CN112642397A

CN112642397A - Composite material and preparation method and application thereof

Info

Publication number: CN112642397A
Application number: CN201910963781.7A
Authority: CN
Inventors: 刘增让; 刘爱华; 李毅; 刘剑利; 徐翠翠; 许金山; 袁辉志; 陶卫东
Original assignee: China Petroleum and Chemical Corp; Qilu Petrochemical Co of Sinopec
Current assignee: China Petroleum and Chemical Corp; Qilu Petrochemical Co of Sinopec
Priority date: 2019-10-11
Filing date: 2019-10-11
Publication date: 2021-04-13
Anticipated expiration: 2039-10-11
Also published as: CN112642397B

Abstract

The invention relates to the technical field of desulfurization, and discloses a composite material and a preparation method and application thereof. The composite material comprises modified activated carbon and an active component loaded on the modified activated carbon, wherein the modified activated carbon comprises activated carbon, an oxide of an alkali metal and an oxide of silicon, and the weight ratio of the activated carbon to the oxide of the alkali metal to the oxide of silicon is 100 (0.2-3) to (0.8-5); the active component contains iron oxide and rare earth element oxide, and the weight ratio of the active carbon to the iron oxide to the rare earth element oxide is 100 (0.5-5) to (1-10). The invention also discloses a preparation method of the composite material and application of the composite material in desulfurization. The composite material of the invention has higher penetrating sulfur capacity as an adsorbent.

Description

Composite material and preparation method and application thereof

Technical Field

The invention relates to the technical field of desulfurization, in particular to a composite material and a preparation method and application thereof.

Background

SO₂Is the leading cause of acid rain; SO (SO)₂Can destroy the physiological function of plants and slow down the growth of crops and trees; human body inhales higher concentration SO₂Gas, can produce strong stimulation to respiratory tract. SO (SO)₂Has received wide attention as a main atmospheric pollutant. It is reported that, for example, in China, SO₂The emission causes 40% of the territorial area to be endangered by acid rain, and the annual loss caused thereby is as high as 1100 billion yuan. Thus, pollution control and SO reduction₂The emission is an important task for sustainable development of the economic society of China.

SO is generated in the flue gas of the industrial heating furnace, the sulfur tail gas and the catalytic cracking regeneration flue gas₂With the stricter environmental regulations, SO₂The task of emission reduction is imminent. At present, the methodThe first is wet method, i.e. the waste gas is treated by using a certain liquid absorbent, emulsion absorbent or absorption solution, and the second is dry method, i.e. the sulfur dioxide in the flue gas is removed by using powder or granular absorbent, absorbent or catalyst. The most representative, most rapidly developing wet desulfurization technique is alkaline scrubbing desulfurization, such as DuPont^TMLABSORBTM technology from BELCO. The wet desulphurization technology of alkaline washing after flue gas can realize 50mg/m³The process has lower discharge amount, but the process generates new secondary pollutant-sodium sulfate-containing wastewater which cannot be directly discharged, and the investment of the retreatment process is huge. At present, petrochemical industry has completely prohibited various devices from being additionally provided with flue gas alkaline desulfurization processes. The dry desulphurization is considered to be the desulphurization process with the most application prospect due to the characteristics of simple operation, low equipment investment, no secondary pollution and the like, which develop rapidly in recent years. Therefore, in recent years, the research and development of the dry flue gas desulfurization technology are generally regarded as important at home and abroad. If a mature dry desulfurization technology can be adopted for removing sulfur dioxide in flue gas, SO can be reduced₂And the emission amount is reduced, various environmental protection regulation requirements are met, and the atmospheric environment is protected.

The core of the dry desulfurization process is the sorbent. The dry adsorption desulfurization adsorbent mainly comprises a molecular sieve and active carbon. The activated carbon is carbon with strong adsorption capacity, which is obtained by taking coal, wood, fruit shells and the like as raw materials and carrying out high-temperature (300-. The characteristic properties of hydrophobicity, non-polarity and thermal stability of the activated carbon enable the activated carbon to be easily modified and activated in the using process, and the activated carbon has unique surface chemical properties and a unique void structure, so that the loading capacity and the adsorption performance of the activated carbon are enhanced. The active carbon has developed pores, the adsorbable micropore surface area accounts for more than 95 percent of the total surface area, the active carbon has large specific surface area, and SO can be effectively adsorbed₂And the like. Activated carbon to SO₂The adsorption of (b) is influenced by the surface properties such as the form and distribution of pore diameter. The common active carbon has small sulfur capacity, low removal rate and poor precision, and the active carbon is often modified to achieve more idealAnd (4) desulfurization effect. The change of the chemical properties of the surface of the activated carbon to improve the adsorption rate and the sulfur capacity of the activated carbon is the main research direction of activated carbon desulfurization at present.

CN106031861A discloses a composite adsorbent for removing acid gases NOx and/or SO from gas mixtures by adsorption and conversion₂The composite adsorbent comprises a physical adsorbent and a chemical adsorbent, wherein the physical adsorbent is used for adsorbing acid gas, water molecules and oxygen contained in a gas mixture, the chemical adsorbent is used for reacting with acid substances in the composite adsorbent, the weight ratio of the physical adsorbent to the chemical adsorbent is 0.1-5.0, and the porosity of the composite adsorbent is 0.2-0.85.

Although the above documents report some adsorbents for removing sulfur compounds and corresponding desulfurization methods, there are problems in specific applications such as low sulfur removal rate (saturated sulfur capacity is usually in the range of 5 to 10%) and low sulfur penetration capacity of the desulfurizing agent. The limited adsorption capacity makes the adsorbent consumption and the purification device bulky, increases the device investment cost, and makes the operation process complicated due to frequent regeneration.

Disclosure of Invention

The invention aims to solve the problem that the desulfurization rate and the penetrating sulfur capacity are difficult to be considered in the prior art, and provides modified activated carbon and a composite material as well as a preparation method and application thereof.

In order to achieve the above object, a first aspect of the present invention provides a composite material comprising a modified activated carbon and an active component supported on the modified activated carbon, wherein the modified activated carbon comprises activated carbon, an oxide of an alkali metal and an oxide of silicon and the weight ratio of the activated carbon, the oxide of an alkali metal and the oxide of silicon is 100 (0.2-3): 0.8-5); the active component contains iron oxide and rare earth element oxide, and the weight ratio of the active carbon to the iron oxide to the rare earth element oxide is 100 (0.5-5) to (1-10).

In a second aspect the present invention provides a method of making a composite material, the method comprising:

(1) in the presence of a solvent, mixing and kneading activated carbon, an alkali metal precursor, a silicon-containing binder and an optional pore-expanding agent, molding, drying and roasting to obtain modified activated carbon, wherein the activated carbon, the alkali metal precursor and the silicon-containing binder are used in such an amount that the weight ratio of the activated carbon to the alkali metal elements to the silicon elements in the modified activated carbon is 100 (0.2-3) to 0.8-5;

(2) contacting a precursor of an active component with the modified activated carbon to load the modified activated carbon with the active component, wherein the precursor of the active component contains a precursor of iron and a precursor of a rare earth element, and the precursor of the active component is used in an amount such that the weight ratio of the activated carbon to the iron to the rare earth element in the obtained composite material is (0.5-5) to (1-10);

wherein the weight of the alkali metal element, the silicon element, the iron element and the rare earth element is calculated by oxide.

A third aspect of the invention provides a composite material made by the method as described above.

A fourth aspect of the invention provides the use of a modified activated carbon or composite material as described above in adsorptive desulfurization.

In a fifth aspect, the present invention provides a method of desulfurization, the method comprising: contacting a sulfur-containing gas to be treated with a composite material as described above;

alternatively, the method comprises: preparing a composite material according to the method described above; then the sulfur-containing gas is contacted with the composite material.

