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Title:
A NON-METAL BASED METAL PASSIVATOR ADDITIVE COMPOSITION FOR FCCU FEED STOCKS
Document Type and Number:
WIPO Patent Application WO/2024/028884
Kind Code:
A1
Abstract:
The present invention relates to a non-metal based metal passivator additive composition and a process for preparing the same. In particular, this invention relates to a non metal based nickel passivator additive composition comprising (i) 60-80% by weight of propylene glycol as a solvent (ii) 20-50% by weight of boric acid. The composition acts as a nickel passivator for FCCU feed stocks.

Inventors:
KANDANELLI RAMESH (IN)
KANALA RAGHAVAKRISHNA (IN)
KUKADE SOMANATH (IN)
KUMAR PRAMOD (IN)
BALASUBRAMANIAM RAVI (IN)
Application Number:
PCT/IN2022/051109
Publication Date:
February 08, 2024
Filing Date:
December 20, 2022
Export Citation:
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Assignee:
HINDUSTAN PETROLEUM CORPORATON LTD (IN)
International Classes:
C10G11/02
Domestic Patent References:
WO2022040303A12022-02-24
WO2021017456A12021-02-04
Foreign References:
US4756820A1988-07-12
US4663018A1987-05-05
CN107376986A2017-11-24
US9441167B22016-09-13
US9895680B22018-02-20
CN111686791A2020-09-22
Other References:
JIAN SHENG ET AL.: "Oxidative dehydrogenation of light alkanes to olefins on metal-free catalysts", A JOURNAL PUBLISHED IN CHEMICAL SOCIETY REVIEWS, December 2020 (2020-12-01)
Attorney, Agent or Firm:
SINGH, Manisha et al. (IN)
Download PDF:
Claims:
We claim: 1 A non-metal based metal passivator additive composition comprising: (i) 60-80% by weight of glycol as a solvent; and (ii) 20-50% by weight a boron containing compound. 2. The composition as claimed in claim 1, wherein the glycol is selected from ethylene glycol and propylene glycol. 3. The composition as claimed in claim 1, wherein the glycol is propylene glycol. 4. The composition as claimed in claim 1, wherein the boron containing compound is selected from borax, tri-(n-butyl)borate, tri-(n-phenyl)borate, and boric acid. 5. The composition as claimed in claim 1, wherein the boron containing compound is boric acid. 6. A process for preparation of non-metal based metal passivator additive composition comprising mixing 60-80% by weight of glycol as a solvent with 20-50% by weight a boron containing compound in a stirrer for 3-4 hours between 60-120 ⁰C. 7. The process as claimed in claim 6, wherein the glycol is selected from ethylene glycol and propylene glycol. 8. The process as claimed in claim 6, wherein the glycol is propylene glycol. 9. The process as claimed in claim 6, wherein the boron containing compound is selected from borax, tri-(n-butyl)borate, tri-(n-phenyl)borate, and boric acid. 10. The process as claimed in claim 6, wherein the boron containing compound is boric acid.
AMENDED CLAIMS received by the International Bureau on 19 May 2023 (19.05.2023)

We claim:

1 A non-metal based metal passivator additive composition comprising:

(i) 60-80% by weight of propylene glycol as a solvent; and

(ii) 20-40% by weight a boron containing compound.

2. The composition as claimed in claim 1, wherein the boron containing compound is selected from borax, tri-(n-butyl)borate, tri-(n-phenyl)borate, and boric acid.

3. The composition as claimed in claim 1, wherein the boron containing compound is boric acid.

4. A process for preparation of non-metal based metal passivator additive composition comprising mixing 60-80% by weight of propylene glycol as a solvent with 20-40% by weight a boron containing compound in a stirrer for 3-4 hours between 60-120 °C.

5. The process as claimed in claim 4, wherein the boron containing compound is selected from borax, tri-(n-butyl)borate, tri-(n-phenyl)borate, and boric acid.

