Hydrodechlorination catalyst and preparation method and application thereof

Abstract

The invention relates to the field of biological oil treatment and discloses a hydrodechlorination catalyst as well as a preparation method and application thereof. The hydrodechlorination catalyst comprises a modified carrier and an active metal component loaded on the modified carrier, and the modified carrier comprises a carrier and alkaline earth metal; the active metal component comprises a group VIB metal component and a group VIII metal component; on the basis of the total weight of the modified carrier, the content of alkaline earth metal in terms of oxide is 20-50 wt%; wherein the breakthrough chlorine capacity of the hydrodechlorination catalyst is not less than 20%. The hydrodechlorination catalyst provided by the invention is used in a hydrodechlorination reaction of biological oil and fat, and shows good dechlorination activity and chlorine adsorption activity.

Description

Technical Field

[0001] The invention relates to the field of biological oil and fat processing, and in particular to a hydrodechlorination catalyst and a preparation method and application thereof. Background Art

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

[0003] However, bio-oils contain high levels of chlorine and oxygen, which can easily generate hydrogen chloride and water during the hydrorefining process. Hydrogen chloride and water will generate highly concentrated hydrochloric acid under liquid phase conditions, especially under water dew point conditions, which will not only cause serious corrosion to the reactor, heat exchanger and corresponding pipelines, but also form ammonium chloride salts to block equipment pipelines. These problems pose serious safety hazards to the safe and stable operation of the device. In view of this, the removal of chlorine in bio-oils has become a key technical problem.

[0004] CN104560413B and CN110628511A respectively disclose a method for treating waste restaurant oil by hydrogenation and dechlorination and a method for preparing liquid paraffin by dechlorination and hydrogenation of waste animal and plant oils. The method mainly uses a dechlorination adsorbent in a post-dechlorination reactor to adsorb the hydrogen chloride generated during the refining process. However, the use of a high-pressure dechlorination reactor generates additional equipment investment. At the same time, part of the hydrogen chloride generated during the refining process dissolves in the liquid phase oil product at high temperature, resulting in a low penetration capacity of the dechlorination adsorbent. A large amount of dechlorination adsorbent needs to be loaded to fully adsorb the hydrogen chloride. Therefore, the increase in equipment investment and the large-scale use of dechlorination adsorbents seriously affect the high-value conversion of bio-oils, and it is crucial to develop a low-cost, efficient and environmentally friendly dechlorination method. Summary of the invention

[0005] The purpose of the present invention is to overcome the problems existing in the prior art and provide a hydrodechlorination catalyst and its preparation method and application. The hydrodechlorination catalyst of the present invention is used in the hydrodechlorination reaction of bio-oil, and exhibits good dechlorination activity and chlorine adsorption activity.

[0006] In order to achieve the above object, the present invention provides a hydrodechlorination catalyst, 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 metal component of Group VIB and a metal component of Group VIII; the content of the alkaline earth metal in terms of oxide is 20-50% by weight based on the total weight of the modified carrier;

[0007] Wherein, the breakthrough chlorine capacity of the hydrodechlorination catalyst is not less than 20%.

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

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

[0010] A second aspect of the present invention provides a method for preparing a hydrodechlorination catalyst, the method comprising the following steps:

[0011] (1) mixing a carrier precursor and an alkaline earth metal precursor to form a mixture, and then optionally drying and calcining the mixture to obtain a modified carrier;

[0012] (2) introducing active metal components onto the modified support obtained in step (1) by impregnation; the active metal components include Group VIB metal components and Group VIII metal components;

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

[0014] The third aspect of the present invention provides an application of the hydrodechlorination catalyst described in the first aspect or the hydrodechlorination catalyst prepared by the preparation method described in the second aspect in the hydrodechlorination reaction of bio-oil.

[0015] Through the above technical solution, the beneficial effects of the present invention include:

[0016] The catalyst of the present invention adopts a carrier modified with a high content of alkaline earth metal and a bimetallic hydrogenation active metal component, and exhibits good dechlorination activity and chlorine adsorption activity. When applied to the hydrogenation and dechlorination reaction of bio-oil, it can convert organic chlorine in the oil into hydrogen chloride and adsorb hydrogen chloride on the catalyst in situ, realize gas phase adsorption of hydrogen chloride, and solve the problem of chloride ion corrosion on the device in the process of bio-oil processing. DETAILED DESCRIPTION

[0017] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0018] In the present invention, "optionally" means containing or not containing, adding or not adding, adopting or not adopting.

