Hydrodechlorination catalysts, methods for making and using the same

Abstract

The present application relates to the field of biological oil processing, and discloses a hydrogenation dechlorination catalyst, a preparation method and application thereof.A hydrogenation dechlorination catalyst, the catalyst comprising a modified carrier and an active metal component loaded on the modified carrier, the modified carrier comprising a carrier and an alkaline earth metal; the active metal component comprising a group VIB metal component and a group VIII metal component; the content of the alkaline earth metal, calculated as an oxide, is 20-50 wt% based on the total weight of the modified carrier; wherein the breakthrough chlorine capacity of the hydrogenation dechlorination catalyst is not less than 20%. The hydrogenation dechlorination catalyst according to the present application is used in biological oil hydrogenation dechlorination reaction, and shows good dechlorination activity and adsorption chlorine activity.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of biological oil processing, in particular to a hydrogenation dechlorination catalyst, a preparation method and application thereof. BACKGROUND

[0002] At present, the petroleum and petrochemical industry, as the main source of carbon emissions, is facing increasingly severe challenges and tests. In order to achieve the goal of carbon emission reduction, energy transformation is imminent. Biomass raw materials have the characteristics of being renewable, abundant in source and carbon neutral, which can provide diversified clean energy supply for transportation and greatly reduce carbon emissions. As a major biomass raw material, biological oil has high value conversion, which meets the requirements of circular economy, is conducive to maintaining energy security, and has higher strategic significance and social value than economic benefits, so its application has attracted widespread attention. Using biological oil as raw material, through the hydrogenation refining process, biological diesel can be directly produced, the preparation process is green and low-carbon, and it is the main way of high-value conversion of biological oil.

[0003] However, the content of chlorine and oxygen in biological oil is high, and hydrogen chloride and water are easily generated in the hydrogenation refining process. Hydrogen chloride and water will generate high-concentration hydrochloric acid under liquid phase conditions, especially under water dew point conditions, which not only causes serious corrosion to the reactor, heat exchanger and corresponding pipeline, but also forms ammonium chloride salt to block the equipment pipeline, which all pose serious safety hazards to the safe and stable operation of the device. In view of this, the removal of chlorine in biological oil has become a key technical problem.

[0004] CN104560413B and CN110628511A respectively disclose a kind of catering waste oil hydrogenation dechlorination treatment method and a kind of waste animal and vegetable oil dechlorination hydrogenation method for liquid paraffin, mainly using dechlorination adsorbent in post-positioned dechlorination reactor to adsorb the hydrogen chloride generated in refining process, but the use of high-pressure dechlorination reactor produces additional equipment investment, and part of the hydrogen chloride generated in the refining process is dissolved in the liquid phase oil at high temperature, resulting in low chlorine capacity of the dechlorination adsorbent penetration, which requires a large amount of dechlorination adsorbent to be loaded to fully adsorb hydrogen chloride. Therefore, the increase of equipment investment and the large use of dechlorination adsorbent seriously affect the high-value conversion of biological oil, and it is crucial to develop a low-cost, efficient and environmentally friendly dechlorination method. SUMMARY

[0005] The purpose of the present application is to overcome the problems existing in the prior art, and to provide a hydrogenation dechlorination catalyst, a preparation method and application thereof. The hydrogenation dechlorination catalyst according to the present application is used in the hydrogenation dechlorination reaction of biological oil, which shows good dechlorination activity and adsorption chlorine activity.

[0006] To achieve the above object, the present application provides a hydrogenation dechlorination catalyst in one aspect, which comprises a modified carrier and an active metal component supported on the modified carrier, wherein the modified carrier comprises a carrier and an alkaline earth metal; the active metal component comprises a Group VIB metal component and a Group VIII metal component; and the content of the alkaline earth metal, calculated as an oxide, is 20-50% by weight, based on the total weight of the modified carrier.

[0007] Preferably, the hydrogenation dechlorination catalyst has a breakthrough chlorine capacity of not less than 20%.

[0008] Preferably, the specific surface area of the modified carrier is 150-250 m 2 / g, preferably 180-220 m 2 / g; and the pore volume is 0.5-0.7 cm 3 / g, preferably 0.55-0.65 cm 3 / g.

