CN113231067B - Dearsenifying agent for light distillate oil hydrogenation and preparation method and application thereof - Google Patents

Dearsenifying agent for light distillate oil hydrogenation and preparation method and application thereof Download PDF

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CN113231067B
CN113231067B CN202110592907.1A CN202110592907A CN113231067B CN 113231067 B CN113231067 B CN 113231067B CN 202110592907 A CN202110592907 A CN 202110592907A CN 113231067 B CN113231067 B CN 113231067B
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agent
roasting
carrier
tio
γal
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CN113231067A (en
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王连英
辛靖
杨国明
陈松
陈禹霏
张海洪
范文轩
吕艳艳
卢德庆
刘剑
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China National Offshore Oil Corp CNOOC
CNOOC Oil and Petrochemicals Co Ltd
CNOOC Research Institute of Refining and Petrochemicals Beijing Co Ltd
CNOOC Qingdao Heavy Oil Processing Engineering Technology Research Center Co Ltd
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China National Offshore Oil Corp CNOOC
CNOOC Oil and Petrochemicals Co Ltd
CNOOC Research Institute of Refining and Petrochemicals Beijing Co Ltd
CNOOC Qingdao Heavy Oil Processing Engineering Technology Research Center Co Ltd
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    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/205—Metal content

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  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to a dearsenization agent for light distillate oil hydrogenation, and a preparation method and application thereof, wherein the dearsenization agent comprises the following components in percentage by mass: niO 5-20%, tiO 2 10-35%, mgO 0.5-2.5%, C7-14%, and gamma Al in balance 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein the carrier in the dearsenization agent is TiO 2 ‑γAl 2 O 3 The active component of the composite carrier is NiO, and the auxiliary agent is MgO and C. The hydrogenation dearsenization agent in the invention adopts TiO 2 ‑Al 2 O 3 Binary composite carrier is prepared by mixing TiO 2 Compounding to Al 2 O 3 In the pore canal structure, not only Al can be reserved 2 O 3 Can exert TiO as well as the whole skeleton 2 Excellent catalytic performance, improved dispersivity of active metal components, and higher catalyst performance of the dearsenization agentThe de-arsenic agent has certain desulfurization performance by the design of components, and the application range of the de-arsenic agent is improved.

Description

Dearsenifying agent for light distillate oil hydrogenation and preparation method and application thereof
Technical Field
The invention relates to the field of catalytic dearsenization, in particular to a dearsenization agent for light distillate oil hydrogenation and a preparation method thereof.
Background
In petroleum hydrocarbons, arsenic is most often present in the form of organic compounds with hydrocarbon groups. In the petroleum refining process, arsenide enters fractions such as naphtha, gasoline and diesel oil, residual oil and the like according to the boiling point, and the arsenide is used as harmful substances in hydrocarbon cracking, hydrogenation and catalytic reforming processes, so that the subsequent processing of crude oil is seriously affected.
The hydrogenation catalyst generally takes VIII group metal element as an active component, and arsenic element existing in organic and inorganic forms in oil products is easily reduced to AsH under the condition of high Wen Lin hydrogen 3 As (III) has strong reducibility, is easy to combine with d-orbit electrons of VIII group metal elements to form coordination bonds so As to inactivate toxins therein, and the poisoning forms are difficult to eliminate by means of activation or regeneration and the like. Even if the raw oil contains trace amount of arsenide, the catalyst can be subjected to permanent poisoning and deactivation, so that the operation stability of the device is directly affected, and the operation period is shortened. Thus, pre-dearsenification of feedstock oils is becoming increasingly important in order to ensure catalyst activity and long-term operation of the unit.
CN1055957C discloses a hydrocarbon dearsenifying agent consisting of 2-12wt% copper, 0-10wt% nickel and the balance of a catalyst selected from gamma-Al 2 O 3 Or a carrier of amorphous aluminum silicate. However, the dearsenifying agent needs to be reduced by hydrogen before being used for hydrocarbon dearsenification, so that at least part of Cu and Ni in the dearsenification agent are converted into a metal reduction state, the process is complex, and the energy consumption is increased.
US6759364B2 discloses a hydrocarbon hydrogenation dearsenification agent, which adopts a porous carrier to load metal, wherein the active metal is VIB group metal with the content of more than 8 percent and a certain amount of VIII group metal, and the atom ratio of the VIII group metal to the VIB group metal is between 1.5 and 2.5. Mainly comprises alumina, nickel with the content of more than 8 percent, molybdenum with the content of more than 8 percent and phosphorus with the content of between 0.1 and 3 percent. The method is used for dearsenifying naphtha and light distillate oil, but the problems that the excessive content of olefin in the naphtha can cause diene polymerization, cause coking and the like are not considered.
CN106660018A discloses a method for preparing and using hydrocarbon hydrodearsenical agent, the catalyst comprises alumina carrier, interlayer molybdenum and phosphorus component, and nickel component coating. However, the preparation process is complicated and requires secondary impregnation.
CN105562000a discloses a normal temperature dearsenic agent, and a preparation method and application thereof, the dearsenic agent comprises a carrier and Cu-Ni active components loaded on the carrier, wherein the Cu-Ni active components are CuO and NiO; the mass ratio of the carrier to the CuO to the NiO is 100 (1-10), and the carrier is 1-10, and is used for removing inorganic arsenic in the catalytic cracking gasoline. The dearsenization agent adopts a titanium-aluminum composite carrier, but the amount of active metal is low, secondary impregnation is needed, the arsenic capacity of the dearsenization agent is low, only inorganic arsenide in oil products can be removed, and the raw material adaptation is poor.
