CN102921282A - Gas desulfurizing agent and preparation method thereof - Google Patents

Gas desulfurizing agent and preparation method thereof Download PDF

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CN102921282A
CN102921282A CN2012104586944A CN201210458694A CN102921282A CN 102921282 A CN102921282 A CN 102921282A CN 2012104586944 A CN2012104586944 A CN 2012104586944A CN 201210458694 A CN201210458694 A CN 201210458694A CN 102921282 A CN102921282 A CN 102921282A
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surfactant
solution
gas
sodium phosphate
desulfurization
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王树立
马路
李恩田
周诗岽
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Changzhou University
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Changzhou University
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Abstract

本发明涉及一种气体脱硫剂,具体涉及一种添加了复合型表面活性剂的可再生的磷酸钠溶液。所述气体脱硫剂配方为:十二水合磷酸钠:3~23%(wt);十二醇:0.05~0.1%(wt);表面活性剂:其占总溶液的浓度为10×10-5~25×10-5mol/L;酸性水溶液量以使脱硫液的pH值在8.5~9.0为准;余量为水。本发明的气体脱硫剂能够广泛地应用于天然气脱硫、烟气脱硫等气体脱硫脱碳领域。

Figure 201210458694

The invention relates to a gas desulfurizer, in particular to a renewable sodium phosphate solution added with a composite surfactant. The formula of the gas desulfurizer is: sodium phosphate dodecahydrate: 3-23% (wt); lauryl alcohol: 0.05-0.1% (wt); surfactant: its concentration in the total solution is 10×10 -5 ~25×10 -5 mol/L; the amount of acidic aqueous solution so that the pH value of the desulfurization solution is 8.5~9.0; the balance is water. The gas desulfurization agent of the invention can be widely used in the fields of gas desulfurization and decarbonization such as natural gas desulfurization and flue gas desulfurization.

