Antifoulants Comprising Tin, Antimony and Aluminum for Thermal Cracking Processes

Other objects and advantages of the invention will be apparent from the foregoing brief description of the invention and the claims as well as the detailed description of the drawings in which:

FIG. 1 is a diagrammatic illustration of the test apparatus used to test the antifoulants of the present invention;

FIG. 2 is a graphical illustration of the effect of a combination of tin and chromium; and

FIG. 3 is a graphical illustration of the effect of a combination of chromium and antimony.

The invention is described in terms of a cracking furnace used in a process for the manufacture of ethylene. However, the applicability of the invention described herein extends to other processes wherein a cracking furnace is utilized to crack a feed material into some desired components and the formation of coke on the walls of the cracking tubes in the cracking furnace or other metal surfaces associated with the cracking process is a problem.

Any suitable organic chromium compound may be utilized as an antifoulant or in the combination of chromium and antimony antifoulant, in the combination of tin and chromium antifoulant or in the combination of tin, antimony and chromium antifoulant. Also, elemental chromium may be used in the combination antifoulants. However, the use of inorganic chromium compounds should be avoided since the use of such compounds is believed to impair the performance of the combination antifoulants. Also, inorganic chromium compounds do not have a beneficial effect when used along as antifoulants.

Examples of organic chromium compounds that can be used include complexes of zero-valent chromium(0) such as bis(benzene) chromium(0), bis- (cyclopentadienyl) chromium(0), cyclopentadienyl-benzene chromuim(0), tris(propynyl) chromium(0), chromium(0) hexacarbonoyl, cyclopentadienyl tricarbonyl chromium(0) hydride, naphthalenen tricarbonyl chromium(0) and the like; chromium(III) carboxylates with up to 16 C-atoms as chromium(III) acetate, chromium(III) hexanoate, chromium(III) 2-ethyl- hexanoate, chromuim(III) n-octanoate, chromium(III) hexadecanoate, chromium(III) oxalate, chromium(III) citrate, chromium(III) tartrate, chromium(III) benzoate, chromium(III) naphthenate; and diketones such as chromium(III) acetylacetonate. Presently, chromium(III) 2-ethyl- hexanoate is preferred.

Any suitable form of antimony may be utilized in the combination of chromium and antimony antifoulant or in the combination or tin, antimony and chromium antifoulant. Elemental antimony, inorganic antimony compounds and organic antimony compounds as well as mixtures of any two or more thereof are suitable sources of antimony. The term "antimony" generally refers to any one of these antimony sources.

Examples of some inorganic antimony compounds which can be used include antimony oxides such as antimony trioxide, antimony tetroxide, and antimony pentoxide; antimony sulfides such as antimony trisulfide and antimony pentasulfide; antimony sulfates such as diantimony trisulfate; antimonic acids such as metaantimonic acid, orthoantimonic acid and pyroantimonic acide; antimony halides such as antimony trifluoride, antimony trichloride, antimony tribromide,a ntimony triiodide, antimony pentafluordie and antimony pentachloride; antimonyl halides such as antimonyl chloride and antimonyl trichloride. Of the inorganic antimony compounds, those which do not contain halogen are preferred.

Examples of some organic antimony compounds which can be used include antimony carboxylates such as antimony triformate, antimony trioctoate, antimony triacetate, antimony tridodecanoate, antimony trioctadecanoate, antimony tribenzoate, and antimony tris(cyclohexenecarboxylate); antimony thiocarboxylates such as antimony tris(thioacetate), antimony tris(dithioacetate) and antimony tris(dithiopentanoate); antimony thiocarbonates such as antimony tris(O-propyl dithiocarbonate); antimony carbonates such as antimony tris(ethyl carbonates); trihydrocarbylantimony compounds such as triphenylantimony; trihydrocarbylantimony oxides such as triphenylantimony oxide; antimony salts of phenolic compounds such as antimony triphenoxide; antimony salts ofo thiophenolic compounds such as antimony tris(-thiophenoxide); antimony sulfonates such as antimony tris(benzenesulfonate) and antimony tris(p-toluenesulfonate); antimony carbamates such as antimony tris(diethylcarbamate); antimony thiocarbamates such as antimony tris(dipropyldithiocarbamate), antimony tris(-phenyldithiocarbamate) and antimony tris(butylthiocarbamate); antimony phosphites such as antimony tris(diphenyl phosphite); antimony phosphates such as antimony tris(dipropyl phosphate); antimony thio phosphates such as antimony tris(0,0-dipropyl thiophosphate) and antimony tris(0,0-dipropyl dithiophosphate) and the like. At present antimony 2-ethylhexanoate is preferred.

