CN106693632B - Zinc oxide-based normal-temperature deep desulfurizing agent and preparation method and application thereof - Google Patents

Zinc oxide-based normal-temperature deep desulfurizing agent and preparation method and application thereof Download PDF

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CN106693632B
CN106693632B CN201710025806.XA CN201710025806A CN106693632B CN 106693632 B CN106693632 B CN 106693632B CN 201710025806 A CN201710025806 A CN 201710025806A CN 106693632 B CN106693632 B CN 106693632B
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salt
zinc oxide
zinc
desulfurizer
nitrate
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CN106693632A (en
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张磊
叶丽萍
陈孙维
罗勇
李建龙
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Shanghai Research Institute of Chemical Industry SRICI
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Abstract

The invention relates to a zinc oxide base normal temperature deep desulfurizer and a preparation method and application thereof, wherein in the preparation process, a mixed solution of zinc salt, aluminum salt and auxiliary agent metal salt is subjected to one-step coprecipitation reaction to form a composite precipitate, and the composite precipitate is aged, dried and roasted to obtain the zinc oxide base normal temperature deep composite desulfurizer; the prepared zinc oxide-based normal-temperature deep desulfurizer is used for H in various gaseous and liquid materials in the field of petroleum and coal chemical industry2The S is deeply removed at normal temperature, namely a fixed bed is adopted for operation, and the liquid volume space velocity is controlled to be 1-12 h under the conditions that the reaction temperature is 20-60 ℃ and the operation pressure is 0.1-5 MPa‑1Or the gas phase space velocity is 1000-30000 h‑1H with the content of 1-1000 ppm in the material to be treated2S is removed to be less than or equal to 0.03 ppm. Compared with the prior art, the penetrating sulfur capacity of the prepared desulfurizer at normal temperature reaches 26.1%, the desulfurization precision reaches below 0.03ppm, and the preparation method is simple and can be used for large-scale industrial production.

Description

Zinc oxide-based normal-temperature deep desulfurizing agent and preparation method and application thereof
Technical Field
The invention belongs to the technical field of energy and chemical materials, relates to a zinc oxide-based normal-temperature deep desulfurizing agent, a preparation method and application thereof, and particularly relates to a zinc oxide-based desulfurizing agent for performing normal-temperature deep removal on hydrogen sulfide in various gaseous and liquid materials in the fields of petroleum and coal chemical industry, and a preparation method and application thereof.
Background
Hydrogen sulfide (H)2S) are widely present in petroleum and coal chemical products such as olefins, liquefied petroleum gas, natural gas, synthesis gas, and the like. During the transportation and storage of these chemical raw materials, H2S can corrode equipment and piping. Especially in the subsequent deep processing and utilization process, very small amount of H2The presence of S can result in catalyst poisoning. Therefore, in the industrial production process, the deep removal of hydrogen sulfide is an essential important link and is an important component of the chemical raw material purification process.
H in chemical raw material2The removal of S usually adopts two technologies of dry desulfurization and wet desulfurization. Although the wet desulphurization has mature technology, the problems of high energy consumption, large equipment investment and the like exist in the desulphurization process, and the greatest defect is that only H can be used2S is removed to about 1-10 ppm, and deep desulfurization cannot be realized. In contrast, dry desulfurization has the characteristics of high desulfurization precision, small equipment investment, low energy consumption and the like. In dry desulfurization, the zinc oxide desulfurizer has the advantages of high desulfurization precision, large sulfur capacity, stable performance and the like, and is widely applied to fine desulfurization of chemical raw materials. However, the conventional zinc oxide desulfurizer usually has high sulfur capacity and desulfurization activity only under the medium-high temperature condition of 180-400 ℃, so that the energy consumption in the desulfurization process is high, and many chemical raw materials are easy to generate side reaction and deteriorate at the temperature. But at normal temperature, the desulfurization activity and the sulfur capacity are obviously reduced, and the sulfur capacity is generally lower than 12%. In order to improve the low-temperature desulfurization activity and sulfur capacity of the zinc oxide desulfurizer, those skilled in the art have begun to move from a pure zinc oxide desulfurizer to a zinc oxide-based composite metal oxide desulfurizer.
Chinese patent CN 1046213C discloses a calcium aluminoferrite cement (mainly comprising CaO and Fe) prepared from zinc oxide (such as zinc oxide, zinc hydroxide, zinc carbonate or basic zinc carbonate) and structural assistant2O3、Al2O3) The normal-temperature zinc oxide-based composite desulfurizer consists of the components, wherein the content of an active component ZnO is more than 80-95% (m/m). The zinc oxide desulfurizer is at 20 ℃ for 1500h-1Under the condition of time, the sulfur capacity is only 8.2 percent, and the desulfurization precision can only reach below 0.05 ppm.
