WO2007073141A1 - Application de materiau adsorbant microporeux de carbone permettant de separer selectivement des paraffines ayant de 5 a 10 atomes de carbone - Google Patents

Application de materiau adsorbant microporeux de carbone permettant de separer selectivement des paraffines ayant de 5 a 10 atomes de carbone Download PDF

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WO2007073141A1
WO2007073141A1 PCT/MX2006/000147 MX2006000147W WO2007073141A1 WO 2007073141 A1 WO2007073141 A1 WO 2007073141A1 MX 2006000147 W MX2006000147 W MX 2006000147W WO 2007073141 A1 WO2007073141 A1 WO 2007073141A1
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amc
adsorption
paraffins
adsorbent material
microporous carbon
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English (en)
Spanish (es)
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Georgina Cecilia LAREDO SÁNCHEZ
J. Jesús CASTILLO MUNGUÍA
Carla Rossana LÓPEZ CISNEROS
RUÍZ Edith MENESES
María del Carmen MARTÍNEZ GUERRERO
Obet MARROQUÍN DE LA ROSA
Fidencio HERNÁNDEZ PÉREZ
José Luis CANO DOMÍNGUEZ
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Instituto Mexicano Del Petróleo
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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
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/02—Monomers containing chlorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/02—Monomers containing chlorine
    • C08F214/04—Monomers containing two carbon atoms
    • C08F214/06—Vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/02—Monomers containing chlorine
    • C08F214/04—Monomers containing two carbon atoms
    • C08F214/08—Vinylidene chloride
    • 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
    • C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
    • B01D15/18—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to flow patterns
    • B01D15/1814—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to flow patterns recycling of the fraction to be distributed
    • B01D15/1821—Simulated moving beds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/20—Organic adsorbents
    • B01D2253/202—Polymeric adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/24—Hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702—Hydrocarbons
    • B01D2257/7022—Aliphatic hydrocarbons

