CN101874968A - Iron complex desulfurizer suitable for super-gravity desulfurization - Google Patents
Iron complex desulfurizer suitable for super-gravity desulfurization Download PDFInfo
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Abstract
The invention belongs to the technical field of gas purification, and in particular relates to an iron complex desulfurizer suitable for super-gravity desulfurization. The active ingredients of the iron complex desulfurizer are the following components: a soluble iron salt, an iron salt complexing agent, hydrosulfide absorbants comprising alkaline matters and alcamines, and additives comprising a stabilizing agent, a synergist, a sulfur granule settling agent and a corrosion inhibitor. The iron complex desulfurizer has the advantages of large accumulative saturation sulfur capacity (reaching 0.60g/L), high absorption speed, high efficiency, stable solution performance without degradation, easy recovery of sulfur, less side reactions, low running cost and the like; and the accumulative saturation sulfur capacity and the absorption speed are obviously improved, so the iron complex desulfurizer is suitable for the characteristics of small liquid circulating volume and short retention time of the super-gravity desulfurization, fully takes the obvious advantages of the super-gravity technology in the wet desulphurization, and is a high-efficiency, economic, practical and environment-friendly iron complex desulfurizer.
Description
Technical field
The invention belongs to the gas purification technique field, be specifically related to a kind of complexing iron desulfurizing agent that is suitable for high gravity desulfurization, be applicable to removing of sulphide-rich gas such as natural gas, refinery gas, synthesis gas, industrial waste gas.
Background technology
In the prior art about the research of complexing iron desulfurizing agent aspect:
1. LO-CAT, the LO-CAT II complexing iron sulfur removal technology of U.S.'s air resource company exploitation, the SulFerox complexing iron sulfur removal technology of the common exploitation of U.S. Shell Oil and DowChemical company, these two kinds of technology all belong to EDTA complexing iron sulfur removal technology, this type of technology has advantages such as desulfuration efficiency height, doctor solution internal circulating load are few, but its desulfurization operations cost is higher, the saturated Sulfur capacity of doctor solution is lower, only be 0.212g/L (referring to first annual meeting data of chemical fertilizer association of Chemical Industry and Engineering Society of China, 1986.12).
2. the FD method of Chinese University of Fuzhou exploitation, this technology is complexing agent with the sulfosalicylic acid, and the saturated Sulfur capacity of doctor solution significantly improves, and can reach 0.403g/L, and the desulfurization operations cost significantly reduces (referring to first annual meeting data of chemical fertilizer association of Chemical Industry and Engineering Society of China, 1986.12).But the doctor solution poor stability of this method, side reaction is many, and the sulphur consumption increases.
3. the improvement complexing iron sulfur removal technology of research institute of Nanjing of China chemical industry group company exploitation adopts the solution of compositions such as complexing agent, stabilizing agent, sulfur modifier and corrosion inhibiter to carry out desulfurization (referring to CN 1354038A).The result shows that this method has the desulfuration efficiency height, and solution property is stable, and sulphur easily reclaims, and can remove advantage such as most of organic sulfur.
Summary of the invention
The saturated Sulfur capacity that desulfurizing agent exists in the existing sulfur removal technology is low in order to solve in the present invention, doctor solution poor stability, the high deficiency of running cost, and a kind of complexing iron desulfurizing agent that is suitable for high gravity desulfurization is provided.
The present invention adopts following technical scheme to realize:
Be suitable for the complexing iron desulfurizing agent of high gravity desulfurization, its active ingredient is made up of following component: soluble ferric iron salt; The molysite complexing agent; The sulfohydrate absorbent comprises alkaline matter and alcamines material; And additive, comprise stabilizing agent, synergist, sulfur granules sedimentation agent and corrosion inhibiter;
Above-mentioned each components contents is as follows:
(1) total concentration of iron 0.1～6g/L, wherein Fe in the soluble ferric iron salt
3+Mass ratio with total iron: 0.8～1.0/1,
(2) molysite complexing agent concentration 1～9g/L,
(3) alkaline matter concentration 8～40g/L,
(4) alcamines material concentration 0.01～0.8g/L,
(5) stabilizer concentration 0.01～3g/L,
(6) synergist concentration 0.01～0.1g/L,
(7) sulfur granules sedimentation agent concentration 0.01～1g/L,
(8) density of corrosion inhibitor 0.01～3g/L,
The pH value of described complexing iron desulfurizing agent is 8～9.
