CN110586028A - Desulfurizing agent and preparation method and application thereof - Google Patents
Desulfurizing agent and preparation method and application thereof Download PDFInfo
- Publication number
- CN110586028A CN110586028A CN201910948661.XA CN201910948661A CN110586028A CN 110586028 A CN110586028 A CN 110586028A CN 201910948661 A CN201910948661 A CN 201910948661A CN 110586028 A CN110586028 A CN 110586028A
- Authority
- CN
- China
- Prior art keywords
- oxide
- metal oxide
- precursor
- desulfurizing agent
- desulfurizer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0259—Compounds of N, P, As, Sb, Bi
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
- C10K1/004—Sulfur containing contaminants, e.g. hydrogen sulfide
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/32—Purifying combustible gases containing carbon monoxide with selectively adsorptive solids, e.g. active carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/42—Materials comprising a mixture of inorganic materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/042—Purification by adsorption on solids
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0485—Composition of the impurity the impurity being a sulfur compound
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to the technical field of a desulfurizing agent, and particularly relates to a desulfurizing agent and a preparation method and application thereof. The desulfurizer provided by the invention comprises the following components in percentage by mass: 35-70% of metal oxide A, 5-20% of metal oxide B, 20-40% of metal oxide C and 1-5% of phosphorus pentoxide; the metal oxide A is zinc oxide, and the metal oxide C is aluminum oxide; the metal oxide B is at least one selected from manganese oxide, copper oxide, iron oxide, gallium oxide and cobalt oxide. The desulfurizer has strong wear resistance, large sulfur capacity, large specific surface area and pore volume, still has higher activity after being regenerated for many times, and can better remove hydrogen sulfide in synthesis gas (containing fuel gas).
Description
Technical Field
The invention relates to the technical field of a desulfurizing agent, and particularly relates to a desulfurizing agent and a preparation method and application thereof.
Background
The synthesis gas (containing fuel gas) prepared by coal gasification is the basis of novel coal chemical industry, is mainly used for synthesizing ammonia in the prior art, is mainly used for producing methanol, glycol, natural gas, special oil products and the like at present, and is also used for synthesizing fine chemicals.
The sulfur-containing compounds in the synthesis gas not only can cause corrosion of production equipment and pipelines and influence production safety, but also can cause poisoning and inactivation on the catalyst of subsequent chemical reaction and directly influence the yield and quality of the final product. The sulfur-containing compounds in the synthesis gas are removed, so that the safety production can be improved, the subsequent reaction efficiency can be guaranteed, and important sulfur resources can be recovered from the sulfur-containing compounds.
The synthesis gas desulfurization mainly comprises two modes of wet desulfurization and dry desulfurization. The wet desulfurization has three processes of chemical absorption, physical absorption and physical and chemical absorption, and has the advantages that the desulfurizer can be continuously circulated for desulfurization and regeneration, is suitable for large-scale production and can recover sulfur. The wet desulphurization has the disadvantages that the wet desulphurization is generally used in the normal-temperature and low-temperature desulphurization process, and the operation energy consumption is too high for medium-temperature or high-temperature synthesis gas. The dry desulfurization includes adsorption reaction methods such as zinc oxide and activated carbon methods, and particularly, the zinc oxide desulfurization is the most extensive. Dry desulfurization has many advantages of both inorganic sulfur removal and organic sulfur removal, both high temperature desulfurization and low temperature desulfurization, and high desulfurization accuracy, but dry desulfurization is not a desulfurizer regeneration, only periodic operation, not suitable for the removal of a large amount of sulfides. Therefore, the development of the dry-method adsorbent capable of continuously carrying out adsorption regeneration is not only suitable for the desulfurization of the synthesis gas at different temperatures, but also capable of saving energy and reducing consumption, and is an urgent problem to be solved for the desulfurization of the synthesis gas.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention relates to a desulfurizing agent, which comprises the following components in percentage by mass:
35-70% of metal oxide A, 5-20% of metal oxide B, 20-40% of metal oxide C and 1-5% of phosphorus pentoxide;
the metal oxide A is zinc oxide, and the metal oxide C is aluminum oxide;
the metal oxide B is at least one selected from manganese oxide, copper oxide, iron oxide, gallium oxide and cobalt oxide.
