CN109529578B

CN109529578B - Process device and process method for liquid-phase reaction desulfurization of hydrogen sulfide and sulfur dioxide

Info

Publication number: CN109529578B
Application number: CN201710857845.6A
Authority: CN
Inventors: 李磊; 齐慧敏; 王海波; 金平; 方向晨; 刘炬; 石平利; 王昊辰
Original assignee: China Petroleum and Chemical Corp; Sinopec Dalian Research Institute of Petroleum and Petrochemicals
Current assignee: Sinopec Dalian Petrochemical Research Institute Co ltd; China Petroleum and Chemical Corp
Priority date: 2017-09-21
Filing date: 2017-09-21
Publication date: 2021-07-09
Anticipated expiration: 2037-09-21
Also published as: CN109529578A

Abstract

A process device and a process method for liquid-phase reaction desulfurization of hydrogen sulfide and sulfur dioxide comprise a reactor and a separator, wherein the reactor is sequentially provided with a tail gas absorption area, a reaction area and a settling area from top to bottom; the settling zone is connected with the separator, and the other end of the separator is connected to the top of the tail gas absorption zone of the reactor; the reaction zone is provided with a gas pipe which consists of a gas main pipe and a gas branch pipe, all pipelines in the gas pipe are mutually communicated, and two ends of the main pipe II are closed. The device is used for carrying out desulfurization reaction of hydrogen sulfide and sulfur dioxide, and the reaction solution comprises water and at least one organic alkaline compound which can be dissolved in water, so that the pH value of the solution is more than or equal to 7.2. The device and the method can ensure that the reaction gas entering the reactor forms the injection with a certain radian, promote the self-stirring of the liquid, are beneficial to the uniform dispersion of the gas in the reaction solution, and greatly increase the dissolution rate and the reaction rate of the gas in the reaction solution; the response time of the reaction of the hydrogen sulfide and the sulfur dioxide is below 15s, the reaction condition is mild, the obtained sulfur does not need to be refined, the purity is high, the equipment is simple and easy to process, the investment is low, and the operation is safe.

Description

Process device and process method for liquid-phase reaction desulfurization of hydrogen sulfide and sulfur dioxide

Technical Field

The invention relates to a process device for liquid-phase reaction desulfurization of hydrogen sulfide and sulfur dioxide and a method for desulfurization by using the process device, belonging to the field of industrial production or industrial waste gas purification.

Background

Because of the economic development of China, the demand of crude oil is continuously reduced, and the domestic crude oil is not enough to meet the national demand, so that imported crude oil is continuously input into China. 38101 million tons of crude oil imported from China in 2016, 1-12 months, are increased by 13.6% compared with the same period in the last year. Along with the annual increase of the imported crude oil quantity in China, the proportion of the high-sulfur crude oil is larger and larger, a series of high-sulfur crude oil processing technologies are developed for various large oil refining enterprises, and the high-sulfur crude oil generates a large amount of H in the processing processes of hydrofining, hydrocracking, catalytic cracking and the like₂S acid gas and SO₂The flue gas of (1).

For containing SO₂The treatment of the flue gas is divided into a dry method, a semi-dry method and a wet method, and the wet method has the advantages of high desulfurization rate, reliable device operation, simple operation and the like, so the existing flue gas desulfurization technology of various countries in the world mainly takes wet method desulfurization as a main technology. The traditional wet desulphurization technology mainly comprises a limestone-gypsum method, a double alkali desulphurization method, a sodium alkali desulphurization method, an ammonia desulphurization method and the like.

For containing H₂The treatment of S acid gas is currently two recovery techniques which are commonly used in industry,one is catalytic oxidation with a fixed bed, the most common method being the claus process; another is the LO-CAT process developed by Merichem Gas Technology Products (GTP).

Conventional claus plants consist of a high temperature section and two or three conversion sections. The high temperature section comprises H₂S combustion furnace and waste heat boiler, the Claus process using H in gas₂S in a Claus furnace, reacting H₂Partial oxidation of S to SO₂The combustion reaction equation is H₂S+1.5O₂→SO₂+H₂O, H of about 1/3₂S reacts with air at about 1200 ℃ in a combustion furnace to generate SO₂The rest of unreacted H₂S and SO₂The Claus reaction is continuously completed in the conversion section with lower temperature by means of the catalyst to generate sulfur. The reaction equation in the Claus converter is 2H₂S+SO₂→3S+2H₂O。

The reaction process of the LO-CAT process is carried out in a weakly alkaline liquid phase system, and H is subjected to reaction by using a chelated iron catalyst₂S is converted into elemental sulfur. The reaction principle is as follows: h₂S gas is dissolved in water and ionized into H⁺And HS^-：H₂S→H⁺+HS^-. Catalyst Fe in solution³⁺And HS^-Oxidation-reduction reaction occurs, HS^-Is converted into elemental sulfur, Fe³⁺Is reduced to Fe²⁺：HS^-+2Fe³⁺→S+2Fe²⁺+H⁺. The process adopts air (oxygen) as a regeneration medium of the iron catalyst to convert Fe²⁺Oxidation to Fe³⁺The activity of the catalyst is recovered by the following steps: 2Fe²⁺+1/2O₂+H₂O→2Fe³⁺+2OH^-. The general chemical reaction equation is: h₂S+1/2O₂→S+H₂O

