CN109569707B - Catalyst for preparing fuel oil by tar hydrogenation - Google Patents
Catalyst for preparing fuel oil by tar hydrogenation Download PDFInfo
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- CN109569707B CN109569707B CN201710895330.5A CN201710895330A CN109569707B CN 109569707 B CN109569707 B CN 109569707B CN 201710895330 A CN201710895330 A CN 201710895330A CN 109569707 B CN109569707 B CN 109569707B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
- B01J29/7415—Zeolite Beta
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/10—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing platinum group metals or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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Abstract
The invention relates to a catalyst for preparing fuel oil by hydrogenation of tar, which mainly solves the problems of low desulfurization rate, denitrification rate and fuel oil yield in the prior art. The invention adopts the catalyst for preparing the fuel oil by hydrogenating the tar, and the catalyst comprises an active component, an auxiliary agent and a carrier; the technical scheme that the active component comprises Rh and the auxiliary comprises alkali metal achieves better effect, and can be used for preparing fuel oil by hydrogenation of coal tar and/or ethylene tar.
Description
Technical Field
The invention relates to the technical field of preparing fuel oil by hydrogenating tar, in particular to a catalyst for hydrogenating the fuel oil prepared from the tar.
Background
The problem of energy supply has become a prominent problem in the economic development and safety of China. Under the condition of limited petroleum resources, the energy and fuel source ways are expanded, and the development of deep processing technology and products has important display and strategic significance. Coal tar is a byproduct of coal coking, dry distillation and gasification processes, and the domestic yield of the coal tar exceeds 1000 million tons. At present, a part of coal tar in China is used for extracting chemicals such as naphthol and the like. The other part is simply treated and then burnt as inferior fuel oil to generate a large amount of sewage or NOx、SOxAnd the like. The deep removal of hetero atoms such as sulfur, nitrogen and the like and the saturation of unsaturated olefin and aromatic hydrocarbon of the coal tar raw material can be completed by adopting a hydrogenation process so as to improve the H/C ratio of the coal tar, improve the stability of the coal tar, obtain high-quality fuel oil and reduce the environmental pollution. Ethylene tar is a byproduct in the production process of ethylene, and mainly contains aromatic compound and carbonThe hydrogen ratio is high and the ash content is low. Ethylene tar is mostly used as a poor fuel except for a small amount of carbon black, but the ethylene tar is not easy to burn, has low heat value, and is easy to generate black smoke and coke during burning to cause environmental pollution. Therefore, the fuel oil produced by the hydrogenation process by using the tar as the raw material can generate obvious economic and social benefits and effectively relieve the current situation of energy shortage in China.
Research and development of a technology for producing gasoline and diesel oil by hydrogenating coal tar have been developed and rapidly developed in China, for example, a document "experimental research on producing fuel oil by hydrogenating coal tar" (Tibet. Industrial safety and environmental protection, 2007,33(7):56-57) and a document "experimental research on producing gasoline and diesel oil by hydrogenating high-temperature coal tar" (Yanjing, Lvcaishan, Liuyi Hua, Dajian Wen. petrochemical, 2006,35(1):33-36) are respectively carried out on the experimental research on hydrogenating coal tar, but the octane number of the obtained gasoline and the cetane number of the diesel oil are low and do not meet the national standard requirements. The reports on the hydrogenation of coal tar at home and abroad are few, and only a few reports (for example, patent US3253202) are related. The research on the technology of producing gasoline and diesel oil by hydrogenating ethylene tar is less, and only a few reports (for example, patent CN200810228387.0) are related at present.
The tar hydrogenation technology aims at producing high-quality gasoline and diesel fuel and improving the yield of oil products as much as possible, and is mainly characterized by a catalyst. The final effect of preparing fuel oil by hydrogenating tar depends on the performance of the catalyst, and the components (active components, auxiliaries and carriers), the preparation method and conditions (forming conditions, roasting temperature, roasting medium and the like) of the catalyst determine the performance of the catalyst. Catalysts having the same chemical composition have different microscopic properties (such as the size of active material grains, the pore size distribution of the catalyst, the dispersion uniformity of active components on the surface of the catalyst, etc.) if the preparation method and conditions are different, resulting in great differences in the performance of the catalysts.
When the catalyst in the prior art is used for preparing fuel oil by hydrogenation of coal tar and/or ethylene tar, the yield of the fuel oil is low, and the sulfur content and the nitrogen content in the fuel oil are high.
Disclosure of Invention
The invention aims to solve the technical problems of low desulfurization rate, denitrification rate and fuel oil yield in the prior art, and provides a hydrogenation catalyst for preparing fuel oil from tar, which has the advantages of high desulfurization rate, denitrification rate and fuel oil yield.
The second technical problem to be solved by the present invention is a method for preparing the catalyst.
The third technical problem to be solved by the present invention is to use the catalyst described in one of the above technical problems.
