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Method for removing calcium from crude oil

a crude oil and calcium technology, applied in the petroleum industry, hydrocarbon oil refining, etc., can solve the problems of residual product contamination, heavy damage to refinery tower trays and other equipment, and solids other than salts are equally harmful,

Inactive Publication Date: 2007-06-07
GENERAL ELECTRIC CO
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

[0015] In a more specific aspect of the invention, citric acid or its salts are used as the sequestrant, and the sequestered calcium containing complex is calcium citrate. The deposit control polymer inhibits calcium citrate scale formation in the water phase and along surfaces that contact the water phase. While calcium citrate scale control is important, the treatment should also not adversely affect desalter operation (longer water drop rates, etc.).

Problems solved by technology

Chloride salts are predominantly the source of highly corrosive HCl, which is severely damaging to refinery tower trays and other equipment.
Solids other than salts are equally harmful.
For example, sand, clay, volcanic ash, drilling muds, rust, iron sulfide, metal, and scale may be present and can cause fouling, plugging, abrasion, erosion and residual product contamination.
These materials promote fouling and can cause catalyst poisoning in subsequent refinery processes, such as catalytic cracking methods, and they may also contaminate finished products.
When the bottoms are fed, for example, to coker units, contamination of the end-product coke is most undesirable.
For example, in the production of high grade electrodes from coke, iron contamination of the coke can lead to electrode degradation and failure in processes, such as those used in the chlor-alkali industry.
Problems for the refiners associated with high calcium include exceeding metal specs for fuels oils that have resids blended in, poisoning catalysts for residual catalytic crackers, adversely affecting coke specs for metals, and contributing to crude unit fouling and delayed coker furnace fouling.
The method of Reynolds, while likely successful at the extraction of low levels of calcium (<30 ppm), has two significant drawbacks which make it impractical for use with the high calcium crudes.
One is that since the extraction process is stoichiometric, at the high levels of citric acid needed in the wash water, its pH drops significantly (to below 3) and causes a corrosion issue in the wash water circuit.
Thus, one can see that deposition of calcium citrate is an issue at typical desalter temperatures (250° F.-300° F.) and concentrations encountered when extracting higher levels of calcium with the typical 5% wash water rate.
Deposition in the brine heat exchanger and transfer piping was one of the problems that was experienced.

Method used

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  • Method for removing calcium from crude oil
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  • Method for removing calcium from crude oil

Examples

Experimental program
Comparison scheme
Effect test

example 1

[0043] In order to assess the efficacy of various candidate materials in inhibiting calcium citrate crystal formation, a solution (solution A) of 1,000 ppm (as solids) calcium chloride, and 1,000 ppm (as solids) citric acid was prepared. NaOH was added to bring the pH up to 7.1. Treated and untreated solutions were heated at 100° C. for 1-1.5 hours. Results are shown in Table 1.

TABLE 1TreatmentObservations1100 ml solution A: untreatedA lot of fine crystals precipitated on bottom(assumed 100%). The water is clear.2100 ml solution A + sulfuric acid dilutionAbout 25% (compare to the untreated)to have pH 5.1crystallize growing.The water is clear.3100 ml solution A + sulfuric acid dilutionAbout 40% (compare to the untreated)to have pH 6.1crystallize growing.The water is clear.4100 ml solution A + 50 ppm activeA lot of fine and floc precipitate.HEDP (DeQuest 2010)The water is cloudy.5100 ml solution A + 50 ppm active NTAA few (water is clear.6100 ml solution A + 50 ppm ComparativeA lot ...

example 2

[0044] Additional tests utilizing the procedure of Example 1 were conducted. Results are reported in Table 2.

TABLE 2TreatmentObservations2.1100 ml solution A: untreatedA lot of fine crystals precipitated onbottom (assumed 100%). The water isclear.2.2100 ml solution A + 10 ppm active NTAA lot of fine crystals precipitated onbottom (about 100%). The water is clear.2.3100 ml solution A + 20 ppm active NTAA lot of fine crystals precipitated onbottom (about 60%). The water is clear.2.4100 ml solution A + 30 ppm active NTALesser fine crystals precipitated onbottom (about 30%). The water is clear.2.5100 ml solution A + 40 ppm active NTAAbout 5% crystals on bottom.The water is clear.2.6100 ml solution A + 50 ppm active NTAVery few crystals on bottom.The water is clear.

example 3

[0045] Further tests utilizing the procedure of Example 1 were undertaken. Results are shown in Table 3.

TABLE 3TreatmentObservations3.1100 ml solution A: untreatedA lot of fine crystals precipitated onbottom (assumed 100%), the water isclear water. 0.0595 g crystals3.2100 ml solution A + 35 ppm active NTAAbout 5-10% crystals on bottom.The water is clear.3.3100 ml solution A + 35 ppm active EDTA-About 5-10% crystals on bottom.free acidThe water is clear.3.4100 ml solution A + 70 ppm Product AClean and clear water. No crystals.3.5100 ml solution A + 70 ppm Product BClean and clear water. No crystals.3.6100 ml solution A + 70 ppm Product PBTCAbout 5-10% crystals on bottom.The water is clear.3.7100 ml solution A + 70 ppm ProductNo crystals observed, but the water isDeQuest 2060cloudy.3.10100 ml solution A + 30 ppm Product AClean and clear water. No crystals.3.11100 ml solution A + 50 ppm Product AClean and clear water. No crystals.3.12100 ml solution A + 70 ppm Product AClean and clea...

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PUM

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Abstract

Methods for reducing calcium deposition along surfaces in contact with the water phase of a resolved water / oil emulsion are disclosed. High calcium crude oil and the like are contacted with a sequestrant to form a sequestered calcium containing complex that partitions to the water phase in the resolved emulsion. A specifically formulated polymeric deposit control agent is added to the water phase to inhibit calcium deposit formation therein and along surfaces in contact with the water phase.

Description

FIELD OF INVENTION [0001] The invention pertains to improved methods for removing calcium from a hydrocarbonaceous medium via extraction by a sequestrant. The sequestrant, when added to the hydrocarbonaceous medium, results in the formation of a calcium complex that partitions to the water phase as the hydrocarbonaceous medium is brought in contact with an aqueous wash phase. A specifically formulated deposit control agent is brought into contact with the water phase to control calcium based deposit formation. BACKGROUND OF THE INVENTION [0002] All crude oil contains impurities which contribute to corrosion, heat exchanger fouling, furnace coking, catalyst deactivation, and product degradation in refinery and other processes. These contaminants are broadly classified as salts, bottom sediment, and water (BS+W), solids, and metals. The amounts of these impurities vary, depending upon the particular crude. Generally, crude oil salt content ranges between about 3-200 pounds per 1,000 b...

Claims

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Application Information

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IPC IPC(8): C10G17/00C10G45/00
CPCC10G21/12C10G21/27C10G53/10C10G53/02C10G53/04C10G29/20C10G53/06
Inventor GOLIASZEWSKI, ALAN E.ENGEL, DAVID BIRENBAUMMAY, ROGER C.
Owner GENERAL ELECTRIC CO
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