CN117903857A - Sulfur-free odorizing agent ingredient preparation process - Google Patents
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000004615 ingredient Substances 0.000 title claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 51
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 44
- -1 amide compounds Chemical class 0.000 claims abstract description 34
- 238000003756 stirring Methods 0.000 claims abstract description 33
- LNIMMWYNSBZESE-UHFFFAOYSA-N 2-Ethyl-3-methylpyrazine, 9CI Chemical compound CCC1=NC=CN=C1C LNIMMWYNSBZESE-UHFFFAOYSA-N 0.000 claims abstract description 28
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims abstract description 19
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 239000006084 composite stabilizer Substances 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 101000623895 Bos taurus Mucin-15 Proteins 0.000 claims abstract description 6
- 239000012747 synergistic agent Substances 0.000 claims abstract description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 30
- 239000003112 inhibitor Substances 0.000 claims description 29
- NQRYJNQNLNOLGT-UHFFFAOYSA-N tetrahydropyridine hydrochloride Natural products C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 26
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- ZFRKQXVRDFCRJG-UHFFFAOYSA-N skatole Chemical group C1=CC=C2C(C)=CNC2=C1 ZFRKQXVRDFCRJG-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 12
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 12
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims description 12
- 239000003381 stabilizer Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 2
- 238000009472 formulation Methods 0.000 claims 4
- POCUPXSSKQAQRY-UHFFFAOYSA-N hydroxylamine;hydrate Chemical compound O.ON POCUPXSSKQAQRY-UHFFFAOYSA-N 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- OWZPCEFYPSAJFR-UHFFFAOYSA-N 2-(butan-2-yl)-4,6-dinitrophenol Chemical compound CCC(C)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O OWZPCEFYPSAJFR-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 230000009977 dual effect Effects 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000008447 perception Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 2
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
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Abstract
The invention discloses a sulfur-free odorizing agent ingredient preparation process, which belongs to the technical field of odorizing agents and comprises the following steps: the following raw materials in percentage by mass are prepared: 38% of methyl acrylate, 2% of 2-ethyl-3-methyl pyrazine, 1.7-1.9% of amide compounds, 1% of synergistic agent, 0.1-0.3% of composite stabilizer and the balance of ethyl acrylate, wherein the sum of the mass percentages of the raw materials is 100%; adding an amide compound and a synergist into a mixer, and stirring and mixing to obtain a first component; adding methyl acrylate, 2-ethyl-3-methyl pyrazine and ethyl acrylate into a mixer, and stirring and mixing to obtain a component II; the component one is added into the component two, and the composite stabilizer is added after stirring and mixing for 3-5min, and the sulfur-free odorizing agent is obtained after continuous stirring.
Description
Technical Field
The invention belongs to the technical field of odorizing agents, and particularly relates to a sulfur-free odorizing agent ingredient manufacturing process.
Background
The gas odorization is one of the active safety guarantee measures of gas companies, and is highly valued by people. The conventional odorants are tetrahydrothiophene (THT) and mercaptan mixture (TBM), and both the two odorants contain sulfur (S), SO 2 gas can be generated during combustion, the combustion quality of fuel gas is affected, the product quality of some industrial users is also affected, and the environment is polluted. Along with the continuous improvement of the requirements of people on clean energy sources, the control of the sulfur content in natural gas is continuously enhanced, and the use of sulfur-free odorizing agents becomes a development trend in the future. The sulfur-free odorizing agent has the same function as the conventional odorizing agent, is a substance capable of playing a role in warning, has strong mixing capability with natural gas, is in a gaseous state in a gas pipeline, has no corrosiveness, and does not harm human bodies and the environment during combustion.
The most widely used sulfur-free odorizing agent at present is colorless transparent liquid with pungent odor, the main raw materials are methyl acrylate and ethyl acrylate, the content is more than 95%, but the methyl acrylate and the ethyl acrylate are sensitive to light and heat, so that the sulfur-free odorizing agent has a relatively harsh storage condition, and the stability of the sulfur-free odorizing agent is poor under the condition of heating or illumination, so that the content of effective components is reduced, and the product is deteriorated.
