ht. .I. Hydrogen Enrrgy, Vol. 23, No. 5, pp. 315.

319, 1998
8 1998 Inte~mational Association for Hydrogen Energy
Pergamon Elsevier Science Ltd
All rights reserved. Printed in Great Britain
PII: SO360-3199(97)00073-h 036~-3199/98 $19.00+0.00

HYDROCARBON STEAM-REFORMING PROCESS: FEEDSTOCK AND

CATALYSTS FOR HYDROGEN PRODUCTION IN CHINA

HA0 SHU-REN
Research Institute of Qilu Petrochemical Co., SINOPEC, Zibo, Shandong, People’s Republic of China 255400

Abstract-The hydrocarbon steam-reforming process has been a main method for the production of hydrogen in
China. A catalyst series used for the steam reforming of various hydrocarbons and industrial methanol has been
developed. In China there are more than 20 sets of steam-reforming plants operating using natural gas, refinery off
gases, LPCJ, naphtha and methanol as the feedstock. 0 1998 International Association for Hydrogen Energy

INTRODUCTION the first natural gas steam-reforming plant for hydrogen

production was built in the Daqing Refinery of China.
At present, the petroleum-refining industry requires more Since then steam-reforming catalysts and processes have
and more hydrogen for the refining of petroleum prod- been developed and improved continuously in China,
ucts and processing of heavy oil. In addition, the petro- which made the steam-reforming plants operate at higher
chemical industry and fine chemical industry also require temperatures and pressures using heavy hydrocarbons as
a large amount of high purity hydrogen. the feedstock. At present, there are more than 20 sets of
There are three basic methods for hydrogen pro- hydrogen production units operating using refinery off
duction: the water-gas method using coal or coke as the gases, LPG and naphtha as feedstock. In addition, there
feedstock, the partial oxidization method using heavy or are two small units for hydrogen production with meth-
residual oil as the feedstock and the steam-reforming anol as the feedstock, as shown in Tables l-4.
method using various kinds of hydrocarbons as the feed-
stock. The latter is the most widespread way for obtaining
hydrogen in industry.
At present, steam reforming of natural gas to obtain PROCESS
hydrogen is the most rational method because its invest- Steam-reforming of hydrocarbons is the most wide-
ment and production costs are lower than others. spread way for producing hydrogen and synthetic gas in
However, the limited availability of natural gas in China, the refinery, chemical or petrochemical industries. Natu-
and in some other countries, severely restrains its appli- ral gas reforming is most rational in a technical and
cation. economic appraisal. At present, a conventional puri-
Steam reforming of residual refinery gases can also fication system is mainly used for ammonia and methanol
obtain hydrogen. The refinery gases are commonly from production. and PSA has been used for hydrogen pro-
the primary distillation, FCC, delayed coking, vis- duction.
breaking and hydrocracking. They are now popular as Compared with methane, the composition of various
fuel gases because it is complex to hydrosaturate the naphtha is relatively complex, it contains straight chain
olefins and to hydrodesulfurize the organic sulphides alkanes, cyclane and aromatics. In the naphtha steam-
which they contain. reforming process, these hydrocarbons react with steam
In hydrocarbon steam-reforming process, the trans- on the catalyst, and also undergo a catalytic cracking
portation and supply will be convenient and flexible when reaction and a homogeneous phase thermal cracking
naphthas are the feedstocks. Therefore various naphthas reaction. In most industrial units, the temperature of the
are popularly used for the production of hydrogen in catalyst beds in steam reformer tubes is in the range of
refineries and petrochemical factories. 50~800°C. That means the cracking reaction can take
The technique of hydrocarbon steam-reforming for place easily, large amounts of cracked products may
producing hydrogen has been developed step by step result in carbon deposition by further polymerization,
since the 1960s in China. At the beginning of the 1960s aromatization and hydrogen transfer reactions. There-

