UA72747C2 - A method for reduction of pollutants in internal combustion engines with use of glyoxal as fuel additive - Google Patents

Abstract

Glyoxal in an aqueous solution is used in a fuel additive in order to reduce pollutants in the exhaust gases of gasoline and diesel engines. It is sufficient to add glyoxal in aqueous solution to gasoline in the dilution in the ratio of 1:1.000 to 1:20.000 and higher in order to obtain a reduction of unburned hydrocarbons and carbon monoxide in vehicles with catalytic conveners at idle and at increased idle of almost 100 %. Esterified aliphais and polyethyleneglycol are added as emulsifiers and solubilizers. Additionally, glyoxal can be used in form of its acetals and herniacetals with the resultant product being added to the fuel in combustion engines in order to reduce the pollutant emission and carbon panicles/deposits.

Description

Description of the invention

The present invention relates to fuel additives for internal combustion engines, in particular to gasoline, diesel and those using fuel oil, which contribute to the reduction of harmful emissions and accumulation of coke, increase efficiency, ensure smooth operation, and also have a cleaning effect on the combustion chamber of the engine.

Fuels for internal combustion engines and turbines harm the environment due to, among other factors, incomplete combustion in the engines, which is accompanied by emissions of hydrocarbons, carbon monoxide 70 and nitrogen oxides. The use of metal-ceramic catalytic converters is known, which reduce this harmful effect, with the help of catalytic afterburning of products formed at the exit from the engine. The energy released in this case, however, cannot be used for the main process of energy production in the engine.

It should also be noted that the efficiency of the catalytic converter can decrease over time, which in turn causes an increase in the level of pollution. The addition of a fuel additive prior to the combustion stage would have clear 19 advantages in addition to conventional exhaust emission treatment methods.

Improving the quality of fuel by adding various additives is a common method that has been used before. So, for example, according to OE-P5 582718, there are known fuel additives that improve its detonation properties. These include salts of heavy metals, in particular: salts of copper, nickel, cobalt, zinc and chromium, as well as condensation products of amines with compounds containing one or more oxygen groups together with a carbonyl group, which are added to fuel in order to increase detonation resistance. OE-P5 448 620 and OE-RZ 455 525 describe fuel containing iron or nickel carbonyl, cobalt and/or molybdenum. However, such methods have not become widely accepted, because the use of metal carbonyls causes the deposition of metal oxides in the combustion chamber and they are toxic. OE-P5 801865 describes the use of fuel additives represented by toluene, benzene, acetone, trichloroethylene or isobutyl alcohol, and in addition metal carbonyls, although the main drawback - the deposition of metal oxides in the combustion chamber remains the same. OB-A 1221488 Ge) describes fuel additives that contain tricarbonylmethyl-cyclopentadienyl manganese, tetraethyl lead or other organometallic and organic components that have two ester groups. The state of the art consists of the following organic fuel additives, which include: a mixture of aromatic amine and polyalkylphenol according to OBE-P5 845-286; derivatives of tetrarylhydrazine, diarylnitrosoamine and triarylmethyl according to OE-RB5 505928; aldehydes, quinones and ketones according to OB-RZ 612073; ketones of the general formula К-СО-К", where K is a cyclic radical, К' is an aliphatic radical, "its with at least six carbon atoms according to the US patent Mo 2,100,287; hydroquinone soluble in benzene according to OB-P5 486609; derivatives of complex esters according to OE-RB 703030, alcohols according to OB-P5 843328, condensation products of alkylene oxides - and alkylphenols according to OE-P5 1937000, anthracene derivatives according to the US patent Mo1,885,190, with 1,4-dialkylarylaryl-aminoanthraquinone according to ER 0909597581. 325 In the US patent Mo1 ,973,745 describes a method of fuel oxidation with air or oxygen at elevated temperatures, possibly in the presence of a catalyst. OBE-RB 699273 describes a method of dehydrogenation of non-flammable oils from the vapor series of diesel oils into flammable oils in the presence of oxidizing agents, such as air, oxygen, ozone, peroxides, chromic acid or nitric acid at a temperature of 150-3502C, possibly "at elevated pressures and better in the presence of a catalyst. Ozonation of fuels is also described in OB-P5 324294 and Z7Z 70 OE-RBZ 553943. According to OBE-P 5 324294 ozonides such as ethylene ozonides or a mixture of one of the conventional fuels with ozonide are used in internal combustion engines. The disadvantage of the method is the instability of ozonides, so "with their preservation for a long time, a change in the oxygen carrier is possible, partly the problems are related to environmental pollution, which were not known at the time. According to Yuoe-RZ 553943, a mixture of hydrocarbons is ozonated under pressure in the presence an oxygen carrier, such as turpentine oil, and small amounts of substances that promote inflammation. The procedures described in the above-mentioned patents have not found industrial application. The substances described are partly toxic, carcinogenic, or too expensive to use. They have not found any value. on the petrochemical market. OE 1144971 shows the use of tetraethyl lead with additives of monocarboxylic acids to increase the octane number to 20. In OE 1271455, diketones in combination with tetraethyl lead are patented as anti-knock substances. US patent Mo2,655,440 describes aliphatic polyesters of the general formula K-(OX)4-O-K, as additives that increase the cetane number . OE 19527423A1 describes the ozonation of gasoline containing benzene, and together with other oxidation products, glyoxal will be formed. This process has the disadvantage that ozonation equipment for oil refineries is unusual and expensive.

