MIXED LIQUIFIED PYROLYSIS GAS WITH RECYCLED CONTENT

BACKGROUND

Waste plastic pyrolysis plays a part in a variety of chemical recycling technologies. Typically, waste plastic pyrolysis facilities focus on producing recycled content pyrolysis oil (r-pyoil) that can be readily transported to an onsite or offsite facility for further use in making recycled content products.

In addition to r-pyoil, waste plastic pyrolysis produces heavy components (e.g., waxes, tar, and char) and recycled content pyrolysis gas (r-pygas). Although r-pygas produced by the waste plastic pyrolysis typically has 100 percent recycled content, it is common practice for the r-pygas to be burned as fuel to provide heat for the pyrolysis reaction. Although burning r-pygas as fuel for pyrolysis may be economically efficient, such practice runs counter to one of the main goals of chemical recycling, which is to transform as much of the waste plastic as possible in new products. Thus, a better use for r-pygas is needed.

SUMMARY

In one aspect, the present technology concerns a process for producing a readily storable and transportable light hydrocarbon feedstock having recycled content from waste plastic, where the process comprises the following steps: (a) pyrolyzing waste plastic to thereby produce a recycled content pyrolysis gas (r-pygas); (b) liquifying at least a portion of the r-pygas to thereby provide a recycled content liquified pyrolysis gas (r-LPyG), wherein the liquifying is carried out using a method comprising compression, cooling, or compression and cooling of the r-pygas; and (c) maintaining at least a portion of the r-LPyG in a liquified state during storing, transporting, or storing and transporting of the r-LPyG.

In one aspect, the present technology concerns a process for producing liquified pyrolysis gas having recycled content (r-LPyG), where the process comprises the following steps: (a) pyrolyzing waste plastic to thereby produce a recycled content pyrolysis gas (r-pygas); (b) using at least a portion of the r-pygas gas as fuel for the pyrolyzing of step (a); (c) liquifying at least a portion of the r-pygas to thereby provide a recycled content liquified pyrolysis gas (r-LPyG); and (d) performing one or both of the following steps—(i) storing the r-LPyG in liquified state for a continuous storage period of at least 1 hour and/or (ii) loading the r-LPyG into a transportation apparatus configured to transport the r-LPyG in a liquified state for a distance of at least 1 mile.

In one aspect, the present technology concerns a process for producing liquified pyrolysis gas having recycled content (r-LPyG), where the process comprises the following steps: (a) pyrolyzing waste plastic to thereby produce a recycled content pyrolysis gas (r-pygas) and a recycled content pyrolysis oil (r-pyoil); (b) liquifying at least a portion of the r-pygas to thereby provide a recycled content liquified pyrolysis gas (r-LPyG); (c) loading at least a portion of the r-LPyG into a first transportation apparatus configured to transport the r-LPyG in a liquified state; and (d) loading at least a portion of the r-pyoil into a second transportation apparatus configured to transport the r-pyoil in a liquid state.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a block flow diagram illustrating the main steps of a process and facility for making and using recycled content liquified pyrolysis gas (r-LPyG);

FIG. 2 is a block flow diagram illustrating the main steps of a process and facility for producing r-LPyG in accordance with a first embodiment of the present technology;

FIG. 3 is a block flow diagram illustrating the main steps of a process and facility for producing r-LPyG in accordance with a second embodiment of the present technology;

FIG. 4 is a block flow diagram illustrating the main steps of a process and facility for producing r-LPyG in accordance with a third embodiment of the present technology;

FIG. 5 is a block flow diagram illustrating the main steps of a process and facility for using r-LPyG as a feed to a cracking facility; and

FIG. 6 is a computer simulation flow diagram of a process for producing r-LPyG.

DETAILED DESCRIPTION

We have discovered new methods and systems for providing a readily storable and transportable feed material produced from a recycled content stream previously burned as fuel. More specifically, we have discovered that pyrolysis gas produced from the pyrolysis of waste plastic can be liquified for use as a storable and/or transportable feed to a chemical manufacturing facility.

FIG. 1 illustrates one embodiment of a process and system for use in chemical recycling of waste plastic. The process depicted in FIG. 1 starts with a pyrolysis step where waste plastic is pyrolyzed to produce a pyrolysis effluent. The pyrolysis effluent is then subjected to separation to provide at least a recycled content pyrolysis oil (r-pyoil), a recycled content pyrolysis gas (r-pygas), and a recycled content pyrolysis residue (r-pyrolysis residue).

As used herein, the term “r-pygas” refers to a composition obtained from waste plastic pyrolysis that is gaseous at 25° C. at 1 atm. As used herein, the terms “r-pyoil” refers to a composition obtained from waste plastic pyrolysis that is liquid at 25° C. and 1 atm. As used herein, the term “r-pyrolysis residue” refers to a composition obtained from waste plastic pyrolysis that is not r-pygas or r-pyoil and that comprises predominantly pyrolysis char and pyrolysis heavy waxes. As used herein, the term “pyrolysis char” refers to a carbon-containing composition obtained from pyrolysis that is solid at 200° C. and 1 atm. As used herein, the term “pyrolysis heavy waxes” refers to C20+ hydrocarbons obtained from pyrolysis that are not pyrolysis char, pyrolysis gas, or pyrolysis oil.

In an embodiment or in combination with any embodiment mentioned herein, the r-pyoil can be the predominate product produced by the waste plastic pyrolysis step, with the r-pygas being a minor/coproduct of the pyrolysis step. For example, the amount by weight of r-pygas produced from pyrolyzing the waste plastic can be less than 75, or less than 50, or less than 40, or less than 30, or less than 20 weight percent of the amount of r-pyoil produced from pyrolyzing the waste plastic. Additionally, or alternatively, the pyrolyzing can convert 30 to 95, or 40 to 90, or 50 to 80, or 55 to 75 weight percent of the waste plastic feedstock into the r-pyoil and/or the pyrolyzing can convert 0.5 to 50, or 1 to 40, or 2 to 30, or 4 to 25 weight percent of the waste plastic feedstock into the r-pygas.

As shown in FIG. 1, since the r-pyoil produced by the process in FIG. 1 is a liquid at standard temperature and pressure, the r-pyoil can be readily stored and/or transported in a liquid state. As depicted in FIG. 1, after storage and/or transportation, the r-pyoil can be further processed and/or used for its intended end use, which can include the manufacture of recycled content chemical products. Because r-pyoil is a liquid that is readily storable and transportable (e.g., via railcar tanks, tank trucks, tanker ships, and/or pipelines), the end use facility for the r-pyoil can be located remotely from the facility where the r-pyoil is produced. For example, the processing and/or end use of the r-pyoil can be carried out at a facility or site that is at least 1, or at least 10, or at least 50, or at least 500, or at least 1000 miles from the location of the pyrolysis facility.

The r-pygas produced by the process in FIG. 1 is a gas and standard temperature and pressure. As discussed above, in the past, the r-pygas produced by commercial-scale waste plastic pyrolysis facilities was used as fuel to provide heat for the pyrolysis reaction. This burning of 100% recycled content r-pygas runs counter to a basic principle of chemical recycling, which is to promote a circular economy for plastics and chemicals, where as much recycled content as possible from waste plastic is reused to make new products. In addition, burning 100% recycled content r-pygas negatively affects the life cycle analysis (LCA) of the waste plastic pyrolysis facility.

As shown in FIG. 1, in accordance with embodiments of the present technology, little or none of the r-pygas from the separation step is used as fuel for the pyrolysis step. Rather, all or most of the r-pygas exiting the separation step is fed to a liquification process/facility, where the r-pygas is liquified to produce a recycled content liquified pyrolysis gas (r-LPyG). For example, at least 50, or at least 75, or at least 90, or at least 95, or 100 weight percent of the r-pygas recovered from the separation step is provided to the liquification step, while less than 50, or less than 25, or less than 10, or less than 5, or 0 weight percent of the r-pygas recovered from the separation step is used as fuel for the pyrolysis reaction. Existing pyrolysis facilities seeking to incorporate the present technology may reduce and/or eliminate the use of r-pygas as fuel for the pyrolysis reaction and start and/or increase the flow of r-pygas to the liquification process.

