CN111036276B - Tungsten-based pre-vulcanized-free hydrotalcite hydrodesulfurization catalyst and preparation method thereof - Google Patents

Tungsten-based pre-vulcanized-free hydrotalcite hydrodesulfurization catalyst and preparation method thereof Download PDF

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CN111036276B
CN111036276B CN201911247267.XA CN201911247267A CN111036276B CN 111036276 B CN111036276 B CN 111036276B CN 201911247267 A CN201911247267 A CN 201911247267A CN 111036276 B CN111036276 B CN 111036276B
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hydrotalcite
tungsten
nickel
tetrathiotungstate
catalyst
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CN111036276A (en
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王豪
杨振东
杨帆
杨晗
吴雁
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Southwest Petroleum University
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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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B01J27/25—Nitrates
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • 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
    • C10G45/08—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 in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • 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
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1048—Middle distillates
    • 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
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1048—Middle distillates
    • C10G2300/1055—Diesel having a boiling range of about 230 - 330 °C
    • 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
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • 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
    • C10G2300/70—Catalyst aspects
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil

Abstract

The invention discloses a tungsten-based unsulfided hydrotalcite hydrodesulfurization-free catalyst and a preparation method thereof. The preparation method comprises the following steps: s1, preparing nickel aluminum hydrotalcite; s2, dissolving ammonium tetrathiotungstate in boiled deionized water to prepare an ammonium tetrathiotungstate solution; s3, mixing the nickel-aluminum hydrotalcite with an ammonium tetrathiotungstate solution, adjusting the pH value to 7-9, carrying out ion exchange reaction at 50-70 ℃ for 12-28 h, filtering, washing and drying the obtained exchange product to obtain the tetrathiotungstate intercalated nickel-aluminum hydrotalcite; s4, roasting the tetrathiotungstate intercalated nickel-aluminum hydrotalcite for 2-4 hours at 300-600 ℃ in a nitrogen atmosphere to obtain the tungsten-based unsulfurized hydrotalcite hydrodesulfurization-free catalyst. The catalyst of the invention realizes high dispersion and high loading of active metal components, and the catalyst shows higher hydrodesulfurization activity in the hydrodesulfurization reaction of oil products.

Description

Tungsten-based pre-vulcanized-free hydrotalcite hydrodesulfurization catalyst and preparation method thereof
Technical Field
The invention relates to the technical field of catalytic hydrodesulfurization, and particularly relates to a tungsten-based pre-vulcanization-free hydrotalcite catalyst and a preparation method thereof.
Background
In recent years, with the stricter environmental protection requirements, the upgrading pace of clean oil products is gradually accelerated. Hydrodesulfurization is a main means for producing clean oil products, and the development of a high-activity catalyst is the key for improving the depth of hydrodesulfurization. The main active components of the hydrodesulfurization catalyst are VIB group metal Mo or W as a main agent, VIII group metal Co or Ni as an auxiliary agent, and the hydrodesulfurization catalyst can be divided into a supported catalyst and a non-supported catalyst according to whether a carrier is used or not.
The supported catalyst mainly uses alumina or molecular sieve as a carrier, and is the most commonly used hydrodesulfurization catalyst in industry. Because of the restriction of the specific surface area and the pore volume of the carrier and the need of high-temperature roasting in the preparation process, the active components are easy to agglomerate due to the salting-out phenomenon, so that the dispersion degree of the active components is low, and the high dispersion of the active metals under high loading is difficult to realize, thereby the activity of the catalyst is limited to a certain extent. Compared with the traditional supported catalyst, the unsupported catalyst has more active center quantity and excellent hydrogenation performance. However, the method has the problems of relatively small specific surface area and pore volume, easy collapse of pore structure, easy agglomeration of metal active components, poor mechanical strength and the like, and limits industrial application.