Chinese patent CN 102078749B discloses a zinc oxide-based fine desulfurizer which is composed of basic zinc carbonate, copper carbonate, alumina cement, iron oxyhydroxide and a binder. When the weight portion of basic zinc carbonate is 60 portions, copper carbonate is 25 portions, gamma-iron oxyhydroxide is 6 portions and alumina cement is 11 portions, the desulfurization precision of the prepared zinc oxide-based fine desulfurizing agent at 20 ℃ reaches 0.02ppm, but the sulfur capacity is 13.8%.
Chinese patent CN 101591557B discloses an improved normal temperature desulfurizer prepared from active zinc oxide, manganese carbonate, mixed auxiliary agent (kaolin, attapulgite, bentonite or high-volume sulfur powder), alkaline auxiliary agent (sodium metaaluminate with causticization coefficient of 1.45-1.55) and binder (carboxymethyl cellulose or methyl cellulose solution). Under the test condition of 25 ℃, when the content of zinc oxide in the desulfurizer is more than or equal to 95 percent, the sulfur capacity of the desulfurizer is the highest and is 12 percent.
Chinese patent CN 102961959B discloses a zinc oxide fine desulfurizer prepared by mixing and extruding active zinc oxide, high-alumina powder, bentonite, calcium hydroxide and sodium carboxymethylcellulose into strips. The fine desulfurizing agent is at 25 ℃ and the airspeed of 1h-1Under the condition, 12ppm of H in liquid propylene2S is removed to 0.03ppm, and the sulfur capacity is 3.1%.
Chinese patent CN 101485954A discloses a desulfurizing agent prepared by mixing nano zinc oxide, copper oxide, a binder, a pore-forming agent and water to form a mixture, and then kneading, molding, drying and roasting the mixture. The desulfurization precision of the desulfurizer at 30 ℃ can only reach below 0.05ppm, the penetrating sulfur capacity is 15.5%, and the requirement cannot be met, which is probably caused by insufficient and uniform mixing of active components of nano zinc oxide and copper oxide in the preparation process of kneading molding.
In summary, although many years of research shows that the desulfurization performance of the zinc oxide-based desulfurizing agent is greatly improved, the current technology related to the zinc oxide-based desulfurizing agent still has the following disadvantages: 1) the sulfur capacity of the desulfurizer needs to be further improved, and particularly the sulfur capacity at normal temperature is generally lower than 15%; 2) the desulfurization precision is not enough, and the hydrogen sulfide is difficult to remove to be less than 0.03 ppm; 3) the low-temperature activity of the desulfurizer is insufficient, and the desulfurizer is usually required to be carried out at a higher temperature to achieve a good desulfurization effect and a high sulfur capacity, so that the energy consumption and the operation cost are increased; 4) there is still a need to find a simpler preparation method of the desulfurizer, which can improve the utilization rate of the active components and reduce the cost. Therefore, it is necessary to develop a deep desulfurizer for trace hydrogen sulfide, which has good low-temperature activity, high sulfur capacity and high stability under normal temperature and pressure conditions, low synthesis cost and easy industrialization, and develop a corresponding desulfurization process, and the deep desulfurizer has important significance for deep removal and purification of hydrogen sulfide in petroleum and coal chemical raw materials.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a zinc oxide-based normal-temperature deep desulfurizer which can realize large-scale production, is economical and practical, and has high sulfur capacity and high desulfurization precision at normal temperature and normal pressure, and a preparation method and application thereof.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of a zinc oxide-based normal-temperature deep desulfurizing agent specifically comprises the following steps:
step (1): dissolving zinc salt, aluminum salt and auxiliary metal salt in water, respectively preparing salt solutions with the molar concentration of 0.05-3 mol/L, mixing, and uniformly stirring to obtain mixed metal salt solutions;
step (2): preparing a precipitator solution with the molar concentration of 0.05-3 mol/L;
and (3): adding the precipitant solution prepared in the step (2) into the mixed metal salt solution prepared in the step (1), stirring and reacting for a period of time to prepare precursor slurry, and then fully stirring the precursor slurry for aging treatment;
and (4): and (4) performing centrifugal separation on the aged precursor slurry in the step (3), collecting the precipitate, and washing, drying and roasting the precipitate to obtain the zinc oxide-based normal-temperature deep desulfurizer.
The molar ratio of the zinc salt to the aluminum salt to the auxiliary metal salt in the mixed metal salt solution in the step (1) is 100: 1-30: 1-50.
The zinc salt in the step (1) comprises one or more of zinc nitrate, zinc chloride, zinc sulfate or zinc acetate, and the aluminum salt comprises one or more of aluminum nitrate, aluminum chloride or aluminum sulfate.
The assistant metal salt in the step (1) comprises one or more of calcium salt, manganese salt, ferric salt, cobalt salt, nickel salt or copper salt.
The calcium salt comprises one of calcium acetate, calcium sulfate, calcium nitrate or calcium chloride, the manganese salt comprises one of cobalt acetate, manganese sulfate, manganese nitrate or manganese chloride, the ferric salt comprises one of ferric acetate, ferric sulfate, ferric nitrate or ferric chloride, the cobalt salt comprises one of cobalt acetate, cobalt sulfate, cobalt nitrate or cobalt chloride, the nickel salt comprises one of nickel acetate, nickel sulfate, nickel nitrate or nickel chloride, and the copper salt comprises one of copper acetate, copper sulfate, copper nitrate or copper chloride.