6. The process as claimed in claim 4, wherein the boron containing compound is boric acid.

AMENDED SHEET (ARTICLE 19)

Description:
A NON-METAL BASED METAL PASSIVATOR ADDITIVE COMPOSITION FOR FCCU FEED STOCKS FIELD OF THE INVENTION The present invention relates to a non-metal based metal passivator additive composition and a process for preparing the same. In particular, this invention relates to a non metal based nickel passivator additive composition comprising (i) 60-80% by weight of glycol as a solvent (ii) 20- 50% by weight of boron containing compound. The composition acts as a nickel passivator for Fluid Catalytic Cracking Unit (FCCU) feed stocks. BACKGROUND OF THE INVENTION Fluid catalytic cracking (FCC) is one of the most important conversion processes used in petroleum refineries. It is widely used to convert the high-boiling, high-molecular weight hydrocarbon fractions obtained from distillation of petroleum crude oils into more valuable streams that are routed to gasoline, LPG, diesel and other products. Cracking of petroleum hydrocarbons was originally done by thermal cracking, which has been almost completely replaced by catalytic cracking because it produces more gasoline with a higher octane rating. It also produces byproduct gases that have more carbon-carbon double bonds (i.e. more olefins), and hence more economic value, than those produced by thermal cracking. The feedstock to FCC is usually gas oil or residual feed stocks boiling above 370+ and an average molecular weight ranging from 200 to 600 or higher. In the FCC process, the feedstock is heated to a high temperature and under moderate pressure, is brought into contact with a hot, powdered catalyst. The heated catalyst breaks the long-chain molecules of the high-boiling hydrocarbon liquids into much shorter molecules, which are collected as a vapor. FCC units operate either on maximum gasoline mode or the maximum distillate mode, which depends on seasonal product demand. FCCU feed (Vacuum Gas Oil) have metals such as Nickel, Vanadium, Iron etc., which slowly get deposited on FCC catalysts. Cracking residue feeds in FCC units increase the level of contaminant Ni and V metals on cracking catalysts. Residue feeds contain higher content of nickel and vanadium. This results in decreasing catalytic activity and increasing undesirable dehydrogenation reaction in the reactor. This dehydrogenation reaction will increase in gas production in the form of higher hydrogen and coke yields. WO2021017456A1 provides an anti-metal liquid yield booster for catalytic cracking and a preparation method therefor. The liquid yield booster is composed of a VPI-5 molecular sieve, and an antimony-based nickel passivator and a heteropoly acid together loaded in a pore channel thereof, wherein the mass fractions of the components are: 70-98% of a VPI-5 molecular sieve; 0.5-20% of an antimony-based nickel passivator; and 1-10% of heteropoly acid. With the anti-metal liquid yield booster of this prior art, a nickel-porphyrin compound can be concentrated in the pore channel of the VPI-5 for a cracking reaction, and the resulting metal nickel is controlled to remain in the pore channel of the VPI-5, such that the toxicity thereof to a catalytic cracking catalyst is reduced, and furthermore, the nickel element is more quickly exposed and reacted with the nickel passivator, and this is favorable for improving the reaction selectivity and reducing the generation of coke, and there is increased production of liquid products such as gasoline and diesel oil. US9895680B2 discloses fluid catalytic cracking (FCC) compositions, methods of manufacture and use. FCC catalyst compositions comprise particles containing a non-zeolitic component and one or more boron oxide components. The FCC catalyst composition contains a zeolite component and optionally a rare earth component and a transition alumina. FCC catalytic compositions may comprise a first particle type containing one or more boron oxide components and a first matrix component mixed with a second particle type containing a second matrix component, and a zeolite. The FCC catalyst compositions can be used to crack hydrocarbon feeds, particularly resid feeds containing high V and Ni, resulting in lower hydrogen and coke yields. CN111686791A provides a catalytic cracking gasoline octane number auxiliary agent and a preparation method thereof, belonging to the field of catalyst preparation, and the method comprises the following steps: (1) preparing a ZSM-5 molecular sieve with a mesoporous- micro hierarchical pore structure: mixing and pulping a required boron-containing compound, a ZSM-5 molecular sieve and deionized water according to the mass ratio of the elemental boron to the deionized water of 0.005-0.05: 1: 5-50, continuously stirring at the temperature of 30-95 ℃ for ion exchange for 0.5-3 h, filtering, washing, roasting the obtained filter cake at the temperature of 400-800 ℃ for 1-3 h under the condition of 100% steam to obtain the ZSM- 5 zeolite molecular sieve with the mesoporous-microporous structure, (2) mixing and pulping the obtained ZSM-5 molecular sieve with the mesoporous-microporous structure, clay and binder according to the solid content of 10-30 wt% with the deionized water, and then carrying out spray forming, washing, filtering and drying to obtain the octane number auxiliary agent of the catalytic cracking gasoline, wherein the octane number auxiliary agent of the catalytic cracking gasoline is used for catalytic cracking, has the characteristics of low liquefied gas yield and high gasoline