The conventional hydrodesulfurization catalyst is prepared in an oxidation state, and is required to be subjected to pre-vulcanization treatment before use, namely, at a high temperature (300-400 ℃) and a high pressure (3-4 MPa), namely, a vulcanizing agent (CS)2、H2S, high sulfur oil, etc.) for a long time (1 to 7 days). Has the problems of long treatment time, high cost, toxic vulcanizing agent and the like.
Hydrotalcite is a Layered Double Hydroxide (LDHs) whose lamellae are formed by divalent and trivalent metals by sharing oxygen sides and between which are anions that balance the excess positive charge of the lamellae. LDHs have flexible adjustable modification of laminate metal and interlayer anion, and the size and Mg can be substituted by isomorphous substitution of the laminate2+And Al3+Close metal cations are introduced into the lamina and various anions can be intercalated between the layers by ion exchange. In addition, the composite metal oxide formed after the roasting of the LDHs has higher specific surface area, larger pore volume and good mechanical strength. By utilizing the characteristics of LDHs, a metal main agent Mo or W with hydrogenation catalytic activity is introduced into the interlayer, a metal auxiliary agent Ni or Co is introduced into a laminate to synthesize tungstate or molybdate intercalated LDHs, and the LDHs is roasted to prepare hydrorefining catalytic activityThe catalyst can realize the combination of high dispersion and high loading of active components, and meanwhile, a shorter laminate formed after roasting can play a good supporting role, so that the catalyst has better mechanical strength, larger specific surface area and pore structure, and has the advantages of both supported catalysts and unsupported catalysts.
CN 103657672 discloses the preparation and application of an ultra-deep hydrodesulfurization multi-metal unsupported catalyst with a layered structure. The LDHs layered structure of Ni or Co and other + 2-valent metals is prepared by a coprecipitation method, anion intercalation LDHs with Mo and W between layers is prepared by ion exchange, and finally, the unsupported hydrodesulfurization catalyst is obtained by vulcanization, and has good hydrodesulfurization activity. Wang et al (Fuel Process. Technol 160(2017)178, Fuel,228 (2018)) 332 introduce tungstate radicals into the interlayer of LDHs with a laminate of NiAlZr by an ion exchange method, and prepare the NiW hydrodesulfurization catalyst after roasting and sulfurization. The method realizes high load under high content of active metal, and has large specific surface area and high hydrodesulfurization activity. However, the hydrodesulfurization catalyst prepared by inserting tungstate or molybdate into the LDHs layers by using tungstate or molybdate as a precursor is still an oxidation state catalyst, and still needs to be presulfurized at high temperature and high pressure for a long time for use, so that the problems of high cost, long time consumption, poor safety and the like still exist.
CN 106268872 discloses a method for preparing MoS2The method of the LDHs hydrogenation catalyst without presulfiding. Firstly, MgFe (II) Fe (III) LDHs is synthesized, and composite metal oxide is formed as a carrier after high-temperature roasting; then carrying out hydrothermal reaction on ammonium tetrathiomolybdate and ionic liquid with the carrier at 150-200 ℃ for 12h in the presence of a reducing agent to obtain MoS2the/LDHs catalyst is used for the suspension bed hydrodesulfurization reaction of heavy oil, extra heavy oil and residual oil, and can obtain good hydrodesulfurization effect. The method is still essentially the conventional preparation method of the supported catalyst, and the nano MoS2The preparation process always needs expensive ionic liquid (1-methyl-3-carboxyethyl imidazole tetrafluoroborate or 1-ethyl-3-methyl imidazole tetrafluoroborate) and reducing agent (hydroxylamine hydrochloride, hydrazine hydrate or sodium borohydride), the preparation condition needs high temperature, and the cost is high.