Disclosure of Invention
The invention aims to provide a preparation process of a sulfur-free odorizing agent ingredient, which aims to solve the problem of harsh storage conditions of the existing sulfur-free odorizing agent.
The aim of the invention can be achieved by the following technical scheme:
The sulfur-free odorizing agent ingredient preparation process comprises the following steps:
S1, preparing the following raw materials in percentage by mass: 38% of methyl acrylate, 2% of 2-ethyl-3-methyl pyrazine, 1.7-1.9% of amide compounds, 1% of synergistic agent, 0.1-0.3% of composite stabilizer and the balance of ethyl acrylate, wherein the sum of the mass percentages of the raw materials is 100%;
S2, adding the amide compound and the synergist into a mixer, and stirring for 10-15min at the rotating speed of 300-360r/min to obtain a component I;
S3, adding methyl acrylate, 2-ethyl-3-methyl pyrazine and ethyl acrylate into a mixer, and stirring and mixing for 15-20min at the rotating speed of 200-300r/min to obtain a component II;
s4, adding the first component into the second component, stirring and mixing for 3-5min at the rotating speed of 200-300r/min, adding the compound stabilizer, and continuing stirring for 5-10min to obtain the sulfur-free odorizing agent.
Further, in the stirring process in the step S3, the temperature is controlled to be less than or equal to 10 ℃.
Wherein the compound stabilizer is prepared by compounding 4, 6-binitro-2-sec-butylphenol and a piperidine free radical type double polymerization inhibitor.
Further, the composite stabilizer consists of 4, 6-binitro-2-sec-butylphenol and piperidine radical type double polymerization inhibitor according to the mass of 1: 1-5.
Further, the piperidine radical type double polymerization inhibitor is obtained by the steps of:
adding hydroxylamine aqueous solution into a reaction kettle, adding ethanol solution of TEMPO methyl methacrylate, stirring at room temperature for reaction for 24 hours, and spin-evaporating water to obtain a piperidine free radical type double polymerization inhibitor, wherein the molar ratio of the hydroxylamine to the TEMPO methyl methacrylate is 1:2, the mass fraction of the hydroxylamine aqueous solution is 50%, and the ethanol solution of TEMPO methyl methacrylate is prepared from TEMPO methyl methacrylate and absolute ethanol according to the dosage ratio of 1g:5-10mL, hydroxylamine and TEMPO methyl methacrylate are used as raw materials, and amino and methyl acrylate are used for reaction to obtain the piperidine free radical type double polymerization inhibitor.
Further, the synergist is 3-methylindole.
Further, the amide compound is one of N, N-dimethylformamide and N, N-dimethylacetamide.
The invention has the beneficial effects that:
1. The invention provides a sulfur-free odorizing agent ingredient preparation process, the odorizing agent obtained by the process does not contain sulfur elements, does not corrode equipment pipelines, meets the environmental protection standard, has high odor grade and good stability, and has very good application value as a combustible gas leakage warning additive.
2. According to the invention, 3-methylindole with specific composition is introduced into the traditional sulfur-free odorizing agent composed of methyl acrylate and ethyl acrylate, so that the sulfur-free odorizing agent has good compatibility with each component of the sulfur-free odorizing agent, has bad odor, can greatly improve the odor grade of the sulfur-free odorizing agent, has a certain absorption effect on ultraviolet rays due to the existence of the conjugated double bond of the 3-methylindole, and can act together with a composite stabilizer to improve the light stability of the odorizing agent.
