MXPA99003005A - Removal of calcium from crudes - Google Patents
Removal of calcium from crudesInfo
- Publication number
- MXPA99003005A MXPA99003005A MXPA/A/1999/003005A MX9903005A MXPA99003005A MX PA99003005 A MXPA99003005 A MX PA99003005A MX 9903005 A MX9903005 A MX 9903005A MX PA99003005 A MXPA99003005 A MX PA99003005A
- Authority
- MX
- Mexico
- Prior art keywords
- metal
- resin
- charged metal
- crude
- feed stream
- Prior art date
Links
- 239000011575 calcium Substances 0.000 title claims abstract description 17
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 229920005989 resin Polymers 0.000 claims abstract description 15
- 239000011347 resin Substances 0.000 claims abstract description 15
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 6
- ZVAYUUUQOCPZCZ-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)aniline Chemical group CCOP(=O)(OCC)CC1=CC=C(N)C=C1 ZVAYUUUQOCPZCZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003208 petroleum Substances 0.000 claims abstract description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 3
- 229920001577 copolymer Polymers 0.000 claims description 10
- 238000005119 centrifugation Methods 0.000 claims description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N divinylbenzene Substances C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 4
- 125000005609 naphthenate group Chemical group 0.000 claims description 3
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000001805 chlorine compounds Chemical class 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical group OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 2
- 150000004707 phenolate Chemical class 0.000 claims description 2
- 229920001888 polyacrylic acid Polymers 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 150000002739 metals Chemical class 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 5
- 229920001429 Chelating resin Polymers 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 231100000614 Poison Toxicity 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
Abstract
The present invention is a process to remove a +2 ionic charged metal from a petroleum feed. The process includes contacting the feed with a resin that includes carboxyl, sulfonic and/or phosphonic groups. In a preferred embodiment the metal is a Group II metal. In particular, the metal is calcium.
Description
ELIMINATION OF CALCIUM FROM RAWS
BACKGROUND OF THE INVENTION The present invention relates to a process for removing certain crude petroleum metals. In particular, the metal is calcium. The calcium present in the crudes can cause scaling in the heaters and heat exchangers and poison of the catalysts used in the processing of the crudes. Therefore, the rich ones in Ca are less valuable than the crude ones with little Ca. A process to eliminate Ca allows to increase the value of these crude oils. This invention is particularly valuable when a Ca-rich crude is processed in a corrosion-resistant medium, where the increase in acidity that accompanies the process of the present invention is not a drawback.
SUMMARY OF THE INVENTION The present invention is a process for removing a metal with 2+ ionic charge from a petroleum feed stream. The process includes contacting the feed stream with a resin that includes carboxyl, sulfonic and / or phosphonic groups. In a preferred embodiment, the metal is a group II metal. In particular, the metal is calcium.
DESCRIPTION OF THE PREFERRED MODALITY The present invention is a process for removing metals with 2+ ionic charge from a petroleum feed stream. The metals include Ca, Mg, Mn and Zn. Calcium is particularly important. The process includes contacting the feed stream with a resin that includes carboxyl, sulfonic, and / or phosphonic groups. These metals can be in various forms, including naphthenates, phenolates, chlorides or sulfates. The resins may contain carboxyl, sulphonic or phosphonic groups. Preferably, the resins are crosslinked, therefore not soluble in the crude. Suitable resins are styrene-divinylbenzene sulfonated copolymers, methacrylic-divinylbenzene copolymers, polyacrylic acid, polyvinylsulfonic acid, phosphorylated styrene-divinylbenzene copolymers, polymethacrylic acid and styrene-divinylbenzene copolymers with linked iminodiacetic acid groups. The resin may be in the form of a bed through which the crude is passed; otherwise, the resin can be suspended in the crude and separated at the end of the treatment by filtration or centrifugation. The temperature at which the treatment occurs must be sufficiently high to reduce the crude viscosity and quite low to avoid the decomposition of the resin. A temperature between 50 and 150 ° C is generally satisfactory. After use, the resins can be regenerated by acid treatment. The following examples illustrate the invention without limiting it.