The invention aims to solve the problems that the existing zinc oxide desulfurizer can not be repeatedly regenerated and reused, and the physical state of the zinc oxide desulfurizer is not suitable for the fluidized bed process of desulfurization regeneration circulation of the desulfurizer.
According to one aspect of the invention, the invention also relates to a preparation method of the desulfurizing agent, which comprises the following steps:
and (3) molding and roasting the slurry containing the precursors of the components to obtain the desulfurizer.
The preparation method of the desulfurizer is simple and easy to implement, and the desulfurizer can be obtained by uniformly mixing precursors of the components and then carrying out molding and roasting operations.
According to another aspect, the invention also relates to the use of a desulphurisation agent in a fluidised bed desulphurisation process.
The desulfurizer of the invention is used in the process of a regenerative circulating fluidized bed, and can better remove hydrogen sulfide in gas raw materials.
Compared with the prior art, the invention has the beneficial effects that:
(1) the desulfurizer obtained by the invention has strong wear resistance, large sulfur capacity, large specific surface area and pore volume, and high activity after repeated regeneration, and can better remove hydrogen sulfide in synthesis gas (containing fuel gas).
(2) The preparation method of the desulfurizer is simple and easy to implement, and the desulfurizer with excellent performance can be obtained by uniformly mixing the components, molding and roasting. The desulfurizer is used for the process of a regenerative and cyclic fluidized bed, and can better remove hydrogen sulfide in gas raw materials.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
According to one aspect of the invention, the invention relates to a desulfurizing agent, which comprises the following components in percentage by mass:
35-70% of metal oxide A, 5-20% of metal oxide B, 20-40% of metal oxide C and 1-5% of phosphorus pentoxide;
the metal oxide A is zinc oxide, and the metal oxide C is aluminum oxide;
the metal oxide B is at least one selected from manganese oxide, copper oxide, iron oxide, gallium oxide and cobalt oxide.
In one embodiment, the oxide a is 35% to 70% by mass, and may alternatively be 40%, 45%, 50%, 55%, 60% or 65%.
In one embodiment, the metal oxide B is 5% to 20% by mass, and may be selected from 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18% or 19%.
The zinc oxide-based desulfurizer of the invention is modified by metal oxides such as manganese oxide, iron oxide, copper oxide, oxidation and the like, and the activity attenuation of the desulfurizer is not obvious after the desulfurizer is regenerated for many times.
In one embodiment, the phosphorus pentoxide is 1% to 5%, optionally 1.5%, 2%, 2.5%, 3%, 3.5%, 4% or 4.5% by mass.
The desulfurizer containing phosphorus pentoxide is particularly suitable for desulfurizing synthesis gas with high steam content so as to maintain the desulfurization activity of the desulfurizer.
In one embodiment, the metal oxide C is 20% to 40% by mass, and may also be selected from 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38% or 39%.
The desulfurizer obtained by the coordination of zinc oxide, phosphorus pentoxide, aluminum oxide and metal oxide B (at least one of manganese oxide, copper oxide, iron oxide, gallium oxide and cobalt oxide) has excellent wear resistance, large sulfur capacity, large specific surface area and pore volume, and still has high activity after being regenerated for many times, so that hydrogen sulfide in synthesis gas (containing fuel gas) can be better removed.
Preferably, the desulfurizing agent comprises the following components in percentage by mass:
55-63% of metal oxide A, 10-15% of metal oxide B, 25-32% of metal oxide C and 2-3% of phosphorus pentoxide. By further optimizing the proportion of the metal oxide A, the metal oxide B, the metal oxide C and the phosphorus pentoxide, the desulfurizer which has better wear resistance, larger sulfur capacity and higher activity after multiple regenerations can be obtained.
Preferably, the phosphorus pentoxide is obtained by decomposing a precursor of phosphorus pentoxide, and the precursor of phosphorus pentoxide includes at least one of phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate and ammonium dihydrogen phosphate.
