CN110538676B

CN110538676B - Catalyst for hydrogenation refining of cracked tar

Info

Publication number: CN110538676B
Application number: CN201810529518.2A
Authority: CN
Inventors: 韩亚梅; 刘仲能; 钱斌; 刘师前; 朱瑾
Original assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Current assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date: 2018-05-29
Filing date: 2018-05-29
Publication date: 2021-12-28
Anticipated expiration: 2038-05-29
Also published as: CN110538676A

Abstract

The invention relates to a catalyst for hydrofining cracked tar, which mainly solves the problems of low desulfurization rate, denitrification rate and fuel yield in the prior art. The invention adopts a catalyst for hydrofining cracked tar, and the catalyst comprises an active component, an auxiliary agent and a carrier; the active component comprises any one of Co, Mo and W, and the auxiliary agent comprises Sb, so that the technical scheme has a good effect, and can be used for preparing fuel oil by hydrogenation of coal tar and/or ethylene tar.

Description

Catalyst for hydrogenation refining of cracked tar

Technical Field

The invention belongs to the technical field of fuel oil preparation by tar hydrogenation, and particularly relates to a catalyst for hydrofining cracked 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 NO_x、SO_xAnd 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, the main component of the ethylene tar is aromatic compounds, the carbon-hydrogen ratio is high, and the ash content is very 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 tar is used as the raw material to produce the fuel oil through the hydrogenation processObvious economic and social benefits can be generated, and the current situation of energy shortage in China is effectively relieved.

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 yield in the prior art, and provides a catalyst for hydrofining cracked tar, which has the advantages of high desulfurization rate, denitrification rate and fuel 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 the hydrofining of the cracked tar comprises an active component, an auxiliary agent and a carrier; the active component comprises any one selected from Co, Mo and W, and the auxiliary agent comprises Sb. 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 1-50 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 active component preferably includes Co, Mo and W.

In the technical scheme, the content of Co is preferably 4-12 g/L.

In the technical scheme, the content of Mo is preferably 5-15 g/L.

In the technical scheme, the content of W is preferably 3-10 g/L.

In the above technical solution, as one of more preferable technical solutions, the auxiliary includes Cu and Sb, 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 Cu to Sb is not particularly limited, but is, for example, but not limited to, 0.1 to 10, and more specific examples of the ratio may be 0.21, 0.31, 0.41, 0.51, 0.81, 0.91, 1.01, 1.51, 2.01, 2.51, 3.01, 3.51, 4.01, 4.51, 5.01, 5.51, 6.01, 6.51, 7.01, 7.51, 8.01, 8.51, 9.01, 9.51, or the like.

In the above technical solution, as a second preferable technical solution, the auxiliary agent includes Sb and Bi, 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 Sb to Bi is not particularly limited, but is, for example, but not limited to, 0.1 to 10, and more specific examples of the ratio may be 0.21, 0.31, 0.41, 0.51, 0.81, 0.91, 1.01, 1.51, 2.01, 2.51, 3.01, 3.51, 4.01, 4.51, 5.01, 5.51, 6.01, 6.51, 7.01, 7.51, 8.01, 8.51, 9.01, 9.51, or the like.

In the above technical solution, as a third preferred technical solution, the additive further includes Cu and Bi, and the Cu and Bi have a synergistic effect in improving the desulfurization rate, the denitrification rate and the fuel yield. In this case, the weight ratio of Cu and Bi is not particularly limited, but is, for example, 0.1 to 10, and more specific examples of the ratio are 0.21, 0.31, 0.41, 0.51, 0.81, 0.91, 1.01, 1.51, 2.01, 2.51, 3.01, 3.51, 4.01, 4.51, 5.01, 5.51, 6.01, 6.51, 7.01, 7.51, 8.01, 8.51, 9.01, 9.51, and the like.

In the technical scheme, the auxiliary agent simultaneously comprises Cu, Sb and Bi, and the three have ternary synergistic effect in the aspects of improving the desulfurization rate, the denitrification rate and the fuel yield.

