JP2989449B2 - Method and apparatus for gasifying glass fiber reinforced plastic - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for gasifying and effectively utilizing glass fiber reinforced plastic (GFRP) waste. A method and apparatus for generating.

[0002]

2. Description of the Related Art Conventionally, organic substances such as wood, agricultural crops (sugar cane, corn, etc.) and general plants (algae, weeds, etc.) have been gasified. Recently, plastics as industrial waste, waste paper, and waste automobiles have been used. Waste gasification technology mainly composed of organic substances such as so-called shredder dust obtained by crushing plastics has been developed and used effectively. In the conventional gasification method, a one-stage moving bed type or fluidized bed type pyrolysis furnace or combustion furnace is generally used, and is mainly implemented for the purpose of recovering waste heat. Recently, a technique for recovering oil by thermally decomposing waste containing plastics in a single-stage pyrolysis furnace has been developed.

[0003]

The above-mentioned conventional method has the following problems. (1) Since a plurality of materials are generally mixed in plastics, the thermal decomposition temperature is wide, and the
In a staged pyrolysis furnace or combustion furnace, its operation is very difficult, soot (soot) is generated by undecomposed carbon, and coking is generated on the apparatus wall. (2) Since the plastics are heated to a high temperature of about 1,200 ° C. or more by combustion, the walls of the combustion furnace are easily damaged. (3) In the case of GFRP, plastic is caulked due to high temperature inside GFRP due to combustion reaction with oxygen and oxygen shortage due to rapid oxygen consumption, and it is difficult to completely gasify the plastic part. Cannot be taken out and used effectively.

The present invention has been made in view of the above-mentioned state of the art, and aims to provide a method and an apparatus capable of gasifying only a plastic part of GFRP, extracting a glass fiber part, and collecting an effective component from plastic gas generated by gasification of plastic. Is what you do.

[0005]

Means for Solving the Problems The present invention relates to (1) In a gasification section, oxygen and water vapor are added to a supplied glass fiber reinforced plastic raw material to obtain 650 to 650 g.
A first step of heating to 750 ° C. to gasify the plastic material and recover the remaining glass fiber; and guiding the gasified plastic gas to a plastic gas decomposition section to further oxidize by adding oxygen or oxygen and water vapor. A gasification treatment method for glass fiber reinforced plastic, which comprises a second step of recovering generated CO and H ₂ , and (2) being rotatably installed in a horizontal shape formed in a cylindrical shape,
A gasification furnace comprising a heating section for adding oxygen and water vapor to the supplied glass fiber reinforced plastic raw material and heating it to 650 to 750 ° C. to gasify the plastic material, and a recovery section for recovering glass fiber remaining by the heating. ,
A plastic gas cracking furnace which is connected to the gasification furnace and is erected to add oxygen or oxygen and water vapor to the plastic gas introduced from the gasification furnace and partially oxidize at 700 to 1,000 ° C .; purification of the gas generated from the furnace CO, gasifier fiberglass reinforced plastic for carrying out the method of the characterized by comprising the gas purification column for recovering H ₂ (1), is.

[0006]

In the first step of the method of the present invention, the GFRP raw material is added to oxygen and water vapor in the gasification section at 650
It is heated to ７750 ° C., whereby only the GFRP plastic is completely gasified. In the gasification at this time, the use of only oxygen is conceivable, but in this case, since the temperature may be locally high, the oxygen is diluted with steam to use it more completely. In this case, the gasification conditions in the first step are as follows: oxygen / GFRP is 0.09 to 0.1.
50 Nl (oxygen) / g (GFRP), steam /
GFRP is preferably 2.0 g (steam) / g (GFRP) or more. The gas generated in the first step is CO, CO ₂ , H
It is composed of hydrocarbon compounds having a boiling point from room temperature to about 750 ° C. in addition to ₂ , O ₂ , methane, ethane, propane and the like. Hereinafter, this gas is referred to as a plastic gas. In this first step, the melting point of the glass fiber is about 830.
Since the temperature is ° C, the glass fiber remains in the original form and is recovered in a solid state.

