CN104353326A - Steric hindrance amine desulfurizing agent and preparation method thereof - Google Patents
Steric hindrance amine desulfurizing agent and preparation method thereof Download PDFInfo
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- CN104353326A CN104353326A CN201410558597.1A CN201410558597A CN104353326A CN 104353326 A CN104353326 A CN 104353326A CN 201410558597 A CN201410558597 A CN 201410558597A CN 104353326 A CN104353326 A CN 104353326A
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- butylamine
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Abstract
The invention belongs to the technical field of preparation of chemical reagents, and in particular relates to a preparation method for steric hindrance amine desulfurizing agent 1, 3-bi-tert-butylamine-2 propanol. 1, 3-bi-tert-butylamine-2 propanol crystals can be prepared through the following steps: adding 1, 3-dichloro-2 propanol and tert-butylamine, of which the proportion is 1: 2-4, as well as a reaction medium of which the inventory is 20-200wt% of the total inventory of the raw materials in percentage by weight into a reaction kettle, and performing self-compression reaction for 2-3 hours, and performing alkali neutralization reaction, extraction, drying, filtration, reduced pressure distillation and cooling crystallization on the reaction product to obtain the 1, 3-bi-tert-butylamine-2 propanol crystals. The desulfurizing agent synthetized by the preparation method disclosed by the invention has the advantages that the steric hindrance is large, the boiling point is high, the selectivity of a desulphurization process is greatly improved, and the usage scope is greatly expanded, so that the economic benefits, the environmental benefits and the social benefits of a gas purification technology of sulfur containing natural gas, refinery gas, liquified gas and the like are improved.
Description
Technical field
The invention belongs to the preparing technical field of chemical reagent, particularly relate to a kind of preparation method of sterically hindered amines desulfurizing agent 1,3-bis-tert-butylamine base-2-propyl alcohol.
Background technology
Sulfur-containing gas, refinery gas, liquefied gas all have to pass through desulfurization process and could use, and its method mainly adopts amine desulfurization.In recent years, at CO
2under a large amount of existent condition, selective absorbing H
2the technology of S receives increasing attention.Because it not only saves equipment investment, reduce operating cost, and can high CO be processed
2/ H
2the CLAUS device exhaust of S ratio, meets the environmental requirement of increasingly stringent.
At present, selectively removing H is realized
2the method of S has two: thermodynamic selectivity desulfurization and kinetic selectivity desulfurization.Thermodynamic selectivity desulfurization is realized the impact of chemical reaction equilibrium constant by research course of reaction condition, and present stage, the computational methods of reaction equilibrium constant are very large for the dependence of model, and the foundation of model is very complicated.Large quantifier elimination also shows, affects sweetening process and is optionally reaction rate but not process condition.The selective of sweetening process is improved, at present also more not gratifying method by changing process condition and thermodynamics method.
Kinetic selectivity desulfurization utilizes amine absorbent and H
2s, CO
2reaction speed this feature different realize.Various amine in process for purifying and H
2the reaction of S is a proton-exchange reaction, and this is a transient response, and this absorption process is gas-film controlled, therefore under industrial absorbent condition, and H
2s absorption rate is in fact all identical to various amine.And CO
2with reaction between amine is very complicated, large quantifier elimination shows, CO
2different with the reaction mechanism of primary amine, secondary amine and tertiary amine, reaction rate differs greatly.It is generally acknowledged under industrial absorbent condition, CO
2absorption process be the long response time of reaction rate and Liquid film diffusion two ore control.
Following developing stage is roughly experienced with the research that kinetic selectivity desulfurization is carried out for starting point:
(1) based on the MEDA aqueous solution, add a certain amount of auxiliary agent, thus improve the selective of absorption process;
(2) by MEDA is combined with physical solvent, improve sulphur analysis, improve assimilation effect;
(3) from MOLECULE DESIGN angle, synthesize a series of selective higher, the better sterically hindered amine desulfurizing agent of assimilation effect.
Summary of the invention
The object of the invention is to: take background technology as foundation, design and prepare the sterically hindered amine desulfurizing agent 1 of a kind of high selectivity, 3-bis-tert-butylamine base-2 propyl alcohol, this desulfurizing agent is greatly sterically hindered, boiling point is high, make that sweetening process is selective to be improved greatly, the scope of application is expanded greatly, thus increases economic efficiency.
Technical scheme of the present invention is as follows: tert-butylamine and 1,3-dichloroisopropanol are in reaction medium, and carry out the reaction of heating self-pressure, product, through alkali neutralization reaction, extraction, can obtain 1,3-bis-tert-butylamine base-2 propyl alcohol after drying, filtration, rectifying, crystallisation by cooling.