The LO-CAT process can only treat the H-containing gas₂Acid gas of S, H₂S is converted into elemental sulfur. Claus process and various improved Claus processes for H in raw material gas₂S content is required, H in raw material gas₂The S content is at least more than 10 percent,if H is present in the feed gas₂If the S content is lower, the product is concentrated and enters a Claus device; because the Claus process adopts a combustion method to treat H₂S, so that the gas to be treated cannot directly enter a Claus combustion furnace if it is flammable, and H must be purified by an amine purification process or the like₂S is removed and then enters a Claus furnace; the Claus process requires first reacting H₂Partial oxidation of S to SO₂Then the two react to generate sulfur, because the desulfurization efficiency of the Claus process is limited, a plurality of reactors are required to carry out cascade reaction, and the reaction temperature is higher; with the more and more severe environmental emission indexes, a Claus tail gas treatment device must be matched to meet the environmental protection requirement. In addition, the LO-CAT process and the Claus process can only treat the gas containing H₂S acid gases are difficult to treat H simultaneously₂S gas and SO₂Gases, to address the deficiencies of both processes, have developed some that can simultaneously treat H-containing gases₂S and SO₂And (3) processing of gas.

From the Nissan corporation, CN86101352, a Claus reaction in pure water without any additives is disclosed, H being carried out when the pH of the aqueous medium in the reactor is below 2₂S and SO₂The reaction of liquid phase to sulfur is the most intense, so the reaction pressure is adopted>5kg/cm²(gauge pressure), pH value<2. Temperature of>The liquid-phase Claus reaction is carried out at 120 ℃ to recover the sulfur.

CN201310546164.X discloses a method for treating hydrogen sulfide gas by using water mist and water vapor as catalysts, wherein H is treated by using water mist and water vapor as catalysts₂S and SO₂The reaction is carried out, the optimal reaction temperature is 50-60 ℃, and the conversion rate of sulfur can reach about 90%.

CN201310071884.5 discloses a catalytic system for desulfurization treatment of industrial sulfur-containing waste gas and a process thereof, wherein the catalytic system comprises polyol, an acidic catalyst and water, a low-temperature water phase reaction is adopted in the reaction process, and two streams of the catalytic system respectively contain H₂S and SO₂The total sulfur removal rate is improved to 99.95 percent by treating the waste gas.

CN201610841891.2 discloses a preparation method of a sulfur nanoparticle dispersion liquidProcess for carrying out H predominantly in the solution phase₂S and SO₂The solution phase is water or a mixed solution of a small molecular organic solvent which is easy to dissolve in water and water, and the added small molecular organic solvent is ethanol, methanol, dimethylformamide and the like, so that the obtained sulfur nanoparticles have better dispersion stability; the reaction temperature of the system is 40-80 ℃, and the solution phase is in a stirring state in the reaction process so as to ensure that H is in a stirring state₂S and SO₂The sulfur nanoparticles are mixed in the solution phase sufficiently and uniformly to obtain a sulfur nanoparticle dispersion liquid having a small and uniform size as a sulfur active material for secondary power source technology (lithium sulfur batteries, etc.).

CN201110075021.6 discloses a catalyst containing H₂The desulfurization method of S mixed gas comprises the step of reacting H-containing gas at 0-80 DEG C₂S and SO₂The mixed gas is introduced into a spray absorption tower or a spray absorption tower filled with the tetramethylguanidine hydroxy acid salt composite desulfurizer to circulate, and the two gases react in a liquid phase to generate sulfur.

Korean institute of science and technology in CN200580018462.5 discloses a method for simultaneously removing H₂S and SO₂The mixed gas is contacted with water or an aqueous solution containing a first heterogeneous catalyst for desulfurization to utilize SO₂To oxidize H₂S, the treatment efficiency of the tail gas containing 3-5% of sulfur can reach more than 99%.

French oil company applied for a series of applications containing H₂S and SO₂A method and an apparatus for treating a mixed gas, disclosed in CN200610058953.9, wherein the temperature of the mixed gas in contact with a solvent containing a catalytic system is 20 to 160 ℃, the catalytic system at least contains a compound having at least one functional group a composed of a carboxylic acid functional group and at least one functional group B having at least one nitrogen atom and undergoing an acid-base reaction with the at least one functional group a under the conditions for carrying out the method; CN97120663.5, CN96196144.9 and CN97120546.9 disclose respectively the synthesis of a compound containing H₂S and SO₂A method and apparatus for treating a mixed gas.

In the above-disclosed patent, H₂S and SO₂In pure waterThe pressure, temperature and pH value required by the medium reaction are very harsh, buffer solution or catalyst is required to be added in the organic solvent or aqueous solution for reaction so as to keep the organic solvent or aqueous solution acidic, the stronger the acidity (the lower the pH value) is, the more beneficial the reaction is, and the buffer solution or catalyst is required to be supplemented periodically during the operation of the device so as to keep the acidic condition required by the reaction, so that the operation cost of the device is increased; because the obtained liquid-phase sulfur solution contains buffer solution or catalyst, the purity of the sulfur product can not meet the market demand, and a sulfur refining device is matched to improve the purity of the sulfur product.

Disclosure of Invention

In the prior art, the reaction conditions of hydrogen sulfide and sulfur dioxide in a liquid phase are harsh, a catalyst or a buffer solution is generally needed, side reactions are easily generated in the process, the obtained sulfur product has more impurities, and the refining is difficult.

