CN113559819A - Adsorbent for ultra-deep desulfurization of aromatic hydrocarbon, preparation method and desulfurization method - Google Patents

Adsorbent for ultra-deep desulfurization of aromatic hydrocarbon, preparation method and desulfurization method Download PDF

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CN113559819A
CN113559819A CN202110740580.8A CN202110740580A CN113559819A CN 113559819 A CN113559819 A CN 113559819A CN 202110740580 A CN202110740580 A CN 202110740580A CN 113559819 A CN113559819 A CN 113559819A
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adsorbent
desulfurization
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aromatic hydrocarbon
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董森
罗国华
刘树俊
徐新
郭学华
王亚涛
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KAILUAN (GROUP) CO Ltd
Beijing Institute of Petrochemical Technology
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • 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
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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Abstract

The invention relates to the technical field of aromatic hydrocarbon desulfurization, and particularly discloses an adsorbent for ultra-deep desulfurization of aromatic hydrocarbon, a preparation method and a desulfurization method. The adsorbent comprises Al2O3Carrier, and Al supported on the carrier2O3An active metal component and a coagent on a support; wherein the active metal component is a simple Ni substance and/or a Ni-Mo alloy with a porous honeycomb structure; al in adsorbent2O3The content of the carrier is 50-80 wt%, the content of the active metal component is 20-50 wt%, and the content of the active additive is 0-10 wt%. Mixing Ni-based alloy powder, an active assistant, pseudoboehmite and a gelling agent, kneading into gel, molding, drying, roasting, and soaking and activating by strong base to obtain the adsorbent. The desulfurization adsorbent of the invention is adoptedUnder the relatively mild condition, the benzene containing sulfur is deeply desulfurized through simple selective adsorption, and the benzene product with ultra-low sulfur content can be produced.

Description

Adsorbent for ultra-deep desulfurization of aromatic hydrocarbon, preparation method and desulfurization method
Technical Field
The invention relates to the technical field of aromatic hydrocarbon desulfurization, in particular to an adsorbent for ultra-deep desulfurization of aromatic hydrocarbon, a preparation method and a desulfurization method.
Background
Aromatic hydrocarbon is an important basic organic chemical raw material, and can be used for a series of important chemical products such as synthetic rubber, synthetic resin, synthetic fiber, medicine, pesticide, explosive, dye and the like. At present, most raw material aromatic hydrocarbons in China are mainly produced by catalytic reforming, methyl aromatic disproportionation, methyl aromatic hydrogenation dealkylation and other methods in the petrochemical industry, and the other main source is coking aromatic hydrocarbons obtained by hydrofining by-product crude aromatic hydrocarbons in the coking process in the coal chemical industry. A large amount of impurities exist in the coking aromatic hydrocarbon, so that the coking aromatic hydrocarbon cannot be directly used for chemical production. Especially, the thiophene sulfur-containing impurities which are similar to aromatic hydrocarbons in physical and chemical properties are most difficult to remove. The application range of aromatic hydrocarbon in the field of fine chemical engineering is limited to a great extent by thiophenic sulfur, for example, the process for producing maleic anhydride by oxidizing aromatic hydrocarbon requires that the content of thiophene in the aromatic hydrocarbon is not higher than 500 ppm; when the aromatic hydrocarbon is used as a raw material for producing aromatic hydrocarbon amine, the content of thiophene in the aromatic hydrocarbon is required to be not higher than 10 ppm; in the process of preparing cyclohexene by selective hydrogenation of Ru-based catalyst, the requirement on the thiophene content in aromatic hydrocarbon is more strict, and the thiophene content needs to be controlled at ppb level, otherwise, thiophene sulfide causes irreversible poisoning and inactivation on noble metal Ru catalyst, the service life of the Ru catalyst is seriously influenced, and the production cost is greatly improved. At present, the sulfur content in raw material aromatic hydrocarbon in China is usually about 1ppm, and the index requirement of a selective hydrogenation unit of catalytic aromatic hydrocarbon of a Ru-based catalyst on sulfide in the raw material aromatic hydrocarbon can not be met obviously. Therefore, the method needs to be matched with an aromatic deep desulfurization process, and has very important significance for protecting the aromatic selective hydrogenation Ru-based catalyst subsequently and prolonging the service life of the catalyst.