Any suitable form of tin may be utilized in the combination of tin and chromium antifoulant or in the combination of tin, antimony and chromium antifoulant. Elemental tin, inorganic tin compounds, and organic tin compounds as well as mixtures of any two or more thereof are suitable sources of tin. The term "tin" generally refers to any one of these tin sources.

Examples of some inorganic tin compounds which can be used include tin oxides such as stannous oxide and stannic oxide; tin sulfides such as stannous sulfide and stannic sulfide; tin sulfates such as stannous sulfate and stannic sulfate; stannic acids such as metastannic acid and thiostannic acid; tin halides such as stannous fluoride, stannous chloride, stannous bromide, stannous iodide, stannic fluoride, stannic chloride, stannic bromide and stannic iodide, tin phosphates such as stannic phosphate; tin oxyhalides such as stannous oxychloride and stannic oxychloride; and the like. Of the inorganic tin compounds those which do not contain halogen are preferred as the source of tin.

Examples of some organic tin compounds which can be used include tin carboxylate such as stannous formate, stannous acetate, stannous butyrate, stannous octoate, stannous decanoate, stannous oxalate, stannous benzoate, and stannous cyclohexanecarboxylate; tin thiocarboxylate such as stannnous thioacetate and stannous dithioacetate; dihydrocarbyltin bis(hydrocarbyl mercaptoalkanoates) such as dibutyltin bis(isooctyl mercaptoacetate) and dipropyltin bis(butyl mercaptoacetate); tin thiocarbonates such as stannous O-ethyl dithiocarbonate; tin carbonates such as stannous propyl carbonate; tetrahydrocaryltin compounds such as tetrabutyltin, tetraoctyltin, tetradodecyltin, and tetraphenyltin; dihydrocarbyltin oxides such as dipropyltin oxide, dibutyltin oxide, dioctyltin oxide, and diphenyltin oxide; dihydrocarbyltin bis(hhdrocarbyl metcaptide)s such as dibutyltin bis(dodecyl mercaptide); tin salts of phenolic compounds such as stannous thiophenoxide; tin sulfonate such as stannous benzenesulfonate and stannous-p-toluenesulfonate; tin carbamates such as stannous diethylcarbamate; tin thiocarbamates such as stannous propylthiocarbamate and stannous diethyldithiocarbamate; tin phosphites such as stannous diphenyl phosphite; tin phosphates such as stannous dipropyl phosphate; tin thiophosphate such as stannous O,O-dipropyl thiophosphate, stannous O,O-dipropyl dithiophosphate and stannic O,O-dipropyl dithiophosphate, dihydrocarbyltin bis(O,OO-dihydrocarbyl thiophosphate)s such as dibutyltin bis(O,O-dipropyl dithiophosphate); and the like. At present stannous 2-ethylhexanoate is preferred.

Any of the listed sources of tin may be combined with any of the listed sources of chromium to form the combination of tin and chromium antifoulant or the combination of tin, antimony and chromium antifoulant. In like manner, any of the listed sources of chromium may be combined with any of the listed sources of antimony to form the combination of chromium and antimony antifoulant or the combination of tin, antimony and chromium antifoulant.

Any suitable concentration of chromium in the combination of chromium and antimony antifoulant may be utilized. A concentration of chromium in the range of about 5 mole percent to about 90 mole percent is presently preferred because the effect of the combination of chromium and antimony antifoulant is reduced outside of this range. In like manner, any suitable concentration of chromium may be utilized in the combination of chromium and tin antifoulant. A concentration of chromium in the range of about 10 mole percent to about 90 mole percent is presently preferred because the effect of the combination of chromium and tin antifoulant is reduced outside of this range.

