WO2001005908A1 - A process for producing gasoline and diesel from waste plastics and/or heavy oil - Google Patents

A process for producing gasoline and diesel from waste plastics and/or heavy oil Download PDF

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Publication number
WO2001005908A1
WO2001005908A1 PCT/CN2000/000196 CN0000196W WO0105908A1 WO 2001005908 A1 WO2001005908 A1 WO 2001005908A1 CN 0000196 W CN0000196 W CN 0000196W WO 0105908 A1 WO0105908 A1 WO 0105908A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
heavy oil
reaction
catalytic cracking
diesel
Prior art date
Application number
PCT/CN2000/000196
Other languages
French (fr)
Inventor
Li Xing
Original Assignee
Enercon Technologies, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Enercon Technologies, Inc. filed Critical Enercon Technologies, Inc.
Priority to BR0012623-3A priority Critical patent/BR0012623A/en
Priority to EP00943524A priority patent/EP1228165A4/en
Priority to JP2001511126A priority patent/JP2003528937A/en
Priority to CA002379529A priority patent/CA2379529A1/en
Priority to AU58015/00A priority patent/AU5801500A/en
Priority to KR1020027000608A priority patent/KR20020052168A/en
Publication of WO2001005908A1 publication Critical patent/WO2001005908A1/en

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Classifications

    • 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
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
    • 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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • 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
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
    • 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
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste

Definitions

  • the present invention relates to a process for producing low-boiling
  • the outside wall is apt to be deformed when the
  • a spiral reactor utilized in some special fields is similar to the above.
  • an object of the invention is to provide a process for
  • the process of the present invention comprises the steps of:
  • step (b) introducing the products in step (a) into a fixed bed to perform a
  • Said first catalyst is made as follows: powder A1 2 0 3 is mixed with
  • the ratio between powder A1 2 0 3 and water glass is 1 :3-5 by weight
  • the materials can be any material. According to the process of the invention, the materials can be any material.
  • Figure 1 is an operational flow chart of the process in the invention.
  • the process of the present invention comprises the steps of:
  • step (b) introducing the products in step (a) into a fixed bed to perform a
  • the process of the invention further comprises a step of: (c) recycling the first catalyst in the reaction.
  • reaction of pyrolysis and first catalytic cracking may be
  • the of the first catalyst may be controlled at 500-l,000°C, preferably 600-
  • reaction of second catalytic cracking is carried out with a
  • the second catalyst used in the invention may be the commonly
  • the first catalyst after being heated to a high
  • the materials are decomposed into gaseous
  • the first catalyst is not only used as a heating medium
  • Said first catalyst is made as follows: powder A1 2 0 3 is mixed with
  • A1 2 0 3 and water glass to be used is 1 :3-5 by weight and that between the
  • invention is generally of a Mo is' scale of hardness of 7-9 and a diameter
  • said pyrolysis and first catalytic cracking may
  • chamber to the pyrolysis reactor is controlled at 500-1000C, preferably
  • the temperature of the first catalyst is kept at 400-800°C, preferably 500-600°C when it leaves the pyrolysis reactor.
  • catalytic reaction is undertaken at 230-600°C, preferably 300-450°C.
  • catalyst DL-1 being composed of (Wt. %): 8% of CHO-l(a
  • the first catalyst 16 in the combustion chamber 21 is heated to 500-
  • the materials are heavy oils, they may be pumped into the sealed pyrolysis reactor 14 via an inlet 28.
  • the materials are mixed directly with
  • a blower 3 is
  • the first catalyst 16 is hereby recovered and falls
  • the first catalyst was heated up to 600-700°C and then led
  • reaction pressure was kept at 0.05-0.1 MPa.
  • the recovered first catalyst was introduced into the reactor 14

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Catalysts (AREA)
  • Liquid Carbonaceous Fuels (AREA)

Abstract

The invention relates to a process for producing gasoline and diesel from waste plastics and/or heavy oil and comprises the steps of: (a) mixing waste plastics and/or heavy oil with a first catalyst in a pyrolysis reactor at a high temperature to carry out a pyrolysis and a first catalytic cracking; and (b) introducing the products in step (a) into a fixed bed to perform a second catalytic cracking with a second catalyst. The process further comprises the step (c) recycling the first catalyst in the reaction.

