Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10H—PRODUCTION OF ACETYLENE BY WET METHODS
  • C10H21/00—Details of acetylene generators; Accessory equipment for, or features of, the wet production of acetylene
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10H—PRODUCTION OF ACETYLENE BY WET METHODS
  • C10H15/00—Acetylene gas generators with carbide feed, with or without regulation by the gas pressure

Definitions

• This invention relates to an improved, eocnomical, efficient process for generating an acetylene base fuel gas of enhanced stability and safety and of high BTU content that will burn, for example, to heat boilers or power internal combustion engines, with a minimum amount of deleterious emissions.
• the invention also relates to a process for producing an acetylene base fuel gas with no undesirable by-products, such as calcium hydroxide, which create disposal problems. Instead, the by-product of this process is an excellent top cylinder lubricant (TCL) when the gas is used as a fuel for internal combustion engines.
• TCL top cylinder lubricant
• the acetylene produced by both processes is thermodynamically unstable even at room temperatures and even in the absence of air, as is well known in the art.
• the thermal decomposition of acetylene can proceed so rapidly that explosions and detonations may result. Consequently, governmental safety regulations prescribe detailed procedures for handling, storage, and shipment of acetylene.
• the above-mentioned Osborg patent also suggests the addition of an inert "carrier” liquid, e.g., an alcohol, an amine, or a glycol, to the water to have better control and reduce the exothermic heat of the reaction.
• an inert "carrier” liquid e.g., an alcohol, an amine, or a glycol
• a glycol to the water for anti-freeze purposes also is suggested in "Acetylene, Its Properties, Manufacture and Uses" by Miller, VoL I, 1965, Academic Press, pages 291-192.
• Unfortunately, each of the processes of Mackusick, Osborg and the publication "Acetylene, etc.” remain plagued by the formation of unwanted lime as a by-product.
• creosote If the creosote is undiluted, however, it must be neutralized with potassium hydrate or other suitable alkali before the carbide is used to produce acetylene by contact with water. If the creosote is diluted, the protection from air or water is weakened greatly, although the carbide may be used without neutralization but with the acetylene- generating reaction with water slowed considerably. These prior processes for avoiding premature hydrolysis of carbide suffer from the problem that pretreatment of the carbide prior generation of acetylene is required or else the generation slowed to an impractical rate.
• a further object of the present invention is to provide a novel top cylinder lubricant composition which forms a part of an acetylene base fuel gas for an internal combustion engine.
• an improved process for producing an acetylene base relatively safe fuel gas of enhanced stability which comprises reacting a metal carbide (preferably an alkylene earth metal carbide) with an aqueous liquid activator reagent comprising water, a water-soluble reaction-rate-controlling substance (preferably a lower alkylene glycol) and a strong inorganic acid, such as hydrochloric, sulfuric, phosphoric, carbonic or nitric or mixtures thereof.
• a metal carbide preferably an alkylene earth metal carbide
• an aqueous liquid activator reagent comprising water, a water-soluble reaction-rate-controlling substance (preferably a lower alkylene glycol) and a strong inorganic acid, such as hydrochloric, sulfuric, phosphoric, carbonic or nitric or mixtures thereof.
• calcium carbide is reacted with a liquid aqueous activator reagent which comprises water, a lower alkylene glycol (preferably ethylene glycol) and a strong inorganic acid (preferably hydrochloric acid).
• a liquid aqueous activator reagent which comprises water, a lower alkylene glycol (preferably ethylene glycol) and a strong inorganic acid (preferably hydrochloric acid).
• the invention further provides a means for stablizing calcium carbide so as to render it impermeable to air and moisture by coating particles of calcium carbide with an air and moisture impermeable film, preferably of nitrocellulose and a polyester resin, which is attacked and dissolved when brought in contact with the aqueous liquid activator reagent of the present invention.
• the acetylene base fuel produced according to the present invention is a gaseous reaction product which further includes vaporized or entrained by-product compounds which are a most effective top cylinder lubricant for an internal combustion engine.
• the acetylene base fuel gas produced according to the present invention exhibits enhanced BTU output over that of natural gas, i.e., up to about 1447 per cubic foot for the gas of the present invention as contrasted to about 1448 BTU for pure acetylene and about 879 BTU for natural gas.
• a significant advantage which resides in the process herein disclosed is the elimination of lime waste disposal problems attendant the conventional reaction of calcium carbide with water. Utilizing the aqueous liquid activator of the present invention the formation of lime waste by-product is eliminated and provides for a reagent medium which can be used for extended periods of time without replenishment.
• the acetylene base fuel gas which is produced in accordance with the present invention is characterized by having enhanced storage capabilities.
• acetylene produced according to conventional methods from carbide needs be made in a reactor and stored in the presence of a flammable solvent filler, such as acetone, at a pressure not to exceed 15 psi.
• the acetylene base fuel gas obtained according to the present invention may be stored at relatively high pressures (e.g., up to 250 psi) without the presence of a solvent filler such as acetone, thereby permitting high storage capabilities. Storage in the presence of the activator actually enhances the ability of the gas to be stored at high pressures.
• the acetylene base fuel gas obtained in accordance with the present invention is relatively stable and will not decompose readily at room temperatures, even in the presence of air.
