WO2023170700A1 - Naphtha hydrotreating catalyst and process of preparation thereof - Google Patents

Naphtha hydrotreating catalyst and process of preparation thereof Download PDF

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Publication number
WO2023170700A1
WO2023170700A1 PCT/IN2022/051082 IN2022051082W WO2023170700A1 WO 2023170700 A1 WO2023170700 A1 WO 2023170700A1 IN 2022051082 W IN2022051082 W IN 2022051082W WO 2023170700 A1 WO2023170700 A1 WO 2023170700A1
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Prior art keywords
chelating agent
molybdenum
range
catalyst
nickel
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PCT/IN2022/051082
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French (fr)
Inventor
Narasimharao KANNA
Santhoshkumar Reddy SANDIRI
Kanuparthy Naga RAJA
Valavarasu GNANASEKARAN
Ramachandra Rao BOJJA
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Hindustan Petroleum Corporation Limited
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Publication of WO2023170700A1 publication Critical patent/WO2023170700A1/en

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Classifications

    • 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
    • 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
    • B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/883—Molybdenum and nickel
    • 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
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
    • 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
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B01J27/19—Molybdenum
    • 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
    • B01J37/0205—Impregnation in several steps
    • 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
    • C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C

Definitions

  • the present invention relates to a hydrotreating catalyst and a process for preparing the same. More particularly the present invention relates to a process for preparing a hydrotreating catalyst comprising two steps spray impregnation technique, in the first step, spray solution consists of molybdenum source is complexed with a combination of at least two chelating agents in which at least one chelating agent is phosphorus containing chelating agent and the other chelating agent is an organic chelating agent, which stabilizes the complex during impregnation and apparently enhances the dispersion of molybdenum.
  • nickel source along with chelating agent were deposited on molybdenum loaded alumina support. Unlike other method, after loading nickel along with chelating agents, the final catalyst is uncalcined.
  • the conventional Hydrotreating/Hydrodesulphurization catalysts are mostly prepared by multistep synthesis approach by impregnation and catalysts contains of Mo, W promoted with Ni or Co supported on alumina (for example y-AhOs).
  • Various methodologies such as controlling promoters, tuning active phase and tailoring the structure of supports (AI2O3) have been utilized to enhance the performance of the catalyst for Hydrodesulfurization (HDS).
  • Development of a novel preparation method which could enhance metals dispersion involving minimum number of synthesis steps is highly desirable for industrial scale production of Naphtha Hydrotreating catalyst (DHT).
  • US 2020/0325404 Al discloses a naphtha hydrotreating process, using at least three catalysts, comprising: a first step a) in the presence of the first catalyst comprising a support; a second step b) in the presence of the second catalyst comprising a support and an active phase, said active phase containing a Group 9 or 10 metal and a Group 6 metal; a third step c) in the presence of the third catalyst comprising a support and an active phase, said active phase containing a Group 6 metal; the content of Group 6 metal of the third catalyst is less than the content of Group 6 metal of said second catalyst; the ratio of the “loaded specific surface area” of said first catalyst to that of said second catalyst is greater than or equal to 1.20; the ratio of the “loaded specific surface area” of said third catalyst to that of said second catalyst is greater than 1.07.
  • US 2018/0237706 Al discloses processes for desulfurizing a fluid catalytic cracker (FCC) naphtha feedstock, straight run naphtha feedstocks and combinations thereof. Naphtha boiling range feed is passed over a silicon trap prior to being hydrodesulfurized in an olefin-retentive, catalytic naphtha hydrodesulfurization process.
  • FCC fluid catalytic cracker
  • US20100243530A1 relates to a process for preparing a hydrotreatment catalyst, comprising the following steps: a) at least one step for impregnation of a calcined and/or dried catalytic precursor containing at least one element from group VIII and/or at least one element from group VIB and an amorphous support, using an impregnation solution constituted by at least one phosphorus-containing compound in solution in at least one polar solvent with a dielectric constant of more than 20; b) a step for maturing said impregnated catalytic precursor from step a); c) a step for drying, without a subsequent calcining step, said catalytic precursor from step b).
