A hydrocarbon steam primary reforming catalyst and its preparation method

Abstract

The present invention discloses a hydrocarbon steam primary reforming catalyst, which comprises a carrier, active components and promoters. The carrier accounts for 70%-85% of the total mass of the catalyst. The carrier is an alumina carrier. The active components contain metals Ni and Co, and the promoters contain metals Zn, Mo and Cs. The molar ratio of Ni, Co, Zn, Mo and Cs is 10:0.1-1:0.5-2:0.1-2:0.05-1. This catalyst can tolerate high sulfur content in the methane feed gas, weaken the catalyst poisoning problem caused by high sulfur content in the feed gas. In addition, the catalyst can exhibit high activity under catalytic conditions of 850 °C. At the same time, the catalyst has high mechanical strength and is suitable for popularization and application.

Description

Technical Field

[0001] The present invention relates to the technical field of natural gas conversion catalysts, and particularly relates to a steam reforming catalyst for hydrocarbons in the first stage and a preparation method thereof. Background Art

[0002] The hydrocarbon steam reforming method for hydrogen production is currently the most widely used hydrogen production method in the world. It was invented and utilized by Badische Anilin- und Soda-Fabrik, and was first industrialized by Imperial Chemical Industries (ICI) of the United Kingdom. The working pressure of this hydrogen production method is 2.0 - 4.0 MPa. In recent years, due to the continuous improvement of the reforming hydrogen production furnace type and the continuous update of the reformed gas purification process, the hydrocarbon steam reforming process for hydrogen production has become the most economical and reliable way to produce hydrogen currently.

[0003] Patent CN201310257310.7 discloses a low-temperature hydrocarbon steam reforming catalyst, a preparation method and an application thereof. The catalyst is a nickel-magnesium-aluminum system catalyst, with metallic Ni as the active component, MgO and Al2O3 as the carriers, and Al2O3 as the promoter. In this catalyst, calculated by the weight of the oxides, it contains 35 - 45 w% of NiO, and the rest are MgO and Al2O3. Among them, the molar ratio of Mg / Al is 1.4 - 9.0. During the precipitation process of preparing this catalyst, ultrasonic waves are used for the reaction. It is applicable to the low-temperature reforming of hydrocarbon raw material steam with a dry point below 210°C, has good low-temperature reforming activity, high strength, strong adaptability to raw materials and process conditions, and the conversion rate of hydrocarbons above C2 > 99%. Using this catalyst enhances the adaptability to raw materials, reduces the severity of the reforming furnace operation, is beneficial to energy conservation and consumption reduction of the device, can reduce production costs, and can extend the service life of the reforming catalyst. However, for a hydrocarbon steam reforming system with a relatively high temperature, its catalytic activity is significantly reduced.

[0004] Patent CN201610742043.6 discloses a preparation method of a hydrocarbon steam reforming catalyst. The preparation method includes the following steps: (1) Mix magnesium salt and aluminum salt evenly, add urea or ammonium bicarbonate and then grind; then add nickel salt and cerium salt / lanthanum salt, continue to grind, and transfer to a crystallization kettle with a polytetrafluoroethylene lining for crystallization reaction. After the reaction is completed, a catalyst semi-finished product is obtained; (2) Add a shaping aid to the catalyst semi-finished product for granulation and shaping, drying, and calcination to obtain a catalyst finished product. In this patent, a catalyst semi-finished product with a hydrotalcite-like structure is prepared by the solid solution method. The catalyst for hydrocarbon steam reforming reaction prepared with the catalyst semi-finished product with a hydrotalcite-like structure as the precursor has good thermal stability, improves the catalyst stability, and extends the service life of the catalyst. The catalyst prepared by this method can withstand the hydrocarbon steam reforming reaction at a relatively high temperature. However, the catalyst shows poor performance in terms of tolerating the S content in the raw material gas, and it is necessary to further improve the tolerance of the catalyst to S in the raw material gas to avoid the problem of catalyst sulfur poisoning. Summary of the Invention

[0005] In view of the problems that the current hydrocarbon steam primary reforming catalyst has difficulty in withstanding high-temperature reaction conditions and is prone to sulfur poisoning due to the low sulfur content in the feed gas that the catalyst can tolerate, the present invention provides a hydrocarbon steam primary reforming catalyst and a preparation method thereof.

