Patent Grant
10358613
The present invention relates to an industrial high temperature reformer (aka Kim reformer-XT) which is obtained by improving a high temperature reformer (Korean Patent No. 0637340) patented to the present applicant, i.e., a small-sized experimental reformer (aka Kim reformer). In the process, its production capacity of syngas has improved from 100 m3/hour to 500 m3/hour or more, and also relates to its reforming method.
The high temperature reformer technology began when the German chemist Lurgi suggested a coal-gas reaction(C+H2O→CO+H2). Before the present applicant disclosed the patented high temperature reformer (patent documents 1 through 7), the coal-gas reaction was limited to coal gasification; ground coal is combusted with oxygen gas in order to bring up the reactor temperature, and then hot steam is injected into the coal furnace. This method of coal gasification is known as the partial oxidation method, and the resulting reaction temperature runs just around 1,000° C., and a mixture of hydrocarbons are generated. However syngas(CO+H2) after extensive gas separation amounts to about 5% of total gas mixture produced. Furthermore, the temperature of the reforming furnace could not be maintained at 1200° C. or higher by burning coal. Currently, it is known that only the SASOL company of South Africa maintains an economical syngas production.
At the end of the last century, the present applicant reexamined the Lurgi coal-gas reaction. The results of the experiment (see non-patent document 1) were significantly different from the facts which were widely known at the time. The results of the experiment were as in the following. 1) The temperature at which all carbon reformed without catalyst to carbon monoxide gas and all hydrogen atom reduced into H2 gas was just above 1200° C.; 2) Not only carbon of coal, but of all carbonaceous substance reformed into carbon monoxide (CO) at 1200° C. or higher; 3) At the temperature above 1200° C., all hydrocarbons including methane disappeared quickly, and all other hydrocarbons were not detected by a gas detector. The only detected carbon species were CO and CO2. Since the gas generated at a temperature of 1200° C. or higher did not contain any carbon species except for CO gas, unlike in a conventional gasification method, it was not necessary to carry out the gas separation process. The present applicant conducted additional experiments with great interest in the results of 2). The experiments were conducted on a waste tire, crude rubber, synthetic resin and biomass, and only biomass had a problem. The reason for this is that biomass contains a large amount of moisture, and thus the region near the carbons of biomass could not be heated to a temperature of 1200° C. within a short period of time. In particular, the carbon reforming reaction was an endothermic reaction, and a heat of 1200° C. required for the reforming reaction was not supplied to the carbons.
When the present applicant became aware that the Lurgi coal-gas reaction reached the thermal equilibrium at 1200° C., the present applicant constructed a reforming furnace capable of maintaining a temperature of 1200° C., i.e., the most efficient condition for the reaction. The reforming furnace was named Kim reformer (see patent document 1), and was constructed for experimental purposes.
However, the Kim reformer merely produces syngas at a capacity of 100 m3/hour, and has a problem in that 30% of generated syngas has to be burnt and used as heat source for the purpose of the continuous operation thereof. In other words, for the Kim reformer to be widely used for industrial purposes, the reformer can be said to be economic only when the reformer can produce syngas at a capacity of 500 m3/hour or more.
The object of the present invention is to provide an industrial high temperature reformer and the reforming method which can produce syngas at a capacity of 500 m3/hour or more. In the industrial high temperature reformer and the reforming method, a temperature of the reforming furnace is maintained at 1000° C. or higher by burning the coke, and a temperature of at least an upper half of the reforming furnace is maintained at 1200° C. or higher by burning the syngas, thereby reforming all carbonaceous feedstock which is supplied to the reforming furnace.
In order to accomplish the above object, the present invention provides an industrial high temperature reformer comprising: a reforming furnace reforming carbonaceous feedstock; a carbonaceous feedstock inlet supplying carbonaceous feedstock to the reforming furnace; a coke supply unit supplying coke to the reforming furnace; a first oxygen inlet supplying oxygen to the reforming furnace; a steam inlet supplying steam to the reforming furnace; a syngas outlet formed in an upper section of the reforming furnace; and a syngas inlet supplying syngas to the reforming furnace; wherein a temperature of the reforming furnace is maintained at 1000° C. or higher by burning the coke with the oxygen, and a temperature of at least an upper half of the reforming furnace is maintained at 1200° C. or higher by burning the syngas supplied via the syngas inlet.
