CN105712300A - Process for converting hydrogen sulfide into sulfur - Google Patents
Process for converting hydrogen sulfide into sulfur Download PDFInfo
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- CN105712300A CN105712300A CN201410723826.0A CN201410723826A CN105712300A CN 105712300 A CN105712300 A CN 105712300A CN 201410723826 A CN201410723826 A CN 201410723826A CN 105712300 A CN105712300 A CN 105712300A
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Abstract
The invention discloses a process for converting hydrogen sulfide into sulfur. According to the process, a gas mixture of H2S and CO2 is used as feed gas, wherein a mol ratio of H2S to CO2 is 0.01 to 100; a mixture of nanometer carbon fiber and lanthanum nickelate is used as a catalyst, wherein a mol ratio of nanometer carbon fiber to lanthanum nickelate is 200: 1 to 1: 200; and sulphur is produced under the conditions that a temperature is 80 to 800 DEG C, gaseous hourly space velocity is 1000 to 50000 ml/(gcat.h) and gas pressure is 0.05 to 5 MPa. The process can effectively activate and utilize CO2 so as to allow H2S to be converted into sulphur and has the characteristics of high reaction selectivity, good stability and good adaptability.
Description
Technical field
The invention belongs to material manufacture and energy and environment application, be specifically related to a kind of convert the method that hydrogen sulfide is sulfur.
Background technology
Hydrogen sulfide is widely present in the natural products such as crude oil, natural gas, volcanic gas and hot spring, it is possible to result from the organic process of bacterial decomposition.In industrial processes, there is hydrogen sulfide to produce in mining and the production field such as non-ferrous metal metallurgy, the Low-temperature carbonization of coal, rubber, process hides, sugaring, printing and dyeing, excavate marshland, irrigation canals and ditches, sewer, tunnel and remove rubbish, the operation such as feces also has hydrogen sulfide to exist.It is a kind of acute extremely toxic substance, and corrosivity is strong, thus health and commercial production all can cause high risks, is also one of polluter of being formed of acid rain.
For containing high concentration H2The process of S gas, industrial commonly used claus process absorption method, its principle is as follows:
H2S+(3/2)O2→SO2+H2O(1)
SO2+2H2S→2H2O+(3/n)Sn(2)
Claus process can obtain sulfur, turns waste into wealth, and meets the strategy of sustainable development, has become the mature technology that hydrogen sulfide waste gas is administered at present.But the H for low concentration2S(is less than l5%) process of gas, Claus method is owing to being limited by thermodynamical equilibrium, economically uneconomical.
In recent years, selective catalytic oxidation technology is arisen at the historic moment as a kind of novel sulfur removal technology, and is developed rapidly.This process is to use O under the effect of catalyst2(or air) is by H2S is direct oxidation into the process of simple substance sulphur, and the dominant response of generation is:
H2S+1/2O2→(1/n)Sn+H2O(3)
But this reaction is a strong exothermal reaction, in adiabatic reactor, the often H of reaction 1%2S, will result in the temperature rise of 60 DEG C, after reaction bed temperature is more than 280 DEG C, just has substantial amounts of SO2Generate, be therefore only used for processing the H of low concentration2S gas.Another great drawback is in that, this technology is by artificially adding O2The processing step of (or air) realizes, and the one side that arranges of this type of step adds the complexity of process operation, and there is a possibility that reaction unit is in explosion limit scope, on the other hand, and O2Concentration is contrary to conversion ratio and the selective effect tendency of course of reaction, so O2Addition need to strictly control.Meanwhile, if reaction system is in anaerobic condition, then catalyst easily inactivates；If O2It is excessive to add, then the existence of remaining oxygen will increase follow-up separating difficulty, or the quality of successor is produced impact.
Therefore, H2S administers field in the urgent need to developing novel H2The technique that S is converted into sulfur.
