GB2267096A - Purification of hydrocarbons - Google Patents

Purification of hydrocarbons Download PDF

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Publication number
GB2267096A
GB2267096A GB9210081A GB9210081A GB2267096A GB 2267096 A GB2267096 A GB 2267096A GB 9210081 A GB9210081 A GB 9210081A GB 9210081 A GB9210081 A GB 9210081A GB 2267096 A GB2267096 A GB 2267096A
Authority
GB
United Kingdom
Prior art keywords
bed
oxide
absorbent material
hydrocarbons
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
GB9210081A
Other versions
GB9210081D0 (en
Inventor
Ian William Mckernan
Michael John Holder
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Molecular Products Ltd
Original Assignee
Molecular Products Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Molecular Products Ltd filed Critical Molecular Products Ltd
Priority to GB9210081A priority Critical patent/GB2267096A/en
Publication of GB9210081D0 publication Critical patent/GB9210081D0/en
Priority to PCT/GB1993/000935 priority patent/WO1993023159A1/en
Priority to EP93911924A priority patent/EP0640011A1/en
Publication of GB2267096A publication Critical patent/GB2267096A/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
    • 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
    • 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
    • B01J20/30—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
    • B01J20/3028—Granulating, agglomerating or aggregating
    • 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
    • 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

Abstract

A solid particulate absorbent material, for removing acidic contaminants from hydrocarbons, comprises sodium hydroxide and/or potassium hydroxide; alumina and/or zinc oxide; lime; and, optionally, copper II oxide. A hydrocarbon containing an acidic contaminant is purified by passing the hydrocarbon through a bed of the particulate absorbent material.

Description

PURIFICATION PROCESS This invention is concerned with improvements in and relating to compositions for removing acidic contaminants from hydrocarbons and to processes for purifying hydrocarbons using such compositions.
A wide variety of hydrocarbon materials1 both liquid and gaseous, are treated to remove unwanted acidic contaminants. Thus, for example, olefins (such as ethylene and propylene) are purified (e.g. to remove hydrogen sulphide, carbonyl sulphide, carbon dioxide and/or sulphur dioxide) prior to catalysis to avoid poisoning or otherwise adversely affecting the catalyst employed; and liquefied petroleum gas (LPG) is treated to remove contaminants such as hydrogen sulphide and low molecular weight mercaptans. Other hydrocarbons which may be treated include gas condensates and halogenated hydrocarbons, which may be treated to remove traces of hydrogen chloride and phosgene.
The bulk removal of acidic contaminants from hydrocarbons is commonly effected by washing the hydrocarbons with caustic solutions or amines. However, in order to obtain very low levels of contaminant (e.g.
of the order of parts per billion) it is necessary to purify the hydrocarbon by passing it through a bed of an absorbent purifying material. It is an object of the present invention to provide an improved material for use in such a purification process.
According to one embodiment of the invention there is provided a solid absorbent material, for removing acidic contaminants from hydrocarbons, which absorbent material comprises sodium hydroxide and/or potassium hydroxide (especially the former); alumina and/or zinc oxide (especially the former); and lime (calcium hydroxide).
The composition also preferably contains copper II oxide; especially when the composition is to be used in the treatment of dry (anhydrous) hydrocarbon materials.
The composition of the invention suitably contains upto 10 by weight of sodium hydroxide and/or potassium hydroxide; upto 40% by weight of aluminium oxide and/or zinc oxide; from 40 to 97% by weight of lime; and from upto 40% by weight of copper oxide (when present).
Preferred compositional ranges for the above components are set out in the following Table.
Table Component Preferred range Most preferred range of content (wit.) of content (wt. W) NaOH and/or up to 10 up to 10 KOH A12 3 up to 40 up to 5(A1203) and/or 20 to 40 (ZnO) ZnO Ca(OH)2 40 to 97 40 to 60 CuO up to 20 10 to 20 It has been found that the water content of the composition of the invention is of importance and thus the composition suitably contains from 2 to 5% by weight of water.
The compositions in accordance with the invention may simply be formed by making a mixture of the various components together with sufficient water to form a plastic dough and subsequently forming the dough into particulate form and drying it. In accordance with a preferred form of the invention, the dough is extruded into rods (e.g. of a diameter of 0.5 to 5 mm), and these are later broken up (after drying) into pieces of a length of 0.5 to 10 mm.
The invention also provides a method of treating a hydrocarbon material, to remove acidic contaminants therefrom, by passing the hydrocarbon through a bed formed of particulate material in accordance with the invention. In accordance with conventional practice, an installation for treating hydrocarbon materials in accordance with the invention may suitably comprise two packed beds, the material to be treated being passed through the first bed (bed A), and then the second bed (bed B), in series. When the first bed has become exhausted or absorbed contaminant to its practical limit (as judged, for example, by the amount of contaminant present in the material issuing from the bed) the bed may then be recharged with fresh material whilst the material to be treated is passed through the second bed (bed B) only.When the first bed has been replaced, the material to be treated is then passed, sequentially, through the original second bed (bed B) and thence to the original first bed (bed A) until the original second bed (bed B) has become exhausted, after which bed B is replenished and the cycle of operations recommenced.
In order that the invention may be well understood the following Examples are given by way of illustration only.
Examples 1-5 Absorbet materials having the compositions listed in Table 2 below were prepared by mixing sodium hydroxide liquid and the other (solid constituents to give a still paste. The paste was extruded, dried and granulated after which particles between 1 and 3.3 mm were separated, after which their moisture content was adjusted to 3% by weight.
Table 2 (Dry Basis) Sodium Calcium Alumina Zinc Copper(II) hydroxide hydroxide oxide oxide (g) (g) (g) (g) (g) Example 1 111 1000 0 0 0 Example 2 37 1000 183 0 0 Example 3 200 1000 300 500 0 Example 4 232 1000 349 512 232 Example 5 239 1000 0 762 381 By way of comparison the following commercially available products were also tested: Sodalime, Activated alumina Both these products were crushed and separated to the same particle size as those of examples 1 to 5.
The sample materials were tested under simulated use conditions. A nitrogen gas with not more than 60 ppmv water and of known carbonyl sulphide (COS) concentration was passed upwards through a 3mm diameter, 120mm high sample bed at a GHSV of 700. The concentration of COS in the exit gas was monitored by a gas chromatographic technique. The breakthrough times equivalent to 90k and 50coo removal efficiency were noted. The results are summarised in table 3.
Table 3 (Breakthrough times for products of example 1 to 5, soda lime and activated aluminium) Inlet COS Breakthrough times 90W efficiency 50k efficiency (ppmv) (hours) (hours) Example 1 900 3.0 4.0 Example 2 1300 4.5 5.7 Example 3 1000 2.0 4.1 Example 4 980 1.8 3.7 Example 5 1038 8.7 13.6 Sodalime 1300 4.0 5.0 Activated 1370 2.7 3.3 alumina The product of Example 5 was further tested under simulated use conditions. This time a nitrogen gas with a moisture level equivalent to 50% of its saturation capacity and of known carbonyl sulphide (COS) concentration was passed upwards through a 3mm diameter, 120mm high sample bed at a GHSV of 700. The concentration of COS in the exit gas was again monitored by a gas chromatographic technique. The breakthrough times equivalent to 90% and 50% removal efficiency were noted.
Table 4 (Breakthrough time at 50% saturation) Inlet COS Breakthrough times 90% efficiency 50k efficiency (ppmv) (hours) (hours) 1179 16 24