In order to deeply remove thiophene sulfides in aromatic hydrocarbons, the currently common method mainly comprises catalytic hydrofining and selective adsorption desulfurization processes. The catalytic hydrogenation deep desulfurization process is usually carried out under relatively harsh hydrogenation conditions by using a Co-Mo-S catalyst, so that the operation difficulty is high, and the production cost is high. While the adsorption desulfurization, which is a green desulfurization method mainly based on non-hydrogenation technology, has been widely studied due to the advantages of small investment of process equipment, simple process, easily controlled conditions, and the like. However, the existing aromatic hydrocarbon desulfurization adsorbent has the main problems of low sulfur adsorption capacity and high preparation cost of the adsorbent, for example, the deep desulfurization process matched with the Ru-based selective aromatic hydrocarbon hydrogenation process adopts a noble metal Pd-supported adsorbent, which can reduce the sulfur content in the aromatic hydrocarbon to below 10ppb, but the adsorbent has low adsorption capacity and cannot be regenerated, so that the preparation cost of the adsorbent is high. Therefore, the aromatic hydrocarbon desulfurization adsorbent with low cost and high sulfur capacity is very important for reducing the cost of the aromatic hydrocarbon selective hydrogenation process, improving the market competitiveness of enterprises and promoting the industrial technology upgrading of domestic cyclohexene.
Disclosure of Invention
Aiming at the problems of high preparation cost and low adsorption capacity of the conventional aromatic hydrocarbon desulfurization adsorbent, the invention provides an adsorbent for ultra-deep desulfurization of aromatic hydrocarbon, a preparation method and a desulfurization method2O3On the carrier, the sulfur adsorption capacity of the adsorbent is obviously improved, and the production cost of the desulfurization adsorbent is reduced.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the application provides an adsorbent for ultra-deep desulfurization of aromatic hydrocarbon, which comprises Al2O3Carrier, and Al supported on the carrier2O3An active metal component and a coagent on a support; wherein the active metal component is a simple Ni substance with a porous cellular structure and/or a Ni-Mo alloy; and Al in the adsorbent2O3The content of the carrier is 50-80 wt%, the content of the active metal component is 20-50 wt%, and the content of the active additive is 0-10 wt%.
The adsorption desulfurization technology operated by the existing industrial device is most commonly used as an adsorbent of alumina-supported metal Pd, the preparation cost is very high, the sulfur adsorption capacity is low, and the operation cost of the aromatic hydrocarbon desulfurization device is directly obviously increased.
Compared with the prior art, the invention selects non-noble metal Ni-based metal (such as Ni simple substance or Ni-Mo alloy) as an active component, has the special porous honeycomb shape, regular pore channel structure, large pore volume and specific surface area, improves the contact area with sulfur-containing aromatic hydrocarbon raw material, provides physical adsorption space and chemical adsorption active site for the adsorption of sulfur compounds, greatly improves the sulfur adsorption capacity, and is beneficial to improving the mechanical strength of the adsorbent due to the existence of the Ni-based metal skeleton of the honeycomb structure, thereby improving the stability of the adsorbent; the active auxiliary agent is selectively added, and the sulfur adsorption capacity of the adsorbent can be further improved through the synergistic effect of the active auxiliary agent and the Ni-based metal framework, so that ultra-deep desulfurization is realized.
Preferably, the coagent is ZnO or MoO3Or Ag2At least one of O.
The preferable active auxiliary agent and the Ni-based metal framework have synergistic effect, so that the sulfur adsorption capacity of the adsorbent is improved, and the selective adsorption effect of the adsorbent on organic sulfur compounds which are difficult to remove in aromatic hydrocarbons, such as mercaptan, thioether, thiophene, alkylthiophene and other thiophene compounds, is improved, so that the sulfide content is reduced to below 10ppb, and the ultra-deep desulfurization is realized.
Preferably, the adsorbent comprises the following components in percentage by mass: al (Al)2O350-70% of carrier, 25-45% of active metal component and 1-6% of active assistant.