In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:

the technical purpose of the first aspect of the invention is to provide a process unit for liquid-phase reaction desulfurization of hydrogen sulfide and sulfur dioxide, which comprises a reactor and a separator, wherein the reactor is sequentially provided with a tail gas absorption area, a reaction area and a settling area from top to bottom; the settling zone is connected with the separator, and the other end of the separator is connected to the top of the tail gas absorption zone of the reactor; the reaction zone is provided with the gas pipe, and it is fixed in on the reactor, the gas pipe is responsible for and the gas branch pipe is constituteed by gas, the gas is responsible for and is responsible for the T-pipe that II are constituteed by being responsible for I and being responsible for, is responsible for I opening on the reaction zone wall, and the level extends to reactor center and communicates and is responsible for II, is responsible for II and sets up in reactor center and perpendicular to and is responsible for I, be responsible for II and be connected with a plurality of groups of gas branch pipes from top to bottom, every group gas branch pipe extends and symmetric distribution to the wall along the horizontal direction, each pipeline communicates each other in the gas pipe, and it seals to be.

In the process device, 1-6 groups, preferably 2-4 groups, of the gas branch pipes are further arranged.

In the process device, furthermore, each group of gas branch pipes is provided with 2-8 branch pipes, and each branch pipe is an arc-shaped pipe. The design of the arc-shaped pipe is beneficial to forming a driving force for the reaction solution after the reaction gas is sprayed out of the arc-shaped pipe, so that the reaction solution is promoted to rotate in the reactor to form a self-stirring effect, the dissolution of the gas in the reaction solution can be greatly increased, the gas is uniformly dispersed, and the reaction rate is improved.

In the process device, further, the ratio of the diameter of the tail gas absorption area to the diameter of the reaction area is 0.1: 1-1: 1, and the tail gas absorption area and the reaction area are connected through the conical reducing pipe when the diameter of the tail gas absorption area is smaller than that of the reaction area.

In the above process unit, further, trays and/or packing are disposed in the off-gas absorption zone. The tray is provided with at least one layer, and the tray with excellent anti-blocking performance is selected from at least one of a float valve tray, a sieve tray, a guide sieve tray, a tongue fixing tray, a float tongue tray and a three-dimensional mass transfer tray; the filler is selected from at least one of Raschig ring filler, pall ring filler, intalox saddle filler, arc saddle filler, metal ring intalox saddle filler, stepped ring filler, nano ring filler, corrugated plate filler and grid filler.

In the above process apparatus, further, the settling zone is cylindrical, dished, hemispherical, ellipsoidal or inverted conical, preferably hemispherical, ellipsoidal or inverted conical, and most preferably inverted conical.

The technical purpose of the second aspect of the invention is to provide a process method for liquid-phase reaction desulfurization of hydrogen sulfide and sulfur dioxide by using the process device, wherein a gas containing hydrogen sulfide and a gas containing sulfur dioxide are introduced into a reaction zone through a gas pipe, the reaction zone and a settling zone are filled with a reaction solution, the reaction solution comprises water and at least one organic alkaline compound capable of being dissolved in water, and the organic alkaline compound enables the pH value of the solution to be more than or equal to 7.2; the sulfur generated by the reaction of the hydrogen sulfide and the sulfur dioxide is deposited in a settling zone and enters a separator, the sulfur and the reaction solution are obtained through liquid-solid separation, the reaction solution flows back to the top of a tail gas absorption zone and is in countercurrent contact with the reaction tail gas in the reaction zone, the unreacted reaction gas enters the reaction zone after being absorbed, and the absorbed tail gas is discharged.

In the process method, the pH value of the reaction solution in the reaction zone is preferably 7.2-13.0; more preferably, the pH value is 8.0 to 12.0, most preferably 8.0 to 10.0.

In the process, as a further preference, the mass fraction of the organic alkaline compound in the reaction solution in the reaction zone is 0.1-30% by weight of the total weight of the reaction solution; preferably 2% -30%; more preferably 5% to 20%.

In the above process, the organic basic compound selected has a solubility in water of 0.1g/100g or more, preferably 1g/100g or more.

In the above-mentioned process, it should be noted that the organic alkaline compound in the solution is widely selected, and can be dissolved in water in principle, and has a certain solubility in water, so that the organic alkaline compound which makes the solution alkaline can promote the desulfurization reaction, and those organic alkaline compounds which can be mutually dissolved with water in any proportion can achieve better effect.

In the above process, as a further preference, the organic basic compound is selected from compounds having a structural formula containing at least 1 nitrogen atom; preferably a compound having a structural formula containing 1 to 3 amino nitrogens, more preferably a compound having 1 or 2 amino nitrogens.

In the above process, as a further preference, the organic basic compound is selected from at least one of the following compounds: hydroxylamine, C1-C10 aliphatic amines, C1-C10 alcamines, C1-C10 alicyclic amines, C6-C10 aromatic amines, pyridine derivatives, imidazole derivatives, pyrazine derivatives, pyrazole or pyrazole derivatives.

Furthermore, the pyridine derivative, the imidazole derivative, the pyrazine derivative or the pyrazole derivative is a derivative in which H in pyridine, imidazole, pyrazine or pyrazole is substituted by alkyl, amino, alkylamino, hydroxyl or alkyl alcohol. The alkyl group in the alkyl group, the alkyl amino group and the alkyl alcohol is a C1-C3 alkyl group.

In the above process, the aliphatic amine is preferably a C1-C6 aliphatic amine; the alcohol amine is C1-C6 alcohol amine, the alicyclic amine is C1-C6 alicyclic amine, and the aromatic amine is C6-C8 aromatic amine.

