"The cost,in 2003 dollars, of the product was in the neighborhood of $13/Lb
or >$150/gallon, as much as the deposit. So ~$10K for each drum delivered. "
I really appreciate the learned honesty of those on the list advising
against HTP hobbyist projects. It's given me a serious pause for thought.
Just out of curiosity, I wonder if anyone here's been following the
development of these new catalysts for HTP production. There are multiple
that have been published in the past two years, specifically the CAT group
at Rice U's carbon black catalyst. H2, O2, di water and electricity in,
H2O2 out. These groups are eyeing this new tech for water cleaning in
remote areas. It appears to be an adequate alternative to buying low
percentage peroxide.
Providing these studies aren't bunk, they don't make the process of boiling
out the water any easier but obtaining HTP being half the battle
https://science.sciencemag.org/content/366/6462/226.full
On Sat, Jul 24, 2021 at 4:14 PM roxanna Mason <rocketmaster.ken@xxxxxxxxx>
wrote:
With all of the aforementioned and rell known pros and cons of HTP, if one
still wants to pursue using it there is still the
nagging fundamental problem
of availability and cost.
I worked at a company where we tested hybrid rocket motors using FMC 98%
HTP and aluminized HTPB in a 5" aluminum case motor.
The hoops we had to jump through was a monumental pain in the drain. Once
approved to take delivery of the first drum, a $5K deposit had to be paid
on each 30 gal aluminum drum.
The cost,in 2003 dollars, of the product was in the neighborhood of $13/Lb
or >$150/gallon, as much as the deposit. So ~$10K for each drum delivered.
Of course once you ramp up on quantity usage the drum goes away and a tank
car replaces it, no deposit but a facility tank replaces that. We never got
that far as the phase 3 SBIR was not won.
I've seen independent small companies offering 85,90,95% HTP but know
nothing else about their protocols and prices. I looked into making it but
that's another can of worms. People have died doing that including
rotovapping. The vapor is more dangerous than the liquid, not much
different than nitrous.
In pursuit of the holy oxidizer never ends as each new crop of young
rocket engineers enter the arena more than willing to reinvent the
wheel, too often the square one.
The book ;Ignition; by Clark should be required reading.
Good luck and God's Blessings to all who want to give it a go. Who knows,
perhaps the Elon Musk of HTP is out there.
Ken
On Fri, Jul 23, 2021 at 9:46 PM Alexander Mikhailov <
alexander.mikhailov@xxxxxxxxx> wrote:
Attempting to switch topic a bit. Here is a rough translation of an
article in "Chemical industry", 2015, a Russian magazine, talking
about HTP catalyst. Sorry for possible mistakes and overall style,
tried to remain close to the text.
This is supposed to be read in a monospace font.
-----
New reuseable high efficiency catalyst of highly concentrated hydrogen
peroxide decomposition
Kosyh V.A., Guseinov Sh.L., Efimov N.K.
AO "GNIIHTEOS", Moscow
Highly concentrated hydrogen peroxide, stabilizing, stainless steel,
catalyst
The results of the development and properties study of high-performance
reusable
solid catalyst for decomposition of highly concentrated hydrogen peroxide
without the use of noble metals with long-term stable performance and long
service life are presented. The total operating time of the catalyst
package
is more than 3500 seconds, while no catalyst activity reduction and no
traces
of destruction have been found. Experimental results have shown stable
results
of the main parameters in all test modes of the studies (reactor pressure,
temperature, entrainment, etc.) which allows to conclude that there is no
destruction of the catalyst and no loss of its properties. This confirms
the
prospect of using the developed catalyst as a reusable decomposition
catalyst
"PV-85" and "PV-98". Thorough elaboration of a technology and full-scale
production of a new solid catalyst require broad-scale research and tests.
Usage of HTP in rocketry has not lost its relevance.
HTP has high density and specific impulse, is very interesting as a single
component fuel and is a great oxidizer. Thanks to unique qualities over
many
years HTP is used in rocketry both as the only component and as an
oxidizer
in two component systems, as well as a source of overheated steam gas to
drive
turbopumps of rocket engines used in "Soyuz" rocket family.