A sixth aspect of the present invention provides a system having a desulfurization function, including:

an oxidation unit for treating the sulfur-containing gas and recovering sulfur;

the hydrogenation purification unit is connected with the oxidation unit and is used for carrying out hydrogenation reduction on the oxidation tail gas discharged from the oxidation unit and recovering hydrogen sulfide in a reduction product obtained by hydrogenation reduction;

the incineration unit is used for incinerating the purified tail gas discharged by the hydrogenation purification unit;

an adsorption unit for adsorbing S-containing gas obtained by incinerationO₂SO in flue gas₂The adsorbent used in the adsorption unit is a composite material as described above.

The seventh aspect of the present invention provides a method of desulfurization, comprising:

(a) oxidizing the sulfur-containing gas to be treated and recovering sulfur;

(b) carrying out hydrogenation reduction on the oxidized tail gas and recovering hydrogen sulfide in a reduction product obtained by hydrogenation reduction;

(c) incinerating the tail gas after hydrogenation reduction;

(d) SO that the SO contained in the obtained material after incineration₂The flue gas is contacted with an adsorbent to adsorb SO₂The adsorbent is a composite material as described above.

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

(1) the composite material of the invention has higher penetrating sulfur capacity when being used as an adsorbent. The specific surface area of the composite material is more than 550m²The pore volume is more than 0.35ml/g, the good adsorbability of the composite material is ensured, and SO₂At removal rates greater than 99%, the breakthrough sulfur capacity is greater than 12% (and in preferred embodiments may be greater than 15%).

(2) The composite material has good regeneration performance.

(3) The composite material of the invention has simple preparation process and no secondary pollution in the preparation process.

(4) The composite material can promote the development of a dry desulfurization technology and provide a clean sulfur-containing waste gas treatment method which has no secondary pollution and meets the environmental protection requirement.

Drawings

FIG. 1 is a schematic block diagram of a system according to a preferred embodiment of the present invention;

fig. 2 is a schematic structural view of a system according to another preferred embodiment of the present invention.

Description of the reference numerals

12 first-stage condenser of 11 thermal reaction furnace

13 first-stage catalytic converter 14 second-stage condenser

15 three-stage condenser of two-stage catalytic converter 16

17 liquid sulfur pool 21 hydrogenation reactor

22 hydrogenation tail gas cooler 23 quench tower

24 absorption tower 31 incineration unit

41 first absorption column 42 second absorption column

111 tail gas reheater 222 flue gas heat exchanger

Detailed Description

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

In the present invention, the volume of the gas is defined as standard conditions (STP) (0 deg.C (273K)) and 1.01X 10⁵Pa) of the volume; "silicon to aluminum ratio" means the molar ratio between the silicon element and the aluminum element; "ppm" is a volume concentration unit.

The modified activated carbon comprises activated carbon, alkali metal oxide and silicon oxide, wherein the weight ratio of the activated carbon to the alkali metal oxide to the silicon oxide is 100 (0.2-3) to (0.8-5).

According to the modified activated carbon of the present invention, the weight ratio of the activated carbon to the alkali metal oxide is preferably 100 (0.5-2).

According to the modified activated carbon, the weight ratio of the activated carbon to the oxide of silicon is preferably 100 (1-2.8).

According to the invention, the alkali metal oxide can be common alkali metal (such as lithium, sodium, potassium and the like) oxides with different valence states, especially common alkali metal precursors after high-temperature roastingAnd (4) obtaining the oxide. Preferably, the oxide of an alkali metal is K₂O and/or Na₂O。

According to the invention, the silicon oxide can be common silicon oxides with different valence states, in particular to an oxide obtained by high-temperature roasting of a common silicon precursor. Preferably, the oxide of silicon is SiO₂。

According to a preferred embodiment of the present invention, the modified activated carbon has a specific surface area of 600m or more²(ii)/g, more preferably 650-750m²/g。

According to a preferred embodiment of the present invention, the modified activated carbon has a pore volume of 0.4ml/g or more, more preferably 0.4 to 0.45 ml/g.

The method for preparing the modified activated carbon comprises the following steps: in the presence of a solvent, mixing and kneading activated carbon, an alkali metal precursor, a silicon-containing binder and an optional pore-expanding agent, molding, drying and roasting, wherein the activated carbon, the alkali metal precursor and the silicon-containing binder are used in such an amount that the weight ratio of the activated carbon to the alkali metal to the silicon in the modified activated carbon is 100 (0.2-3) to (0.8-5), wherein the weight of the alkali metal and the silicon is calculated by oxides.

According to the method for preparing the modified activated carbon, the activated carbon and the alkali metal precursor are used in such an amount that the weight ratio of the activated carbon to the alkali metal element in the obtained modified activated carbon is preferably 100 (0.5-2).

According to the method for preparing the modified activated carbon, the activated carbon and the silicon-containing binder are used in such an amount that the weight ratio of the activated carbon to the silicon element in the obtained modified activated carbon is preferably 100 (1-2.8).

According to the method for preparing the modified activated carbon, the activated carbon can be various common activated carbons, and preferably, the specific surface area of the activated carbon is more than or equal to 700m²(ii)/g, more preferably 700-²/g。

According to the method for preparing modified activated carbon of the present invention, the alkali metal precursor is not particularly limited, and may be various common alkali metal-containing water-soluble compounds, preferably, the alkali metal precursor is at least one of alkali metal bicarbonate, alkali metal carbonate, alkali metal nitrate and alkali metal sulfate, more preferably at least one of sodium bicarbonate, potassium bicarbonate, sodium carbonate and potassium carbonate.

According to the method for preparing modified activated carbon of the present invention, there is no particular requirement for the siliceous binder, and preferably, the siliceous binder is silica and/or silicate, more preferably, silica sol and/or water glass. As is well known to those skilled in the art, water glass is commonly referred to as sodium silicate (Na)₂O·nSiO₂) So that it can provide both Si as a silicon-containing binder and Na as an alkali metal precursor, in which case the total amount of water glass and alkali metal (sodium) precursor is such that Na is present in the resulting product₂The content of O is within the above range.

According to the method for preparing the modified activated carbon, the pore-expanding agent is a selectively used substance, and the specific surface area of the modified activated carbon can be further improved by using the pore-expanding agent. The amount of the pore-expanding agent is not particularly required, but preferably the weight ratio of the activated carbon to the pore-expanding agent is 100 (1-10).

According to the method for preparing the modified activated carbon, the pore-expanding agent can be various pore-expanding agents, and preferably, the pore-expanding agent is a substance which can be decomposed at the temperature of not higher than 450 ℃. More preferably, the pore-enlarging agent is at least one of sesbania powder, polyethylene glycol, starch and citric acid.

According to the method for preparing the modified activated carbon, the drying mode is not particularly required, but the drying is carried out by adopting a split drying method in order to further improve the performance of the obtained modified activated carbon. Preferably, the drying method is as follows: drying at 40-80 deg.C for 2-4 hr; and then dried for 4-6h at the temperature of 100 ℃ and 160 ℃, preferably at the temperature of 110 ℃ and 130 ℃.

According to the method for preparing modified activated carbon of the present invention, there is no particular requirement on the conditions of calcination, but preferably, the conditions of calcination include: the calcination temperature is 400-700 ℃, more preferably 450-600 ℃. Still preferably, the firing conditions further include: the calcination time is 3-8h, more preferably 4-6 h.

The method for producing modified activated carbon according to the present invention has no particular requirement for the solvent, and may be a common organic solvent and/or inorganic solvent. Preferably, however, the solvent is water. The amount of the solvent can be controlled by those skilled in the art according to the requirements of kneading and molding, and will not be described herein.

The process for producing modified activated carbon according to the present invention can be kneaded and formed in a conventional manner, for example, by means of a forming apparatus such as a plodder or the like.

The invention also provides modified activated carbon prepared by the method.