In the above process, as a more specific embodiment, the organic basic compound is selected from the group consisting of hydroxylamine, trimethylamine, ethylenediamine, 1, 2-propanediamine, 1, 3-propanediamine, ethanolamine, diethanolamine, triethanolamine, diglycolamine, isopropanolamine, N-methyldiethanolamine, N-dimethylethanolamine, N, at least one of N-diethylethanolamine, benzylamine, o-xylylenediamine, m-xylylenediamine, p-xylylenediamine, tetrahydropyrrole, 1-methyl-3-pyrrolidinol, piperidine, morpholine, triethylenediamine, diethylenetriamine, piperazine, 2-methylpiperazine, pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, pyrazine, hydroxypyrazine, aminopyrazine, methylpyrazine, imidazole, and pyrazole.

It will be understood by those skilled in the art that in the desulfurization reaction of hydrogen sulfide and sulfur dioxide, the pressure and temperature increase is favorable for the reaction under the liquid phase environment, and in the past research, the conditions for the liquid phase desulfurization reaction are harsh, and it is generally necessary to increase the reaction temperature and the reaction pressure. However, in the method of the present invention, there is no special requirement for the temperature and pressure of the reaction of hydrogen sulfide and sulfur dioxide for desulfurization, and from the viewpoint of energy saving, the hydrogen sulfide and sulfur dioxide can be easily reacted in the reaction system of the present invention under normal temperature and pressure. As a new reaction system, the invention still gives suitable reaction temperature and pressure: the temperature is 0-90 ℃, and preferably 20-35 ℃; the reaction pressure is 0.1 to 5MPa, preferably 0.1 to 1.5MPa, and more preferably normal pressure.

In the above process, as a further preferred,h in the introduced reaction gas₂S or SO₂The volume fractions of (A) are respectively 0.1-100%, preferably 3-100%, and more preferably 10-100%; in the above process, the gas containing hydrogen sulfide is mainly derived from industrial tail gas such as petroleum refining, coal chemical industry, natural gas treatment, fine chemical industry, paper making, pharmacy, fertilizer, sewage treatment, geothermal power generation, and the like, and includes but is not limited to pure hydrogen sulfide gas, refinery acid gas, claus tail gas, natural gas purified tail gas, and the above concentrated gas, and the like. The sulfur dioxide-containing gas includes but is not limited to pure sulfur dioxide gas, S-Zorb device regeneration flue gas, sulfuric acid production tail gas, coal-fired boiler flue gas, coal-fired power plant flue gas, catalytic cracking catalyst regeneration flue gas, process heating furnace flue gas, coking flue gas, steel sintering flue gas, concentrated flue gas and the like.

Furthermore, the theoretical reaction ratio of hydrogen sulfide to sulfur dioxide in the reaction gas is 2:1, and in the process method, the hydrogen sulfide and the sulfur dioxide are preferably introduced according to the ratio of 0.1: 1-5: 1, and more preferably 1: 1-3: 1; most preferably in a 2:1 ratio. If the aim of removing hydrogen sulfide is to remove hydrogen sulfide, introducing sulfur dioxide-containing gas in a slight excess amount according to the reaction proportion; if the aim is to remove sulfur dioxide, a gas containing hydrogen sulfide is introduced in a slight excess amount according to the reaction proportion.

In the above process, the hydrogen sulfide-containing gas and the sulfur dioxide-containing gas may be mixed in advance and then introduced into the reactor together, or one of the reaction gases may be introduced first for a certain period of time, and after a certain amount of dissolution has been achieved in the reaction solution, the other gas may be introduced. Wherein, one reaction gas is preferably introduced firstly to ensure that the pH of the reaction solution in the reactor is slightly acidic (the pH range is less than 7.0), and then another reaction gas is introduced, so that the reaction between the two gases can be carried out more quickly and effectively; accordingly, an in-line pH detector is preferably provided in the reactor.

In the above process, it should be noted that, during the reaction, the sulfur particles generated in the reaction zone are deposited in the settling zone at the bottom of the reactor under the action of its own gravity, the sulfur slurry is continuously or intermittently pumped out to the separator on-line from the outlet of the settling zone, and after liquid-solid separation, the sulfur is washed and dried for many times to obtain high-purity sulfur; the separated reaction solution flows back to the tail gas absorption area and enters the reactor for recycling, and fresh reaction solution can be supplemented into the tail gas absorption area and flows back to the upper part of the tail gas absorption area.

Compared with the prior art, the invention has the following advantages:

(1) by adopting the process device, the gas pipe of the reactor is designed to ensure that the reaction gas entering the reactor forms a spray with a certain radian, and the liquid in the reaction zone is pushed to rotate clockwise or anticlockwise, so that the self-stirring is realized, the uniform dispersion of the gas in the reaction solution is facilitated, and the dissolution rate and the reaction rate of the gas in the reaction solution are greatly increased.

(2) When the liquid in the reactor rotates, the sulfur slurry in the settling zone at the lower part of the reactor is driven to rotate, so that deposition and scaling of sulfur on the wall of the reactor are prevented, the sulfur particles are prevented from agglomerating and blocking a pipeline, and the safe, stable and long-period operation of the device is ensured.

(3) The invention relates to a process method for desulfurizing hydrogen sulfide and sulfur dioxide by reaction, which adopts water containing organic alkaline compounds as reaction solution to realize H₂S and SO₂The desulfurization reaction is carried out in a water phase environment, and the reaction time of the two can be greatly shortened under the conditions of normal temperature and normal pressure, which shows that the dissolution rates of the two in water tend to be similar, so that the reaction is easier to occur. And on the other hand, with H₂S and SO₂The reaction solution is increased in acidity (pH value is reduced), the alkalinity caused by the addition of the organic alkaline compound is neutralized, the reaction is facilitated under an acidic environment, and the rate of the reaction of the organic alkaline compound and the organic alkaline compound to generate the sulfur is greatly increased.