[0006] To solve the above technical problems, the present invention provides the following technical solutions:

[0007] A hydrocarbon steam primary reforming catalyst includes a carrier, active components, and promoters. The carrier accounts for 70%-85% of the total mass of the catalyst. The carrier is an alumina carrier. The active components contain metals Ni and Co, and the promoters contain metals Zn, Mo, and Cs. The molar ratio of Ni, Co, Zn, Mo, and Cs is 10∶0.1-1∶0.5-2∶0.1-2∶0.05-1.

[0008] Further, the alumina carrier is a carrier modified with metal Fe.

[0009] Further, the preparation method of the catalyst includes the following steps:

[0010] 1) Immerse the γ-Al2O3 carrier in an iron sulfate solution for impregnation, then dry and calcine it. Use a grinding instrument to grind the calcined γ-Al2O3 carrier into particles, and then put them into a high-pressure reaction kettle, add deionized water, treat for a period of time, and then dry in an oven to obtain a modified γ-Al2O3 carrier.

[0011] 2) Prepare a solution A by dissolving soluble salts containing Ni and Co, and prepare a solution B by dissolving soluble salts containing Zn, Mo, and Cs. Immerse the modified γ-Al2O3 carrier in an equal volume of solution B for impregnation, then carry out primary aging, drying, and then immerse it in an equal volume of solution A, followed by secondary aging, drying, and calcination to prepare the catalyst. Further, in step 1), the concentration of the iron sulfate solution is 100-200 g / L, and the impregnation time is 4-8 h.

[0012] Further, in step 1), after impregnation, it is dried at 120°C for 6 h, and the calcination conditions are 1000°C for 7 h, with a heating rate of 5°C / min.

[0013] Further, in step 1), the calcined γ-Al2O3 carrier is ground into 30-mesh particles. In the high-pressure reaction kettle, the volume of deionized water is 1.5-2 times that of the calcined γ-Al2O3 carrier, and the time in the high-pressure reaction kettle is 3-6 h.

[0014] Further, the soluble salts containing Ni, Co, Zn, Mo, and Cs in step 2) are nitrates.

[0015] Further, the initial aging time in step 2) is 3 h, the drying conditions for both times are drying at 120 °C for 4 - 6 h, the secondary aging time is 4 h, and it is calcined in a muffle furnace. The calcination conditions are 1200 °C in a nitrogen atmosphere for 6 - 8 h.

[0016] Further, the catalytic reaction conditions of the catalyst are: the inlet temperature of the conversion tube is 550 °C, the outlet temperature of the conversion tube is 850 °C, the operating pressure is from atmospheric pressure to 5.0 MPa, and the space velocity of the raw material gas during the reaction is ≤ 2300 h -1 。

[0017] Further, the catalyst can tolerate an S content in the raw material gas of ≤ 2.5 ppm.

[0018] The present invention has the following beneficial effects:

[0019] 1. A hydrocarbon steam primary reforming catalyst provided by the present invention. During the preparation process, the carrier of the catalyst is modified, which can enable the carrier to tolerate a high content of sulfur in the raw material gas, avoiding the phenomenon of catalyst sulfur poisoning when the sulfur content in the raw material gas is too high due to insufficient pre - desulfurization treatment of the raw material gas, thereby affecting the activity and service life of the catalyst. Most catalysts on the market can basically tolerate an S content in the raw material gas of ≤ 0.5 ppm, while through the modification of the carrier, the catalyst can tolerate an S content in the raw material gas of up to 2.5 ppm under relatively harsh environmental conditions and can maintain good activity.