In order to solve one of the above technical problems, the technical solution of the present invention is as follows:
the catalyst for preparing the fuel oil by hydrogenating the tar comprises an active component, an auxiliary agent and a carrier; the active component comprises Rh, and the auxiliary comprises alkali metal. The auxiliary agent increases the desulfurization rate, the denitrification rate and the gasoline and diesel oil yield.
In the technical scheme, the content of the active component is preferably 0.5-20 g/L.
In the technical scheme, the content of the auxiliary agent is preferably 0.5-10 g/L.
In the above technical solution, the alkali metal preferably includes at least one of K and Cs.
In the above technical scheme, the auxiliary agent further comprises an alkaline earth metal.
In the above-described embodiment, the alkaline earth metal preferably includes at least one of Ca and Mg.
The alkali metal and the alkaline earth metal have synergistic effect in the aspects of improving the desulfurization rate, the denitrification rate and the gasoline and diesel oil yield. The weight ratio between the alkali metal and the alkaline earth metal is not particularly limited, but is, for example, not limited to, 0.1 to 10, and more specific examples of the ratio may be 0.201, 0.301, 0.401, 0.501, 0.801, 0.901, 1.01, 1.501, 2.001, 2.501, 3.001, 3.501, 4.001, 4.501, 5.001, 5.501, 6.001, 6.501, 7.001, 7.501, 8.001, 8.501, 9.001, 9.51, and the like.
In the above technical solutions, as one of more preferable technical solutions, the alkaline earth metal includes Ca and Mg, and the two elements have a synergistic effect in improving the desulfurization rate, the denitrification rate, and the fuel yield. In this case, the weight ratio of Ca to Mg is not particularly limited, but is, for example, 0.1 to 10, and more specific examples of the ratio may be 0.201, 0.301, 0.401, 0.501, 0.801, 0.901, 1.01, 1.501, 2.001, 2.501, 3.001, 3.501, 4.001, 4.501, 5.001, 5.501, 6.001, 6.501, 7.001, 7.501, 8.001, 8.501, 9.001, 9.501, and the like.
In the above-mentioned technical solution, as a second preferable technical solution, the alkali metal includes K and Cs, and the two elements have a synergistic effect in improving the desulfurization rate, the denitrification rate and the fuel yield. In this case, the weight ratio of K to Cs is not particularly limited, but is, for example, 0.1 to 10, and more specific examples of the ratio may be 0.201, 0.301, 0.401, 0.501, 0.801, 0.901, 1.01, 1.501, 2.001, 2.501, 3.001, 3.501, 4.001, 4.501, 5.001, 5.501, 6.001, 6.501, 7.001, 7.501, 8.001, 8.501, 9.001, 9.501, and the like.
In the above-mentioned technical solutions, the support is not particularly limited, and those skilled in the art can select it reasonably without inventive work, but preferably at least one of alumina and zeolite Beta.
In the above technical solution, the carrier more preferably comprises alumina and Beta zeolite.
In the technical scheme, the weight part ratio of the alumina to the Beta zeolite is preferably 0.5-10. Such as, but not limited to, 1.01, 1.51, 2.01, 2.51, 3.01, 3.51, 4.01, 4.51, 5.01, 5.51, 6.01, 7.01, 8.01, 9.01, and the like.
To solve the second technical problem, the technical solution of the present invention is as follows:
the method for preparing the catalyst according to any of the preceding technical solutions, comprising the steps of:
(1) mixing the carrier with an active component solution and an auxiliary agent solution;
(2) drying
(3) And (4) roasting.
In the above technical solution, the drying process conditions are not particularly limited, for example, but not limited to, the drying temperature is 60-120 ℃, and the drying temperature is, for non-limiting example, 80 ℃, 90 ℃, 100 ℃, 110 ℃ and the like in this range.
In the above technical solution, the drying time is, for example, but not limited to, at least 4 hours, for example, 4 to 18 hours, and non-limiting examples in this range include 5, 6, 7, 8, 9, 10, 11, 12, and the like.
In the above technical scheme, the baking temperature is preferably 300 to 700 ℃, for example, but not limited to 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃ and the like.
In the above technical scheme, the time for the calcination is preferably 1 to 8 hours, such as but not limited to 2.0 hours, 2.5 hours, 3.0 hours, 3.5 hours, 4.0 hours, 4.5 hours, 5.0 hours, 5.5 hours, 6.0 hours, 6.5 hours, 7.0 hours, 7.5 hours and the like.
In the above technical solution, the atmosphere for calcination is preferably an oxygen-containing atmosphere, such as but not limited to air.
In the above technical solution, the shape of the hydrogenation catalyst is not particularly limited, and may be, for example, a sphere, a bar, a ring, a wheel, a cylinder, a clover or a sheet.
In the above technical scheme, the drying equipment for catalyst preparation may be a commonly used vacuum drying oven, forced air drying oven, rotary dryer, spray dryer, caterpillar dryer or film dryer, etc.
In the above technical scheme, the roasting equipment for catalyst preparation can be a common vertical continuous roasting furnace, a drum roasting furnace or a kiln roasting furnace, etc.