Description

A PROCESS FOR PRODUCING GASOLINE AND DIESEL FROM
WASTE PLASTICS AND/OR HEAVY OIL
Field of the Invention
The present invention relates to a process for producing low-boiling
point hydrocarbons from waste plastics and/or heavy oil, and more
particularly to a process for producing gasoline and diesel through
pyrolysis and catalytic cracking of waste plastics and/or heavy oil.
Background of the Invention
Many methods for preparing low-boiling hydrocarbons from waste
plastics and high-boiling hydrocarbons are known. U.S. Patent No.
4,851,601 and EP-A-0607862 (Applicant: MAZDA MOTOR
CORPORATION) disclose a reaction of pyrolysis in a reactor kettle
(vertical or horizontal), wherein the outside wall of the kettle is heated at
a high temperature while the materials therein are heated indirectly.
In this method, the outside wall is apt to be deformed when the
reactor is heated directly at a high temperature. The materials are readily
sintered on the inside wall because of local over-heating so that the
conversion yield of the reaction and the life of the reactor are greatly
decreased. In addition, the coefficient of the reactor's heat transfer is
relatively low, it is difficult to drain the reaction residues, and the catalytic reaction in the fixed bed needs a separate heat supply. These are
the common drawbacks of the reactor kettle in the prior art.
A spiral reactor utilized in some special fields is similar to the above.
Heat is indirectly transferred when it works. The outside wall of the
reactor is heated directly at a very high temperature, making the materials
in the reactor indirectly heated. Therefore, the heat transfer coefficient is
not satisfactory. Particularly, because the screw therein is apt to be
deformed at a high temperature, making it hard to seal the two ends of the
screw so that gas generated in the reaction may be exhausted.
Summary of the Invention
Accordingly, an object of the invention is to provide a process for
producing gasoline and diesel from waste plastics and/or heavy oil
(including high-boiling hydrocarbons) to overcome the shortcomings in
the prior art as described above.
The process of the present invention comprises the steps of:
(a) mixing waste plastics and/or heavy oil with a first catalyst at a
high temperature in a pyrolysis reactor to carry out a reaction of pyrolysis
and first catalytic cracking simultaneously; and
(b) introducing the products in step (a) into a fixed bed to perform a
reaction of second catalytic cracking. Said first catalyst is made as follows: powder A1203 is mixed with
water glass to obtain a slurry, and the resultant slurry is then mixed with
catalyst HZSM-5. The resultant mixture is dried, formed, granulated, and
heated to obtain the first catalyst.
The ratio between powder A1203 and water glass is 1 :3-5 by weight
and that between the slurry and HZSM-5 is 1 :0.2-0.5 by weight.
According to the process of the invention, the materials can be
converted to gasoline and diesel with a high yield, and the requirements
for the reactor are not strictly defined because the first catalyst is used to
heat the materials directly.
Brief Description of the Drawing
Figure 1 is an operational flow chart of the process in the invention.
Detailed Description of the Invention
The process of the present invention comprises the steps of:
(a) mixing waste plastics and/or heavy oil with a first catalyst at a
high temperature in a pyrolysis reactor to carry out a reaction of pyrolysis
and first catalytic cracking simultaneously; and
(b) introducing the products in step (a) into a fixed bed to perform a
reaction of second catalytic cracking.
The process of the invention further comprises a step of: (c) recycling the first catalyst in the reaction.
The reaction of pyrolysis and first catalytic cracking may be
conducted under the standard atmosphere or higher, and the temperature
of the first catalyst may be controlled at 500-l,000°C, preferably 600-
700°C.
The reaction of second catalytic cracking is carried out with a
second catalyst in the fixed bed at 300-600°C, preferably 300-450°C.
The second catalyst used in the invention may be the commonly
used catalyst in the reaction of catalytic cracking in the art.
In the invention, the first catalyst after being heated to a high
temperature in the combustion chamber the first catalyst is charged into a
pyrolysis reactor by using a spiral conveyor. Waste plastics (or heavy oil)
are charged into the sealed pyrolysis reactor, and there they are directly
mixed with the hot first catalyst to perform a reaction of pyrolysis and
first catalytic cracking. The materials are decomposed into gaseous
hydrocarbons and residues. The gaseous hydrocarbons then enter a fixed
bed in the reactor and are further decomposed into smaller molecules via
a second catalytic cracking. Gaseous substances from the reaction are
collected by means of the conventional process in the prior art so as to
obtain gasoline and diesel. Said first catalyst and residues in the reaction
are introduced into a gasification chamber by a screw, and further into a
separator by a spiral conveyor. Hot flue gas is led into the separator with a blower, which blows said mixture into a cyclone separator so as to
collect a solid mixture. Said mixture is introduced into a combustion
chamber by a spiral conveyor. In the combustion chamber, organic
substances in the mixture are burnt out, while the first catalyst is heated
and delivered to the spiral reactor again.
In the above-mentioned process, the feedstock is mixed directly with
hot first catalyst, and pyrolysis and the first catalytic cracking take place
at the same time. The first catalyst is not only used as a heating medium
