Rapid Catalyst Screening Reactors

Rapid screening of catalysts
Analysis of a variety of sample types
Multi-modes of operation

Tandem µ-Reactor
Rx-3050TR

Single µ-Reactor
Rx-3050SR

OverviewTwo accessories, the Selective Sampler and theMicroJet Cryo-Trap, enable the products formed in up
to eight thermal zones, to be automatically analyzed.
Both reactors are designed to heat and cool rapidly
which increase the number of catalysts that can becharacterized in a given period of time. Threedifferent reaction gases can be connected to thesystem so that each catalyst can be evaluated undera variety of reaction conditions.

Two types of rapid catalyst screening reactors(Tandem µ-Reactor and Single µ-Reactor) have beendeveloped to facilitate the rapid characterization ofcatalysts. These µ-Reactors are easily interfaced to agas chromatography-mass spectroscopy (GC/MS)
system, allowing real-time monitoring of the chemical
species generated by vapor phase contact reaction
with a catalyst. The catalyst is packed into a quickchange catalyst reaction tube prior to testing.

Rapid catalyst evaluation using a mass spectrometer (MS) as a detector
In the Tandem µ-Reactor, two reactors (upper andlower), are individually temperature-controlled. The
upper reactor (1st Reactor) is used to preheat a gas,
vaporize a liquid, or thermally decompose organic
solids to generate gases. The catalyst reaction tube ispacked with a catalyst and placed in the lower reactor(2nd Reactor).

Pack areaction tube
with catalyst

Introduce
sampleReaction tube

Volatiles released from the heated or thermallydecomposed sample stream flow into the catalyst
reaction tube in the lower reactor via carrier gas flow,where they react with the catalyst. Then the products
formed flow into the GC for analysis. The catalyst isevaluated by noting what compounds are found andtheir relative distribution using MS detection.

Heating/Pyrolysis

Catalyticreaction• Gas/liquid: preheating orvaporization• Solid: pyrolysis

Three temperature
program modes

Vaporization/Pyrolysis

ReactorSolidSample cup

MS or GC/MSanalysis

1) Online monitoringm/z: x

1st Reactor

Catalyst

m/z: yGas/liquidm/z: zMicro syringe,
Syringe pump

⇒ Temperature

Catalyst
2) GC/MS analysis

1st Reactor
2nd Reactor1st Reactor
GC

2nd Reactor

MS⇒ TimeCatalyst

To GC

Rapid catalyst evaluation system
2Features of the Rapid Catalyst Screening Reactors
1. Internal design of the reactors

Sample introduced here.

Stainless steel tube

Tandem µ-Reactor

Carrier gas orreaction gas(deactivated with quartz)

Cooling gas IN

1st Reactor furnace
1st Interface

1st Reactor

Tandem µ-Reactor consists of two reactors
connected in series. The 1st Reactor is used topreheat a gaseous sample, vaporize a liquidsample, or pyrolyze a solid sample. The 1stReactor operates at a constant temperature. Thevolatiles exit the 1st Reactor and flow to the 2ndReactor. A dedicated reaction temperature
controller controls the heating and cooling of thereactor. It also has a switching valve and flow
controller so that one of three reaction gases canbe introduced during the testing.

OUT

Interface needle
Reaction Gas

2nd Reactor furnace

Cooling gas IN

Catalyst reaction
tube (quartz)

OUT

2nd Reactor

Catalyst

The 2nd Reactor has a quick-change catalyst
reaction tube. The temperature of the reactor canbe programmed through a variety of heating
modes such as isothermal, linear, and stepwise
temperature programs.

2nd Interface

Parameters such as reactor temperatures,interface (ITF) temperatures, time, and settings
for other accessory devices are set through theoperating software on the PC. Method set points
and real-time actual temperatures and times arealso displayed.

Split gas OUT

Selective sampler(optional)
Separation column

MicroJet Cyro-Trap(optional)

GC Oven
Reaction gases

Flow control of reaction gas
Three different gases can be connected to thereactor controller. The flow rate of each gas iscontrolled by a separate mass flow controller. The
reaction gas switching valve is used to select thereaction gas that flows to the reactor. (Note: theflow control knob for reaction gas 3 is located on therear of the Tandem 1st Reactor controller.)

