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50 To 60% (Weight Ratio), and As By-Products, A Gas
50 To 60% (Weight Ratio), and As By-Products, A Gas
PRIORART LIST
Patent Literature
[Patent Literature 1] JP 2009-001 826 A
SUMMARY OF INVENTION
Technical Problem
[0008] From the viewpoints ofthe current global situation, the conservation ofthe natural
environment, and the creation ofa sustainable society, it has been becoming more and more
important to develop an alternative resource to petroleum. However, among solar power,
wind power, and biomass, which are regarded as representatives of sustainable energy, only
the biomass can yield a renewable substance. In this sense, there is an urgent demand to
develop a technology for producing a renewable substance including a fuel form origin ated
from biomass.
[0009] The inventors of the present invention have previo usly proposed an external heating
steam gasification method involving using solid plant biomass as a raw material (JP
2009-001826 A). This gasification method is a technology involving: in the absence of any
catalyst, feeding finely pulv erized biomass into a reaction tube filled with high-tempera- tire
steam and heating the reaction tube from outside to subject the steam and biomass to a steam
reforming reaction in a furnace having a low oxygen concentration in the absence of any
catalyst, to thereby generate a high-quality synthesis gas containing hydrogen and carbon
monoxide as main comp onents. The method can provide a good-quality synthesis gas
directly from solid biomass.
i: 0010] However, the above-mentioned process involves directly gasifying solid biomass,
and hence has the following problem(s): there is a difficulty in the handling of the raw
material; andlor it is not easy to scale up a plant; and/or biomass, the ash of which has a lowmelting point (for example, 800 C. or less), cannot be used. In view ofthis, the inventors
ofthe present application have conceived a product ion method for a synthesis gas involving
using a liquid biof uel, which is obtained through pyrolysis ofbiomass, as a raw material.
[0011] As a technique for obtaining a synthesis gas from hydrocarbon, there is known steam
reforming. However, this method is only known to be used in the case ofusing, as a raw
material, a gaseous or low-boiling point (generally 250 C. or less) hydrocarbon such as
natural gas (main component; methane) or naphtha. In this method, the use of a catalyst is
essential, and Ni is oflen used. The temperature ofan outlet is kept from 800 to 950 C.
during operation and a reforming furnace therefor has its inside lined with refractory bricks.
A large number of cylindrical reaction tubes filled with an Ni catalyst are suspended in
reforming furnace. The reforming furnace is heated from outside to supply heat needed for a
reforming reaction to proceed. The heating is generally per- formed by combusting the same
fuel as the raw material at a side wall. Optimal values for an operation pressure or the like is
selected in consideration of factors including gas purificat ion at a later stage, a target
product, and the like, and is about
1-10 MPa.
[0012] This method is not applicable to a liquid heavier (having a higher boiling point) than
naphtha, i.e., heavy oil or the like, and a partial oxidation method is used for such liquid. The
Texaco process, the Shell process, and the like are well known partial oxidation methods. The
partial oxidation method involves combusting part of a heavy oil raw material using oxygen
obtained from air by a cryogenic separation method, to thereby provide high temperature
needed for the reaction. The reaction temperature is from 1 ,300 to 1 ,500 C. The pressure is
determined depending on gas purification at a
later stage, a target product, and the like as in the case of hydrogen reforming and is from 1 to
8 MPa. This process involves operation at high temperature. Hence waste heat recovery and
generation of soot are unavoidable and efforts are made into recovery/effective utilization
thereof.
[0013] In contrast, hitherto, generation of a synthesis gas from a liquid biofuel has never been
studied. The liquid biofuel has not been recognized as a material for steam reforming because
ofits properties (being like tar and having a high viscosity and a high boiling point) and the
like. The application ofthe partial oxidation process is conceivable. In this case, however part
of the liquid biofuel is used in comb ustion, and hence it is conceivable that the amounts of
effect ive H2 and CO components in the generated synthesis gas decreases. In any case,
partly because it is only recently that the liquid biofuel has started to attract attention, there is
found no literature that makes a particular mention ofthe production of a high-quality liquid
fuel such as gasoline, light oil, or methanol from the liquid biofuel.
Solution to problem
[0014]
inventions.
(1) A production method for a synthesis gas, comprising:
supplying a steam and a liquid biofuel generated through pyrolysis ofbiomass to a
gasification space in a reaction tube; and heating the gasification space from outside through
a tube wall of the reaction tube to cause a steam reforming reaction to occur.
