CN114130178A - Composite desulfurizer, preparation method and application thereof - Google Patents
Composite desulfurizer, preparation method and application thereof Download PDFInfo
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- B01D53/34—Chemical or biological purification of waste gases
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/50—Sulfur oxides
- B01D53/507—Sulfur oxides by treating the gases with other liquids
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- B01D53/34—Chemical or biological purification of waste gases
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- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
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Abstract
The invention discloses a composite desulfurizer, a preparation method and application thereof; the compound desulfurizer comprises a compound containing hydroxyl and amino, a saccharide compound, a compound salt, a surfactant and a pH regulator; wherein, the compound containing hydroxyl and amino is prepared from (R) -3-chlorphenyl oxirane and 3- (benzyloxy) benzene-1, 2-diamine or N-tert-butyloxycarbonyl-1, 3-propane diamine. The composite desulfurizer prepared by the invention has better self-corrosion resistance and higher SO2、H2The S removal rate and the excellent oil solubility stability are achieved.
Description
Technical Field
The invention relates to a desulfurizer, and in particular relates to a composite desulfurizer, a preparation method and application thereof.
Background
With the increasing use of coal and fossil fuel, SO generated by combustion2The harm of gas to the atmospheric environment and the ecological system is becoming more and more serious, so that research and development of a green, environment-friendly and efficient desulfurization method becomes urgent. The traditional flue gas desulfurization technology has the defects of large investment, difficult regeneration of absorbent and SO2Difficult to recycle, and the novel composite desulfurization technology has high desulfurization efficiency, strong regenerability and SO2Good recycling effect,No secondary pollution, etc., meets the requirement of green environment-friendly organic chemicals, and has very wide application prospect in the aspects of economic benefit and environmental protection.
The development of a desulfurizing agent and various desulfurization techniques become important means for solving the problem of environmental pollution. Currently, desulfurization methods are classified into absorption methods, adsorption methods, oxidation methods, biological methods, pulse corona methods, and the like according to the characteristics of the removal method; the process can be divided into regenerative solvent absorption desulfurization, fixed bed adsorption desulfurization, membrane separation method desulfurization, biological desulfurization, physical field desulfurization and the like.
The prior art, for example, publication No. CN100411712A discloses a composite desulfurizer, which is used for flue gas desulfurization and acid-containing wastewater treatment. It comprises raw materials of lime, thiourea byproduct and thiourea byproduct, wherein the thiourea byproduct contains calcium hydroxide. The composite desulfurizer can adsorb various components of waste gas and waste water, such as SO2、SO3、H2S, organic sulfur, normal butyl sulfur and the like, and the desulfurization rate can reach 96 percent. The atomizing nozzle is not easy to block, and the pipeline is not easy to scale.
Disclosure of Invention
The invention aims to provide a high-SO-content alloy with good self-corrosion resistance2、H2The composite desulfurizer has high S removal rate and excellent oil solubility stability.
The technical scheme adopted by the invention for realizing the purpose is as follows:
a composite desulfurizer comprises a compound containing hydroxyl and amino;
wherein, the structural formula of the compound containing hydroxyl and amido is as follows:
Preferably, the compound containing a hydroxyl group and an amine group is prepared from (R) -3-chlorophenyloxirane and 3- (benzyloxy) benzene-1, 2-diamine or N-tert-butoxycarbonyl-1, 3-propanediamine.
The compound containing hydroxyl and amino is prepared by adopting (R) -3-chlorphenyl ethylene oxide and 3- (benzyloxy) benzene-1, 2-diamine or N-tert-butyloxycarbonyl-1, 3-propane diamine, and the compound is used as a component of the compound desulfurizer to prepare the compound desulfurizer, wherein the compound desulfurizer has excellent self corrosion resistance, reduces the corrosion performance to a production device, and ensures that production equipment has longer service life; simultaneously, the compound desulfurizer interacts with the components in the compound desulfurizer to improve SO of the compound desulfurizer2The absorption and desorption performance of the catalyst; in addition, the composite desulfurizer has good oil solubility stability and excellent removal efficiency on hydrogen sulfide.