In this case, the first oxygen inlet can be formed in the lower section of the reforming furnace, and a second oxygen inlet can be formed in the mid-section of the reforming furnace. The two carbonaceous feedstock inlets can be formed in the mid-section of the reforming furnace, and the second oxygen inlet can be formed in between the two carbonaceous feedstock inlets.
The oxygen supplied to the reforming furnace can be fully used up to burn the coke and the syngas supplied via the syngas inlet. The syngas supplied via the syngas inlet can be part of syngas discharged via the syngas outlet, and the high temperature syngas discharged via the syngas outlet can pyrolyze the carbonaceous feedstock and be then cooled.
Furthermore, the present invention provides the industrial high temperature reforming method comprising: a first step of supplying coke to a reforming furnace; a second step of supplying oxygen to the reforming furnace, and maintain a temperature of the reforming furnace at 1000° C. or higher by burning the coke; a third step of supplying steam to the reforming furnace; a fourth step of maintaining a temperature of at least an upper half of the reforming furnace at 1200° C. or higher by burning a gas mixture (CO2, H2O, CO, and H2) generated through the burning of the coke and the steam and/or syngas supplied to the reforming furnace; and a fifth step of supplying carbonaceous feedstock to the reforming furnace, and generating syngas by reforming the carbonaceous feedstock.
In this case, the oxygen used to burn the coke at the second step may be supplied via a lower section of the reforming furnace, and the oxygen used to burn the gas mixture and/or syngas at the fourth step may be supplied via a mid-section of the reforming furnace. The syngas at the fourth step may be part of the syngas generated at the fifth step, and the high temperature syngas generated at the fifth step may pyrolyze the carbonaceous feedstock and be then cooled.
In an industrial high temperature reformer (Kim reformer-XT) according to the present invention, the overall reforming furnace is maintained at 1000° C. or higher by using an abundant coke pile as the main heat source, and at least the upper half of the reforming furnace is maintained at 1200° C. or higher by using syngas as an auxiliary heat source, thereby providing the effect of rapidly reforming carbonaceous feedstock in a gaseous state and generating syngas.
The present invention provides an industrial high temperature reformer comprising: a reforming furnace 10 reforming carbonaceous feedstock; a carbonaceous feedstock inlet 20 supplying carbonaceous feedstock to the reforming furnace 10; a coke supply unit 30 supplying coke to the reforming furnace 10; a first oxygen inlet 40 supplying oxygen to the reforming furnace 10; a steam inlet 50 supplying steam to the reforming furnace 10; a syngas outlet 60 formed in an upper section of the reforming furnace 10; and a syngas inlet 70 supplying syngas to the reforming furnace 10; wherein a temperature of the reforming furnace 10 is maintained at 1000° C. or higher by burning the coke with the oxygen, and a temperature of at least an upper half of the reforming furnace 10 is maintained at 1200° C. or higher by burning the syngas supplied via the syngas inlet 70.
An industrial high temperature reformer (Kim reformer-XT) according to the present invention is a significantly efficient reformer which generates syngas by reforming carbons, constituting all the carbonaceous feedstock, into carbon monoxide CO without a catalyst and then reducing hydrogen into hydrogen gas. The temperature of the reforming furnace 10 may be maintained at 1000° C. or higher by heat generated in the coke pile, and the temperature of at least the upper half of the reforming furnace may be continuously maintained at 1200° C. or higher by circulating a portion of the syngas generated at 1200° C. or higher and burning it. It burns just enough syngas required for maintaining the temperature of the at least the upper half of the reforming furnace 10 at 1200° C. or higher, rather than the whole reforming furnace 10. This mechanism may be viewed as a significantly energy efficient invention.
The reforming furnace 10 has the height of 3 m and the outer diameter of 1 m. The carbonaceous feedstock inlets 20 are formed about the mid-section of the reforming furnace 10, one above the mid-section and the other below it. When the temperature of the upper half of the reforming furnace 10 reaches to 1200° C. or higher, gaseous carbonaceous substance and well ground (μm size) powder form of carbon react quickly to generate syngas. However when the feedstock is liquid or solid, it takes time for carbon atoms of liquid or solid feedstock to come to a thermal equilibrium with surrounding temperature of 1200° C. Although in the case of coal, the time may be reduced by finely grinding coal to micrometer size, significant energy consumption may occur during this process. Accordingly, if coal is pyrolyzed and reduced into flue gas, and oil, and then injected into the reformer, a rapid reforming may follow and syngas is generated. Waste plastics may also be pyrolyzed as in the case of coal, or a pyrolyzer may be directly connected to the carbonaceous feedstock inlet 20 and carbonaceous feedstock (flue gas, and oil) obtained through pyrolysis may be supplied.
