MXPA97000736A - Auxiliary of sedimentation for solids enhydrocarbu - Google Patents

Abstract

The present invention relates to methods for accelerating the sedimentation of insoluble solids in oil and water finely divided into liquid hydrocarbons using an effective amount of an alkylphenolformaldehyde resin alkoxylate having a molecular weight of about 500 to 5,000. Preferably, the hydrocarbon is a suspension of fluidized catalytic disintegrator containing catalytic fines gastad

Description

SEDIMENTATION AUXILIARY FOR SOLIDS IN HYDROCARBONS FIELD OF THE INVENTION The present invention relates to methods for accelerating the sedimentation of solids in liquid hydrocarbons. The methods of the present invention are particularly effective in accelerating the sedimentation of catalytic fines by FCC (fluidized catalytic disintegrator) in an oily suspension. BACKGROUND OF THE INVENTION Unrefined hydrocarbons such as crude oil, resins and bottom streams often contain finely divided solid matter which often must be removed before use or processing. These solids may include solids of a soil-like nature, finely divided silicas, muds, silt and coke, and metal solids for corrosion of oxide and sulfur. These solids may include traces of metal particles such as lead, nickel, chromium and the like and their salts. For example, the fluidized catalytic disintegrator (FCC) units use a fluidized bed of zeolitic aluminosilicate mud particles to disintegrate coarse fractions of petroleum into thinner fractions at elevated temperatures. The catalyst is finally deactivated by impoverishment or coking. These spent fines must be removed from the FCC on a continuous basis so that the fresh catalyst can be added. A part of this oily suspension containing the spent fines is then usually settled in tanks, although hydrocyclones are sometimes used to accelerate the separation process. Both native and synthetic components of the oily suspension have a dispersing effect that delays the sedimentation of the fines. The present inventor has discovered that certain chemical agents, when added to the oily suspension, have an antidispersing or coagulating effect which accelerates the sedimentation process. This produces a cleaner settling oil (typically <0.05% by weight of ash) in a shorter period of time and can then be sold as a supply of carbon black or residual fuel oil. DESCRIPTION OF THE RELATED ART U.S. Patent No. 4,539,099 discloses a method for improving the rate of sedimentation by gravity of suspended solids of the hydrocarbon oil by the addition of an oxyalkylated glycol ester of phenol-formaldehyde resin. U.S. Patent No. 5,476,988 describes the use of quaternary ammonium compounds and U.S. Patent No. 5,481,059 discloses the use of alkylphenolformaldehyde alkoxylates crosslinked with polyacrylic acid for this application.