  • WO2021218982A1 discloses a hydrogenation catalyst and a preparation method therefor and a use thereof.
  • the catalyst comprises a carrier and hydrogenation active metal components loaded on the carrier.
  • the hydrogenation active metal components contain at least one VIB group metal component and at least one VIII group metal component, and the carrier consists of phosphorus- containing alumina.
  • the hydrogenation catalyst has an excellent heteroatom removal effect and excellent stability.
  • WO2014083252A1 relates to a hydrotreatment catalyst comprising a support, at least one metal selected from group VIB, and at least one metal selected from group VIII of the periodic table, wherein the group VIB metal content, expressed in terms of oxides, is of 6 to 25 wt.% relative to the total weight of the catalyst, the group VIII metal content, expressed in terms of oxides, is of 0.5 to 7 wt.% relative to the total weight of the catalyst, the support comprising at least 90 wt.% of alumina, and wherein said alumina is obtained from a mixed and extruded boehmite gel and the specific surface area of said catalyst is 60 to 250 m 2 /g.
  • US20090298677A discloses a chelated hydroprocessing catalyst exhibiting low moisture is obtained by hearing an impregnated, calcined carrier to a temperature higher than 200° C. and less than a temperature and for a period of time that would cause substantial decomposition of the chelating agent.
  • the present invention relates to an improved nickel-molybdenum-alumina catalyst suitable for naphtha hydrotreating and other hydrogenating reactions and to the method of manufacture of such improved performance of the catalyst.
  • the present invention provides a process for preparing a hydrotreating catalyst comprising:
  • molybdenum solution comprises a molybdenum source and a combination of at least two chelating agents, in which at least one chelating agent is phosphorus containing chelating agent and the other chelating agent is an organic chelating agent; and
  • nickel in a single step using spray impregnation and by adding a nickel solution on the molybdenum loaded alumina and then followed by drying to obtain the hydrotreating catalyst, wherein the nickel solution comprises a nickel source and an organic chelating agent.
  • the present invention also provides a hydrotreating catalyst comprising MoOs in the range of 10- 25 wt.%, P2O5 in the range of 0.01-0.1 wt.%, NiO in the range of 4.0-6.0 wt.%, AI2O3 in the range of 65-80 wt.%, versus the total weight of the catalyst.
  • a method for preparing a catalyst comprising two steps spray impregnation technique
  • spray solution consists of molybdenum salt
  • a combination of chelating agents citric acid and phosphino carboxylic acid
  • chelating agents citric acid and phosphino carboxylic acid
  • spray solution consists of molybdenum salt
  • a combination of chelating agents citric acid and phosphino carboxylic acid
  • active metal, and non-metal were loaded on the alumina support.
  • the active metal includes Ni, Mo, etc.
  • the non-metal includes phosphorous, boron, etc.

Abstract

The present invention relates to a hydrotreating catalyst and a process for preparing the same. More particularly the present invention relates to a process for preparing a hydrotreating catalyst comprising two steps spray impregnation technique, in the first step, spray solution consists of molybdenum source is complexed with a combination of at least two chelating agents in which at least one chelating agent is phosphorus containing chelating agent and the other chelating agent is an organic chelating agent, which stabilizes the complex during impregnation and apparently enhances the dispersion of molybdenum. In second step, nickel source along with chelating agent were deposited on molybdenum loaded alumina support. Unlike other method, after loading nickel along with chelating agents, the final catalyst is uncalcined.

