Preparation method of liquid fuel

Abstract

The invention discloses a preparation method of liquid fuel, which comprises the following steps: S1, reducing a catalyst in a reducing atmosphere I to obtain an activated catalyst; s2, mixing the raw materials with solid acid and the activated catalyst, and carrying out catalytic hydrogenolysis reaction in a reducing atmosphere II to obtain a product containing liquid fuel; the raw materials are waste rubber products and / or waste latex products; the solid acid is selected from at least one of HY, Hbeta and a hydrogen type ZSM-5 molecular sieve; the catalyst comprises a carrier and an active component, the active component is loaded on the carrier; the carrier is selected from nano oxide; the active component comprises active metal elements; the active metal element is selected from at least one of VIII group elements. The reaction does not involve a plurality of reactors, and the process is environment-friendly, simple and convenient in process, mild in reaction condition and high in treatment efficiency.

Description

Technical Field

[0001] This application relates to a method for preparing liquid fuel, belonging to the field of chemical engineering. Background Technology

[0002] Waste rubber and waste latex refer to products discarded during the use of tires, gloves, and other similar items. These waste products are often unusable in production and use, leading to serious environmental pollution and resource waste. Therefore, how to effectively utilize waste rubber and waste latex products to achieve resource recycling is an urgent problem to be solved.

[0003] In recent years, with the increasing severity of the global energy crisis and environmental pollution, people have begun to pay attention to the development and utilization of renewable energy. Among them, liquid fuels, as a clean and efficient energy source, have received widespread attention. The main components of waste rubber products and waste latex products are hydrocarbon elements, and they are highly renewable, possessing the potential to produce liquid fuels through chemical conversion.

[0004] Therefore, research on producing liquid fuels from waste rubber and latex products is of great significance. First, it can effectively solve the problem of waste rubber and latex product disposal, reducing environmental pollution and resource waste. Second, as a clean and efficient energy source, liquid fuels can replace traditional fossil fuels, reducing greenhouse gas emissions and helping to mitigate global climate change. Finally, the technology for producing liquid fuels from waste rubber and latex products can provide new ideas and methods for the development and utilization of renewable energy, promoting the transformation of the energy structure and sustainable development.

[0005] However, existing methods for producing liquid fuels using waste rubber and waste latex products still suffer from low conversion efficiency, low yield, and poor selectivity. Summary of the Invention

[0006] The purpose of this application is to provide a method for preparing liquid fuel, which utilizes waste rubber products and / or waste latex products to produce liquid fuel in a one-step reaction through a C=C hydrogenation and C-C bond partial breaking strategy. The reaction does not involve multiple reactors, and the process is environmentally friendly, simple, has mild reaction conditions, and high processing efficiency.

[0007] According to one aspect of this application, a method for preparing a liquid fuel is provided, comprising the following steps:

[0008] S1. The catalyst is reduced in a reducing atmosphere I to obtain an activated catalyst;

[0009] S2. The raw materials are mixed with solid acid and activated catalyst, and a catalytic hydrogenolysis reaction is carried out in reducing atmosphere II to obtain products containing liquid fuel.

[0010] The raw materials are waste rubber products and / or waste latex products;

[0011] The solid acid is selected from at least one of HY, Hβ, and hydrogen-form ZSM-5 molecular sieve;

[0012] The catalyst includes a support and an active component;

[0013] The active component is loaded on the carrier;

[0014] The carrier is selected from nano-oxides;

[0015] The active component includes active metal elements;

[0016] The active metal element is selected from at least one element in Group VIII.

[0017] Optionally, the waste rubber products are selected from at least one of natural rubber, rubber tires, rubber gloves, rubber stoppers, rubber shoe soles, rubber gaskets, and rubber tubes.

[0018] Optionally, the waste latex products are selected from at least one of latex gloves, latex tubes, latex pillows, latex balloons, latex mattresses, and latex caps.

[0019] Optionally, the hydrogen-form ZSM-5 molecule is selected from at least one of H-ZSM-5(21), H-ZSM-5(85), H-ZSM-5(130), and H-ZSM-5(200).

[0020] Optionally, the nano-oxide is selected from at least one of nano-zirconia, nano-zinc oxide, nano-titanium dioxide, fumed silica, nano-indium oxide, and nano-cerium oxide.

[0021] Optionally, the Group VIII element is selected from at least one of ruthenium, rhodium, platinum, palladium, iridium, and nickel.

