JPS59205332A - Production of olefin from hydrocarbon - Google Patents
Production of olefin from hydrocarbonInfo
- Publication number
- JPS59205332A JPS59205332A JP58080035A JP8003583A JPS59205332A JP S59205332 A JPS59205332 A JP S59205332A JP 58080035 A JP58080035 A JP 58080035A JP 8003583 A JP8003583 A JP 8003583A JP S59205332 A JPS59205332 A JP S59205332A
- Authority
- JP
- Japan
- Prior art keywords
- reactor
- hydrocarbons
- reaction
- foamed metal
- foamed
- Prior art date
- Legal status (The legal status 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 status listed.)
- Pending
Links
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 21
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 21
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 title description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims abstract 3
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 12
- 239000000295 fuel oil Substances 0.000 abstract description 8
- 238000004939 coking Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 238000000197 pyrolysis Methods 0.000 abstract description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract description 3
- 150000001342 alkaline earth metals Chemical class 0.000 abstract description 3
- -1 ethylene, propylene Chemical group 0.000 abstract description 3
- 239000000571 coke Substances 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910002090 carbon oxide Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000567 combustion gas Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 229920006248 expandable polystyrene Polymers 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
Description
【発明の詳細な説明】
本発明は、炭化水素原料よジオレフィンを製造する方法
に関する。更に詳しくは、本発明は、内熱式加熱法傾よ
シ重質油から、コーキングのおそれなしにオレフィンを
製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing diolefins from hydrocarbon feedstocks. More particularly, the present invention relates to a process for producing olefins from internally heated decanted heavy oils without fear of coking.
従来、エタン、プロパンをはじめとする軽質のガス状炭
化水素及びナフサ、灯軽油等の軽質油をオレフィンに転
換する方法としては、スチームクラッキングと呼称され
る管式熱分解法が、用いられていることは、周知の通り
である。この方法では熱は外部から管壁を通して、供給
されるため、伝熱速度及び、反応温度に限界があり、通
常８５０℃以下、滞留時間０．１〜０．５秒の反応条件
が採用されている。しかし、このような装置及び反応条
件の制約から使用できる原料は、せいぜい軽油までに限
定され、残油等の重質油には、適用できない。Conventionally, a tube pyrolysis method called steam cracking has been used to convert light gaseous hydrocarbons such as ethane and propane, and light oils such as naphtha and kerosene into olefins. This is well known. In this method, heat is supplied from the outside through the tube wall, so there are limits to the heat transfer rate and reaction temperature, and the reaction conditions are usually 850°C or less and a residence time of 0.1 to 0.5 seconds. There is. However, due to such restrictions on equipment and reaction conditions, the raw material that can be used is limited to light oil at most, and cannot be applied to heavy oil such as residual oil.
この外部加熱方式に代わる方法として、水素あるいは、
炭化水素等の可燃ガスを、酸素により燃焼して、高温ガ
スをつくり、この高温ガスを、原料炭化水素の加熱用熱
源として炭化水素を熱分解する方法が提案されている。As an alternative to this external heating method, hydrogen or
A method has been proposed in which combustible gas such as hydrocarbons is combusted with oxygen to produce high-temperature gas, and the high-temperature gas is used as a heat source for heating raw material hydrocarbons to thermally decompose the hydrocarbons.
この方法では、反応に必要な熱は高温ガスより、直接原
料炭化水素に供給されるため、管式熱分解法で生じる伝
熱速度及び反応温度の制限が著しく改善され、高温・短
滞留時間の反応が可能となる。In this method, the heat required for the reaction is supplied directly to the feedstock hydrocarbon from the high-temperature gas, so the heat transfer rate and reaction temperature limitations that occur in the tube pyrolysis method are significantly improved, and the high temperature and short residence time are reduced. reaction becomes possible.
しかし、このような、内部加熱方式を用いたとしても、
原料炭化水素が、常圧残油、減圧残油等の重質油になる
と、壁面でのコーキングが激しく、そのままでは長時間
の安定運転は、困難であり、実質的に、使用できるのは
、減圧軽油等の留出油に、限定されているのが現状であ
る。However, even if such an internal heating method is used,
When the feedstock hydrocarbon becomes heavy oil such as atmospheric residual oil or vacuum residual oil, coking on the wall is severe and stable operation for long periods of time is difficult. Currently, it is limited to distillate oils such as vacuum gas oil.