As discussed in further detail below with reference to FIGS. 2-4, the liquification step can included compression, cooling, absorption, and/or separation steps sufficient to liquefy at least 50, or at least 75, or at least 90, or at least 95, or at least 99 weight percent of the C3-C5 compounds present in the r-pygas produced from the pyrolysis step and introduced into the liquification step. The liquification step can also be sufficient to liquefy at least 20, or at least 30, or at least 40, or at least 50, or at least 60, or at least 70, or at least 80, or at least 90, or at least 95 weight percent of the total r-pygas produced from the pyrolysis step and introduced into the liquifying step.

FIG. 1 shows that a non-condensable gas can be produced from the liquification process. The non-condensable gas can contain components that do not liquefy during the compression, cooling, absorption, and/or separation steps of the liquification process. For example, the non-condensable gas can comprise ethane and lighter components in an amount of at least 25, or at least 40, or at least 50, or at least 60, or at least 70 weight percent. Examples of ethane and lighter components that can be present in the non-condensable gas include methane, ethane, hydrogen (H2), carbon monoxide (CO), and carbon dioxide (CO2).

In an embodiment or in combination with any embodiment mentioned herein, at least 20, or at least 30, or at least 40, or at least 50, or at least 75, or at least 90, or at least 95, or at least 99 weight percent of the ethane and lighter compounds present in the r-pygas produced from the pyrolysis step and introduced into the liquification process are not liquified in the liquification process and exit the liquification process with the non-condensable gas. The pyrolysis facility can produce the r-LPyG in an amount by weight that is at least 1.5, or at least 2, or at least 5, or at least 10 times greater than the amount of the non-condensable gas produced.

As depicted in FIG. 1, after liquification, the r-LPyG can be readily stored and/or transported in a liquified state. Following storage and/or transportation, the r-LPyG can be further processed and/or used for its intended end use. Because the r-LPyG is readily storable and transportable (e.g., via railcar tanks, tank trucks, tanker ships, and/or pipelines), the end use facility for the r-LPyG can be located remotely from the pyrolysis facility where the r-pyoil, r-pygas, and/or r-LPyG are produced. For example, the processing and/or end use of the r-LPyG can be carried out at a facility or site that is at least 1, or at least 10, or at least 50, or at least 500, or at least 1000 miles from the location of the pyrolysis facility.

In an embodiment or in combination with any embodiment mentioned herein, there is provided a waste plastic pyrolysis facilities that (a) produces a pyrolysis effluent comprising r-pygas and a recycled content pyrolysis oil (r-pyoil), liquefying the r-pyas to produce r-LPyG, loading the r-LPyG to transportable container, and shipping the r-LPyG in the transportable container from the pyrolysis facility, wherein the r-LPyG is transported in a liquified state to a destination for at least 1, at least 10, at least 50, at least 100, at least 500, or at least 1000 miles. The container received at the destination may be the same container in which the r-LPyG was shipped from the pyrolysis facility, or may be a different container

In an embodiment or in combination with any embodiment mentioned herein, the r-LPyG storage and/or transportation step depicted in FIG. 1 can involve maintaining the r-LPyG in a liquified state for a continuous period of at least 1, or at least 2, or at least 4, or at least 8, or at least 12, or at least 24, or at least 36 hours. The r-LPyG can be maintained in a liquified state by keeping it cooled and/or pressurized. For example, the r-LPyG can be maintained at a temperature of less than 20, or less than 15, or less than 10, or less than 5, or less than 0° C. and/or a pressure of at least 1, or at least 1.25, or at least 1.5, or at least 2, or at least 3, or at least 4 barg.

In an embodiment or in combination with any embodiment mentioned herein, the apparatus in which the r-LPyG is stored and/or transported can be insulated, cooled, and/or pressurized. For example, the r-LPyG storage/transportation apparatus can be an insulated, cooled, and/or pressurized tank, conduit, and/or pipeline. The tank can be a stationary tank or a tank located on a rail car, truck, trailer, or ship. In one embodiment, after liquification, the r-LPyG is immediately loaded into a railcar tank that maintains the r-LPyG in a liquified state while it is transported via railway to the r-LPyG processing and/or end use site/facility. In another embodiment, the r-LPyG is immediately loaded into a relatively large stationary storage tank located at the pyrolysis facility, where the storage tank maintains the r-LPyG in a liquified state until one or more transportable tanks (e.g., on railcars, trucks, trailers, or ships) are ready to be loaded from the stationary storage tank. In yet another embodiment, the r-LPyG is immediately loaded into a stationary tank that maintains the r-LPyG in a liquified state until it is introduced into a pipeline or conduit for transport to the r-LPyG processing and/or end use site/facility.

In an embodiment or in combination with any embodiment mentioned herein, the r-LPyG processing and/or end use site/facility and the pyrolysis facility (including pyrolysis, separation, and/or liquification) can be co-located. When the facilities are co-located, the r-LPyG may not need to be maintained in a liquified state for as long or transported as far as when the facilities are located remotely from one another. However, even when the facilities are co-located, liquification of the r-pygas may be necessary to ensure, for example, that a consistent supply of r-LPyG is provided to the processing and/or end use facility. Such a consistent supply can be provided using an onsite storage tank(s) for maintaining relatively large volumes of the r-LPyG in a liquified state. These onsite storage tanks can ensure a consistent supply for r-LPyG, even if the rate of r-pygas produced by the pyrolysis facility fluctuates or has intermittent stoppages.

In an embodiment or in combination with any embodiment mentioned herein, the pyrolysis facility/process is a commercial scale facility/process receiving the waste plastic feedstock at an average annual feed rate of at least 100, or at least 500, or at least 1,000, or at least 2,000 pounds per hour, averaged over one year. Further, the pyrolysis facility can produce the r-oil and r-pygas in combination at an average annual rate of at least 100, or at least 1,000, or at least 5,000, at least 10,000, at least 50,000, or at least 75,0000 pounds per hour, averaged over one year.

In an embodiment or in combination with any embodiment mentioned herein, the r-LPyG processing and/or end use site/facility can be located remotely from the r-pyoil processing and/or end use site facility. In that case, the producer of the r-pyoil and the r-LPyG transports the r-pyoil and/or r-LPyG to different locations and/or different entities by different transportation routes.

Alternatively, the r-LPyG processing and/or end use site/facility can be co-located and/or co-owned with the r-pyoil processing and/or end use site/facility. In that case, the producer of the r-pyoil and the r-LPyG can transport the r-pyoil and/or r-LPyG to the same site/facility, possibly even using the same transportation mode. For example, both r-pyoil and r-LPyG could be transported using a single train, with certain railcars carrying tanks of r-pyoil and other railcars carrying tanks of r-LPyG.

As discussed in more detail below with reference to FIG. 5, in an embodiment or in combination with any embodiment mentioned herein, the processing and/or end use facilities receiving the r-LPyG and/or the r-pyoil can include a cracking facility used to produce chemicals such as olefins, which can then be used to produce a wide variety of chemical products. Thus, use of r-LPyG and/or the r-pyoil in a cracking facility can provide recycled content to a wide variety of chemical products.

FIG. 2 provides a more detailed view of the pyrolysis, separation, and liquefaction steps previously introduced with reference to FIG. 1. As shown in FIG. 2, the sorted waste plastic can initially be fed to a pyrolysis reactor. The pyrolysis reaction involves chemical and thermal decomposition of the sorted waste plastic. Although all pyrolysis processes may be generally characterized by a reaction environment that is substantially free of oxygen, pyrolysis processes may be further defined, for example, by the pyrolysis reaction temperature within the reactor, the residence time in the pyrolysis reactor, the reactor type, the pressure within the pyrolysis reactor, and the presence or absence of pyrolysis catalysts.

The pyrolysis reactor depicted in FIG. 2 can be, for example, a film reactor, a screw extruder, a tubular reactor, a tank, a stirred tank reactor, a riser reactor, a fixed bed reactor, a fluidized bed reactor, a rotary kiln, a vacuum reactor, a microwave reactor, or an autoclave.

The pyrolysis reaction can involve heating and converting the waste plastic feedstock in an atmosphere that is substantially free of oxygen or in an atmosphere that contains less oxygen relative to ambient air. For example, the atmosphere within the pyrolysis reactor may comprise not more than 5, not more than 4, not more than 3, not more than 2, not more than 1, or not more than 0.5 weight percent of oxygen.

