CN104826463B - A kind of sour gas produces NaHS technique and device - Google Patents

A kind of sour gas produces NaHS technique and device Download PDF

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CN104826463B
CN104826463B CN201410046322.XA CN201410046322A CN104826463B CN 104826463 B CN104826463 B CN 104826463B CN 201410046322 A CN201410046322 A CN 201410046322A CN 104826463 B CN104826463 B CN 104826463B
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reactor
liquid
gas
technique
sour gas
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CN201410046322.XA
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CN104826463A (en
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彭德强
王璐瑶
齐慧敏
陈新
王岩
孟凡飞
陈建兵
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中国石油化工股份有限公司
中国石油化工股份有限公司抚顺石油化工研究院
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Abstract

The present invention provides a kind of sour gas to produce NaHS technique and device, described Acidic Gas Treating technique adopts gas-liquid two-phase counter-current absorption to react, with NaOH solution as absorbing liquid, process sour gas and produce NaHS, in described technique, first order reaction generates liquid and secondary response generates liquid self-loopa and uses, and first order reaction generation liquid loops back two grades of pans and uses as diluent.Pass through between two-stage rotary drill reactor to arrange make-up carrier gass pipeline, introduce make-up carrier gass, reduce CO in sour gas2Concentration, most of CO2It is carried over device together with carrier gas, control Na2CO3And NaHCO3Content, prevent from producing a large amount of Na2CO3Cause to crystallize, blocking pipeline is it is ensured that device long-term operation.Using rotary drill reactor as gas-liquid reactor, high mass transfer and reaction efficiency.The Acidic Gas Treating process is simple of the present invention, achievable sour gas purifies the double goal with pollutant resources, and described Acidic Gas Treating system scale is little, energy consumption is low and is not easily blocked.

Description

A kind of sour gas produces NaHS technique and device

Technical field

The present invention provides a kind of sour gas to produce NaHS technique and device, belongs to sour gas field of purification, especially relates to And the treating method and apparatus 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 most of at present small-sized refinery substantially adopts the processing method of post combustion emission.This method one Aspect causes the waste of resource, on the other hand brings huge pressure, the development space of impact enterprise to environmental protection.For protection ring Border and guarantee making full use of of resource, it is imperative the sour gas of small-sized refinery to be carried out recycle.

The process of big-and-middle-sized sour gas, mainly uses sour gas and prepares sulfur, 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 technology;Another kind is that U.S. Merichem is public The LO-CAT Technology 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 sulfur quality are steady Fixed, but because long flow path, investment are big, Claus technique can only process the sour gas of high concentration, generally works as the H in unstripped gas2S When volume fraction is less than 20%, device is just difficult to operate.Therefore, Claus technique is suitable for producing the dress of more than sulfur 5000t per year Put.

LO-CAT technique makes H using the iron catalyst of multicomponent chelate2S is converted into elementary sulfur, H2The removal efficiency of S exceedes 99.9%.LO-CAT technique can be suitable for the acid tolerance larger and H of fluctuation2S content 0~100% various operating modes, raw material fit Answer condition wide in range, adapt to the practical situation of sour gas fluctuation change.And LO-CAT liquid redox treatment scheme does not make With any poisonous chemicalss, and any harmful exhaust gas by-products will not be produced, environmentally safe catalyst is permissible Constantly regenerating in processing procedure.But it is slightly worse than Crouse because LO-CAT has operating cost height, sulfur purity and color and luster Technique, and the sulphur granule meeting blockage phenomenon producing in process of production, therefore, LO-CAT technique is producing sulfur per year In below 5000t scale, economy is poor(With respect to two grades of Claus+ tail gas hydrogenation reduction+solvent absorption technology).

For small-sized refinery, because acid tolerance is relatively small, using two grades of Claus+ tail gas hydrogenation reduction+solvents There is long flow path, complex operation, investment greatly in absorption techniqueses technique, scale and benefit are poor.And there is also one using LO-CAT technology Secondary investment larger, catalyst and patent royalties higher the problems such as.

