CN112354568B - Magnesium-based coke oven gas hydrodesulfurization catalyst and preparation method thereof - Google Patents

Magnesium-based coke oven gas hydrodesulfurization catalyst and preparation method thereof Download PDF

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CN112354568B
CN112354568B CN202011282489.8A CN202011282489A CN112354568B CN 112354568 B CN112354568 B CN 112354568B CN 202011282489 A CN202011282489 A CN 202011282489A CN 112354568 B CN112354568 B CN 112354568B
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magnesium
nitrogen
coke oven
oven gas
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CN112354568A (en
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张俊洋
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Binzhou Zhongke Catalysis Technology Co ltd
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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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/10—Magnesium; Oxides or hydroxides thereof
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • 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
    • B01J37/0027—Powdering
    • B01J37/0036—Grinding
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/002—Removal of contaminants
    • C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
    • C10K1/004—Sulfur containing contaminants, e.g. hydrogen sulfide
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/34—Purifying combustible gases containing carbon monoxide by catalytic conversion of impurities to more readily removable materials

Abstract

The invention discloses a magnesium-based coke oven gas hydrodesulfurization catalyst and a preparation method thereof. The preparation method of the catalyst comprises the following steps: mixing graphite, magnesium powder, polyurethane and N-doped titanium oxide in a hydrogen atmosphere, and then carrying out ball milling to obtain the material; wherein: the mass ratio of the graphite to the magnesium powder to the polyurethane to the N-doped titanium oxide is (3); the weight average molecular weight of the polyurethane is 75000-120000; the N-doped titanium oxide is prepared by the following method: mixing a titanium-containing raw material and an N-containing raw material for reaction to obtain the catalyst; the molar ratio of the titanium element in the titanium-containing raw material to the nitrogen element in the nitrogen-containing raw material is 1. The magnesium-based coke oven gas hydrodesulfurization catalyst can realize a thiophene conversion rate of not less than 37% at 300 ℃, and the stability of the magnesium-based coke oven gas hydrodesulfurization catalyst is obviously improved.

Description

Magnesium-based coke oven gas hydrodesulfurization catalyst and preparation method thereof
Technical Field
The invention relates to the technical field of coke oven gas hydrodesulfurization catalysts, in particular to a magnesium-based coke oven gas hydrodesulfurization catalyst and a preparation method thereof.
Background
The coke oven gas is a combustible gas obtained while coke, tar and other chemical products are produced from coking coal prepared from several kinds of bituminous coal through high-temperature dry distillation in a coke oven, and is a coking byproduct. The coke oven gas contains more than 20 percent of methane, and the methane in the coke oven gas is converted into carbon monoxide and hydrogen in a certain proportion, so that the composition requirement of the synthesis gas under the process condition of preparing the methanol can be met. The key point of synthesizing the methanol by the coke oven gas is deep desulfurization, and the hydrodesulfurization degree of organic sulfur is an important factor influencing the service life of the methane conversion catalyst and the methanol synthesis catalyst.
The sulfur-containing compounds in the coke oven gas can be divided into two types according to the chemical combination state: one class is inorganic, primarily hydrogen sulfide; the other is sulfur organic compound, such as carbon disulfide, thiophene, sulfur oxide, etc. When the reaction is carried out at a higher temperature, the organic sulfur-containing compounds are almost completely converted into hydrogen sulfide, so that the sulfur contained in the hydrogen sulfide in the coke oven gas accounts for more than 90 percent of the total sulfur in the gas.
However, the currently used hydrogenation catalysts containing sulfur compounds are generally Co-Mo, ni-Mo, fe-Mo and the like, the reaction temperature is 350-450 ℃, the reaction pressure is 1.0-2.5MPa, however, the Co, ni and Mo catalysts have few resources, high cost and high volatility, and the hydrogenation reaction is carried out at high temperature and high pressure, so that the requirements on equipment materials are high. The magnesium-based hydrodesulfurization catalyst with mild reaction conditions is unstable in structure and extremely high in activity, and is easy to spontaneously combust or oxidize when exposed to air.
Therefore, how to effectively improve the stability of the magnesium-based hydrodesulfurization catalyst is a technical problem to be solved urgently in the field.