[0020] 2. A hydrocarbon steam primary reforming catalyst provided by the present invention. In addition to Ni, Co is added to the active components of the catalyst, and Zn, Mo, and Cs are introduced as promoters. The introduced promoter components are beneficial to improving the high - temperature tolerance of the catalyst, so that the catalyst can still maintain a high activity under high - temperature conditions.

[0021] 3. A hydrocarbon steam primary reforming catalyst provided by the present invention. The preparation process of the catalyst is simple, the operation process is convenient, and it is suitable for popularization and application. Specific Embodiments

[0022] The following will clearly and completely describe the technical solutions of the present invention in conjunction with specific embodiments.

[0023] Example 1

[0024] Preparation of the catalyst:

[0025] 1) Immerse the γ-Al2O3 support in a ferric sulfate solution with a concentration of 150 g / L for impregnation. The impregnation is an excessive impregnation, that is, the volume of the ferric sulfate solution is greater than the volume of the γ-Al2O3 support. The impregnation time is 6 h, and then dry it in an oven at 120 °C for 6 h. Then transfer it to a muffle furnace for calcination. The calcination temperature is 1000 °C and the time is 7 h. The heating rate in the early stage of calcination is 5 °C / min. Grind the calcined γ-Al2O3 support into 300-mesh particles using a grinder, and then put it into a high-pressure reactor. Add deionized water with a volume 2 times that of the calcined γ-Al2O3 support, treat it for 5 h, and then dry it in an oven at 100 °C for 6 h to obtain a modified γ-Al2O3 support;

[0026] 2) According to the modified support accounting for 80% of the total mass of the catalyst, weigh nitrates containing Ni and Co to prepare solution A with a molar ratio of Ni to Co of 10:0.5, and weigh nitrates containing Zn, Mo, and Cs to prepare solution B with a molar ratio of Zn, Mo, and Cs of 1:1:0.5. The molar ratio of Ni to Zn in the nitrate containing Ni and the nitrate containing Zn is 10:1. The solvents for preparing solution A and solution B are deionized water. Immerse the modified γ-Al2O3 support in an equal volume of solution B, age it initially for 3 h and dry it in an oven at 120 °C for 5 h. Then place the dried sample in an equal volume of solution A for impregnation. After secondary aging for 4 h, dry it in an oven at 120 °C for 5 h. Place the dried sample in a muffle furnace for calcination. The calcination conditions are 1200 °C under a nitrogen atmosphere and calcination for 8 h to prepare the catalyst.

[0027] Example 2

[0028] Preparation of the catalyst:

[0029] 1) Immerse the γ-Al2O3 support in a ferric sulfate solution with a concentration of 100 g / L for impregnation. The impregnation is an excessive impregnation, that is, the volume of the ferric sulfate solution is greater than the volume of the γ-Al2O3 support. The impregnation time is 4 h, and then dry it in an oven at 120 °C for 6 h. Then transfer it to a muffle furnace for calcination. The calcination temperature is 1000 °C and the time is 7 h. The heating rate in the early stage of calcination is 5 °C / min. Grind the calcined γ-Al2O3 support into 300-mesh particles using a grinder, and then put it into a high-pressure reactor. Add deionized water with a volume 1.5 times that of the calcined γ-Al2O3 support, treat it for 6 h, and then dry it in an oven at 100 °C for 6 h to obtain a modified γ-Al2O3 support;

[0030] 2) According to the modified carrier accounting for 70% of the total mass of the catalyst, weigh the nitrates containing Ni and Co with a molar ratio of Ni to Co of 10:0.1 to prepare solution A, and weigh the nitrates containing Zn, Mo and Cs with a molar ratio of Zn:Mo:Cs of 0.5:0.1:1 to prepare solution B. The molar ratio of Ni to Zn in the nitrate containing Ni and the nitrate containing Zn is 10:0.5. The solvents for preparing solution A and solution B are deionized water. Immerse the modified γ-Al2O3 carrier in an equal volume of solution B, age for 3 h for the first time and dry in an oven at 120 °C for 4 h. Then place the dried sample in an equal volume of solution A for impregnation. After aging for 4 h for the second time and drying in an oven at 120 °C for 5 h, place the dried sample in a muffle furnace for calcination. The calcination conditions are 1200 °C in a nitrogen atmosphere for 8 h to prepare the catalyst.