Less for the total tolerance of small-sized sour gas, can be using the less new desulfurization process of investment, by H2S reclaims system Sour gas is carried out burning and generates SO by standby sulphite first2, it is then fed into absorption tower and carry out chemical absorbing generation sulphite Solution, then solution is reacted with alkaline absorbent, prepare sulphite fluid product, or generate sulphite crystal, warp The operation such as separate, be dried and being prepared into sulphite solid product.This device flow process is shorter, and reaction is simple, and operating flexibility is big, can fit Answer the impact to production process for the small-sized sour gas fluctuation, solids or liquid product can be produced by selecting different operations Product, select different absorbent can produce different types of sulphite, and realize tail gas qualified discharge by three sections of absorptions, real The purpose of existing cleaning of off-gas.But it is serious to there is equipment corrosion in actual production process, the higher determination of maintenance cost.

CN101143714A discloses a kind of method that sour gas using high hydrocarbon-containing prepares sulphuric acid, acid hydrogen sulfide gas Respectively enter burning in first, second sulfureted hydrogen burning stove in proportion, from the first combustion furnace high-temperature furnace gas out, by furnace gas Cooler, is cooled to uniform temperature by air, subsequently into the second combustion furnace with supplement sulfide hydrogen sour gas continue with Surplus air one combust 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 antacid.This process can only produce 98% industrial sulphuric acid it is impossible to productive value more High oleum, simultaneously as the transport of sulphuric acid, storage all acquire a certain degree of difficulty, therefore, oil plant market stable nearby needs 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 therein2S composition and cement material occur chemical reaction to generate CaSO4, other are harmful to Composition is also sintered and converts, fundamentally solve Acidic Gas Treating a difficult problem, meanwhile, sour gas as a kind of gaseous fuel, Make cement plant energy-saving fuel, the dual purpose realized environmental conservation and solve fuel, but, this method has certain limitation Property, it is not easy to promote.

CN101337661A is a kind of to be prepared in the method for NaHS, is first respectively adopted Caustic soda and lime cream absorbs and contains sulfur Change interstitial fluid in hydrogen and the sour gas generation of carbon dioxide, then mixed in proportion, obtain the NaHS product of low-carbon (LC) acid group. It is purer hydrogen sulfide gas that the method does not require sour gas, but flow process is longer, and automaticity is low.

Document《Absorb hydrogen sulfide with sodium hydroxide solution and produce sodium sulfide industrial technology》(Shangfang is given birth,《Inorganic chemicals industry》, The 2nd phase of volume 44,2012 2 months) hydrogen sulfide sodium hydroxide solution absorbs and produces the production technology of sodium sulfide by this technique, Absorb hydrogen sulfide with 380~420g/L sodium hydroxide solution in packed tower, control of reaction end point sodium sulfide mass concentration is 330 ~350g/L, hydrogen sulfide absorption rate reaches 95%~98%.This technique not only can effective protection environment, and can be enterprise create effect Benefit.But, this process products sodium sulfide is apt to deteriorate, and is difficult to store.

For small-sized sour gas, need a kind of to consider the factors such as safe and environment-friendly, economy Acidic Gas Treating method.

Content of the invention

For deficiency of the prior art, the present invention provides a kind of sour gas to produce NaHS technique and device, with now Technology is had to compare, sour gas of the present invention produces NaHS technique and produces satisfaction requirement while realizing sour gas qualified discharge NaHS product, realize sour gas purify and pollutant resources double goal.

Sour gas of the present invention produces NaHS technique, with NaOH solution as absorbing liquid, processes sour gas and produces NaHS, tool Body comprises the steps:

(1)Sour gas enters A reactor, contacts with the reaction solution of second reactor and is reacted, and reaction generates Liquid is divided into three tunnels, and the first via is discharged as product, and the second tunnel returns A reactor cyclic absorption;3rd tunnel returns to two grades of centres Tank;

(2)Through step(1)Reacted sour gas enters second reactor together with make-up carrier gass, with alkali liquor protective pot Reaction solution contact reacted;Reaction solution is divided into two-way, and the first via enters A reactor as absorbing liquid, the Two tunnels loop back second reactor;

(3)Through step(2)Reacted gas phase is entered alkali liquor protective pot and is reacted with NaOH solution, reacted sour gas Discharge, reaction solution enters second reactor.

In present invention process, through step(3)Acidity after process is discharged further after coalescer demisting.

In present invention process, described A reactor and second reactor are gas-liquid mass transfer consersion unit, specially bubbling One of tower reactor, filler tower reactor, impact flow reactor, rotary drill reactor and venturi reactor, preferably Rotary drill reactor.