More preferably, the compound containing hydroxyl and amine groups is prepared by the following method: heating (R) -3-chlorphenyl oxirane and dilute sulfuric acid solution to react to prepare a substance a; and (2) reacting the substance a with a 3- (benzyloxy) benzene-1, 2-diamine solution or an N-tert-butyloxycarbonyl-1, 3-propane diamine solution under the heating condition to obtain a compound containing hydroxyl and amino.
Preferably, the composite desulfurizer also comprises a saccharide compound, a composite salt, a surfactant and a pH regulator.
More preferably, the compound desulfurizer comprises, by weight, 4.5-6.5 parts of a compound containing hydroxyl and amino, 3.5-7.5 parts of a saccharide compound, 1.5-3.5 parts of a compound salt, 0.1-0.25 part of a surfactant and 0.25-1 part of a pH regulator.
More preferably, the saccharide compound is one or more of stevioside, xylitol, lactitol, sodium gluconate and calcium gluconate.
Further preferably, the weight ratio of stevioside, lactitol and calcium gluconate in the saccharide compound is 1:1: 2-5.
More preferably, the complex salt comprises calcium phosphate, sodium acetate, sodium humate.
Further preferably, the weight ratio of the calcium phosphate to the sodium acetate to the sodium humate in the composite salt is 1:1: 0.35-0.55.
More preferably, the surface active agent is one or a mixture of several of dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride and octadecyl trimethyl ammonium chloride.
More preferably, the pH regulator is one or a mixture of sodium hydroxide, sodium carbonate and sodium bicarbonate.
The invention also discloses a preparation method of the composite desulfurizer, which comprises the following steps:
adding a compound containing hydroxyl and amino, a saccharide compound, a composite salt, a surfactant and a pH regulator into a solvent, and uniformly mixing to obtain the composite desulfurizer.
The invention also discloses the application of the composite desulfurizer in removing SO2And/or H2Use in S.
In order to make the composite desulfurizer have more excellent desulfurization effect and better oil solubility stability, the preferable measures adopted also comprise: adding 1-3 parts of erythritol and 5 '-disodium inosinate compound into the composite desulfurizer, wherein the weight ratio of the erythritol to the 5' -disodium inosinate compound is 0.45-0.65: 1. The addition of the erythritol and 5' -disodium inosinate compound interacts with other components of the composite desulfurizer, so that the desulfurization effect and the oil solubility stability of the composite desulfurizer are further improved.
According to the invention, as the compound containing hydroxyl and amino is prepared from (R) -3-chlorphenyl oxirane and 3- (benzyloxy) benzene-1, 2-diamine or N-tert-butyloxycarbonyl-1, 3-propane diamine and is used as a component of the composite desulfurizer to prepare the composite desulfurizer, the composite desulfurizer has excellent self-corrosion resistance, reduces the corrosion performance to a production device, and enables production equipment to have longer service life; simultaneously, the compound desulfurizer interacts with the components in the compound desulfurizer to improve SO of the compound desulfurizer2The absorption and desorption performance of the catalyst; in addition, the composite desulfurizer has good oil solubility stability and excellent removal efficiency on hydrogen sulfide. Therefore, the invention has better self-corrosion resistance and higher SO2、H2The composite desulfurizer has high S removal rate and excellent oil solubility stability.
Detailed Description
For further illustration of the present invention, the present invention is described in detail with reference to the following examples, but it should be understood that these examples are carried out on the premise of the technical solution of the present invention, and the detailed embodiments and the specific operation procedures are given only for further illustration of the features and advantages of the present invention, not for limitation of the claims of the present invention, and the scope of the present invention is not limited to the following examples.
Further, in the embodiment of the present invention, the compound containing hydroxyl and amine groups is prepared by the following steps: putting 90-120 parts by weight of (R) -3-chlorophenyl oxirane and 50-80 parts by weight of 5-10% dilute sulfuric acid solution into a three-neck round-bottom flask, performing magnetic stirring, heating to 75-85 ℃ for reaction for 0.5-1 h, then adding 50-60 parts by weight of (R) -3-chlorophenyl oxirane, heating to 90-100 ℃ for reaction for 2-3 h, after the reaction is finished, adjusting the pH to 6.5-7.0, filtering, and distilling under reduced pressure to obtain a substance a;
dissolving 10-15 parts of 3- (benzyloxy) benzene-1, 2-diamine or 8-12 parts of N-tert-butyloxycarbonyl-1, 3-propane diamine in 50-80 parts of anhydrous methanol, heating to 55-65 ℃ under stirring conditions to completely dissolve reactants, then adding 24.5-37.5 parts of the substance a, continuing to react for 1-2 hours under the heating conditions, then adding 30-40 parts of a 10-15% sodium hydroxide solution, continuing to react for 4-6 hours after the addition is finished, performing suction filtration, distilling the filtrate under reduced pressure, washing, performing suction filtration, and recrystallizing to obtain the compound containing hydroxyl and amino.
