CN103691274A - Method for production regulation of chelated iron desulfurization process - Google Patents
Method for production regulation of chelated iron desulfurization process Download PDFInfo
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Abstract
The present invention relates to a gas treatment method, specifically to a method for production regulation of a chelated iron desulfurization process. According to the method, solid phase impurities and liquid phase impurities are removed from hydrogen sulfide-containing raw material gas through an acid-gas separator, the obtained material sequentially passes through a pre-absorption tower and an absorption tower, and reacts with the chelated iron barren solution so as to remove the hydrogen sulfide gas, and the purified nature gas enters a purified gas separator to remove water, is subjected to measurement detection, and then is directly and externally output. With the method, normal use can be achieved even when the hydrogen sulfide content in the raw material gas is changed, and production requirements can be met through adaptable regulation of other parameters according to the method so as to avoid regulation of the production process. In addition, according to the actual situation requirements of the production, the optimal desulfurization solution circulation amount is selected so as to reduce equipment loss, reduce pump power consumption and avoid waste of energy sources.
Description
Technical field
The present invention relates to a kind of gas processing method, is a kind of method of producing regulation and control for Complexing Iron sulfur removal technology specifically.
Background technology
At present, the selexol process technique that selexol process is conventional roughly can have following 3 types:
(1) absorption-regenerative technique: can be subdivided into again physical solvent absorption process and chemical solvent absorption method 2 classes by the type of lyosoption, the chemical absorption method that the various hydramine of wherein take are solvent is most widely used method in current gas purifying process.These class methods, when removing hydrogen sulfide, also will remove a certain amount of carbon dioxide.
(2) oxidation-reduced form technique: be applicable under given conditions normal pressure or low pressure, in the desulfurization of low sulfur-containing gas, this type of technique is carbon dioxide removal not substantially.
(3) biological desulfurization process: development is because of its safety and environmental protection, H
2s removal efficiency is high, sulfur purity height is to be also one of direction of giving priority to of current desulfur technology.
Complex iron belongs to absorption-regenerative technique, also there is the patent making improvements in existing field, if number of patent application is CN01134105.X, the applying date is 2001.10.30, name is called the patent of invention of " improvement complex iron method for removing sulfide from gas ", its technical scheme is: improvement complex iron method for removing sulfide from gas, belongs to gas purification technique field.The invention is characterized in that Complexing Iron desulfurizing agent mainly contains molysite, complexing agent, absorbent and stabilizing agent, sulfur modifier and corrosion inhibiter, doctor solution pH value is preferably 6.5 ~ 8.5; According to different Sulfur Contained Raw Gas, the composition of desulfurizing agent is different from proportioning.
Above-mentioned patent is according to different Sulfur Contained Raw Gas, with the desulfurizing agent of different proportionings, reacts.But in actual applications, hydrogen sulfide content can change along with gas well recovery time, if slight change just needs proportioning desulfurizing agent again, and perhaps technique make the appropriate adjustments, needs that like this can not realistic large-scale production.
Summary of the invention
In order to overcome existing Complexing Iron sulfur removal technology, exist when Sulfur Contained Raw Gas changes of contents, need to change proportioning between desulfurizing agent proportioning and technique and each composition and select the problems such as not good, even the existing special a kind of a kind of method of producing regulation and control for Complexing Iron sulfur removal technology that hydrogen sulfide content variation also need not change original technique that proposes.
Concrete scheme of the present invention is as follows:
A method of producing regulation and control for Complexing Iron sulfur removal technology, is characterized in that:
Hydrogen sulfide containing unstripped gas is removed solid phase and liquid phase impurity by acid gas separator, then enter successively pre-absorption tower and absorption tower, and reacting hydrogen sulfide gas with Complexing Iron lean solution wherein, the natural gas after purification enters purge gas separator and sloughs moisture, directly outer defeated after detecting by metering;
In described absorption tower, the Complexing Iron rich solution that is absorbed with sulphur enters regenerator by rich solution flash tank and contacts with oxygen in air, again form can absorbing hydrogen sulphide lean solution, lean solution enters separating tank, by lean pump, again enter absorption tower, complete the circulation of whole doctor solution, rich solution and lean solution form described doctor solution; The sulphur foam forming in regenerator enters sulphur foam tank, by drum unit, sloughs the moisture in sulphur, forms sulphur cream;
Its key reaction is as follows successively:
1) doctor solution absorbs H
2s
2) desulphurization reaction
3) regenerative response
2NaHCO
3?→?Na
2CO
3+?CO
2?+H
2O
The parameter of described each composition should meet following relational expression:
In formula:
---concentration of hydrogen sulfide in unstripped gas, g/m
3;
---lean solution Fe
2+concentration, g/L;
The pH value of described doctor solution is 8.15-8.5, rich solution Fe in pre-absorption tower
2+in content and rich solution, lean solution, the ratio of total iron content is 1/2.