315
 316 HA0 SHU-REN

Table I. Plants using 2402/2405

Reformer
Plant names types Feed Product Capacity

Refinery of Jilin Chemical Co. Top-fired Naphtha H2 20 000 m’/h

No. 3 Plant of Fushun Petrochemical Co. Side-fired Naphtha HZ 20 000 m’/h x 3
Refinery of Jinzhou Petrochemical Co. Side-fired Naphtha/LPG H* 10000m2/hx2
Refinery of Jinxi Petrochemical Co. Side-fired Naphtha/refinery gas HZ 10000m3/h x 2
Refinery of Liaoyang Chemical Fiber Co. Top-fired Naphtha H* 25 000 m”h x 2
No. 1 Chemical Plant of Liaoyang Chemical Faber Co. Side-fired C, - C, Ha 5000 m’/h
Refinery of Liaohe Petrochemical Co. Side-fired Naphtha/oil field gas H: IO 000 m,/h
Refinery of Dalian West Pacific Co. Top-fired Naphtha H* 30 000 m’/h x 2
No. 1 plant of the Refinery of Qilu Petrochemical Co. Top-fired Topping distillate oil H* 20 000 ml/h
Refinery of Jinling Petrochemical Co. Side-fired HP hydrogenated naphtha Hz 20 000 mi/h x 2
Wuhan Qingshan Refinery Top-fired Naphtha HZ 5000 m’/h
Lanzhou Refinery Side-fired Naphtha HZ IO 000 ml/h x 2
Jinmen Refinery Side-tired Naphtha/refinery gas H, 10000mJ/hx2
Changling Refinery Side-tired Naphtha/refinery gas HZ IO 000 m’/h x 2
Refinery of Maoming Petrochemical Co. Side-fired Naphtha Hz 20 000 m’ih x 2
Refinery of Zhenhai Petrochemical Works Side-fired Naphtha HZ 20000m’/h x 2
Refinery of Tianjin Petrochemical Co. Side-fired Naphtha H1 20 000 m’jh

Table 2. Plants using Z409/Z405G

Reformer
Plant names types Feed Product Capacity

Hunan Dongting Fertilizer Plant Top-fired Naphtha 300 000 t/a

Hubei Chemical Fertilizer Plant Top-fired Naphtha 300 000 t/a
Chemical Fertilizer Plant of Guangzhou Petrochemical Works Side-fired Naphtha 300 000 t/a
Shanghai Wujing Chemical Fertilizer Plant Top-fired Naphtha 300 000 t/a
Yingshan Petrochemical Plant of Baling Petrochemical Co. Top-fired Naphtha 17000m’/h
No. 2 Plant of the Refinery of Qilu Petrochemical Co. Top-fired Naphtha 40 000 m’/h
Ningbo Haili Chemical Co. Side-fired Naphtha 2 000 m’/h
Nanxing Co. of Korea Top-fired Naphtha 150000t/ax2
Aromatic Plant of Yangzi Petrochemical Co. Top-fired Naphtha 36 000m3/h x 2

Table 3. Plants using Z412/2413

Reformer
Plant names types Feed Product Capacity

Henan Puyang Chemical Fertilizer Plant Top-fired Oil field accompanying NH, 30 000 t/a
gas
Shandong Dongming Chemical Fertilizer Plant Top-fired Oil field accompanying NH, 30 000 t/a
gas
The Second Chemtcal Fertilizer Plant of QiLu Petrochemical Co. Top-fired Oil field accompanying NH, 300 000 t/a
gas
Sichuan Vinylon Plant Top-fired Natural gas CH,OH 100000 ta

Table 4. Plants usmg methanol as the feedstock

Plant names Reformer types Feed Product Capacity

Bo Xm oil and fat plant Shell-tube Methanol H* 1000 m’/h

Ghangzhou Electrochemistry plant Shell-tube Methanol Hz 1000 m’/h
 HYDROCARBON STEAM-REFORMING PROCESS 317

