CN112473669A - Low-temperature low-pressure direct hydrogenation catalyst for coal-based 1, 4-butynediol and preparation method thereof - Google Patents

Low-temperature low-pressure direct hydrogenation catalyst for coal-based 1, 4-butynediol and preparation method thereof Download PDF

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CN112473669A
CN112473669A CN202011369315.5A CN202011369315A CN112473669A CN 112473669 A CN112473669 A CN 112473669A CN 202011369315 A CN202011369315 A CN 202011369315A CN 112473669 A CN112473669 A CN 112473669A
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butynediol
ethanol
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王长真
赵永祥
李海涛
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Shanxi University
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Abstract

The invention relates to a low-temperature low-pressure direct hydrogenation catalyst for coal-based 1, 4-butynediol and a preparation method thereof. The basic structural unit of the catalyst has a monodisperse spherical coating structure, and the catalyst consists of a uniform silicon oxide inner core and a metal phyllosilicate shell layer. The preparation steps are as follows: (1) preparing an ethanol-water solution, and adjusting with ammonia water; (2) preparing a mixed solution; (3) centrifugally filtering the mixed solution, washing with ethanol and deionized water, respectively, and drying the filtered articles to obtain uniformly layered SiO with a coating structure2@SiO2Nanosphere(ii) a (4) Taking the prepared SiO2@SiO22.0g of nanospheres are dispersed in water, and are refluxed and stirred with a metal nickel precursor and urea to carry out nickel phyllosilicate deposition; (5) centrifugally filtering the solution, washing, filtering and drying to obtain Ni-Si-PS @ SiO2A precursor; (6) the obtained Ni-X-Si-PS @ SiO2Preparing secondary deposition Ni-Si-PS @ SiO2A precursor; (7) depositing Ni-Si-PS @ SiO twice2Calcining the precursor in air atmosphere to obtain the low-temperature low-pressure hydrogenation catalyst Ni-Si-PS @ SiO2。