The precipitator in the step (2) comprises one or more of sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium carbonate, potassium bicarbonate, potassium hydroxide, ammonia water, ammonium carbonate or ammonium bicarbonate.
The molar ratio of the mixed metal salt to the precipitant in the step (3) is 1: 1-4; the conditions for the stirring reaction were: stirring and reacting for 0.5-2 h at 20-80 ℃; the conditions of the aging treatment were: aging for 2-8 h at 60-90 ℃.
The drying conditions in the step (4) are as follows: drying for 2-8 h at 80-120 ℃; the roasting conditions are as follows: roasting for 2-6 h at 300-500 ℃.
The zinc oxide-based normal-temperature deep desulfurizer prepared by the method.
Application of zinc oxide-based normal-temperature deep desulfurizer for H in various gaseous and liquid materials in the field of petroleum and coal chemical industry2Deep removal of S at ambient temperature, i.e. miningOperating by using a fixed bed, and controlling the liquid volume space velocity to be 1-12 h under the conditions that the reaction temperature is 20-60 ℃ and the operation pressure is 0.1-5 MPa-1Or the gas phase space velocity is 1000-30000 h-1H with the content of 1-1000 ppm in the material to be treated2S is removed to be less than or equal to 0.03 ppm.
Said compound containing H2S in the petroleum and coal chemical industry, the gaseous and liquid materials are one or more of olefin, alkane, liquefied petroleum gas, natural gas and synthetic gas, and the material is H2The S content is 1-1000 ppm, preferably not more than 100 ppm.
The preparation method of the zinc oxide-based normal-temperature deep desulfurizing agent comprises the steps of carrying out one-step coprecipitation reaction on a mixed solution of zinc salt, aluminum salt and auxiliary agent metal salt to form a composite precipitate, and aging, drying and roasting to obtain the zinc oxide-based normal-temperature deep composite desulfurizing agent. The preparation method of the zinc oxide-based normal-temperature deep composite desulfurizer has a simple preparation process and can be used for large-scale industrial production. The penetrating sulfur capacity of the desulfurizer prepared by the invention at normal temperature reaches 26.1%, and the desulfurization precision reaches below 0.03 ppm. It is especially suitable for deep removal of hydrogen sulfide from various gaseous and liquid materials at normal temperature in the fields of petroleum and coal chemical industry.
Compared with the prior art, the invention has the following characteristics:
1) the aluminum oxide structure auxiliary agent and the transition metal electronic auxiliary agent are added in one step by adopting a coprecipitation method, so that the specific surface area and the pore structure of the ZnO adsorbent are increased, and the interaction between the ZnO active component and the transition metal auxiliary agent is enhanced, thereby greatly improving the low-temperature sulfur capacity and the desulfurization precision of the zinc oxide-based desulfurizer;
2) compared with the traditional zinc oxide desulfurizer, the normal-temperature sulfur capacity of the desulfurizer prepared by the invention is greatly improved, the energy consumption in the desulfurization process is reduced, the utilization rate of the desulfurizer is improved, and the cost is reduced;
3) the preparation method provided by the invention is simple in preparation process, mild in operation condition, suitable for industrial scale-up production and good in application prospect.
Detailed Description
The present invention will be described in detail with reference to specific examples.
Example 1:
a preparation method of a zinc oxide-based normal-temperature deep composite desulfurizer adopts the following steps:
(1) dissolving zinc nitrate, aluminum nitrate and manganese nitrate in water, respectively preparing salt solutions with the concentration of 0.1mol/L, mixing, and fully stirring to be uniform to obtain mixed metal salt solutions; wherein the molar ratio of the zinc nitrate to the aluminum nitrate to the manganese nitrate is 100:15: 5; simultaneously preparing a sodium carbonate solution with the concentration of 0.1 mol/L;
(2) adding a sodium carbonate solution into the mixed salt solution, wherein the molar ratio of the mixed salt to the sodium carbonate is 1:1.5, and reacting for 1h under stirring at 70 ℃ to obtain precursor slurry; then fully stirring the obtained precursor slurry, and aging for 4 hours at the temperature of 80 ℃;
(3) carrying out centrifugal separation on the precursor slurry, collecting precipitate, washing the precipitate by deionized water, drying at 90 ℃ for 6h, and roasting at 350 ℃ for 4h to obtain the zinc oxide-based normal-temperature deep composite desulfurizer;
the zinc oxide-based normal-temperature deep composite desulfurizer is crushed after tabletting and granulation, a sample of 40-60 meshes is screened out, fixed bed operation is adopted, and the reaction temperature is 30 ℃, the gas volume space velocity is 3000h-1，H2Under the evaluation condition of standard gas (nitrogen as bottom gas) with the S concentration of 1%, the penetrating sulfur capacity reaches 26.1%, and the desulfurization precision reaches below 0.03 ppm.