Any suitable concentration of antimony and chromium in the combination of tin, antimony and chromium antifoulant may be utilized. A concentration of antimony in the range of about 10 mole percent to abou 65 mole percent is presently preferred. In like manner, a concentration of chromium in the range of about 10 mole percent to about 65 mole percent is presently preferred.

In general, the combinationn antifoulants of the present invention are effective to reduce the buildup of coke on any of the high temperature steels. Commonly used steels in cracking tubes are Incology 800, Inconel 600, HK40, 11/4 chromium-1/2 molybdenum steel, and Type 304 Stainless Steel. The composition of these steels in weight percent is as follows:

The antifoulants of the present invention may be contacted with the Metals either by pretreating the Metals with the antifoulant, adding the antifoulant to the hydrocarbon containing feedstock or preferably both.

If the Metals are to be pretreated, a preferred pretreatment method is to contact the Metals with a solution of the antifoulant. The cracking tubes are preferably flooded with the antifoulant. The antifoulant is allowed to remain in contact with the surface of the cracking tubes for any suitable length of time. A time of at least about one minute is preferred to insure that all of the surface of the cracking tube has been treated. The contact time would typically be about ten minutes or longer in a commercial operation. However, it is not believed that the longer times are of any substantial benefit other than to fully assure an operator that the cracking tube has been treated.

It is typically necessary to spray or brush the antifoulant solution on the Metals to be treated other than the cracking tubes but flooding can be used if the equipment can be subjected to flooding.

Any suitable solvent may be utilized to prepare the solution of antifoulant. Suitable solvents include water, oxygen-containing organic liquids such as alcohols, ketones and esters and aliphatic and aromatic hydrocarbons and their derivatives. The presently preferred solvents are normal hexane and toluene although kerosene would be a typically used solvent in a commercial operation.

Any suitable concentration of the antifoulant in the solution may be utilized. It is desirable to use a concentration of at least 0.1 molar and concentrations may be 1 molar or higher with the strenght of the concentrations being limited by metallurgical and economic considerations. The presently preferred concentration of antifoulant in the solution is in the range of about 0.2 molar to about 0.5 molar.

Solutions of antifoulants can also be applied to the surface of the cracking tube by spraying or brushing when the surfaces are accessible but application in this manner has been found to provide less protection against coke deposition than immersion. The cracking tubes can also be treated with finely divided powders of the antifoulants but, again, this method is not considered to be particularly effective.

In addition to pretreating of the Metals with the antifoulant or as an alternate method of contacting the Metals with the antifoulant, any suitable concentration of the antifoulant may be added to the feed stream flowing through the cracking tube. A concentration of antifoulant in the feed stream of at least ten parts per million by weight of the metal(s) contained in the antifoulant based on the weight of the hydrocarbon portion of the feed stream should be used. Presently preferred concentrations of antifoulant metals in the feed stream are in the range of about 20 parts per million to about 100 parts per million based on the weight of the hydrocarbon portion of the feed stream. Higher concentratons of the antifoulant may be added to the feed stream but the effectiveness of the antifoulant does not substantially increase and economic considerations generally preclude the use of higher concentrations.

The antifoulant may be added to the feed stream in any suitable manner. Preferably, the addition of the antifoulant is made nder conditions whereby the antifoulant becomes highly dispersed. Preferably, the antifoulant is injected in solution through an orifice under pressure to atomize the solution. The solvents previously discussed may be utilized to form the solutions. The concentration of the antifoulant in the solution should be such as to provide the desired concentation of antifoulant in the feed stream.

Steam is generally utilized as a diluent for the hydrocarbon containing feedstock flowing to the cracking furnace. The steam/hydrocarbon molar ratio is considered to have very little effect on the antifoulants of the present invention.