In present invention process, step(2)In, described make-up carrier gass are any gas not reacted with sour gas and NaOH solution Body, specially low-pressure gas, nitrogen, in noble gases any one, make-up carrier gass and total acidic air volume are than for 1:1~3:1, It is preferably 1.5:1~2:1.

In present invention process, step(1)In, loop back the second road reaction solution and the A reactor of A reactor The volume ratio that overall reaction generates liquid is 1/3~9/10, preferably 1/2~4/5.

In present invention process, step(1)In, loop back the 3rd road reaction solution and the A reactor of two grades of pans Overall reaction generate liquid volume ratio be 1/4~3/5, preferably 1/3~1/2.

In present invention process, step(2)In, loop back the second road reaction solution and the second reactor of second reactor The volume ratio that overall reaction generates liquid is 1/3~9/10, preferably 5/6~8/9.

In present invention process, through step(2)In sour gas after process, hydrogen sulfide content is 5-30 mg/Nm3.

In present invention process, the consumption of NaOH solution is design load, according to H in sour gas2S, CO2The fixation that content determines Value, according to the amount of sour gas, according to H in sour gas2NaOH solution amount needed for the complete Response calculation of S, design load is required NaOH The 80 ~ 99% of solution usage, preferably 85 ~ 95%.

In present invention process, because production process has fluctuation, the addition of NaOH solution needs to adjust at any time, and NaOH is molten The addition of liquid passes through step(2)In sour gas after process, hydrogen sulfide content is adjusted, and is added by adjusting valve regulation NaOH solution Enter amount it is ensured that through step(2)In sour gas after process, hydrogen sulfide content is 5-30 mg/Nm3, and ensureing H2S is up to standard In the case of discharge, NaOH solution is not excessive.

In present invention process, described sour gas is hydrogen sulfide containing gas, can be various sources containing H2S-acid gas, CO in sour gas2Volume fraction is less than 7%, preferably smaller than 5%.Described NaOH solution mass concentration is 20%~60%, preferably 32% ~38%.

In present invention process, in A reactor and second reactor, reaction temperature is 80 DEG C~95 DEG C, preferably 85 DEG C~ 90℃.

In present invention process, when A reactor and second reactor adopt rotary drill reactor, described revolving bed is anti- The rotating speed answering device revolving bed is 50~5000 revs/min, preferably 150~2000 revs/min.When reaction mass stops in reactor Between be 2~600 seconds, preferably 10~100 seconds.

Acidic Gas Treating technique of the present invention, controlling A reactor to discharge liquid phase is NaHS solution, and products pot is through analysis inspection After survey is qualified, starts through product pump carrying device, realize continuous discharge.

The present invention also provides a kind of Acidic Gas Treating device, and described device includes A reactor, second reactor, one-level Pans, two grades of pans and alkali liquor protective pot, wherein, A reactor and second reactor are respectively provided with gas phase entrance, gas Mutually outlet, liquid phase entrance and liquid-phase outlet, sour gas suction line is connected with the gas phase entrance of A reactor, A reactor Gaseous phase outlet be connected with the gas phase entrance of second reactor, and in the two connecting pipeline arrange make-up carrier gass pipeline, two grades The gaseous phase outlet of reactor is connected with alkali liquor protective pot gas phase entrance, and the gaseous phase outlet pipeline of second reactor is provided with sulfuration Hydrogen content detection means, alkali liquor protective pot gaseous phase outlet connects clean gas outlet pipeline, alkali liquor inlet pipeline and alkali liquor protective pot Liquid phase entrance connects, and alkali liquor protective pot liquid-phase outlet is connected with second reactor liquid phase entrance, second reactor liquid-phase outlet warp It is divided into two-way, a road is connected with A reactor liquid phase entrance, another road and second reactor liquid phase entrance after two grades of pans Connect;A reactor liquid-phase outlet is divided into three tunnels after one-level pans, goes out with A reactor liquid phase entrance, product respectively Expects pipe line, two grades of pans connect.

In Acidic Gas Treating device of the present invention, described A reactor and second reactor are gas-liquid mass transfer consersion unit, It is specially in bubbling column reactor, filler tower reactor, impact flow reactor, rotary drill reactor and venturi reactor Kind, preferably rotary drill reactor.