Disclosure of Invention
The invention aims to overcome the defect of poor stability of a magnesium-based hydrodesulfurization catalyst in the prior art, and provides a magnesium-based coke oven gas hydrodesulfurization catalyst and a preparation method thereof.
The invention provides a preparation method of a magnesium-based coke oven gas hydrodesulfurization catalyst, which comprises the following steps:
mixing graphite, magnesium powder, polyurethane and N-doped titanium oxide in a hydrogen atmosphere, and then carrying out ball milling to obtain the material; wherein:
the mass ratio of the graphite to the magnesium powder to the polyurethane to the N-doped titanium oxide is 3:7 to (1-5);
the weight average molecular weight of the polyurethane is 75000-120000;
the N-doped titanium oxide is prepared by the following method: mixing a titanium-containing raw material and an N-containing raw material for reaction to obtain the catalyst; the molar ratio of the titanium element in the titanium-containing raw material to the nitrogen element in the nitrogen-containing raw material is 1:2-2:1.
In the present invention, the pressure of the hydrogen gas is preferably 0.5 to 1.5MPa, for example, 1.0MPa.
In the present invention, it is preferable that the mass ratio of the graphite, the magnesium powder, the polyurethane and the N-doped titanium oxide is 3:7: (1-4), for example, 3:7:3:2, 3:7:4:1 or 3:7:1:4.
In the present invention, preferably, the weight average molecular weight of the polyurethane is 100000-120000, for example 100000 or 120000.
In the method for preparing the N-doped titanium oxide, the titanium-containing raw material is preferably titanium ethoxide.
In the method for producing N-doped titanium oxide according to the present invention, the titanium-containing raw material is preferably dissolved in a solvent and then mixed with the nitrogen-containing raw material. When the titanium-containing feedstock is titanium ethoxide, the solvent may be benzene.
In the method for preparing N-doped titanium oxide according to the present invention, the nitrogen-containing raw material is preferably triethylamine.
In the method for producing N-doped titanium oxide according to the present invention, the molar ratio of the titanium element in the titanium-containing raw material to the nitrogen element in the nitrogen-containing raw material is preferably 1:1 to 2:1, for example, 1:1 or 2:1.
In the present invention, in the method for preparing the N-doped titanium oxide, the reaction temperature may be 250 to 270 ℃, for example, 260 ℃.
In the present invention, in the method for preparing N-doped titanium oxide, the reaction time may be 2 to 4 days, for example, 3 days.
In the method for preparing the N-doped titanium oxide, the N-doped titanium oxide may be washed and dried according to a conventional operation in the art.
Wherein, the washing solvent can be ethanol.
Wherein the temperature of the drying may be 90 ℃.
In the present invention, it is preferred that the ball-to-feed ratio in the ball mill is (40-50): 1, for example 45: 1.
In the invention, preferably, in the ball milling, the rotation speed of a main shaft is 260-280 r.min -1 E.g. 270 r.min -1 。
In the present invention, it is preferable that the ball milling time is 2 to 4 hours, for example, 3 hours.
The invention also provides the magnesium-based coke oven gas hydrodesulfurization catalyst prepared by the preparation method of the magnesium-based coke oven gas hydrodesulfurization catalyst.
The positive progress effects of the invention are as follows:
the magnesium-based coke oven gas hydrodesulfurization catalyst can realize the thiophene conversion rate of more than or equal to 37% at 300 ℃, and the stability of the magnesium-based coke oven gas hydrodesulfurization catalyst is obviously improved.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. Experimental procedures without specifying specific conditions in the following examples were selected in accordance with conventional procedures and conditions, or in accordance with commercial instructions.
Example 1
(1) N-doped titanium oxide (N-TiO for short) 2 ) The preparation of (1): adding 0.04mol of titanium ethoxide into 20mL of benzene, stirring to light yellow, adding 0.08mol of triethylamine (the molar ratio of the titanium ethoxide to the triethylamine is 1: 2), uniformly stirring, sealing in a reaction kettle, keeping the temperature at 260 ℃ for 3 days, washing a product with ethanol, and drying at 90 ℃ to obtain the N-doped titanium oxide.