Figure 201210458694

Description

A kind of gas sweetening agent and preparation method thereof
Technical field
The present invention relates to a kind of gas sweetening agent, be specifically related to a kind of reproducible sodium radio-phosphate,P-32 solution that has added compound surfactant.Can be widely used in the gas sweetening decarburization fields such as selexol process, flue gas desulfurization.
Background technology
The energy overwhelming majority that mankind nowadays is used is non-renewable coal, oil and natural gas.Present domestic sulfur Gas Fields (mass fraction of sulphur be 2% one 4%) gas output accounts for 60% of national gas output, and most sulfide all are the impurity that is harmful to for natural gas, hydrogen sulfide particularly, not only the visual plants such as storage tank and pipeline are caused heavy corrosion, and serious harm the Nature and the mankind's is healthy.To fundamentally address these problems, just must consider to remove the hydrogen sulfide in the natural gas.The industrial desulfurizer of widely using is tower structure, and doctor solution is chemical desulfurization liquid.Consider that from economic angle selected chemical desulfurization liquid should possess the performance of regeneration, mainly contains hydramine, carbonate, natrium citricum, phosphate, ammoniacal liquor, seawater etc.Phosphate belongs to Multiple Weak Acid salt, and its aqueous solution has certain cushioning effect, and is higher to the absorptive capacity of acid gas, and have certain non-oxidizability, if control concentration of aqueous solution well, can suppress well the generation of thiosulfate and other impurity.So phosphate has good application prospect at desulfuration field.But the solubility of phosphate in water is not very high, and the simple aqueous phosphatic desulfuration efficiency that utilizes is not very high, so can utilize some activating agents of interpolation to improve its desulfuration efficiency.And surfactant can reduce the surface tension of solution, can produce a large amount of minute bubbles when gas enters in the solution, thereby has increased the gas-liquid contact area, is conducive to the absorption of hydrogen sulfide.
The aobvious alkalescence of aqueous phosphatic, selected surface-active should have alkali resistance, salt tolerance.Then require this surfactant to have high foaming characteristic and stability in order to produce a large amount of minute bubbles.Anion-nonionic type surfactant combines the many merits of ionic and nonionic surface active agent, such as good dissolubility and stability, good salt-resistant temperature performance, good compatibility and efficient foaming capacity etc.Need add lastingly a kind of foam stabilizer for the foam that can make generation in addition and anion-nonionic type surfactant is used.
Why adopt the anion-nonionic surfactant mainly to be because the anti-salt action of nonionic surface active agent is better, and foaming capacity is slightly poor, the anionic surfactant foaming capacity is good, but its anti-salt action is relatively poor.And when both form binary mixture, given full play to its advantage separately, overcome the deficiency of the two.
Summary of the invention
The objective of the invention is provides the efficient natural gas desulfurizer for the deficiencies in the prior art.For achieving the above object, the present invention adopts following technical scheme:
The present invention utilizes surfactant and acidic aqueous solution to keep the pH value of doctor solution, increases absorptive capacity to hydrogen sulfide with this.
A kind of natural gas desulfurizing agent of the present invention, its composition and formula rate are:
Salt: 3 ~ 23%(wt);
Foam stabilizer: 0.05 ~ 0.1%(wt);
Surfactant: its concentration that accounts for total solution is 10 * 10 -5~ 25 * 10 -5Mol/L;
The acidic aqueous solution amount so that the pH value of doctor solution be as the criterion 8.5 ~ 9.0.
Surplus is water.
Wherein said salt is sodium phosphate dodecahydrate (Na 3PO 412H 2O);
Wherein said foam stabilizer is lauryl alcohol;
Wherein said surfactant is the compound of anion surfactant and non-ionic surface active agent, and wherein anion surfactant is a kind of of lauryl sodium sulfate (SDS), α-alkene sulfonic acid sodium (AOS) etc.; Non-ionic surface active agent is APG (APG08-10).Anion surfactant and non-ionic surface active agent respectively account for 50%.
Wherein said acid is phosphoric acid.
The preparation method of described a kind of natural gas desulfurizing agent, carry out according to following step: first that sodium phosphate is soluble in water under 25 ~ 30 ℃ according to aforementioned proportion, add foam stabilizer and surfactant, stirred about 20 ~ 30 minutes, and be adjusted to needed pH value with acidic aqueous solution.
The invention has the advantages that:
(1) applied range.Do not have toxicity, renewable performance is good, can be in field extensive uses such as selexol process, flue gas desulfurization decarburizations.
