CN101870883A - Method for producing sulfur through separation, vulcanization and hydrogen oxidation of circling foam - Google Patents
Method for producing sulfur through separation, vulcanization and hydrogen oxidation of circling foam Download PDFInfo
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- CN101870883A CN101870883A CN200910083005A CN200910083005A CN101870883A CN 101870883 A CN101870883 A CN 101870883A CN 200910083005 A CN200910083005 A CN 200910083005A CN 200910083005 A CN200910083005 A CN 200910083005A CN 101870883 A CN101870883 A CN 101870883A
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Abstract
The invention relates to a method for producing sulfur through separation, vulcanization and hydrogen oxidation of circling foam, which comprises the following steps: adding anionic surfactant into a circling foam separation tower, adjusting the pH to be 8-10, filling air to generate foam, enriching sulphur granules on the surface of the foam, and separating sulfur from the solution through collecting the foam. In the method, the content of surfactant in 1g of solution of the sulphur granules is 0.05-0.14g, the gas flow velocity in the empty tower is 0.5-2.5cm/s, the average grain diameter of the separated sulphur granules is 0.5-25 mum, the surfaces of the granules are positive when the pH is 8-10, and the content of the sulphur granules in the solution is no higher than 2g/L. The method can adopt continuous operation or batch operation. Compared with settlement separation, the separation rate of the method is high, and the separation rate of the sulphur granules is up to 85 percent. Moreover, the method has the advantages of low solvent entrainment, low energy consumption and low solvent consumption, and has broad application prospects in wet oxidation and absorption of hydrogen sulfide.
Description
Technical field
The invention belongs to gas purification technique and solid-liquid separation technique field.Definite saying so relates to a kind of H that separates from solution
2The method of the small sulfur granule that generates when the S oxidation absorbs.
Background technology
H
2S gas is to influence quality product in Sweet natural gas, the oil-refining chemical, causes one of main gas of environmental pollution.At H
2In the absorption process of S, a class wet oxidation absorption process is arranged, its characteristics for adopt catalyzer in solution with H
2S is oxidized to elemental sulfur, and for example the oxidation of vanadium base absorbs sulfur removal technology, the iron-based oxidation absorbs sulfur removal technology etc.The wet oxidation absorption process has developed into over one hundred kind so far, and what industrial application value was wherein arranged just has a kind more than 20.These class methods generally have characteristics such as desulfuration efficiency height, running cost are low, environmental friendliness, come into one's own day by day.But these class methods are at the sulphur particle diameter that reaction process produces very little (the hundreds of nanometer is to several microns), and have special surface properties, easily are adsorbed in reactor wall or filler and free settling not.Prior art improves the settling ratio of sulphur by adding methods such as dispersion, flocculation agent, and methods such as sedimentation liquid employing filtration are separated sulphur.For example the liquid-phase oxidation reduction of U.S. Pat 4774071, US05149459 report absorbs H
2In the technology of S, all adopt the filtering method recovery sulphur of sedimentation liquid.
Because the content of sulphur is low in the sedimentation liquid, makes a large amount of solution circulate between separating unit and reactor, not only increased the loss of energy consumption and sweetening agent, and separating effect is not ideal enough.
Be based on the foam separating technology (Foam separation) of interface difference for a kind of separation method efficiently of small solid particulate.In containing the solution of tensio-active agent, blast air, form foam, based on the surface tension of bubble and liquid surface, charged character etc. difference, particle is in the bubble surface enrichment, and further concentrate along with the coalescence of bubble, can realize separating of particle and liquid by collecting bubble, molecule is had higher separation efficiency.
The circulation foam separation is to utilize Airlift circulating reactor to carry out the technology of foam separation, because bubble is evenly distributed in the loop reactor, bubble turbulence fierceness, gas-to-liquid contact is abundant, separated material is enriched on the foam surface faster, thereby can significantly improves the efficient of foam separation.The circulation foam separation in the acquisition of aspects such as metal ion, protein separation successful Application.H
2To several micrometer ranges, the surface is charged in the hundreds of nanometer for the size of the sulfur granule that the S oxidation generates, and possesses the possibility of circulation foam separation.Utilize the circulation foam separation to reclaim the sulfur granule that hydrogen sulfide liquid phase oxidation generates, can simplify the composition of sweetening agent, reduce catalyzer cost and consumption, reduce the running cost and the energy consumption of process, have broad application prospects at oil and gas and chemical field.
