WO2020012351A1 - Composition adsorbante régénérative pour l'élimination de chlorures à partir d'hydrocarbures et son procédé de préparation - Google Patents

Composition adsorbante régénérative pour l'élimination de chlorures à partir d'hydrocarbures et son procédé de préparation Download PDF

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Publication number
WO2020012351A1
WO2020012351A1 PCT/IB2019/055832 IB2019055832W WO2020012351A1 WO 2020012351 A1 WO2020012351 A1 WO 2020012351A1 IB 2019055832 W IB2019055832 W IB 2019055832W WO 2020012351 A1 WO2020012351 A1 WO 2020012351A1
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range
composition
adsorbent composition
amount
adsorbent
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PCT/IB2019/055832
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English (en)
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Satish Kumar
Satish Dasharath SHEWALE
Vijayalaxmi Ravi PURANIK
Prakash Kumar
Raksh Vir Jasra
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Reliance Industries Limited
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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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
    • B01J20/041—Oxides or hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28004—Sorbent size or size distribution, e.g. particle size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28011—Other properties, e.g. density, crush strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/2803—Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3007—Moulding, shaping or extruding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3014—Kneading
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3042—Use of binding agents; addition of materials ameliorating the mechanical properties of the produced sorbent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
    • B01J20/3458—Regenerating or reactivating using a particular desorbing compound or mixture in the gas phase
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/34—Regenerating or reactivating
    • B01J20/3483—Regenerating or reactivating by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
    • 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
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/02—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material
    • C10G25/03—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material with crystalline alumino-silicates, e.g. molecular sieves
    • C10G25/05—Removal of non-hydrocarbon compounds, e.g. sulfur compounds
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/42—Materials comprising a mixture of inorganic materials
    • 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