Description

Low-temperature low-pressure direct hydrogenation catalyst for coal-based 1, 4-butynediol and preparation method thereof
Technical Field
The invention relates to a low-temperature low-pressure direct hydrogenation catalyst for coal-based 1, 4-butynediol and a preparation method thereof, belonging to the technical field of catalysts.
Background
At present, the main method for industrially producing the 1, 4-butanediol is to use coal-based 1, 4-butynediol for hydrogenation preparation. However, in the hydrogenation process of 1, 4-butynediol, the hydrogenation intermediate species 1, 4-butenediol is easily isomerized into a 2-hydroxytetrahydrofuran byproduct with a hemiacetal structure and finally converted into cyclic acetal 2- (4' -hydroxybutoxy) -tetrahydrofuran, and the final byproduct and 1, 4-butanediol form an azeotrope, which cannot be removed by a conventional rectification method, so that the purity and chromaticity of the 1, 4-butanediol product are seriously reduced, and the quality of the 1, 4-butanediol and the application thereof in the downstream field are directly influenced.
Chinese patent CN 102145286B discloses a Ni-SiO2/Al2O3The catalyst can effectively realize hydrolysis and hydro-conversion of cyclic acetal 2- (4' -hydroxybutoxy) -tetrahydrofuran, but the preparation process is complex. Chinese patent CN106902826B discloses a Ni-Al coated steel sheet2O3@Al2O3-SiO2The catalyst and the preparation method thereof have harsh hydrogenation reaction conditions (the reaction temperature is 100-150 ℃ and the pressure is 10-20 MPa) in order to realize the conversion of the cyclic acetal 2- (4' -hydroxybutoxy) -tetrahydrofuran. At present, the methods for eliminating the reaction by-product in industrial and experimental researches are all methods for promoting the high-temperature and high-pressure conversion of the by-product by using a modified catalyst.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a low-temperature low-pressure direct hydrogenation catalyst for coal-based 1, 4-butynediol and a preparation method thereof.
In order to solve the technical problems, the invention adopts the technical scheme that:
a low-temperature low-pressure direct hydrogenation catalyst for coal-based 1, 4-butynediol is characterized in that a basic structural unit of the catalyst has a monodisperse spherical coating structure, and the catalyst consists of a uniform silicon oxide inner core and a metal phyllosilicate shell layer.
Furthermore, the inner core of the silicon oxide in the basic structural unit of the catalyst is solid, and the diameter is 250 nm-550 nm; the metal phyllosilicate shell is porous and spongy, the thickness of the shell is 50-115 nm, and the specific surface area is 200m2/g～400m2The pore diameter is 2.5 nm-4.0 nm, the chemical composition is Ni-Si-PS, and PS is layered phyllosilicate.
A preparation method of a low-temperature low-pressure direct hydrogenation catalyst for coal-based 1, 4-butynediol comprises the following steps:
(1) preparing an ethanol-water solution, and adjusting the pH value to 7.5-9.0 by ammonia water;
(2) raising the temperature to 30-60 ℃, firstly slowly adding 30-120 mL/L of silicon precursor into the ethanol-water solution, violently stirring for 1-10 h, continuously adding 5-30 mL/L of silane coupling and pore-forming agent and 50-100 mL/L of silicon precursor, and violently stirring the mixed solution for 1-10 h;
(3) after the mixed solution is centrifugally filtered, the mixed solution is washed by ethanol and deionized water for 3-5 times respectively, and filtered objects are dried for 6-15 hours at the temperature of 80-150 ℃ to obtain SiO with a uniformly layered coating structure2@SiO2Nanospheres;
(4) taking the SiO prepared in the step (3)2@SiO2Dispersing 2.0g of nanospheres in 150-500 mL of water, respectively dissolving 0.005-0.010 mol of metal nickel precursor and 0.2-0.4 mol of urea in the water, heating to 60-120 ℃, and performing reflux stirring for 2-6 h to perform nickel phyllosilicate deposition;
(5) after the solution is centrifugally filtered, washing the solution with ethanol and deionized water for 3-5 times respectively, and drying the filtered product at 80-150 ℃ for 4-24 h to obtain primary deposited Ni-Si-PS @ SiO2A precursor;
(6) calcining the obtained solid in air atmosphere at 400-600 ℃ for 2-10 h, then switching to flowing hydrogen atmosphere for reduction for 2-5 h, wherein the heating rate is 1-10 ℃/min, and obtaining the coal-based 1, 4-butynediol with the Ni content of 5-10 percent for one-step direct preparation of coal-based 1, 4-butynediolLow-temperature low-pressure hydrogenation catalyst Ni-Si-PS @ SiO for hydrogenation to 1, 4-butanediol2。
A preparation method of a low-temperature low-pressure direct hydrogenation catalyst for coal-based 1, 4-butynediol comprises the following steps:
(1) preparing an ethanol-water solution, and adjusting the pH value to 7.5-9.0 by ammonia water;
(2) raising the temperature to 30-60 ℃, firstly slowly adding 30-120 mL/L of silicon precursor into the ethanol-water solution, violently stirring for 1-10 h, continuously adding 5-30 mL/L of silane coupling and pore-forming agent and 50-100 mL/L of silicon precursor, and violently stirring the mixed solution for 1-10 h;
(3) after the mixed solution is centrifugally filtered, the mixed solution is washed by ethanol and deionized water for 3-5 times respectively, and filtered objects are dried for 6-15 hours at the temperature of 80-150 ℃ to obtain SiO with a uniformly layered coating structure2@SiO2Nanospheres;