(2) Graphite, magnesium powder, polyurethane (Mw-75000) and N-TiO in the step (1) 2 The mixture is loaded into a ball milling tank according to the mass ratio of 3:7:3:2, and the ball-material ratio (mass ratio) is 45: 1. The setting operation frequency of the ball mill is 45Hz, and the corresponding main shaft rotating speed is 270 r.min -1 The alternation run time was 15min.
(3) The method comprises the steps of blowing air in a ball milling tank completely by using hydrogen in a high-pressure reaction kettle, filling hydrogen into the tank to 1Mpa, carrying out ball milling on an ND7-2L type planetary ball mill once every 0.5h to keep the hydrogen pressure of the tank at 1Mpa continuously, and carrying out ball milling for 3h.
(4) And after the ball milling is finished, taking materials in a glove box under the protection of argon, tabletting and forming the taken materials by using an XYP-24 type powder tabletting machine, and crushing the materials into millimeter-grade particles.
Example 2
(1) N-doped titanium oxide (N-TiO for short) 2 ) The preparation of (1): adding 0.06mol of titanium ethoxide into 20mL of benzene, stirring to light yellow, adding 0.06mol of triethylamine (the molar ratio of the titanium ethoxide to the triethylamine is 1: 1), uniformly stirring, sealing in a reaction kettle, keeping the temperature at 260 ℃ for 3 days, cleaning the product with ethanol, and drying at 90 ℃ to obtain the N-doped titanium oxide.
(2) Mixing graphite, magnesium powder, polyurethane (Mw-100000) and N-doped titanium oxide in the step (1) according to the massThe mixture is put into a ball milling tank according to the weight ratio of 3:7:3:2, and the ball material ratio (mass ratio) is 45: 1. The setting operation frequency of the ball mill is 45Hz, and the corresponding main shaft rotating speed is 270 r.min -1 The alternation run time was 15min.
(3) The method comprises the steps of blowing air in a ball milling tank completely by using hydrogen in a high-pressure reaction kettle, filling hydrogen into the tank to 1Mpa, carrying out ball milling on an ND7-2L type planetary ball mill once every 0.5h to keep the hydrogen pressure of the tank at 1Mpa continuously, and carrying out ball milling for 3h.
(4) And after the ball milling is finished, taking materials in a glove box under the protection of argon, tabletting and forming the taken materials by using an XYP-24 type powder tabletting machine, and crushing the materials into millimeter-grade particles.
Example 3
(1) N-doped titanium oxide (N-TiO for short) 2 ) The preparation of (1): adding 0.08mol of titanium ethoxide into 20mL of benzene, stirring to light yellow, adding 0.04mol of triethylamine (the molar ratio of the titanium ethoxide to the triethylamine is 2: 1), uniformly stirring, sealing in a reaction kettle, keeping the temperature at 260 ℃ for 3 days, washing a product with ethanol, and drying at 90 ℃ to obtain the N-doped titanium oxide.
(2) And (2) filling graphite, magnesium powder, polyurethane (Mw-120000) and the N-doped titanium oxide in the step (1) into a ball milling tank according to the mass ratio of 3:7:3:2, wherein the ball-material ratio (mass ratio) is 45: 1. The setting operation frequency of the ball mill is 45Hz, and the corresponding main shaft rotating speed is 270 r.min -1 The alternation run time was 15min.
(3) The method comprises the steps of blowing air in a ball milling tank completely by using hydrogen in a high-pressure reaction kettle, filling hydrogen into the tank to 1Mpa, carrying out ball milling on an ND7-2L type planetary ball mill once every 0.5h to keep the hydrogen pressure of the tank at 1Mpa continuously, and carrying out ball milling for 3h.
(4) And after the ball milling is finished, taking materials in a glove box under the protection of argon, tabletting the taken materials by using an XYP-24 type powder tabletting machine, and crushing the materials into millimeter-grade particles.
Example 4
Step (2) is as follows, and the rest is the same as in example 2.
(2) Doping graphite, magnesium powder, polyurethane (Mw-100000) and N in the step (1)The titanium oxide is filled into a ball milling tank according to the mass ratio of 3:7:4:1, and the ball material ratio (mass ratio) is 45: 1. The setting operation frequency of the ball mill is 45Hz, and the corresponding main shaft rotating speed is 270 r.min -1 The alternation run time was 15min.
