A hydrodeoxygenation catalyst and its application

Abstract

The present invention provides a hydrodeoxygenation catalyst, which comprises, based on 100% total catalyst mass, 6.0-20.0 ω% of magnesium aluminum spinel, 55.0-75.0 ω% of aluminum oxide, 0.5-5.0 ω% of an yttrium-modified metal-organic framework Y / MIL-101, 0.5-14.0 ω% of an HZSM-5 molecular sieve, 1.0-12.0 ω% of nickel oxide, 5.0-20.0 ω% of molybdenum oxide, and 0.5-4.5 ω% of phosphorus pentoxide. The catalyst has a simple preparation method, excellent hydrodeoxygenation performance, increased branched alkane content in the product, a low product pour point, a wide range of applications, and high industrialization prospects.

Description

Technical Field

[0001] The present invention belongs to the field of catalysts, and in particular relates to a hydrodeoxygenation catalyst and an application thereof. Background Art

[0002] Although fossil energy plays an important role in people's lives, the reserves of fossil resources are decreasing year by year and are facing a crisis of depletion. In addition, CO2, a product of fossil fuel combustion, will cause a greenhouse effect, and a large amount of acidic gases such as SO2 emitted will form acid rain, polluting the environment, threatening human health, and destroying the ecological balance. With energy shortages and increasingly stringent environmental protection standards worldwide, the development of green and clean energy to replace fossil energy is of great significance to global energy security and green sustainable development. Among them, biomass energy, as one of the most promising clean fuels, has attracted widespread attention at home and abroad. The biomass oil obtained by pyrolysis of biomass energy has a high oxygen content, resulting in the disadvantages of low calorific value, high water content and poor thermal stability. Therefore, biomass oil cannot be used directly as fuel and must be hydrogenated and deoxygenated to improve its quality.

[0003] Regarding biomass oil hydrodeoxygenation, when the oxygen content in biomass oil, especially tung oil, exceeds 10%, further increasing the alkane yield after reaching approximately 80% becomes increasingly difficult. Furthermore, considering the product's pour point further increases the research and development challenges. Patent EP1728844A1 developed a bio-oil-to-biodiesel catalyst. This catalyst uses alumina as a carrier and nickel-molybdenum as active metals. The deoxygenation rate of soybean oil is 85% to 99%, the diesel yield is 76w% to 98w%, and a by-product of 1.2w% to 10.4w% water. The catalyst activity is average, and the stability needs to be improved. Patent CN101831315A uses alumina as a catalyst carrier and nickel-molybdenum as active components. Under 5.0MPa conditions, over 90% of sunflower oil undergoes hydrodecarboxylation, resulting in a significant loss of carbon chains, which reduces the biodiesel yield. The catalyst stability needs to be improved. Patent CN1597859A uses aluminum oxide and silicon oxide as catalysts, with nickel, cobalt, copper, iron, titanium, and lanthanum as active metals. Hydrodeoxygenation is performed at 2.0 MPa to 15.0 MPa and a hydrogen-to-oil ratio of 200:1 to 1500:1. The resulting Fischer-Tropsch oil achieves an olefin saturation rate of 99.8% to 99.9% and a deoxygenation rate of 97% to 99.9%. The complex and high loading of supported metals results in a complex and costly production process, harsh reaction conditions, and high energy consumption. However, the olefin double bonds are not fully saturated, the deoxygenation rate is low, and the catalytic activity is average. Patent CN112830499A developed a monodisperse SSZ-32 molecular sieve-supported precious metal platinum catalyst for the hydroisomerization of long-chain normal alkanes. The catalyst was found to produce a highly selective mixture of isoparaffins, suppress the formation of cracking products, and significantly increase the proportion of single-branched products. However, the catalyst production process is complex and the supported metals are expensive. Patent CN 112159682 A first hydrogenates a mixture of waste animal and vegetable oils and renewable alkanes using a modified molecular sieve-alumina carrier loaded with two or three of nickel, molybdenum, cobalt, and tungsten. Platinum or palladium is then loaded onto the modified molecular sieve-alumina carrier for hydroisomerization, effectively lowering the pour point of the renewable alkanes to below -15°C and achieving a yield exceeding 80 wt.%. However, this process is complex, and the active components in the hydroisomerization stage are expensive.

