CN114561236B - Environment-friendly additive suitable for combustible gas leakage warning - Google Patents
Environment-friendly additive suitable for combustible gas leakage warning Download PDFInfo
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- CN114561236B CN114561236B CN202210082132.8A CN202210082132A CN114561236B CN 114561236 B CN114561236 B CN 114561236B CN 202210082132 A CN202210082132 A CN 202210082132A CN 114561236 B CN114561236 B CN 114561236B
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- 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
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- 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
- C10L2230/10—Function and purpose of a components of a fuel or the composition as a whole for adding an odor to the fuel or combustion products
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
Abstract
The invention discloses an environment-friendly additive suitable for warning combustible gas leakage, which is prepared by compounding 80-90% of an odor agent, 5-20% of a synergistic agent and 1-10% of a stabilizing agent, wherein the odor agent consists of a component A and a component B, the component A consists of one or more of C1-C6 alkyl acrylate, C1-C4 alkyl butenoate and C1-C4 alkyl pentenoate, and the component B consists of an amide compound and a nitrogen-containing heterocyclic compound. The environment-friendly additive component does not contain sulfur, avoids corroding equipment pipelines, can meet the environment-friendly requirement, has a synergistic effect, can reach the odor level of 3-4 levels at lower concentration, has good stability, and has good application prospect as a combustible gas leakage warning additive.
Description
Technical Field
The invention relates to the technical field of environmental protection and safety of combustible gas, in particular to an odorant for warning leakage of the combustible gas such as natural gas, biogas, hydrogen and the like.
Background
At present, most of the fuel gas used by us is odorless, and in order to ensure that the fuel gas is perceived by people in the early stage of leakage, namely when the explosion limit is not reached, the addition of a fuel gas alarm with odor to the fuel gas is necessary. For example, natural gas is colorless and odorless, inflammable and explosive, and even a trace amount of leakage can be timely found and remedied after the odor agent for warning the leakage of the fuel gas is added once the leakage is difficult to find in the transportation or use process. When the natural gas concentration reaches 20% of the lower explosive limit concentration, it should be perceived, so the addition of malodorous agents is critical. The requirements to be met when the gas odorizing agent is selected are relatively large, the gas and the odorizing agent with low concentration are mixed together, the gas is ensured to have a special warning odor, and meanwhile, the odorizing agent is ensured not to hurt human bodies, gas management and gas equipment. The CJJ/T148-2010 "town gas odorizing technical Specification" has the following requirements on the quality of the gas odorizing agent: (1) The odor of the odorizing agent is obviously different from other odors in daily environment, and the odor disappears slowly; (2) Under the temperature and pressure conditions in the gas pipeline system, the odorizing agent should not be condensed; (3) The odorizing agent should not be dissolved in water to an extent of more than 2% (mass fraction); (4) The odorizing agent stored under normal temperature and normal pressure should not decompose and deteriorate during the effective period; (5) Under the temperature and pressure conditions of pipeline transportation, the odorizing agent should not react with fuel gas chemically or promote reaction; (6) no solid precipitate should be generated after the odorizing agent burns; (7) The odorizing agent and the combustion products thereof should not corrode or damage the materials and delivery systems with which they are in contact; (8) The odorizing agent should have a content that is noticeable in air.
At present, the odorizing agent of town gas at home and abroad is tetrahydrothiophene (abbreviated as THT). The odorization standard is 16-25mg/Nm 3 Its smell is considered to be the smell closest to the gas being burned. Meanwhile, as the chemical property of tetrahydrothiophene is very stable, the tetrahydrothiophene is the most stable compound in a plurality of odorizing agents, and compared with other odorizing agents, the tetrahydrothiophene has very good oxidation resistance, stable chemical property and long lasting time of odor.
However, the molecular formula of tetrahydrothiophene contains sulfur, and the existence of sulfur not only has certain corrosion to equipment pipelines, but also generates sulfur dioxide after burning along with fuel gas, so that certain environmental pollution is caused. With the growing concern of global and regional environmental problems, including the gradual appearance of environmental pollution damage caused by the industries of natural gas and biomass fuels, the related stricter standards and regulations are brought out successively, and in the case of natural gas, the total sulfur content is not higher than 20mg/m in the new gas quality standard 3 . The standard has high requirements on sulfur-containing gas desulfurization, and needs to be realized by upgrading a new desulfurization process technology or a desulfurization solvent. Therefore, the search for a sulfur-free alternative to tetrahydrothiophene would be a major market trend.