3. The invention introduces a compound stabilizer into a sulfur-free odorizing agent composed of traditional methyl acrylate and ethyl acrylate, and is specifically formed by compounding a 4, 6-dinitro-2-sec-butylphenol and a piperidine free radical type dual polymerization inhibitor, wherein the 4, 6-dinitro-2-sec-butylphenol is a phenolic polymerization inhibitor, the piperidine free radical type dual polymerization inhibitor has the advantages of a hydroxylamine polymerization inhibitor and a piperidine free radical type polymerization inhibitor, the molecular structure contains hydroxylamine and tetramethyl piperidine-1-oxygen free radical, the polymerization inhibitor has good polymerization inhibition effect on methyl acrylate and ethyl acrylate by compounding the hydroxylamine and the tetramethyl piperidine-1-oxygen free radical, and especially the 4, 6-dinitro-2-sec-butylphenol has higher electrophilicity, can attract electrons of 0-H on the piperidine free radical type dual polymerization inhibitor to approach hydrogen atoms, thereby reducing the electron density of oxygen atoms, weakening the 0-H bond, facilitating the release of protons, accelerating the rate of generating nitrogen-oxygen free radicals, and being beneficial to improving the photo and thermal stability of the odorizing agent.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1:
The sulfur-free odorizing agent ingredient preparation process comprises the following steps:
s1, preparing the following raw materials in percentage by mass: 38kg of methyl acrylate, 2kg of 2-ethyl-3-methyl pyrazine, 1.7kg of N, N-dimethylformamide, 1kg of 3-methylindole, 0.1kg of composite stabilizer and 57.2kg of ethyl acrylate;
s2, adding N, N-dimethylformamide and 3-methylindole into a mixer, and stirring for 10min at the rotating speed of 300r/min to obtain a component I;
S3, adding methyl acrylate, 2-ethyl-3-methyl pyrazine and ethyl acrylate into a mixer, stirring and mixing for 15min at the rotating speed of 200r/min, and controlling the temperature to be less than or equal to 10 ℃ in the stirring process to obtain a component II;
S4, adding the first component into the second component, stirring and mixing at the rotating speed of 200r/min for 3min, adding the compound stabilizer, and continuing stirring for 5min to obtain the sulfur-free odorizing agent.
Wherein the composite stabilizer consists of 4, 6-binitro-2-sec-butylphenol and piperidine free radical type double polymerization inhibitor according to the mass of 1:1, and mixing.
The piperidine radical type double polymerization inhibitor is obtained by the following steps:
3.3kg of a 50wt% hydroxylamine aqueous solution was added to the reaction vessel, followed by addition of a mixed solution of 24.2kg of TEMPO methyl methacrylate and 242L of absolute ethanol, followed by stirring at room temperature for reaction for 24 hours, and water was distilled off by rotary evaporation to obtain a piperidine radical type double polymerization inhibitor.
Example 2:
The sulfur-free odorizing agent ingredient preparation process comprises the following steps:
S1, preparing the following raw materials in percentage by mass: 38kg of methyl acrylate, 2kg of 2-ethyl-3-methyl pyrazine, 1.8kg of N, N-dimethylacetamide, 1kg of 3-methylindole, 0.2kg of composite stabilizer and 57kg of ethyl acrylate;
S2, adding N, N-dimethylacetamide and 3-methylindole into a mixer, and stirring for 13min at the rotating speed of 320r/min to obtain a component I;
S3, adding methyl acrylate, 2-ethyl-3-methyl pyrazine and ethyl acrylate into a mixer, stirring and mixing for 18min at the rotating speed of 250r/min, and controlling the temperature to be less than or equal to 10 ℃ in the stirring process to obtain a component II;
S4, adding the first component into the second component, stirring and mixing at the rotating speed of 260r/min for 4min, adding the compound stabilizer, and continuing stirring for 8min to obtain the sulfur-free odorizing agent.
Wherein the composite stabilizer consists of 4, 6-binitro-2-sec-butylphenol and piperidine free radical type double polymerization inhibitor according to the mass of 1:3, mixing.
The piperidine radical type double polymerization inhibitor is obtained by the following steps:
3.3kg of a 50wt% hydroxylamine aqueous solution was added to the reaction vessel, followed by addition of a mixed solution of 24.2kg of TEMPO methyl methacrylate and 121L of absolute ethanol, followed by stirring at room temperature for reaction for 24 hours, and water was distilled off by rotary evaporation to obtain a piperidine radical type double polymerization inhibitor.