Description

NAPHTHA HYDROTREATING CATALYST AND PROCESS OF PREPARATION THEREOF
FIELD OF INVENTION
The present invention relates to a hydrotreating catalyst and a process for preparing the same. More particularly the present invention relates to a process for preparing a hydrotreating catalyst comprising two steps spray impregnation technique, in the first step, spray solution consists of molybdenum source is complexed with a combination of at least two chelating agents in which at least one chelating agent is phosphorus containing chelating agent and the other chelating agent is an organic chelating agent, which stabilizes the complex during impregnation and apparently enhances the dispersion of molybdenum. In second step, nickel source along with chelating agent were deposited on molybdenum loaded alumina support. Unlike other method, after loading nickel along with chelating agents, the final catalyst is uncalcined.
BACKGROUND OF THE INVENTION
The conventional Hydrotreating/Hydrodesulphurization catalysts are mostly prepared by multistep synthesis approach by impregnation and catalysts contains of Mo, W promoted with Ni or Co supported on alumina (for example y-AhOs). Various methodologies, such as controlling promoters, tuning active phase and tailoring the structure of supports (AI2O3) have been utilized to enhance the performance of the catalyst for Hydrodesulfurization (HDS). Development of a novel preparation method which could enhance metals dispersion involving minimum number of synthesis steps is highly desirable for industrial scale production of Naphtha Hydrotreating catalyst (DHT).
US 2020/0325404 Al discloses a naphtha hydrotreating process, using at least three catalysts, comprising: a first step a) in the presence of the first catalyst comprising a support; a second step b) in the presence of the second catalyst comprising a support and an active phase, said active phase containing a Group 9 or 10 metal and a Group 6 metal; a third step c) in the presence of the third catalyst comprising a support and an active phase, said active phase containing a Group 6 metal; the content of Group 6 metal of the third catalyst is less than the content of Group 6 metal of said second catalyst; the ratio of the “loaded specific surface area” of said first catalyst to that of said second catalyst is greater than or equal to 1.20; the ratio of the “loaded specific surface area” of said third catalyst to that of said second catalyst is greater than 1.07.
US 2018/0237706 Al discloses processes for desulfurizing a fluid catalytic cracker (FCC) naphtha feedstock, straight run naphtha feedstocks and combinations thereof. Naphtha boiling range feed is passed over a silicon trap prior to being hydrodesulfurized in an olefin-retentive, catalytic naphtha hydrodesulfurization process.
WO/2021/161328 describes a hydrodesulfurization (HDS) catalyst and a process for preparation the catalyst and a method of hydro-desulfurizing a hydrocarbon feedstock using the hydrodesulfurization catalyst.
US20100243530A1 relates to a process for preparing a hydrotreatment catalyst, comprising the following steps: a) at least one step for impregnation of a calcined and/or dried catalytic precursor containing at least one element from group VIII and/or at least one element from group VIB and an amorphous support, using an impregnation solution constituted by at least one phosphorus-containing compound in solution in at least one polar solvent with a dielectric constant of more than 20; b) a step for maturing said impregnated catalytic precursor from step a); c) a step for drying, without a subsequent calcining step, said catalytic precursor from step b).
WO2021218982A1 discloses a hydrogenation catalyst and a preparation method therefor and a use thereof. The catalyst comprises a carrier and hydrogenation active metal components loaded on the carrier. The hydrogenation active metal components contain at least one VIB group metal component and at least one VIII group metal component, and the carrier consists of phosphorus- containing alumina. When the hydrogenation catalyst is measured by a hydrogen-temperature programmed reduction (H 2-TPR) method, the ratio S=P iow-temPerature peak/P high -temperature peak of the peak height P low-temperature peak of a low-temperature reduction peak located at 300-500 DEG C to the peak height P high-temperature peak of a high-temperature reduction peak located at 650-850 DEG C is between 0.5-2.0, preferably 0.7-1.9, and further preferably 0.8-1.8. When being used for hydrotreatment, the hydrogenation catalyst has an excellent heteroatom removal effect and excellent stability. WO2014083252A1 relates to a hydrotreatment catalyst comprising a support, at least one metal selected from group VIB, and at least one metal selected from group VIII of the periodic table, wherein the group VIB metal content, expressed in terms of oxides, is of 6 to 25 wt.% relative to the total weight of the catalyst, the group VIII metal content, expressed in terms of oxides, is of 0.5 to 7 wt.% relative to the total weight of the catalyst, the support comprising at least 90 wt.% of alumina, and wherein said alumina is obtained from a mixed and extruded boehmite gel and the specific surface area of said catalyst is 60 to 250 m2/g.