(4) Process apparatus and method utilizing the invention, H₂S and SO₂The reaction desulfurization can be carried out at normal temperature and normal pressure, the reaction response time is less than 15 seconds, the required reaction condition is mild, the equipment is simple and easy to process, the investment is low, and the operation is safe.

(5) In the process of the invention, the reaction solution used absorbs H₂S and SO₂The sulfur can be generated by reaction without buffer solution or catalyst, thereby reducing the content of the sulfurThe operation cost is low, the sulfur in the obtained slurry does not contain buffer solution or catalyst, the separation is easy, the sulfur refining cost is reduced, and the purity of the sulfur product is improved.

(6) In the process, the reaction solution in the reaction zone can be recycled after separation, so that the hydrogen sulfide and the sulfur dioxide in the reaction tail gas can be absorbed to ensure that the tail gas reaches the standard and is discharged, the hydrogen sulfide and the sulfur dioxide in the reaction tail gas can be recovered for further reaction, and the yield of sulfur and the treatment capacity of waste gas are increased.

(7) Conventional and improved Claus process on H in raw material gas₂The S content is required to be more than 10%, and the low-concentration product enters a Claus device after being concentrated; the reaction system of the invention is suitable for H with any proportion₂S and SO₂Can be reacted with a compound containing H₂Acid gas of S and SO₂The flue gas flow and the composition of the flue gas are greatly changed.

Additional features and advantages of the invention will be set forth in the detailed description which follows.

Drawings

FIG. 1 is a schematic view of a process apparatus of example 1;

FIG. 2 is a top view of the gas tubes of the reaction zone of FIG. 1;

the system comprises a reactor 100, a separator 200, a tail gas absorption area 101, a reaction area 102, a settling area 103, a gas pipe 104, a main gas pipe 1041-1, a main pipe I1041-2, a main pipe II, a main gas pipe 1042, a gas branch pipe 105 and an online pH monitor.

Detailed Description

The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.

Example 1

A process device for liquid-phase reaction desulfurization of hydrogen sulfide and sulfur dioxide, as shown in fig. 1, comprising a reactor 100 and a separator 200, wherein the reactor 100 comprises a tail gas absorption zone 101, a reaction zone 102 and a settling zone 103 from top to bottom; the ratio of the diameter of the tail gas absorption area 101 to the diameter of the reaction area 102 is 1:2, and the tail gas absorption area 101 and the reaction area are connected through a cone-shaped reducing pipe. A float valve tray is arranged in the tail gas absorption area 101; the reaction zone 102 is provided with a gas pipe 104 which is fixed on the reactor 100, the gas pipe 104 is composed of a gas main pipe 1041 and a gas branch pipe 1042, the gas main pipe 1041 is a t-shaped pipe composed of a main pipe i 1041-1 and a main pipe ii 1041-2, the main pipe i 1041-1 opens on the wall of the reaction zone 102, extends horizontally to the center of the reactor 100 and is communicated with the main pipe ii 1041-2, the main pipe ii 1041-2 is arranged at the center of the reactor 100 and is vertical to the main pipe i 1041-1, the main pipe ii 1041-2 is connected with 4 groups of gas branch pipes 1042 from top to bottom, each group of gas branch pipes 1042 is provided with 4 arc branch pipes, extends to the wall along the horizontal direction and is symmetrically distributed, as shown in fig. 2; all pipelines in the gas pipe 104 are communicated with each other, and two ends of the main pipe II 1041-2 are closed; the wall of the reaction zone 102 is also provided with an online pH monitor 105, the settling zone 103 is in an inverted cone shape, the outlet at the bottom of the settling zone is connected with a separator 200, and the other end of the separator 200 is connected to the upper part of the tail gas absorption zone 101 of the reactor.

Example 2

The process method for performing the reaction desulfurization of the hydrogen sulfide and the sulfur dioxide by using the process device shown in FIG. 1 comprises the following steps:

firstly, pure SO is added₂Gas is introduced into the reaction zone 102 of the reactor 100 through the gas pipe 104, the gas is sprayed into the reaction solution in the reaction zone through the main pipe I1041-1 and the main pipe II 1041-2 in sequence by the gas branch pipe 1042, the reaction solution is an aqueous solution of an organic alkaline compound, the reaction solution is driven to rotate, the effect of self-stirring of the liquid in the reactor is realized, and SO is beneficial to SO₂The gas is uniformly dispersed in the reaction solution, and SO is greatly increased₂The dissolution rate of the gas in the reaction solution was adjusted to 6.5 by the pH on-line monitor 105, and then pure H was introduced into the reaction zone 102₂S gas, liquid in the reaction area 102 quickly turns yellow, and the liquid react to generate sulfur immediately; sulfur enters the settling zone 103 under the action of gravity, flows out from the bottom of the settling zone 103 along with part of reaction solution, is pumped into a separator 200 by a pump to separate the sulfur from the reaction solution, is supplied with fresh reaction solution in the separated reaction solution, is pressurized by the pump and is sent to the separatorTo the top of the tail gas absorption zone 101, the tail gas is firstly contacted with the reaction tail gas in the reaction zone 102 in a reverse direction to remove a small amount of incompletely reacted SO in the tail gas₂And H₂And S, entering the reaction zone 102 for recycling, and exhausting the absorbed tail gas.

The organic alkaline compound aqueous solution used in the process is a phenylmethylamine solution with the mass fraction of 30 percent and SO₂The gas flow is 300mL/min, H₂The S gas flow rate is 600 mL/min. Introduction of H₂The reaction response time of the two gases after S is 5S, and the reaction temperature and pressure in the reactor 100 are normal temperature and normal pressure.