The temperature in the pyrolysis reactor can be adjusted so as to facilitate the production of certain end products. In an embodiment or in combination with any embodiment mentioned herein, the peak pyrolysis temperature in the pyrolysis reactor can be at least 325° C., or at least 350° C., or at least 375° C., or at least 400° C. Additionally or alternatively, the peak pyrolysis temperature in the pyrolysis reactor can be not more than 800° C., not more than 700° C., or not more than 650° C., or not more than 600° C., or not more than 550° C., or not more than 525° C., or not more than 500° C., or not more than 475° C., or not more than 450° C., or not more than 425° C., or not more than 400° C. More particularly, the peak pyrolysis temperature in the pyrolysis reactor can range from 325 to 800° C., or 350 to 600° C., or 375 to 500° C., or 390 to 450° C., or 400 to 500° C.

The residence time of the feedstock within the pyrolysis reactor can be at least 1, or at least 5, or at least 10, or at least 20, or at least 30, or at least 60, or at least 180 seconds. Additionally, or alternatively, the residence time of the feedstock within the pyrolysis reactor can be less than 2, or less than 1, or less than 0.5, or less than 0.25, or less than 0.1 hours. More particularly, the residence time of the feedstock within the pyrolysis reactor can range from 1 second to 1 hour, or 10 seconds to 30 minutes, or 30 seconds to 10 minutes.

The pyrolysis reactor can be maintained at a pressure of at least 0.1, or at least 0.2, or at least 0.3 barg and/or not more than 60, or not more than 50, or not more than 40, or not more than 30, or not more than 20, or not more than 10, or not more than 8, or not more than 5, or not more than 2, or not more than 1.5, or not more than 1.1 barg. The pressure within the pyrolysis reactor can be maintained at atmospheric pressure or within the range of 0.1 to 60, or 0.2 to 10, or 0.3 to 1.5 barg.

The pyrolysis reaction in the reactor can be thermal pyrolysis, which is carried out in the absence of a catalyst, or catalytic pyrolysis, which is carried out in the presence of a catalyst. When a catalyst is used, the catalyst can be homogenous or heterogeneous and may include, for example, certain types of zeolites and other mesostructured catalysts.

In the embodiment depicted in FIG. 2, the pyrolysis effluent exiting the pyrolysis reactor can be subjected to separation in a fractionation column and a separator S5. As depicted in FIG. 2, the pyrolysis effluent fed to the fractionation column can be separated into a residual oil/heavy wax fraction, a heavy pyoil fraction, a light pyoil fraction, and an overhead vapor. The overhead vapor from the fractionation column can be fed to separator S5 which separates it into a liquid naphtha fraction and a gaseous r-pygas fraction. At least a portion of the liquid naphtha exiting separator S5 can be introduced as reflux into an upper inlet of the fractionation column.

In an embodiment or in combination with any embodiment mentioned herein, the r-pygas exiting the top of separator S5 can have the composition shown below in Table 1.

TABLE 1

r-Pygas Composition

End Points
Ranges

Component
Units
More than . . .
Less than . . .
Broad
Middle
Narrow

C1-C5
Wt. %
50, 75, 90, 95
99.9, 99.5, 99, 98
50-99.99
75-99.5
90-99

C1-C2
Wt. %
0.0, 0.01, 0.1, 1, 5
40, 30, 20, 15
0.01-40
1-30
5-20

Ethane and
Liq.
0.0, 0.01, 1, 2, 4
20, 10, 5, 4, 2
0-20
0.1-10
2-5

Lighter
Vol. %

C2-C4
Wt. %
25, 50, 75, 80
99, 98, 95, 90

25-99
50-98
75-95

C3-C5
Wt. %
50, 60, 70, 80, 90, 95
99.9, 99.5, 99, 98,
50-99.5
80-99
90-98

97, 96, 95

C5+
Wt. %
0.0, 0.01, 0.1, 0.5, 1
50, 25, 10, 5, 1
0.01-50
0.1-25
0.5-5

C6+
Wt. %
0.0, 0.01, 0.1, 0.5, 1
25, 10, 5, 1, 0.05
0.0-25
0.01-5
0.5-1

C2
Wt. %
0.01, 0.1, 1, 5
40, 30, 20, 15
0.01-40
1-30
5-20

C3
Wt. %
1, 10, 20, 30
99, 80, 60, 50
0.1-80
10-40
30-50

C4
Wt. %
1, 5, 15, 20
95, 75, 50, 40
1-95
5-75
15-40

C5
Wt. %
0.1, 1, 2, 5
90, 50, 25, 15
0.1-90
1-20
2-25

Methane
Wt. %
0.0, 0.01, 0.1, 1, 2
20, 10, 5, 1
0-20
0.1-10
1-5

Ethane
Wt. %
0.01, 0.1, 1, 5
40, 30, 20, 15
0.01-40
1-30
5-20

Ethylene
Wt. %
0.01, 0.1, 0.5, 1
50, 25, 10, 5
0.01-50
0.1-25
0.5-10

Propane
Wt. %
0.01, 0.1, 1, 5
50, 40, 30, 20
0.01-50
1-30
5-20

Propylene
Wt. %
0.5, 1, 5, 15, 20
95, 75, 50, 40
0.5-95
5-75
15-40

Butanes
Wt. %
0.1, 1, 2, 5
90, 50, 25, 15
0.1-90
1-20
2-25

Butylenes
Wt. %
0.0, 0.01, 0.1, 1, 5
30, 15, 10, 5
0.01-30
0.1-15
0.5-5

Butenes
Wt. %
0.0, 0.01, 0.1, 1, 5
50, 40, 30, 25
0.01-50
1-40
5-25

Butadienes
Wt. %
0.0, 0.001, 0.01, 0.1, 1
10, 1, 0.1, .01
0-10
0-1
0.001-0.1

Pentanes
Wt. %
0.0, 0.1, 1, 2, 5
90, 50, 25, 15
0.1-90
1-20
2-25

Pentenes
Wt. %
0.0, 0.001, 0.01, 0.1, 1
20, 10, 5, 1
0-20
0-10
0.01-5

Pentadienes
Wt. %
0.0, 0.001, 0.01, 0.1, 1
10, 1, 0.1, .01
0-10
0-1
0.001-0.1

Alkanes
Wt. %
10, 20, 30, 40
80, 70, 60, 50

10-80
20-70
30-60

Hydrogen
Wt. %
0.0, 0.001, 0.01, 0.1, 1
10, 1, 0.1, 0.01
0-10
0-1
0.001-0.1

H2O
Wt. %
0.0, 0.001, 0.01, 0.025
5, 2, 1, 0.1, 0.01
0.0-5
0.0-1
0.001-0.1

CO
ppmw
0.0, 0.05, 0.1, 0.5, 1
50, 10, 5, 1, 0.5
0.0-50
0.05-5
0.5-1

CO2
ppmw
0.0, 0.1, 0.5, 1, 1.5, 2
100, 50, 25, 5, 1
0.0-100
0.1-25
1-5

COx
ppmw
0.0, 0.1, 0.5, 1, 1.5, 2
200, 75, 10, 5, 1
0.0-200
0.1-75
1.5-10

Total Org.
ppmw
0.0, 0.1, 0.5, 1, 1.5, 2
100, 50, 25, 5, 1
0.0-100
0.1-25
1-5

Oxygenates

Total Sulfur
ppmw
0.0, 0.001, 0.01, 0.025,
200, 100, 50, 25, 15,
0.0-200
0.001-50
0.025-15

(ppmw)

0.05
5

Arsine
ppbw
0.0
1000, 400, 200, 100
—
—
—

Total
ppmw
0.0
100, 50, 20, 10, 5
—
—
—

Nitrogen

Nitrogen as
ppmw
0.0
100, 50, 25, 15, 5
—
—
—

N2

Methyl
ppmw
0.0
100, 50, 20, 10, 5
—
—
—

Acetate

Propadiene
ppmw
0.0
100, 50, 20, 10, 5
—
—
—

Methanol
ppmw
0.0
50, 25, 10, 5, 1
—
—
—

Total
ppmw
0.0
50, 25, 10, 5, 1
—
—
—

Chlorine

Oxygen as
ppmw
0.0
50, 25, 10, 5, 1
—
—
—

O2

As used herein, the term “Cx” or “Cx hydrocarbon,” refers to a hydrocarbon compound including “x” total carbons per molecule, and encompasses all olefins, paraffins, aromatics, heterocyclic, and isomers having that number of carbon atoms. For example, each of normal, iso, and tert-butane and butene and butadiene molecules would fall under the general description “C4.”