CN108246302A discloses a preparation method of a catalytic gasoline hydrogenation dearsenification agent, wherein the dearsenification agent comprises 7-20wt% of NiO and 2.5-4.9wt% of MoO 3 0-15wt% TiO 2 The balance of Al 2 O 3 Mixing aluminum oxide or a mixture of aluminum oxide and titanium oxide with sesbania powder uniformly, adding an organic polymer pore-forming agent, a binder and deionized water, kneading, extruding, forming, drying and carrying out high-temperature heat treatment to obtain the dearsenifying agent carrier. And (3) carrying out hydrothermal treatment and reaming on the dearsenifying agent carrier to obtain the dearsenifying agent modified carrier. The dearsenifying agent carrier is a mixture of aluminum oxide and titanium oxide, simple dry mixing can not ensure uniform mixing of the aluminum oxide and the titanium oxide, the carrier has smaller specific surface, is unfavorable for improving the activity of the dearsenifying agent, and does not reflect the arsenic capacity of the dearsenifying agent. In addition, the dearsenifying agent is mainly suitable for catalyzing gasoline to remove arsenic, and has a narrow raw material adaptation surface.
CN108246242A discloses a preparation method of a catalytic gasoline hydrogenation dearsenification agent, wherein the dearsenification agent comprises 7-20wt% of NiO and 0-15wt% of TiO 2 The balance of Al 2 O 3 Mixing aluminum oxide or a mixture of aluminum oxide and titanium oxide with sesbania powder uniformly, adding an organic polymer pore-forming agent, a binder and deionized water, kneading, extruding, forming, drying and carrying out high-temperature heat treatment to obtain the dearsenifying agent carrier. And (3) carrying out hydrothermal treatment and reaming on the dearsenifying agent carrier to obtain the dearsenifying agent modified carrier. The dearsenifying agent carrier is a mixture of aluminum oxide and titanium oxide, simple dry mixing can not ensure uniform mixing of the aluminum oxide and the titanium oxide, and the carrier has smaller specific surface, which is unfavorable for the activity of the dearsenifying agentThe property is improved, and the arsenic capacity is not reflected. In addition, the dearsenifying agent is mainly suitable for catalyzing gasoline to remove arsenic, and has a narrow raw material adaptation surface.
However, the existing dearsenization agent still has the problems of poor raw material adaptability, such as secondary desulfurization treatment for sulfur-containing components, poor quality, high content of olefin and oxygen in catalytic gasoline naphtha, easy coking in the processing process due to olefin polymerization, and the like.
Disclosure of Invention
In view of the problems existing in the prior art, the invention aims to provide a dearsenifying agent for hydrogenation of light distillate oil and a preparation method thereof, and the hydrodearsenating agent has desulfurizing activity and stronger coking resistance, can effectively inhibit olefin polymerization, and is suitable for the hydrodearsenation process of light distillate oil, including naphtha, catalytic gasoline and the like.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a dearsenization agent for hydrogenation of light distillate oil, which comprises the following components in percentage by mass: niO 5-20%, tiO 2 10-35%, mgO 0.5-2.5%, C7-14%, and gamma Al in balance 2 O 3 ；
Wherein the carrier in the dearsenization agent is TiO 2 -γAl 2 O 3 The active component of the composite carrier is NiO, and the auxiliary agent is MgO and C.
The hydrogenation dearsenization agent in the invention adopts TiO 2 -Al 2 O 3 Binary composite carrier is prepared by mixing TiO 2 Compounding to Al 2 O 3 In the pore canal structure, not only Al can be reserved 2 O 3 Can exert TiO as well as the whole skeleton 2 The catalyst has excellent catalytic performance, improves the dispersity of active metal components, has higher catalytic activity and excellent stability, further has certain desulfurization performance by the design of the components, and improves the application range of the dearsenic agent.
In the present invention, niO in the dearsenifying agent may be 5 to 20% by mass, for example, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19% or 20% by mass, but is not limited to the listed values, and other non-listed values in this range are equally applicable.
In the invention, tiO in the dearsenization agent 2 The content of the catalyst is 15 to 35% by mass, and for example, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34% or 35% by mass may be used, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above range are equally applicable.
In the present invention, mgO in the dearsenifying agent is 0.5 to 2.5% by mass, for example, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4% or 2.5% by mass, but not limited to the listed values, and other non-listed values in this range are equally applicable.
In the present invention, the content of C in the dearsenifying agent is 7 to 14% by mass, for example, 7%, 8%, 9%, 10%, 11%, 12%, 13% or 14% by mass, etc., but the present invention is not limited to the recited values, and other non-recited values in the range are equally applicable.
As a preferable technical scheme of the invention, the dearsenization agent comprises the following components in percentage by mass: niO 8-16%, tiO 2 15-35%, mgO 1-1.5%, C8-12%, and gamma Al in balance 2 O 3 。
In a second aspect, the present invention provides a process for the preparation of a dearsenic agent according to the first aspect, said process comprising the steps of:
(1) TiO is mixed with 2 -γAl 2 O 3 Mixing the composite carrier with pretreatment liquid, and then sequentially carrying out first drying and first roasting to obtain a carrier;
(2) And (3) carrying out impregnation treatment on the carrier obtained in the step (1) by using a nickel salt solution, and carrying out solid-liquid separation, and then sequentially carrying out second drying and second roasting to obtain the dearsenifying agent.