Summary of the invention
The objective of the invention is to develop a kind of with circulation foam separation H
2The method of the sulfur granule that the S wet oxidation generates to improve the separation efficiency of sulphur, reduces H
2The agent consumption and the energy consumption of S wet oxidation method.
The objective of the invention is to be achieved through the following technical solutions: comprise a kind of circling and bubbling separation column, be made of bubbling segment and foam collection section that bubbling segment is a gas lift type common loop reactor, the foam collection section is the gas-liquid separator of overflow slot type; In described circling and bubbling separation column, add tensio-active agent and produce foam, regulating pH is 8～10, bubbling air is enriched in foam surface with sulfur granule, by collecting foam, sulphur is separated from solution.
The present invention is applicable to and separates various H
2Sulfur granule that generate, that satisfy following feature in the S oxidation absorption process: median size is 0.5～25 μ m, and is 8～10 scope endoparticle surface positively charged at pH.The content of sulfur granule is not higher than 2g/L in the treatment soln.
Described circling and bubbling separation column, the diameter ratio of bubbling segment and foam collection section is 1: 1.4～1: 1.7, aspect ratio is 1: 0.5～1: 0.9; The diameter ratio of overflow groove weir, foam collection section and foam collection section is 1: 1～1: 1.4, and aspect ratio is 0.1: 1～0.3: 1.
Described tensio-active agent is an anion surfactant, is specially Sodium dodecylbenzene sulfonate (SDBS) or sodium lauryl sulphate (SDS).The content of tensio-active agent is: whenever contain in the solution of 1g sulfur granule and contain tensio-active agent 0.05～0.14g.
The amount of described bubbling air is: the maintenance empty tower gas velocity is 0.5～2.5cm/s.
Circulation foam separation H of the present invention
2The technology of the sulfur granule that the S oxidation generates can adopt operate continuously, also can take batch formula operation.The operate continuously mode is: tensio-active agent and sulfur granule solution mix the back and go into tower with certain flow, collect foam continuously from bottom, foam collection section, obtain sulfur granule after the filtration; Discharge the solution that separates behind the sulphur from bubbling segment bottom, and guarantee that liquid amount is constant in the tower.Andnon-continuous operation manner is: in the disposable adding tower of sulfur granule solution, tensio-active agent stream adds tower, collects foam continuously from bottom, foam collection section, obtains sulfur granule after the filtration, after the resolution of sulphur reaches requirement, finishes one batch operation.
In advantage of the present invention and beneficial effect be:
1) separation efficiency height: sulfur granule flash liberation rate can reach more than 85%;
2) doctor solution is carried secretly few: the desulfuration solution of carrying secretly in the foam of collection is less than 5% of the desulfuration solution cumulative volume;
3) energy consumption and agent consumption is low: since foam mutually in the content of sulfur granule very high, and the desulfuration solution that foam is carried secretly in mutually is seldom, the amount of filtrate of therefore filtering the back return mechanism is little, thereby energy consumption and agent consumption are low.
Description of drawings
The structure iron of Fig. 1 circling and bubbling separation column.
1, foam collection section 2, bubbling segment 3, air intlet pipe 4, leakage fluid dram 5, gas distributor 6, loop reactor guide shell 7, overflow weir 8, foam receiving tank 9, collection foam mouth
Embodiment
The specific embodiment of the present invention is as follows:
Circling and bubbling separation column is made of bubbling segment 2 and foam collection section 1, and bubbling segment 1 is a gas lift type common loop reactor, comprises reactor guide shell 6 and gas distributor 5; Foam collection section 1 is the gas-liquid separator of overflow slot type, is provided with overflow weir 7.The diameter ratio of bubbling segment and foam collection section is 1: 1.4～1: 1.7, and aspect ratio is 1: 0.5～1: 0.9; The diameter ratio of overflow groove weir, foam collection section and foam collection section is 1: 1～1: 1.4, and aspect ratio is 0.1: 1～0.3: 1.
Operate continuously: pump into circling and bubbling separation column after tensio-active agent and the solution that contains sulfur granule mix, air forms stable foam in the loop reactor guide shell 6 that the air intlet pipe 3 and the gas distributor 5 of tower bottom blasts bubbling segment 2 in the tower.At bubbling segment 2, sulfur granule is enriched in the bubble interface in bubble and the continuous contact process of liquid phase, and rises to foam collection section 1 with foam.In the foam collection section, liquid phase of carrying secretly in the foam and foam separation, foam flows out from the collection foam mouth 9 of foam collection section overflow weir 7 outer bottoms.From collecting foam mouth 9 collection foams and with methods such as filtrations foam solution being separated with sulfur granule, sulphur dried recovered, liquid phase are returned the foam separation device and are continued to use.Solution behind the separation sulphur is discharged from the leakage fluid dram 4 of tower bottom, keeps the liquid amount in the tower constant during discharge opeing.In the entire operation process, adjust pH, make it remain on 8～10 by HCl and NaOH solution.