このような、重質油のりアクタ−内壁へのコーキング防
止のために、炭酸ガスのようなイナートガスで、内壁を
おおう方法が提案されている。しかし、この方法では、
飛沫として飛んでくるに未分解炭化水素の壁面への付着
を、防ぐことは困難であり、実効をあげようとすれば、
かなり大量のイナートガスをリアクター内に導入する必
要がある。その結果第一に、供給した大骨のイナートガ
スの回収設備及び、動力が増大し、第二に、原料炭化水
素の分解それ自体には、有効に作用しないイナートガス
を、反応温度まで、加熱する必要があるため、エネルギ
ー収支が、著しく悪化するという問題がある。In order to prevent such heavy oil from forming on the inner wall of the actuator, a method of covering the inner wall with an inert gas such as carbon dioxide has been proposed. However, with this method,
It is difficult to prevent undecomposed hydrocarbons flying as droplets from adhering to walls, and if we are to be effective,
It is necessary to introduce a fairly large amount of inert gas into the reactor. As a result, firstly, the equipment and power needed to recover the supplied large-scale inert gas have increased, and secondly, it is necessary to heat the inert gas, which does not work effectively on the decomposition of raw material hydrocarbons, to the reaction temperature. Therefore, there is a problem that the energy balance deteriorates significantly.
本発明者等は、重質油からもコーキングのおそれなく、
高い安定した、オレフィン収率が得られる熱分解法を鋭
意研究した結果、リアクター内壁に、重質分の分解機能
を持った触媒を担持させたりアクタ−が、極めて有効で
あることを見出し、本発明に到達したものである。すな
わち、本発明によれば、
（１） 炭化水素の分解に必要な熱は、水素、−酸化
炭素又は、炭化水素の燃焼により生じた高温ガスにより
、内熱的に供給されるだめ、外部加熱法では困難であっ
たような高温、短滞留時間での分解が可能となり、その
結果、高いオレフィン収率が得られる、
（２）重質油からも、コーキングのおそれなく、オレフ
ィンが製造でき、安定した運転が可能となる、
（３） 反応器壁での重質分の分解により、高いガス
化率が得られ、有用成分の回収が増大する、（４）
触媒は、発泡金属内に担持することにより、容易に、リ
アクター内壁に付設でき、しかも、反応壁だけであるか
ら、その量は極めて少なく、しかも、全体の熱分解反応
にはほとんど影響しない、
等の利点がある。The present inventors have discovered that even from heavy oil there is no fear of coking.
As a result of intensive research into a thermal decomposition method that can provide a high and stable olefin yield, we discovered that supporting a catalyst on the inner wall of the reactor, which has the function of decomposing heavy components, is extremely effective. This invention has been achieved. That is, according to the present invention, (1) The heat necessary for decomposing hydrocarbons is supplied internally by hydrogen, carbon oxide, or high-temperature gas generated by combustion of hydrocarbons; (2) Olefins can be produced from heavy oil without the risk of coking; (3) Decomposition of heavy components on the reactor wall provides a high gasification rate and increases the recovery of useful components. (4)
By supporting the catalyst in foam metal, it can be easily attached to the inner wall of the reactor, and since it is only on the reaction wall, its amount is extremely small and has almost no effect on the overall thermal decomposition reaction. There are advantages.
本発明について更に詳しく説明すると、まず、反応に必
要な熱は、水素、−酸化炭素又は炭化水素を酸素により
燃焼することによシ供給される。すなわち、上記燃焼に
よシ、１３００〜２５００℃の高温燃焼ガスを製造し、
この高温ガス中に、原料である炭化水素を供給する。そ
の結果、原料炭化水素は、急速に加熱されて、所定の反
応温度となり、分解して、メタン、エチレン、プロピレ
ン等に転化する。この時、原料又は未分解炭化水素の一
部が、反応器の壁に到達するが、反応器壁に存在する触
媒によりＯｎＨｍ ＋ ｎＨ２Ｏ−＋ ｎｅｏ ＋ （
ｍ＋２ｎ） ／ ２ Ｈ２の反応が生じ、ＯＯとＨ，を
生成して分解する。To explain the present invention in more detail, first, the heat necessary for the reaction is supplied by burning hydrogen, carbon oxide, or hydrocarbon with oxygen. That is, by the above combustion, a high temperature combustion gas of 1300 to 2500°C is produced,
Hydrocarbons, which are raw materials, are fed into this high-temperature gas. As a result, the feedstock hydrocarbon is rapidly heated to a predetermined reaction temperature, decomposed and converted into methane, ethylene, propylene, etc. At this time, a part of the raw material or undecomposed hydrocarbons reaches the wall of the reactor, but due to the catalyst present on the wall of the reactor, OnHm + nH2O- + neo + (
m+2n)/2H2 reaction occurs, producing OO and H, which are decomposed.
