Vinylidene chloride copolymer-based carbon molecular sieve adsorbent compositions and processes therefor

Patent metadata

Field	Value
Publication number	US-10239043-B2
Application number	US-201515320334-A
Country	US
Kind code	B2
Filing date	Jun 22, 2015
Priority date	Jun 30, 2014
Publication date	Mar 26, 2019
Grant date	Mar 26, 2019

Abstract

Novel carbon molecular sieve (CMS) compositions comprising carbonized vinylidene chloride copolymer having micropores with an average micropore size ranging from 3.0 to 5.0. These materials offer capability in separations of gas mixtures including, for example, propane/propylene; nitrogen/methane; and ethane/ethylene. Such may be prepared by a process wherein vinylidene chloride copolymer beads, melt extruded film or fiber are pretreated to form a precursor that is finally carbonized at high temperature. Preselection or knowledge of precursor crystallinity and attained maximum pyrolysis temperature enables preselection or knowledge of a average micropore size, according to the equation ?=6.09+(0.0275×C)−(0.00233×T), wherein ? is the average micropore size in Angstroms, C is the crystallinity percentage and T is the attained maximum pyrolysis temperature in degrees Celsius, provided that crystallinity percentage ranges from 25 to 75 and temperature in degrees Celsius ranges from 800 to 1700. The beads, fibers or film may be ground, post-pyrolysis, and combined with a non-coating binder to form extruded pellets, or alternatively the fibers may be woven, either before or after pre-treatment, to form a woven fiber sheet which is thereafter pyrolyzed to form a woven fiber adsorbent.

First claim

The invention claimed is:

1. A molecular sieve composition comprising unsupported carbonized polyvinylidene chloride copolymer prepared by a process comprising pyrolyzing an unsupported polyvinylidene chloride polymer precursor having a precursor crystallinity percentage at an attained maximum pyrolysis temperature, wherein the molecular sieve composition has micropores having an average micropore size ranging from 3.0 Å to 4.3 Å, wherein the average micropore size of the molecular sieve composition further characterized according to the equation
σ=6.09+(0.0275 ×C )−(0.00233 ×T )

wherein σ is the average micropore size in Angstroms, C is the precursor crystallinity percentage, and T is the attained maximum pyrolysis temperature, wherein the precursor has a crystallinity percentage, as measured by differential scanning calorimetry, ranging from 25 to 75%.

2. The molecular sieve composition of claim 1 , wherein the attained maximum pyrolysis temperature in degrees Celsius is from 1000 to 1500.

3. The molecular sieve composition of claim 2 being further characterized as having an average micropore volume according to the equation
V= 0.346+0.00208 ×C− 0.000152 ×T

wherein V is the average micropore volume in milliliters per gram.

4. The molecular sieve composition of claim 2 wherein the polyvinylidene chloride polymer precursor is pre-treated, prior to pyrolysis, to at least 10 percent dehydrochlorinate it, to form a pre-treated precursor.

5. The molecular sieve composition of claim 4 wherein the polyvinylidene chloride copolymer precursor is prepared by polymerization or melt-extrusion to form a precursor bead, a precursor film or a precursor fiber,
the polyvinylidene chloride copolymer precursor optionally comprising vinylidene chloride and at least one additional monomer selected from a vinyl monomer, a vinyl chloride monomer, an acrylate monomer, a methacrylate monomer, a styrenic monomer, acrylonitrile, methacrylonitrile, itaconic acid, chlorotrifluoroethylene, and mixtures thereof, and
the melt-extrusion being optionally carried out at a stretch ratio from 1 to 8,
the precursor bead, the precursor film or the precursor fiber optionally having an average thickness or average cross-sectional diameter or average width, as applicable, ranging from 10 micrometers to 1000 micrometers.

6. The molecular sieve composition of claim 4 wherein
the pre-treatment is carried out at a temperature ranging from 100° C. to 180° C. for a time ranging from 1 hour to 48 hours, and optionally, in the case of the precursor film or the precursor fiber, applying tension, simultaneously with the pre-treatment, in an amount from 0.01 megapascals to 10 megapascals.

7. The molecular sieve composition of claim 5 further comprising
weaving the precursor fiber to form a precursor woven sheet, prior to pyrolysis; and
pre-treating the precursor woven sheet either before or after weaving;
wherein the pyrolysis of the precursor woven sheet forms a woven fiber adsorbent being characterized as having voids representing from 10 percent to 50 percent, as measured by mercury porosimetry, of the total volume thereof.

8. The molecular sieve composition of claim 1 further comprising
grinding the pyrolyzed molecular sieve composition to form particles having an average size ranging from 10 micrometers to 1000 micrometers;
combining the particles with at least a non-coating binder and water to form a pellet precursor material; and
pelletizing the pellet precursor material to form a structured pellet adsorbent.

9. The molecular sieve composition of 1 being used to separate a mixture selected from
(a) propane and propylene;
(b) nitrogen and methane;
(c) ethane and ethylene;
(d) carbon dioxide and nitrogen; and
(e) n-butane and iso-butane;
the molecular sieve composition having been prepared such that it has an average micropore size that is suitable to enable separation of the selected mixture.

10. A process for separating two gases in a mixture thereof, comprising contacting a mixture of two gases, wherein at least one gas has a representative molecular diameter ranging from 3.0 Å to 5.0 Å, and the molecular sieve composition of claim 1 , under conditions suitable to adsorb, in the micropores of the molecular sieve composition, at least 5 weight percent of the at least one gas, under conditions such that the at least 5 weight percent of the at least one gas is separated from the other gas; and then desorbing the at least one gas.

Assignees

• Dow Global Technologies Llc

Inventors

• Liu Junqiang
• Beyer Douglas E
• Calverley Edward M
• Han Chan

Classifications

• B01J20/28016

  Particle form · CPC title

• Y02P20/156

  Methane [CH4] · CPC title

• B01J20/3028

  Granulating, agglomerating or aggregating · CPC title

• B01D71/34

  Polyvinylidene fluoride · CPC title

• B01D2257/504

  Carbon dioxide · CPC title