The optimized dosage of each component in the adsorbent is beneficial to improving the adsorption capacity of the adsorbent to various sulfides in the aromatic hydrocarbon and improving the sulfur adsorption capacity.
The second aspect of the present application provides a preparation method of the above adsorbent for ultra-deep desulfurization of aromatic hydrocarbons, comprising the following steps:
step a, carrying out ball milling on the Ni-based alloy to obtain Ni-based alloy powder; wherein the Ni-based alloy powder is Ni-Al alloy and/or Ni-Mo-Al alloy;
b, mixing the Ni-based alloy powder, the active auxiliary agent or the precursor of the active auxiliary agent, the pseudo-boehmite and a peptizing agent, kneading into glue, molding, drying and roasting to obtain an adsorbent precursor;
and c, adding the adsorbent precursor into a strong base solution, soaking and activating for 6-10 h at the temperature of 40-80 ℃, separating a product, and washing to obtain the adsorbent.
Compared with the prior art, the preparation method of the adsorbent for ultra-deep desulfurization of aromatic hydrocarbon provided by the invention has the advantages that the preparation method is simple, the production cost of the adsorbent is low, the prepared adsorbent has strong selective adsorption capacity on various sulfides in the aromatic hydrocarbon, the adsorbed sulfides in the aromatic hydrocarbon product can reach the requirement of below 10ppb, and the adsorption sulfur capacity of the adsorbent is higher than that of Pd/Al in the prior industrial application2O3The sulfur adsorption capacity is more than 4 times, and the method has high economic benefit and is suitable for industrial application.
Preferably, in the step a, the Ni-based alloy powder has a particle size of 100 mesh to 300 mesh.
The preferred particle size of the Ni-based alloy powder is beneficial to fully mixing the alloy powder with pseudo-boehmite and a precursor of the active additive, thereby being beneficial to the uniform dispersion of the Ni-based metal active component and the active additive on the carrier.
Preferably, in the step b, the mass ratio of the Ni-based alloy powder to the pseudo-boehmite is 1:1 to 4: 6.
Optionally, ZnO or Ag is used as the active assistant2And O, selecting a precursor of the active assistant in the step b, wherein the precursor of the active assistant is soluble zinc salt or soluble silver salt, and preferably zinc nitrate or silver nitrate.
In particular, ZnO or Ag is taken as the active auxiliary agent2O, the step b is: uniformly mixing the Ni-based alloy powder and pseudo-boehmite to obtain mixed powder; then adding the active assistantThe precursor and the peptizing agent are mixed to obtain a mixed solution, the mixed solution is added into the mixed powder, and the mixed solution is kneaded into glue, molded, dried and roasted to obtain the adsorbent precursor. The precursor of the active assistant is mixed with the peptizing agent and then added into the mixed powder, which is beneficial to the uniform dispersion and loading of the active assistant on the carrier.
MoO for coagent3In other words, MoO is directly added during the preparation process of step b3And (3) powder.
In particular, MoO is specific for the coagent3For example, step b is: and uniformly mixing the Ni-based alloy powder, the active assistant and the pseudo-boehmite to obtain mixed powder, then adding a peptizing agent into the mixed powder, kneading into glue, molding, drying and roasting to obtain an adsorbent precursor.
Preferably, in the step b, the peptizing agent is 5 wt% -15 wt% nitric acid water solution, and the volume ratio of the total mass of the Ni-based alloy powder and the pseudo-boehmite to the peptizing agent is 2.0-2.2:1, wherein the unit of the mass is gram, and the unit of the volume is milliliter.
Preferably, in the step b, the roasting temperature is 850-880 ℃, and the roasting time is 3-4 h.
The preferred firing temperature and time are favorable for Al2O3Conversion to alpha-Al2O3And is favorable for improving the compressive strength of the adsorbent.
Preferably, in step c, the strong alkali solution is a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution with a mass concentration of 5 wt% to 20 wt%.
The adsorbent precursor is activated in a strong alkaline solution, Al in the alloy is dissolved by alkali and converted into sodium metaaluminate, the rest metal forms framework metal with a honeycomb structure, the framework metal has a regular pore channel structure and large pore volume, the adsorption and removal capacity of the adsorbent on various sulfides can be remarkably improved, and the existence of Ni-based active metal components of the honeycomb framework metal structure can also improve the mechanical strength of the adsorbent, provide certain lateral compressive strength for the adsorbent and adapt to the filling requirement of a fixed bed.