[0031] Example 3

[0032] Preparation of the catalyst:

[0033] 1) Immerse the γ-Al2O3 carrier in a 200 g / L ferric sulfate solution for impregnation. The impregnation is an excessive impregnation, that is, the volume of the ferric sulfate solution is greater than the volume of the γ-Al2O3 carrier. The impregnation time is 8 h, then dry in an oven at 120 °C for 6 h, and then transfer to a muffle furnace for calcination. The calcination temperature is 1000 °C and the time is 7 h. The heating rate in the early stage of calcination is 5 °C / min. Grind the calcined γ-Al2O3 carrier into 300-mesh particles using a grinder, and then put it into a high-pressure reactor, add deionized water with a volume 2 times that of the calcined γ-Al2O3 carrier, treat for 3 h, and then dry in an oven at 100 °C for 6 h to obtain the modified γ-Al2O3 carrier;

[0034] 2) According to the modified carrier accounting for 85% of the total mass of the catalyst, weigh the nitrates containing Ni and Co with a molar ratio of Ni to Co of 10:1 to prepare solution A, and weigh the nitrates containing Zn, Mo and Cs with a molar ratio of Zn:Mo:Cs of 2:2:0.05 to prepare solution B. The molar ratio of Ni to Zn in the nitrate containing Ni and the nitrate containing Zn is 10:2. The solvents for preparing solution A and solution B are deionized water. Immerse the modified γ-Al2O3 carrier in an equal volume of solution B, age for 3 h for the first time and dry in an oven at 120 °C for 6 h. Then place the dried sample in an equal volume of solution A for impregnation. After aging for 4 h for the second time and drying in an oven at 120 °C for 4 h, place the dried sample in a muffle furnace for calcination. The calcination conditions are 1200 °C in a nitrogen atmosphere for 6 h to prepare the catalyst.

[0035] Example 4

[0036] Preparation of the catalyst:

[0037] 1) Immerse the γ-Al2O3 support in a ferric sulfate solution with a concentration of 150 g / L for impregnation. The impregnation is an excessive impregnation, that is, the volume of the ferric sulfate solution is greater than the volume of the γ-Al2O3 support. The impregnation time is 4 h, then dry it in an oven at 120 °C for 6 h, and then transfer it to a muffle furnace for roasting. The roasting temperature is 1000 °C and the time is 7 h. The heating rate in the early stage of roasting is 5 °C / min. Grind the roasted γ-Al2O3 support into 300-mesh particles using a grinder, and then put it into a high-pressure reactor. Add deionized water with a volume twice that of the roasted γ-Al2O3 support, treat it for 5 h, and then dry it in an oven at 100 °C for 6 h to obtain the modified γ-Al2O3 support;

[0038] 2) According to the modified support accounting for 75% of the total mass of the catalyst, weigh nitrates containing Ni and Co to prepare solution A with a molar ratio of Ni to Co of 10:0.8, and weigh nitrates containing Zn, Mo, and Cs to prepare solution B with a molar ratio of Zn:Mo:Cs of 1.5:0.5:0.1. The molar ratio of Ni to Zn in the nitrate containing Ni and the nitrate containing Zn is 10:1.5. The solvents for preparing solution A and solution B are deionized water. Immerse the modified γ-Al2O3 support in an equal-volume solution B for impregnation, carry out primary aging for 3 h and dry it in an oven at 120 °C for 5 h. Then place the dried sample in an equal-volume solution A for impregnation. After secondary aging for 4 h, dry it in an oven at 120 °C for 5 h. Place the dried sample in a muffle furnace for roasting. The roasting conditions are at 1200 °C in a nitrogen atmosphere for 8 h to prepare the catalyst.