According to one embodiment of the invention, the composite material is characterized by comprising activated carbon, an oxide of an alkali metal, an oxide of silicon, an oxide of iron and an oxide of a rare earth element, wherein the weight ratio of the activated carbon, the oxide of the alkali metal, the oxide of silicon, the oxide of iron and the oxide of the rare earth element is 100 (0.2-3): (0.8-5): (0.5-5): 1-10. According to this embodiment of the invention, the composite material can be obtained from all precursors by kneading, molding, drying and firing. In this embodiment, the specific surface area of the composite material is preferably 560m or more²(ii)/g, more preferably 570-²(ii) in terms of/g. Preferably, the pore volume of the composite material is not less than 0.38ml/g, more preferably 0.38-0.42 ml/g. Preferably, the saturated sulfur capacity of the composite material is equal to or greater than 15%, more preferably 18-20%. Preferably, the composite material has a breakthrough sulfur capacity of 12% or more, more preferably 12-15%.

According to another embodiment of the present invention, the present invention provides a composite material, characterized in that the composite material comprises modified activated carbon and an active component supported on the modified activated carbon, wherein the modified activated carbon comprises activated carbon, an oxide of an alkali metal and an oxide of silicon and the weight ratio of the activated carbon, the oxide of an alkali metal and the oxide of silicon is 100 (0.2-3): 0.8-5; the active component containing iron oxide and rare earth elementsThe weight ratio of the active carbon to the iron oxide to the rare earth element oxide is 100 (0.5-5) to (1-10). According to this embodiment of the present invention, the composite material can be obtained by preparing the modified activated carbon and then loading the active component. In this embodiment, the specific surface area of the composite material is preferably 550m or more²/g, more preferably 560-590m²(ii) in terms of/g. Preferably, the pore volume is 0.35ml/g or more, more preferably 0.36 to 0.4 ml/g. Preferably, the saturated sulfur capacity is 18% or more, more preferably 20-25%. Preferably, the breakthrough sulfur capacity is 12% or more, more preferably 15.5-16%.

According to the invention, the weight ratio between the activated carbon and the oxide of the alkali metal is preferably 100 (0.5-2), such as 100:0.5, 100:0.6, 100:1, 100:1.2, 100:1.5, 100:1.7, 100:1.8, 100:2 or any value between the above values.

According to the invention, the weight ratio between the activated carbon and the oxide of silicon is preferably 100 (1-2.8), such as 100:1, 100:1.5, 100:1.6, 100:1.7, 100:2, 100:2.2, 100:2.5, 100:2.8 or any value between the above mentioned values.

According to the invention, the weight ratio between the activated carbon and the iron oxide is preferably 100 (1-2.2), such as 100:1, 100:1.5, 100:1.7, 100:2, 100:2.1, 100:2.2 or any value between the above mentioned values.

According to the invention, the weight ratio between the activated carbon and the oxide of the rare earth element is preferably 100 (2-5), such as 100:2, 100:2.2, 100:2.5, 100:3, 100:3.5, 100:3.8, 100:4, 100:4.5, 100:5 or any value between the above values.

According to the composite material of the present invention, the alkali metal oxide may be common oxides of alkali metals (such as lithium, sodium, potassium, etc.) with different valence states, especially an oxide obtained by high temperature roasting a common alkali metal precursor. Preferably, the oxide of an alkali metal is K₂O and/or Na₂O。

According to the composite material of the present invention, the silicon oxide may be common silicon oxides with different valence states, especially an oxide obtained by high temperature roasting a common silicon precursor. Preference is given toThe oxide of silicon is SiO₂。

According to the composite material of the present invention, the iron oxide may be common iron oxides with different valence states, especially an oxide obtained by high temperature roasting a common iron precursor. Preferably, the iron oxide is Fe₂O₃。

According to the composite material of the present invention, the oxide of the rare earth element may be an oxide of common rare earth elements of different valence states, such as lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), yttrium (Y), and scandium (Sc), and particularly an oxide obtained by high-temperature baking a precursor of the common rare earth element. Preferably, the oxide of a rare earth element is CeO₂And/or La₂O₃. Further preferably, the oxide of the rare earth element is CeO₂And La₂O₃And CeO₂And La₂O₃The weight ratio of (A) to (B) is 1-3. The preferred oxides of rare earth elements are selected to further enhance the adsorption properties of the composite material.

According to an embodiment of the present invention, there is provided a method of making a composite material, characterized in that the method comprises: in the presence of a solvent, mixing and kneading activated carbon, an alkali metal precursor, a silicon-containing binder, an iron precursor, a rare earth element precursor and an optional pore-enlarging agent, molding, drying and roasting, wherein the use amounts of the activated carbon, the alkali metal precursor, the silicon-containing binder, the iron precursor and the rare earth element precursor are such that the weight ratio of the activated carbon, the alkali metal element, the silicon element, the iron element and the rare earth element in the obtained composite material is 100 (0.2-3): (0.8-5): (0.5-5): (1-10), and the weights of the alkali metal element, the silicon element, the iron element and the rare earth element are calculated by oxides. In this embodiment, the drying is preferably performed by: drying at 40-80 deg.C for 2-4 hr; and then dried for 4-6h at 100-. Preferably, the conditions of the calcination include: the calcination temperature is 400-700 ℃, more preferably 450-600 ℃. Preferably, the roasting conditions further include: the calcination time is 3-8h, more preferably 4-6 h.

According to another embodiment of the present invention, there is provided a method of making a composite material, characterized in that the method comprises:

In step (1) of this embodiment: the drying mode is preferably as follows: drying at 40-80 deg.C for 2-4 hr; and then dried for 4-6h at 100-. Preferably, the conditions of the calcination include: the calcination temperature is 400-700 ℃, more preferably 450-600 ℃. The roasting conditions further include: the calcination time is 3-8h, more preferably 4-6 h.

In step (2) of this embodiment, the molecular sieve composite can be loaded with the active component by a conventional method, and preferably, the modified activated carbon is loaded with the active component by: the modified activated carbon is subjected to an equal volume impregnation with a solution of a precursor containing an active component, the impregnated matter is dried, and the dried product is calcined.

More preferably, the conditions for equal volume impregnation include: the temperature is 5 to 40 ℃ and more preferably 20 to 30 ℃. More preferably, the conditions for equal volume impregnation further comprise: the time is 20min to 3h, more preferably 0.5 to 1 h.

More preferably, the conditions for drying the impregnate include: the temperature is 80 to 160 ℃, and more preferably 110-. More preferably, the conditions for drying the impregnate further comprise: the time is 2 to 10 hours, more preferably 4 to 6 hours.

More preferably, the conditions under which the dried product is calcined include: the calcination temperature is 300-500 ℃, and more preferably 350-450 ℃. More preferably, the conditions for subjecting the dried product to calcination further include: the calcination time is 2 to 10 hours, and more preferably 3 to 5 hours.

According to the method of the invention, the amount of the activated carbon and the alkali metal precursor is such that the weight ratio between the activated carbon and the alkali metal element in the obtained composite material is preferably 100 (0.5-2), such as 100:0.5, 100:0.6, 100:1, 100:1.2, 100:1.5, 100:1.7, 100:1.8, 100:2 or any value between the above values.

According to the method of the invention, the amount of the activated carbon and the silicon-containing binder is such that the weight ratio of the activated carbon to the silicon element in the obtained composite material is preferably 100 (1-2.8), such as 100:1, 100:1.5, 100:1.6, 100:1.7, 100:2, 100:2.2, 100:2.5, 100:2.8 or any value therebetween.

According to the method of the present invention, the amount of the activated carbon and the iron precursor is such that the weight ratio between the activated carbon and the iron element in the obtained composite material is preferably 100 (1-2.2), such as 100:1, 100:1.5, 100:1.7, 100:2, 100:2.1, 100:2.2 or any value between the above values.