Selected gas added
before 2nd Reactor

Reaction gas
switching valve
AUX2

Flow control knob
for reaction gas 1

AUX1

AUX3

Close

Flow control knob
for reaction gas 2

Tandem 1st Reactor controller

Single µ-Reactor
The flow control system for the Single µ-Reactor
is identical to that of the Tandem µ-reactor. Thecontroller has three adjustable gas flow valvesand a stream selection valve.

Carrier gas orreaction gas
Reaction gases

Coolinggas
Selected gas

Heating and analysis modes of the reactor arealso the same as those of Tandem µ-reactor.
Isothermal, linear, and stepwise temperature
programs are available through the software.
Only liquids or gases can be introduced to theSingle µ-Reactor. Solids cannot be analyzed
with the Single µ-Reactor.

AUX2
AUX1

AUX3

CloseGC Oven

Reactor flow controller

3Features of the Rapid Catalyst Screening Reactor
2. Highly precise temperature control for minimal reactor
temperature fluctuations
1st Reactor

The thermal profile of the catalyst reaction tube inside the
2nd reactor between 100 and 700ºC is shown in the figure
below. The temperature variation within a 40 mm length ofthe catalyst bed is ±0.1ºC and the maximum temperaturedeviation is 3ºC at 400ºC. The reactor temperature can beeasily calibrated using an external temperature sensor thatis inserted into the center of the reactor.

1st Interface heater
Reaction gas

Reactor Temperature
Catalyst reaction tube
0100300500

700ºC

100 200300

400 500

700ºC20

2nd Reactor

40120 mm6040 mm80100120mm

2nd Interface heater

Precisely controlled temperatures
GC Injector

100℃

250℃

400℃
0.5ºC

Separation column

3. Rapid heating and cooling
Reactor temperature

900ºC50-900ºC thencool to 50ºC

500

50-500ºC thencool to 50ºC

5005

101520Time

4253035 min

The temperature profile shown on the left is obtainedby rapid heating the reactor from 50 to 500ºC (bluetrace) and also from 50 to 900ºC (red trace). After a
10 minute hold at the final temperature, the furnace
was cooled. Note that it took about 5 minutes to coolfrom 900ºC to 500ºC. The time required to cool down
to 50ºC is about 15-20 minutes depending on whether
the reactor was set to 500ºC or 900ºC. This rapid
heating and cooling feature makes catalyst reaction
tube change-over simple, quick and easy after theeach catalyst has been evaluated.

Features of the Rapid Catalyst Screening Reactor
4. Exchanging the catalyst reaction tube
Quick-change catalyst reaction tubes
For the Tandem µ-Reactor, remove the 1stReactor. The reaction tube (located in the2nd Reactor) can then be easily replacedby lifting the tube from the top of thereactor.

Tandem µ-Reactor

Single µ-Reactor
O-ringCatalyst reaction tube(Quartz)

When using the Single µ-Reactor, simply
unscrew the liquid sampler, and lift thereaction tube as shown in the figure on thefar right.

µ-Reactor

Liquid Sampler(syringe injection)

Packing the catalyst reaction tube
O-ring
The catalyst reaction tube (4 mm o.d.; 3 mm i.d.) is packed witha catalyst. Small amounts of quartz wool are placed both at thebottom and top of the catalyst bed to keep it in position. Thefigure on the right shows the packed catalyst reaction tube
inserted into the deactivated stainless steel tube.
The useable vertical length of the catalyst bed is 40 mm.
Catalysts with the particle size of 20 to 60 mesh are used.
Normally the catalyst reaction tubes are used, however if alarger volume of catalyst is required for testing, the deactivatedstainless steel reaction tube can also be packed.

Catalyst reaction tube
(4 mm o.d.; 3 mm i.d.)

Quartz wool

78 mm

Max
40 mm

Catalyst bed
Quartz wool

Deactivatedstainless steel tube
(6 mm o.d.; 5 mm i.d.)

Auto-Shot Sampler (optional)The analysis of solid samples can beautomated using the Auto-ShotSampler. The figure on the left(center)showstheAuto-Shot
Sampler, with the housing cover
removed, installed on the Tandem µReactor.

Tandemµ-Reactor
MSGC

The Auto-Shot Sampler carouselholds up to 48 sample cups (Ecocups).
After analysis the sample
cups are ejected into the glass
receptacle (indicated by the whitearrow).

