CN104826465B - Multi-stage countercurrent absorption process and system for acidic gas - Google Patents
Multi-stage countercurrent absorption process and system for acidic gas Download PDFInfo
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- CN104826465B CN104826465B CN201410046324.9A CN201410046324A CN104826465B CN 104826465 B CN104826465 B CN 104826465B CN 201410046324 A CN201410046324 A CN 201410046324A CN 104826465 B CN104826465 B CN 104826465B
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Abstract
The invention provides a multi-stage countercurrent absorption process and system for acidic gas. The absorption process employs a gas-liquid two-phase countercurrent absorption reaction and uses a NaOH solution as an absorption liquid to treat acidic gas so as to produce NaHS. According to the process, a crystallizer and a separator are arranged in a primary reaction and a secondary reaction, and heat is taken out of a reactor; and through filling of the NaOH solution in stages, peak clipping of reaction heat is realized, and local crystallization caused by generation of heat spots is prevented. A combination of a Venturi reactor and a rotating packed bed reactor is used as a reaction apparatus which is flexible to operate and has high mass transfer efficiency. The acidic gas absorption process provided by the invention is simple and can achieve the dual objectives of purification of acidic gas and reclamation of pollutants; and the acidic gas absorption system has the advantages of small scale, low energy consumption and low proneness to obstruction.
Description
Technical field
The present invention provides a kind of sour gas multi-stage countercurrent absorption technique method and system, belongs to sour gas field of purification, special
It is not related to the processing method and system of a kind of purification being suitable to containing sulfohydrate sour gas and pollutant resources.
Background technology
Sour gas mostly come from the devices such as sewage stripping, desulphurization of recycle hydrogen, dry gas desulfurization, main in sour gas
Containing H2S、CO2.The sour gas of current most of small-sized refinery is substantially using the processing method discharged after burning.This method one
Aspect causes the waste of resource, on the other hand brings huge pressure to environmental protection, influences the development space of enterprise.It is protection ring
Border and ensure making full use of for resource, it is imperative that the sour gas of small-sized refinery recycle.
The treatment of big-and-middle-sized sour gas, mainly uses sour gas to prepare sulphur, and the more commonly used at present has two kinds
Technology, one kind is two grades of Claus+ tail gas hydrogenation reduction+solvent absorption process technologies；Another kind is U.S. Merichem public
The LO-CAT technologies of gas technology Products Co., Ltd of department exploitation.
Two grades of Claus+ tail gas hydrogenation reduction+solvent absorption technical matters maturations, stable operation, product sulphur quality are steady
It is fixed, but because long flow path, investment are big, Claus techniques can only process the sour gas of high concentration, generally as the H in unstripped gas2S
When volume fraction is less than 20%, device is just difficult to operate.Therefore, Claus techniques are suitable for producing per year the dress of more than sulphur 5000t
Put.
LO-CAT techniques make H using the iron catalyst of multicomponent chelate2S is converted into elementary sulfur, H2The removal efficiency of S exceedes
99.9%.LO-CAT techniques can be adapted to the larger and H of acid tolerance fluctuation2Various operating modes of the S contents 0~100%, raw material is fitted
Answer condition wide in range, adapt to the actual conditions of sour gas fluctuating change.And LO-CAT liquid redox treatment schemes do not make
With any poisonous chemicals, and any harmful exhaust gas by-products will not be produced, environmentally safe catalyst can be with
It is constantly regenerating in processing procedure.But because there is operating cost high, sulfur purity and color and luster slightly worse than Crouse in LO-CAT
Technique, and the sulphur particle meeting blockage phenomenon for producing in process of production, therefore, LO-CAT techniques are producing sulphur per year
Economy is poor in below 5000t scales（Relative to two grades of Claus+ tail gas hydrogenation reduction+solvent absorption technologies）.
For small-sized refinery, because acid tolerance is relatively small, using two grades of Claus+ tail gas hydrogenations reduction+solvents
There is long flow path, complex operation, investment greatly in absorption techniques technique, scale and benefit are poor.And there is also one using LO-CAT technologies
Secondary investment is larger, the problems such as catalyst and patent royalties higher.
It is smaller for the total tolerance of small-sized sour gas, can be using the less new desulfurization process of investment, by H2S reclaims system
Standby sulphite, carries out burning generation SO by sour gas first2, being then fed into absorption tower carries out chemical absorbing generation sulphite Solution, then solution and alkaline absorbent are reacted, prepare sulphite fluid product, or generation sulphite crystal, warp The operation such as separation, dry is prepared into sulphite solid product.The device flow is shorter, and reaction is simple, and operating flexibility is big, can fit Influence of the small-sized sour gas fluctuation to production process is answered, solid or liquid product can be produced by selecting different operations product, the different absorbent of selection can produce different types of sulphite, and realize tail gas qualified discharge by three sections of absorptions, it is real The purpose of existing cleaning of off-gas.But it is serious to there is equipment corrosion in actual production process, maintenance cost determination higher.
CN101143714A discloses a kind of method that sour gas of utilization high hydrocarbon-containing prepares sulfuric acid, acid hydrogen sulfide gas
Burning in first, second sulfureted hydrogen burning stove is respectively enterd in proportion, from the first combustion furnace high-temperature furnace gas out, by furnace gas
Cooler, uniform temperature is cooled to by air, subsequently into the second combustion furnace with supplement sulfide hydrogen sour gas continue with
The combust of surplus air one in furnace gas, the second combustion furnace high-temperature furnace gas out enter waste heat boiler heat accumulation, enter back into purification work
Section, conversion section, dry absorption section carry out conventional relieving haperacidity.This process can only produce 98% industrial sulphuric acid, it is impossible to which productive value is more
Oleum high, simultaneously as the transport of sulfuric acid, storage acquire a certain degree of difficulty, therefore, the market of stabilization needs near oil plant
Seeking Truth limits the key factor of its development.
CN1836767A discloses a kind of processing method of oil-extraction plant acidic gas, by the use of sour gas as cement plant shaft kiln
Fuel, when sour gas burns in kiln, H therein2There is chemical reaction with cement material and generate CaSO in S compositions4, other are harmful to
Composition is also sintered and converts, fundamentally solve Acidic Gas Treating problem, meanwhile, sour gas as a kind of gaseous fuel,
Make cement plant energy-saving fuel, realize environmental protection and solve the dual purpose of fuel, but, this method has certain limitation
Property, it is not easy to promote.
In a kind of methods for preparing NaHS of CN101337661A, caustic soda is first respectively adopted and milk of lime absorbs and contains sulphur
Change interstitial fluid in the sour gas generation of hydrogen and carbon dioxide, then mixed in proportion, obtain the NaHS product of low-carbon (LC) acid group.
The method does not require that sour gas is purer hydrogen sulfide gas, but flow is more long, and automaticity is low.
Document《Hydrogen sulfide is absorbed with sodium hydroxide solution produce vulcanized sodium industrial technology》(Shangfang is given birth,《Inorganic chemicals industry》,
The 2nd phase of volume 44,2 months 2012) hydrogen sulfide sodium hydroxide solution absorbs and produces the production technology of vulcanized sodium by the technique,
Hydrogen sulfide is absorbed in packed tower with 380~420g/L sodium hydroxide solutions, control of reaction end point vulcanized sodium mass concentration is 330
~350g/L, hydrogen sulfide absorption rate is up to 95%~98%.The technique not only can effective environmental protection, and effect can be created for enterprise
Benefit.But, this process products vulcanized sodium is apt to deteriorate, and is difficult storage.