[0004] Current hydrodeoxygenation catalysts suffer from either poor activity or high material costs. Some catalysts with good activity and reasonable price produce high levels of linear alkanes in the hydrodeoxygenation product, while the branched alkanes content needs to be improved. To simultaneously achieve good bio-oil hydrodeoxygenation performance, high branched alkanes production, a low pour point, and excellent hydrothermal stability, it is necessary to develop a new catalyst. Summary of the Invention

[0005] The object of the present invention is to provide a hydrodeoxygenation catalyst to solve the problems of poor hydrothermal stability and hydrodeoxygenation performance of existing non-precious metal-loaded hydrodeoxygenation catalysts and limited effect on reducing the freezing point of the product.

[0006] The present invention also aims to provide an application of a hydrodeoxygenation catalyst.

[0007] To achieve the above object, the present invention provides a hydrodeoxygenation catalyst, which, based on the total mass of the catalyst as 100%, comprises 6.0w% to 20.0w% of magnesia-alumina spinel, 55.0w% to 75.0w% of aluminum oxide, 0.5w% to 5.0w% of yttrium-modified metal-organic framework Y / MIL-101, 0.5w% to 14.0w% of HZSM-5 molecular sieve, 1.0w% to 12.0w% of nickel oxide, 5.0w% to 20.0w% of molybdenum oxide and 0.5w% to 4.5w% of phosphorus pentoxide.

[0008] The hydrodeoxygenation catalyst of the present invention is prepared by impregnating MIL-101 in a soluble salt solution of yttrium to obtain a yttrium-modified metal organic framework Y / MIL-101. This method of loading yttrium onto MIL-101 is a conventional loading method in the art and is not further limited.

[0009] The hydrodeoxygenation catalyst of the present invention is prepared by:

[0010] Magnesium aluminum spinel, macroporous alumina, yttrium-modified metal organic framework Y / MIL-101, and HZSM-5 molecular sieve are mixed to obtain a dry powder mixture, and then small-pore alumina, nitric acid, and deionized water are added. The mixture is kneaded, shaped, dried, and calcined to obtain a shaped composite support. A nickel source, a molybdenum source, and a phosphorus source are impregnated onto the composite support by an impregnation method, and then aged, dried, and calcined to obtain a catalyst. The impregnation is preferably performed by co-impregnation of equal volumes.

[0011] During the catalyst preparation process, auxiliary agents such as molding agents and extrusion aids commonly used in the art may be added to the dry powder mixture.

[0012] In the hydrodeoxygenation catalyst of the present invention, the mass ratio of the small pore alumina to the dry powder is 1:3-8, preferably 1:5, the mass ratio of nitric acid to the dry powder mixture and the total mass of the small pore alumina is 1:25-50, preferably 1:38, and the mass ratio of deionized water to the dry powder mixture is 1:1.1-1.5, preferably 1:1.35.

[0013] For the hydrodeoxygenation catalyst of the present invention, the drying and calcination conditions during the preparation of the shaped composite carrier are as follows: drying at 70°C to 140°C for 8 to 14 hours, preferably drying at 120°C for 12 hours, and calcining at 450°C to 600°C for 4 to 8 hours, preferably calcining at 500°C for 8 hours; the drying and calcining conditions after the impregnation step are drying at 90°C to 180°C for 6 to 15 hours, preferably drying at 120°C for 11 hours, and calcining at 350°C to 650°C for 2.5 to 7.5 hours, preferably calcining at 550°C for 3.5 hours.

[0014] In the hydrodeoxygenation catalyst of the present invention, the nickel source is one or more of nickel nitrate, basic nickel carbonate and nickel acetate; the molybdenum source is one or more of ammonium dimolybdate, ammonium tetramolybdate, ammonium heptamolybdate and molybdenum oxide; and the phosphorus source is one or more of phosphoric acid, monoammonium phosphate, diammonium phosphate and ammonium phosphate.

[0015] In the hydrodeoxygenation catalyst of the present invention, the pore diameter of the macroporous alumina is 6-9 nm, and the pore diameter of the small-pore alumina is 3-4 nm.

[0016] To achieve the above object, the present invention also provides an application of a hydrodeoxygenation catalyst in the hydrodeoxygenation reaction of unsaturated oils and fats.