fore, the catalyst used for naphtha steam-reforming must in steam reforming becomes larger. The typical naphthas
be of good resistance to carbon deposition. This is the are shown in Table 5.
key factor for whether the catalyst can be used ordinarily The refinery off gases can be used as feedstock for
or not. This is also the fundamental difference between production of hydrogen, but they generally contain
the naphtha steam-reforming catalyst and the natural gas olefins, hydrogen and paraffins. The amount of olefins is
steam-reforming catalyst. The process of gaseous and about lo-30%. Additionally, other components in small
liquid hydrocarbon steam reforming are basically same. quantities are present, for example, carbon oxides, acety-
The main difference between them is the catalysts charged lene and certain dienes. There are other impurities too,
in the reformer. such as hydrogen sulphide, organic sulphides and nitro-
High market prices of naphtha increase the cost of gen. Therefore hydro-saturation or separation of olefins
hydrogen production. The refinery gases are a low-cost is required. The typical refinery off gases are shown in
raw material. But they contain olefins which are unsuit- Table 6.
able for steam reforming. If used directly as the feedstock, In order to optimize the economics, it is necessary
the olefins in the gases would cause severe coke depo- to use different kinds of feedstocks or their mixtures
sition. There is a technological process which has been alternately, which complicates the aspects of process con-
developed in China. It is refinery off gas autohy- trolling and the choice of reforming catalyst. This is par-
drogenation. The catalyst used for autohydrogenation ticularly popular in refineries, where different
possesses high activity at low temperature. The gas passes hydrocarbons with a low price are used for hydrogen
once through and does not recycle. Though the hydro- production, such as the several hydrogen plants which
genation reaction is considerably exothermic, due to the were designed on the basis of using different hydro-
lower inlet temperature of the catalyst bed, the outlet carbons as feedstocks as shown in Tables 14.
temperature can be maintained within certain limits to Whatever feedstock is used, it is necessary to remove
keep coking under control. The olefins in the reactor organic sulphur and chlorine before use. The sulphur
outlet are decreased to about 1%. If the amount of olefins content must be reduced by hydrodesulphurization to less
in refinery off gas is too high, the refinery off gas should
be pretreated with the absorb-column charged diesel or
gasolene to decrease the olefins to about 10%. Then
Table 5. Naphtha feedstock used for steam reforming
refinery off gas is fed into the hydrogenation reactor.
There are two small plants for hydrogen production High High
using methanol as the feedstock in China. The reactor of Light Typical FBP aromatics
steam reforming of methanol is the tube-type reactor.
The double-function catalyst is charged in the tubes and IBP’C 30 35 45 45
the heat conductive oil passes through the shell side. FBP ‘C < 100 170 210 170
In the reforming process, methanol decomposition is an Aromatics (%) < 5 7 11-15 20
endothermic reaction and CO shift is an exothermic reac- Unsaturates (%) < 1 <I <I <I
tion, which can save energy. The insufficient heat is sup- AMW <80 100 110-125 115
Specific gravity <0.67 0.71 0.75 -0.76 0.75
plied by the heat conductive oil. Methanol decomposition
C/H 5-5.1 5.6 5.8 - 6.2 5.8
and shift reaction take place in one reactor. The mech-
anism of the reaction is as follows:

CH,OH+CO+2H>-Q
Table 6. Refinery gases used for steam reforming
CO+ H,0-+C02+HZ+Q.
Catalytic,
The reforming gas passes through the washing tower Coke, Coke. Hydrocraking, dry gas
rich gas dry gas dry gas (average)
and is then sent to the PSA to obtain hydrogen with a
purity of 99.99%.
H, 9.39 16.45 62.56 20.3
C: 41.83 56.85 28.1 25.5
C; 18.17 15.16 0.99 15.2
G 3.41 4.37 16.1
FEEDSTOCK CT: 9.51 2.00 3.x7 1.5
C; 4.4 1.66 3.5
Hydrocarbons ranging from natural gas to heavy c: 4.68 0.14 4.48 0.8
naphthas with FBP 210-C and containing 20% aromatics G 2.9 0.08 0.6
CY 2.06 0.25
can be used as feedstock for continuous steam-reforming
processes. The choice of feedstock is largely a function C, 0.7 0.08
co + co, 1.5 5.6
of availability and economics. 0.81 < 200 ppm 0.5
H,S 30 mm
In this article the naphthas, in general, are various N, 0.64 I.E.8 10.4
liquid hydrocarbons above C5 free from olefins. With the C/H 1.79 1.85
growth in carbon number, the tendency to form carbon
318 HA0 SHU-REN