[0022] Optionally, the size of the carrier is 20–200 nm.

[0023] Optionally, the size of the carrier is independently selected from any value among 20nm, 40nm, 60nm, 80nm, 100nm, 120nm, 140nm, 160nm, 180nm, and 200nm, or a range between any two of the above points.

[0024] Optionally, the content of the active component in the catalyst is 5-10 wt%.

[0025] Optionally, the content of the active component in the catalyst is independently selected from any value of 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, or a range between any two of the above points.

[0026] Optionally, the mass of the solid acid is 1 to 200% of the mass of the raw material.

[0027] Optionally, the mass of the solid acid is a value of the mass of the raw material independently selected from any value among 1%, 2.5%, 5%, 7.5%, 10%, 15%, 20%, 40%, 60%, 80%, 100%, 120%, 140%, 160%, 180%, and 200%, or a range between any two of the above points.

[0028] Preferably, the mass of the solid acid is 5% to 100% of the mass of the raw material.

[0029] Optionally, the mass of the catalyst is 1 to 200% of the mass of the raw material.

[0030] Optionally, the mass of the catalyst is a value of the mass of the raw material independently selected from any value among 1%, 2.5%, 5%, 7.5%, 10%, 15%, 20%, 40%, 60%, 80%, 100%, 120%, 140%, 160%, 180%, and 200%, or a range between any two of the above points.

[0031] Preferably, the mass of the catalyst is 5% to 100% of the mass of the raw material.

[0032] Optionally, the catalyst preparation steps include: impregnating the active component onto a support, drying it, and obtaining the catalyst.

[0033] Optionally, the active component precursor is selected from at least one of ruthenium, rhodium, platinum, palladium, iridium, and nickel chloride or nitrate.

[0034] Optionally, the impregnation is an equal-volume impregnation method.

[0035] Optionally, the drying temperature is 80–110°C.

[0036] Optionally, the drying temperature is independently selected from any value among 80°C, 90°C, 100°C, and 110°C, or a range between any two of the above points.

[0037] Optionally, the drying time is 12 to 24 hours.

[0038] Optionally, the drying time is independently selected from any value among 12h, 14h, 16h, 18h, 20h, 22h, and 24h, or a range between any two of the above points.

[0039] Optionally, the reducing atmosphere I is a hydrogen atmosphere.

[0040] Optionally, the reduction temperature is 200–350°C.

[0041] Optionally, the reduction temperature is independently selected from any value among 200℃, 225℃, 250℃, 275℃, 300℃, 325℃, and 350℃, or a range between any two of the above points.

[0042] Optionally, the restoration time is 2 to 6 hours.

[0043] Optionally, the restoration time is independently selected from any value among 2h, 3h, 4h, 5h, and 6h, or a range between any two of the above points.

[0044] Optionally, the reducing atmosphere II is a hydrogen atmosphere.

[0045] Optionally, the catalytic hydrogenolysis reaction is carried out under closed conditions.

[0046] Optionally, the catalytic hydrogenolysis reaction is carried out in a high-pressure reactor.

[0047] Optionally, the temperature of the catalytic hydrogenolysis reaction is 120–350°C.

[0048] Optionally, the temperature of the catalytic hydrogenolysis reaction is independently selected from any value among 120°C, 140°C, 160°C, 180°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, 300°C, and 350°C, or a range between any two of the above points.

[0049] Optionally, the temperature of the catalytic hydrogenolysis reaction is 180–300°C.

[0050] Optionally, the temperature of the catalytic hydrogenolysis reaction is 200–260°C.

[0051] Optionally, the catalytic hydrogenolysis reaction takes 1 to 60 hours.

[0052] Optionally, the time for the catalytic hydrogenolysis reaction is independently selected from any value among 1h, 2h, 4h, 5h, 8h, 12h, 16h, 20h, 30h, and 60h, or a range between any two of the above points.

[0053] Optionally, the catalytic hydrogenolysis reaction takes 2 to 30 hours.

[0054] Optionally, the catalytic hydrogenolysis reaction takes 5 to 20 hours.

[0055] Optionally, the pressure of the catalytic hydrogenolysis reaction is 0.1 to 8 MPa.

[0056] Optionally, the pressure of the catalytic hydrogenolysis reaction is independently selected from any value of 0.1 MPa, 0.5 MPa, 1 MPa, 2 MPa, 3 MPa, 4 MPa, 5 MPa, 6 MPa, 7 MPa, 8 MPa or a range between any two of the above points.