As a preferred technique of the present inventionScheme, step (1) the TiO 2 -γAl 2 O 3 The composite carrier is prepared by a precipitation method, a coprecipitation method or a sol-gel method.
Wherein, gamma Al in the precipitation method 2 O 3 Is prepared by roasting pseudo-boehmite powder for 3-5 hours in an air atmosphere at 550-600 ℃. The aluminum source of the coprecipitation method or sol-gel method may be a conventional aluminum source in the art such as aluminum salt or the like.
In the present invention, the temperature during the firing is 550 to 600 ℃, and for example, 550 ℃, 560 ℃, 570 ℃, 580 ℃, 590 ℃,600 ℃ or the like can be used, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above range are applicable.
In the present invention, the time for baking in the air atmosphere is 3 to 5 hours, and for example, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, or the like may be used, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above range are equally applicable.
Preferably, the specific surface area of the pseudo-boehmite powder is 220-270m 2 Per g, pore volume of 0.7-1.2cm 3 And/g, wherein the average pore diameter is 5-25nm, and the pores with the pore diameters of 4-10nm account for more than 20% of all pores.
In the invention, the specific surface area of the pseudo-boehmite powder is 220-270m 2 /g, for example, may be 220m 2 /g、230m 2 /g、240m 2 /g、250m 2 /g、260m 2 /g or 270m 2 For example,/g, etc., but are not limited to the recited values, other non-recited values within this range are equally applicable.
In the invention, the pore volume of the pseudo-boehmite powder is 0.7-1.2cm 3 Per g, for example, may be 0.7cm 3 /g、0.75cm 3 /g、0.8cm 3 /g、0.85cm 3 /g、0.9cm 3 /g、0.95cm 3 /g、1cm 3 /g、1.05cm 3 /g、1.1cm 3 /g、1.15cm 3 /g or 1.2cm 3 For example,/g, etc., but are not limited to the recited values, other non-recited values within this range are equally applicable.
In the present invention, the average pore diameter of the pseudo-boehmite powder is 5 to 25nm, for example, 5nm, 15nm, 20nm, 25nm, or the like, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above range are equally applicable.
Preferably, the titanium source in the preparation process of the composite carrier in the step (1) comprises 1 or a combination of at least 2 of titanium sulfate, titanium nitrate, titanium acetate or titanium trichloride, preferably titanium sulfate.
Preferably, the titanium source and gamma Al are used in the preparation of the composite carrier in the step (1) 2 O 3 The mass ratio is (0.74-1.73): 1, and may be, for example, 0.74:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, or 1.7:1, etc., but not limited to the recited values, and other non-recited values within this range are equally applicable.
In a preferred embodiment of the present invention, the pretreatment liquid in step (1) is an aqueous solution of a water-soluble organic compound and a magnesium salt.
Preferably, the water-soluble organic matter comprises 1 or a combination of at least 2 of sucrose, glucose, citric acid, ethylene glycol, tartaric acid, acetic acid, preferably glucose and/or sucrose.
Preferably, the pretreatment liquid in step (1) contains water-soluble organic substances in an amount calculated as carbon element as the TiO 2 -γAl 2 O 3 The mass of the composite carrier may be 9.6 to 17%, for example, 9.6%, 10%, 11%, 12%, 13%, 14%, 15%, 16% or 17%, etc., but is not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the magnesium salt comprises 1 or a combination of at least 2 of magnesium nitrate, magnesium sulfate, magnesium acetate, basic magnesium carbonate or magnesium chloride.
Preferably, the magnesium salt in the pretreatment liquid in the step (1) is added in an amount calculated as magnesium oxide to the TiO 2 -γAl 2 O 3 The mass of the composite carrier may be 1.2 to 2.1%, for example, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 2% or 2.1%, etc., but is not limited to the recited values, and other non-recited values within this range are equally applicable.
As a preferred embodiment of the present invention, the TiO in the mixing in the step (1) 2 -γAl 2 O 3 The solid-liquid ratio g/mL of the composite carrier and the pretreatment liquid is 1 (0.8-0.9), for example, 1:0.8, 1:0.81, 1:0.82, 1:0.83, 1:0.84, 1:0.85, 1:0.86, 1:0.87, 1:0.88, 1:0.89 or 1:0.9, etc., but the present invention is not limited to the recited values, and other non-recited values in the range are equally applicable.
In a preferred embodiment of the present invention, the temperature of the first drying in the step (1) is 100 to 150 ℃, and for example, it may be 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃ or the like, but not limited to the values recited, and other values not recited in the range are equally applicable.
Preferably, the first drying time in step (1) is 3-6h, for example, 3h, 4h, 5h or 6h, etc., but not limited to the recited values, and other non-recited values within this range are equally applicable.
Preferably, the first firing of step (1) is performed under a protective atmosphere comprising nitrogen or an inert gas.
Preferably, the temperature of the first firing in the step (1) is 500 to 800 ℃, for example, 500 ℃, 550 ℃,600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, or the like, but not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the time of the first calcination in step (1) is 4-8 hours, for example, may be 4 hours, 5 hours, 6 hours, 7 hours or 8 hours, etc., but is not limited to the recited values, and other non-recited values within the range are equally applicable.