In Acidic Gas Treating device of the present invention, it is provided with poly- between alkali liquor protective pot gaseous phase outlet and clean gas outlet pipeline Knot device, described coalescer is cylindrical tube, and end socket includes upper cover and low head, internal setting cylindrical shape screen cloth, prevents net Activating QI entrainment.

In Acidic Gas Treating device of the present invention, A reactor, second reactor generate liquid and respectively enter one-level pans With two grades of pans, one-level pans and two grades of pans setting heat transmission equipments, pans temperature is controlled to be 85 DEG C~120 DEG C, It is preferably 90 DEG C~95 DEG C, prevent intermediate product from crystallizing.

In Acidic Gas Treating device of the present invention, alkali liquor protective pot is provided with level control device, according to alkali liquor protective pot liquid Position controls alkali liquor protective pot to generate liquid rate of discharge, prevents liquid level too low, and absorbing liquid pump evacuates short circuit, pump is caused damage, shadow Ring device stably to operate.

Compared with prior art, Acidic Gas Treating technique of the present invention and system have the advantage that:

1st, the Acidic Gas Treating technique of the present invention, using two-stage gas-liquid two-phase counter-current absorption course of reaction, is respectively provided with First order reaction and the self-loopa re-absorption operation of secondary response generation liquid, improve reaction depth, make material fully and sour gas Contact is it is ensured that NaHS liquid-phase product meets national product quality standard, Na in product NaHS2The content of S is less than 4%;By two grades Reaction mass circulates, and so that alkali liquor is fully contacted with remaining sour gas so that H in purified gas2S content is less than 30 mg/Nm3, really Protect the target of the existing qualified discharge of the weary QI excess after Acidic Gas Treating.

2nd, Acidic Gas Treating technique of the present invention, second reactor generates liquid composition and is mainly Na2S、NaHS、Na2CO3With NaHCO3, with excessive H after entrance A reactor2S reacts, and generates NaHS, CO simultaneously2Meeting is replaced out, enters with sour gas Enter second reactor, cause CO in second reactor2Concentration sharply increases, if directly contact with alkali liquor can cause in a large number Na2CO3And NaHCO3Produce, easy Crystallization Plugging pipeline, this technique is passed through in A reactor gaseous phase outlet and second reactor In gas phase entrance connecting pipeline, make-up carrier gass pipeline is set, introduces make-up carrier gass, greatly reduce sour gas concentration, especially acid CO in property gas2Concentration, most of CO2It is carried over device together with carrier gas, control Na2CO3And NaHCO3Content, prevent produce A large amount of Na2CO3Cause to crystallize, blocking pipeline is it is ensured that device long-term operation.

3rd, Acidic Gas Treating technique of the present invention, using three-level gas-liquid two-phase counter-current absorption course of reaction.By arranging three-level Alkali liquor protective pot is it is ensured that alkali liquor and sour gas are fully contacted reaction so that H in purified gas2S content is less than 30 mg/Nm3It is ensured that The target of the existing qualified discharge of the weary QI excess after Acidic Gas Treating.

4th, Acidic Gas Treating technique of the present invention, is respectively provided with first order reaction generation liquid and secondary response generates certainly following of liquid Ring re-absorption operation, improves reaction depth, so that material is fully contacted it is ensured that NaHS liquid-phase product meets state's family property with sour gas Quality standard, Na in product NaHS2The content of S is less than 4%;By secondary response Matter Transfer, make alkali liquor abundant and remaining Sour gas contact is so that H in purified gas2S content is less than 30 mg/Nm3It is ensured that the existing qualified discharge of the weary QI excess after Acidic Gas Treating Target.By the liquid-phase product NaHS solution obtaining first order reaction, loop back two grades of pans and use as diluent, tool There iss buffer, reduce secondary response and generate the Na in liquid2S concentration, prevents Na2S crystallization separates out it is ensured that device length is all Phase is run.

5th, Acidic Gas Treating system of the present invention adopt high-gravity rotating bed as gas-liquid reactor, can achieve improve mass transfer with The target of reaction efficiency, rotary drill reactor is that efficient mass transfer equipment is quickly carried out it is ensured that reacting, 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 greatly reduces.And by CO in sour gas2When reacting with NaOH, generate nano level Na2CO3Crystalline solid, from And prevent Na during fluid conveying2CO3Crystalline solid blocks pipeline.Material, on the bed assembly inwall of high-speed rotation, forms and acutely hits Hit, realize strengthening mixing;Material, when flowing through bed, is constantly cut into drop, brin and liquid film by bed, greatly achieves The Surface Renewal of high-viscosity material with mix, eliminate concentration difference it is ensured that generate nano level Na2CO3Crystalline solid.