The task of this invention is to reduce pollutant emissions, fuel and product consumption

GF) basis. Environmental pollution associated with incomplete combustion of fuel in internal combustion engines, emissions of carbon monoxide, as well as emissions of nitrogen oxides are well known. The following use of catalytic converters, etc. allows at best to partially suspend these emissions.

Therefore, preference should be given to optimizing the combustion process through direct energy conversion. 60 The present invention accomplishes this task in a largely technically acceptable and efficient manner.

In this invention, pollutant emissions from internal combustion engines are reduced due to the addition of glyoxal, its derivatives and adducts in aqueous solutions to the fuel used in internal combustion engines. The best are fuel additives of various acetals and hemiacetals or their mixtures obtained by acetalation of glyoxal. for Additional information, features and benefits will be given in the description below.

Fig. 1 is a graph of the reduction of CO emissions achieved when using the additives described in the invention in an idling engine.

Fig. 2 - the same schedule for reducing hydrocarbon emissions (HC) (idling);

Fig. 3 - the same schedule for reducing CO emissions (increasing idling mode);

Fig. 4 - the same schedule for reducing hydrocarbon emissions (HC) (increasing idling mode);

Fig. 5 - a graph of emissions from a diesel engine of carbon particles (soot) depending on time, when adding additives according to the invention, which ensure a reduction of such emissions; and

Fig. 6 is a graph of the reduction of emissions of nitrogen oxides (NOx) depending on time when adding additives according to the 7/0 invention, which reduce such emissions.

Application EP 94/02052, now issued US patent No. 5,762,655, describes a method of optimizing the combustion process in an internal combustion engine. In this method, ozonized products added to gasoline and diesel fuel provide a catalytic effect, resulting in a drastic reduction in hydrocarbon under-burning and a reduction in carbon monoxide emissions. On the one hand, this method has the advantage of achieving high efficiency. However, on the other hand, this method has the disadvantage of relative high cost, because ozonating systems must be included in oil refineries and plants producing fuel for internal combustion engines.

The purpose of this invention is to obtain certain advantages in comparison with the previously described ozonation process, but without increasing the corresponding costs.

In this invention, aqueous solutions of glyoxal are used as the main part of the fuel additive to reduce harmful emissions. Glyoxal is obtained by oxidation of glycol in its aqueous solutions - according to a method known in the industry. At the same time, glyoxal can be added to the fuel either together with fuel emulsifiers or with chemical compounds, as shown below. Compared to previous proposals, the present method has the advantage that a product can be used that is produced on an industrial scale, so it is economically and technically easily feasible, and therefore the substance described here is relatively stable on storage compared to oxides, which are obtained in the process of ozonation i) according to the previously proposed method, and which have a very low stability during storage.