Definitions

  • the present invention relates to the application of microporous carbon adsorbent material, from the calcination of Poly (vinylidene-co-vinyl chloride) (PVDC-PVC), Poly (vinylidene chloride-methyl co-acrylate) (PVDC-AM), Poly (vinylidene-co-acrylonitrile chloride) (PVDC-ACN), Poly (methyl acrylate-co-acrylonitrile) (AM-ACN), and other related copolymers, generically known as Sarán , for the selective adsorption of paraffins of 5 to 10 carbon atoms (C 5 to C-io), in particular of linear, mono-branched and multi-branched paraffins, contained in gasoline fractions; wherein the separation depends on the adsorption properties of the components according to the length of the chain and the number of branches.
  • PVDC-PVC Poly (vinylidene chloride-methyl co-acrylate)
  • PVDC-ACN Poly (vinylidene-
  • the linear alkanes have a size of 0.42 nm and the mono-branched ones of 0.55 nm.
  • the average size ranges from 0.55 nm, while for 2,2- and 3,3- the size is 0.67-0.71 nm.
  • Trisubstituted alkanes and ethyl substituted have an average size of 0.61-0.67 nm. This broadly justifies the selection of microporous materials with a pore diameter preferably between 0.4-0.7 nm, for the design of selective separation techniques. (Jiménez-Cruz and Laredo, Fuel, 2004, 83, 2183).
  • the separation process preferably considers adsorption of linear paraffins using ZSM-11 type zeolites and silicalite.
  • This effluent, poor in linear alloys, is introduced into the second unit that is filled with a selective adsorbent for methyl-branched aliens with the exception of isopentane, which exits with the effluent rich in multi-branched alloys.
  • the adsorbents used in this invention are zeolites such as silicalite, ferrite, ZSM-5, ZSM-11, ZSM-23, ZSM-35 and ZSM-48. This process has particular application when coupled to a hydro-isomerization process that converts linear and mono-branched paraffins to a mixture that also contains multi-branched paraffins.
  • the process of desorption and regeneration of the adsorbent can be carried out by depressurization (DCP) or by changes in temperature (DCT).
  • DCP depressurization
  • DCT changes in temperature
  • microporous carbon adsorbent material in adsorption processes in liquid phase or gas phase, due to its high adsorption capacity and selectivity in the separation of paraffins of 5 to 10 atoms of carbon (C5-C 1 0), in particular linear, mono-branched and multi-branched paraffins, due to its pore size distribution, preferably between 0.4-0.7 nm, whereby the continuous adsorption selectivity of the paraffins depending on the size of the molecules, allowing to select the cutoff point where it is most convenient.
  • microporous carbon adsorbent material derived from the calcination of copolymers generically known as Sarán, in the processes of paraffin separation C 5 -C 10 , contained in fractions of gasoline.
  • Another object of the present invention is to apply a microporous carbon adsorbent material in liquid phase or gas phase adsorption processes, which mainly has the following advantages: 1) high adsorption capacity and selectivity in the separation of C 5 -Ci paraffins 0 , in particular linear, mono-branched and multi-branched paraffins; 2) high selectivity for The separation of the paraffins .C 5 -Ci 0 , depending on the length of the chain and its degree of branching and 3) .Improvement in the octane number by separating paraffins with different degree of branching.
  • FIG. 1 Scanning electron microscopy photography of the microporous carbon adsorbent material of the present invention (AMC).
  • FIG. 1 Schematic representation of the equipment at the bank scale, to evaluate the separation by selective adsorption of C 5 -Ci 0 paraffins in gas phase, Examples 7 to 9.
  • FIG. 3 Selectivity by compound against sample weight of non-adsorbed product for a quaternary mixture composed of n-heptane (nC 7 ), 2-methyl heptane (2MC 7 ), 2,2-dimethyl hexane (22DMC 6 ) and isooctane ( iC 8 or 224TMC 5 ), by the microporous carbon adsorbent material of the present invention (AMC) and zeolitic molecular meshes used commercially in the selective separation of paraffins, Example 7.
  • AMC microporous carbon adsorbent material of the present invention
  • zeolitic molecular meshes used commercially in the selective separation of paraffins
  • nC 4 n-butane
  • nC 5 n-pentane
  • cyclopentane (CC 5 ) n-hexane
  • nC 6 2-methyl pentane
  • 3-methyl pentane (3MC 5 ) 2,2-dimethyl butane (22DMC 4 ), 2, 3-dimethyl butane (23DMC 4 ), cyclohexane (CC 6 ) and methyl-cyclopentane (MCC 5 ).
  • Example 8 Comparative graphs of the Selectivity by compound, of results obtained by the microporous carbon adsorbent material of the present invention (AMC) and with zeolitic molecular meshes used commercially in the selective separation of paraffins,
