A process for the preparation of high density jet fuel components from furfuryl alcohol and isoprene
Patent Information
- Application Number
- CN202311513003.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2023-11-14
- Publication Date
- 2026-10-30
- Estimated Expiration
- 2043-11-14
AI Technical Summary
[0018]1、本发明的原料糠醇可由农林废弃生物质中半纤维素组分经水解-脱水反应得到，异戊二烯可经农林废弃生物质经发酵而来，均属于可再生资源。
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of biomass liquid fuel technology, specifically relating to a method for preparing high-density aviation fuel components from furfuryl alcohol and isoprene. Background Technology
[0002] High-density fuels refer to artificially synthesized fuels with a density greater than 0.85 g / cm³. 3 High-density fuels are liquid hydrocarbons with a polycyclic structure. Compared to traditional fuels, they have higher density and calorific value, and are widely used in aerospace vehicles such as missiles, rockets, near-space vehicles, spacecraft, and satellites, enabling them to have greater payload capacity, longer flight range, higher flight speed, and greater maneuverability. Currently, high-density fuels used worldwide are mainly produced from petroleum-based compounds and their derivatives through the Diels-Alder reaction, followed by isomerization and hydrogenation reactions. With the increasing depletion of fossil resources and the growing environmental problems (dust, acid rain, greenhouse effect, etc.) generated during the preparation and utilization of high-density fuels, reducing dependence on fossil fuels and utilizing abundant, economical, green, renewable, and environmentally friendly lignocellulosic biomass resources to replace existing fossil resources for the production of high-density fuels is of great significance. Summary of the Invention
[0003] To address the shortcomings of existing technologies, the present invention aims to provide a method for preparing high-density aviation fuel components from furfuryl alcohol and isoprene, thereby solving the problems in the prior art.
[0004] The objective of this invention can be achieved through the following technical solutions:
[0005] A method for preparing high-density aviation fuel components from furfuryl alcohol and isoprene includes the following steps:
[0006] S1, furfuryl alcohol, isoprene, Lewis acid FeZn-F68, n-hexane and deionized water are added to the reactor, and the mixture is stirred under a hydrogen or nitrogen atmosphere to carry out a cascade reaction of directional controllable aqueous phase reforming and Diels-Alder to obtain a polycyclic alkane precursor.
[0007] S2, after purifying the polycyclic alkane precursor, it is added to the reaction vessel, along with a hydrogenation catalyst and a solid catalyst, to carry out a hydrogenation deoxygenation reaction to obtain polycyclic alkanes.
[0008] Furthermore, the molar ratio of furfuryl alcohol to isoprene is 1:1-3.
[0009] Furthermore, in S1, the reaction temperature in the reactor is 110-160℃, and the reaction time is 6-36h.
[0010] Furthermore, in S1, when the reaction atmosphere is nitrogen, the nitrogen pressure is 3-7 MPa; when the reaction atmosphere is hydrogen, the hydrogen pressure is 2-8 MPa.
[0011] Furthermore, in S1, the stirring rate is 300 rpm / min.
[0012] Furthermore, in S2, the mass ratio of the polycyclic alkane precursor, the hydrogenation catalyst, and the solid catalyst is 10:1-5:2-10.
[0013] Furthermore, the hydrogenation catalyst is one of Ru / C, Pd / C, or Pt / C.
[0014] Furthermore, the solid acid catalyst is one of HZSM-5, HY, MCM-41 and Hβ.
[0015] Furthermore, the reaction temperature of the hydrogenation deoxygenation reaction is 120–170°C, the reaction time is 5–10 h, and the hydrogen pressure is 3–6 MPa.
[0016] A high-density biomass fuel comprising aviation fuel components prepared using the method described above.
[0017] The beneficial effects of this invention are:
[0018] 1. The raw material furfuryl alcohol of the present invention can be obtained from the hemicellulose component of agricultural and forestry waste biomass through hydrolysis-dehydration reaction, and isoprene can be obtained from agricultural and forestry waste biomass through fermentation. Both are renewable resources.