[0009] Preferably, the modified carrier does not have a spinel structure.

[0010] The present application provides a method for preparing a hydrogenation dechlorination catalyst in a second aspect, which comprises the following steps:

[0011] (1) mixing a carrier precursor and an alkaline earth metal precursor to form a shaped body, and then performing optional drying and calcination to obtain a modified carrier;

[0012] (2) introducing an active metal component onto the modified carrier obtained in step (1) by an impregnation method; the active metal component comprises a Group VIB metal component and a Group VIII metal component.

[0013] Preferably, the amount of the alkaline earth metal precursor is such that the content of the alkaline earth metal, calculated as an oxide, in the prepared modified carrier is 20-50% by weight, based on the total weight of the modified carrier.

[0014] The present application provides a use of the hydrogenation dechlorination catalyst of the first aspect or the hydrogenation dechlorination catalyst prepared by the method of the second aspect in a biological oil hydrogenation dechlorination reaction in a third aspect.

[0015] The present application has the following advantages through the above technical solutions:

[0016] The catalyst of the present application uses a carrier modified with a high content of alkaline earth metal in combination with a bimetallic hydrogenation active metal component, and exhibits good dechlorination activity and adsorption activity of chlorine. When applied in a biological oil hydrogenation dechlorination reaction, the catalyst can convert organic chlorine in the oil product into hydrogen chloride and adsorb the hydrogen chloride in situ on the catalyst, realizing gas-phase adsorption of hydrogen chloride, and can solve the problem of corrosion of chlorine ions to the device in the processing of biological oil. DETAILED DESCRIPTION

[0017] The endpoints of the ranges and any values disclosed herein are not limited to the precise values recited as the exact dimensions are not considered critical for the invention. The endpoints of the ranges and any values are provided as approximations only and are understood to encompass a range of values around the end value. Unless otherwise stated, the endpoints of the ranges are not to be understood as being singularly and inclusively unless expressly stated as such.

[0018] In the present invention, “optionally” means containing or not containing, adding or not adding, using or not using.

[0019] The present invention provides a hydrodechlorination catalyst, which comprises a modified carrier and an active metal component supported on the modified carrier, the modified carrier comprising a carrier and an alkaline earth metal; the active metal component comprising a Group VIB metal component and a Group VIII metal component; the content of the alkaline earth metal, calculated as the oxide, being 20-50% by weight based on the total weight of the modified carrier.

[0020] The breakthrough chlorine capacity of the hydrodechlorination catalyst is not less than 20%.

[0021] The hydrodechlorination catalyst of the present invention has a high breakthrough chlorine capacity and exhibits good adsorption chlorine activity. In the present invention, the breakthrough chlorine capacity of the hydrodechlorination catalyst is not less than 20%, preferably 20-32%.

[0022] The breakthrough chlorine capacity of the catalyst of the present invention is measured by the high-temperature dechlorination agent chlorine capacity test method for alkaline earth metals (GB / T 38108-2019).

[0023] In the present invention, the content of the alkaline earth metal, calculated as the oxide, is 20-50% by weight based on the total weight of the modified carrier, preferably 20-40% by weight, more preferably 25-35% by weight, for example, it can be 20% by weight, 25% by weight, 30% by weight, 35% by weight, 40% by weight, 45% by weight, 50% by weight, and any value in the range constituted by any two of these values. The inventors of the present invention have found that in this preferred case, it is beneficial to improve the adsorption chlorine activity of the catalyst.

[0024] The content of the alkaline earth metal in the catalyst of the present invention is measured by X-ray fluorescence spectroscopy (XRF).

[0025] Preferably, the alkaline earth metal element is selected from at least one of magnesium, calcium, strontium and barium elements, preferably magnesium and / or calcium, more preferably magnesium. In this preferred embodiment, the catalyst has higher structural stability.

[0026] The modified carrier has a large specific surface area, a suitable pore volume, a suitable interaction force with the active metal component and a high structural stability, which is beneficial to improve the dechlorination activity and the chlorine adsorption activity.

[0027] According to the present application, preferably, the specific surface area of the modified carrier is 150-250 m 2 / g, preferably 180-220 m 2 / g.

