US2015203761A1PendingUtilityA1
Catalytic Pyrolysis Process And Pyrolysis Products So Formed
Est. expiryAug 8, 2032(~6 yrs left)· nominal 20-yr term from priority
Inventors:Milena VasicMartinus Henricus PronkRuben Van DurenMelle KochLeonardus Cornelis Albertus Van Den OetelaarDavid Van Der Beek
C10C 5/00C10L 1/02C10G 2300/1011C10L 2200/0469C10B 53/02C10G 1/086C10L 2290/02C10B 49/22C10B 57/06Y02P30/20Y02E50/30Y02E50/10
32
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Claims
Abstract
Biomass material is pyrolyzed in the absence of air, O 2 , H 2 , and solvent (e.g., H 2 O) at 500° C. or above in a reactor containing (i) a catalyst which as charged is a rehydrated calcined calcium-containing layered dihydroxide comprised of particles having an average particle size in the range of about 40 to about 400 microns (preferably in the range of about 50 to about 150 microns), which optionally is in a pre-agglomerized form, and (ii) a particulate fluidizable heat transfer medium, preferably sand; and condensing and isolating pyrolysis oil produced and collecting and isolating non-condensable gases separately from the condensed isolated liquid pyrolysis oil product. Pyrolysis oil obtained directly from the pyrolysis has a total acid number less than 70 mg/KOH/g; and a weight percentage of O 2 removal of 72 wt % or more as determined by a described test procedure and as calculated using an expression given in the text.
Claims
exact text as granted — not AI-modifiedThat which is claimed is:
1 . A pyrolysis process for producing partially condensable vaporous products from a particulate or subdivided biomass material which is untreated except for optional drying and/or size reduction, said process comprising;
A) subjecting said biomass material to pyrolysis at one or more temperatures of 500° C. and above in a reactor containing (i) a catalyst which as charged to the reactor is a rehydrated calcined calcium-containing layered dihydroxide comprised of particles having an average particle size of about 40 to about 400 microns, which catalyst optionally is in a pre-agglomerized flowable or fluidizable shaped form, and (ii) a particulate fluidizable heat transfer medium, preferably sand, to form pyrolysis products; and B) condensing and isolating liquid pyrolysis oil product from said pyrolysis products and collecting and isolating non-condensable gases separately from the liquid pyrolysis oil product.
2 . A pyrolysis process as in claim 1 wherein said catalyst as charged into the reactor contains about 0.1 to about 20 wt % of calcium, and wherein the contents of the reactor is and remains free of separately added metal components other than (a) divalent and trivalent metal contents of the layered dihydroxide of said catalyst and (b) the added calcium content of said catalyst.
3 . A pyrolysis process as in claim 1 wherein said catalyst as charged into the reactor has a layered dihydroxide component which comprises, consists essentially of, or consists of a magnesium/aluminum layered dihydroxide.
4 . A pyrolysis process as in claim 3 wherein said magnesium/aluminum layered dihydroxide has a molar ratio of MgO to Al 2 O 3 of about 2:1 to about 8:1.
5 . A process as in claim 1 wherein said pyrolysis is a fast pyrolysis.
6 . A process as in claim 1 wherein the biomass material is a lignocellulosic biomass, and wherein said pyrolysis is a fast pyrolysis.
7 . A process as in claim 1 wherein said liquid pyrolysis oil product has a total acid number measured in terms of milligrams of KOH/gram of liquid product that is lower than a total acid number measured in the same way on a liquid pyrolysis oil product obtained by pyrolysis under the same conditions except for use of sand alone (100 parts by weight) or a combination of a layered dihydroxide (25 parts by weight) and sand (75 parts by weight) in place of said catalyst (25 parts by weight) and sand (75 parts by weight), and wherein said pyrolysis is a fast pyrolysis.
8 . A process as in claim 1 wherein the biomass material fed has a weight percentage of oxygen removed as determined by the General Pyrolysis Test Procedure and as calculated in accordance with the expression
O
removal
=
X
CO
·
M
O
/
M
CO
+
X
CO
2
·
2
M
O
/
M
CO
2
+
X
H
2
O
·
M
O
/
M
H
2
O
O
feed
/
100
%
wherein:
O removal is wt % of oxygen removed (wt % based on oxygen in the biomass material fed)
M O : molar mass of O=15.999 (g/mol)
X CO : yield of CO (wt % on biomass material fed)
M CO : molar mass of CO=28.01 (g/mol)
X CO2 : yield of CO 2 (wt % on biomass material fed)
M CO2 : molar mass of CO 2 =44.01 (g/mol)
X H2O : yield of H 2 O (wt % on biomass material fed)
M H2O : molar mass of H 2 O=18.02 (g/mol)
O feed : oxygen content in the biomass material fed (wt %),
is higher than the weight percentage, as determined in the same way, of oxygen removed from biomass material subjected to pyrolysis under the same conditions except for use of sand alone (100 parts by weight) or a combination of a layered dihydroxide (25 parts by weight) and sand (75 parts by weight) in place of the rehydrated calcined calcium-containing layered dihydroxide catalyst (25 parts by weight) and sand (75 parts by weight), and wherein said pyrolysis is a fast pyrolysis.
9 . A fast pyrolysis process which comprises:
A) introducing a particulate or subdivided solid state biomass material which is untreated except for optional drying and/or size reduction into a fluidized bed reactor containing a particulate fluidizable heat transfer medium, preferably sand, and a catalyst which when charged to the reactor was a rehydrated calcined calcium-containing layered dihydroxide comprised of particles having an average particle size of about 40 to about 400 microns, which catalyst optionally was in a pre-agglomerized flowable or fluidizable shaped form, said reactor being operated under fast pyrolysis conditions to produce partially condensable vaporous products; and B) continuously removing condensable vaporous products from the reactor condensing and isolating liquid pyrolysis oil product from said condensable vaporous products and collecting and isolating non-condensable gases separately from the liquid pyrolysis oil product.
10 . A condensed and isolated liquid pyrolysis oil product obtained directly by pyrolysis of biomass material wherein said pyrolysis oil product without treatment that alters the pyrolysis oil during or after pyrolysis, said liquid pyrolysis oil product being characterized by having:
a) a total acid number less than 70 milligrams of KOH/gram of liquid product; and b) a weight percentage of oxygen removed from the biomass material fed of at least 72 wt % as determined by the General Pyrolysis Test Procedure and as calculated in accordance with the expression
O
removal
=
X
CO
·
M
O
/
M
CO
+
X
CO
2
·
2
M
O
/
M
CO
2
+
X
H
2
O
·
M
O
/
M
H
2
O
O
feed
/
100
%
wherein:
O removal is wt % of oxygen removed (wt % based on oxygen in the biomass material fed)
M O : molar mass of O=15.999 (g/mol)
X CO : yield of CO (wt % on biomass material fed)
M CO : molar mass of CO=28.01 (g/mol)
X CO2 : yield of CO 2 (wt % on biomass material fed)
M CO2 : molar mass of CO 2 =44.01 (g/mol)
X H2O : yield of H 2 O (wt % on biomass material fed)
M H2O : molar mass of H 2 O=18.02 (g/mol)
O feed : oxygen content in the biomass material fed (wt %).
11 . A pyrolysis oil product as in claim 10 further characterized by having a higher weight percentage of carbon dioxide removed as determined by said General Pyrolysis Test Procedure as compared to products prepared without a catalyst and tested in said General Pyrolysis Test Procedure.Join the waitlist — get patent alerts
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