In particular, biomass has a large amount of moisture, and thus tar is left even when biomass is dried. However, tar is the main source of carbons, and thus a large amount of syngas can be obtained by continuously reforming tar.
In the case of food waste, hydrocarbon may be separated from water via a hydrogenation process (see Korean Patent 1146582 issued to the present applicant). Since the temperature of the syngas outlet 60 is equal to or higher than 1200° C., the high temperature syngas generated in the reformer may be used as a heat source required for the high temperature hydrolysis of food waste to recover the hydrocarbons from the food waste.
When a large number of carbon sources are obtained by performing appropriate preprocessing of waste, biomass, etc. and then reforming is performed, a large amount of syngas can be produced, and hydrogen gas, other renewable energy resources and various chemical materials can be produced.
A coke supply unit 30 configured to supply coke is formed in the lower part of the mid-section of the reforming furnace 10, and the coke supply unit 30 may include a supply pipe 31 configured such that a transfer screw is formed therein and a hopper 32 formed above the supply pipe 31 and may be modified into various forms, such as a hydraulic cylinder, a blower, and the like. Petroleum coke or coal coke generated during coal gasification may be used. In Korea, oil refinery companies treat petroleum coke as waste, and thus using petroleum coke as the main heat source is recommended as being renewables.
A first oxygen inlet 40 configured to supply oxygen is formed in the lower section of the reforming furnace 10. The coke supplied by the coke supply unit 30 is stacked in the lower section of the reforming furnace 10, and the first oxygen inlet 40 supplies oxygen to a pile formed by the stacked coke. Furthermore, a steam inlet 50 configured to supply steam is formed above the first oxygen inlet 40, a syngas inlet 70 configured to supply syngas is formed in the mid-section of the reforming furnace 10, a second oxygen inlet 42 may be formed between the two carbonaceous feedstock inlets 20, and an ash remover 35 is formed at the lower end of the reforming furnace 10.
The coke pile supplied via the coke supply unit 30 and located in the lower section of the reforming furnace 10 is burnt along with the oxygen supplied via the first oxygen inlet 40, and provides high temperature heat equal to or higher than 1500° C. A gas mixture (CO2, H2O, CO, and H2; generated from the burning of the coke and the use of the steam supplied via the steam inlet) generated in the coke pile rises up to the upper section of the reforming furnace 10, and maintains the temperature of the entire reforming furnace 10 at 1000° C. or higher. The gas mixture and/or syngas (supplied via the syngas inlet 70) may be burnt, and maintain the temperature of at least the upper half of the reforming furnace 10 at 1200° C. or higher. When the temperature of the upper half of the reforming furnace 10 is maintained at 1200° C. or higher, the carbonaceous feedstock entering via the carbonaceous feedstock inlets 20 is reformed and generates syngas, and the generated syngas is discharged via the syngas outlet 60 formed in the upper section of the reforming furnace 10 and is then stored. In this case, a portion of the syngas discharged from the syngas outlet 60 may be redirected to the reforming furnace 10 via the syngas inlet 70, is burnt therein, and continuously maintains the temperature of at least the upper half of the reforming furnace 10 at 1200° C. or higher.
In other words, the overall reforming furnace 10 is maintained at 1000° C. or higher by the burning of the coke, and the temperature of at least the upper half of the reforming furnace 10 is increased to 1200° C. or higher by burning a small amount of syngas (CO+H2) generated in the coke pile and/or the syngas supplied via the syngas inlet 70. Thereafter, reforming is sustained by injecting carbonaceous feedstock. A sufficient amount of the generated syngas is transferred to the upper half of the reforming furnace thru circulating a portion of the generated syngas. The generated syngas is to supplement the syngas rising from the coke pile, thereby providing the heat source required for the endothermic reforming reaction. When the upper half of the reforming furnace maintains the thermal equilibrium at the 1200° C. or higher, the reforming reaction takes place very rapidly.
In this case, in order to activate the burning of the gas mixture (generated through the burning of the coke and the use of the steam supplied via the steam inlet) and/or the syngas (supplied via the syngas inlet 70), a second oxygen inlet 42 may be formed at the mid-section of the reforming furnace 10, and the upper half of the reforming furnace 10 may be effectively maintained at 1200° C.