Various methods of washing with water have been described. U.S. Patent Number 4,407,707 discloses a method for removing solids particles from the hydrocarbon oil by adding an alkoxylated sorbitan fatty ester (optionally with an organosulfonic acid or salt and / or a demulsifier) to the oil, then removing the solids from the oil with water to the oil. 5-50%. U.S. Patent No. 2,952,620 discloses a process for removing solids from the hydrocarbon oil by washing the oil with water containing a nonionic surfactant. It is said that a non-ionic surfactant works with this method of washing with water. There is no indication or suggestion of such surfactants, which would implicitly include those of U.S. Patent Nos. 4,407,707 and 5,539,099, having an effect in the absence of washing with water. U.S. Patent No. 4,889,618 discloses a process for removing solids from hydrocarbon oil by washing the oil with water containing concentrated caustic soda. DETAILED DESCRIPTION OF THE INVENTION The present invention relates to methods for accelerating the sedimentation of insoluble solids in finely divided oil and water into liquid hydrocarbons comprising the addition of an alkylphenolformaldehyde resin alkoxylate to the liquid hydrocarbon. More particularly, the present invention relates to methods for accelerating the sedimentation of catalytic fines by fluidized catalytic disintegrator (FCC) spent in an oily suspension comprising the addition of an alkylphenolformaldehyde resin alkoxylate to the oily suspension. Alkylphenolformaldehyde resin alkoxylates generally have molecular weights in the range of 500 to 5,000 with a gaaa of 1,000 to 2,500 preferably. The alkyl group can be linear or branched and have from 1 to 24 carbon atoms with a preferred range of 4 to 9. The alkoxy group has from 2 to 4 carbon atoms with 2 preferably. The alkoxylation comprises from 20 to 80% by weight of the molecule with 50% preference. Alkylphenolformaldehyde resin alkoxylates, which for purposes of the present invention include mixtures of these compounds, prove to be effective in a variety of liquid hydrocarbons. These liquid hydrocarbons are generally unrefined hydrocarbons that are prone to contain finely divided insoluble solids in oil and water. For purposes of the present invention, liquid hydrocarbons include but are not limited to crude oils and crude oil fractions or residues boiling above 400 ° F. The actual dose ranges for the alkylphenolformaldehyde resin alkoxylates depend on the characteristics of the hydrocarbon to be treated. These characteristics may vary and include the type of hydrocarbon, the type and amount of finely divided solids present, the solubility in oil and water of the finely divided solids and the presence of other impurities and surfactants in the liquid hydrocarbon. For the purposes of this invention, the term "effective amount" is the amount of alkylphenolformaldehyde resin alkoxylates necessary to accomplish the purpose of the treatment. The effective amount will vary from 1 part to 1000 parts of alkylphenol formaldehyde resin alkoxylates per million parts of hydrocarbon, preferably in a range of 10 to 100 parts per million parts of hydrocarbon. The alkylphenolformaldehyde resin alkoxylate can be fed to the hydrocarbon to be treated without mixing or in a suitable solvent which is compatible with the alkoxylate and the hydrocarbon. Examples of such solvents include but are not limited to petroleum distillates, aromatic naphthas, mineral oils, alkyl ethers, esters and alcohols. The following examples are to show the effectiveness of the present invention as an accelerator for sedimenting the insoluble solids in oil and water finely divided into hydrocarbons and should not be construed as limiting the scope of the invention. EXAMPLES Auxiliary Catalyst Sedimentation Test This test measures the fraction of FCC catalytic fines which settle to the bottom of a sample suspension compared to the amount that remains dispersed at the top. This test simulates the sedimentation of the suspension in tanks between room temperature and 200 ° F (93 ° C). Experimental Collect 100 mL of FCCU suspension in 6 oz. (177 ml) bottles. Put the bottles in a water bath and heat at the process temperature. Remove each bottle from the bath and provide the appropriate treatment to the desired bottles. Place the bottles in an isolated stirrer at high speed for 10 minutes. Return the bottles to the bath and let stand without moving during the predetermined sedimentation period. This predetermined settling time for a target is established by analyzing several untreated bottles according to the procedure of this test at various time intervals centered on the residence time of the tank (eg, 5 hours, 1 day, 3 days, 7 days). days) . The test methods vary at the point at which the sample is divided between the upper and lower portions for analysis at the end of the sedimentation period. The size of the upper portion is used to designate the method used (for example, the "95% method" means that the top 95% of the sample was separated). For many samples, the "50% method" described below is used. For samples that sediment extremely fast, a sedimentation time and the "95% method" described below are used. For very low sedimentation samples, a long settling time and the 20% or 10% variation of the 50% method is used. 50% Method (or 20% or 10%) Remove the 50 Ls from the top (or 20% or 10%) with a syringe being careful not to move the sample or insert the needle down the 50 mL line ( or 80 or 90) and transfer to a clean bottle. This is the "superior" sample. The original bottle contains the "bottom" sample. 95% Method Empty -95 mLs (ie, what will be easily emptied) into a clean bottle. This is the "superior" sample. The remaining -5 mLs in the original bottle is the "bottom" sample. Put filter pads in small Petri dishes, dry at 220 ° F (104 ° C) for one hour, remove from the oven and allow to cool in a desiccator. Shake the oily sample vigorously and carefully empty it, up to 50 mL at a time, into a graduated 100 mL centrifuge tube, then double the volume, up to 100 mL, with xylene or toluene. Heat the centrifuge tube to 180 ° F (82 ° C) in a water bath. Centrifuge for 15 minutes.

Weigh and write down the weight of the filter. Place the filter in a paraboloid filtration funnel and wet with xylene or toluene to ensure a good seal for the vacuum filtration.