[0017] The application of the present invention is carried out in a continuous flow fixed bed reactor under a hydrogen atmosphere at a reaction temperature of 320°C to 380°C, preferably 340°C; a reaction pressure of 3.0 MPa to 6.0 MPa, preferably 4.0 MPa; a reaction hydrogen to oil ratio of 500:1 to 1200:1, preferably 1000:1; and a reaction space velocity of 0.6 h -1 ~2.0h -1 , preferably 0.8h -1 .

[0018] In the application of the present invention, the oxygen content of the unsaturated oil is 11-13w%.

[0019] Beneficial effects of the present invention:

[0020] By doping magnesium-aluminum spinel and alumina with yttrium-modified metal-organic frameworks (Y / MIL-101) and HZSM-5 molecular sieves, this catalyst possesses abundant acidic sites, excellent isomerization and hydrodeoxygenation activity, adjustable isomerization ratio, simple operation, good hydrothermal stability, and a low product pour point. It achieves virtually complete oxygen removal, achieving an alkane yield of 82.9% by weight and lowering the product pour point to -25°C. The catalyst's simple preparation method, excellent hydrodeoxygenation performance, increased branched-chain alkane content in the product, a low product pour point, and a wide range of applications suggest high industrial potential. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1Schematic diagram of the catalyst of the present invention. DETAILED DESCRIPTION

[0022] The present invention is described in detail below by way of examples. It is necessary to point out that the following examples are only used to further illustrate the present invention and are not to be construed as limiting the scope of protection of the present invention. Those skilled in the art may make some non-essential improvements and adjustments to the present invention based on the above disclosure.

[0023] Source of raw materials:

[0024]

[0025] Preparation of yttrium-modified metal-organic framework Y / MIL-101:

[0026] First, MIL-101 was synthesized by a hydrothermal method: 1.8 g of chromium nitrate nonahydrate and 0.7 g of terephthalic acid were added to 25 mL of deionized water, stirred to dissolve, and then placed in a polytetrafluoroethylene-lined autoclave and kept at a constant temperature of 220°C for 10 hours. The solid-liquid mixture was cooled to room temperature and filtered, washed, and dried.

[0027] Y / MIL-101 was then prepared by the impregnation method: 0.35 g of MIL-101 and 4 mL of a 25 mmol / L Y(NO3)3 solution were placed in a polytetrafluoroethylene-lined reactor, sealed, and kept at a constant temperature of 140°C for 10 h. The solid-liquid mixture was cooled to room temperature and filtered, washed, and dried.

[0028] Example 1

[0029] Weigh 6.4 g of magnesium aluminum spinel, 45.6 g of macroporous alumina, 1.2 g of yttrium-modified metal organic framework Y / MIL-101, 4.8 g of HZSM-5 molecular sieve, 0.29 g of methyl cellulose, 1.7 g of citric acid, and 1.2 g of sesbania powder, mix the dry powders evenly, add 1.5 g of nitric acid dropwise to 51.0 g of deionized water, add 15.3 g of small-pore alumina to the deionized water, stir evenly, and then mix with the dry powder, extrude into a cylindrical shape, dry at 100 ° C for 8 h, and calcine at 550 ° C for 4 h to obtain a shaped carrier.

[0030] The catalyst was prepared by the equal volume co-impregnation method. 4.6 g nickel nitrate, 10.9 g ammonium molybdate and 1.3 g phosphoric acid were prepared into an aqueous solution. The shaped carrier was placed in the co-impregnation solution for impregnation and aging for 18 h, dried at 110 ° C for 9 h, and calcined at 450 ° C for 4.5 h to obtain the catalyst.

[0031] 10.0 ml of catalyst was weighed and loaded into a continuous flow fixed bed reactor. The reactor was sulfurized at 320 ° C for 6 h. The reaction temperature was controlled at 320 ° C, the reaction pressure was 5.0 MPa, the reaction hydrogen-oil ratio was 500:1, and the reaction space velocity was 1.4 h. -1 In a hydrogen atmosphere with n-hexane as solvent, tung oil with an oxygen content of 12.3w% was almost completely freed of oxygen under the action of a catalyst, with a removal rate of over 99%. The liquid products were biodiesel and water. After separating the water, sampling and analysis showed that the yield of alkanes reached 81.6w%, and the product had a freezing point of -11°C and a colorless and transparent appearance.