Next, the plastic gas from which the glass fiber has been recovered is sent to a plastic gas decomposing section in the second step, where oxygen or a mixture of oxygen and water vapor is further added and partially oxidized. As the combustion conditions in the second step, the plastic gas is converted into GFRP as a raw material, and oxygen / GFRP is 0.11 to 0.71 Nl (oxygen) / g (GFRP) according to the first step, and the oxygen and GFRP are steam together with oxygen. When adding water vapor / GFRP is 3.0 g (water vapor)
/ G (GFRP) or less. The gas discharged from the plastic gas decomposition section is then sent to a gas purification tower where it is purified and used as synthesis gas.

The operation of the apparatus of the present invention is the same as that of the above-described method of the present invention, and a description thereof will be omitted.

An embodiment of the method of the present invention will be described below with reference to FIG. FIG. 1 is a process flow chart showing the gasification treatment method of GFRP of the present invention. As shown in the figure, this flow is composed of a gasification section 1, a plastic gas decomposition section 2 erected and connected to the gasification section 1, and a gas purification section 3. In the gasification unit 1, previously finely crushed with a plastic in the GFRP is heated by addition of oxygen 7 and steam 6 to the supplied GFRP material A to generate a plastic gas A ₁ is gasified and remains in the subsequent solid The first step of recovering the glass fiber A _{2 in a} shape is performed,
Plastic the gas decomposition unit 2 in the first step according more oxygen 7 and must direct the plastic gas A ₁ which is gasified by partial oxidation by the addition of water vapor 6, generated at this time C
A second step of recovering O and H ₂ is performed.

Next, the procedure of the gasification treatment method will be described. The GFRP raw material A is finely crushed in advance and supplied to a gasification furnace (gasification unit) 1. In the gasification furnace 1, oxygen 7 and an appropriate amount of water vapor 6 are added to reduce the oxygen partial pressure to 10 to 15% or less. And heated to 650-750 ° C. As a result, the plastic, which is the raw material of the GFRP raw material A, is gasified without forming soot or caulk.
Glass fiber A ₂ mixed in RP (melting point about 830
C) remains in the furnace and is recovered from the outlet of the gasification furnace 1 (first step).

On the other hand, the plastic gas A ₁ generated in the first step is thereafter led into a plastic gas cracking furnace (plastic gas cracking section) 2 where the oxygen 7 and local oxygen If necessary, an appropriate amount of steam 6 is added to reduce the partial pressure to 10 to 15% or less, so that the plastic gas A ₁ is CH + ＣＨO ₂ → CO + 1 / 2H.
Active ingredient gases CO and H ₂ are generated by the reaction of ₂ + Q / 2 (where CH represents a plastic gas) without producing soot or caulk. Further, the remainder of the plastic gas A ₁ is further reduced by 70
It is heated to 0 to 1,000 ° C., and the added water vapor 6 prevents local high temperature by an endothermic reaction of CH + H ₂ O → CO + 3 / 2H ₂ (endothermic reaction). Highly active component gases CO and H ₂ are generated while suppressing the concentration.
O and H ₂ pass through the heat recovery unit 3 and are further purified by the gas purification tower 4 and separately collected (second step).

The CO and H ₂ are used for fuel, methanol synthesis and the like. Since heat is absorbed during the above-mentioned reaction, by adjusting the amount of steam 6 to be added, the reaction is allowed to proceed gently and CO, H ₂ having a high concentration at an appropriate temperature.
Can be manufactured efficiently.

Next, an embodiment of the apparatus of the present invention will be described with reference to FIG. FIG. 2 is a diagram showing a configuration of the GFRP gasifier of the present invention. As shown in the figure, the apparatus is formed in a cylindrical shape, and is provided with a gasification furnace (kiln) 1 rotatably installed in a horizontal state, a plastic gas cracking furnace 2 connected and installed in the gasification furnace 1, and a cooling apparatus. And a gas purification tower 4.