At present, it is necessary to a kind of consider the factors such as safe and environment-friendly, economy for small-sized sour gas
Acidic Gas Treating method.
The content of the invention
For deficiency of the prior art, the present invention provides a kind of sour gas multi-stage countercurrent absorption technique method and system,
Compared with prior art, sour gas multi-stage countercurrent absorption technique method and system of the present invention is realizing the same of sour gas qualified discharge
When production meet require NaHS products, realize sour gas purification and pollutant resources double goal.
Sour gas absorption technique method of the present invention, with NaOH solution as absorbing liquid, treatment sour gas production NaHS, including such as
Lower step：
（1）Sour gas enters first-stage reactor, is contacted with the reaction solution of second reactor and is reacted, reaction generation
Liquid point two-way, the first via is discharged as product, and first-stage reactor is entered after the crystallized separation in the second tunnel；
（2）By step（1）Reacted sour gas enters second reactor, the life with NaOH solution and third-stage reactor
Reacted into liquid contact；Reaction solution point two-way, the first via enters first-stage reactor as absorbing liquid, and the second tunnel is crystallized
Enter second reactor after separation；
（3）By step（2）Reacted sour gas enters third-stage reactor, and being contacted with level four reaction apparatus generation liquid is carried out
Reaction, reaction solution point two-way, the first via enters second reactor as absorbing liquid, and the second tunnel loops back third-stage reactor；
（4）By step（3）Reacted sour gas enters level four reaction apparatus, with NaOH solution reaction, reacted acid
Property gas discharge, reaction solution point two-way, the first via enters third-stage reactor as absorbing liquid, and the second tunnel loops back fourth-order reaction
Device.
In present invention process method, step（1）In, the second road reaction solution generates liquid with first-stage reactor overall reaction
Volume flow ratio is 1/3~9/10, preferably 5/6~8/9.
In present invention process method, step（2）In, the second road reaction solution generates liquid with second reactor overall reaction
Volume flow ratio is 1/3~9/10, preferably 5/6~8/9.
In present invention process method, step（3）In, the second road reaction solution generates liquid with third-stage reactor overall reaction
Volume flow ratio is 1/3~9/10, preferably 5/6~8/9.
In present invention process method, step（4）In, the second road reaction solution generates liquid with level four reaction apparatus overall reaction
Volume flow ratio is 1/3~9/10, preferably 5/6~8/9.
In present invention process method, by step（4）Hydrogen sulfide content is 5-30 mg/Nm in sour gas after treatment3。
In present invention process method, by step（4）Sour gas after treatment is further discharged after coalescer demisting.
In present invention process method, second reactor, the volume flow ratio of the NaOH solution addition of level four reaction apparatus are
1:1~3:1, preferably 3:2~2:1.
In present invention process method, the consumption of NaOH solution is design load, according to H in sour gas2S, CO2What content determined
Fixed value, according to the amount of sour gas, according to H in sour gas2S and CO280 ~ 99%, preferably the 85 ~ 95%. of NaOH solution consumption needed for NaOH solution amount needed for complete Response calculation, design load is
In present invention process method, the addition of NaOH solution is adjusted by hydrogen sulfide content in the sour gas after step (4) treatment, by adjusting valve regulation NaOH solution addition, ensure that by hydrogen sulfide content in the sour gas after step (4) treatment be 5-30mg/Nm3, and ensureing H2The not excessive of NaOH solution in the case of S qualified discharges
In present invention process method, the sour gas is hydrogen sulfide containing gas, can be various sources containing H2S sour gas, CO in the sour gas2Volume fraction be less than 7%, preferably smaller than 5%.The NaOH solution mass concentration is 20%~60%,
Preferably 32%~38%.
In present invention process method, first-stage reactor and second reactor reaction temperature be 70 DEG C~100 DEG C, preferably 80
DEG C~95 DEG C.
In present invention process method, third-stage reactor and level four reaction apparatus reaction temperature be 60 DEG C~90 DEG C, preferably 65
DEG C~80 DEG C.
In present invention process method, the first-stage reactor, second reactor, third-stage reactor, level four reaction apparatus are drum
One kind or several in bubble tower reactor, filler tower reactor, impact flow reactor, rotary drill reactor and venturi reactor
Kind.
In present invention process method, third-stage reactor, level four reaction apparatus are preferably rotary drill reactor.
In present invention process method, first-stage reactor, second reactor are preferably venturi reactor.
In present invention process method, the venturi reactor from top to bottom divides three sections, and epimere is liquid phase storage tank, and stage casing is Straight tube reaction tube, hypomere is gas-liquid separation cylinder; The straight tube reaction tube be from top to bottom followed successively by feed zone, contraction section, trunnion section, Expansion segment and discharging section; Feed zone top forms sleeve structure with liquid phase storage tank, and discharging pars infrasegmentalis is connected with gas-liquid separation cylinder, liquid Phase storage tank is provided with gas phase entrance, and gas phase entry position is provided with circulation fluid and enters higher than end entrance on feed zone, liquid phase storage groove sidewall Mouthful; The tube wall of straight tube reaction tube is provided with absorbing liquid entrance, and absorbing liquid entrance is located at trunnion top; Gas-liquid separation cylinder is provided with gas phase and goes out Mouth and liquid-phase outlet.
In present invention process method, first-stage reactor and second reactor use venturi reactor, and second tunnel is followed
The reaction solution of loopback first-stage reactor enters first-stage reactor from circulation fluid entrance and absorbing liquid entrance respectively.From circulation fluid
Entrance enters the reaction solution and the reaction solution volume flow for entering first-stage reactor from absorbing liquid entrance of first-stage reactor
Amount is than being 1/6~1/2, preferably 1/4~1/3.Second tunnel loops back the reaction solution of second reactor respectively from circulation fluid
Entrance and absorbing liquid entrance enter first-stage reactor.From circulation fluid entrance enter the reaction solution of second reactor with from absorption
The reaction solution volume flow ratio that liquid entrance enters second reactor is 1/6~1/2, preferably 1/4~1/3.
In present invention process method, the venturi reactor, feed zone upper end opens up teeth groove, and tooth slot structure is sector Groove, the preferably one kind in square teeth groove and triangle teeth groove, lance tooth slot structure .Space width is 3mm ~ 20mm, preferably 5mm ~ 8mm; 30 ~ 60 ° of of 15 ~ 90 ° of Its bottom angle is, preferably
In present invention process method, the venturi reactor, absorbing liquid entrance connection liquid phase distributor, liquid phase distributor is arranged on straight tube reaction tube center line, and absorbing liquid is sprayed from top to bottom, and liquid phase distributor is settable 1 ~ 10, preferably 4 ~ 6
In present invention process method, third-stage reactor and level four reaction apparatus use rotary drill reactor, the rotating speed of the revolving bed of rotary drill reactor is 50 ~ 5000 revs/min, and preferably 150 ~ 2000 revs/min reaction masses residence times in reactor are 2 ~ 600 seconds, preferably 10 ~ 100 seconds
In present invention process method, it is NaHS solution to control first-stage reactor to discharge liquid phase, and products pot is closed through analysis detection
After lattice, start, through product pump carrying device, to realize continuous discharge.