(2) desulfurized effect is good.Composite desulfurizing agent effectively reduces surface tension.By surface tension test, composite desulfurizing agent reduces by 15 ~ 33% than single component sodium carbonate surface tension under same temperature conditions, makes gas form easily minute bubbles, has effectively increased the gas liquid ratio surface area, improved mass transfer rate, desulfuration efficiency is reached more than 95%.
(3) cost is low, good economy performance.Active desulfurizing agent cost of the present invention is low, and consumption is few, and acidity load is high, and desulfuration efficiency is high and power consumption is few.Hydrogen sulfide is desorbed, can realize recycling.The existence of surfactant can also be removed dirt effectively, prevents the accumulation of pollutant.
Description of drawings
Fig. 1 is the selexol process process device figure
1. gas cylinder; 2. pressure gauge; 3. flowmeter; 4. gas distributor; 5. doctor solution case; 6. pump; 7. desulfurizing tower; 8. chromatograph; 9. thermometer.
The specific embodiment
Embodiment 1
The quality percentage composition that accounts for solution by sodium phosphate dodecahydrate is 3.0%(300g), lauryl alcohol is 0.05%(5.2g), water (10000g), the concentration of anionic and non-ionic surface active agent APG is 5 * 10 -5Mol/L(mol).According to aforementioned proportion, first that sodium phosphate is soluble in water under 25 ~ 30 ℃, add foam stabilizer and surfactant, stirred afterwards 20 ~ 30 minutes, add phosphate aqueous solution and make its pH value 8.5 ~ 9.0, the configuration doctor solution.
Embodiment 2
The quality percentage composition that accounts for solution by sodium phosphate dodecahydrate is 23.0%(3000g), lauryl alcohol is 0.05%(6.5g), water (10000g), the concentration of anionic and non-ionic surface active agent APG is 5 * 10 -5Mol/L(mol).According to aforementioned proportion, first that sodium phosphate is soluble in water under 25 ~ 30 ℃, add foam stabilizer and surfactant, stirred 20 ~ 30 minutes, add phosphate aqueous solution and make its pH value 8.5 ~ 9.0, the configuration doctor solution.
Embodiment 3
The quality percentage composition that accounts for solution by sodium phosphate dodecahydrate is 23.0%(3000g), lauryl alcohol is 0.1%(13g), water (10000g), the concentration of anionic and non-ionic surface active agent APG is 12.5 * 10 -5Mol/L(mol).According to aforementioned proportion, first that sodium phosphate is soluble in water under 25 ~ 30 ℃, add foam stabilizer and surfactant, stirred 20 ~ 30 minutes, add phosphate aqueous solution and make its pH value 8.5 ~ 9.0, the configuration doctor solution.
Embodiment 4
The quality percentage composition that accounts for solution by sodium phosphate dodecahydrate is 3.0%(300g), lauryl alcohol is 0.05%(5.2g), water (10000g), the concentration of anion surfactant α-alkene sulfonic acid sodium and non-ionic surface active agent APG is 5 * 10 -5Mol/L(mol).According to aforementioned proportion, first that sodium phosphate is soluble in water under 25 ~ 30 ℃, add foam stabilizer and surfactant, stirred 20 ~ 30 minutes, add phosphate aqueous solution and make its pH value 8.5 ~ 9.0, the configuration doctor solution.
The desulfurization of embodiment 5 natural gas desulfurizing agents
According to selexol process process chart as shown in Figure 1, sulfide hydrogen be 5% natural gas from gas cylinder 1 through pressure gauge 2 and through flowmeter 3 metered flows, flow set is 1 m 3/ h, 3 m 3/ h, 5 m 3/ h, 7 m 3/ h.Enter desulfurizing tower 7 after the gas dosing, the diameter 100mm of desulfurizing tower 7, high 1500mm.The gas distributor 4 of installing in the desulfurizing tower bottom can form bubble with gas.In the doctor solution case 5 electric heater is housed, can changes fluid temperature, design temperature is 23 ℃ in the present embodiment, is drawn the doctor solution temperature that enters in the tower by thermometer 9.Circulate by pump 6, the hydrogen sulfide in the gas is desulfurized liquid and absorbs in desulfurizing tower 7.Purified gas outflow desulfurizing tower 7 enters chromatograph 8 and analyzes.Move continuously under these conditions 30 minutes, desulfuration efficiency is in 91.2% ~ 96.7% scope.
The extraction hydrogen sulfide content is 100mg/m 3Doctor solution rich solution 1L, utilize the vacuum membrane distillation method under 55 ℃ and 65 ℃, to carry out respectively desorption and regeneration, the rich solution flow is controlled at 50L/h, shows that through 30 minutes regeneration tests regeneration rate can reach more than 95%, the results are shown in Table 2.
Table 1 desulfurization
Prescription Temperature/℃ Soak time/min Desulfuration efficiency/%
Embodiment 1 23 30 93.6
Embodiment 2 23 30 91.2
Embodiment 3 23 30 96.7
Embodiment 4 23 30 96.3
Table 2 rich solution regeneration tests
Prescription Temperature/℃ Recovery time/min Regeneration efficiency %
Embodiment 1 55 30 95.1
Embodiment 2 55 30 95.7
Embodiment 3 65 30 96.8
Embodiment 4 65 30 97.2