Optionally, the finally prepared adsorbent for ultra-deep desulfurization of aromatic hydrocarbon is stored in water or ethanol for later use.
The third aspect of the application also provides a method for ultra-deep desulfurization of aromatic hydrocarbon, which utilizes the adsorbent of any one of the above items to perform adsorption desulfurization on sulfur-containing aromatic hydrocarbon raw materials.
Preferably, the method for ultra-deep desulfurization of aromatic hydrocarbons comprises the following steps:
adopting a fixed bed reactor, wherein the fixed bed reactor is filled with the adsorbent of any one of the above items;
and (3) introducing a sulfur-containing aromatic hydrocarbon raw material into the fixed bed reactor for adsorption desulfurization to obtain a desulfurized aromatic hydrocarbon product.
Preferably, the pressure of adsorption desulfurization is 0.5MPa-2MPa, the temperature of adsorption desulfurization is 150-200 ℃, and the feeding airspeed of sulfur-containing aromatic hydrocarbon raw material is 1h-1-2h-1。
Optionally, in order to further improve the sulfur adsorption capacity, the desulfurization adsorbent prepared by the method is filled in a constant temperature section of a fixed adsorption bed layer and then pre-reduced by the adsorbent. The pre-reduction of the adsorbent is carried out in a hydrogen atmosphere, the reduction temperature is 200-300 ℃, the hydrogen partial pressure is 1-3 MPa, and the hydrogen volume space velocity is 100h-1-250h-1The pre-reduction time is 3-6 h.
The method for ultra-deep desulfurization of aromatic hydrocarbon provided by the invention has the advantages that the adsorption condition is mild, the sulfur adsorption capacity is high, the sulfide content in the aromatic hydrocarbon can reach below 10ppb after sulfur-containing aromatic hydrocarbon is subjected to adsorption desulfurization by the adsorbent provided by the invention, the requirement of a device for producing cyclohexene by selective hydrogenation of Ru-based catalytic benzene in a cyclohexanone device on the sulfur content of raw material benzene is completely met, the preparation cost of the adsorbent is low, the preparation method is simple, and the industrial popularization value is high.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of a desulfurization adsorbent prepared in example 1 of the present invention;
FIG. 2 shows the adsorbent precursor, desulfurization adsorbent and Al prepared in example 1 of the present invention2O3X-ray diffraction pattern (XRD) of the support, wherein a: the precursor of the adsorbent is prepared by the following steps,b: desulfurization adsorbent, C: al (Al)2O3A carrier;
FIG. 3 is a graph of the adsorptive desulfurization breakthrough curve for the desulfurization adsorbent prepared in example 2 of the present invention;
FIG. 4 shows industrial Pd/Al2O3Sorbent desulfurization breakthrough curve.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In order to better illustrate the invention, the following examples are given by way of further illustration.
In the following examples, all reagents were commercially available unless otherwise specified, and the experimental procedures were carried out according to the conventional experimental procedures unless otherwise specified.
Example 1
A preparation method of an adsorbent for benzene ultra-deep desulfurization comprises the following steps:
step a, grinding Ni-Al alloy balls to a granularity of 100-300 meshes to obtain Ni-based alloy powder; weighing 50g of pseudo-boehmite and 50g of Ni-Al alloy powder respectively according to the mass ratio of 1:1, fully grinding and uniformly mixing to obtain mixed powder;
step b, adding 47.6mL of nitric acid aqueous solution with the mass fraction of 15% into the mixed powder, fully kneading to form gel, extruding into strips with the diameter of 2.5mm by using an electric strip extruding machine, naturally airing in air, drying at 120 ℃ for 4h, and then roasting in a muffle furnace at 850 ℃ for 4h to obtain an adsorbent precursor;
and c, adding the adsorbent precursor into a NaOH solution with the mass fraction of 10%, uniformly dispersing, soaking and activating for 8 hours at 50 ℃, filtering, washing the solid to be neutral by deionized water to obtain a desulfurization adsorbent, and storing in water for later use.
