**2.1 Experimental study of CH4 pyrolysis and catalytic effects of chamber material**

To make clear the fundamental characteristics of methane pyrolysis, the authors conducted the experimental investigation. In the present section, we introduced the experimental results by Higashino, K. et. al. ( Higashino, K. et. al. 2009A ) The test apparatus shown in the Figure 1 is employed. The CH4 gas (99.99% of purity) is supplied from the test gas bottle to silica glass tube, where is heated by the electronic furnace. The nitrogen gas can be also fed to gas flow passage to purge the CH4 gas. The flowrates of those gases are controlled by using flowrate control valves and pressure control valves. To investigate its catalytic effects on pyrolysis reaction, 10 pieces of combustion chamber materials (10mm length x 5mm width x 0.5mm thickness) are placed into the alumina board, which are located in this tube. The materials of those test pieces are Inconel 718, Inconel 600 and A286. The formers of two are Nickel based alloy and have mechanical strength under high temperature condition. They were utilized for combustion chamber material, however, Nickel has the catalytic effects to accelerate the thermal decomposition of CH4. On the other hand, A286 is Iron based alloy, but contains Ni of 25%. The details of test conditions and properties of those materials are summarized in Table.1. Prior to the test, the oxide film on the surface of the test pieces was hydrogenated at 500 0C because it can hamper accurate evaluation of the catalytic effects. The gas sampling point is located in the downstream of the heating section, where the test gas is sampled to investigate its chemical composition. The test gas was ventilated after diluting with the air at draft.

Two types of heating methods are employed, constant temperature heating and ascendant heating. In ascendant heating, temperature of the electronic furnace increases with time linearly. The existence of pyrolysis can be found by analyzing the sampled gas by using gas chromatograph with thermal conductivity detector. During the heating tests, gas sampling is conducted in every 5 minutes. The volume of the sampled gas is about 0.5 ml per one time. The progression of CH4 pyrolysis is evaluated by the CH4 conversion rate (%) as expressed in equation (1)

$$\text{Conversion Rate} = \left[ 1 - \frac{\left( A\_{\text{CH4}} / \lambda\_{\text{CH4}} \right)}{\left( A\_{\text{CH4}} / \lambda\_{\text{CH4}} \right) + \left( A\_{\text{H2}} / \lambda\_{\text{H2}} \right)} \right] \times 100\tag{1}$$

where *A* and indicate the area shown in the gas chromatograph results and thermal conductivity, respectively. The subscripts of CH4 and H2 indicate CH4 and hydrogen, respectively. For the gas chromatograph with thermal conductivity detector, volumetric fractions of chemical species can be *A* divided by .

Fig. 2. Effects of Alumina Board on Methane and Propane Pyrolysis.

(a) Constant temperature heating at 500 0C (b) Constant temperature heating at 700 0C

Control of LNG Pyrolysis and Application to Regenerative Cooling Rocket Engine 147

2.5

2.0

CH4 inversion rate [%]

1.5

1.0

0.5

0.0

Before the present tests, it must be evaluated whether the alumina board has any catalytic effects. If this alumina board has the catalytic effects on CH4 or C3H8 decomposition, it is very difficult to evaluate the accurate catalytic effect quantitatively. Figure 2 shows that time histories of methane conversion rates with pseudo LNG of 1 vol% C3H8 for ascendant heating tests. The pseudo LNG mean the gas mixture of CH4 and C3H8. In the heating tube, there is no INCONEL 600 piece, but the test conditions with and without alumina board are conducted. CH4 conversions on those two conditions are compared each other. Those two CH4 conversion rate have no differences and it is clear that the present alumina board has

Figure 3 shows the results of pure CH4 gas heating test. Fig.3 (a), (b) and (c) are the results of constant temperature heating test at 500 0C, 700 0C and 800 0C, respectively. As shown Fig.3(a), CH4 conversion rate are always equal to 0 at 500 0C as shown in Fig.3(a). This means CH4 pyrolysis did not occurred at this temperature. However, CH4 pyrolysis is admitted at 700 0C if any test pieces are placed in CH4 gas and CH4 conversion rate are greater in order of Inconel 600, Inconel 718 and A286 condition. The progression of CH4 pyrolysis is proportional to the amounts of Ni in alloys, because Ni contents are 78%, 53.5% and 25% for Inconel 600, Inconel 718 and A286, respectively. This result indicates that Ni has the catalytic effect to promote this reaction. CH4 conversion rate decrease with time for all of test pieces conditions. It is considered that the carbon deposits have adhered on the surface of test pieces and inhibit the catalytic effects. At 800 0C, the time histories of CH4 conversion rate are very different from those at 700 0C, especially for A286 condition. For A286 condition, CH4 conversion rate is decreased until 10 minutes, however, it turned to increase after that. A286 contains more Iron than Inconel 718 and Inconel 600. The carbon deposit on the A286 surface combined with Iron, if CH4 pyrolysis proceeded. The carbon and Iron are combined to produce Iron carbide, which also has the catalytic effects. It is considered that it causes the tendency of A286 condition in Fig.2(c). The results of the ascendant temperature

400 500 600 700 800 900

:Inconel718(Ni53.8%) :Inconel600(Ni78%) :A286(Ni25%) :pure CH4

Temperature [℃]

:Inconel718(Ni53.5%) :Inconel600(Ni78%) :A286(Ni25%) :pure CH4

time [min]

(c) Constant temperature heating at 800 0C (d) Ascendant Heating

7.0

6.0

5.0

CH4 inversion rate[%]

4.0

3.0

2.0

1.0

0.0

0 10 20 30 40 50 60 70

no catalytic effect on the CH4 and C3H8 pyrolysis.

Fig. 3. CH4 Conversion Rate for pure CH4 Gas heating tests.

where *A* and indicate the area shown in the gas chromatograph results and thermal conductivity, respectively. The subscripts of CH4 and H2 indicate CH4 and hydrogen, respectively. For the gas chromatograph with thermal conductivity detector, volumetric

*Conversion Rate*

fractions of chemical species can be *A* divided by .

With Alumina Board

Fig. 2. Effects of Alumina Board on Methane and Propane Pyrolysis.

0 10 20 30 40 50 60 70

time [min]

(a) Constant temperature heating at 500 0C (b) Constant temperature heating at 700 0C

Without Alumina Board

0

:Inconel718(Ni53.5%) :Inconel600(Ni78%) :A286(Ni25%) :pure CH4

10

CH4

3.0

2.5

CH4 inversion rate[%]

2.0

1.5

1.0

0.5

0.0

Conversion Rate [ % ]

20

30

40

50

 4 4 4 4 22 1 100 *CH CH CH CH H H*

  (1)

:Inconel718(Ni53.5%) :Inconel600(Ni78%) :A286(Ni25%) :pure CH4

time [min]

*A*

500 600 700 800 900 1000 1100

3.0

2.5

CH4 inversion rate[%]

2.0

1.5

1.0

0.5

0.0

0 10 20 30 40 50 60 70

Temperature [ ℃ ]

*A A*

Fig. 3. CH4 Conversion Rate for pure CH4 Gas heating tests.