After the device runs stably for 2 hours, the sulfur obtained by separating the separator 200 is washed for a plurality of times, dried and weighed, and H is calculated according to the balance of materials₂The conversion of S was 94.8%.

Example 3

The process method for performing the reaction desulfurization of the hydrogen sulfide and the sulfur dioxide by adopting the device shown in the figure 1 comprises the following steps:

the same procedure as in example 2 was repeated except that the aqueous solution of the organic basic compound was a 20% solution of benzylamine.

Introduction of H₂The reaction response time of the two gases after S is 5S, calculated according to the material balance, H₂The conversion of S was 94.9%.

Example 4

isopropanolamine solution with 20% of aqueous solution of organic basic compound, SO₂Gas flow rate of 400mL/min, H₂The flow rate of S gas was not more than 800mL/min, but the other conditions were the same as in example 2.

Calculated from the material balance, H₂The conversion of S was 98.5%.

Example 5

the same procedure as in example 2 was repeated except that the aqueous solution of the organic basic compound was a 15% trimethylamine solution.

Based on material balance calculation，H₂The conversion of S was 97.3%.

Example 6

the organic alkaline compound aqueous solution is 15% diglycolamine, H is firstly introduced into the reactor₂S gas with the flow rate of 300mL/min, and when the pH on-line monitor 105 shows 6.8, introducing SO₂The gas flow rate was 150mL/min, and the other conditions were the same as in example 2.

Calculated from the material balance, SO₂The conversion of (a) was 98.8%.

Example 7

the organic alkaline compound aqueous solution is 5% pyridine, and H is firstly introduced into the reactor₂S gas with the flow rate of 500mL/min, and when the pH on-line monitor 105 shows 6.8, introducing SO₂The gas flow rate was 250mL/min, and the other conditions were the same as in example 2.

Calculated from the material balance, SO₂The conversion of (3) was 97.0%.

Example 8

a 2% solution of tetrahydropyrrole in water, SO, excluding the aqueous solution of an organic basic compound₂The gas flow is 250mL/min, H₂The flow rate of S gas was not more than 500mL/min, but the other conditions were the same as in example 2.

Calculated from the material balance, H₂The conversion of S was 92.8%.

Example 9

the used organic alkaline compound aqueous solution is 0.5 percent of 1-methyl-3-pyrrolidinol, H is firstly introduced into a reactor₂S gas with the flow rate of 300mL/min is introduced when the pH on-line monitor 105 shows 6.8SO₂The gas flow rate was 150mL/min, and the other conditions were the same as in example 2.

Calculated from the material balance, SO₂The conversion of (a) was 78.8%.

Example 10

1, 3-propanediamine solution containing 20% of organic alkaline compound aqueous solution, SO₂The gas flow rate is 500mL/min, H₂The flow rate of S gas was not more than 1000mL/min, and the other conditions were the same as in example 2.

Calculated from the material balance, H₂The conversion of S was 99.2%.

Example 11

the organic alkaline compound aqueous solution is 10% ethylenediamine solution, SO₂The total flow rate of gas is 300mL/min, H₂The total flow rate of S gas is 600 mL/min; other operating conditions were the same as in example 2.

Calculated from the material balance, H₂The conversion of S was 96.6%.

Example 12

the organic alkaline compound aqueous solution is 1% p-xylylenediamine solution, SO₂The total flow rate of gas is 150mL/min, H₂The total flow rate of S gas is 300 mL/min; other operating conditions were the same as in example 2.

Calculated from the material balance, H₂The conversion of S was 74.2%.

Example 13

a solution of triethylenediamine (SO) in an aqueous solution of 20% excluding an organic basic compound₂The total flow rate of gas is 500mL/min, H₂The total flow rate of S gas was not more than 1000mL/min, and the other conditions were the same as in the examples2。

Calculated from the material balance, H₂The conversion of S was 99.5%.

Example 14

piperazine solution with 10% of water solution of organic alkaline compound, SO₂The gas flow rate is 350mL/min, H₂The flow rate of S gas was not more than 700mL/min, but the other conditions were the same as in example 2.

Calculated from the material balance, H₂The conversion of S was 98.5%.

Example 15

removing pyrazine in 3% concentration in water solution of organic alkaline compound, SO₂The gas flow rate is 500mL/min, H₂The flow rate of S gas was not more than 1000mL/min, and the other conditions were the same as in example 2.

Calculated from the material balance, H₂The conversion of S was 96.9%.

Example 16

removing hydroxypyrazine 5% in water solution of organic alkaline compound, SO₂Gas flow rate of 200mL/min, H₂The flow rate of S gas was not more than 400mL/min, but the other conditions were the same as in example 2.

Calculated from the material balance, H₂The conversion of S was 96.7%.

Example 17

morpholine solution with 25% of organic alkaline compound aqueous solution, SO₂Gas flow rate is 1000mL/min, H₂The flow rate of S gas was not more than 2000mL/min, but the other conditions were the same as in example 2.

Calculated from the material balance, H₂The conversion of S was 99.7%.

Example 18

imidazole solution with 10 percent of organic alkaline compound aqueous solution, SO₂The gas flow rate is 500mL/min, H₂The flow rate of S gas was not more than 1000mL/min, and the other conditions were the same as in example 2.

Calculated from the material balance, H₂The conversion of S was 98.8%.

Example 19

imidazole solution with 6 percent of water solution except organic alkaline compound, SO₂The gas flow rate is 500mL/min, H₂The flow rate of S gas was not more than 1000mL/min, and the other conditions were the same as in example 2.