It should be noted that the separation scheme (i.e., the fractionation column and separator S5) depicted in FIG. 2 is just one example of a scheme for separating the pyrolysis effluent into useful fractions. Other separation schemes can be implemented depending on the circumstances.

As shown in FIG. 2, the r-pygas can be liquified by subjecting it to one or more compression steps/stages (e.g. CS1, CS2, and CS3), one or more cooling steps (e.g., C1, C2, and C3), one or more separation steps (e.g., S1, S2, and S3), and one or more pumping steps (e.g., P1, P2, and P3).

Although FIG. 2 illustrates three compression steps/stages, the number of compression stages can range from 1 to 15, or from 2 to 10, or from 3 to 6. Each compression stage can provide a pressure increase such that the outlet pressure of each stage is 1.5 to 3.5, or 1.75 to 3.0, or 2 to 2.5 times greater than the inlet pressure of the stage.

In an embodiment or in combination with any embodiment mentioned herein, the inlet pressure to compressor stage CS1 can be 1 to 4, or 1.1 to 2.5, or 1.2 to 1.8 barg; the outlet pressure of compressor stage CS1 and the inlet pressure to CS2 can be 2.0 to 6.0, or 3.0 to 4.0, or 3.2 to 3.8 barg; the outlet pressure of compressor stage CS2 and the inlet pressure to CS3 can be 6 to 12, or 7 to 11, or 8 to 10 barg; and the outlet pressure from compressor stage CS3 can be 15 to 35, 18 to 28, or 20 to 25 barg.

The cooling carried out after each compression stage can be sufficient to cause at least a portion of the effluent from the preceding compression stage to condense. Such cooling can be carried out using indirect heat exchange with a cooling fluid (such as cooling water) in heat exchangers C1, C2, and C3.

As shown in FIG. 2, the cooled streams exiting heat exchangers C1, C2, and C3 can then be subjected to vapor liquid in separators S1, S2, and S3, respectively. The separated vapors from the tops of separators S1 and S2 are fed to compression stages CS2 and CS3, respectively. The separated vapors from the top of separator S3 comprises non-condensable gas. The separated liquids from the bottoms of separators S1, S2, and S3 are pumped via pumps P1, P2, and P3, respectively, to a r-LPyG storage and/or transportation apparatus.

FIG. 3 shows a pyrolysis and r-pygas liquification process and system similar to the one depicted in FIG. 2, however the system of FIG. 3 includes self-refrigeration to enhance recovery of C3-C5 compounds in the r-LpyG. Specifically, the embodiment depicted in FIG. 3 takes a portion of the liquid effluent from pump P3 and routes it through an expander E1, where its pressure is reduced and it is cooled. The resulting cooled stream from expander E1 is then used in heat exchanger C3 to cool the compressed fluid discharged from compression stage CS3. In this way, a portion of compressed fluid discharged from compression stage CS3 is used for self-refrigeration in heat exchanger C3. The stream from expander E1 used to cool the fluid discharged from compression stage CS3 is heated in the heat exchanger C3 and then routed to the separator S5.

FIG. 4 shows a pyrolysis and r-pygas liquification process and system similar to the ones depicted in FIGS. 2 and 3, however the system of FIG. 4 includes absorption and self-refrigeration to enhance recovery of C3-C5 compounds in the r-LpyG.

The initial steps of the system depicted in FIG. 4 can be the same as those depicted in FIGS. 2 and 3. However, in FIG. 4, the overhead vapor stream from separator S3, which can be referred to as a “wet gas,” is be fed to an absorber for recovery of C2-C5 components present in the wet gas. A light pyoil stream, described in further detail below, is fed to an upper inlet of the absorber for use as the absorption liquid. In the absorber, the downwardly flowing liquid light pyoil contacts the upwardly flowing wet gas and the liquid light pyoil absorbs C2-C5 components from the wet gas. A liquid rich oil stream containing the absorbed C2-C5 component exits a bottom outlet of the absorber, while a dry gas stream exits a top outlet of the absorber.

The rich oil stream exiting the bottom of the absorber is pumped by pump P4 to an expander E1, where its pressure is let down to cause cooling of the rich oil stream. From expander E1, the cooled rich oil stream is fed to a pyoil recovery column, which separates the cooled rich oil stream from expander E1 into a liquid light pyoil stream and an overhead vapor stream. The liquid light pyoil stream exits a bottom outlet of the pyoil recovery column and is then pumped via a pump P5 to the upper inlet of the absorber for use as the absorption liquid. In certain embodiments, all or part of the naphtha and light pyoil streams produced by the separation system (e.g., fractionation column and separator S5) immediately downstream of the pyrolysis reactor can be used as all or part of the absorption liquid fed to the upper inlet of the absorption column.

The overhead vapor stream exiting the pyoil recovery column is sequentially cooled in heat exchangers C4 (via cooling water), C5 (via expanded non-condensable gas), and C6 (via expanded r-LPyG) to thereby cause condensing of at least a portion of the overhead stream. The resulting cooled stream is supplied to a separator S4 for separation into a dry gas stream and a liquid stream comprising C2-C5 components. The liquid stream exiting the separator S4 then passes to a pump P6. The pump P6 pumps a first portion of the liquid stream to the r-LPyG storage and/or transportation apparatus (e.g., tank or pipeline). A second portion of the liquid stream exiting the pump P6 can be passed through an expander E4, where its pressure is let down and it is cooled. The cooled stream from expander E4 is then used in heat exchanger C6 to cool the overhead stream from the pyoil recovery column.

The non-condensable dry gas exiting the upper outlet of the absorber is passed through an expander E2, where its pressure is reduced to cause cooling of the non-condensable gas stream. The cooled non-condensable gas from expander E2 is then passed through the heat exchanger C5 and used to cool the vapor stream exiting the overhead of the pyoil recovery column. After being warmed in the heat exchanger C5, the non-condensable (“NC Gas in FIG. 4) gas can exit the process, or all or part of the NC gas can be used as fuel to provide heat for the pyrolysis reaction.

In an embodiment or in combination with any embodiment mentioned herein, the systems depicted in FIGS. 2-4 can produce a r-LPyG having a composition summarized in Table 2, below.