Described regenerator expulsion pressure remains between 0.22～0.26MPa, lean solution Fe
2+concentration is 0.15-0.25g/L, and described doctor solution temperature is 40 ℃ to 45 ℃, and the concentration of described total iron is 1.85-2.25g/L.
Also comprise and add desulfuration solution medicament step, described desulfuration solution medicament comprises desulfurizing agent, stabilizing agent, ferrous salt and sodium carbonate, above-mentioned medicament is added in desalted water and configured, in filling process, according to the order of sodium carbonate, desulfurizing agent, ferrous salt, stabilizing agent, add successively.
Described adding in desulfuration solution medicament step,, in desulfurizing agent mother liquor, alkali, desulfurizing agent, stabilizing agent, total iron adding amount computational methods are:
In formula:
---the adding amount of ferrous salt, desulfurizing agent, stabilizing agent, alkali, kg;
---the cumulative volume of solution in system, m
3;
Doctor solution before each dosing, is exactly desulfurizing agent mother liquor for dosing next time after adding, and for dosing next time, this is added and solution before is just called mother liquor, the sodium carbonate that alkali refers to altogether;
Ideal concentration just refers to have added wants the value that reaches after medicament, measured concentration just refers to before dosing the concentration of each medicament in solution.
Described flash tank pressure remains on 0.6～0.7MPa, and liquid level remains on 1200mm.
The invention has the advantages that:
Even if 1, use the hydrogen sulfide content change in this patent method unstripped gas also can normally use, according to this method, other parameters carried out to accommodation and can meet Production requirement, and avoided production technology to adjust.And according to the actual conditions needs of producing, select best desulfuration solution internal circulating load, reduce the loss of equipment, reduce the power consumption of pump, avoid the waste of the energy.
2, each composition result of calculation and the measured value that after relational expression proportioning of the present invention, obtain are comparatively approaching, and error all, in 3%, can be good at representing the relation between parameters, and computational accuracy is also comparatively accurate.
3, the pH value of doctor solution is generally considered the crux variable of complex iron absorption technology of hydrogen sulfide by oxidation technique, and pH value is between 8.15～8.5, and outer gas transmission body hydrogen sulfide content is all at 2mg/m
3below, desulfuration efficiency all can reach need of production.According to considering of sodium carbonate consumption and dosing proportioning, doctor solution pH value is remained on to 8.3 left and right, desulfurized effect is good.
4, pre-absorption tower rich solution Fe
2+content is about 1/2 best results with the ratio of total iron, and this guarantees the higher desulfuration efficiency in absorption tower, and is beneficial to the normal output of sulphur foam on regenerator.
5, when regenerator expulsion pressure remains between 0.22～0.26MPa, make now lean solution Fe
2+concentration is about 0.15-0.25g/L, and rich solution is fully regenerated, and also there will not be Fe simultaneously
2+peroxidating, sulphur foam also can normally form.
6, meeting under the normal prerequisite of producing of sulfur removal technology, sulphur depositional phenomenon has to a certain degree and alleviates, and regenerator sulphur foam emits tower phenomenon obviously to reduce; Total iron index reduces, and also makes ferrous salt addition reduce, more economical economically.
7, adopt dosing method of the present invention, make medicament adding amount increasingly steady, reagent consumption amount obviously reduces.
Accompanying drawing explanation
Fig. 1 is Complexing Iron sulfur removal technology schematic diagram.
Fig. 2 is H
2s exists form with the changing trend diagram of pH value.
Fig. 3 is H
2the relation curve of S removal efficiency and temperature.