As a preferred embodiment of the present invention, the nickel salt in the nickel salt solution in the step (2) includes 1 or at least 2 of nickel nitrate, basic nickel carbonate, nickel acetate and nickel citrate, preferably nickel nitrate.
Preferably, the nickel salt solution in the step (2) contains 9.5-10.23% of nickel by mass percent, for example, 9.5%, 9.6%, 9.7%, 9.8%, 9.9%, 10%, 10.1%, 10.2% or 10.23% of nickel, but not limited to the listed values, and other non-listed values in the range are equally applicable.
Preferably, the solid-to-liquid ratio of the carrier and the nickel salt solution in the impregnation treatment in the step (2) is (0.85-1.15): 1, and may be, for example, 0.85:1, 0.9:1, 0.95:1, 1:1, 1.1:1, or 1.15:1, etc., but not limited to the recited values, and other non-recited values within this range are equally applicable.
Preferably, the temperature of the second drying in the step (2) is 110-140 ℃, for example, 110 ℃, 120 ℃, 130 ℃, 140 ℃ or the like, but not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the second drying time in step (2) is 2-5h, for example, 2h, 3h, 4h or 5h, but not limited to the recited values, and other non-recited values within this range are equally applicable.
Preferably, the temperature of the second baking in the step (2) is 400-600 ℃, for example, 400 ℃,450 ℃, 500 ℃, 550 ℃,600 ℃ or the like, but not limited to the recited values, and other non-recited values within the range are equally applicable.
Preferably, the second calcination in step (2) is performed for 3-6 hours, for example, 3 hours, 4 hours, 5 hours, or 6 hours, but not limited to the recited values, and other non-recited values within the range are equally applicable.
As a preferable technical scheme of the invention, the preparation method comprises the following steps:
(1) TiO is mixed with 2 -γAl 2 O 3 Mixing the composite carrier with pretreatment liquid, and then sequentially carrying out first drying and first roasting to obtain a carrier;
(2) Carrying out impregnation treatment on the carrier obtained in the step (1) by using a nickel salt solution, carrying out solid-liquid separation, and sequentially carrying out second drying and second roasting to obtain the dearsenification agent;
the pretreatment liquid in the step (1) is an aqueous solution of water-soluble organic matters and magnesium salts; the water-soluble organic matter comprises 1 or at least 2 of sucrose, glucose, citric acid, glycol, tartaric acid and acetic acid, and the TiO in the mixture 2 -γAl 2 O 3 The solid-liquid ratio g/mL of the composite carrier and the pretreatment liquid is 1 (0.8-0.9); the first roasting is carried out under a protective atmosphere, and the protective atmosphere comprises nitrogen or inert gas;the temperature of the first roasting is 500-800 ℃; the first roasting time is 4-8 hours;
the solid-to-liquid ratio of the carrier and the nickel salt solution in the impregnation treatment in the step (2) is (0.85-1.15): 1; the second roasting is carried out under a protective atmosphere, wherein the protective atmosphere comprises nitrogen or inert gas; the temperature of the second roasting is 400-600 ℃; the second roasting time is 3-6h.
In a third aspect, the present invention provides the use of a dearsenifying agent according to the first aspect for dearsenification in the hydrogenation of light ends, said dearsenifying agent being sulfided prior to use. The sulfuration condition is 220-300 ℃, sulfuration is 7-30h, hydrogen partial pressure is 1-2MPa, hydrogen oil volume ratio (100-300): 1, distillate oil hydrogenation dearsenification reaction condition is: the reaction pressure is 1-4MPa, the reaction temperature is 240-340 ℃, the hydrogen-oil volume ratio (100-300) is 1, and the volume space velocity is 2h -1 -50h -1 。
The temperature is 220 to 300 ℃, and may be 220 ℃, 230 ℃, 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, 300 ℃, or the like, for example, but not limited to the values recited, and other values not recited in the range are equally applicable.
The vulcanization time is 7 to 12 hours, for example, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours or 12 hours, etc., and the hydrogen partial pressure is 1 to 2MPa, for example, 1MPa, 1.1MPa, 1.2MPa, 1.3MPa, 1.4MPa, 1.5MPa, 1.6MPa, 1.7MPa, 1.8MPa, 1.9MPa or 2MPa, etc., but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above range are equally applicable.
The hydrogen-oil volume ratio (100-200): 1 may be, for example, 100:1, 110:1, 120:1, 130:1, 140:1, 150:1, 160:1, 170:1, 180:1, 190:1, or 200:1, etc., but is not limited to the recited values, and other non-recited values within this range are equally applicable.
The distillate oil hydrogenation dearsenification reaction conditions are as follows: the reaction pressure may be 1 to 4MPa, for example, 1MPa, 2MPa, 3MPa, 4MPa, or the like, but is not limited to the values recited, and other values not recited in the range are equally applicable.
The reaction temperature may be 240 to 320℃and may be 240℃and 250℃and 260℃and 270℃and 280℃and 290℃and 300℃and 310℃or 320℃respectively, but the reaction temperature is not limited to the values listed, and other values not listed in the above range are equally applicable.