Before the present tests, it must be evaluated whether the alumina board has any catalytic effects. If this alumina board has the catalytic effects on CH4 or C3H8 decomposition, it is very difficult to evaluate the accurate catalytic effect quantitatively. Figure 2 shows that time histories of methane conversion rates with pseudo LNG of 1 vol% C3H8 for ascendant heating tests. The pseudo LNG mean the gas mixture of CH4 and C3H8. In the heating tube, there is no INCONEL 600 piece, but the test conditions with and without alumina board are conducted. CH4 conversions on those two conditions are compared each other. Those two CH4 conversion rate have no differences and it is clear that the present alumina board has no catalytic effect on the CH4 and C3H8 pyrolysis.

Figure 3 shows the results of pure CH4 gas heating test. Fig.3 (a), (b) and (c) are the results of constant temperature heating test at 500 0C, 700 0C and 800 0C, respectively. As shown Fig.3(a), CH4 conversion rate are always equal to 0 at 500 0C as shown in Fig.3(a). This means CH4 pyrolysis did not occurred at this temperature. However, CH4 pyrolysis is admitted at 700 0C if any test pieces are placed in CH4 gas and CH4 conversion rate are greater in order of Inconel 600, Inconel 718 and A286 condition. The progression of CH4 pyrolysis is proportional to the amounts of Ni in alloys, because Ni contents are 78%, 53.5% and 25% for Inconel 600, Inconel 718 and A286, respectively. This result indicates that Ni has the catalytic effect to promote this reaction. CH4 conversion rate decrease with time for all of test pieces conditions. It is considered that the carbon deposits have adhered on the surface of test pieces and inhibit the catalytic effects. At 800 0C, the time histories of CH4 conversion rate are very different from those at 700 0C, especially for A286 condition. For A286 condition, CH4 conversion rate is decreased until 10 minutes, however, it turned to increase after that. A286 contains more Iron than Inconel 718 and Inconel 600. The carbon deposit on the A286 surface combined with Iron, if CH4 pyrolysis proceeded. The carbon and Iron are combined to produce Iron carbide, which also has the catalytic effects. It is considered that it causes the tendency of A286 condition in Fig.2(c). The results of the ascendant temperature

Control of LNG Pyrolysis and Application to Regenerative Cooling Rocket Engine 149

Ascendant Heating Test up to 850 0C 3.0 ― ―

Figure 4 shows the photographs of Inconel 718 test pieces employed for the ascendant heating test. It is clearly observed that carbon deposit on the surface of the test pieces. EPMA analysis is conducted to investigate the chemical constituents of those depositions. Figure 5 shows the results of MPMA analysis for ascendant heating test. These results also indicate that carbon deposits on the surface of the test piece after this test. MPMA can evaluate the thickness of the carbon deposit film on the test piece surfaces, which are indicated in Table 2. In the case of Inconel 600, which has the maximum Ni constituent among these 3 materials, the carbon deposit films are measured in the constant temperature heating test ( 700 and 800 0C ) and the ascendant heating condition. The thickness of the carbon deposit film is 3.0m at constant temperature heating condition of 800 0C. However, that of A286 is 6.0 m and the thickest among those 3 materials at same heating condition. Measuring the mass difference of test pieces before and after test, the total mass of carbon deposit is amount to 3.7mg which is equivalent to CH4 of 4.933mg. The total mass of CH4

> <sup>4</sup> <sup>4</sup> <sup>ˆ</sup> *CH*

where *P*, *Q*, *R*ˆ and *MCH4* are pressure(=0.2MPa), volume flowrate(=20ml/min), Universal gas constant and molecular weight of CH4. *T* and *t* are the temperature and test period. The

*PQt <sup>m</sup>*

ratio of thermal decomposed CH4 to total amount of supplied CH4 is 0.308 %.

 (a) Before Ascendant heating b) After Ascendant Heating Fig. 6. Results of Raman Analysis of Inconel 718 for Ascendant Heating Test.

*CH*

*RM T* (2)

Table 2. Thicknesses of Carbon Deposit Films on the Surface of Test Pieces.

gas fed on can be evaluated as 1.603 g from equation (2).

Constant temperature heating Test

Test Condition Thickness of Carbon deposit films ( m )

700 0C 2.0 ― ―

800 0C 3.5 4.0 6.0

Inconel 600 Inconel 718 A286

heating test are shown in Fig.3(d). CH4 pyrolysis begins at about 800 0C for no-test piece condition, while it does at 650 0C if any test pieces are placed in CH4.

(a) Before Ascendant Heating (b)After Ascendant Heating

Fig. 4. Photographs of the Inconel 718 Test Pieces Before and After Ascendant Heating test

(b) After Ascendant Heating Test

Fig. 5. Results of MPMA Analysis for test pieces in Ascendant Heating test.

heating test are shown in Fig.3(d). CH4 pyrolysis begins at about 800 0C for no-test piece

(a) Before Ascendant Heating (b)After Ascendant Heating

Fig. 4. Photographs of the Inconel 718 Test Pieces Before and After Ascendant Heating test

(a) Before Ascendant Heating Test

(b) After Ascendant Heating Test

Fig. 5. Results of MPMA Analysis for test pieces in Ascendant Heating test.

condition, while it does at 650 0C if any test pieces are placed in CH4.


Table 2. Thicknesses of Carbon Deposit Films on the Surface of Test Pieces.

Figure 4 shows the photographs of Inconel 718 test pieces employed for the ascendant heating test. It is clearly observed that carbon deposit on the surface of the test pieces. EPMA analysis is conducted to investigate the chemical constituents of those depositions. Figure 5 shows the results of MPMA analysis for ascendant heating test. These results also indicate that carbon deposits on the surface of the test piece after this test. MPMA can evaluate the thickness of the carbon deposit film on the test piece surfaces, which are indicated in Table 2. In the case of Inconel 600, which has the maximum Ni constituent among these 3 materials, the carbon deposit films are measured in the constant temperature heating test ( 700 and 800 0C ) and the ascendant heating condition. The thickness of the carbon deposit film is 3.0m at constant temperature heating condition of 800 0C. However, that of A286 is 6.0 m and the thickest among those 3 materials at same heating condition. Measuring the mass difference of test pieces before and after test, the total mass of carbon deposit is amount to 3.7mg which is equivalent to CH4 of 4.933mg. The total mass of CH4 gas fed on can be evaluated as 1.603 g from equation (2).

$$
\dot{m}\_{\text{CH4}} = \frac{PQt}{\left(\hat{R}\!/\text{M}\_{\text{CH4}}\right)T} \tag{2}
$$

where *P*, *Q*, *R*ˆ and *MCH4* are pressure(=0.2MPa), volume flowrate(=20ml/min), Universal gas constant and molecular weight of CH4. *T* and *t* are the temperature and test period. The ratio of thermal decomposed CH4 to total amount of supplied CH4 is 0.308 %.