TABLE 2

Mixed r-LPyG Composition

End Points
Ranges

Component
Units
More than . . .
Less than . . .
Broad
Middle
Narrow

C1-C5
Wt. %
50, 75, 90, 95
99.9, 99.5, 99, 98
50-99.99
75-99.5
90-99

C1-C2
Wt. %
0.0, 0.01, 0.1, 1, 5
40, 30, 20, 15
0.01-40
1-30
5-20

Ethane and
Liq
0.0, 0.001, 0.01, 0.02,
10, 5, 2, 1, 0.5
0-10
0.001-5
0.02-2

Lighter
Vol. %
0.05

C2-C4
Wt. %
25, 50, 75, 80
99, 98, 95, 90

25-99
50-98
75-95

C3-C5
Wt. %
75, 90, 95, 97, 98, 99
99.99, 99.9, 99.5,
75-99.99
95-99.9

97-99.5

C5+
Wt. %
0.0, 0.01, 0.1, 0.5, 1
50, 25, 10, 5, 1
0.01-50
0.1-25
0.5-5

C6+
Wt. %
0.0, 0.01, 0.1, 0.5, 1
25, 10, 5, 1, 0.05
0.0-25
0.01-5
0.5-1

C2s
Wt. %
0.01, 0.1, 1, 5
40, 30, 20, 15
0.01-40
1-30
5-20

C3s
Wt. %
1, 10, 20, 30
99, 80, 60, 50
0.1-80
10-40
30-50

C4s
Wt. %
1, 5, 15, 20
95, 75, 50, 40
1-95
5-75
15-40

C5s
Wt. %
0.1, 1, 2, 5
90, 50, 25, 15
0.1-90
1-20
2-25

Methane
Wt. %
0.0, 0.001, 0.01, 0.1, 1
10, 1, 0.1, .01
0-10
0-1
0.001-0.1

Ethane
Wt. %
0.01, 0.1, 1, 5
40, 30, 20, 15
0.01-40
1-30
5-20

Ethylene
Wt. %
0.01, 0.1, 0.5, 1
50, 25, 10, 5
0.01-50
0.1-25
0.5-10

Propane
Wt. %
0.01, 0.1, 1, 5
50, 40, 30, 20
0.01-50
1-30
5-20

Propylene
Wt. %
0.5, 1, 5, 15, 20
95, 75, 50, 40
0.5-95
5-75
15-40

Butanes
Wt. %
0.1, 1, 2, 5
90, 50, 25, 15
0.1-90
1-20
2-25

Butylenes
Wt. %
0.0, 0.01, 0.1, 1, 5
30, 15, 10, 5
0.01-30
0.1-15
0.5-5

Butenes
Wt. %
0.0, 0.01, 0.1, 1, 5
50, 40, 30, 25
0.01-50
1-40
5-25

Butadienes
Wt. %
0.0, 0.001, 0.01, 0.1, 1
10, 1, 0.1, .01
0-10
0-1
0.001-0.1

Pentanes
Wt. %
0.0, 0.1, 1, 2, 5
90, 50, 25, 15
0.1-90
1-20
2-25

Pentenes
Wt. %
0.0, 0.001, 0.01, 0.1, 1
20, 10, 5, 1
0-20
0-10
0.01-5

Pentadienes
Wt. %
0.0, 0.001, 0.01, 0.1, 1
10, 1, 0.1, .01
0-10
0-1
0.001-0.1

Alkanes
Wt. %
10, 20, 30, 40
80, 70, 60, 50

10-80
20-70
30-60

Hydrogen
Wt. %
0.0, 0.001, 0.01, 0.1, 1
10, 1, 0.1, .01
0-10
0-1
0.001-0.1

H2O
Wt. %
0.0, 0.001, 0.01, 0.025
5, 2, 1, 0.1, 0.01
0.0-5
0.0-1
0.001-0.1

CO
ppmw
0.0, 0.05, 0.1, 0.5, 1
50, 10, 5, 1, 0.5
0.0-50
0.05-5
0.5-1

CO2
ppmw
0.0, 0.1, 0.5, 1, 1.5, 2
100, 50, 25, 5, 1
0.0-100
0.1-25
1-5

COx
ppmw
0.0, 0.1, 0.5, 1, 1.5, 2
200, 75, 10, 5, 1
0.0-200
0.1-75
1.5-10

Total Org.
ppmw
0.0, 0.1, 0.5, 1, 1.5, 2
100, 50, 25, 5, 1
0.0-100
0.1-25
1-5

Oxygenates

Total Sulfur
ppmw
0.0, 0.001, 0.01, 0.025,
200, 100, 50, 25, 15,
0.0-200
0.001-50
0.025-15

(ppmw)

0.05
5

Arsine
ppbw
0.0
1000, 400, 200, 100
—
—
—

Total
ppmw
0.0
100, 50, 20, 10, 5
—
—
—

Nitrogen

Nitrogen as
ppmw
0.0
100, 50, 25, 15, 5
—
—
—

N2

Methyl
ppmw
0.0
100, 50, 20, 10, 5
—
—
—

Acetate

Propadiene
ppmw
0.0
100, 50, 20, 10, 5
—
—
—

Methanol
ppmw
0.0
50, 25, 10, 5, 1
—
—
—

Total
ppmw
0.0
50, 25, 10, 5, 1
—
—
—

Chlorine

Oxygen as
ppmw
0.0
50, 25, 10, 5, 1
—
—
—

O2

FIG. 5 illustrates an embodiment where the r-LPyG is provided as a feed to an existing or newly built cracking facility. The cracking facility depicted in FIG. 5 includes a cracker feed that is subjected to cracking in a cracker furnace to produce a cracked effluent. The cracked effluent is then subjected to a quench process to produce a quenched effluent. The quenched effluent is subjected to compression and then separation. The separation can be accomplish using a number of different columns/fractionators for separating the stream from the compressor into an r-C5+ stream, an r-ethylene stream, an r-propylene stream, an r-C4 stream, and an r-propane stream.

The cracking facility depicted in FIG. 5 can be located remotely relative to the waste plastic pyrolysis and r-LPyG production facilities described. Alternatively, the cracking facility depicted in FIG. 5 can be co-located with the waste plastic pyrolysis and r-LPyG production facilities described above.

As illustrated in FIG. 5, the r-LPyG transported to the cracking facility can undergo optional treatment prior to being fed to the cracking facility. Alternatively, the r-LPyG can be fed from the r-LPyG storage and/or transportation apparatus (e.g., railcar tank or pipeline) directly to the cracking facility without requiring any additional treatment.

FIG. 5 shows that the r-LPyG can be introduced into the cracker facility in a variety of locations. Generally, however, the r-LPyG will be introduced downstream of the cracker furnace(s) and upstream of the final fractionator/column in the separation section.

Feeding the r-LPyG to the cracker facility allows for recycled content from the r-LPyG to be supplied to the various products of the cracking facility, such as r-ethylene, r-propylene, and r-C5+ compounds. In addition, the r-propane, and optionally the r-C4, present in the r-LPyG can be separated in the separation section combined with the main feed to the cracker furnace, thereby providing recycled content to the cracker feed.

EXAMPLE

In this example, computer modeling is used to simulate a process and system for liquifying recycled content pyrolysis gas (r-pygas). FIG. 6 illustrates the equipment and lines of the r-pygas liquification system, as well as the temperature, pressure, mass flow rate, and molar vapor fraction for each stream. In FIG. 6, C1, C2, C3, and C4 are compressors; E1, E2, E3, and E4 are heat exchangers; and F1, F2, F3 and F4 are vapor/liquid separators.

The below table provides property and composition details for each of the liquid streams (L1-L4) and vapor streams (V1-V4) shown in FIG. 6.

TABLE 3

Simulation Results for 4-Stage Liquification of r-Pygas (See FIG. 6)