than 0.5 ppm, preferably less than 0.2 ppm. The chlorine
content should be reduced to less than 0.5ppm by
dechlorination.
The resource of natural gas is relatively small in China,
yet most of it is used for the production of chemical
fertilizer which is urgently needed for Chinese agriculture.
Therefore, the feedstock for hydrocarbon steam-reform-
ing to produce hydrogen is mainly naphtha, LPG and LPG
refinery off gas in China.
aI
2- F
CATALYST Natural ti
gas I- G
The operation conditions of hydrocarbon steam-
reforming processes are quite severe. It is a complex prob- Section in Upper Lower Upper Lower Upper Lower
lem to choose a good and suitable catalyst. Because not the bed
only the property of the feedstocks but also other impor- Catalyst 2409 Z405G 2402 2405 Z412WZ413W
tant factors such as the operating condition and furnace
design feature should be considered. Fig. 1. Selection of catalyst according to the feed.
To reform heavy feedstock, the catalyst with high
resistance to carbon deposition is particularly required.
If the steam to carbon ratio is increased, the carbon Z402/2405 and Z409/Z405G developed by the Research
deposition can be decreased, but this is not economical. Institute of Qilu Petrochemical Co. SINOPEC, can par-
Steam reforming of hydrocarbons is a complex system ticularly reform the hydrocarbons from methane to naph-
including the breaking of C-C and C-H bonds, the for- tha with FBP less than 210°C.
ming of C-O bonds, the hydrogenation of CO and olefins, Z301/2302 are anti-olefin steam-reforming catalysts.
the shift CO with H,O, etc. Therefore the catalyst should They are used for reforming refinery gas containing about
possess a good comprehensive performance to fit com- 10% olefins and have been used in No. 1 Chemical Fer-
plicated reaction systems. The tests show that hydro- tilizer Factory of Qilu Petrochemical Co.
carbon steam-reforming catalysts should possess the Commercial applications have shown that the catalysts
functions of both metal catalysts and acid-base catalysts. stated above have good comprehensive performances
In the actual commercial application, the catalyst which are high activity, carbon deposition resistivity, low
should be selected according to such factors as the process temperature reducibility, as well as high strength and
conditions, reformer type and the composition of the stability. They can be used in both top-fired and side-fired
feedstock. For specific process conditions, the rate of furnaces. Their physical chemical properties are listed in
carbon formation increases with the increase of carbon Tables 7 and 8. Typical operation conditions are given in
number. So when the process conditions, such as space Table 9.
velocity, S/C ratio and temperature are determined, the QMH-01 is a double-function catalyst developed by
reforming catalysts which have good activity and high the Research Institute of Qilu Petrochemical Co. SINO-
resistance to carbon deposition are selected mainly based PEC. It is used for methanol steam reforming. QMH-01
on the composition of the hydrocarbon, as shown in Fig. is characterized by a very high activity and selectivity in
1. the temperature range 200- 3OO’C, H,O/C range 1 - 2.0.
After more than 10 years of development, catalyst ser-
ies have been developed in China. They are suitable for REMARK
the reforming of natural gas, refinery off gas, LPG and With the development of the refining and petro-
naphtha. The catalyst series of Z301/2302, Z412/2413, chemical industry, hydrogen production has increased

Table 7. Physical properties of 2402, 2409,2405,Z40SG, 2412 and 2413

Radical crushing
O.D. x H x I.D. strength
Name (min) Bulk density (kg/l) (N/grain) Color

2402 @l6x6xQ6-7 0.95 - 1.20 > 250 Gray

2409 @16X6X@6 0.9.5- 1.20 z 270 Yellowish brown
2405 @16x 16x@6 0.95- 1.05 ,450 Light gray
Z405G @16x 16x6 0.95- 1.1 > 600 Light gray
2412 @ 16 x 9, wheel-shaped l.O- 1.15 > 400 Gray
2413 @I 6 x 16, wheel-shaped l.O- 1.15 > 700 Gray
 HYDROCARBON STEAM-REFORMING PROCESS 319

Table 8. Chemical composition of 2402, 2409, 2405, Z405G, 24 I2 and 2413

Main component, wt%

Name NiO W Promoter Support
2402 19-23 5-6 Complex mixture
2409 20-24 6-7 Rare earth Complex mixture
2405 lo- 12 CA,
Z405G lo- 12 CA\
2412 11-14 Rare earth r-Al,Oz
2413 1 I - 14 Rare earth r-Al203

CA. calcium aluminate.

Table 9. Typical operation conditions

Bed temperature Inlet pressure LHSV FBP of the feed

Name ( ‘Cl (Pa) (kg/h 1. cat) H,O,‘C ( C)
Z402/2405 450 - 900 3.0 x IOh 0.65- 1.29 3.5 - 6.c~ <I85
Z409iZ405G 450 - 900 3.0 x loo 0.65’- 1.29 3.5-6.0 <210
Z412iZ413 450- 1000 3.0 x IO6 V,<2000h-’ 3.0- 6.0

quickly in China. Hydrocarbon steam reforming has been steam reforming to produce widespread hydrogen. The
the main method for the production of hydrogen in application showed that the performance of the hydro-
China. The technological process has reached higher carbon steam-reforming catalyst series has come up to
levels. Various hydrocarbon feedstock can be applied for the advanced world standards.