Example 5
Step (2) is as follows, and the rest is the same as in example 2.
(2) And (2) filling graphite, magnesium powder, polyurethane (Mw-100000) and the N-doped titanium oxide in the step (1) into a ball milling tank according to the mass ratio of 3:7:1:4, wherein the ball-material ratio (mass ratio) is 45: 1. The setting operation frequency of the ball mill is 45Hz, and the corresponding main shaft rotating speed is 270 r.min -1 The alternation run time was 15min.
Example 6
The procedures (2) and (3) are as follows, and the rest is the same as in example 2.
(2) And (2) filling graphite, magnesium powder, polyurethane (Mw-100000) and the N-doped titanium oxide in the step (1) into a ball milling tank according to the mass ratio of 3:7: 5:1, wherein the ball-material ratio (mass ratio) is 45: 1. The setting operation frequency of the ball mill is 45Hz, and the corresponding main shaft rotating speed is 270 r.min -1 The alternation run time was 15min.
(3) The ball milling time was 2h, as in example 2.
Example 7
The procedures (2) and (3) are as follows, and the rest is the same as in example 2.
(2) And (2) filling graphite, magnesium powder, polyurethane (Mw-100000) and the N-doped titanium oxide in the step (1) into a ball milling tank according to the mass ratio of 3:7:1: 5, wherein the ball-material ratio (mass ratio) is 45: 1. The setting operation frequency of the ball mill is 45Hz, and the corresponding main shaft rotating speed is 270 r.min -1 The alternation run time was 15min.
(3) The ball milling time was 4h, as in example 2.
Comparative example 1
Step (1) is as follows, and the rest is the same as in example 2.
(1) N-doped zirconia (N-ZrO for short) 2 ) The preparation of (1): 0.04mol of zirconium ethoxide is added to 20mL of benzene, stirred to light yellow, and 0.04mol of triethylamine (triethylamine and ethyl) is addedThe molar ratio of zirconium alkoxide is 1: 1), the mixture is evenly stirred and then sealed in a reaction kettle, the temperature is kept for 3 days at 250 ℃, and the product is cleaned by ethanol and dried at 90 ℃ to obtain the N-doped zirconium oxide.
Comparative example 2
Step (1) is as follows, and the rest is the same as in example 2.
(1) N-doped titanium oxide (N-TiO for short) 2 ) The preparation of (1): adding 0.03mol of titanium ethoxide into 20mL of benzene, stirring to light yellow, adding 0.09mol of triethylamine (the molar ratio of triethylamine to titanium ethoxide is 1: 4), uniformly stirring, sealing in a reaction kettle, keeping the temperature at 260 ℃ for 3 days, washing a product with ethanol, and drying at 90 ℃ to obtain the N-doped titanium oxide.
Comparative example 3
Step (1) is as follows, and the rest is the same as in example 2.
(1) N-doped titanium oxide (N-TiO for short) 2 ) The preparation of (1): adding 0.09mol of titanium ethoxide into 20mL of benzene, stirring to light yellow, adding 0.03mol of triethylamine (the molar ratio of triethylamine to titanium ethoxide is 3: 1), uniformly stirring, sealing in a reaction kettle, keeping the temperature at 260 ℃ for 3 days, washing a product with ethanol, and drying at 90 ℃ to obtain the N-doped titanium oxide.
Comparative example 4
Step (2) is as follows, and the rest is the same as in example 2.
(2) And (2) filling graphite, magnesium powder, polyurethane (Mw-60000) and the N-doped titanium oxide in the step (1) into a ball milling tank according to the mass ratio of 3:7:3:2, wherein the ball-material ratio (mass ratio) is 45: 1. The setting operation frequency of the ball mill is 45Hz, and the corresponding main shaft rotating speed is 270 r.min -1 The alternation run time was 15min.
Comparative example 5
Step (2) is as follows, and the rest is the same as in example 2.
(2) And (2) filling graphite, magnesium powder, polyurethane (Mw-150000) and the N-doped titanium oxide in the step (1) into a ball milling tank according to the mass ratio of 3:7:3:2, wherein the ball-material ratio (mass ratio) is 45: 1. The setting operation frequency of the ball mill is 45Hz, and the corresponding main shaft rotating speed is 270 r.min -1 The alternation run time was 15min.