A kind of sour gas absorption system of the present invention, the system includes that first-stage reactor, second reactor, three-level are anti- Answer device, level four reaction apparatus, one-level pans, two grades of pans, three-level pans, level Four pans, first degree crystalline device, two grades of knots Brilliant device, one-level knockout drum and the second-order separation tank, wherein, first-stage reactor, second reactor, third-stage reactor and level four reaction apparatus It is respectively provided with gas phase entrance, gaseous phase outlet, liquid phase entrance and liquid-phase outlet; Sour gas suction line enters with first-stage reactor gas phase Mouthful connection, the gaseous phase outlet of first-stage reactor is connected with the gas phase entrance of second reactor, the gaseous phase outlet of second reactor and The gas phase entrance connection of third-stage reactor, the gaseous phase outlet of third-stage reactor is connected with the gas phase entrance of level four reaction apparatus, level Four Reactor gaseous phase outlet is connected with clean gas outlet pipeline, and clean gas outlet pipeline is provided with hydrogen sulfide content detection means; Two The liquid phase entrance of stage reactor and level four reaction apparatus is connected with alkali liquor inlet pipeline respectively, and level four reaction apparatus liquid-phase outlet is through level Four It is divided into two-way after pans, is connected with third-stage reactor liquid phase entrance and level four reaction apparatus liquid phase entrance respectively; Third-stage reactor Liquid-phase outlet is connected with third-stage reactor liquid phase entrance and second reactor liquid phase entrance respectively after three-level pans; Two grades anti- Answer device liquid-phase outlet point two-way, the first via is connected with first-stage reactor liquid phase entrance, the second tunnel successively through secondary crystallizer, two grades It is connected with second reactor liquid phase entrance after knockout drum, two grades of pans; First-stage reactor liquid-phase outlet point two-way, the first via with Product discharge pipeline connect, the second tunnel successively after first degree crystalline device, one-level knockout drum, one-level pans with first-stage reactor liquid Phase entrance is connected.
Sour gas absorption system of the present invention, make-up cooling water is respectively provided with the first degree crystalline device and secondary crystallizer
Entrance and circulating backwater are exported.
Sour gas absorption system of the present invention, is provided between level four reaction apparatus gaseous phase outlet and clean gas outlet pipeline
Coalescer, the coalescer is cylindrical tube, and end socket includes upper cover and low head, and inside sets cylindric screen cloth, prevents
Purified gas entrainment.
Sour gas absorption system of the present invention, the first-stage reactor, second reactor, third-stage reactor, level Four are anti-
Answer device for gas-liquid mass transfer consersion unit, specially bubbling column reactor, filler tower reactor, impact flow reactor, revolving bed is anti-
Answer one or more in device and venturi reactor.
Sour gas absorption system of the present invention, first-stage reactor, second reactor are preferably venturi reactor, three-level
Reactor, level four reaction apparatus are preferably rotary drill reactor.
The present invention provides a kind of sour gas absorption system, and the system includes that first-stage reactor, second reactor, three-level are anti-
Answer device, level four reaction apparatus, one-level pans, two grades of pans, three-level pans, level Four pans, first degree crystalline device, two grades of knots
Brilliant device, one-level knockout drum and the second-order separation tank；Wherein, first-stage reactor, second reactor are venturi reactor, the literary mound
In reactor points three sections, epimere is liquid phase storage tank, and stage casing is straight tube reaction tube, and hypomere is gas-liquid separation cylinder；The straight tube reaction
Pipe is from top to bottom followed successively by feed zone, contraction section, trunnion section, expansion segment and discharging section；Feed zone top is formed with liquid phase storage tank
Sleeve structure, discharging section is connected with gas-liquid separation cylinder, and liquid phase storage tank is provided with gas phase entrance, and gas phase entry position is higher than on feed zone
End entrance, liquid phase storage groove sidewall is provided with circulation fluid entrance；The tube wall of straight tube reaction tube is provided with absorbing liquid entrance, absorbing liquid entrance
Positioned at trunnion top；Gas-liquid separation cylinder is provided with gaseous phase outlet and liquid-phase outlet；Third-stage reactor and level four reaction apparatus are respectively provided with
Gas phase entrance, gaseous phase outlet, absorbing liquid entrance and liquid-phase outlet；Sour gas suction line connects with first-stage reactor gas phase entrance
Connect, the gaseous phase outlet of first-stage reactor is connected with the gas phase entrance of second reactor, the gaseous phase outlet and three-level of second reactor
The gas phase entrance connection of reactor, the gaseous phase outlet of third-stage reactor is connected with the gas phase entrance of level four reaction apparatus, fourth-order reaction
Device gaseous phase outlet is connected with clean gas outlet pipeline, and clean gas outlet pipeline is provided with hydrogen sulfide content detection means；Two grades anti-
The absorbing liquid entrance of device and level four reaction apparatus is answered to be connected with alkali liquor inlet pipeline respectively, level four reaction apparatus liquid-phase outlet is through in level Four
Between be divided into two-way after tank, be connected with third-stage reactor absorbing liquid entrance and level four reaction apparatus absorbing liquid entrance respectively；Third-order reaction
Device liquid-phase outlet is connected with third-stage reactor absorbing liquid entrance and second reactor absorbing liquid entrance respectively after three-level pans；
Second reactor liquid-phase outlet point two-way, the first via is connected with first-stage reactor absorbing liquid inlet, and the second tunnel is successively through two
It is connected with second reactor absorbing liquid entrance and circulation fluid entrance respectively after level crystallizer, the second-order separation tank, two grades of pans；One
Stage reactor liquid-phase outlet point two-way, the first via is connected with product discharge pipeline, and the second tunnel is successively through first degree crystalline device, a fraction
It is connected with first-stage reactor absorbing liquid entrance and circulation fluid entrance respectively after tank, one-level pans.
Sour gas absorption system of the present invention, make-up cooling water is respectively provided with the first degree crystalline device and secondary crystallizer
Entrance and circulating backwater are exported.
Sour gas absorption system of the present invention, the venturi reactor, feed zone upper end is to open up teeth groove, teeth groove knot
Structure is the one kind in fan-shaped teeth groove, square teeth groove and triangle teeth groove, preferably lance tooth slot structure.Space width be 3mm ~
20mm, preferably 5mm ~ 8mm；Its bottom angle is 15 ~ 90 °, preferably 30 ~ 60 °.
Sour gas absorption system of the present invention, the venturi reactor, absorbing liquid entrance connection liquid phase distributor, liquid
Distributed mutually device is arranged on straight tube reaction tube center line, and absorbing liquid is sprayed from top to bottom, and liquid phase distributor is settable 1 ~ 10, excellent
Select 4 ~ 6.Absorbing liquid entrance be arranged on the straight tube on contraction section top reaction pipe outer wall on, be preferably provided at liquid phase storage tank bottom with
Between contraction section.
Sour gas absorption system of the present invention, the gas-liquid separation cylinder of the venturi reactor sets and takes hot facility, controls
Temperature processed is 85 DEG C~120 DEG C, preferably 90 DEG C~95 DEG C, prevents intermediate product from crystallizing.
Compared with prior art, sour gas absorption technique method and device of the present invention has the following advantages that：
1st, sour gas absorption technique method of the present invention, using level Four gas-liquid two-phase counter-current absorption course of reaction, there is provided instead
The self-loopa that liquid should be generated reabsorbs operation, improves reaction depth, material is fully contacted with sour gas, it is ensured that NaHS liquid phases
Product meets national product quality standard, Na in product NaHS2The content of S is less than 4%；Circulated by reaction mass, fill alkali lye
Divide and contacted with sour gas so that H in purified gas2S contents are less than 30 mg/Nm3, it is ensured that the sour gas after treatment realizes qualified discharge
Target.