r-LPyG

L1 + L2 +

Stream
—
r-Pygas
L1
L2
L3
L4
L3 + L4
V1
V2
V3
V4

Phase
—
Vap
Liq
Liq
Liq
Liq
Liq
Vap
Vap
Vap
Vap

Temp
F.
120
99
99
99
99
—
99
99
99
99

Press
psia
19.7
255
505
755
1005
—
254
504
755
1005

Mass
lb/hr
100
51.9
22.7
6.8
3.1
84.5
Wt. %
48.1
25.4
15.5
18.6

Flows

Hydrogen
lb/hr
0.2
0.0
0.0
0.0
0.0
0.0
0.0%
0.2
0.2
0.2
0.2

Methane
lb/hr
4.2
0.3
0.5
0.3
0.2
1.3
1.5%
3.9
3.4
2.9
3.1

Ethane
lb/hr
11.3
2.8
2.7
1.1
0.6
7.3
8.6%
8.5
5.8
4.0
4.6

Ethylene
lb/hr
3.9
0.8
0.8
0.4
0.2
2.2
2.6%
3.1
2.3
1.7
1.9

Propane
lb/hr
17.3
8.2
4.8
1.5
0.6
15.1
17.9%
9.1
4.3
2.2
2.8

Propylene
lb/hr
24.3
10.9
6.7
2.1
0.9
20.8
24.6%
13.4
6.7
3.6
4.5

Isobutane
lb/hr
8.2
5.5
1.9
0.4
0.1
7.9
9.4%
2.7
0.8
0.3
0.4

Butane
lb/hr
0.0
0.0
0.0
0.0
0.0
0.0
0.0%
0.0
0.0
0.0
0.0

Propadiene
lb/hr
0.0
0.0
0.0
0.0
0.0
0.0
0.0%
0.0
0.0
0.0
0.0

Acetylene
lb/hr
0.0
0.0
0.0
0.0
0.0
0.0
0.0%
0.0
0.0
0.0
0.0

T2-Butene
lb/hr
8.2
5.9
1.7
0.3
0.1
8.0
9.5%
2.2
0.6
0.2
0.3

1-Butene
lb/hr
10.2
7.0
2.2
0.5
0.2
9.8
11.7%
3.2
0.9
0.3
0.5

Isobutene
lb/hr
1.0
0.7
0.2
0.0
0.0
1.0
1.1%
0.3
0.1
0.0
0.0

C2-Butene
lb/hr
0.0
0.0
0.0
0.0
0.0
0.0
0.0%
0.0
0.0
0.0
0.0

Pentane
lb/hr
7.6
6.6
0.9
0.1
0.0
7.6
9.0%
1.0
0.1
0.0
0.0

1:3-BD
lb/hr
0.0
0.0
0.0
0.0
0.0
0.0
0.0%
0.0
0.0
0.0
0.0

M-Acetyl
lb/hr
0.4
0.2
0.1
0.0
0.0
0.4
0.4%
0.2
0.1
0.0
0.1

Pentenes
lb/hr
0.6
0.5
0.1
0.0
0.0
0.6
0.7%
0.1
0.0
0.0
0.0

Pentadiene
lb/hr
0.0
0.0
0.0
0.0
0.0
0.0
0.0%
0.0
0.0
0.0
0.0

CyclC5DI
lb/hr
0.0
0.0
0.0
0.0
0.0
0.0
0.0%
0.0
0.0
0.0
0.0

N-Hex-01
lb/hr
2.6
2.5
0.1
0.0
0.0
2.6
3.1%
0.1
0.0
0.0
0.0

CO2
lb/hr
0.0
0.0
0.0
0.0
0.0
0.0
0.0%
0.0
0.0
0.0
0.0

Hydro-01
lb/hr
0.0
0.0
0.0
0.0
0.0
0.0
0.0%
0.0
0.0
0.0
0.0

CO
lb/hr
0.0
0.0
0.0
0.0
0.0
0.0
0.0%
0.0
0.0
0.0
0.0

H2O
lb/hr
0.0
0.0
0.0
0.0
0.0
0.0
0.0%
0.0
0.0
0.0
0.0

Table 3 shows, for example, that the system depicted in FIG. 6 is effective to condense a substantial portion of the C3-C5 hydrocarbons to produce the r-LPyG, while a substantial portion of the ethane and lighter components exit the process as vapor (e.g., the non-condensable/dry gas).

Definitions

It should be understood that the following is not intended to be an exclusive list of defined terms. Other definitions may be provided in the foregoing description, such as, for example, when accompanying the use of a defined term in context.

As used herein, the terms “a,” “an,” and “the” mean one or more.

As used herein, the term “and/or,” when used in a list of two or more items, means that any one of the listed items can be employed by itself or any combination of two or more of the listed items can be employed. For example, if a composition is described as containing components A, B, and/or C, the composition can contain A alone; B alone; C alone; A and B in combination; A and C in combination, B and C in combination; or A, B, and C in combination.

As used herein, the phrase “at least a portion” includes at least a portion and up to and including the entire amount or time period.

As used herein, the term “chemical pathway” refers to the chemical processing step or steps (e.g., chemical reactions, physical separations, etc.) between an input material and a product material, where the input material is used to make the product material.

As used herein, the term “chemical recycling” refers to a waste plastic recycling process that includes a step of chemically converting waste plastic polymers into lower molecular weight polymers, oligomers, monomers, and/or non-polymeric molecules (e.g., hydrogen, carbon monoxide, methane, ethane, propane, ethylene, and propylene) that are useful by themselves and/or are useful as feedstocks to another chemical production process(es).

As used herein, the term “co-located” refers to the characteristic of at least two objects being situated on a common physical site, and/or within one mile of each other.

As used herein, the term “commercial scale facility” refers to a facility having an average annual feed rate of at least 500 pounds per hour, averaged over one year.

As used herein, the terms “comprising,” “comprises,” and “comprise” are open-ended transition terms used to transition from a subject recited before the term to one or more elements recited after the term, where the element or elements listed after the transition term are not necessarily the only elements that make up the subject.

As used herein, the term “cracking” refers to breaking down complex organic molecules into simpler molecules by the breaking of carbon-carbon bonds.

As used herein, the terms “credit-based recycled content,” “non-physical recycled content,” and “indirect recycled content” all refer to matter that is not physically traceable back to a waste material, but to which a recycled content credit has been attributed.

As used herein, the term “directly derived” refers to having at least one physical component originating from waste material.

As used herein, the terms “including,” “include,” and “included” have the same open-ended meaning as “comprising,” “comprises,” and “comprise” provided above.

As used herein, the term “indirectly derived” refers to having an applied recycled content (i) that is attributable to waste material, but (ii) that is not based on having a physical component originating from waste material.

As used herein, the term “located remotely” refers to a distance of at least 0.1, 0.5, 1, 5, 10, 50, 100, 500, or 1000 miles between two facilities, sites, or reactors.

As used herein, the term “mass balance” refers to a method of tracking recycled content based on the mass of the recycled content in various materials.

As used herein, the terms “physical recycled content” and “direct recycled content” both refer to matter that is physically traceable back to a waste material.

As used herein, the term “predominantly” means more than 50 percent by weight. For example, a predominantly propane stream, composition, feedstock, or product is a stream, composition, feedstock, or product that contains more than 50 weight percent propane.

As used herein, the term “pyrolysis” refers to thermal decomposition of one or more organic materials at elevated temperatures in an inert (i.e., substantially oxygen free) atmosphere.

As used herein, the terms “pyrolysis gas” and “pygas” refer to a composition obtained from pyrolysis that is gaseous at 25° C.

As used herein, the terms “pyrolysis oil” or “pyoil” refers to a composition obtained from pyrolysis that is liquid at 25° C. and 1 atm.

As used herein, the term “pyrolysis residue” refers to a composition obtained from pyrolysis that is not pyrolysis gas or pyrolysis oil and that comprises predominantly pyrolysis char and pyrolysis heavy waxes.

As used herein, the term “recycled content” refers to being or comprising a composition that is directly and/or indirectly derived from recycled material. Recycled content is used generically to refer to both physical recycled content and credit-based recycled content. Recycled content is also used as an adjective to describe material having physical recycled content and/or credit-based recycled content.

As used herein, the term “recycled content credit” refers to a non-physical measure of physical recycled content that can be directly or indirectly (i.e., via a digital inventory) attributed from a first material having physical recycled content to a second material having less than 100 percent physical recycled content.

As used herein, the term “total recycled content” refers to the cumulative amount of physical recycled content and credit-based recycled content from all sources.

As used herein, the term “waste material” refers to used, scrap, and/or discarded material.

As used herein, the terms “waste plastic” and “plastic waste” refer to used, scrap, and/or discarded plastic materials.

Additional Claim Supporting Description—First Embodiment

In a first embodiment of the present technology there is provided a process producing a readily storable and transportable light hydrocarbon feedstock having recycled content from waste plastic, where the process comprises the following steps: (a) pyrolyzing waste plastic to thereby produce a recycled content pyrolysis gas (r-pygas); (b) liquifying at least a portion of the r-pygas to thereby provide a recycled content liquified pyrolysis gas (r-LPyG), wherein the liquifying is carried out using a method comprising compression, cooling, or compression and cooling of the r-pygas; and (c) maintaining at least a portion of the r-LPyG in a liquified state during storing, transporting, or storing and transporting of the r-LPyG.

The first embodiment described in the preceding paragraph can also include one or more of the additional aspects/features listed in the following bullet pointed paragraphs. Each of the below additional features of the first embodiment can be standalone features or can be combined with one or more of the other additional features to the extent consistent. Additionally, the following bullet pointed paragraphs can be viewed as dependent claim features having levels of dependency indicated by the degree of indention in the bulleted list (i.e., a feature indented further than the feature(s) listed above it is considered dependent on the feature(s) listed above it).