The cracking furnace may be operated at any suitable temperature and pressure. In the process of steam cracking of light hydrocarbons to ethylene, the temperature of the fluid flowing through the cracking tubes increases during its transit through the tubes and will attain a maximum temperature at the exit of the cracking furnace of about 850.degree. C. The wall temperature of the cracking tubes will be higher and may be substantially higher as an insulating layer of coke accumulates within the tubes. Furnace temperature of nearly 2000.degree. C. may be employed. Typical pressures for a cracking operation will generally be in the range of about 10 to about 20 psig at the outlet of the cracking tube.

Before referring specifically to the examples which will be utilized to further illustrate the present invention, the laboratory apparatus will be described by referring to FIG. 1 in which a 9 millimeter quartz reactor 11 is illustrated. A part of the quartz reactor 11 is located inside the electric furnace 12. A metal coupon 13 is supported inside the reactor 11 on a two millimeter quartz rod 14 so as to provide only a minimal restriction to the flow of gases through the reactor 11. A hydrocarbon feed stream (ethylene) is provided to the reactor 11 through the combination of conduit means 16 and 17. Air is provided to the reactor 11 through the combination of conduit means 18 and 17.

Nitrogen flowing through conduit means 21 is passed through a heated saturator 22 and is provided through conduit means 24 to the reactor 11. Water is provided to the saturator 22 from the tank 26 through conduit means 27. Conduit means 28 is utilized for pressure equalization.

Steam is generated by saturating the nitrogen carrier gas flowing through the saturator 22. The steam/nitrogen ratio is varied by adjusting the temperature of the electrically heated saturator 22.

The reaction effluent is withdrawn from the reactor 11 through conduit means 31. Provision is made for diverting the reaction effluent to a gas chromatograph as desired for analysis.

In determining the rate of coke deposition on the metal coupon, the quantity of carbon monoxide produced during the cracking process was considered to be proportional to the quantity of coke deposited on the metal coupon. The rationale for this method of evaluating the effectiveness of the antifoulants was the assumption that carbon monoxide was produced from deposited coke by the carbon-steam reaction. Metal coupons examined at the conclusion of cracking runs bore essentially no free carbon which supports the assumption that the coke has been gasified with steam.

The selectivity of the converted ethylene to carbon monoxide was calculated according to equation 1 in which nitrogen was used as an internal standard. ##EQU1## The conversion was calculated according to equation 2. ##EQU2## The CO level for the entire cycle was calculated as a weighted average of all the analyses taken during a cycle according to equation 3. ##EQU3##

The percent selectivity is directly related to the quantity of carbon monoxide in the effluent flowing from the reactor.

Incology 800 coupons, 1".times.174".times.116", , were employed in this example. Prior to the application of a coating, each Incoloy 800 coupon was thoroughly cleaned with acetone. Each antifoulant was thena pplied by immersing the coupon in a minimum of 4 mL of the antifoulant/solvent solution for 1 minute. A new coupon was used for each antifoulant. The coating was then followed by heat treatment in air at 700.degree. C. for 1 minute to decompose the antifoulant to its oxide and to remove any residual solvent. A blank coupon, used for comparisons, was prepared by washing the coupon in acetone and heat treating in air at 700.degree. C. for 1 minute without any coating. The preparation of the various coatings are given below.

0.5M Sb: 2.76 g of Sb(C.sub.8 H.sub.15 O.sub.2).sub.3 (antimony 2-ethylhexanoate)