[0032] Example 2

[0033] Weigh 8.0g of magnesium aluminum spinel, 21.2g of macroporous alumina, 0.4g of yttrium-modified metal organic framework Y / MIL-101, 2.0g of HZSM-5 molecular sieve, 0.3g of methyl cellulose, 0.8g of citric acid, and 0.8g of sesbania powder, mix the dry powders evenly, take 0.8g of nitric acid and add it dropwise to 29.7g of deionized water, add 5.1g of small-pore alumina to the deionized water, stir evenly, then mix with the dry powder, extrude into a clover shape, dry at 80°C for 9h, and calcine at 500°C for 5h to obtain a shaped carrier.

[0034] The catalyst was prepared by the equal volume co-impregnation method. 9.3 g nickel nitrate, 6.5 g ammonium molybdate and 0.8 g phosphoric acid were prepared into an aqueous solution. The shaped carrier was placed in the co-impregnation solution for impregnation and aging for 12 h, dried at 115 ° C for 7 h, and calcined at 350 ° C for 7.5 h to obtain the catalyst.

[0035] 10.0 ml of catalyst was weighed and loaded into a continuous flow fixed bed reactor. The reactor was sulfurized at 320 ° C for 6 h. The reaction temperature was controlled at 370 ° C, the reaction pressure was 6 MPa, the reaction hydrogen-oil ratio was 600:1, and the reaction space velocity was 1.5 h. -1 In a hydrogen atmosphere, with n-nonane as solvent, the oxygen content of waste cooking oil with a double bond saturation and hydrogenation deoxygenation catalyst is almost completely removed, with a removal rate of more than 99%. The liquid products are biodiesel and water. After separating the water, sampling and analysis show that the yield of alkanes reaches 81.2w%, the product has a freezing point of -9℃, and is colorless and transparent in appearance.

[0036] Example 3

[0037] Weigh 3.2g of magnesium aluminum spinel, 26.0g of macroporous alumina, 0.4g of yttrium-modified metal organic framework Y / MIL-101, 3.6g of HZSM-5 molecular sieve, 0.7g of methyl cellulose, 0.5g of citric acid, and 1.1g of sesbania powder, mix the dry powders evenly, take 1.6g of nitric acid and add it dropwise to 30.5g of deionized water, add 7.1g of small-pore alumina to the deionized water, stir evenly, then mix with the dry powder, extrude into a four-leaf clover shape, dry at 90°C for 14h, and calcine at 450°C for 6.5h to obtain a shaped carrier.

[0038] The catalyst was prepared by the equal volume co-impregnation method. 18.1 g of basic nickel carbonate, 3.8 g of ammonium molybdate, and 0.4 g of phosphoric acid were prepared into an aqueous solution. The shaped carrier was placed in the co-impregnation solution for impregnation and aging for 15 h, dried at 130 ° C for 8 h, and calcined at 500 ° C for 5 h to obtain the catalyst.

[0039] 10.0 ml of catalyst was weighed and loaded into a continuous flow fixed bed reactor. The reactor was sulfurized at 320 ° C for 6 h. The reaction temperature was controlled at 380 ° C, the reaction pressure was 4.0 MPa, the reaction hydrogen-oil ratio was 800:1, and the reaction space velocity was 2.0 h -1 In a hydrogen atmosphere, with n-undecane as solvent, the methylated waste cooking oil with an oxygen content of 11.6w% was almost completely freed of oxygen under the action of double bond saturation and hydrodeoxygenation catalyst, with a removal rate of over 99%. The liquid products were biodiesel and water. After separating the water, sampling and analysis showed that the yield of alkanes reached 80.9w%, the product had a freezing point of -17°C, and was colorless and transparent in appearance.

[0040] Example 4

[0041] Weigh 8.0 g of magnesium aluminum spinel, 46.0 g of macroporous alumina, 2.0 g of yttrium-modified metal organic framework Y / MIL-101, 6.4 g of HZSM-5 molecular sieve, 1.9 g of methyl cellulose, 1.3 g of citric acid, and 1.9 g of sesbania powder, mix the dry powders evenly, take 1.7 g of nitric acid and add it dropwise to 60.5 g of deionized water, add 11.2 g of small-pore alumina to the deionized water, stir evenly, then mix with the dry powder, extrude into a cylindrical shape, dry at 110 ° C for 10 h, and calcine at 550 ° C for 6 h to obtain a shaped carrier.