To solve the third technical problem, the technical scheme of the invention is as follows: the application of the catalyst in the technical scheme of one of the technical problems in the preparation of fuel oil by hydrogenation of coal tar and/or ethylene tar.
The technical key of the invention is the selection of the catalyst, and for the specific method, the technical personnel in the field can reasonably select the catalyst without creative labor. For example:
the method for preparing fuel oil by hydrogenating tar comprises the steps of taking dehydrated medium-temperature coal tar and hydrogen as raw materials, filling a hydrogenation catalyst in a fixed bed reactor, and contacting the reaction raw materials with the catalyst in any one of the technical schemes to carry out tar hydrogenation to prepare the fuel oil.
In the technical scheme, the reaction temperature is preferably 250-400 ℃, more preferably 300-400 DEG C
In the technical scheme, the volume airspeed of the tar liquid is 0.1-3.0 h-1More preferably 0.3 to 2.0 hours-1。
In the technical scheme, the reaction pressure is 5-15 MPa, and more preferably 8-13 MPa.
In the technical scheme, the volume ratio of the hydrogen to the tar is 500-1800: 1, and more preferably 800-1500: 1.
In the technical scheme, natural montmorillonite or other acidic natural ores with a light cracking function accounting for 3-25% of the mass of the hydrogenation catalyst or natural ores diluted by heat-resistant inert materials such as quartz sand can be filled on the hydrogenation catalyst bed layer, or the natural ores can not be filled.
In the above technical scheme, before the tar is fed, the hydrogenation catalyst can be pre-vulcanized by using a vulcanizing agent (for example, carbon disulfide or dimethyl disulfide, etc.), and the specific process conditions for pre-vulcanization can be reasonably selected by those skilled in the art without creative labor. For example, the prevulcanisation conditions may be: the vulcanization temperature is 250-300 ℃, and the liquid volume airspeed of the vulcanized oil is 0.5-2.0 h-1The pressure of the vulcanization reaction is 3-10 MPa, the volume ratio of hydrogen to vulcanized oil (500-2000): 1, and the vulcanization time is 12-48 hours.
The catalyst of the present invention is not particularly limited in the source and nature of tar, and may be, for example, coal tar or ethylene tar. When coal tar is used, the coal tar in general can be hydrotreated by the catalyst of the invention, and the properties of the coal tar are as follows:
the N content is 5000-15000 ppm, the S content is 1000-10000 ppm, and the distillation range is 180-500 ℃. In order to compare, the coal tar adopted by the specific embodiment of the invention has the N content of 8100ppm, the S content of 4200ppm and the distillation range of 180-500 ℃.
The sulfur content is measured according to GB/T6324.4-86 method for measuring trace sulfur in organic liquid products, and the nitrogen content is measured according to ZD/B15-56-1999 method for analyzing nitrogen in oil products.
The desulfurization rate [% of sulfur in coal tar-sulfur content in liquid phase product)/sulfur in coal tar ] is 100%
The denitrogenation rate [ ((nitrogen content in coal tar-nitrogen content in liquid phase product)/nitrogen content in coal tar) × 100%
Gasoline and diesel yield%
In the above calculation formula, those skilled in the art understand that the liquid phase product refers to the hydrogenation product before the separation of gasoline and diesel oil, and the H generated after hydrogenation is easily removed by simple methods in the prior art2S or NH3Removal, e.g. caustic washing, can remove H2S, acid washing can remove NH3Etc., so that the sulfur content in the liquid phase product is not counted by H2S, nitrogen content in liquid-phase product is not counted by NH3。
The type of reactor to which the catalyst of the present invention is applied is not particularly limited, and for example, but not limited to, a fixed bed reactor, and other types of reactors such as fluidized bed, moving bed, etc. are also possible.
By adopting the invention, the desulfurization rate is up to 93%, the denitrification rate is up to 92%, and the yield of gasoline and diesel oil is up to 90%, so that the beneficial technical effect is achieved, and the method can be used in the production of fuel oil by hydrogenation of coal tar and/or ethylene tar.
Detailed Description
[ example 1 ]
1. Preparation of the support
100 parts of commercially available activated aluminum hydroxide dry glue powder, 9 parts of Beta zeolite molecular sieve raw powder, 5 parts of 1:1 nitric acid, 1.8 parts of citric acid, 4 parts of sesbania powder and 40 parts of distilled water are uniformly mixed, extruded, dried at 110 ℃ for 10 hours and roasted at 480 ℃ in air atmosphere for 5 hours to obtain a cylindrical carrier with the diameter of 1.3mm and the length of 3 mm.
2. Catalyst preparation
(i) Mixing 1L of cylindrical carrier with 900ml of rhodium nitrate-calcium acetate mixed aqueous solution (containing 5g of Rh and 4g of Ca);
(ii) drying at 110 ℃ for 10 h;
(iii) roasting the mixture for 3 hours at 500 ℃ in air atmosphere to obtain the catalyst.
By ICP analysis, the catalyst composition was: rh, 5 g/L; ca, 4 g/L.