[0019] 2. The target product of this invention is made from C 10 Or C 10 With C 15 Polycyclic alkane fuels composed of mixtures have a high density and are an ideal type of high-density fuel composition.
[0020] 3. This invention realizes the conversion of renewable lignocellulosic biomass resources into high-density fuels, which effectively promotes the high-value utilization of low-value agricultural and forestry waste and the reduction of carbon emissions. Attached Figure Description
[0021] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, for those skilled in the art, other drawings can be obtained based on these drawings without creative effort.
[0022] Figure 1 This is a flowchart of the process for synthesizing high-density aviation fuel components using furfuryl alcohol and isoprene according to the present invention. Detailed Implementation
[0023] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0024] It should be noted that furfuryl alcohol, a raw material in this invention, can be obtained from the hemicellulose component of agricultural and forestry waste biomass through a hydrolysis-dehydration reaction, and isoprene can be obtained from agricultural and forestry waste biomass through fermentation; both are renewable resources. The specific process for preparing high-density aviation fuel components from furfuryl alcohol and isoprene is as follows: Figure 1 As shown, the following examples will be used to illustrate the concept.
[0025] Example 1
[0026] The steps for preparing polycyclic alkane precursors using furfuryl alcohol and isoprene as raw materials are as follows:
[0027] 20 mmol furfuryl alcohol, 50 mmol isoprene, 0.1 g Lewis acid FeZn-F68 (prepared by precipitation), 20 ml n-hexane, and 20 ml deionized water were added to a high-pressure reactor equipped with a mechanical stirrer. The stirring rate was 300 rpm / min, and the reaction was carried out at 110 °C for 24 h under a hydrogen atmosphere with a hydrogen pressure of 5 MPa. After the reaction was completed, the yield of the polycyclic alkane precursor was 65.6%, and the conversion rate of furfuryl alcohol was 97.6%.
[0028] The synthesis method of FeZn-F68 is as follows: A mixture of 40 mL deionized water and 0.4 mol ZnCl2 is slowly added to 80 mL of 0.1 mol / L K4[Fe(CN)6] solution. Then, under stirring, a mixture of 60 g of poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (i.e., F68) with a molecular weight of 8400 and 20 mL of deionized water is added, and the mixture is stirred continuously for 12 h. After washing and filtering with deionized water, FeZn-F68 is obtained by drying at 160 °C for 18 h.
[0029] Example 2
[0030] The difference between Example 2 and Example 1 is as follows:
[0031] The reaction temperature was 120℃, and the yield of the collected polycyclic alkane precursor was 65.5%, with a furfuryl alcohol conversion rate of 98.2%.
[0032] Example 3
[0033] The difference between Example 3 and Example 1 is as follows:
[0034] The reaction temperature was 130℃, and the yield of the collected polycyclic alkane precursor was 67.3%, with a furfuryl alcohol conversion rate of 100%.
[0035] Example 4
[0036] The difference between Example 4 and Example 1 is as follows:
[0037] The reaction temperature was 140℃, and the yield of the collected polycyclic alkane precursor was 73.9%, with a furfuryl alcohol conversion rate of 100%.
[0038] Example 5
[0039] The difference between Example 5 and Example 1 is as follows:
[0040] The reaction temperature was 150℃, and the yield of the collected polycyclic alkane precursor was 80.6%, with a furfuryl alcohol conversion rate of 100%.
[0041] Example 6
[0042] The difference between Example 6 and Example 1 is:
[0043] The reaction temperature was 140℃, with 20 mmol of furfuryl alcohol and 20 mmol of isoprene. The yield of the collected polycyclic alkane precursor was 72.5%, and the conversion rate of furfuryl alcohol was 95.3%.
[0044] Example 7
[0045] The difference between Example 7 and Example 1 is as follows:
[0046] The reaction temperature was 140℃, the amount of furfuryl alcohol was 20 mmol, and the amount of isoprene was 30 mmol. The yield of the collected polycyclic alkane precursor was 69.2%, and the conversion rate of furfuryl alcohol was 97.5%.