6th, two-stage countercurrent absorption technique of the present invention and device are particularly suited for processing small-sized sour gas, with prior art Compare, equipment scale is little, energy consumption is low, operating cost is few, generate the NaHS product that can be used for the industries such as printing and dyeing, papermaking, be easy to Transport, and have certain market value.

Brief description

Fig. 1 is that sour gas of the present invention produces NaHS technique and schematic device.

Specific embodiment

Sour gas of the present invention produces NaHS technique and device, with NaOH solution as absorbing liquid, processes oil plant acid Gas produces NaHS product, using three-level gas-liquid two-phase counter-current absorption course of reaction.It is respectively provided with first order reaction and secondary response life Become liquid self-loopa re-absorption operation;Product liquid is recycled to the second order reaction and uses as diluent.

The present invention provides a kind of sour gas to produce NaHS device, and described device includes A reactor 3, secondary response Device 4,2, two grades of pans 5 of one-level pans, alkali liquor protective pot 8 and coalescer 6, wherein, A reactor 3 and second reactor 4 are respectively provided with gas phase entrance, gaseous phase outlet, liquid phase entrance and liquid-phase outlet, the gas of sour gas suction line 1 and A reactor Phase entrance connects, and the gaseous phase outlet of A reactor is connected with the gas phase entrance of second reactor, and in the two connecting pipeline Setting make-up carrier gass pipeline 11, the gaseous phase outlet of second reactor is connected with alkali liquor protective pot gas phase entrance, second reactor Hydrogen sulfide content detection means 16 is provided with gaseous phase outlet pipeline, alkali liquor protective pot gaseous phase outlet connects after coalescer 6 only Activating QI outlet line 13, alkali liquor protective pot arranges level control device 17, alkali liquor inlet pipeline 12 and alkali liquor protective pot liquid phase Entrance connects, and alkali liquor protective pot liquid-phase outlet is connected with second reactor liquid phase entrance, and second reactor liquid-phase outlet is through two grades It is divided into two-way, a road 10 is connected with A reactor liquid phase entrance after pans 5;Another road 14 and second reactor liquid phase entrance Connect;A reactor liquid-phase outlet is divided into three tunnels after one-level pans 2, and a road 7 is connected with product discharge pipeline, the second tunnel 9 are connected with two grades of pans, and the 3rd tunnel 15 is connected with A reactor liquid phase entrance.

Acidic Gas Treating technique of the present invention, the sour gas from sour gas suction line 1 initially enters A reactor, with From the generation liquid haptoreaction of second reactor, sour gas after A reactor 3 is processed with from make-up carrier gass pipe The carrier gas of line 11 enters second reactor 4 together, contacts hybrid reaction with the solution from alkali liquor protective pot 8, reacted acid Property gas enter after alkali liquor protective pot removes surplus hydrogen sulfide therein further, after coalescer 6 demisting, by clean gas outlet Pipeline 13 qualified discharge;Secondary response generates liquid and enters two grades of pans 5, is then divided into two-way, and wherein one tunnel 14 is inhaled by two grades Receive liquid pump conveying and loop back second reactor 4, be circulated flowing, realize depth and absorb;Another road 10 is inhaled as first order reaction Receipts liquid is delivered to A reactor 3 by pump and is reacted with sour gas.First order reaction generates liquid and enters one-level pans 2, then It is divided into three tunnels, the first via 7 is delivered in finished pot by pump;Second tunnel 9, by being pumped in two grades of pans, makes as diluent With there is the effect of buffer, thus reducing the Na in secondary response liquid2S concentration, prevents Na2S crystallization separates out, the second tunnel 15 By being pumped in A reactor, it is circulated absorption so that material reaction fully, realizes the absorption of absorbing liquid depth.