Turn on the vacuum pump and pour a small amount of hot oil from the centrifuge tube into the filtering funnel and let it filter. Rinse with xylene or toluene. Continue adding small amounts and rinsing until the entire sample has filtered. Then rinse the centrifuge tube and funnel with more xylene or toluene until they are clean. Remove the filter cup and wash, under vacuum, the filter pad with xylene or toluene followed by petroleum ether or heptane. Dry the filter pad in an oven at 220 ° F (104 ° C) for one hour. Let cool in a desiccator and weigh again. Put the filters in glass Petri dishes and the ash in a muffle furnace at -900 ° F. Weigh again to determine the catalytic weights, being careful not to move the loose ash in the filters. The sedimented% is calculated by the following methods: 20% method: sediment% = lower ore - 4 x upper part (g) lower part + upper part (g) 50% method: sediment% = lower part - upper part (g) lower part + upper part (g) 95% method: sedimented% = lower part - upper part / 19 (g) lower part + upper part (g) A sedimentation period must be chosen which produces around 40 to 50% sedimented. Repeat the optimal, determined procedure of the targets, after providing chemical treatments in the process dose. Table I lists the various compounds tested and their individual chemical formulas. TABLE I Chemical Legend Treatment Description A NR5-E05 (ac) B NR5E05 (be) C NR5-E05 (be) + NR4-P01-E04 (be) D BR8-E03 (ac) E AR4-E04 (ac) + NR6 -P03-E04 (be) F NR3-E05 (ac) + AR4-E04 (ac) G NR5-E05 (be) + AR4-E04 (ac) N = nonylphenolic resin B = butylphenolic resin A = amylphenolic resin R? = x moles of phenol per resin, on average EO? = x moles of ethylene oxide per phenol, on average PO? = x moles of propylene oxide per phenol, on average (ac) = acid catalyzed resin (be) = base catalyzed resin The results of this test are presented in the Tables II to VII. South Refinery Settled 14 days at 170 ° F (76 ° C) 50% Method Active Treatment 75 pp TABLE II Treatment * Sedimentation A -1 B 15 C 4 D 7 E 54 F 50 G 47 White 21 As shown in Table II, the combination of amylphenolfor aldehyde ethoxylate resin and ethylene nonylphenolformaldehyde / propylene oxide resin resin proved effective in the sedimentation of insoluble solids in oil and water. TABLE III Middle East Refinery Settled 6 days at 170 ° F (76 ° C) 50% Method Active treatment 75 ppm% Sedimentation Treatment Fluid # 1 Fluid # 2 A -19 * 72 B 65 * 70 C 78 D 75 E 74 F 79 G 78 White 72 70 These tests were repeated due to a supposed procedural error. TABLE IV West Refinery Settled 14 days at 70 ° F (21 ° C) 95% Method Active treatment 75 ppm% Sedimentation Fluid Treatment # 1. Fluid # 2 Fluid # 3 A 93 BB 9 988 9 933 85 C 93 D 92 E 91 F 94 G 92 White 92 88 75 These test results demonstrated that resin alkoxylates with various alkyl chains and resin combinations with different chains of alkyl are effective as aids in sedimentation. These results also demonstrated that the combinations of acid catalyzed resins and base catalyzed resins are effective in the present invention. Compound B was selected for further testing, although it did not work for the first two applications, because other unrelated treatments worked well there, considering that, for the third application, no better treatment of any kind is found. This complementarity with alternative treatments He did the most valuable treatment although it was used less frequently. TABLE V Southern Refinery Distinct Sedimentation 1 day at 170 ° F (76 ° C) 50% and 95% methods Active treatment at 75 ppm Treatment 50% Method 95% Method B 48 55 White 46 49 TABLE VI Second Refinery Middle East Settled 1 day at 200 ° F (93 ° C) 95% Method Active treatment 30 ppm% Sedimentation Treatment Fluid # 1 Fluid # 2 A 16 21 White 17 13 The results in Tables V to VII demonstrate the effectiveness of the catalyzed resin of nonylphenolformaldehyde ethoxylate base in accelerated sedimentation in a wide range of suspensions and in low doses (30 ppm) of treatment. These compounds are available in the market, for example from BASF Corp. as Pluradyne DB-7935. TABLE VII Third Middle East Refinery Settled 1 day at 160 ° F (71 ° C) 90% method, average of duplicates Active treatment of 75 ppm Treatment% Sedimentation B 85 White 65 While this invention has been described with respect to its particular modalities, it is apparent that many other forms and modifications of this invention will be obvious to those skilled in the art. The appended claims and this invention are generally to be construed as encompassing all of these obvious forms and modifications which are within the true spirit and scope of the present invention.

Claims (12)

1. NOVELTY OF THE INVENTION Having described the foregoing invention, the content of the following is claimed as property: CLAIMS: 1. A method for accelerating the sedimentation of insoluble solids in oil and water, finely divided into liquid hydrocarbons comprising the addition of an amount Effectiveness of an alkylphenolformaldehyde resin alkoxylate to liquid hydrocarbons.
2. 2. The method according to claim 1 wherein the alkylphenolformaldehyde resin alkoxylate has a molecular weight range of about 500 to 5,000.
3. 3. The method according to claim 1 wherein the alkylphenolformaldehyde resin alkoxylate has a molecular weight range of from about 1,000 to 2,500.
4. 4. The method according to claim 1 wherein the alkylphenolformaldehyde resin alkoxylate has a range of alkyl group of 1 to about 24 carbon atoms.
5. 5. The method according to claim 1 wherein the alkylphenolformaldehyde resin alkoxylate has a range of alkyl group of about 4 to 9 carbon atoms.
6. 6. The method according to claim 1 wherein the alkylphenolformaldehyde resin alkoxylate has alkoxy groups ranging from 2 to 4 carbon atoms each. The method according to claim 1 wherein the alkoxylation comprises from 20 to 80% by weight of the alkylphenolformaldehyde resin alkoxylate. The method according to claim 1 wherein the alkylphenolformaldehyde resin alkoxylate is a base catalyzed nonylphenolic resin ethoxylate wherein the ethoxylation comprises about 50% by weight of the ethoxylate. 9. The method according to claim 1 wherein the finely divided insoluble solids in water and water are catalytic fines by catalytic disintegrator. The method according to claim 1 wherein the liquid hydrocarbon is selected from the group consisting of crude petroleum and fractions or residues of crude oils having boiling points of more than 400 ° F (204 ° C). 11. The method according to claim 1 wherein the hydrocarbon is a catalytic suspension of fluidized catalytic disintegrator. The method according to claim 1 wherein the alkylphenolformaldehyde resin alkoxylate is added to the hydrocarbon in an amount ranging from 1 part to about 1000 parts per million parts of hydrocarbon.