According to the method of the present invention, the amount of the activated carbon and the rare earth element precursor is preferably 100 (2-5), such as 100:2, 100:2.2, 100:2.5, 100:3, 100:3.5, 100:3.8, 100:4, 100:4.5, 100:5 or any value therebetween, in the obtained composite material.

According to the method for preparing the composite material, the activated carbon can be various common activated carbons, and preferably, the specific surface area of the activated carbon is more than or equal to 700m²(ii)/g, more preferably 700-²/g。

According to the method for preparing the composite material of the present invention, the alkali metal precursor is not particularly limited, and may be various common alkali metal-containing water-soluble compounds, preferably, the alkali metal precursor is at least one of alkali metal bicarbonate, alkali metal carbonate, alkali metal nitrate and alkali metal sulfate, more preferably at least one of sodium bicarbonate, potassium bicarbonate and potassium carbonate.

According to the method for preparing a composite material of the present invention, there is no particular requirement for the siliceous binder, and preferably, the siliceous binder is silica and/or a silicate, more preferably, silica sol and/or water glass. As is well known to those skilled in the art, water glass is commonly referred to as sodium silicate (Na)₂O·nSiO₂) So that it can provide both Si as a silicon-containing binder and Na as an alkali metal precursor, in which case the total amount of water glass and alkali metal (sodium) precursor is such that Na is present in the resulting product₂The content of O is within the above range.

According to the method for preparing the composite material, the pore-expanding agent is a selectively used substance, and the specific surface area of the composite material can be further improved by using the pore-expanding agent. The amount of the pore-expanding agent is not particularly required, but preferably the weight ratio of the activated carbon to the pore-expanding agent is 100 (1-10).

According to the method for preparing the composite material of the present invention, the pore-expanding agent may be any of the existing pore-expanding agents, and preferably, the pore-expanding agent is a substance that can be decomposed at a temperature of not higher than 450 ℃. More preferably, the pore-enlarging agent is at least one of sesbania powder, polyethylene glycol, starch and citric acid.

According to the method for preparing the composite material of the present invention, the iron precursor may be various common iron-containing water-soluble compounds. Preferably, the precursor of iron is a soluble iron salt, preferably ferric nitrate and/or ferric chloride.

According to the method for preparing the composite material, the precursor of the rare earth element can be various existing water-soluble compounds containing the rare earth element, preferably, the precursor of the rare earth element is soluble rare earth metal salt, more preferably nitrate of the rare earth metal and/or chloride of the rare earth metal.

Further preferably, the precursor of the rare earth element contains a precursor of cerium and a precursor of lanthanum, and the amounts of the precursor of cerium and the precursor of lanthanum are such that the weight ratio of the cerium to the lanthanum in the obtained composite material is 1-3. As mentioned above, the precursor of cerium is preferably cerium nitrate and/or cerium chloride; the lanthanum precursor is preferably lanthanum nitrate and/or lanthanum chloride.

The method for producing a composite material according to the present invention has no particular requirement for a solvent, and may be a common organic solvent and/or inorganic solvent. Preferably, however, the solvent is water. The amount of the solvent can be controlled by those skilled in the art according to the requirements of kneading and molding, and will not be described herein.

The method for producing the composite material according to the present invention can be carried out by kneading and molding in a conventional manner, for example, by means of a molding apparatus such as a plodder or the like.

The invention also provides a composite material prepared by the method.

The invention also provides the application of the modified activated carbon or the composite material in adsorption desulfurization, especially in samples with low sulfur content (such as sulfur dioxide content not higher than 0.2 vol% (namely 6000 mg/m)³) For example flue gas) to be subjected to adsorptive desulfurization.

The invention also provides a desulfurization method, which is characterized by comprising the following steps: contacting a sulfur-containing gas to be treated with a composite material as described above;

The desulfurization method according to the present invention is particularly suitable for the removal of sulfur from samples having a low sulfur content, and therefore, it is preferable that the sulfur dioxide content in the sulfur-containing gas is not higher than 0.2 vol%. On the other hand, when the sulfur dioxide content in the sulfur-containing gas is higher than 0.2 vol%, the method preferably further comprises reducing the sulfur dioxide content in the sulfur-containing gas to less than 0.2 vol% before contacting with the composite material.

According to the desulfurization method of the present invention, the conditions of the contact are not particularly required, but preferably, the conditions of the contact include: the temperature is 100-150 ℃. Preferably, the contacting conditions further comprise: the gas volume space velocity is 1500-2000h^-1。

According to the invention, the composite material not only has good adsorbability, but also has excellent regeneration performance. Thus, the method further comprises: regenerating the composite material. There is no particular requirement on the method of regeneration, for example, the mode of regeneration may be thermal regeneration and/or water wash regeneration. The composite material of the present invention may be thermally regenerated and/or water-washed regenerated using conventional conditions.

More preferably, the thermal regeneration is performed by gas purging under the following conditions: the gas volume space velocity is 1000-fold and 1500h^-1The temperature is 150 ℃ and 250 ℃, and the purge gas is an inert gas (such as nitrogen).

More preferably, the conditions of the water wash regeneration include: the liquid hourly space velocity is 0.5-1.5h^-1The temperature is 25-40 ℃.

According to the desulfurization method, the sulfur-containing gas is at least one of heating furnace flue gas, sulfur tail gas and catalytic cracking regeneration flue gas in the petroleum refining industry.

The present invention also provides a system having a desulfurization function, characterized in that the system comprises:

an oxidation unit for treating the sulfur-containing gas and recovering sulfur;

an adsorption unit for adsorbing SO-containing gas obtained by incineration₂SO in flue gas₂The adsorbent used in the adsorption unit is a composite material as described above.

According to the system of the present invention, in order to facilitate regeneration of the composite material in the adsorption unit, the adsorption unit includes an inlet and an outlet for regenerant, thereby facilitating introduction of a heat source or water wash into the adsorption unit for regeneration of the composite material.

According to the system of the present invention, in order to realize continuous operation of the system, it is preferable that the adsorption unit comprises at least two adsorption towers (e.g., a first adsorption tower 41 and a second adsorption tower 42) for alternately using SO-containing gas obtained by continuous adsorption incineration₂SO in flue gas₂. When the composite material is regenerated by thermal regeneration, as shown in fig. 1, hot gas (e.g., hot nitrogen) can be introduced from the bottom of the adsorption tower, and the generated regeneration gas is discharged from the top of the adsorption tower, and can be further introduced into the oxidation unit for reprocessing. When the composite material is regenerated by adopting a water washing regeneration mode, as shown in fig. 2, water washing water can be introduced from the top of the adsorption tower, and the generated regenerated dilute acid is discharged from the bottom of the adsorption tower and can be further introduced into the oxidation unit for reprocessing.

According to the system of the invention, the oxidation unit can comprise a liquid sulfur pool 17, and a thermal reaction furnace 11, a primary condenser 12 and a catalytic converter which are connected in sequence, wherein the liquid sulfur pool 17 is connected with the primary condenser 12 and the catalytic converter and is used for collecting cooled liquid sulfur. In order to recover the sulfur more effectively, preferably, the oxidation unit comprises a liquid sulfur pool 17, and a thermal reaction furnace 11, a first-stage condenser 12, a first-stage catalytic converter 13, a second-stage condenser 14, a second-stage catalytic converter 15 and a third-stage condenser 16 which are connected in sequence, wherein the liquid sulfur pool 17 is respectively connected with the first-stage condenser 12, the second-stage condenser 14 and the third-stage condenser 16 and is used for collecting the cooled liquid sulfur.

According to the system of the present invention, the hydrogenation purification unit may include a hydrogenation reactor 21, a hydrogenation tail gas cooler 22, a quench tower 23 and an absorption tower 24, which are connected in sequence. The oxidized tail gas discharged from the oxidation unit is subjected to hydrogenation reduction in a hydrogenation reactor 21, then enters a hydrogenation tail gas cooler 22 and a quenching tower 23 to be cooled, and then enters an absorption tower 24 to absorb hydrogen sulfide in the reduction product.