Acidic Gas Treating technique of the present invention includes three below process:

(1)A reactor

In A reactor, dominant response is as follows:Undressed sour gas and secondary response generate liquid(NaHS、 Na2CO3、NaHCO3, Na2S)Reacted, in H2In the case of S excess, secondary response generates the Na in liquid2CO3、NaHCO3、 Na2S respectively with H2S reacts, and generates NaHS solution.The NaHS solution generating divides three tunnels, and the first via is delivered in products pot by pump; Secondary route is pumped back in A reactor, is circulated absorption so that material reaction fully, realizes the suction of absorbing liquid depth Receive;3rd route is pumped back in second reactor, uses as diluent, has the effect of buffer, thus reducing two Level generates the Na in liquid2S concentration, prevents Na2S crystallization separates out.

(2)Second reactor

The main reaction of second reactor is as follows:Gas phase is " weary gas " and the make-up carrier gass of first order reaction gas phase, wherein H2S Concentration substantially reduces, but still is not reaching to discharge standard;Secondary response liquid phase generates liquid and first order reaction for alkali liquor protective pot Generate the mixed solution of liquid.Through reacting further, gas phase is purified, and generates certain density Na2S solution, by two grades Recycle liquid pump is delivered to A reactor and continues reaction as absorbing liquid.

Carry CO due in sour gas charging secretly2Component, second reactor generates liquid composition and is mainly NaHS, Na2S、Na2CO3 And NaHCO3, with excessive H after entrance A reactor2S reacts, and generates NaHS, CO simultaneously2Meeting is replaced out, with sour gas Enter second reactor, cause CO in second reactor2Concentration sharply increases, if directly contact with alkali liquor can cause in a large number Na2CO3And NaHCO3Produce, easy Crystallization Plugging pipeline, this technique is passed through in A reactor gaseous phase outlet and second reactor In gas phase entrance connecting pipeline, make-up carrier gass pipeline is set, introduces make-up carrier gass, greatly reduce sour gas concentration, especially acid CO in property gas2Concentration, most of CO2It is carried over device together with carrier gas, control Na2CO3And NaHCO3Content, prevent produce A large amount of Na2CO3Cause to crystallize, blocking pipeline is it is ensured that device long-term operation.

(3)Alkali liquor protective pot

The reaction that alkali liquor protective pot mainly occurs is as follows:Gas phase is the reacted gas of second reactor, with fresh NaOH Solution is absorbing liquid, in H2In the case that S is micro, NaOH and and H2S reacts, and generates a small amount of Na2S.Ensure purified gas row up to standard Put, the liquid phase part of generation is delivered to second reactor as absorbing liquid by pump and continues reaction.

The reaction effect of the present invention is described with reference to embodiment, but does not therefore limit the scope of the invention.

Embodiment 1

Using process unit as shown in Figure 1, with sour gas and mass concentration be 35% alkali liquor as raw material, reacted. CO in sour gas2Volume fraction is 7%, H2S volume fraction is 92%, and hydro carbons volume fraction is 1%.

In the embodiment of the present invention, A reactor and second reactor adopt rotary drill reactor, one-level rotating bed reaction In device and two grades of rotary drill reactors, reaction temperature is 85 DEG C.One-level pans and two grades of pans temperature are 90 DEG C.Revolving bed Rotating speed be 1500 revs/min.Reaction mass time of staying in reactor is 10 seconds.

In present invention process, step(1)In, loop back the second road reaction solution and the one-level of one-level rotary drill reactor The volume flow ratio that rotary drill reactor overall reaction generates liquid is 1:2;Step(1)In, loop back the 3rd tunnel of two grades of pans Reaction solution is 1 with the volume flow ratio of the overall reaction generation liquid of one-level rotary drill reactor:3;Step(2)In, loop back Second road reaction solution of two grades of rotary drill reactors and the volume flow ratio of two grades of rotary drill reactor overall reaction generation liquid For 5:6.

In present invention process, step(2)In, through step(1)Reacted sour gas and make-up carrier gass be mixed into Enter two grades of rotary drill reactors, described make-up carrier gass are low-pressure gas, make-up carrier gass and total acidic air volume ratio is for 2:1, instead 1 should be the results are shown in Table.

Comparative example 1

Same as Example 1, difference generates liquid for first order reaction and is not recycled to two grades of pans, and reaction result is shown in Table 1.

Comparative example 2

Identical with comparative example 1, difference charges gas pipeline for of no help, and reaction result is shown in Table 1.