Catalyzing HTP leads to active decomposition into the overheated steam and
oxygen [1, 2]. However the high temperature of decomposition (over 980 C
for
H2O2 with concentration 95% and over 520 C for H2O2 with concentration
85%)
causes destruction of known solid catalysts, used today for HTP
decomposition.
Metals like silver, gold, platinum and palladium, in addition to such
oxides
as manganese dioxide are active catalysts for HTP decomposition [3, 4, 5].
However these catalysts have limited performance resource for HTP
decomposition. Limitations include low melting temperatures, low activity
and sensitivity to stabilizers, present in hydrogen peroxide solutions,
e.g.
to decompose HTP PV-85 of GOST P 50632-93 it's not very effective to use
the
catalysts made of precious metals because of inhibiting properties of
stabilizers, present in the HTP.
The goal of this work is the development and making of modern solid
catalyst
for HTP decomposition for repeated use - Zh-30-S-OM.
This development has a high potential for future use in reaction control
systems (RCS) of space satellites, rocket main liquid fuel engines and for
development of life support systems of interplanetary spacecrafts (in gas-
generators, sources of heat, water, oxygen).
Main stages of catalyst making process
The newly developed catalyst Zh-30-S-OM is a mix, made of granules of
porous
carrier, obtained by sinthering of charge, prepared from powdered carbonyl
iron, sodium nitrate (saltpeter) and sodium carbonate (soda ash), and
carrier
granules with deposited on them active substances, which are potassium
permanganate and sodium carbonate in the form of water solution. Before
usage
the catalyst is stabilized by hydrogen peroxide of concentration 75% over
time
period of 450 s under pressure of 10 atm.
Technological process of making the catalyst has the following main
stages:
- Preparation of basic materials
- Making the charge
- Sinthering the mixture
- Processing and oxidizing of the obtained carrier
- Coating with active salts
- Stabilizing the catalyst in reactor.
Technological process
1. Drying of the saltpeter
The sodium nitrate is unpacked from paper or polyethylene bags onto
backing
sheets or metal sheets covered with cardboard or paper, making a layer of
10-15 mm, leaving for at least a day in the room temperature. If
necessary the
crumpled saltpeter is put in a container, moistened with distilled water
of
quantity approximately 0.5 liter per bag of saltpeter and left in a closed
container for at least 4 hours, and remaining crumples are broken with a
metal
tool. The dried saltpeter is sifted with mesh no. 09 by GOST 3826-82
[side of
cell as light passes: 0.9 mm, wire diameter: 0.22; 0.36 mm] and put into
tightly closed container. Saltpeter is analyzed on amount of vapors. If
there
is more vapors than 0.2%, the saltpeter is dried again, as described
above.
2. Moistening of soda ash
Before moistening the ash is sifted with mesh no. 05 [cells 0,50 mm, wire
0,20;
0,25; 0,30 mm]. Moisture content is determined in the ash. The calculated
amount of water is put in a pressure tank. The ash is put on a baking
sheet
under the pressure tank injector. The ash is moisturized with distilled
water
from the tank, pressurized by air. The moistening is made while
continuously
mixing the ash by hand until the process is complete. The moist ash is
sifted
with mesh no. 05 and put into tightly closed containers and left for 1-2
days. After that soda is sifted again using the same sieve. The formed
lumps
are thrown to waste. In the sifted ash the water content is determined,
the
water should measure by mass about 20-22%, if there is less water then the
ash is moisturized again.
3. Making the charge
The components (powdered iron, soda ash, saltpeter) are weighted and
poured
into intermediate containers, from which they are loaded into a mixer. The
sequence of loading: first soda ash and saltpeter, then iron.
The charge is stirred for 5-7 minutes. The mixing is done with periodic
(2-4
times) change of mixer direction of rotation. After mixing in the mixer
the
charge is unloaded into a baking sheet and weighted, then mixed by hand
for
at least 2 minutes. The losses during mixing shouldn't be more than 100 g.
If the charge isn't mixed well enough it's allowed to mix it again in the
mixer for 5-7 minutes.
