CN103691274B - A kind of method of producing regulation and control for Complexing Iron sulfur removal technology - Google Patents
A kind of method of producing regulation and control for Complexing Iron sulfur removal technology Download PDFInfo
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Abstract
The present invention relates to a kind of gas processing method, a kind of method of producing regulation and control for Complexing Iron sulfur removal technology specifically, hydrogen sulfide containing unstripped gas is by acid gas separator removing solid phase and liquid phase impurity, then pre-absorption tower and absorption tower is entered successively, and react with wherein Complexing Iron lean solution and deviate from hydrogen sulfide gas, natural gas after purification enters purge gas separator and sloughs moisture, by directly outer defeated after gauge check; Even if use the hydrogen sulfide content in this patent method unstripped gas to change also can normally use, carrying out accommodation according to this method to other parameters can meet Production requirement, and avoids and adjust production technology.And according to the actual conditions needs produced, select best desulfuration solution internal circulating load, reduce the loss of equipment, reduce the power consumption of pump, avoid the waste of the energy.
Description
Technical field
The present invention relates to a kind of gas processing method, specifically a kind of method of producing regulation and control for Complexing Iron sulfur removal technology.
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 method and chemical solvent absorption method 2 class by the type of lyosoption, the chemical absorption method being wherein solvent with various hydramine is most widely used method in current natural gas process for purifying.These class methods, while removing hydrogen sulfide, also will remove a certain amount of carbon dioxide.
(2) oxidization-reduction type technique: be applicable under given conditions normal pressure or low pressure, in the desulfurization of low sulfur-containing gas, this type of technique not carbon dioxide removal substantially.
(3) biological desulfurization process: develop because of its safety and environmental protection, H
2s removal efficiency is high, sulfur purity height is also one of direction of giving priority to of current desulfur technology.
Complex iron belongs to absorption-regenerative technique, also there is the patent made 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 Complexing Iron desulfurizing agent mainly containing 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, reacts with the desulfurizing agent of different ratio.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, like this can not the needs of realistic large-scale production.
Summary of the invention
Exist when Sulfur Contained Raw Gas changes of contents to overcome existing Complexing Iron sulfur removal technology, need to change desulfurizing agent proportioning and technique and between each composition, proportioning selects the problems such as not good, propose the change of a kind of hydrogen sulfide content even if existing and also need not change a kind of of original technique and produce for Complexing Iron sulfur removal technology the method for regulation and control especially.
Concrete scheme of the present invention is as follows:
Produce a method for regulation and control for Complexing Iron sulfur removal technology, it is characterized in that:
Hydrogen sulfide containing unstripped gas is by acid gas separator removing solid phase and liquid phase impurity, then pre-absorption tower and absorption tower is entered successively, and react with wherein Complexing Iron lean solution and deviate from hydrogen sulfide gas, the natural gas after purification enters purge gas separator and sloughs moisture, by directly outer defeated after gauge check;
In described absorption tower, the Complexing Iron rich solution being absorbed with sulphur enters regenerator by rich solution flash tank and contacts with oxygen in air, again being formed can the lean solution of absorbing hydrogen sulphide, lean solution enters separating tank, again absorption tower is entered by lean pump, complete the circulation of whole doctor solution, rich solution and the doctor solution described in lean solution composition; The sulphur foam formed in regenerator enters sulphur foam tank, is sloughed the moisture in sulphur by drum unit, 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;
---rich solution Fe
2+concentration, g/L;
---lean solution Fe
2+concentration, g/L;
---the internal circulating load of doctor solution, m
3/ h;
---raw gas flow, m
3/ h;
---coefficient, 1.36.
The pH value of described doctor solution is 8.15-8.5, rich solution Fe in pre-absorption tower
2+content is 1/2 with the ratio of total iron content in rich solution, lean solution.
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 DEG C to 45 DEG C, 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 configures, add successively according to the order of sodium carbonate, desulfurizing agent, ferrous salt, stabilizing agent in filling process.
Describedly 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 ideal concentration of ferrous salt, desulfurizing agent, total alkali, g/L;
---the measured concentration of ferrous salt, desulfurizing agent, total alkali, g/L;
---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 wants the value reached after just referring to and having added medicament, measured concentration just refers to the concentration of each medicament in solution before dosing.
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 in this patent method unstripped gas to change also can normally use, carrying out accommodation according to this method to other parameters can meet Production requirement, and avoids and adjust production technology.And according to the actual conditions needs produced, 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 obtained after relational expression proportioning of the present invention and measured value comparatively close, error is all within 3%, and can be good at representing the relation between parameters, 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 about 8.3, and 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 ensures the desulfuration efficiency that absorption tower is higher, and is beneficial to the normal output of sulphur foam on regenerator.