CN 109821557 discloses a supported MoS prepared by ionic liquid step by step2A method for preparing a hydrodesulfurization catalyst by using LDHs. Firstly, synthesizing ZnAl LDHs, and using the modified ZnAl LDHs as a carrier after being modified by ionic liquid; then mixing ammonium tetrathiomolybdate, ionic liquid (1-methyl-3-carboxyethyl imidazole tetrafluoroborate) and reducing agent (hydroxylamine hydrochloride, hydrazine hydrate or sodium borohydride) with the carrier, carrying out hydrothermal reaction for 10-12 h at 80-120 ℃, filtering, drying, and roasting for 2-3 h at 400-500 ℃ to obtain MoS2The LDHs catalyst is used for the hydrodesulfurization reaction of heavy oil, extra heavy oil and residual oil in a suspension bed. The method is also a conventional preparation method of the supported catalyst, and still needs to use expensive ionic liquid and reducing agent, needs to prepare at high temperature in multiple steps, and has complex process and higher cost.
Wang et al (Molecular Catalysis 468(2019)1) will transfer MoS4 2-Inserting NiAl LDHs layers to prepare the hydrogenation catalyst without pre-vulcanization in one step. The method introduces ammonium tetrathiomolybdate into the NiAl LDHs interlayer by ion exchange at room temperature, and prepares MoS by one step after washing, filtering and drying4 2-The intercalated NiAl LDHs is activated by nitrogen and used as a pre-vulcanization-free hydrodesulfurization catalyst for diesel oil desulfurization. The method is simple to prepare, does not need expensive raw materials and multi-step high-temperature treatment, and has higher desulfurization activity compared with the conventional oxidation state catalyst.
In the prior art, molybdenum is used as a main active metal in preparation of the non-prevulcanization hydrogenation catalyst by adopting LDHs. The reserves of tungsten ore are the first in the world in China, and the deep hydrodesulfurization, denitrification and aromatic saturation activities of the tungsten-based catalyst are all higher than those of the molybdenum-based catalyst.
Disclosure of Invention
The invention aims to provide a tungsten-based non-presulfurized hydrotalcite catalyst for hydrodesulfurization of oil products, aiming at the problems that the existing oxidation state catalyst needs a complicated presulfurization process, the preparation of the existing non-presulfurization catalyst is complicated and the like.
The invention also aims to provide a preparation method of the tungsten-based unsulfided hydrotalcite catalyst.
The invention provides a tungsten-based unsulfided hydrotalcite hydrodesulfurization-free catalyst, which is nickel-aluminum hydrotalcite activated by nitrogen at high temperature and containing tetrathiotungstate intercalation. The tungsten-based pre-vulcanized-free hydrotalcite-type hydrodesulfurization catalyst is obtained by introducing thiotungstate anions into the nickel-aluminum hydrotalcite interlayer and then activating the thiotungstate anions at high temperature by nitrogen.
In the catalyst, the main agent of the catalytic active component is W, the auxiliary agent is Ni, and the other metal of the laminate is Al. The molar ratio of the Ni element to the Al element is (1-4): 1. preferably, in the catalyst, when the molar ratio of the Ni element to the Al element is 2: when 1, the molar ratio of the sum of the molar amounts of the Ni and W elements to the Ni element is 5: 4.
The preparation method of the tungsten-based unsulfided hydrotalcite hydrodesulfurization-free catalyst comprises the following steps:
s1, preparing nitrate type nickel aluminum hydrotalcite, which comprises the following steps:
s11, dissolving soluble nickel salt and soluble aluminum salt in boiled deionized water to prepare a mixed salt solution; the concentration of nickel salt in the mixed salt solution is 0.01-0.8 mol/L, and the concentration of aluminum salt is 0.01-0.2 mol/L; dissolving NaOH in boiled deionized water to prepare an alkali solution; the concentration of NaOH in the alkali solution is 0.2-2 mol/L.
S12, slowly dripping the alkali solution into the mixed salt solution, stirring to generate a precipitate, and controlling the pH value to be 6-10; and carrying out hydrothermal crystallization on the precipitate at the temperature of 80-120 ℃ for 8-20 h, filtering, washing and vacuum drying to obtain nitrate type nickel-aluminum hydrotalcite.
S2, dissolving ammonium tetrathiotungstate in boiled deionized water to prepare an ammonium tetrathiotungstate solution; wherein the concentration of the ammonium tetrathiotungstate is 0.05-0.3 mol/L.