According to the system of the invention, the incineration unit may be an incinerator and/or a catalytic incineration reactor.

According to the system of the present invention, the oxidation unit, the hydrorefining unit and the incineration unit are used for reducing the content of sulfur dioxide in the sulfur-containing gas, and the adsorption unit provided with the adsorption material is used for further reducing the content of sulfur dioxide.

The invention also provides a desulfurization method, which is characterized by comprising the following steps:

(a) oxidizing the sulfur-containing gas to be treated and recovering sulfur;

(c) incinerating the tail gas after hydrogenation reduction;

According to the present invention, in the step (d), there is no particular requirement for the conditions of the contacting, but preferably, the conditions of the contacting include: the temperature is 100-150 ℃. Preferably, the contacting conditions further comprise: the gas volume space velocity is 1500-2000h^-1。

According to the invention, the composite material not only has good adsorbability, but also has excellent regeneration performance. Thus, the method further comprises regenerating the adsorbent. There is no particular requirement on the method of regeneration, for example, the mode of regeneration may be thermal regeneration and/or water wash regeneration. The composite material of the present invention may be thermally regenerated and/or water-washed regenerated using conventional conditions.

More preferably, the thermal regeneration is performed by gas purgingThe conditions include: the gas volume space velocity is 1000-fold and 1500h^-1The temperature is 150 ℃ and 250 ℃, and the purge gas is an inert gas (such as nitrogen).

The regeneration time can be selected by those skilled in the art as long as the sulfur capacity of the regenerated composite material can be restored to 95% or more of the original state.

According to the present invention, the oxidation in the step (a) is not particularly required, as long as sulfur can be obtained by subjecting the sulfur-containing gas to the claus reaction. For example, the oxidation may be by: and (3) sequentially carrying out combustion, primary cooling and catalytic reaction on the sulfur-containing gas.

Preferably, the conditions of combustion include: the temperature is 900 ℃ and 1400 ℃, and the retention time is 2-3 s. In the present invention, "residence time" means the residence time of the sulfur-containing gas in the combustion vessel, i.e., the time from the entry of the gas into the furnace to the exit of the furnace, i.e., the reaction time of the gas.

Preferably, the primary cooling conditions are such that the temperature of the cooled gas is 120-.

Preferably, the conditions of the catalytic reaction include: the catalyst is an alumina-based catalyst and/or a titania-based catalyst, and the gas volume space velocity is 500-^-1The temperature is 200-350 ℃.

More preferably, the catalytic reaction is performed by sequentially performing a first-stage catalytic reaction, a second-stage cooling, a second-stage catalytic reaction and a third-stage cooling. Further preferably, the conditions of the primary catalytic reaction include: the catalyst is an alumina-based catalyst and/or a titania-based catalyst, and the gas volume space velocity is 600-800h^-1The temperature is 290-330 ℃. Further preferably, the secondary cooling is performed under conditions such that the temperature of the cooled gas is 130-160 ℃. Further preferably, the conditions of the secondary catalytic reaction include that the catalyst is an alumina-based catalyst, and the gas volume space velocity is 600-^-1The temperature is 220-250 ℃. Further preferably, the conditions of the tertiary cooling are such thatThe temperature of the cooled gas is 130-160 ℃.

In the present invention, the main component of the alumina-based catalyst is Al₂O₃The specific surface area is more than or equal to 350m²(ii)/g, pore volume ≥ 0.45ml/g, and is commercially available, for example, as LS-02 catalyst from Qiulu chemical research institute, Inc., Shandong. The main component of the titania-based catalyst is TiO₂The specific surface area is more than or equal to 180m²(ii)/g, pore volume ≥ 0.3ml/g, and is commercially available, for example, as LS-981 catalyst from Qiulu chemical research institute, Inc., Shandong.

According to the present invention, in the step (b), the conditions of the hydrogenation reduction may include: the hydrogenation catalyst is Co-Mo series tail gas hydrogenation catalyst, and the gas volume space velocity is 500-^-1The temperature is 220-350 ℃. Preferably, the hydrogen sulfide in the reduction product obtained by the hydrogenation reduction is recovered by: and cooling the reduction product obtained by hydrogenation reduction to 30-40 ℃, and absorbing hydrogen sulfide in the cooled product by using amine liquid. The concentration of ammonia in the amine liquor may be 20-50 wt%.

In the present invention, the Co-Mo-based tail gas hydrogenation catalyst may be modified Al₂O₃The Claus tail gas low-temperature hydrogenation catalyst which is used as a carrier and takes cobalt, molybdenum and the like as active metal components has the specific surface area of more than or equal to 200m²The/g may be obtained commercially, for example, as LSH-02 catalyst from Qiulu chemical research institute, Inc., Shandong. The Co-Mo series tail gas hydrogenation catalyst can also be modified Al₂O₃The catalyst is used as carrier and has Co and Mo as active metal components and specific surface area not less than 300m²The/g may be obtained commercially, for example, from LS-951T catalyst from Qiulu chemical research institute, Inc., Shandong.

According to the present invention, in the step (c), the incineration conditions may include a temperature of 600 ℃ and 800 ℃ and a residence time of 2 to 3 seconds.

According to the present invention, in the step (c), the incineration may be a conventional incineration manner. Preferably, the incineration is catalytic incineration, and the conditions of the catalytic incineration include: the catalyst isThe catalyst for catalytic incineration with iron and vanadium has the temperature of 250-350 ℃ and the space velocity of 500-1000h^-1. The catalytic incineration catalyst containing iron and vanadium comprises the following specific components: fe₂O₃2-8% by weight, V₂O₅1-4 wt%, and the balance of white carbon black.

According to the invention, CO is present in the sulfur-containing gas₂Is 3-5% of SO₂Has a volume content of 20-1000ppm, a volume content of NOx of 20-150ppm, O₂Is 3-5%, H₂The content of O is 3-10 wt%.

According to the invention, the method is implemented in a system as described above.

The present invention will be described in detail below by way of examples. In the following examples:

activated carbon was purchased from suzhou charcoal cyclone activated carbon ltd;

the alkaline silica sol is purchased from Qingdao Kangsui chemical Co., Ltd;

the molecular weight of the polyethylene glycol is 1900-2200, which is purchased from Tata chemical Co., Ltd in Sn-free market;

the sesbania powder has a molecular weight of 20.6 ten thousand and is purchased from plant gum factories in Lankao county, Henan province;

the molecular weight of the starch is 5.5 ten thousand, and the starch is purchased from Shandong Hengren Industrial Co Ltd;

SiO in water glass₂26.5 wt% from sincerity chemical Limited liability company, Anodont;

the type of the extruder is ZYDJ-30, and the manufacturer is ZiBoyue Cheng machinery Co., Ltd;

the determination method of the element composition is an X-ray fluorescence method, and the specific detection refers to GB/T30905-2014;

the detection method of the specific surface area and the pore volume refers to GB/T6609.35-2009.

Example 1

This example illustrates the composite (or adsorbent) of the present invention and its preparation.

925g of specific surface area is weighed to be 906m²Coconut shell activated carbon per gram, sodium bicarbonate with a purity of 99% by weight 32.67 grams, pure 28 gramsPolyethylene glycol with the degree of 99 wt% is uniformly mixed with the three to form a material A.

66.67g of basic silica Sol (SiO) were weighed₂Content 30 wt%), the silica sol was dissolved in 360g of deionized water, and the mixture was stirred uniformly to prepare a binder.

Adding the binder into the material A, and extruding and molding on a strip extruding machine to obtain the product

The obtained strip-shaped material is dried at 60 ℃ for 3 hours, then dried at 120 ℃ for 5 hours, and then roasted at 550 ℃ for 4 hours to prepare the modified activated carbon (or adsorbent carrier), and the specific surface area and the pore volume of the modified activated carbon are measured, and the results are shown in Table 4.