Fig. 6. Results of Raman Analysis of Inconel 718 for Ascendant Heating Test.

Control of LNG Pyrolysis and Application to Regenerative Cooling Rocket Engine 151

CH4 and radical species like H atom, CH3 and C2H5 are produced. The radical species can attack to CH4 and promote its pyrolysis. The effects of those radical species are significant

The chemical compositions of LNG are varied from the production area. Thus, in the present section, LNG is modelled by CH4 and C3H8 mixture, which is call as pseudo-LNG in the present study. The details of test conditions are listed in Table 3. The test pieces materials are selected as Inconel 600, Haetelloy –X, SMC, OFMC and OMC. Hastelloy-X is one of the Ni-based alloy, as well as Inconel 600. SMC, OFMC and OMC are Copper based Alloys and included in the test pieces materials. Copper has high heat conductivity, thus, is also used for combustion chamber material. Test apparatus is same one shown in Fig.1. The results in

To investigate the effects of C3H8 addition of CH4, the ascendant heating test is conducted for pseudo-LNG, whose volumetric fraction of C3H8 is 1.0 %. In these tests, the catalytic effects are also experimentally evaluated. C3H8 molecules begin to decompose as well as CH4, if test gas would be heated. The test gas is sampled and the volumetric fractions of the remained C3H8 are measured by the gas chromatograph. Figure 8 shows the C3H8 residual ratios, which means the ratio of the remained and the initial volumetric fractions of C3H8. If there is no test piece, C3H8 begin to decrease at 527 0C ( 800 K ), which is about 300 0C lower

Ascendant From Room temperature to 1273

SMC Cu: 99.13% Zr :0.8% Cr :0.7%

OMC Cu: 99.12% Zr :0.1% Cr :0.7%

Inconel 600 Ni: 78% Cr : 15% Fe: 7% Hastelloy-X Ni: 47% Cr : 22 % Fe: 19%

this section are referred from Higashino, K. ( Higashino, K. et. al 2009B )

even if mole fraction of C3H8 is a few percent.

than pure CH4 pyrolysis without test piece.

Temperature (°C) Isothermal 627, 727, 827

Table 3. List of Test Condition of Pseudo-LNG Heating Test.

Flowrate (ml/min) 20

Test Duration

C3H8

Volumetric Fraction of

Constituents of test piece materials

Pressure ( MPaA ) From 0.14 to 0.20

Material of Test Pieces SMC, OMC, Inconel 600, Hastelloy-X Test Piece configuration 10mm L X 10mm W X 1 or 2 mm T

Isothermal 4800 sec

Ascendant 15000 sec ( max )

OFMC Cu: 99.99%

If the test pieces of Inconel 600 or Hastelly-X are employed, C3H8 residual ratios begin to decrease at 377 0C. Thus, these materials have the catalytic effects to promote the C3H8 pyrolysis. On the other hand, tendency of C3H8 residual ratio with SMC test pieces are

1 , 3, 5 percent

The crystal structures of carbon deposits on the test piece surface are investigated by Raman analysis. Figure 6 shows the results of Raman analysis of Inconel 718 test pieces before and after the ascendant heating test. The two peaks are appeared in the test pieces after heating and the right peak is more distinguished than the left one, which means the pyrolytic carbon is deposited [Yoshikawa, S. 1991]. If the left peak would be higher than the right one, amorphous carbon is deposited, in contrast. For other materials in ascendant heating condition, Raman analysis of Inconel 600 shows the same tendencies with Inconel 718, however, that of A286 indicates that the amorphous carbon was deposited. In the constant temperature heating conditions for those 3 materials, pyrolytic carbon is deposited in lower temperature heating and amorphous carbon in higher temperature. The amorphous carbons are appeared in higher than 700 0C for Inconel 718 and A286 and 800 0C for Inconel 600. The pyrolytic carbon is easier to peel off from the metallic surface than the amorphous carbon, thus, pyrolytic carbon must be careful for the design of a regenerative cooling engine. It is considered that the crystal of the pyrolytic carbon has a strong combination with a metal.

Fig. 7. Results of XRD Analysis of Inconel 718 and A286.

The XRD analysis is also empolyed for these test pieces. XRD analyses can make clear the internal crystal structure of these metallic materials and prevail that the peaks for Inconel 718 do not change after heating test as shown in Figure 7. Those for Inconel 600 also do not change, however for A286, the peaks of XRD analysis are changed after the ascendant heating. This means that the Iron carbide is produced on the surface of A286 test pieces.

#### **2.2 CH4 – C3H8 mixture pyrolysis and catalytic effects**

The main constituent of LNG is CH4 and the others are C2H6, C3H8 and larger hydrocarbon molecule. Non-hydrocarbon constituents are N2 or H2S. The higher purity of CH4 is, the more favourable propellant is. LNG from Alaska or Canada have higher purity of CH4, however, those from South East Asia have 10 to 15 vol. % of C2H6 and C3H8, which may be used for a rocket propellant because of cost. C3H8 is known to be decomposed easier than

The crystal structures of carbon deposits on the test piece surface are investigated by Raman analysis. Figure 6 shows the results of Raman analysis of Inconel 718 test pieces before and after the ascendant heating test. The two peaks are appeared in the test pieces after heating and the right peak is more distinguished than the left one, which means the pyrolytic carbon is deposited [Yoshikawa, S. 1991]. If the left peak would be higher than the right one, amorphous carbon is deposited, in contrast. For other materials in ascendant heating condition, Raman analysis of Inconel 600 shows the same tendencies with Inconel 718, however, that of A286 indicates that the amorphous carbon was deposited. In the constant temperature heating conditions for those 3 materials, pyrolytic carbon is deposited in lower temperature heating and amorphous carbon in higher temperature. The amorphous carbons are appeared in higher than 700 0C for Inconel 718 and A286 and 800 0C for Inconel 600. The pyrolytic carbon is easier to peel off from the metallic surface than the amorphous carbon, thus, pyrolytic carbon must be careful for the design of a regenerative cooling engine. It is considered that the crystal of the pyrolytic carbon has a strong combination with a metal.

(a) Inconel 718 b) A286

The XRD analysis is also empolyed for these test pieces. XRD analyses can make clear the internal crystal structure of these metallic materials and prevail that the peaks for Inconel 718 do not change after heating test as shown in Figure 7. Those for Inconel 600 also do not change, however for A286, the peaks of XRD analysis are changed after the ascendant heating. This means that the Iron carbide is produced on the surface of A286 test pieces.

The main constituent of LNG is CH4 and the others are C2H6, C3H8 and larger hydrocarbon molecule. Non-hydrocarbon constituents are N2 or H2S. The higher purity of CH4 is, the more favourable propellant is. LNG from Alaska or Canada have higher purity of CH4, however, those from South East Asia have 10 to 15 vol. % of C2H6 and C3H8, which may be used for a rocket propellant because of cost. C3H8 is known to be decomposed easier than

Fig. 7. Results of XRD Analysis of Inconel 718 and A286.