US20090298677A discloses a chelated hydroprocessing catalyst exhibiting low moisture is obtained by hearing an impregnated, calcined carrier to a temperature higher than 200° C. and less than a temperature and for a period of time that would cause substantial decomposition of the chelating agent.
In view of above, it is desirable to provide an improved catalyst suitable for naphtha hydrotreating. Also, it is desirable to provide a process for preparing a naphtha hydrotreating catalyst which enhances metals dispersion involving minimum number of synthesis steps.
SUMMARY OF THE INVENTION
The present invention relates to an improved nickel-molybdenum-alumina catalyst suitable for naphtha hydrotreating and other hydrogenating reactions and to the method of manufacture of such improved performance of the catalyst.
Accordingly, the present invention provides a process for preparing a hydrotreating catalyst comprising:
(a) impregnating molybdenum in a single step by adding a molybdenum solution on a calcined alumina support and then followed by aging, drying and calcination to obtain a molybdenum loaded alumina (Mo-Alumina), wherein the molybdenum solution comprises a molybdenum source and a combination of at least two chelating agents, in which at least one chelating agent is phosphorus containing chelating agent and the other chelating agent is an organic chelating agent; and (b) loading nickel in a single step using spray impregnation and by adding a nickel solution on the molybdenum loaded alumina and then followed by drying to obtain the hydrotreating catalyst, wherein the nickel solution comprises a nickel source and an organic chelating agent.
The present invention also provides a hydrotreating catalyst comprising MoOs in the range of 10- 25 wt.%, P2O5 in the range of 0.01-0.1 wt.%, NiO in the range of 4.0-6.0 wt.%, AI2O3 in the range of 65-80 wt.%, versus the total weight of the catalyst.
In one of the preferred features of the present invention, a method for preparing a catalyst comprising two steps spray impregnation technique, in the first step, spray solution consists of molybdenum salt is complexed with a combination of chelating agents (citric acid and phosphino carboxylic acid), which stabilizes the complex during impregnation and apparently enhances the dispersion of Mo. In the first step impregnation was performed on alumina support at pH of 5. In second step, nickel salt solution along with chelating agent were deposited on molybdenum loaded alumina support. Unlike other method, after loading Ni along with chelating agents, the final catalyst is uncalcined.
DETAILED DESCRIPTION OF THE INVENTION
Those skilled in the art will be aware that the present disclosure is subject to variations and modifications other than those specifically described. It is to be understood that the present disclosure includes all such variations and modifications. The disclosure also includes all such steps of the process, features of the product, referred to or indicated in this specification, individually or collectively, and all combinations of any or more of such steps or features.
The terms and words used in the following description and claims are not limited to the bibliographical meanings, but, are merely used by the inventor to enable a clear and consistent understanding of the invention. Accordingly, it should be apparent to those skilled in the art that the following description of exemplary embodiments of the present invention are provided for illustration purpose only and not for the purpose of limiting the invention as defined by the appended claims and their equivalents. It is to be understood that the singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise.
Features that are described and/or illustrated with respect to one embodiment may be used in the same way or in a similar way in one or more other embodiments and/or in combination with or instead of the features of the other embodiments.
It should be emphasized that the term “comprises/comprising” when used in this specification is taken to specify the presence of stated features, integers, steps or components but does not preclude the presence or addition of one or more other features, integers, steps, components or groups thereof.