45.43g of iron nitrate (Fe (NO) was weighed₃)₃) 26.58g lanthanum nitrate hexahydrate (La (NO)₃)₃·6H₂O), 50.45g of cerous nitrate hexahydrate (Ce (NO)₃)₃·6H₂O) is dissolved in deionized water, the mixture is stirred evenly to form a stable solution, the volume is determined according to the adding amount of the adsorbent carrier, active component impregnation liquid is obtained, the adsorbent carrier is impregnated at 25 ℃ according to an isometric impregnation method, the impregnation time is 1h, the impregnated material is dried at 120 ℃ for 6h and roasted at 400 ℃ for 4h, the adsorbent is prepared, the element composition measurement result of the adsorbent is shown in table 2, and the specific surface area and pore volume measurement result is shown in table 4.

Examples 2 to 11

Adsorbents were prepared according to the respective procedures and conditions of example 1 except that the composition, the preparation conditions or the concentration of the impregnation solution were changed, the specific preparation conditions are shown in table 1, the contents of the respective metal oxides and activated carbon in the finally obtained adsorbent products are shown in table 2, and the measurement results of the specific surface area and the like are shown in table 4.

TABLE 1

TABLE 2

Example numbering	Na₂O	SiO₂	Fe₂O₃	CeO₂	La₂O₃	Activated carbon
							Example 1	1	2	1.5	2	1	Balance of
Example 2	1	2	1	1	1	Balance of
							Example 3	1	2	2	3	1	Balance of
Example 4	1	1	1.5	2	2	Balance of
							Example 5	0.5	2	1.5	2.5	1	Balance of
Example 6	1.5	2.5	1.5	1.5	1.5	Balance of
							Example 7	1	1.5	1.5	2	1.5	Balance of
Example 8	1	1	1.5	3	3	Balance of
							Example 9	0.5	2	1.5	0.5	1	Balance of
Example 10	(K₂O)1	2	2.5	2	1	Balance of
							Example 11	(K₂O)1	2	0.5	2	1	Balance of

Example 12

Mixing ratio surface area of 906m²Coconut shell activated carbon/g, sodium bicarbonate with a purity of 99 wt.%, polyethylene glycol with a purity of 99 wt.%, alkaline silica Sol (SiO)₂30 percent by weight) of ferric nitrate, lanthanum nitrate hexahydrate, cerium nitrate hexahydrate and deionized water, the amount of polyethylene glycol was 2g and the amount of deionized water was 12g, relative to 100g of activated carbon, and the amounts of the other components were such that the weight ratios among activated carbon, alkali metal elements, silicon elements, iron elements and rare earth elements in the obtained adsorbent were the same as in example 1. And extruding the obtained mixture on a strip extruding machine for strip forming to obtain a strip-shaped material with the thickness of 3-5mm multiplied by 10mm, then drying the strip-shaped material at 60 ℃ for 3 hours, then drying the strip-shaped material at 120 ℃ for 5 hours, and then roasting the dried strip-shaped material at 550 ℃ for 4 hours to prepare the adsorbent, wherein the measurement results of the specific surface area are shown in table 4.

Example 13

Mixing ratio surface area of 906m²Coconut shell activated carbon/g, sodium bicarbonate with a purity of 99 wt.%, polyethylene glycol with a purity of 99 wt.%, alkaline silica Sol (SiO)₂30 percent by weight) of ferric nitrate, lanthanum nitrate hexahydrate, cerium nitrate hexahydrate and deionized water, the amount of polyethylene glycol was 5g and the amount of deionized water was 12g, relative to 100g of activated carbon, and the amounts of the other components were such that the weight ratios among activated carbon, alkali metal elements, silicon elements, iron elements and rare earth elements in the obtained adsorbent were the same as in example 5. And extruding the obtained mixture on a strip extruding machine for strip forming to obtain a strip-shaped material with the thickness of 3-5mm multiplied by 10mm, then drying the strip-shaped material at 60 ℃ for 3 hours, then drying the strip-shaped material at 120 ℃ for 5 hours, and then roasting the dried strip-shaped material at 550 ℃ for 4 hours to prepare the adsorbent, wherein the measurement results of the specific surface area are shown in table 4.

Example 14

An adsorbent was prepared according to the respective procedures and conditions of example 1, except that polyethylene glycol was replaced with equal weight of cellulose.

Comparative examples 1 to 6

Adsorbents were prepared according to the respective procedures and conditions of example 1 except that the concentration of the impregnation solution was changed so that the contents of the respective metal oxides and activated carbon in the finally obtained adsorbent products were as shown in Table 3, and the results of measuring the specific surface area and the like were as shown in Table 4.

TABLE 3

Numbering	Na₂O	SiO₂	Fe₂O₃	CeO₂	La₂O₃	Activated carbon
							Comparative example 1	1	2	0	2	1	Balance of
Comparison ofExample 2	1	2	1	0	1.5	Balance of
							Comparative example 3	1	2	2	3	0	Balance of
Comparative example 4	1	2	1.5	0	0	Balance of
							Comparative example 5	1.5	0	1.5	1.5	1.5	Balance of
Comparative example 6	0	1.5	1.5	2	1.5	Balance of

Comparative examples 7 to 9

An adsorbent was prepared according to the respective procedures and conditions of example 1, except that iron nitrate was replaced with equal weights (in terms of metal oxides) of copper nitrate, manganese nitrate and zinc nitrate, respectively.

Comparative example 10

An adsorbent was prepared by following the respective procedures and conditions of example 1, except that lanthanum nitrate hexahydrate and cerium nitrate hexahydrate were replaced with nickel nitrate in equal weight (in terms of metal oxide).

Comparative example 11

An adsorbent was prepared according to the respective procedures and conditions of example 1, except that the alkaline silica sol was replaced with concentrated sulfuric acid of equal weight.

Test example 1

The adsorbents prepared in examples and comparative examples were subjected to evaluation of adsorption activity:

the reactor of the micro-reaction device is made of a stainless steel pipe with the inner diameter of 20mm and is placed in a constant temperature box. The loading amount of the adsorbent is 10ml, and the upper part of the adsorbent is filled with quartz sand with the same granularity for mixing and preheating. Analysis of SO in reactor inlet and outlet gases by using a morphological sulfur chromatograph manufactured by AC company₂The content of (a).

The chromatographic conditions were as follows:

a chromatographic column: agilent 7890B

A detector: antek 7090(SCD)

A chromatographic column: the stainless steel column has a length of 30m, an inner diameter of 0.32mm and a liquid film thickness of 4 μm; liquid film specification PDMS-1

Column temperature: 250 deg.C

Detector temperature: 950 ℃ C

Temperature of the gasification chamber: 275 deg.C

Carrier gas (N)₂) Flow rate: 90 ml/min;

sample introduction amount: 1 μ L

Inlet gas volume composition of CO₂3% by volume, SO₂0.03 vol% (900 mg/m)³)、H₂O3% by volume and the balance N₂The space velocity of the gas volume is 1750h^-1The reaction temperature was 120 ℃.

Calculating the adsorbent to SO according to the formula₂Removal rate of eta SO₂：

Wherein N is₀And N₁Then represent the inlet and outlet SO, respectively₂The volume concentration of (c).

The sulfur capacity was calculated according to the following formula:

wherein M is_SulfurDenotes the weight of sulfur adsorbed by activated carbon, M_{Catalytic converter}Represents the weight of the adsorbent used for adsorbing sulfur; the saturated sulfur capacity refers to the maximum amount of sulfur that can be absorbed by the desulfurizer per unit weight, that is, the fresh adsorbent is continuously contacted with the sulfur-containing gas, and when the sulfur content of the sulfur-containing gas before and after the contact with the adsorbent is equal, the percentage of the sulfur content absorbed by the adsorbent in the adsorbent is the saturated sulfur capacity.