The desulfurization adsorbent prepared in this example was characterized by the following composition: al (Al)2O3 62.55％，Ni 35.35％，NiO 2.1％。
The SEM image of the desulfurization adsorbent prepared in this example is shown in fig. 1, and it can be seen from the figure that Ni — Al is activated by alkali impregnation and then exists on the surface of the alumina carrier in the form of a skeleton metal nickel of a porous honeycomb structure.
The XRD pattern of the desulfurization adsorbent prepared in this example is shown in FIG. 2, from which it can be seen that the calcined adsorbent precursor (curve A) shows obvious Al typical of Ni-Al binary alloy3Ni2And a crystal plane diffraction peak of AlNi; and the precursor is subjected to desulfurization adsorbent (curve B) after being subjected to strong base impregnation activity, and Al3Ni2And the intensity of the crystal face diffraction peak of AlNi is greatly reduced, and the crystal face diffraction peak at the 2 theta-45-degree position is in a dispersion shape, which shows that amorphous skeleton nickel is generated in the leaching process; curve C is pure Al2O3XRD pattern of the carrier, in which alpha-Al is not seen2O3While alpha-Al is observed in the XRD pattern of the desulfurization adsorbent (curve B)2O3(012) Diffraction peaks of crystal planes (113), (116) and (214), and therefore, alpha-Al2O3Is generated in the high-temperature roasting process of the precursor, and is a main component for endowing the compressive strength of the adsorbent.
Pre-reduction of the adsorbent: pulverizing the desulfurization adsorbent, placing 10mL adsorbent with particle size of 380-830 μm into constant temperature section of stainless steel fixed adsorption tube with inner diameter of 12mm, and placing at 280 deg.C, hydrogen pressure of 2MPa and hydrogen volume space velocity of 240h-1Pre-reduction for 3h, after which the temperature is lowered to the adsorption temperature.
Desulfurization performance of the adsorbent: benzene containing 9.69-9.79mg/Kg of thiophene is used as a raw material, and the space velocity of the feeding of the benzene raw material is 2h-1The adsorption pressure is 2.0MPa, the adsorption temperature is 165 ℃ for adsorption desulfurization, the thiophene in the benzene can be completely adsorbed by the adsorbent, and the thiophene sulfide cannot be detected in the adsorbed benzene product by GC-FPD analysis. According to the process requirement, when the content of thiophene in the adsorption product reaches 10ppb, the bed layer is considered to be penetrated, the corresponding thiophene adsorption capacity is the penetration capacity, and the penetration capacity of the adsorbent is tested to be 7.98 mg/g-abs.
Example 2
A preparation method of an adsorbent for benzene ultra-deep desulfurization comprises the following steps:
step a, grinding Ni-Al alloy balls to a granularity of 100-300 meshes to obtain Ni-based alloy powder; weighing 40g of pseudo-boehmite and 60g of Ni-Al alloy powder according to the mass ratio of 4:6, fully grinding and uniformly mixing to obtain mixed powder;
b, adding 50mL of 5% nitric acid aqueous solution into the mixed powder, fully kneading to form gel, extruding into strips with the diameter of 2.5mm by using an electric strip extruding machine, naturally airing in air, drying at 120 ℃ for 4h, and then roasting in a muffle furnace at 880 ℃ for 3h to obtain an adsorbent precursor;
and c, adding the adsorbent precursor into a KOH solution with the mass fraction of 20%, uniformly dispersing, carrying out immersion activation for 10h at 40 ℃, filtering, washing the solid to be neutral by using deionized water to obtain a desulfurization adsorbent, and storing in water for later use.
The desulfurization adsorbent prepared in this example was characterized by the following composition: al (Al)2O3 53.05％，Ni 44.32％，NiO 2.63％。
Pre-reduction of the adsorbent: pulverizing the desulfurization adsorbent, placing 10mL adsorbent with particle size of 380-830 μm into constant temperature section of stainless steel fixed adsorption tube with inner diameter of 12mm, and placing at 250 deg.C, hydrogen pressure of 1MPa and hydrogen volume space velocity of 200h-1Pre-reduction for 3h, after which the temperature is lowered to the adsorption temperature.