Further, in an embodiment of the present invention, a method for preparing a composite desulfurizing agent includes:
according to the weight parts, 4.5-6.5 parts of a compound containing hydroxyl and amino, 3.5-7.5 parts of a saccharide compound (wherein the weight ratio of stevioside to lactitol to calcium gluconate is 1:1: 2-5), 1.5-3.5 parts of a compound salt (wherein the weight ratio of calcium phosphate to sodium acetate to sodium humate is 1:1: 0.35-0.55), 0.1-0.25 part of a surfactant and 0.25-1 part of a pH regulator are added into 200-400 parts of a solvent and uniformly mixed to obtain the compound desulfurizer.
In the embodiment of the present invention, the solvent used in the composite desulfurizing agent is water.
The technical solution of the present invention is further described in detail with reference to the following embodiments:
example 1:
the preparation method of the compound containing hydroxyl and amino comprises the following steps: putting 100 parts by weight of (R) -3-chlorphenyl ethylene oxide and 75 parts by weight of dilute sulfuric acid solution with the concentration of 5% in a three-neck round-bottom flask, magnetically stirring, heating to 80 ℃ for reaction for 0.5h, then adding 55 parts by weight of (R) -3-chlorphenyl ethylene oxide, heating to 100 ℃ for reaction for 2h, after the reaction is finished, adjusting the pH to 7.0, filtering, and distilling under reduced pressure to obtain a substance a;
dissolving 12 parts of 3- (benzyloxy) benzene-1, 2-diamine in 60 parts of anhydrous methanol, heating to 60 ℃ under the stirring condition to completely dissolve reactants, then adding 28 parts of the substance a, continuously reacting for 1 hour under the heating condition, then adding 35 parts of sodium hydroxide solution with the concentration of 12.5 percent, continuously reacting for 5 hours after the addition is finished, carrying out suction filtration, carrying out reduced pressure distillation on the filtrate, washing, suction filtration and recrystallization to obtain a compound containing hydroxyl and amino, wherein the structural formula of the compound is as follows:
。
the nuclear magnetic resonance apparatus (AVANCE 300, BRUKER, Germany) is adopted to carry out structural characterization on the following components:1H NMR(400MHz, DMSO)：10.49(s, 2H, NH)、7.63(d, 2H, CH)、7.51(d, 2H, CH)、7.42(t, 2H, CH)、7.38(s, 1H, CH)、7.34(t, 1H, CH)、7.25(t, 2H, CH)、6.99(d, 2H, CH)、6.89(t, 1H, CH)、6.83(d, 1H, CH)、6.62(d, 1H, CH)、5.99(d, 1H, CH)、5.18(d, 2H, OH)、5.14(s, 2H, CH2)、4.86(m, 2H, CH)、4.61(t, 2H, OH)、4.07(T, 4H, CH2)。
example 2:
a method for preparing a compound containing hydroxyl and amine groups, which is different from the compound of example 2: dissolving 10.5 parts of N-tert-butyloxycarbonyl-1, 3-propanediamine in 70 parts of anhydrous methanol, heating to 60 ℃ under stirring to completely dissolve the reactants, adding 30 parts of the above substance a, continuing to react for 1 hour under the heating condition, and adding 40 parts of the above substance a12.5 percent of sodium hydroxide solution, continuously reacting for 5 hours after the sodium hydroxide solution is added, filtering, distilling the filtrate under reduced pressure, washing, filtering, recrystallizing to obtain the compound containing hydroxyl and amido, wherein the structural formula is as follows:
。
the structural representation of the compound by adopting a nuclear magnetic resonance spectrometer is as follows:1H NMR(400MHz, DMSO)：7.85(s, 1H, CH)、7.71(d, 1H, CH)、7.39(t, 1H, CH)、7.18(t, 1H, CH)、7.15(t, 1H, CH)、6.89(s, 1H, CH)、6.76(d, 1H, CH)、6.45(d, 1H, CH)、6.41(t, 1H, NH)、5.19(d, 2H, OH)、4.89(m, 2H, CH)、4.60(t, 2H, OH)、4.35(t, 2H, CH2)、4.07(t, 4H, CH2)、3.37(m, 2H, CH2)、2.05(m, 2H, CH2)、1.43(s, 9H, CH3)。