[0019] In one aspect, the present invention provides a hydrodechlorination catalyst, the catalyst comprising 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 comprises a VIB group metal component and a VIII group metal component; based on the total weight of the modified carrier, the content of the alkaline earth metal in terms of oxide is 20-50% by weight;

[0020] Wherein, 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 chlorine adsorption activity. In the present invention, the breakthrough chlorine capacity of the hydrodechlorination catalyst is not less than 20%, preferably 20-32%.

[0022] The penetration chlorine capacity of the catalyst described in the present invention is measured by the chlorine capacity test method of alkaline earth metal high-temperature dechlorination agent (GB / T38108-2019).

[0023] In the present invention, based on the total weight of the modified support, the content of the alkaline earth metal in terms of oxide is 20-50% by weight, 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 formed by any two of these values. The inventors of the present invention have found that in this preferred case, the chlorine adsorption activity of the catalyst is improved.

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

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

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

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

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

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

[0030] According to the present invention, preferably, the modified carrier does not have a spinel structure. In this preferred embodiment, the catalyst is conducive to fully adsorbing hydrogen chloride generated by the dechlorination reaction, and further conducive to improving the chlorine adsorption activity of the catalyst.

[0031] It should be noted that when the modified carrier has a spinel structure, it will be unfavorable for the carrier to adsorb hydrogen chloride, affecting the chlorine adsorption activity of the catalyst.

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

[0033] The hydrodechlorination catalyst of the present invention adopts a specific type of bimetallic active component, which is more conducive to improving the dechlorination activity compared with the monometallic active component. In order to make the hydrodechlorination catalyst show better dechlorination activity in the hydrogenation reaction, preferably, based on the total weight of the hydrodechlorination catalyst, the content of the VIB group metal component is 5-20wt%, preferably 5-15wt%, more preferably 10-15wt% in terms of oxide; the content of the VIII group metal component is 0.5-10wt%, preferably 0.8-5wt%, more preferably 1-3wt%.

[0034] In the catalyst of the present invention, the sum of the contents of the various components is 100%.

[0035] The content of active metal components in the catalyst of the present invention is measured by X-ray fluorescence spectrometry (XRF).

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

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

[0038] A second aspect of the present invention provides a method for preparing a hydrodechlorination catalyst, the method comprising the following steps:

[0039] (1) mixing a carrier precursor and an alkaline earth metal precursor to form a mixture, and then optionally drying and calcining the mixture to obtain a modified carrier;

[0040] (2) introducing active metal components onto the modified support obtained in step (1) by impregnation; the active metal components include Group VIB metal components and Group VIII metal components;

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

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

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

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

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

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

[0047] The present invention has a wide range of choices for the alkaline earth metal precursor, which can be any conventional choice in the art, as long as it contains 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 invention, preferably, the alkaline earth metal acid salt is selected from at least one of alkaline earth metal carbonates, alkaline earth metal nitrates, alkaline earth metal phosphates and alkaline earth metal sulfates, preferably alkaline earth metal carbonates, more preferably alkaline earth metal basic carbonates.

[0049] The type of the carrier precursor of the present invention is a conventional choice in the art. Preferably, the carrier precursor is selected from at least one of pseudo-boehmite, boehmite, aluminum sol, acidified aluminum sol, amorphous hydrated aluminum oxide, aluminum trihydrate, boehmite, silica sol, phosphate aluminum sol, silica aluminum sol, zircon sol and titanium sol.

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

[0051] The present invention has no particular limitation on the specific stirring conditions, which can be appropriately selected according to the specific circumstances, as long as the purpose of uniform mixing can be achieved.

[0052] In the present invention, the stirring may be performed in a container with a stirring device or in a beater.