One factor of this decision should be taken into account in practice - we are talking about the relative solubility of glyoxal in water when it is added to gasoline. However, it was found that if polyglycol is added to a 4095 solution of glyoxal with an ordinary emulsifier consisting of etherified aliphatic compounds, an unexpectedly good solution in gasoline can be obtained. Thus, for example, TOml of 4095 glyoxal solution and 10ml of the standard, which does not include an emulsion base consisting of etherified aliphatic compounds (i.e., "EsosoOl-ACC" of the Rysyz Oie company), as well as 10ml of polyethylene glycol can be easily mixed with 50Oml gasoline Some time after mixing, a slightly cloudy emulsion additive is obtained. If you add 1 ml of methyl tert-butyl ether to it, the mixture will later become completely transparent. However, it is very important to first obtain M a homogeneous mixture from an aqueous solution of glyoxal, an emulsifier and polyethylene glycol, and then add this mixture to gasoline. Thus, an emulsion additive to gasoline is obtained that is stable during storage. High-quality gasoline is characterized by the absence of phase separation. An aqueous solution of glyoxal or concentrated glyoxal can also be added to "Adzagzoie" (a product of the company EGG E Adiyivaipe) as described in Rosyz 22/1999 p.188-189. "

In practice, the method proposed in the invention, which consists in the addition of X0O0ml of an emulsifying additive to 40 with s liters of gasoline, proved to be sufficient to reduce the amount of unburned hydrocarbons by 9595 in engines with catalytic converters at increasing idle speed and at idle speed after the machines passed five;" kilometers in city traffic conditions. Naturally, carbon monoxide could not be found for a long time under these conditions. A reduction in nitrogen oxides (NOx) emissions of approximately 9,096 was also achieved.

The following tables present the results of statistical studies based on the results of the -I test with gasoline to which the above additives were added. Because only 4 g of glyoxal was added to 40 l of gasoline, it can be assumed that glyoxal was effective as a homogeneous catalyst at the ppt level (10 7). where Moreover, water additives in the amount of uOml per 40 liters of gasoline are so small that they do not cause engine corrosion. Any and all components of the described supplement are easily ignited and non-toxic, so the possibility of a toxic effect can be excluded. In diesel fuel, the aqueous solution of glyoxal, described above, dissolves even more easily than in gasoline. In this case, a milky-turbid mixture is obtained, the phase system of which is more stable. Fuels to which this additive was added, during tests in diesel engines of cars at idle speed and at increasing idle speed (1095 increase according to the ECE standard) on average reduce normal emissions or coke deposits by 30-4095 or nitrogen oxides by 2090.

The following tables 1 and 2, as well as the graphs presented in Fig. 1-5, show the results of checking the emissions obtained with the addition of glioxapy solution according to this invention: ime) in otozlyavv 1boio1mB words 00000100 oto 00000000 00100019 in table 000000106100018 06.26. 1998 0.01 o Ge Z took 00000105 9 1 I | юю ббавляє 000001100001000105 дбав 000000010001000188 баз 0000000100010000153 овал 0000000100601000193 бвзатюв 00000005 00180000 дев 00000010 о пазл 0000000100000100102909 бззвлюя 0000000106010001864 базвлює 0000000100001000162 озовиявв 1бої ово сов 00000100 44 і пакт 00000000 00700518 болю 000000000о6 10001 базвлюв 00000000 507 бездям 00000000 002 | 0011568 standard deviation | 003 | 002 | 2767 | боб й холостого ходу) п-22 о ото 00000001001001вв08 бло 000000100010000156015 бло 000000010001000115 м зо бтовляя 0000001090000000м4 дбає 00000001000100001052 - давл 00000001000000000000ю95 м дбав 0000000000и010000100ю01005 ововлявв 1 оо 181 ся зв овал 0000001000000000502 м ват 000000010001000010915 овал 000000100000000030 ват 00000000 0910ю109 « дев 0000001000000и06 2 базвлюв 00000000000110000107105 не with bazvlyuv 00000000000050000108005. Pave 0000001000000000018005 g »Basics 00000000001001010101010000000000000000

WITH

1 "m Conditions of the experiment:

All BMW type 5 cars (525 or 528)

Measuring equipment: Pidaz AMI. Toure 465 (Sga, A!yzigia)

Zepzog AMI. Toure 1554 o Fig. 1-4 (data taken from tables 1 and 2) graphically present the average values of pollutant emissions for a stationary engine (BMW type 5 (525 or 528)) operating with standard gasoline without use and with its use glyoxal emulsions according to the present invention.