Table 1 embodiment and comparative example reaction result

Embodiment 1 Comparative example 1 Comparative example 2 NaHS product design 40% 41% 41% Na2S content <3% <4% <4% H in purified gas2S content(mg/Nm3 25 30 30 Device service cycle 650h 450h 400

Claims (29)

1. a kind of sour gas produces NaHS technique, with NaOH solution as absorbing liquid, processes sour gas and produces NaHS, including such as Lower step:
(1)Sour gas enters A reactor, contacts with the reaction solution of second reactor and is reacted, reaction solution divides For three tunnels, as product discharge, the second tunnel return A reactor cyclic absorption, the 3rd tunnel returns to two grades of centres to the first via Tank;
(2)Through step(1)Reacted sour gas enters second reactor together with make-up carrier gass, anti-with alkali liquor protective pot Liquid contact should be generated reacted;Reaction solution is divided into two-way, and the first via enters A reactor, the second tunnel as absorbing liquid Loop back second reactor;
(3)Through step(2)Reacted sour gas is entered alkali liquor protective pot and is reacted with NaOH solution, reacted sour gas row Put, reaction solution enters second reactor;
Wherein, described make-up carrier gass are the arbitrary gas not reacted with sour gas and NaOH solution, specially low-pressure gas, nitrogen In gas, noble gases any one.
2. according to the technique described in claim 1 it is characterised in that:Make-up carrier gass and total acidic air volume are than for 1:1~3:1.
3. according to the technique described in claim 2 it is characterised in that:Make-up carrier gass and total acidic air volume are than for 1.5:1~2: 1.
4. according to the technique described in claim 1 it is characterised in that:Described A reactor and second reactor 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 of device.
5. according to the technique described in claim 4 it is characterised in that:Described A reactor and second reactor are that revolving bed is anti- Answer device.
6. according to the technique described in claim 1 it is characterised in that:Step(1)In, the second tunnel looping back A reactor is anti- The volume ratio that liquid should be generated with A reactor overall reaction generation liquid is 1/3~9/10.
7. according to the technique described in claim 6 it is characterised in that:Step(1)In, the second tunnel looping back A reactor is anti- The volume ratio that liquid should be generated with A reactor overall reaction generation liquid is 1/2~4/5.
8. according to the technique described in claim 1 it is characterised in that:Step(1)In, the 3rd tunnel looping back two grades of pans is anti- The volume ratio that liquid should be generated with the overall reaction generation liquid of A reactor is 1/4~3/5.
9. according to the technique described in claim 8 it is characterised in that:Step(1)In, the 3rd tunnel looping back two grades of pans is anti- The volume ratio that liquid should be generated with the overall reaction generation liquid of A reactor is 1/3~1/2.
10. according to the technique described in claim 1 it is characterised in that:Step(2)In, loop back the second tunnel of second reactor The volume ratio that reaction solution and second reactor overall reaction generate liquid is 1/3~9/10.
11. according to the technique described in claim 10 it is characterised in that:Step(2)In, loop back the second tunnel of second reactor The volume ratio that reaction solution and second reactor overall reaction generate liquid is 5/6~8/9.
12. according to the technique described in claim 1 it is characterised in that:Through step(2)In sour gas after process, hydrogen sulfide contains Measure as 5-30 mg/Nm3.
13. according to the technique described in claim 1 it is characterised in that:The addition of NaOH solution passes through step(2)After process In sour gas, hydrogen sulfide content is adjusted, by adjusting valve regulation NaOH solution addition it is ensured that through step(2)Acid after process Property gas in hydrogen sulfide content be 5-30 mg/Nm3, and ensureing H2In the case of S qualified discharge, NaOH solution is not excessive.
14. according to the technique described in claim 1 it is characterised in that:Described sour gas is the hydrogen sulfide containing gas in various sources Body, wherein CO2Volume fraction be less than 7%.
15. according to the technique described in claim 1 it is characterised in that:Described NaOH solution mass concentration is 20%~60%.
16. according to the technique described in claim 15 it is characterised in that:Described NaOH solution mass concentration is 32%~38%.
17. according to the technique described in claim 1 it is characterised in that:In A reactor and second reactor, reaction temperature is 80 DEG C~95 DEG C.
18. according to the technique described in claim 17 it is characterised in that:In A reactor and second reactor, reaction temperature is 85 DEG C~90 DEG C.