The hydrogen oil volume ratio (100-300): 1 may be, for example, 100:1, 150:1, 200:1, 250:1, or 300:1, etc., but is not limited to the recited values, and other non-recited values within this range are equally applicable.
Volume space velocity of 10-50h -1 For example, it may be 10 hours -1 、20h -1 、30h -1 、40h -1 Or 50h -1 And the like, but are not limited to the recited values, and other non-recited values within this range are equally applicable.
In the present invention, the amount of the additive which is not described in the preparation process can be derived from the content of each component in the product.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) The hydrogenation dearsenization agent in the invention adopts TiO 2 -Al 2 O 3 Binary composite carrier is prepared by mixing TiO 2 To Al 2 O 3 In the pore canal structure, not only Al can be reserved 2 O 3 Can exert TiO as well as the whole skeleton 2 The catalyst has excellent catalytic performance, improves the dispersity of active metal components, and shows higher catalytic activity and excellent stability.
(2) According to the hydrogenation dearsenifying agent carrier, magnesium and carbon are introduced through resetting components, the specific surface pore volume is increased, the catalytic hydrogenation saturation performance of the catalyst is adjusted, coking caused by olefin polymerization in light distillate oil is effectively avoided, and the hydrogenation dearsenifying agent carrier can be used for removing arsenic in catalytic cracking gasoline rich in unsaturated hydrocarbon.
Drawings
FIG. 1 is a graph showing the acidity of the catalysts obtained in example 1 of the present invention and comparative example 1.
The present invention will be described in further detail below. The following examples are merely illustrative of the present invention and are not intended to represent or limit the scope of the invention as defined in the claims.
Detailed Description
For a better illustration of the present invention, which is convenient for understanding the technical solution of the present invention, exemplary but non-limiting examples of the present invention are as follows:
example 1
The embodiment provides an dearsenization agent for hydrogenation of light distillate oil, which comprises the following components in percentage by mass: niO 14%, tiO 2 15%, mgO 1%, C10%, and gamma Al in balance 2 O 3 ；
Wherein the carrier in the dearsenization agent is TiO 2 -γAl 2 O 3 The active component of the composite carrier is NiO, and the auxiliary agent is MgO and C.
The preparation method comprises the following steps:
1) 90.2g of titanium sulfate is weighed and placed in 500mL of deionized water, stirred and dissolved, 120g of gamma-Al obtained by roasting pseudo-boehmite powder at 580℃ is taken 2 O 3 Adding into titanium sulfate solution, slowly dripping ammonia water under stirring, adjusting pH to 8, precipitating for 3 hr, vacuum filtering, repeatedly washing with deionized water, oven drying the obtained white solid at 120deg.C for 3 hr, and calcining at 580 deg.C to obtain TiO 2 -Al 2 O 3 The composite carrier is denoted as mixed powder FT1.
(2) 120mL of deionized water was measured with a measuring cylinder and added to a beaker, and another 50.0g of glucose, 12.7g of Mg (NO 3 ) 2 Adding the above materials, stirring for 20min, dissolving completely, mixing well, and fixing volume to 140mL. Adding the solution into mixed powder FT1 for 3 times, kneading, extruding to obtain clover-shaped wet strip with diameter of 1.6mm, oven drying at 120deg.C for 5 hr, and calcining at 650deg.C in nitrogen atmosphere for 4 hr to obtain TiO containing Mg and carbon 2 -Al 2 O 3 The binary composite carrier, namely the hydrogenation dearsenifying agent carrier, is marked as ZT1.
(3) 109.0g of nickel nitrate hexahydrate was weighed, added to 70mL of deionized water, stirred until the metal salt was completely dissolved, and the volume was fixed to 130mL, 172g of carrier ZT1 was impregnated with the solution in an equal volume, then dried at 120℃for 3 hours, and calcined at 450℃in a nitrogen atmosphere tube furnace for 3 hours, to prepare catalyst C1.
The performance indexes of the obtained carrier and the dearsenicating agent are shown in tables 1 and 2, and the acidity characterization of the obtained dearsenicating agent is shown in figure 1.
Example 2
The embodiment provides an dearsenization agent for hydrogenation of light distillate oil, which comprises the following components in percentage by mass: niO 12%, tiO 2 25% MgO 1%, C8% and gamma Al for the rest 2 O 3 ；
Wherein the carrier in the dearsenization agent is TiO 2 -γAl 2 O 3 The active component of the composite carrier is NiO, and the auxiliary agent is MgO and C.
The preparation method comprises the following steps:
(1) Respectively weighing 150.3g of titanium sulfate and 794.7g of aluminum nitrate nonahydrate, placing in a large beaker, adding 2L of deionized water for dissolution, slowly dripping ammonia water under stirring, adjusting pH to 8, precipitating and aging for 3h, performing vacuum filtration and filtration, repeatedly washing with deionized water, placing the obtained white solid in a 140 ℃ oven for drying for 3h, placing in a tubular furnace for roasting at 600 ℃ under the air atmosphere, and obtaining TiO 2 -γAl 2 O 3 Composite powder FT2.
(2) 100mL of deionized water was weighed into a beaker using a measuring cylinder, and 38.0g of sucrose, 12.7g of Mg (NO 3 ) 2 Adding the above materials, stirring for 20min until the materials are fully dissolved, uniformly mixing, and fixing the volume to 150mL. Adding the solution into mixed powder FT2, kneading, extruding to obtain clover-shaped wet strip with diameter of 1.6mm, oven drying at 120deg.C for 3 hr, and calcining at 800deg.C under argon atmosphere for 8 hr to obtain TiO containing Mg and carbon 2 -γAl 2 O 3 The binary composite carrier, namely the hydrogenation dearsenifying agent carrier, is marked as ZT2.
