CN112175179B - Preparation method of polymeric triazine derivative desulfurizing agent - Google Patents
Preparation method of polymeric triazine derivative desulfurizing agent Download PDFInfo
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- CN112175179B CN112175179B CN202011011748.3A CN202011011748A CN112175179B CN 112175179 B CN112175179 B CN 112175179B CN 202011011748 A CN202011011748 A CN 202011011748A CN 112175179 B CN112175179 B CN 112175179B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
- C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
- C08G65/263—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups containing heterocyclic amine groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/52—Hydrogen sulfide
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Abstract
The invention relates to a preparation method of a polymeric triazine derivative desulfurizing agent, which is characterized in that ethylene oxide is utilized to modify on the basis of hydroxyethyl hexahydro-s-triazine, so that short-chain monoethanolamine is not regenerated after desulfurization, but long-chain polyether substances with good water solubility are generated, the existence of the long-chain polyether substances with good water solubility can not increase scaling tendency, the long-chain polyether substances can also be used as an excellent penetrating agent, the dissolution speed of hydrogen sulfide and the mass transfer speed of the hydrogen sulfide in a solution are obviously increased, the desulfurization reaction is promoted, the desulfurizing agent is more environment-friendly and reliable than the traditional desulfurizing agent, the modified desulfurizing agent is more stable in an acidic environment, the hydrolysis ring-opening speed is reduced, the long-term stability is kept high-efficiency, and the desulfurizing temperature adaptability is further enhanced.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a preparation method of a novel polymeric triazine derivative desulfurizing agent.
Background
Hexahydro s-triazine is a common desulfurizing agent, has higher desulfurizing efficiency, has advantages in thermal stability and desulfurizing capability, can selectively remove hydrogen sulfide in carbon dioxide environment, and is a desulfurizing agent suitable for on-site filling of oil and gas fields. However, the hexahydro-s-triazine can be seriously precipitated and blocked in the field, and the main reason is that after the hexahydro-s-triazine reacts with hydrogen sulfide, 3, 5-di (2-hydroxyethyl) -1,3, 5-dithiazide and 5-hydroxyethyl dithiazide in the product can be dissolved in water, but the product is also mono-ethanol, and the substance is an organic alcohol amine, and the pH value of the solution can be obviously improved after a large amount of the organic alcohol amine is accumulated, so that scaling is caused.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of a novel polymeric triazine derivative desulfurizing agent, and the invention utilizes ethylene oxide to modify on the basis of hexahydro-s-triazine, so that the ethylene oxide is not regenerated into short-chain monoethanolamine after desulfurization, but long-chain polyether substances with good water solubility, the existence of the substances does not increase the scaling trend, and meanwhile, the substances are excellent penetrating agents, can obviously increase the dissolution rate of hydrogen sulfide and the mass transfer rate in solution, promote the desulfurization reaction, and are more environment-friendly and reliable than the traditional desulfurizing agents.
The aim of the invention is achieved by the following technical scheme: a process for the preparation of a novel polymeric triazine derivative desulfurization agent comprising the steps of:
s1: adding a certain amount of ethanol, formaldehyde and 2-amino ethanol into a reaction kettle, reacting for a period of time at a set temperature, and separating and purifying to obtain hydroxyethyl hexahydro s-triazine;
s2: and (2) adding a certain amount of ethanol, ethylene oxide, the hydroxyethyl hexahydros-triazine prepared in the step (S1) and a catalyst into another reaction kettle, heating, and reacting for a period of time to obtain the target desulfurizing agent.
The reaction temperature in the step S1 is-10-10 ℃, and the reaction temperature in the step S2 is 110-120 ℃.
The catalyst in the step S2 is potassium hydroxide.
The molar ratio of potassium hydroxide to hydroxyethyl hexahydro-S-triazine in the step S2 is 0.5-1.5, and the molar ratio of ethylene oxide to hydroxyethyl hexahydro-S-triazine in the step S2 is 0.1-0.5.
The invention has the following advantages:
1. the invention is more stable in an acidic environment after modification, the speed of hydrolysis ring opening is reduced, and the high-efficiency stability can be maintained for a long time;
2. the desulfurizer has stronger penetrating agent due to the existence of polyether groups, so that the desulfurization efficiency is improved, and the desulfurization rate can be improved when the desulfurizer is used on site;
3. the adaptability of the modified substance at the desulfurization temperature is further enhanced, and the experimental result shows that the desulfurization capability of the substance can still be maintained to be more than 95% after the substance is treated at 100 ℃.
Drawings
FIG. 1 is a synthetic route diagram of the present invention;
FIG. 2 is a graph of performance tests according to the present invention;
fig. 3 is a temperature adaptability test chart of the present invention.
Detailed Description
The present invention will be further described with reference to the accompanying drawings, but the scope of the present invention is not limited to the following.
As shown in FIG. 1, the preparation method of the novel polymeric triazine derivative desulfurizing agent comprises the following steps:
s1: adding a certain amount of ethanol, formaldehyde and 2-amino ethanol into a reaction kettle, and reacting for a period of time at 0 ℃ to synthesize hydroxyethyl hexahydro s-triazine;
s2: and (3) adding a certain amount of ethanol, ethylene oxide, hydroxyethyl hexahydro S-triazine prepared in the step (S1) and potassium hydroxide into another reaction kettle, heating to 120 ℃, and continuously reacting for a period of time under the catalysis of potassium hydroxide to obtain the target desulfurizing agent.
