of the présent invention, the présent invention is more particularly applicable under following conditions:-
a) basic or alkaline conditions of wash water;
b) at pH of wash water, which is preferably 6 or more, more preferably 9 or more;
* <
c) at pH of mixture in desalter, which is 6 or more, preferably between about 6 to about 9;
d) at pH of wash water or desalter System, which may vary from about 6 to about 11 due to basic or alkaline conditions.
It may be noted that basic or alkaline conditions may be achieved by one or more of the compounds selected from a group comprising ammonia, ammonium hydroxide, nitrogen compounds, amine compounds, basic compounds and alkaline compounds.
It may also be noted that treatment of crude oil or wash water for removal of calcium can be carried out by any known method.
In accordance with one of the embodiments of the présent invention, the treatment is carried out as described in the following examples a reference to which is drawn herein for the purpose of describing and claiming the method for removal of calcium from the crude oil containing calcium naphthenate under basic or alkaline conditions.
In accordance with one of the embodiments of the présent invention, the treatment for the purpose of describing and claiming the method for removal of calcium from the crude oil containing calcium naphthenate is carried out by heating the reacting mixture to about 130°C.
The présent invention is now explained with the help of following experimental studîes conducted by the inventor, which hâve been incorporated for explaining its best mode and are not intended to limit its scope.
Examples of the Invention:In following experimental studîes, each additive - glyoxylic acid (additive of présent invention), glycolic acid, malic acid, maleic anhydride, and D-gluconic acid (additives of prior art) was individually charged with calcium napthenate (Ca-naphthenate) solution in toluene into a stainless steel autoclave and reacted at 130°C.
In accordance with one of the embodiments, the solution of Ca-Napthenate was prepared in toluene followed by addition of selected additive and ultra pure water [demineralized (DM) water] without pH adjustment (for présent additive, and prior art additives - glycolic acid, malic acid) and with pH adjustment (for présent additive, and prior art additives - glycolic acid, malic acid, maleic anhydride, and D-gluconic acid). The individual resulted solutions were heated to 130°C for 10, 20 and 30 mins followed by cooling to room température. The individual resulted reacted solution was poured into a separatîng funnel and shaken. The two separated layers were formed with top layer being the hydro carbonaceous layer and the bottom iayer being the aqueous layer. The top layer was analyzed for Ca content using Inductive Coupled Plasma [ICP], and the dried sample from top layer was also analyzed for its Acid Value.
As per preferred method of experimental studîes, about 75 grams of Ca-naphthenate in toluene having an amount of Ca of 2247 ppm in the hydrocarbon layer, and about 75 grams of DM water having amount of selected additive as per Table - I, II, III and IV, wherein amount of selected additive is expressed in its 100% active form were reacted for 10, 20 and 30 mins.
In case of Experiment Nos. 4-8 [Table II], 9-11 [Table III] and 12-14 [Table IV] the pH of solution of additive in DM water was adjusted to pH 9 by using ammonium hydroxide.
The results for experiments without pH adjustment are gîven Table - I for 10 min treatment, and for experiments after pH adjustment to pH 9 are given in Table - Il for 10 min 5 treatment, in Table - III for 20 min treatment, and Table - IV for 30 min treatment.
As efficiency of présent additive in removing Ca was more than 99%, further experiments for treatment for 20 and 30 minutes were not performed without pH adjustment.
Experiment Nos. 1, 2, and 3 without pH adjustment [Table -1]:10
The pH of water used for extraction after adding selected additive without pH adjustment was found to be as follows:pH of Glyoxylic Acid was found to be 2.17;
pH of Glycolic Acid was found to be 2.52; and pH of Malic Acid was found to be 2.3.