[0047] Example 8
[0048] The difference between Example 8 and Example 1 is:
[0049] The reaction temperature was 140℃, the amount of furfuryl alcohol was 20 mmol, and the amount of isoprene was 40 mmol. The yield of the collected polycyclic alkane precursor was 69.3%, and the conversion rate of furfuryl alcohol was 98.3%.
[0050] Example 9
[0051] The difference between Example 9 and Example 1 is as follows:
[0052] The reaction temperature was 140℃, the amount of furfuryl alcohol was 20 mmol, and the amount of isoprene was 60 mmol. The yield of the collected polycyclic alkane precursor was 73.4%, and the conversion rate of furfuryl alcohol was 100%.
[0053] Example 10
[0054] The difference between Example 10 and Example 1 is as follows:
[0055] The reaction temperature was 140℃ and the reaction time was 6h. The yield of the collected polycyclic alkane precursor was 67.4%, and the conversion rate of furfuryl alcohol was 100%.
[0056] Example 11
[0057] The difference between Example 11 and Example 1 is as follows:
[0058] The reaction temperature was 140℃ and the reaction time was 12h. The yield of the collected polycyclic alkane precursor was 52.1%, and the conversion rate of furfuryl alcohol was 100%.
[0059] Example 12
[0060] The difference between Example 12 and Example 1 is as follows:
[0061] The reaction temperature was 140℃ and the reaction time was 36h. The yield of the collected polycyclic alkane precursor was 71.0%, and the conversion rate of furfuryl alcohol was 100%.
[0062] Example 13
[0063] The difference between Example 13 and Example 1 is:
[0064] The reaction temperature was 150℃, and the nitrogen atmosphere was 3 MPa. The yield of the collected polycyclic alkane precursor was 70.2%, and the conversion rate of furfuryl alcohol was 90.6%.
[0065] Example 14
[0066] The difference between Example 14 and Example 1 is:
[0067] The reaction temperature was 150℃, and the nitrogen atmosphere was 7 MPa. The yield of the collected polycyclic alkane precursor was 72.4%, and the conversion rate of furfuryl alcohol was 93.7%.
[0068] Example 15
[0069] The difference between Example 15 and Example 1 is that:
[0070] The reaction temperature was 150℃, the nitrogen atmosphere was 5 MPa, 10 ml of n-hexane and 30 ml of deionized water were used, and the yield of the collected polycyclic alkane precursor was 60.6%, and the conversion rate of furfuryl alcohol was 80.3%.
[0071] Example 16
[0072] The difference between Example 16 and Example 1 is that:
[0073] The reaction temperature was 150℃, the nitrogen atmosphere was 5 MPa, 30 ml of n-hexane and 10 ml of deionized water were used, and the yield of the collected polycyclic alkane precursor was 63.4%, and the conversion rate of furfuryl alcohol was 88.6%.
[0074] Example 17
[0075] The difference between Example 17 and Example 1 is:
[0076] Under a nitrogen atmosphere with a nitrogen pressure of 5 MPa, the yield of the collected polycyclic alkane precursor was 41.9%, and the conversion rate of furfuryl alcohol was 79.4%.
[0077] Example 18
[0078] The difference between Example 18 and Example 1 is:
[0079] The reaction temperature was 120℃, and the nitrogen atmosphere was 5 MPa. The yield of the collected polycyclic alkane precursor was 53.0%, and the conversion rate of furfuryl alcohol was 80.2%.
[0080] Example 19
[0081] The difference between Example 19 and Example 1 is that:
[0082] The reaction temperature was 130℃, and the nitrogen atmosphere was 5 MPa. The yield of the collected polycyclic alkane precursor was 65.2%, and the conversion rate of furfuryl alcohol was 90.8%.
[0083] Example 20
[0084] The difference between Example 20 and Example 1 is as follows:
[0085] The reaction temperature was 140℃, and the nitrogen atmosphere was 5 MPa. The yield of the collected polycyclic alkane precursor was 68.1%, and the conversion rate of furfuryl alcohol was 97.6%.