Calculated from the material balance, H₂The conversion of S was 96.5%.

Example 20

a 5% solution of diethylenetriamine in water, SO₂Gas flow rate of 400mL/min, H₂The flow rate of S gas was not more than 800mL/min, but the other conditions were the same as in example 2.

Calculated from the material balance, H₂The conversion of S was 97.1%.

Example 21

n-methyldiethanolamine solution with the organic alkaline compound aqueous solution of 10 percent, SO₂Gas flow rate of 200mL/min, H₂The flow rate of S gas was not more than 400mL/min, but the other conditions were the same as in example 2.

Calculated from the material balance, H₂The conversion of S was 99.7%.

Example 22

a 15% solution of N-methyldiethanolamine in water solution except organic alkaline compound, SO₂The gas adopts S-Zorb regeneration flue gas (SO)₂Volume fraction of 4.5%), flow rate of 500mL/min, H₂The S gas is acid gas (acid gas generated by rich liquid regeneration of a desulphurization device such as dry gas, liquefied gas and the like, wherein H is₂55% S by volume) and a flow rate of 80mL/min, the same conditions as in example 2 were applied.

Calculated from the material balance, H₂The conversion of S was 96.8%.

Example 23

removing organic alkaline compound in water solution of 8% N, N-dimethylethanolamine, SO₂The gas adopts catalytic cracking regeneration flue gas (SO)₂Volume fraction of 1.45%), flow rate of 1000mL/min, H₂The S gas is acidic gas (sewage stripping acidic gas, wherein H) of a certain petrochemical enterprise₂S volume content of 60%), flow rate of 50mL/min, and other conditions were the same as in example 2.

Calculated from the material balance, H₂The conversion of S was 94.0%.

Example 24

triethanolamine solution (20% except organic alkaline compound water solution), SO₂The gas adopts pure SO₂The flow rate is 300mL/min, H₂The S gas is acid gas (concentrated acid gas, wherein H) of a certain petrochemical enterprise₂95% S by volume) and a flow rate of 630mL/min, under the same conditions as in example 2.

Calculated from the material balance, H₂The conversion of S was 99.2%.

Example 25

alkalization removalThe compound water solution is 12% triethanolamine solution, SO₂The gas adopts S-Zorb regeneration flue gas (SO)₂Volume fraction of 4.5%), flow rate of 1000mL/min, H₂The S gas is acid gas (acid gas generated by rich liquid regeneration of a desulphurization device such as dry gas, liquefied gas and the like, wherein H is₂55% S by volume) and a flow rate of 160mL/min, the same conditions as in example 2 were used.

Calculated from the material balance, H₂The conversion of S was 97.2%.

Example 26

triethanolamine solution containing 6% of water solution of organic alkaline compound, SO₂The gas adopts S-Zorb regeneration flue gas (SO)₂Volume fraction of 4.5%), flow rate of 1000mL/min, H₂The S gas is acid gas (acid gas generated by rich liquid regeneration of a desulphurization device such as dry gas, liquefied gas and the like, wherein H is₂55% S by volume) and a flow rate of 160mL/min, the same conditions as in example 2 were used.

Calculated from the material balance, H₂The conversion of S was 95.1%.

Example 27

4-methylpyridine solution with 12% of organic alkaline compound aqueous solution, SO₂The gas adopts coal-fired boiler flue gas (SO)₂Volume content of 0.5%), flow rate of 5000mL/min, H₂The S gas is acid gas (concentrated acid gas, wherein H) of a certain petrochemical enterprise₂95% S by volume) and a flow rate of 50mL/min, under the same conditions as in example 2.

Calculated from the material balance, H₂The conversion of S was 94.2%.

Example 28

removing organic basic compoundsThe aqueous solution is a mixed amine solution of 5% of 2-methylpyridine and 5% of 1, 2-propane diamine, SO₂The gas adopts coal-fired boiler flue gas (SO)₂Volume content of 0.5%), flow rate of 3000mL/min, H₂The S gas is acid gas (concentrated acid gas, wherein H) of a certain petrochemical enterprise₂95% S by volume) and a flow rate of 30mL/min, under the same conditions as in example 2.

Calculated from the material balance, H₂The conversion of S was 92.7%.

Example 29

removing organic alkaline compound solution of mixed amine solution of 1% methylpyrazine and 9% N-methyldiethanolamine, SO₂The gas adopts catalytic cracking regeneration flue gas (SO)₂Volume fraction of 1.45%), flow rate of 2000mL/min, H₂The S gas is acidic gas (sewage stripping acidic gas, wherein H) of a certain petrochemical enterprise₂S volume content of 60%), flow rate of 95mL/min, and other conditions were the same as in example 2.

Calculated from the material balance, H₂The conversion of S was 96.0%.

Example 30

a mixed amine solution of 5% of diethylenetriamine, 5% of ethanolamine and 5% of N, N-diethylethanolamine excluding the organic alkali compound aqueous solution, SO₂The gas adopts catalytic cracking regeneration flue gas (SO)₂Volume fraction of 1.45%), flow rate of 2000mL/min, H₂The S gas is acidic gas (sewage stripping acidic gas, wherein H) of a certain petrochemical enterprise₂S volume content of 60%), flow rate of 95mL/min, and other conditions were the same as in example 2.

Calculated from the material balance, H₂The conversion of S was 97.8%.