The gasification furnace 1 is heated by adding oxygen 7 and water vapor 6 to GFRP raw material A, which has been finely crushed and supplied in advance, and gasifies the plastic in GFRP to generate a plastic gas A _1. There consists recovery unit for recovering from the discharge port 5 a glass fiber a ₂ remaining after gasification, plastic gas decomposition furnace 2,
A plastic gas A formed in a tubular or box-like shape, connected to the gasifier 1 and erected, and guided from the gasifier 1
₁ is a plastic gas cracking furnace 2 which is partially oxidized by adding oxygen 7 and steam 6 as required. Heat recovery unit 3
Is a device for recovering heat from the gas generated in the plastic gas cracking furnace 2, and the gas cooled in the heat recovery unit 3 is purified in the gas purification tower 4.

Next, a gasification treatment procedure by the present gasifier will be described. First, the GFRP raw material A is finely crushed in advance and supplied to the rotating gasification furnace 1. In the gasification furnace 1, oxygen 7 and water vapor 6 are added and heated to 650 to 750 ° C., whereby the plastic material of GFRP is gasified to generate a plastic gas A ₁ ,
Glass fiber mixed in RP (melting point about 830 ° C) A
₂ remains in the furnace 1, moves with the rotation of the gasification furnace 1, and is collected from the discharge port 5.

On the other hand, the plastic gas A ₁ is led to the plastic gas decomposition furnace 2. Then, in the cracking furnace 2, oxygen 7 and an appropriate amount of steam 6 are further added as required, so that the plastic gas A ₁ becomes CH + 3 / 2O ₂ → CO
The reaction of ₂ + 1/2 H ₂ O + Q is caused to cause about 700 to 1,0
Oxidation (combustion) occurs at 00 ° C. to generate heat Q The gas is led to the heat recovery unit 3, where the heat quantity Q is recovered.

Gasified in a gasification furnace 1 and
Plastic gas A guided to gas cracking furnace 2₁Is oxygen 7
Plus an appropriate amount of steam 6 added as needed
Chick gas A₁Part of is CH + 1 / 2O_Two→ CO + 1 / 2H
_TwoCO, H by the reaction of + Q / 2_TwoCause
Plastic gas A₁Depends on the amount of heat Q generated at this time.
And further heated to 700-1,000 ° C. and added water
CH + H by steam 6 _TwoO → CO + 3 / 2H_TwoBy the reaction of
Effective component gas CO, H_TwoIs generated
CO, H_TwoWith other combustion gases
After being guided to the heat recovery unit 3 and cooled (heat recovery),
To the purification column 4_TwoHarmful substances such as HCl,
Absorbed / separated and collected. C thus recovered
O, H_TwoIs used for refining fuel and methanol.

Further, as described above, heat absorption is performed by adding steam 6 together with oxygen 7 in the gasification furnace 1 and the plastic gas cracking furnace 2, so that the amount of steam 6 is appropriately adjusted, By allowing the reaction to proceed slowly and gasifying GFRP at an appropriate temperature, glass fiber recovery and heat recovery can be performed effectively, and highly concentrated CO and H ₂ can be efficiently removed at an appropriate temperature. Can be manufactured.

[0019]

EXAMPLES Hereinafter, specific examples of the present invention will be described to further clarify the effects of the present invention.

(Example 1) GFR for boats having the following analysis values
P was cut into about 5 mm squares, and GFRP raw material A was gasified in accordance with the flow shown in FIG. 1, heat recovery was performed, and then gas purification was performed to collect synthesis gas. The gasification section 1 and the combustion section 2 both use a quartz tube having an inner diameter of 5 cm, the total length of the quartz tubes of the gasification section 1 and the plastic gas decomposition section 2 is set to 2 m, and the temperature of the gasification section 1 is set to 2 m. The temperature of the plastic gas decomposition section 2 can be changed to 600 to 1,000 ° C. and the GFRP raw material A can be set in the gasification section 1.
At a constant rate of 0.5 g / min. Analysis value of GFRP C: 50.4 wt% H: 4.4 wt% O: 7.5 wt% Water content: 0.0 wt% Ash content (including glass fiber): 37.7 wt%

Gasification section 1 and plastic gas decomposition section 2
Were set as shown in Table 1, and a quartz wool or filter was provided at the inlet of the heat recovery unit 3 to collect soot and tar in the generated gas when it was generated.
After the test for a predetermined time (about 35 minutes), the glass fiber was taken out, its appearance was observed, and unburned carbon was analyzed. The results are shown in Table 1.