5, when regenerator expulsion pressure remains between 0.22 ~ 0.26MPa, now lean solution Fe is made
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 be formed.
6, meeting under the prerequisite that sulfur removal technology normally produces, sulphur depositional phenomenon has and to a certain degree 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
2the existing forms of S is with the changing trend diagram of pH value.
Fig. 3 is H
2the relation curve of S removal efficiency and temperature.
Detailed description of the invention
A kind of method of producing regulation and control for Complexing Iron sulfur removal technology, hydrogen sulfide containing unstripped gas is by acid gas separator removing solid phase and liquid phase impurity, then the absorption towers such as pre-absorption tower are entered successively, and react with wherein Complexing Iron lean solution and deviate from hydrogen sulfide gas, natural gas after purification enters purge gas separator and sloughs moisture, by directly outer defeated after gauge check;
In described absorption tower, the Complexing Iron rich solution being absorbed with sulphur enters regenerator by rich solution flash tank and contacts with oxygen in air, again being formed can the lean solution of absorbing hydrogen sulphide, lean solution enters separating tank, again absorption tower is entered by lean pump, complete the circulation of whole doctor solution, rich solution and the doctor solution described in lean solution composition; The sulphur foam formed in regenerator enters sulphur foam tank, is sloughed the moisture in sulphur by drum unit, forms sulphur cream.
Composition graphs 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 obtained 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 flows upwards in first grade absorption tower, deviates from hydrogen sulfide with doctor solution counter current contacting, enters two-level absorption tower from the upper outlet of first grade 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, bottom-up flowing, removes hydrogen sulfide with doctor solution counter current contacting, enters top, three grades of absorption towers from two-level absorption tower outlet.
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, enters decontaminating separator from three grades of absorption tower outlets.
Rich solution in flash tank enters injector by flash tank pressure from regenerator top, mix with the air that self-priming enters and oxidation reaction occurs, and in regenerator further oxidation regeneration, most of elemental sulfur of precipitation is suspended in regenerator top, and overflow enters sulphur foam tank.Complexing Iron lean solution after regeneration is from the air flotating chamber flowing to separating tank, and lean solution is then back to top, absorption tower at different levels by lean pump by the lean solution chamber of separating tank.
The lean solution of regenerator enters separating tank, is separated the sulphur in lean solution by air supporting further, isolated sulphur overflow or utilize Slag Scraping Device to discharge, and 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;
---rich solution Fe
2+concentration, g/L;
---lean solution Fe
2+concentration, g/L;
---the internal circulating load of doctor solution, m
3/ h;
---raw gas flow, m
3/ h;
---coefficient, 1.36.
The pH value of doctor solution is 8.15-8.5, rich solution Fe in pre-absorption tower
2+content is 1/2 with the ratio of total iron content in rich solution, lean solution.
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 DEG C to 45 DEG C, 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 configures, add successively according to the order of sodium carbonate, desulfurizing agent, ferrous salt, stabilizing agent in filling process.
Describedly 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 ideal concentration of ferrous salt, desulfurizing agent, total alkali, g/L;
---the measured concentration of ferrous salt, desulfurizing agent, total alkali, g/L;
---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 wants the value reached after just referring to and having added medicament, measured concentration just refers to the concentration of each medicament in solution before dosing.
Described flash tank pressure remains on 0.6 ~ 0.7MPa, and liquid level remains on 1200mm.
Wherein
, table 1 is the example adopting above-mentioned calculating formula to obtain numerical value.
Table 1
Concentration of hydrogen sulfide is surveyed to such as table 2 according to this calculating concentration of hydrogen sulfide and Chinese measuring technology center research institute:
Concentration of hydrogen sulfide surveyed by table 2 and formulae discovery concentration of hydrogen sulfide contrasts
Can find out according to Data Comparison, this formulae discovery result and measured value comparatively close, error is all within 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 controls and adjusts, its main use can be divided into:
(1) rich or poor liquid Fe is obtained according to assay office
2+concentration, in conjunction with gas production and the doctor solution internal circulating load calculating unstripped gas concentration of hydrogen sulfide of actual production;
(2) when unstripped gas concentration of hydrogen sulfide is known, in conjunction with gas production, rich or poor liquid Fe can be obtained
2+relational expression between concentration and doctor solution internal circulating load, can instruct the ferrous adjustment of solution, ensures normally to produce;
(3) when 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, thus suitably can regulate doctor solution internal circulating load according to concentration of hydrogen sulfide change;
(4) rich solution Fe
2+concentration ideal value is about the half of total iron, lean solution Fe
2+concentration ideal value is 0.15-0.25g/L, can according to desirable Fe
2+concentration, when unstripped gas concentration of hydrogen sulfide is known, realizes the Proper Match of gas production and doctor solution internal circulating load, thus instructs Production adjustment.