The specific embodiment
A kind of method of producing regulation and control for Complexing Iron sulfur removal technology, hydrogen sulfide containing unstripped gas is removed solid phase and liquid phase impurity by acid gas separator, then enter successively the absorption towers such as pre-absorption tower, and react hydrogen sulfide gas with Complexing Iron lean solution wherein, natural gas after purification enters purge gas separator and sloughs moisture, directly outer defeated after detecting by metering;
In described absorption tower, the Complexing Iron rich solution that is absorbed with sulphur enters regenerator by rich solution flash tank and contacts with oxygen in air, again form can absorbing hydrogen sulphide lean solution, lean solution enters separating tank, by lean pump, again enter absorption tower, complete the circulation of whole doctor solution, rich solution and lean solution form described doctor solution; The sulphur foam forming in regenerator enters sulphur foam tank, by drum unit, sloughs the moisture in sulphur, forms sulphur cream.
In conjunction with Fig. 1, specifically, technological process is as follows:
Hydrogen sulfide containing unstripped gas enters pre-absorption tower by acid gas separator, lean solution enters pre-absorption tower injector from pre-absorption tower top, hydrogen sulfide containing unstripped gas enters pre-absorption tower injector from the side, and gas-liquid mixed reaction removes hydrogen sulfide, and rich solution is expelled to flash tank from outlet at bottom.The natural gas obtaining enters first grade absorption tower from outlet.
Lean solution enters first grade absorption tower shower nozzle from first grade absorption tower top, discharges flash tank downwards from the outlet of first grade absorption tower rich solution; Natural gas enters from bottom, through the liquid in first grade absorption tower, upwards flows, and deviates from hydrogen sulfide with doctor solution counter current contacting, from the top outlet of first grade absorption tower, enters two-level absorption tower.
Lean solution enters two-level absorption tower from two-level absorption tower top, discharges flash tank downwards from the outlet of two-level absorption tower rich solution; Natural gas enters from two-level absorption tower bottom, and bottom-up flowing, removes hydrogen sulfide with doctor solution counter current contacting, from two-level absorption tower outlet, enters top, three grades of absorption towers.
Lean solution enters three grades of absorption towers from top, three grades of absorption towers, discharges flash tank downwards from three grades of absorption tower rich solution outlets; Natural gas enters from bottom, three grades of absorption towers, and bottom-up flowing, removes hydrogen sulfide with doctor solution counter current contacting, from three grades of absorption tower outlets, enters decontaminating separator.
Rich solution in flash tank enters injector by flash tank pressure from regenerator top, the air entering with self-priming mixes generation oxidation reaction, and in regenerator further oxidation regeneration, most of elemental sulfur of separating out is suspended in regenerator top, overflow enters sulphur foam tank.Complexing Iron lean solution after regeneration is from the air flotating chamber that flow to separating tank, and the lean solution chamber of separating tank is back to top, absorption tower at different levels by lean solution by lean pump.
The lean solution of regenerator enters separating tank, and by the sulphur in the further separated lean solution of air supporting, isolated sulphur overflow or utilize Slag Scraping Device to discharge, enters sulphur foam tank; Lean solution enters lean solution chamber through liquid level regulator.
Its key reaction is as follows successively:
1) doctor solution absorbs H
2s
2) desulphurization reaction
3) regenerative response
2NaHCO
3?→?Na
2CO
3+?CO
2?+H
2O
The parameter of described each composition should meet following relational expression:
In formula:
---concentration of hydrogen sulfide in unstripped gas, g/m
3;
---the internal circulating load of doctor solution, m
3/ h;
The pH value of doctor solution is 8.15-8.5, rich solution Fe in pre-absorption tower
2+in content and rich solution, lean solution, the ratio of total iron content is 1/2.
Regenerator expulsion pressure remains between 0.22～0.26MPa, lean solution Fe
2+concentration is 0.15-0.25g/L, and described doctor solution temperature is 40 ℃ to 45 ℃, and the concentration of described total iron is 1.85-2.25g/L.
Also include and add desulfuration solution medicament step, described desulfuration solution medicament comprises desulfurizing agent, stabilizing agent, ferrous salt and sodium carbonate, above-mentioned medicament is added in desalted water and configured, in filling process, according to the order of sodium carbonate, desulfurizing agent, ferrous salt, stabilizing agent, add successively.
Described adding in desulfuration solution medicament step,, in desulfurizing agent mother liquor, alkali, desulfurizing agent, stabilizing agent, total iron adding amount computational methods are:
In formula:
---the adding amount of ferrous salt, desulfurizing agent, stabilizing agent, alkali, kg;
---the measured concentration of ferrous salt, desulfurizing agent, total alkali, g/L;
Doctor solution before each dosing, is exactly desulfurizing agent mother liquor for dosing next time after adding, and for dosing next time, this is added and solution before is just called mother liquor, the sodium carbonate that alkali refers to altogether;
Ideal concentration just refers to have added wants the value that reaches after medicament, measured concentration just refers to before dosing the concentration of each medicament in solution.