4. Compacting the charge
Sinthering the charge is done in special molds. Before putting the charge
in,
the internal surface of molds is cleaned with metal brush. A sheet of
smoking
paper is put to the bottom of the mold. Charge is split into masses of
0.5 kg
+/- 0.005 kg, put into molds, the surface is leveled and the charge is
separated from the walls by a thin plate by inclining it, then the charge
is
covered with a sheet of smoking paper, the cover is put and pressure is
applied with pneumatic press under pressure of 0.38-0.45 MPa for the time
period of 25-30 s.
The remaining part of the charge after pressing is not used in production
and
thrown to waste.
5. Sinthering the charge
Molds with charge are put into the sinthering cabinet. The time between
completing the charge mixing and starting sinthering shouldn't be longer
than
60 minutes. Into the corner holes of mold covers put the ignition
mixture, made
of powdered iron and saltpeter, taken in proportion 1:1 by volume. The
mixture
is ignited and the charge is ignited from it. Because of iron powder
oxidizing
with saltpeter a high temperature is developed and charge sinthers. Soda
ash
decomposes with gas exhaustion, which makes necessary porosity of sinther.
Combined reaction of charge sinthering is going according to the following
equation:
Fe + NaNO3 -> sinther + N2 + CO2
(gases leave the sinther)
The sinther is constituted of Na2O, unoxidized iron, FeO and sodium
ferrites:
water-soluble NaFeO2 and hydrolytically resistant Na2FeO2.
Sinthering continues up until the charge stops burning. After that the
molds
are cooled in the cabinet for at least 30 min. The sinther is removed from
molds and colled. The cooled bars are cleaned from remaining paper and
stored
in closed containers.
6. Crushing and splitting of sinther
The bars of sinther are crushed on guillotine directional crusher. The
crusher
knife is set at about 6.7-7.3 mm from the stop. The sinther stripes are
ground
into granules of cubic shape - fractions of 6-10 mm.
Chipped sinther (unoxidized carrier) is sifted through sieve with cells of
diameter 6.0 +/- 0.1 mm to remove the trifle and then through the sieve
with
cells of diameter 10 +/- 0.1 mm. Granules which didn't pass through the
second
sieve are run in manually to the necessary size. Ground sinther is stored
in
a closed container.
7. Oxidizing the carrier
Oxidation of the carrier is done in an oxidizer with an electric heater.
Unoxidized carrier is loaded into a mesh drum, covered with steel mesh
no. 2
or no. 3, 4, 5 according to GOST 3826-82 [cell: 2, 3, 4, 5 mm, wire: 0.40;
0.50; 0.60; 0.80; 1.00; 1.20; 1.60; 2.00 mm]. The drum is installed in the
oxidizer.
Oxidizer is heated to the temperature of 350 +/- 5 C, the duration of
heating
should not exceed 2 hours. After that, when the drum is rotating, the
vacuum
pump is turned on, to supply the oxidizer with air. In front of vacuum
pump
a trap is set for catching the dust.
The temperature in the oxidizer is raised up to 500 +/- 5 C; duration of
the
heating between 350-500 C should be 30-90 min. Oxidation of the carrier is
done with temperature 490-525 C over 4.5-5 hours. Amount of supplied air
is
33-40 liter/min. Overall duration of oxidizing, including the heating from
350 C, is 5.0-6.5 hours.
When temperature is 490-525 C Na2FeO2 is partially oxidized to NaFeO2,
and as
a result the amount of water-soluble base grows.
Oxidation of iron happens mostly to Fe2O3, which in this conditions is
the most
stable form of iron oxide.
Combined reaction of oxidation of carrier is going according to the
following
equation:
4 Na2FeO2 + O2 -> 4 NaFeO2 + 2Na2O
After oxidation process is complete the heating is turned off and the air
supply is stopped.
To cool the partial product one can rotate the oxidizer drum for no longer
than 2 hours after turning the heater off. Oxidizer is cooled to the
temperature no higher than 60 C, carrier is unloaded into tin cans and
weighted.
The oxidation degree is determined by the growth of mass. After oxidation
the
mass gain should be from 9 to 16% of mass of loaded unoxidized carrier.
In case of insufficient mass growth of oxidized carrier it's allowed to
repeat the oxidation. Repeated oxidation is done with the same process
over
the time period of 1-2 hours.