Definitions

  • the present disclosure relates to a regenerative adsorbent composition for removal of chlorides from chloride containing hydrocarbon feed and a process for its preparation.
  • Chemisorption refers to adsorption method wherein the adsorbed material(s) is/are held by chemical bonds.
  • Extruding aid refers to an additive which reduces or eliminates surface defects that appear during extrusion process.
  • Adsorption capacity refers to the amount of adsorbate taken up by the adsorbent per unit mass (or volume) of the adsorbent.
  • the adsorption capacity of the adsorbent composition refers to the amount of the chloride ions that is adsorbed per gram of the adsorbent composition till the chloride content in the treated hydrocarbon feed is ⁇ 1 ppm.
  • LDH Layered double hydroxides
  • C represents layers of metal cations
  • a and B are layers of hydroxide (HO ) anions
  • Z are layers of other anions and neutral molecules (such as water).
  • Ion exchanged Zeolite refers to the zeolites wherein the metal cations present in the zeolite are exchanged with other ions such as alkali metal, alkaline earth metal, hydronium ions and ammonium ions or mixture thereof.
  • the zeolite framework is open, contain channels and interconnected voids filled with exchangeable cations to balance the negative charge of zeolite lattice.
  • Organo-chlorine compounds such as carbon tetrachloride and perchloroethylene are added continuously in the process to maintain the chlorine level on the Continuous Catalytic reforming (CCR) catalyst.
  • the organic chlorides may become a part of the hydrocarbon product during the reaction of the hydrocarbon streams from which the hydrocarbon product is produced. If chemically-combined chlorines, such as organic chlorides, are not removed from the hydrocarbon streams, the presence of organic chlorides in the resultant hydrocarbon products, particularly gasoline or other fuels, can cause corrosion of processing equipment and engine parts, as well as other detrimental effects like loss in the activity of the metal-containing reforming catalysts to such an extent that the catalyst loses its ability to promote the various individual reforming reactions.
  • the catalyst may lose its ability to promote the desired reforming reactions such that the catalyst loses the desired selectivity for desired products.
  • Chloride contamination is particularly harmful in the processes involving disproportionation and alkylation of toluene to para-xylene and para- ethyl toluene over ZSM-5 zeolite catalysts which also contain magnesium.
  • An object of the present disclosure is to ameliorate one or more problems of the prior art or to at least provide a useful alternative.
  • An object of the present disclosure is to provide an adsorbent composition for removing chloride compounds from the chloride containing hydrocarbon feed.
  • the present disclosure relates to a regenerative adsorbent composition for removal of chlorides from the chloride containing hydrocarbon feed and a process for its preparation.
  • the present disclosure provides a regenerative adsorbent composition comprising an ion exchanged zeolite; bauxite; a layered double hydroxide; and a binder.
  • the regenerative adsorbent composition comprising an ion exchanged zeolite in an amount in the range of 30 to 50 wt% of the total mass of the composition on dry basis; bauxite in an amount in the range of 1 to 20 wt% of the total mass of the composition on dry basis; a layered double hydroxide in an amount in the range of 40 to 60 wt% of the total mass of the composition on dry basis; and a binder in an amount in the range of 1 to 20 wt% of the total mass of the composition on dry basis.
  • the present disclosure provides a process for preparing an adsorbent composition for removal of chlorides from chloride containing hydrocarbon feed.
  • the process comprises dry mixing the ion exchanged zeolite with bauxite, a layered double hydroxide, and a binder to obtain a dry mixture.
  • the mixture is kneaded in a fluid medium, at least one surfactant and at least one extruding aid.
  • the kneaded mixture is extruded to form shaped articles, followed by drying and calcining the shaped articles to obtain the adsorbent composition.
  • the present disclosure provides a process for removal of chlorides from chloride containing hydrocarbon feed using the regenerative adsorbent composition.
  • the process involves passing chloride containing hydrocarbon feed through a bed consisting of the adsorbent composition comprising an ion exchanged zeolite, bauxite, a layered double hydroxide, and a binder to obtain a treated hydrocarbon feed having chloride content less than 1 ppm.
  • the present disclosure provides a process for regeneration of an adsorbent composition by purging the adsorbent composition with a stream selected from air, nitrogen, and carbon dioxide at a temperature in the range of 250-550 °C and for a time period in the range of 4 to 6 hours.
  • the regeneration of the adsorbent composition can also be carried out by purging the adsorbent composition with a stream at a temperature in the range of 100-150 °C for a time period in the range of 4 to 6 hours.
  • the process further comprises calcining at a temperature in the range of 300 to 600 °C for a time period in the range of 3 to 5 hours to obtain a regenerated adsorbent composition.