Claims (3)

1. 一种气体脱硫剂,其特征在于其成分及配方比例为: 1. A gas desulfurizer, characterized in that its composition and formula ratio are: 十二水合磷酸钠:3~23%(wt); Sodium phosphate dodecahydrate: 3~23% (wt); 十二醇:0.05~0.1%(wt); Lauryl alcohol: 0.05~0.1% (wt); 表面活性剂:其占总溶液的浓度为10×10-5~25×10-5 mol/L; Surfactant: its concentration in the total solution is 10×10 -5 ~25×10 -5 mol/L; 酸性水溶液量以使脱硫液的pH值在8.5~9.0为准; The amount of acidic aqueous solution is such that the pH value of the desulfurization solution is 8.5~9.0; 余量为水; The remainder is water; 其中所述的表面表面活性剂为阴离子表面活性剂与非离子表面活性剂的复合物,阴离子表面活性剂与非离子表面活性剂各占50%; Wherein said surfactant is the compound of anionic surfactant and nonionic surfactant, and anionic surfactant and nonionic surfactant each account for 50%; 其中所述的酸为磷酸。 Wherein said acid is phosphoric acid. 2.根据权利要求1所述的气体脱硫剂,其特征在于所述阴离子表面活性剂为十二烷基硫酸钠或α—烯烃磺酸钠;非离子表面活性剂为烷基多糖苷。 2. The gas desulfurizer according to claim 1, characterized in that the anionic surfactant is sodium lauryl sulfate or sodium α-olefin sulfonate; the nonionic surfactant is alkyl polyglycoside. 3.一种天然气脱硫剂的制备方法,步骤如下:按照权利要求1所述配比,在25~30℃下先将磷酸钠溶于水中,加入十二醇和表面活性剂,搅拌20~30分钟左右,用酸性水溶液调节pH为8.5~9.0。 3. A preparation method of a natural gas desulfurizer, the steps are as follows: according to the proportioning described in claim 1, sodium phosphate is first dissolved in water at 25-30°C, then dodecyl alcohol and surfactant are added, and stirred for 20-30 minutes Adjust the pH to 8.5~9.0 with an acidic aqueous solution.
CN2012104586944A 2012-11-15 2012-11-15 Gas desulfurizing agent and preparation method thereof Pending CN102921282A (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103933852A (en) * 2013-08-25 2014-07-23 贵州兴化化工股份有限公司 Method for reducing energy consumption of desulfurizer in desulfurization process
CN106731509A (en) * 2017-02-23 2017-05-31 安徽师范大学 A kind of cleaning solution of purifying industrial waste gases and preparation method thereof
CN106914118A (en) * 2017-02-27 2017-07-04 常州大学 A kind of compound doctor solution of Novel lemon acid sodium
CN107297113A (en) * 2017-07-06 2017-10-27 常州大学 A kind of waste gas residual heat is reclaimed and pollutant integrated conduct method and system
CN108246088A (en) * 2018-02-12 2018-07-06 安徽海德化工科技有限公司 One vegetable oil desulphurization plant desulfurizer therefor
CN108380031A (en) * 2018-02-12 2018-08-10 安徽海德化工科技有限公司 The preparation method of one vegetable oil desulphurization plant desulfurizer therefor
CN110891670A (en) * 2017-03-13 2020-03-17 图里诺研究合作有限公司 Specific liquid solutions suitable for cooling and capturing pollutants in diesel engine exhaust
CN111054102A (en) * 2019-12-25 2020-04-24 浙江佳运能源技术有限公司 Sulfur wetting agent for wet-process chelated iron desulfurization and preparation and use methods thereof
US10669172B2 (en) 2017-08-23 2020-06-02 Ecolab Usa Inc. Elemental sulfur dispersant to control fouling in water systems
CN115845924A (en) * 2022-12-22 2023-03-28 河北络合科技有限公司 Catalyst for biogas desulfurization and preparation method and application thereof

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103933852A (en) * 2013-08-25 2014-07-23 贵州兴化化工股份有限公司 Method for reducing energy consumption of desulfurizer in desulfurization process
CN106731509A (en) * 2017-02-23 2017-05-31 安徽师范大学 A kind of cleaning solution of purifying industrial waste gases and preparation method thereof
CN106914118A (en) * 2017-02-27 2017-07-04 常州大学 A kind of compound doctor solution of Novel lemon acid sodium
CN110891670A (en) * 2017-03-13 2020-03-17 图里诺研究合作有限公司 Specific liquid solutions suitable for cooling and capturing pollutants in diesel engine exhaust
CN107297113A (en) * 2017-07-06 2017-10-27 常州大学 A kind of waste gas residual heat is reclaimed and pollutant integrated conduct method and system
US10669172B2 (en) 2017-08-23 2020-06-02 Ecolab Usa Inc. Elemental sulfur dispersant to control fouling in water systems
CN108246088A (en) * 2018-02-12 2018-07-06 安徽海德化工科技有限公司 One vegetable oil desulphurization plant desulfurizer therefor
CN108380031A (en) * 2018-02-12 2018-08-10 安徽海德化工科技有限公司 The preparation method of one vegetable oil desulphurization plant desulfurizer therefor
CN111054102A (en) * 2019-12-25 2020-04-24 浙江佳运能源技术有限公司 Sulfur wetting agent for wet-process chelated iron desulfurization and preparation and use methods thereof
CN111054102B (en) * 2019-12-25 2022-06-14 浙江佳运能源技术有限公司 Sulfur wetting agent for wet-process chelated iron desulfurization and preparation and use methods thereof
CN115845924A (en) * 2022-12-22 2023-03-28 河北络合科技有限公司 Catalyst for biogas desulfurization and preparation method and application thereof
CN115845924B (en) * 2022-12-22 2024-08-02 河北络合科技有限公司 Catalyst for biogas desulfurization and preparation method and application thereof

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Application publication date: 20130213