**2.2 CH4 – C3H8 mixture pyrolysis and catalytic effects** 

CH4 and radical species like H atom, CH3 and C2H5 are produced. The radical species can attack to CH4 and promote its pyrolysis. The effects of those radical species are significant even if mole fraction of C3H8 is a few percent.

The chemical compositions of LNG are varied from the production area. Thus, in the present section, LNG is modelled by CH4 and C3H8 mixture, which is call as pseudo-LNG in the present study. The details of test conditions are listed in Table 3. The test pieces materials are selected as Inconel 600, Haetelloy –X, SMC, OFMC and OMC. Hastelloy-X is one of the Ni-based alloy, as well as Inconel 600. SMC, OFMC and OMC are Copper based Alloys and included in the test pieces materials. Copper has high heat conductivity, thus, is also used for combustion chamber material. Test apparatus is same one shown in Fig.1. The results in this section are referred from Higashino, K. ( Higashino, K. et. al 2009B )

To investigate the effects of C3H8 addition of CH4, the ascendant heating test is conducted for pseudo-LNG, whose volumetric fraction of C3H8 is 1.0 %. In these tests, the catalytic effects are also experimentally evaluated. C3H8 molecules begin to decompose as well as CH4, if test gas would be heated. The test gas is sampled and the volumetric fractions of the remained C3H8 are measured by the gas chromatograph. Figure 8 shows the C3H8 residual ratios, which means the ratio of the remained and the initial volumetric fractions of C3H8. If there is no test piece, C3H8 begin to decrease at 527 0C ( 800 K ), which is about 300 0C lower than pure CH4 pyrolysis without test piece.


Table 3. List of Test Condition of Pseudo-LNG Heating Test.

If the test pieces of Inconel 600 or Hastelly-X are employed, C3H8 residual ratios begin to decrease at 377 0C. Thus, these materials have the catalytic effects to promote the C3H8 pyrolysis. On the other hand, tendency of C3H8 residual ratio with SMC test pieces are

Control of LNG Pyrolysis and Application to Regenerative Cooling Rocket Engine 153

 sup <sup>4</sup> 3 8 <sup>ˆ</sup> 0.95 0.05 *ply*

where those notations are same as equation(2), but the subscripts means the chemical species. The mass fraction of carbon atoms in pseudo LNG with C3H8 5.0 vol.% is given as

> sup 4 3 8 0.95 0.05 3 0.95 0.05 *C atom C C ply CH C H*

The mass of carbon atom in supplied pseudo LNG is calculated as 1.768 g and, then, the ratio of thermal decomposed gas to total supplied gas are about 4.4 %. In the previous section, the ratio of the decomposed CH4 gas to total supplied gas are only 0.308 % at the constant temperature heating of 800 0C. This temperature is higher than the present test; however, higher ratio of pseudo LNG gas is thermally decomposed. The addition of C3H8 is

The experimental results described in the previous section are theoretically investigated in the present section. The reaction model of CH4 pyrolysis are considered as described by

*CH H CH H H C H*

 

4 3

4 3 3 24 2

*CH CH H CH C H H*

*n*

pyrolysis proceed as follow. C3H8 pyrolysis begins via the following reactions.

38 37

 

2 4

2

decompose further and produce H atom and C2H4.

where *n* is higher than 3 in Cn molecule.

*CH CH H*

However, if the catalytic effects are considerable, larger hydrocarbon molecules are

*n C H C molecule Aromaticit y*

On the other hand, if C3H8 is involved in the CH4 pyrolysis, the reactions of CH4 and C3H8

38 25 3 *CH CH H C H C H CH*

Those reactions can occur at the lower temperature than CH4 pyrolysis. C2H5 radicals

*CH CH H* 25 24

 

*m M M m MM*

*PQt <sup>m</sup>*

very effective to promote the pyrolysis of CH4 and C3H8.

**2.3 Analytical model of CH4 and C3H8 pyrolysis** 

Ichikawa [ Ichikawa 2001 ].

produced.

equation (4).

*CH C H*

*RM M T* (3)

(4)

almost same as that without test pieces. SMC does not have the catalytic effects. If the temperature is more than 727 0C, C3H8 residual ratios are less than 100 ppm, and too low to be detected by gas chromatograph.

The thicknesses of the carbon film on the test piece surface are measured by using the electron microscope and its results are shown in Figure 9. The heating condition of Fig.9 is the constant temperature heating of 727 0C. The thicknesses of the carbon film on SMC and OMC are less than 10 m. On the other hands, the thicknesses of the carbon film on Inconel 600 and Hastelloy-X enlarge if the volumetric fraction of C3H8 is greater than 3.0 percent. Especially for Inconel 600, the thicknesses of the carbon film grows up to 442.3 mm at 5.0 volumetric percent of C3H8, while it is 2.4m and 38.5m at 1.0 and 3.0 vol.% of C3H8, respectively.

Fig. 8. C3H8 residual ratio of Pseudo LNG with C3H8 1.0 vol.% at the ascendant heating.

Fig. 9. Thickness of Carbon Films on Test Pieces for Constant temperature heating of 727 0C.

For Inconel 600 with C3H8 5.0 vol.%, the amounts of carbon deposited on the test pieces are measured by the electronic balance and evaluated as 78.2 mg. As well as equation (2) for pure CH4, the total mass of pseudo LNG can be calculated as 2.324g by equation (3).

$$\dot{m}\_{\text{supply}} = \frac{PQt}{\left(\hat{R}\left[0.95M\_{\text{CH}4} + 0.05M\_{\text{C}3H8}\right]\right)T} \tag{3}$$

where those notations are same as equation(2), but the subscripts means the chemical species. The mass fraction of carbon atoms in pseudo LNG with C3H8 5.0 vol.% is given as equation (4).

$$\frac{\dot{m}\_{\text{C atom}}}{\dot{m}\_{\text{supply}}} = \frac{0.95M\_{\text{C}} + 0.05 \times 3 \times M\_{\text{C}}}{0.95M\_{\text{CH4}} + 0.05M\_{\text{C3H8}}} \tag{4}$$

The mass of carbon atom in supplied pseudo LNG is calculated as 1.768 g and, then, the ratio of thermal decomposed gas to total supplied gas are about 4.4 %. In the previous section, the ratio of the decomposed CH4 gas to total supplied gas are only 0.308 % at the constant temperature heating of 800 0C. This temperature is higher than the present test; however, higher ratio of pseudo LNG gas is thermally decomposed. The addition of C3H8 is very effective to promote the pyrolysis of CH4 and C3H8.