Said components:
(1) soluble ferric iron salt is FeSO
4.7H
2O and/or FeCl
3And/or Fe
2(SO
4)
3
(2) the molysite complexing agent is two or more carboxylic acid or their sodium salt or sylvite, and carboxylic acid is sulfosalicylic acid, citric acid, tartaric acid or salicylic acid; They and Fe
3+/ Fe
2+Extremely strong complexing power is all arranged, can prevent effectively that solution from producing iron class precipitation, keeps solution property stable;
(3) alkaline matter is alkali-metal carbonate or bicarbonate, as: sodium carbonate, potash etc., can make acid sulfide gas enter liquid phase fast from gas phase, reach the purpose of from mist, separating sulfide;
(4) the alcamines material is monoethanolamine, diethanol amine or triethanolamine etc., and they are Fe
3+Extremely strong complexing agent promotes Fe
3+The sulphur effect of analysing of (complex state) increases saturated Sulfur capacity, is again sulfide absorbent efficiently, can strengthen the infiltration rate to sulfide;
(5) stabilizing agent be benzene sulfonate, inorganic sodium, compound sugar and halogenation phenolic compound etc. quality compare mixture; As: sodium 1,3-benzenedisulfate, to xylene disulfonic acid sodium, paratoluenesulfonic acid sodium salt, sodium hydrogensulfite, sodium hydrogen phosphate, sodium dihydrogen phosphate, sucrose, maltose, 2,4-chlorophenesic acid, 2,4,6-trichlorophenol, 2,4,6,-T etc.They can effectively improve the stability of iron complex, reduce the degraded of complexing iron;
(6) synergist is anthraquinones or their sodium salt or sylvite, and they both can improve Fe under alkali condition
2+The oxidation regeneration speed of (complex state) has increased the saturated Sulfur capacity of doctor solution again simultaneously;
(7) the sulfur granules sedimentation agent comprises saturated straight chain alcohol, oligosaccharides and the high-valency metal salt of non-ionic surface active agent, C7～18, can make sulfur granules rapid polymerization within a short period of time and sedimentation separation;
(8) corrosion inhibiter comprises sodium tungstate, sodium cinnamate, sucrose, potassium chromate and naphthoquinones-2-sulfonate sodium, and it can reduce the corrosion of doctor solution of the present invention to the desulphurization plant material effectively, and corrosion rate can reduce more than 16 times.
In the sulfur granules sedimentation agent:
(1) non-ionic surface active agent is the polyethylene glycol ethers, and relative molecular mass is 1500～5000, is 25～35% of sulfur granules sedimentation agent gross mass;
(2) the saturated straight chain alcohol of C7～18 is molecular formula C
nH
2n+2O, the mixture of two or more in the saturated straight chain alcohol of n=7～18 is 40～50% of sulfur granules sedimentation agent gross mass;
(3) oligosaccharides is sucrose or maltose or their sodium salt or sylvite, is 10～20% of sulfur granules sedimentation agent gross mass;
(4) the high-valency metal salt is AlCl
3, Al
2(SO
4)
3Or MgCl
2, be 10～18% of sulfur granules sedimentation agent gross mass;
In the corrosion inhibiter: the mass ratio of sodium tungstate, sodium cinnamate, sucrose, potassium chromate and naphthoquinones-2-sulfonate sodium is 2～3.5: 0.5～1.2: 1～1.5: 2.5～3.5: 2～2.5.