Table -1
| Expt. no. | Additive | Wt. of additive (gm) | Acid Value (mgKOH/gm) | Ca in Top layer (ppm) | % Efficiency for removal of Ca |
| 1 | Glyoxylic Acid [Présent invention] | 0.62 | 213.40 | 9 | 99.6 |
| 2 | Glycolic Acid \prior art] | 0.64 | 165 | 465 | 79.3 |
| 3 | Malic Acid \prior art] | 0.5645 | 174 | 368 | 83.6 |
Experiment Nos. 4, 5, 6, 7 and 8 after 10 mins treatment and pH adjustment to pH 9 [Table
- II]:Table - Il
| Expt. no. | Additive | Wt. of additive (gm) | Acid Value (mgKOH/gm ) | Ca in Top layer (PPm) | % Efficiency for removal of Ca |
| 4 | Glyoxylic Acid [Présent | 0.62 | 121.06 | 867 | 61.4 |
Μ ί
| invention] | |||||
| 5 | Glycolic Acid [prior art] | 0.64 | 94.36 | 1481 | 34 |
| 6 | Malic Acid [prior art] | 0.5645 | 101.93 | 1291 | 42.5 |
| 7 | Maleic anhydride [prior art] | 0.413 | 66.8 | 1691 | 24.7 |
| 8 | D-Gluconic acid [prior art] | 1.65 | 111.5 | 1315 | 41.5 |
Experiment Nos. 9, 10 and 11 after 20 mins treatment and pH adjustment to pH 9 [Table -
III]:-
Table - III
| Expt. no. | Additive | Wt.of additive (gm) | Acid Value (mgKOH/gm ) | Ca in Top layer (ppm) | % Efficiency for removal of Ca |
| 9 | Glyoxylic Acid [Présent invention] | 0.62 | 137.42 | 644 | 71.3 |
| 10 | Glycolic Acid [prior art] | 0.64 | 96.43 | 1467 | 34.7 |
| 11 | Malic Acid [prior art] | 0.5645 | 105.19 | 1261 | 46.86 |
Experiment Nos. 12, 13 and 14 after 30 mins treatment and pH adjustment to pH 9 [Table — IV]:10
Table - IV
| Expt. no. | Additive | Wt. of additive (gm) | Acid Value (mgKOH/gm ) | Ca in Top layer (PPm) | % Efficiency for removal of Ca |
| 12 | Glyoxylic Acid [Présent invention] | 0.62 | 151.92 | 562 | 75 |
| 13 | Glycolic Acid | 0.64 | 101.34 | 1429 | 36.5 |
w
I
| [prior art] | |||||
| 14 | Malte Acid [prior art] | 0.5645 | 108.76 | 1219 | 45.7 |
From above Tables, it can be observed and conciuded that the Ca content in the top layer is, surprisingly and unexpectedly, much lower for the layer obtained after treatment with additive of présent invention as compared to the top layers obtained after treatment with prior art additives.
The Acid Value of the dried sample obtained from the top layer after treatment with additive of présent invention is higher than that of the dried samples obtained from the top layers after treatment with additives of prior art.
The above experiments confirm that additive of présent invention has much better efficiency to remove Ca from crude oil (or its blends) containing Ca-naphthenate not only at low pH of about 2.17 just after treatment of 10 mins., but it also has much better efficiency to remove Ca from crude oil (or its blends) containing Ca-naphthenate even at high pH of about 9 after treatment of about 10, 20 and 30 mins.
Therefore, from above experimental studies, it can be conciuded that glyoxylic acid of présent invention is better additive than prior art additives, as the calcium removing efficiency of glyoxylic acid, surprisingly and unexpectedly, even at low pH, just after 10 minutes of treatment, is more than 99% as compared to 79.3% and 83.6% for glycolic and malic acid respectively [re Table - I];
even at high pH of about 9 and under alkaline conditions, after 10 minutes of treatment, is more than 60% as compared to 34%, 42.5%, 24.7%, and 41.5% for glycolic acid, malic acid, maleic anhydride, and D-Gluconic acid respectively [re Table - II];
even at high pH of about 9 and under alkaline conditions, after 20 minutes of treatment, is more than 70% as compared to 34.7% and 46.86% for glycolic and malic acid respectively [re Table-III]; and even at high pH of about 9 and under alkaline conditions, after 30 mins of treatment, is about 75% as compared to 36.5% and 45.7% for glycolic and malic acid respectively [re Table -
IV] ·
Experiment Nos. 15,16 and 17 after 10 mins treatment and pH adjustment to 10.4 [Table -
V] >
In another set of experiments [Examples 15, 16 and 17 - re Table V], 650ml of crude oil containing calcium Naphthanate (with calcium content of about 400 ppm) was tested after mixing in 73ml of wash water having 100 ppm of ammonia and pH of 10.4. The ratio of crude oil to water was maintained at about 90 to 10. The mixing was carried out in a high speed blender for 30 seconds. The mixture was then poured into the EDDA tubes (Electro static Desalting Déhydration Apparatus, supplied by Inter AV, USA) to just about 100 ml mark, and a calcium removing agent - glycolic acid and dl malic acid (prior art additives), glyoxylic acid (présent 5 invention additive), demulsifier (about 30 ppm) were was added individually in a tube. With every test, a blank test without the calcium removing agent was conducted for comparison purposes. The tubes with respective calcium removing agent were placed in the EDDA heating block at the desired test température of 130° C. The tubes were then capped with electrode caps and placed in the heating block for approximately ten minutes. The tubes were shaken for 10 2 minutes and placed back in the heating block to reheat for ten minutes. The electrode cover was then placed over the tubes and locked into place. The 3000 volts voltage was applied for eight minutes. At the end of eight minutes, the tubes were taken out for measuring the amount of water, which is the percent water drop. The calcium content of the crude phase was measured after 10 minutes using ICP (Inductive coupled plasma) in each tube, and results are 15 given in Table V.
