**[SOP for working with H2 Gas]{.underline}**

1.0 Introduction

This document is the standard operating procedure (SOP) for
spectroscopic studies of alkene hydrogenation reactions at elevated
temperature and pressure. This SOP covers the experimental plan, safe
operation and emergency procedures in the event of an off-normal event.
The system will be used at the APS, Sector 20 BM. The system is used for
x-ray studies of IPA/benzene/H~2~ solutions.

1.1 Description of the System

A small pressure vessel having an internal volume of 3 milliliters is
used to study a chemical reaction using X-ray absorption spectroscopy.
During operation, the contents of this vessel are heated to 100°C and
750 psi with H~2~ gas. The volume of this heated material is small. The
cell is loaded and pressurized in the laboratory hood. The entire
apparatus is then transferred to the hutch for in situ reactions
studies. This SOP covers the procedure for loading, filling the cell and
emptying the process line after completion of an experiment.

More specifically the apparatus and procedure is described as follows.
The complete apparatus is shown in the attached Figure. The apparatus
consist of four main components, a lecture bottle, an injection
reservoir, an accumulator and the x-ray cell. The entire assembly shown
in the Figure is mounted on a 12 inch square pad that can be easily
transported between the lab hood and the x-ray hutch. All of the sample
preparation is completed in the laboratory hood and pressurized
initially to 200 psi. The entire assembly is transported to the hutch
were the x-ray cell is heated to 100C and pressurized to 750 psi to
initiate the reaction.

All of the components are constructed from commercially available
pressure fittings (High Pressure Equipment, Inc) that are rated to at
least 10,000 psi. The entire system will be leak check with an inert gas
prior to use. The possibility of leaks during the experiment in the
x-ray hutch are very low.

The total gas volume contained within the apparatus is very low. The
total amount of H~2~ in the lecture bottle is 2 ft^3^ after expansion to
ambient conditions. In the unlikely event that this gas rapidly escapes
during the experiment, this represents a total volume ratio in the hutch
of about 0.1% which is far below the flammability/explosive limit.

1.2 Types of risks

Exposure to hydrogen gas.

Exposure of hot surfaces

Exposure to high pressure equipment

Exposure to organic solvent (10% benzene in IPA)

Special guidelines have been developed to minimize these risks during
normal operation or in the event of and off-normal event. These are
discussed in the following sections.

1.3 Qualified Operators for the System

The conditions of operation requires that operators be familiar with all
aspects of the equipment and in particular be well-versed in the
contents of this document.

**2.0 GENERAL PROCEDURES**

2.1 General Practices and Precautions

The system will be used at the Advanced Photon Source of Argonne
National Laboratory.

During normal operation of the system, safety glasses are to be worn at
all times when operating this equipment including during mixing and
loading of the cell.

2.2 Safety Features in APS Bldg.

Safety Shower: Located in the chem lab.

Eye Wash: Located in the chem lab.

Fire extinguisher: In the hallway.

Fume Hood: Located in the chem lab.

Fire Alarm: In the hallway.

These facilities provide the basis for safe handling of this
hydrogenation apparatus.

**2.3 Precautions for Known Hazards**

2.3.1 Precautions for Hydrogen Gas

Standard procedures for handling hydrogen gas should be followed. All
equipment during operation should be approached with care and assumed
that it is under pressure until otherwise observed.

During normal operation the cell will be at 750 psi. The cell, the
tubing and fittings are all designed for operation to 10,000 psi. There
is a safety or rupture disc that is rated at 3,000 psi which is well
above the lecture bottle pressure of 1800 psi.

Prior to filling with H~2~ gas the entire system will be purge with an
inert gas (He, Ar, or N~2~) and leak checked. The cell will be filled
with H2 gas to 200 psi while the apparatus in the laboratory hood. After
transport of the apparatus to the x-ray hutch the spectroscopy cell will
be heated to 100°C and filled to 750 psi with H2. After completion of
the experimentation the entire system will be transport back to the
laboratory hood and will be purged with an inert gas to remove residual
H~2~.

2.3.2 Precautions for Hot/Cold Surfaces

Standard procedures for handling hot surfaces should be followed. All
equipment during operation should be approached with care and assumed
that it is at elevated temperature until otherwise observed.

During operation, only one component of the system, the spectroscopy
cell will be at elevated temperature. This cell temperature is no hotter
than 100°C. The spectroscopy cell will be covered with a small
fiberglass blanket to completely cover all exposed surfaces.

2.3.3 Exposure to High Pressure Equipment

This system consists of high pressure equipment and tubing. The vessels
and piping are rated to 10000 psi, and is protected by a rupture disk
rated at 3000 psi. No tightening or loosening should be performed on any
fittings or pipes that are above 100psi.

2.3.4 Exposure to organic liquids

Material handling for this system is to be done in accordance with
current safe practices. Isopropyl alcohol will be used in this system as
a mixture containing up to 10% benzene or cyclohexene, 1% triethylamine
and less than 1% by weight of a Rh catalyst. These materials should be
handled in a chemical fume hood with gloves and safety glasses.

Only 3 ml of solution (with 0.3 ml benzene) will be used during each
experimental acquisition. In the case of a spill, absorb with sand or
other non-combustible material. Collect spilled material in appropriate
container for disposal. The vapor pressure of benzene is 75 mmHg @ 20 C
and the evaporation rate is 5.1 (butyl acetate=1) . Since the quantities
are low and the evaporation rate is limiting, the maximum air
concentration in the hutch will be well below the exposure limit (5 ppm
OSHA STEL 15 minute(s)) in the event of a spill.

During the experimental operation a small amount of liquid (3.0 ml) will
be heated to 100°C. The heated volume is relatively small.

Benzene is potentially fatal on contact with the skin, causes
respiratory tract irritation, skin irritation, eye irritation,
aspiration hazard, blood damage, central nervous system depression,
cancer hazard (in humans). Do not breathe gas, fumes, vapor, or spray.
In case of contact with eyes, rinse immediately with plenty of water and
seek medical advice. In case of skin contact, wash skin with soap and
water for at least 15 minutes

2.4 Handling Experimental Solutions

As a part of experimental planning, waste materials should be considered
and their production minimized. The operators of the system will take
special precautions so that no liquid waste material is discharged into
the environment. Used IPA/benzene solutions and system rinse material
will be stored in properly managed satellite accumulation areas during
the project and disposed of as per APS requirements.

**3.0 OPERATIONAL PROCEDURES**

By following the prescribed Cell Loading, and System Operation
checklists, the operators can insure the system is safely operated. Any
significant deviations from the checklist procedures must be noted both
on the checklist and in a LRB.

3.1 CELL LOADING AND PURGING

1.  Don safety gear. Required gear for this operation are safety glasses
    and 8 inch Viton gloves. Two researchers must be present for loading
    operations.

2.  All filling operations will be conducted in a laboratory fume hood.

3.  In a beaker placed in a hood, mix the 5 ml aliquot of isopropyl
    alcohol containing up to 10% benzene or cyclohexene, 1%
    triethylamine and less than 1% by weight of a Rh catalyst according
    to the experimental plan. More preferably, the reagents will be
    mixed using anaerobic techniques which include, syringing the liquid
    reagents into a sealed mixing vessel to minimize vapor loss to the
    environment.

4.  Using a glass syringe, transfer 3 ml of this IPA solution into the
    x-ray cell.

5.  Attach the x-ray cell to the hydrogenation apparatus.

6.  Purge the entire system with inert gas prior to filling with H2 and
    pressurize to 350 psi and check for leaks.

7.  Fill system with H2 to 200 psi and discharge 6 times to purge inert
    gas from the cell and solution.

3.2 SYSTEM PREPARATION, OPERATION AND RINSING

1.  Don safety gear. Required gear for this operation are safety glasses
    and 8 inch Viton gloves. Two operators must be present for
    operations.

2.  Transport the hydrogenation system from the laboratory hood to the
    x-ray hutch.

3.  Insert heaters with and heat the solution in the x-ray cell to 100°C
    while gradually increasing the pressure to 750 psi.

4.  Acquire spectra of the reacting system for 2 hrs or until reaction
    completion.

5.  After data collection is complete. Cool the apparatus. Transport the
    hydrogenation apparatus into the laboratory hood. Decrease the
    pressure through the discharge valve. Purge the reactor with inert
    gas and disconnect from the pressure apparatus. Collect the reacted
    effluent from this operation in appropriate waste container or
    sampling vial for future analysis.

**4.0 EMERGENCY SHUTDOWN PROCEDURES**

Emergency shutdown procedures must be used whenever there is a risk of
injury to personnel or equipment posed by the application of the regular
shutdown procedures. This includes shutdowns due to:

 rapid release of pressure (leaks or blown rupture discs);

! unusual operating conditions;

 building evacuation during a run;

 loss of electrical power;

 other unusual or potentially hazardous circumstances as determined by
the operators.

[Emergency Shutdown Procedure]{.underline}

1.  Turn OFF the heater controllers

2.  Close the outlet valve on the H~2~ lecture bottle.

![](media/image1.png){width="6.001388888888889in"
height="4.170833333333333in"}