3. Catalyst evaluation
50ml of a catalyst was charged in a fixed bed reactor, and the catalyst was presulfided using aviation kerosene containing 3% by mass of dimethyl disulfide as a sulfur oil. The vulcanization conditions are as follows: the vulcanization temperature is 280 ℃, and the liquid volume space velocity of the vulcanized oil is 1.5h-1Hydrogen pressure 5MPa, volume ratio of hydrogen to vulcanized oil 1000:1, and vulcanization time 24 hours.
And (3) carrying out coal tar hydrogenation reaction on the vulcanized catalyst. The reaction conditions are as follows: the reaction temperature is 390 ℃, and the volume space velocity of coal tar liquid is 0.6h-1The reaction pressure is 10MPa, and the volume ratio of hydrogen to coal tar is 1200: 1.
For convenience of explanation and comparison, the composition of the catalyst and the catalyst evaluation results are shown in table 1.
[ example 2 ]
1. Preparation of the support
100 parts of commercially available activated aluminum hydroxide dry glue powder, 9 parts of Beta zeolite molecular sieve raw powder, 5 parts of 1:1 nitric acid, 1.8 parts of citric acid, 4 parts of sesbania powder and 40 parts of distilled water are uniformly mixed, extruded, dried at 110 ℃ for 10 hours and roasted at 480 ℃ in air atmosphere for 5 hours to obtain a cylindrical carrier with the diameter of 1.3mm and the length of 3 mm.
2. Catalyst preparation
(i) Mixing 1L of cylindrical carrier with 900ml of rhodium nitrate-magnesium acetate mixed aqueous solution (containing 5g of Rh and 4g of Mg);
(ii) drying at 110 ℃ for 10 h;
(iii) roasting the mixture for 3 hours at 500 ℃ in air atmosphere to obtain the catalyst.
By ICP analysis, the catalyst composition was: rh, 5 g/L; mg, 4 g/L.
3. Catalyst evaluation
50ml of a catalyst was charged in a fixed bed reactor, and the catalyst was presulfided using aviation kerosene containing 3% by mass of dimethyl disulfide as a sulfur oil. The vulcanization conditions are: the vulcanization temperature is 280 ℃, and the liquid volume space velocity of the vulcanized oil is 1.5h-1Hydrogen pressure 5MPa, volume ratio of hydrogen to vulcanized oil 1000:1, and vulcanization time 24 hours.
And (3) carrying out coal tar hydrogenation reaction on the vulcanized catalyst. The reaction conditions are as follows: the reaction temperature is 390 ℃, and the volume space velocity of coal tar liquid is 0.6h-1The reaction pressure is 10MPa, and the volume ratio of hydrogen to coal tar is 1200: 1.
For convenience of explanation and comparison, the composition of the catalyst and the catalyst evaluation results are shown in table 1.
[ example 3 ]
1. Preparation of the support
100 parts of commercially available activated aluminum hydroxide dry glue powder, 9 parts of Beta zeolite molecular sieve raw powder, 5 parts of 1:1 nitric acid, 1.8 parts of citric acid, 4 parts of sesbania powder and 40 parts of distilled water are uniformly mixed, extruded, dried at 110 ℃ for 10 hours and roasted at 480 ℃ in air atmosphere for 5 hours to obtain a cylindrical carrier with the diameter of 1.3mm and the length of 3 mm.
2. Catalyst preparation
(i) Mixing 1L of cylindrical carrier with 900ml of rhodium nitrate-potassium acetate mixed aqueous solution (containing 5g of Rh and 4g of K);
(ii) drying at 110 ℃ for 10 h;
(iii) roasting the mixture for 3 hours at 500 ℃ in air atmosphere to obtain the catalyst.
By ICP analysis, the catalyst composition was: rh, 5 g/L; k, 4 g/L.
3. Catalyst evaluation
50ml of a catalyst was charged in a fixed bed reactor, and the catalyst was presulfided using aviation kerosene containing 3% by mass of dimethyl disulfide as a sulfur oil. The vulcanization conditions are as follows: the vulcanization temperature is 280 ℃, and the liquid volume space velocity of the vulcanized oil is 1.5h-1Hydrogen pressure 5MPa, volume ratio of hydrogen to vulcanized oil 1000:1, and vulcanization time 24 hours.
And (3) carrying out coal tar hydrogenation reaction on the vulcanized catalyst. The reaction conditions are as follows: the reaction temperature is 390 ℃, and the volume space velocity of coal tar liquid is 0.6h-1The reaction pressure is 10MPa, and the volume ratio of hydrogen to coal tar is 1200: 1.
For convenience of explanation and comparison, the composition of the catalyst and the catalyst evaluation results are shown in table 1.
[ example 4 ]
1. Preparation of the support
100 parts of commercially available activated aluminum hydroxide dry glue powder, 9 parts of Beta zeolite molecular sieve raw powder, 5 parts of 1:1 nitric acid, 1.8 parts of citric acid, 4 parts of sesbania powder and 40 parts of distilled water are uniformly mixed, extruded, dried at 110 ℃ for 10 hours and roasted at 480 ℃ in air atmosphere for 5 hours to obtain a cylindrical carrier with the diameter of 1.3mm and the length of 3 mm.