The formula of criticizing operation: the disposable adding circling and bubbling separation column of solution that contains sulfur granule.Tensio-active agent adds in the tower with given pace stream.Air blasts in the tower through the gas distributor of tower bottom, forms stable foam.Sulfur granule is enriched in the bubble interface at bubbling segment, and constantly rises to the foam collection section with foam.In the foam collection section, liquid phase of carrying secretly in the foam and foam separation are collected a mouthful collection foam from bottom, foam collection section, and by methods such as filtrations the foam liquid phase are separated with sulfur granule, and liquid phase is returned the foam separation device and continued to use the sulphur dried recovered.After the resolution of sulphur reaches requirement, finish one batch operation.
Present embodiment is for adopting operate continuously mode, circulation foam separation H
2The sulfur granule that the S oxidation obtains.Sulfur granule median size 21 μ m are 8～10 o'clock at pH, and the surface potential of sulfur granule is 10～1mV.The bubbling segment diameter 170mm of circling and bubbling separation column, high 1300mm.Foam collection section diameter 290mm highly is 660mm, overflow weir diameter 228mm, high 100mm.Adopt operate continuously, tensio-active agent SDBS pumps into from the knockout tower bottom after mixing with the solution that contains sulfur granule, is discharged by bottom, foam collection section after the foam enrichment, and behind the filtration sulphur, filtrate is incorporated desulfuration solution to be separated into, the sulphur dried recovered.Discharge on desulfuration solution self-separation tower bubbling segment top behind the separation sulphur.Sulphur content is 0.5g/L in the solution, and feeding rate is 1L/min, and in the entire operation process, by adjusting discharge opeing speed, amount of liquid is 27～30L in the control knockout tower.The consumption of tensio-active agent is: the content that whenever contains tensio-active agent in the desulfuration solution of sulfur granule of 1g is 0.10g, and the empty tower gas velocity of air is 1.0cm/s.During stable operation, the separation rate of sulfur granule is 93% under these conditions.
Present embodiment is for adopting batch formula operating method, circulation foam separation H
2The sulfur granule that the S oxidation obtains.The character of sulfur granule is with embodiment 1.The bubbling segment structure of circling and bubbling separation column is with embodiment 1, and foam collection section diameter 240mm highly is 1000mm, overflow height of weir 240mm.The disposable adding apparatus circulation foam separation device of solution (content is 2g/L) that contains sulfur granule, and amount of liquid is 27～30L in the control knockout tower.Surfactant SDS adds in the circulation foam separation device with given pace stream, and the content that guarantees tensio-active agent in the desulfuration solution of the sulfur granule that whenever contains 1g is 0.12g, and the empty tower gas velocity of air is 1.0cm/s.In the time of under these conditions behind the stable operation 20min, the separation rate of sulfur granule reaches 89%.
Present embodiment is for adopting circulation foam separation iron-based liquid-phase oxidation H
2The sulfur granule that S obtains.Tripping device is with embodiment 2, and sulfur granule median size 0.5 μ m is 8～10 o'clock at pH, and the surface potential of sulfur granule is 24～1mV.Adopt operate continuously, the content of sulphur is 0.3g/L in the solution, and feeding rate is 1L/min, and amount of liquid is 27～30L in the control knockout tower.The content of tensio-active agent SDBS is: whenever contain in the desulfuration solution of sulfur granule of 1g and contain tensio-active agent 0.1g, the empty tower gas velocity of air is 1.0cm/s.During stable operation, the separation rate of sulfur granule is greater than 95% under these conditions.
Embodiment 4
Present embodiment is the separating effect under the different surfaces active agent content.Tripping device is with embodiment 1, and sulfur granule character is with embodiment 3.Adopt operate continuously, except that sulphur content, other operational conditions are with embodiment 3, and when the desulfuration solution of the sulfur granule that contains 1g contained tensio-active agent SDBS0.05g, 0.08g and 0.14g, the separation rate of sulfur granule was followed successively by 86%, 92% and 94% during stable operation.