Described flash tank pressure remains on 0.6～0.7MPa, and liquid level remains on 1200mm.
Wherein
Table 1
According to this, calculate concentration of hydrogen sulfide and Chinese measuring technology center research institute and survey concentration of hydrogen sulfide to such as table 2:
Table 2 actual measurement concentration of hydrogen sulfide and formula calculate concentration of hydrogen sulfide contrast
According to Data Comparison, can find out, this formula result of calculation and measured value are comparatively approaching, and error is all in 3%, illustrate that this revises rear empirical equation comparatively accurate, therefore, can be used as the guiding formula that in Complexing Iron sulfur removal technology production process, parameters is controlled and adjusted, its main use can be divided into:
(1) according to assay office, obtain rich or poor liquid Fe
2+concentration, calculates unstripped gas concentration of hydrogen sulfide in conjunction with gas production and the doctor solution internal circulating load of actual production;
(2), in the situation that unstripped gas concentration of hydrogen sulfide is known, in conjunction with gas production, can obtain rich or poor liquid Fe
2+relational expression between concentration and doctor solution internal circulating load, can instruct the ferrous adjusting of solution, guarantees normally to produce;
(3) in the situation that output is certain, according to the rich or poor liquid Fe of actual measurement
2+concentration, can obtain the relational expression between doctor solution internal circulating load and unstripped gas concentration of hydrogen sulfide, thereby can change and suitably regulate doctor solution internal circulating load according to concentration of hydrogen sulfide;
(4) rich solution Fe
2+concentration ideal value is half left and right of total iron, lean solution Fe
2+concentration ideal value is 0.15-0.25g/L, can be according to desirable Fe
2+concentration, in the situation that unstripped gas concentration of hydrogen sulfide is known, realizes the Proper Match of gas production and doctor solution internal circulating load, thereby instructs output to regulate.
For example: the about 12g/m3 of 1 well concentration of hydrogen sulfide, desirable Fe
2+concentration is: rich solution 0.8 g/L, and lean solution 0.1g/L, according to the production system in current 9.5 ten thousand side/skies, substitution formula can be calculated reasonable solution circulation amount and is:
According to result of calculation, 1 well solution circulation amount is remained on to 170m
3the operation of/h left and right, parameters and index are all produced normally.By long-term practice, check, this formula can be good at representing the relation between parameters, and computational accuracy is also comparatively accurate, has very high reference and guiding value.
Press H
2s ionization equilibrium rule, as calculated, H under different pH values in solution
2s, HS
-, S
2-percentage:
H in the lower solution of the different pH values of table 3
2there is form in S
The pH value of solution is generally considered the crux variable of complex iron absorption technology of hydrogen sulfide by oxidation technique.As can be seen from Table 3, the H in the aqueous solution when pH value increases
2s percentage sharply reduces, and HS
-content but greatly increase, the pH value of doctor solution increases desulfurization favourable.In table, data can be found out, the H when the pH of solution value approaches 6 in solution
2s concentration sharply reduces, and HS
-sharply increase; After pH value is greater than 8, H
2it is minimum that S concentration reaches, HS
-reach maximum; Although too high pH value is to H
2the impact of the concentration of S is very little, but HS
-in pH value, be can sharply reduce for 12 o'clock, S
2-increase rapidly, unfavorable to desulfurization, there is iron precipitation to generate simultaneously, be both unfavorable for the steady running of system, make again impurity content in sulphur increase.Moreover too high pH value increases sodium carbonate addition, is inappropriate economically.So the pH value of controlling lean solution in daily production is 8.0～9.0th, suitable.Theoretically, pH value during 8.0～9.0, HS
-content and desulfuration efficiency still with the increase of pH value, increase, if but to improve pH value and just must increase considerably the adding amount of sodium carbonate, reasonable not economically.By on-the-spot tracking evaluation, 9.5 * 10
4m
3/ d, unstripped gas hydrogen sulfide content 12g/m
3condition under, pH value is between 8.15～8.5, outer gas transmission body hydrogen sulfide content is all at 2mg/m
3below, desulfuration efficiency all can reach need of production.According to considering of sodium carbonate consumption and dosing proportioning, solution pH value is remained on to 8.3 left and right, desulfurized effect is best.