#### **2.3 Analytical model of CH4 and C3H8 pyrolysis**

152 Heat Exchangers – Basics Design Applications

almost same as that without test pieces. SMC does not have the catalytic effects. If the temperature is more than 727 0C, C3H8 residual ratios are less than 100 ppm, and too low to

The thicknesses of the carbon film on the test piece surface are measured by using the electron microscope and its results are shown in Figure 9. The heating condition of Fig.9 is the constant temperature heating of 727 0C. The thicknesses of the carbon film on SMC and OMC are less than 10 m. On the other hands, the thicknesses of the carbon film on Inconel 600 and Hastelloy-X enlarge if the volumetric fraction of C3H8 is greater than 3.0 percent. Especially for Inconel 600, the thicknesses of the carbon film grows up to 442.3 mm at 5.0 volumetric percent of C3H8, while it is 2.4m and 38.5m at 1.0 and 3.0 vol.% of C3H8,

500 600 700 800 900 1000

Fig. 8. C3H8 residual ratio of Pseudo LNG with C3H8 1.0 vol.% at the ascendant heating.

Fig. 9. Thickness of Carbon Films on Test Pieces for Constant temperature heating of 727 0C.

For Inconel 600 with C3H8 5.0 vol.%, the amounts of carbon deposited on the test pieces are measured by the electronic balance and evaluated as 78.2 mg. As well as equation (2) for

pure CH4, the total mass of pseudo LNG can be calculated as 2.324g by equation (3).

temperature (K)

be detected by gas chromatograph.

100

90

C3H8 residual ratio(%)

80

70

:SMC :Hastelloy-X :Inconel600 :no test piece

60

respectively.

The experimental results described in the previous section are theoretically investigated in the present section. The reaction model of CH4 pyrolysis are considered as described by Ichikawa [ Ichikawa 2001 ].

$$\begin{array}{rcl} \text{CH}\_4 & \rightarrow & \text{CH}\_3\cdot + H\cdot\\ & & \rightarrow & \text{CH}\_2 + H\_2 \\ & & \rightarrow & \text{CH}\cdot + \text{H}\_2 + H\cdot \\ & & \rightarrow & \text{C} & + 2H\_2 \\ \end{array}$$

However, if the catalytic effects are considerable, larger hydrocarbon molecules are produced.

$$\begin{array}{rcl} \text{CH}\_4 & \rightarrow & \text{CH}\_3\cdot + \text{H}\cdot\\ 2\text{CH}\_3\cdot & \rightarrow & \text{C}\_2\text{H}\_4 + \text{H}\_2\\ m\text{C}\_2\text{H}\_4 & \rightarrow & \text{C}\_n\text{ molecule} \quad + & \text{Aronaticity} \end{array}$$

where *n* is higher than 3 in Cn molecule.

On the other hand, if C3H8 is involved in the CH4 pyrolysis, the reactions of CH4 and C3H8 pyrolysis proceed as follow. C3H8 pyrolysis begins via the following reactions.

$$\begin{array}{rcl} \text{C}\_3\text{H}\_8 & \rightarrow & \text{C}\_3\text{H}\_7\cdot + & H\cdot\\ \text{C}\_3\text{H}\_8 & \rightarrow & \text{C}\_2\text{H}\_5\cdot + \text{CH}\_3\cdot \end{array}$$

Those reactions can occur at the lower temperature than CH4 pyrolysis. C2H5 radicals decompose further and produce H atom and C2H4.

$$\text{C}\_2\text{H}\_5\cdot \begin{array}{rcl} \rightarrow & \text{C}\_2\text{H}\_4 \ + & H\cdot \end{array}$$

Control of LNG Pyrolysis and Application to Regenerative Cooling Rocket Engine 155

Fig. 12. Time Histories of Principal Chemical Species Mole Fraction for C3H8 1.0 vol.% and

Figure 10 show the numerical results of the time histories of CH3 radical for constant temperature heating of CH4. The mole fraction of CH3 is rapidly increased at 900 0C, while they remain to low values less than 800 0C. This figure indicates that the CH4 pyrolysis begins at temperature between 800 and 900 0C, which agrees with the experimental data shown in Figure 3(d). Figure 11 shows the time histories of mole fractions of CH4 for pseudo LNG with C3H8 1.0 vol.% and indicates the simulation of the experimental results in Fig.8. The mole fraction of CH4 for 700 0C is instantaneously decreased, thus this numerical results is also agreed with the experimental data. Figure 12 shows the time histories of mole fraction of the principal chemical species for pseudo LNG with C3H8 1.0 vol.% and 700 0C. The mole fraction of CH4 is rapidly decreased at 2.5 sec. At same time, the radical species, such as H atom, CH3 and C2H5 reach to maximum values. As described previously, those radical species are involved in CH4 pyrolysis. Especially, C2H5 and C3H7 are the products of C3H8 pyrolysis and precursors of CH3 and H atom. C2H5 and C3H7 play important role in promoting CH4 pyrolysis. After 3.0 sec, the mole fractions of those species are constant and

700 0C.

reach to equilibrium.

**3. Coking inhibition by graphite coating** 

**3.1 Experimental evaluation of graphite coating for coking inhibition** 

In the previous section, it is indicated that CH4 or CH4 and C3H8 gas mixture (pseudo LNG) can decomposed under high temperature conditions and carbon deposites. This coking phenomena can be accelerated by the catalytic effects of combustion chamber material. Thus, thermal design of regenerative cooling passage will be difficult because fuel temperature must be kept lower to prevent coking at there. However, if some inert materials would lay on the metallic surface, those catalytic effects might be prevented. Thus, the

H atom can attack to CH4 to decompose it.

$$\text{CH}\_4 + \text{H} \cdot \text{ } \rightarrow \text{ } \cdot \text{CH}\_3 \cdot + \text{H}\_2$$

This reaction proceeds much faster than CH4 solo pyrolysis. Thus, the addition of C3H8 to CH4 can promote the CH4 pyrolysis. Various reaction models have been proposed to simulate combustion of lighter hydrocarbon molecules like CH4, C2H4, C2H6 and C3H8. Among them, GRI-Mech Ver.3.0 is one of the most widely employed model ( Smith, G. P. ). The authors developed the numerical code to simulate those experimental results by using the GRI-Mech. Ver.3.0.

Fig. 10. Time History of CH3 mole fraction for Constant temperature heating of pure CH4 gas.

Fig. 11. Time History of CH4 mole fraction for constant temperature heating of pseudo LNG with C3H8 1.0 vol.%.

*CH H CH H* 4 3 <sup>2</sup>

This reaction proceeds much faster than CH4 solo pyrolysis. Thus, the addition of C3H8 to CH4 can promote the CH4 pyrolysis. Various reaction models have been proposed to simulate combustion of lighter hydrocarbon molecules like CH4, C2H4, C2H6 and C3H8. Among them, GRI-Mech Ver.3.0 is one of the most widely employed model ( Smith, G. P. ). The authors developed the numerical code to simulate those experimental results by using

Fig. 10. Time History of CH3 mole fraction for Constant temperature heating of pure CH4

Fig. 11. Time History of CH4 mole fraction for constant temperature heating of pseudo LNG

H atom can attack to CH4 to decompose it.

the GRI-Mech. Ver.3.0.

gas.

with C3H8 1.0 vol.%.

Fig. 12. Time Histories of Principal Chemical Species Mole Fraction for C3H8 1.0 vol.% and 700 0C.