Penetration sulfur capacity: under certain use conditions, the adsorbent can absorb the weight percentage of sulfur while ensuring the process purification degree index. In other words, when the sulfur content in the outlet process gas is higher than the process purification index, all the waste catalyst is immediately unloaded, and the sulfur capacity measured by averaging is called breakthrough sulfur capacity. In the present invention, SO₂Penetration is considered to be achieved when the removal rate is reduced to 99%, i.e. the penetration sulfur capacity in the present invention means SO₂The sulfur capacity of the adsorbent when the removal rate is reduced to 99%, and the total time of the adsorbent used when the sulfur capacity is penetrated is defined as the adsorption time.

The analytical results are shown in Table 4.

TABLE 4

From the results in table 4, it can be seen that the composite material of the present invention has a high sulfur penetration capacity.

Test example 2

SO removal was performed on the adsorbents prepared in example 1 and comparative example 1₂Test (the concrete method is the same as test example 1), when the adsorbent is used for SO₂The adsorption of the sulfur-containing adsorbent is penetrated, and the SO-containing adsorbent stops penetrating when the sulfur capacity of the adsorbent is reached₂And (4) adsorbing the gas, and converting nitrogen to investigate the regeneration performance of the adsorbent. The regeneration conditions are as follows: space velocity of 1200h^-1The temperature is 200 ℃, the purging gas is nitrogen, and the regeneration time is 6 h. SO removal with regenerated sorbent₂Test shows that the adsorbent is regenerated while reaching the sulfur capacity, and the adsorbent is regenerated continuously for 5 times and the adsorbent SO after each regeneration₂The breakthrough sulfur capacity results are shown in Table 5.

TABLE 5

From the data in table 5, it can be seen that the breakthrough sulfur capacity of the sorbent of the invention remains substantially unchanged and the composite of the invention exhibits good regeneration performance. Further experiments demonstrated that the regeneration performance of the adsorbents obtained in examples 2-7 was similar to that of example 1 (results not shown).

Test example 3

Desulfurization was carried out using the system of the present invention, as shown in fig. 1, comprising:

the oxidation unit is used for treating sulfur-containing gas and recovering sulfur and comprises a liquid sulfur pool 17, and a thermal reaction furnace 11, a first-stage condenser 12, a first-stage catalytic converter 13, a second-stage condenser 14, a second-stage catalytic converter 15 and a third-stage condenser 16 which are sequentially connected, wherein the liquid sulfur pool 17 is respectively connected with the first-stage condenser 12, the second-stage condenser 14 and the third-stage condenser 16 and is used for collecting cooled liquid sulfur;

the hydrogenation purification unit is connected with the oxidation unit, is used for carrying out hydrogenation reduction on the oxidation tail gas discharged by the oxidation unit and recovering hydrogen sulfide in a reduction product obtained by hydrogenation reduction, and comprises a hydrogenation reactor 21, a hydrogenation tail gas cooler 22, a quench tower 23 and an absorption tower 24 which are sequentially connected;

the incineration unit 31 is used for incinerating the purified tail gas discharged by the hydrogenation purification unit;

an adsorption unit for adsorbing SO-containing gas obtained by incineration₂SO in flue gas₂The adsorbent used in the adsorption unit is the composite material prepared by the invention, and comprises a first adsorption tower 41 and a second adsorption tower 42, wherein the two adsorption towers can be alternately used for realizing continuous adsorption;

the heat exchange unit comprises a tail gas reheater 111 and a flue gas heat exchanger 222, wherein the tail gas reheater 111 is arranged between the oxidation unit and the hydrogenation purification unit and is used for heating the oxidation tail gas discharged by the oxidation unit; the flue gas heat exchanger 222 is arranged between the incineration unit and the adsorption unit and used for reducing the temperature of the flue gas generated by incineration.

The desulfurization step was as follows (the specific operating conditions are shown in Table 6):

(a) treating sulfur-containing gas in an oxidation unit and recovering sulfur

The thermal reaction unit is an acid gas (CO) containing 85% by volume of hydrogen sulfide₂Is 10% by volume, the hydrocarbon content is 2% by volume, NH₃Content of 3 vol%) was partially combusted in the thermal reaction furnace 11 to sulfur dioxide: under high temperature, hydrogen sulfide and sulfur dioxide are subjected to a Claus reaction to generate elemental sulfur and process gas, and the elemental sulfur enters a liquid sulfur pool 17 after being cooled by a primary condenser 12 to obtain liquid sulfur;

the process gas enters a first-stage catalytic converter 13, a second-stage condenser 14, a second-stage catalytic converter 15 and a third-stage condenser 16 of the catalytic reaction unit in sequence. After Claus catalytic conversion, elemental sulfur enters a liquid sulfur pool 17 through a secondary condenser 14 and a tertiary condenser 16; and the Claus tail gas after reaction enters a tail gas purification unit.

(b) The oxidized tail gas is subjected to hydrogenation reduction in a hydrogenation purification unit, and hydrogen sulfide in a reduction product obtained by hydrogenation reduction is recovered

The Claus tail gas is heated to 236 ℃ by the tail gas reheater 111, then enters the hydrogenation reactor 21, under the action of the hydrogenation catalyst in the hydrogenation reactor 21, the sulfur-containing compounds are hydrogenated and converted into hydrogen sulfide, and then is cooled by the hydrogenation tail gas cooler 22 and the quench tower 23, enters the absorption tower 24 with amine liquid, and absorbs the hydrogen sulfide in the hydrogenation tail gas, so as to obtain the purified tail gas.

(c) Incinerating the tail gas after hydrogenation reduction in an incineration unit

The purified tail gas is introduced into an incineration unit (incinerator) 31 to be incinerated to generate SO₂The flue gas is introduced into the adsorption unit.

(d) In an adsorption unit the SO-containing material obtained by incineration₂The flue gas is contacted with an adsorbent to adsorb SO₂

The flue gas enters the first adsorption tower 41 in an adsorption state after being subjected to heat exchange to 145 ℃ by the flue gas heat exchanger 222, and SO in the flue gas is adsorbed₂Then the purified flue gas is discharged through a chimney to purify SO in the flue gas₂Emission control index of 20mg/m³. In the initial stage of operation, no SO is detected in the purified flue gas₂After 650 hours of operation, SO appears in the flue gas₂And the concentration is 1mg/m³Continuing to operate for 780h, and then, adding SO in the flue gas₂Up to 8mg/m³After the operation is continued for 900 hours, SO in the flue gas₂Up to 20mg/m³The first adsorption tower 41 is cut off, and the second adsorption tower 42 is switched to adsorb the incineration exhaust gas. At the same time, the first adsorption tower 41 is charged with regenerated hot nitrogen for thermal regeneration, and SO is generated by regeneration₂The regeneration gas is introduced into the primary catalytic converter 13 for reprocessing. The regeneration time was 100h (relative to 20 m)³The adsorbent of (a). SO in the purified flue gas to be discharged from the second adsorption tower 42₂Up to 20mg/m³In this case, the first adsorption tower 41 after regeneration is switched to perform adsorption. Finally, the concentration is controlled to be 20mg/m³AdsorptionPrecision, can realize the flue gas SO of the sulfur recovery device₂The discharge concentration is lower than 20mg/m³Meets the current most strict environmental protection regulation₂Reduced to 50mg/m³The following requirements are set forth. Moreover, the regeneration mode is simple, and the whole treatment process is continuously clean.

Test example 4

The acid gas was desulfurized according to the system and method of test example 3 except that the incinerator of the incineration unit was replaced with a catalytic incineration reactor and the regeneration was carried out in a water wash regeneration, as shown in fig. 2, in the following manner: and (3) introducing water washing water into the first adsorption tower 41 to regenerate the adsorbent, wherein the regenerated dilute acid is generated by regeneration and is introduced into the thermal reaction furnace 11 for reprocessing. The regeneration time was 140 h. The specific operating conditions for each step are shown in table 6.