  • Example 8 a) For: n -hexane (nC 6 ), 2-methyl pentane (2MC 5 ), 3-methyl pentane (3MC 5 ), 2,2-dimethyl butane (22DMC 4 ) ' and 2,3-dimethyl butane (23DMC 4 ), of Ia multicomponent mixture of Example 8.
  • b) For linear hydrocarbons, of the multicomponent mixture of Example 8: n-butane (nC 4 ), n-pentane (nC 5 ) and n-hexane (nC 6 ).
  • FIG. 7 Selectivity vs. Octane number in the separation of the mixture of Example 8 with the microporous carbon adsorbent material of the present invention (AMC), for the following compounds: n-butane (nC 4 ), n-pentane (nC 5 ), n- hexane (nC 6 ), isopentane or 2-methyl butane (2MC 4 ), 2-methyl pentane (2MC 5 ), 3-methyl pentane (3MC 5 ), 2,2-dimethyl butane (22DMC 4 ), 2,3- dimethyl butane (23DMC 4 ). ,
  • Example 9 Comparative graphs of the Selectivity by compound, of results obtained with the application of the microporous carbon adsorbent material of the present invention (AMC) and with zeolitic molecular meshes used commercially in the selective separation of paraffins,
  • Example 9 a) For hydrocarbons of 7 carbon atoms: n-heptane (nC 7 ), 3-methyl hexane (3MC 6 ), 2,3-dimethyl pentane (23DMC 5 ), 2,2,3-trimethyl butane (223TMC 4 ), of Ia multi-component mixture of Example 9.
  • n-octane (nC 8 ), 2-methyl heptane (2MC 7 ), 3-methyl heptane (3MC 7 ), 2,2-dimethyl hexane (22DMC 6 ), 2,4-dimethyl hexane (24DMC 6 ), 2,5-dimethyl hexane (25DMC 6 ) and isooctane (iC 8 or 224TMC 5 ), of the multi-component mixture of Example 9.
  • FIG. 10 Selectivity vs. Octane number in the separation of the multicomponent mixture of Example 9 with the microporous carbon adsorbent material of the present invention (AMC), for all the compounds of the mixture: n-heptane (nC 7 ), 3-methyl hexane (3MC 6 ), 2,3-dimethyl pentane (23DMC 5 ), 2,2,3-trimethyl butane (223TMC 4 ) ' n-octane (nC 8 ), 2-methyl heptane (2MC 7 ), 3-methyl heptane (3MC 7 ), 2,2-dimethyl hexane (22DMC 6 ), 2,4-dimethyl hexane (24DMC 6 ), 2,5-dimethyl hexane (25DMC 6 ) and isooctane (iC 8 or 224TMC 5 ).
  • AMC microporous carbon adsorbent material of the present invention
  • the present invention relates to the application of microporous carbon adsorbent material, from the calcination of Poly (vinylidene chloride-co-vinyl chloride) (PVDC-PVC), Poly (vinylidene chloride-methyl co-acrylate) (PVDC-AM), Poly (vinylidene-co-acrylonitrile chloride) (PVDC-ACN), Poly (methyl acrylate-co-acrylonitrile) (AM-ACN), and other related copolymers, generically known as Sarán , for the selective adsorption of paraffins of 5 to 10 carbon atoms (C 5 -C 10 ), in particular of linear, mono-branched and multi-branched paraffins, contained in gasoline fractions; wherein the separation depends on the adsorption properties of the components according to the length of the chain and the number of branches.
  • PVDC-PVC Poly (vinylidene chloride-methyl co-acrylate)
  • PVDC-ACN Poly (vinyliden
  • the charges to be treated by the adsorbent material considered in this invention are all those natural or synthetic mixtures consisting mainly of paraffins of 5 to 10 carbon atoms (C5-C 10 ), which can be formed by linear, mono-branched and multi-branched.
  • the term multi-branched includes all those paraffins with degree of branching two or higher.
  • the separation processes may be operated in the liquid phase or in the gas phase and may be based on pressure change adsorption (ACP), temperature change adsorption (ACT), chromatography (elution or countercurrent chromatography) or they may be the result of a combination of any of these.
  • ACP pressure change adsorption
  • ACT temperature change adsorption
  • chromatography elution or countercurrent chromatography
  • the process of desorption and regeneration of the adsorbent can be carried out by depressurization (DCP) or by changes in temperature (DCT).
  • DCP depressurization
  • DCT changes in temperature
  • Adsorption separation processes can be carried out in the liquid phase or in the gas phase.
  • AMC the gas phase adsorption process was carried out in a fixed bed and in a liquid phase in a stirred tank.
  • AMC material can be used in any adsorption system that considers fixed beds, agitated beds, moving beds, simulated moving beds, etc.
  • the adsorbents used in the examples of the present invention were the AMC material and commercial zeolites in the selective separation of paraffins (Zeolites 5A and ZSM-5).
  • AMC microporous carbon materials
  • the application of microporous carbon materials (AMC) from the calcination of the Saran according to the technique described in Example 1, for the selective adsorption of paraffins of 5 to 10 carbon atoms (C 5 -Ci 0 ), has considerable advantages in terms of the increase in the octane number and adsorption capacity, compared to the commercially used zeolitic molecular meshes.