[0057] Optionally, the pressure of the catalytic hydrogenolysis reaction is 1 to 6 MPa.

[0058] Optionally, the pressure of the catalytic hydrogenolysis reaction is 2 to 5 MPa.

[0059] Optionally, the yield of the liquid fuel is 30-90%.

[0060] Optionally, the waste rubber products and / or waste latex products are pretreated before the reaction: cut into small pieces of about 2 mm.

[0061] Optionally, step S2 further includes replacing the reaction atmosphere with at least one of argon, nitrogen, and hydrogen before the reaction.

[0062] Alternatively, the reaction is carried out in a high-pressure reactor, sealed at room temperature and standard atmospheric pressure.

[0063] Optionally, during the reaction, the pressure inside the reactor is the high pressure generated by the thermal expansion of hydrogen gas.

[0064] In the preparation of the liquid fuel, excessively low temperatures can lead to low substrate conversion rates, while excessively high temperatures can result in the generation of gaseous products. Within a certain time range, the conversion rate increases with the increase of catalytic hydrogenolysis reaction time. However, after the reaction time is extended to a certain point, the products will continue to break down into gaseous alkanes with shorter carbon chains as time is further extended.

[0065] The beneficial effects that this application can produce include:

[0066] (1) This application discloses a novel route for preparing liquid fuel using waste rubber products and / or waste latex products under relatively mild conditions through C=C hydrogenation and partial C / C bond breaking strategies. This route opens up new applications for the catalytic conversion of waste rubber products and / or waste latex products through C=C hydrogenation and partial C / C bond breaking strategies, and provides a new method for synthesizing liquid fuels with significant application value.

[0067] (2) The method for preparing liquid fuel provided in this application involves the direct catalytic hydrogenation of waste rubber products and / or waste latex products into liquid fuel, without involving multiple reactors. Moreover, the process is environmentally friendly, simple, easy to operate, has mild reaction conditions, and high processing efficiency.

[0068] (3) The liquid fuel preparation method provided in this application has a high yield of liquid fuel, which can reach 90%. Attached Figure Description

[0069] Figure 1 The results of gas chromatography-mass spectrometry analysis of the liquid fuel prepared in Example 1 of this application are shown. Detailed Implementation

[0070] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.

[0071] Unless otherwise specified, the raw materials and reagents used in the embodiments of this application were all purchased commercially.

[0072] The analysis method in the embodiments of this application is as follows:

[0073] Quantitative analysis of liquid products using gas chromatography.

[0074] Qualitative analysis of the liquid products was performed using gas chromatography-mass spectrometry (GC-MS).

[0075] The liquid fuel yield calculation formula in the embodiments of this application is as follows:

[0076]

[0077] Where m C7 m C8 m C9 ·····m C26 This represents the mass of liquid alkane with different carbon numbers.

[0078] Example 1

[0079] Catalyst pretreatment: 0.12 g 5 wt% Ru / ZrO2 (30 nm) was reduced at 250 °C under a hydrogen atmosphere for 3 h. In a reactor, 0.5 g natural rubber, 0.1 g Ru / ZrO2, and 0.1 g HY were added, purged with nitrogen, then with hydrogen, and the pressure was increased to 4 MPa. The reaction was carried out at 240 °C for 16 h. After the reaction, the temperature was lowered to room temperature, and the liquid product was collected for quantitative analysis by GC. The liquid fuel yield was 90%.

[0080] The prepared liquid fuel was qualitatively analyzed by gas chromatography-mass spectrometry (GC-MS), and the analytical results are as follows: Figure 1As shown. By Figure 1 It can be seen that the product is a branched chain alkane, and it basically retains the structural characteristics of polyisoprene.

[0081] The gas chromatography-mass spectrometry analysis results of the liquid fuel yields obtained in Examples 2-32 are similar to those in Example 1.

[0082] Example 2

[0083] Catalyst pretreatment: 0.12 g 5 wt% Ru / ZrO2 (30 nm) was reduced at 200 °C under a hydrogen atmosphere for 3 h. In a reactor, 0.5 g natural rubber, 0.1 g Ru / ZrO2, and 0.1 g HY were added, purged with nitrogen, then with hydrogen, and the pressure was increased to 4 MPa. The reaction was carried out at 240 °C for 16 h. After the reaction, the temperature was lowered to room temperature, and the liquid product was collected for quantitative analysis by GC. The liquid fuel yield was 82%.