• a further advantage of the process of this invention is that the reaction is far less exothermic than that of calcium carbide with water alone. In fact, the amount of heat generated in the reaction is so low as to require no cooling of the generator.
• the reaction of calcium carbide in water results in a heat of reaction of 215° F whereas the heat of reaction utilizing the reagent of the present invention is 140° F.
• the present invention provides a process for producing an acetylene base fuel gas which comprises the steps of reacting carbide, preferably an alkaline earth metal carbide, with an aqueous liquid activator reagent composed of water, a water-soluble reaction-rate-controlling substance (preferably a water-soluble lower alkylene glycol) and an inorganic strong acid.
• carbide preferably an alkaline earth metal carbide
• aqueous liquid activator reagent composed of water, a water-soluble reaction-rate-controlling substance (preferably a water-soluble lower alkylene glycol) and an inorganic strong acid.
• the preferred carbide is calcium carbide. It will be appreciated by those skilled in the art, however, that other carbides can be employed, such as aluminum carbide and iron carbide, at a resulting increase in cost.
• Suitable inorganic strong acids include hydrochloric, sulfuric, phosphoric, carbonic and nitric acids, or mixtures thereof, with hydrochloric acid being preferred for ready availability, low cost and lack of unpleasant side reactions.
• reaction-rate-controlling substance not only retards the rate of reaction but also contributes to the stability of the gas produced. In addition the substance serves to lower the reaction temperature.
• Suitable reaction-rate-controlling substances are water-soluble alkylene glycols and water-soluble alcohols, or mixtures thereof, with the glycols being preferred because of their inflammability.
• the liquid activator reagent is prepared by mixing the water and substance components and then introducing the acid, such as hydrochloric acid, into the water-substance mixture.
• the carbide then is added, at a controlled rate, to the reagent, rather than vice-versa, for better control of the release of gas.
• the reaction of the liquid activator reagent with calcium carbide can be carried out at atmospheric pressure or at moderate pressures, say on the order of 18 psi, and produces a fuel gas containing upwards of 89%, or even more, acetylene, which fuel gas also contains vaporized and/or entrained compounds which form a most effective top cylinder lubricant for an internal combustion engine.
• a decrease in the proportion of the glycol in the reagent increases the reaction rate and vice-versa.
• an increase in the proportion of the acid increases the reaction rate and vice-versa.
• the reaction proceeds uniformly and relatively slowly without foaming (which occurs in the conventional "wet" method of producing acetylene and which inhibits release of the gas) and without the formation of a by-product hydroxide percipitate. If the glycol proportion is decreased below the minimum level, the gas tends to become unstable and hazardous like acetylene generated by the reaction of calcium carbide with water only.
• the glycol proportion should be large enough to insure stability of the gas with the attendant advantage of being subjectable to higher pressures without danger, and so that the reaction can be better controlled, i.e., uniformly regulated. Further, a decrease in the glycol proportion results in a decrease in the TCL by-product, so it would seem that the glycol enters into the reaction. If the acid proportion is decreased below the minimum level, an undesirable hydroxide by-product precipitate is formed which presents a disposal problem.
• the gas is produced at a uniform rate leaving a greasy oily by-product residue, having some particulate matter, floating on the liquid reagent.
• This residue can be removed easily by circulating the reagent through an appropriate filtering system.
• the by-product residue forms an excellent lubricant for moving parts.
• the reagent can be used for long periods of time without replenishment.
• the main reactant is the carbide.
• TCL top cylinder lubricant
• the efficacy of the by-product residue as TCL has been demonstrated by use of the gas as fuel for a Tecumseh air-cooled, one cylinder, 3 HP internal combustion engine. The engine has been so fueled and operated for at least 1000 hours, sometimes at over rated RPMs, with no signs of cylinder, piston, piston ring, or valve wear.
• the gaseous fuel of this invention mixes with air more readily than gasoline and when burned produces far less undesirable and deleterious emissions than the burning of gasoline and air.
• a 1974 Dodge van with no catalytic converter was equipped to be selectively powered with gasoline or the gaseous fuel of this invention and the emissions were measured by a State of Arizona vehicle inspection station.
• the maximum emissions allowed at that inspection were 400 parts per million (PPM) of hydrocarbon (HC) and 5.5% carbon monoxide (CO).
• PPM parts per million
• HC hydrocarbon
• CO carbon monoxide
• the inspection emission results were 410 HC (PPM) and 14.5% CO and the vehicle failed to pass inspection.
• the inspection emission results were 60 HC (PPM) and 0.14% CO and the vehicle passed the inspection by a large margin.
• the process of the present invention employs a special 3-component liquid activator reagent which reacts with the calcium carbide to achieve the results described.
• the liquid activator reagent comprises water, a water-soluble alkylene glycol or alcohol and a strong inorganic acid, preferably hydrochloric acid.
• water-soluble alkylene glycol is intended to include all glycols having substantial solubility in water.
• ethylene glycol is employed in the formation of the liquid activator reagent.
• water-soluble alcohols is intended to include all alcohols (primary, secondary and tertiary) having substantial solubility in water and generally includes those having from 1 to 8 carbon atoms. Suitable alcohols include methanol, ethanol, isopropanol, butanol and mixtures thereof. Alcohols are not preferred, however, because in general they make the activator reagent flammable.