S3, mixing the nitrate type nickel-aluminum hydrotalcite with an ammonium tetrathiotungstate solution, adjusting the pH value to 7-9 by using ammonia water, carrying out ion exchange reaction for 12-28 h at 50-70 ℃, filtering, washing and drying the obtained exchange product, and obtaining the tetrathiotungstate intercalated nickel-aluminum hydrotalcite.
S4, roasting the tetrathiotungstate intercalated nickel-aluminum hydrotalcite at 300-600 ℃ for 2-4 h in a nitrogen atmosphere to obtain the tungsten-based pre-vulcanized-free hydrotalcite type hydrodesulfurization catalyst.
Preferably, the soluble nickel salt and the soluble aluminum salt are Ni (NO), respectively3)2·6H2O and Al (NO)3)3·9H2O。
Preferably, in the step S3, the pH value is adjusted to 8.5-9, and the ion exchange reaction is carried out for 20-28 h at the temperature of 50-55 ℃; in step S4, the mixture is baked for 4 hours at 300-350 ℃.
Compared with the prior art, the invention has the advantages that:
compared with the conventional supported and unsupported hydrodesulfurization catalysts, the catalyst provided by the invention has the advantage of high active metal dispersion degree; compared with the existing oxidation state hydrotalcite-like hydrodesulfurization catalyst, the catalyst provided by the invention does not need to be presulfurized, so that the cost can be saved and the processing period can be shortened; compared with the prior molybdenum-based hydrotalcite-type non-presulfurization hydrodesulfurization catalyst, the catalyst of the invention has simple preparation method and does not need expensive ionic liquid and reducing agent. The problems that the existing oxidation state catalyst needs a complex pre-vulcanization process, the existing non-pre-vulcanization catalyst is complex to prepare and the like are solved, high dispersion and high load of active metal components are realized, and the obtained catalyst shows high hydrodesulfurization activity in the hydrodesulfurization reaction of oil products.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and description, and is in no way intended to limit the invention.
The Ni/Al in the following examples and comparative examples means the ratio of the number of moles of Ni and Al elements in the mixed salt solution.
Example 1
Weighing Ni (NO) according to the proportion of Ni/Al 2:13)2·6H2O and Al (NO)3)3·9H2Dissolving O in boiled deionized water, fixing the volume to 100mL, and preparing a mixed salt solution with the total concentration of two metal salts being 1 mol/L; weighing 8.0g of NaOH, dissolving in boiled deionized water, fixing the volume to 100mL, and preparing 2mol/L aqueous alkali as a precipitator; pouring the mixed salt solution into a 250mL flask, and magnetically stirring; then dropwise adding an alkali solution, stopping dropwise adding the alkali solution when the pH value of the solution is 8, and continuously stirring for 0.5 h; then pouring the obtained mixed solution into a hydrothermal reaction kettle, and reacting for 12 hours at 100 ℃; washing the obtained precipitate with deionized water for several times until the washing liquid is neutral; then drying the filtrate at 80 ℃ for 6h in vacuum; the obtained sample is nitrate type nickel aluminum hydrotalcite (Ni)2Al-NO3-LDH)。
Example 2
Weighing Ni (NO) according to the proportion of Ni/Al being 3:13)2·6H2O and Al (NO)3)3·9H2Dissolving O in boiled deionized water, and fixing the volume to 100mL to prepare a mixed salt solution with the total concentration of two metal salts being 1 mol/L; weighing 8.0g of NaOH, dissolving in boiled deionized water, fixing the volume to 100mL, and preparing into 2mol/L aqueous alkali as a precipitator; pouring the mixed salt solution into a 250mL flask, and magnetically stirring; then dropwise adding an alkali solution, stopping dropwise adding the alkali solution when the pH value of the solution is 9, and continuously stirring for 0.5 h; then pouring the obtained mixed solution into a hydrothermal reaction kettle, and reacting for 8 hours at 120 ℃; washing the obtained precipitate with deionized water for several times until the washing liquid is neutral; then drying the filtrate at 80 ℃ for 6h in vacuum; the obtained sample is nitrate type nickel aluminum hydrotalcite (Ni)3Al-NO3-LDH)。