was mixed with enough pure n-hexane to make 10.0 mL

of solution referred to hereinafter as solution A. 0.5M Sn: 2.02 g of Sn(C.sub.8 H.sub.15 O.sub.2).sub.2 (stannous 2-ethylhexanoate) was dissolved in enough pure n-hexane to make 10.0 mL of solution referred to hereinafter as solution B. 0.5M Cr(NO.sub.3).sub.3 : 2.0 g of Cr(NO.sub.3).sub.3 .sup.. 9 H.sub.2 O was dissolved in 10 mL of water. This solution is referred to hereinafter as solution C. 0.5M Cr(C.sub.8 H.sub.15 O.sub.2).sub.3 : 4.64 g of 50.9 wt-% Cr(III) 2-ethylhexanoate in 2-ethylhexanoic acid (Alfa Chemical Company, Lot 060679) was mixed with enough toluene to make 10 mL of the solution referred to hereinafter as solution D. 0.5M Cr-Sb: 2.55 g of 50.9 wt-% Cr(III) 2-ethylhexanoate in 2-ethylhexanoic acid and 1.38 g of Sb 2-ethylhexanoate were mixed with enough n-hexane to make 10 mL of the solution referred to hereinafter as solution E. 0.5M Cr-Sn: 2.32 g of 50.9 wt-% Cr(III) 2-ethylhexanoate in 2-ethylhexanoic acid and 1.01 g of stannous 2-ethylhexanoate were mixed with enough x-hexane to make 10 mL of the solution referred to hereinafter as solution F. 0.1M Cr-Sb: A 2.0 mL aliquot of solution E was added to a raduated cylinder and enough toluene was added to make 10.0 mL. The resulting solution is referred to hereinafter as solution G. 0.1M Sn-Sb-Cr: 0.68 g of Sn(C.sub.8 H.sub.15 O.sub.2).sub.2, 0.92 g of Sb(C.sub.8 H.sub.15 O.sub.2).sub.3 and 1.56 g of CR(C.sub.8 H.sub.15 O.sub.2).sub.3 was dissolved in 2-ethylhexanoic acid in a graduated cylinder. Enough toluene was added to make 10.0 mL. A 2.0 mL aliquot of this solution was then added to a graduated cylinder and enough toluene was added to again make 10.0 mL. The resulting solution is referred to hereinafter as solution H.

The temperature of the quartz reactor was maintained so that the hottest zone was 900.+-.5.degree. C. A coupon was placed in the reactor while the reactor was at reaction temperature.

A typical run consisted of three 20 hour coking cycles (ethylene, nitrogen and steam), each of which as followed by a 5 minute nitrogen purge and a 50 minute decoking cycle (nitrogen, steam and air). During a coking cycle, a gas mixture consisting of 73 mL per minute ethylene, 145 mL per minute nitrogen and 73 mL per minute steam passed downflow through the reactor. Periodically, snap samples of the reactor effluent were analyzed in a gas chromatograph. The steam/hydrocarbon molar ratio was 1:1.

Table I summarizes results of cyclic runs (with either 2 or 3 cycles) made with Incoloy 800 coupons that had been immersed in the test solutions A-H previously described.

Results ofo runs 2, 3, 4 and 5 in which tin, antimony and chromium were used separately, show that only tin and the organic compound of chromium were effective in substantially reducing the rate of carbon deposition on Incolooy 800 under conditions simulating those in an ethan cracking process. Binary combinations of these elements used in runs 6 and 7 show some very surprising effects. Run 6, in which antimony and chromium were combined, and run 7, in which tin and chromium were combined, show that these combinations are unexpectedly much more effective than results of runs in which they were used separately would lead one to expect.

In runs 8 and 9, 0.1M solutions were used in order to show any improvement provided by the trinary combination. A comparison of runs 8 and 9 shows that the combiantion of tin, antimony and chromium antifoulant, while a good antifoulant, is not more effective than the best binary combiantion (Sb-Cr).

Using the process conditions of Example, a plurality of runs were made using antifoulants which contained different ratios of tin and chromium and different ratios of chromium and antimony. Each run employed a new Incoloy 800 coupon which has been cleaned and treated as described in Example 1. The antifoulant solutions were prepared as described in Example 1 with the exception that the ratio of the elements was varied. The results of these tests are illustrated in FIGS. 2 and 3.

Referring to FIG. 2, it can be seen that the combination of tin and chromium was particularly effective when the concentration of chromium ranged from about 10 mole percent to about 90 mole percent. Outside of this range, the effectiveness of the combiantion of tin and chromium was reduced.

Referring now to FIG. 3, it can be seen that the combination of chromium and antimony was effective when the concentration of chromium was in the range of about 5 mole percent to about 90 mole percent. Again, the effectiveness of the combination of chromium and antimony is reduced outside of this range.

Reasonable variations and modifications are possible by those skilled in the art within the scope of the described invention and the appended claims.