(2) A production method for a synthesis gas according to the above mentioned item (1),
wherein the liquid biofuel is obtained by separating a liquid part from a product generated
through pyrolysis ofa solid biomass.
(3) A production method according to the above mentioned item (1 ) or (2), wherein the
gasification space is free from a catalyst.
(4) A production method according to any one of the above mentioned items (1) to (3),
wherein a molar ratio ofthe steam supplied to the gasification space to a carbon in the liquid
biofuel is 0.3 or more.
(5) A production method according to any one of the above mentioned items (1) to (4),
wherein the gasification space is heated to from 8000 C. to 1 ,2000 C.
(6) A production method according to any one of the above mentioned items (1) to (5),
wherein a pressure in the gasific ation space is from 0.1 to 10 MPa.
(7) A production method according to any one of the above mentioned items (1 ) to (6),
wherein: the liquid biofuel has a viscosity offrom 10 to 50 centistokes; and the liquid biofuel
is supplied to the gasification space by spraying.
(8) A production method according to any one of the above mentioned items (1) to (7),
wherein the liquid biofuel is generated by heating a solid biomass to from 400 to 5000 C. w i
thout ac tive ly p erfo rming deo x i dat i o n treatment.
(9) A production method according to any one of the above mentioned items (1) to (8),
wherein the steam reforming reaction comprises a chemical reaction of the following formula [11, where ql=45 to 55%, q2=20 to 30%, q3=8 to 12%, and q4=15 to 25%, p1 is about
0.3 when a temperature in the gasification space is 8000 C. and p 1 is about 1 .0 when the
temperature in the gasification space is 1 ,0000 C.
CmH2On+P 1 H20q 1 H2+q2CO+q3CH4+q4CO2
[11
The present application discloses the following
(1 0) A device for producing a synthesis gas, comprising: a reaction tube having a gasification
space separated from an outside by a tube wall; a supply tube for supplying a steam and a
liquid biofuel generated through pyrolysis ofbiomass to the reaction tube; and heating means
for heating the gasificat ion space from outside through the tube wall.
(1 1 ) A device and a method for synthesizing a liquid fuel configured to produce a
hydrocarbon-based liquid fuel such as methanol, gasoline, or light oil through chemical
synthesis using, as a raw material, a gas containing hydrogen and car- bon monoxide as main
components, the gas being obtained by the production method according to the above
mentioned item (1).
[0015] The inventors ofthe present invention had a convict ion that a synthesis gas can be
generated through a reaction of a liquid biofuel using steam (steam reforming), because the
liquid biofuel is an oxygen-containing fuel. Then, the invent ors have found that the liquid
biofuel can be converted into a high-quality synthesis gas without utilizing any catalyst and
without needing a high temperature of from 1 ,300 to 1 ,5000 C. to attain the invention
according to the above-mentioned item (1), through experiments on various conditions
includi ng the addition amount ofthe steam.
I 0016] In each ofthe inventions according the above-men- tioned items (1) and (10),
although it is necessary to first convert a solid into a liquid fuel, the following excellent
effect(s) can be achieved: even biomass, the ash ofwhich has a low-melting point of 8000 C.
or less and which cannot be used as a raw material in the prior process (JP 2009-001826 A),
can be utilized irrespective ofthe melting point ofthe ash thereof; and/or the handling of the
raw material is markedly facilitated; and/or the collection and transportation ofthe raw
material become easy; andJor ash, foreign matter and the like are removed before supply to a
gasification plant, and hence the plant can be built with a simple structure economically,
thereby enabling development into a large-scale plant having high economic efficiency.
[0017] As compared to a process involving directly utilizi ng solid biomass, the process ofthe
present invention involvi ng two stages, i.e., liquefaction and gasification, may reduce total
thermal efficiency in some cases. However, which of the processes is more economical
depends on, for example, a distance between the location of the biomass raw material (solid)
and the gasification plant. That is, it is assumed that:
when the scale is so small that solid biomass can be locally produced and consumed, it is
often advantageous in terms of thermal efficiency and plant cost to treat the biomass as a
solid; and on the other hand, when the gasification plant has a large treatment capacity, the
present invention, in which the biomass is first turned into a liquid at a few to several tens of
biomass locations and then transported and collected to the gasification plant to be processed,
is more excellent in econ omic efficiency in many cases.
[0018] It is preferable that the tube wall ofthe reaction tube is capable of providing heat
needed for the steam reforming reaction from outside to the gasification space by radiation or
the like; and separating the gasification space from an outside space (blocking an inflow and
an outflow ofsubstances (mole cules and particles) between the gasification space and the
outside space).