[0042] The catalyst was prepared by the equal volume co-impregnation method. 15.6 g nickel nitrate, 16.3 g ammonium molybdate and 1.1 g phosphoric acid were prepared into an aqueous solution. The shaped carrier was placed in the co-impregnation solution for impregnation and aging for 24 h, dried at 100 ° C for 10 h, and calcined at 650 ° C for 2.5 h to obtain the catalyst.

[0043] 10.0 ml of catalyst was weighed and loaded into a continuous flow fixed bed reactor. The reactor was sulfurized at 320 ° C for 6 h. The reaction temperature was controlled at 350 ° C, the reaction pressure was 3.0 MPa, the reaction hydrogen-oil ratio was 1000:1, and the reaction space velocity was 1.0 h -1 In a hydrogen atmosphere with n-octane as the solvent, tung oil with an oxygen content of 12.0w% was almost completely deoxygenated with the help of a double bond saturation and hydrodeoxygenation catalyst, with a removal rate of over 99%. The liquid products were biodiesel and water. After separation of the water, sampling and analysis showed that the yield of alkanes reached 81.3w%, and the product had a pour point of -13°C and a colorless and transparent appearance.

[0044] Example 5

[0045] Weigh 8.8 g of magnesium aluminum spinel, 40.0 g of macroporous alumina, 0.8 g of yttrium-modified metal organic framework Y / MIL-101, 12.0 g of HZSM-5 molecular sieve, 2.4 g of methyl cellulose, 0.9 g of citric acid, and 1.6 g of sesbania powder, mix the dry powders evenly, take 1.9 g of nitric acid and add it dropwise to 54.2 g of deionized water, add 12.1 g of small-pore alumina to the deionized water, stir evenly, then mix with the dry powder, extrude into a cylindrical shape, dry at 120 ° C for 12 h, and calcine at 500 ° C for 8 h to obtain a shaped carrier.

[0046] The catalyst was prepared by the equal volume co-impregnation method. 35.8 g nickel nitrate, 10.9 g ammonium molybdate and 0.8 g phosphoric acid were prepared into an aqueous solution. The shaped carrier was placed in the co-impregnation solution for impregnation and aging for 22 h, dried at 120 ° C for 11 h, and calcined at 550 ° C for 3.5 h to obtain the catalyst.

[0047] 10.0 ml of catalyst was weighed and loaded into a continuous flow fixed bed reactor. The reactor was sulfurized at 320 ° C for 6 h. The reaction temperature was controlled at 340 ° C, the reaction pressure was 4.0 MPa, the reaction hydrogen-oil ratio was 1000:1, and the reaction space velocity was 0.8 h -1 In a hydrogen atmosphere with n-octane as the solvent, tung oil with an oxygen content of 12.4w% was almost completely deoxygenated under the action of a double bond saturation and hydrodeoxygenation catalyst, with a removal rate of over 99%. The liquid products were biodiesel and water. After separating the water, sampling and analysis showed that the yield of alkanes reached 81.7w%, and the product had a pour point of -25°C and a colorless and transparent appearance.

[0048] Example 6

[0049] Weigh 11.2 g of magnesium aluminum spinel, 46.4 g of macroporous alumina, 1.6 g of yttrium-modified metal organic framework Y / MIL-101, 0.8 g of HZSM-5 molecular sieve, 3.2 g of methyl cellulose, 1.4 g of citric acid, and 2.0 g of sesbania powder, mix the dry powders evenly, add 1.9 g of nitric acid dropwise to 62.0 g of deionized water, add 13.5 g of small-pore alumina to the deionized water, stir evenly, and then mix with the dry powder, extrude into a cylindrical shape, dry at 130 ° C for 11 hours, and calcine at 600 ° C for 4 hours to obtain a shaped carrier.