Example 1 The reaction apparatus was a glass vessel equipped with stirrer and reflux condenser, immersed in an oil bath. 50 g of Kome 6/1 crude with a content of 930 ppm of Ca, 42 ppm of Mn and 2.6 ppm of Zn were placed in the reactor. 15.6 g of styrene-divinylbenzene sulfonated copolymer, known under the trade name Amberlite IR-120 and with a capacity of 1.9 milliequivalents / ml were added. The mixture was stirred at 70 ° C for 7 hours. Then the solid was separated by centrifugation and then the treated crude was analyzed by the metals. The content of Ca, Mn and Zn had dropped to 107, 4.9 and 0.9 ppm, respectively. Infrared spectroscopy showed that the band at 1708 cm, which corresponds to the carboxyl group, is more intense than in the untreated crude and the band at 1600 cm ", corresponding to naphthenate, was less intense than in the untreated crude. showed that the metals were in the form of the carboxylates and that the elimination of the metals had released the carboxylic acids.The following reaction is considered to have taken place:
Example 2 The reaction apparatus was the same as in Example 1. 50 g of Kome 6/1 crude was placed in the reactor. Then 2.15 g of a copolymer of methacrylic acid with divinylbenzene, known under the trade name Amberlite IRP-64 and with a capacity of 10 milliequivalents / g were added. The mixture was stirred at 70 ° C for 6 hours. Then the solid was separated by centrifugation and the crude was analyzed. The content of Ca, Mn and Zn had dropped to 66, 2.2 and 0.7 ppm, respectively. The following reaction is considered:
Example 3 The reaction apparatus was the same as in Example 1. 50 g of crude Kome 6/1 were placed in the apparatus. Then, 7.6 g of the sulfonated styrene-divinylbenzene copolymer, with a capacity of 3.3 milliequivalent / gram and with the trade name of Amberlyst XN 1010 were added. The mixture was stirred at 70 ° C for 7 hours. After the separation of the solids by centrifugation, the oil contained 147 ppm of Ca, 9 ppm of Mn and 0.7 ppm of Zn, that is, much less than in the untreated Kome 6/1.
Claims (12)
1. A process for removing a metal with 2+ ionic charge dissolved in the oil phase of an oil feed stream consisting of contacting the feed stream with a resin that includes a group selected from the group consisting of carboxyl, sulphonic groups and phosphonic and combinations thereof.
2. The process of claim 1, wherein the resin is crosslinked.
The process of claim 1, wherein the resin includes sulfonated styrene-divinylbenzene copolymers, ethacrylyl divinylbenzene copolymers, polyacrylic acid, polyvinylsulfonic acid, phosphorylated styrene-divinylbenzene copolymers, polymethacrylic acid, and styrene-divinylbenzene copolymers with linked iminodiacetic acid groups.
4. The process of claim 1, wherein the charged metal is a group II metal.
5. The process of claim 1, wherein the charged metal is calcium.
The process of claim 1, wherein the resin is in the form of a bed through which a petroleum feed stream is passed.
7. The process of claim 1, wherein the resin is suspended in the crude and separated at the end of the treatment by filtration or centrifugation.
8. The process of claim 1, wherein the process is carried out at a temperature between 50 ° C and 150 ° C.
9. The process of claim 1, wherein the charged metal is in the form of naphthenates.
10. The process of claim 1, wherein the charged metal is in the form of phenolates. The process of claim 1, wherein the charged metal is in the form of chlorides. The process of claim 1, wherein the charged metal is in the sulfate form.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/726015 | 1996-10-04 | ||
| US726015 | 1996-10-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| MXPA99003005A true MXPA99003005A (en) | 1999-09-01 |
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