# US 11,306,164 B2 · Water purification material for petrochemicals

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- Number: US 11,306,164 B2
- Document ID: US11306164B2
- Status: Granted
- Kind: B2
- Application number: 16/373,041
- Filed: 2019-04-02
- Published: 2020-10-08
- Granted: 2022-04-19
- Earliest claimed: 2019-04-02
- Assignees: King Fahd University of Petroleum and Minerals
- Applicants: King Fahd University of Petroleum and Minerals
- Inventors: Tawfik Abdo Saleh Awadh; Nadeem Baig
- Web page: https://patentgrep.com/patent/US11306164B2

## CPC

- C08F 12/08: Styrene
- B01J 20/205: {Carbon nanostructures, e.g. nanotubes, nanohorns, nanocones, nanoballs (carbon nanotubes per se C01B32/15)}
- B01J 20/262: {obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation (macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds per se C08G)}
- C02F 1/288: {using composite sorbents, e.g. coated, impregnated, multi-layered}
- C08F 2/34: Polymerisation in gaseous state
- C08F 2/48: by ultraviolet or visible light
- C08F 8/00: Chemical modification by after-treatment (graft polymers, block polymers, crosslinking with unsaturated monomers or with polymers C08F251/00 - C08F299/00; of conjugated diene rubbers C08C)
- C08F 283/002: {on to polymers modified by after-treatment}
- C08F 283/006: {on to polymers provided for in C08G18/00 (C08F283/004 takes precedence)}
- C08J 5/042: {with carbon fibres}
- C08J 7/0423: {with at least one layer of inorganic material and at least one layer of a composition containing a polymer binder}
- C08J 7/06: with compositions not containing macromolecular substances
- C08J 7/18: using wave energy or particle radiation
- C08L 25/06: Polystyrene
- C08L 51/003: {grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds (C08L51/04, C08L51/06 take precedence)}
- C08L 75/04: Polyurethanes
- C02F 2101/32: Hydrocarbons, e.g. oil
- C02F 2103/365: {from petrochemical industry (e.g. refineries)}
- C02F 2305/08: Nanoparticles or nanotubes
- C08J 2325/06: Polystyrene
- C08J 2375/04: Polyurethanes
- C08J 2425/06: Polystyrene
- Y02W 10/37: using solar energy
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C02F: TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE (separation in general B01D; special arrangements on waterborne vessels of installations for treating water, waste water or sewage, e.g. for producing fresh water, B63J; adding materials to water to prevent corrosion C23F; treating radioactively-contaminated liquids G21F9/04; regeneration of reactants for recirculation into processes, see the relevant places for the processes)
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- Y02W: CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT

## Abstract

Vapor phase polymerization can be used to synthesize a 3D porous network of polystyrene-containing, branched carbon nanofibers on polyurethane(s), optionally using natural light (NL) initiation. NL styrene polymerization in a confined reactor containing CNF-grafted PU can provide a stable porous network. The NL can vaporize the styrene by increasing the reactor temperature and generate styrene radicals. Without CNF, the polymerization on polyurethane (PU) provides a delicate, fragile surface. Radical styrene in vapor phase can interact with CNF to produce polystyrene branches by generating active sites on CNF, while reinforcing the 3D porous structure. After polymerization, the PU surface area increased from 9 to 184 m2/g and pore size decreased from 2567 to 10 Å. 3D porous networks of NL-assisted PS branched CNF supported PU can provide a hydrophobic, oleophilic surface with a water contact angle of approx 148±3°, rapidly gravity separating hexane and water without external force.

## Claims

### Claim 1

A three dimensional porous network composite, comprising:
a substrate comprising a polyurethane;
carbon nanostructures directly contacting the substrate;
branches comprising a radically polymerized monomer, wherein the branches are covalently bonded to the carbon nanostructures.

### Claim 2 (depends on 1)

The composite of claim 1, having a surface area in a range of from 100 to 300 m2/g and a pore size in a range of from 5 to 25 Å.

### Claim 3 (depends on 1)

The composite of claim 1, having a water contact angle in a range of from 130 to 160°.

### Claim 4 (depends on 1)

The composite of claim 1, wherein the substrate comprises at least 90 wt. %, based on a total substrate weight, of polyurethane.

### Claim 5 (depends on 1)

The composite of claim 1, wherein the polyurethane has a specific surface area in a range of from 7.5 to 12.5 m2/g.

### Claim 6 (depends on 1)

The composite of claim 1, wherein the carbon nanostructures comprise at least 50 wt. %, based on total nanostructure weight, of carbon nanofibers.

### Claim 7 (depends on 1)

The composite of claim 1, wherein the radically polymerized monomer comprises an olefin, a styrene, a (meth)acrylate, a vinyl compound, or a mixture of these.

### Claim 8 (depends on 1)

The composite of claim 1, wherein the radically polymerized monomer comprises a styrene.

### Claim 9 (depends on 1)

The composite of claim 1, wherein the radically polymerized monomer comprises at least 85 wt. %, based on total monomer weight, of a styrene.

### Claim 10 (depends on 9)

The composite of claim 9, wherein the styrene is unsubstituted styrene.

### Claim 11 (depends on 1)

The composite of claim 1, having ridges, visible by SEM, with average heights in a range of from 0.5 to 5 μm.

### Claim 12 (depends on 1)

The composite of claim 1, wherein the branches have an average length of at least 1.25 nm and an Mn of at least 520.

### Claim 13 (depends on 1)

A filter, comprising the composite of claim 1.

### Claim 14

A method of fabricating a three dimensional porous network composite, the method comprising:
vapor phase polymerizing a radically polymerizable monomer onto a surface of a polyurethane substrate hosting carbon nanostructures, in a reactor while irradiating with at least one of UV light and visible light,
wherein the polymerizing occurs on the surface of the carbon nanostructure.

### Claim 15 (depends on 14)

The method of claim 14, wherein the reactor is at least one of a sealed reactor and a glass reactor, and
the at least one of the UV light and the visible light is at least partially provided by sunlight.

### Claim 16 (depends on 14)

The method of claim 14, wherein the monomer comprises styrene
and the carbon nanostructures comprise carbon nanofibers.

### Claim 17 (depends on 14)

The method of claim 14, further comprising:
contacting the polyurethane substrate with a suspension of the carbon nanostructures in an organic solvent to form a surface modified polyurethane directly contacting the carbon nanostructures.

### Claim 18 (depends on 1)

A method of purifying contaminated water, the method comprising:
contacting contaminated water comprising a hydrophobic organic fluid with a layer of a thickness in a range of from 1 to 5 cm comprising the composite of claim 1,
wherein at least 90 wt. % of the water does not pass through the layer, and
wherein at least 90 wt. % of the organic fluid passes through the layer.

### Claim 19 (depends on 18)

The method of claim 18, wherein the organic fluid comprises a fraction of crude oil.