  • Figure 1 shows a scanning electron microscopy photograph of the adsorbent material, where the morphology of the particles can be seen.
  • a pore size between 0.4 to 1.0 nm is estimated, with 60% between 0.5 to 0.7 nm, and a surface area (BET) of 840 m 2 / g, according to the texture analysis by adsorption-desorption of nitrogen .
  • the process of liquid phase adsorption for different mixtures of paraffins is carried out by placing 1 g of the adsorbent and 10 g of the mixture in a micro-reactor at 30 0 C temperature. To obtain the adsorption data, samples of the liquid phase (0.1 ml) were taken at different time intervals and analyzed by PIONA chromatography (analysis of paraffins, isoparaffins, olefins, naphthenic and aromatic).
  • a column formed by a stainless steel tube 36 cm long and 0.48 cm internal diameter was used.
  • the tubular adsorber was packed with the adsorbent (6.5 ml, 70-140 mesh).
  • AMC microporous carbon adsorbent material
  • All the materials used in the examples were previously activated with a stream of nitrogen (60 ml / min) at a temperature of 340-500 0 C.
  • the mixture to be separated was fed to the column by means of a piston pump at a speed of 30 ml / min ( Figure 2).
  • the recovered hydrocarbon mixture was collected for analysis on the PIONA chromatograph in vials of 0.3 ml capacity.
  • the adsorption temperature used was 150-200 0 C, preferably 175 0 C. Once the adsorption process was carried out, the adsorbent was regenerated at 500 0 C for 15 minutes with a nitrogen flow of 30 ml / min.
  • Figure 2 shows a scheme of the equipment at the bank scale used to carry out the gas phase adsorption tests, which is mainly constituted by: 1) Feed of the paraffin mixture, 2) Feed of the entrainment gas, 3 ) Temperature sensor, 4) Heating jacket, 5) Column packed with adsorbent material, 6) Back pressure valve, 7) Temperature control fluid outlet, 8) Temperature control fluid inlet, 9) Condenser, 10) Raffinate flow control valve, and 11) Raffinate output.
  • microporous carbon adsorbent material considered in the application object of the present invention, is based on the differences in geometric properties (size and shape), polarity, diffusivity and kinetic properties, excluding chemical reactions of adsorbates
  • AMC microporous carbon adsorbent material
  • adsorbent material were prepared by pyrolysis of the following copolymers: Sarán 415, Sarán 469, Sarán 43710-7, Sarán XU and Sarán 43040-4.
  • the pyrolysis was developed in two stages: pressure copolymer tablets (10,000 kg / cm 2 (9,806.65 bar)) were prepared. These tablets were placed inside a quartz tube that was introduced into a homo cylindrical with temperature control and inert atmosphere of helium, inside a hood with gas extraction. The temperature rose at a heating rate of 5 ° C / min to reach 300 0 C (4 h). In the second stage Ia temperature was raised at a rate of 5 ° C / min to 900 0 C, where it was maintained for 12 hours.
  • liquid phase adsorption tests were carried out using a synthetic quaternary mixture consisting of: n-heptane (nC7), 2-methyl. heptane (2MC7), 2,5-dimethyl hexane (25DMC6) and isooctane (iC8 or 224TMC5), all in a 25% volume ratio.
  • nC7 n-heptane
  • 2MC7 2-methyl. heptane
  • 25DMC6 2,5-dimethyl hexane
  • iC8 or 224TMC5 isooctane
  • the adsorption tests were carried out as follows: One gram of the adsorbent material from the respective copolymer (Saran 415, Sarán 469, Sarán 43710-7, Sarán XU and Sarán 43040-4) was placed inside a 50 ml micro-reactor with temperature control and stirring. The test was carried out at constant temperature (30 0 C) and magnetic stirring between 260 and 350 rpm. For these experiments, a 2 cm diameter magnetic star bar was used. After 24 hours, samples of the supernatant liquid were taken, avoiding the removal of the adsorbent, which were placed in micro vials for analysis by PIONA gas chromatography.
  • the results of the adsorption tests are shown in Table 1. As can be seen in Table 1, the results do not show significant differences between the various Sarán materials used. Due to this, the material obtained from the calcination of Sarán 415 was chosen as the representative, since it has the greatest surface area, and it was subjected to the adsorption tests illustrated in the following examples.
  • This material identified as a microporous carbon adsorbent (AMC), has a flake shape in accordance with scanning electron microscopy (Figure 1), a pore size of between 0.4 to 1.0 nm is estimated, with 60% between 0.5 to 0.7 nm, and a surface area (BET) of 840 m 2 / g.
  • AMC microporous carbon adsorbent
  • AMC Zeolite 5A or Zeolite ZSM-5