but also as a catalyst, which can be recycled.
Said first catalyst is made as follows: powder A1203 is mixed with
water glass to obtain a slurry, and the resultant slurry is then mixed with
catalyst HZSM-5; and the resultant mixture is dried, formed, granulated,
and heated at a temperature of 550-800°C. The ratio between powder
A1203 and water glass to be used is 1 :3-5 by weight and that between the
slurry and HZSM-5 is 1 :0.2-0.5 by weight. Said first catalyst used in the
invention is generally of a Mo is' scale of hardness of 7-9 and a diameter
of 0.2-0.5mm.
In the above process, said pyrolysis and first catalytic cracking may
be conducted under standard atmosphere or higher. The reaction
temperature, when the first catalyst is transmitted from the combustion
chamber to the pyrolysis reactor, is controlled at 500-1000C, preferably
600-700°C. The temperature of the first catalyst is kept at 400-800°C, preferably 500-600°C when it leaves the pyrolysis reactor.
Said second catalytic cracking is carried out in the fixed bed
inside the gasification chamber. Heat required in the second catalytic
cracking is provided by the gasification chamber itself. The second
catalytic reaction is undertaken at 230-600°C, preferably 300-450°C. A
particular catalyst DL-1 being composed of (Wt. %): 8% of CHO-l(a
commodity produced by China Qilu Petrochemical Factory), 24% of
REY, 25% of flokite (silicon/aluminum =12/1) and 43% of catalyst ZSM-
5 is used in the second catalytic cracking after being thoroughly mixed
and calcined.
The present invention will be more distinct with reference to the
accompanying drawings.
Referring to Fig. 1, a first catalyst 16 in the granular form is charged
into a combustion chamber 21 from a storage tank 26 with a spiral
conveyor 27. Fuel oil (or recuperated pyrolysis gas) and air are sprayed
into the combustion chamber 21 simultaneously via nozzles 18, 19 and 20.
The first catalyst 16 in the combustion chamber 21 is heated to 500-
1,000°C and subsequently led into a storage tank 17. A spiral conveyor
29 is started by a motor 1 to push the first catalyst 16 continuously into a
pyrolysis reactor 14. At the same time, the materials to be treated are
pushed by a screw (or reciprocating) extruder 4 into a spiral reactor 14. If
the materials are heavy oils, they may be pumped into the sealed pyrolysis reactor 14 via an inlet 28. The materials are mixed directly with
the first catalyst 16 in the reactor 14 to undergo a pyrolytic reaction and a
first catalytic cracking. Rotated and pushed by the spiral conveyor 2,
gaseous hydrocarbons generated from the reaction and residues move
forward to enter a vaporizer 13. Gaseous hydrocarbons enter a fixed bed
12 in the vaporizer 13 through the vaporization region, and react with a
second catalyst to generate gaseous hydrocarbons with small molecules,
which will be fractionated in a fractional column 9 to obtain gasoline and
diesel by means of the conventional process. A mixture 10 of reaction
residues and the first catalyst 16 entering the bottom of the vaporizer 13
is driven into a separator 8 via a spiral conveyor 2. A blower 3 is
employed to push the high-temperature flue gas into the separator 8 via
an entrance 6. Solid mixture 25 containing the first catalyst are flown up
to enter a cyclone 24 because they are lighter. Other heavy residues enter
the bottom of the separator 8 and are discharged from a hole 7. Thus, the
solid mixture 25 in the cyclone 24 drops into a storage tank 26, and then
is charged into the combustion chamber 21 by the spiral conveyor 27. In
the combustion chamber 21, organic substances in the mixture 25 are
burnt out and inorganic dusts are extracted together with high-
temperature flue gas. The first catalyst 16 is hereby recovered and falls
into the storage tank 17, subsequently. The heated first catalyst is then
charged into the reactor 14 by the spiral conveyor 29. The invention is further described by the following examples.
Example 1
Water glass (1,600kg, modulus>3) and powder A1203 (400kg) were
completely mixed to obtain a slurry. The slurry was mixed with catalyst
HZSM-5 (800kg). The resultant mixture was dried, formed, granulated,
and heated at 800°C for 4 hours to obtain the first catalyst with a Mohs'
scale of hardness of 8.5 and a diameter of 0.4 mm.
2,000 kg of the first catalyst prepared as indicated above was charged
into the combustion chamber 21, and simultaneously sprays 0# diesel (or
recuperated pyrolysis gas) and air were led into the combustion chamber
21 to burn. The first catalyst was heated up to 600-700°C and then led
into the pyrolysis reactor 14. The screw (or reciprocating) extruder 4 was
used to push 1 ,400kg of waste plastics (PP25%, PS25%, and PE50%) into
the reactor 14 to perform the reaction. The temperature at the stock inlet
of the reactor 14 was controlled at 600-700°C, whereas the temperature at
the residue outlet thereof was controlled at 500-600°C. The catalyst DL-1
was arranged in the fixed bed 12, and the second catalytic reaction was
conducted therein. The reaction pressure was kept at 0.05-0.1 MPa.
Gasoline and diesel were obtained from the fractional column 9. The
mixture of the first catalyst and residues was charged into the combustion chamber 21 and was heated up to 600-700°C therein to separate the first
catalyst. The recovered first catalyst was introduced into the reactor 14
for heat supply.
Products generated from this Example are listed below:
1. Gasoline, 630kg, RON=93.5, components (by wt%): paraffin 19.9%,
cyclanes 12%, olefin 48%, arenes 9.9%, others 10.2%;
2. Diesel, 420kg, cetane value=52, components (by wt%): paraffin
15%, cyclanes 8%, olefm 55%, arenes 10%, others 12%;
3. Inorganic residues 140kg;
4. Flammable gas 210kg.