Example 2:
a preparation method of a zinc oxide-based normal-temperature deep composite desulfurizer adopts the following steps:
(1) dissolving zinc acetate, aluminum nitrate and nickel nitrate in water, respectively preparing salt solutions with the concentration of 0.05mol/L, mixing, and fully stirring to be uniform to obtain mixed metal salt solutions; wherein the molar ratio of the zinc acetate to the aluminum nitrate to the nickel nitrate is 100:1: 20; preparing an ammonium carbonate solution with the concentration of 0.05 mol/L;
(2) adding an ammonium carbonate solution into the mixed salt solution, wherein the molar ratio of the mixed salt to the ammonium carbonate is 1:2, and reacting for 2 hours at 20 ℃ under stirring to obtain precursor slurry; then fully stirring the obtained precursor slurry, and aging for 2h at the temperature of 90 ℃;
(3) carrying out centrifugal separation on the precursor slurry, collecting precipitate, washing the precipitate by deionized water, drying at 80 ℃ for 8h, and roasting at 350 ℃ for 4h to obtain the zinc oxide-based normal-temperature deep composite desulfurizer;
the zinc oxide-based normal-temperature deep composite desulfurizer is crushed after tabletting and granulation, a sample of 40-60 meshes is screened out, fixed bed operation is adopted, and the reaction temperature is 30 ℃, the gas volume space velocity is 3000h-1，H2Under the evaluation condition of standard gas (nitrogen as bottom gas) with the S concentration of 1%, the penetrating sulfur capacity reaches 25.8%, and the desulfurization precision reaches below 0.03 ppm.
Example 3:
a preparation method of a zinc oxide-based normal-temperature deep composite desulfurizer adopts the following steps:
(1) dissolving zinc chloride, aluminum nitrate and cobalt nitrate in water, respectively preparing salt solutions with the concentration of 3mol/L, mixing, and fully stirring to be uniform to obtain mixed metal salt solutions; wherein the molar ratio of the zinc chloride to the aluminum nitrate to the cobalt nitrate is 100:25: 15; preparing 3mol/L ammonium bicarbonate solution at the same time;
(2) adding an ammonium bicarbonate solution into the mixed salt solution, wherein the molar ratio of the mixed salt to the ammonium bicarbonate is 1:4, and reacting for 2 hours at the temperature of 60 ℃ under stirring to obtain precursor slurry; then fully stirring the obtained precursor slurry, and aging for 4 hours at the temperature of 80 ℃;
(3) carrying out centrifugal separation on the precursor slurry, collecting precipitate, washing the precipitate by deionized water, drying at 120 ℃ for 2h, and roasting at 300 ℃ for 6h to obtain the zinc oxide-based normal-temperature deep composite desulfurizer;
the zinc oxide-based normal-temperature deep composite desulfurizer is crushed after tabletting and granulation, a sample of 40-60 meshes is screened out, fixed bed operation is adopted, and the reaction temperature is 30 ℃, the gas volume space velocity is 3000h-1，H2Standard gas (nitrogen) with S concentration of 1%As bottom gas), the penetration sulfur capacity reaches 23.6%, and the desulfurization precision reaches below 0.03 ppm.
Example 4:
a preparation method of a zinc oxide-based normal-temperature deep composite desulfurizer adopts the following steps:
(1) dissolving zinc nitrate, aluminum nitrate and ferric nitrate in water, respectively preparing salt solutions with the concentration of 0.2mol/L, mixing, and fully stirring to be uniform to obtain mixed metal salt solutions; wherein the molar ratio of the zinc nitrate to the aluminum nitrate to the ferric nitrate is 100:15: 1; simultaneously preparing a sodium bicarbonate solution with the concentration of 0.2 mol/L;
(2) adding a sodium bicarbonate solution into the mixed salt solution, wherein the molar ratio of the mixed salt to the sodium bicarbonate is 1:2, and reacting for 2 hours at 50 ℃ under stirring to obtain precursor slurry; fully stirring the obtained precursor slurry, and aging at the temperature of 60 ℃ for 8 h;
(3) carrying out centrifugal separation on the precursor slurry, collecting precipitate, washing the precipitate by deionized water, drying at 100 ℃ for 8h, and roasting at 450 ℃ for 2h to obtain the zinc oxide-based normal-temperature deep composite desulfurizer;
the zinc oxide-based normal-temperature deep composite desulfurizer is crushed after tabletting and granulation, a sample of 40-60 meshes is screened out, fixed bed operation is adopted, and the reaction temperature is 30 ℃, the gas volume space velocity is 3000h-1，H2Under the evaluation condition of standard gas (nitrogen as bottom gas) with the S concentration of 1%, the penetrating sulfur capacity reaches 24.5%, and the desulfurization precision reaches below 0.03 ppm.