Disclosure of Invention
The invention provides an environment-friendly additive for warning leakage of combustible gas, which is compounded by an odor agent, a synergist and a stabilizer, wherein the weight percentages of the components are as follows: 80-90% of an odor agent, 5-20% of a synergistic agent and 1-10% of a stabilizing agent, wherein the odor agent consists of a component A and a component B, the component A consists of one or more of acrylic acid C1-C6 alkyl ester, butenoic acid C1-C4 alkyl ester and pentenoic acid C1-C4 alkyl ester, and the component B consists of an amide compound and a nitrogen-containing heterocyclic compound. The environment-friendly additive provided by the invention has the advantages that the components do not contain sulfur, so that corrosion to equipment pipelines is avoided, the environment-friendly additive can meet the environment-friendly requirement, the components can play a synergistic effect, the odor level can reach 3-4 levels under lower concentration, the environment-friendly additive has better stability, and the environment-friendly additive has a very good application prospect as a combustible gas leakage warning additive and has higher popularization value.
In order to solve the technical problems, the invention provides an environment-friendly additive for warning the leakage of combustible gas, which comprises the following specific components in percentage by weight:
an environment-friendly additive suitable for combustible gas leakage warning is prepared by compounding an odor agent, a synergist and a stabilizer; the mass fraction of each component is as follows: 80-90% of odor agent, 5-20% of synergistic agent and 1-10% of stabilizer.
Preferably, the malodor agent is comprised of a component a and a component B; the component A is one or more of acrylic acid C1-C6 alkyl ester, butenoic acid C1-C4 alkyl ester and pentenoic acid C1-C4 alkyl ester; the component B consists of an amide compound and a nitrogen-containing heterocyclic compound.
Preferably, the mass fraction of the A component in the odor agent is 40-60%, and the rest is the B component; the mass ratio of the amide compound to the nitrogen-containing heterocyclic compound in the component B is 0.5-3:1.
Preferably, the amide compound is one or more of N, N-dimethylformamide and N, N-dimethylacetamide; the nitrogen-containing heterocyclic compound is pyridine.
Preferably, the synergist consists of one or more of C1-C4 alkyl substituted pyrazine, double C1-C4 alkyl substituted pyrazine, single C1-C4 acyl substituted pyrazine, double C1-C4 acyl substituted pyrazine and C3-C9 carboxylic acid.
Preferably, the stabilizer consists of one or more of hydroquinone, antioxidant 2246 and vitamin E.
Preferably, the synergistic agent is any one or two of 2-methyl pyrazine and valeric acid; the stabilizer is antioxidant 2246.
The intensity of the malodour was determined according to the Sales grade adopted in the natural gas-gas odorizing guidelines ISO/TS 16922, the malodour grade of the additive being 3-4.
The beneficial effects of the invention are as follows:
the invention provides an environment-friendly additive for warning leakage of combustible gas, which is compounded by an odor agent, a synergist and a stabilizer, wherein the weight percentages of the components are as follows: 80-90% of an odor agent, 5-20% of a synergistic agent and 1-10% of a stabilizing agent, wherein the odor agent consists of a component A and a component B; the component A is one or more of acrylic acid C1-C6 alkyl ester, butenoic acid C1-C4 alkyl ester and pentenoic acid C1-C4 alkyl ester; the component B consists of an amide compound and a nitrogen-containing heterocyclic compound. The environment-friendly additive provided by the invention does not contain sulfur components, so that corrosion to equipment pipelines is avoided, the product can meet the environment-friendly requirement, each component can play a role in synergy, the odor grade can reach 3-4 grades under lower concentration, the environment-friendly additive has better stability, and the environment-friendly additive has a very good application prospect as a combustible gas leakage warning additive.
Detailed Description
The invention is further described below, but the scope of the invention is not limited to the following:
example 1:
1.0g of methyl acrylate, 2.0g of ethyl acrylate, 1.0g of N, N-dimethylformamide and 1.0g of pyridine are weighed, uniformly mixed, and then 0.1g of antioxidant 2246 and 1g of 2-methylpyrazine are added into the mixture, and uniformly stirred and mixed to form the composite additive.
Example 2:
3.0g of methyl 3-butenoate, 1.0g of N, N-dimethylformamide and 1.0g of pyridine are weighed, uniformly mixed, then 0.1g of antioxidant 2246 and 1g of 2-methylpyrazine are added into the mixture, and uniformly stirred and mixed to form the composite additive.
Example 3:
3.0g of methyl 2-pentenoate, 1.0g of N, N-dimethylformamide and 1.0g of pyridine are weighed, uniformly mixed, then 0.1g of antioxidant 2246 and 1g of 2-methylpyrazine are added into the mixture, and uniformly stirred and mixed to form the composite additive.
Example 4:
1.0g of methyl acrylate, 2.0g of ethyl acrylate, 0.7g of N, N-dimethylformamide and 1.4g of pyridine are weighed, uniformly mixed, and then 0.1g of antioxidant 2246 and 1g of 2-methylpyrazine are added into the mixture, and uniformly stirred and mixed to form the composite additive.