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 from the group consisting of alumina and mordenite.

In the above technical solution, the carrier more preferably comprises alumina and mordenite.

In the technical scheme, the weight part ratio of the alumina to the mordenite is preferably (75-95): (5-25).

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 ingredient solution;

(2) drying;

(3) roasting;

(4) mixing with an auxiliary agent solution;

(5) drying;

(6) and (4) roasting.

In the above technical solution, the drying conditions are not particularly limited, for example, but not limited to, the drying temperature in step (2) and step (5) is independently selected from 60 to 120 ℃ (for non-limiting example, within this range, 80 ℃, 90 ℃, 100 ℃, 110 ℃, etc.), and the drying time in step (2) and step (5) is, for example, but not limited to, at least independently 6 hours, for example, 6 to 18 hours (for non-limiting example, within this range, 7, 8, 9, 10, 11, 12, etc.); the roasting temperature in the step (3) and the roasting temperature in the step (6) are independently and preferably 400-600 ℃, more preferably 350-550 ℃, and the roasting time in the step (3) and the step (6) is independently and preferably 3-8 hours; the atmosphere for calcination is preferably 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 ℃, and more preferably 300-400 ℃.

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 4-25% 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 N content of 8200ppm, S content of 4000ppm and 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 as high as 97.3%, the denitrification rate is as high as 98.0%, the yield of gasoline and diesel oil is as high as 90.1%, and beneficial technical effects are 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, 8 parts of mordenite molecular sieve raw powder, 6 parts of 1:1 nitric acid, 1.9 parts of citric acid, 4.5 parts of sesbania powder and 48 parts of distilled water are uniformly mixed, extruded, dried at 110 ℃ for 10 hours and roasted at 470 ℃ 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

Mixing 1L of cylindrical carrier with 900ml of cobalt nitrate-ammonium molybdate-ammonium metatungstate mixed aqueous solution (containing 8g of Co, 10g of Mo and 6g of W), drying at 110 ℃ for 8h, and roasting at 450 ℃ in air atmosphere for 5h to obtain the catalyst precursor.

By ICP analysis, the catalyst composition was: co, 8 g/L; mo, 10 g/L; w, 6 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: vulcanization temperature 280 ℃, vulcanized oilLiquid volume space velocity of 1.5h^-1Hydrogen pressure 5MPa, volume ratio of hydrogen to vulcanized oil 1100:1, 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 380 ℃, and the volume space velocity of coal tar liquid is 0.7h^-1The reaction pressure is 10MPa, and the volume ratio of hydrogen to coal tar is 1100: 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

2. Catalyst preparation

The catalyst precursor is mixed with 900ml of bismuth trichloride aqueous solution (containing 4g of Bi), dried at 110 ℃ for 10h, and roasted at 490 ℃ for 5h in an air atmosphere to obtain the catalyst.

By ICP analysis, the catalyst composition was: co, 8 g/L; mo, 10 g/L; w, 6 g/L; bi, 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 1100:1, and vulcanization time 24 hours.

And (3) carrying out coal tar hydrogenation reaction on the vulcanized catalyst. The reaction conditions are as follows: reaction temperature of 380 ℃ and coal tar liquid volumeSpace velocity of 0.7h^-1The reaction pressure is 10MPa, and the volume ratio of hydrogen to coal tar is 1100: 1.

[ example 3 ]

1. Preparation of the support

2. Catalyst preparation

The catalyst precursor was mixed with 900ml of an aqueous copper nitrate solution (containing 4g of Cu), dried at 110 ℃ for 10 hours, and calcined at 490 ℃ for 5 hours in an air atmosphere to obtain a catalyst.

By ICP analysis, the catalyst composition was: co, 8 g/L; mo, 10 g/L; w, 6 g/L; cu, 4 g/L.

3. Catalyst evaluation

[ example 4 ]

1. Preparation of the support

2. Catalyst preparation

The catalyst precursor is mixed with 900ml of antimony trichloride aqueous solution (containing 4g of Sb), dried at 110 ℃ for 10h, and roasted at 490 ℃ for 5h in air atmosphere to obtain the catalyst.