Example 5:
a preparation method of a zinc oxide-based normal-temperature deep composite desulfurizer adopts the following steps:
(1) dissolving zinc nitrate, aluminum nitrate and copper nitrate in water, respectively preparing salt solutions with the concentration of 0.5mol/L, mixing, and fully stirring to be uniform to obtain mixed metal salt solutions; wherein the molar ratio of the zinc nitrate to the aluminum nitrate to the copper nitrate is 100:15: 5; simultaneously preparing a potassium carbonate solution with the concentration of 0.5 mol/L;
(2) adding a potassium carbonate solution into the mixed salt solution, wherein the molar ratio of the mixed salt to the potassium carbonate is 1:1.5, and reacting for 1h at 70 ℃ under stirring to obtain precursor slurry; then fully stirring the obtained precursor slurry, and aging for 4 hours at the temperature of 80 ℃;
(3) carrying out centrifugal separation on the precursor slurry, collecting precipitate, washing the precipitate by deionized water, drying at 100 ℃ for 8 hours, and roasting at 400 ℃ for 4 hours to obtain the zinc oxide-based normal-temperature deep composite desulfurizer;
the zinc oxide-based normal-temperature deep composite desulfurizer is crushed after tabletting and granulation, a sample of 40-60 meshes is screened out, fixed bed operation is adopted, and the reaction temperature is 30 ℃, the gas volume space velocity is 3000h-1，H2Under the evaluation condition of standard gas (nitrogen as bottom gas) with the S concentration of 1%, the penetrating sulfur capacity reaches 25.3%, and the desulfurization precision reaches below 0.03 ppm.
Example 6:
a preparation method of a zinc oxide-based normal-temperature deep composite desulfurizer adopts the following steps:
(1) dissolving zinc nitrate, aluminum nitrate and calcium chloride in water, respectively preparing salt solutions with the concentration of 0.1mol/L, mixing, and fully stirring to be uniform to obtain mixed metal salt solutions; wherein the molar ratio of the zinc nitrate to the aluminum nitrate to the calcium chloride is 100:15: 30; preparing an ammonium carbonate solution with the concentration of 0.1 mol/L;
(2) adding an ammonium carbonate solution into the mixed salt solution, wherein the molar ratio of the mixed salt to the ammonium carbonate is 1:1, and reacting for 2 hours at the temperature of 60 ℃ under stirring to obtain precursor slurry; then fully stirring the obtained precursor slurry, and aging for 2h at the temperature of 90 ℃;
(3) carrying out centrifugal separation on the precursor slurry, collecting precipitate, washing the precipitate by deionized water, drying at 110 ℃ for 4h, and roasting at 450 ℃ for 4h to obtain the zinc oxide-based normal-temperature deep composite desulfurizer;
the zinc oxide-based normal-temperature deep composite desulfurizer is crushed after tabletting and granulation, a sample of 40-60 meshes is screened out, fixed bed operation is adopted, and the reaction temperature is 30 ℃, the gas volume space velocity is 3000h-1，H2Concentration of SUnder the evaluation condition of 1% standard gas (nitrogen as bottom gas), the penetrating sulfur capacity reaches 24.8%, and the desulfurization precision reaches below 0.03 ppm.
Example 7:
a preparation method of a zinc oxide-based normal-temperature deep composite desulfurizer adopts the following steps:
(1) dissolving zinc nitrate, aluminum nitrate and manganese nitrate in water, respectively preparing salt solutions with the concentration of 0.5mol/L, mixing, and fully stirring to be uniform to obtain mixed metal salt solutions; wherein the molar ratio of the zinc nitrate to the aluminum nitrate to the manganese nitrate is 100:30: 50; simultaneously preparing a sodium carbonate solution with the concentration of 0.5 mol/L;
(2) adding a sodium carbonate solution into the mixed salt solution, wherein the molar ratio of the mixed salt to the sodium carbonate is 1:2, and reacting for 0.5h under stirring at 80 ℃ to obtain precursor slurry; then fully stirring the obtained precursor slurry, and aging for 2h at the temperature of 90 ℃;
(3) carrying out centrifugal separation on the precursor slurry, collecting precipitate, washing the precipitate by deionized water, drying at 100 ℃ for 8h, and roasting at 500 ℃ for 2h to obtain the zinc oxide-based normal-temperature deep composite desulfurizer;
the zinc oxide-based normal-temperature deep composite desulfurizer is crushed after tabletting and granulation, a sample of 40-60 meshes is screened out, fixed bed operation is adopted, and the reaction temperature is 30 ℃, the gas volume space velocity is 3000h-1，H2Under the evaluation condition of standard gas (nitrogen as bottom gas) with the S concentration of 1%, the penetrating sulfur capacity reaches 25.9%, and the desulfurization precision reaches below 0.03 ppm.