[0028] According to the present application, preferably, the pore volume of the modified carrier is 0.5-0.7 cm 3 / g, preferably 0.55-0.65 cm 3 / g.

[0029] The specific surface area and the pore volume of the modified carrier are measured by BET physical adsorption-desorption analysis.

[0030] According to the present application, preferably, the modified carrier does not have a spinel structure. In this preferred embodiment, it is beneficial to the catalyst to fully adsorb the hydrogen chloride generated in the dechlorination reaction, which is further beneficial to improve the chlorine adsorption activity of the catalyst.

[0031] It should be noted that when the modified carrier has a spinel structure, it is not beneficial to the adsorption of hydrogen chloride by the carrier, which affects the chlorine adsorption activity of the catalyst.

[0032] The carrier according to the present application can be a conventional selection in the art. Preferably, the carrier is a heat-resistant inorganic oxide, preferably at least one selected from the group consisting of silicon oxide, aluminum oxide, zirconium oxide and titanium oxide, and more preferably aluminum oxide. With this preferred embodiment, the modified carrier has a higher specific surface area and pore volume, and has a higher crushing strength.

[0033] The hydrogen dechlorination catalyst according to the present application uses a specific type of bimetallic active component, which is more beneficial to improve the dechlorination activity compared to a single metal active component. In order to make the hydrogen dechlorination catalyst exhibit better dechlorination activity in the hydrogenation reaction, preferably, based on the total weight of the hydrogen dechlorination catalyst, the content of the Group VIB metal component is 5-20 wt%, preferably 5-15 wt%, and more preferably 10-15 wt% as calculated in terms of oxide; the content of the Group VIII metal component is 0.5-10 wt%, preferably 0.8-5 wt%, and more preferably 1-3 wt%.

[0034] In the catalyst according to the present application, the content of each component adds up to 100%.

[0035] The content of the active metal component in the catalyst according to the present application is measured by X-ray fluorescence spectroscopy (XRF).

[0036] The Group VIB metal component can be a conventional selection in the art. Preferably, the Group VIB metal component is selected from at least one of chromium, molybdenum and tungsten, preferably molybdenum and / or tungsten.

[0037] The Group VIII metal component can be a conventional selection in the art. Preferably, the Group VIII metal component is nickel and / or cobalt.

[0038] The second aspect of the present application provides a method for preparing a hydrodechlorination catalyst, which comprises the following steps:

[0039] (1) mixing a carrier precursor with an alkaline earth metal precursor to form a shape, and then performing optional drying and calcination to obtain a modified carrier;

[0040] (2) introducing an active metal component onto the modified carrier obtained in step (1) by an impregnation method; the active metal component comprises a Group VIB metal component and a Group VIII metal component;

[0041] Preferably, the amount of the alkaline earth metal precursor is such that the content of the alkaline earth metal in the modified carrier prepared, based on the total weight of the modified carrier, is 20-50% by weight, calculated as the oxide.

[0042] According to the present application, preferably, the specific surface area of the modified carrier is 150-250 m 2 / g, preferably 180-220 m 2 / g.

[0043] According to the present application, preferably, the pore volume of the modified carrier is 0.5-0.7 cm 3 / g, preferably 0.55-0.65 cm 3 / g.

[0044] According to the present application, preferably, the modified carrier does not have a spinel structure.

[0045] According to the present application, preferably, the amount of the alkaline earth metal precursor is such that the content of the alkaline earth metal in the modified carrier prepared, based on the total weight of the modified carrier, is 20-40% by weight, calculated as the oxide, more preferably 25-35% by weight.

[0046] According to the present application, preferably, the alkaline earth metal is selected from at least one of Mg, Ca, Sr and Ba elements, preferably magnesium and / or calcium, more preferably magnesium.

[0047] The present application has a wide range of selection for the type of the alkaline earth metal precursor, which can be a conventional selection in the art, as long as it contains an alkaline earth metal. Preferably, the alkaline earth metal precursor is an alkaline earth metal oxide and / or an alkaline earth metal acid salt.

[0048] According to the present application, preferably, the alkaline earth metal acid salt is selected from at least one of carbonates of alkaline earth metal, nitrates of alkaline earth metal, phosphates of alkaline earth metal and sulfates of alkaline earth metal, preferably carbonates of alkaline earth metal, more preferably basic carbonates of alkaline earth metal.