[0019] The molar ratio ofthe steam to be supplied (supplied steam) to the gasification space
to carbon in the liquid biofuel ([H20j/[C1) is preferably 0.3 or more. With this, it is possible
to: effectively prevent the generation ofsoot during the steam
[0007]
PRIORART LIST
Sastra paten
[Paten Sastra 1] JP 2009-001 826 A
Ringkasan Penemuan
Masalah Teknis
[0008] Dari sudut pandang tersebut yang situasi global saat ini,
konservasi tersebut yang lingkungan alam, dan penciptaan ofa
masyarakat yang berkelanjutan, telah menjadi lebih dan lebih penting
untuk mengembangkan sumber daya alternatif untuk minyak bumi.
Namun, di antara tenaga surya, tenaga angin, dan biomassa, yang
dianggap sebagai perwakilan dari energi berkelanjutan, hanya biomassa
dapat menghasilkan zat terbarukan. Dalam hal ini, ada kebutuhan
mendesak untuk mengembangkan teknologi untuk memproduksi zat
terbarukan termasuk asal bentuk bahan bakar diciptakan dari biomassa.
[0009] Para penemu dari penemuan ini telah previo usly mengusulkan
metode gasifikasi pemanasan uap eksternal yang melibatkan
menggunakan biomassa tanaman yang solid sebagai bahan baku (JP
2009-001826 A). Metode gasifikasi ini adalah teknologi yang melibatkan:
dengan tidak adanya katalis apapun, makan halus pulv biomassa erized
ke dalam tabung reaksi diisi dengan high-temperatur uap ban dan
memanaskan tabung reaksi dari luar subjek uap dan biomassa untuk
reaksi steam reforming dalam tungku memiliki konsentrasi oksigen yang
rendah dengan tidak adanya katalis apapun, dengan demikian
menghasilkan gas sintesis berkualitas tinggi yang mengandung hidrogen
dan karbon monoksida sebagai onents comp utama. Metode ini dapat
memberikan gas sintesis berkualitas baik langsung dari biomassa padat.
[0010] Namun, proses tersebut di atas melibatkan langsung gasifying
biomassa padat, dan karenanya memiliki masalah berikut (s): ada
kesulitan dalam penanganan bahan baku; andlor tidak mudah untuk
meningkatkan tanaman; dan / atau biomassa, abu yang memiliki titik
leleh rendah (misalnya, 800 C atau kurang), tidak dapat digunakan.
Dalam pandangan ofthis, para penemu ofthe aplikasi ini telah disusun
metode ion produk gas sintesis melibatkan menggunakan uel biof cair,
yang diperoleh melalui pirolisis ofbiomass, sebagai bahan baku.
[0011] Sebagai teknik untuk mendapatkan gas sintesis dari hidrokarbon,
ada dikenal steam reforming. Namun, metode ini hanya dikenal untuk
digunakan dalam kasus ofusing, sebagai bahan baku, titik gas atau rendah
didih (umumnya 250 C atau kurang) hidrokarbon seperti gas alam
(komponen utama; metana) atau nafta. Dalam metode ini, penggunaan
katalis sangat penting, dan Ni oflen digunakan. Suhu ofan outlet disimpan
800-950 C selama operasi dan tungku reformasi untuk itu memiliki
bagian dalamnya dilapisi dengan bata tahan api. Sejumlah besar tabung
reaksi silinder diisi dengan katalis Ni tersuspensi dalam reformasi tungku.
The reformasi tungku dipanaskan dari luar untuk memasok panas yang
dibutuhkan untuk reaksi reformasi untuk melanjutkan. Pemanasan
umumnya per- dibentuk oleh pembakaran bahan bakar yang sama
sebagai bahan baku pada dinding samping. Nilai optimal untuk tekanan
operasi atau seperti yang dipilih dengan pertimbangan faktor termasuk
ion gas purificat pada tahap berikutnya, produk sasaran, dan sejenisnya,
dan sekitar 1-10 MPa.