[0053] In the mixing process of step (1), water may be added or not. Generally, from the perspective of improving the uniformity of mixing, it is preferred to add water during the mixing process. The present invention does not specifically limit the amount of water to ensure smooth subsequent molding. Preferably, the weight ratio of water to alkaline earth metal precursor is 3-15:1.

[0054] During the mixing process of step (a), a peptizing agent and an extrusion aid may or may not be added.

[0055] The present invention has no particular limitation on the type and amount of the peptizer and the extrusion aid, which can be selected conventionally in the art to ensure smooth molding.

[0056] The present invention does not particularly limit the molding method of step (1), and can adopt molding methods commonly used in the art, such as at least one of extrusion molding, spray molding, spheronization and tableting. The present invention preferably adopts extrusion molding.

[0057] The present invention also has no particular limitation on the shape of the molded product obtained by molding in step (1), and it can be one or more of spherical, honeycomb, bird's nest, sheet, strip (such as clover, disc, cylinder and Raschig ring).

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

[0059] The drying in step (1) can be oven drying or vacuum drying. Preferably, the drying conditions in step (1) include: a temperature of 60-280°C, preferably 80-250°C, more preferably 110-200°C; a time of 1-48 hours, preferably 2-24 hours, more preferably 2-12 hours.

[0060] Preferably, the calcination conditions in step (1) include: a temperature of 300-600°C, preferably 350-550°C; a time of 1-10 hours, preferably 2-8 hours. The calcination is generally carried out in an air atmosphere, which may include a flowing atmosphere or a static atmosphere. This preferred embodiment is conducive to obtaining a modified carrier without a spinel structure.

[0061] The present invention has no particular limitation on the order of introducing the Group VIB metal component and the Group VIII metal component in step (2); they may be introduced together or separately.

[0062] In the preparation method provided by the present invention, the impregnation method in step (2) can be a saturated impregnation method or a supersaturated impregnation method. There is no particular limitation on the environment of the impregnation method, and the impregnation method can be carried out in a sealed condition or in an open environment according to conventional methods in the art.

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

[0064] Preferably, the amount of the active metal component-containing compound is such that in the prepared hydrodechlorination catalyst, based on the total weight of the hydrodechlorination catalyst, the content of the VIB group metal component is 5-20wt%, preferably 5-15wt%, calculated as oxide; the content of the VIII group metal component is 0.5-10wt%, preferably 0.8-5wt%.

[0065] The types of the VIB group metal component and the VIII group metal component of the present invention are the same as those of the first aspect and will not be described in detail herein.

[0066] The present invention has no particular limitation on the type of the active metal component-containing compound, as long as it contains active metal components, and can be any conventional choice in the art.

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

[0068] The drying and calcining in step (2) can be carried out by conventional methods in the art, and the conditions can be the same as those of the drying and calcining in step (1).

[0069] The third aspect of the present invention provides an application of the hydrodechlorination catalyst described in the first aspect or the hydrodechlorination catalyst prepared by the preparation method described in the second aspect in the hydrodechlorination reaction of bio-oil.

[0070] The catalyst of the present invention can be applied to the treatment of bio-oils with different organochlorine concentrations. Preferably, the content of organochlorine in the bio-oil is not less than 10 mg / kg, preferably 50-100 mg / kg.

[0071] Preferably, the organic chlorine comes from chlorine-containing organic matter in biological oils and fats, and the chlorine-containing organic matter includes at least one of chlorinated alkanes, chlorinated olefins and chlorinated aromatics.

[0072] The present invention has a wide range of choices for the types of biological fats to be processed, which can be plant fats or animal fats, for example, one or more of waste cooking oil, swill oil, palmitic acid oil, coconut oil, palm oil, etc.

[0073] The conditions for the bio-oil hydrodechlorination reaction of the present invention are carried out in accordance with conventional methods in the art. Preferably, the conditions for the hydrodechlorination reaction include: a temperature of 200-350°C, preferably 250-300°C; a pressure of 3-15MPa, preferably 5-8MPa; a liquid hourly volume space velocity of 0.1-10h -1 , preferably 0.5-3h -1 ; The volume ratio of hydrogen to oil is 300-3000, preferably 800-1200.

[0074] Preferably, the hydrodechlorination catalyst is sulfided before use.