The desulfurizer containing phosphorus pentoxide and prepared by modifying the zinc oxide-based desulfurizer by phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate and ammonium dihydrogen phosphate is particularly suitable for desulfurizing synthesis gas with high water vapor content so as to keep the desulfurization activity of the desulfurizer.
Preferably, the zinc oxide is obtained by decomposing a precursor of zinc oxide, and the precursor of zinc oxide comprises at least one of nano basic zinc carbonate, nano zinc oxide, zinc nitrate and zinc chloride;
preferably, the precursor of the zinc oxide is nano basic zinc carbonate.
The zinc oxide-based desulfurizer has high desulfurization precision, and particularly has high desulfurization activity and large sulfur capacity for nanometer basic zinc carbonate and nanometer zinc oxide.
Preferably, the metal oxide B is obtained by decomposing a precursor of the metal oxide B, and the precursor of the metal oxide B is selected from nitrates and/or chlorides corresponding to the metals in the metal oxide, preferably nitrates;
the precursor of manganese oxide comprises manganese nitrate, the precursor of copper oxide comprises copper nitrate, the precursor of iron oxide comprises iron nitrate, the precursor of gallium oxide comprises gallium nitrate, and the precursor of cobalt oxide comprises cobalt nitrate.
Preferably, the alumina is obtained by decomposing an alumina precursor, the alumina precursor comprising an aluminum-based catalyst support and an aluminum-based binder;
preferably, the aluminum-based catalyst support comprises pseudoboehmite;
preferably, the aluminum-based binder comprises an aluminum sol.
The zinc oxide-based desulfurizer prepared by using the pseudo-boehmite as the catalyst carrier and the alumina sol as the binder has strong wear resistance, large specific surface area and pore volume, and is particularly suitable for the working conditions of fluidized bed adsorption desulfurization and regeneration.
According to another aspect of the present invention, the present invention also relates to a method for preparing a desulfurizing agent, comprising the steps of:
and (3) molding and roasting the slurry containing the precursors of the components to obtain the desulfurizer.
The preparation method of the desulfurizer is simple to operate, and precursors of the components are mixed and stirred uniformly, and then molding and roasting operations are carried out to obtain the desulfurizer with excellent performance.
Preferably, the slurry is obtained by mixing the precursors of the respective components and water.
Calculating the mass of the precursor of each corresponding component according to the content of each component of the desulfurizer, and mixing and stirring the precursor of each component and a proper amount of water to obtain slurry.
In one embodiment, the weight ratio of the precursor of metal oxide a, the precursor of metal oxide B, the precursor of metal oxide C, and the precursor of phosphorus pentoxide in the slurry is 2520: 235: 907: 32, a first step of removing the first layer;
the precursor of the metal oxide C comprises an aluminum-based catalyst carrier and an aluminum-based binder, wherein the weight ratio of the aluminum-based binder to the aluminum-based catalyst carrier is 715: 192.
Preferably, the slurry has a solids content of 25% to 35%.
In one embodiment, the slurry has a solids content of 25% to 35%, and may alternatively be 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, or 34%.
Preferably, the specific preparation method of the slurry comprises the following steps:
and mixing and stirring the precursor of the metal oxide C and water for 2-10 h, adding the precursor of the metal oxide A, the precursor of the metal oxide B and the precursor of phosphorus pentoxide, and mixing and stirring for 2-10 h to obtain slurry.
In one embodiment, the precursor of the metal oxide C and water are mixed and stirred for 2-10 h. 3h, 4h, 5h, 6h, 7h, 7.5h, 8h, 8.5h, 9h or 9.5h can also be selected.
In one embodiment, the precursor of the metal oxide A, the precursor of the metal oxide B and the precursor of the phosphorus pentoxide are added and mixed for 2-10 h, and 3h, 4h, 5h, 6h, 7h, 7.5h, 8h, 8.5h, 9h or 9.5h can be selected.
The aluminum-based binder, the aluminum-based catalyst carrier and water are mixed and stirred for 2-10 hours to obtain uniform slurry, and then the precursor of zinc oxide, the precursor of metal oxide and the precursor of phosphorus pentoxide are added and mixed for 2-10 hours, so that the components are uniformly mixed, the pore structure of the desulfurizer is effectively improved, and the desulfurization performance of the desulfurizer is improved.