example 3:
a preparation method of the composite desulfurizer comprises the following steps:
according to the parts by weight, 5 parts of the compound containing hydroxyl and amino in example 1, 4.5 parts of carbohydrate compound (wherein the weight ratio of stevioside, lactitol and calcium gluconate is 1:1: 3), 2.5 parts of compound salt (wherein the weight ratio of calcium phosphate, sodium acetate and sodium humate is 1:1: 0.35), 0.15 part of hexadecyltrimethylammonium chloride and 0.45 part of sodium bicarbonate are added into 250 parts of water, and the mixture is stirred and mixed uniformly to obtain the compound desulfurizer.
Example 4:
a method for preparing a composite desulfurizing agent, which is different from that in example 3: the compound containing hydroxyl and amine groups in example 1 in the composite desulfurizing agent was replaced with the compound containing hydroxyl and amine groups in example 2.
Example 5:
a method for preparing a composite desulfurizing agent, which is different from that in example 3: in the carbohydrate, the weight ratio of stevioside, lactitol and calcium gluconate is 1:1: 5.
Example 6:
a method for preparing a composite desulfurizing agent, which is different from that in example 3: in the compound salt, the weight ratio of the calcium phosphate to the sodium acetate to the sodium humate is 1:1: 0.55.
Example 7:
a method for preparing a composite desulfurizing agent, which is different from that in example 3: and adding 1.5 parts of erythritol and citric acid fatty glyceride compound into the composite desulfurizer, wherein the weight ratio of the erythritol to the citric acid fatty glyceride compound is 0.45: 1.
Example 8:
a method for preparing a composite desulfurizing agent, which is different from that in example 7: and 3 parts of erythritol and citric acid fatty glyceride compound are added into the composite desulfurizer.
Example 9:
a method for preparing a composite desulfurizing agent, which is different from that in example 7: the weight ratio of the erythritol to the citric acid fatty glyceride compound in the composite desulfurizer is 0.65: 1.
Example 10:
a method for preparing a composite desulfurizing agent, which is different from that in example 7: the compound containing hydroxyl and amine groups in example 1 was replaced with diethanolamine in the complex desulfurizing agent.
Example 11:
a method for preparing a composite desulfurizing agent, which is different from that in example 7: the compound containing hydroxyl and amine groups in example 1 was not added to the composite desulfurizing agent.
Comparative example 1:
a method for preparing a composite desulfurizing agent, which is different from that in example 3: the compound containing hydroxyl and amine groups in example 1 was replaced with diethanolamine in the complex desulfurizing agent.
Comparative example 2:
a method for preparing a composite desulfurizing agent, which is different from that in example 7: the compound containing hydroxyl and amine groups in example 1 was not added to the composite desulfurizing agent.
Test example 1:
1. composite desulfurizer corrosion performance test
And (3) hanging the steel sheets for 144h at 90 ℃ by adopting a static hanging sheet method, dissolving 10g of experimental sample in 50mL of water to prepare a solution sample, and testing the corrosion condition of the composite desulfurizer solution on the N80 steel sheets.