2. Catalyst preparation
(i) Mixing 1L of cylindrical carrier with 900ml of rhodium nitrate-cesium acetate mixed aqueous solution (containing 5g of Rh and 4g of Cs);
(ii) drying at 110 ℃ for 10 h;
(iii) roasting the mixture for 3 hours at 500 ℃ in air atmosphere to obtain the catalyst.
By ICP analysis, the catalyst composition was: rh, 5 g/L; cs, 4 g/L.
3. Catalyst evaluation
50ml of a catalyst was charged in a fixed bed reactor, and the catalyst was presulfided using aviation kerosene containing 3% by mass of dimethyl disulfide as a sulfur oil. The vulcanization conditions are as follows: the vulcanization temperature is 280 ℃, and the liquid volume space velocity of the vulcanized oil is 1.5h-1Hydrogen pressure 5MPa, volume ratio of hydrogen to vulcanized oil 1000:1, and vulcanization time 24 hours.
And (3) carrying out coal tar hydrogenation reaction on the vulcanized catalyst. The reaction conditions are as follows: the reaction temperature is 390 ℃, and the volume space velocity of coal tar liquid is 0.6h-1The reaction pressure is 10MPa, and the volume ratio of hydrogen to coal tar is 1200: 1.
For convenience of explanation and comparison, the composition of the catalyst and the catalyst evaluation results are shown in table 1.
[ example 5 ]
1. Preparation of the support
100 parts of commercially available activated aluminum hydroxide dry glue powder, 9 parts of Beta zeolite molecular sieve raw powder, 5 parts of 1:1 nitric acid, 1.8 parts of citric acid, 4 parts of sesbania powder and 40 parts of distilled water are uniformly mixed, extruded, dried at 110 ℃ for 10 hours and roasted at 480 ℃ in air atmosphere for 5 hours to obtain a cylindrical carrier with the diameter of 1.3mm and the length of 3 mm.
2. Catalyst preparation
(i) Mixing 1L of cylindrical carrier with 900ml of rhodium nitrate-calcium acetate-potassium acetate mixed aqueous solution (containing 5g of Rh, 2g of Ca and 2g of K);
(ii) drying at 110 ℃ for 10 h;
(iii) roasting the mixture for 3 hours at 500 ℃ in air atmosphere to obtain the catalyst.
By ICP analysis, the catalyst composition was: rh, 5 g/L; ca, 2 g/L; k, 2 g/L.
3. Catalyst evaluation
50ml of a catalyst was charged in a fixed bed reactor, and the catalyst was presulfided using aviation kerosene containing 3% by mass of dimethyl disulfide as a sulfur oil. The vulcanization conditions are as follows: the vulcanization temperature is 280 ℃, and the liquid volume space velocity of the vulcanized oil is 1.5h-1Hydrogen pressure 5MPa, volume ratio of hydrogen to vulcanized oil 1000:1, and vulcanization time 24 hours.
And (3) carrying out coal tar hydrogenation reaction on the vulcanized catalyst. The reaction conditions are as follows: the reaction temperature is 390 ℃, and the volume space velocity of coal tar liquid is 0.6h-1The reaction pressure is 10MPa, and the volume ratio of hydrogen to coal tar is 1200: 1.
For convenience of explanation and comparison, the composition of the catalyst and the catalyst evaluation results are shown in table 1.
[ example 6 ]
1. Preparation of the support
100 parts of commercially available activated aluminum hydroxide dry glue powder, 9 parts of Beta zeolite molecular sieve raw powder, 5 parts of 1:1 nitric acid, 1.8 parts of citric acid, 4 parts of sesbania powder and 40 parts of distilled water are uniformly mixed, extruded, dried at 110 ℃ for 10 hours and roasted at 480 ℃ in air atmosphere for 5 hours to obtain a cylindrical carrier with the diameter of 1.3mm and the length of 3 mm.
2. Catalyst preparation
(i) Mixing 1L of cylindrical carrier with 900ml of rhodium nitrate-calcium acetate-strontium acetate mixed aqueous solution (containing 5g of Rh, 2g of Ca and 2g of Cs);
(ii) drying at 110 ℃ for 10 h;
(iii) roasting the mixture for 3 hours at 500 ℃ in air atmosphere to obtain the catalyst.
By ICP analysis, the catalyst composition was: rh, 5 g/L; ca, 2 g/L; cs, 2 g/L.
3. Catalyst evaluation
50ml of a catalyst was charged in a fixed bed reactor, and the catalyst was presulfided using aviation kerosene containing 3% by mass of dimethyl disulfide as a sulfur oil. The vulcanization conditions are as follows: the vulcanization temperature is 280 ℃, and the liquid volume space velocity of the vulcanized oil is 1.5h-1Hydrogen pressure 5MPa, volume ratio of hydrogen to vulcanized oil 1000:1, and vulcanization time 24 hours.