[0049] The kind of the carrier precursor according to the present application is selected from the conventional selection in the art. Preferably, the carrier precursor is selected from at least one of pseudoboehmite, boehmite, aluminum sol, acidified aluminum sol, amorphous hydrated aluminum oxide, aluminum trihydrate, monohydrate gibbsite, silicon sol, phosphoalumina, silica-alumina sol, zirconium sol and titanium sol.

[0050] Preferably, the mixing in step (1) is carried out under stirring.

[0051] The present application does not have a particular limitation on the specific conditions of the stirring, which can be properly selected according to the specific circumstances, as long as the purpose of uniform mixing can be achieved.

[0052] In the present application, the stirring can be carried out in a container with a stirring device, or in a beater.

[0053] During the mixing in step (1), water can be added or not. Generally, from the perspective of improving the uniformity of mixing, it is preferred to add water during the mixing. The present application does not have a particular limitation on the amount of water, which is subject to the smooth forming in the subsequent step. Preferably, the weight ratio of water to alkaline earth metal precursor is 3-15:1.

[0054] During the mixing in step (a), a peptizing agent and a extrusion aid can be added or not.

[0055] The present application does not have a particular limitation on the kind and amount of the peptizing agent and the extrusion aid, which can be selected conventionally in the art, subject to the smooth forming.

[0056] The present application does not have a particular limitation on the forming mode in step (1), which can adopt the conventional forming mode in the art, for example, at least one of extrusion forming, spray forming, round forming and tablet forming, and the present application preferably adopts extrusion forming.

[0057] The present application does not have a particular limitation on the shape of the formed product in step (1), which can be one or more than two of spherical, honeycomb, bird nest, sheet, strip (such as clover, disc, cylinder and Rasi ring).

[0058] The drying and calcination in step (1) can be carried out by the conventional method in the art.

[0059] The drying in step (1) can be oven drying or vacuum drying. Preferably, the drying in step (1) is carried out at a temperature of 60-280°C, preferably 80-250°C, more preferably 110-200°C, for a time period of 1-48 hours, preferably 2-24 hours, more preferably 2-12 hours.

[0060] Preferably, the calcination in step (1) is carried out at a temperature of 300-600°C, preferably 350-550°C, for a time period of 1-10 hours, preferably 2-8 hours. The calcination is generally carried out in an air atmosphere, which can include a flowing atmosphere or a static atmosphere. With this preferred embodiment, a modified support without spinel structure is obtained.

[0061] The present application does not particularly limit the order of introducing the Group VIB metal component and the Group VIII metal component in step (2), and they can be introduced together or separately.

[0062] In the preparation method provided by the present application, the impregnation method in step (2) can be saturation impregnation or supersaturation impregnation. The environment for the impregnation method is not particularly limited, and it can be carried out under a sealed condition or in an open environment according to the conventional method in the art.

[0063] Preferably, step (2) comprises: impregnating the modified support in an impregnation solution containing an active metal component compound, and then drying and calcining.

[0064] Preferably, the active metal component compound is used in an amount such that the content of the Group VIB metal component in the hydrogen dechlorination catalyst prepared is 5-20 wt%, preferably 5-15 wt%, and the content of the Group VIII metal component is 0.5-10 wt%, preferably 0.8-5 wt%, based on the total weight of the hydrogen dechlorination catalyst, in terms of oxides.

[0065] The types of the Group VIB metal component and the Group VIII metal component are the same as those in the first aspect, and will not be described here again.

[0066] The present application does not particularly limit the type of the active metal component compound, and it can be a conventional selection in the art as long as it contains an active metal component.

[0067] The present application does not particularly limit the conditions for the impregnation, and the specific impregnation method is a conventional selection in the art. For example, the conditions for the impregnation include: the impregnation temperature can be 20-300°C, preferably 20-100°C; and the impregnation time can be 1-20 hours, preferably 1-6 hours.

[0068] The drying and calcination in step (2) can be performed by using the methods conventional in the art, and the conditions can be the same as those in the drying and calcination in step (1).