(3) 93.4g of nickel nitrate hexahydrate is weighed and added into 90mL of deionized water until the metal salt is completely dissolved, the volume is fixed to 100mL, 176g of carrier ZT2 is immersed in the solution in an equal volume, then the solution is dried for 5h at 140 ℃ and baked for 5h in an argon atmosphere tube furnace at 600 ℃ to prepare the catalyst C2.
The performance index of the obtained carrier and the dearsenicating agent are shown in tables 1 and 2.
Example 3
The embodiment provides an dearsenization agent for hydrogenation of light distillate oil, wherein the dearsenization agentComprises the following components in percentage by mass: niO 10%, tiO 2 35% MgO 1.5%, C12% and gamma Al in balance 2 O 3 ；
Wherein the carrier in the dearsenization agent is TiO 2 -γAl 2 O 3 The active component of the composite carrier is NiO, and the auxiliary agent is MgO and C.
The preparation method comprises the following steps:
(1) 210.4g of titanium sulfate is weighed and placed in 500mL of deionized water, stirred and dissolved, 83g of gamma-Al obtained by roasting pseudo-boehmite powder at 580℃ is taken 2 O 3 Adding into titanium sulfate solution, slowly dripping ammonia water under stirring, adjusting pH to 8, precipitating for aging for 3 hr, vacuum filtering, repeatedly washing with deionized water, oven drying the obtained white solid at 120deg.C for 3 hr, and calcining at 580 deg.C in hollow atmosphere of tubular furnace to obtain TiO 2 -γAl 2 O 3 The composite powder is denoted as mixed powder FT3.
(2) 120mL of deionized water was measured with a measuring cylinder and added to a beaker, and 60.0g of glucose, 19.1g of Mg (NO) was additionally weighed 3 ) 2 Adding the above materials, stirring for 20min, dissolving completely, mixing well, and fixing volume to 150mL. Adding the solution into mixed powder FT1 for 3 times, kneading, extruding to obtain clover-shaped wet strip with diameter of 1.6mm, oven drying at 110deg.C for 5 hr, and calcining at 650deg.C in nitrogen atmosphere for 4 hr to obtain TiO containing Mg and carbon 2 -Al 2 O 3 The binary composite carrier, namely the hydrogenation dearsenifying agent carrier, is marked as ZT3.
(3) 77.8g of nickel nitrate hexahydrate is weighed and added into 70mL of deionized water, stirred until metal salt is completely dissolved, fixed to 90mL, 180g of carrier ZT1 is immersed in the solution in an equal volume, then the solution is dried at 120 ℃ for 3h, and the solution is baked for 3h in a nitrogen atmosphere tube furnace at 450 ℃ to prepare the catalyst C3.
The performance index of the obtained carrier and the dearsenicating agent are shown in tables 1 and 2.
Comparative example 1
The difference from example 1 was only that no magnesium source (magnesium nitrate) was added during the preparation to prepare catalyst D1. The performance indexes of the obtained carrier and the dearsenicating agent are shown in tables 1 and 2, and the acidity characterization of the obtained dearsenicating agent is shown in figure 1.
Comparative example 2
The difference from example 1 was only that no glucose was added to prepare catalyst D2. The performance index of the obtained carrier and the dearsenicating agent are shown in tables 1 and 2.
The activity of the catalysts obtained in the examples and comparative examples was evaluated using an arsenic-containing light distillate, including naphtha and catalytic gasoline, and the source of exogenous arsenic was triphenylarsenic. The method is characterized in that the method is carried out on a 300mL continuous isothermal fixed bed hydrogenation pilot plant test device, inert porcelain ball particles are filled at the top and the bottom of a reactor, the uniform distribution of material flows is ensured, an arsenic removal agent bed layer is supported, and an arsenic removal agent is filled in a constant temperature section of the reactor. The test hydrogen is high-purity hydrogen dehydrated by a molecular sieve under high pressure, and adopts a process flow of hydrogen passing through once. The dearsenization agent needs to be pre-vulcanized, hydrogen is used as a medium for drying and wet vulcanization of the dearsenization agent, 2.5wt% of DMDS is added into the vulcanized oil which is straight-run naphtha, after the device is qualified in airtight, the temperature is increased to 150 ℃ at a temperature increasing rate of 20 ℃/h, the vulcanized oil is fed after the constant temperature is kept for 2 hours, after the constant temperature is kept for 4 hours, the temperature is increased to 230 ℃ at the constant temperature for 4 hours, the temperature is increased to 260 ℃ at the constant temperature for 3 hours at the temperature of 20 ℃/h, and the vulcanization is finished after the temperature is increased to 290 ℃ at the constant temperature for 3.5 hours at the temperature of 20 ℃/h. The experimental conditions are that the reaction temperature is 300 ℃, the pressure is 2.5MPa, and the liquid hourly space velocity is 50h -1 The hydrogen oil volume ratio (hydrogen gas/raw oil) was 100:1. The dearsenification and desulfurization performances of naphtha are shown in Table 3, and the dearsenification and desulfurization performances of catalytic gasoline are shown in Table 4.