Example 3:
The sulfur-free odorizing agent ingredient preparation process comprises the following steps:
s1, preparing the following raw materials in percentage by mass: 38kg of methyl acrylate, 2kg of 2-ethyl-3-methyl pyrazine, 1.9kg of N, N-dimethylformamide, 1kg of 3-methylindole, 0.3kg of composite stabilizer and 56.8kg of ethyl acrylate;
S2, adding N, N-dimethylformamide and 3-methylindole into a mixer, and stirring for 15min at the rotating speed of 360r/min to obtain a component I;
S3, adding methyl acrylate, 2-ethyl-3-methyl pyrazine and ethyl acrylate into a mixer, stirring and mixing for 20min at the rotating speed of 300r/min, and controlling the temperature to be less than or equal to 10 ℃ in the stirring process to obtain a component II;
S4, adding the first component into the second component, stirring and mixing for 5min at the rotating speed of 300r/min, adding the compound stabilizer, and continuing stirring for 10min to obtain the sulfur-free odorizing agent.
Wherein the composite stabilizer consists of 4, 6-binitro-2-sec-butylphenol and piperidine free radical type double polymerization inhibitor according to the mass of 1:5, mixing.
The piperidine radical type double polymerization inhibitor is obtained by the following steps:
3.3kg of a 50wt% hydroxylamine aqueous solution was added to the reaction vessel, followed by addition of 24.2kg of a solution ester composed of TEMPO methyl methacrylate and 186L of absolute ethanol, followed by stirring at room temperature for reaction for 24 hours, and water was distilled off by rotary evaporation to obtain a piperidine radical type double polymerization inhibitor.
Comparative example 1:
in the sulfur-free odorizing agent ingredient preparation process, compared with the example 1, the following raw materials in percentage by mass are prepared in the step S1 of the example 1: 38kg of methyl acrylate, 2kg of 2-ethyl-3-methylpyrazine, 1.7kg of N, N-dimethylformamide, 1kg of 3-methylindole, 0.1kg of a compound stabilizer and 57.2kg of ethyl acrylate are replaced by the following raw materials in percentage by mass: 38kg of methyl acrylate, 2-ethyl-3-methylpyrazine 2kg, 1.7kg of N, N-dimethylformamide, 0.1kg of composite stabilizer and 58.2kg of ethyl acrylate, and the rest of the preparation process is the same as in example 1.
Comparative example 2:
Compared with the preparation process of the sulfur-free odorizing agent ingredient in the example 1, the compound stabilizer is prepared from 4, 6-binitro-2-sec-butyl phenol and piperidine free radical type double polymerization inhibitor according to the mass of 1:2 are mixed to form the composite stabilizer which is replaced by 4, 6-binitro-2-sec-butylphenol, and the rest of the preparation process is the same as that of the example 1.
Comparative example 3:
Compared with the preparation process of the sulfur-free odorizing agent ingredient in the example 1, the compound stabilizer is prepared from 4, 6-binitro-2-sec-butyl phenol and piperidine free radical type double polymerization inhibitor according to the mass of 1:2 is mixed to form a ' substituted ' composite stabilizer which is a piperidine radical type double polymerization inhibitor ', the preparation process of the piperidine radical type double polymerization inhibitor is the same as that of the example 1, and the rest preparation processes are the same as that of the example 1.