[0069] The third aspect of the present application provides an application of the hydrogenation dechlorination catalyst in the first aspect or the hydrogenation dechlorination catalyst prepared by the preparation method in the second aspect in a biological oil hydrogenation dechlorination reaction.

[0070] The catalyst in the present application can be applied in the treatment of biological oil with different concentrations of organic chlorine. Preferably, the content of organic chlorine in the biological oil is not less than 10 mg / kg, and preferably is 50-100 mg / kg.

[0071] Preferably, the organic chlorine is from chlorinated organic matter in the biological oil, and the chlorinated organic matter includes at least one of chlorinated alkane, chlorinated alkene and chlorinated aromatic hydrocarbon.

[0072] The biological oil treated in the present application can be plant oil or animal oil, for example, one or more of catering waste oil, gutter oil, swill oil, palm acidified oil, coconut oil, palm oil, etc.

[0073] The conditions of the biological oil hydrogenation dechlorination reaction in the present application are performed by referring to the methods conventional in the art. Preferably, the conditions of the hydrogenation dechlorination reaction include: the temperature is 200-350℃, and preferably is 250-300℃; the pressure is 3-15 MPa, and preferably is 5-8 MPa; the liquid hourly space velocity is 0.1-10 h -1 , and preferably is 0.5-3 h -1 ; the hydrogen / oil volume ratio is 300-3000, and preferably is 800-1200.

[0074] Preferably, the hydrogenation dechlorination catalyst is vulcanized before use.

[0075] The present application does not have special limitations on the specific conditions of the vulcanization, and the vulcanization can be performed by referring to the methods conventional in the art.

[0076] The present application will be described in detail by examples below.

[0077] In the examples below, the content of organic chlorine is measured by X-ray fluorescence spectroscopy method, and the content of inorganic chlorine is measured by ion chromatography analysis method.

[0078] Example 1

[0079] (1) Preparation of modified support: 1 kg of pseudo-boehmite dry gel powder (70 wt% Al203) and 300 g of magnesium oxide, and 30 g of sesbania powder were mixed uniformly, then 1200 mL of water and 20 mL of nitric acid were added, and then kneaded and extruded on a double screw extruder to obtain Φ1.3 mm butterfly-shaped strips, which were then dried at 120°C for 3 hours and calcined at 500°C in air for 3 hours to obtain modified support A1.

[0080] (2) Preparation of hydrodechlorination catalyst: Molybdenum oxide and basic cobalt carbonate were dispersed in water to form an impregnation solution. The A1 modified support was saturated impregnated with the impregnation solution at 25°C for 1 hour, then dried at 120°C for 2 hours, and calcined at 400°C in air for 3 hours to obtain a hydrodechlorination catalyst C1. The composition and performance parameters of the catalyst are shown in Table 1.

[0081] Example 2

[0082] (1) Preparation of modified support: 1 kg of pseudo-boehmite dry gel powder (70 wt% Al203) and 377 g of calcium oxide, and 30 g of sesbania powder were mixed uniformly, then 1200 mL of water and 20 mL of nitric acid were added, and then kneaded and extruded on a double screw extruder to obtain Φ1.3 mm butterfly-shaped strips, which were then dried at 120°C for 3 hours and calcined at 500°C in air for 3 hours to obtain modified support A2.

[0083] (2) Preparation of hydrodechlorination catalyst: Molybdenum oxide and basic cobalt carbonate were dispersed in water to form an impregnation solution. The A2 modified support was saturated impregnated with the impregnation solution at 25°C for 1 hour, then dried at 120°C for 2 hours, and calcined at 400°C in air for 3 hours to obtain a hydrodechlorination catalyst C2. The composition and performance parameters of the catalyst are shown in Table 1.

[0084] Example 3

[0085] (1) Preparation of modified support: 1 kg of pseudo-boehmite dry gel powder (70 wt% Al203) and 329 g of magnesium oxide, and 30 g of sesbania powder were mixed uniformly, then 1200 mL of water and 20 mL of nitric acid were added, and then kneaded and extruded on a double screw extruder to obtain Φ1.3 mm butterfly-shaped strips, which were then dried at 120°C for 3 hours and calcined at 500°C in air for 3 hours to obtain modified support A3.