[0084] Example 3

[0085] Catalyst pretreatment: 0.12 g 5 wt% Ru / ZrO2 (30 nm) was reduced at 300 °C under a hydrogen atmosphere for 3 h. In a reactor, 0.5 g natural rubber, 0.1 g Ru / ZrO2, and 0.1 g HY were added, purged with nitrogen, then with hydrogen, and the pressure was increased to 4 MPa. The reaction was carried out at 240 °C for 16 h. After the reaction, the temperature was lowered to room temperature, and the liquid product was collected for quantitative analysis by GC. The liquid fuel yield was 78%.

[0086] Example 4

[0087] Catalyst pretreatment: 0.12 g 5 wt% Ru / ZrO2 (30 nm) was reduced at 250 °C under a hydrogen atmosphere for 3 h. In a reactor, 0.5 g natural rubber, 0.1 g Ru / ZrO2, and 0.1 g Hβ were added, purged with nitrogen, then with hydrogen, and the pressure was increased to 4 MPa. The reaction was carried out at 240 °C for 16 h. After the reaction, the temperature was lowered to room temperature, and the liquid product was collected for quantitative analysis by GC. The liquid fuel yield was 73%.

[0088] Example 5

[0089] Catalyst pretreatment: 0.12 g 5 wt% Ru / ZrO2 (30 nm) was reduced at 250 °C under a hydrogen atmosphere for 3 h. In the reactor, 0.5 g natural rubber, 0.1 g Ru / ZrO2, and 0.1 g H-ZSM-5 (21) were added, purged with nitrogen, then with hydrogen, and the pressure was increased to 4 MPa. The reaction was carried out at 240 °C for 16 h. After the reaction, the temperature was lowered to room temperature, and the liquid product was collected for quantitative analysis by GC. The liquid fuel yield was 73%.

[0090] Example 6

[0091] Catalyst pretreatment: 0.12 g 5 wt% Ru / ZrO2 (30 nm) was reduced at 250 °C under a hydrogen atmosphere for 3 h. In a reactor, 0.5 g natural rubber, 0.1 g Ru / ZrO2, and 0.1 g H-ZSM-5 (85) were added, purged with nitrogen, then with hydrogen, and the pressure was increased to 4 MPa. The reaction was carried out at 240 °C for 16 h. After the reaction, the temperature was lowered to room temperature, and the liquid product was collected for quantitative analysis by GC. The liquid fuel yield was 79%.

[0092] Example 7

[0093] Catalyst pretreatment: 0.12 g 5 wt% Ru / ZrO2 (30 nm) was reduced at 250 °C under a hydrogen atmosphere for 3 h. In a reactor, 0.5 g natural rubber, 0.1 g Ru / ZrO2, and 0.1 g H-ZSM-5 (130) were added, purged with nitrogen, then with hydrogen, and the pressure was increased to 4 MPa. The reaction was carried out at 240 °C for 16 h. After the reaction, the temperature was lowered to room temperature, and the liquid product was collected for quantitative analysis by GC. The liquid fuel yield was 76%.

[0094] Example 8

[0095] Catalyst pretreatment: 0.12 g 5 wt% Ru / ZrO2 (30 nm) was reduced at 250 °C under a hydrogen atmosphere for 3 h. In a reactor, 0.5 g natural rubber, 0.1 g Ru / ZrO2, and 0.1 g H-ZSM-5 (200) were added, purged with nitrogen, then with hydrogen, and the pressure was increased to 4 MPa. The reaction was carried out at 240 °C for 16 h. After the reaction, the temperature was lowered to room temperature, and the liquid product was collected for quantitative analysis by GC. The liquid fuel yield was 66%.

[0096] Example 9

[0097] Catalyst pretreatment: 0.12 g 5 wt% Ru / ZrO2 (30 nm) was reduced at 250 °C under a hydrogen atmosphere for 3 h. In a reactor, 0.5 g natural rubber, 0.1 g Ru / ZrO2, and 0.05 g HY were added, purged with nitrogen, then with hydrogen, and the pressure was increased to 4 MPa. The reaction was carried out at 240 °C for 16 h. After the reaction, the temperature was lowered to room temperature, and the liquid product was collected for quantitative analysis by GC. The liquid fuel yield was 81%.