Embodiment 5
Present embodiment is the separating effect under the different air capacities.Tripping device is with embodiment 1, and sulfur granule character is with embodiment 3.Adopt operate continuously, outside the deacration amount, other operational conditions are with embodiment 3, when empty tower gas velocity is respectively 0.5cm/s, and 1.0cm/s, when 1.7cm/s and 2.5cm/s, the separation rate of sulfur granule is followed successively by 88%, 95%, 95% and 93% during stable operation.
Claims (3)
1. the method for the sulphur that generates of a circulation foam separation hydrogen sulfide oxidation is characterized in that:
(1) solution that will contain sulfur granule adds circling and bubbling separation column, and circling and bubbling separation column is made of bubbling segment and foam collection section, and bubbling segment is a gas lift type common loop reactor, and the foam collection section is the gas-liquid separator of overflow slot type;
(2) in circling and bubbling separation column, add anion surfactant, regulating pH is 8～10, bubbling air, tensio-active agent produces foam, and sulfur granule is enriched in foam surface, by collecting foam, sulphur is separated from solution;
The content of tensio-active agent is: whenever contain in the solution of 1g sulfur granule and contain tensio-active agent 0.05～0.14g;
Empty tower gas velocity is 0.5～2.5cm/s;
(3) sulfur granule satisfies following feature: median size is 0.5～25 μ m, and is 8～10 scope endoparticle surface positively charged at pH; The content of sulfur granule is not higher than 2g/L in the solution.
2. the method for the sulphur that circulation foam separation hydrogen sulfide oxidation according to claim 1 generates, it is characterized in that: anion surfactant is Sodium dodecylbenzene sulfonate or sodium lauryl sulphate.
3. the method for the sulphur that circulation foam separation hydrogen sulfide oxidation according to claim 1 generates, it is characterized in that: the diameter ratio of described circling and bubbling separation column bubbling segment and foam collection section is 1: 1.4～1: 1.7, and aspect ratio is 1: 0.5～1: 0.9; The diameter ratio of overflow groove weir, foam collection section and foam collection section is 1: 1～1: 1.4, and aspect ratio is 0.1: 1～0.3: 1.
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| CN 200910083005 CN101870883B (en) | 2009-04-24 | 2009-04-24 | Method for producing sulfur through separation, vulcanization and hydrogen oxidation of circling foam |
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| CN 200910083005 CN101870883B (en) | 2009-04-24 | 2009-04-24 | Method for producing sulfur through separation, vulcanization and hydrogen oxidation of circling foam |
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| CN101870883B CN101870883B (en) | 2013-07-31 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105176826A (en) * | 2015-10-20 | 2015-12-23 | 清华大学 | Method for harvesting microalgae through alkalescence flocculation-foam separation and separation device |
| CN105584994A (en) * | 2014-10-22 | 2016-05-18 | 中国石油化工股份有限公司 | Method for recovering sulphur from desulfurizing rich liquor |
| CN108793802A (en) * | 2018-06-08 | 2018-11-13 | 太原理工大学 | A kind for the treatment of process of coal chemical industry low-quality sulfur |
| CN113404465A (en) * | 2021-06-02 | 2021-09-17 | 陈湘红 | Auxiliary device for removing crude oil hydrogen sulfide by using foam separant after petroleum exploitation |
| CN113416587A (en) * | 2021-06-30 | 2021-09-21 | 中石化中原石油工程设计有限公司 | Oxidation regeneration tower of natural gas desulfurization system |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105584994A (en) * | 2014-10-22 | 2016-05-18 | 中国石油化工股份有限公司 | Method for recovering sulphur from desulfurizing rich liquor |
| CN105176826A (en) * | 2015-10-20 | 2015-12-23 | 清华大学 | Method for harvesting microalgae through alkalescence flocculation-foam separation and separation device |
| CN105176826B (en) * | 2015-10-20 | 2018-08-03 | 清华大学 | A kind of method and separator of alkalescent flocculation-foam fraction factor microalgae |
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| CN108793802B (en) * | 2018-06-08 | 2021-05-04 | 太原理工大学 | Treatment process of low-quality sulfur in coal chemical industry |
| CN113404465A (en) * | 2021-06-02 | 2021-09-17 | 陈湘红 | Auxiliary device for removing crude oil hydrogen sulfide by using foam separant after petroleum exploitation |
| CN113416587A (en) * | 2021-06-30 | 2021-09-21 | 中石化中原石油工程设计有限公司 | Oxidation regeneration tower of natural gas desulfurization system |
| CN113416587B (en) * | 2021-06-30 | 2024-04-09 | 中石化石油工程技术服务有限公司 | Oxidation regeneration tower of natural gas desulfurization system |
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