[0086] (2) Preparation of hydrodechlorination catalyst: Molybdenum oxide and basic cobalt carbonate were dispersed in water to form an impregnation solution. The A2 modified support was saturated impregnated with the impregnation solution at 25°C for 1 hour, then dried at 120°C for 2 hours, and calcined at 400°C in air for 3 hours to obtain a hydrodechlorination catalyst C2. The composition and performance parameters of the catalyst are shown in Table 1.

[0087] Comparative Example 1

[0088] The procedure of Example 1 was followed except that the amount of magnesium oxide was changed so that the content of alkaline earth metal, as oxide, in the total weight of the modified carrier was 15 wt%.

[0089] Hydrodechlorination catalyst D1 was obtained, the composition and performance parameters of which are shown in Table 1.

[0090] Comparative Example 2

[0091] The procedure of Example 1 was followed except that step (1) was not performed, and instead the pseudo-boehmite dry gel powder was first extruded into a strip, dried at 120°C for 3 hours, and calcined at 500°C in an air atmosphere for 3 hours to obtain an alumina carrier; then the alumina carrier was impregnated with an aqueous solution of magnesium nitrate (1 g / mL), dried at 120°C for 3 hours, and calcined at 500°C in an air atmosphere for 3 hours, and then the above impregnation-drying-calcination operation was repeated twice to obtain a modified carrier S1, wherein the content of alkaline earth metal, as oxide, in the modified carrier was 30 wt%.

[0092] Hydrodechlorination catalyst D2 was obtained, the composition and performance parameters of which are shown in Table 1.

[0093] Table 1

[0094]

[0095] Test Example 1

[0096] A hydrodechlorination catalyst prepared in the foregoing examples and comparative examples was loaded into a fixed-bed hydrogenation reactor, and the catalyst loading amount was 100 mL. The hydrodechlorination catalyst was subjected to programmed temperature sulfidation: using straight-run kerosene containing 2% by mass of dimethyl disulfide as a sulfidation oil, the temperature was raised at a rate of 20°C / h from 110°C to 230°C and maintained for 6 h; then the temperature was raised at a rate of 20°C / h to 360°C and maintained for 6 h. After mixing hydrogen and a biological oil feedstock (composition shown in Table 2), the mixture was introduced into the hydrogenation reactor to perform a hydrodechlorination reaction, and a reaction product was obtained. The reaction product was subjected to gas-liquid separation to obtain a dechlorinated oil product and reaction-generated water. The hydrodechlorination reaction operating conditions were: the average temperature of the reaction bed was 260°C, the pressure was 6.4 MPa, the biological oil feedstock flow rate was 100 mL / h, and the hydrogen amount was 100 L / h. The obtained oil product was analyzed for organic chlorine content, and the separated water was analyzed for inorganic chlorine content, and the results after 48 h of reaction are shown in Table 3.

[0097] Test Example 2

[0098] The method of Test Example 1 was followed, except that the catalyst was replaced by a hydrogenation deoxygenation finishing catalyst of RJW-3 type (produced by Changling Catalyst Factory). The organic chlorine content of the obtained oil product was analyzed, and the inorganic chlorine content of the separated water was analyzed. The results after 48 h of reaction are shown in Table 3.

[0099] Test Example 3

[0100] A hydrogenation deoxygenation finishing catalyst of RJW-3 type (produced by Changling Catalyst Factory) was loaded into a fixed-bed hydrogenation reactor, and the catalyst loading amount was 100 mL. A dechlorination adsorbent of WGL-A type (produced by Wenzhou Catalyst Factory) was loaded into a dechlorination reactor, and the catalyst loading amount was 100 mL. The hydrogenation dechlorination catalyst was subjected to programmed temperature sulfuration: using straight-run kerosene containing 2% by mass of dimethyl disulfide as sulfuration oil, the temperature was raised from 110°C to 230°C at a rate of 20°C / h, and maintained for 6 h; then the temperature was raised to 360°C at a rate of 20°C / h, and maintained for 6 h. After the hydrogen and the biological oil and fat raw material were mixed, the mixture was introduced into the hydrogenation reactor to perform hydrogenation reaction, and a hydrogenation reaction product was obtained. The hydrogenation reaction product was introduced into the dechlorination reactor to perform dechlorination reaction, and after dechlorination, the product was introduced into a separation system to perform separation. After gas-liquid separation, dechlorination oil product and reaction generated water were obtained. The operation conditions of the hydrogenation reactor were as follows: the average temperature of the deoxygenation reaction bed was 320°C, the average temperature of the dechlorination reaction bed was 260°C, the pressure was 6.4 MPa, the biological oil and fat flow rate was 100 mL / h, and the hydrogen flow rate was 100 L / h.