[0075] The present invention has no particular limitation on the specific conditions of the vulcanization, and the vulcanization can be carried out according to conventional methods in the art.

[0076] The present invention will be described in detail below through examples.

[0077] In the following examples, the organic chlorine content parameter is measured by X-ray fluorescence spectroscopy; the inorganic chlorine content is measured by ion chromatography analysis.

[0078] Example 1

[0079] (1) Preparation of modified carrier: 1 kg of pseudo-boehmite dry rubber powder (70 wt% Al2O3) and 300 g of magnesium oxide and 30 g of sesbania powder were mixed evenly, and then 1200 ml of water and 20 mL of nitric acid were added. The mixture was kneaded and extruded on a twin-screw extruder to obtain butterfly-shaped strips of Φ1.3 mm. The strips were then dried at 120°C for 3 hours and calcined at 500°C in air atmosphere for 3 hours to obtain modified carrier A1.

[0080] (2) Preparation of hydrodechlorination catalyst: Molybdenum oxide and basic cobalt carbonate were dispersed in water to form an impregnation solution. The impregnation solution was used to saturate the A1 modified carrier at 25°C for 1 hour, then dried at 120°C for 2 hours, and calcined at 400°C in an air atmosphere 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 carrier: 1 kg of pseudo-boehmite dry rubber powder (70 wt% Al2O3), 377 g of calcium oxide, and 30 g of sesbania powder were mixed evenly, 1200 ml of aqueous solution and 20 mL of nitric acid were added, and then kneaded and extruded on a twin-screw extruder to obtain butterfly-shaped strips of Φ1.3 mm, which were then dried at 120°C for 3 hours and calcined at 500°C in air atmosphere for 3 hours to obtain modified carrier A2.

[0083] (2) Preparation of hydrodechlorination catalyst: Molybdenum oxide and basic cobalt carbonate were dispersed in water to form an impregnation solution. The impregnation solution was used to saturate the A2 modified carrier at 25°C for 1 hour, then dried at 120°C for 2 hours, and calcined at 400°C in an air atmosphere 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 carrier: 1 kg of pseudo-boehmite dry rubber powder (70 wt% Al2O3), 329 g of magnesium oxide, and 30 g of sesbania powder were mixed evenly, 1200 ml of aqueous solution and 20 mL of nitric acid were added, and then kneaded and extruded on a twin-screw extruder to obtain butterfly-shaped strips of Φ1.3 mm, which were then dried at 120°C for 3 hours and calcined at 500°C in air atmosphere for 3 hours to obtain modified carrier A3.

[0086] (2) Preparation of hydrodechlorination catalyst: Molybdenum oxide and basic nickel carbonate were dispersed in water to form an impregnation solution. The impregnation solution was used to saturate the A3 modified carrier at 25°C for 1 hour, then dried at 120°C for 2 hours, and calcined at 400°C in an air atmosphere for 3 hours to obtain a hydrodechlorination catalyst C3. The composition and performance parameters of the catalyst are shown in Table 1.

[0087] Comparative Example 1

[0088] The method of Example 1 was followed, except that the amount of magnesium oxide was changed so that the content of alkaline earth metal calculated as oxide was 15 wt % based on the total weight of the modified support.

[0089] The hydrodechlorination catalyst D1 was obtained, and its composition and performance parameters are shown in Table 1.

[0090] Comparative Example 2

[0091] The method of Example 1 is followed, except that step (1) is not performed. Instead, the pseudo-boehmite dry rubber powder is first extruded into strips, 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 an aqueous solution of magnesium nitrate (1 g / mL) is impregnated on the alumina carrier, 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 is repeated twice to obtain a modified carrier S1, wherein the content of alkaline earth metals in the modified carrier as oxides is 30 wt%.

[0092] The hydrodechlorination catalyst D2 was obtained, and its composition and performance parameters are shown in Table 1.