[0022]

[Table 1]

(Embodiment 2) Next, an embodiment of the GFRP gasifier according to the present invention will be described. This device has the same configuration as the device described with reference to FIG. Hereinafter, the specifications, operating conditions, and operating results of each part of the device are shown. Note that the same GFRP raw material as described in Example 1 was used. ○ Equipment specifications Gasification furnace 1: Diameter 150 × Length 500 (mm) Gasification furnace rotation speed: 6 rpm Plastic gas decomposition furnace 2: Diameter 200 × Length 150
0 (mm) ○ operating conditions the gasifier 1 Temperature: 710 ° C. steam supply amount of the gasification furnace 1: 4.4Nm ³ / h oxygen supply of the gasification furnace 1: 0.9 Nm ³ / h plastic gas decomposition furnace 2 Temperature: 985 ° C Oxygen supply rate of plastic gas cracking furnace 2: 1.0 N
m ³ / h ○ Operation result Generated gas amount: 15.3 Nm ³ / h Gas composition: H ₂ = 38.0, CO = 41.0, CO
₂ = 21.0 (vol%) (H ₂ and CO gas concentrations are high and can be used sufficiently as a gas for producing methanol) Gasification rate (CO, CO with respect to carbon 100 in GFRP)
Ratio of carbon converted to ₂ ): 100% Residue: only white glass fiber containing no unreacted carbon component and coking material (continuous recovery)

[0024]

According to the present invention, in the gasification section (gasification furnace), the GFRP raw material is gasified by adding oxygen and an appropriate amount of water vapor. Can be recovered.
Further, the gasified plastic gas is decomposed under mild conditions in a plastic gas decomposition section (plastic gas decomposition furnace), so that a synthesis gas can be obtained without causing damage to the furnace wall due to high-temperature combustion as in the past. be able to.

[Brief description of the drawings]

FIG. 1 is an explanatory view of one embodiment of the gasification method of GFRP of the present invention.

FIG. 2 is an explanatory view of one embodiment of a gasification treatment apparatus for GFRP of the present invention.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Ritsuo Hashimoto 4-22, Kannonshinmachi, Nishi-ku, Hiroshima-shi, Hiroshima Mitsubishi Heavy Industries, Ltd. Hiroshima Research Laboratory (72) Inventor Hirotoshi Horizoe Kannon-Shinmachi 4 in Nishi-ku, Hiroshima-shi, Hiroshima No. 6-22 Mitsubishi Heavy Industries, Ltd. Hiroshima Research Laboratory (56) References JP-A-4-215882 (JP, A) US Patent 3,476,664 (US, A) (58) Fields investigated (Int. Cl. ⁶ , DB Name) C10J 3/00 B09B 3/00

Claims (2)

(57) [Claims] A first step of adding oxygen and water vapor to the supplied glass fiber reinforced plastic raw material, heating the glass fiber reinforced plastic raw material to 650 to 750 ° C., gasifying the plastic material, and collecting the remaining glass fiber; A glass fiber reinforced process comprising: introducing a gasified plastic gas to a plastic gas decomposition section, further adding oxygen or oxygen and water vapor to partially oxidize the gas, and recovering generated CO and H _2. Gasification method for plastics. 2. A heating method for rotatably mounting a glass fiber reinforced plastic raw material supplied thereto in a horizontal manner and adding oxygen and steam to the supplied glass fiber reinforced plastic material and heating it to 650 to 750 ° C. to gasify the plastic material. Gasifier, comprising: a gas recovery unit for recovering glass fibers remaining after the heating; a gasification furnace which is connected to the gasification furnace and erected, and further comprises oxygen or oxygen and water vapor added to the plastic gas introduced from the gasification furnace. plastic gas decomposition furnace for partial oxidation at 700～1,000 ° C. by the addition of, and claims 1, purifying the gas generated from the decomposition furnace CO, characterized by comprising the gas purification column for recovering of H ₂ An apparatus for gasifying glass fiber reinforced plastics for performing the method of claim 1 .