Process for adsorption of sulfur compounds from hydrocarbon streams

a technology of hydrocarbons and sulfur compounds, applied in the field of process for adsorption of sulfur compounds from hydrocarbon streams, can solve the problems of low capacity and sorbent non-regenerability, affecting the commercial application of such process for ultradeep desulfurization of diesel fuel, and limiting the sulfur capacity of ni° phase even at high nickel dispersion of >30%, etc., to achieve the effect of increasing the loading of the nickel phosphide complex

Inactive Publication Date: 2008-05-01
EXXON RES & ENG CO
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

[0002] The present invention provides a process for removing sulfur compounds from liquid hydrocarbon streams by using a high capacity adsorbent which is a composite material containing particles of nickel phosphide complex having a Ni / P ratio ranging from about 0.5:4, preferably about 2:3 and most preferably about 2.2:2.5. The composite is preferably distributed in a phase containing silica, alumina or carbon, and obtained by reduction of composite material consisting of nickel phosphate (Ni2P2O7), nickel oxide, and / or nickel hydroxide, ammonium phosphate ((NH4)2HPO4), wherein the composite material is preferably formed by deposition of nickel and phosphorus salts onto silica, mesoporous silica, silica-alumina or carbon materials. The invention further includes using a sorbent where part of silica or carbon is removed from the said composite material after reduction increasing the loading of the nickel phosphide complex. The process for desulfurization according to this invention is preferably a one-stage process that is carried out at temperature in range from 150° C. to 400° C., and it does not require a hydrogen enriched atmosphere. The process can be carried out both in a batch mode and in a continuous mode. The affinity of the adsorbent towards sulfur compounds enables ultra-deep desulfurization down to the levels of about 1 ppm and less. The present invention can adsorb more than 1 g sulfur per 100 g of adsorbent. The invention further enables periodic regeneration of the sorbent by removing the adsorbed sulfur in reductive atmosphere that increases the effective total sulfur capacity to more than about 2.0 g sulfur per 100 g.

Problems solved by technology

The sulfur capacity of Ni° phase in the first process even at high nickel dispersion of >30% is limited by the tendency of Ni° to convert the existing unsaturated hydrocarbons in fuel to carbonaceous deposits.
This is also one of the reasons that the deactivated nickel sorbents cannot be regenerated by reductive treatment and oxidative regeneration techniques need to be employed to restore the material.
In case of diesel fuels derived from fossil sources that do not contain oxygenates but include mono-, bi- and triaromatics with high coke-forming ability, the processes implementing Ni°-based sorbents yields very low sulfur capacity of less than 0.1 g per 100 g. This low capacity and sorbent non-regenerability substantially impairs the commercial application of such process for ultradeep desulfurization of diesel fuels.

Method used

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  • Process for adsorption of sulfur compounds from hydrocarbon streams
  • Process for adsorption of sulfur compounds from hydrocarbon streams
  • Process for adsorption of sulfur compounds from hydrocarbon streams

Examples

Experimental program
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Effect test

example 1

Comparative

[0024] In 250 ml flask placed in a heating bath, provided by magnetic stirrer and condenser, 5 g of silica gel (PROMEKS, PI-258) calcined at 500° C. for 2 h with surface area of 220 m2 / g and pore diameter of 26 nm was placed with a mixture of two solutions 0.5 g aluminum tri-sec butoxide with 100 mL toluene, and 1.5 g triethylamine with 100 mL. The toluene suspension was vigorously stirred at 85° C. for 6 h, and then the solid was separated by filtration. The alumina-grafted mesoporous silica solid was suspended in 150 mL of ethanol solution containing 0.22 g of water and it was stirred at room temperature for 24 h. The alumina-grafted mesoporous silica solid then filtered and dried with vacuum at 85° C. for 2 h, followed by gradual calcinations in periods of 2 hours at temperatures 250° C. and 400° C. and then calcinated in air for 4 hours at 500° C. The alumina-grafted mesoporous silica material exhibit surface area of 243 m2 / g and a narrow mesopore size distribution, ...