In Complexing Iron solution, iron ion is mainly Fe in lean solution
3+, in rich solution, be mainly Fe
2+, in daily production, main by measuring total concentration of iron and the Fe of rich or poor liquid
2+concentration is determined Fe
3+, Fe
2+concentration, Fe
3+concentration is total concentration of iron and Fe
2+concentration poor.
Complexing Iron solution oxide absorbs H
2the process of S belongs to redox reaction fast.Work as H
2s gas contacts and is converted into HS with solution
-after, with the Fe in solution
3+react rapidly, make the Fe at gas-liquid interface place
3+concentration declines rapidly.Work as Fe
3+when concentration is lower, because reaction makes interface Fe
3+concentration is down to very low degree, the Fe in doctor solution main body
3+do not diffuse in time again desulfurization liquid interface, this has just caused H
2s can not be absorbed in time, makes H
2s absorptivity is lower.And Fe in the doctor solution
3+when concentration is higher, although gas liquid film place is owing to absorbing H
2s consumes Fe
3+, but still can maintain certain Fe
3+concentration, is enough to and the H being come by gas phase main diffusion
2s reaction, so can keep H
2s absorptivity is higher.
Different initial Fe
3+the experiment of absorbent, experimental result has also been verified and has been worked as Fe
3+while being greater than certain value, mass transfer rate is subject to Fe
3+impact reduces, H
2the absorptivity of S is subject to Fe
3+affect less, H now
2the absorptivity of S is higher.
The different initial Fe of table 4
3+the experimental result of absorbent
There is aborning the problem of not producing sulphur, show as regenerator formation sulphur foam less, thinner, blacking up, easily rushed broken, reagent consumption is more, chemical examination records desulfurizing agent and total iron index usually lower than normal value, needing repeatedly to add every day medicament, could to maintain reluctantly indices normal, adds that to observe after several hours output sulphur after medicament still undesired.Fe in chemical examination pre-absorption tower rich solution
2+too high levels, is almost 3/4 of total iron content, sometimes even suitable with total iron.By theory analysis, Fe in rich solution in absorption tower
2+excessive concentration, Fe when reaction is described
3+consume morely, concentration is on the low side, makes Fe
3+cannot be completely by HS
-be oxidized to simple substance S, unnecessary HS
-with Fe
2+reaction generates FeS, shows as absorption tower rich solution blackout, and the sulphur of output is reduced; Too much Fe
2+can in regenerator, generate Fe with oxygen reaction
2o
3, be deposited on container bottom, thereby reduce total iron content, affect desulfurized effect.By regulating air inflow and the solution circulation amount on each absorption tower to reduce rich solution Fe
2+after content, solution sulphur foam blackout phenomenon disappears, and regenerator sulphur foam recovers normal gradually.In production operation after this, if detect Fe in the rich solution of absorption tower
2+during too high levels, can, by regulating pre-absorption tower air intake valve and bypass valve, reduce Fe
2+the air inflow on too high levels absorption tower, improves Fe
2+the air inflow on the too low absorption tower of content, realizes the reasonable diffluence between absorption tower; Or improve absorption tower flow, improve Fe in the unit interval
3+inlet, reduce Fe
2+content, makes absorption tower rich solution Fe
2+it is 1/2 ideal that the ratio of content and total iron is about, and this guarantees the higher desulfuration efficiency in absorption tower, and is beneficial to the normal output of sulphur foam on regenerator.
Regenerator is the place that Complexing Iron rich solution is regenerated as lean solution, Fe in rich solution
2+the oxygen reaction that passes through to suck with injector be regenerated as Fe
3+, its regenerative response is:
In regeneration of waste liquor process, the expulsion pressure of regenerator is key parameter, and it also has material impact to the formation of regenerator sulphur foam simultaneously.When expulsion pressure is higher, the air capacity of suction is just more, Fe
2+just more fully oxidized, if it is too much to absorb air, will cause iron ion peroxidating, generate Fe
2o
3deng impurity, cause the waste of medicament; Simultaneously; too high expulsion pressure also makes solution in regenerator fluctuate strong; the sulphur foam of surface floating is smashed; the drusen solution main body of circling round, suspends with solution, and overflow to the sulphur of sulphur foam tank reduces; sulphur cannot normally remove; in the past for a long time, the drusen suspending with solution was deposited in container and pipeline gradually, resulted in blockage.When expulsion pressure is too low, the oxygen that injector is sucked is not enough, Fe
2+regenerate abundant not, Fe in lean solution
3+concentration is on the low side, reduces lean solution desulfuration efficiency in absorption tower.