2nd, sour gas absorption technique method of the present invention, adds NaOH solution, respectively to second reactor, level Four by being classified
Reactor fills NaOH solution, adjusts response intensities at different levels, carries out peak clipping treatment to reaction heat, it is ensured that temperature of reactor at different levels exist
In zone of reasonableness, heat spot is prevented, cause local-crystalized, cause reaction terminating.
3, sour gas absorption technique method of the present invention, by setting first degree crystalline device, one-level knockout drum, secondary crystallizer, The second-order separation tank, reaction solution enters temperature-controllable low temperature crystallization device, and reaction solution is ejected into crystallizer through spraying into mist shape cryogenic tube bundle outer surface, ordered crystalline is realized in tube bank outer surface, annular scraper is set outside cryogenic tube bundle, will the outer crystallization of tube bank thing is scraped in solution, and rapidly enter knockout drum, realize liquid, Gu separate, realize that crystal is removed, reduce intermediate reaction generation the solid holdup of liquid, improve purpose product yield and purity, and take out partial reaction heat, reduce the concentration raising that evaporation causes, it is anti- Only there is crystallization.
4th, using venturi reactor of the present invention as first-stage reactor and second reactor, reaction solution passes through literary mound
In reactor circulation fluid entrance enter reactor reservoir, when circulation fluid position be higher than feed zone entrance when, the reaction of circulation
Generation liquid forms overflow, is distributed with wall manifold state in whole wall of reactor, and uniform liquid film is formed in reactor wall,
With liquid film as division board, not only prevent crystal from separating out adhesive reaction device inwall, meanwhile, with liquid film as heat-absorbing medium, take out anti-
Should be hot, effectively prevent reaction solution excessive vaporization.
5th, sour gas absorption plant of the present invention is using high-gravity rotating bed as gas-liquid reactor, be capable of achieving to improve mass transfer with
The target of reaction efficiency, rotary drill reactor is efficient mass transfer equipment, it is ensured that reaction is quickly carried out, and reduces the generation of side reaction,
Reduce impurity content in product.Meanwhile, because rotary drill reactor mass-transfer efficiency is the hundreds of of common tower reactor mass-transfer efficiency
Times, reactor scale is greatly reduced.And by CO in sour gas2When being reacted with NaOH, nano level Na is generated2CO3Crystalline solid, from
And Na when preventing fluid from conveying2CO3Crystalline solid blocks pipeline.Material on the bed component inwall of high-speed rotation, acutely hit by formation
Hit, realize reinforcing mixing；Material is constantly cut into drop, brin and liquid film when bed is flowed through by bed, greatly realizes
The Surface Renewal of high-viscosity material with mix, eliminate concentration difference, generate nano level Na2CO3Crystalline solid.
6th, sour gas absorption technique of the present invention and device are particularly suited for processing small-sized sour gas, with prior art phase
Than equipment scale is small, and energy consumption is low, and operating cost is few, and generation can be used for the NaHS products of the industries such as printing and dyeing, papermaking, is easy to fortune
It is defeated, and have certain market value.
Brief description of the drawings
Fig. 1 is a kind of sour gas absorption technique method and device schematic diagram of the invention.
Fig. 2 is second sour gas absorption technique method and device schematic diagram of the invention.
Fig. 3 is venturi reactor schematic diagram in second sour gas absorption technique method and device of the invention.
Specific embodiment
Sour gas counter-current absorption process of the present invention and device, with NaOH solution as absorbing liquid, treatment oil plant is acid
Gas produces NaHS products, using level Four gas-liquid two-phase counter-current absorption course of reaction.
As shown in figure 1, the first sour gas absorption system of the invention, the system includes first-stage reactor 1, second order reaction Device 2, third-stage reactor 3, level four reaction apparatus 4, first degree crystalline device 5, one-level knockout drum 6, one-level pans 7, secondary crystallizer 8 The second-order separation tank 9, two grades of pans 10, three-level pans 11, level Four pans 12, wherein, first-stage reactor 1, second order reaction Device 2, third-stage reactor 3, the are respectively provided with gas phase entrance of level four reaction apparatus 4, gaseous phase outlet, liquid phase entrance and liquid-phase outlet, acid Gas suction line 26 is connected with the gas phase entrance of first-stage reactor, the gaseous phase outlet of first-stage reactor and the gas phase of second reactor The gas phase entrance connection of entrance connection, the gaseous phase outlet of second reactor and third-stage reactor, the gaseous phase outlet of third-stage reactor Connected with level four reaction apparatus gas phase entrance, the gaseous phase outlet of level four reaction apparatus is connected with clean gas outlet pipeline 27, and purified gas go out The on mouthful pipeline 27 of It is provided with hydrogen sulfide content detection means 29, the respectively with two of alkali liquor inlet pipeline 13 is by pipeline 15, pipeline 14 The liquid phase entrance connection of level pans and level four reaction apparatus, level four reaction apparatus liquid-phase outlet is divided into two after level Four pans 12 Road, 18 is connected with level four reaction apparatus liquid phase entrance all the way, 19 is connected with third-stage reactor liquid phase entrance all the way, third-stage reactor liquid Mutually outlet point two-way after three-level pans 11, the and two grades are instead of 20 is connected with third-stage reactor liquid phase entrance all the way, and another road 21 Device liquid phase entrance is answered to connect; Second reactor liquid-phase outlet point two-way, the first via 22 is connected with first-stage reactor liquid phase entrance, the The are connected after secondary crystallizer 8 of Two tunnels 23, of the second-order separation tank with second reactor liquid phase entrance successively of 9, two grades of pans 10; One Stage reactor liquid-phase outlet point two-way, the is connected with product discharge pipeline of the first via 24, the successively through first degree crystalline device 5 of the second tunnel 25 It is connected with first-stage reactor liquid phase entrance after one-level knockout drum 6, one-level pans 7, the first degree crystalline device and secondary crystallizer The and circulating backwater 17. of On be respectively arranged with make-up cooling water 16
Shown in Fig. 1, sour gas multi-stage countercurrent absorption technique method of the present invention, the sour gas from sour gas suction line 26
First-stage reactor 1 is initially entered, with the generation liquid haptoreaction from second reactor, reaction solution is divided into two-way, first
Road is discharged as product, and the second tunnel enters first degree crystalline device, in the presence of make-up cooling water, crystallisation by cooling, subsequently into one-level
Knockout drum carries out solid-liquor separation, and isolated liquid enters one-level pans, first-stage reactor is then recycled into, by one
Sour gas after stage reactor treatment enters second reactor 2, is contacted with generation liquid and alkali lye NaOH from third-stage reactor
Reaction, reaction solution is divided into two-way, and the first via 22 enters first-stage reactor as absorbing liquid through first-stage reactor liquid phase entrance,
Second tunnel generation liquid enters secondary crystallizer, and in the presence of make-up cooling water, crystallisation by cooling is carried out subsequently into one-level knockout drum
Solid-liquor separation, it is Na that isolated solid is most of2CO3Crystallization, can be used for sewage treatment plant regulation PH and uses after taking-up, point
Enter two grades of pans from the liquid for obtaining, second reactor is entered through pump, enter by the reacted sour gas of second reactor
Enter third-stage reactor, with level four reaction apparatus generation liquid reaction, reacted generation liquid enters three-level pans, then the first via 21
Enter second reactor as absorbing liquid, the second tunnel 20 loops back third-stage reactor；By the reacted acidity of third-stage reactor
Gas enters level four reaction apparatus, and with NaOH solution reaction, reacted sour gas is after the further demisting of coalescer 28 by purification
The qualified discharge of gas outlet line 27, reacted generation liquid enters point two-way after level Four pans, and the first via 19 is used as absorbing liquid
Into third-stage reactor, the second tunnel 18 loops back level four reaction apparatus, is respectively provided with the first degree crystalline device and secondary crystallizer
There are make-up cooling water 16 and circulating backwater 17.