And (3) carrying out coal tar hydrogenation reaction on the vulcanized catalyst. The reaction conditions are as follows: the reaction temperature is 390 ℃, and the volume space velocity of coal tar liquid is 0.6h-1The reaction pressure is 10MPa, and the volume ratio of hydrogen to coal tar is 1200: 1.
For convenience of explanation and comparison, the composition of the catalyst and the catalyst evaluation results are shown in table 1.
[ example 7 ]
1. Preparation of the support
100 parts of commercially available activated aluminum hydroxide dry glue powder, 9 parts of Beta zeolite molecular sieve raw powder, 5 parts of 1:1 nitric acid, 1.8 parts of citric acid, 4 parts of sesbania powder and 40 parts of distilled water are uniformly mixed, extruded, dried at 110 ℃ for 10 hours and roasted at 480 ℃ in air atmosphere for 5 hours to obtain a cylindrical carrier with the diameter of 1.3mm and the length of 3 mm.
2. Catalyst preparation
(i) Mixing 1L of cylindrical carrier with 900ml of rhodium nitrate-magnesium acetate-potassium acetate mixed aqueous solution (containing 5g of Rh, 2g of Mg and 2g of K);
(ii) drying at 110 ℃ for 10 h;
(iii) roasting the mixture for 3 hours at 500 ℃ in air atmosphere to obtain the catalyst.
By ICP analysis, the catalyst composition was: rh, 5 g/L; mg, 2 g/L; k, 2 g/L.
3. Catalyst evaluation
Charging 5 in fixed bed reactor0ml of catalyst, the catalyst was presulfided using aviation kerosene containing 3% by mass of dimethyl disulfide as a sulfur oil. The vulcanization conditions are as follows: the vulcanization temperature is 280 ℃, and the liquid volume space velocity of the vulcanized oil is 1.5h-1Hydrogen pressure 5MPa, volume ratio of hydrogen to vulcanized oil 1000:1, and vulcanization time 24 hours.
And (3) carrying out coal tar hydrogenation reaction on the vulcanized catalyst. The reaction conditions are as follows: the reaction temperature is 390 ℃, and the volume space velocity of coal tar liquid is 0.6h-1The reaction pressure is 10MPa, and the volume ratio of hydrogen to coal tar is 1200: 1.
For convenience of explanation and comparison, the composition of the catalyst and the catalyst evaluation results are shown in table 1.
[ example 8 ]
1. Preparation of the support
100 parts of commercially available activated aluminum hydroxide dry glue powder, 9 parts of Beta zeolite molecular sieve raw powder, 5 parts of 1:1 nitric acid, 1.8 parts of citric acid, 4 parts of sesbania powder and 40 parts of distilled water are uniformly mixed, extruded, dried at 110 ℃ for 10 hours and roasted at 480 ℃ in air atmosphere for 5 hours to obtain a cylindrical carrier with the diameter of 1.3mm and the length of 3 mm.
2. Catalyst preparation
(i) Mixing 1L of cylindrical carrier with 900ml of rhodium nitrate-magnesium acetate-strontium acetate mixed aqueous solution (containing 5g of Rh, 2g of Mg and 2g of CS);
(ii) drying at 110 ℃ for 10 h;
(iii) roasting the mixture for 3 hours at 500 ℃ in air atmosphere to obtain the catalyst.
By ICP analysis, the catalyst composition was: rh, 5 g/L; mg, 2 g/L; cs, 2 g/L.
3. Catalyst evaluation
50ml of a catalyst was charged in a fixed bed reactor, and the catalyst was presulfided using aviation kerosene containing 3% by mass of dimethyl disulfide as a sulfur oil. The vulcanization conditions are as follows: the vulcanization temperature is 280 ℃, and the liquid volume space velocity of the vulcanized oil is 1.5h-1Hydrogen pressure 5MPa, volume ratio of hydrogen to vulcanized oil 1000:1, and vulcanization time 24 hours.
Coal tar hydrogenation reaction of the vulcanized catalystShould be used. The reaction conditions are as follows: the reaction temperature is 390 ℃, and the volume space velocity of coal tar liquid is 0.6h-1The reaction pressure is 10MPa, and the volume ratio of hydrogen to coal tar is 1200: 1.
For convenience of explanation and comparison, the composition of the catalyst and the catalyst evaluation results are shown in table 1.
[ example 9 ]
1. Preparation of the support
100 parts of commercially available activated aluminum hydroxide dry glue powder, 9 parts of Beta zeolite molecular sieve raw powder, 5 parts of 1:1 nitric acid, 1.8 parts of citric acid, 4 parts of sesbania powder and 40 parts of distilled water are uniformly mixed, extruded, dried at 110 ℃ for 10 hours and roasted at 480 ℃ in air atmosphere for 5 hours to obtain a cylindrical carrier with the diameter of 1.3mm and the length of 3 mm.