Example 8:
a preparation method of a zinc oxide-based normal-temperature deep composite desulfurizer adopts the following steps:
(1) dissolving zinc nitrate, aluminum nitrate and copper nitrate in water, respectively preparing salt solutions with the concentration of 1mol/L, mixing, and fully stirring to be uniform to obtain mixed metal salt solutions; wherein the molar ratio of the zinc nitrate to the aluminum nitrate to the copper nitrate is 100:15: 15; simultaneously preparing a potassium carbonate solution with the concentration of 1 mol/L;
(2) adding a potassium carbonate solution into the mixed salt solution, wherein the molar ratio of the mixed salt to the potassium carbonate is 1:1.5, and reacting for 1h at 60 ℃ under stirring to obtain precursor slurry; then fully stirring the obtained precursor slurry, and aging for 4 hours at the temperature of 80 ℃;
(3) carrying out centrifugal separation on the precursor slurry, collecting precipitate, washing the precipitate by deionized water, drying at 100 ℃ for 8h, and roasting at 350 ℃ for 4h to obtain the zinc oxide-based normal-temperature deep composite desulfurizer;
the zinc oxide-based normal-temperature deep composite desulfurizer is crushed after tabletting and granulation, a sample of 40-60 meshes is screened out, fixed bed operation is adopted, and the reaction temperature is 30 ℃, the gas volume space velocity is 3000h-1，H2Under the evaluation condition of standard gas (nitrogen as bottom gas) with the S concentration of 1%, the penetrating sulfur capacity reaches 26.0%, and the desulfurization precision reaches below 0.03 ppm.
Example 9:
the application of the zinc oxide-based normal-temperature deep composite desulfurizer comprises the following steps:
tabletting and granulating the zinc oxide-based normal-temperature deep composite desulfurizer obtained in the example 1, crushing, screening out a 40-60-mesh sample, weighing 1g of the desulfurizer, filling the desulfurizer in a fixed bed device according to the height-diameter ratio of 3:1, feeding the desulfurizer from top to bottom by using a constant-pressure direct-current pump, and reacting at the temperature of 30 ℃, the pressure of 3MPa and the liquid volume airspeed of 12h at the reaction temperature of 3 ℃ and the liquid volume airspeed of 12 MPa-1Under the conditions of (1), 10ppm of H in propylene can be added2S is removed to be below 0.03ppm, and the penetrating sulfur capacity reaches 24.8 percent.
Example 10:
the application of the zinc oxide-based normal-temperature deep composite desulfurizer comprises the following steps:
tabletting and granulating the zinc oxide-based normal-temperature deep composite desulfurizer obtained in the example 5, crushing, screening out a 40-60-mesh sample, weighing 1g of the desulfurizer, filling the desulfurizer into a fixed bed device according to a height-diameter ratio of 3:1, and reacting at 20 ℃, under a pressure of 0.1MPa and a gas volume space velocity of 10000h-1Under the conditions of (1), 10ppm of H in ethylene can be added2S is removed to be below 0.03ppm, and the penetrating sulfur capacity reaches 25.4 percent.
Comparative example 1:
a preparation method of a zinc oxide desulfurizer comprises the following steps:
(1) dissolving zinc nitrate in water to prepare a salt solution with the concentration of 0.1 mol/L; simultaneously preparing a sodium carbonate solution with the concentration of 0.1 mol/L;
(2) adding a sodium carbonate solution into the zinc nitrate solution, wherein the molar ratio of the zinc nitrate to the sodium carbonate is 1:1.5, and reacting for 1h at 70 ℃ under stirring to obtain precursor slurry; then fully stirring the obtained precursor slurry, and aging for 4 hours at the temperature of 80 ℃;
(3) carrying out centrifugal separation on the precursor slurry, collecting precipitate, washing the precipitate by deionized water, drying at 90 ℃ for 6h, and roasting at 350 ℃ for 4h to obtain a zinc oxide desulfurizer;
tabletting and granulating the zinc oxide desulfurizer, crushing, screening a 40-60 mesh sample, and operating by adopting a fixed bed at the reaction temperature of 30 ℃ and the gas volume space velocity of 3000h-1，H2Under the evaluation condition of standard gas (nitrogen as bottom gas) with the S concentration of 1%, the penetrating sulfur capacity is 8.1%, and the desulfurization precision reaches below 0.03 ppm.
Comparative example 2:
a preparation method of a zinc oxide-based normal-temperature deep composite desulfurizer adopts the following steps:
(1) dissolving zinc nitrate and aluminum nitrate in water, respectively preparing salt solutions with the concentration of 0.1mol/L, mixing, and fully stirring to be uniform to obtain mixed metal salt solutions; wherein the molar ratio of the zinc nitrate to the aluminum nitrate is 100: 15; simultaneously preparing a sodium carbonate solution with the concentration of 0.1 mol/L;
(2) adding a sodium carbonate solution into the mixed salt solution, wherein the molar ratio of the mixed salt to the sodium carbonate is 1:1.5, and reacting for 1h under stirring at 70 ℃ to obtain precursor slurry; then fully stirring the obtained precursor slurry, and aging for 4 hours at the temperature of 80 ℃;
(3) carrying out centrifugal separation on the precursor slurry, collecting precipitate, washing the precipitate by deionized water, drying at 90 ℃ for 6h, and roasting at 350 ℃ for 4h to obtain the zinc oxide-based normal-temperature deep composite desulfurizer;
to make thisThe zinc oxide-based normal-temperature deep composite desulfurizer is crushed after tabletting and granulation, a sample of 40-60 meshes is screened out, fixed bed operation is adopted, and the reaction temperature is 30 ℃, the gas volume space velocity is 3000h-1，H2Under the evaluation condition of standard gas (nitrogen as bottom gas) with the S concentration of 1%, the penetrating sulfur capacity reaches 14.3%, and the desulfurization precision reaches below 0.03 ppm.