[0086] Example 21
[0087] The difference between Example 21 and Example 1 is that:
[0088] The reaction temperature was 150℃, and the nitrogen atmosphere was 5 MPa. The yield of the collected polycyclic alkane precursor was 65.7%, and the conversion rate of furfuryl alcohol was 92.6%.
[0089] Example 22
[0090] The difference between Example 22 and Example 1 is as follows:
[0091] The reaction temperature was 160℃, and the nitrogen atmosphere was 5 MPa. The yield of the collected polycyclic alkane precursor was 64.2%, and the conversion rate of furfuryl alcohol was 86.2%.
[0092] Example 23
[0093] The difference between Example 23 and Example 1 is that:
[0094] The reaction temperature was 140℃, the amount of furfuryl alcohol was 20 mmol, the amount of isoprene was 20 mmol, and the nitrogen atmosphere was 5 MPa. The yield of the collected polycyclic alkane precursor was 51.6%, and the conversion rate of furfuryl alcohol was 80.2%.
[0095] Example 24
[0096] The difference between Example 24 and Example 1 is that:
[0097] The reaction temperature was 140℃, the amount of furfuryl alcohol was 20 mmol, the amount of isoprene was 30 mmol, and the nitrogen atmosphere was 5 MPa. The yield of the collected polycyclic alkane precursor was 55.0%, and the conversion rate of furfuryl alcohol was 84.3%.
[0098] Example 25
[0099] The difference between Example 25 and Example 1 is:
[0100] The reaction temperature was 140℃, the amount of furfuryl alcohol was 20 mmol, the amount of isoprene was 40 mmol, and the nitrogen atmosphere was 5 MPa. The yield of the collected polycyclic alkane precursor was 60.0%, and the conversion rate of furfuryl alcohol was 90.9%.
[0101] Example 26
[0102] The difference between Example 26 and Example 1 is that:
[0103] The reaction temperature was 140℃, the amount of furfuryl alcohol was 20 mmol, the amount of isoprene was 60 mmol, and the reaction was carried out under a nitrogen atmosphere with a nitrogen pressure of 5 MPa. The yield of the collected polycyclic alkane precursor was 66.0%, and the conversion rate of furfuryl alcohol was 97.6%.
[0104] Example 27
[0105] The difference between Example 27 and Example 1 is as follows:
[0106] The reaction temperature was 140℃, the reaction time was 6h, and the nitrogen atmosphere was 5MPa. The yield of the collected polycyclic alkane precursor was 48.6%, and the conversion rate of furfuryl alcohol was 97.2%.
[0107] Example 28
[0108] The difference between Example 28 and Example 1 is as follows:
[0109] The reaction temperature was 140℃, the reaction time was 12h, and the nitrogen atmosphere was 5MPa. The yield of the collected polycyclic alkane precursor was 54.4%, and the conversion rate of furfuryl alcohol was 95.3%.
[0110] Example 29
[0111] The difference between Example 29 and Example 1 is as follows:
[0112] The reaction temperature was 140℃, the reaction time was 36h, and the nitrogen atmosphere was 5MPa. The yield of the collected polycyclic alkane precursor was 59.5%, and the conversion rate of furfuryl alcohol was 96.3%.
[0113] Example 30
[0114] The difference between Example 30 and Example 1 is that:
[0115] The reaction temperature was 140℃, the hydrogen atmosphere was 2 MPa, and the yield of the collected polycyclic alkane precursor was 59.6%, while the conversion rate of furfuryl alcohol was 82.3%.
[0116] Example 31
[0117] The difference between Example 31 and Example 1 is:
[0118] The reaction temperature was 140℃, the hydrogen atmosphere was 8 MPa, and the yield of the collected polycyclic alkane precursor was 62.4%, while the conversion rate of furfuryl alcohol was 86.9%.
[0119] Example 32
[0120] The difference between Example 32 and Example 1 is as follows:
[0121] The reaction temperature was 140℃, with 10 ml of n-hexane and 30 ml of deionized water. The yield of the collected polycyclic alkane precursor was 50.4%, and the conversion rate of furfuryl alcohol was 70.6%.