Claims (6)

  1. CLAIMS: 1. A solid particulate absorbent material, for removing acidic contaminants from hydrocarbons, which absorbent material comprises sodium hydroxide and/or potassium hydroxide; alumina and/or zinc oxide; and lime.
  2. 2. An absorbent material as claimed in claim 1 comprising sodium hydroxide, alumina and lime.
  3. 3. An absorbent material as claimed in claim 1 or claim 2 also containing copper II oxide.
  4. 4. A composition as claimed in any one of the preceding claims containing up to 10% by weight of sodium hydroxide and/or potassium hydroxide; up to 40% by weight of aluminium oxide and/or zinc oxide; from 40 to 97% by weight of lime; and up to 20% by weight of copper oxide, manganese oxide and/or cobalt oxide.
  5. 5. An absorbent material as claimed in claim 1 substantially as hereinbefore described with reference to the Examples.
  6. 6. A method of removing acidic contaminants from hydrocarbons which comprises passing the hydrocarbons through a bed of an absorbent material as claimed in any one of the preceding claims.
GB9210081A 1992-05-11 1992-05-11 Purification of hydrocarbons Withdrawn GB2267096A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
GB9210081A GB2267096A (en) 1992-05-11 1992-05-11 Purification of hydrocarbons
PCT/GB1993/000935 WO1993023159A1 (en) 1992-05-11 1993-05-06 Purification process
EP93911924A EP0640011A1 (en) 1992-05-11 1993-05-06 Purification process

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB9210081A GB2267096A (en) 1992-05-11 1992-05-11 Purification of hydrocarbons

Publications (2)

Publication Number Publication Date
GB9210081D0 GB9210081D0 (en) 1992-06-24
GB2267096A true GB2267096A (en) 1993-11-24

Family

ID=10715299

Family Applications (1)

Application Number Title Priority Date Filing Date
GB9210081A Withdrawn GB2267096A (en) 1992-05-11 1992-05-11 Purification of hydrocarbons

Country Status (3)