The sulfur-free odorizing agents obtained in examples 1 to 3 and comparative examples 1 to 3 were tested, including olfactory grade and stability, and the intensity of the odor was determined according to the Sales grade adopted in the "natural gas-gas odorizing guide" ISO/TS 16922, the grade of which was 0 to 5 grade, 1 grade was odorless, 0.5 grade was very weak odor (odor perception lower limit), 1 grade was weak odor, 2 grade was medium odor (warning odor grade), 3 grade was strong odor, 4 grade was very strong odor, 5 grade was maximum odor (odor perception upper limit), and the test procedure was as follows:
Olfactory grade: the anhydrous ethanol is selected as a dilution solution, the sulfur-free odorizing agent prepared in the examples 1-3 and the comparative examples 1-3 is diluted into sulfur-free odorizing agent solution with the concentration of 10mg/m 3, the sulfur-free odorizing agent solution with the concentration of 10mg/m 3 is uniformly sprayed on filter paper, 40 independent testees are selected to smell, the smell grade of each testee is recorded, and finally, the average value is calculated;
Stability: the sulfur-free odorizing agents obtained in examples 1-3 and comparative examples 1-3 were placed at 60℃for 6 months, sampled to detect the content of methyl acrylate thereof, the sulfur-free odorizing agents obtained in examples 1-3 and comparative examples 1-3 were placed in glass bottles, and subjected to outdoor natural light irradiation for 30 days, sampled to detect the content of methyl acrylate thereof;
The test results are shown in Table 1:
；
As can be seen from the data recorded in Table 1, the sulfur-free odorizing agent obtained in examples 1 to 3 has not only a high olfactory grade but also good photo-thermal stability compared with comparative examples 1 to 3, and in particular, the 3-methylindole in the present invention is removed as can be seen from the test results of examples 1 and comparative example 1, the obtained sulfur-free odorizing agent has not only a reduced olfactory grade but also a deteriorated photo-thermal stability, and the test results of examples 1, comparative example 2 and comparative example 3 show that the sulfur-free odorizing agent has a poor photo-thermal stability compared with the combination of both when the stabilizers are all 4, 6-dinitro-2-sec-butylphenol or a piperidine radical type double polymerization inhibitor, so that the sulfur-free odorizing agent prepared in the present invention has a high stability and a high olfactory grade and has a very good application value as a combustible gas leakage warning additive.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (6)
1. The sulfur-free odorizing agent ingredient preparation process is characterized by comprising the following steps of:
S1, preparing the following raw materials in percentage by mass: 38% of methyl acrylate, 2% of 2-ethyl-3-methyl pyrazine, 1.7-1.9% of amide compounds, 1% of synergistic agent, 0.1-0.3% of composite stabilizer and the balance of ethyl acrylate, wherein the sum of the mass percentages of the raw materials is 100%;
S2, adding the amide compound and the synergist into a mixer, and stirring and mixing for 10-15min at the rotating speed of 300-360r/min to obtain a component I;
S3, adding methyl acrylate, 2-ethyl-3-methyl pyrazine and ethyl acrylate into a mixer, stirring and mixing for 15-20min at the rotating speed of 200-300r/min, and controlling the temperature to be less than or equal to 10 ℃ to obtain a component II;
s4, adding the first component into the second component, stirring and mixing for 3-5min at the rotating speed of 200-300r/min, adding the compound stabilizer, and continuing stirring for 5-10min to obtain the sulfur-free odorizing agent.
2. The process for preparing the sulfur-free odorizing agent ingredient according to claim 1, wherein the compound stabilizer comprises 4, 6-binitro-2-sec-butylphenol and piperidine radical double polymerization inhibitor according to the mass of 1: 1-5.
3. The process for preparing a sulfur-free odorizing agent formulation of claim 2, characterized in that the piperidine radical type double polymerization inhibitor is obtained by:
adding hydroxylamine water solution into a reaction kettle, adding ethanol solution of TEMPO methyl methacrylate, stirring at room temperature for reaction for 24 hours, and spin-evaporating water to obtain the piperidine free radical type double polymerization inhibitor.
4. The process for preparing a sulfur-free odorizing agent formulation of claim 3, wherein the molar ratio of hydroxylamine to TEMPO methyl methacrylate is 1:2, the mass fraction of the hydroxylamine aqueous solution is 50%, and the ethanol solution of TEMPO methyl methacrylate is prepared from TEMPO methyl methacrylate and absolute ethanol according to the dosage ratio of 1g:5-10 mL.
5. The process for preparing a sulfur-free odorizing agent formulation of claim 1, wherein the synergist is 3-methylindole.
6. The process for preparing a sulfur-free odorizing agent formulation of claim 1, wherein the amide compound is one of N, N-dimethylformamide and N, N-dimethylacetamide.
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