[0098] Example 10

[0099] Catalyst pretreatment: 0.12 g 5 wt% Ru / ZrO2 (30 nm) was reduced at 250 °C under a hydrogen atmosphere for 3 h. In a reactor, 0.5 g natural rubber, 0.1 g Ru / ZrO2, and 0.15 g HY were added, purged with nitrogen, then with hydrogen, and the pressure was increased to 4 MPa. The reaction was carried out at 240 °C for 16 h. After the reaction, the temperature was lowered to room temperature, and the liquid product was collected for quantitative analysis by GC. The liquid fuel yield was 74%.

[0100] Example 11

[0101] Catalyst pretreatment: 0.12 g 5 wt% Ru / ZrO2 (30 nm) was reduced at 250 °C under a hydrogen atmosphere for 3 h. In a reactor, 0.5 g natural rubber, 0.1 g Ru / ZrO2, and 0.2 g HY were added, purged with nitrogen, then with hydrogen, and the pressure was increased to 4 MPa. The reaction was carried out at 240 °C for 16 h. After the reaction, the temperature was lowered to room temperature, and the liquid product was collected for quantitative analysis by GC. The liquid fuel yield was 63%.

[0102] Example 12

[0103] Catalyst pretreatment: 0.12 g 5 wt% Ru / ZrO2 (30 nm) was reduced at 250 °C under a hydrogen atmosphere for 3 h. In a reactor, 0.5 g natural rubber, 0.1 g Ru / ZrO2, and 0.1 g HY were added, purged with nitrogen, then with hydrogen, and the pressure was increased to 0.1 MPa. The reaction was carried out at 240 °C for 16 h. After the reaction, the temperature was lowered to room temperature, and the liquid product was collected for quantitative analysis by GC. The liquid fuel yield was 33%.

[0104] Example 13

[0105] Catalyst pretreatment: 0.12 g of 5 wt% Ru / ZrO2 (30 nm) was reduced at 250 °C under a hydrogen atmosphere for 3 h. In a reactor, 0.5 g of natural rubber, 0.1 g of Ru / ZrO2, and 0.1 g of HY were added, purged with nitrogen, then with hydrogen, and the pressure was increased to 1 MPa. The reaction was carried out at 240 °C for 16 h. After the reaction, the temperature was lowered to room temperature, and the liquid product was collected for quantitative analysis by GC. The liquid fuel yield was 51%.

[0106] Example 14

[0107] Catalyst pretreatment: 0.12 g 5 wt% Ru / ZrO2 (30 nm) was reduced at 250 °C under a hydrogen atmosphere for 3 h. In a reactor, 0.5 g natural rubber, 0.1 g Ru / ZrO2, and 0.1 g HY were added, purged with nitrogen, then with hydrogen, and the pressure was increased to 2 MPa. The reaction was carried out at 240 °C for 16 h. After the reaction, the temperature was lowered to room temperature, and the liquid product was collected for quantitative analysis by GC. The liquid fuel yield was 73%.

[0108] Example 15

[0109] Catalyst pretreatment: 0.12 g 5 wt% Ru / ZrO2 (30 nm) was reduced at 250 °C under a hydrogen atmosphere for 3 h. In a reactor, 0.5 g natural rubber, 0.1 g Ru / ZrO2, and 0.1 g HY were added, purged with nitrogen, then with hydrogen, and the pressure was increased to 3 MPa. The reaction was carried out at 240 °C for 16 h. After the reaction, the temperature was lowered to room temperature, and the liquid product was collected for quantitative analysis by GC. The liquid fuel yield was 86%.

[0110] Example 16

[0111] Catalyst pretreatment: 0.12 g 5 wt% Ru / ZrO2 (30 nm) was reduced at 250 °C under a hydrogen atmosphere for 3 h. In a reactor, 0.5 g natural rubber, 0.1 g Ru / ZrO2, and 0.1 g HY were added, purged with nitrogen, then with hydrogen, and the pressure was increased to 4 MPa. The reaction was carried out at 200 °C for 16 h. After the reaction, the temperature was lowered to room temperature, and the liquid product was collected for quantitative analysis by GC. The liquid fuel yield was 30%.