[0012] Metode ini tidak berlaku untuk lebih berat (memiliki titik didih lebih
tinggi) cair dari nafta, yaitu, minyak berat atau sejenisnya, dan metode
oksidasi parsial digunakan untuk cairan tersebut. Texaco proses, proses
Shell, dan sejenisnya dikenal metode oksidasi parsial. Metode oksidasi
parsial melibatkan pembakaran bagian dari bahan baku minyak berat
dengan menggunakan oksigen yang diperoleh dari udara dengan metode
pemisahan cryogenic, dengan demikian memberikan suhu tinggi yang
diperlukan untuk reaksi. Suhu reaksi adalah dari 1, 300-1, 500 C Tekanan
ditentukan tergantung pada pemurnian gas di
tahap selanjutnya, produk sasaran, dan sejenisnya seperti dalam kasus
hidrogen reformasi dan dari 1 sampai 8 MPa. Proses ini melibatkan operasi
pada suhu tinggi. Oleh karena itu pemanfaatan kembali limbah panas dan
generasi jelaga yang tidak dapat dihindari dan upaya dibuat menjadi
recovery / pemanfaatan yang efektif dari padanya.
[0013] Sebaliknya, sampai sekarang, generasi gas sintesis dari biofuel cair
belum pernah diteliti. Biofuel cair belum diakui sebagai bahan untuk
steam reforming karena ofits properti (menjadi seperti tar dan memiliki
viskositas tinggi dan titik didih yang tinggi) dan sejenisnya. Aplikasi
tersebut yang proses oksidasi parsial dibayangkan. Dalam hal ini, namun
bagian dari biofuel cair digunakan dalam sisir ustion, dan karena itu dapat
dibayangkan bahwa jumlah efek ive H2 dan komponen CO dalam gas
sintesis yang dihasilkan menurun. Dalam hal apapun, sebagian karena
hanya baru-baru ini bahwa biofuel cair telah mulai menarik perhatian,
tidak ditemukan ada literatur yang membuat menyebutkan tertentu
tersebut yang produksi bahan bakar cair berkualitas tinggi seperti bensin,
minyak ringan, atau metanol dari biofuel cair.
Pemecahan masalah
[0014]
penemuan.
(1) Sebuah metode produksi untuk gas sintesis, terdiri dari:
memasok uap dan biofuel cair yang dihasilkan melalui proses pirolisis
ofbiomass ke ruang gasifikasi dalam tabung reaksi; dan memanaskan
ruang gasifikasi dari luar melalui dinding tabung tabung reaksi
menyebabkan reaksi steam reforming terjadi.
(2) Sebuah metode produksi untuk gas sintesis menurut disebutkan di
atas item (1), dimana biofuel cair diperoleh dengan memisahkan bagian
cair dari produk yang dihasilkan melalui pirolisis ofa biomassa padat.
(3) Metode produksi sesuai dengan yang disebutkan di atas item (1) atau
(2), dimana ruang gasifikasi bebas dari katalis.
(4) Metode produksi sesuai dengan salah satu dari item yang disebutkan
di atas (1) ke (3), dimana rasio molar ofthe uap dipasok ke ruang
gasifikasi untuk karbon dalam biofuel cair 0,3 atau lebih.
(5) Sebuah metode produksi sesuai dengan salah satu dari item yang
disebutkan di atas (1) ke (4), dimana ruang gasifikasi dipanaskan sampai
dari 8000 C. 1, 2000 C.
(6) Metode produksi sesuai dengan salah satu dari item yang disebutkan
di atas (1) ke (5), dimana tekanan dalam ruang gasific asi adalah 0,1-10
MPa.
(7) Sebuah metode produksi sesuai dengan salah satu dari item yang
disebutkan di atas (1) sampai (6), dimana: biofuel cair memiliki offrom
viskositas 10 sampai 50 centistokes; dan biofuel cair dipasok ke ruang
gasifikasi dengan penyemprotan.
(8) Sebuah metode produksi sesuai dengan salah satu dari item yang
disebutkan di atas (1) ke (7), dimana biofuel cair yang dihasilkan dengan
memanaskan biomassa padat untuk 400-5000 C. wi thout ac tive ly p erfo
rming deo pengobatan ion dat xi.
(9) Sebuah metode produksi sesuai dengan salah satu dari item yang
disebutkan di atas (1) ke (8), dimana reaksi reformasi uap terdiri dari
reaksi kimia berikut untuk-mula [11, di mana ql = 45 sampai 55%, q2 =
20 sampai 30%, Q3 = 8 sampai 12%, dan Q4 = 15 sampai 25%, p1 adalah
sekitar 0,3 ketika suhu di ruang gasifikasi adalah 8000 C dan p 1 adalah
sekitar 1 0,0 ketika suhu di gasifikasi tersebut ruang 1, 0000 C.