Fig. 1 shows the amount of carbon monoxide in vol.9o when the engine is idling. After the application of 60% aqueous solution of glyoxapy emulsion containing 4 g of glyoxal in 10 ml of water per 40 l of gasoline, which corresponds to the ratio of additive to fuel-1:10000, a reduction in the content of CO from 0.02 to 0.0106.95 CO was achieved, i.e. 0.0106.96 of the additive causes a reduction in the CO content by 5095. Fig. 2 shows the amount of hydrocarbon emissions (CH) in vol.vol, ppt (06.95 x 1077) under the same conditions. Thus, the use of the additive causes a reduction in emissions by approximately 7595, which corresponds to a decrease from 27.00x1 07 rev.95 to 6.82x107 rev.95. because Fig. 3 shows the amount of carbon monoxide at an increasing idle speed (1095 according to the ECE standard)

under the same qualitative and quantitative conditions. When using standard gasoline, emissions amounted to 0.05 rev.965.

After adding the additive, their number decreased to 0.0106.95, which corresponds to a reduction of 8095. The amount of hydrocarbons also decreased (see Fig. 4) from 20.14x10 706.95 to 7.23x10706.95 (increasing idle speed).

Fig. 5 shows the reduction of emissions of carbon particles over time (diesel engine type AUDI, 5 cylinders, 14 Ok.s.) after using the additive according to this invention. This additive is 5 bml of 1,1,2,2-tetraethoxyethane per 10.3 liters of diesel fuel, which corresponds to the additive: fuel ratio of 1:2060, i.e. 0.048595. After adding the additive, the amount of carbon particles emitted rapidly decreased from 27.56 carbon particles/m to 3.78 carbon particles/m in 21 minutes, corresponding to a reduction of 86.3905. After another 91 70 minutes of leakage, the amount is reduced to 0.82 carbon particles/m, corresponding to a total reduction of 9795 carbon particles emitted.

Finally, Fig. b6 shows the reduction of emissions of nitrogen oxides (NOX) (10 7 rpm 95) in exhaust gases depending on the operating time of a gasoline engine, type Ford Van MB (1996) with an increase in idling speed from 1300 to 1370 rpm. Without the use of the Additive proposed in the invention, the measured amount of oxides was 75 Z40x10 706.95. After using 0.086965 (-5Oml) of 1,1,2,2-tetramethoxyethane (TME), the number of oxides in 25 min. reduced to 135x10 "rev.9b5, and after leaking for another 15 minutes, their number decreased to 37xX10 7rev.95, which corresponds to a total reduction of approximately 9095. The best version of the invention, which uses for fuel additives instead of an aqueous solution of glyoxal acetal and glyoxal hemiacetal. The production of acetals is a well-known process in organic chemistry, described, for example, in "Organic Chemistry" by Morison and Boyd, 2nd edition, 1969, p. 633, etc. To describe acetals, a compound of the general formula B-CH( EYE ".

For example, in the simplest case, acetaldehyde reacts with methanol in the presence of NSI to obtain dimethyl acetal of acetaldehyde. Similarly, alcohols, being added to aldehydes, allow obtaining hemiacetals in reactions catalyzed by acids or bases. Hemiacetals are converted into acetals in the presence of alcohol and an acid catalyst. See also "Organic Chemistry" by Holt, Rinehart and Winston, c 1964, pp. 308-310. Such acetals and hemiacetals can be obtained according to the existing state of the art d) described above. In particular, the method of obtaining these products is as follows: bbO0m of molecular sieves 4. A is placed in a column-type reactor. A mixture of bOOg glyoxal is hydrated and 180 g of amberlite 15 (a polymer in ion exchange form) is placed in this reactor on top of the molecular sieves. The contents of the column are heated to 802C.