  • adsorbent AMC, Zeolite 5A or Zeolite ZSM-5
  • 1O ml of a mixture of n-heptane in 5% volume isooctane was added.
  • the isooctane is used as a solvent since in previous adsorption tests, it was found that this substance is not adsorbed in the AMC and Zeolites 5A and ZSM-5 adsorbents.
  • the test was conducted at the conditions listed in Example 1: a constant temperature (30 0 C) and magnetic stirring between 260 and 350 rpm. For these experiments, a 2 cm diameter magnetic star bar was used. Samples of the supernatant liquid were taken after 24 hours, avoiding the removal of the adsorbent, which were placed in micro vials for analysis by chromatography of PIONA gases. The results of adsorption tests are shown in Table 2.
  • n-heptane The adsorption of these paraffins with respect to n-heptane, calculated by means of formula (1), is shown in Table 5.
  • the n-heptane was selected because it is linear and is the one with the easiest adsorption.
  • the tubular adsorber was packed with 7 ml of the adsorbent.
  • AMC n-heptane
  • 2MC 7 2-methyl heptane
  • 22DMC 6 2,2-dimethyl hexane
  • iC 8 or 224TMC 5 isooctane
  • the Zeolites 5A (5.50 g) and ZSM-5 (3.20 g, CBV 28.014, Zeolyst), 70-140 mesh, were dried in the same way as that used for the AMC material.
  • the gas phase adsorption tests were carried out at the bank scale under the aforementioned conditions.
  • the multi-component mixture was introduced in a single feed and 0.1 ml samples were collected at the exit of the column at different times, for analysis.
  • the results shown in Table 7 were obtained, for the first 10 samples or fractions collected.
  • gm / gadsorb e nte grams of sample recovered per gram of adsorbent.
  • Figure 3 allows comparing the selectivities of the AMC material with the commercial Zeolites 5A and ZSM-5.
  • the AMC material has a higher selectivity (lower affinity) for branched or high octane compounds, than that presented by commercial Zeolites, in addition to maintaining said selectivity for a longer period of time.
  • Figure 4 shows that the selectivity of the AMC for 2,2-dimethyl hexane (22DMC 6 ) and 2,2,4-trimethyl pentane (224TMC 5 ) with octane numbers of 75 and 100 respectively is 2 , while for Zeolita 5A it is 1.3 and 1.4, and for Zeolita ZSM 5 it is 1.4 and 1.75.
  • the selectivity of both compounds in the AMC material is 0, while that for Zeolite 5A it is 1.3 and 0, and 0.45 and 0.25 for Zeolite ZSM 5.
  • a higher selectivity for this type of compounds means a lower affinity and therefore, they are less susceptible to the adsorption process. It is important to note in this Example that the AMC material has the greatest difference in selectivities (relative value of 2) between the compounds to be separated, this considerably facilitates the separation of the high and low octane compounds.
  • Figure 5 shows the comparison of the selectivities of the AMC material with the commercial Zeolites 5A and ZSM-5, in said figure it is confirmed that the AMC material has a higher selectivity (lower affinity) for branched or high octane compounds, than Ia presented by the commercial Zeolites.
  • Example 7 As in Example 7, to make a further comparison of the AMC material with the commercial Zeolites 5A and ZSM-5, from Figure 5 the selectivity values of these materials were obtained for a sample weight of 0.04 g / g of material, which are presented in Figure 6.
  • Figure 6 shows that the AMC material has a selectivity directly related to the type of hydrocarbon.
  • the selectivity increases as the number of branches increases, with the highest selectivity for the paraffins with quaternary carbons.
  • ⁇ selectivity decreases as the length of the chain increases. This direct effect of the structure on the selectivity is much less evident for Zeolites 5A and ZSM 5.
  • g m / gadsorbent grams of sample recovered per gram of adsorbent Table 10. Selectivity of fractions 1 to 5 with respect to the load, for the different adsorbents: AMC and commercial Zeolites.
  • Figure 9 shows that the AMC material has a selectivity directly related to the type of hydrocarbon.
  • the selectivity increases as the number of branches increases, with the greater selectivity for the paraffins with quaternary carbons.
  • Figure 9b for the 8-carbon compounds.
  • Paraffins with quaternary carbons, particularly those with substitutions in position 2.2 have no possibility of penetrating into the pores of the AMC material and therefore the separation of these highly branched and high octane paraffins is highly favored. Additionally, the molecular carbon meshes obtained from the calcination of Sarán have selectivities highly dependent on the number of branches and the number of carbons, which allows very specific separations to be carried out.