Sour gas absorption system shown in second implementation method of the invention, the system includes first order reaction of As shown in Fig. 2 Device 1, second reactor 2, third-stage reactor 3, level four reaction apparatus 4, one-level pans 7, two grades of pans 10, three-level pans The and the second-order separation tank 9 of 11st, level Four pans 12, first degree crystalline device 5, secondary crystallizer 8, one-level knockout drum 6; Wherein, one-level is anti- Device, second reactor are answered using venturi reactor, the venturi reactor from top to bottom divides three sections, and epimere is liquid phase storage tank 34, stage casing is straight tube reaction tube 30, and hypomere is gas-liquid separation cylinder 41; The straight tube reaction tube is from top to bottom followed successively by feed zone The and discharging section 40 of 33rd, contraction section 37, trunnion section 38, expansion segment 39; Feed zone top forms sleeve structure, discharging with liquid phase storage tank Section 40 is connected with gas-liquid separation cylinder 41, and liquid phase storage tank is provided with gas phase entrance 31, and gas phase entry position is higher than end entrance on feed zone, Liquid phase storage groove sidewall is provided with circulation fluid entrance 32; The tube wall of straight tube reaction tube is provided with absorbing liquid entrance 35, absorbing liquid entrance position In trunnion top; The and liquid-phase outlet 43 of Gas-liquid separation cylinder is provided with gaseous phase outlet 42; Third-stage reactor and level four reaction apparatus set respectively Put gas phase entrance, gaseous phase outlet, absorbing liquid entrance and liquid-phase outlet; The and first-stage reactor gas phase entrance of Sour gas suction line 26 Connection, the gaseous phase outlet of first-stage reactor is connected with the gas phase entrance of second reactor, the gaseous phase outlet of second reactor and three The gas phase entrance connection of stage reactor, the gaseous phase outlet of third-stage reactor is connected with the gas phase entrance of level four reaction apparatus, and level Four is anti- Device gaseous phase outlet is answered to be connected with clean gas outlet pipeline 27, clean gas outlet pipeline is provided with hydrogen sulfide content detection means 29; The is connected by the liquid phase entrance of pipeline 15 of Alkali liquor inlet pipeline 13, pipeline 14 respectively with two grades of pans and level four reaction apparatus, and four Stage reactor liquid-phase outlet is divided into two-way after level Four pans, 19 is connected with third-stage reactor absorbing liquid entrance all the way, another The and level four reaction apparatus absorbing liquid entrance are connected of Road 18; Third-stage reactor liquid-phase outlet point two-way after three-level pans, all the way 20 It is connected with third-stage reactor absorbing liquid entrance, 21 is connected with second reactor absorbing liquid entrance all the way; Second reactor liquid phase goes out Mouth point two-way, the is connected with first-stage reactor absorbing liquid entrance of the first via 22, and the second tunnel 23 is successively through secondary crystallizer 8, two fractions Enter second reactor through second reactor absorbing liquid entrance and circulation fluid entrance respectively after 9, two grades from tank pans 10; One-level Reactor liquid-phase outlet point two-way, the is connected with product discharge pipeline of the first via 24, the is successively through first degree crystalline device 5 of and the second tunnel 25 Enter first-stage reactor through first-stage reactor absorbing liquid entrance and circulation fluid entrance respectively after level knockout drum 6, one-level pans 7 The are respectively arranged with the first degree crystalline device and secondary crystallizer. of 16 and circulating backwater of Make-up cooling water 17
As shown in Fig. 2 sour gas multi-stage countercurrent absorption technique method of the present invention, the sour gas head from acid gas pipeline 26
First-stage reactor 1 is introduced into, with the generation liquid haptoreaction from second reactor, reaction solution is divided into two-way, the first via
Discharged as product, the second tunnel enters first degree crystalline device, in the presence of make-up cooling water, crystallisation by cooling, subsequently into a fraction
Carry out solid-liquor separation from tank, isolated liquid enters one-level pans, respectively by first-stage reactor absorbing liquid entrance and
Circulation fluid entrance enters first-stage reactor, and the first order reaction for entering first-stage reactor through circulation fluid entrance generates liquid in first order reaction
Downflow weir is formed in device, is distributed with wall manifold state on whole first-stage reactor wall, formed uniformly in reactor wall
Liquid film, with liquid film as division board, not only prevents crystal from separating out adhesive reaction device inwall, meanwhile, with liquid film as heat-absorbing medium, take
Go out reaction heat, effectively prevent Na2S solution excessive vaporizations.Enter second reactor by the sour gas after first-stage reactor treatment
2, with the generation liquid from third-stage reactor and alkali lye NaOH haptoreactions, reaction solution is divided into two-way, and the first via is used as suction
Receive liquid and enter first-stage reactor through first-stage reactor absorbing liquid entrance, the second tunnel generation liquid enters secondary crystallizer, given in circulation
In the presence of water, crystallisation by cooling carries out solid-liquor separation subsequently into one-level knockout drum, and isolated solid major part is
Na2CO3Crystallization, can be used for sewage treatment plant regulation PH and uses after taking-up, isolated liquid enters two grades of pans, respectively
Second reactor is entered by second reactor absorbing liquid entrance and circulation fluid entrance, second reactor is entered through circulation fluid entrance
Second order reaction generation liquid downflow weir is formed in second reactor, carried out with wall manifold state on whole second reactor wall
Distribution, uniform liquid film is formed in reactor wall, with liquid film as division board, not only prevents crystal from separating out in adhesive reaction device
Wall, meanwhile, with liquid film as heat-absorbing medium, reaction heat is taken out, effectively prevent Na2S solution excessive vaporizations.It is anti-by second reactor
Sour gas after answering enters third-stage reactor, and with level four reaction apparatus generation liquid reaction, reacted generation liquid enters in the middle of three-level
Tank, then enters second reactor as absorbing liquid all the way, and the second tunnel loops back third-stage reactor；Reacted by third-stage reactor
Sour gas afterwards enters level four reaction apparatus, and with NaOH solution reaction, reacted sour gas is after the demisting of coalescer 28 through purification
The qualified discharge of gas outlet line 27, reacted generation liquid enters point two-way after level Four pans, and the first via is entered as absorbing liquid
Enter third-stage reactor, the second tunnel loops back level four reaction apparatus.
Sour gas multi-stage countercurrent absorption technique method of the present invention includes following four process：
（1）Course of reaction in first-stage reactor
Key reaction is as follows in first-stage reactor：Undressed sour gas and second order reaction generation liquid（Main composition
It is Na2S and NaHS, part Na2CO3、NaHCO3Mixed solution, in H2In the case of S excess, the Na in second order reaction generation liquid2S
With H2S reacts, and generates NaHS and part NaHCO3Solution.Reaction solution enters temperature-controllable low temperature first degree crystalline device, reaction solution
Cryogenic tube bundle outer surface is ejected into through spraying into mist shape, NaHCO is realized in tube bank outer surface3Ordered crystalline, outside cryogenic tube bundle
Annular scraper is set, during the outer crystal of tube bank scrapes solution, and one-level knockout drum will be rapidly entered, realize liquid, solid separation
NaHCO3, realize that crystal is removed, the solid holdup that intermediate reaction generates liquid is reduced, purpose product yield and purity are improved, and take
Go out partial reaction heat, the concentration that reduction evaporation causes is improved, prevents crystallization.Realize that the NaHS solution after separating is divided to two
Road, the first via is discharged as product through pipeline；Second tunnel enters first degree crystalline device, under the cooling effect of recirculated water, is had
Sequence is crystallized, and separation of solid and liquid is carried out subsequently into one-level knockout drum, and isolated liquid enters one-level pans.