The desulfurization performance result shows that the sulfur capacity of the zinc oxide-based normal-temperature deep composite desulfurizer obtained by the preparation method of the zinc oxide-based normal-temperature deep composite desulfurizer is up to 26.1% at normal temperature and is far higher than that of the zinc oxide normal-temperature desulfurizer in comparative examples 1-2, which shows that zinc, aluminum and transition metal additive elements in the zinc oxide-based normal-temperature deep composite desulfurizer obtained by the one-step coprecipitation method are uniformly dispersed, so that the specific surface area and pore channel structure of a ZnO adsorbent are increased, and the interaction between a ZnO active component and the transition metal additive is enhanced, so that the low-temperature sulfur capacity and desulfurization precision of the zinc oxide-based desulfurizer are greatly improved.
Example 11:
the preparation method of the zinc oxide-based normal-temperature deep desulfurizing agent comprises the following steps:
step (1): dissolving zinc salt, aluminum salt and auxiliary agent metal salt in water, respectively preparing salt solutions with the molar concentration of 0.05mol/L, mixing, and uniformly stirring to obtain mixed metal salt solutions;
step (2): preparing a precipitator solution with the molar concentration of 0.05 mol/L;
and (3): adding the precipitant solution prepared in the step (2) into the mixed metal salt solution prepared in the step (1), stirring and reacting for a period of time to prepare precursor slurry, and then fully stirring the precursor slurry for aging treatment;
and (4): and (4) performing centrifugal separation on the aged precursor slurry in the step (3), collecting the precipitate, and washing, drying and roasting the precipitate to obtain the zinc oxide-based normal-temperature deep desulfurizer.
Wherein the molar ratio of the zinc salt to the aluminum salt to the auxiliary metal salt in the mixed metal salt solution in the step (1) is 100:1: 1. The zinc salt is zinc sulfate and the aluminum salt is aluminum nitrate. The auxiliary agent metal salt is nickel salt, and the nickel salt is formed by mixing nickel acetate and nickel sulfate according to the mass ratio of 1:1.
And (3) the precipitator in the step (2) is ammonia water.
In the step (3), the molar ratio of the mixed metal salt to the precipitator is 1: 4; the conditions for the stirring reaction were: stirring and reacting for 2h at 20 ℃; the conditions of the aging treatment were: aging at 60 deg.C for 8 h.
The drying conditions in the step (4) are as follows: drying at 80 deg.C for 8 h; the roasting conditions are as follows: roasting at 300 deg.c for 6 hr.
The zinc oxide-based normal-temperature deep desulfurizer prepared by the method.
Application of zinc oxide-based normal-temperature deep desulfurizer for H in various gaseous and liquid materials in the field of petroleum and coal chemical industry2The normal temperature deep removal of S is that a fixed bed is adopted for operation, the liquid volume space velocity is controlled to be 1h under the conditions that the reaction temperature is 20 ℃ and the operation pressure is 0.1MPa-1H with the content of 1-1000 ppm in the material to be treated2S is removed to be less than or equal to 0.03 ppm.
Example 12:
the preparation method of the zinc oxide-based normal-temperature deep desulfurizing agent comprises the following steps:
step (1): dissolving zinc salt, aluminum salt and auxiliary metal salt in water, respectively preparing salt solutions with the molar concentration of 3mol/L, mixing, and uniformly stirring to obtain mixed metal salt solutions;
step (2): preparing a precipitator solution with the molar concentration of 3 mol/L;
and (3): adding the precipitant solution prepared in the step (2) into the mixed metal salt solution prepared in the step (1), stirring and reacting for a period of time to prepare precursor slurry, and then fully stirring the precursor slurry for aging treatment;
and (4): and (4) performing centrifugal separation on the aged precursor slurry in the step (3), collecting the precipitate, and washing, drying and roasting the precipitate to obtain the zinc oxide-based normal-temperature deep desulfurizer.
Wherein the molar ratio of the zinc salt to the aluminum salt to the auxiliary metal salt in the mixed metal salt solution in the step (1) is 100:30: 50. The zinc salt is zinc chloride and the aluminum salt is aluminum sulfate. The auxiliary agent metal salt is formed by mixing manganese salt, ferric salt and cobalt salt according to the molar ratio of 1:1:1, wherein the manganese salt is manganese sulfate, the ferric salt is ferric nitrate, and the cobalt salt is cobalt sulfate.