Example 5:
1.0g of methyl acrylate, 2.0g of ethyl acrylate, 1.5g of N, N-dimethylformamide and 0.5g of pyridine are weighed, uniformly mixed, and then 0.1g of antioxidant 2246 and 1g of 2-methylpyrazine are added into the mixture, and uniformly stirred and mixed to form the composite additive.
Example 6:
1.0g of methyl acrylate, 2.0g of ethyl acrylate, 1.0g of N, N-dimethylformamide and 1.0g of pyridine are weighed, uniformly mixed, and then 0.1g of antioxidant 2246 and 1g of valeric acid are added into the mixture, and uniformly stirred and mixed to form the composite additive.
Comparative example 1:
1.0g of methyl acrylate, 2.0g of ethyl acrylate and 2.0g of pyridine are weighed, uniformly mixed, then 0.1g of antioxidant 2246 and 1g of 2-methyl pyrazine are added into the mixture, and uniformly stirred and mixed to form the composite additive.
Comparative example 2:
1.0g of methyl acrylate, 2.0g of ethyl acrylate and 2.0g of N, N-dimethylformamide are weighed, the substances are uniformly mixed, then 0.1g of antioxidant 2246 and 1g of 2-methylpyrazine are added into the mixture, and the mixture is uniformly stirred and mixed to form the composite additive.
Application example one:
the odorizing agent in GB50028-2006 "town gas design Specification" is defined as follows: an organic compound or mixture having a strong odor. When added to a gas at very low concentrations, the gas is rendered to have a particular, unpleasant, warning odor so that the leaking gas is perceived when it reaches 20% of its lower explosion limit or reaches a harmful concentration allowed for the human body. The smell intensity of the odorizing agent refers to the intensity of the taste that is perceived. However, the odor discrimination and intensity determination are different from each other, and the odor intensity is determined by the Sales grade adopted in the "natural gas-gas odorizing guide" ISO/TS 16922, and the grade thereof is 0-5 grade. As shown in table 1:
TABLE 1
| Odor rating | Smell sense |
| 0 | Odorless |
| 0.5 | Very weak malodour (lower limit of perception of smell) |
| 1 | Weak odor |
| 2 | Medium odor (Warning odor grade) |
| 3 | Strong odor |
| 4 | The odor is very strong |
| 5 | Maximum odor (upper limit of odor sensation) |
When the odor level reaches level 2, normal persons with ordinary olfactory ability can perceive the presence of gas in the air.
In the application example of the present invention, ethanol was selected as a dilution solution, and the composite additives prepared in the above examples 1 to 7 and comparative examples 1 to 2 were further diluted to 10mg/m 3 Concentration multiplexMixing with additive solution, and concentrating to 10mg/m 3 Uniformly spraying the composite additive solution on filter paper, selecting 40 independent testers to smell, recording the smell grade of each testee, and finally calculating an average value. The results obtained are shown in Table 2:
TABLE 2
The odor of the composite additive prepared in the application examples 1-6 is very strong after dilution, the olfactory grade is 3-4, the N, N-dimethylformamide is not added in the comparative example 1, the pyridine is not added in the comparative example 2, the prepared composite additive has weak odor, the mixture of methyl acrylate, ethyl acrylate and N, N-dimethylacetamide and pyridine in proper proportion is proved to have synergistic effect as an odor agent, the odor grade of the product can be improved, and the composite additive has very high application prospect as a combustible gas leakage warning additive.
Application example two:
the compound additive solution prepared in example 1 of the present invention was left for the same time to examine the stability of the formulation with the content of the main component varied.
The detection method comprises the following steps:
(1) after the composite additive solution prepared in example 1 was left at 20℃for 20 days and 40 days, respectively, samples were taken to examine the content of the main component thereof.
(2) Temperature rise investigation: the composite additive solution prepared in example 1 was left at 45℃for 20 days and 40 days, respectively, and then sampled for measuring the content of the main component. The results are shown in Table 3.
TABLE 3 Table 3
As can be seen from Table 3, the composite additive provided by the invention has better stability.
The invention discloses an environment-friendly additive suitable for combustible gas leakage warning, which is formed by compounding 80-90% of an odor agent, 5-20% of a synergist and 1-10% of a stabilizer, wherein the odor agent consists of a component A and a component B, the component A consists of one or more of C1-C6 alkyl acrylate, C1-C4 alkyl butenoate and C1-C4 alkyl pentenoate, and the component B consists of an amide compound and a nitrogen-containing heterocyclic compound. The environment-friendly additive component does not contain sulfur, avoids corroding equipment pipelines, can meet the environment-friendly requirement, has a synergistic effect, can reach the odor level of 3-4 levels at lower concentration, has good stability, and has good application prospect as a combustible gas leakage warning additive.