Example 3
Weighing Ni (NO) according to the proportion of Ni/Al to 1:13)2·6H2O and Al (NO)3)3·9H2Dissolving O in boiled deionized water, and fixing the volume to 100mL to prepare a mixed salt solution with the total concentration of two metal salts being 1 mol/L; weighing 4.0g of NaOH, dissolving in boiled deionized water, fixing the volume to 100mL, and preparing 1mol/L aqueous alkali as a precipitator; pouring the mixed salt solution into a 250mL flask, and magnetically stirring; then adding an alkali solution dropwise when the pH value of the solution isWhen 7, stopping dropping the alkali solution, and continuing stirring for 0.5 h; then pouring the obtained mixed solution into a hydrothermal reaction kettle, and reacting for 15 hours at 110 ℃; washing the obtained precipitate with deionized water for several times until the washing liquid is neutral; then drying the filtrate at 80 ℃ for 6h in vacuum; the obtained sample is nitrate type nickel-aluminum hydrotalcite (NiAl-NO)3-LDH)。
Example 4
Weighing Ni (NO) according to the proportion of Ni/Al being 4:13)2·6H2O and Al (NO)3)3·9H2Dissolving O in boiled deionized water, and fixing the volume to 100mL to prepare a mixed salt solution with the total concentration of two metal salts being 1 mol/L; weighing 0.8g of NaOH, dissolving in boiled deionized water, fixing the volume to 100mL, and preparing 0.2mol/L aqueous alkali as a precipitator; pouring the mixed salt solution into a 250mL flask, and magnetically stirring; then dropwise adding an alkali solution, stopping dropwise adding the alkali solution when the pH value of the solution is 10, and continuously stirring for 0.5 h; then pouring the obtained mixed solution into a hydrothermal reaction kettle, and reacting for 20 hours at 80 ℃; washing the obtained precipitate with deionized water for several times until the washing liquid is neutral; then drying the filtrate at 80 ℃ for 6h in vacuum; the obtained sample is nitrate type nickel aluminum hydrotalcite (Ni)4Al-NO3-LDH)。
Example 5
1g of Ni obtained in example 1 was weighed2Al-NO3LDH was dispersed in 0.05 mol/L50 mL ammonium tetrathiotungstate solution to obtain a suspension using 2% NH3·H2Adjusting the pH value of the suspension to 8 by O, and stirring and reacting for 24 hours at the temperature of 60 ℃; deionized water and CCl for the obtained black solid4And sequentially washing and filtering the ethanol; vacuum drying the obtained solid at 60 ℃ for 2 h; the obtained sample is tetrathiotungstate intercalated hydrotalcite, and the tetrathiotungstate intercalated hydrotalcite is activated for 2 hours at 300 ℃ in a nitrogen atmosphere to obtain a catalyst which is named as Cat-A.
Example 6
1g of Ni obtained in example 1 was weighed2Al-NO3LDH dispersed in 50mL of ammonium tetrathiotungstate solution at a concentration of 0.05mol/L, using 2% NH3·H2Adjusting the pH value of the suspension to 8 by O, and stirring and reacting for 24 hours at the temperature of 60 ℃; what is needed isDeionized water and CCl for obtaining black solid4And sequentially washing and filtering the ethanol; vacuum drying the obtained solid at 60 ℃ for 2 h; the obtained sample is tetrathiotungstate intercalated hydrotalcite, and the tetrathiotungstate intercalated hydrotalcite is activated for 4 hours at 400 ℃ in a nitrogen atmosphere to obtain a catalyst which is named as Cat-B.