[0093] Table 1

[0094]

[0095] Test Example 1

[0096] The fixed bed hydrogenation reactor was loaded with the hydrodechlorination catalyst prepared in the above examples and comparative examples, with a catalyst loading of 100 mL. The hydrodechlorination catalyst was subjected to programmed temperature rise sulfurization: straight-run kerosene containing 2% dimethyl disulfide by mass was used as sulfurized oil, and the temperature was raised from 110°C to 230°C at a rate of 20°C / h, and maintained for 6 hours; then the temperature was raised to 360°C at a rate of 20°C / h, and maintained for 6 hours. After the hydrogen and the bio-oil raw material (composition is shown in Table 2) were mixed, they entered the hydrogenation reactor for hydrodechlorination reaction to obtain a reaction product. The reaction product was separated into gas and liquid to obtain a dechlorinated oil product and reaction generated water. The operating conditions of the hydrodechlorination reaction were: the average temperature of the reaction bed was 260°C, the pressure was 6.4MPa, the bio-oil flow rate was 100mL / h, and the hydrogen volume was 100L / h. The obtained oil product was analyzed for organic chlorine content, and the separated water was analyzed for inorganic chlorine content. The results of the reaction for 48 hours are shown in Table 3.

[0097] Test Example 2

[0098] The method of Test Example 1 was followed, except that the catalyst was replaced with RJW-3 hydrodeoxygenation refining catalyst (produced by Changling Catalyst Factory). The organic chlorine content of the obtained oil was analyzed, and the inorganic chlorine content of the separated water was analyzed. The results of the reaction for 48 hours are shown in Table 3.

[0099] Test Example 3

[0100] RJW-3 hydrodeoxygenation refining catalyst (produced by Changling Catalyst Factory) was loaded into the fixed bed hydrogenation reactor, with a catalyst loading of 100 mL; WGL-A dechlorination adsorbent (produced by Wenzhou Catalyst General Factory) was loaded into the dechlorination reactor, with a catalyst loading of 100 mL. The hydrodechlorination catalyst was subjected to programmed temperature rise sulfurization: straight-run kerosene containing 2% dimethyl disulfide by mass was used as the sulfurized oil, and the temperature was raised from 110°C to 230°C at a rate of 20°C / h, and maintained for 6 hours; then the temperature was raised to 360°C at a rate of 20°C / h, and maintained for 6 hours. After the hydrogen and bio-oil raw materials were mixed, they entered the hydrogenation reactor for hydrogenation reaction to obtain hydrogenation reaction products. The hydrogenation reaction products entered the dechlorination reactor for dechlorination reaction, and the dechlorinated products entered the separation system for separation. After gas-liquid separation, dechlorinated oil products and reaction water were obtained. The operating conditions of the hydrogenation reactor are as follows: the average temperature of the deoxygenation reaction bed is 320°C, the average temperature of the dechlorination reaction bed is 260°C, the pressure is 6.4MPa, the bio-oil flow rate is 100mL / h, and the hydrogen volume is 100L / h.

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

[0102] Table 2

[0103] project Waste cooking oil Carbon content, %(w) 76.9 Hydrogen content, %(w) 11.7 Organic chlorine 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 oil products reflects the dechlorination activity of the hydrodechlorination catalyst;

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

[0108] It can be seen from the results of Table 3 that the hydrodechlorination catalyst of the present invention is used for the hydrodechlorination reaction of bio-oil, and compared with the hydrodeoxygenation refining catalyst, it shows a considerable dechlorination activity, but has a significantly higher chlorine adsorption activity. Moreover, the hydrodechlorination catalyst described in Examples 1-3 participates in the hydrodechlorination reaction of bio-oil and has a low chlorine content in the product and the generated water, which can avoid the corrosion of the device caused by the high chlorine content in the liquid phase. When only RJW-3 type catalyst is used, the chlorine content in the generated water is as high as 266mg / L, and such a high chlorine content will cause serious corrosion to the device. When RJW-3 / WGL-A is used in combination, the chlorine content in the water is still as high as 213mg / L, and the chlorine content is still very high, which will also cause serious corrosion to the device.

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

Claims

1. A hydrodechlorination catalyst, comprising 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 metal component of Group VIB and a metal component of Group VIII; and the content of the alkaline earth metal in terms of oxide is 20-50% by weight based on the total weight of the modified carrier; in, The breakthrough chlorine capacity of the hydrodechlorination catalyst is not less than 20%.