The method comprises the following steps:
(a) heating, self-pressure reaction: first by raw material tert-butylamine, 1,3-dichloroisopropanol and reaction medium (water, methyl alcohol, ethanol class low-carbon alcohols) on request ratio drop in reactor, heat up, self-pressure reaction 2.0 ~ 3.0 hours at 130 ~ 160 DEG C of temperature; The mol ratio added between raw material be 1,3-dichloroisopropanol: tert-butylamine=1: 2.0 ~ 4.0, and add reaction medium amount be 20 ~ 200wt% of the total inventory of raw material by weight percentage;
B () neutralization reaction: pour out after above-mentioned reactant is cooled to 60 ~ 70 DEG C, add saturated NaOH solution, carries out neutralisation treatment 0.5 ~ 1.0 hour to reactant;
C () extracts: extract (three times) the solution after neutralisation treatment with ethyl acetate, obtain upper layer of extraction liquid;
D () is dry, filtration: extract anhydrous magnesium sulfate in c is carried out drying 2 hours, filters;
(e) decompression distillation: decompression distillation is carried out to liquid in d and can obtain crystal 1,3-bis-tert-butylamine base isopropyl alcohol, pressure 0.01 ~ 0.05MPa.
After distilling remaining ingredient crystallisation by cooling in (f) e, needle-like target crystal can be obtained.
The purity (content) of above-mentioned raw materials tert-butylamine, 2-chloroethoxyethanol and reaction medium (methyl alcohol, ethanol) and used NaOH is to be analyzed pure, and water is UP level pure water.
The product that the present invention produces after testing its boiling point is 292.0 DEG C, steric hindrance coefficient-Es=3.4, vivacity PKa=10.04 ± 0.1.It is good that above feature makes the present invention have desulfuration selectivity, and absorptive capacity is large, applied range, and solvent internal circulating load is few, and operating cost is low, to advantages such as gas cleaning benefit are high.
Accompanying drawing illustrates: accompanying drawing 1 is the hydrogen nuclear magnetic resonance spectrogram of 1,3-bis-tert-butylamine base-2-propyl alcohol.
Specific implementation method:
Embodiment 1
A, by purity be >=99.0% tert-butylamine 103.90ml, content be 98% 1,3-bis-chloro-2-propyl alcohol 32.9121g, absolute ethyl alcohol 100ml drop in reactor, be heated to 130 ~ 145 DEG C, self-pressure reacts 2.0 hours;
B, above-mentioned reactant is cooled to 70 DEG C after pour out, add saturated NaOH solution (10%), under reflux conditions neutralization reaction is after 0.5 hour, is cooled to≤30 DEG C;
C, with ethyl acetate, the solution after neutralisation treatment to be extracted (3 × 70ml), obtain upper layer of extraction liquid;
D, extract anhydrous magnesium sulfate in C is carried out drying 2 hours, filter.
E, carry out decompression distillation, crystallisation by cooling to liquid in D, can obtain target crystal 48.6015g, through infrared, nuclear-magnetism chromatography is 1,3-bis-tert-butylamine base isopropyl alcohol, and productive rate is 96.1%.
The processing step of embodiment 2 the present embodiment is identical with embodiment 1.
First be the tert-butylamine 52..20ml of >=99.0% by purity, content is 98% 1,3-bis-chloro-2-propyl alcohol 16.4846g, UP level pure water 50ml drops in reactor, be heated to 130 ~ 145 DEG C, self-pressure reacts 2.0 hours, be cooled to about 65 DEG C to pour out, add saturated NaOH solution again and the neutralisation treatment 0.5 hour of refluxing at 80 DEG C, then about 25 DEG C are cooled to, with EA extraction, then drying, filtration, crystallisation by cooling after decompression distillation, can 1 be obtained, 3-bis-tert-butylamine base isopropyl alcohol 24.1796g, productive rate is 95.6%.
Embodiment 3 the present embodiment makes reaction medium with distilled water and absolute ethyl alcohol, by 51.90ml tert-butylamine, 16.4832g 1, the chloro-2-propyl alcohol of 3-bis-and 25ml water, 25ml absolute ethyl alcohol mixes, be placed in reactor, reaction temperature 130 ~ 145 DEG C, after self-pressure reacts 2.0 hours, be cooled to 65 DEG C together with reactor to pour out, add saturated NaOH solution again 70 DEG C of backflow neutralisation treatment 0.5 hour, cool the temperature to room temperature (about 28 DEG C), extract with EA, drying again, filter, after decompression distillation, crystallisation by cooling can obtain 1, 3-bis-tert-butylamine base isopropyl alcohol 24., 2793g, productive rate is 96.0%.