- wherein the pyrolyzing of step (a) produces a pyrolysis effluent comprising the r-pygas and a recycled content pyrolysis oil (r-pyoil), wherein the process further comprises separating the r-pygas and the r-pyoil.
  - further comprising transporting the r-LPyG in a liquified state for a distance of at least 1, 10, 50, 100, 500, or 1000 miles and/or optionally transporting the r-pyoil in a liquid state for a distance of at least 1, 10, 50, 100, 500, or 1000 miles.
    - wherein the r-LPyG and r-pyoil are transported to two different facilities spaced from one another by at least 1, 10, 50, 100, 500, or 1000 miles.
    - wherein the r-LPyG and r-pyoil are transported to the same facility.
  - further comprising transporting one of the r-pygas and r-pyoil a longer distance of at least 1, 10, 50, 100, 500, or 1000 miles for use in a remote facility and transporting the other of the pygas and r-pyoil a shorter distance of not more than 1, 0.5, 0.25, or 0.1 miles for use in a co-located facility.
    - wherein the co-located facility receives the r-pyoil and the remote facility receives the r-LPyG.
- wherein the pyrolyzing converts 0.5 to 50, 1 to 40, 2 to 30, or 4 to 25 weight percent of the waste plastic to the r-pygas.
  - wherein the pyrolyzing converts 30 to 95, 40 to 90, 50 to 80, or 55 to 75 weight percent of the waste plastic to a recycled content pyrolysis oil (r-pyoil).
- wherein the pyrolyzing is carried out at a peak pyrolysis temperature of 325 to 800° C., 350 to 600° C., 375 to 500° C., 390 to 450° C., or 400 to 500° C.
  - wherein the pyrolyzing is thermal pyrolysis carried out in the substantial absence of a catalyst.
  - wherein the pyrolyzing is catalytic pyrolysis carried out in the presence of a catalyst.
  - wherein the pyrolyzing is carried out at a pressure of 0.1 to 60 barg, 0.2 to 10 barg, or 0.3 to 1.5 barg and a residence time of 1 second to 1 hour, 10 seconds to 30 minutes, or 30 seconds to 10 minutes.
- further comprising using at least a portion of the r-pygas as fuel for the pyrolyzing of step (a).
  - further comprising reducing or eliminating use of the r-pygas as fuel for the pyrolyzing of step (a) and then commencing or increasing the rate of the r-pygas liquifying of step (b).
- wherein the liquifying of step (b) includes subjecting the r-pygas to 1 to 15, 2 to 10, or 3 to 6 compression steps.
  - wherein each compression step is followed by a cooling step.
    - wherein each cooling step is followed by a vapor/liquid separation step.
      - wherein the r-LPyG comprises a combination of separated liquids recovered from at least 2, 3, 4, or all of the vapor/liquid separation steps.
- wherein the liquefying of step (b) liquefies at least 20, 30, 40, 50, 60, 80, 90, or 95 weight percent of the r-pygas produced in step (a).
- wherein the liquifying of step (b) liquefies at least 50, 60, 70, 80, 90, or 95 weight percent of at least one, two, three, four, five, six, or seven of the following r-pygas components:
  - i.) ethylene,
  - ii.) propane,
  - iii.) propylene,
  - iv.) butanes,
  - v.) butenes,
  - vi.) pentanes, and/or
  - vii.) pentenes.
- wherein the liquifying of step (b) liquefies less than 75, 50, 25, 10, 5, or 1 weight percent of at least one, two, three, four, or five of the following r-pygas components:
  - i.) hydrogen,
  - ii.) methane,
  - iii.) ethane,
  - iv.) CO, and/or
  - v.) CO2.
- wherein the liquifying of step (b) liquefies at least 50, 75, 90, 95, or 99 weight percent of each of the propane, propylene, butane, and butenes in the r-pygas.
  - wherein the liquifying of step (b) liquefies less than 25, 10, 5, 1, or 0.1 weight percent of each of the hydrogen, methane, CO, and CO2 in the r-pygas.
- further comprising recovering a non-condensable gas that originates from the r-pygas and has been subjected to the liquifying of step (b), but is not liquified by the liquifying of step (b).
  - wherein the liquifying of step (b) produces the r-LPyG in an amount by weight that is at least 1.5, 2, 5, or 10 times greater than the amount by weight of the non-condensable gas produced.
  - further comprising using at least a portion of the recovered non-condensable gas as fuel to provide heat for the pyrolyzing of step (a).
  - wherein the non-condensable gas comprises ethane and lighter components in an amount of at least 25, 40, 50, 60, or 70 weight percent.
- wherein the maintaining of step (c) is carried out for a continuous period of at least 1, 2, 4, 8, 12, 24, or 36 hours.
- wherein the maintaining of step (c) includes continuously keeping the r-LPyG at a temperature of less than 20, 15, 10, 5, or 0° C. and/or a pressure of at least 1, 1.25, 1.5, 2, 3, or 4 barg.
- wherein the maintaining of step (c) includes storing the r-LPyG in liquified state for a continuous storage period of at least 1, 2, 4, 8, 12, 24, or 36 hours.
  - wherein said storing is carried out in a storage apparatus that is insulated, cooled, and/or pressurized.
    - wherein the storage apparatus comprises a pressurized tank.
- wherein the maintaining of step (c) includes transporting the r-LPyG in a liquified state for a distance of at least of at least 1, 10, 50, 100, 500, or 1000 miles.
  - wherein the transporting is carried out in a transportation apparatus that is insulated, cooled, and/or pressurized.
    - wherein the transportation apparatus comprises a pressurized tank and/or pressurized pipeline.
- wherein the maintaining of step (c) includes storing the r-LPyG in liquified state for a continuous storage period of at least 1, 2, 4, 8, 12, 24, or 36 hours and transporting the r-LPyG in a liquified state for a distance of at least of at least 1, 10, 50, 100, 500, or 1000 miles.
- wherein the r-pygas comprises at least 50, 75, 90, or 95 weight percent of C1-C5 compounds.
- wherein the r-pygas comprises at least 50, 60, 70, 80, 90 or 95 weight percent of C3-C5 compounds.
- wherein the r-pygas comprises less than 80, 50, 40, or 25 weight percent of C1-C2 compounds.
- wherein the r-pygas comprises less than 50, 25, 10, or 5 weight percent of C6+ compound.
- wherein the r-pygas exhibits at least one, two, three, four, or all five of the following characteristics:
  - i.) the r-pygas comprises 75 to 99.5 weight percent of C1-C5 compounds,
  - ii.) the r-pygas comprises 50 to 98 weight percent of C2-C4 compounds,
  - iii.) the r-pygas comprises 1 to 40 weight percent of C2 compounds,
  - iv.) the r-pygas comprises 10 to 60 weight percent of C3 compounds, and/or
  - v.) the r-pygas comprises 5 to 75 weight percent of C4 compounds.
- wherein the r-pygas exhibits at least one, two, three, four, five, six, seven, eight, nine, ten, eleven, twelve, thirteen, fourteen, or all fifteen of the following characteristics:
  - i.) the r-pygas comprises 0.1 to 10 weight percent of methane,
  - ii.) the r-pygas comprises 1 to 30 weight percent of ethane,
  - iii.) the r-pygas comprises 0.1 to 25 weight percent of ethylene,
  - iv.) the r-pygas comprises 1 to 30 weight percent of propane,
  - v.) the r-pygas comprises 5 to 75 weight percent of propylene,
  - vi.) the r-pygas comprises 1 to 20 weight percent of butanes,
  - vii.) the r-pygas comprises 0.1 to 15 weight percent of butylenes,
  - viii.) the r-pygas comprises 1 to 20 weight percent of pentanes,
  - ix.) the r-pygas comprises 0 to 10 weight percent of pentenes,
  - x.) the r-pygas comprises 0 to 1 weight percent of pentadienes,
  - xi.) the r-pygas comprises 0 to 1 weight percent of hydrogen,
  - xii.) the r-pygas comprises 0.05 to 5 ppmw of carbon monoxide,
  - xiii.) the r-pygas comprises 0.1 to 25 ppmw of carbon dioxide,
  - xiv.) the r-pygas comprises 0 to 1 ppmw of total sulfur, and/or
  - xv.) the r-pygas comprises 0 to 1 weight percent of water.
- wherein the r-LPyG comprises at least 50, 75, 90, or 95 weight percent of C1-C5 compounds.
- wherein the r-LPyG comprises at least 25, 50, 75, or 80 weight percent of C2-C4 compounds.
- wherein the r-LPyG comprises less than 60, 40, 20, or 15 weight percent of C1-C2 compounds.
- wherein the r-LPyG comprises less than 50, 25, 10, or 5 weight percent of C6+ compound.
- wherein the r-LPyG exhibits at least one, two, three, four, or all five of the following characteristics:
  - i.) the r-LPyG comprises 75 to 99.5 weight percent of C1-C5 compounds,
  - ii.) the r-LPyG comprises 50 to 98 weight percent of C2-C4 compounds,
  - iii.) the r-LPyG comprises 1 to 30 weight percent of C2 compounds,
  - iv.) the r-LPyG comprises 10 to 60 weight percent of C3 compounds, and/or
  - v.) the r-LPyG comprises 5 to 75 weight percent of C4 compounds.
- wherein the r-LPyG exhibits at least one, two, three, four, five, six, seven, eight, nine, ten, eleven, twelve, thirteen, fourteen, or all fifteen of the following characteristics:
  - i.) the r-LPyG comprises 0.1 to 1 weight percent of methane,
  - ii.) the r-LPyG comprises 1 to 30 weight percent of ethane,
  - iii.) the r-LPyG comprises 0.1 to 25 weight percent of ethylene,
  - iv.) the r-LPyG comprises 1 to 30 weight percent of propane,
  - v.) the r-LPyG comprises 5 to 75 weight percent of propylene,
  - vi.) the r-LPyG comprises 1 to 20 weight percent of butanes,
  - vii.) the r-LPyG comprises 0.1 to 15 weight percent of butylenes,
  - viii.) the r-LPyG comprises 1 to 20 weight percent of pentanes,
  - ix.) the r-LPyG comprises 0 to 10 weight percent of pentenes,
  - x.) the r-LPyG comprises 0 to 1 weight percent of pentadienes,
  - xi.) the r-LPyG comprises 0 to 1 weight percent of hydrogen,
  - xii.) the r-LPyG comprises 0.05 to 5 ppmw of carbon monoxide,
  - xiii.) the r-LPyG comprises 0.1 to 25 ppmw of carbon dioxide,
  - xiv.) the r-LPyG comprises 0.001 to 50 ppmw of total sulfur, and/or
  - xv.) the r-LPyG comprises 0 to 1 weight percent of water.
- wherein the r-LPyG exhibits at least one, two, three, four, five, six, seven, eight, nine, ten, eleven, twelve, thirteen, fourteen, fifteen, or all sixteen of the following characteristics:
  - i.) the r-LPyG comprises at least 97 weight percent of C3-C5 compounds,
  - ii.) the r-LPyG comprises less than 2 liquid volume percent of ethane and lighter components,
  - iii.) the r-LPyG comprises less than 1 weight percent of C6+ compounds,
  - iv.) the r-LPyG comprises less than 1 ppmw of CO,
  - v.) the r-LPyG comprises less than 5 weight percent of CO2,
  - vi.) the r-LPyG as comprises less than 0.1 weight percent of H2O,
  - vii.) the r-LPyG comprises less than 200 ppbw of arsine,
  - viii.) the r-LPyG comprises less than 10 ppmw of total nitrogen,
  - ix.) the r-LPyG comprises less than 15 ppmw of nitrogen as N2,
  - x.) the r-LPyG comprises less than 10 ppmw of methyl acetate,
  - xi.) the r-LPyG comprises less than 10 ppmw of propadiene,
  - xii.) the r-LPyG comprises less than 5 ppmw of methanol,
  - xiii.) the r-LPyG comprises less than 15 ppbw of total sulfur,
  - xiv.) the r-LPyG comprises less than 5 ppmw of total chlorine,
  - xv.) the r-LPyG comprises less than 5 weight percent of total organic oxygenates, and/or
  - xvi.) the r-LPyG comprises less than 5 ppmw of oxygen as O2.
- wherein the combined concentration of hydrogen, methane, and ethane on a weight basis in the r-LPyG is less than 95, 90, 80, 70, 60, or 50 percent of the combined concentration of hydrogen, methane, and ethane on a weight basis in the r-pygas.
- wherein the concentration of hydrogen on a weight basis in the r-LPyG is less than 95, 90, 80, 70, 60, or 50 percent of the concentration of hydrogen on a weight basis in the r-pygas.
- wherein the concentration of methane on a weight basis in the r-LPyG is less than 95, 90, 80, 70, 60, or 50 percent of the concentration of methane on a weight basis in the r-pygas.
- wherein the concentration of ethane on a weight basis in the r-LPyG is less than 95, 90, 80, 70, 60, or 50 of the concentration of ethane on a weight basis in the r-pygas.