（2）Course of reaction in second reactor
Key reaction is as follows in second reactor：Gas phase is " the weary gas " of first order reaction gas phase, wherein H2S concentration is still
It is higher, it is not reaching to discharge standard；Second order reaction liquid phase is the mixed solution that alkali lye and third-order reaction generate liquid, in H2S excess
In the case of, Na2S and NaOH mixed liquors and H2S reacts, and generates Na2S and NaHS mixed liquors.Due to carrying CO secretly in sour gas2Group
Point, CO2With NaOH reaction generations Na2CO3、NaHCO3.Reaction solution Na2S, NaHS and part Na2CO3、NaHCO3Mixed liquor,
Reaction solution point two-way, the first via enters first-stage reactor as absorbing liquid, and the second tunnel enters secondary crystallizer, by circulation
The mode of heat is accessed between water, generation liquid is cooled to 85 DEG C~95 DEG C, reaction solution is ejected into cryogenic tube bundle through spraying into mist shape
Outer surface, Na is realized in tube bank outer surface2CO3、NaHCO3Ordered crystalline, sets annular scraper outside cryogenic tube bundle, by the outer knot of tube bank
Brilliant thing is scraped in solution, and rapidly enters one-level knockout drum, realizes liquid, solid separation, isolates most of Na2CO3、NaHCO3,
Realize that crystal is removed, reduce the solid holdup that intermediate reaction generates liquid, improve purpose product yield and purity, and it is anti-to take out part
Should heat, control the reaction temperature of second reactor, prevent from generating liquid and cross the concentration that thermal evaporation causes and improve, prevent crystallization.
Liquid phase in knockout drum flows into pans and is delivered in second reactor by three-level absorbing liquid pump, is circulated flowing.Two grades anti-
The Na in liquid should be generated2CO3、NaHCO3 Crystallization separate out and reduce solid holdup in liquid phase, reducing production flow line and blocking causes
Influence device normally produce.
（3）Course of reaction in third-stage reactor
Key reaction is as follows in third-stage reactor：Third-order reaction gas phase is " the weary gas " that gas phase is reacted in the second level, wherein
H2S concentration is greatly reduced, but still is not carried out qualified discharge requirement.Third-order reaction generates liquid with fourth-order reaction（It is most of
NaOH and a small amount of Na2S mixed liquors）It is absorbing liquid, in H2In the case that S is slightly excessive, NaOH and Na2S mixed liquors and H2S reacts, raw
Into Na2S and NaHS, reaction solution point two-way, the first via enters second reactor as absorbing liquid, in the second tunnel generation liquid warp
Between tank enter third-stage reactor in, be circulated flowing, realize absorbing liquid depth absorption and circulation take heat.
（4）Course of reaction in level four reaction apparatus
Key reaction is as follows in level four reaction apparatus：Fourth-order reaction gas phase is " the weary gas " that the third level reacts gas phase, wherein
H2S concentration is extremely low, basically reaches emission request.Fourth-order reaction with NaOH solution as absorbing liquid, in H2In the case that S is a small amount of, NaOH
With H2S reacts, and generates a small amount of Na2S。
With reference to embodiment, the present invention is further described, but does not therefore limit the scope of the invention.
Embodiment 1
Using process and system as shown in Figure 1, with sour gas and NaOH solution as raw material, reacted.It is acid
CO in gas2Volume fraction is 7%, H2S volume fractions are 92%, and hydro carbons volume fraction is 1%.NaOH solution mass concentration is 38%.
In embodiment 1, first-stage reactor and second reactor use venturi reactor, third-stage reactor and fourth-order reaction
Device uses rotary drill reactor, and the venturi reactor and rotary drill reactor can be that venturi generally in the art reacts
Device and rotary drill reactor.
In embodiment 1, the second road reaction solution and first-stage reactor overall reaction for looping back first-stage reactor generate liquid
Volume flow ratio be 5：6.The the second road reaction solution and second reactor overall reaction for looping back second reactor generate liquid
Volume flow ratio be 5：6.The the second road reaction solution and third-stage reactor overall reaction for looping back third-stage reactor generate liquid
Volume flow ratio be 5：6.The the second road reaction solution and level four reaction apparatus overall reaction for looping back level four reaction apparatus generate liquid
Volume flow ratio be 5：6.
In embodiment 1, second reactor, the alkali lye addition volume flow ratio of level four reaction apparatus are 2：1.
In one-level venturi reactor and two grades of venturi reactors reaction temperature be 80 DEG C of three-level rotary drill reactors and
The reaction temperature of level Four rotary drill reactor is 75 DEG C.The revolving bed of three-level rotary drill reactor and level Four rotary drill reactor
Rotating speed is 1500 revs/min.Three-level rotary drill reactor and level Four rotary drill reactor reaction mass residence time in reactor
It it is 10 seconds, reaction result is shown in Table 1.
Embodiment 2
Using process and system as shown in Figure 2, in embodiment 2, first-stage reactor and second reactor use Fig. 3
Shown venturi reactor, third-stage reactor and level four reaction apparatus use rotary drill reactor.
In embodiment 2, the reaction solution for looping back first-stage reactor through first-stage reactor absorbing liquid entrance is anti-with one-level
The volume flow ratio for answering device overall reaction to generate liquid is 5：8.The anti-of first-stage reactor is looped back through first-stage reactor circulation fluid entrance
The volume flow ratio that liquid should be generated with first-stage reactor overall reaction generation liquid is 5：24.
Reaction solution and the second reactor overall reaction of second reactor are looped back through second reactor absorbing liquid entrance
The volume flow ratio for generating liquid is 5：8.Through second reactor circulation fluid entrance loop back the reaction solution of second reactor with
The volume flow ratio of second reactor overall reaction generation liquid is 5：24.
The the second road reaction solution for looping back third-stage reactor generates the volume flow of liquid with third-stage reactor overall reaction
Than being 5：6.The the second road reaction solution for looping back level four reaction apparatus generates the volume flow of liquid with level four reaction apparatus overall reaction
Than being 5：6.
In embodiment 2, second reactor, the volume flow ratio of the alkali lye addition of level four reaction apparatus are 2：1.
Reaction temperature is 80 DEG C in one-level venturi reactor and two grades of venturi reactors.Three-level rotary drill reactor and
The reaction temperature of level Four rotary drill reactor is 75 DEG C.The revolving bed of three-level rotary drill reactor and level Four rotary drill reactor
Rotating speed is 1500 revs/min.Three-level rotary drill reactor and level Four rotary drill reactor reaction mass residence time in reactor
It it is 10 seconds, reaction result is shown in Table 1.
Comparative example 1
Same as Example 1, difference is alkali lye only from the filling of fourth stage reactor.