Country Link
EP (1) EP0640011A1 (en)
GB (1) GB2267096A (en)
WO (1) WO1993023159A1 (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5856265A (en) * 1997-05-23 1999-01-05 La Roche Industries, Inc. Alumina body formation using high pH
EP0908508A1 (en) * 1997-09-16 1999-04-14 Air Products And Chemicals, Inc. Process for the removal of water, CO2, ethane and C3+ hydrocarbons from a gas stream
WO1999039819A1 (en) * 1998-02-06 1999-08-12 Imperial Chemical Industries Plc Absorbents
US5972303A (en) * 1994-01-18 1999-10-26 Phillips Petroleum Company Olefin purification
US6013600A (en) * 1997-05-23 2000-01-11 Laroche Industries Inc. Alumina bodies containing alkali or alkaline earth metal compounds
US6159898A (en) * 1997-05-23 2000-12-12 Uop Llc Alumina bodies containing alkali or alkaline earth metal compounds
US6168769B1 (en) 1993-12-06 2001-01-02 Phillips Petroleum Company Olefin purification
WO2001003827A1 (en) * 1999-07-11 2001-01-18 Solmecs (Israel) Ltd. Sorbent composition

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB938716A (en) * 1961-07-21 1963-10-02 Exxon Research Engineering Co Purification of olefinic gases containing carbonyl sulfide
GB1235435A (en) * 1968-06-17 1971-06-16 Stamicarbon Process for the purification of olefines
GB1356996A (en) * 1970-09-04 1974-06-19 Basf Ag Process for the removal of gaseous chlorine compounds from gases
GB1421798A (en) * 1973-08-21 1976-01-21 Dow Chemical Co Neutralization of acidic contaminants in organic process streams
US4835338A (en) * 1987-08-31 1989-05-30 Aluminum Company Of America Process for removal of carbonyl sulfide from organic liquid by adsorption using alumina adsorbent capable of regeneration

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1904381A (en) * 1929-11-11 1933-04-18 Universal Oil Prod Co Refining of hydrocarbon oils
US2423688A (en) * 1945-05-18 1947-07-08 Dewey And Almy Chem Comp Soda lime composition
US2423689A (en) * 1945-05-18 1947-07-08 Dewey And Almy Chem Comp Soda lime composition
US2479520A (en) * 1945-08-01 1949-08-16 Willson Products Inc Gas-absorbing material and process of making same
FR2295782A1 (en) * 1974-12-27 1976-07-23 Inst Francais Du Petrole PROCESS FOR DEPURING A GAS CONTAINING HYDROGEN SULFIDE AND CONTACT MASSES USABLE FOR THIS PURPOSE
US4571445A (en) * 1984-12-24 1986-02-18 Shell Oil Company Process for removal of sulfur compounds from conjugated diolefins
DE3543530A1 (en) * 1985-12-10 1987-10-15 Saxonlord Ltd Process for producing pellets which, inter alia, contain alkali metal oxides and/or alkaline earth metal oxides
JPS6380830A (en) * 1986-09-25 1988-04-11 Osaka Oxygen Ind Ltd Exhaust gas treatment agent in semiconductor industry
GB8714232D0 (en) * 1987-06-17 1987-07-22 Ici Plc Sulphur compounds removal
CA2014500C (en) * 1989-04-17 1996-09-24 Yoshitsugu Sakata Acidic gas absorbent and process for production thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB938716A (en) * 1961-07-21 1963-10-02 Exxon Research Engineering Co Purification of olefinic gases containing carbonyl sulfide
GB1235435A (en) * 1968-06-17 1971-06-16 Stamicarbon Process for the purification of olefines
GB1356996A (en) * 1970-09-04 1974-06-19 Basf Ag Process for the removal of gaseous chlorine compounds from gases
GB1421798A (en) * 1973-08-21 1976-01-21 Dow Chemical Co Neutralization of acidic contaminants in organic process streams
US4835338A (en) * 1987-08-31 1989-05-30 Aluminum Company Of America Process for removal of carbonyl sulfide from organic liquid by adsorption using alumina adsorbent capable of regeneration

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6168769B1 (en) 1993-12-06 2001-01-02 Phillips Petroleum Company Olefin purification
US5972303A (en) * 1994-01-18 1999-10-26 Phillips Petroleum Company Olefin purification
US5856265A (en) * 1997-05-23 1999-01-05 La Roche Industries, Inc. Alumina body formation using high pH
US6013600A (en) * 1997-05-23 2000-01-11 Laroche Industries Inc. Alumina bodies containing alkali or alkaline earth metal compounds
US6159898A (en) * 1997-05-23 2000-12-12 Uop Llc Alumina bodies containing alkali or alkaline earth metal compounds
EP0908508A1 (en) * 1997-09-16 1999-04-14 Air Products And Chemicals, Inc. Process for the removal of water, CO2, ethane and C3+ hydrocarbons from a gas stream
WO1999039819A1 (en) * 1998-02-06 1999-08-12 Imperial Chemical Industries Plc Absorbents
US6558641B1 (en) 1998-02-06 2003-05-06 Imperial Chemical Industries Plc Absorbents
WO2001003827A1 (en) * 1999-07-11 2001-01-18 Solmecs (Israel) Ltd. Sorbent composition

Also Published As

Publication number Publication date
WO1993023159A1 (en) 1993-11-25
GB9210081D0 (en) 1992-06-24
EP0640011A1 (en) 1995-03-01

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