Example 7
1g of Ni obtained in example 1 was weighed2Al-NO3LDH dispersed in 50mL of ammonium tetrathiotungstate solution at a concentration of 0.05mol/L, using 2% NH3·H2Adjusting the pH value of the suspension to 7 by O, and stirring and reacting for 28 hours at the temperature of 60 ℃; deionized water and CCl for the obtained black solid4And sequentially washing and filtering the ethanol; vacuum drying the obtained solid at 60 ℃ for 2 h; the obtained sample is tetrathiotungstate intercalated hydrotalcite, and the tetrathiotungstate intercalated hydrotalcite is activated for 2 hours at 500 ℃ in a nitrogen atmosphere to obtain a catalyst which is named as Cat-C.
Example 8
1g of Ni obtained in example 1 was weighed2Al-NO3LDH dispersed in 50mL of ammonium tetrathiotungstate solution at a concentration of 0.05mol/L, using 2% NH3·H2Adjusting the pH value of the suspension to 9 by O, and stirring and reacting for 18h at the temperature of 60 ℃; deionized water and CCl for the obtained black solid4And sequentially washing and filtering the ethanol; vacuum drying the obtained solid at 60 ℃ for 2 h; the obtained sample is tetrathiotungstate intercalated hydrotalcite, and the tetrathiotungstate intercalated hydrotalcite is activated for 2 hours at 600 ℃ in a nitrogen atmosphere to obtain a catalyst which is named as Cat-D.
Example 9
1g of Ni obtained in example 2 was weighed3Al-NO3LDH dispersed in 50mL of ammonium tetrathiotungstate solution at a concentration of 0.05mol/L, using 2% NH3·H2Adjusting the pH value of the suspension to 8 by O, and stirring and reacting for 28 hours at the temperature of 50 ℃; deionized water and CCl for the obtained black solid4Washing with ethanol, and filtering sequentially; vacuum drying the obtained solid at 60 ℃ for 2 h; the obtained sample is tetrathiotungstate intercalated hydrotalcite, and the tetrathiotungstate intercalated hydrotalcite is activated for 2 hours at 600 ℃ in a nitrogen atmosphere to obtain a catalyst which is named as Cat-E.
Example 10
1g of Ni obtained in example 2 was weighed3Al-NO3-LDH was dispersed in 50mL of a 0.05mol/L ammonium tetrathiotungstate solution using 2% NH3·H2Adjusting the pH value of the suspension to 9 by O, and stirring and reacting for 12 hours at the temperature of 50 ℃; deionized water and CCl for the obtained black solid4And sequentially washing and filtering the ethanol; vacuum drying the obtained solid at 60 ℃ for 2 h; the obtained sample is tetrathiotungstate intercalated hydrotalcite, and the tetrathiotungstate intercalated hydrotalcite is activated for 2 hours at 500 ℃ in a nitrogen atmosphere to obtain a catalyst which is named as Cat-F.
Example 11
1g of NiAl-NO obtained in example 3 was weighed3LDH dispersed in 50mL of ammonium tetrathiotungstate solution at a concentration of 0.05mol/L, using 2% NH3·H2Adjusting the pH value of the suspension to 8.5 by O, and stirring and reacting for 24 hours at the temperature of 50 ℃; deionized water and CCl for the obtained black solid4And sequentially washing and filtering the ethanol; vacuum drying the obtained solid at 60 ℃ for 2 h; the obtained sample is tetrathiotungstate intercalated hydrotalcite, and the tetrathiotungstate intercalated hydrotalcite is activated for 4 hours at 350 ℃ in the nitrogen atmosphere to obtain a catalyst which is named as Cat-G.
Example 12
1g of Ni obtained in example 4 was weighed4Al-NO3LDH dispersed in 50mL of ammonium tetrathiotungstate solution at a concentration of 0.05mol/L, using 2% NH3·H2Adjusting the pH value of the suspension to 9 by O, and stirring and reacting for 28 hours at the temperature of 55 ℃; deionized water and CCl for the obtained black solid4And sequentially washing and filtering the ethanol; vacuum drying the obtained solid at 60 ℃ for 2 h; the obtained sample is tetrathiotungstate intercalated hydrotalcite, and the tetrathiotungstate intercalated hydrotalcite is activated for 4 hours at 300 ℃ in the nitrogen atmosphere to obtain a catalyst which is named as Cat-H.