  • the adsorbent composition of the present disclosure can be regenerated at last 5 times and can be used effectively to remove chlorides from the chloride containing hydrocarbon feed.
  • Figure 1 illustrates a schematic representation of a set up for removal of the chloride content from the hydrocarbon feed using the adsorbent composition of the present disclosure.
  • Embodiments are provided so as to thoroughly and fully convey the scope of the present disclosure to the person skilled in the art. Numerous details are set forth, relating to specific components, and process, to provide a complete understanding of embodiments of the present disclosure. It will be apparent to the person skilled in the art that the details provided in the embodiments should not be construed to limit the scope of the present disclosure. In some embodiments, well-known processes, well-known apparatus structures, and well-known techniques are not described in detail. The terminology used, in the present disclosure, is only for the purpose of explaining a particular embodiment and such terminology shall not be considered to limit the scope of the present disclosure.
  • Presence of chlorides in hydrocarbon products has an adverse effect on downstream processes as well as it causes corrosion of the processing equipments.
  • Catalytic and adsorption techniques are usually employed for removal of chlorides from refinery/ hydrocarbon products.
  • Conventional techniques used for the removal of chloride compounds are complex and expensive.
  • the present disclosure provides a regenerative adsorbent composition capable of removing low levels of chlorides from the diverse hydrocarbon feeds.
  • the adsorbent composition comprises an ion exchanged zeolite; bauxite; a layered double hydroxide; and a binder.
  • the adsorbent composition typically comprises an ion exchanged zeolite in an amount in the range of 30 to 50 wt% of the total mass of the composition on dry basis, preferably 36 to 44 wt%; bauxite in an amount in the range of 1 to 20 wt% of the total mass of the composition on dry basis, preferably 4 to 6 wt%; a layered double hydroxide in an amount in the range of 40 to 60 wt% of the total mass of the composition on dry basis, preferably 48 to 52 wt%; and a binder in an amount in the range of 1 to 20 wt% of the total mass of the composition on dry basis, preferably 4 to 6 wt%.
  • the adsorbent composition comprises an ion exchanged zeolite in an amount in the range of 40 wt% of the total mass of the composition on dry basis; bauxite in an amount in the range of 5 wt% of the total mass of the composition on dry basis; a layered double hydroxide in an amount in the range of 50 wt% of the total mass of the composition on dry basis; and a binder in an amount in the range of 5 wt% of the total mass of the composition on dry basis.
  • the adsorbent composition has bulk density in the range of 0.5 to 0.7 g/cc; a BET Surface area in the range of 200 to 500 m 2 /g; a crushing strength in the range of 2.5 to 3.5 Kgf/cm 2 ; and a particle size in the range of 1 to 6 mm.
  • the adsorbent composition has a bulk density of 0.6 g/cc; a BET Surface area of 213 m /g; and a crushing strength in the range of 3.0 Kgf/cm .
  • organic chlorides present in the hydrocarbon feed get decomposed into a corresponding unsaturated hydrocarbon molecules, and molecule of hydrogen chloride, which is later picked up by the adsorbent.
  • the metal ions present in the zeolite contribute both in providing the acidity of the adsorbent composition along with the adsorption of hydrogen chloride, leading to the formation of respective chloride salt. Overall, both physical and chemisorption occurs, thereby indicating the renewability of the adsorbent, as physio-sorption is reversible in nature.
  • the ion exchanged zeolite is faujasite zeolite having Si/Al ratio in the range of 1.4 to 3.0; and the cation of the zeolite being partially exchanged with at least one metal selected from copper and indium.
  • the particle size of the ion exchanged zeolite is in the range of 0.2 to 0.5 pm, preferably 0.3 pm.
  • bauxite comprises aluminium oxide (Al 2 0 3 ) in an amount in the range of 40 to 60 wt% of the total mass of bauxite; iron oxide (Fe 2 0 3 ) in an amount in the range of 5 to 15 wt% of the total mass of bauxite; silica (Si0 2 ) in an amount in the range of 2 to 10 wt% of the total mass of bauxite; titanium oxide (Ti0 2 ) in an amount in the range of 1 to 5 wt% of the total mass of bauxite; calcium oxide (CaO) in an amount in the range of 1 to 5 wt% of the total mass of bauxite; and water in an amount in the range of 15 to 30 wt% of the total mass of bauxite.
  • the particle size of bauxite is in the range of 0.2 to 0.3 pm, preferably 0.25 pm.
  • the layered double hydroxide is hydrotalcite having magnesium oxide (MgO) to aluminium oxide (Al 2 0 3 ) ratio in the range of 4 to 5, a BET surface area in the range of 10 to 20 m /g and a particle size in the range of 0.30 to 0.60 pm.
  • the particle size of the layered double hydroxide is in the range of 0.2 to 0.4 pm, preferably 0.3 pm.
  • the binder is at least one selected from bentonite clay and kaolinite clay. In accordance with the exemplary embodiment of the present disclosure, the binder is bentonite clay and the particle size of the bentonite clay is in the range of 0.1 to 0.2 pm, preferably 0.15 pm.