Embodiment 4 the present embodiment is using 50ml absolute ethyl alcohol as reaction medium, together with 52.10ml tert-butylamine, 16.4827g1, the chloro-2-propyl alcohol of 3-bis-is placed in reactor, at 140 DEG C of temperature, self-pressure reacts 3.0 hours, pour out after being cooled to 65 DEG C, add saturated NaOH solution again 70 DEG C of backflow neutralisation treatment 0.5 hour, cool the temperature to room temperature (about 25 DEG C), extract with EA, drying again, filter, crystallisation by cooling after decompression distillation, can 1 be obtained, 3-bis-tert-butylamine base isopropyl alcohol 24., 8119g, productive rate is 98.1%, contrast four examples, this scheme purity maximum output is the highest.
Claims (5)
1. a synthesis of sterically hindered amine desulfurizer, is characterized in that: this desulfurizing agent label is that F is synthesized by following component: A: the chloro-2-propyl alcohol of tert-butylamine, B:1,3-bis-, C: NaOH, D: absolute ethyl alcohol, E:UP level distilled water.Wherein the volume fraction of A is that the mass fraction of >=99.0%, B is 98%, C need be made into saturated solution (10%); E is UP level pure water.
2. a preparation method for synthesis of sterically hindered amine desulfurizer, is characterized in that: the method comprises the following steps:
A () puts into A, B and D according to ratio in claims 1 in steel bomb, be heated to 130 ~ 145 DEG C, and self-pressure reacts 2.0 hours;
B product in a is cooled to 70 DEG C by () after, add saturated NaOH solution (10%), under reflux conditions neutralization reaction is after 0.5 hour, be cooled to≤30 DEG C;
C () extracts the solution after neutralisation treatment with ethyl acetate, obtain upper layer of extraction liquid;
D extract anhydrous magnesium sulfate in c is carried out drying 2 hours by (), filter;
E () carries out rectifying to liquid in d, can obtain F crystal after cooling.
3. the preparation method of a kind of synthesis of sterically hindered amine desulfurizer according to claim 2, is characterized in that: described selected reaction medium is UP level pure water.
4. the preparation method of a kind of synthesis of sterically hindered amine desulfurizer according to claim 3, is characterized in that: described selected reaction medium is pure water and absolute ethyl alcohol, and both volume ratios are 1:1.
5. the preparation method of a kind of synthesis of sterically hindered amine desulfurizer according to claim 4, is characterized in that: choose best reaction condition, make F purity the highest, output is the highest.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106279712A (en) * | 2015-06-24 | 2017-01-04 | 中国石油化工股份有限公司 | A kind of polyamidoamine chelating agen and its preparation method and application |
| CN116943408A (en) * | 2023-06-30 | 2023-10-27 | 江苏创新石化有限公司 | Hindered amine composite desulfurizing agent and preparation method thereof |
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| CN1623978A (en) * | 2003-12-05 | 2005-06-08 | 四川省精细化工研究设计院 | Process for producing tertiary butylamine ethoxy ethyl alcohol with space steric effect |
| CN101507891A (en) * | 2009-02-24 | 2009-08-19 | 江苏大海水处理设备有限公司 | Liquid composition capable of removing sulfide in gas |
| CN103357261A (en) * | 2013-06-24 | 2013-10-23 | 宜兴汉光高新石化有限公司 | Compound desulfurizer and preparation method thereof |
| CN103920380A (en) * | 2013-01-15 | 2014-07-16 | 永清华茂生物药业有限公司 | Desulfurizing agent |
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2014
- 2014-10-21 CN CN201410558597.1A patent/CN104353326A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1623978A (en) * | 2003-12-05 | 2005-06-08 | 四川省精细化工研究设计院 | Process for producing tertiary butylamine ethoxy ethyl alcohol with space steric effect |
| CN101507891A (en) * | 2009-02-24 | 2009-08-19 | 江苏大海水处理设备有限公司 | Liquid composition capable of removing sulfide in gas |
| CN103920380A (en) * | 2013-01-15 | 2014-07-16 | 永清华茂生物药业有限公司 | Desulfurizing agent |
| CN103357261A (en) * | 2013-06-24 | 2013-10-23 | 宜兴汉光高新石化有限公司 | Compound desulfurizer and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106279712A (en) * | 2015-06-24 | 2017-01-04 | 中国石油化工股份有限公司 | A kind of polyamidoamine chelating agen and its preparation method and application |
| CN106279712B (en) * | 2015-06-24 | 2019-05-17 | 中国石油化工股份有限公司 | A kind of polyamidoamine chelating agent and its preparation method and application |
| CN116943408A (en) * | 2023-06-30 | 2023-10-27 | 江苏创新石化有限公司 | Hindered amine composite desulfurizing agent and preparation method thereof |
| CN116943408B (en) * | 2023-06-30 | 2024-01-30 | 江苏创新石化有限公司 | Hindered amine composite desulfurizing agent and preparation method thereof |
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