Comparative example 1
1g of Ni obtained in example 1 was weighed2Al-NO3LDH dispersed in 50mL of Na at a concentration of 0.05mol/L2WO4Aqueous solution, using 2% NH3·H2Adjusting the pH value of the suspension to 9 by O, and stirring and reacting for 24 hours at the temperature of 60 ℃; washing the obtained blue solid by using deionized water; then drying the obtained solid at 80 ℃ for 6 h; the obtained sample is tungstate intercalated hydrotalcite, and the tungstate intercalated hydrotalcite is roasted for 3 hours at 450 ℃ in the air atmosphere to obtain a catalyst which is named Cat-I.
Comparative example 2
1g of Ni obtained in example 2 was weighed3Al-NO3LDH dispersed in 50mL of Na at a concentration of 0.05mol/L2WO4Aqueous solution, using 2% NH3·H2Adjusting the pH value of the suspension to 9 by O, and stirring and reacting for 24 hours at the temperature of 60 ℃; washing the obtained blue solid by using deionized water; then drying the obtained solid at 80 ℃ for 6 h; the obtained sample is tungstate intercalated hydrotalcite, and the tungstate intercalated hydrotalcite is roasted for 3 hours at 450 ℃ in the air atmosphere to obtain a catalyst which is named Cat-J.
Comparative example 3
1g of Ni obtained in example 1 was weighed2Al-NO3LDH dispersed in 50mL of (NH) at a concentration of 0.05mol/L4)2MoS4Aqueous solution, using 2% NH3·H2Adjusting the pH value of the suspension to 8 by O, and stirring and reacting for 24 hours at the temperature of 40 ℃; washing the obtained black solid by using deionized water; then the obtained solid is dried for 6 hours in vacuum at 80 ℃; the obtained sample is tetrathiomolybdate intercalated hydrotalcite, and the tetrathiomolybdate intercalated hydrotalcite is roasted for 3 hours at the temperature of 300 ℃ in the nitrogen atmosphere to obtain a catalyst which is named as Cat-K.
Test example 1
In this test example, the activity of the hydrodesulfurization catalysts of examples 5 to 12 of the present invention and the hydrodesulfurization catalyst of the comparative example was evaluated in accordance with the following method, and the results were shown.
The hydrodesulfurization reaction adopts the following conditions: the space velocity of the reaction volume is 2.5h-1The volume ratio of hydrogen to oil is 400, the total pressure is 4.0MPa, the reaction temperature is 300 ℃, and the reaction raw material is straight-run diesel oil with the sulfur content of 1877 mg/kg. And after the reaction is carried out for 24 hours, sampling and analyzing after the activity of the catalyst is stable. The sulfur content in the sample was determined by TSN-3000 type sulfur-nitrogen analyzer, and the desulfurization rate of the catalyst is shown in Table 1.
Catalysts Cat-G and Cat-H in comparative examples 1 and 2 required a presulfiding treatment before activity evaluation, i.e., the catalysts were presulfided at 300 ℃ for 4 hours using a catalyst containing 3 wt% CS2The cyclohexane solution is vulcanized oil, and the volume space velocity is 2.5h-1The volume ratio of hydrogen to oil is 400, the total pressure is 4.0MPa, and the vulcanization temperature is 300 ℃. After the presulfurization is completed, the reaction material is switched to be reaction raw materialThe same is true for the above. The evaluation of the hydrodesulfurization activity of the catalyst Cat-I in comparative example 3 was the same as in examples 5 to 12.