Comparative example 6
Step (2) is as follows, and the rest is the same as in example 2.
(2) And (2) filling graphite, magnesium powder, polyamide (Mw-100000) and the N-doped titanium oxide in the step (1) into a ball milling tank according to the mass ratio of 3:7:3:2, wherein the ball-material ratio (mass ratio) is 45: 1. The setting operation frequency of the ball mill is 45Hz, and the corresponding main shaft rotating speed is 270 r.min -1 The alternation run time was 15min.
Effect example 1
The experimental raw materials and reagents mainly comprise thiophene, argon, carbon dioxide, lead nitrate, ethanol and the like. Wherein, the purity of the thiophene is 99.0 percent (the content of impurities, namely carbon disulfide is less than 0.1 percent, and the content of nonvolatile substances is less than 0.01 percent), the purity of argon is 99.9 percent, the purity of carbon dioxide is 99.9 percent, and lead nitrate and ethanol are analytically pure.
The specific method comprises the following steps: charging 1.0g of granular hydrogen storage material and 5mL of thiophene into a reaction kettle, discharging air in the kettle by using hydrogen, then charging the hydrogen into the kettle until the pressure is 0.9MPa, heating the reaction kettle to 300 ℃, keeping the temperature for 30min, and then purging the gas in the reaction kettle by using argon to generate H 2 The concentration of S is 0.5 mol.L -1 Pb (NO) of 3 ) 2 Absorbing the solution, and absorbing the unreacted thiophene by using an ethanol solution.
The results of the relevant performance tests of the catalysts are shown in table 1.
TABLE 1
Figure BDA0002779465040000071
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Claims (7)

1. The preparation method of the magnesium-based coke oven gas hydrodesulfurization catalyst is characterized by comprising the following steps of:
mixing graphite, magnesium powder, polyurethane and nitrogen-doped titanium oxide in a hydrogen atmosphere with the air pressure of 0.5-1.5MPa, and then carrying out ball milling to obtain the material; wherein:
the mass ratio of the graphite to the magnesium powder to the polyurethane to the nitrogen-doped titanium oxide is 3 (1-5) to (1-5);
the weight average molecular weight of the polyurethane is 75000-120000;
the nitrogen-doped titanium oxide is prepared by adopting the following method: mixing a titanium-containing raw material and a nitrogen-containing raw material for reaction to obtain the catalyst; the molar ratio of the titanium element in the titanium-containing raw material to the nitrogen element in the nitrogen-containing raw material is 1; the titanium-containing raw material is titanium ethoxide, the nitrogen-containing raw material is triethylamine, the reaction temperature is 250-270 ℃, and the reaction time is 2-4 days;
in the ball milling, the ball-material ratio is (40-50): 1, the main shaft rotating speed is 260-280 r.min -1 The ball milling time is 2-4 hours.
2. The preparation method of the magnesium-based coke oven gas hydrodesulfurization catalyst of claim 1, wherein the mass ratio of the graphite, the magnesium powder, the polyurethane and the nitrogen-doped titanium oxide is 3 (1-4) to (1-4).
3. The method for preparing the magnesium-based coke oven gas hydrodesulfurization catalyst of claim 2, wherein the mass ratio of the graphite, the magnesium powder, the polyurethane and the nitrogen-doped titanium oxide is 3.
4. The method of claim 1, wherein the weight average molecular weight of the polyurethane is 100000-120000.
5. The method for preparing the magnesium-based coke oven gas hydrodesulfurization catalyst of claim 1, wherein in the method for preparing the nitrogen-doped titanium oxide, the molar ratio of titanium element in the titanium-containing raw material to nitrogen element in the nitrogen-containing raw material is 1.
6. The method for preparing the magnesium-based coke oven gas hydrodesulfurization catalyst of claim 1, wherein in the ball milling, the ball-to-feed ratio is 45 -1 The ball milling time was 3 hours.
7. The magnesium-based coke oven gas hydrodesulfurization catalyst prepared by the preparation method of the magnesium-based coke oven gas hydrodesulfurization catalyst of any one of claims 1 to 6.
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