Desulfurization performance of the adsorbent: benzene containing 9.69-9.79mg/Kg of thiophene is used as a raw material, and the feeding space velocity of the benzene raw material is 2h-1The adsorption pressure is 0.7MPa, the adsorption temperature is 150 ℃, the thiophene in the benzene can be completely adsorbed by the adsorbent, and the thiophene sulfide cannot be detected in the adsorbed benzene product by GC-FPD analysis. According to the process requirement, when the content of thiophene in the adsorption product reaches 10ppb, the bed layer is considered to be penetrated, the corresponding thiophene adsorption capacity is the penetration capacity, the adsorption desulfurization penetration curve is shown in figure 3, the specific data is shown in table 1, and the penetration capacity of the adsorbent is tested to be 5.14 mg/g-abs.
TABLE 1 results of the test for selective adsorption of thiophene by the adsorbent of example 2
Figure BDA0003141251910000091
Adopts Pd/Al commonly used in industrial devices2O3The adsorbent is subjected to desulfurization performance test according to the same method, the adsorption desulfurization penetration curve is shown in figure 4, the specific data is shown in table 2, and industrial Pd/Al is obtained through test2O3The breakthrough capacity of the adsorbent was 1.03 mg/g-abs. As can be seen, the desulfurization adsorbent prepared in this example had a sulfur breakthrough capacity of Pd/Al2O35 times of the adsorbent.
TABLE 2 Pd/Al for commercial operation2O3Test results of selective adsorption of thiophene by adsorbent
Figure BDA0003141251910000101
Example 3
A preparation method of an adsorbent for benzene ultra-deep desulfurization comprises the following steps:
step a, grinding Ni-Al alloy balls to a granularity of 100-300 meshes to obtain Ni-based alloy powder; weighing 50g of pseudo-boehmite and 50g of Ni-Al alloy powder respectively according to the mass ratio of 1:1, fully grinding and uniformly mixing to obtain mixed powder;
step b, adding 12.07g of silver nitrate into 46mL of nitric acid water solution with the mass fraction of 15% to obtain a mixed solution; then dropwise adding the mixed solution into the mixed powder, fully kneading to form glue, extruding into strips with the diameter of 2.5mm by an electric strip extruding machine, naturally airing in the air, drying at 120 ℃ for 4h, and roasting in a muffle furnace at 850 ℃ for 4h to obtain an adsorbent precursor;
and c, adding the adsorbent precursor into a NaOH solution with the mass fraction of 10%, uniformly dispersing, soaking and activating for 8 hours at 50 ℃, filtering, washing the solid to be neutral by deionized water to obtain a desulfurization adsorbent, and storing in water for later use.
The desulfurization adsorbent prepared in this example was characterized by the following composition: al (Al)2O3 59.1％，Ni 33.4％，Ag2O 5.53％，NiO 1.97％。
Pre-reduction of the adsorbent: pulverizing the desulfurization adsorbent, placing 10mL adsorbent with particle size of 380-830 μm into constant temperature section of stainless steel fixed adsorption tube with inner diameter of 12mm, and placing at 220 deg.C, hydrogen pressure of 1.5MPa and hydrogen volume space velocity of 150h-1Pre-reduction for 4h, after which the temperature is lowered to the adsorption temperature.
Desulfurization performance of the adsorbent: benzene containing 10.1mg/Kg of thiophene is used as a raw material, and the feeding airspeed of the benzene raw material is 2h-1The adsorption pressure is 2.0MPa, the adsorption temperature is 165 ℃, the thiophene in the benzene can be completely adsorbed by the adsorbent, and the thiophene sulfide cannot be detected in the adsorbed benzene product by GC-FPD analysis. Definition, when the content of thiophene in the adsorption product reaches 10ppb, the bed layer is considered to be penetrated, the corresponding thiophene adsorption capacity is penetration capacity, and the penetration capacity of the adsorbent is tested to be 9.15 mg/g-abs.