Preferably, the shaping is spray shaping;
preferably, in the spray forming process, the temperature of a hearth is 350-450 ℃, the temperature of an outlet of a drying tower is 150-250 ℃, and the spray pressure of the drying tower is 2.5-4.5 MPa;
in one embodiment, the furnace temperature is 350-450 deg.C, and can be selected from 355 deg.C, 360 deg.C, 365 deg.C, 370 deg.C, 375 deg.C, 380 deg.C, 385 deg.C, 390 deg.C, 395 deg.C, 400 deg.C, 405 deg.C, 410 deg.C, 415 deg.C, 420 deg.C, 425 deg.C, 430 deg.C, 435 deg.C, 440.
In one embodiment, the temperature at the outlet of the drying tower is 150-250 ℃, and 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃ or 240 ℃ can be selected.
In one embodiment, the spray pressure of the drying tower is 2.5-4.5 MPa, and 2.7MPa, 3MPa, 3.2MPa, 3.5MPa, 3.7MPa, 4MPa or 4.2MPa can be selected.
The particle size distribution of the desulfurizer obtained by adopting the spray forming process with specific temperature, time and pressure is particularly suitable for the working conditions of fluidized bed adsorption desulfurization and regeneration.
Preferably, the method further comprises the step of drying the spray-molded material, wherein the drying temperature is 120-150 ℃, and the drying time is 5-10 hours.
In one embodiment, the drying temperature is 120-150 deg.C, and can be selected from 125 deg.C, 130 deg.C, 135 deg.C, 140 deg.C or 145 deg.C.
In one embodiment, the drying time is 5-10 h, and 6h, 7h, 8h or 9h can be selected.
Preferably, the roasting temperature is 520-650 ℃, and the roasting time is 4-8 h.
In one embodiment, the temperature of the calcination is 520-650 deg.C, and 530 deg.C, 540 deg.C, 550 deg.C, 560 deg.C, 570 deg.C, 580 deg.C, 590 deg.C, 600 deg.C, 610 deg.C, 620 deg.C, 630 deg.C or 640 deg.C can be selected.
In one embodiment, the roasting time is 4-8 h, and 4.5h, 5h, 5.5h, 6h, 6.5h, 7h or 7.5h can be selected.
The precursors of each component are decomposed into corresponding oxides by roasting at a specific temperature for a specific time, and the precursors are more favorable for the formation of pore channels of the desulfurizer during decomposition, so that the sulfur capacity and the desulfurization activity of the desulfurizer are improved.
In a preferred embodiment, the method for preparing the desulfurizing agent comprises the following steps:
mixing and stirring an aluminum-based binder, an aluminum-based catalyst carrier and water for 2-10 h, adding a precursor of zinc oxide, a precursor of metal oxide B (at least one of manganese oxide, copper oxide, iron oxide, gallium oxide and cobalt oxide) and a precursor of phosphorus pentoxide, and mixing and stirring for 2-10 h to obtain slurry; spray-drying and molding the slurry, controlling the temperature of a spray-drying hearth to be 350-450 ℃, the outlet temperature of a drying tower to be 150-250 ℃, the spray pressure of the drying tower to be 2.5-4.5 MPa, drying the spray-molded material at the temperature of 120-150 ℃ for 5-10 hours, and then roasting at the temperature of 520-650 ℃ for 4-8 hours to obtain a finished product desulfurizer; the solid content of the slurry is 25-35%.
According to another aspect, the invention also relates to the use of a desulphurising agent in a fluidised bed desulphurisation process. The desulfurizer is used for the process of a regenerative and cyclic fluidized bed, and can better remove hydrogen sulfide in gas raw materials.
The present invention will be further explained with reference to specific examples and comparative examples.