Accordingly, the present invention provides a process for preparing a hydrotreating catalyst comprising:
(a) impregnating molybdenum in a single step by adding a molybdenum solution on a calcined alumina support and then followed by aging, drying and calcination to obtain a molybdenum loaded alumina (Mo-Alumina), wherein the molybdenum solution comprises a molybdenum source and a combination of at least two chelating agents in which at least one chelating agent is phosphorus containing chelating agent and the other chelating agent is an organic chelating agent; and
(b) loading nickel in a single step using spray impregnation and by adding a nickel solution on the molybdenum loaded alumina and then followed by drying to obtain the hydrotreating catalyst, wherein the nickel solution comprises a nickel source and an organic chelating agent.
In one of the features of the present invention, in the step (b) the hydrotreating catalyst is obtained by adding the nickel solution on the molybdenum loaded alumina of step (a) and then followed by drying without calcination. In another feature of the present invention, the molybdenum source is selected from ammonium heptamolybdate, phosphomolybdic acid, or molybdenum trioxide; and the nickel source is selected from nickel acetate, nickel nitrate, or nickel oxide.
In one of the features of the present invention, the chelating agent is an organic compound based chelating agent or their combination derived from an organic complexing agent that is an organic acid that contains a -COOH functional group and at least one additional functional group selected from carboxylic acid -COOH, amino carboxylic acid -NH2-COOH, phosphino carboxylic acid -PO4-COOH, thio phospho amino carboxylic acid -P-SH-NH2-COOH, hydroxamic acid -NOH-C=O or thio amino carboxylic acid -SH-NH2-COOH. In another feature of the present invention, the chelating agents are combination with amino acid and acid; or phosphino carboxylic acid and thio phospho amino carboxylic acid and acid; or organic acid and phosphino carboxylic acid; or hydroxamic acid and acid; or thio amino carboxylic acid and chemical derived acid.
In yet another feature of the present invention, the phosphorus containing chelating agent of step (a) is selected from phosphino carboxylic acid or thio phospho amino carboxylic acid.
In yet another feature of the present invention, the combination of chelating agents used in step (a) is in the range of 0.01-2 wt.%.
In yet another feature of the present invention, the organic chelating agent is selected from citric acid, nitrilotriacetic acid, ethylene glycol, or hexamethylene tetraamine.
In yet another feature of the present invention, the organic chelating agent used in step (b) is in the range of 0.01-2 wt.%.
In yet another feature of the present invention, the combination of chelating agents used in step (a) is the combination of citric acid and phosphino carboxylic acid; and the organic chelating agent used in step (b) is citric acid. In one of the features of the present invention, pH of the molybdenum solution is between 5-5.2.
In another feature of the present invention, in the step (a) aging is carried out at room temperature, drying is carried out at a temperature in the range of 25-120 °C and calcination is carried out at a temperature in the range of 350-600°C; and in the step (b) drying is carried out at a temperature in the range of 25-120°C.
In yet another feature of the present invention, the calcined alumina support is obtained by calcining an alumina at a temperature in the range of 400-600°C.
The present invention also provides a hydrotreating catalyst comprising MoOs in the range of 10- 25 wt.%, P2O5 in the range of 0.01-0.1 wt.%, NiO in the range of 4.0-6.0 wt.%, AI2O3 in the range of 65-80 wt.%, versus the total weight of the catalyst.
In one of the features of the present invention, the hydrotreating catalyst further comprises chelating agent in the range of 0.01-2 wt.%, versus the total weight of the catalyst and the chelating agent is selected from citric acid, nitrilotriacetic acid, ethylene glycol, or hexamethylene tetraamine.
In one of the features of the present invention chelating agent during addition of Mo is removed after calcination. But chelating agent is present after addition of Ni, because only drying is carried out at final step.
