Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
  • C10L3/003—Additives for gaseous fuels
  • C10L3/006—Additives for gaseous fuels detectable by the senses

Definitions

• the present invention relates to the use of mixtures containing alkyl acrylates and / or alkyl methacrylates and phenols and / or
• Phenol ether for the odorization of natural gas a process for the odorization of natural gas and natural gas containing these mixtures.
• Gas odorization is the addition of odor-intensive substances (odorants) that act as warning or alarm substances to otherwise odorless gases.
• Natural gas mainly consists of methane (typical methane contents are in the range of 50 to 99% by weight, mostly in the range of 60 to 90% by weight) and, depending on its origin, can also contain different proportions of ethane, propane and higher molecular weight hydrocarbons.
• gas is therefore odorized by adding odor-intensive substances.
• Germany for example, it is stipulated that all gases that do not have a sufficient own smell and are distributed in the public gas supply are odorized according to DVGW worksheet G 280
• DNGW German Gas and Water Association
• shock odorization up to three times the amount of odorant is added to the gas compared to conventional odorization. Shock odorization is used, for example, when commissioning new networks or line sections to quickly reach the minimum odorant concentration or to detect small leaks in the gas installation.
• THT and mercaptans are ideal for reliable gas odorization.
• the combustion of gases odorized in this way produces sulfur oxides as combustion products - several hundred tons per year nationwide.
• JP-B-51-007481 mentions that acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate and butyl acrylate are known to have weak odorization properties for fuel gases and are of practically no significance in this regard.
• the document describes and claims allyl acrylate as an effective odorant.
• odorant containing an alkyne and at least 2 compounds selected from a group consisting of methyl acrylate, ethyl acrylate, methymethacrylate, allyl methacrylate, ethyl propionate, methyl n-butyrate, Methyl iso-butyrate and prenyl acrylate, and optionally tert-butyl mercaptan, are suitable for the odorization of fuel gases.
• object of the present invention is the use of mixtures containing at least one acrylic acid-C ⁇ -C 6 alkyl ester or at least one methacrylic acid-C ⁇ -C 6 alkyl esters, at least one compound of formula (I)
• R 1 represents hydrogen, methyl or ethyl
• R 2 to R 4 are independently hydrogen, an alkoxy group with 1 to
• R 1 and R 4 together form a total of 5- to 7-membered ring which is optionally substituted with alkoxy groups with 1 to 4 carbon atoms or alkyl groups with 1 to 4 carbon atoms, the ring members of which
• Methane content of at least 60% by weight.
• Another object of the present invention is a process for the odorization of fuel gases with a methane content of at least 60% by weight with the mixtures according to the invention.
• the present invention further relates to fuel gases with a methane content of at least 60% by weight. mixtures according to the invention.
• the mixtures (odorants) according to the invention are excellent alternatives to known sulfur-free odorants.
• the alkyl or alkenyl groups with up to 5 carbon atoms can be methyl, ethyl, ethenyl, n-propyl, 1-propen-1-yl, 2-propen-l-yl, 2-propyl -, 1-
• the alkoxy groups with 1 to 4 carbon atoms can be methoxy
• R 1 represents hydrogen or methyl
• R 2 to R 4 are independently hydrogen, an alkoxy group with 1 to
• R 1 and R 4 together form a total of 5- or 6-membered ring which is optionally substituted with alkoxy groups with 1 or 2 carbon atoms, alkyl groups with 1 to 4 carbon atoms or alkenyl groups with 2 to 4 carbon atoms, the ring members of carbon atoms and Nitrogen atoms exist, wherein R 1 and R 4 together have at least one carbon atom and one nitrogen atom as ring members.
• the compounds of formula (I) preferred according to the invention are liquid at 25 ° C. and 1013 mbar. These liquids can also be highly viscous or oily.
• Particularly advantageous compounds are phenols and correspond to the formula (Ia):
• R 2 to R 4 are independently hydrogen, an alkoxy group with 1 to
• ortho-phenols and 2,3-, 2,4-, 2,5- or 2,6-substituted phenols.
• R "to R 4 independently of one another are hydrogen, an alkoxy group with 1 to 3 carbon atoms, in particular methoxy, isopropoxy, an alkyl group with 1 to 3 carbon atoms or an alkenyl group with 2 or 3 carbon atoms, in particular methyl, ethyl, isopropyl, vinyl, allyl.
• R 5 denotes hydrogen, acetyl, propionyl, an alkyl group with 1 to 3 carbon atoms, an alkenyl group with 2 or 3 carbon atoms, in particular methyl, ethyl, isopropyl, vinyl, allyl;
• R 6 represents hydrogen, an alkyl group having 1 to 3 carbon atoms or an alkenyl group having 2 or 3 carbon atoms, in particular hydrogen, methyl, ethyl, isopropyl, vinyl, allyl;
• A means hydrogen, methyl or a lone pair of electrons
• the acrylic acid -CC 6 -alkyl esters are advantageously selected from the group comprising methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate , Acrylic acid-n-pentyl ester, acrylic acid-isopentyl ester and
• C 4 -C 4 -alkyl acrylates in particular methyl acrylates, ethyl acrylates, n-propyl acrylates, isopropyl acrylates, n-butyl acrylates and isobutyl acrylates.
• Very particularly preferred are methyl acrylates, ethyl acrylates, n-propyl acrylates, isopropyl acrylates, n-butyl acrylates and isobutyl acrylates.
• Acrylic C 1 -C 4 alkyl esters are methyl acrylate, ethyl acrylate and n-butyl acrylate.