Oxidized carrier is sifted through sieve with cells of diameter 6.0 +/-
0.1
mm to remove the trifle, and then through the sieve with cells of diameter
10 +/- 0.1 mm.
+--+------->---------+ +--+
+--+ | | | +-+
4+->-+
+-+ 8+--+ | -+- -+- | +--+
|
| +--+ | | \7/ \ / |
|
| v | x x |
+--+ |
|\ /| +--+ | | / \ / \ | +-+
5+>+
+-| x |-+10+--+----+-+--+----+ | -+- -+- | |
+--+ |
| |/ \| +--+ v v v v | | +--+ v | |
|
| | | | | | | | | | | |
+-+
^ +-++ +-++ +-++ +-++|+-+-++ | +-----+------+ 6 - o | |
| | | | | | | | ||| /| | | | v | |
| 9| | | | | | ||| / | | | | | |
|P1
| | | | | | | ||| /11| v ---+--- ---+--- | o
+--+-+
| | | | | | | ||+----+ | / \ / \ | v |
1 |
| | | | | | | || | / 2 \ / 3 \ | | |
|
| | | | | | | || || || || | |
|
| | | | | | | || || || || | |
|P2
| | | | | | | || || || || |
+--+-+
+--+ +--+ +--+ +--+| || || || |
|P3
| | | | | | \ / \ / | |
|T1
-+- | | | | | \ / \ / | |
+----
\ / | | | | | ---+--- ---+--- | |
T2 T3
x -+- | -+- | | v v | |
/ \ \ / | \ / | | -+- -+- | |
-+- x -+- x | | \ / \ / | |
| / \ \ / / \ | | x x | |
| -+- x -+- | | / \ / \ | |
| | / \ | | | -+- -+- | |
| | -+- | | +------+----->------+------+ |
+----+----+----+--+------------------------------------+
Picture 1. Technological scheme of the steam generating plant
1- reactor, 2,3 - tank for HTP 250 l, 4,5 - liquid disconnect valve, 6 -
check valves, 7 - valve, 8 - drainage valve, 9 - nitrogen tank, 10 -
nitrogen reductor, 11 - tank for HTP 3 l
8. Preparation of solution of active salts
The solution of active salts is prepared in the tanks with steam jackets.
Potassium permanganate, soda ash and distilled water are loaded into the
tank
and the heating starts. When the temperature of 82-100 C is reached, the
solution is mixed until complete dissolution of salts.
9. Coating with active salts
Coating with active salts is done in coating ovens using electrical
heating.
Oxidized carrier is loaded into a meshed drum, covered with steel mesh.
The
drum is installed into the oven and heating starts. When the oven
temperature
reaches 240 +/- 5 C, the rotating of the drum starts. Pouring the
solution of
active salts is done when the temperature in the oven reaches 270-300 C.
Duratino of active salts coating is 7-10 hours. As water is evaporated
from the
solution after 3 hours of the process the water is added to the solution
container. After all the solution is poured the product is dried in the
drum
with the same temperature over 15-20 min. After that the heating is
turned off,
the cover is lifted, the product is run in over 15-20 min and drum
rotation is
stopped. The oven is cooled to 60 C, the obtained catalyst is unloaded and
weighted.
The amount of coated active salts is determined by the mass growth. The
mass
growth of the catalyst during coating should be 35-50% by mass.
10. Stabilizing catalyst in the reactor
Potassium permanganate is often considered a catalyst of hydrogen peroxide
decomposition, however by itself it is not such a thing. When reacting
with
HTP, potassium permanganate is decomposed with creation of manganese
oxide,
which actually works as the catalyst of HTP decomposition. During
reaction the
amount of potassium permanganate is reduced because of decomposition.
Combined equations of reactions can be represented in the following way:
3 H2O2 + 2 KMnO4 -> 2 MnO2 + 2 KOH + 3 O2 + 2 H2O + Q
(under MnO2)
2 H2O2 -------------> 2 H2O + O2 + Q
Catalyst stabilizing is done in a special reactor.
Hydrogen peroxide of concentration 75% is supplied to the reactor for 450
s,
under working pressure of 10 atm, in this case pressure and temperature
stabilize on 380-400 s of the process.