Summary of the invention
It is desirable to provide a kind of novel H2The technique that S is converted into sulfur.This technique can activation utilization CO effectively2Make H2S is converted into sulfur, and has reaction selectivity height, good stability, adaptable feature.
A kind of H2S is converted into the technique of sulfur, with containing H2S and CO2Gaseous mixture be unstripped gas, wherein H2S and CO2Mol ratio be 0.01-100, preferred 0.1-10, best 1-5, with carbon nano-fiber and nickel acid lanthanum mixture for catalyst, wherein carbon nano-fiber is 200: 1-1: 200 with the weight ratio of nickel acid lanthanum, it is preferably 50: 1-1: 50, it is preferably 5: 1-1: 5, is 80-800 DEG C in temperature, it is preferred to 120-700 DEG C, being preferably 200-600 DEG C, gas space velocity is 1000-50000ml/(gcatH), it is preferred to 5000-40000ml/(gcatH), it is desirable to for 10000-30000ml/(gcatH), gas pressure is 0.05-5MPa, it is preferred to 0.1-4MPa, it is desirable to generate sulfur when for 0.5-3MPa.
In present invention process, described carbon nano-fiber diameter is 10 ~ 500nm, and length is 0.5um～1mm.Carbon nano-fiber can adopt commercial goods, such as the carbon nano-fiber that Beijing Deco Dao Jin Science and Technology Ltd. provides, it would however also be possible to employ prior art is prepared, for instance adopts method disclosed in CN1446628 to be prepared.
In present invention process, described nickel acid lanthanum adopts citric acid method to prepare.Concrete preparation process is as follows: Lanthanum (III) nitrate, nickel nitrate and citric acid are dissolved separately in distilled water and prepare corresponding solution, the nickel nitrate of above-mentioned preparation and lanthanum nitrate hexahydrate is mixed, and dropping citric acid solution obtains colloid, prepares nickel acid lanthanum after drying, roasting.
Concentration respectively 0.5-2mol/L, 0.5-2mol/L and the 1-3mol/L of the Lanthanum (III) nitrate of preparation, nickel nitrate and citric acid solution in above-mentioned nickel acid lanthanum preparation process.Nickel nitrate solution and the mixing of lanthanum nitrate hexahydrate equal-volume, constant temperature stirring 0.1-1h at 60-100 DEG C.At nickel nitrate and the isopyknic citric acid solution of Lanthanum (III) nitrate mixed solution and dripping, colloid is constant temperature stirring 2-8h, freeze-day with constant temperature 8-15h at 100-140 DEG C at 80-120 DEG C, it is subsequently placed in Muffle furnace, at 600-900 DEG C, constant temperature calcining 2-8h, naturally cools to room temperature, obtains nickel acid lanthanum.
In present invention process, after being mixed homogeneously by nickel acid lanthanum, prepare H with carbon nano-fiber2S is converted into sulfur, and the method for mix homogeneously can be mechanical mixture, but is not limited to mechanical mixture.
Having a major advantage in that of present invention process:
1, carbon nano-fiber provided by the invention and nickel acid lanthanum mixed catalyst, can utilize CO2Make H2S is converted into sulfur, is conducive to CO2Reduction of discharging and the utilization of resources.
2, carbon nano-fiber provided by the invention and nickel acid lanthanum mixed catalyst, for H2S and CO2Reaction is converted in the technical process of sulfur, has the advantages that reaction selectivity is high.
3, carbon nano-fiber provided by the invention and nickel acid lanthanum mixed catalyst, containing H2S and CO2Sour gas in there is good stability, adaptable feature.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is expanded on further.Should be understood that these embodiments are merely to illustrate the present invention rather than restriction the scope of the present invention.The experimental technique of unreceipted actual conditions in the following example, generally conventionally condition or according to manufacturer it is proposed that condition.Unless otherwise indicated, otherwise all of percent, ratio, ratio or number be by weight.
The unit in percent weight in volume in the present invention is well-known to those skilled in the art, for instance refer to the weight of solute in the solution of 100 milliliters.