Table V
| Expt. no. | Additive | Wt. of additive (gm) | Ca in Top layer (ppm) |
| 15 | Glyoxylic Acid [Présent invention] | 0.115 | 5 |
| 16 | Glycolic Acid [prior art] | 0.119 | 51 |
| 17 | Malic Acid [prior art] | 0.105 | 45 |
The calcium content of the crude phase of the blank run was 274 ppm.
Thus, from Table V, it can be concluded that glyoxylic acid of présent invention is far better additive than prior art additives for calcium removing even at high pH of about 10.4 and under alkaline conditions, as can be seen from the calcium content of the top layer, which is surprisingly and unexpectedly, as low as 5 ppm as compared to 51 ppm and 45 ppm for glycolic and malic acid respectively. Therefore, it can also be concluded from Table V that Glyoxylic acid removes calcium from the crude phase at much faster rate and more effectively than prior art additives at high pH and under alkaline conditions.
As performance of présent additive for 10 minutes interval was far better / superior than prior art additives, further experiments were not required for higher time intervals, and hence, were not carried out.
>
t
In another set of Experiment Nos. 18-20, 21-23 and 24-26, the pH of solution of additive in DM water was adjusted to pH 6 by using ammonium hydroxide, which can also be compared with findings on without pH adjustment.
The results for experiments after pH adjustment to pH 6 are given in Table - VI for 10 5 min treatment, in Table - VII for 20 min treatment, and Table - VIII for 30 min treatment.
Experiment Nos. 18 to 20 after 10 mins treatment and pH adjustment to pH 6 [Table - VI]:Table - VI
| Expt. no. | Additive | Wt. of additive (gæ) | Acid Value (mgKOH/gm ) | Ca in Top layer (ppm) | % Efficiency for removal of Ca |
| 18 | Glyoxylic Acid [Présent invention] | 0.62 | 137.2 | 720 | 67.9 |
| 19 | Glycolîc Acid (prior art] | 0.64 | 96.5 | 1213 | 46 |
| 20 | Malic Acid [prior art] | 0.5645 | 109.0 | 1255 | 44.1 |
Experiment Nos. 21 to 23 after 20 mins treatment and pH adjustment to pH 6 [Table VII]:15 Table-VII
| Expt. no. | Additive | Wt. of additive (gm) | Acid Value (mgKOH/gm ) | Ca in Top layer (PPm) | % Efficiency for removal of Ca |
| 21 | Glyoxylic Acid [Présent invention) | 0.62 | 158.1 | 490 | 78.2 |
| 22 | Glycolîc Acid [prior art] | 0.64 | 98.0 | 1202 | 46.5 |
| 23 | Malic Acid [prior art] | 0.5645 | 111.0 | 1205 | 46.4 |
V' t
Experiment Nos. 24 to 26 after 30 mins treatment and pH adjustment to pH 6 [Table VIII]:Table-VIII
| Expt. no. | Additive | Wt. of additive (gm) | Acid Value (mgKOH/gm ) | Ca in Top layer (ppm) | % Efficiency for removal of Ca |
| 24 | Glyoxylic Acid [Présent invention] | 0.62 | 174 | 427 | 81.0 |
| 25 | Glycolic Acid [prior art] | 0.64 | 105.5 | 1195 | 46.8 |
| 26 | Malic Acid [prior art] | 0.5645 | 113.2 | 1170 | 47.9 |
Therefore, from above experimental studies too, it can be concluded that glyoxylic acid of présent invention is far better additive than prior art additives, as the calcium removîng efficiency of glyoxylic acid, surprisingly and unexpectedly, even at pH of 6 and under alkaline conditions, after 10 minutes of treatment, is about 10 67.9% as compared to 46% and 44.1 % for glycolic and malic acid respectively [re Table - VI];
even at pH of 6 and under alkaline conditions, after 20 minutes of treatment, is about 78.2% as compared to 46.5% and 46.4% for glycolic and malic acid respectively [re Table - VII]; and even at pH of 6 and under alkaline conditions, after 30 mins of treatment, is about 81% 15 as compared to 46.8% and 47.9% for glycolic and malic acid respectively [re Table - VIII],