The suitable pH value of doctor solution of the present invention is 8～9.
The preparation method who is suitable for the complexing iron desulfurizing agent of high gravity desulfurization of the present invention, it is characterized in that step is as follows: make solvent with water, add soluble ferric iron salt earlier, fully after the stirring and dissolving, add again after the molysite complexing agent treats to dissolve fully, add alcamines material, stabilizing agent, synergist, sulfur granules sedimentation agent and corrosion inhibiter successively, treat that all substances dissolve fully, with alkaline matter regulator solution pH value to 8～9, can be mixed with doctor solution of the present invention at last.
In the application process, with the desulfurizing agent and the gas counter current contacting in overweight machine that contains sulfide that contains high valence iron of the present invention, sulfide in gas phase is absorbed by complexing iron doctor solution, and simultaneous oxidation becomes sulphur, and complexing iron doctor solution itself is reduced into Fe
2+(complex state); Fe in reclaim equiment
2+(complex state) contacts with oxygen and is oxidized to Fe
3+(complex state) and recover oxidability returns then and continues to absorb sulfide in the overweight machine; The sulphur that forms in reclaim equiment rapid polymerization and fall to reclaim equiment bottom under the effect of sulfur granules sedimentation agent is regularly discharged from the bottom and is sent into centrifuge and isolate sulphur.The key reaction of whole process is as follows:
H
2S+Na
2CO
3＝NaHCO
3+NaHS
2Fe
3+L+HS
-=2Fe
2+L+S ↓+H
+(L represents complex state)
2Fe
2+L+1/2O
2+ H
+=2Fe
3+L+OH
-(L represents complex state)
Specifically, added special-purpose absorbent and synergist in (1) doctor solution of the present invention, when keeping 99% above desulfurization degree, can in 2～5 seconds, realize fast Absorption, and the saturated Sulfur capacity of doctor solution is increased to 0.60g/L sulfide; (2) the saturated Sulfur capacity height of doctor solution of the present invention, absorption rate are fast, are more suitable in the high gravity desulfurization technology; Compare tower desulfur technology, the energy conservation and consumption reduction effects of present technique is obvious, and running cost is significantly reduced; (3) added unique sulfur granules sedimentation agent in the doctor solution of the present invention, can make sulfur granules rapid polymerization and sedimentation separation in 5～10 minutes; (4) added unique stabilizing agent in the doctor solution of the present invention, can make doctor solution in 3 months continuous running degradation amount less than 5%.
The present invention has saturated Sulfur capacity height (can reach 0.60g/L), absorption rate fast (absorbing sulfide in 2～5 seconds fully), and sulphur easily reclaims advantages such as (in 5～10 minutes sulfur granules granularity increase be 20～30 microns and sedimentation separation); Simultaneously, used cheap industrial goods soluble ferric iron salt, carboxylic-acid substance etc. that the doctor solution expense is significantly reduced; Unique stabilizing agent makes the doctor solution degradation amount that absorbs behind the sulfide less than 5%, and long-time stable homogeneous, has promoted the combination property of doctor solution; Be suitable for the characteristics that the high gravity desulfurization liquid circulation amount is few, the time of staying is short, given full play to the significant advantage of high-gravity technology aspect wet desulphurization, on energy-saving and cost-reducing basis, reduced running cost.
The specific embodiment
The present invention will be described below in conjunction with example, but it does not limit protection scope of the present invention.
At first, the example of sulfur granules sedimentation agent is as follows:
Example a: the sulfur granules sedimentation agent, form (mass percent) by following ingredients: polyethylene glycol ethers (relative molecular mass is 1500) 35%, the saturated straight chain alcohol 41% of C7, C17, sucrose 10%, AlCl
314%.
Example b: the sulfur granules sedimentation agent, form (mass percent) by following ingredients: polyethylene glycol ethers (relative molecular mass is 4000) 28%, the saturated straight chain alcohol 40% of C8, C9, C17, maltose 20%, MgCl21
2%.