Unless otherwise defined, the same meaning that all specialties used in literary composition are familiar with one skilled in the art with scientific words.Additionally, any method similar or impartial to described content and material all can be applicable in the inventive method.The use that preferably implementation described in literary composition and material only present a demonstration.
In present invention process, the concrete preparation process of described Nano carbon fibers peacekeeping nickel acid lanthanum mixed catalyst is as follows:
(1) by Lanthanum (III) nitrate, nickel nitrate and citric acid solid, being dissolved in distilled water respectively and obtain corresponding clear transparent solutions, solution concentration is 1mol/L, 1mol/L and 1.5mol/L respectively；Above-mentioned nickel nitrate and lanthanum nitrate hexahydrate equal-volume are mixed in there-necked flask, constant temperature stirring 0.5h at 80 DEG C；In above-mentioned there-necked flask, dropping and the isopyknic citric acid solution of above-mentioned mixed liquor, obtain colloid；By above-mentioned colloid constant temperature stirring 6h, freeze-day with constant temperature 12h at 120 DEG C at 90 DEG C, being subsequently placed in Muffle furnace, at 850 DEG C, constant temperature calcining 6h, naturally cools to room temperature, obtains nickel acid lanthanum solid.
(2) nickel acid lanthanum solid step (1) obtained (is provided by Beijing Deco Dao Jin Science and Technology Ltd. with carbon nano-fiber, described carbon nano-fiber diameter is 10 ~ 500nm, length is 0.5um～1mm, mechanical mixture is uniform, and described carbon nano-fiber is 200:1-1:200 with the weight ratio with nickel acid lanthanum；It is preferably 50:1-1:50；It is preferably 5:1-1:5.
In present invention process, the conversion ratio of hydrogen sulfide and the selectivity definition of sulfur are as follows:
Sulfur selectivity is more high, it was shown that selectivity of catalyst is more good.The use time of catalyst is more long, it was shown that the stability of catalyst is more good.Other composition such as H in unstripped gas2O、CH4The impact of catalyst performance is more little, it was shown that the adaptability of catalyst is more strong.
Embodiment 1
It is 5: 1 by the weight ratio of carbon nano-fiber and nickel acid lanthanum mixed catalyst sample 1g, carbon nano-fiber and nickel acid lanthanum, loads in reactor, pass into H2S and CO2Molar content respectively 50% and 50% gaseous mixture, gas space velocity is 30000ml/(gcatH), being warming up to 80 DEG C, gas pressure is 0.1MPa.Assaying reaction device exit gas composition after 0.5h, calculating sulfur selectivity is 92%, and hydrogen sulfide conversion ratio is 12.8%.In 100h, hydrogen sulfide conversion ratio and sulfur selectivity remain unchanged.
Embodiment 2
It is 1: 5 by the weight ratio of carbon nano-fiber and nickel acid lanthanum mixed catalyst sample 1g, carbon nano-fiber and nickel acid lanthanum, loads in reactor, pass into H2S and CO2Molar content respectively 50% and 50% gaseous mixture, gas space velocity is 50000ml/(gcatH), being warming up to 600 DEG C, gas pressure is 0.05MPa.Assaying reaction device exit gas composition after 0.5h, calculating sulfur selectivity is 76%, and hydrogen sulfide conversion ratio is 42.8%.In 100h, hydrogen sulfide conversion ratio and sulfur selectivity remain unchanged.
Embodiment 3
It is 10: 1 by the weight ratio of carbon nano-fiber and nickel acid lanthanum mixed catalyst sample 1g, carbon nano-fiber and nickel acid lanthanum, loads in reactor, pass into H2S and CO2Molar content respectively 30% and 70% gaseous mixture, gas space velocity is 5000ml/(gcatH), being warming up to 800 DEG C, gas pressure is 5MPa.Assaying reaction device exit gas composition after 0.5h, calculating sulfur selectivity is 50%, and hydrogen sulfide conversion ratio is 40.8%.In 50h, hydrogen sulfide conversion ratio and sulfur selectivity remain unchanged.