So far, those skilled in the art will recognize that while embodiments of the present invention have been shown and described in detail herein, many other variations or modifications that are in accordance with the principles of the present invention may be directly ascertained or inferred from the present disclosure without departing from the spirit and scope of the present invention. Accordingly, the scope of the present invention should be understood and deemed to cover all such other variations or modifications.
Claims (6)
1. An environment-friendly additive suitable for combustible gas leakage warning is characterized by being compounded by an odor agent, a synergist and a stabilizer; the mass fraction of each component is as follows: 80-90% of odor agent, 5-20% of synergistic agent and 1-10% of stabilizer;
the odor agent consists of a component A and a component B; the component A is one or more of acrylic acid C1-C6 alkyl ester, butenoic acid C1-C4 alkyl ester and pentenoic acid C1-C4 alkyl ester; the component B consists of an amide compound and a nitrogen-containing heterocyclic compound;
the mass fraction of the component A in the odor agent is 40-60%, and the rest is the component B; the mass ratio of the amide compound to the nitrogen-containing heterocyclic compound in the component B is 0.5-3:1;
the amide compound is one or more of N, N-dimethylformamide and N, N-dimethylacetamide; the nitrogen-containing heterocyclic compound is pyridine.
2. The environmental protection additive suitable for combustible gas leakage warning according to claim 1, wherein the synergist is composed of one or more of C1-C4 alkyl substituted pyrazine, double C1-C4 alkyl substituted pyrazine, single C1-C4 acyl substituted pyrazine, double C1-C4 acyl substituted pyrazine and C3-C9 carboxylic acid.
3. An environmental protection additive suitable for flammable gas leakage warning according to claim 1, wherein the stabilizer consists of one or more of hydroquinone, antioxidant 2246, vitamin E.
4. The environmental protection additive suitable for combustible gas leakage warning according to claim 1, wherein the synergist is any one or two of 2-methyl pyrazine and valeric acid.
5. An environmental protection additive suitable for flammable gas leak warning according to claim 1, wherein the stabilizer is antioxidant 2246.
6. An environmental protection additive for flammable gas leak warning according to any of claims 1-5, wherein the intensity of malodor is determined according to the Sales class adopted in the natural gas-gas malodor guidelines ISO/TS 16922, said additive having a malodor class of 3-4.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210082132.8A CN114561236B (en) | 2022-01-24 | 2022-01-24 | Environment-friendly additive suitable for combustible gas leakage warning |
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| CN202210082132.8A CN114561236B (en) | 2022-01-24 | 2022-01-24 | Environment-friendly additive suitable for combustible gas leakage warning |
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| CN114561236B true CN114561236B (en) | 2023-06-27 |
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| CN117903857A (en) * | 2024-03-19 | 2024-04-19 | 辽宁厚安科技有限公司 | Sulfur-free odorizing agent ingredient preparation process |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19837066A1 (en) * | 1998-08-17 | 2000-02-24 | Haarmann & Reimer Gmbh | Odorizing a gas, e.g. city gas comprises adding an acrylic acid, nitrogen compound and antioxidant to the gas |
| DE10240028A1 (en) * | 2002-08-27 | 2004-03-11 | Symrise Gmbh & Co. Kg | Mixture e.g. for odorizing liquefied gas comprises at least two alkyl acrylates, sulfur compound, third component and optionally an antioxidant |
| DE10359743A1 (en) * | 2003-12-19 | 2005-07-14 | Symrise Gmbh & Co. Kg | Odorization of fuel gas with low-sulfur odorants |
| FR2902798B1 (en) * | 2006-06-26 | 2009-04-24 | Arkema France | ODORIZING MIXTURE FOR GASEOUS FUEL ODORLESS |
| DE202006018157U1 (en) * | 2006-11-28 | 2007-03-22 | Symrise Gmbh & Co. Kg | Odorant, useful in fuel gas, comprises acrylic acid methyl ester and/or acrylic acid ethyl ester, 2,3-methylethylpyrazine, hydroquinone monomethylether and tertiary-butylhydroxytoluene and/or butylhydroxyanisole |
| CN101608118B (en) * | 2008-06-19 | 2012-07-18 | 中国石油天然气股份有限公司 | Inhibitor for preventing the formation of natural gas hydrates of high-sulfur acid gas fields |
| US20100005706A1 (en) * | 2008-07-11 | 2010-01-14 | Innospec Fuel Specialties, LLC | Fuel composition with enhanced low temperature properties |
| CN113956904A (en) * | 2021-11-25 | 2022-01-21 | 沈阳光正工业有限公司 | Sulfur-free odor additive for combustible gas and preparation method thereof |
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