example 2

[0028] A sample of 6 g of silica gel (PROMEKS, PI-258) with surface area of 220 m2 / g and pore diameter of 26 nm was calcined for 2 hours at 500° C. for 2 h. Its water capacity at the wetness point was 2.7 cc (H2O) / g. 16.2 ml of transparent solution was prepared by mixing 6 ml of distilled H2O and 2.5 ml of 68% HNO3, adding 9 g of Ni(NO3)2*6H2O (0.031 mol Ni) and slowly inserting 4.1 g of (NH4)2HPO4 (0.031 mol P). Stirring was continued for 30 min until all the salts were dissolved yielding a transparent, green solution with pH of 4.0. The solution was inserted inside the pores of silica gel by incipient wetness method. The impregnated material was dried for 4 hours in air at 120° C. (heating rate 5° C. / min) and then calcined for 6 hours at 500° C. (heating rate 1° C. / min). EDX analysis of the calcined composite indicated the content of Ni, P, Si, O to be 22.9, 10.9, 35.1 and 31.1 wt % respectively and the atomic ratio of Ni / P was 1.1.

[0029] 0.5 g of the above composite material was...

example 3

[0030] A sample of 10 g of silica gel (PQ Co-PM5308) with surface area of 480 m2 / g and average pore diameter of 10 nm was calcined for 2 hours at 500° C. Its water capacity at the wetness point was 2.31 cc (H2O) / g (silica). 23 ml of transparent solution was prepared by mixing 8 ml of distilled H2O and 3.25 ml of 68% HNO3, adding 16.25 g of Ni(NO3)2*6H2O (0.056 mol Ni) and slowly inserting 3.75 g of (NH4)2HPO4 (0.028 mol P). Stirring was continued for 30 min until all the salts were dissolved yielding a transparent, green solution with pH of 3.5. The impregnated material was dried for 4 h in air at 120° C. (heating rate 5° C. / min) and then calcined for 6 h at 500° C. (heating rate 1° C. / min). EDX analysis of the calcined composite indicated the content of Ni, P, Si, O to be 26.2, 6.4, 38.9 and 28.5 wt % respectively and the atomic ratio of Ni / P was 1.97.

[0031] 0.5 g of the above composite material was reduced in a quartz reactor under atmospheric pressure with an H2 flux of 1000 cc*...

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Abstract

The present invention provides a high capacity adsorbent for removing sulfur from hydrocarbon streams. The adsorbent comprises a composite material containing particles of a nickel phosphide complex NixP. The adsorbent is utilized in a sulfur removal process that does not require added hydrogen, and run at relatively low temperatures ranging from about 150° C. to about 400° C. The process of this invention enables “ultra-deep” desulfurization down to levels of about 1 ppm and less.

Description

[0001] This application claims the benefit of U.S. Provisional Application No. 60 / 855,241 filed Oct. 30, 2006.SUMMARY OF THE INVENTION [0002] The present invention provides a process for removing sulfur compounds from liquid hydrocarbon streams by using a high capacity adsorbent which is a composite material containing particles of nickel phosphide complex having a Ni / P ratio ranging from about 0.5:4, preferably about 2:3 and most preferably about 2.2:2.5. The composite is preferably distributed in a phase containing silica, alumina or carbon, and obtained by reduction of composite material consisting of nickel phosphate (Ni2P2O7), nickel oxide, and / or nickel hydroxide, ammonium phosphate ((NH4)2HPO4), wherein the composite material is preferably formed by deposition of nickel and phosphorus salts onto silica, mesoporous silica, silica-alumina or carbon materials. The invention further includes using a sorbent where part of silica or carbon is removed from the said composite materia...

Claims

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Application Information

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Patent Type & Authority Applications(United States)
IPC IPC(8): C10G29/06
CPCB01J20/02B82Y30/00B01J20/0259B01J20/08B01J20/103B01J20/20B01J20/28083B01J20/3234B01J20/3236C10G25/003C10G2300/1055C10G2300/202C10G2400/04B01J20/28007B01J20/28061B01J20/28064B01J20/3416B01J20/3458B01J20/3483B01J2220/42B01J20/0225B01D53/14B01J20/06B01J20/32B01J27/185
Inventor LANDAU, MIRON V.HERSKOWITZ, MORDECHAYREIZNER, IEHUDITKONRA, YARONGUPTA, HIMANSHUAGNIHOTRI, RAJEEVBERLOWITZ, PAUL J.KEGERREIS, JAMES E.
Owner EXXON RES & ENG CO
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