Embodiment 4
It is 1: 50 by the weight ratio of carbon nano-fiber and nickel acid lanthanum mixed catalyst sample 1g, carbon nano-fiber and nickel acid lanthanum, loads in reactor, pass into H2S、CO2And CH4Molar content respectively 50%: 10%: 40% gaseous mixture, gas space velocity is 1000ml/(gcatH), being warming up to 400 DEG C, gas pressure is 1MPa.Assaying reaction device exit gas composition after 0.5h, calculating sulfur selectivity is 61%, and hydrogen sulfide conversion ratio is 22.8%.In 50h, hydrogen sulfide conversion ratio and sulfur selectivity remain unchanged.
Embodiment 5
It is 1: 50 by the weight ratio of carbon nano-fiber and nickel acid lanthanum mixed catalyst sample 1g, carbon nano-fiber and nickel acid lanthanum, loads in reactor, pass into H2S、CO2And H2O molar content respectively 50%: 10%: 40% gaseous mixture, gas space velocity is 10000ml/(gcatH), being warming up to 200 DEG C, gas pressure is 0.5MPa.Assaying reaction device exit gas composition after 0.5h, calculating sulfur selectivity is 77%, and hydrogen sulfide conversion ratio is 21.6%.In 50h, hydrogen sulfide conversion ratio and sulfur selectivity remain unchanged.
Embodiment 6
It is 1: 1 by the weight ratio of carbon nano-fiber and nickel acid lanthanum mixed catalyst sample 1g, carbon nano-fiber and nickel acid lanthanum, loads in reactor, pass into H2S and CO2Molar content respectively 50% and 50% gaseous mixture, gas space velocity is 10000ml/(gcatH), being warming up to 120 DEG C, gas pressure is 3MPa.Assaying reaction device exit gas composition after 0.5h, calculating sulfur selectivity is 87%, and hydrogen sulfide conversion ratio is 7.8%.In 100h, hydrogen sulfide conversion ratio and sulfur selectivity remain unchanged.
Comparative example 1
Only loading the carbon nano-fiber of 1g, without nickel acid lanthanum, all the other are with embodiment 1, and calculating sulfur selectivity is 68%, and hydrogen sulfide conversion ratio is 1.8%.
Comparative example 2
Only loading the nickel acid lanthanum of 1g, without carbon nano-fiber, all the other are with embodiment 1, and calculating sulfur selectivity is 58%, and hydrogen sulfide conversion ratio is 0.5%.
The foregoing is only presently preferred embodiments of the present invention, it is not limited to the substantial technological context of the present invention, the substantial technological content of the present invention is broadly to be defined in the right of application, any technology entities that other people complete or method, if defined with the right of application is identical, also or the change of a kind of equivalence, all it is covered by being considered among this right.
Claims (10)
1. a H2The technique that S is converted into sulfur, it is characterised in that: with containing H2S and CO2Gaseous mixture be unstripped gas, wherein H2S and CO2Mol ratio be 0.01-100, with carbon nano-fiber and nickel acid lanthanum mixture for catalyst, wherein carbon nano-fiber is 200:1-1:200 with the weight ratio of nickel acid lanthanum, is 80-800 DEG C in temperature, and gas space velocity is 1000-50000ml/(gcatH), gas pressure generates sulfur when being 0.05-5MPa.
2. technique according to claim 1, it is characterised in that: H2S and CO2Mol ratio be 0.1-10, the weight ratio of carbon nano-fiber and nickel acid lanthanum is 50:1-1:50, is 120-700 DEG C in temperature, and gas space velocity is 5000-40000ml/(gcatH), gas pressure generates sulfur when being 0.1-4MPa.