Such as: 1 well concentration of hydrogen sulfide is about 12g/m3, desirable Fe
2+concentration is: rich solution 0.8 g/L, lean solution 0.1g/L, and according to the production system in current 9.5 ten thousand sides/sky, substitution formulae discovery can obtain reasonable solution circulation amount and be:
According to result of calculation, 1 well solution circulation amount is remained on 170m
3about/h runs, and parameters and index are all produced normally.Checked by long-term practice, 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.
By H
2s ionization equilibrium rule, as calculated, H under different pH value in the solution
2s, HS
-, S
2-percentage:
H in solution under the different pH value of table 3
2the existing forms of 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 when pH value increases in the aqueous solution
2s percentage sharply reduces, and HS
-content but greatly increase, namely the pH value of doctor solution increases desulfurization favourable.As can be seen from table in data, when solution pH value close to 6 time solution in H
2s concentration sharply reduces, and HS
-then sharply increase; After pH value is greater than 8, H
2s concentration reaches minimum, HS
-reach maximum; Although too high pH value is to H
2the impact of the concentration of S is very little, but HS
-can sharply reduce when pH value is 12, S
2-rapid increase, unfavorable to desulfurization, there is iron to precipitate simultaneously and generate, be both unfavorable for the steady running of system, make again impurity content in sulphur increase.Moreover too high pH value makes sodium carbonate addition increase, and is inappropriate economically.So the pH value controlling lean solution in daily production is 8.0 ~ 9.0 is suitable.Theoretically, pH value during 8.0 ~ 9.0, HS
-content and desulfuration efficiency still increase with the increase of pH value, but just must increase considerably the adding amount of sodium carbonate to improve pH value, 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, 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, solution pH value is remained on about 8.3, and 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, mainly through measuring total concentration of iron and the Fe of rich or poor liquid
2+concentration determines Fe
3+, Fe
2+concentration, Fe
3+concentration is total concentration of iron and Fe
2+the difference of concentration.
Complexing Iron solution oxide absorbs H
2the process of S belongs to redox reaction fast.Work as H
2s gas contacts with solution and is converted into HS
-after, with the Fe in solution
3+rapid reaction, makes 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 to desulfurization liquid interface in time again, this just causes H
2s can not be absorbed in time, makes H
2s absorptivity is lower.And as the Fe in doctor solution
3+when concentration is higher, although gas liquid film place is owing to absorbing H
2s consumes Fe
3+, but still can certain Fe be maintained
3+concentration, is enough to and the H come by gas phase main diffusion
2s reacts, so can keep H
2s absorptivity is higher.
Different initial Fe
3+the experiment of absorbent, experimental result also demonstrates works as Fe
3+when being greater than certain value, mass transfer rate is by Fe
3+impact reduces, H
2the absorptivity of S is by Fe
3+affect less, now H
2the absorptivity of S is higher.
The different initial Fe of table 4
3+the experimental result of absorbent
There is the problem of not producing sulphur aborning, 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, need repeatedly to add medicament every day and could maintain indices reluctantly normally, observe output sulphur after several hours after adding medicament still abnormal.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, illustrate reaction time Fe
3+consume more, concentration is on the low side, makes Fe
3+cannot completely by HS
-be oxidized to simple substance S, unnecessary HS
-with Fe
2+reaction generates FeS, shows as absorption tower rich solution blackout, the sulphur of output is reduced; Too much Fe
2+fe can be generated with oxygen reaction in regenerator
2o
3, be deposited on container bottom, thus reduce total iron content, affect desulfurized effect.Rich solution Fe is reduced by regulating the air inflow on each absorption tower and solution circulation amount
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, 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+content and the ratio of total iron are about 1/2 ideal, and this ensures the desulfuration efficiency that absorption tower is higher, 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+be regenerated as Fe by the oxygen reaction sucked with injector
3+, its regenerative response is:
In solution reclaiming 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 more, Fe
2+just more fully oxidized, if it is too much to absorb air, iron ion peroxidating will be caused, generate Fe
2o
3deng impurity, cause the waste of medicament; Simultaneously; too high expulsion pressure also makes solution fluctuation in regenerator strong; the sulphur foam floated in surface is smashed; drusen circles round solution main body, and with solution suspension, overflow reduces to the sulphur of sulphur foam tank; sulphur cannot normally remove; in the past for a long time, the drusen with solution suspension 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+regeneration is 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 electric valve adopts automatic mode to control, the change of interlocking flash tank liquid level, rich solution outlet electric valve aperture changes accordingly, this makes the amount of solution frequent fluctuation entering 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 by rich solution flash tank rich solution outlet electric valve adopt manual mode control, directly by a certain aperture of Zhong Kong hilllock personnel's manual setting, under the stable prerequisite of guarantee flash tank liquid level, maintain the constant of rich solution outlet electric valve aperture as far as possible, make the basic held stationary of amount of solution entering regenerator, regenerator expulsion pressure also just stabilizes.After expulsion pressure is stable, by regulating solution circulation amount, injector number and flash tank pressure to change expulsion pressure, observe under different expulsion pressure condition, the formation effect of regenerator sulphur foam.Grope through long-term practice, 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 that gathering removes, and a large amount of lean solution is rushed to sulphur foam tank simultaneously, 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 regenerated 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 be formed.
