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piefm atioi m hxseo&ehous p b rtilio ts 11 fimfMEif
OF OILLULOSIG .1IATMJA1S WXfl AMIIOSm
by
Jotin Wesley Anderson
A D issertation Submitted to the
Graduate Faculty in P artial Fulfillm ent of
The Requirements for the Degree of
" ' ' DOST OK Of PHILOSOPHY '
Major Subjecti Ghemica1 Engineering
Approvedt
S ell qW 'la'jor" ‘Bepar|)te®nt
Sean'"’ of wattoaM^'GolIeg©
loss State College
19 SO
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UMI Number: DP12460
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TASK. OF CONTENTS
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i* i C M A i i r . , * . i
II* XSTROfctfCMOir. ' 3
m ummswrn* i
in * • BBYXBff Tin. ♦ * • ............. . . . . . . . . . . .
A* Reaction of.Ammonia with. Cellules i© ■
Materials and Oth®** Organic®« . . . . . . 7
8* Reaction of Organic Matter with Acid dr
Acidic Compounds f Followed toy Ammon1stIon
of the l e s l d u e . . . . . . 18
If. THBCRSfXOAL O O f S l S S E A T I O I S l i
A* I n t r o d u c t i o n . ....** 18
1* Products• Resulting from the Reaction
Between Cellulosic Waste M aterials and
Ammonia at lierated Temperatures* *♦».*..«**. 17
C* Reaction Products from the Reaction of
Ammonia m the Residue Resulting from the
Hydrolysis of Cellules 1c Waste M aterials#.** 18
V* SMAhh ROM* IASGRATORY PS0CSBBE1* ' m
A. AmmoniatIon of Corneotos at High Temperatures' 88
1. Itulpmemt . . . . . . . . . . . . . . . . . . . . . . ............ gg
g# Operating procedure.*#.*.**#*.**...#.#*, 84
B. Hydrolysis and Ammoniation of Cellules 1©
Waste M aterials .......... 84
1* Equipments... 04
8. Operating procedure ■ 88
VI. BXMIHNTAE H S S 0 2 M , ,**,,*# 28
A. Ammonia t ion of C o r n c o t o s 88
1, Effect of smmoniatien temperature****..# 08
T 9 V 9 / S/
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Pag©
2. Iffeat ©f reaction tin© on nitrogen
content resulting, from antmonlation ©f
©©rneobs. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
g.* Discuss i©n of the re su lts. . ........................ ... 31
4. Discussion of other wriabl®#*. 31
1. Hydrolyais and Ammoniation of Cellulosic
■' M aterials 34
1* Hydrolysis studies with dilute sulfuric
m e id . 34.
.a* Effect of liquid/solid rati© and
acid c o n c e n t r a t i o n * * 35
to* If feet of hydrolysis tiia© 46
c. , Iff© st of hydrolysis temperature.**-.. 4i
d. Effect of particle sis© ©nr the
yield.of' n i t r o g e n * *.»*.*.**.*. 51
©* Effect of moisture content hefore '
ammoniations. . . . . . . . . . . . . . . . . . . . . . . . 56
f* -Iffeet of aaattoniatlon tint©#.**'.*.»•. 56
g* Effect of aaaaoniation temperature.** .'61
h. Effect of sample drying temperature
in sample a n a ly s is ...... 61
1. Hydrolysis and 'aaajjonlation of '
pentoaen^eentainlng compounds.............. 64
j* Discussion of results#*.**. 67
2. Hydrolysis studies with dllut©
phosphoric acid*...................... 68
a* Effect of sample drying temperature. 68
b. Effect of hydrolysis tim e, using
/ 3 #28 per cent H^PO^•••.< •••« •.....•• 62
0. Discussion of the re s u lts.,...* .* * .. '69
3* Hydrolysis by normal superphosphate*...* 75
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Pag#
&• Effect of HgO/cob rati© and cob/
superphosphate ratio on the
nitrogen y l ® I d 75
4. Hydrolysis by concentrated super*
phosphate * .......... 80
a* Effect of cob/concentre ted super
phosphate on nitrogen yield at a
fixed UgG/eob r a t i © 80
5* HydrolysIs by ammonium su lfate..... 84
?n, mmwfwm or iio iim iis iquipmm................. 86
fill* mmVQT Et&W&T 1 0 1 * , . . , . . 9 8
A* Summary ©f Analytical Data on
Products A, B, and 0 ..* .* .......... . . . . . . 95
B» Exposure to Atmosphere.......................... 93
0. lygroioopielty, , 96
1. Apparatus. , 97
8# Procedure •# •••...« ..................................................99
5 , Experimental results 99
a. Dynamic method............................... 99
b. S tatic method. «*.*•• 103
4. Discussion of re su lts..•.,.....**••»•**•- 103
D* Caking O h a r a c t e r i a t l c s . 107
1. Apparatus and procedure*.*,.**.....*..* 107
t* Results............... 108
E* nitrogen Forme in Products A, 1, and C..*** l i t
P. greenhouse Plant-Orowth Testa................. 113
1* P r o c e d u r e . . , , . . . . . ■ 113
2. Experiment*1 results , . . . . H i
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3* Ms sussion. of re su lts .