TABLE 1 desulfurization rates of straight-run diesel with various catalysts
Figure BDA0002307961010000071
As can be seen from Table 1, the tungsten-based unsulfurized hydrotalcite-like catalyst prepared by the method of the present invention does not require a complicated high-temperature high-pressure presulfurization process, and has a desulfurization rate significantly higher than that of the conventional oxidized hydrotalcite-like catalyst and also higher than that of the molybdenum-based unsulfurized hydrotalcite-like catalyst.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (9)

1. A tungsten-based unsulfided hydrotalcite hydrodesulfurization catalyst is characterized in that the catalyst is nickel-aluminum hydrotalcite which is activated by nitrogen at high temperature and contains tetrathiotungstate intercalation; the preparation method of the catalyst comprises the following steps:
s1, preparing nitrate type nickel aluminum hydrotalcite;
s2, dissolving ammonium tetrathiotungstate in boiled deionized water to prepare an ammonium tetrathiotungstate solution;
s3, mixing nitrate type nickel-aluminum hydrotalcite with ammonium tetrathiotungstate solution, adjusting the pH value to 7-9, carrying out ion exchange reaction for 12-28 h at 50-70 ℃, and using deionized water and CCl to obtain an exchange product4And the ethanol is washed and filtered in turn,drying to obtain tetrathiotungstate intercalation nickel-aluminum hydrotalcite;
s4, roasting the tetrathiotungstate intercalated nickel-aluminum hydrotalcite at 300-600 ℃ for 2-4 h in a nitrogen atmosphere to obtain the tungsten-based pre-vulcanized-free hydrotalcite type hydrodesulfurization catalyst.
2. The tungsten-based unsulfurized hydrotalcite hydrodesulfurization catalyst according to claim 1, wherein the molar ratio of the Ni element to the Al element is (1 to 4): 1.
3. the tungsten-based unsulfided hydrotalcite-like hydrodesulfurization catalyst according to claim 2 wherein the molar ratio of Ni element to Al element is 2:1, the molar ratio of the sum of the molar amounts of the Ni and W elements to the Ni element is 5: 4.
4. The tungsten-based unsulfurized hydrotalcite hydrodesulfurization catalyst according to claim 1, wherein the thiotungstate anion is introduced between layers of the nickel-aluminum hydrotalcite, and then the nickel-aluminum hydrotalcite is activated at high temperature by nitrogen gas to obtain the tungsten-based unsulfurized hydrotalcite hydrodesulfurization catalyst.
5. The tungsten-based unsulfided hydrotalcite hydrodesulfurization catalyst of claim 1 wherein the concentration of the ammonium tetrathiotungstate solution is 0.05 to 0.3 mol/L.
6. The tungsten-based unsulfurized hydrotalcite hydrodesulfurization catalyst according to claim 1, wherein in step S3, the pH is adjusted to 8.5 to 9, and the ion exchange reaction is carried out at 50 to 55 ℃ for 20 to 28 hours.
7. The tungsten-based unsulfurized hydrotalcite-like hydrodesulfurization catalyst according to claim 1, wherein in step S4, the calcination is carried out at 300 to 350 ℃ for 4 hours.
8. The tungsten-based unsulfurized hydrotalcite-like hydrodesulfurization catalyst according to claim 1, wherein the specific method for preparing nitrate type nickel aluminum hydrotalcite in step S1 is as follows:
s11, dissolving soluble nickel salt and soluble aluminum salt in boiled deionized water to prepare a mixed salt solution, and dissolving NaOH in boiled deionized water to prepare an alkali solution;
s12, slowly dripping the alkali solution into the mixed salt solution, stirring to generate a precipitate, and controlling the pH value to be 6-10; and carrying out hydrothermal crystallization on the precipitate at the temperature of 80-120 ℃ for 8-20 h, filtering, washing and vacuum drying to obtain nitrate type nickel-aluminum hydrotalcite.
9. The tungsten-based unsulfurized hydrotalcite hydrodesulfurization catalyst according to claim 8, wherein in step S11, the mixed salt solution has a nickel salt concentration of 0.01 to 0.8mol/L, an aluminum salt concentration of 0.01 to 0.2mol/L, and an alkali solution has a NaOH concentration of 0.2 to 2 mol/L.
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