The oxygen inside the reforming furnace 10 is completely used up to burn the coke, the gas mixture (generated through the burning of the coke and the use of the steam supplied via the steam inlet), and the syngas (supplied via the syngas inlet), and thus no oxygen is detected in the syngas outlet 60. There should be no oxygen left within the reforming furnace 10 at all time, strictly oxygen deficient mode.
It is preferred that the oxygen supplied via the first oxygen inlet 40 is completely used up to burn the coke and that the oxygen supplied via the second oxygen inlet 42 is used to burn the gas mixture (generated through the burning of the coke and the use of the steam supplied via the steam inlet) and/or the syngas (supplied via the syngas inlet).
The high temperature syngas discharged via the syngas outlet 60 is cooled via a pyrolyzing furnace in which biomass, coal, or the like, i.e., solid or liquid carbonaceous feedstock, is pretreated, and the syngas having the remaining heat is cooled to room temperature and stored in a storage tank.
The present invention provides the industrial high temperature reforming method comprising: the first step of supplying coke to a reforming furnace; the second step of supplying oxygen to the reforming furnace, and maintain a temperature of the reforming furnace at 1000° C. or higher by burning the coke; the third step of supplying steam to the reforming furnace; the fourth step of maintaining a temperature of at least an upper half of the reforming furnace at 1200° C. or higher by burning a gas mixture (CO2, H2O, CO, and H2) generated through the burning of the coke and the steam and/or syngas supplied to the reforming furnace; and the fifth step of supplying carbonaceous feedstock to the reforming furnace, and generating syngas by reforming the carbonaceous feedstock.
The first step is the step of supplying coke to the reforming furnace 10 via the coke supply unit 30. The supplied coke is congregated in the lower section of the reforming furnace 10, and forms a coke pile.
The second step is the step of supplying oxygen to the reforming furnace 10, and maintaining the temperature of the reforming furnace 10 at 1000° C. or higher by burning the coke. At the third step, steam is supplied to the reforming furnace 10 via the steam inlet 50.
The fourth step is the step of maintaining the temperature of at least the upper half of the reforming furnace 10 at 1200° C. or higher. The temperature of at least the upper half of the reforming furnace 10 is increased to 1200° C. or higher by burning a gas mixture (CO2, H2O, CO, and H2) generated through the burning of the coke and the use of the steam and/or the syngas supplied to the reforming furnace 10 via the syngas inlet 70.
When the temperature of the at least the upper half of the reforming furnace 10 is maintained at 1200° C. or higher, carbonaceous feedstock is supplied to the reforming furnace 10 via the carbonaceous feedstock inlets 20, syngas is generated by reforming the carbonaceous feedstock, and the generated syngas is discharged via the syngas outlet 60.
In this case, the oxygen used to burn the coke at the second step can be supplied via the first oxygen inlet 40 which is formed in a lower section of the reforming furnace 10, and the oxygen used to burn the gas mixture or syngas at the fourth step can be supplied via the second oxygen inlet 42 which is formed at the mid-section of the reforming furnace 10. The syngas at the fourth step can be part of the syngas generated at the fifth step, and the high temperature syngas generated at the fifth step can pyrolyze the carbonaceous feedstock and be then cooled.
A main heat source is the coke pile located in the lower section of the reforming furnace 10. A high temperature of 1500 to 1800° C. is generated by burning the coke along with the oxygen. When steam is gradually supplied over the coke pile located in the lower section of the reforming furnace 10 via the steam inlet 50, a gas mixture (CO2, H2O, CO, and H2) rises up and heats the overall reforming furnace 10 to 1000° C. or higher. When hydrogen gas H2 is continuously detected at the syngas outlet 60, oxygen gas O2 is gradually injected in small amounts via the second oxygen inlet 42. When the amount of syngas generated in the coke pile is increased by increasing the supply of the steam via the steam inlet 50 and the temperature of the upper half of the reforming furnace 10 reaches 1200° C. or higher by carefully increasing the oxygen injected via the second oxygen inlet 42, carbonaceous feedstock is introduced via the carbonaceous feedstock inlets 20. A part of the syngas (<10%) discharged via the syngas outlet 60 is supplied to the reforming furnace 10 via the syngas inlet 70. The purpose of the supplied syngas is to exhaust the oxygen gas entering via the first oxygen inlet 40 and/or second oxygen inlet 42 and to maintain the temperature of the upper half of the reforming furnace 10 at 1200° C. or higher. A region above 1200° C. is a region in which the heat balance and the reforming reaction to start are established, and therefore the reforming reaction takes place most efficiently without the presence of a catalyst. The syngas production capacity of the industrial high temperature reformer (Kim reformer-XT) according to the present invention is 500 m3 or more. When the temperature of the upper half of the reforming furnace 10 is decreased to 1200° C. or lower, the supply of the carbonaceous feedstock may be stopped and the process may be re-started, or the amounts of syngas supplied to the syngas inlet 70 may be increased, and then the oxygen supply.
Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that the scope and spirit of the present invention are not limited to these embodiments, and various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.
The present invention can produce syngas at a capacity having improved from 100 m3/hour to 500 m3/hour or more by improving a small-sized experimental reformer into an industrial reformer.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2015-0159511 | Nov 2015 | KR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/KR2016/012639 | 11/4/2016 | WO | 00 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2017/082590 | 5/18/2017 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 4272255 | Coates | Jun 1981 | A |
| 4306506 | Rotter | Dec 1981 | A |
| 4400181 | Snell | Aug 1983 | A |
| 4459138 | Soung | Jul 1984 | A |
| 5026403 | Michel-Kim | Jun 1991 | A |
| 5034021 | Richardson | Jul 1991 | A |
| 6083862 | Wheelock | Jul 2000 | A |
| 6333015 | Lewis | Dec 2001 | B1 |
| 6790383 | Kim | Sep 2004 | B2 |
| 7556659 | Kim | Jul 2009 | B2 |
| 8753411 | Kim | Jun 2014 | B2 |
| 8858661 | Kim | Oct 2014 | B2 |
| 8997664 | Broglio | Apr 2015 | B2 |
| 20020069798 | Aguadas Ellis | Jun 2002 | A1 |
| 20020095866 | Hassett | Jul 2002 | A1 |
| 20030106266 | Bryan | Jun 2003 | A1 |
| 20040232046 | Tanaka | Nov 2004 | A1 |
| 20060265954 | Dogru | Nov 2006 | A1 |
| 20070012229 | Rehmat | Jan 2007 | A1 |
| 20090165382 | Rappas | Jul 2009 | A1 |
| 20090188165 | Ariyapadi | Jul 2009 | A1 |
| 20100024300 | Chornet | Feb 2010 | A1 |
| 20100051875 | Chornet | Mar 2010 | A1 |
| 20100155669 | Tsang | Jun 2010 | A1 |
| 20100314583 | Banerjee | Dec 2010 | A1 |
| 20110088321 | Kim | Apr 2011 | A1 |
| 20110116979 | Yamamoto | May 2011 | A1 |
| 20110179762 | Kim | Jul 2011 | A1 |
| 20120036777 | Patel | Feb 2012 | A1 |
| 20120061618 | Santoianni | Mar 2012 | A1 |
| 20120199795 | Gorodetsky | Aug 2012 | A1 |
| 20120271072 | Robinson | Oct 2012 | A1 |
| 20140158941 | Liu | Jun 2014 | A1 |
| 20160186276 | Winter | Jun 2016 | A1 |
| 20170037328 | Wormser | Feb 2017 | A1 |
| 20180057762 | Lucas | Mar 2018 | A1 |
| 20180086994 | Kresnyak | Mar 2018 | A1 |
| Number | Date | Country |
|---|---|---|
| 100391121 | Jul 2003 | KR |
| 100637340 | Oct 2006 | KR |
| 20-0434845 | Dec 2006 | KR |
| 100887137 | Mar 2009 | KR |
| 20110044316 | Apr 2011 | KR |
| 20130072703 | Jul 2013 | KR |
| 2010035430 | Feb 2012 | WO |
| Entry |
|---|
| Decision of Patent Allowance dated Apr. 5, 2016 of corresponding Korean application No. 10-2015-0159511; 3 pgs. |
| International Search Report dated Feb. 3, 2017 of corresponding International application No. PCT/KR2016/012639; 5 pgs. |
| H. Y. Kim, “A low cost production of hydrogen from carbonaceous wastes”, International Journal of Hydrogen Energy 28 (2003), pp. 1179-1186. |
| Kim Hyun Yong, “Method of gasification in IGCC system”, International Journal of Hydrogen Energy 32 (2007), pp. 5088-5093. |
| Number | Date | Country | |
|---|---|---|---|
| 20180127667 A1 | May 2018 | US |