TABLE 1 Corrosion test results of the composite desulfurizing agent itself
As can be seen from Table 1, the mass loss Δ m values of examples 3 to 6 were less than 3mg, those of comparative example 3 and comparative examples 1 to 2, and those of example 3 were less than those of comparative examples 1 to 2, which demonstrated that the use of (R) -3-chlorophenylethylene oxide together with 3- (benzyloxy) benzene-1, 2-diamine or N-t-butoxycarbonyl-1, 3-propanediamine produced a compound containing a hydroxyl group and an amine group as a component of the composite desulfurizing agent, which interacted with the component in the composite desulfurizing agent, to reduce the corrosion performance of the composite desulfurizing agent to production equipment. The mass loss Deltam values of examples 7 to 9 are lower than 2mg, the mass loss Deltam values of comparative examples 3 and 7 to 9, examples 10 and 1, and examples 11 and 2 are lower than that of example 3, the mass loss Deltam value of example 10 is lower than that of comparative example 1, and the mass loss Deltam value of example 11 is lower than that of comparative example 2, which shows that the addition of the erythritol-citric acid fatty acid glyceride complex in the composite desulfurizing agent further reduces the corrosion performance of the composite desulfurizing agent on production equipment, so that the production equipment has longer service life.
2. SO absorption by composite desulfurizer2Performance testing
Experimental samples: the composite desulfurizing agents of examples 3 to 11 and comparative examples 1 to 2; respectively dissolving 10g of experimental sample in 50mL of water to prepare solution samples;
to SO2And (3) absorption: adding the prepared solution sample into a 500mL three-necked bottle, heating in water bath at the controlled temperature of 60 ℃, and stirring. Opening SO after the heating temperature is stable2And a nitrogen pressure reducing valve to regulate the gas flow. Separately controlling nitrogen and SO2Flow rate of gas, SO2The mixed gas was introduced into the absorption system at a concentration of 15mg/L and a total flow rate of 0.5L/min. Timed measurement of SO in solution3 2-Concentration until S in solutionO3 2-The concentration is substantially constant, and the absorbent solution obtained at this time is considered to be saturated. The absorption effect is expressed as a desulfurization degree AE (%) and SO in the gas phase is measured by a flue gas analyzer2The concentration of (a):
AE(%)=(y1-y0)/y1×100%
in the formula: y is1Is inlet gas SO2Concentration (mg/L); y is0Is outlet gas SO2Concentration (mg/L).
TABLE 2 Experimental sample pairs SO2Absorption test results of
As can be seen from Table 2, the outlet gas SO in examples 3 to 62Is less than 0.071mg/L, and AE value is more than 99.5%, comparing example 3 with comparative examples 1-2, and outlet gas SO in example 32The concentration of (A) is lower than that of comparative example 1-2, and the AE value is higher than that of comparative example 1-2, which shows that the compound containing hydroxyl and amino is prepared by adopting (R) -3-chlorphenyl oxirane and 3- (benzyloxy) benzene-1, 2-diamine or N-tert-butyloxycarbonyl-1, 3-propane diamine, and the compound is used as the component of the composite desulfurizer, and the compound interacts with the component in the composite desulfurizer, so that the desulfurization efficiency of the composite desulfurizer is improved, and the compound is superior to the desulfurizer with similar components. Example 7-9 Exit gas SO2The AE value of the composite desulfurizing agent is lower than 0.03mg/L and higher than 99.8%, the AE values of comparative examples 3 and examples 7-9, example 10 and comparative example 1, and example 11 and comparative example 2 are higher than those of example 3, the AE value of example 10 is higher than that of comparative example 1, and the AE value of example 11 is higher than that of comparative example 2, which shows that the desulfurizing effect of the composite desulfurizing agent is further improved by adding the erythritol and citric acid fatty acid glyceride complex to the composite desulfurizing agent.
3. Composite desulfurizer desorption performance test
And (3) testing desorption performance: the saturated absorbent solution after the completion of the absorption reaction was transferred in an amount of 100mL into a weighed three-necked flask, weighed for the total weight, and the pH of the absorbent solution was measured. The desorption process adopts oil bath heating and beatingBoiling condensed water, slowly raising the heating temperature to about 100 ℃, heating under reflux at 105 ℃, and desorbing SO2The gas was absorbed with 30% sodium hydroxide. The reaction was stopped by heating for 2 h. And weighing after the absorption liquid is cooled to room temperature. Then adding a certain amount of deionized water to the original weight, taking out 20mL of solution, measuring the pH value of the solution, and calculating SO in the absorbent solution3 2-、 SO4 2-The quantitative concentration of the substance(s). The desorption effect is expressed as the desorption rate DE (%), SO in the liquid phase2(SO3 2-) The concentration was measured iodometrically:
DE(%)=(c0-c1)/c0×100%
in the formula: c. C0For SO in pregnant solution before desorption3 2-Content (mg/L); c. C1For SO in pregnant solution before desorption3 2-Content (mg/L).