• the glycol component is merely mixed with the water component of the activator, for example, in a vessel containing an appropriate agitator, and the acid is then added to the water-glycol mixture.
• the relative proportions of water, glycol and acid in the liquid activator reagent will have an effect on the rate of the reaction, the final composition of the fuel gas, and the by-product residue or top cylinder lubricant which are produced when the liquid activator reagent is reacted with calcium carbide.
• the water present in the aqueous liquid activator reagent may be added separately or obtained from the acid employed.
• the amount of water present must be sufficient to provide the necessary reaction with the carbide material.
• the presence of the alkylene glycol serves to control the rate of reaction and hence rate of formation of the acetylene base fuel gas, as well as the amount of the TCL by-product, and should be sufficient to provide a smooth even generation of safer more stable gas and an adequate amount of TCL when the gas is used to fuel an internal combustion engine.
• the presence of the strong inorganic acid should be sufficient to eliminate the formation of a lime (calcium hydroxide) by-product.
• the liquid reagent of this invention can be prepared and shipped as a two-component concentrate composition, namely, a mixture of a water-soluble alkylene glycol or alcohol and a strong inorganic acid in proper proportions, the mixture to be added to the appropriate amount of water at the reaction site.
• a suitable concentrate contains from about 35 to 82% by weight of the glycol or alcohol component, e.g., ethylene glycol, and from about 18 to 65% by weight of the acid.
• Such a concentrate when mixed with water forming about 30 to 60% by weight of the mixture results in the desired activator reagent.
• the calcium carbide particles so as to render the same impermeable to air and moisture. This is accomplished by coating the particles of calcium carbide with a film, impervious to air and moisture but dissoluble by the reagent, preferably composed of nitrocellulose and a polyester resin. In carrying out such a process, one merely contacts the particles of calcium carbide with a slurry of nitrocellulose and polyester resin in a suitable organic solvent such as acetone, isopropyl alcohol or mixtures thereof.
• a suitable organic solvent such as acetone, isopropyl alcohol or mixtures thereof.
• the excess slurry is drained and the particles may be dried, for example in a convection dryer, to yield particles having a film thereon impermeable to air and moisture. While the resulting coated particles are impermeable to air and moisture, upon contact with the aqueous liquid activator reagent of the present invention, the coating is broken down or dissolved and reaction occurs to generate the desired acetylene base fuel gas.
• the fuel gas and associated by-product residue which is an excellent top cylinder lubricant (TCL), are formed by reacting the liquid activator reagent, described above, with granular calcium carbide.
• the calcium carbide is metered, as required, into a closed reactor or generator containing the liquid activator reagent to produce the requisite quantity of the gaseous acetylene base fuel.
• the generator desirably is operated at approximately 15-20 psi, preferably aboaut 1.8 psi.
• the reaction goes to completion when the quantity of water in the liquid activator reagent in the generator is approximately stoichiometrically equivalent to the calcium carbide metered and charged to the generator, according to the theoretical equation Any calcium hydroxide produced by the reaction is converted to a soluble salt, e.g., CaCl, by reaction with the acid and goes into solution in the reagent.
• a soluble salt e.g., CaCl
• TCL gaseous acetylene base fuel
• All that is presently known is that at least a portion of the calcium moiety of the solid calcium carbide fuel appears to react with the glycol and acid components of the liquid activator reagent to form a compound which is at least transiently volatile, or is entrained, and some of which passes from the generator along with the gaseous fuel.
• the mixture of the compound and gaseous fuel then can be fed into the carburetor of an internal combustion engine or to a fuel burner for a boiler or the like.
• Experimental observation has determined that the TCL compound is present in a substantially constant amount in the upper portion of the combustion cylinders of an engine when fueled by the gas of this invention.
• the step of production of the liquid activator reagent consists of two sub-steps involving the mixing of water and the alkylene glycol component.
• the mixed water-glycol composition is then further mixed by addition of the acid thereto followed by additional mixing.
• this concentrate is added to the appropriate amount of water at the reaction site.
• the resulting liquid activator reagent is then charged into a gas production generator into which solid calcium carbide granules are metered.
• the reaction product from the generator comprising the acetylene base gas-TCL composition mixture is then metered to its point of use, i.e., a burner for a boiler or the like or the carburetion system of an internal combustion engine, where it is burned to provide power.
• the gaseous product had a molecular weight of 26.3, specific gravity of 0.909 (calculated) and a heating value (BTU-calculated) of 1358 per cubic foot (dry basis) at 14.696 psia at 60" F.
• Example One The procedure of Example One was repeated using an activator having the following composition (parts by weight): The resulting gas was collected in a collection tube at 16 psia and upon analysis, found to have the following composition: The gaseous product had a specific gravity of 0.894 (calculated) and a heating value (BTU-calculated) of 1424 per cubic foot (dry basis) at 14.696 psia at 60°F.
• the gaseous product had a specific gravity of 0.892 (calculated) and a heating value (BTU-calculated) of 1437 per cubic foot (dry basis) at 14.696 psia at 60°F.
• the gas produced as described can fuel the internal combustion engine of an automobile without detectable atmospheric pollution, with about one-half the amount of acetylene base gas being required to power the engine as compared to natural gas.