In the present invention, active metal, and non-metal were loaded on the alumina support. The active metal includes Ni, Mo, etc. The non-metal includes phosphorous, boron, etc. These metals were loaded with in two steps on the alumina support in the following order:
Synthesis of Mo loaded Alumina:
Mo loading was loaded in single step on calcined Alumina support. Mo source is Ammonium heptamolybdate. Chelating agents were added to Mo solution. The organic compound-based chelating agent or their mixtures derived from an organic complexing agent that is an organic acid that contains a -COOH functional group and at least one additional functional group selected from carboxylic acid -COOH, amino carboxylic acid -NH2-COOH, phosphino carboxylic acid -PO4-COOH, thio phospho amino carboxylic acid -P-SH-NH2-COOH, hydroxamic acid -NOH-C=O or thio amino carboxylic acid -SH-NH2-COOH. pH of the metal solution should be between 5-5.2. The obtained material is aged at room temperature and dried at 90 °C. The obtained final material is calcined at 500 °C.
Synthesis of Mo-Ni loaded alumina:
Ni loading on Mo-Alumina was done in single step spray impregnation. Ni source is Nickel acetate. Organic chelating agents along with Ni source will be spray impregnated on the alumina source Chelating agent here is Citric acid. In spray impregnation step Ni and chelating additive components can be deposited onto Alumina in single step loading. The obtained material is only dried with avoiding final calcination step.
Hydrotreating catalyst comprising MoOs in the range of 10-25 wt.%, P2O5 in the range of 0.01- 0.1 wt.%, NiO in the range of 4.0-6.0 wt.%, AI2O3 in the range of 65-80 wt.%.
Application of the present invention is for the naphtha hydrotreating catalyst preparation. The present invention can enhance the usefulness of an existing technology by functioning more effectively in terms of formation of active centres will be relatively highly when compared to prior art. The phosphino carboylic acid (PCA) as chelating agent enhances the dispersion of Molybdenum. The present invention methodology can also be applied for catalysts design for the vegetable oil conversion to aviation fuels.
EXAMPLES:
Having described the basic aspects of the present invention, the following non-limiting example illustrates the specific embodiments thereof. Those skilled in the art will appreciate that many modifications may be made in the invention without changing the essence of invention. Example 1: Catalyst without using chelating agent
An alumina was calcined at 550°C to obtain a calcined alumina support. 12g of Ammonium heptamoly date was impregnated on 37g of calcined alumina support. The obtained material is dried at 90 °C and calcined at 500 °C. In the next step, 8g of Nickel acetate was impregnated to above material followed by drying at 90 °C. The final catalyst comprises 20 wt.% MoOs, 5 wt.% NiO, and 70 wt.% AI2O3.
Example 2: Catalyst with Citirc acid as chelating agent for Mo and Ni
An alumina was calcined at 550°C to obtain a calcined alumina support. 12g of Ammonium heptamoly date was impregnated on 37g of calcined alumina support using citric acid as chelating agent. The obtained material is dried at 90 °C and calcined at 500 °C. In the next step, 8g of Nickel acetate and citric acid were impregnated to above material followed by drying at 90 °C. The final catalyst comprises 5 wt.% NiO, 20 wt.% MoO3, and 70 wt.% AI2O3.
Example 3: Catalyst with Citric acid and phosphino carboxylic acid for Mo and Citric acid as Chelating agent for Ni
An alumina was calcined at 550°C to obtain a calcined alumina support. 12g of Ammonium heptamoly date was impregnated on 37g of calcined alumina support using citric acid and phosphino carboxylic acid as chelating agents. The obtained material is dried at 90 °C and calcined at 500 °C. In the next step, 8g of Nickel acetate and citric acid were impregnated to above material followed by drying at 90 °C. The final catalyst comprises 20 wt.% MoO3, 5 wt.% NiO, 69 wt.% AI2O3, 0.1 wt.% P2Os and 0.4% wt.% citric acid.