TABLE 6

Test example 5

The acid gas was desulfurized according to the system and method of test example 3, except that the temperature of the adsorption unit was 80 ℃ and the gas volume space velocity was 1000h^-1. SO in flue gas when the running time is 720h₂Up to 20mg/m³。

The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims

1. A composite material is characterized by comprising modified activated carbon and an active component loaded on the modified activated carbon, wherein the modified activated carbon comprises activated carbon, an oxide of an alkali metal and an oxide of silicon, and the weight ratio of the activated carbon to the oxide of the alkali metal to the oxide of silicon is 100 (0.2-3) to (0.8-5), preferably 100 (0.5-2) to (1-2.8); the active component contains iron oxide and rare earth element oxide, and the weight ratio of the active carbon to the iron oxide to the rare earth element oxide is 100 (0.5-5) to (1-10), preferably 100 (1-2.2) to (2-5).

2. The composite material according to claim 1, wherein the oxide of an alkali metal is K₂O and/or Na₂O, the oxide of silicon being SiO₂The oxide of iron being Fe₂O₃The oxide of the rare earth element is CeO₂And/or La₂O₃；

Preferably, the oxide of the rare earth element is CeO₂And La₂O₃And CeO₂And La₂O₃The weight ratio of (A) to (B) is 1-3;

preferably, the specific surface area of the modified activated carbon is more than or equal to 600m²/g, preferably 650-750m²(ii)/g; the pore volume is more than or equal to 0.4ml/g, preferably 0.4-0.45 ml/g;

preferably, the specific surface area of the composite material is more than or equal to 550m²/g, preferably 560-590m²(ii)/g; the pore volume is more than or equal to 0.35ml/g, preferably 0.36-0.4 ml/g; the saturated sulfur capacity is more than or equal to 18 percent, and the saturated sulfur capacity is preferably 20 to 25 percent; the penetrating sulfur capacity is more than or equal to 12 percent, and preferably 15.5 to 16 percent.

3. A method of making a composite material, the method comprising:

(1) in the presence of a solvent, kneading, molding, drying and roasting the activated carbon, the alkali metal precursor, the silicon-containing binder and an optional pore-expanding agent to obtain modified activated carbon, wherein the activated carbon, the alkali metal precursor and the silicon-containing binder are used in such an amount that the weight ratio of the activated carbon to the alkali metal elements to the silicon elements in the modified activated carbon is 100 (0.2-3) to 0.8-5, preferably 100 (0.5-2) to 1-2.8;

(2) contacting a precursor of an active component with the modified activated carbon to enable the modified activated carbon to load the active component, wherein the precursor of the active component contains a precursor of iron and a precursor of a rare earth element, and the precursor of the active component is used in an amount such that the weight ratio of the activated carbon to the iron to the rare earth element in the obtained composite material is 100 (0.5-5) to (1-10), preferably 100 (1-2.2) to (2-5);

4. The method according to claim 3, wherein the specific surface area of the activated carbon is 700m or more²(ii)/g, more preferably 700-²/g；

Preferably, the precursor of the alkali metal is at least one of a bicarbonate, a carbonate, a nitrate and a sulfate of the alkali metal, more preferably at least one of sodium bicarbonate, potassium bicarbonate and potassium carbonate;

preferably, the siliceous binder is silica and/or a silicate, more preferably silica sol and/or water glass;

preferably, the weight ratio of the activated carbon to the pore-expanding agent is 100 (1-10);

more preferably, the pore-expanding agent is a substance capable of decomposing at a temperature of not higher than 450 ℃;

further preferably, the pore-expanding agent is at least one of sesbania powder, polyethylene glycol, starch and citric acid;

preferably, the precursor of the iron is soluble iron salt, more preferably ferric nitrate and/or ferric chloride;

preferably, the precursor of the rare earth element is soluble rare earth metal salt, more preferably nitrate of the rare earth metal and/or chloride of the rare earth metal;

further preferably, the precursor of the rare earth element contains a precursor of cerium and a precursor of lanthanum, and the amounts of the precursor of cerium and the precursor of lanthanum are such that the weight ratio of the cerium to the lanthanum in the obtained composite material is 1-3.

5. The method according to claim 3 or 4, wherein in step (1):

the drying mode is as follows: drying at 40-80 deg.C for 2-4 hr; drying at the temperature of 100-160 ℃, preferably at the temperature of 110-130 ℃ for 4-6 h;

preferably, the conditions of the calcination include: the roasting temperature is 400-700 ℃, preferably 450-600 ℃, and the roasting time is 3-8h, preferably 4-6 h;

and/or, in step (2):

the mode of loading the modified activated carbon with the active component is as follows: soaking the modified active carbon with a solution of a precursor containing an active component in an equal volume, drying the soaked matter, and roasting the dried product;

preferably, the conditions for equal volume impregnation include: the temperature is 5-40 ℃, preferably 20-30 ℃; the time is 20min to 3h, preferably 0.5 to 1 h;

preferably, the conditions for drying the impregnate include: the temperature is 80-160 ℃, and the temperature is preferably 110-130 ℃; the time is 2 to 10 hours, preferably 4 to 6 hours;

preferably, the conditions under which the dried product is calcined include: the roasting temperature is 300-500 ℃, preferably 350-450 ℃, and the roasting time is 2-10h, preferably 3-5 h.

6. A composite material obtainable by the process of any one of claims 3 to 5.

7. Use of the composite material of claim 1, 2 or 6 in adsorptive desulfurization.

8. A method of desulfurization, the method comprising: contacting a sulfur-containing gas to be treated with the composite material of claim 1, 2 or 6;

alternatively, the method comprises: preparing a composite material according to the method of any one of claims 3 to 5; then contacting the sulfur-containing gas with the obtained composite material;

preferably, the sulfur dioxide content in the sulfur-containing gas is not higher than 6000mg/m³；

Preferably, when the sulfur dioxide content in the sulfur-containing gas is higher than 6000mg/m³The method may further comprise reducing the sulphur dioxide content of the sulphur-containing gas to 6000mg/m prior to contacting with the composite material³The following;

preferably, the conditions of the contacting include: the temperature is 100-150 ℃, and the gas volume space velocity is 1500-2000h^-1；

Preferably, the method further comprises: regenerating the composite material;

more preferably, the regeneration mode is thermal regeneration and/or water washing regeneration;

further preferably, the thermal regeneration is performed by gas purging, and the gas purging conditions include: the gas volume space velocity is 1000-fold and 1500h^-1The temperature is 150 ℃ and 250 ℃, and the sweeping gas is nitrogen;

further preferably, the conditions of the water washing regeneration include: the liquid hourly space velocity is 0.5-1.5h^-1The temperature is 25-40 ℃;

preferably, the sulfur-containing gas is at least one of heating furnace flue gas, sulfur tail gas and catalytic cracking regeneration flue gas in the petroleum refining industry.

9. A system having a desulfurization function, characterized by comprising:

an oxidation unit for treating the sulfur-containing gas and recovering sulfur;

an adsorption unit for adsorbing SO-containing gas obtained by incineration₂SO in flue gas₂The adsorbent used in the adsorption unit is the composite material according to any one of claims 1, 2 or 6.

10. A method of desulfurization, the method comprising:

(a) oxidizing the sulfur-containing gas to be treated and recovering sulfur;

(c) incinerating the tail gas after hydrogenation reduction;

(d) SO that the SO contained in the obtained material after incineration₂The flue gas is contacted with an adsorbent to adsorb SO₂The adsorbent is the composite material of claim 1, 2 or 6;

preferably, the method is implemented in a system according to claim 9.