[0039] Example 5

[0040] Preparation of the catalyst:

[0041] 1) Immerse the γ-Al2O3 support in a ferric sulfate solution with a concentration of 120 g / L for impregnation. The impregnation is an excessive impregnation, that is, the volume of the ferric sulfate solution is greater than the volume of the γ-Al2O3 support. The impregnation time is 4 h, then dry it in an oven at 120 °C for 6 h, and then transfer it to a muffle furnace for roasting. The roasting temperature is 1000 °C and the time is 7 h. The heating rate in the early stage of roasting is 5 °C / min. Grind the roasted γ-Al2O3 support into 300-mesh particles using a grinder, and then put it into a high-pressure reactor. Add deionized water with a volume twice that of the roasted γ-Al2O3 support, treat it for 5 h, and then dry it in an oven at 100 °C for 6 h to obtain the modified γ-Al2O3 support;

[0042] 2) According to the modified carrier accounting for 70% of the total mass of the catalyst, weigh the nitrates containing Ni and Co according to the molar ratio of Ni to Co being 10:0.3 to prepare solution A, and weigh the nitrates containing Zn, Mo and Cs according to the molar ratio of Zn:Mo:Cs being 0.6:1.8:0.08 to prepare solution B. The molar ratio of Ni to Zn in the nitrate containing Ni and the nitrate containing Zn is 10:0.6. The solvent for preparing solution A and solution B is deionized water. Immerse the modified γ-Al2O3 carrier in an equal volume of solution B, age for 3 h for the first time and dry in an oven at 120 °C for 5 h. Then place the dried sample in an equal volume of solution A for impregnation, age for 4 h for the second time and dry in an oven at 120 °C for 5 h. Place the dried sample in a muffle furnace for roasting. The roasting conditions are 1200 °C under a nitrogen atmosphere for 8 h to prepare the catalyst.

[0043] Comparative Example 1

[0044] Preparation of the catalyst:

[0045] Change the concentration of the iron sulfate solution in step 1) to 50 g / L, and other conditions are the same as in Example 1.

[0046] Comparative Example 2

[0047] Preparation of the catalyst:

[0048] Change the iron sulfate solution in step 1) to ferric chloride hexahydrate, and other conditions are the same as in Example 1.

[0049] Comparative Example 3

[0050] Preparation of the catalyst:

[0051] Delete the operation in the high-pressure reactor in step 1), and other conditions are the same as in Example 1.

[0052] Comparative Example 4

[0053] Preparation of the catalyst: The deionized water added in the operation in the high-pressure reactor in step 1) is 4 times the volume of the roasted γ-Al2O3 carrier, and other conditions are the same as in Example 1.

[0054] Comparative Example 5

[0055] Preparation of the catalyst:

[0056] Shorten the treatment time of the operation in the high-pressure reactor in step 1) to 1 h, and other conditions are the same as in Example 1.

[0057] Comparative Example 6

[0058] Preparation of the catalyst:

[0059] The molar ratio of Ni to Co in step 2) was 10:3, and other conditions were the same as in Example 1.

[0060] Comparative Example 7

[0061] Preparation of the catalyst:

[0062] The molar ratio of Ni to Co in step 2) was 10:0.01, and other conditions were the same as in Example 1.

[0063] Comparative Example 8

[0064] Preparation of the catalyst:

[0065] The molar ratio of Zn, Mo and Cs in step 2) was 0.1:5:3, and the molar ratio of Ni to Zn was 10:0.1. Other conditions were the same as in Example 1.

[0066] Comparative Example 9

[0067] Preparation of the catalyst:

[0068] The primary aging time in step 2) was 1 h, and other conditions were the same as in Example 1.

[0069] Comparative Example 10

[0070] Preparation of the catalyst:

[0071] The secondary aging time in step 2) was 8 h, and other conditions were the same as in Example 1.