• the methacrylic acid -C ⁇ 6 alkyl esters are advantageously selected from the group consisting of methacrylic acid methyl ester, methacrylic acid ethyl ester, methacrylic acid n-propyl ester, methacrylic acid isopropyl ester, methacrylic acid n-butyl ester, methacrylic acid iso-butyl ester, methacrylic acid tert. -butyl ester, methacrylic acid-n-pentyl ester, methacrylic acid-isopentyl ester and methacrylic acid-n-hexyl ester.
• methacrylic acid -CC alkyl in particular methyl methacrylate, methyl methacrylate, n-propyl methacrylic acid, methacrylic acid isopropyl ester, methacrylic acid n-butyl ester and methacrylic acid isobutyl ester.
• methacrylic C 1 -C 4 -alkyl esters are methacrylic acid methyl ester and methacrylic acid ethyl ester.
• Preferred odorants contain at least 2 or at least 3 acrylic acid alkyl esters, at least 2 or at least 3 methacrylic acid alkyl esters or at least one acrylic acid alkyl ester and at least one methacrylic acid alkyl ester.
• Particularly preferred odorants contain at least 2 or at least 3 acrylic acid alkyl esters.
• the acrylic mixtures contain the low molecular weight
• Acrylic acid alkyl ester and the higher molecular weight acrylic acid alkyl ester preferably in a weight ratio of 9: 1 to 1: 9, preferably from 7: 3 to 3: 7.
• the odorant contains, at the same time, at least two C 1 -C 4 -alkyl esters, very preferably methyl and
• the compounds of the formula (I) can be used in the mixtures according to the invention in amounts of 1 to 100, preferably 10 to 100, in particular 20 to 50 parts by weight per 1000 parts by weight of C 1 -C 6 -alkyl ester and / or methacrylic acid.
• Ci-C ö alkyl esters are used.
• Common antioxidants can be added to the odorant according to the invention, for example, to increase stability. become.
• Examples include vitamin C and derivatives (e.g. ascorbyl palmitate, ascorbyl acetate), tocopherpole and derivatives (e.g. vitamin E, vitamin E - acetate), vitamin A and derivatives (vitamin A - palmitate) phenolic benzylamines, formic acid, acetic acid, benzoic acid, Sorbic acid, hexamethylenetetramine, tert-butylhydroxytoluene, tert-butylhydroxyanisole, ⁇ -hydroxy acids (eg citric acid, lactic acid, malic acid), hydroquinone monomethyl ether.
• Preferred antioxidants are tert-butylhydroxy toluene (BHT, Jonol), tert-butylated hydroxyanisole, hydroquinone monomethyl ether and ⁇ -tocopherol.
• the odorants advantageously contain one, two or three antioxidants, and one or two antioxidants are preferred.
• the antioxidants are preferably used in amounts of 0.01 to 5, in particular 0.05 to 2, especially 0.1 to 1 part by weight per 1000 parts by weight of acrylic acid alkyl ester and / or methacrylic acid ester.
• the total amount of antioxidants in the odorant is usually in the range 0.001-1% by weight, preferably in the range 0.01-0.5% by weight, particularly preferably in the range 0.05-0.25% by weight.
• the amount of odorant based on the gas to be odorized is typically in the range 5-100 mg / m 3 , preferably 5-50 mg / m 3 , particularly preferably 10-40 mg / m 3 and very particularly preferably 12-30 mg / m 3rd
• Me-Ac methyl acrylate; Et-Ac: ethyl acrylate; Bu-Ac: n-butyl acrylate; Me-Me: methyl methacrylate; Et-Me: ethyl methacrylate; Bu-Me: n-butyl methacrylate; BHT: tert-butylated hydroxytoluene; BHA: tert-butylated hydroxyanisole; Hydr: hydroquinone monomethyl ether example 1
• the odorants according to the invention were evaluated in terms of their odor and their warning intensity against unodorized natural gas (blank value) in concentrations of 10, 25 and 50 mg / m 3 natural gas (methane content: 85% by weight).
• concentrations correspond to the typical concentrations of odorant in natural gas under normal conditions or with shock odorization.
• the experiment was carried out at room temperature (about 20 ° C.) in such a way that the odorant was metered into a gas stream in a tube. At the end of this
• Table 2 shows the evaluations for phenols of the formula (Ia), which were carried out as described in Example 1.
• Table 3 shows the evaluations for anisoles of the formula (Ib), which were carried out as described in Example 1.
• Table 4 shows the evaluations for compounds of the formula (Ic), which were carried out as described in Example 1.
• Table 5 shows evaluations for phenols and phenol ethers which are not in accordance with the invention, and were carried out as described in Example 1.
• Table 6 shows odorants according to the invention with acrylates containing antioxidants.
• Table 7 shows odorants according to the invention with methacrylates containing antioxidants.
• Table 8 shows odorants according to the invention containing mixtures of compounds of the formula (I) according to the invention and antioxidants.
• Table 9 shows odorants according to the invention with acrylates and methacrylates containing 0.1 parts by weight of antioxidants (BHT or BHA).
• BHT antioxidants

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• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Solid-Sorbent Or Filter-Aiding Compositions (AREA)
• Treating Waste Gases (AREA)
• Liquid Carbonaceous Fuels (AREA)

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• 2002
  • 2002-08-05 DE DE10235756A patent/DE10235756A1/de not_active Withdrawn
• 2003
  • 2003-08-02 DE DE50307299T patent/DE50307299D1/de not_active Expired - Lifetime
  • 2003-08-02 AT AT03784163T patent/ATE362505T1/de not_active IP Right Cessation
  • 2003-08-02 EP EP03784163A patent/EP1529093B1/fr not_active Expired - Lifetime
  • 2003-08-02 WO PCT/EP2003/008597 patent/WO2004015040A1/fr not_active Ceased
  • 2003-08-02 AU AU2003258565A patent/AU2003258565A1/en not_active Abandoned

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