  • the chloride adsorption capacity of the adsorbent composition is in the range of 20 to 30 wt%.
  • the adsorbent composition comprises faujasite zeolite in an amount of 44 wt% and having particle size of 0.3 pm; bauxite in an amount of 5 wt% and having particle size of 0.25 pm; hydrotalcite in an amount of 50 wt% and having particle size of 0.3 pm; and bentonite clay in an amount of 5 wt% and having particle size of 0.15 pm.
  • the present disclosure provides a process for preparing an adsorbent composition for removal of chlorides from the chloride containing hydrocarbon feed. The process is described in detail herein below:
  • the ion exchanged zeolite is mixed with a layered double hydroxide, bauxite and a binder to obtain a dry mixture.
  • the so obtained mixture is kneaded in a fluid medium comprising a pre-determined amount of water, at least one surfactant and at least one extruding aid.
  • the kneaded mixture is then extruded to form shaped articles; followed by drying under inert atmosphere at a temperature in the range of 80 °C to 150 °C for a time period in the range of 1 hour to 5 hours.
  • the dried articles are further calcined under inert atmosphere at a temperature in the range of 300 °C to 600 °C for a time period in the range of 3 hours to 6 hours to obtain the adsorbent composition.
  • the fluid medium used for kneading the mixture is a combination of ethanol and water.
  • the amount of water in the fluid medium is in the range of 70 to 80 wt%.
  • the amount of extruding aid in the fluid medium is in the range of 1 to 10 wt% and the extruding aid is at least one selected from the group consisting of stearic acid, palmetic acid, oleic acid, calcium stearate and zinc stearate.
  • the surfactant is used in an amount in the range of 1 to 10 wt% and the surfactant is at least one fatty acid selected from the group consisting of behenic acid, lauric acid, and lignoceric acid.
  • the process comprises dry mixing the faujasite zeolite with hydrotalcite, bauxite and bentonite clay to obtain a dry mixture.
  • a fluid medium consisting of a mixture of ethanol and water, along with 5 wt% of calcium stearate and 5 wt% of lauric acid are added to the dry mixture to obtain a resultant mixture.
  • the resultant mixture is kneaded to obtain a kneaded mixture; followed by extruding the kneaded mixture to form shaped articles.
  • the so obtained shaped articles are dried at 150 °C for 2 hours, followed by calcining at 550 °C for 5 hours to obtain the adsorbent composition.
  • the present disclosure provides a process for removal of chlorides from the chloride containing hydrocarbon feed.
  • the process involves the step of passing chloride containing hydrocarbon feed through a bed consisting of the adsorbent composition comprising an ion exchanged zeolite, bauxite, a layered double hydroxide, and a binder to obtain a treated hydrocarbon feed having substantially reduced chloride content.
  • the chloride containing hydrocarbon feed is passed through a bed consisting of the adsorbent composition at a temperature in the range of 30 to 50 °C, under a pressure in the range of 30 to 40 kg/cm ; and at a liquid hourly space velocity (LHSV) in the range of 0.5 per hour to 5 per hour.
  • LHSV liquid hourly space velocity
  • the chloride containing hydrocarbon feed is contacted with an adsorbent composition at 40 °C, under a pressure of 35 kg/cm ; and at a liquid hourly space velocity (LHSV) in the range of 2 per hour.
  • LHSV liquid hourly space velocity
  • the chloride containing hydrocarbon feed is pre-heated at a temperature in the range of 30 to 50 °C so that a uniform temperature is obtained through out the bed consisting of the adsorbent composition.
  • the hydrocarbon feed treated in accordance with the present disclosure has chloride content of less than 1 ppm.
  • the present disclosure provides a process for regeneration of an adsorbent composition.
  • the process comprises purging the adsorbent composition with a stream selected from air, nitrogen, and carbon dioxide at a temperature in the range of 250-550 °C and for a time period in the range of 4 to 6 hours. Further the regenerated catalyst is activated by calcining at a temperature in the range of 300 to 600 °C for a time period in the range of 3 to 5 hours.
  • the regeneration of the adsorbent composition can also be carried out by purging the adsorbent composition with steam at a temperature in the range of 100-150 °C for a time period in the range of 4 to 6 hours.
  • the process further comprises calcining at a temperature in the range of 300 to 600 °C for a time period in the range of 3 to 5 hours to obtain a regenerated adsorbent composition.
  • the regenerated adsorbent is capable of 100% adsorption after I st regeneration. Still further, the physicochemical properties of the regenerated adsorbent are similar to the fresh adsorbent, further no leaching of active metal ions present in the zeolite is observed.
  • the adsorbent of the present disclosure can be re-generated at least 5-6 time/cycles and has an adsorption capacity up to 60 % to 70 % of the fresh adsorbent composition.
  • Figure-1 discloses a schematic representation of the process for removal of chlorides from the chloride containing hydrocarbon feed.