[0050] The catalyst was prepared by the equal volume co-impregnation method. 37.4 g nickel nitrate, 6.5 g ammonium molybdate and 1.4 g phosphoric acid were prepared into an aqueous solution. The shaped carrier was placed in the co-impregnation solution for impregnation and aging for 16 h, dried at 90 ° C for 15 h, and calcined at 550 ° C for 4 h to obtain the catalyst.

[0051] 10.0 ml of catalyst was weighed and loaded into a continuous flow fixed bed reactor. The reactor was sulfurized at 320 ° C for 6 h. The reaction temperature was controlled at 335 ° C, the reaction pressure was 3.5 MPa, the reaction hydrogen-oil ratio was 1100:1, and the reaction space velocity was 0.6 h -1 In a hydrogen atmosphere with n-octane as the solvent, tung oil with an oxygen content of 12.1w% was almost completely deoxygenated with the help of a double bond saturation and hydrodeoxygenation catalyst, with a removal rate of over 99%. The liquid products were biodiesel and water. After separation of the water, sampling and analysis showed that the yield of alkanes reached 82.9w%, and the product had a pour point of -4°C and was colorless and transparent in appearance.

[0052] Example 7

[0053] Weigh 4.4 g of magnesium aluminum spinel, 23.2 g of macroporous alumina, 1.8 g of yttrium-modified metal organic framework Y / MIL-101, 1.2 g of HZSM-5 molecular sieve, 1.6 g of methyl cellulose, 0.8 g of citric acid, and 1.2 g of sesbania powder, mix the dry powders evenly, take 0.8 g of nitric acid and add it dropwise to 30.3 g of deionized water, add 4.2 g of small-pore alumina to the deionized water, stir evenly, then mix with the dry powder, extrude into a cylindrical shape, dry at 140 ° C for 10 h, and calcine at 450 ° C for 7 h to obtain a shaped carrier.

[0054] The catalyst was prepared by the equal volume co-impregnation method. 15.1 g of basic nickel carbonate, 6.8 g of ammonium molybdate and 1.0 g of phosphoric acid were prepared into an aqueous solution. The shaped carrier was placed in the co-impregnation solution for impregnation and aging for 30 h, dried at 180 ° C for 6 h, and calcined at 600 ° C for 3 h to obtain the catalyst.

[0055] 10.0 ml of catalyst was weighed and loaded into a continuous flow fixed bed reactor. The reactor was sulfurized at 320 ° C for 6 h. The reaction temperature was controlled at 360 ° C, the reaction pressure was 3.5 MPa, the reaction hydrogen-oil ratio was 1200:1, and the reaction space velocity was 1.2 h-1 In a hydrogen atmosphere with n-octane as the solvent, tung oil with an oxygen content of 12.5w% was almost completely deoxygenated under the action of a double bond saturation and hydrodeoxygenation catalyst, with a removal rate of over 99%. The liquid products were biodiesel and water. After the water was separated, sampling and analysis showed that the yield of alkanes reached 82.3w%, and the product had a pour point of -6°C and a colorless and transparent appearance.

[0056] Comparative Example 1

[0057] Weigh 8.0g of magnesium aluminum spinel, 46.0g of macroporous alumina, 2.0g of metal organic framework MIL-101, 6.4g of HZSM-5 molecular sieve, 1.9g of methyl cellulose, 1.3g of citric acid, and 1.9g of sesbania powder, mix the dry powders evenly, take 1.7g of nitric acid and add it dropwise to 60.5g of deionized water, add 11.2g of small-pore alumina to the deionized water, stir evenly, then mix with the dry powder, extrude into a cylindrical shape, dry at 110°C for 10h, and calcine at 550°C for 6h to obtain a shaped carrier.

[0058] The catalyst was prepared by the equal volume co-impregnation method. 15.6 g nickel nitrate, 16.3 g ammonium molybdate and 1.1 g phosphoric acid were prepared into an aqueous solution. The shaped carrier was placed in the co-impregnation solution for impregnation and aging for 24 h, dried at 100 ° C for 10 h, and calcined at 650 ° C for 2.5 h to obtain the catalyst.