[0112] Example 17

[0113] Catalyst pretreatment: 0.12 g 5 wt% Ru / ZrO2 (30 nm) was reduced at 250 °C under a hydrogen atmosphere for 3 h. In a reactor, 0.5 g natural rubber, 0.1 g Ru / ZrO2, and 0.1 g HY were added, purged with nitrogen, then with hydrogen, and the pressure was increased to 4 MPa. The reaction was carried out at 210 °C for 16 h. After the reaction, the temperature was lowered to room temperature, and the liquid product was collected for quantitative analysis by GC. The liquid fuel yield was 48%.

[0114] Example 18

[0115] Catalyst pretreatment: 0.12 g of 5 wt% Ru / ZrO2 (30 nm) was reduced at 250 °C under a hydrogen atmosphere for 3 h. In a reactor, 0.5 g of natural rubber, 0.1 g of Ru / ZrO2, and 0.1 g of HY were added, purged with nitrogen, then with hydrogen, and the pressure was increased to 4 MPa. The reaction was carried out at 220 °C for 16 h. After the reaction was completed, the temperature was lowered to room temperature, and the liquid product was collected for quantitative analysis by GC. The liquid fuel yield was 69%.

[0116] Example 19

[0117] Catalyst pretreatment: 0.12 g 5 wt% Ru / ZrO2 (30 nm) was reduced at 250 °C under a hydrogen atmosphere for 3 h. In a reactor, 0.5 g natural rubber, 0.1 g Ru / ZrO2, and 0.1 g HY were added, purged with nitrogen, then with hydrogen, and the pressure was increased to 4 MPa. The reaction was carried out at 230 °C for 16 h. After the reaction, the temperature was lowered to room temperature, and the liquid product was collected for quantitative analysis by GC. The liquid fuel yield was 83%.

[0118] Example 20

[0119] Catalyst pretreatment: 0.12 g of 5 wt% Ru / ZrO2 (30 nm) was reduced at 250 °C under a hydrogen atmosphere for 3 h. In a reactor, 0.5 g of natural rubber, 0.1 g of Ru / ZrO2, and 0.1 g of HY were added, purged with nitrogen, then with hydrogen, and the pressure was increased to 4 MPa. The reaction was carried out at 250 °C for 16 h. After the reaction was completed, the temperature was lowered to room temperature, and the liquid product was collected for quantitative analysis by GC. The liquid fuel yield was 84%.

[0120] Example 21

[0121] Catalyst pretreatment: 0.12 g 5 wt% Ru / ZrO2 (30 nm) was reduced at 250 °C under a hydrogen atmosphere for 3 h. In a reactor, 0.5 g natural rubber, 0.1 g Ru / ZrO2, and 0.1 g HY were added, purged with nitrogen, then with hydrogen, and the pressure was increased to 4 MPa. The reaction was carried out at 260 °C for 16 h. After the reaction, the temperature was lowered to room temperature, and the liquid product was collected for quantitative analysis by GC. The liquid fuel yield was 75%.

[0122] Example 22

[0123] Catalyst pretreatment: 0.12 g 5 wt% Ru / ZrO2 (30 nm) was reduced at 250 °C under a hydrogen atmosphere for 3 h. In a reactor, 0.5 g natural rubber, 0.1 g Ru / ZrO2, and 0.1 g HY were added, purged with nitrogen, then with hydrogen, and the pressure was increased to 4 MPa. The reaction was carried out at 270 °C for 16 h. After the reaction, the temperature was lowered to room temperature, and the liquid product was collected for quantitative analysis by GC. The liquid fuel yield was 54%.

[0124] Example 23

[0125] Catalyst pretreatment: 0.12 g 5 wt% Ru / ZrO2 (30 nm) was reduced at 250 °C under a hydrogen atmosphere for 3 h. In a reactor, 0.5 g natural rubber, 0.1 g Ru / ZrO2, and 0.1 g HY were added, purged with nitrogen, then with hydrogen, and the pressure was increased to 4 MPa. The reaction was carried out at 240 °C for 4 h. After the reaction, the temperature was lowered to room temperature, and the liquid product was collected for quantitative analysis by GC. The liquid fuel yield was 44%.

[0126] Example 24

[0127] Catalyst pretreatment: 0.12 g 5 wt% Ru / ZrO2 (30 nm) was reduced at 250 °C under a hydrogen atmosphere for 3 h. In a reactor, 0.5 g natural rubber, 0.1 g Ru / ZrO2, and 0.1 g HY were added, purged with nitrogen, then with hydrogen, and the pressure was increased to 4 MPa. The reaction was carried out at 240 °C for 8 h. After the reaction, the temperature was lowered to room temperature, and the liquid product was collected for quantitative analysis by GC. The liquid fuel yield was 68%.