3. technique according to claim 1, it is characterised in that: H2S and CO2Mol ratio be 1-5, the weight ratio of carbon nano-fiber and nickel acid lanthanum is 5:1-1:5, is 200-600 DEG C in temperature, and gas space velocity is 10000-30000ml/(gcatH), gas pressure generates sulfur when being 0.5-3MPa.
4. technique according to claim 1, it is characterised in that: described carbon nano-fiber diameter is 10 ~ 500nm, and length is 0.5um～1mm.
5. technique according to claim 1, it is characterised in that: carbon nano-fiber adopts commercial goods or adopts prior art to be prepared.
6. technique according to claim 1, it is characterised in that: described nickel acid lanthanum adopts citric acid method to prepare.
7. technique according to claim 6, it is characterized in that: the concrete preparation process of nickel acid lanthanum is as follows: Lanthanum (III) nitrate, nickel nitrate and citric acid are dissolved separately in distilled water and prepare corresponding solution, the nickel nitrate of above-mentioned preparation and lanthanum nitrate hexahydrate are mixed, dropping citric acid solution obtains colloid, prepares nickel acid lanthanum after drying, roasting.
8. technique according to claim 7, it is characterised in that: the concentration of Lanthanum (III) nitrate, nickel nitrate and citric acid solution respectively 0.5-2mol/L, 0.5-2mol/L and 1-3mol/L.
9. technique according to claim 7, it is characterized in that: nickel nitrate solution and the mixing of lanthanum nitrate hexahydrate equal-volume, constant temperature stirring 0.1-1h at 60-100 DEG C, at nickel nitrate and the isopyknic citric acid solution of Lanthanum (III) nitrate mixed solution and dripping, colloid is constant temperature stirring 2-8h, freeze-day with constant temperature 8-15h at 100-140 DEG C at 80-120 DEG C, it is subsequently placed in Muffle furnace, at 600-900 DEG C, constant temperature calcining 2-8h, naturally cools to room temperature, obtains nickel acid lanthanum.
10. technique according to claim 1, it is characterised in that: nickel acid lanthanum and carbon nano-fiber mechanical mixture uniformly prepare H afterwards2S is converted into the catalyst of sulfur.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116605835A (en) * | 2023-05-04 | 2023-08-18 | 中国科学院山西煤炭化学研究所 | Method for improving conversion rate of synthesis gas prepared by reaction of hydrogen sulfide and carbon dioxide |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1163858A (en) * | 1996-04-30 | 1997-11-05 | 李晓东 | Process for recovering sulfur from gas containing hydrogen sulfide |
-
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1163858A (en) * | 1996-04-30 | 1997-11-05 | 李晓东 | Process for recovering sulfur from gas containing hydrogen sulfide |
Non-Patent Citations (4)
| Title |
|---|
| GAVIN TOWLER.ET AL: "Development of a Zero-Emissions Sulfur-Recovery Process.1.Thermochmistry and Reaction Kinetics of Mixtures of H2S and CO2 at High Temperature", 《IND.ENG.CHEM.RES》 * |
| GAVIN TOWLER.ET AL: "Development of a Zero-Emissions Sulfur-Recovery Process.2.Sulfur-Recovery Process Based on the Reaction of H2S and CO2 at High Temperature", 《IND.ENG.CHEM.RES》 * |
| 贾太轩等: "溶胶-凝胶法制备LaNiO3及其催化性能", 《工业催化》 * |
| 郑瑛等: "钙钛矿型复合载氧体的制备及释氧性能研究", 《中国电机工程学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116605835A (en) * | 2023-05-04 | 2023-08-18 | 中国科学院山西煤炭化学研究所 | Method for improving conversion rate of synthesis gas prepared by reaction of hydrogen sulfide and carbon dioxide |
| CN116605835B (en) * | 2023-05-04 | 2024-03-22 | 中国科学院山西煤炭化学研究所 | Method for improving conversion rate of synthesis gas prepared by reaction of hydrogen sulfide and carbon dioxide |
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