Claims

1. The process method for liquid-phase reaction desulfurization of hydrogen sulfide and sulfur dioxide is characterized by being realized by adopting the following process devices: the process device comprises a reactor and a separator, wherein the reactor sequentially comprises a tail gas absorption area, a reaction area and a settling area from top to bottom; the settling zone is connected with the separator, and the other end of the separator is connected to the top of the tail gas absorption zone of the reactor; the reactor is characterized in that the reaction area is provided with a gas pipe which is fixed on the reactor and consists of a gas main pipe and gas branch pipes, the gas main pipe is a T-shaped pipe consisting of a main pipe I and a main pipe II, the main pipe I is opened on the wall of the reaction area, horizontally extends to the center of the reactor and is communicated with the main pipe II, the main pipe II is arranged at the center of the reactor and is vertical to the main pipe I, the main pipe II is connected with a plurality of groups of gas branch pipes from top to bottom, each group of gas branch pipes extends to the wall of the reactor along the horizontal direction and is symmetrically distributed, all pipelines in the gas pipe are mutually communicated, and two ends;

the process method comprises the following steps: introducing a gas containing hydrogen sulfide and a gas containing sulfur dioxide into a reaction zone through a gas pipe, wherein a reaction solution is filled in the reaction zone and a settling zone, the reaction solution comprises water and at least one organic alkaline compound capable of being dissolved in water, and the organic alkaline compound is selected from at least one of the following compounds: hydroxylamine, C1-C10 aliphatic amines, C1-C10 alcamines, C1-C10 alicyclic amines, C6-C10 aromatic amines, pyridine derivatives, imidazole derivatives, pyrazine derivatives, pyrazole or pyrazole derivatives; the organic alkaline compound enables the pH value of the solution to be more than or equal to 7.2; the sulfur generated by the reaction of the hydrogen sulfide and the sulfur dioxide is deposited in a settling zone and enters a separator, the sulfur and the reaction solution are obtained through liquid-solid separation, the reaction solution flows back to the top of a tail gas absorption zone and is in countercurrent contact with the reaction tail gas in the reaction zone, the unreacted reaction gas enters the reaction zone after being absorbed, and the absorbed tail gas is discharged.

2. The process of claim 1, wherein the reaction solution in the reaction zone has a pH of 7.2 to 13.0.

3. The process of claim 2, wherein the reaction solution in the reaction zone has a pH of 8.0 to 12.0.

4. The process of claim 1, wherein the mass fraction of the organic basic compound in the reaction solution in the reaction zone is 0.1% to 30% based on the total weight of the reaction solution.

5. The process of claim 4, wherein the reaction solution in the reaction zone comprises 2% to 30% by weight of the organic basic compound, based on the total weight of the reaction solution.

6. The process as claimed in claim 1, wherein the organic basic compound is selected to have a solubility in water of 0.1g/100g water or more.

7. A process according to claim 6, wherein the organic basic compound is selected to have a solubility in water of 1g/100g water.

8. The process according to claim 1, wherein the pyridine, imidazole, pyrazine or pyrazole derivative is a derivative in which H in pyridine, imidazole, pyrazine or pyrazole is substituted by alkyl, amino, alkylamino, hydroxyl or alkyl alcohol.

9. The process of claim 1, wherein the fatty amines are C1-C6 fatty amines; the alcohol amine is C1-C6 alcohol amine, the alicyclic amine is C1-C6 alicyclic amine, and the aromatic amine is C6-C8 aromatic amine.

10. The process according to claim 1, wherein the organic basic compound is selected from the group consisting of hydroxylamine, trimethylamine, ethylenediamine, 1, 2-propanediamine, 1, 3-propanediamine, ethanolamine, diethanolamine, triethanolamine, diglycolamine, isopropanolamine, N-methyldiethanolamine, N-dimethylethanolamine, N, at least one of N-diethylethanolamine, benzylamine, o-xylylenediamine, m-xylylenediamine, p-xylylenediamine, tetrahydropyrrole, 1-methyl-3-pyrrolidinol, piperidine, morpholine, triethylenediamine, diethylenetriamine, piperazine, 2-methylpiperazine, pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, pyrazine, hydroxypyrazine, aminopyrazine, methylpyrazine, imidazole, and pyrazole.

11. The process of claim 1, wherein the gas manifolds are arranged in 1-6 groups.

12. A process according to claim 11, wherein the gas manifolds are arranged in 2 to 4 groups.

13. The process method according to claim 1, wherein 2 to 8 branch pipes are provided for each group of gas branch pipes, and each branch pipe is a circular arc type pipe.

14. The process method according to claim 1, wherein the ratio of the diameter of the tail gas absorption zone to the diameter of the reaction zone is 0.1: 1-1: 1, and the tail gas absorption zone and the reaction zone are connected through a cone-shaped reducing pipe when the diameter of the tail gas absorption zone is smaller than that of the reaction zone.

15. A process according to claim 1, wherein trays and/or packing are provided in the off-gas absorption zone.

16. A process according to claim 1, wherein said settling zone is cylindrical, dished, hemispherical, ellipsoidal or inverted conical.

17. A process as claimed in claim 16 wherein said settling zone is hemispherical, ellipsoidal or inverted conical.

18. The process of claim 1, wherein the gas is introducedH in the reaction gas₂S or SO₂The volume fractions of (A) are respectively 0.1-100%.

19. The process of claim 1, wherein the ratio of hydrogen sulfide to sulfur dioxide in the reaction gas is 0.1:1 to 5: 1.

20. The process according to claim 1, wherein the hydrogen sulfide-containing gas and the sulfur dioxide-containing gas are introduced simultaneously, or one reaction gas is introduced so that the reaction solution in the reactor has a pH of less than 7.0, and then another reaction gas is introduced.