Example 1
A preparation method of a desulfurizing agent comprises the following steps:
715g of alumina sol (Al)2O321 percent) and 2285g of deionized water are added, 192g of pseudo-boehmite (32 percent loss) is slowly added with stirring, after 2.0h of stirring, 32g of ammonium dihydrogen phosphate, 235g of copper nitrate and 2520g of basic zinc carbonate are slowly added with stirring, and then the mixture is stirred for 5.0 h. Spray drying and forming under the conditions of the furnace temperature of 400 ℃, the outlet temperature of 200 ℃ and the spray pressure of 4.0MPa, drying the formed adsorbent at 150 ℃ for 5.0h, and roasting at 600 ℃ for 5.0h to obtain the desulfurizer.
Example 2
A preparation method of a desulfurizing agent comprises the following steps:
715g of alumina sol (Al)2O321 percent of the total weight of the components, 2285g of deionized water is added, 192g of pseudo-boehmite (32 percent loss due to ignition) is slowly added with stirring, 32g of ammonium dihydrogen phosphate, 206g of manganese nitrate and 2520g of basic zinc carbonate are slowly added with stirring after 2 hours of stirring, and then the mixture is stirred for 5 hours. Spray drying and forming under the conditions of the furnace temperature of 400 ℃, the outlet temperature of 200 ℃ and the spray pressure of 4.0MPa, drying the formed adsorbent for 5h at 150 ℃, and roasting at 600 ℃ for 5h to obtain the desulfurizer.
Example 3
A preparation method of a desulfurizing agent comprises the following steps:
taking 650g of alumina sol (Al)2O319 percent of the total weight of the raw materials, 2505g of deionized water is added, 192g of pseudo-boehmite (32 percent of ignition loss) is slowly added while stirring, 37g of ammonium phosphate, 100g of manganese nitrate, 95g of copper nitrate and 2450g of nano zinc oxide are slowly added while stirring after 3 hours of stirring, and then the mixture is stirred for 6 hours. Spray drying and forming under the conditions that the temperature of a hearth is 350 ℃, the outlet temperature is 250 ℃ and the spray pressure is 4.5MPa, drying the formed adsorbent for 5 hours at 120 ℃, and roasting at 650 ℃ for 4 hours to obtain the desulfurizer.
Example 4
A preparation method of a desulfurizing agent comprises the following steps:
735g of aluminum sol (Al)2O3Content 21.6%) and adding 2380g of deionized water, slowly adding 192g of pseudo-boehmite (32% of ignition loss) while stirring, slowly adding 34g of ammonium phosphate, 42g of manganese nitrate, 33g of ferric nitrate, 55g of copper nitrate, 40g of gallium nitrate, 35g of cobalt nitrate and 2370g of nano zinc oxide while stirring after stirring for 5 hours, and then stirring for 8 hours. Spray drying and forming under the conditions that the temperature of a hearth is 450 ℃, the outlet temperature is 150 ℃ and the spray pressure is 2.5MPa, drying the formed adsorbent for 8 hours at 130 ℃, and roasting at 600 ℃ for 6 hours to obtain the desulfurizer.
Comparative example 1
A method for preparing a desulfurizing agent was carried out in the same manner as in example 1 except that ammonium dihydrogen phosphate and copper nitrate were not added.
Comparative example 2
The preparation method of the desulfurizing agent is the same as that of the embodiment 1 except that ammonium dihydrogen phosphate is not added.
Test examples
1. The physical properties of the desulfurizing agents obtained in examples 1 to 4 and comparative examples 1 to 2 are shown in Table 1;
TABLE 1 physical Properties of the desulfurizing agent
As can be seen from Table 1, the desulfurizing agent obtained by the process of the present invention has a high specific surface area and pore volume and is excellent in abrasion resistance. The specific surface area, pore volume and wear resistance of the desulfurizing agent prepared in the comparative examples 1-2 are relatively poor.
2. The desulfurizing agents prepared in examples 1 to 4 and comparative examples 1 to 2 were subjected to adsorption regeneration performance tests, and the test results are shown in table 2, and the specific test methods are as follows:
(1) evaluating the filling amount of the desulfurizer by using a fixed bed test device to be 5.0 g;
(2) the raw material gas for evaluation contains H2S2000mg/m3The water vapor content is 30 percent, and the balance is nitrogen;
(3) the evaluation conditions are normal pressure, temperature of 300 ℃ and gas space velocity of 2000h-1The total sulfur content of purified gas is more than 1mg/m3The desulfurizing agent is considered to be penetrated and inactivated, and the inactivated desulfurizing agent is regenerated by air at the temperature of 550 ℃ and normal pressure.