Preparation of hydroxyethyl hexahydro s-triazine:
adding 5mol of formaldehyde, 5mol of 2-aminoethanol and 200ml of ethanol into a reaction kettle, stirring, reacting for 2 hours at 0 ℃, preserving heat for 1 hour, and separating and purifying to obtain the hydroxyethyl hexahydro s-triazine.
Example 1:
100ml of ethanol is added into a reaction kettle as a solvent, 1mol of prepared hydroxyethyl hexahydro s-triazine, 0.1mol of ethylene oxide and 0.5mol of potassium hydroxide are added, stirring is carried out, the temperature is raised to 120 ℃, and the target desulfurizing agent is obtained after reaction for 3 hours.
Example 2:
100ml of ethanol is added into a reaction kettle as a solvent, 1mol of prepared hydroxyethyl hexahydro s-triazine, 0.3mol of ethylene oxide and 1mol of potassium hydroxide are added, stirring is carried out, the temperature is raised to 120 ℃, and the target desulfurizing agent is obtained after 3 hours of reaction.
Example 3:
100ml of ethanol is added into a reaction kettle as a solvent, 1mol of prepared hydroxyethyl hexahydro s-triazine, 0.5mol of ethylene oxide and 1.5mol of potassium hydroxide are added, stirring is carried out, the temperature is raised to 120 ℃, and the target desulfurizing agent is obtained after reaction for 3 hours.
Performance test of desulfurizing agent:
taking 5ml of the desulfurizing agent prepared in the embodiment 1-3, adding the desulfurizing agent into an absorption bottle containing 95ml of clear water, and uniformly stirring. A mixed gas of nitrogen and hydrogen sulfide having a hydrogen sulfide concentration of 4000ppm was introduced. The gas flow rate is controlled to be 20ml/min, and the mixed gas is fully contacted with the desulfurizing agent diluent. And then measuring the content of hydrogen sulfide in the mixed gas after desulfurization treatment by using a hydrogen sulfide detector at the outlet of the absorption bottle.
Temperature adaptability test:
5ml of the desulfurizing agent synthesized in example 2 was treated at 30℃at 40℃at 50℃at 60℃at 70℃at 80℃at 90℃and at 100℃respectively, and then added to an absorption bottle containing 95ml of clear water, followed by stirring uniformly. A mixed gas of nitrogen and hydrogen sulfide having a hydrogen sulfide concentration of 4000ppm was introduced. The gas flow rate is controlled to be 20ml/min, and the mixed gas is fully contacted with the desulfurizing agent diluent. And then measuring the content of hydrogen sulfide in the mixed gas after desulfurization treatment by using a hydrogen sulfide detector at the outlet of the absorption bottle.
As can be seen from FIG. 2, the desulfurization effect is best when the molar ratio of potassium hydroxide to hydroxyethyl hexahydro-s-triazine is 1:1 and the molar ratio of hydroxyethyl hexahydro-s-triazine to ethylene oxide is 1:0.3; as can be seen from fig. 3, after the modified desulfurizing agent is treated at 100 ℃, the desulfurizing ability of the substance can still be maintained to be more than 95%, and the control group is a blank control without desulfurizing agent.
Claims (2)
1. The application of a polymeric triazine derivative in a desulfurizing agent is characterized in that the preparing method of the desulfurizing agent comprises the following steps:
s1: adding a certain amount of ethanol, formaldehyde and 2-amino ethanol into a reaction kettle, reacting for a period of time at a set temperature, and separating and purifying to obtain hydroxyethyl hexahydro s-triazine; the reaction temperature is-10-10 ℃;
s2: adding a certain amount of ethanol, ethylene oxide, hydroxyethyl hexahydro S-triazine prepared in the step S1 and a catalyst into another reaction kettle, heating, and reacting for a period of time to obtain a target desulfurizing agent; the molar ratio of the catalyst to the hydroxyethyl hexahydro-S-triazine is 0.5-1.5, the reaction temperature in the step S2 is 110-120 ℃, and the molar ratio of the ethylene oxide to the hydroxyethyl hexahydro-S-triazine in the step S2 is 0.1-0.5.
2. The use according to claim 1, characterized in that: the catalyst in the step S2 is potassium hydroxide.
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| CN114763338A (en) * | 2021-01-15 | 2022-07-19 | 中国石油化工股份有限公司 | Crude oil desulfurizing agent and preparation method thereof |
| CN113599990B (en) * | 2021-07-13 | 2024-02-27 | 克拉玛依市杰德科技有限责任公司 | Anhydrous desulfurizing agent and application thereof |
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| CN117720891A (en) * | 2023-12-13 | 2024-03-19 | 成都汇能恒源科技有限公司 | Sulfur removal agent for drilling fluid and preparation method and application thereof |
| CN118577100A (en) * | 2024-06-26 | 2024-09-03 | 宜兴汉光高新石化有限公司 | Efficient compound desulfurization and decarbonization solvent and preparation method thereof |
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