The embodiment of table 1 and comparative example reaction result
Claims (48)
1. a kind of sour gas multi-stage countercurrent absorption technique method, with NaOH solution as absorbing liquid, processes sour gas production NaHS, bag
Include following steps：
（1）Sour gas enters first-stage reactor, is contacted with the reaction solution of second reactor and is reacted, reaction solution point
Two-way, the first via is discharged as product, and first-stage reactor is entered after the crystallized separation in the second tunnel；
（2）By step（1）Reacted sour gas enters second reactor, with NaOH solution and the generation liquid of third-stage reactor
Contact is reacted；Reaction solution point two-way, the first via enters first-stage reactor, the crystallized separation in the second tunnel as absorbing liquid
Enter second reactor afterwards；
（3）By step（2）Reacted sour gas enters third-stage reactor, and being contacted with level four reaction apparatus generation liquid is carried out instead
Should, reaction solution point two-way, the first via enters second reactor as absorbing liquid, and the second tunnel loops back third-stage reactor；
（4）By step（3）Reacted sour gas enters level four reaction apparatus, with NaOH solution reaction, reacted sour gas
Discharge, reaction solution point two-way, the first via enters third-stage reactor as absorbing liquid, and the second tunnel loops back level four reaction apparatus；
Wherein first-stage reactor, second reactor are venturi reactor, and the venturi reactor from top to bottom divides three sections, on
Section is liquid phase storage tank, and stage casing is straight tube reaction tube, and hypomere is gas-liquid separation cylinder；The straight tube reaction tube be from top to bottom followed successively by into
Material section, contraction section, trunnion section, expansion segment and discharging section；Feed zone top forms sleeve structure with liquid phase storage tank, and discharge pars infrasegmentalis
It is connected with gas-liquid separation cylinder, liquid phase storage tank is provided with gas phase entrance, and gas phase entry position is higher than end entrance, liquid phase storage tank on feed zone
Side wall is provided with circulation fluid entrance；The tube wall of straight tube reaction tube is provided with absorbing liquid entrance, and absorbing liquid entrance is located at trunnion top；Gas
Liquid cylinder is provided with gaseous phase outlet and liquid-phase outlet.
2. according to the process described in claim 1, it is characterised in that：Step（1）In, loop back the second of first-stage reactor
Road reaction solution is 1/3~9/10 with the volume flow ratio of first-stage reactor overall reaction generation liquid.
3. according to the process described in claim 2, it is characterised in that：Step（1）In, loop back the second of first-stage reactor
Road reaction solution is 5/6~8/9 with the volume flow ratio of first-stage reactor overall reaction generation liquid.
4. according to the process described in claim 1, it is characterised in that：Step（2）In, loop back the second of second reactor
Road reaction solution is 1/3~9/10 with the volume flow ratio of second reactor overall reaction generation liquid.
5. according to the process described in claim 4, it is characterised in that：Step（2）In, loop back the second of second reactor
Road reaction solution is 5/6~8/9 with the volume flow ratio of second reactor overall reaction generation liquid.
6. according to the process described in claim 1, it is characterised in that：Step（3）In, loop back the second of third-stage reactor
Road reaction solution is 1/3~9/10 with the volume flow ratio of third-stage reactor overall reaction generation liquid.
7. according to the process described in claim 6, it is characterised in that：Step（3）In, loop back the second of third-stage reactor
Road reaction solution is 5/6~8/9 with the volume flow ratio of third-stage reactor overall reaction generation liquid.
8. according to the process described in claim 1, it is characterised in that：Step（4）In, loop back the second of level four reaction apparatus
Road reaction solution is 1/3~9/10 with the volume flow ratio of level four reaction apparatus overall reaction generation liquid.
9. according to the process described in claim 8, it is characterised in that：Step（4）In, loop back the second of level four reaction apparatus
Road reaction solution is 5/6~8/9 with the volume flow ratio of level four reaction apparatus overall reaction generation liquid.
10. according to the process described in claim 1, it is characterised in that：The NaOH solution of second reactor, level four reaction apparatus
The volume flow ratio of addition is 1:1~3:1.
11. according to the process described in claim 10, it is characterised in that：Second reactor, level four reaction apparatus NaOH it is molten
The volume flow ratio of liquid addition is 3:2~2:1.
12. according to the process described in claim 1, it is characterised in that：The addition of NaOH solution passes through step（4）Treatment
Hydrogen sulfide content regulation in sour gas afterwards, by adjusting valve regulation NaOH solution addition, it is ensured that by step（4）After treatment
Sour gas in hydrogen sulfide content be 5-30 mg/Nm3, and ensureing H2NaOH solution is not excessive in the case of S qualified discharges.
13. according to the process described in claim 1, it is characterised in that：By step（4）Sour gas after treatment is further
Discharged after coalescer demisting.
14. according to the process described in claim 1, it is characterised in that：By step（4）Vulcanize in sour gas after treatment
Hydrogen content is 5-30 mg/Nm3。
15. according to the process described in claim 1, it is characterised in that：The reaction temperature of first-stage reactor and second reactor
Spend is 70 DEG C~100 DEG C.
16. according to the process described in claim 15, it is characterised in that：The reaction temperature of first-stage reactor and second reactor
Spend is 80 DEG C~95 DEG C.
17. according to the process described in claim 1, it is characterised in that：Temperature is reacted in third-stage reactor and level four reaction apparatus
Spend is 60 DEG C~90 DEG C.
18. according to the process described in claim 17, it is characterised in that：Temperature is reacted in third-stage reactor and level four reaction apparatus
Spend is 65 DEG C~80 DEG C.
19. according to the process described in claim 1, it is characterised in that：Third-stage reactor, level four reaction apparatus are gas-liquid mass transfer
Consersion unit, specially bubbling column reactor, filler tower reactor, impact flow reactor, rotary drill reactor and venturi are anti-
Answer one or more in device.
20. according to the process described in claim 1, it is characterised in that：Third-stage reactor, level four reaction apparatus are that revolving bed is anti-
Answer device.
21. according to the process described in claim 20, it is characterised in that：Third-stage reactor and level four reaction apparatus are using rotation
The rotating speed of the revolving bed of bed reactor, three-level rotary drill reactor and level Four rotary drill reactor is 50~5000 revs/min.
22. according to the process described in claim 21, it is characterised in that：The rotating speed of revolving bed is 150~2000 revs/min.
23. according to the process described in claim 20, it is characterised in that：Third-stage reactor and level four reaction apparatus are using rotation
Bed reactor, reaction mass residence time in three-level rotary drill reactor and level Four rotary drill reactor is 2~600 seconds.
24. according to the process described in claim 23, it is characterised in that：Reaction mass is in three-level rotary drill reactor and four
The residence time is 10~100 seconds in level rotary drill reactor.
25. according to the process described in claim 1, it is characterised in that：The reaction solution warp of the second road first-stage reactor
Enter first-stage reactor from circulation fluid entrance and absorbing liquid entrance respectively after Crystallization Separation.
26. according to the process described in claim 25, it is characterised in that：Enter the anti-of first-stage reactor from circulation fluid entrance
It is 1/6~1/2 that liquid should be generated with the reaction solution volume flow ratio from absorbing liquid entrance into first-stage reactor.
27. according to the process described in claim 26, it is characterised in that：Enter the anti-of first-stage reactor from circulation fluid entrance
It is 1/4~1/3 that liquid should be generated with the reaction solution volume flow ratio from absorbing liquid entrance into first-stage reactor.
28. according to the process described in claim 25, it is characterised in that：The reaction solution warp of the second road second reactor
Enter first-stage reactor from circulation fluid entrance and absorbing liquid entrance respectively after Crystallization Separation.