After completion of the process the reactor is cooled to the room
temperature, the catalyst is unloaded and stored in a tightly closed
container.
Testing the catalyst Zh-30-S-OM
Determining the efficiency of the catalyst is done on a special stand
(pic. 1)
when decomposing the oxidizer PV-85 [HTP, 85%] in an experimental reactor
(pic. 2). At the same time the catalyst conformance to the performance
requirements for generated steam pressure, pressure difference in a
catalyst
layer, steam temperature is checked under different relative loads, which
are achieved when using the regular catalyst.
+-8+
| |
P1 +-----2+
===+ |
+-++---+------+---++-+
| || || |
| || +------+ || |
| || / \ || |
+-++-+------5---+-++-+
| |
| |
| |
| +6+ |
| +-+ |
| 1
| |
| |
|=======4==|
| || / |
| --||-- |
P2 | / || 3 |
==+--+----+--+
\ /
++ ++
| |
| |
++ ++
||----10
++ ++ T1 T2 T3
P3 | | || || || +--9-+
===+ +------++---- -----++----- ----++--------+---/
| | \\ 7 \\
+----+------------- ------------ -------------+---\
+----+
Picture 2. Experimental reactor for catalytic decomposition of HTP.
1 - reactor body, 2 - cover, 3 - screw (to swirl the flow), 4,5 - pack of
meshes, 6 - catalyst, 7 - pipe for steam exhaust, 8 - injector, 9 - flow
rate
limiter, 10 - fitting for steam exhaust, P1,P2,P3 - fittings for pressure
sensors, T1,T2,T3 - fittings for temperature sensors
Technological scheme of the facility for decomposition of high test
peroxide
The facility includes a fire room, room for reactor preparation, room for
accepting the HTP, room for distilled water preparation and also a panel
for
controlling the process, gathering and processing the information.
Tanks 2 and 3 ensure the supply of HTP into reactor 1 to conduct testing
in
the mode of "Determination of the period of stable performance". For this
mode
high values of specific load of 3-3.4 kg/kg*s^-1 are typical. The tank 11
ensures the supply of the oxidizer into reactor 1 to measure the time to
reach stable state by temperature and pressure, and also to test in
conditions
of low specific load 0.1-0.4 kg/kg*s^-1.
Pressurized nitrogen for the stand is supplied from tank battery 9. The
regulation of supply of pressurized nitrogen is done from the control
panel,
placed in the stand control room.
Reactor 1 is made from stainless steel and has removable top cover 2.
Internal
diameter of cylindrical part of reactor is 60 mm. The reactor has stacks
of
stainless steel meshes 4.5 with diameter of 60 mm correspondingly of 10
and 2
layers, which hold the catalyst between them.
To ensure different required flow rate of HTP and also the required
pressure
of steam gas mixture at the reactor input for the supply of the oxidizer,
a detachable injector 8 is installed, and the output pipe for steam gas
mixture ends with nozzle 9 with diameter 3 mm.
The reactor and the pipe for the output of the steam gas mixture have
pressure and temperature sensors, their readings are registered at the
control panel automatically. After each test the reactor is disassembled
and
the catalyst is weighted to determine the loss of active mass.
To estimate the possibility of developing the technology of making,
developing and mass producing of the new catalyst of PV-85 and PV-98 the
following was done:
1. An experimental pilot batch of the catalyst Zh-30-S-O modernized
(Zh-30-S-OM) is produced with the mass of 270 g.
2. Testing of Zh-30-S-OM is done in 3 different modes.
All testing is done with one catalyst pack.
Mode 1 - a sequence of long tests with minimal specific flow of HTP
The mass of spent HTP V - 2.8 l, concentration of HTP C - 83.1%, nominal
pressure at reactor input P_s - 13 kgs/cm^3. Reactor size: length - 150
mm,
diameter - 40 mm.
Mode description:
- Process duration - 350 s
- Input reactor pressure - 13 atm
- Reactor pressure - 11 atm
- Temperature at the reactor exit - 495 C
- Mass flow of HTP - 0.008 kg/s
- Catalyst mass loss - 0.42% by mass
- Specific load - 0.041 kg_HTP/kg_cat*s^-1
There were 6 tests in this mode. First 3 tests were done with several day
delay
between firings. Following tests were done as a series of three firings
350 s
each.