Figure 10 show the numerical results of the time histories of CH3 radical for constant temperature heating of CH4. The mole fraction of CH3 is rapidly increased at 900 0C, while they remain to low values less than 800 0C. This figure indicates that the CH4 pyrolysis begins at temperature between 800 and 900 0C, which agrees with the experimental data shown in Figure 3(d). Figure 11 shows the time histories of mole fractions of CH4 for pseudo LNG with C3H8 1.0 vol.% and indicates the simulation of the experimental results in Fig.8. The mole fraction of CH4 for 700 0C is instantaneously decreased, thus this numerical results is also agreed with the experimental data. Figure 12 shows the time histories of mole fraction of the principal chemical species for pseudo LNG with C3H8 1.0 vol.% and 700 0C. The mole fraction of CH4 is rapidly decreased at 2.5 sec. At same time, the radical species, such as H atom, CH3 and C2H5 reach to maximum values. As described previously, those radical species are involved in CH4 pyrolysis. Especially, C2H5 and C3H7 are the products of C3H8 pyrolysis and precursors of CH3 and H atom. C2H5 and C3H7 play important role in promoting CH4 pyrolysis. After 3.0 sec, the mole fractions of those species are constant and reach to equilibrium.

#### **3. Coking inhibition by graphite coating**

#### **3.1 Experimental evaluation of graphite coating for coking inhibition**

In the previous section, it is indicated that CH4 or CH4 and C3H8 gas mixture (pseudo LNG) can decomposed under high temperature conditions and carbon deposites. This coking phenomena can be accelerated by the catalytic effects of combustion chamber material. Thus, thermal design of regenerative cooling passage will be difficult because fuel temperature must be kept lower to prevent coking at there. However, if some inert materials would lay on the metallic surface, those catalytic effects might be prevented. Thus, the

Control of LNG Pyrolysis and Application to Regenerative Cooling Rocket Engine 157

Activated Carbon Amorphous Carbon

Graphite No Pieces

0 10 20 30 40 50 60

Time [min]

Fig. 13. CH4 conversion rate of pseudo LNG with C3H8 5.0 vol.% for constant temperature

In the present section, the authors investigate the catalytic effects of carbon compounds such as, graphite, amorphous and activated carbon. Figure 13 indicates time histories of the CH4 conversion rate in 700 0C constant temperature heating tests. The test gas is the pseudo LNG gas with C3H8 5.0 vol.%.Activated carbon, amorphous carbon and graphite are used for test pieces to investigate their catalytic effects. It is indicated that activated and amorphous carbon have the catalytic effects to thermal decomposition for this gas. On the other hand, graphite does not have them. This reason is considered that graphite would have been chemically inert. The results in Fig.13 indicate that graphite is chemically inert for LNG thermal decomposition. Based on these results, inhibition effects of graphite coating on the surface of INCONEL 600 test pieces are experimentally evaluated. For comparison, conditions of n-hexane coating, no coating and no test pieces conditions (Only alumina board is located.) are also investigated. Figure 14 show the CH4 conversion rates in ascendant heating test for those four carbon coating conditions. Ten test pieces are used for one heating test. From Fig.14(a), CH4 begins to decompose at 600 to 700 0C. As described in the previous section, it begins to decompose at 800 or 900 0C with no catalytic conditions. Addition of C3H8 can reduce the CH4 decomposition temperature. C3H8 can be decomposed at lower temperature than CH4, and radical species caused by C3H8 pyrolysis can attack to CH4, resulting of reduction of thermal decomposition temperature. In Fig.14(a) and (b), pyrolysis inhibition by graphite coating is apparent. Conversion rates for graphite coating condition increase more moderate than even those for no piece condition. Although, this reason is not clear, it is no doubt that graphite coating is effective to inhibit the catalytic effect of INCONEL 600. Moreover, these inhibitions are more effective for the decomposition of C3H8 than that of CH4. This fact is more meaningful for the practical application of LNG rocket engine because most of LNG gas contains a few percent of C3H8.

0

LNG highly purified by CH4 is very costly.

heating of 700 0C.

1

CH4

Conversion Rate [%]

2

3

4

5

6

7

authors present to coat the graphite layer on the metallic surface for the purpose of preventing of coking. Graphite is a kind of the carbon materials and chemically inert. Therefore, graphite layer on the metallic surface is considered to confine the catalytic effect. With those test pieces, the heating tests are conducted for CH4, pseudo LNG and N2+C3H8 gas mixture.

The experimental apparatus is same with the previous sections. The conditions of the graphite coating tests are listed as Table 4.


Table 4. Test Conditions for Graphite Coating Tests.

To evaluate the C3H8 pyrolysis, C3H8 conversion rate is introduced in equation (5) as well as CH4 conversion rate.

$$\text{Conversion Rate} = \left[ 1 - \frac{\left( A\_{\text{C3H8}} / \lambda\_{\text{C3H8}} \right)}{\left( A\_{\text{C3H8}} / \lambda\_{\text{C3H8}} \right) + \left( A\_{\text{H2}} / \lambda\_{\text{H2}} \right)} \right] \times 100\tag{5}$$

The definition of equation (5) is same as equation (1), except subscript of C3H8.

If the carbon deposited in a regenerative cooling passage would have chemical activation, like as amorphous or activated carbon, these might be able to accelerate the thermal decomposition of CH4 and C3H8 because those carbon deposit will play role of catalysis.

authors present to coat the graphite layer on the metallic surface for the purpose of preventing of coking. Graphite is a kind of the carbon materials and chemically inert. Therefore, graphite layer on the metallic surface is considered to confine the catalytic effect. With those test pieces, the heating tests are conducted for CH4, pseudo LNG and N2+C3H8

The experimental apparatus is same with the previous sections. The conditions of the

Inconel 600 ( Ni 73.58%, Cr 16.18%, Fe 9.16% )

Isothermal Heating with 627℃, 700℃, 800℃

Ascendant Heating from Room Temp. to 1000℃

test pieces are located in n-hexane vapor for 60 min with 800℃.

Graphite powder are mixed with ethanol and Surface of INCONEL

 38 38 38 38 2 2 1 100 *CH CH CH CH H H*

  (5)

Then, they are located in N2 gas for 60min with 800℃.

They are located in N2 gas for 60 min with 800℃

*A*

*A A*

To evaluate the C3H8 pyrolysis, C3H8 conversion rate is introduced in equation (5) as well as

If the carbon deposited in a regenerative cooling passage would have chemical activation, like as amorphous or activated carbon, these might be able to accelerate the thermal decomposition of CH4 and C3H8 because those carbon deposit will play role of catalysis.

CH4 95% + C3H8 5%(Pseudo LNG) CH4 99% + C3H8 1%(Pseudo LNG)

CH4 more than 99.9%

N2 95% + C3H8 5%

Activated Carbon Amorphous Carbon

60 min at Isothermal Heating 120 min for Ascendant Heating

n-Hexane Coating :

Graphite Coating :

600 are coverd with them.