TABLE 2 desulfurization and regeneration Performance of the desulfurizing agent
| Examples and comparative examples | Sulfur capacity of fresh desulfurizing agent% | Sulfur capacity of desulfurizing agent after 50 times of regeneration% |
| Example 1 | 19.1 | 16.5 |
| Example 2 | 18.3 | 16.1 |
| Example 3 | 20.1 | 16.8 |
| Example 4 | 19.5 | 17.0 |
| Comparative example 1 | 20.3 | 6.5 |
| Comparative example 2 | 18.5 | 9.7 |
The desulfurizing agent obtained by the method can be used for synthesizing gas H2The S concentration is reduced to 1.0mg/m3(ii) a The sulfur capacity of the desulfurizer is as high as 18.3-25 g (sulfur)/100 g (desulfurizer); the desulfurization activity is kept above 80% after 50 times of desulfurizer regeneration; the desulfurizing agent has strong wear resistance in the adsorption regeneration cycle process, and the wear index is lower than 3.0 percent. Although the fresh desulfurizer prepared in the comparative examples 1-2 has high sulfur capacity, the activity of the desulfurizer is greatly reduced after 50 times of regeneration.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The desulfurizer is characterized by comprising the following components in percentage by mass:
35-70% of metal oxide A, 5-20% of metal oxide B, 20-40% of metal oxide C and 1-5% of phosphorus pentoxide;
the metal oxide A is zinc oxide, and the metal oxide C is aluminum oxide;
the metal oxide B is at least one selected from manganese oxide, copper oxide, iron oxide, gallium oxide and cobalt oxide.
2. The desulfurizing agent according to claim 1, wherein the phosphorus pentoxide is obtained by decomposition of a phosphorus pentoxide precursor comprising at least one of phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate and ammonium dihydrogen phosphate.
3. The desulfurizing agent according to claim 1, wherein the zinc oxide is obtained by decomposing a precursor of zinc oxide, the precursor of zinc oxide comprising at least one of nano basic zinc carbonate, nano zinc oxide, zinc nitrate and zinc chloride;
preferably, the precursor of the zinc oxide is nano basic zinc carbonate.
4. The desulfurization agent according to claim 1, wherein the metal oxide B is obtained by decomposition of a precursor of the metal oxide B, wherein the precursor of the metal oxide B is selected from nitrates and/or chlorides, preferably nitrates, corresponding to the metals in the metal oxide;
preferably, the alumina is obtained by decomposing an alumina precursor, the alumina precursor comprising an aluminum-based catalyst support and an aluminum-based binder;
preferably, the aluminum-based catalyst support comprises pseudoboehmite;
preferably, the aluminum-based binder comprises an aluminum sol.
5. The method for preparing a desulfurizing agent according to any one of claims 1 to 4, comprising the steps of:
and (3) molding and roasting the slurry containing the precursors of the components to obtain the desulfurizer.
6. The desulfurization agent preparation method according to claim 5, wherein the slurry is mainly obtained by mixing precursors of the respective components and water.
7. The preparation method of desulfurizing agent according to claim 5 or 6, wherein the specific preparation method of the slurry comprises the following steps:
and mixing and stirring the precursor of the metal oxide C and water for 2-10 h, adding the precursor of the metal oxide A, the precursor of the metal oxide B and the precursor of phosphorus pentoxide, and mixing and stirring for 2-10 h to obtain slurry.
8. The method for preparing a desulfurizing agent according to claim 5, wherein the shaping is spray shaping;
preferably, in the spray forming process, the temperature of a hearth is 350-450 ℃, the temperature of an outlet of a drying tower is 150-250 ℃, and the spray pressure of the drying tower is 2.5-4.5 MPa;
preferably, the method further comprises the step of drying the spray-molded material, wherein the drying temperature is 120-150 ℃, and the drying time is 5-10 hours.