この００ とＨ！ は一部更に反応して（３０＋ ５
Ｈ２→ ＯＨ４＋ Ｈ，０の反応によシ、メタンに転化
する。このように、反応器壁では触媒の作用により、未
分解炭化水素が分解され、有価な００ 、 Ｈ，、Ｏ’
Ｈ４等に転化すると共に、コーキング物の生成が抑制さ
れる。This 00 and H! partially reacts further (30 + 5
It is converted to methane by the reaction H2→OH4+ H,0. In this way, undecomposed hydrocarbons are decomposed on the reactor wall by the action of the catalyst, and valuable 00, H,, O'
While converting to H4 etc., the generation of coking substances is suppressed.
分解反応に必要なスチームは、高温燃焼ガスの生成の際
に一部生成するが、別途系外から補給することが望まし
い。また、生成した、Ｃｏ 及び水素は、メタンにし
て利用することもできるが、前に述べた反応熱供給用の
内熱源として使うこともできる。また、水素の生成は、
重質油を分解する場合系内に不足する水素を補って、オ
レフィン収率を増加させる効果をもつ。A portion of the steam required for the decomposition reaction is generated during the generation of high-temperature combustion gas, but it is desirable to supply it separately from outside the system. Further, the produced Co 2 and hydrogen can be used as methane, but they can also be used as the internal heat source for supplying the reaction heat mentioned above. In addition, the generation of hydrogen is
When cracking heavy oil, it has the effect of increasing the olefin yield by supplementing the hydrogen that is lacking in the system.
触媒としては、アルカリ金属又は、アルカリ土類金属の
酸化物、又は酸化ニッケルのうちから選ばれる酸化物が
好ましく、特に酸化カルシウムが望ましい。これらの触
媒を反応器壁に付設するため、触媒は発泡金属に、担持
された後、この発泡金属を反応器内壁にとシつける。The catalyst is preferably an oxide selected from oxides of alkali metals or alkaline earth metals, or nickel oxide, and calcium oxide is particularly desirable. In order to attach these catalysts to the reactor wall, the catalyst is supported on a foamed metal, and then this foamed metal is attached to the reactor inner wall.
発泡金属とは、発泡樹脂に金属をメッキした後、高温で
焼成することにより、有機物である樹脂を焼散させるこ
とによって得られるもので、例えば発泡ポリスチレンに
Ｎｌ 、 Ｏｒ などをメッキし、これを焼成すると
、発泡クロム、発泡ニッケルになる。Foamed metal is obtained by plating metal on foamed resin and then firing it at high temperature to burn off the organic resin.For example, foamed polystyrene is plated with Nl, Or, etc. When fired, it becomes foamed chromium and foamed nickel.
分解ガスは急冷により反応を凍結した後、公知の精製分
離系に入り、製品として取り出される。以上、この方法
は、スチームの存在は不可欠であるが、他の水素、メタ
ン等の共存ガスの存在を何ら制限するものではない。After the cracked gas freezes the reaction by rapid cooling, it enters a known purification separation system and is taken out as a product. As described above, although the presence of steam is essential for this method, the presence of other coexisting gases such as hydrogen and methane is not restricted in any way.
以下に本発明の１実施例を示す。An example of the present invention is shown below.
上部に燃焼室、下部に急冷部を持った反応器に、中東系
減圧残油を供給し、熱分解した。燃焼室には水素を供給
し、これを酸素を含むスチームの存在下で燃焼した。生
成した高温ガスは反応器入口で、予熱された原料残油と
接触させた。分解ガスは、反応器下部に設置された、急
冷部に設けられた水噴射ノズルにより直接冷却して、収
率を検討した。反応器内壁には、各種触媒を担持した、
発泡クロムをとりつけた。結果を表１に示す。Middle Eastern vacuum residue was fed into a reactor with a combustion chamber in the upper part and a quenching part in the lower part, and was thermally decomposed. The combustion chamber was supplied with hydrogen, which was combusted in the presence of oxygen-containing steam. The generated high-temperature gas was brought into contact with preheated raw material residual oil at the reactor inlet. The cracked gas was directly cooled by a water injection nozzle provided in a quenching section installed at the bottom of the reactor, and the yield was examined. Various catalysts are supported on the inner wall of the reactor.