Example c: the sulfur granules sedimentation agent, form (mass percent) by following ingredients: polyethylene glycol ethers (relative molecular mass is 5000) 25%, the saturated straight chain alcohol 50% of C7, C9, C18, the sodium salt 15% of sucrose, Al
2(SO
4)
310%.
Example d: the sulfur granules sedimentation agent, form (mass percent) by following ingredients: polyethylene glycol ethers (relative molecular mass is 3000) 31%, the saturated straight chain alcohol 41% of C9, C16, C18, sucrose 10%, AlCl
318%.
Example e: the sulfur granules sedimentation agent, form (mass percent) by following ingredients: polyethylene glycol ethers (relative molecular mass is 2000) 33%, the saturated straight chain alcohol 43% of C9, C16, C18, sucrose 10%, AlCl
314%.
Secondly, the example of corrosion inhibiter:
Example a: the mass ratio of sodium tungstate, sodium cinnamate, sucrose, potassium chromate and naphthoquinones-2-sulfonate sodium is 2: 0.5: 1.5: 3.5: 2.5.
Example b: the mass ratio of sodium tungstate, sodium cinnamate, sucrose, potassium chromate and naphthoquinones-2-sulfonate sodium is 3.5: 1: 1: 2.5: 2.
Example c: the mass ratio of sodium tungstate, sodium cinnamate, sucrose, potassium chromate and naphthoquinones-2-sulfonate sodium is 3: 0.8: 1.3: 2.8: 2.1.
Example d: the mass ratio of sodium tungstate, sodium cinnamate, sucrose, potassium chromate and naphthoquinones-2-sulfonate sodium is 2.6: 1.2: 1: 3.2: 2.
Embodiment 1:
Handle sulfur compound 1.0～1.5g/m with doctor solution of the present invention
3Industrial waste gas (wherein, H
2S content＞96%, other is organic sulfur CS
2, COS etc.).
(1) composition of doctor solution:
Total iron: 0.5g/L, wherein Fe
3+With the mass ratio of total iron be 0.95
Sulfosalicylic acid: 1.0g/L
Tartaric acid: 0.5g/L
Sodium carbonate: 10g/L
Diethanol amine: 0.80g/L
Paratoluenesulfonic acid sodium salt, sodium hydrogensulfite, sucrose and 2, the mixture of mass ratioes such as 4-chlorophenesic acid: 0.4g/L
2,7-anthraquinone disulphonate: 0.02g/L
Sulfur granules sedimentation agent example e:0.04g/L
Corrosion inhibiter example d:0.3g/L
Regulate doctor solution pH value: 8～9
All the other: water
Doctor solution concrete configuration method: make solvent with water, add soluble ferric iron salt earlier, fully after the stirring and dissolving, add again after the molysite complexing agent treats to dissolve fully, add alcamines material, stabilizing agent, synergist, sulfur granules sedimentation agent and corrosion inhibiter successively, treat that all substances dissolve fully, at last with alkaline matter regulator solution pH value to 8～9.
Absorption technique condition when (2) handling gaseous mixture with doctor solution is:
Mixed gas flow: 1000L/h
Doctor solution flow: 20～30L/h
Overweight machine rotating speed: 1500r/min
Absorb temperature: 22～28 ℃
(3) desulfurized effect such as following table
Above-mentioned doctor solution is continuously running 96 hours in overweight machine, and the total iron content in the doctor solution remains at 1.14g/L, and desulfurization degree remains at more than 99% (organic sulfur CS wherein
2, removal efficiency＞85% such as COS), doctor solution desulfuration efficiency height of the present invention is described, good stability can make gaseous mixture reach and produce required purification standard.
Embodiment 2:
Handle sulfur compound 2.5～3.0g/m with doctor solution of the present invention
3Industrial waste gas (wherein, H
2S content＞91%, other is organic sulfur CS
2, COS etc.).