Example 4
A preparation method of an adsorbent for benzene ultra-deep desulfurization comprises the following steps:
step a, grinding Ni-Al alloy balls to a granularity of 100-300 meshes to obtain Ni-based alloy powder; weighing 50g of pseudo-boehmite and 50g of Ni-Al alloy powder respectively according to the mass ratio of 1:1, fully grinding and uniformly mixing to obtain mixed powder;
step b, adding 6.62g of zinc nitrate hexahydrate into 50mL of nitric acid aqueous solution with the mass fraction of 15% to obtain a mixed solution; then dropwise adding the mixed solution into the mixed powder, fully kneading to form glue, extruding into strips with the diameter of 2.5mm by an electric strip extruding machine, naturally airing in the air, drying at 120 ℃ for 4h, and roasting in a muffle furnace at 850 ℃ for 4h to obtain an adsorbent precursor;
and c, adding the adsorbent precursor into a NaOH solution with the mass fraction of 10%, uniformly dispersing, carrying out immersion activation for 6h at 80 ℃, filtering, washing the solid to be neutral by deionized water to obtain a desulfurization adsorbent, and storing in water for later use.
The desulfurization adsorbent prepared in this example was characterized by the following composition: al (Al)2O3 61.6％，Ni 34.83％，ZnO 1.51％，NiO 2.06％。
Pre-reduction of the adsorbent: pulverizing the desulfurization adsorbent, placing 10mL adsorbent with particle size of 380-830 μm into constant temperature section of stainless steel fixed adsorption tube with inner diameter of 12mm, and placing at 250 deg.C, hydrogen pressure of 2.5MPa and hydrogen volume space velocity of 200h-1Pre-reduction for 5h, after which the temperature is lowered to the adsorption temperature.
Desulfurization performance of the adsorbent: using benzene containing 9.7mg/Kg of thiophene as raw material, the space velocity of feeding benzene raw material is 1.5h-1The adsorption pressure is 2.0MPa, the adsorption temperature is 185 ℃, the thiophene in the benzene can be completely adsorbed by the adsorbent, and the thiophene sulfide cannot be detected in the adsorbed benzene product by GC-FPD analysis. Definition, when the content of thiophene in the adsorption product reaches 10ppb, the bed layer is considered to be penetrated, the corresponding thiophene adsorption capacity is penetration capacity, and the penetration capacity of the adsorbent is tested to be 15.68 mg/g-abs.
Example 5
A preparation method of an adsorbent for benzene ultra-deep desulfurization comprises the following steps:
step a, grinding Ni-Al alloy balls to a granularity of 100-300 meshes to obtain Ni-based alloy powder; weighing 50g of pseudo-boehmite and 50g of Ni-Al alloy powder respectively according to the mass ratio of 1:1, and adding 1g of MoO3Fully grinding and uniformly mixing the powder to obtain mixed powder;
b, adding 48mL of 15% nitric acid aqueous solution into the mixed powder, fully kneading to form gel, extruding into strips with the diameter of 2.5mm by using an electric strip extruding machine, naturally airing in air, drying at 120 ℃ for 4h, and roasting in a muffle furnace at 850 ℃ for 4h to obtain an adsorbent precursor;
and c, adding the adsorbent precursor into a NaOH solution with the mass fraction of 10%, uniformly dispersing, soaking and activating for 8 hours at 50 ℃, filtering, washing the solid to be neutral by deionized water to obtain a desulfurization adsorbent, and storing in water for later use.
Characterized by this exampleThe prepared desulfurization adsorbent comprises the following components: al (Al)2O3 69.1％，Ni 27.21％，NiO 2.55％，MoO3 1.14％。
Pre-reduction of the adsorbent: pulverizing the desulfurization adsorbent, placing 10mL adsorbent with particle size of 380-830 μm into constant temperature section of stainless steel fixed adsorption tube with inner diameter of 12mm, and placing at 250 deg.C, hydrogen pressure of 2.2MPa and hydrogen volume space velocity of 100h-1Pre-reduction for 6h, after which the temperature is lowered to the adsorption temperature.