TABLE 3 respective experimental sample pairs SO2Results of desorption test
As can be seen from Table 3, examples 3 to 6 had an absorption amount of more than 0.1782mol and a DE value of more than 99%, comparative examples 3 and comparative examples 1 to 2, example 3 had an absorption amount of more than comparative examples 1 to 2 and a DE value of more than comparative examples 1 to 2, which shows that a compound containing a hydroxyl group and an amine group was prepared using (R) -3-chlorophenylethylene oxide and 3- (benzyloxy) benzene-1, 2-diamine or N-t-butoxycarbonyl-1, 3-propanediamine and was used as a component of a composite desulfurizing agent, which interacted with a component in the composite desulfurizing agent, increasing the desorption ability of the composite desulfurizing agent and being superior to a desulfurizing agent of a similar component, enabling effective recycling. Comparing example 3 with examples 7-9, example 10 with comparative example 1, and example 11 with comparative example 2, the DE values of examples 7-9 and example 3 are not significantly different, the DE value of example 10 is not significantly different from comparative example 1, and the DE value of example 11 is not significantly different from comparative example 2, which shows that the addition of erythritol and citric acid fatty acid glyceride complex in the composite desulfurizing agent has no significant negative effect on the desorption capability of the composite desulfurizing agent.
4. Oil solubility stability test of composite desulfurizing agent
And weighing 30mL of a desulfurizer sample, pouring the desulfurizer sample into the crude oil, standing the mixture for 30min, and observing the layering phenomenon of the desulfurizer sample and the crude oil to calculate the dissolution rate of the desulfurizer dissolved in the crude oil.
TABLE 4 dissolution rate of the composite desulfurizing agent in crude oil
As can be seen from Table 4, the dissolution rate of the composite desulfurizing agent in examples 3-6 in crude oil is higher than 88%, the dissolution rate of the composite desulfurizing agent in comparative example 3 and comparative examples 1-2, and the dissolution rate of the composite desulfurizing agent in example 3 in crude oil is higher than that of comparative examples 1-2, which shows that the compound containing hydroxyl and amine groups is prepared by using (R) -3-chlorophenyl oxirane and 3- (benzyloxy) benzene-1, 2-diamine or N-tert-butoxycarbonyl-1, 3-propanediamine, and is used as a component of the composite desulfurizing agent, which interacts with the component in the composite desulfurizing agent, the dissolution rate of the composite desulfurizing agent in crude oil is increased, and the composite desulfurizing agent has excellent oil-soluble stability; the dissolution rate of the composite desulfurizer in examples 7-9 in crude oil is not less than 92.5%, the dissolution rate of the composite desulfurizer in examples 3 and 7-9, examples 10 and 1, and examples 11 and 2 in examples 7-9 in crude oil is higher than that in example 3, the dissolution rate of the composite desulfurizer in example 10 in crude oil is higher than that in comparative example 1, and the dissolution rate of the composite desulfurizer in example 11 in crude oil is higher than that in comparative example 2, which shows that the oil solubility stability of the composite desulfurizer is further improved by adding erythritol and citric acid fatty acid glyceride complex into the composite desulfurizer.
5. Test of hydrogen sulfide removal performance of composite desulfurizer
The sulfur capacity refers to the amount of hydrogen sulfide absorbed per unit of saturated desulfurizer. The apparent sulfur capacity is measured by a hydrogen sulfide measuring port of a hydrogen sulfide absorption device. The apparent sulfur capacity can accurately simulate the desulfurization condition of the desulfurizer on the oil field. In the experiment, 10ml of sodium sulfide was taken from 5 sampling bottles, and the solution contained 1g of sulfide ions per liter. Adding 20mL of crude oil, then respectively adding 0mL, 0.5mL, 1mL, 1.25mL and 1.5mL of composite desulfurizer, and diluting to 20 mL; finally, 10mL of hydrochloric acid was added. Shaking and standing for 30min, and measuring the concentration of the hydrogen sulfide gas in the sample bottle. The concentration of hydrogen sulfide gas was measured by a Honeywell minmax hydrogen sulfide detector. And (4) drawing the measurement result on a chart, and determining the apparent sulfur capacity of the desulfurizer by calculating a regression curve.