The operation initial stage, because rich solution flash tank rich solution outlet motor-driven valve adopts automatic mode to control, interlocking flash tank liquid level changes, rich solution outlet motor-driven valve aperture changes accordingly, this makes to enter the solution amount frequent fluctuation of regenerator, suddenly big or suddenly small, directly causes regenerator expulsion pressure to fluctuate widely between 0.18～0.4MPa, bad, very unstable during regenerator sulphur formation of foam effect fashion.After adopt manual mode to control rich solution flash tank rich solution outlet motor-driven valve, the direct a certain aperture of You Zhongkong hilllock personnel's manual setting, guaranteeing that flash tank liquid level is stably under prerequisite, maintain the constant of rich solution outlet motor-driven valve aperture as far as possible, make to enter the basic held stationary of solution amount of regenerator, regenerator expulsion pressure is also just stable.After expulsion pressure is stable, by regulator solution internal circulating load, injector number and flash tank pressure, change expulsion pressure, observe under different expulsion pressure conditions the formation effect of regenerator sulphur foam.Through long-term practice, grope, it is comparatively suitable that regenerator expulsion pressure remains between 0.22～0.26MPa, when expulsion pressure is too high, the rolling of regenerator solution is severe, sulphur foam is easily broken up, and is unfavorable for assembling removing, and simultaneously a large amount of lean solutions are rushed to sulphur foam tank, reduce drusen concentration in sulphur foam tank, reduce drum unit sulphur removal efficiency; When expulsion pressure is too low, injector oxygen intake quantity not sufficient, rich solution regeneration is abundant not, the Fe regenerating in lean solution
3+less, affect the removal efficiency of hydrogen sulfide.When regenerator expulsion pressure remains between 0.22～0.26MPa, make now lean solution Fe
2+concentration is about 0.15-0.25g/L, and rich solution is fully regenerated, and also there will not be Fe simultaneously
2+peroxidating, sulphur foam also can normally form.
The desulphurization reaction of Complexing Iron sulfur removal technology is:
This reaction is carried out fast and thoroughly, and chemical reaction equilibrium constant is very large, and temperature is ignored substantially on the impact of chemical balance, its reaction rate of temperature major effect.H under different temperatures
2the removal efficiency of S as shown in the figure.
The impact of temperature on hydrogen sulfide stripping rate under table 5 experiment condition
Under above-mentioned experiment condition, reaction is carried out respectively 30 minutes, and experimental result is as Fig. 3.
As seen from the figure, along with the increase of Complexing Iron solution temperature, the removal efficiency of hydrogen sulfide increases gradually, when temperature reaches after approximately 40 ℃, and removal efficiency kept stable.Therefore, doctor solution temperature preferably remains on more than 40 ℃.
The impact of Complexing Iron doctor solution temperature is also embodied in its impact on solution physical characteristic.Solution temperature raises, and the viscosity of solution and surface tension are reduced, and also makes drusen in solution assemble gradually increase simultaneously, thereby cause regenerator cannot form the overflow of sulphur foam, removes.Drusen is suspended in solution, enter separating tank, in separating tank, solution is comparatively tranquil, under gravity fractionation, on part drusen, float on solution surface, a part of particle deposition is in container bottom, and a part enters pipeloop with solution, cause the obstructions such as the front screen pack of lean pump, liquid level gauge, pumping unit, container, have a strong impact on production.
Because temperature raises and the impact of exothermic heat of reaction, solution temperature remains on more than 48 ℃ for a long time, the highlyest even reaches 53 ℃.During this time, regenerator is almost without sulphur foam output, and the upper employee that stands salvages sulphur foam on separating tank every day and maintains production, and workload is very large.By installing interim cooling system additional, underground well water was directly evacuated in heat(ing) coil afterwards, with the mutual heat exchange of desulfuration solution, by solution temperature be down to approximately 46 ℃ following after, on regenerator, sulphur foam recovers normal gradually.By repeatedly observing and find, when solution temperature rises to 47 ℃, the sulphur foam of regenerator can suddenly disappear, and 47 ℃ may be a critical-temperature of sulphur formation of foam gathering.Consider, it is most suitable that solution temperature remains on 40 ℃ to 45 ℃.