[0101] The organic chlorine content of the obtained oil product was analyzed, and the inorganic chlorine content of the separated water was analyzed. The results after 48 h of reaction are shown in Table 3.

[0102] Table 2

[0103] Item Restaurant waste oil Carbon content, % (w) 76.9 Hydrogen content, % (w) 11.7 Organochlorine content, mg / kg 50 Sulfur content, mg / kg 49.6 Nitrogen content, mg / kg 72 Oxygen content, % (w) 11 Fe, mg / kg 20 Ni, mg / kg <1 V, mg / kg <1 Na, mg / kg 2.5 Ca, mg / kg 2.7 P, mg / kg 12 Si, mg / kg 2.3

[0104] Table 3

[0105]

[0106] Note: The organic chlorine content in the oil product reflects the dechlorination activity of the hydrogenation dechlorination catalyst;

[0107] The chlorine (HCl) content in the generated water reflects the adsorption chlorine activity of the hydrogenation dechlorination catalyst.

[0108] As can be seen from the results in Table 3, the hydrogenation dechlorination catalyst of the present application is used for the hydrogenation dechlorination reaction of biological oil, and compared with the hydrogenation deoxygenation refining catalyst, it exhibits equivalent dechlorination activity, but has obviously higher adsorption chlorine activity. Moreover, the chlorine content in the product and the generated water after the hydrogenation dechlorination catalysts described in Examples 1-3 are used for the hydrogenation dechlorination reaction of biological oil is relatively low, which can avoid the corrosion of the device caused by high liquid phase chlorine content. When only the RJW-3 catalyst is used, the chlorine content in the generated water is as high as 266 mg / L, and such high chlorine content will cause serious corrosion of the device. When the RJW-3 / WGL-A is used in combination, the chlorine content in the water is still as high as 213 mg / L, and the chlorine content is still very high, which will also cause serious corrosion of the device.

[0109] The preferred embodiments of the present application are described in detail above, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as disclosed by the present application and belong to the protection scope of the present application.

Claims

1. A hydrodechlorination catalyst, comprising a modified support and an active metal component supported on the modified support, wherein the modified support comprises a support and an alkaline earth metal; the active metal component comprises a Group VIB metal component and a Group VIII metal component; the content of the alkaline earth metal, based on the total weight of the modified support, is 20-50% by weight in terms of oxide; wherein the breakthrough chlorine capacity of the hydrodechlorination catalyst is not less than 20%. The preparation method of the modified support comprises: mixing a support precursor with an alkaline earth metal precursor, shaping, and then performing optional drying and calcination to obtain the modified support. 2.The catalyst according to claim 1, wherein the breakthrough chlorine capacity of the hydrodechlorination catalyst is 20-32%. 3.The catalyst according to claim 1, wherein the content of the alkaline earth metal, based on the total weight of the modified support, is 20-40% by weight in terms of oxide. 4.The catalyst according to claim 3, wherein the content of the alkaline earth metal, based on the total weight of the modified support, is 25-35% by weight in terms of oxide. 5.The catalyst according to claim 1, wherein the alkaline earth metal is magnesium and / or calcium. 6.The catalyst according to claim 5, wherein the alkaline earth metal is magnesium. 7.The catalyst according to claim 1, wherein The specific surface area of the modified carrier is 150-250 m 2 / g, and the pore volume is 0.5-0.7 cm 3 / g. 8.The catalyst according to claim 7, wherein The specific surface area of the modified support is 180-220 m 2 / g, and the pore volume is 0.55-0.65 cm 3 / g. 9.The catalyst according to claim 1, wherein the modified support does not have a spinel structure. 10.The catalyst according to claim 1, wherein the support is alumina. 11.The catalyst according to any one of claims 1-10, wherein the content of the Group VIB metal component, based on the total weight of the hydrodechlorination catalyst, is 5-20% by weight in terms of oxide, and the content of the Group VIII metal component is 0.5-10% by weight in terms of oxide. 12.The catalyst according to claim 11, wherein the content of the Group VIB metal component, based on the total weight of the hydrodechlorination catalyst, is 5-15% by weight in terms of oxide, and the content of the Group VIII metal component is 0.8-5% by weight in terms of oxide. 13.The catalyst according to any one of claims 1-10, wherein the Group VIB metal component is molybdenum and / or tungsten; and the Group VIII metal component is nickel and / or cobalt. 14.A method for preparing a hydrodechlorination catalyst, comprising the following steps: (1) mixing a support precursor with an alkaline earth metal precursor, shaping, and then performing optional drying and calcination to obtain a modified support; (2) introducing an active metal component onto the modified support obtained in step (1) by an impregnation method; the active metal component comprises a Group VIB metal component and a Group VIII metal component; wherein the amount of the alkaline earth metal precursor is such that the content of the alkaline earth metal, based on the total weight of the modified support, is 20-50% by weight in terms of oxide. 15.The method according to claim 14, wherein ​ The specific surface area of the modified support is 150-250 m 2 The pore volume of the modified support is 0.5-0.7 cm 3 / g.