19. according to the technique described in claim 1 it is characterised in that:When A reactor and second reactor adopt revolving bed During reactor, the rotating speed of the revolving bed of one-level rotary drill reactor and two grades of rotary drill reactors is 50~5000 revs/min.
20. according to the technique described in claim 19 it is characterised in that:One-level rotary drill reactor and two grades of rotary drill reactors Revolving bed rotating speed be 150~2000 revs/min.
21. according to the technique described in claim 1 it is characterised in that:When A reactor and second reactor adopt revolving bed During reactor, reaction mass time of staying in one-level rotary drill reactor and two grades of rotary drill reactors is 2~600 seconds.
22. according to the technique described in claim 21 it is characterised in that:Reaction mass is in one-level rotary drill reactor and two grades of rotations In rotated bed reactor, the time of staying is 10~100 seconds.
23. according to the technique described in claim 1 it is characterised in that:Step(3)Sour gas after process is further through coalescer Discharge after demisting.
24. adopt the sour gas described in any claim in claim 1 to 23 to produce the device of NaHS technique, and it is special Levy and be:Described device includes A reactor, second reactor, one-level pans, two grades of pans and alkali liquor protective pot, its In, A reactor and second reactor are respectively provided with gas phase entrance, gaseous phase outlet, liquid phase entrance and liquid-phase outlet, sour gas Suction line is connected with the gas phase entrance of A reactor, the gas phase entrance of the gaseous phase outlet of A reactor and second reactor Connect, and make-up carrier gass pipeline, the gaseous phase outlet of second reactor and alkali liquor protective pot gas phase are arranged on the two connecting pipeline Entrance connects, and the gaseous phase outlet pipeline of second reactor is provided with hydrogen sulfide content detection means, alkali liquor protective pot gas phase goes out Mouth connects clean gas outlet pipeline, and alkali liquor inlet pipeline is connected with alkali liquor protective pot liquid phase entrance, alkali liquor protective pot liquid-phase outlet It is connected with second reactor liquid phase entrance, second reactor liquid-phase outlet is divided into two-way after two grades of pans, a road and one-level Reactor liquid phase entrance connects, and another road is connected with second reactor liquid phase entrance;A reactor liquid-phase outlet is through in one-level Between be divided into three tunnels after tank, be connected with A reactor liquid phase entrance, product discharge pipeline, two grades of pans respectively.
25. according to the device described in claim 24 it is characterised in that:Alkali liquor protective pot gaseous phase outlet and clean gas outlet pipeline Between be provided with coalescer, described coalescer is cylindrical tube, and end socket includes upper cover and low head, the cylindric sieve of internal setting Net.
26. according to the device described in claim 24 it is characterised in that:Described A reactor and second reactor pass for gas-liquid Qualitative response equipment, specially bubbling column reactor, filler tower reactor, impact flow reactor, rotary drill reactor and venturi One of reactor.
27. according to the device described in claim 26 it is characterised in that:Described A reactor and second reactor are revolving bed Reactor.
28. according to the device described in claim 24 it is characterised in that:Alkali liquor protective pot is provided with level control device.
29. according to the device described in claim 24 it is characterised in that:One-level pans and two grades of pans setting heat exchange set Standby.
CN201410046322.XA 2014-02-10 2014-02-10 A kind of sour gas produces NaHS technique and device CN104826463B (en)

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CN106669391B (en) * 2015-11-05 2019-03-19 中国石油化工股份有限公司大连石油化工研究院 A kind of purification process technique of high concentrate NOx technology tail gas
CN106669383B (en) * 2015-11-05 2019-03-19 中国石油化工股份有限公司大连石油化工研究院 The processing method of the process tail gas containing NOx
CN106669390B (en) * 2015-11-05 2019-03-19 中国石油化工股份有限公司大连石油化工研究院 A kind of denitration process method of the process tail gas containing NOx
CN106669389B (en) * 2015-11-05 2019-03-19 中国石油化工股份有限公司大连石油化工研究院 A kind of processing method of the process tail gas containing NOx
CN106430388A (en) * 2016-08-24 2017-02-22 四川恒成钾盐化工有限公司 Technology for removing and recovering hydrogen sulfide in brine
CN108067089B (en) * 2016-11-11 2019-08-06 中国石油化工股份有限公司抚顺石油化工研究院 A kind of method and apparatus producing NaHS

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