Desulfurization performance of the adsorbent: using benzene containing thiophene 100.7mg/Kg as raw material, and feeding the benzene raw material at an airspeed of 2h-1The adsorption pressure is 1.0MPa, the adsorption temperature is 150 ℃, the thiophene in the benzene can be completely adsorbed by the adsorbent, and the thiophene sulfide cannot be detected in the adsorbed benzene product by GC-FPD analysis. Definition, when the content of thiophene in the adsorption product reaches 10ppb, the bed layer is considered to be penetrated, the corresponding thiophene adsorption capacity is penetration capacity, and the penetration capacity of the adsorbent is tested to be 34.17 mg/g-abs.
NiO in the adsorbents in the above examples 1-5 is generated by air oxidation of a trace amount of Ni during calcination, and NiO is reduced to Ni simple substance again during pre-reduction of the adsorbents.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (10)

1. The adsorbent for ultra-deep desulfurization of aromatic hydrocarbon is characterized by comprising Al2O3Carrier, and Al supported on the carrier2O3An active metal component and a coagent on a support; wherein the active metal component is a simple Ni substance and/or a Ni-Mo alloy with a porous honeycomb structure; and Al in the adsorbent2O3The content of the carrier is 50-80 wt%, the content of the active metal component is 20-50 wt%, and the content of the active additive is 0-10 wt%.
2. The adsorbent for ultra-deep desulfurization of aromatic hydrocarbons according to claim 1, wherein the co-agent is ZnO, MoO3Or Ag2At least one of O.
3. The adsorbent for ultra-deep desulfurization of aromatic hydrocarbons according to claim 1 or 2, wherein the adsorbent comprises the following components in percentage by mass: al (Al)2O350-70% of carrier, 25-45% of active metal component and 1-6% of active assistant.
4. The method for preparing the adsorbent for ultra-deep desulfurization of aromatic hydrocarbons according to any one of claims 1 to 3, characterized by comprising the steps of:
step a, carrying out ball milling on the Ni-based alloy to obtain Ni-based alloy powder; wherein the Ni-based alloy powder is Ni-Al alloy and/or Ni-Mo-Al alloy;
b, mixing the Ni-based alloy powder, the active auxiliary agent or the precursor of the active auxiliary agent, the pseudo-boehmite and a peptizing agent, kneading into glue, molding, drying and roasting to obtain an adsorbent precursor;
and c, adding the adsorbent precursor into a strong base solution, soaking and activating for 6-10 h at the temperature of 40-80 ℃, separating a product, and washing to obtain the adsorbent.
5. The method for preparing an adsorbent for ultra-deep desulfurization of aromatic hydrocarbons according to claim 4, wherein the particle size of the Ni-based alloy powder in step a is 100 mesh to 300 mesh.
6. The method for preparing the adsorbent for ultra-deep desulfurization of aromatic hydrocarbons according to claim 4, wherein in the step b, the peptizing agent is a 5 wt% to 15 wt% nitric acid aqueous solution, and the volume ratio of the total mass of the Ni-based alloy powder and the pseudo-boehmite to the peptizing agent is 2.0 to 2.2:1, wherein the unit of mass is g, and the unit of volume is ml; and/or
In the step b, the roasting temperature is 850-880 ℃, and the roasting time is 3-4 h.
7. The method for preparing the adsorbent for ultra-deep desulfurization of aromatic hydrocarbons according to claim 4, wherein in the step c, the strong alkali solution is an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution having a mass concentration of 5 wt% to 20 wt%.
8. A process for the ultra-deep desulfurization of aromatic hydrocarbons, characterized in that the sulfur-containing aromatic hydrocarbon feedstock is subjected to adsorptive desulfurization using the adsorbent according to any one of claims 1 to 3.
9. The method for ultra-deep desulfurization of aromatic hydrocarbons according to claim 8, comprising the steps of:
using a fixed bed reactor, wherein the adsorbent of any one of claims 1-3 is packed;
and (3) introducing a sulfur-containing aromatic hydrocarbon raw material into the fixed bed reactor for adsorption desulfurization to obtain a desulfurized aromatic hydrocarbon product.
10. The method for ultra-deep desulfurization of aromatic hydrocarbons according to claim 9, wherein the pressure of the adsorption desulfurization is 0.5MPa to 2MPa, the temperature of the adsorption desulfurization is 150 ℃ to 200 ℃, and the space velocity of the sulfur-containing aromatic hydrocarbon feedstock is 1h-1-2h-1。
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