[0122] Example 33
[0123] The difference between Example 33 and Example 1 is:
[0124] The reaction temperature was 140℃, with 30 ml of n-hexane and 10 ml of deionized water. The yield of the collected polycyclic alkane precursor was 60.3%, and the conversion rate of furfuryl alcohol was 80.4%.
[0125] Examples 2-33 are similar to Example 1, investigating the effects of different temperatures, furfuryl alcohol to isoprene molar ratios, and reaction times on the directional controllable aqueous reforming and Diels-Alder cascade reaction in a high-pressure reactor equipped with a mechanical stirrer. The corresponding reaction conditions and results are shown in Table 1 below.
[0126] Table 1. Effects of different temperatures, furfuryl alcohol:isoprene molar ratios, and times on furfuryl alcohol conversion and precursor yield.
[0127]
[0128]
[0129] in:
[0130] 'a' indicates that in Example 13, the nitrogen pressure was 3 MPa.
[0131] b indicates that in Example 14, the nitrogen pressure was 7 MPa.
[0132] c indicates that in Example 15, the nitrogen pressure was 5 MPa, and the mixture consisted of 10 ml of n-hexane and 30 ml of deionized water.
[0133] d indicates that in Example 16, the nitrogen pressure was 5 MPa, and the mixture consisted of 30 ml of n-hexane and 10 ml of deionized water.
[0134] e indicates that in Examples 17-29, the nitrogen pressure is 5 MPa.
[0135] f indicates that in Example 30, the hydrogen pressure is 2 MPa.
[0136] g indicates that the hydrogen pressure in Example 31 is 8 MPa.
[0137] h indicates that in Example 32, the hydrogen pressure was 5 MPa, and the mixture consisted of 10 ml of n-hexane and 30 ml of deionized water.
[0138] i indicates that in Example 33, the hydrogen pressure is 5 MPa, and the mixture consists of 30 ml of n-hexane and 10 ml of deionized water.
[0139] Example 34
[0140] The process of preparing polycyclic alkane products (high-density aviation fuel components are mainly polycyclic alkanes) by hydrogenation deoxygenation of polycyclic alkane precursors obtained under a nitrogen atmosphere includes:
[0141] 20 ml of n-hexane, 1 g of purified polycyclic alkane precursor (obtained under nitrogen atmosphere), 0.1 g Ru / C, and 0.2 g Hβ were added to a high-pressure reactor equipped with a mechanical stirrer. The hydrogen pressure was 5 MPa, and the reaction was carried out at 150 °C for 5 h. After the reaction, the precursor conversion rate was 98.2%, and the polycyclic alkane yield was 90.3%. The density of the obtained product was 0.904 g / cm³. 3 Its calorific value is 35.21 MJ / L.
[0142] Example 35
[0143] The process of preparing polycyclic alkane products (high-density aviation fuel components) by hydrodeoxygenation reaction using polycyclic alkane precursors obtained under a nitrogen atmosphere includes:
[0144] 20 ml of n-hexane, 1 g of purified polycyclic alkane precursor (obtained under nitrogen atmosphere), 0.5 g Ru / C and 1 g Hβ were added to a high-pressure reactor equipped with a mechanical stirrer. The hydrogen pressure was 3 MPa, and the reaction was carried out at 120 °C for 5 h. After the reaction was completed, the precursor conversion rate was 85.2% and the polycyclic alkane yield was 75.6%.
[0145] Example 36
[0146] The process of preparing polycyclic alkane products (high-density aviation fuel components) by hydrodeoxygenation reaction using polycyclic alkane precursors obtained under a nitrogen atmosphere includes:
[0147] 20 ml of n-hexane, 1 g of purified polycyclic alkane precursor (obtained under nitrogen atmosphere), 0.5 g Ru / C and 1 g Hβ were added to a high-pressure reactor equipped with a mechanical stirrer. The hydrogen pressure was 6 MPa, and the reaction was carried out at 170 °C for 10 h. After the reaction was completed, the precursor conversion rate was 90.2% and the polycyclic alkane yield was 88.3%.