Mode 2 - pulse mode tests with maximum specific flow of HTP
The tests are done with the following conditions.
Mass of spent HTP V - 2.8 l, HTP concentration C - 83.1%, nomimal pressure
at the reactor input P_s - 25 kgs/sm^3. Reactor size: length - 150 mm,
diameter - 60 mm.
Mode description:
- Process duration - 8.4 s
- Input reactor pressure - 25 atm
- Reactor pressure - 23 atm
- Temperature at the reactor exit - 490 C
- Mass flow - 0.33 kg/s
- Loss after series of tests - 1.34% by mass
- Specific load - 1.8 kg_HTP/kg_cat*s^-1
There were 10 tests done in a row in this mode.
Mode 3 - a series of long tests with maximum specific flow of HTP
The tests are done with the following conditions.
Mass of spent HTP V_H2O2 - 160 l, concentration of HTP - 83.1%, nominal
pressure at the reactor input P_s - 25 kgs/sm^3, reactor size: length -
150 mm, diameter - 60 mm.
Mode description:
- Process duration - 411 s
- Input reactor pressure - 25 atm
- Reactor pressure - 23 atm
- Temperature at the reactor exit - 500 C
- Mass flow - 0.33 kg/s
- Loss after series of tests - 1.5% by mass
- Specific load - 1.8 kg_HTP/kg_cat*s^-1
There were 4 tests in this mode (pic. 3)
[No picture 3 is provided. It's pretty much horizontal line at 22 over the
whole time, rapid (practically vertical) rise at the beginning and
similarly
rapid fall at the end. Picture subtitle is "Pressure changes in reactor
during
tests with maximum flow rate of HTP".]
Overall time of catalyst pack working is more than 3500 seconds, with all
that
no reduction of activity or evidence of catalyst destruction were found.
Experiment results showed stable values of main test parameters in all
modes
of experiments (pressure in the reactor, temperature, losses etc.) which
allows to conclude that there is no destruction of the catalyst or losses
of
its qualities. This confirms the promise of using the developed catalyst
as
a reuseable catalyst for decomposition of PV-85 and PV-98.
To create a technology for developing and mass production of the new solid
catalyst more wide exploration and testing is needed.
References
1. Schumb W.C., Satterfield C.N., Wentworth R.L. Hydrogen Peroxide. Edit
by
Gorbanev A.I., Doctor of Engineering. M: IL, (Moscow: publishing house
"Foreign Literature"), 1958, 578 p
2. Almazov O.A. Hydrogen peroxide oxidizers // Monograph, FGUP 25
GNIIMORF. M., (Moscow: FSUE The 25th State Scientific Research
Institute of
chemmotology of the Russian Ministry of Defense), 2004
3. Kuehl D., Marchetto M. Mixed oxide catalyst and its use in the
catalytic
decomposition of hydrogen peroxide. // Patent GB 1399042, 1972
4. Rusek J, Anderson N. High-activity catalyst for hydrogen peroxide
decomposition. // Patent US H1948 H, 2001
5. Mays J.A., Lohner K.A., Sevener K.M., Jensen J.J. Mixed metal
oxide-based
high temperature catalysts for hydrocarbon combustion and
decomposition of
propellants. // Patent US 20040198594, 2004
Authors
Kosyh Vitalii Andreevich
GNTs RF AO "GNIIHTEOS", senior scientist, candidate of technical sciences
Address: 105118, Moscow, sh. Entuziastov, 38
Work phone: 8(495)673-6330
e-mail: v.a.kosyh@xxxxxxxxx
Guseinov Shirin Latif ogly
GNTs RF AO "GNIIHTEOS", lt. General director of science, doctor of
technical
sciences,
Address: 105118, Moscow, sh. Entuziastov, 38
Work phone: 8(495)873-1315
E-mail: rejhan@xxxxx
Efimov Nikolai Konstantinovich
GNTs RF AO "GNIIHTEOS", doctor of technical sciences, direction adviser
Address: 105118, Moscow, sh. Entuziastov, 38
Work phone: 8(495)673-4953
e-mail: info@xxxxxx
-----
Alex
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