The determination of the effective arsenic capacity of the dearsenifying agent is carried out under the condition of high arsenic, namely a accelerating arsenic capacity test. Besides arsenic contained in the raw oil, arsenic-containing substances are required to be added, so that the arsenic content in the raw oil reaches more than 100 mug/g, hundreds of times of the arsenic content in the industrial raw oil, the arsenic removal performance of the arsenic removal agent is inspected, when the arsenic removal rate is lower than 90%, oil feeding is stopped, and the actual arsenic content on the catalyst is analyzed to be the arsenic content of the arsenic removal agent. In the test, triphenylarsenic is adopted as an externally doped arsenic source, the dearsenification agent in the example 1 is subjected to arsenic capacity test investigation, the reaction temperature is 280 ℃, the pressure is 2.5MPa, and the liquid hourly space velocity is 10h -1 The hydrogen oil volume ratio (hydrogen gas/raw oil) was 100:1. The arsenic content results are detailed in Table 5
Table 1 Performance index of dearsenicator Carriers in examples and comparative examples
TABLE 2 Performance index of dearsenicating agent in examples and comparative examples
TABLE 3 dearsenification and desulfurization index for dearsenification in naphtha
TABLE 4 dearsenification and desulfurization index for catalyst removal of arsenic in gasoline
TABLE 5 arsenic capacity results for the dearsenicating agent of example 1
Sample numbering As/μg·kg -1 Arsenic removal rate/%
Raw oil 200 /
30h product 0.70 99.65
60h product 0.92 98.92
90h product 1.13 99.44
120h product 2.59 98.70
150h product 21.60 89.2
Generally, according to NH 3 NH in TPD spectra 3 The desorption temperature, the strength of the acid center can be classified into weak acid (100-250 ℃), medium strong acid (250-400 ℃) and strong acid (> 400 ℃), and as can be seen from FIG. 1, the signal peak of the magnesium-containing dearsenifying agent (example 1) shifts to the weak acid region and the peak area decreases, indicating a decrease in acidity, compared with the dearsenifying agent without magnesium (comparative example 1).
The results of the above examples and comparative examples show that the catalyst prepared by the method provided by the invention is used for dearsenifying light distillate oil under typical process conditions, especially under high space velocity conditions, the dearsenifying rate is more than 99%, the dearsenifying agent can effectively ensure the bromine index of raw oil to be relatively stable, olefin polymerization coke is avoided, and the dearsenifying agent has a certain desulfurization and denitrification effect and can be matched with a hydrofining catalyst for application. In addition, the pore volume of the dearsenization agent is increased by introducing auxiliary carbon, so that the arsenic volume of the dearsenization agent is increased to be more than 5wt% and the long-period application of the catalyst is ensured.
The applicant states that the detailed structural features of the present invention are described by the above embodiments, but the present invention is not limited to the above detailed structural features, i.e. it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope of the present invention and the scope of the disclosure.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.

Claims (25)

1. The dearsenization agent for the hydrogenation of the light distillate oil is characterized by comprising the following components in percentage by mass: niO 5-20%, tiO 2 10-35%, mgO 0.5-2.5%, C7-14%, and gamma Al in balance 2 O 3 ；
Wherein the carrier in the dearsenicating agentIs TiO 2 -γAl 2 O 3 The active component of the composite carrier is NiO, and the auxiliary agent is MgO and C;
the preparation method specifically comprises the following steps:
(1) TiO is mixed with 2 -γAl 2 O 3 Mixing the composite carrier with pretreatment liquid, and then sequentially carrying out first drying and first roasting to obtain a carrier; the pretreatment liquid is an aqueous solution of water-soluble organic matters and magnesium salts; the water-soluble organic matter comprises 1 or at least 2 of sucrose, glucose, citric acid, ethylene glycol, tartaric acid and acetic acid; the first roasting is carried out under a protective atmosphere, and the protective atmosphere comprises nitrogen or inert gas; the temperature of the first roasting is 500-800 ℃;
(2) Carrying out impregnation treatment on the carrier obtained in the step (1) by using a nickel salt solution, carrying out solid-liquid separation, and sequentially carrying out second drying and second roasting to obtain the dearsenification agent; the second roasting is carried out under a protective atmosphere, wherein the protective atmosphere comprises nitrogen or inert gas; the temperature of the second roasting is 400-600 ℃.
2. The dearsenization agent of claim 1, wherein the dearsenization agent comprises, in mass percent: niO 8-16%, tiO 2 15-35%, mgO 1-1.5%, C8-12%, and gamma Al in balance 2 O 3 。
3. The method for preparing the dearsenic agent according to claim 1 or 2, wherein the method comprises the steps of:
(1) TiO is mixed with 2 -γAl 2 O 3 Mixing the composite carrier with pretreatment liquid, and then sequentially carrying out first drying and first roasting to obtain a carrier; the pretreatment liquid is an aqueous solution of water-soluble organic matters and magnesium salts; the water-soluble organic matter comprises 1 or at least 2 of sucrose, glucose, citric acid, ethylene glycol, tartaric acid and acetic acid; the first roasting is carried out under a protective atmosphere, and the protective atmosphere comprises nitrogen or inert gas; the temperature of the first roasting is 500-800 ℃;
(2) Carrying out impregnation treatment on the carrier obtained in the step (1) by using a nickel salt solution, carrying out solid-liquid separation, and sequentially carrying out second drying and second roasting to obtain the dearsenification agent; the second roasting is carried out under a protective atmosphere, wherein the protective atmosphere comprises nitrogen or inert gas; the temperature of the second roasting is 400-600 ℃.