[0072] Comparative Example 11

[0073] Preparation of the catalyst:

[0074] The modified γ-Al2O3 support in step 2) was first impregnated in Solution A, dried after primary aging for 4 h, then impregnated in Solution B, and the secondary aging time was 8 h. Other conditions were the same as in Example 1.

[0075] Comparative Example 12

[0076] Preparation of the catalyst:

[0077] The modified γ-Al2O3 support in step 2) was 60% of the total mass of the catalyst, and other conditions were the same as in Example 1.

[0078] Comparative Example 13

[0079] Preparation of the catalyst:

[0080] The modified γ-Al2O3 support in step 2) was 95% of the total mass of the catalyst, and other conditions were the same as in Example 1.

[0081] Method for measuring catalyst activity

[0082] The catalytic conditions are as follows:

[0083] Before use, the catalyst is reduced under the following conditions: H2O / C (mol) = 6, reduction pressure 0.15 Mpa, reduction space velocity 10000 h -1 , reduction temperature 650 °C, reduction time 1.5 h.

[0084] Reaction conditions: In the conversion tube, the reduced catalyst is under a reaction pressure of 0.2 Mpa, feed gas space velocity 20000 h -1 , H2O / C (mol) = 4, H2O / H2 (mol) = 10, inlet temperature of the conversion tube is 550 °C, outlet temperature of the conversion tube is 850 °C. After the reaction is completed, the methane content at the outlet and inlet of the conversion tube is detected, and then the methane conversion rate is determined.

[0085] The catalysts prepared in Examples 1 - 5 and Comparative Examples 1 - 5 above are used to detect the methane conversion rate after reduction, where the S content in the feed gas is 2.5 ppm. The specific detection results are shown in Table 1 below.

[0086] Table 1

[0087]

[0088] The catalysts prepared in Example 1 and Comparative Examples 1 - 5 above are used to detect the methane conversion rate after reduction, where the S content in the feed gas is 0.5 ppm. The specific detection results are shown in Table 2 below.

[0089] Table 2

[0090]

[0091] According to the comparison of the detection results in Table 1 and Table 2 above, from the results of Comparative Examples 1 - 2, it can be seen that when the S content in the feed gas is 2.5 ppm, the iron modification treatment of the carrier can significantly affect the activity of the catalyst, resulting in a decrease in catalyst activity. While in Table 2, when the S content in the feed gas is low, although the activity is lower than that in Example 1, the influence on the activity is not significant compared with the high S content in the feed gas.

[0092] From the results of Comparative Examples 3 - 5, it can be seen that the treatment of the carrier in the autoclave has a reduced influence on the low S content and high S content in the feed gas compared with the iron modification treatment, but the fact that the catalyst is not treated in the autoclave will indeed cause a decrease in activity when the S content in the feed gas is high; in addition, when treating in the autoclave, the content of deionized water added during the treatment process and the treatment time will both affect the activity of the catalyst.

[0093] The catalysts prepared in the above Example 1 and Comparative Examples 6-11 were used to detect the methane conversion rate after reduction. The S content in the raw material gas was 2.5 ppm, and the specific detection results are shown in Table 3 below.

[0094] Table 3

[0095]

[0096] From the detection results in Table 3 above, it can be seen that in Comparative Examples 6-8, when the content of the active component or the promoter was changed, it was found that the final activity of the catalyst also decreased significantly; in Comparative Examples 9-10, during the process of loading the active component and the promoter onto the carrier, when the aging time was changed, the activity also decreased, indicating that the aging time cannot be changed casually. Changing the aging time will indirectly affect the loading amount of the active component and the promoter, and ultimately affect the activity of the catalyst.

[0097] In Comparative Example 11, the carrier was first impregnated in Solution A containing the active component, and then impregnated in Solution B containing the promoter. It was found that the activity of the catalyst decreased rapidly. The reason for this phenomenon may be that the subsequent impregnation of Solution B containing the promoter on the carrier may affect the performance of the active component, thereby directly leading to a significant decrease in the catalyst activity.