Sulfur capacity is one of important technical index of weighing a sulfur method, and for wet desulphurization, Sulfur capacity refers to the quantity of unit volume desulphurization circulating liquid absorbing hydrogen sulphide.Sulfur capacity and the iron concentration in solution of Sulfint Process are proportional, therefore can regulate Sulfur capacity by the composition of regulator solution.Sulfur capacity height is no doubt reasonably economically, but too high in some cases Sulfur capacity often cause the serious obstruction of device and sulphur output abnormal.At the operation initial stage, each container has deposited a large amount of sulphur, often causes pumping unit and pipeline to stop up, and regenerator repeatedly occurs that sulphur foam emits tower phenomenon, this and the certain relation of the higher existence of doctor solution Sulfur capacity.Meeting under the normal prerequisite of producing of sulfur removal technology, after total iron content is reduced to 1.3g/L from the 2.2g/L at the beginning of driving a well, sulphur depositional phenomenon has to a certain degree and alleviates, regenerator sulphur foam emits tower phenomenon obviously to reduce; Total iron index reduces, and also makes ferrous salt addition reduce, more economical economically.
Due to Complexing Iron solution autophage in running, often to desulphurization system, supplement a certain amount of medicament day by day, normal to guarantee parameters index, desulphurization system is operated steadily.At the beginning of going into operation, due to the inadequate science of dosing method, cause the medicament adding cannot effectively form Complexing Iron solution, medicament adding amount is excessive, sometimes more than the medicament total amount of annotating every day reaches 800kg, and the medicament parameter fluctuation of desulfurizing agent content, total alkali, total iron content is larger, steady not, to production, makes a big impact.Medicament addition sequence is not right, also can make in medicament layoutprocedure, to form a large amount of medicament foams, even from underground tank, overflows, and causes medicament waste, simultaneously contaminated environment.Through long-term follow dosing experiment, progressively optimize dosing method, make medicament adding amount increasingly steady, reagent consumption amount obviously reduces, and dosing method Optimized Measures is:
1. desulfuration solution medicament by desulfurizing agent, stabilizing agent, ferrous salt and sodium carbonate according to a certain percentage, at underground tank, by desalted water, join, in filling process, according to the order of sodium carbonate, desulfurizing agent, ferrous salt, stabilizing agent, add successively, prevent from forming medicament foam overflow underground tank;
2. in the situation that only having total alkali index on the low side, can add separately sodium carbonate; At desulfurizing agent or total iron content when on the low side, due to Complexing Iron forms must be under alkaline environment, even if do not need to supplement sodium carbonate, when configuration medicament, also must add a certain amount of sodium carbonate, make solution keep alkalescence, then add successively according to a certain percentage desulfurizing agent, ferrous salt, stabilizing agent necessary;
3. desulfurizing agent, ferrous salt, stabilizing agent must coordinate together and add according to a certain percentage, can not add separately, lack wherein one and all cannot effectively form Complexing Iron solution;
4. when underground tank preparation medicament, need open tracing system winter, keep underground tank solution temperature, be beneficial to effective preparation of medicament;
In 1 well desulfurizing agent mother liquor, alkali, desulfurizing agent, stabilizing agent, total iron adding amount computational methods are:
In formula:
---the adding amount of ferrous salt, desulfurizing agent, stabilizing agent, alkali, kg;
5. if in system, solution is sufficient, during dosing, from lean solution chamber, put into lean solution confection, open underground tank mixer and stir until medicament dissolves (at least 1 hour) completely, then open underground tank fluid infusion pump and medicament is squeezed into lean solution chamber participate in circulation, until solution circulation after 2 hours, in lab technician's assay solution, whether desulfurizing agent content, total alkali, total iron content reach ideal value, if do not reach ideal value, then continue to adjust dosing method according to test value, until every medicament index reaches ideal value.
By optimizing, medicament addition was about: desulfurizing agent 120kg every day at present, ferrous salt 100kg, sodium carbonate 150kg, stabilizing agent 60kg, the basic held stationary of medicament parameter: total alkali 18～20g/L, total iron 1.5～1.8 g/L, desulfurizing agent 7.0～7.6 g/L, doctor solution desulfuration efficiency and regenerate all right.