5

Control software
Reactor temp. settings

Setting analytical conditions

Operation statusThe left side of the control software screen isused to set up the temperatures, rates andtimes for the reactors, interfaces andaccessory devices such as the MicroJet
Cryo-Trap (MJT) and Selective Sampler (SS).
The right side of the control software screen
displays operation status such as set points,
elapsed time and actual temperatures realtime.
Note the colored graphical icons at the top ofthese screens. Simply clicking on these
toggles the screen view for each of threetemperature analysis modes.

Three analysis modes
The Tandem and Single µ-Reactors can be used in three different modes. These modes differ in how the reactor
temperature is controlled. Isothermal mode 1 has a "Post Heat" function to thermally desorb reaction products in themicro-pores of various types of catalysts. In modes 2 and 3, the furnace temperature can be programmed in either alinear or stepwise progression, up to a maximum of 8 steps. When used with both the optional Selective Sampler andMicroJet Cryo-Trap, a maximum of 8 temperature zones can be automatically and individually analyzed.

1. Isothermal temp. analysis

2. Linear temp. analysis

3. Stepwise temp. analysis

SelectSelectBy checking (√) the appropriate “Sampling” and “Cryo-Trap”
boxes, the volatiles in the selected zones flow into the separation
column. The Cryo-Trap is activated if desired.

Switching analysis modes

Switching between EGA tube and GC separation column

To switch from real-time monitoring, which uses
an EGA tube, to GC/MS analysis using a GC
separation column is a simple process:• Online monitoring analysis• Separation analysis

EGA tube(L = 2.5 m, i.d. = 0.15 mm)

Separation column( L = 30 m, i.d. = 0.25 mm)(1) Switch to the desired analysis mode in thecontrol software,(2) Replace the EGA
separation column.

6tubewiththeGC

The Vent-free GC/MS Adapter (VFA), includedin the standard kit, facilitates switching a GC
separation column and an EGA tube without
venting the MS system. This switchover takes
about 10 minutes.

MSMS
Vent-free GC/MS Adapter (VFA)
m/z: 31
m/z: 18
Temperature→Time→Application 1: Catalytic conversion of ethanol to ethylene
Online – MS analysis

Separation analysis“ Linear temp. mode ”“ Stepwise temp. mode ”
1st µ-Reactor: 100ºC,
2nd µ-Reactor: 100, 250, 300 & 400ºC
Catalyst: H-ZSM-5

1st µ-Reactor: 100ºC,2nd µ-Reactor: 100-400ºC (20 ºC/min)Catalyst: H-ZSM-5

Ethanol

Ethylene

Ethanol (m/z45)
Diethylether (m/z74)
Ethylene (m/z 28)

Diethyl ether

Ethylene

250
300

Water (m/z 18)

200

H2O

100

Peak Area

Peak intensity

Peak intensity

Ethanol

Diethyl ether

TIC

100Reaction temp. vs. Peak area

H2O400ºC
300

1.0400ºC

2.0

2nd µ-Reactor temp.

Catalytic reaction products were monitored
as the reaction temperature was raised at aconstant rate. The amount of ethanolsharply dropped when the temperaturereached 280ºC, while the amount of diethyl
ether increased. Also, the formation ofethylene and water is observed.

100

These are the plots of the peak areas obtained
from the chromatogram on the left as thereactor temperature incrases. It clearly shows
how the function of the ZSM-5 catalyst various
with the temperature of the reactor.

Application 3:
Study of catalyst regeneration

Catalyst: 20 ％ H-ZSM-5, (SiO2/Al2O3＝150) on Al2O3 (20/30 mesh)

1st µ-Reactor & 2nd µ-Reactor: 550ºC, Catalyst: ZeoliteOctadecadienoic acid

Without Catalyst

400ºC

300

The reactor is heated from 100 to 600ºC in a linear modein an air atmosphere.

Courtesy: Dr. Murata of AIST Japan

BeforeAfter 48 hours use*Regeneration

Hexadecadienoic acid

2468*Sample: 3 % ethanol in He
Flow rate: 50 mL/min
2nd Reactor temp.: 550ºC

10 minRegeneration profile

With Catalyst

200

2nd µ-Reactor temp.

Based on the online-MS analysis results, thevolatiles released from each temperature zone
were introduced to a separation column andanalyzed. As the reactor temperature wasraised, ethylene and water were formed while
the amount of ethanol formed dramaticallydecreased.

Application 2: Conversion of Jatropha“press cake” to bio-based chemicals

The constituents obtained byflash pyrolysis of a finely
powdered Jatropha press cakewere primarily two fatty acids(C16 and C18) which have two
double bonds in their structure.

4.0 min

3.0
Time

Carrier gas: AirBenzene(3) Combustion of hydrocarbons
adsorbed in the pores

TolueneWhen the 2nd µ-Reactor
contains a packed bed of aZeolite catalyst, Jatrophapress cake is converted tomonocyclic aromatics suchas benzene, toluene, xylene
and ethyl benzene.

CO2 (m/z:44)(2) Combustion of hydrocarbons
adsorbed on surface(1) Surface adsorptionof H2O and CO2Xylene
Ethyl benzene

H2O (m/z:18)

0.5

1.0

1.5 min

100

200

300

400

500

600

600ºC

10 ºC/min

7

Specifications
Tandem µ-Reactor
Rx-3050TR

Single µ-Reactor
Rx-3050SR-1st Reactor
Temperature control range

40 to 700 ºC (1 ºC step, stainless steel flow path, cooling gas)
40 to 900 ºC (1 ºC step, quartz flow path, cooling gas)

-HeaterCylindrical ceramic heater (400 W)-Flow path material

Stainless steel (surface deactivated with a bonded
silica thin film).

Same as left specification

Interface (ITF) temperature range

40 to 400 ºC (1 ºC step, constant temp. control)-Reaction gas control

Three gas lines manual valve switching,Gas flow rate control (Max 100 mL/min, 1 MPa)

Same as left specification

2nd Reactor

Single µ-Reactor

Temperature control range

40 to 700 ºC (1 ºC step); cooling gas

Same as left specification

Heater

Cartridge heater

Same as left specification

Reaction tube

Catalyst reaction tube (quartz) : 3 mm i.d.; 4 mm o.d.;Length: 78 mm

Same as left specification

Interface (ITF) temperature

40 to 400 ºC (1 ºC step; constant temp. control)Same as left specification

PC (1 USB port and a CD drive), Compatible OS(Microsoft Windows 11, 10, 8.1)

Same as left specification

Temperature control

Isothermal, Linear, and Stepwise Temperature Analyses

Same as left specification

Sampling

Selectively introduces a maximum of 8 zones froman EGA thermogram onto a GC separation column.
Requires Selective Sampler and MicroJet Cryo-Trap

Same as left specification

Pre-requirements

1. GC/MS with Split/Splitless injector
2. Compressed gas for cooling (air or nitrogen)Same as left specification

Power requirement

100 – 120 VAC or 200 – 240 VAC, 50/60 Hz, Max 800 W

Dimension (W x D x H) / (kg)
1st Reactor
2nd Reactor
Temperature control unit

76 x 143 x 195 mm* / 1.8 kg
76 x 143 x 155 mm* / 1.0 kg
120 x 310 x 310 mm / 5.9 kg(100V), 7.2 kg(200V)

Control software
System requirement
OthersAnalyticalmodes

Reaction gas control unit
Standard items

100 – 120 VAC or 200 – 240 VAC,50/60 Hz, Max 400 W

76 x 143 x 155 mm** / 1.6 kg
120 x 310 x 310 mm / 5.5 kg(100V)
6.9 kg(200V)
160 x 280 x 150 mm / 3.3 kg
160 x 280 x 150 mm / 3.3 kg
Vent-free GC/MS Adapter, EGA tube for online analysis, Ultra ALLOY ® capillary column,
Catalytic tube (packed with ZSM-5), Reaction gas controller, Reaction temp. controller etc.

*Height of reactor when mounted on GC injector with single-shot sampler attached. ** Height of reactor when mounted on GC injector with liquid injection sampler attached.

Auto-Shot Sampler

Tandem µ-ReactorReaction gas controller (standard item)
COH2AirMS

GC

Selective Sampler
MicroJet Cryo-Trap
Ultra ALLOY® capillary column
EGA tube (standard items)
Reactor temperature controller(standard item)

Vent-free GC/MS Adapter (standard item)

Rapid Screening Reactor （RSR-GC/MS）System

84-16-20 Saikon, Koriyama, Japan, 963-8862
TEL: 81(24) 935-5100 FAX: 81(24) 935-5102
www.frontier-lab.com
Appearance and specifications are subject to change without notice.

YM230111