[0059] 10.0 ml of catalyst was weighed and loaded into a continuous flow fixed bed reactor. The reactor was sulfurized at 320 ° C for 6 h. The reaction temperature was controlled at 350 ° C, the reaction pressure was 3.0 MPa, the reaction hydrogen-oil ratio was 1000:1, and the reaction space velocity was 1.0 h -1 In a hydrogen atmosphere with n-octane as the solvent, tung oil with an oxygen content of 12.0w% was almost completely deoxygenated under the action of double bond saturation and hydrodeoxygenation catalyst. The liquid products were biodiesel and water. After separation of the water, sampling and analysis showed that the yield of alkanes reached 80.2w%, and the product had a pour point of -10°C and a colorless and transparent appearance.

[0060] Comparative Example 2

[0061] Weigh 8.0 g of magnesium aluminum spinel, 48.0 g of alumina, 6.4 g of HZSM-5 molecular sieve, 1.9 g of methyl cellulose, 1.3 g of citric acid, and 1.9 g of sesbania powder, mix the dry powders evenly, take 1.7 g of nitric acid and add it dropwise to 60.5 g of deionized water, add 11.2 g of small-pore alumina to the deionized water, stir evenly, then mix with the dry powder, extrude into a cylindrical shape, dry at 110°C for 10 h, and calcine at 550°C for 6 h to obtain a shaped carrier.

[0062] The catalyst was prepared by the equal volume co-impregnation method. 15.6 g nickel nitrate, 16.3 g ammonium molybdate and 1.1 g phosphoric acid were prepared into an aqueous solution. The shaped carrier was placed in the co-impregnation solution for impregnation and aging for 24 h, dried at 100 ° C for 10 h, and calcined at 650 ° C for 2.5 h to obtain the catalyst.

[0063] 10.0 ml of catalyst was weighed and loaded into a continuous flow fixed bed reactor. The reactor was sulfurized at 320 ° C for 6 h. The reaction temperature was controlled at 350 ° C, the reaction pressure was 3.0 MPa, the reaction hydrogen-oil ratio was 1000:1, and the reaction space velocity was 1.0 h -1 In a hydrogen atmosphere with n-octane as the solvent, tung oil with an oxygen content of 12.0w% was almost completely deoxygenated under the action of double bond saturation and hydrodeoxygenation catalyst. The liquid products were biodiesel and water. After separation of the water, sampling and analysis showed that the yield of alkanes reached 79.0w%, and the product had a pour point of -6°C and a colorless and transparent appearance.

[0064] Comparative Example 3

[0065] Weigh 8.0 g of magnesium aluminum spinel, 52.4 g of alumina, 2.0 g of yttrium-modified metal organic framework Y / MIL-101, 1.9 g of methyl cellulose, 1.3 g of citric acid, and 1.9 g of sesbania powder, mix the dry powders evenly, take 1.7 g of nitric acid and add it dropwise to 60.5 g of deionized water, add 11.2 g of small-pore alumina to the deionized water, stir evenly, then mix with the dry powder, extrude into a cylindrical shape, dry at 110 ° C for 10 h, and calcine at 550 ° C for 6 h to obtain a shaped carrier.

[0066] The catalyst was prepared by the equal volume co-impregnation method. 15.6 g nickel nitrate, 16.3 g ammonium molybdate and 1.1 g phosphoric acid were prepared into an aqueous solution. The shaped carrier was placed in the co-impregnation solution for impregnation and aging for 24 h, dried at 100 ° C for 10 h, and calcined at 650 ° C for 2.5 h to obtain the catalyst.

[0067] 10.0 ml of catalyst was weighed and loaded into a continuous flow fixed bed reactor. The reactor was sulfurized at 320 ° C for 6 h. The reaction temperature was controlled at 350 ° C, the reaction pressure was 3.0 MPa, the reaction hydrogen-oil ratio was 1000:1, and the reaction space velocity was 1.0 h -1 In a hydrogen atmosphere with n-octane as the solvent, tung oil with an oxygen content of 12.0w% was almost completely deoxygenated under the action of double bond saturation and hydrodeoxygenation catalyst. The liquid products were biodiesel and water. After separation of the water, sampling and analysis showed that the yield of alkanes reached 81.8w%, and the product had a pour point of -2°C and a colorless and transparent appearance.

[0068] Of course, the present invention may have many other embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art may make various corresponding changes and modifications based on the present invention, but these corresponding changes and modifications should all fall within the scope of protection of the claims of the present invention.