fmuwwmi
xx. cost: .ahaixsis.,.................
A. Introduction.;.
1 , Design Conditions. .V
C# Summary of the Costs and Salts
Value of Produst A.. . . . . . . . . . . . . . . .
D# Msemsaien of the R esults....................
X. COHOIitfSXCtS AID lEOOMMIIMf XGSS. . . . . . . .
f t AW® It* fWWTl
XXX. ACJ®»IM>aSKSlT.. . . . . . . . . . . . . . . . . . . . . . . .
XXXI. APPEHDJX* ...........
A. Dias eolation of Ammonium Phosphates
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I* SUMMARY
An investigation was carried out to develop an economical
process for making nitrogenous fe rtiliz e rs from ammonia and
cellulosic waste m aterials auoh as corncobs, cornstalks, and
oat h ulls• In this endeavor, two different methods were in-
*
vestigsted*
One method was based on hydrolysis of the hemioelluloses
in these m aterials with dilute solutions of mineral acids or
salts followed by aamoniatlon with anhydrous aamonla of the
hydrolysate* With corncobs, when 8*25 per cent sulfuric acid
and" a liquid/solid ratio of 2*0 was used for hydrolysis, and
ammoniation was carried out slightly above room temperature,,
a product was obtained containing 7*4 per cent total nitrogen
of which 4.2 per cent was organic nitrogen (Product A)* With
the same hydrolysis conditions and an ammoniation temperature
of 249° C*, a product was obtained containing 9*5 per cent
nitrogen of which 56 per cent was organic nitrogen .(Product B).
In Product A, 86*4 per cent of the to ta l nitrogen was water-
soluble, and in Product B only 17.6 per cent was w ater-soluble,
formal and concentrated superphosphates or dilute phosphoric
acid in the hydrolysis step did not result in as much organic
nitrogen as sulfuric ecld.
The second method Involved the ammoniation of the eellu-
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losic materia la with anhydrous ammonia• By this process, a
product containing 4*6 per cent to ta l nitrogen was obtained
with corncobs at a temperature of 300® C. (Product C). In
this product, a ll the nitrogen was organic and none of It was
water-soluble*
Small-scale engineering equipment for produeting Product
A was built and tested* Products were mad© which were essen
tia lly the same as thosepprepared on a laboratory scale*
An evaluation of Products A, B, and C as fe rtiliz e r mater
ials was made. . Pests were made to determine chemical sta b ility ,
hygroscoplclty, and caking characteristics• Ihese tests showed
that Products A, B, and C could be used in mixed fe rtiliz e rs .
Greenhouse plant-growth tests were carried out. Product A
proved to be better than M llorganlte, a commercial nitrogen
fe rtiliz e r spade from sewage, and was almost as good as ammonium
sulfate. Products B and Q did not compare well with Product
A, ammonium sulfate, or M ilorganite in the plant-growth testsj
however, under different condition® of a longer growing season,
these two products might be b etter.
A preliminary cost analysis indicated that Product A might
compete with ammonium sulfate and could easily undersell Mllor
ganlte*
It is recommended that further pilot plant work be carried
out on the production of Produet A.
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