octane number. Shaun Pan et al. in an article published in November 2015, titled “Creative Catalysis” discloses conventional Ni passivation techniques include the injection of antimony (Sb) and the incorporation of Ni trapping specialty alumina into the FCC catalyst. While antimony can be effective in reducing H2 and coke, it can also lead to increased NOX emissions due to its adverse effects on carbon monoxide (CO) promoters, and operational issues such as slurry heat exchanger fouling. Jian Sheng et al. in a Journal published in Chemical Society Reviews December 2020, titled “Oxidative dehydrogenation of light alkanes to olefins on metal-free catalysts” disclose Metal- free boron- and carbon-based catalysts have shown both great fundamental and practical value in oxidative dehydrogenation (ODH) of light alkanes. In particular, boron-based catalysts show a superior selectivity toward olefins, excellent stability and atom-economy to valuable carbon- based products by minimizing CO2 emission, which are highly promising in future industrialization. The carbonaceous catalysts also exhibited impressive behavior in the ODH of light alkanes helped along by surface oxygen-containing functional groups. The prior art formulations include antimony which is a metal and currently antimony based formulations are already in use in refineries. Further, the prior arts disclose FCC catalyst compositions containing boron oxide. However, the use of metal passivating agent is independent of the catalyst usage. The purpose of adding nickel passivator in the FCC unit is to minimize the yield of hydrogen and dry gas and thus avoid its detrimental effect on the product yields. This is typically used when Ni on E-cat is more than 1000ppm or when H2/CH4 ratio in dry gas is more than 1. Considering the above, the present invention provides a metal passivator, preferably Ni Passivator. This will replace the import dependence as well as bring down the cost of the passivator significantly. SUMMARY OF THE INVENTION Accordingly, the present invention provides a non-metal based metal passivator additive composition comprising: (i) 60-80% by weight of glycol as a solvent; and (ii) 20-50% by weight a boron containing compound. The present invention also provides a process for preparation of non-metal based metal passivator additive composition comprising mixing 60-80% by weight of glycol as a solvent with 20-50% by weight a boron containing compound in a stirrer for 3-4 hours between 60- 120 ⁰C. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 illustrates graph for hydrogen reduction efficiencies of various formulations/composition. DETAILED DESCRIPTION OF THE INVENTION While the invention is susceptible to various modifications and alternative forms, specific embodiment thereof will be described in detail below. It should be understood, however that it is not intended to limit the invention to the particular forms disclosed, but on the contrary, the invention is to cover all modifications, equivalents, and alternative falling within the scope of the invention as defined by the appended claims. The following description with reference to the accompanying drawings is provided to assist in a comprehensive understanding of exemplary embodiments of the invention. It includes various specific details to assist in that understanding but these are to be regarded as merely exemplary. Accordingly, those of ordinary skill in the art will recognize that various changes and modifications of the embodiments described herein can be made without departing from the scope of the invention. In addition, descriptions of well-known functions and constructions are omitted for clarity and conciseness. 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. The term ‘catalyst’ used herein refers to FCC catalyst. The term ‘passivator’ used herein refers to passivation of metal. The term ‘E-cat’ used herein refers to Equilibrium Catalyst of FCC unit. The term ‘hydrothermal deactivation’ used herein refers to deactivation of fresh FCC catalyst in presence of steam to equilibrate it to FCC unit aged catalyst. The term ‘ACE studies’ used herein refers to cracking of hydrocarbon using ACE (Advanced cracking Evaluation) unit. The present invention provides a non-metal based metal passivator additive composition comprising: (i) 60-80% by weight of glycol as a solvent; and (ii) 20-50% by weight of a boron containing compound. In one of the features of the present invention, in the non-metal based metal passivator additive composition the glycol is selected from ethylene glycol and propylene glycol. In one of the preferred features of the present invention, the glycol is propylene glycol. In yet another feature of the present invention, the boron containing compound is selected from borax, tri-(n-butyl)borate, tri-(n-phenyl)borate, and boric acid. In one of the preferred features of the present invention, the boron containing compound is boric acid. In one of the features of the present invention, in the non-metal based metal passivator additive composition the boron containing compound is present in the range of 40-50% by weight. The present invention also provides a process for preparation of non-metal based metal passivator additive composition comprising mixing 60-80% by weight of glycol as a solvent with 20-50% by weight a boron containing compound in a stirrer for 3-4 hours between 60- 120 ⁰C. In one of the features of the present invention, in the process for preparation of non-metal based metal passivator additive composition, the glycol is selected