[0098] In Comparative Example 13, the proportion of the modified carrier in the total mass of the catalyst was changed during the catalyst preparation process. When the proportion of the modified carrier reached 95, the activity of the catalyst decreased.

[0099] The catalysts prepared in Example 1 and Comparative Example 12 were placed in an intelligent particle strength testing machine, and the test samples were gradually stressed until they were broken; this step was repeated 15 times until the test was completed. It was found that the average strength (N / cm) of the catalyst prepared in Example 1 was 430, while the average strength (N / cm) of the catalyst prepared in Comparative Example 12 was 240. Therefore, the catalyst prepared in Example 1 can withstand higher mechanical strength, and reducing the proportion of the modified carrier in the total mass of the catalyst will affect the mechanical strength of the catalyst, thereby affecting the service life of the catalyst and making it unable to withstand the catalytic conditions of high mechanical strength.

Claims

1. A hydrocarbon steam primary reforming catalyst, characterized in that, The catalyst comprises a support, an active component and a promoter. The support accounts for 70%-85% of the total mass of the catalyst. The support is an alumina support. The active component contains metals Ni and Co, and the promoter contains metals Zn, Mo and Cs. The molar ratio of Ni, Co, Zn, Mo and Cs is 10: 0.1-1: 0.5-2: 0.1-2: 0.05-1; The alumina support is a support modified with metal Fe; The preparation method of the catalyst comprises the following steps: 1) Immerse the γ-Al2O3 support in a ferric sulfate solution for impregnation. After drying and calcination, grind the calcined γ-Al2O3 support into particles with a grinder, then put them into a high-pressure reactor, add deionized water, treat for a period of time, and dry in an oven to obtain a modified γ-Al2O3 support; 2) Prepare a solution A by dissolving soluble salts containing Ni and Co, and prepare a solution B by dissolving soluble salts containing Zn, Mo and Cs. Immerse the modified γ-Al2O3 support in an equal volume of solution B for impregnation. After primary aging and drying, immerse it in an equal volume of solution A, and then perform secondary aging, drying and calcination to prepare the catalyst.

2. The hydrocarbon steam primary reforming catalyst according to claim 1, wherein In step 1), the concentration of the ferric sulfate solution is 100-200 g / L, and the impregnation time is 4-8 h.

3. The hydrocarbon steam primary reforming catalyst according to claim 1, characterized in that, In step 1), after impregnation, dry at 120 °C for 6 h. The calcination conditions are 1000 °C for 7 h, and the heating rate is 5 °C / min.

4. The hydrocarbon steam primary reforming catalyst according to claim 1, wherein In step 1), grind the calcined γ-Al2O3 support into 300-mesh particles. In the high-pressure reactor, the volume of deionized water is 1.5-2 times that of the calcined γ-Al2O3 support, and the time in the high-pressure reactor is 3-6 h.

5. The hydrocarbon steam primary reforming catalyst according to claim 1, characterized in that, In step 2), the soluble salts containing Ni, Co, Zn, Mo and Cs are nitrates or sulfates.

6. The hydrocarbon steam primary reforming catalyst according to claim 1, characterized in that, In step 2), the primary aging time is 3 h. The drying conditions for both times are drying at 120 °C for 4-6 h. The secondary aging time is 4 h. Place it in a muffle furnace for calcination. The calcination conditions are 1200 °C under a nitrogen atmosphere and calcination for 6-8 h.

7. The hydrocarbon steam primary reforming catalyst according to claim 1, characterized in that, The catalytic reaction conditions of the catalyst are as follows: the inlet temperature of the conversion tube is 350 - 650 °C, the outlet temperature of the conversion tube is 600 - 950 °C, the operating pressure is atmospheric pressure - 5.0 MPa, and the space velocity of the raw material gas during the reaction is ≤ 2300 h -1 .

8. The hydrocarbon steam primary reforming catalyst according to claim 7, wherein The S content in the raw material gas is ≤2.5 ppm.

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