Then, for example, methanol or ethanol is pumped through amberlite, which is a catalyst, and through molecular sieves in (to absorb water). The methanol:water ratio is 4 mol, in the case of ethanol 12 mol. "AND

The desired compound can be obtained within 16 hours. It is separated and purified to the required compound by means of distillation. Methanol and ethanol are distilled off at a temperature of 402C and a residual pressure of 22 mm Hg. Cleaning takes place at a temperature of 582C and a residual pressure of 20 mm Hg. Art. si

Acetals and hemiacetals according to the present invention are obtained by carrying out acetalation of glyoxal with linear and/or branched alcohols containing 1-16 carbon atoms, and which are represented by such compounds as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, amyl alcohol; diols such as ethanediol, propanediol, butanediol, octanediol, neopentyl glycol, and triols such as glycerol. In addition, mixtures of these mono-, di- and triols can be used. Thus, acetals and hemiacetals according to the present invention can have different alcohol groups of the type -"СНО-СНо-" on the structural unit of glyoxal. Therefore, different physical properties of acetapes and hemiacetals can be adjusted due to the variation of hydroxyl groups. :z" This invention was shown only on the example of two variants of its implementation, which does not limit the possibility of its implementation in various variants and modifications, without changing its essence.

Reduction of CO content in the exhaust of an engine operating at idle speed -I

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Claims (9)

The formula of the invention 1. The method of reducing harmful emissions from internal combustion engines, which includes the following stages: preparation of fuel additives containing aqueous solutions of glyoxal and emulsifiers and/or surfactants, and/or antifreezes; adding an aqueous solution of glyoxal to hydrocarbon fuel; or preparation of fuel additives containing acetals and/or hemiacetals of glyoxal by acylation of glyoxal with alcohols and/or diols and/or triols in the aqueous phase; Ha separation of the final product from the aqueous phase and subsequent addition of the product to hydrocarbon fuel, in which the ratio of fuel additive and fuel is from 1:1000 to 1:20000; about supplying the mentioned fuel to internal combustion engines. 2. The method according to claim 1, which differs in that emulsifiers are esterified aliphatic hydrocarbons and/or polyethylene glycol, and/or surfactants, and antifreezes are methanol, glycerin, glycol. h- C. The method according to claim 2, which differs in that the ratio of glyoxal, esterified aliphatic hydrocarbons and/or polyethylene glycol in the solution used in the fuel additive is 2:1:1. WITH 4. The method according to point C, which includes: h- preliminary mixing of a part of the fuel with the glyoxal-emulsifier mixture; subsequent addition of methyl tert-butyl ether in a ratio of 1:50 to 1:100. with 5. The method according to claim 1, in which acylation of glyoxal is carried out by reacting glyoxal with a second reagent, h- selected from the group containing linear and/or branched C4-C46 alcohols and/or linear and/or branched C4-C46 diols mMabo C .-Si6e triols, with a preferred choice of acylating agent from the group containing methanol, ethanol, isopropanol, tert.-butanol, 1,3-propanediol, neopentyl glycol and glycerol. " 6. The method according to claim 5, which differs in that a mixture of glyoxal and/or various acetals and/or hemiacetals of glyoxal obtained by the acylation reaction of glyoxal is added to the fuel. - c 7. Hydrocarbon fuel for internal combustion engines of vehicles and heating devices, in which the indicated fuel is used, containing a fuel additive consisting of an aqueous solution of glyoxal and an emulsifier and/or surfactant, and/or antifreeze, and/or acetals, and/or hemiacetals of glyoxal, in which the ratio of fuel additive to fuel is from 1:1000 to 1:20000. 8. Fuel according to claim 7, which differs in that the emulsifiers are esterified aliphatic hydrocarbons and/or polyethylene glycol and/or surfactants, and the antifreeze is methanol, glycerin, glycol. 9. Fuel according to claim 8, which differs in that the ratio of the glycol solution, etherified aliphatic hydrocarbons and/or polyethylene glycol is 2:1:1. -And 10. Fuel according to any of claims 7-9, which is characterized by the fact that said acetals and/or hemiacetals contain C 4.16-alkyl groups, and said acetals and/or hemiacetals are preferably obtained by acylation in glyoxal linear or branched mono-, di- and triols containing 1-16 carbon atoms and which, preferably, are selected from the group containing methanol, ethanol, isopropanol, tert.-butanol, 1,3-propanediol, neopentyl glycol and glycerol. Official Bulletin "Industrial Property". Book 1 "Inventions, useful models, topographies of integrated microcircuits", 2005, M 4, 15.04.2005. State Department of Intellectual Property of the Ministry of Education and Science of Ukraine. Name) 60 b5