from ethylene glycol and propylene glycol. In one of the preferred features of the present invention, the glycol is propylene glycol. In one of the features of the present invention, in the process for preparation of non-metal based metal passivator additive composition, the boron containing compound is selected from borax, tri-(n-butyl)borate, tri-(n-phenyl)borate, and boric acid. In one of the preferred features of the present invention, the boron containing compound is boric acid. In one of the features of the present invention, in the non-metal based metal passivator additive composition the boron containing compound is present in the range of 40-50% by weight. In one of the features of the present invention, a non metal based metal passivator additive composition containing (i) 60-80% by weight of propylene glycol as solvent (ii) 20-50% by weight of boric acid. The additive acts as metal passivator for nickel present in FCCU feed stocks. Examples: The present disclosure with reference to the accompanying examples describes the present invention. However, those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments which are disclosed and still obtain a like or similar result without departing from the spirit and scope of the invention. It is understood that the examples are provided for the purpose of illustrating the invention only and are not intended to limit the scope of the invention in any way. Example 1: Methodology: The metalation (Ni & V: 2000ppm each) of the catalyst and passivator loading was carried out using Mitchell’s method where components are artificially added onto the catalyst to simulate E-cat properties. Post impregnation, the catalyst was subjected to hydrogen reduction and hydrothermal deactivation (815 deg C/10hr). Subsequently the catalyst was calcined at 600 °C. Post impregnation the catalysts were utilized for ACE studies for base case data generation. Non-metal based metal passivator additive composition as prepared were loaded on the catalyst and calcined and then ACE studies were carried out for yield data generation. Alternate approach of spiking both Ni & V on the catalyst along with the VGO feed was studied for base case fresh catalyst deactivation and in case of non-metal based metal passivator additive composition of the present invention and commercial passivators were also spiked on the catalyst along with VGO feed to mimic actual commercial catalytic cracking process. Mitchell method: In Mitchell-type methods the FCC catalysts are metallated with vanadium and nickel naphthenates that are dissolved in an organic solvent. The metallation itself is performed by impregnating the FCC catalyst with solutions of the dissolved metal complexes. This artificial deposition of contaminant metals on FCC catalysts is done by pore volume impregnation methods. Methodology: The Mitchell impregnation was performed using vanadium and nickel naphthenates. The FCC catalysts were impregnated with a volume of the impregnation solution that has the pore volume of the catalysts. The organic solvents were burned off with air at 550 °C for 3 h followed by passivator loading on the metallated catalyst and drying at 200 °C for 2 hr. Example 2 Preparation of non-metal based metal passivator additive composition: The formulations/composition were prepared using non-metallic components, with specific roles: Passivator: The active component for strong interaction with Ni and subsequently eliminating deleterious effects. Diluent: A stable solvent to solubilize the active ingredient for aiding in dosing. The above mentioned chemical components (the ingredients as mentioned in Table 1) were weighed in required proportions into a round bottom flask. These components were mixed using magnetic stirrer for about 3-4 hours between 60-120 ⁰C. It was ensured that a clear and homogeneous solution has formed at the end of the reaction. The transparent solution formed was stored and check for its phase stability overnight, before mixing with Ni and V doped catalyst was prepared for further main evaluation. ACE MAT Studies: ACE MAT studies were carried out with all homogeneous formulations/compositions. Primary parameters such as hydrogen yield and hydrogen reduction efficiency were monitored. The hydrogen reduction efficiencies were compared to the existing benchmark used in the refineries Results: Efficiency of the experiments is measured by monitoring the reduction in the hydrogen. To determine the same, hydrogen yields were used, and reduction efficiency was calculated using following formula. The non-metal based metal passivator additive composition synthesized by the procedure of Example 2 have been tabulated in Table 1. Table 1 In addition to the hydrogen yields, the yields of distillates (LPG, Naphtha & Diesel) are given below in table 2: Table 2 The hydrogen reduction efficiencies of various formulations/composition are plotted in Graph- 1. Initial formulations from MP-4 to MP-12 reveal the efficiencies are below 60%. The efficiencies improve further upto 85% for MP-23. The best efficiency was shown by MP-25. The samples MP-25 to MP -30 are results pertaining to lower and higher dosage of the passivator with respect to the feed. Results for lower boron loading have been tabulated in Table 3: Table 3 With lower Boron chemical content in the formulation/composition, the activity is lower. Conclusion: The developed non-metal based metal passivator additive composition could effectively passivate Nickel. The reduction in hydrogen gas is more than 50%. The additives show excellent performance.