2. Catalyst preparation
(i) Mixing 1L of cylindrical carrier with 900ml of rhodium nitrate-calcium acetate-magnesium acetate mixed aqueous solution (containing 5g of Rh, 2g of Ca and 2g of Mg);
(ii) drying at 110 ℃ for 10 h;
(iii) roasting the mixture for 3 hours at 500 ℃ in air atmosphere to obtain the catalyst.
By ICP analysis, the catalyst composition was: rh, 5 g/L; ca, 2 g/L; mg, 2 g/L.
3. Catalyst evaluation
50ml of a catalyst was charged in a fixed bed reactor, and the catalyst was presulfided using aviation kerosene containing 3% by mass of dimethyl disulfide as a sulfur oil. The vulcanization conditions are as follows: the vulcanization temperature is 280 ℃, and the liquid volume space velocity of the vulcanized oil is 1.5h-1Hydrogen pressure 5MPa, volume ratio of hydrogen to vulcanized oil 1000:1, and vulcanization time 24 hours.
And (3) carrying out coal tar hydrogenation reaction on the vulcanized catalyst. The reaction conditions are as follows: the reaction temperature is 390 ℃, and the volume space velocity of coal tar liquid is 0.6h-1The reaction pressure is 10MPa, and the volume ratio of hydrogen to coal tar is 1200: 1.
For convenience of explanation and comparison, the composition of the catalyst and the catalyst evaluation results are shown in table 1.
[ example 10 ]
1. Preparation of the support
100 parts of commercially available activated aluminum hydroxide dry glue powder, 9 parts of Beta zeolite molecular sieve raw powder, 5 parts of 1:1 nitric acid, 1.8 parts of citric acid, 4 parts of sesbania powder and 40 parts of distilled water are uniformly mixed, extruded, dried at 110 ℃ for 10 hours and roasted at 480 ℃ in air atmosphere for 5 hours to obtain a cylindrical carrier with the diameter of 1.3mm and the length of 3 mm.
2. Catalyst preparation
(i) Mixing 1L of cylindrical carrier with 900ml of rhodium nitrate-potassium acetate-strontium acetate mixed aqueous solution (containing 5g of Rh, 2g of K and 2g of Cs);
(ii) drying at 110 ℃ for 10 h;
(iii) roasting the mixture for 3 hours at 500 ℃ in air atmosphere to obtain the catalyst.
By ICP analysis, the catalyst composition was: rh, 5 g/L; k, 2 g/L; cs, 2 g/L.
3. Catalyst evaluation
50ml of a catalyst was charged in a fixed bed reactor, and the catalyst was presulfided using aviation kerosene containing 3% by mass of dimethyl disulfide as a sulfur oil. The vulcanization conditions are as follows: the vulcanization temperature is 280 ℃, and the liquid volume space velocity of the vulcanized oil is 1.5h-1Hydrogen pressure 5MPa, volume ratio of hydrogen to vulcanized oil 1000:1, and vulcanization time 24 hours.
And (3) carrying out coal tar hydrogenation reaction on the vulcanized catalyst. The reaction conditions are as follows: the reaction temperature is 390 ℃, and the volume space velocity of coal tar liquid is 0.6h-1The reaction pressure is 10MPa, and the volume ratio of hydrogen to coal tar is 1200: 1.
For convenience of explanation and comparison, the composition of the catalyst and the catalyst evaluation results are shown in table 1.
[ example 11 ]
1. Preparation of the support
100 parts of commercially available activated aluminum hydroxide dry glue powder, 9 parts of Beta zeolite molecular sieve raw powder, 5 parts of 1:1 nitric acid, 1.8 parts of citric acid, 4 parts of sesbania powder and 40 parts of distilled water are uniformly mixed, extruded, dried at 110 ℃ for 10 hours and roasted at 480 ℃ in air atmosphere for 5 hours to obtain a cylindrical carrier with the diameter of 1.3mm and the length of 3 mm.
2. Catalyst preparation
(i) Mixing 1L of cylindrical carrier with 900ml of rhodium nitrate-calcium acetate-magnesium acetate-potassium acetate-strontium acetate mixed aqueous solution (containing 5g of Rh, 1g of Ca, 1g of Mg, 1g of K and 1g of Cs);
(ii) drying at 110 ℃ for 10 h;
(iii) roasting the mixture for 3 hours at 500 ℃ in air atmosphere to obtain the catalyst.
By ICP analysis, the catalyst composition was: rh, 5 g/L; ca, 1 g/L; mg, 1g/L K, 1 g/L; cs, 1 g/L. 3. Catalyst evaluation
50ml of a catalyst was charged in a fixed bed reactor, and the catalyst was presulfided using aviation kerosene containing 3% by mass of dimethyl disulfide as a sulfur oil. The vulcanization conditions are as follows: the vulcanization temperature is 280 ℃, and the liquid volume space velocity of the vulcanized oil is 1.5h-1Hydrogen pressure 5MPa, volume ratio of hydrogen to vulcanized oil 1000:1, and vulcanization time 24 hours.