9. The preparation method of the desulfurizing agent according to claim 5, wherein the roasting temperature is 520-650 ℃ and the roasting time is 4-8 h.
10. The use of the desulfurizing agent according to any one of claims 1 to 4 in a fluidized bed desulfurization process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910948661.XA CN110586028B (en) | 2019-10-08 | 2019-10-08 | Desulfurizing agent and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910948661.XA CN110586028B (en) | 2019-10-08 | 2019-10-08 | Desulfurizing agent and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110586028A true CN110586028A (en) | 2019-12-20 |
| CN110586028B CN110586028B (en) | 2021-11-19 |
Family
ID=68865658
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910948661.XA Active CN110586028B (en) | 2019-10-08 | 2019-10-08 | Desulfurizing agent and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110586028B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111701411A (en) * | 2020-07-30 | 2020-09-25 | 中国石油化工股份有限公司 | Synthetic gas desulfurizing agent and preparation method and application thereof |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5174919A (en) * | 1991-03-07 | 1992-12-29 | Phillips Petroleum Company | Sulfur absorbents and process for removing sulfur from fluid streams |
| CN1090315A (en) * | 1992-11-28 | 1994-08-03 | 大阪瓦斯株式会社 | The sulfur method of hydrocarbon |
| US20050123462A1 (en) * | 2002-02-18 | 2005-06-09 | Haldor Topsoe A/S | Process for the selective removal of sulphur compounds from synthesis gas |
| CN101433819A (en) * | 2007-11-15 | 2009-05-20 | 中国石油化工股份有限公司 | Desulphurization sorbent composition |
| CN101455966A (en) * | 2007-12-11 | 2009-06-17 | 南化集团研究院 | Methanol synthesis gas desulfurizer and preparation method thereof |
| CN102274721A (en) * | 2010-06-10 | 2011-12-14 | 中国石油化工股份有限公司 | Desulfurization additive for product obtained by hydrocarbon oil cracking and preparation and application thereof |
| CN102451694A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Hydrogenation dethiolizing catalyst, preparation method thereof and application thereof |
| CN103687667A (en) * | 2011-07-22 | 2014-03-26 | 庄信万丰股份有限公司 | Desulphurisation material comprising copper supported on zinc oxide |
| CN104069796A (en) * | 2013-03-29 | 2014-10-01 | 中国石油化工股份有限公司 | Gas desulfurization and adsorption composition, preparation method thereof and method for desulfurizing sulfurous gases |
| CN104511301A (en) * | 2013-09-30 | 2015-04-15 | 中国石油化工股份有限公司 | Desulfurization catalyst, preparation method thereof and hydrocarbon oil desulfurizing method |
| CN105032436A (en) * | 2015-06-30 | 2015-11-11 | 新地能源工程技术有限公司 | Super fine desulfurization agent and preparation method thereof |
| CN105854577A (en) * | 2016-05-09 | 2016-08-17 | 中石化炼化工程（集团）股份有限公司 | Smoke desulfurizer and preparation method thereof |
-
2019
- 2019-10-08 CN CN201910948661.XA patent/CN110586028B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5174919A (en) * | 1991-03-07 | 1992-12-29 | Phillips Petroleum Company | Sulfur absorbents and process for removing sulfur from fluid streams |
| CN1090315A (en) * | 1992-11-28 | 1994-08-03 | 大阪瓦斯株式会社 | The sulfur method of hydrocarbon |
| US20050123462A1 (en) * | 2002-02-18 | 2005-06-09 | Haldor Topsoe A/S | Process for the selective removal of sulphur compounds from synthesis gas |
| CN101433819A (en) * | 2007-11-15 | 2009-05-20 | 中国石油化工股份有限公司 | Desulphurization sorbent composition |
| CN101455966A (en) * | 2007-12-11 | 2009-06-17 | 南化集团研究院 | Methanol synthesis gas desulfurizer and preparation method thereof |
| CN102274721A (en) * | 2010-06-10 | 2011-12-14 | 中国石油化工股份有限公司 | Desulfurization additive for product obtained by hydrocarbon oil cracking and preparation and application thereof |
| CN102451694A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Hydrogenation dethiolizing catalyst, preparation method thereof and application thereof |