Reaction and Results
Key reaction is desulphurization of sulfur containing molecules. Mercaptans, sulfides and disulfides react easily with hydrogen and produces corresponding saturated or aromatic compounds. Sulphur combined into cycles of aromatic structure, like thiophene, benzothiphene, dibenzothiophenes is more difficult to eliminate. These reactions are exothermic in nature, they produce hydrogen sulphide and consume hydrogen. Example:
R-SH (Mercaptan) + H2
Figure imgf000011_0001
Thiophene + 4H2
Figure imgf000011_0002
Benzothiophene + 5 H2
Figure imgf000011_0003
Cyclohexyl Benzene + H2S
Results: Comparative performances
Figure imgf000011_0004
Fresh catalyst is sulfided with sulfiding agent. Typical sulfiding agents were dimethyldisulfide or H2S. Catalyst was sulfide at 300 °C. After sulfidation, Fresh naphtha feed is injected for desulphurization at operating conditions of WHSV: 10.0 hr1, Temp: 315 °C, H2/HC: 137 Nm3/m3, P: 27 Bar, Sulfur in feed 300-1000 ppm.
Time on stream study of Present invention Example 3
Figure imgf000011_0005
Figure imgf000012_0001
*Fresh catalyst is sulfided with sulfiding agent. Typical sulfiding agents were dimethyldisulfide or H2S. Catalyst was sulfide at 300 °C. After sulfidation, fresh naphtha feed is injected for desulphurization at operating conditions of Temp: 315 °C, WHSV: 10.0 hr'1, H2/HC: 137 NmW, P: 26 Barg.
Main Features of the Present Invention:
• Loading of Molybdenum along with chelating agent, wherein the chelating agent is combination of citric acid and phosphino carboxylic acid.
• Ni was loaded using citric acid as chelating.
• Chelating agents are combination with amino acid and acid or phosphino carboxylic acid and thio phospho amino carboxylic acid and acid or hydroxamic acid and acid or thio amino carboxylic acid and chemical derived acids.
Advantages of the Present Invention:
• Reduced the number of preparation steps and enhanced the dispersion of Mo by complexing with citric acid and phosphino carboxylic acid.
• Spray Technique-Loaded Nickel along with complexation agents and uncalcined final catalyst can slows down the formation of NiS2 and apparently M0S2 forms first followed by nickel substitution at edges.

Claims

We claim:
1. A process for preparing a hydrotreating catalyst comprising:
(a) impregnating molybdenum in a single step by adding a molybdenum solution on a calcined alumina support and then followed by aging, drying and calcination to obtain a molybdenum loaded alumina (Mo-Alumina), wherein the molybdenum solution comprises a molybdenum source and a combination of at least two chelating agents, in which at least one chelating agent is phosphorus containing chelating agent and the other chelating agent is an organic chelating agent; and
(b) loading nickel in a single step using spray impregnation and by adding a nickel solution on the molybdenum loaded alumina and then followed by drying to obtain the hydrotreating catalyst, wherein the nickel solution comprises a nickel source and an organic chelating agent.
2. The process as claimed in claim 1, wherein the molybdenum source is selected from ammonium heptamolybdate, phosphomolybdic acid, or molybdenum trioxide; and the nickel source is selected from nickel acetate, nickel nitrate, or nickel oxide.
3. The process as claimed in claim 1, wherein the phosphorus containing chelating agent is selected from phosphino carboxylic acid or thio phospho amino carboxylic acid.
4. The process as claimed in claim 1, wherein the combination of chelating agents used in step (a) is in the range of 0.01-2 wt.%.
5. The process as claimed in claim 1, wherein the organic chelating agent is selected from citric acid, nitrilotriacetic acid, ethylene glycol, or hexamethylene tetraamine.
6. The process as claimed in claim 1, wherein the organic chelating agent used in step (b) is in the range of 0.01-2 wt.%.
7. The process as claimed in claim 1, wherein the combination of chelating agents used in step (a) is the combination of citric acid and phosphino carboxylic acid; and the organic chelating agent used in step (b) is citric acid.