[0148] Example 37
[0149] The process of preparing polycyclic alkane products (high-density aviation fuel components) by hydrodeoxygenation reaction using polycyclic alkane precursors obtained under a hydrogen atmosphere includes:
[0150] 20 ml of n-hexane, 1 g of purified precursor (obtained under hydrogen atmosphere), 0.1 g Ru / C, and 0.2 g Hβ were added to a high-pressure reactor equipped with a mechanical stirrer. The hydrogen pressure was 5 MPa, and the reaction was carried out at 150 °C for 5 h. After the reaction, the precursor conversion rate was 99.6%, and the polycyclic alkane yield was 94.2%. The density of the obtained product was 0.857 g / cm³. 3 Its calorific value is 31.48 MJ / L.
[0151] Furthermore, it is worth mentioning that the hydrogenation catalyst can be one of Ru / C, Pd / C, or Pt / C, and the solid acid catalyst can be one of HZSM-5, HY, MCM-41, or Hβ.
[0152] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.
[0153] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the claimed invention.
Claims
1. A method for preparing high-density aviation fuel components from furfuryl alcohol and isoprene, characterized in that, Includes the following steps: S1, furfuryl alcohol, isoprene, Lewis acid FeZn-F68, n-hexane and deionized water are added to the reactor, and the mixture is stirred under a hydrogen or nitrogen atmosphere to carry out a cascade reaction of directional controllable aqueous phase reforming and Diels-Alder to obtain a polycyclic alkane precursor. S2, after purifying the polycyclic alkane precursor, add it to the reaction vessel, along with a hydrogenation catalyst and a solid acid catalyst, to carry out a hydrogenation deoxygenation reaction to obtain polycyclic alkanes; FeZn-F68 was synthesized by the following method: A mixture of 40 mL deionized water and 0.4 mol ZnCl2 was added to 80 mL of 0.1 mol / L K4[Fe(CN)6] solution; Add 60 g of a mixture of poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) with a molecular weight of 8400 and 20 mL of deionized water while stirring, and continue stirring for 12 h. Then, the sample was washed and filtered with deionized water, and dried at 160℃ for 18 h to obtain FeZn-F68.
2. The method for preparing high-density aviation fuel components from furfuryl alcohol and isoprene according to claim 1, characterized in that, The molar ratio of furfuryl alcohol to isoprene is 1:1-3.
3. The method for preparing high-density aviation fuel components from furfuryl alcohol and isoprene according to claim 1, characterized in that, In S1, the reaction temperature in the reactor is 110-160℃, and the reaction time is 6-36h.
4. The method for preparing high-density aviation fuel components from furfuryl alcohol and isoprene according to claim 1, characterized in that, In S1, when the reaction atmosphere is nitrogen, the nitrogen pressure is 3-7 MPa; when the reaction atmosphere is hydrogen, the hydrogen pressure is 2-8 MPa.
5. The method for preparing high-density aviation fuel components from furfuryl alcohol and isoprene according to claim 1, characterized in that, In S1, the stirring rate is 300 rpm / min.
6. The method for preparing high-density aviation fuel components from furfuryl alcohol and isoprene according to claim 1, characterized in that, In S2, the mass ratio of the polycyclic alkane precursor, the hydrogenation catalyst, and the solid acid catalyst is 10:1-5:2-10.
7. A method for preparing high-density aviation fuel components from furfuryl alcohol and isoprene according to claim 1 or 6, characterized in that, The hydrogenation catalyst is one of Ru / C, Pd / C, or Pt / C.
8. A method for preparing high-density aviation fuel components from furfuryl alcohol and isoprene according to claim 1 or 6, characterized in that, The solid acid catalyst is one of HZSM-5, HY, MCM-41 and Hβ.
9. A method for preparing high-density aviation fuel components from furfuryl alcohol and isoprene according to claim 1, characterized in that, The reaction temperature of the hydrogenation deoxygenation reaction is 120~170 ℃, the reaction time is 5~10 h, and the hydrogen pressure is 3~6 MPa.