16. The method according to claim 15, wherein, The specific surface area of the modified support is 180-220 m 2 / g, and the pore volume of the modified support is 0.55-0.65 cm 3 / g.

17. The method according to claim 14, wherein, the modified support does not have a spinel structure.

18. The method according to claim 14, wherein, the amount of the alkaline earth metal precursor is such that the content of the alkaline earth metal in the modified support prepared, based on the total weight of the modified support, is 20-40% by weight in terms of oxide.

19. The method according to claim 18, wherein, the amount of the alkaline earth metal precursor is such that the content of the alkaline earth metal in the modified support prepared, based on the total weight of the modified support, is 25-35% by weight in terms of oxide.

20. The method according to claim 14, wherein, the alkaline earth metal is magnesium and / or calcium.

21. The method according to claim 20, wherein, the alkaline earth metal is magnesium.

22. The method according to claim 14, wherein, the alkaline earth metal precursor is an alkaline earth metal oxide and / or an alkaline earth metal acid salt.

23. The method according to claim 14, wherein, the support precursor is selected from at least one of pseudoboehmite, boehmite, aluminum sol, amorphous hydrated aluminum oxide, aluminum trihydrate and diaspore.

24. The method according to any one of claims 14-23, wherein, the shaping in step (1) is selected from at least one of extrusion, spray shaping, rounding and tabletting.

25. The method according to any one of claims 14-23, wherein, the drying in step (1) is carried out at a temperature of 60-280°C for a period of 1-48 hours; the calcination in step (1) is carried out at a temperature of 300-600°C for a period of 1-10 hours.

26. The method according to claim 25, wherein, the drying in step (1) is carried out at a temperature of 110-200°C for a period of 2-12 hours; the calcination in step (1) is carried out at a temperature of 350-550°C for a period of 2-6 hours.

27. The method according to any one of claims 14-23, wherein, the content of the Group VIB metal component, based on the total weight of the hydrodechlorination catalyst, is 5-20% by weight in terms of oxide; and the content of the Group VIII metal component, based on the total weight of the hydrodechlorination catalyst, is 0.5-10% by weight.

28. The method according to claim 27, wherein, the content of the Group VIB metal component, based on the total weight of the hydrodechlorination catalyst, is 5-15% by weight in terms of oxide; and the content of the Group VIII metal component, based on the total weight of the hydrodechlorination catalyst, is 0.8-5% by weight.

29. The method according to any one of claims 14-23, wherein, the Group VIB metal component is molybdenum and / or tungsten; and the Group VIII metal component is nickel and / or cobalt.

30. Use of the hydrodechlorination catalyst according to any one of claims 1-13 or prepared by the method according to any one of claims 14-29 in a hydrodechlorination reaction of a biological oil. ​ The content of organic chlorine in the biological oil is not less than 10 mg / kg. The content of organic chlorine in the biological oil is not less than 10 mg / kg.

Images