(1) composition of doctor solution:
Total iron: 2.0g/L, wherein Fe
3+With the mass ratio of total iron be 0.85
Lactic acid: 1.0g/L
Sodium tartrate: 1.5g/L
Salicylic acid: 1.5g/L
Sodium carbonate: 20g/L
Triethanolamine: 0.1g/L
To xylene disulfonic acid sodium, sodium hydrogen phosphate, maltose and 2, the mixture of mass ratioes such as 4-chlorophenesic acid: 1.6g/L
2,6-anthraquinone disulphonate: 0.06g/L
Sulfur granules sedimentation agent example b:0.42g/L
Corrosion inhibiter example c:1.7g/L
Doctor solution pH value: 8～9
All the other: water
Doctor solution concrete configuration method as previously mentioned.
Absorption technique condition when (2) handling gaseous mixture with doctor solution is:
Mixed gas flow: 1000L/h
Doctor solution flow: 20～30L/h
Overweight machine rotating speed: 1500r/min
Absorb temperature: 22～28 ℃
(3) desulfurized effect such as following table
Above-mentioned doctor solution turned round 96 hours in overweight machine continuously, and its effect is with example 1.
Embodiment 3:
Handle sulfur compound 6.5～7.0g/m with doctor solution of the present invention
3Industrial waste gas (wherein, H
2S content＞88%, other is organic sulfur CS
2, COS etc.).
(1) composition of doctor solution:
Total iron: 5.5g/L, wherein Fe
3+With the mass ratio of total iron be 0.8
Sulfosalicylic acid: 3.5g/L
Citric acid: 2.5g/L
Sodium tartrate: 2.5g/L
Sodium carbonate: 38g/L
Triethanolamine: 0.40g/L
To xylene disulfonic acid sodium, sodium dihydrogen phosphate, sucrose and 2,4, the mixture of mass ratioes such as 6-trichlorophenol, 2,4,6,-T: 2.9g/L
2,7-anthraquinone disulphonate: 0.09g/L
Sulfur granules sedimentation agent example c:0.93g/L
Corrosion inhibiter example b:2.9g/L
Doctor solution pH value: 8～9
All the other: water
Doctor solution concrete configuration method as previously mentioned.
Absorption technique condition when (2) handling gaseous mixture with doctor solution is:
Mixed gas flow: 1000L/h
Doctor solution flow: 20～30L/h
Overweight machine rotating speed: 1500r/min
Absorb temperature: 22～28 ℃
(3) desulfurized effect such as following table
Above-mentioned doctor solution turned round 96 hours in overweight machine continuously, and its effect is with example 1.
Above example 1～3 only as the present invention can be practical for example, do not limit content of the present invention.When hydrogen sulfide content in the industrial waste gas changed from low to high, each amounts of components also presented growth trend in the doctor solution; Hydrogen sulfide content is by 1g/m in industrial waste gas
3Be increased to 7g/m
3The time, using desulfurizing agent of the present invention, overweight machine desulfurization degree all can reach more than 99% (organic sulfur CS wherein
2, removal efficiency＞85% such as COS), satisfy the purification requirement of industrial waste gas, have the favorable industrial application prospect.
Claims (6)
1. complexing iron desulfurizing agent that is suitable for high gravity desulfurization, it is characterized in that: its active ingredient is made up of following component: soluble ferric iron salt; The molysite complexing agent; The sulfohydrate absorbent comprises alkaline matter and alcamines material; And additive, comprise stabilizing agent, synergist, sulfur granules sedimentation agent and corrosion inhibiter;
Above-mentioned each components contents is as follows:
(1) total concentration of iron 0.1～6g/L, wherein Fe in the soluble ferric iron salt
3+With the mass ratio of total iron be 0.8～1.0/1,
(2) molysite complexing agent concentration 1～9g/L,
(3) alkaline matter concentration 8～40g/L,
(4) alcamines material concentration 0.01～0.8g/L,
(5) stabilizer concentration 0.01～3g/L,
(6) synergist concentration 0.01～0.1g/L,
(7) sulfur granules sedimentation agent concentration 0.01～1g/L,
(8) density of corrosion inhibitor 0.01～3g/L,
The pH value of described complexing iron desulfurizing agent is 8～9.