And (3) carrying out coal tar hydrogenation reaction on the vulcanized catalyst. The reaction conditions are as follows: the reaction temperature is 390 ℃, and the volume space velocity of coal tar liquid is 0.6h-1The reaction pressure is 10MPa, and the volume ratio of hydrogen to coal tar is 1200: 1.
For convenience of explanation and comparison, the composition of the catalyst and the catalyst evaluation results are shown in table 1.
TABLE 1 composition of catalyst and catalyst evaluation results
Claims (6)
1. The application of the catalyst for preparing fuel oil by hydrogenating tar in preparing fuel oil by hydrogenating coal tar and/or ethylene tar is disclosed, wherein the catalyst comprises an active component, an auxiliary agent and a carrier; the active component comprises Rh, the auxiliary comprises alkali metal and alkaline earth metal, the alkali metal comprises K and Cs, and the alkaline earth metal comprises Ca and Mg; the carrier is alumina and Beta zeolite, and the weight ratio of the alumina to the Beta zeolite is 0.5-10; the reaction temperature for preparing the fuel oil by hydrogenating the coal tar and/or the ethylene tar is 250-400 ℃.
2. The use according to claim 1, wherein the active ingredient content is 0.5 to 20 g/L.
3. Use according to any one of claims 1 to 2, the preparation method of the catalyst comprising:
(1) mixing the carrier with an active component solution and an auxiliary agent solution;
(2) drying
(3) And (4) roasting.
4. Use according to claim 3, wherein the drying temperature is 60 to 120 ℃.
5. Use according to claim 3, wherein the drying time is 4 to 18 hours.
6. The use according to claim 3, wherein the calcination temperature is 300 to 700 ℃.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6177381B1 (en) * | 1998-11-03 | 2001-01-23 | Uop Llc | Layered catalyst composition and processes for preparing and using the composition |
| CN101037614A (en) * | 2006-03-17 | 2007-09-19 | 中国石油天然气股份有限公司 | Hydrofining catalyst, preparation method and application |
| CN102688770A (en) * | 2012-04-28 | 2012-09-26 | 中国科学院青岛生物能源与过程研究所 | Aromatics hydrogenation catalyst and preparation method and application of aromatics hydrogenation catalyst |
| CN103289740A (en) * | 2013-01-23 | 2013-09-11 | 大连理工大学 | Method for preparing clean fuel oil from coal tar |
| CN104525195A (en) * | 2014-12-30 | 2015-04-22 | 中国石油天然气股份有限公司 | Catalyst for preparing isobutene through isobutane dehydrogenation and preparation method and application thereof |
| CN105419864A (en) * | 2015-11-13 | 2016-03-23 | 王树宽 | System and method for preparing high-octane gasoline, aviation kerosene and naphthenic base oil with total-hydrogen-type coal tar |
| CN106807420A (en) * | 2017-03-17 | 2017-06-09 | 钦州学院 | A kind of catalyst and preparation method for petroleum naphtha hydrogenation dearsenification |
| CN106994365A (en) * | 2016-01-26 | 2017-08-01 | 中国石油化工股份有限公司 | A kind of catalyst for hydrogenation de-waxing preparation method and catalyst obtained by this method and its application |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8912110B2 (en) * | 2012-03-29 | 2014-12-16 | Uop Llc | Catalyst for conversion of hydrocarbons |
-
2017
- 2017-09-28 CN CN201710895330.5A patent/CN109569707B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6177381B1 (en) * | 1998-11-03 | 2001-01-23 | Uop Llc | Layered catalyst composition and processes for preparing and using the composition |
| CN101037614A (en) * | 2006-03-17 | 2007-09-19 | 中国石油天然气股份有限公司 | Hydrofining catalyst, preparation method and application |
| CN102688770A (en) * | 2012-04-28 | 2012-09-26 | 中国科学院青岛生物能源与过程研究所 | Aromatics hydrogenation catalyst and preparation method and application of aromatics hydrogenation catalyst |
| CN103289740A (en) * | 2013-01-23 | 2013-09-11 | 大连理工大学 | Method for preparing clean fuel oil from coal tar |
| CN104525195A (en) * | 2014-12-30 | 2015-04-22 | 中国石油天然气股份有限公司 | Catalyst for preparing isobutene through isobutane dehydrogenation and preparation method and application thereof |
| CN105419864A (en) * | 2015-11-13 | 2016-03-23 | 王树宽 | System and method for preparing high-octane gasoline, aviation kerosene and naphthenic base oil with total-hydrogen-type coal tar |
| CN106994365A (en) * | 2016-01-26 | 2017-08-01 | 中国石油化工股份有限公司 | A kind of catalyst for hydrogenation de-waxing preparation method and catalyst obtained by this method and its application |
| CN106807420A (en) * | 2017-03-17 | 2017-06-09 | 钦州学院 | A kind of catalyst and preparation method for petroleum naphtha hydrogenation dearsenification |
Non-Patent Citations (1)
| Title |
|---|
| Hydroprocessing of Coal Tar to Prepare Clean Fuel Oil;Hongyan Wang;《Encyclopedia of Sustainable Technologies》;20170714;第411-422页 * |
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