Claims

1. A hydrodeoxygenation catalyst, characterized in that Based on the total mass of the catalyst as 100%, the catalyst includes 6.0w%~20.0w% of magnesium aluminum spinel, 55.0w%~75.0w% of aluminum oxide, 0.5w%~5.0w% of yttrium-modified metal organic framework Y / MIL-101, 0.5w%~14.0w% of HZSM-5 molecular sieve, 1.0w%~12.0w% of nickel oxide, 5.0w%~20.0w% of molybdenum oxide and 0.5w%~4.5w% of phosphorus pentoxide.

2. The hydrodeoxygenation catalyst according to claim 1, characterized in that Yttrium-modified metal organic framework Y / MIL-101 is prepared by immersing MIL-101 in a soluble salt solution of yttrium.

3. The hydrodeoxygenation catalyst according to claim 2, characterized in that The preparation method of the catalyst is: Magnesium aluminum spinel, macroporous alumina, yttrium-modified metal organic framework Y / MIL-101, and HZSM-5 molecular sieve are mixed to obtain a dry powder mixture, and then small-pore alumina, nitric acid, and deionized water are added, kneaded, molded, dried, and calcined to obtain a molded composite carrier; a nickel source, a molybdenum source, and a phosphorus source are impregnated into the composite carrier by an impregnation method, and then aged, dried, and calcined to obtain a catalyst.

4. The hydrodeoxygenation catalyst according to claim 3, characterized in that The mass ratio of the small pore alumina to the dry powder is 1:3-8, the mass ratio of nitric acid to the dry powder mixture and the total mass of the small pore alumina is 1:25-50, and the mass ratio of deionized water to the dry powder mixture is 1:1.1-1.

5.

5. The hydrodeoxygenation catalyst according to claim 4, characterized in that The mass ratio of the small pore alumina to the dry powder is 1:5, the mass ratio of nitric acid to the dry powder mixture and the total mass of the small pore alumina is 1:38, and the mass ratio of deionized water to the dry powder mixture is 1:1.

35.

6. The hydrodeoxygenation catalyst according to claim 3, characterized in that The drying and calcining conditions during the preparation of the shaped composite carrier are drying at 70°C~140°C for 8h~14h and calcining at 450°C~600°C for 4h~8h; the drying and calcining conditions after the impregnation step are drying at 90°C~180°C for 6h~15h and calcining at 350°C~650°C for 2.5h~7.5h.

7. The hydrodeoxygenation catalyst according to claim 6, characterized in that The drying and calcining conditions during the preparation of the shaped composite carrier are drying at 120°C for 12 hours and calcining at 500°C for 8 hours; the drying and calcining conditions after the impregnation step are drying at 120°C for 11 hours and calcining at 550°C for 3.5 hours.

8. The hydrodeoxygenation catalyst according to claim 3, characterized in that The nickel source is one or more of nickel nitrate, basic nickel carbonate and nickel acetate; the molybdenum source is one or more of ammonium dimolybdate, ammonium tetramolybdate, ammonium heptamolybdate and molybdenum oxide; and the phosphorus source is one or more of phosphoric acid, monoammonium phosphate, diammonium phosphate and ammonium phosphate.

9. The hydrodeoxygenation catalyst according to claim 3, characterized in that The pore size of the macroporous alumina is 6-9 nm, and the pore size of the microporous alumina is 3-4 nm.

10. Use of the hydrodeoxygenation catalyst according to any one of claims 1 to 9 in the hydrodeoxygenation reaction of unsaturated oils and fats.

11. The use according to claim 10, characterized in that In a continuous flow fixed bed reactor, under a hydrogen atmosphere, the reaction temperature is 320°C to 380°C; the reaction pressure is 3.0MPa to 6.0MPa; the reaction hydrogen-oil ratio is 500:1 to 1200:1; the reaction space velocity is 0.6h -1 ~2.0h -1 .

12. The use according to claim 11, characterized in that In a continuous flow fixed bed reactor, under hydrogen atmosphere, the reaction temperature was 340°C; the reaction pressure was 4.0 MPa; the reaction hydrogen-oil ratio was 1000:1; the reaction space velocity was 0.8 h -1 .

13. The use according to claim 10, characterized in that The oxygen content of unsaturated oils is 11-13w%.

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