4. The method of claim 3, wherein the TiO of step (1) 2 -γAl 2 O 3 The composite carrier is prepared by a precipitation method, a coprecipitation method or a sol-gel method; gamma Al in the precipitation method 2 O 3 Is prepared by roasting pseudo-boehmite powder for 3-5 hours in an air atmosphere at 550-600 ℃.
5. The method according to claim 4, wherein the specific surface area of the pseudo-boehmite powder is 220-270m 2 Per g, pore volume of 0.7-1.2cm 3 And/g, wherein the average pore diameter is 5-25nm, and the pores with the pore diameters of 4-10nm account for more than 20% of all pores.
6. The method of claim 3, wherein the titanium source in the preparation of the composite support in step (1) comprises 1 or a combination of at least 2 of titanium sulfate, titanium nitrate, titanium acetate, or titanium trichloride.
7. The method of claim 6, wherein the titanium source in the preparation of the composite carrier in step (1) is titanium sulfate.
8. The method according to claim 3, wherein the composite carrier of step (1) is prepared by mixing a titanium source and γal 2 O 3 The mass ratio is (0.74-1.73): 1.
9. The method according to claim 3, wherein the pretreatment liquid in step (1) contains water-soluble organic substances in an amount calculated as carbon element as TiO 2 -γAl 2 O 3 9.6-17% of the mass of the composite carrier.
10. A process according to claim 3, wherein the water-soluble organic compound of step (1) is glucose and/or sucrose.
11. The method of claim 3, wherein the magnesium salt comprises 1 or a combination of at least 2 of magnesium nitrate, magnesium sulfate, magnesium acetate, basic magnesium carbonate, or magnesium chloride.
12. The method according to claim 3, wherein the magnesium salt is added to the pretreatment liquid in the step (1) in an amount calculated as magnesium oxide to obtain the TiO 2 -γAl 2 O 3 1.2 to 2.1 percent of the mass of the composite carrier.
13. The method of claim 3, wherein said TiO in said mixing of step (1) 2 -γAl 2 O 3 The solid-liquid ratio g/mL of the composite carrier and the pretreatment liquid is 1 (0.8-0.9).
14. A method of preparation according to claim 3, wherein the temperature of the first drying in step (1) is 100-150 ℃.
15. A method of manufacture as claimed in claim 3 wherein the first drying in step (1) is for a period of 3 to 6 hours.
16. The method of claim 3, wherein the first firing in step (1) is for a period of 4 to 8 hours.
17. The method of claim 3, wherein the nickel salt in the nickel salt solution of step (2) comprises a combination of 1 or at least 2 of nickel nitrate, basic nickel carbonate, nickel acetate and nickel citrate.
18. The method of claim 17, wherein the nickel salt in the nickel salt solution of step (2) is nickel nitrate.
19. The method according to claim 3, wherein the nickel salt solution in the step (2) contains 9.5 to 10.23% by mass of nickel.
20. The process according to claim 3, wherein the solid-to-liquid ratio of the carrier and the nickel salt solution in the impregnation treatment in the step (2) is (0.85-1.15): 1.
21. A method of preparation according to claim 3 wherein the second drying in step (2) is at a temperature of 110-140 ℃.
22. A method of manufacture as claimed in claim 3 wherein the second drying in step (2) is for a period of time in the range 2 to 5 hours.
23. The method of claim 3, wherein the second firing in step (2) is for a period of 3 to 6 hours.
24. The method of any one of claims 3-23, wherein the method of preparation comprises the steps of:
(1) TiO is mixed with 2 -γAl 2 O 3 Mixing the composite carrier with pretreatment liquid, and then sequentially carrying out first drying and first roasting to obtain a carrier;
(2) Carrying out impregnation treatment on the carrier obtained in the step (1) by using a nickel salt solution, carrying out solid-liquid separation, and sequentially carrying out second drying and second roasting to obtain the dearsenification agent;
the pretreatment liquid in the step (1) is an aqueous solution of water-soluble organic matters and magnesium salts; the water-soluble organic matter comprises 1 or at least 2 of sucrose, glucose, citric acid, ethylene glycol, tartaric acid and acetic acid; by a means ofThe TiO in the mixture 2 -γAl 2 O 3 The solid-liquid ratio g/mL of the composite carrier and the pretreatment liquid is 1 (0.8-0.9); the first roasting is carried out under a protective atmosphere, and the protective atmosphere comprises nitrogen or inert gas; the temperature of the first roasting is 500-800 ℃; the first roasting time is 4-8 hours;
the solid-to-liquid ratio of the carrier and the nickel salt solution in the impregnation treatment in the step (2) is (0.85-1.15): 1; the second roasting is carried out under a protective atmosphere, wherein the protective atmosphere comprises nitrogen or inert gas; the temperature of the second roasting is 400-600 ℃; the second roasting time is 3-6h.
25. The use of the dearsenifying agent according to claim 1 or 2, characterized in that said dearsenifying agent is used for dearsenification in the hydrogenation of light distillate, said dearsenifying agent being subjected to a vulcanization treatment before use.
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