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  • Carbon And Carbon Compounds (AREA)

Abstract

L'invention concerne l'application de matériau adsorbant microporeux de carbone, provenant de la calcination du poly(chlorure de vinylidène-co-chlorure de vinyle) (PVDC-PVC), du poly(chlorure de vinylidène-co-acrylate de méthyle) (PVDC-AM), du poly(chlorure de vinylidène-co-acrilonitrile) (PVDC-ACN), du poly(acrylate de méthyle-co-acrilonitrile) (AM-ACN) et d'autres copolymères associés, connus sous le nom générique de saran, pour l'adsorption sélective de paraffines ayant de 5 à 10 atomes de carbone (C5 à C10), notamment des paraffines linéaires, mono-ramifiées et multi-ramifiées, contenues dans des fractions d'essence. La séparation dépend des propriétés d'adsorption que présentent les composants conformément à la longueur de la chaîne et au nombre de ramifications. Le matériau adsorbant microporeux de carbone (AMC) présente de meilleures caractéristiques pour ce qui est de la capacité d'adsorption et de sélectivité pour séparer les alcanes conformément à la longueur de la chaîne et au nombre de ramifications en comparaison avec les mailles moléculaires zéolitiques utilisées commercialement. Le processus de séparation, en considérant l'utilisation du matériau AMC, peut se dérouler en phase liquide ou en phase gazeuse et requiert une unité de séparation qui fonctionne par adsorption. Le processus d'adsorption peut être mené à bien par des changements de pression (ACP) ou de température (ACT). Le processus fonctionne dans n'importe quel système d'adsorption qui considère des lits fixes, des lits agités, des lits mobiles, des lits mobiles simulés, etc. Le processus de régénération du matériau AMC peut être mené à bien par désorption par changements de pression (DCP) ou de température (DCT) ou par déplacement au moyen d'un désorbant.
PCT/MX2006/000147 2005-12-20 2006-12-19 Application de materiau adsorbant microporeux de carbone permettant de separer selectivement des paraffines ayant de 5 a 10 atomes de carbone WO2007073141A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
MXPA05013987A MXPA05013987A (es) 2005-12-20 2005-12-20 Aplicacion de material adsorbente microporoso de carbon, para separar selectivamente parafinas de 5 a 10 atomos de carbono.
MXPA/A/2005/013987 2005-12-20

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WO2007073141A1 true WO2007073141A1 (fr) 2007-06-28

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110604999A (zh) * 2019-09-12 2019-12-24 浙江大学 一种pvdc树脂衍生微孔碳材料在吸附分离甲烷和氮气上的应用

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL7111508A (en) * 1971-08-20 1971-10-25 High and low branched hydrocarbons molecular

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL7111508A (en) * 1971-08-20 1971-10-25 High and low branched hydrocarbons molecular

Non-Patent Citations (8)

* Cited by examiner, † Cited by third party
Title
BARTON S.S. ET AL.: "An investigation of the pore structure and molecular sieve properties of polyvinylidene chloride carbons", J. COLL. INTERF. SCI., vol. 49, no. 3, 1974, pages 462 - 468, XP008082100 *
DATABASE CAPLUS [online] GVOZDOVICH T.N. ET AL.: "Use of SARAN-type active carbon in gas chromatography", XP003014778, accession no. STN Database accession no. (1968:470047) *
DATABASE CAPLUS [online] KITAGAWA H. ET AL.: "Preparation of molecular sieve carbon from SARAN waste. Separation of hydrocarbon by a fixed bed adsorber", XP003014777, accession no. STN Database accession no. (1983:507380) *
DATABASE WPI Week 197144, Derwent World Patents Index; AN 1971-69866S, XP003014783 *
FERNANDEZ-MORALES I. ET AL.: "Adsorption capacity of SARAN carbons at high temperatures and under dynamic conditions", CARBON, vol. 22, no. 3, 1984, pages 301 - 304, XP003014784 *
KITAGAWA H. AND YUKI N.: "Adsorptive properties of carbon molecular sieve from SARAN", CARBON, vol. 19, no. 6, 1981, pages 470 - 472, XP003014785 *
KOAGI, vol. 18, no. 2, 1983, pages 109 - 118 *
NEFTEKHIMIYA, vol. 8, no. 3, 1968, pages 476 - 480 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110604999A (zh) * 2019-09-12 2019-12-24 浙江大学 一种pvdc树脂衍生微孔碳材料在吸附分离甲烷和氮气上的应用
CN110604999B (zh) * 2019-09-12 2021-05-07 浙江大学 一种pvdc树脂衍生微孔碳材料在吸附分离甲烷和氮气上的应用

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