The precipitator in the step (2) is ammonium bicarbonate.
In the step (3), the molar ratio of the mixed metal salt to the precipitator is 1: 1; the conditions for the stirring reaction were: stirring and reacting for 0.5h at 80 ℃; the conditions of the aging treatment were: aging at 90 deg.C for 2 h.
The drying conditions in the step (4) are as follows: drying at 120 deg.C for 2 h; the roasting conditions are as follows: roasting at 500 deg.c for 2 hr.
The zinc oxide-based normal-temperature deep desulfurizer prepared by the method.
Application of zinc oxide-based normal-temperature deep desulfurizer for H in various gaseous and liquid materials in the field of petroleum and coal chemical industry2The normal-temperature deep removal of S is carried out by adopting fixed bed operation, and controlling the liquid volume space velocity to be 12h under the conditions that the reaction temperature is 60 ℃ and the operation pressure is 5MPa-1H with the content of 1-1000 ppm in the material to be treated2S is removed to be less than or equal to 0.03 ppm.
The embodiments described above are intended to facilitate the understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (5)

1. A preparation method of a zinc oxide-based normal-temperature deep desulfurizing agent is characterized by comprising the following steps:
step (1): dissolving zinc salt, aluminum salt and auxiliary metal salt in water, respectively preparing salt solutions with the molar concentration of 0.05-3 mol/L, mixing, and uniformly stirring to obtain mixed metal salt solutions;
step (2): preparing a precipitator solution with the molar concentration of 0.05-3 mol/L;
and (3): adding the precipitant solution prepared in the step (2) into the mixed metal salt solution prepared in the step (1), stirring and reacting for a period of time to prepare precursor slurry, and then fully stirring the precursor slurry for aging treatment;
and (4): centrifugally separating the aged precursor slurry in the step (3), collecting the precipitate, washing, drying and roasting the precipitate to obtain the zinc oxide-based normal-temperature deep desulfurizer,
the molar ratio of the zinc salt to the aluminum salt to the auxiliary metal salt in the mixed metal salt solution in the step (1) is 100: 1-30: 1-50,
the molar ratio of the mixed metal salt to the precipitant in the step (3) is 1: 1-4; the conditions for the stirring reaction were: stirring and reacting for 0.5-2 h at 20-80 ℃; the conditions of the aging treatment were: aging for 2-8 h at 60-90 ℃,
the drying conditions in the step (4) are as follows: drying for 2-8 h at 80-120 ℃; the roasting conditions are as follows: roasting for 2-6 h at 300-500 ℃;
the zinc salt in the step (1) comprises one or more of zinc nitrate, zinc chloride, zinc sulfate or zinc acetate, the aluminum salt comprises one or more of aluminum nitrate, aluminum chloride or aluminum sulfate, and the auxiliary metal salt comprises one or more of calcium salt, manganese salt, ferric salt, cobalt salt, nickel salt or copper salt.
2. The method as claimed in claim 1, wherein the calcium salt includes one of calcium acetate, calcium sulfate, calcium nitrate or calcium chloride, the manganese salt includes one of cobalt acetate, manganese sulfate, manganese nitrate or manganese chloride, the iron salt includes one of iron acetate, iron sulfate, iron nitrate or iron chloride, the cobalt salt includes one of cobalt acetate, cobalt sulfate, cobalt nitrate or cobalt chloride, the nickel salt includes one of nickel acetate, nickel sulfate, nickel nitrate or nickel chloride, and the copper salt includes one of copper acetate, copper sulfate, copper nitrate or copper chloride.
3. The method for preparing a zinc oxide based normal temperature deep desulfurization agent according to claim 1, wherein the precipitant in step (2) comprises one or more of sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium carbonate, potassium bicarbonate, potassium hydroxide, ammonia water, ammonium carbonate or ammonium bicarbonate.
4. The zinc oxide-based normal temperature deep desulfurizing agent prepared by the method of any one of claims 1 to 3.
5. The application of the zinc oxide-based normal temperature deep desulfurizer as claimed in claim 4, wherein the zinc oxide-based normal temperature deep desulfurizer is used for H in gaseous and liquid materials in the petroleum and coal chemical industry field2And deeply removing the S at normal temperature.
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101119796A (en) * 2005-01-06 2008-02-06 研究三角协会 Zinc oxide based adsorption agent and method of making and using same

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0055535A1 (en) * 1980-12-31 1982-07-07 Imperial Chemical Industries Plc Fluid purification
US20060283780A1 (en) * 2004-09-01 2006-12-21 Sud-Chemie Inc., Desulfurization system and method for desulfurizing a fuel stream
CN102078813A (en) * 2010-12-13 2011-06-01 昆明理工大学 Catalyst for hydrolyzing carbonyl sulfide at low temperature and preparation method of catalyst

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101119796A (en) * 2005-01-06 2008-02-06 研究三角协会 Zinc oxide based adsorption agent and method of making and using same

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