2. the complexing iron desulfurizing agent that is suitable for high gravity desulfurization according to claim 1 is characterized in that:
(1) soluble ferric iron salt is FeSO
4.7H
2O and/or FeCl
3And/or Fe
2(SO
4)
3
(2) the molysite complexing agent is two or more carboxylic acid or their sodium salt or sylvite;
(3) alkaline matter is alkali-metal carbonate or bicarbonate;
(4) the alcamines material is monoethanolamine, diethanol amine or triethanolamine;
(5) stabilizing agent be benzene sulfonate, inorganic sodium, compound sugar and halogenation phenolic compound etc. quality compare mixture;
(6) synergist is anthraquinones or their sodium salt or sylvite;
(7) the sulfur granules sedimentation agent comprises saturated straight chain alcohol, oligosaccharides and the high-valency metal salt of non-ionic surface active agent, C7～18;
(8) corrosion inhibiter comprises sodium tungstate, sodium cinnamate, sucrose, potassium chromate and naphthoquinones-2-sulfonate sodium.
3. the method that is suitable for the complexing iron desulfurizing agent of high gravity desulfurization according to claim 2 is characterized in that carboxylic acid is sulfosalicylic acid, citric acid, tartaric acid or salicylic acid.
4. the method that is suitable for the complexing iron desulfurizing agent of high gravity desulfurization according to claim 2 is characterized in that in the sulfur granules sedimentation agent:
(1) non-ionic surface active agent is the polyethylene glycol ethers, and relative molecular mass is 1500～5000, is 25～35% of sulfur granules sedimentation agent gross mass;
(2) the saturated straight chain alcohol of C7～18 is molecular formula C
nH
2n+2O, the mixture of two or more in the saturated straight chain alcohol of n=7～18 is 40～50% of sulfur granules sedimentation agent gross mass;
(3) oligosaccharides is sucrose or maltose or their sodium salt or sylvite, is 10～20% of sulfur granules sedimentation agent gross mass; (4) the high-valency metal salt is AlCl
3, Al
2(SO
4)
3Or MgCl
2, be 10～18% of sulfur granules sedimentation agent gross mass
5. the method that is suitable for the complexing iron desulfurizing agent of high gravity desulfurization according to claim 2, it is characterized in that in the corrosion inhibiter: the weight ratio of sodium tungstate, sodium cinnamate, sucrose, potassium chromate and naphthoquinones-2-sulfonate sodium is 2～3.5: 0.5～1.2: 1～1.5: 2.5～3.5: 2～2.5.
6. one kind prepares as claim 1 or 2 or 3 or the 4 or 5 described methods that are suitable for the complexing iron desulfurizing agent of high gravity desulfurization, it is characterized in that step is as follows: make solvent with water, add soluble ferric iron salt earlier, fully after the stirring and dissolving, add again after the molysite complexing agent treats to dissolve fully, add alcamines material, stabilizing agent, synergist, sulfur granules sedimentation agent and corrosion inhibiter successively, treat that all substances dissolve fully, with alkaline matter regulator solution pH value to 8～9, can be mixed with doctor solution of the present invention at last.
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| CN1038311C (en) * | 1993-05-11 | 1998-05-13 | 华东理工大学 | Improved complex iron process to remove sulfide from gas mixture |
| WO2001019496A1 (en) * | 1999-09-15 | 2001-03-22 | Eickmeyer & Associates | Method and composition for removing co2 and h2s from gas mixtures |
| CN1168526C (en) * | 2001-10-30 | 2004-09-29 | 南化集团研究院 | Improved complex iron method for removing sulfide from gas |
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