[0128] Example 25

[0129] Catalyst pretreatment: 0.12 g 5 wt% Ru / ZrO2 (30 nm) was reduced at 250 °C under a hydrogen atmosphere for 3 h. In a reactor, 0.5 g natural rubber, 0.1 g Ru / ZrO2, and 0.1 g HY were added, purged with nitrogen, then with hydrogen, and the pressure was increased to 4 MPa. The reaction was carried out at 240 °C for 12 h. After the reaction, the temperature was lowered to room temperature, and the liquid product was collected for quantitative analysis by GC. The liquid fuel yield was 79%.

[0130] Example 26

[0131] Catalyst pretreatment: 0.12 g of 5 wt% Ru / ZrO2 (30 nm) was reduced at 250 °C under a hydrogen atmosphere for 3 h. In a reactor, 0.5 g of natural rubber, 0.1 g of Ru / ZrO2, and 0.1 g of HY were added, purged with nitrogen, then with hydrogen, and the pressure was increased to 4 MPa. The reaction was carried out at 240 °C for 20 h. After the reaction, the temperature was lowered to room temperature, and the liquid product was collected for quantitative analysis by GC. The liquid fuel yield was 81%.

[0132] Example 27

[0133] Catalyst pretreatment: 0.12 g of 5 wt% Rh / ZrO2 (30 nm) was reduced at 250 °C under a hydrogen atmosphere for 3 h. In a reactor, 0.5 g of natural rubber, 0.1 g of Rh / ZrO2, and 0.1 g of HY were added, purged with nitrogen, then with hydrogen, and the pressure was increased to 4 MPa. The reaction was carried out at 240 °C for 16 h. After the reaction, the temperature was lowered to room temperature, and the liquid product was collected for quantitative analysis by GC. The liquid fuel yield was 58%.

[0134] Example 28

[0135] Catalyst pretreatment: 0.12 g 5 wt% Pt / ZrO2 (30 nm) was reduced at 250 °C under a hydrogen atmosphere for 3 h. In a reactor, 0.5 g natural rubber, 0.1 g Pt / ZrO2, and 0.1 g HY were added, purged with nitrogen, then with hydrogen, and the pressure was increased to 4 MPa. The reaction was carried out at 240 °C for 16 h. After the reaction, the temperature was lowered to room temperature, and the liquid product was collected for quantitative analysis by GC. The liquid fuel yield was 67%.

[0136] Example 29

[0137] Catalyst pretreatment: 0.12 g 5 wt% Ru / TiO2 (30 nm) was reduced at 250 °C under a hydrogen atmosphere for 3 h. In a reactor, 0.5 g natural rubber, 0.1 g Ru / TiO2, and 0.1 g HY were added, purged with nitrogen, then with hydrogen, and the pressure was increased to 4 MPa. The reaction was carried out at 240 °C for 16 h. After the reaction, the temperature was lowered to room temperature, and the liquid product was collected for quantitative analysis by GC. The liquid fuel yield was 73%.

[0138] Example 30

[0139] Catalyst pretreatment: 0.12 g 5 wt% Ru / ZrO2 (30 nm) was reduced at 250 °C under a hydrogen atmosphere for 3 h. In the reactor, 0.5 g rubber gloves, 0.1 g Ru / ZrO2, and 0.1 g HY were added, purged with nitrogen, then with hydrogen, and the pressure was increased to 4 MPa. The reaction was carried out at 240 °C for 16 h. After the reaction was completed, the temperature was lowered to room temperature, and the liquid product was collected for quantitative analysis by GC. The liquid fuel yield was 81%.

[0140] Example 31

[0141] Catalyst pretreatment: 0.12 g of 5 wt% Ru / ZrO2 (30 nm) was reduced at 250 °C under a hydrogen atmosphere for 3 h. In a reactor, 0.5 g of rubber tubing, 0.1 g of Ru / ZrO2, and 0.1 g of HY were added, purged with nitrogen, then with hydrogen, and the pressure was increased to 4 MPa. The reaction was carried out at 240 °C for 16 h. After the reaction, the temperature was lowered to room temperature, and the liquid product was collected for quantitative analysis by GC. The liquid fuel yield was 89%.