Additional Claim Supporting Description—Second Embodiment

In a second embodiment of the present technology there is provided a process for producing liquified pyrolysis gas having recycled content (r-LPyG), where the process comprises the following steps: (a) pyrolyzing waste plastic to thereby produce a recycled content pyrolysis gas (r-pygas); (b) using at least a portion of the r-pygas gas as fuel for the pyrolyzing of step (a); (c) liquifying at least a portion of the r-pygas to thereby provide a recycled content liquified pyrolysis gas (r-LPyG); and (d) performing one or both of the following steps—(i) storing the r-LPyG in liquified state for a continuous storage period of at least 1, 2, 4, 8, 12, 24, or 36 hours and/or (ii) loading the r-LPyG into a transportation apparatus configured to transport the r-LPyG in a liquified state for a distance of at least 1 mile.

The second embodiment described in the preceding paragraph can also include one or more of the additional aspects/features listed in the following bullet pointed paragraphs. Each of the below additional features of the second embodiment can be standalone features or can be combined with one or more of the other additional features to the extent consistent. Additionally, the following bullet pointed paragraphs can be viewed as dependent claim features having levels of dependency indicated by the degree of indention in the bulleted list (i.e., a feature indented further than the feature(s) listed above it is considered dependent on the feature(s) listed above it).

- further comprising reducing and/or eliminating use of the r-pygas for fuel in step (b).
  - further comprising, subsequent to the reducing and/or eliminating, commencing and/or increasing the amount of the r-pygas liquified in step (c).
    - wherein the mass flow rate of the r-pygas to the liquification of step (c) is greater than the mass flow rate of r-pygas to the pyrolysis fuel use of step (b).
  - further comprising starting and/or increasing the use of a non-pygas replacement fuel for the pyrolyzing of step (a).
- further comprising eliminating the use of the r-pygas for fuel in step (b).
  - wherein, subsequent to the eliminating of the r-pygas for fuel, step (c) includes liquifying substantially all of the r-pygas.
  - further comprising switching from the r-pygas to a replacement fuel for the pyrolyzing of step (a).

Additional Claim Supporting Description—Third Embodiment

In a third embodiment of the present technology there is provided a process for producing liquified pyrolysis gas having recycled content (r-LPyG), where the process comprises the following steps: (a) pyrolyzing waste plastic to thereby produce a recycled content pyrolysis gas (r-pygas) and a recycled content pyrolysis oil (r-pyoil); (b) liquifying at least a portion of the r-pygas to thereby provide a recycled content liquified pyrolysis gas (r-LPyG); (c) loading at least a portion of the r-LPyG into a first transportation apparatus configured to transport the r-LPyG in a liquified state; and (d) loading at least a portion of the r-pyoil into a second transportation apparatus configured to transport the r-pyoil in a liquid state.

The third embodiment described in the preceding paragraph can also include one or more of the additional aspects/features listed in the following bullet pointed paragraphs. Each of the below additional features of the third embodiment can be standalone features or can be combined with one or more of the other additional features to the extent consistent. Additionally, the following bullet pointed paragraphs can be viewed as dependent claim features having levels of dependency indicated by the degree of indention in the bulleted list (i.e., a feature indented further than the feature(s) listed above it is considered dependent on the feature(s) listed above it).

- wherein the first transportation apparatus and the second transportation apparatus are individually selected from a pipeline, a tanker railcar, a tanker trailer, or a tanker ship.
- wherein the first transportation apparatus is insulated, cooled, and/or pressurized in order to maintain the r-LPyG in a liquified state during transportation.
  - wherein the first transportation apparatus comprises a pressurized tank or a pressurized pipeline maintained at a pressure sufficient to maintain the r-LPyG in a liquified state at a temperature of 20° C.
- further comprising, prior to the loading of step (c), storing at least a portion of the r-LPyG in a liquified state for a continuous time period of at least 1, 2, 4, 8, 12, 24, or 36 hours.
- further comprising transporting the r-LPyG to a first facility and transporting the r-pyoil to a second facility, wherein the first and second facilities are at different locations.
  - wherein the first and second facilities are spaced from one another by at least 1, 10, 50, 100, 500, or 1000 miles.
  - wherein the first and second facilities are spaced from one another by at least 1, 10, 50, 100, 500, or 1000 miles.
- further comprising transporting at least a portion of the r-LPyG and at least a portion of the r-pyoil to a remote facility located remotely from the pyrolysis facility used to make the r-LPyG and the r-pyoil.
  - wherein the remote facility is spaced from the pyrolysis facility used to make the r-LPyG and the r-pyoil by at least 1, 10, 50, 100, 500, or 1000 miles.

CLAIMS NOT LIMITED TO DISCLOSED EMBODIMENTS

The preferred forms of the invention described above are to be used as illustration only and should not be used in a limiting sense to interpret the scope of the present invention. Modifications to the exemplary embodiments, set forth above, could be readily made by those skilled in the art without departing from the spirit of the present invention.

The inventors hereby state their intent to rely on the Doctrine of Equivalents to determine and assess the reasonably fair scope of the present invention as it pertains to any apparatus not materially departing from but outside the literal scope of the invention as set forth in the following claims.

MIXED LIQUIFIED PYROLYSIS GAS WITH RECYCLED CONTENT

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