| CN103687667A (en) * | 2011-07-22 | 2014-03-26 | 庄信万丰股份有限公司 | Desulphurisation material comprising copper supported on zinc oxide |
| CN104069796A (en) * | 2013-03-29 | 2014-10-01 | 中国石油化工股份有限公司 | Gas desulfurization and adsorption composition, preparation method thereof and method for desulfurizing sulfurous gases |
| CN104511301A (en) * | 2013-09-30 | 2015-04-15 | 中国石油化工股份有限公司 | Desulfurization catalyst, preparation method thereof and hydrocarbon oil desulfurizing method |
| CN105032436A (en) * | 2015-06-30 | 2015-11-11 | 新地能源工程技术有限公司 | Super fine desulfurization agent and preparation method thereof |
| CN105854577A (en) * | 2016-05-09 | 2016-08-17 | 中石化炼化工程（集团）股份有限公司 | Smoke desulfurizer and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 冯庆吉: ""金属改性ZnO精脱硫剂制备与脱硫性能研究"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111701411A (en) * | 2020-07-30 | 2020-09-25 | 中国石油化工股份有限公司 | Synthetic gas desulfurizing agent and preparation method and application thereof |
| CN111701411B (en) * | 2020-07-30 | 2022-02-22 | 中国石油化工股份有限公司 | Synthetic gas desulfurizing agent and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110586028B (en) | 2021-11-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111701411B (en) | Synthetic gas desulfurizing agent and preparation method and application thereof | |
| CN106238091B (en) | A kind of mercaptan-eliminating catalyst and the preparation method and application thereof | |
| CN106672967A (en) | Preparation method for activated carbon for desulfurization and denitrification and activated carbon for desulfurization and denitrification and application | |
| CN105749863A (en) | Compound desulfurizer and preparation method thereof | |
| CN107486223B (en) | Preparation method and application of high-efficiency organic sulfur hydroconversion catalyst | |
| CN110893312A (en) | Novel high-efficiency desulfurizer and preparation method thereof | |
| CN110586028B (en) | Desulfurizing agent and preparation method and application thereof | |
| CN103706228B (en) | A kind of pre-reduction type manganese fimily desulfurizing agent and preparation method thereof | |
| CN103100298A (en) | Process for capturing sulphur impurities using specific retaining materials | |
| CN105498678A (en) | Desulfurization adsorbent, preparation method thereof, and gas desulfurization method | |
| KR100653046B1 (en) | Method for removal of hydrogen sulfide by reaction of catalyst | |
| CN115196590B (en) | Process for co-production of hydrogen by capturing carbon in blast furnace gas | |
| CN114345117B (en) | Ferric oxide composite desulfurizer and preparation method and application thereof | |
| CN107043089B (en) | A kind of technique of the equipressure ammonia synthesis co-production containing carbon chemicals | |
| CN115093885B (en) | Synthetic gas desulfurizing agent suitable for moving bed technological process and preparation method thereof | |
| CN104046399B (en) | Sulfur-tolerant methanation process for preparing natural gases from coke oven gases | |
| CN113976101A (en) | Supported carbonyl sulfide hydrolysis catalyst and preparation method and application thereof | |
| CN115093886B (en) | Circulating moving bed process method and device for desulfurizing and dedusting gasified synthetic gas | |
| CN102851085B (en) | Renewable calcium high-temperature coal gas desulfurizer | |
| FI59118C (en) | FOERFARANDE FOER KATALYTISK HYDROAVSVAVLING AV RESTKOLVAETEOLJOR | |
| CN113171778B (en) | Deep purification desulfurizer for coke oven gas and preparation method and application thereof | |
| CN105727977B (en) | A kind of synthesis gas methanation substitutes the method for preparing catalyst of natural gas | |
| CN112742203B (en) | Gas desulfurizing agent, preparation method thereof and gas desulfurizing method | |
| CN115367769B (en) | Preparation method and application of high-crystallinity hierarchical pore SAPO-56 zeolite molecular sieve | |
| CN113797941B (en) | Catalytic material with hydrogenation performance and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |