Summary of the poster to be presented at the 17th WPC-RIO (Block 2 Forum 5)

A study on the recovery of hydrogen from refinery (hydrogen + methane) gas mixtures using hydrate technology
G.-J. Chen, C.-Y. Sun, C.-F. Ma and T.-M. Guo* High Pressure Fluid Phase Behavior & Property Research Laboratory, School of Chemical Engineering, University of Petroleum, Changping, Beijing 102249, China Hydrogen-containing light hydrocarbon gas mixtures are widely found in the tail gas of petroleum refineries and ethylene plants. The economic recovery of hydrogen from such gas mixtures is of industrial significance. The H2-content in the refinery tail gases varies significantly with specific refining processes. For example, in the tail gas of hydrogenation process is usually quite high (> 60 mol%), while it is quite low in the refinery dry gas ( 20 mol%). The conventional techniques used for hydrogen recovery include adsorption, chemical absorption, membrane separation and deep cooling, however, those techniques are not economically attractive for low H2-content gas mixtures. The new H2-separation technique proposed in this work is based on the fact that hydrogen is a hydrate non-former while methane and some other light hydrocarbons are capable of forming hydrates. By keeping suitable temperature and pressure conditions in a reactor, most light hydrocarbons could be clathrated in the solid hydrate phase (which is subsequently dissociated in a separate vessel), while hydrogen content in the gas phase is thus enriched. The principle flow diagram is shown in Figure 1. The key factors influencing the practicability of this new separation technique are the pressure / temperature conditions and the rate of hydrate formation / decomposition processes. For exploring the feasibility of the process, in this work we have systematically studied the following aspects:

Corresponding author: P.O. Box 902, Beijing 100083, P.R. China. E-mail address: guotm@a-1.net.cn
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Figure 1.

Schematic of the proposed separation process BCH4-hydrate dissociation tank

ACH4-hydrate formation column,

Optimum pressure and temperature conditions for separating (H2 + CH4) feed

mixtures containing various H2-content (20-90 mol%). Maximum H2 enrichment could be achieved and the yield of H2. Suitable promoter (additive) and its optimum concentration to be used for

lowering the hydrate formation pressure (Promoter A) / enhancing the rate of hydrate formation / dissociation process (Promoter B). Kinetic behavior of the formation/dissociation of methane-hydrates. The schematic diagrams of the bench scale separation unit, the apparatus for measuring phase equilibrium conditions and the circulating flow system for studying the kinetic behavior of hydrate formation / dissociation and flow properties are shown in Figures 2 to 4, respectively. Typical experimental results are presented in Tables 1-3. The kinetic data measured on the rate of hydrate formation / dissociation are omitted in this summary.

Figure 2.

Schematic diagram of the hydrogen separation unit Breaction cell (10 L) Cdissociation cell (20 L)

Areaction column (15 L)

Vent RTD

DPT

Sample Cylinder

Air Bath

JEFRI Sapphire Hydrate Cell Magnetic Stirrer HEISE Pressure Gauge RTD

Drain

Gas Supply Hand Pump

Figure 3.

Schematic flow diagram of the apparatus for measuring the hydrate formation/dissociation conditions DP differential transducer detector
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RTD resistance thermocouple

Laser Scattering Device Scanning Thermometer Cooling Jacket Inner Tube Swagelok Union

Differential Pressure Transducer

A B

p
Flowmeter
Mixing Tank

Data Acquisition System Pump Cooling System Gas Cylinder

Circulating Bath

Figure 4. Transparent double-pipe circulating flow loop Inner tube: 25 mm; length 20 m; Max. working pressure: 4.0 MPa; Working temperature range: 20- + 100. Table 1. Typical hydrate formation pressure data of (H2 + CH4) gas mixtures at + 1C Composition of gas P (MPa) mixture (mol%) 22%H2+78%CH4 3.72 36%H2+64%CH4 4.46 47%H2+53% CH4 5.47 58%H2+42% CH4 6.89 70%H2+30% CH4 9.67 90%H2+10% CH4 29.5 (extrapolated) 59%H2+41% 0.65 CH4+Promoter A (6% in liquid) 0.70 68%H2+32% A CH4+Promoter (6%) 85%H2+15% 1.44 CH4+ Promoter A (6%) 95%H2+5% 2.74 CH4+ Promoter A (6%) 7.12 59%H2+41% CH4+Promoter B (2% in liquid) Table 2. Typical hydrogen-content in the dissociated gases
Feed gas composition (mol%) 22%H2+78%CH4 36%H2+64%CH4 59%H2+41%CH4 + Promoter A 68%H2+32%CH4 + Promoter A 75%H2+25%CH4 + Promoter A 78%H2+22%CH4 + Promoter A H2-content in enriched gas (mol%) 31 45 78 88 90 92
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H2-content in dissociated gas (mol%) 0.1 0.2 1.2 2.2 3.1 3.5

Table 3.

Typical hydrogen recovery ratio data for a single equilibrium stage

Run
() 1.0

(MPa) 1.0

P*

Stream
Feed Enriched gas Hydrate Feed Enriched gas Hydrate Feed Enriched gas Hydrate Feed Enriched gas Hydrate Feed Enriched gas

H2 mol%
42.22 56.38 1.24 78.42 85.68 23.41 78.42 88.18 25.87 78.42 92.98 31.77 78.42 87.20

H2Recovery ratio
99.25

1.0

2.0

96.5

1.0

3.0

94.83

1.0

4.0

90.36

3.0

3.0

95.5

Hydrate

25.00
85.89 92.29 18.38 98.1

1.0

3.0

Feed Enriched gas Hydrate

Pressure at solid-liquid-gas three-phase equilibrium

From the experimental results obtained in this study we can conclude that: (1) The phase equilibrium data measured indicate that the hydrogen-content in the (H2 + CH4) gas mixtures containing methane in the range of 10-80 mol% could be enriched to over 95mol% under a temperature slightly above 0 C and a pressure below 5.0 MPa in the presence of a small amount of Promoter A. (2) High hydrogen recovery ratio ( 98 %) could be achieved in a batch single-stage equilibrium separation process. (3) Preliminary kinetic studies showed the effects of liquid flow rate and system pressure on the rate of methane hydrate formation / dissociation in the presence of small amount of kinetic promoter B. (4) Methane hydrate slurries show good flow properties. For further verification of the practicability of the proposed H2-separation process, a pilot scale continuous production unit is under construction.
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