Landscapes

• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Chemistry (AREA)
• Lubricants (AREA)

Priority Applications (1)

Applications Claiming Priority (4)

Publications (2)

Family

ID=26727727

Family Applications (1)

Country Status (12)

Cited By (1)

Citations (2)

• 1980
  • 1980-06-10 CA CA000353665A patent/CA1179138A/en not_active Expired
  • 1980-06-12 IE IE1217/80A patent/IE51141B1/en not_active IP Right Cessation
  • 1980-06-12 AU AU59255/80A patent/AU541763B2/en not_active Ceased
  • 1980-06-13 EP EP80301997A patent/EP0021748B1/de not_active Expired
  • 1980-06-13 DE DE8080301997T patent/DE3069350D1/de not_active Expired
  • 1980-06-17 GR GR62225A patent/GR68769B/el unknown
  • 1980-06-17 BR BR8003766A patent/BR8003766A/pt unknown
  • 1980-06-18 IL IL60346A patent/IL60346A/xx unknown
  • 1980-06-18 PH PH24158A patent/PH16563A/en unknown
  • 1980-06-18 MX MX182818A patent/MX155550A/es unknown
  • 1980-06-18 ES ES493057A patent/ES8105772A1/es not_active Expired
  • 1980-06-18 PT PT71409A patent/PT71409A/pt unknown

Patent Citations (2)

Also Published As

Similar Documents

Legal Events