29. according to the process described in claim 28, it is characterised in that：Enter the anti-of second reactor from circulation fluid entrance
It is 1/6~1/2 that liquid should be generated with the reaction solution volume flow ratio from absorbing liquid entrance into second reactor.
30. according to the process described in claim 29, it is characterised in that：Enter the anti-of second reactor from circulation fluid entrance
It is 1/4~1/3 that liquid should be generated with the reaction solution volume flow ratio from absorbing liquid entrance into second reactor.
31. according to the process described in claim 1, it is characterised in that：The venturi reactor, feed zone upper end opens up
Teeth groove, tooth slot structure is the one kind in fan-shaped teeth groove, square teeth groove and triangle teeth groove.
32. according to the process described in claim 31, it is characterised in that：Tooth slot structure is lance tooth slot structure.
33. according to the process described in claim 1, it is characterised in that：The venturi reactor, the connection of absorbing liquid entrance
Liquid phase distributor, liquid phase distributor is arranged on straight tube reaction tube center line, and absorbing liquid is sprayed from top to bottom, and liquid phase distributor sets
Put 1 ~ 10.
34. according to the process described in claim 33, it is characterised in that liquid phase distributor sets 4 ~ 6.
35. according to the process described in claim 1, it is characterised in that：The sour gas is the sulfide hydrogen in various sources
Gas, CO in sour gas2Volume fraction be less than 7%.
36. according to the process described in claim 1, it is characterised in that：The NaOH solution mass concentration is 20%~60%.
37. according to the process described in claim 36, it is characterised in that：The NaOH solution mass concentration be 32%~
38%。
The acidity of the sour gas multi-stage countercurrent absorption technique method in 38. use claims 1 to 37 described in any claim
Gas utilization system, it is characterised in that：The system includes that first-stage reactor, second reactor, third-stage reactor, level Four are anti-
Answer device, one-level pans, two grades of pans, three-level pans, level Four pans, first degree crystalline device, secondary crystallizer, fractions
From tank and the second-order separation tank；Wherein, first-stage reactor, second reactor are venturi reactor, the venturi reactor point
Three sections, epimere is liquid phase storage tank, and stage casing is straight tube reaction tube, and hypomere is gas-liquid separation cylinder；The straight tube reaction tube is from top to bottom
It is followed successively by feed zone, contraction section, trunnion section, expansion segment and discharging section；Feed zone top forms sleeve structure with liquid phase storage tank, goes out
Material section is connected with gas-liquid separation cylinder, and liquid phase storage tank is provided with gas phase entrance, and gas phase entry position is higher than end entrance, liquid phase on feed zone
Storage groove sidewall is provided with circulation fluid entrance；The tube wall of straight tube reaction tube is provided with absorbing liquid entrance, and absorbing liquid entrance is located on trunnion
Portion；Gas-liquid separation cylinder is provided with gaseous phase outlet and liquid-phase outlet；Third-stage reactor and level four reaction apparatus are respectively provided with gas phase entrance, gas
Phase outlet, absorbing liquid entrance and liquid-phase outlet；Sour gas suction line is connected with first-stage reactor gas phase entrance, first-stage reactor
Gaseous phase outlet be connected with the gas phase entrance of second reactor, the gaseous phase outlet of second reactor enters with the gas phase of third-stage reactor
Mouthful connection, the gaseous phase outlet of third-stage reactor is connected with the gas phase entrance of level four reaction apparatus, level four reaction apparatus gaseous phase outlet with it is net
Change the connection of gas outlet line, clean gas outlet pipeline is provided with hydrogen sulfide content detection means；Second reactor and fourth-order reaction
The absorbing liquid entrance of device is connected with alkali liquor inlet pipeline respectively, and level four reaction apparatus liquid-phase outlet is divided into two after level Four pans
Road, is connected with third-stage reactor absorbing liquid entrance and level four reaction apparatus absorbing liquid entrance respectively；Third-stage reactor liquid-phase outlet is passed through
It is connected with third-stage reactor absorbing liquid entrance and second reactor absorbing liquid entrance respectively after three-level pans；Second reactor liquid
Mutually outlet divides two-way, and the first via is connected with first-stage reactor absorbing liquid entrance, and the second tunnel is successively through secondary crystallizer, the second-order separation
It is connected with second reactor absorbing liquid entrance and second reactor circulation fluid entrance respectively after tank, two grades of pans；First order reaction
Device liquid-phase outlet point two-way, the first via is connected with product discharge pipeline, the second tunnel successively through first degree crystalline device, one-level knockout drum,
It is connected with first-stage reactor absorbing liquid entrance and first-stage reactor circulation fluid entrance respectively after one-level pans.
39. according to the system described in claim 38, it is characterised in that：Set respectively on the first degree crystalline device and secondary crystallizer
Put make-up cooling water entrance and circulating backwater outlet.
40. according to the system described in claim 38, it is characterised in that：The venturi reactor, feed zone upper end is to open up
Teeth groove, tooth slot structure is the one kind in fan-shaped teeth groove, square teeth groove and triangle teeth groove.
41. according to the system described in claim 40, it is characterised in that：The tooth slot structure is lance tooth slot structure.
42. according to the system described in claim 38, it is characterised in that：The venturi reactor, absorbing liquid entrance connection liquid
Distributed mutually device, liquid phase distributor is arranged on straight tube reaction tube center line, and absorbing liquid is sprayed from top to bottom, and liquid phase distributor is set
1 ~ 10.
43. according to the system described in claim 42, it is characterised in that：Liquid phase distributor sets 4 ~ 6.
44. according to the system described in claim 38, it is characterised in that：The straight tube that absorbing liquid entrance is arranged on contraction section top is anti-
Answer in pipe outer wall.
45. according to the system described in claim 44, it is characterised in that：Absorbing liquid entrance is arranged on liquid phase storage tank bottom and shrinks
Between section.
46. according to the system described in claim 38, it is characterised in that：In level four reaction apparatus gaseous phase outlet and clean gas outlet pipe
Coalescer is provided between line, the coalescer is cylindrical tube, and end socket includes upper cover and low head, and inside sets cylindric
Screen cloth.
47. according to the system described in claim 38, it is characterised in that：The third-stage reactor, level four reaction apparatus are passed for gas-liquid
Qualitative response equipment, specially bubbling column reactor, filler tower reactor, impact flow reactor, rotary drill reactor and venturi
One kind in reactor.
48. according to the system described in claim 47, it is characterised in that：The third-stage reactor, level four reaction apparatus are revolving bed
Reactor.
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| US4814104A (en) * | 1987-02-05 | 1989-03-21 | Uop | Tertiary alkanolamine absorbent containing an ethyleneamine promoter and its method of use |
| CN201746324U (en) * | 2010-06-21 | 2011-02-16 | 淄博高汇化工有限公司 | Device for reclaiming sodium sulfhydrate |
| CN102351153A (en) * | 2011-07-04 | 2012-02-15 | 山东雅美科技有限公司 | Method for producing sodium bisulfide products by viscose fiber industrial waste gas |
| CN102408100A (en) * | 2011-08-02 | 2012-04-11 | 山东雅美科技有限公司 | Sodium sulfhydrate product with concentration of 22% and low content of carnallite produced from viscose fiber waste gas |
| CN202876623U (en) * | 2012-11-09 | 2013-04-17 | 沈阳广达化工有限公司 | Continuous absorption tower system of hydrogen sulfide in process of sulphide isobutene production |
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