  • the assembly used in the process for the removal of chlorides comprises a nitrogen source (2), a storage tank (3) and a feed tank (4) adapted to store the chloride containing hydrocarbon feed, a preheater (5) adapted to preheat the chloride containing hydrocarbon feed, a packed bed column (7) loaded with adsorbent composition, an electric heater furnace (6) and a condenser (9).
  • the chloride containing hydrocarbon feed is passed through the packed bed column at a liquid hourly space velocity (LHSV) in the range of 0.5 per hour to 5 per hour with the help of the pump.
  • LHSV liquid hourly space velocity
  • the temperature of the fixed bed column is maintained in the range of 200 to 350 °C with the help of an electric furnace and further passed through condenser to obtain the treated hydrocarbon feed.
  • the chloride containing hydrocarbon feed is pre-heated using an electric heater furnace (6) at a temperature in the range of 30 to 50 °C so that a uniform temperature is obtained through out the bed consisting of the adsorbent composition.
  • the adsorbent is capable of detecting variation in the chloride content in an ongoing process and remove chloride accordingly.
  • the adsorbent composition can be regenerated and reused for a number of cycles, it needs to be disposed of after 3-4 years as compared to yearly disposal in case of existing commercial adsorbents.
  • adsorbent composition of the present disclosure minimizes changeover and thereby increases overall production.
  • the process for preparing the adsorbent composition is cost effective as it involves easily available raw material. Moreover, the adsorbent composition can process feed which is 30-40 times its own weight. - The adsorbent composition has a purification capacity >99% thereby improving its life cycle as well as protecting the process equipment.
  • the adsorbent composition is capable of being operated at mild conditions. It is capable of dehydrochlorination (mild catalytic activity) followed by adsorption and can simultaneously remove both organic and inorganic chlorides from diverse hydrocarbon streams.
  • Ion exchanged zeolite (40 g) having particle size of 0.3 pm was mixed hydrotalcite having stearate and hydroxide as counter ions (50 g) having particle size of 0.3 pm, bauxite (5 g) having particle size of 0.25 pm and bentonite (5 g) having particle size of 0.15 pm to obtain a mixture.
  • the mixture was kneaded using a mixture of water (75 wt%), ethanol (25 wt%), calcium stearate (5 wt%)and lauric acid (5 wt%).
  • the formed dough was extruded using an extruder to obtain extrudates having the size 2 mm.
  • the so obtained extrudates were air dried at 150 °C for 2 hours; followed by calcination at 550 °C for 5 hours to obtain the adsorbent composition.
  • Physiochemical properties of the adsorbent composition are given in Table 1 below.
  • Layered double hydroxide powder having stearate and hydroxide as counter ions 70 g having particle size of 0.3 pm was mixed with bauxite (20 g) having particle size of 0.2 pm and a bentonite (10 g) having particle size of 0.2 pm to obtain a mixture.
  • the mixture was kneaded using a mixture of water (75 wt%), ethanol (25 wt%), calcium stearate (5 wt%) and lauric acid (5 wt%).
  • the formed dough was then extruded using an extruder to obtain extrude having size of 2 mm.
  • the so obtained extrudates were air dried at 150 °C for 2 hours; followed by calcination at 550 °C for 5 hours to obtain the adsorbent composition.
  • the mechanical properties of the adsorbent were measured.
  • Physiochemical properties of the adsorbent composition are given in Table 1 below.
  • the chloride adsorption capacity of the adsorbent was determined to be 8 wt%.
  • the chloride adsorption capacity of the adsorbent was measured by contacting lg of the adsorbent with 10 g of chloride containing hydrocarbon feed containing organic and inorganic chloride (3.5 ppm) in vials. The vial was kept overnight.
  • the chloride measurement was carried out with help of chloride analyzer working on the principle of colorimetric titration.
  • the chloride adsorption capacity of the so obtained adsorbent composition was measured by contacting lg of the adsorbent with 10 g of chloride containing hydrocarbon feed containing organic and inorganic chloride (3.5 ppm) in vials. The vial was kept overnight. The chloride measurement was carried out with help of chloride analyzer working on the principle of colorimetric titration.
  • the chloride content of the treated hydrocarbon feed was found to be 0 ppm.
  • Experiment 7 Measuring chloride adsorption capacity of the adsorbent composition of experiment 1 The adsorbent was kept in contact with a mixture of nitrogen + HC1 (500 ppm) overnight for 12 hours. Chloride analysis of spent adsorbent was done using Mohr’s method.
  • adsorbent was kept in contact with a mixture of nitrogen + HC1 (500 ppm) overnight for 12 hours. Chloride analysis of the spent adsorbent was done using Mohr’s method.
  • the chloride adsorption capacity of the adsorbent was determined to be 20 wt%.
  • the spent adsorbents were regenerated in-situ using hot air at 250 °C. Hot air was passed through the spent bed for 5-6 hours at 250 °C, followed by activating at 350 °C for 3-5 hours.