The definition of equation (5) is same as equation (1), except subscript of C3H8.

Graphite

gas mixture.

Test Pieces

Heating Condition

Heating Time

Test Gas ( vol % )

graphite coating tests are listed as Table 4.

Flowrate of test gas 20 ml /min

Coating Conditions

CH4 conversion rate.

Pressure 0.14 ~ 0.20 MPa

Table 4. Test Conditions for Graphite Coating Tests.

*Conversion Rate*

Fig. 13. CH4 conversion rate of pseudo LNG with C3H8 5.0 vol.% for constant temperature heating of 700 0C.

In the present section, the authors investigate the catalytic effects of carbon compounds such as, graphite, amorphous and activated carbon. Figure 13 indicates time histories of the CH4 conversion rate in 700 0C constant temperature heating tests. The test gas is the pseudo LNG gas with C3H8 5.0 vol.%.Activated carbon, amorphous carbon and graphite are used for test pieces to investigate their catalytic effects. It is indicated that activated and amorphous carbon have the catalytic effects to thermal decomposition for this gas. On the other hand, graphite does not have them. This reason is considered that graphite would have been chemically inert. The results in Fig.13 indicate that graphite is chemically inert for LNG thermal decomposition. Based on these results, inhibition effects of graphite coating on the surface of INCONEL 600 test pieces are experimentally evaluated. For comparison, conditions of n-hexane coating, no coating and no test pieces conditions (Only alumina board is located.) are also investigated. Figure 14 show the CH4 conversion rates in ascendant heating test for those four carbon coating conditions. Ten test pieces are used for one heating test. From Fig.14(a), CH4 begins to decompose at 600 to 700 0C. As described in the previous section, it begins to decompose at 800 or 900 0C with no catalytic conditions. Addition of C3H8 can reduce the CH4 decomposition temperature. C3H8 can be decomposed at lower temperature than CH4, and radical species caused by C3H8 pyrolysis can attack to CH4, resulting of reduction of thermal decomposition temperature. In Fig.14(a) and (b), pyrolysis inhibition by graphite coating is apparent. Conversion rates for graphite coating condition increase more moderate than even those for no piece condition. Although, this reason is not clear, it is no doubt that graphite coating is effective to inhibit the catalytic effect of INCONEL 600. Moreover, these inhibitions are more effective for the decomposition of C3H8 than that of CH4. This fact is more meaningful for the practical application of LNG rocket engine because most of LNG gas contains a few percent of C3H8. LNG highly purified by CH4 is very costly.

Control of LNG Pyrolysis and Application to Regenerative Cooling Rocket Engine 159

n-Hexane No Coating

Graphite Coating No test piece

0 10 20 30 40 50 60 70

0 10 20 30 40 50 60 70

n-Hexane Coating

Graphite Coating No test pieces

No Coating

Time [ min ]

(b) At 700 0C Fig. 15. The Effects of Carbon Coating on CH4 pyrolysis for Constant temperature heating.

On the other hand, n-hexane coating can accelerate CH4 or C3H8 pyrolysis more than no coating test pieces. This means the carbon in n-hexane coating have chemical activation.

For the practical LNG rocket engine, fuel temperature at the exit of regenerative cooling passage may be lower than the pyrolysis initiation temperature. However, it is necessary to grasp this temperature because high temperature turbine driven gas can obtain the turbine

Time [ min ]

(a) At 627 0C

CH4

Conversion rate [%]

CH4

Conversion rate [%]

Fig. 14. The Effects of Carbon Coating for Ascendant Heating.

n-Hexane Coating

Graphite Coating No test pieces

No Coating

500 600 700 800 900 1000

(a)Pseudo LNG with C3H8 5.0 vol.%

500 600 700 800 900 1000

(b) N2 95 vol.% + C3H8 5.0 vol.%

Fig. 14. The Effects of Carbon Coating for Ascendant Heating.

Temperature [ ℃ ]

n-Hexane Coating

Graphite Coating

No test pieces

No Coating

Temperature [ ℃ ]

0

C3H8

Conversion rate [%]

10

CH4

conversion rate [%]

20

30

40

50

Fig. 15. The Effects of Carbon Coating on CH4 pyrolysis for Constant temperature heating.

On the other hand, n-hexane coating can accelerate CH4 or C3H8 pyrolysis more than no coating test pieces. This means the carbon in n-hexane coating have chemical activation.

For the practical LNG rocket engine, fuel temperature at the exit of regenerative cooling passage may be lower than the pyrolysis initiation temperature. However, it is necessary to grasp this temperature because high temperature turbine driven gas can obtain the turbine

Control of LNG Pyrolysis and Application to Regenerative Cooling Rocket Engine 161

(a) Graphite (b) Activated Carbon

(a) No Coating condition (b) n-hexane coating condition

Fig. 17. Raman spectroscopy peaks of deposits on the test pieces after constant temperature

Figure 17 shows the Raman spectroscopy peaks of the deposits on the test pieces after constant temperature heating test. Those pieces are used in No coating and n-hexane coating conditions. For both two conditions at constant temperature heating 700 0C, the peaks at 1350cm-1 is higher than 1570cm-1. On the other hand, at constant temperature heating of 800 0C, peaks at 1350cm-1 are close to that at 1570cm-1. The results in Fig.17 indicate the deposit at 700 0C is similar to activated carbon and has catalytic effects. They are considered to accelerate the pyrolysis of CH4 or C3H8. However, deposits at 800 0C differ from those at 700 0C and are less activated. For practical application to rocket engine designing, heating 700 0C at regenerative cooling passage should be avoided without graphite coating. For heating of LNG at this temperature, coke begins to deposit within fuel passages and promote the thermal decomposition by itself. However, graphite coating is effective to inhibit the coking

heating test.

Fig. 16. Reference Peaks of Carbon Compounds of Raman Spectroscopy.

power. In addition, catalyses are generally effective to accelerate pyrolysis around this temperature range. Therefore, constant temperature heating tests at 627, 700 and 800 ºC are conducted for pseudo LNG gas with 5 vol % C3H8 and Figure 15(a) to (c) show the time histories of those CH4 conversion rates. Five test pieces are employed for one heating test. For 627 0C and 700 0C heating test, CH4 conversion rates for graphite coating condition are much lower than those for n-hexane and No coating conditions and are same level with those for no test piece condition. For 800 0C heating test, no difference appeared in CH4 conversion rates amaong those 4 conditions and catalytic effect is not observed. At 800 0C, the decomposition rates of CH4 or C3H8 may mainly depend on temperature rather than catalytic effect. The results in Fig.15(a) to (c) remarkably show the inhibition effect of graphite coating for LNG gas pyrolysis.

Fig. 15. (cont.) The Effects of Carbon Coating on CH4 pyrolysis for Constant temperature heating.