8. The process as claimed in claim 1, wherein pH of the molybdenum solution is between 5- 5.2.
9. The process as claimed in claim 1, wherein in the step (a) aging is carried out at room temperature, drying is carried out at a temperature in the range of 25-120°C and calcination is carried out at a temperature in the range of 350-600°C; and in the step (b) drying is carried out at a temperature in the range of 25-120°C.
10. The process as claimed in claim 1, wherein the calcined alumina support is obtained by calcining an alumina at a temperature in the range of 400-600°C.
11. A hydrotreating catalyst comprising MoOs in the range of 10-25 wt.%, P2O5 in the range of 0.01-0.1 wt.%, NiO in the range of 4.0-6.0 wt.%, AI2O3 in the range of 65-80 wt.%, versus the total weight of the catalyst.
12. The hydrotreating catalyst as claimed in claim 11, further comprises chelating agent in the range of 0.01-2 wt.%, versus the total weight of the catalyst and the chelating agent is selected from citric acid, nitrilotriacetic acid, ethylene glycol, or hexamethylene tetraamine.
PCT/IN2022/051082 2022-03-11 2022-12-15 Naphtha hydrotreating catalyst and process of preparation thereof WO2023170700A1 (en)

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Citations (10)

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US20100243530A1 (en) 2007-06-25 2010-09-30 Ifp Process for preparing a hydrotreatment catalyst by impregnation with a phosphorus-containing compound
WO2014083252A1 (en) 2012-11-29 2014-06-05 IFP Energies Nouvelles Hydrotreatment catalyst comprising a support obtained from an alumina gel and method for preparing said catalyst
WO2015067585A1 (en) * 2013-11-07 2015-05-14 Shell Internationale Research Maatschappij B.V. Process for preparing a hydrotreating catalyst
WO2017167522A1 (en) * 2016-03-30 2017-10-05 IFP Energies Nouvelles Catecholamine-based catalyst and use thereof in a hydroprocessing and/or hydrocracking method
US20180237706A1 (en) 2017-02-21 2018-08-23 Exxonmobil Research And Engineering Company Desulfurization of a naphtha boiling range feed
US20200325404A1 (en) 2019-04-12 2020-10-15 Axens Naphtha hydrotreating process
WO2021161328A1 (en) 2020-02-11 2021-08-19 Hindustan Petroleum Corporation Limited A composition for dispersed hydrodesulfurization catalyst and process for preparation of the same
WO2021218982A1 (en) 2020-04-28 2021-11-04 中国石油化工股份有限公司 Hydrogenation catalyst and preparation method therefor and use thereof
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Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090298677A1 (en) 2005-12-14 2009-12-03 Advanced Refining Technologies Llc Method of Making Hydroprocessing Catalyst
US20100243530A1 (en) 2007-06-25 2010-09-30 Ifp Process for preparing a hydrotreatment catalyst by impregnation with a phosphorus-containing compound
WO2014083252A1 (en) 2012-11-29 2014-06-05 IFP Energies Nouvelles Hydrotreatment catalyst comprising a support obtained from an alumina gel and method for preparing said catalyst
WO2015067585A1 (en) * 2013-11-07 2015-05-14 Shell Internationale Research Maatschappij B.V. Process for preparing a hydrotreating catalyst
WO2017167522A1 (en) * 2016-03-30 2017-10-05 IFP Energies Nouvelles Catecholamine-based catalyst and use thereof in a hydroprocessing and/or hydrocracking method
US20180237706A1 (en) 2017-02-21 2018-08-23 Exxonmobil Research And Engineering Company Desulfurization of a naphtha boiling range feed
US20200325404A1 (en) 2019-04-12 2020-10-15 Axens Naphtha hydrotreating process
WO2021161328A1 (en) 2020-02-11 2021-08-19 Hindustan Petroleum Corporation Limited A composition for dispersed hydrodesulfurization catalyst and process for preparation of the same
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