Claims (6)
1. for Complexing Iron sulfur removal technology, produce a method for regulation and control, it is characterized in that:
Hydrogen sulfide containing unstripped gas is removed solid phase and liquid phase impurity by acid gas separator, then enter successively pre-absorption tower and absorption tower, and reacting hydrogen sulfide gas with Complexing Iron lean solution wherein, the natural gas after purification enters purge gas separator and sloughs moisture, directly outer defeated after detecting by metering;
In described absorption tower, the Complexing Iron rich solution that is absorbed with sulphur enters regenerator by rich solution flash tank and contacts with oxygen in air, again form can absorbing hydrogen sulphide lean solution, lean solution enters separating tank, by lean pump, again enter absorption tower, complete the circulation of whole doctor solution, rich solution and lean solution form described doctor solution; The sulphur foam forming in regenerator enters sulphur foam tank, by drum unit, sloughs the moisture in sulphur, forms sulphur cream;
Its key reaction is as follows successively:
1). doctor solution absorbs H
2s, CO
2:
2). desulphurization reaction
3). regenerative response
2NaHCO
3
→?Na
2
CO
3
+?CO
2
?+H
2
O
The parameter of described each composition should meet following relational expression:
In formula:
---concentration of hydrogen sulfide in unstripped gas, g/m
3;
---raw gas flow, m
3/ h;
2. a kind of method of producing regulation and control for Complexing Iron sulfur removal technology according to claim 1, is characterized in that: the pH value of described doctor solution is 8.15-8.5, rich solution Fe in pre-absorption tower
2+in content and rich solution, lean solution, the ratio of total iron content is 1/2.
3. a kind of method of producing regulation and control for Complexing Iron sulfur removal technology according to claim 2, is characterized in that: described regenerator expulsion pressure remains between 0.22～0.26MPa, lean solution Fe
2+concentration is 0.15-0.25g/L, and described doctor solution temperature is 40 ℃ to 45 ℃, and the concentration of described total iron is 1.85-2.25g/L.
4. a kind of method of producing regulation and control for Complexing Iron sulfur removal technology according to claim 1, it is characterized in that: also include and add desulfuration solution medicament step, described desulfuration solution medicament comprises desulfurizing agent, stabilizing agent, ferrous salt and sodium carbonate, above-mentioned medicament is added in desalted water and configured, in filling process, according to the order of sodium carbonate, desulfurizing agent, ferrous salt, stabilizing agent, add successively.
5. a kind of method of producing regulation and control for Complexing Iron sulfur removal technology according to claim 4, is characterized in that: described in add in desulfuration solution medicament step, in desulfurizing agent mother liquor, alkali, desulfurizing agent, stabilizing agent, total iron adding amount computational methods are:
In formula:
---the adding amount of ferrous salt, desulfurizing agent, stabilizing agent, alkali, kg;
---the cumulative volume of solution in system, m
3;
Doctor solution before each dosing, is exactly desulfurizing agent mother liquor for dosing next time after adding, and this is added and solution before is just called mother liquor, the sodium carbonate that alkali refers to altogether;
Ideal concentration just refers to have added wants the value that reaches after medicament, measured concentration just refers to before dosing the concentration of each medicament in solution.
6. a kind of method of producing regulation and control for Complexing Iron sulfur removal technology according to claim 1, is characterized in that: described flash tank pressure remains on 0.6～0.7MPa, and liquid level remains on 1200mm.
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| CN105749723B (en) * | 2016-04-22 | 2018-09-11 | 陕西和尊能源科技有限公司 | The purification-recovery system of carbon dioxide in industrial tail gas |
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| CN108622968A (en) * | 2018-04-23 | 2018-10-09 | 上海理工大学 | The minimizing technology of Oil ＆ gas field in sulfur Hydrogen Sulfide in Sewage |
| CN110876883A (en) * | 2018-09-06 | 2020-03-13 | 中国石油化工股份有限公司 | Wet oxidation-reduction method for removing hydrogen sulfide in gas |
| CN110876883B (en) * | 2018-09-06 | 2022-06-21 | 中国石油化工股份有限公司 | Wet oxidation-reduction method for removing hydrogen sulfide in gas |
| CN109381985A (en) * | 2018-11-21 | 2019-02-26 | 北京石油化工学院 | A kind of purifying treatment method of natural gas |
| CN111249907A (en) * | 2018-12-03 | 2020-06-09 | 中国石油化工股份有限公司 | Regeneration device, regeneration system and regeneration method of complex iron desulfurizer |
| CN112175684A (en) * | 2019-07-01 | 2021-01-05 | 众升清源（天津）环保科技有限公司 | Novel process technology for removing H2S from coal bed gas, natural gas and medical tail gas |
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