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Abstract

La présente invention concerne une composition adsorbante régénérative pour l'élimination de chlorures à partir d'une charge d'hydrocarbures contenant des chlorures et son procédé de préparation. La composition adsorbante comprend une zéolite à échange d'ions ; de la bauxite ; un hydroxyde double lamellaire ; et un liant. La présente invention concerne en outre un procédé d'élimination de chlorures à partir d'une charge d'hydrocarbures contenant des chlorures en faisant passer la charge d'hydrocarbures contenant des chlorures à travers un lit constitué de la composition adsorbante. La composition adsorbante selon la présente invention peut être régénérée au moins 5 fois et peut être utilisée efficacement pour éliminer les chlorures d'une charge d'hydrocarbures contenant des chlorures.
PCT/IB2019/055832 2018-07-10 2019-07-09 Composition adsorbante régénérative pour l'élimination de chlorures à partir d'hydrocarbures et son procédé de préparation WO2020012351A1 (fr)

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Cited By (4)

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Publication number Priority date Publication date Assignee Title
CN111514849A (zh) * 2020-04-26 2020-08-11 东营科尔特新材料有限公司 脱氯吸附剂及其制备方法、再生方法和脱有机氯的应用
CN112892580A (zh) * 2021-01-19 2021-06-04 浙江卫星能源有限公司 一种常温气相脱氯剂及其制备方法
CN113274975A (zh) * 2020-09-17 2021-08-20 杨仁春 一种氯离子吸附剂及其制备方法和应用方法
CN115193427A (zh) * 2022-07-27 2022-10-18 山东秋水化学科技有限公司 一种脱氯用分子筛及其制备方法

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WO2004054713A1 (fr) * 2002-12-18 2004-07-01 Albemarle Netherlands B.V. Procede pour preparer des microspheres catalytiques
WO2013175490A1 (fr) * 2012-04-03 2013-11-28 Reliance Industries Limited Flux d'hydrocarbures aromatiques c8-c12 sans oxygénats et son procédé de préparation

Patent Citations (2)

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WO2004054713A1 (fr) * 2002-12-18 2004-07-01 Albemarle Netherlands B.V. Procede pour preparer des microspheres catalytiques
WO2013175490A1 (fr) * 2012-04-03 2013-11-28 Reliance Industries Limited Flux d'hydrocarbures aromatiques c8-c12 sans oxygénats et son procédé de préparation

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111514849A (zh) * 2020-04-26 2020-08-11 东营科尔特新材料有限公司 脱氯吸附剂及其制备方法、再生方法和脱有机氯的应用
CN111514849B (zh) * 2020-04-26 2023-10-31 东营科尔特新材料有限公司 脱氯吸附剂及其制备方法、再生方法和脱有机氯的应用
CN113274975A (zh) * 2020-09-17 2021-08-20 杨仁春 一种氯离子吸附剂及其制备方法和应用方法
CN113274975B (zh) * 2020-09-17 2023-08-25 杨仁春 一种氯离子吸附剂及其制备方法和应用方法
CN112892580A (zh) * 2021-01-19 2021-06-04 浙江卫星能源有限公司 一种常温气相脱氯剂及其制备方法
CN112892580B (zh) * 2021-01-19 2023-08-08 浙江卫星能源有限公司 一种常温气相脱氯剂及其制备方法
CN115193427A (zh) * 2022-07-27 2022-10-18 山东秋水化学科技有限公司 一种脱氯用分子筛及其制备方法

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