2. The catalyst according to claim 1, wherein The breakthrough chlorine capacity of the hydrodechlorination catalyst is 20-32%; Preferably, the content of the alkaline earth metal calculated as oxide is 20-40 wt %, more preferably 25-35 wt %, based on the total weight of the modified support; Preferably, the alkaline earth metal is magnesium and / or calcium, preferably magnesium; Preferably, the specific surface area of ​​the modified carrier is 150-250m 2 / g, preferably 180-220m 2 / g; pore volume is 0.5-0.7cm 3 / g, preferably 0.55-0.65cm 3 / g; Preferably, the modified support does not have a spinel structure; Preferably, the support is alumina.

3. The catalyst according to claim 1 or 2, wherein Based on the total weight of the hydrodechlorination catalyst, the content of the VIB Group metal component is 5-20wt%, preferably 5-15wt%, calculated as oxide; The content of the Group VIII metal component is 0.5-10wt%, preferably 0.8-5wt%; Preferably, the Group VIB metal component is molybdenum and / or tungsten; Preferably, the Group VIII metal component is nickel and / or cobalt.

4. A method for preparing a hydrodechlorination catalyst, the method comprising the following steps: (1) mixing a carrier precursor and an alkaline earth metal precursor to form a mixture, and then optionally drying and calcining the mixture to obtain a modified carrier; (2) introducing active metal components onto the modified support obtained in step (1) by impregnation; the active metal components include Group VIB metal components and Group VIII metal components; The amount of the alkaline earth metal precursor used is such that the content of the alkaline earth metal in the prepared modified carrier, calculated as oxide, is 20-50% by weight based on the total weight of the modified carrier.

5. The method according to claim 4, wherein: The specific surface area of ​​the modified carrier is 150-250m 2 / g, preferably 180-220m 2 / g; the pore volume of the modified carrier is 0.5-0.7cm 3 / g, preferably 0.55-0.65cm 3 / g; Preferably, the modified support does not have a spinel structure.

6. The method according to claim 4, wherein: The amount of the alkaline earth metal precursor is such that the content of the alkaline earth metal in the obtained modified carrier, calculated as oxide, is 20-40% by weight, more preferably 25-35% by weight, based on the total weight of the modified carrier; Preferably, the alkaline earth metal is magnesium and / or calcium, preferably magnesium; Preferably, the alkaline earth metal precursor is an alkaline earth metal oxide and / or an alkaline earth metal acid salt; Preferably, the alkaline earth metal acid salt is selected from at least one of alkaline earth metal carbonates, alkaline earth metal nitrates, alkaline earth metal phosphates and alkaline earth metal sulfates, preferably alkaline earth metal carbonates, more preferably alkaline earth metal basic carbonates.

7. The method according to claim 4, wherein: The carrier precursor is selected from at least one of pseudo-boehmite, boehmite, aluminum sol, amorphous hydrated aluminum oxide, aluminum oxide trihydrate and boehmite.

8. The method according to any one of claims 4 to 7, wherein: The molding in step (1) is selected from at least one of extrusion molding, spray molding, spheronization molding and tableting molding; Preferably, the drying conditions in step (1) include: a temperature of 60-280° C., preferably 110-200° C.; a time of 1-48 hours, preferably 2-12 hours; Preferably, the calcination conditions in step (1) include: a temperature of 300-600° C., preferably 350-550° C.; and a calcination time of 1-10 hours, preferably 2-6 hours.

9. The method according to any one of claims 4 to 8, wherein: Based on the total weight of the hydrodechlorination catalyst, the content of the VIB Group metal component is 5-20wt%, preferably 5-15wt%, calculated as oxide; The content of the Group VIII metal component is 0.5-10wt%, preferably 0.8-5wt%; Preferably, the Group VIB metal component is molybdenum and / or tungsten; Preferably, the Group VIII metal component is nickel and / or cobalt.

10. Use of the hydrodechlorination catalyst according to any one of claims 1 to 3 or the hydrodechlorination catalyst prepared by the preparation method according to any one of claims 4 to 9 in the hydrodechlorination reaction of bio-oil; Preferably, the content of organic chlorine in the biological fat is not less than 10 mg / kg.

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