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.
Under table 5 experiment condition, temperature is on the impact of hydrogen sulfide stripping rate
Under these experimental conditions, reaction carries out 30 minutes respectively, 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, after temperature reaches about 40 DEG C, and removal efficiency kept stable.Therefore, doctor solution temperature preferably remains on more than 40 DEG C.
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 is reduced, also makes drusen in solution assemble increase gradually simultaneously, thus causes regenerator cannot form the overflow of sulphur foam removing.Drusen suspends in the solution, enter separating tank, in separating tank, solution is comparatively tranquil, under gravity fractionation, part drusen floats on solution surface, and a part of particle deposition is in container bottom, and a part enters pipeloop with solution, cause the blocking such as screen pack, liquid level gauge, pumping unit, container before lean pump, have a strong impact on production.
Because temperature raises and the impact of exothermic heat of reaction, solution temperature remains on more than 48 DEG C for a long time, the highlyest even reaches 53 DEG C.Period, 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.Afterwards by installing interim cooling system additional, be directly evacuated in heat(ing) coil by underground well water, heat exchange mutual with desulfuration solution, be down to by solution temperature after below about 46 DEG C, on regenerator, sulphur foam recovers normal gradually.By repeatedly observing discovery, when solution temperature rises to 47 DEG C, the sulphur foam of regenerator can suddenly disappear, and 47 DEG C may be sulphur formation of foam and the critical-temperature assembled.Consider, it is most suitable that solution temperature remains on 40 DEG C to 45 DEG C.
Sulfur capacity is one of important technical index of a measurement sulfur method, and for wet desulphurization, Sulfur capacity refers to the quantity of unit volume desulphurization circulating liquid absorbing hydrogen sulphide.Iron concentration in the sulfur capacity of Sulfint Process and solution is proportional, therefore by regulating the composition of solution to regulate Sulfur capacity.Sulfur capacity height is no doubt rational economically, but often causes Severe blockage and the sulphur output exception of device at Sulfur capacity too high in some cases.At the operation initial stage, each container deposited a large amount of sulphur, and often cause pumping unit and pipeline blocking, 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 prerequisite that sulfur removal technology normally produces, 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 and to a certain degree 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.
Due to Complexing Iron solution autophage in running, often supplement a certain amount of medicament to desulphurization system day by day, to ensure that parameters index is normal, desulphurization system is operated steadily.At the beginning of operation, due to the inadequate science of dosing method, the medicament added is caused cannot effectively to form Complexing Iron solution, medicament adding amount is excessive, sometimes medicament total amount of annotating every day reaches more than 800kg, and desulfurizing agent content, total alkali, total iron content medicament parameter fluctuation comparatively large, not steadily, make a big impact to production.Medicament addition sequence is not right, also can make in medicament layoutprocedure, form a large amount of medicament foam, even overflows from underground tank, causes medicament to waste, simultaneously contaminated environment.Through long-term follow dosing experiment, successive optimization 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, joined by desalted water at underground tank, add successively according to the order of sodium carbonate, desulfurizing agent, ferrous salt, stabilizing agent in filling process, prevent from forming medicament foam overflow underground tank;
2., when only there being total alkali index on the low side, sodium carbonate can be added separately; Desulfurizing agent or total iron content on the low side time, due to Complexing Iron is formed must under alkaline environment, even if do not need supplementary sodium carbonate, also a certain amount of sodium carbonate must be added when configuring medicament, make solution keep alkalescence, then add desulfurizing agent according to a certain percentage successively, ferrous salt, stabilizing agent are necessary;
3. desulfurizing agent, ferrous salt, stabilizing agent must coordinate according to a certain percentage and add together, can not add separately, lack wherein one all cannot effectively form Complexing Iron solution;
4. winter is when underground tank preparation medicament, need open tracing system, 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;
---the ideal concentration of ferrous salt, desulfurizing agent, total alkali, g/L;
---the measured concentration of ferrous salt, desulfurizing agent, total alkali, g/L;
---the cumulative volume of solution in system, m
3.