Experiment Nos. 27 to 29 after 10 mins treatment and pH adjustment to pH 6 with crude [Table-IX]:20 In another set of experiments, crude containing calcium naphthenate dissolved in an equal weight of toluene to hâve concentration of Ca of about 24 ppm was treated with aqueous solution of additives (1:1) by heating to about 130 degree C in a Parr autoclave under autogenous pressure for 10 minutes and separated into organic and aqueous layers in a separating funnel. The bottom aqueous layer was analyzed for calcium content by Ion chromatography, and results are given in Table IX.
Table - IX:
| Expt. | Additive | Wt. of | Ca in Bottom | % Efficiency for |
» Ί' t
| no. | additive (gm) | layer (ppm) | removal of Ca | |
| 27 | Glyoxylic Acid [Présent invention] | 0.00665 | 16.05 | 66.9 |
| 28 | Glycolic Acid [prior art] | 0.00684 | 12.4 | 51.6 |
| 29 | Malic Acid [prior art] | 0.00600 | 11.2 | 46.7 |
From Table IX, it can be concluded that glyoxylic acid of présent invention is better additive than prior art additives, because its calcium removing efficiency from the crude, surprisingly and unexpectedly, is better than prior art additives. It may be noted that just after 10 5 minutes of treatment, efficiency of glyoxylic acid to remove calcium is about 66.9% as compared to 51.6% and 46.7% for glycolic and malic acid respectively [re Table - IX],
When the experimental results of Tables I, II, III and IV are compiled in one Table, it can be observed that under basic or alkaline conditions and at high pH of about 9, the efficiency to remove Ca is reduced for ail the additives, however, the réduction in efficiency of glyoxylic acid 10 is much lower than prior art additives. Further, with increase in treatment time, the efficiency only of glyoxylic acid increases to about 75% in 30 mins treatment confirming that glyoxylic acid is capable of overcoming above-described problems of the prior art. The mechanism for such surprising and unexpected behavior is not know at présent, however, it can be concluded that glyoxylic acid is far better than additives of prior art [Re Table X].
Table X
Experimental Results at pH 9
| % Efficiency for removal of Ca without adjustîng pH | % Efficiency for removal of Ca after adjustîng pH to 9 by ammonium hydroxide | |||
| Additive | After 10 mins | After 20 mins | After 30 mins | |
| Glyoxylic Acid [Présent invention] | 99.6 | 61.4 | 71.3 | 75 |
| Glycolic Acid [prior art] | 79.3 | 34 | 34.2 | 36.5 |
| Malic Acid [prior art] | 83.6 | 42.5 | 46.86 | 45.7 |
t
When the experimental results of Tables I, VI, VII and VIII are compiled in one Table, it can be observed that under basic or alkaline conditions and at a low pH of about 6, the efficiency to remove Ca is reduced for all the additives, however, the réduction in efficiency of glyoxylic acid is much lower than prior art additives. Further, with increase in treatment time, the efficiency only of glyoxylic acid increases to about 81% in 30 mins treatment confirming that glyoxylic acid is capable of overcoming above-described problems of the prior art. The mechanism for such surprising and unexpected behavior is not know at présent, however, it can be concluded that glyoxylic acid is far better than additives of prior art [Re Table XI].