Claims

What I claim is:
1. A process for producing gasoline and diesel from waste plastic and/or
heavy oil comprises the steps of:
(a) mixing waste plastic and/or heavy oil with a first catalyst in a
pyrolysis reactor at high temperature to carry out a pyrolytic reaction and
a first catalytic cracking ; and
(b) introducing the products in step (a) into a fixed bed to perform a
second catalytic cracking with a second catalyst.
2. A process as claimed in Claim 1, wherein said first catalyst is made as
follows: powder A1203 is mixed with water glass to obtain a slurry, and
the resultant slurry is then mixed with catalyst HZSM-5; and resultant
mixture is dried, formed, granulized, and heated at 550-800°C.
3. A process as claimed in Claim 2, wherein the ratio between powder
A1203 and water glass is 1 :3-5 by weight and that between the slurry and
HZSM-5 is 1 :0.2-0.5 by weight.
4. A process as claimed in Claim 3, wherein said first catalyst is of a
Mohs' scale of hardness of 7-9, and a diameter of 0.2-0.5mm.
5. A process as claimed in Claim 1, wherein the process further comprises
the step of:
c) recycling the first catalyst in the reaction.
6. A process as claimed in Claim 1, wherein said catalyst in the fixed bed comprises 8% of CHO-1, 24% of REY, 25% of flokite and 43% of
catalyst ZSM-5, by weight.
7. A process as claimed in Claim 1, wherein the process is performed
under the standard atmosphere or higher.
8. A process as claimed in Claim 1, wherein the temperature of the first
catalyst is controlled at 500-l,000°C before entering the pyrolysis reactor,
and is controlled at 400-800°C while leaving the pyrolysis reactor.
9. A process as claimed in Claim 1, wherein the first catalyst advances in
the same flow direction as that of the waste plastics and/or heavy oil.
PCT/CN2000/000196 1999-07-16 2000-07-13 A process for producing gasoline and diesel from waste plastics and/or heavy oil WO2001005908A1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
BR0012623-3A BR0012623A (en) 1999-07-16 2000-07-13 Process for producing gasoline and diesel from waste plastics and / or heavy oil
EP00943524A EP1228165A4 (en) 1999-07-16 2000-07-13 A process for producing gasoline and diesel from waste plastics and/or heavy oil
JP2001511126A JP2003528937A (en) 1999-07-16 2000-07-13 Process for producing gasoline and diesel from plastic waste and / or heavy oil
CA002379529A CA2379529A1 (en) 1999-07-16 2000-07-13 A process for producing gasoline and diesel from waste plastics and/or heavy oil
AU58015/00A AU5801500A (en) 1999-07-16 2000-07-13 A process for producing gasoline and diesel from waste plastics and/or heavy oil
KR1020027000608A KR20020052168A (en) 1999-07-16 2000-07-13 A process for producing gasoline and diesel from waste plastics and/or heavy oil

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN99216787.6 1999-07-16
CN99216787U CN2408118Y (en) 1999-07-16 1999-07-16 Equipment for producing gasoline and diesel oil by using waste plaste and/or heavy oil

Publications (1)

Publication Number Publication Date
WO2001005908A1 true WO2001005908A1 (en) 2001-01-25

Family

ID=5297315

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2000/000196 WO2001005908A1 (en) 1999-07-16 2000-07-13 A process for producing gasoline and diesel from waste plastics and/or heavy oil

Country Status (8)

Country Link
EP (1) EP1228165A4 (en)
JP (1) JP2003528937A (en)
KR (1) KR20020052168A (en)
CN (1) CN2408118Y (en)
AU (1) AU5801500A (en)
BR (1) BR0012623A (en)
CA (1) CA2379529A1 (en)
WO (1) WO2001005908A1 (en)

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CA2379529A1 (en) 2001-01-25
BR0012623A (en) 2003-04-08
AU5801500A (en) 2001-02-05
EP1228165A4 (en) 2004-01-28
JP2003528937A (en) 2003-09-30
KR20020052168A (en) 2002-07-02
CN2408118Y (en) 2000-11-29
EP1228165A1 (en) 2002-08-07

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