TABLE 5 apparent Sulfur Capacity of the composite desulfurizing agent
As can be seen from Table 5, the apparent sulfur capacity of examples 3-6 is higher than 58mg/L, the apparent sulfur capacity of comparative example 3 and comparative examples 1-2, and the apparent sulfur capacity of example 3 is higher than that of comparative example 1-2, which shows that the compound containing hydroxyl and amine groups is prepared by using (R) -3-chlorophenyl oxirane and 3- (benzyloxy) benzene-1, 2-diamine or N-tert-butoxycarbonyl-1, 3-propanediamine and is used as a component of the composite desulfurizing agent, and the compound interacts with the component in the composite desulfurizing agent, so that the removal efficiency of the composite desulfurizing agent on hydrogen sulfide is improved; the apparent sulfur capacity of the examples 7-9 is higher than 64mg/L, the apparent sulfur capacity of the comparative examples 3 and 7-9, the apparent sulfur capacity of the example 10 and the apparent sulfur capacity of the comparative example 1, the apparent sulfur capacity of the example 7-9 is higher than that of the example 3, the apparent sulfur capacity of the example 10 is higher than that of the comparative example 1, and the apparent sulfur capacity of the example 11 is higher than that of the comparative example 2, which shows that the removal efficiency of the composite desulfurizing agent on hydrogen sulfide is further improved by adding the erythritol and citric acid fatty acid glyceride complex into the composite desulfurizing agent.
Conventional operations in the operation steps of the present invention are well known to those skilled in the art and will not be described herein.
The above embodiments are merely illustrative, and not restrictive, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, all equivalent technical solutions also belong to the scope of the present invention, and the protection scope of the present invention should be defined by the claims.
Claims (10)
1. A composite desulfurizer comprises a compound containing hydroxyl and amino;
the structural formula of the compound containing hydroxyl and amino is as follows:
2. The composite desulfurizing agent according to claim 1, wherein: the compound containing hydroxyl and amino is prepared from (R) -3-chlorphenyl oxirane and 3- (benzyloxy) benzene-1, 2-diamine or N-tert-butyloxycarbonyl-1, 3-propane diamine.
3. The composite desulfurizing agent according to claim 2, wherein: the preparation method of the compound containing hydroxyl and amino comprises the following steps: heating (R) -3-chlorphenyl oxirane and dilute sulfuric acid solution to react to prepare a substance a; and (2) reacting the substance a with a 3- (benzyloxy) benzene-1, 2-diamine solution or an N-tert-butyloxycarbonyl-1, 3-propane diamine solution under the heating condition to obtain a compound containing hydroxyl and amino.
4. The composite desulfurizing agent according to claim 1, wherein: the compound desulfurizer also comprises a saccharide compound, compound salt, a surfactant and a pH regulator.
5. The composite desulfurizing agent according to claim 4, wherein: the composite desulfurizer comprises, by weight, 4.5-6.5 parts of a compound containing hydroxyl and amino, 3.5-7.5 parts of a saccharide compound, 1.5-3.5 parts of a composite salt, 0.1-0.25 part of a surfactant and 0.25-1 part of a pH regulator.
6. The composite desulfurizing agent according to claim 4, wherein: the saccharide compound is one or more of stevioside, xylitol, lactitol, sodium gluconate and calcium gluconate.
7. The composite desulfurizing agent according to claim 4, wherein: the compound salt comprises calcium phosphate, sodium acetate and sodium humate.
8. The composite desulfurizing agent according to claim 4, wherein: the surfactant is one or a mixture of more of dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride and octadecyl trimethyl ammonium chloride.
9. The preparation method of the composite desulfurizing agent of claim 1, comprising:
adding a compound containing hydroxyl and amino, a saccharide compound, a composite salt, a surfactant and a pH regulator into a solvent, and uniformly mixing to obtain the composite desulfurizer.
10. The composite desulfurizing agent of claim 1 for removing SO2And/or H2Use in S.
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