I installed chrome foam. The results are shown in Table 1.
表 １
反応温度１０００℃、滞留時間１０ミリ秒チ１ニア時間
後の発泡メタルの重量変化より計算
蒼２：２時間で閉そく
表１より明らかなように、触媒を担持させることによシ
、そうでない場合（例５）に比べて、著しく、ガス化率
が向上し、コークスの生成が抑制されることがわかる。Table 1: Reaction temperature: 1000°C, residence time: 10 milliseconds Calculated from weight change of foamed metal after 1 hour.As is clear from Table 1, by supporting the catalyst, It can be seen that the gasification rate is significantly improved and the generation of coke is suppressed, compared to the case where it is not used (Example 5).
復代理人 内 １） 明 復代理人 恢 原 亮 −Sub-agent: 1) Akira Sub-agent Ryo Hara -
Claims (1)
フィンを製造する方法において、反応器内壁に、発泡金
属を付設し、この発泡金属中に、アルカリ金属酸化物、
アルカリ土類金属酸化物又は酸化ニッケルのうちから選
ばれた少くとも１種の酸化物を担持させることを特徴と
するオレフィンの製造法。In a method for producing olefins by internally thermally decomposing hydrocarbons in the presence of steam, a foamed metal is attached to the inner wall of the reactor, and alkali metal oxides, alkali metal oxides,
A method for producing an olefin, which comprises supporting at least one oxide selected from alkaline earth metal oxides and nickel oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58080035A JPS59205332A (en) | 1983-05-10 | 1983-05-10 | Production of olefin from hydrocarbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58080035A JPS59205332A (en) | 1983-05-10 | 1983-05-10 | Production of olefin from hydrocarbon |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS59205332A true JPS59205332A (en) | 1984-11-20 |
Family
ID=13707001
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58080035A Pending JPS59205332A (en) | 1983-05-10 | 1983-05-10 | Production of olefin from hydrocarbon |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59205332A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1055637A1 (en) * | 1999-05-27 | 2000-11-29 | Haldor Topsoe A/S | Synthesis gas production by steam reforming |
| EP1584603A3 (en) * | 1999-05-27 | 2007-06-13 | Haldor Topsoe A/S | Steam reforming reactor for synthesis gas production |
| JP2014509328A (en) * | 2010-12-22 | 2014-04-17 | ゼネラル・エレクトリック・カンパニイ | Hydrocarbon cracking method and reactor, and reactor coating method |
| CN107511482A (en) * | 2017-09-12 | 2017-12-26 | 成都新柯力化工科技有限公司 | A kind of method that foam metal is prepared by coke composite foamable agent |
-
1983
- 1983-05-10 JP JP58080035A patent/JPS59205332A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1055637A1 (en) * | 1999-05-27 | 2000-11-29 | Haldor Topsoe A/S | Synthesis gas production by steam reforming |
| US6576158B1 (en) | 1999-05-27 | 2003-06-10 | Haldor Topsoe A/S | Synthesis gas production by steam reforming |
| EP1584603A3 (en) * | 1999-05-27 | 2007-06-13 | Haldor Topsoe A/S | Steam reforming reactor for synthesis gas production |
| JP2014509328A (en) * | 2010-12-22 | 2014-04-17 | ゼネラル・エレクトリック・カンパニイ | Hydrocarbon cracking method and reactor, and reactor coating method |
| JP2016222922A (en) * | 2010-12-22 | 2016-12-28 | ゼネラル・エレクトリック・カンパニイ | Method and reactor for cracking hydrocarbon and method for coating reactor |
| US9850432B2 (en) | 2010-12-22 | 2017-12-26 | General Electric Company | Method and reactor for cracking hydrocarbon and method for coating the reactor |
| CN107511482A (en) * | 2017-09-12 | 2017-12-26 | 成都新柯力化工科技有限公司 | A kind of method that foam metal is prepared by coke composite foamable agent |
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