By ICP analysis, the catalyst composition was: co, 8 g/L; mo, 10 g/L; w, 6 g/L; sb, 4 g/L.

3. Catalyst evaluation

[ example 5 ]

1. Preparation of the support

2. Catalyst preparation

The catalyst precursor was mixed with 900ml of an aqueous solution of copper nitrate-antimony trichloride (containing 2g of Cu and 2g of Sb), dried at 110 ℃ for 10 hours, and calcined at 490 ℃ for 5 hours in an air atmosphere to obtain a catalyst.

By ICP analysis, the catalyst composition was: co, 8 g/L; mo, 10 g/L; w, 6 g/L; cu, 2 g/L; sb, 2 g/L. 3. Catalyst evaluation

[ example 6 ]

1. Preparation of the support

2. Catalyst preparation

The catalyst precursor was mixed with 900ml of an aqueous solution of copper nitrate-bismuth trichloride (containing 2g of Cu and 2g of Bi), dried at 110 ℃ for 10 hours, and calcined at 490 ℃ for 5 hours in an air atmosphere to obtain a catalyst.

By ICP analysis, the catalyst composition was: co, 8 g/L; mo, 10 g/L; w, 6 g/L; cu, 2 g/L; bi, 2 g/L.

3. Catalyst evaluation

[ example 7 ]

1. Preparation of the support

2. Catalyst preparation

The catalyst precursor is mixed with 900ml of antimony trichloride-bismuth trichloride aqueous solution (containing 2g of Sb and 2g of Bi), dried at 110 ℃ for 10h, and roasted at 490 ℃ in an air atmosphere for 5h to obtain the catalyst.

By ICP analysis, the catalyst composition was: co, 8 g/L; mo, 10 g/L; w, 6 g/L; sb, 2 g/L; bi, 2 g/L.

3. Catalyst evaluation

[ example 8 ]

1. Preparation of the support

2. Catalyst preparation

The catalyst precursor was mixed with 900ml of an aqueous solution of copper nitrate-antimony trichloride-bismuth trichloride (containing 1.5g of Cu, 1g of Sb and 1.5g of Bi), dried at 110 ℃ for 10 hours, and calcined at 490 ℃ for 5 hours in an air atmosphere to obtain a catalyst.

By ICP analysis, the catalyst composition was: co, 8 g/L; mo, 10 g/L; w, 6 g/L; cu, 1.5 g/L; sb, 1 g/L; bi, 1.5 g/L.

3. Catalyst evaluation

TABLE 1 composition of catalyst and catalyst evaluation results

Claims

1. The catalyst for the hydrofining of the cracked tar comprises an active component, an auxiliary agent and a carrier; the active components are Co, Mo and W, the auxiliary agent comprises Sb and Bi, and the weight ratio of Sb to Bi is 0.1-10.

2. The catalyst according to claim 1, wherein the active component content is 1 to 50 g/L.

3. The catalyst of claim 1, characterized in that the support is selected from at least one of alumina and mordenite.

4. The catalyst of claim 3, characterized in that the support comprises alumina and mordenite.

5. The catalyst of claim 4 wherein the weight ratio of alumina to mordenite is (75-95) to (5-25).

6. A process for preparing a catalyst as claimed in any one of claims 1 to 5, comprising:

(1) mixing the carrier with an active ingredient solution;

(2) drying;

(3) roasting;

(4) mixing with an auxiliary agent solution;

(5) drying;

(6) and (4) roasting.

7. The method as set forth in claim 6, wherein the drying temperature in the step (2) and the drying temperature in the step (5) are independently selected from 60 to 120 ℃.

8. The method as claimed in claim 6, wherein the calcination temperature in step (3) and step (6) is selected from 400 to 600 ℃.

9. The method as claimed in claim 6, wherein the calcination time in step (3) and step (6) is independently selected from 3 to 8 hours.

10. Use of the catalyst according to any one of claims 1 to 5 in the hydrogenation of coal tar and/or ethylene tar to fuel oil.