It is remarkable that CH4 conversion rates for n-hexane coating and no coating conditions increase more rapidly at 627 and 700 0C than at 800 0C. In general, catalysis used in cracking of hydrocarbon become to deactivate with time passing because cokes deposit on its surface and reduce the catalytic effects. This reason is considered that for less than 700 0C heating, carbon deposited at test pieces is similar compound to amorphous or activated carbon. They are chemically activated and play role of catalysis. Thus, the types of the deposits on the test pieces after constant temperature heating tests are analyzed by Raman spectroscopy. Figure 16(a) and (b) show the reference peaks of graphite and activated carbon, respectively. Raman spectroscopy of graphite has a peak at 1350 cm-1 and that of activated carbon has two peaks at 1300 and 1570cm-1. Peak at 1300cm-1 is higher than 1570cm-1.

power. In addition, catalyses are generally effective to accelerate pyrolysis around this temperature range. Therefore, constant temperature heating tests at 627, 700 and 800 ºC are conducted for pseudo LNG gas with 5 vol % C3H8 and Figure 15(a) to (c) show the time histories of those CH4 conversion rates. Five test pieces are employed for one heating test. For 627 0C and 700 0C heating test, CH4 conversion rates for graphite coating condition are much lower than those for n-hexane and No coating conditions and are same level with those for no test piece condition. For 800 0C heating test, no difference appeared in CH4 conversion rates amaong those 4 conditions and catalytic effect is not observed. At 800 0C, the decomposition rates of CH4 or C3H8 may mainly depend on temperature rather than catalytic effect. The results in Fig.15(a) to (c) remarkably show the inhibition effect of

0 20 40 60 80

n-HexaneCoating

Graphite Coating No test piece

No Coating

Time [ min ]

(c) At 800 0C Fig. 15. (cont.) The Effects of Carbon Coating on CH4 pyrolysis for Constant temperature

It is remarkable that CH4 conversion rates for n-hexane coating and no coating conditions increase more rapidly at 627 and 700 0C than at 800 0C. In general, catalysis used in cracking of hydrocarbon become to deactivate with time passing because cokes deposit on its surface and reduce the catalytic effects. This reason is considered that for less than 700 0C heating, carbon deposited at test pieces is similar compound to amorphous or activated carbon. They are chemically activated and play role of catalysis. Thus, the types of the deposits on the test pieces after constant temperature heating tests are analyzed by Raman spectroscopy. Figure 16(a) and (b) show the reference peaks of graphite and activated carbon, respectively. Raman spectroscopy of graphite has a peak at 1350 cm-1 and that of activated carbon has

two peaks at 1300 and 1570cm-1. Peak at 1300cm-1 is higher than 1570cm-1.

graphite coating for LNG gas pyrolysis.

CH4

heating.

conversion rate [%]

Fig. 16. Reference Peaks of Carbon Compounds of Raman Spectroscopy.

Fig. 17. Raman spectroscopy peaks of deposits on the test pieces after constant temperature heating test.

Figure 17 shows the Raman spectroscopy peaks of the deposits on the test pieces after constant temperature heating test. Those pieces are used in No coating and n-hexane coating conditions. For both two conditions at constant temperature heating 700 0C, the peaks at 1350cm-1 is higher than 1570cm-1. On the other hand, at constant temperature heating of 800 0C, peaks at 1350cm-1 are close to that at 1570cm-1. The results in Fig.17 indicate the deposit at 700 0C is similar to activated carbon and has catalytic effects. They are considered to accelerate the pyrolysis of CH4 or C3H8. However, deposits at 800 0C differ from those at 700 0C and are less activated. For practical application to rocket engine designing, heating 700 0C at regenerative cooling passage should be avoided without graphite coating. For heating of LNG at this temperature, coke begins to deposit within fuel passages and promote the thermal decomposition by itself. However, graphite coating is effective to inhibit the coking

Control of LNG Pyrolysis and Application to Regenerative Cooling Rocket Engine 163

The graphite coating has the possibility to improve an expander cycle rocket engine performance because temperature at an exit of regenerative cooling passage can be higher. That leads to increase the turbine power. Simple analysis of turbopump is considered in the present study. The specification of turbopump and rocket engine are considered as Table.2. The specification of turbopump and rocket engine are same as those studied by Schuff (2006). 90 percent of LNG fuel is used to drive the turbopump and the rest of them are bypassed.

The combustion chamber pressure, Pc, can be given by the power balance and pressure loss at fuel passage. although the detailed analysis is still necessary. Figure 18 show the combustion chamber pressure, Pc, versus Turbine Inlet Temperature (TIT). TIT is considered to be equal to the maximum allowable temperature at the exit of regenerative cooling

The effects of TIT on Pc and vacuum Isp are indicated in Figure 18 and 19, respectively. Vacuum Isp is evaluated with chemical frozen flow in a nozzle and calculated by computational code by Gordon and Mcbride [6]. The higher TIT is, the greater vacuum Isp can be obtained, however, improvement of vacuum Isp is not so great. For example, in the case of nozzle expansion of 40, only 4 sec of vacuum Isp increment ( from 337.5 sec to 342.4 sec ) can be expected when TIT would be varied from 400 K to 900 K. However, combustion

Therefore, practical application of graphite coating may be useful to minimize the combustion chamber size, rather than the improvement of Isp. In such cases, the size of combustion chamber will be depended on heat exchange between fuel and combustor. In our future study, more detailed and practical estimation should be conducted on heat

In the present chapter, the experimental and numerical studies on fundamental chemical phenomena of CH4 and LNG pyrolysis are conducted. CH4 pyrolysis is promoted by the catalytic effects of chamber material and the addition of C3H8. CH4 pyrolysis can begin at temperature of 800 to 900 0C, however, the catalytic effect of combustion chamber materials can reduce the temperature which CH4 pyrolysis begins by 200 0C. In addition, the addition of C3H8 can promote the coking on the test pieces, especially it is apparent if the volumetric fraction of C3H8 is more than 3.0 %. The numerical simulation can predict the experimental

Based on those experimental results, the effective coking inhibition method by graphite coating for LNG rocket engine can be developed and confine pyrolysis temperature up to 700 0C. INCONEL 600 with the graphite coating did not have their catalytic effect on LNG

If this method can be applied to expander cycle rocket engine, the improvement of vacuum Isp can be achieved from 338.6 to 342.5 sec when the nozzle expansion ratio is 40. However, it is expected that the size of combustion chamber may be dramatically reduced. In the next phase, more detailed investigations for heat transfer in regenerative cooling passage and

**3.2 Application of graphite coating to expander cycle rocket engine** 

pressure can be increased to about twice as shown in Fig.18.

transfer analysis and turbopump specification.

results of CH4 and C3H8 pyrolysis.

pyrolysis absolutely.

passage.

**4. Conclusion** 

deposit for such heating conditions. Figure 15 indicate the graphite coating can inhibit coking to thermal decomposition in those temperature ranges.

Fig. 18. Effect of TIT on chamber pressure for Expander Cycled Rocket Engine.

Fig. 19. Effect of TIT on Vacuum Isp for Expander Cycled Rocket Engine.