If 5. in system, solution is sufficient, during dosing, lean solution confection is put into from lean solution chamber, open underground tank mixer to stir until medicament dissolves (at least 1 hour) completely, then open underground tank fluid infusion pump and medicament is squeezed into the participation circulation of lean solution chamber, until solution circulation after 2 hours, whether ideal value is reached by desulfurizing agent content, total alkali, total iron content in lab technician's assay solution, if do not reach ideal value, then continue adjustment dosing method, until every medicament index reaches ideal value according to test value.
By optimizing, current every day, medicament addition was about: desulfurizing agent 120kg, 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 (4)
1. produce a method for regulation and control for Complexing Iron sulfur removal technology, it is characterized in that:
Hydrogen sulfide containing unstripped gas is by acid gas separator removing solid phase and liquid phase impurity, then pre-absorption tower and absorption tower is entered successively, and react with wherein Complexing Iron lean solution and deviate from hydrogen sulfide gas, the natural gas after purification enters purge gas separator and sloughs moisture, by directly outer defeated after gauge check;
In described absorption tower, the Complexing Iron rich solution being absorbed with sulphur enters regenerator by rich solution flash tank and contacts with oxygen in air, again being formed can the lean solution of absorbing hydrogen sulphide, lean solution enters separating tank, again absorption tower is entered by lean pump, complete the circulation of whole doctor solution, rich solution and the doctor solution described in lean solution composition; The sulphur foam formed in regenerator enters sulphur foam tank, is sloughed the moisture in sulphur by drum unit, 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;
---rich solution Fe
2+concentration, g/L;
---lean solution Fe
2+concentration, g/L;
---the internal circulating load of doctor solution, m
3/ h;
---raw gas flow, m
3/ h;
---coefficient, 1.36;
The pH value of described doctor solution is 8.15-8.5, rich solution Fe in pre-absorption tower
2+content is 1/2 with the ratio of total iron content in rich solution, lean solution;
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 DEG C to 45 DEG C, and the concentration of described total iron is 1.85-2.25g/L.
2. 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 configures, add successively according to the order of sodium carbonate, desulfurizing agent, ferrous salt, stabilizing agent in filling process.
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 in add in desulfuration solution medicament step, alkali in desulfurizing agent mother liquor, 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 ideal concentration of ferrous salt, desulfurizing agent, total alkali, g/L;
---the measured concentration of ferrous salt, desulfurizing agent, total alkali, g/L;
---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 wants the value reached after just referring to and having added medicament, measured concentration just refers to the concentration of each medicament in solution before dosing.
4. 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 |
| CN106669402A (en) * | 2016-11-23 | 2017-05-17 | 四川沃兹凯兰科技有限公司 | Gas field sulfur-containing waste gas treatment method |
| CN107824016A (en) * | 2017-12-26 | 2018-03-23 | 重庆丰望环保科技有限公司 | A kind of sewage deodorizing system |
| 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 |
| 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 |
| CN111249907B (en) * | 2018-12-03 | 2022-04-12 | 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 |
| CN110484308A (en) * | 2019-08-27 | 2019-11-22 | 北京北科环境工程有限公司 | A kind of blast furnace gas BKRP desulphurization system |
| CN114806665A (en) * | 2022-05-18 | 2022-07-29 | 西南石油大学 | Complex iron desulfurization process flow suitable for medium-sulfur shale oil associated gas |
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|---|---|---|---|---|
| CN1354038A (en) * | 2001-10-30 | 2002-06-19 | 南化集团研究院 | Improved complex iron method for removing sulfide from gas |
| CN102895870A (en) * | 2012-09-28 | 2013-01-30 | 美景（北京）环保科技有限公司 | Treatment system and treatment method for removing hydrogen sulfide from acid gas |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1354038A (en) * | 2001-10-30 | 2002-06-19 | 南化集团研究院 | Improved complex iron method for removing sulfide from gas |
| CN102895870A (en) * | 2012-09-28 | 2013-01-30 | 美景（北京）环保科技有限公司 | Treatment system and treatment method for removing hydrogen sulfide from acid gas |
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