[0142] Example 32

[0143] Catalyst pretreatment: 0.12 g 5 wt% Ru / ZrO2 (30 nm) was reduced at 250 °C under a hydrogen atmosphere for 3 h. In a reactor, 0.5 g of rubber tire, 0.1 g of Ru / ZrO2, and 0.1 g of HY were added, purged with nitrogen, then with hydrogen, and the pressure was increased to 4 MPa. The reaction was carried out at 240 °C for 16 h. After the reaction, the temperature was lowered to room temperature, and the liquid product was collected for quantitative analysis by GC. The liquid fuel yield was 51%.

[0144] Unless otherwise specified, all figures appearing in this application specification and claims, such as temperature and time, yield, etc., should not be construed as absolutely precise values. Due to the standard deviation of measurement techniques, the measured values ​​inevitably contain a certain degree of experimental error.

[0145] The above description is merely a few embodiments of this application and is not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, it is not intended to limit this application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application using the disclosed technical content are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A method for preparing a liquid fuel, characterized in that, Includes the following steps: S1. The catalyst is reduced in a reducing atmosphere I to obtain an activated catalyst; S2. The raw materials are mixed with solid acid and activated catalyst, and a catalytic hydrogenolysis reaction is carried out in reducing atmosphere II to obtain products containing liquid fuel. The raw materials are waste rubber products and / or waste latex products; The solid acid is selected from at least one of HY, Hβ, and hydrogen-form ZSM-5 molecular sieve; The catalyst includes a support and an active component; The active component is loaded on the carrier; The carrier is selected from nano-oxides; The active component includes active metal elements; The active metal element is selected from at least one element in Group VIII.

2. The preparation method according to claim 1, characterized in that, The waste rubber products are selected from at least one of natural rubber, rubber tires, rubber gloves, rubber stoppers, rubber shoe soles, rubber gaskets, and rubber tubes; The waste latex products are selected from at least one of latex gloves, latex tubes, latex pillows, latex balloons, latex mattresses, and latex caps; Preferably, the hydrogen-form ZSM-5 molecule is selected from at least one of H-ZSM-5 (21), H-ZSM-5 (85), H-ZSM-5 (130), and H-ZSM-5 (200); Preferably, the nano-oxide is selected from at least one of nano-zirconia, nano-zinc oxide, nano-titanium dioxide, fumed silica, nano-indium oxide, and nano-cerium oxide; Preferably, the Group VIII element is selected from at least one of ruthenium, rhodium, platinum, palladium, iridium, and nickel.

3. The preparation method according to claim 1, characterized in that, The carrier has a size of 20–200 nm; Preferably, the content of the active component in the catalyst is 5-10 wt%.

4. The preparation method according to claim 1, characterized in that, The mass of the solid acid is 1 to 200% of the mass of the raw material; Preferably, the mass of the solid acid is 5-100% of the mass of the raw material; preferably, the mass of the catalyst is 1-200% of the mass of the raw material; preferably, the mass of the catalyst is 5-100% of the mass of the raw material.

5. The preparation method according to claim 1, characterized in that, The reducing atmosphere I is a hydrogen atmosphere; The reduction temperature is 200–350°C; The reduction time is 2 to 6 hours.

6. The preparation method according to claim 1, characterized in that, The reducing atmosphere II is a hydrogen atmosphere; Preferably, the catalytic hydrogenolysis reaction is carried out under closed conditions.

7. The preparation method according to claim 1, characterized in that, The temperature of the catalytic hydrogenolysis reaction is 120–350 °C; Preferably, the temperature of the catalytic hydrogenolysis reaction is 180–300°C; Preferably, the temperature of the catalytic hydrogenolysis reaction is 200–260°C.

8. The preparation method according to claim 1, characterized in that, The catalytic hydrogenolysis reaction takes 1–60 h; Preferably, the catalytic hydrogenolysis reaction takes 2 to 30 hours; Preferably, the catalytic hydrogenolysis reaction takes 5 to 20 hours.

9. The preparation method according to claim 1, characterized in that, The pressure for the catalytic hydrogenolysis reaction is 0.1–8 MPa; Preferably, the pressure of the catalytic hydrogenolysis reaction is 1–6 MPa; Preferably, the pressure of the catalytic hydrogenolysis reaction is 2 to 5 MPa.

10. The preparation method according to claim 1, characterized in that, The yield of the liquid fuel is 30-90%.

Images