Table XI
Experimental Results at pH 6
| % Efficiency for removal of Ca without adjusting pH | % Efficiency for removal of Ca after adjusting pH to 6 by ammonium hydroxide | |||
| Additive | After 10 mins | After 20 mins | After 30 mins | |
| Glyoxylic Acid [Présent invention] | 99.6 | 67.9 | 78.2 | 81.0 |
| Glycolic Acid [prior art] | 79.3 | 46 | 46.5 | 46.8 |
| Malic Acid [prior art] | 83.6 | 44.1 | 46.4 | 47.9 |
The above experimental studîes clearly indicate that under basic or alkaline conditions, the calcium removal efficiency of glyoxylic acid is far superior than the prior art additives.
Accordingly, it can be concluded that glyoxylic acid is, surprisingly and unexpectedly, useful for removal of calcium from crude oil or its blends containing the calcium naphthemate even in presence of ammonia or other alkaline or basic compounds at a pH varying from about 5 to about 11, preferably from about 6 to 11, more preferably from about 7 to 11, even more preferably from about 9 to 11 with ease and economically, and therefore, the présent invention provides a solution to long awaited industrial problems in processing mixture of crude oils or its blends containing calcium naphthenate under alkaline or basic conditions.
It may be noted that term “about appearing before value or range of value is not intended to broaden scope of corresponding value or range of value, but is intended to include, within scope of présent invention, the permissible level of experimental errer in the field of the invention,
It may be noted that présent invention has been described with the help of foregoing experiments which hâve been performed on the laboratory scale. It is obvious to persons skilled > ” t in the art to modify présent invention to apply it to industrial scale without deviating from its scope, and such application of présent invention is included in its scope.
Claims (10)
1. A method for removing calcium from crude oil or its blends containing calcium naphthenate, and
i) having no sulfur or having less than 0.2% by wt. sulfur contents of the crude oil or its blend, and ii) having basic or alkalïne conditions, and iii) having a pH varying from about 6 to 11, and iv) wherein said basic or alkalïne conditions of crude oil or its blends or wash water are due to presence of one or more compounds selected from the group comprising ammonium hydroxide, ammonia, nitrogen compounds, basic compounds and alkaline compounds, and
v) wherein no acid and/or aldéhyde having 7-20 carbon atoms is added to the crude oil or the additive, and vi) wherein the additive added to crude oil or its blend or wash water for the desalter consists of glyoxylic acid.
2. A method as claimed in claim 1, wherein the pH varies from about 7 to about 11.
3. A method as claimed in claim 1 or 2, wherein the pH varies from about 9 to about 11.
4. A method as claimed in any one of the preceding claims 1 to 3, wherein the pH is of wash water for desalter used in the crude oil processing System.
5. A method as claimed in any one of the preceding claims 1 to 4, wherein the additive is added in the crude oil phase or wash water for the desalter.
6. Use of glyoxylic acid for removal of calcium from crude oil or its blends containing calcium naphthenate, and
i) having no sulfur or having less than 0.2% by wt. sulfur contents of the crude oil or its blend, and ii) having basic or alkaline conditions, and iii) having a pH varying from about 6 to 11, and iv) wherein said basic or alkaline conditions of crude oil or its blends or wash water are due to presence of one or more compounds selected from the group comprising ammonium hydroxide, ammonia, nitrogen compounds, basic compounds and alkaline compounds, and
v) wherein no acid and/or aldéhyde having 7-20 carbon atoms is added to the crude oil or the additive.
7. Use of glyoxylic acid as claimed in claim 6, wherein the pH varies from about 7 to about 11.
8. Use of glyoxylic acid as claimed in claim 6 or 7, the pH varies from about 9 to about 11.
9. Use of glyoxylic acid as claimed in any one of the preceding claims 6 to 8, the pH is of wash water for desalter used in the crude oil processing system.
10. Use of glyoxylic acid as claimed in any one of the preceding claims 6 to 9, wherein the additive is added in the crude oil phase or wash water for the desalter.
5
11. A method as claimed in any one of the preceding claims 1 to 5, wherein the glyoxylic acid is identifiable by cas no. 298-12-4,
12. A method as claimed in any one of the preceding claims 1 to 5, and 11, wherein the glyoxylic acid is taken in an amount varying from about 1:1 to 1:3 mole ratio of calcium to glyoxylic acid.
10 13. A method as claimed in any one of the preceding claims 1 to 5, and 11-12, wherein the glyoxylic acid is taken in an amount varying from about about 1 to about 2000 ppm in the crude oil or wash water for desalter.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IN3111/MUM/2010 | 2010-11-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| OA16414A true OA16414A (en) | 2015-10-07 |
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