(4) taking the SiO prepared in the step (3)2@SiO2Dispersing 2.0g of nanospheres in 150-500 mL of water, respectively dissolving 0.005-0.010 mol of metal nickel precursor and 0.2-0.4 mol of urea in the water, heating to 60-120 ℃, and performing reflux stirring for 2-6 h to perform nickel phyllosilicate deposition;
(5) after the solution is centrifugally filtered, washing the solution with ethanol and deionized water for 3-5 times respectively, and drying the filtered product at 80-150 ℃ for 4-24 h to obtain primary deposited Ni-Si-PS @ SiO2A precursor;
(6) the primary deposition Ni-X-Si-PS @ SiO obtained in the step (5)2Precursor is substituted for SiO used in step (4)2@SiO2Nanospheres, and repeating the operation of the step (4) and the step (5) to obtain secondary deposition Ni-Si-PS @ SiO2A precursor;
(7) calcining the obtained solid in an air atmosphere at 400-600 ℃ for 2-10 h, then switching to a flowing hydrogen atmosphere for reduction for 2-5 h, wherein the heating rate is 1-10 ℃/min, and obtaining a low-temperature low-pressure hydrogenation catalyst Ni-Si-PS @ SiO for preparing coal-based 1, 4-butynediol with the Ni content of 10-20 percent and directly hydrogenating the coal-based 1, 4-butynediol to 1, 4-butanediol in one step2。
A preparation method of a low-temperature low-pressure direct hydrogenation catalyst for coal-based 1, 4-butynediol comprises the following steps:
(1) preparing an ethanol-water solution, and adjusting the pH value to 7.5-9.0 by ammonia water;
(2) raising the temperature to 30-60 ℃, firstly slowly adding 30-120 mL/L of silicon precursor into the ethanol-water solution, violently stirring for 1-10 h, continuously adding 5-30 mL/L of silane coupling and pore-forming agent and 50-100 mL/L of silicon precursor, and violently stirring the mixed solution for 1-10 h;
(3) after the mixed solution is centrifugally filtered, the mixed solution is washed by ethanol and deionized water for 3-5 times respectively, and filtered objects are dried for 6-15 hours at the temperature of 80-150 ℃ to obtain SiO with a uniformly layered coating structure2@SiO2Nanospheres;
(4) taking the SiO prepared in the step (3)2@SiO2Dispersing 2.0g of nanospheres in 150-500 mL of water, respectively dissolving 0.005-0.010 mol of metal nickel precursor and 0.2-0.4 mol of urea in the water, heating to 60-120 ℃, and performing reflux stirring for 2-6 h to perform nickel phyllosilicate deposition;
(5) after the solution is centrifugally filtered, washing the solution with ethanol and deionized water for 3-5 times respectively, and drying the filtered product at 80-150 ℃ for 4-24 h to obtain primary deposited Ni-Si-PS @ SiO2A precursor;
(6) the primary deposition Ni-X-Si-PS @ SiO obtained in the step (5)2Precursor is substituted for SiO used in step (4)2@SiO2Nanospheres, and repeating the operation of the step (4) and the step (5) to obtain secondary deposition Ni-Si-PS @ SiO2A precursor;
(7) depositing the secondary Ni-X-Si-PS @ SiO obtained in the step (6)2Precursor is substituted for SiO used in step (4)2@SiO2Nanospheres, and repeating the operation of the step (4) and the step (5) to obtain three times of deposited Ni-Si-PS @ SiO2A precursor;
(8) calcining the obtained solid in air atmosphere at 400-600 ℃ for 2-10 h, then switching to flowing hydrogen atmosphere for reduction for 2-5 h, wherein the heating rate is 1-10 ℃/min, and the obtained coal-based 1, 4-butynediol with the Ni content of 15-30% is directly added in one step for preparing coal-based 1, 4-butynediolLow-temperature low-pressure hydrogenation catalyst Ni-Si-PS @ SiO for hydrogenation of hydrogen to 1, 4-butanediol2。
Further, the volume ratio of ethanol to water in the ethanol-water solution in the step (1) is 0.5-10: 1.
Further, the silicon precursor in the step (2) is one of silica sol, ethyl orthosilicate or methyl orthosilicate; the silane coupling and pore-forming agent is one of octadecyl trimethoxy silane, hexadecyl trimethoxy silane, dodecyl trimethoxy silane or aminopropyl trimethoxy silane.
Further, the metallic nickel precursor in step (4) is one of nickel nitrate, nickel acetylacetonate or nickel acetate, preferably nickel acetylacetonate.
Further, in the step (4), the upper limit of the nickel precursor deposition is 0.010mol, and if the upper limit is exceeded, multiple depositions are required.
Further, the upper limit of each deposition of the nickel precursor in the steps (4) and (6) is 0.010mol, and if the upper limit exceeds the upper limit, multiple depositions are required.
Further, the upper limit of the nickel precursor deposition in each of the step (4), the step (6) and the step (7) is 0.010mol, and if the upper limit exceeds the upper limit, multiple depositions are required.
In the preparation method, under the condition of ensuring that the concentration of the nickel precursor deposited once does not exceed the upper limit of the nickel precursor, the Ni-Si-PS @ SiO with the same Ni weight content is prepared by one-time deposition or multiple depositions2The texture and the structural property of the catalyst are not very different, and the low-temperature and low-pressure hydrogenation activity of the 1, 4-butynediol is close (see examples 5 and 7).
The catalyst is suitable for kettle type direct hydroconversion of which the raw material is 25-35 wt% of 1, 4-butynediol aqueous solution. Reaction conditions are as follows: the volume of the raw material is 15 mL-100 mL, the dosage of the catalyst is 0.05 g-0.4 g, the reaction temperature is 25-100 ℃, the hydrogen pressure is 0.5 MPa-5 MPa, and the hydrogenation time is 3 h. The conversion rate of 1, 4-butynediol in a net material phase after hydrogenation is more than or equal to 99.9 percent, the yield of 1, 4-butanediol is more than or equal to 94.0 percent, the byproduct 1, 4-butenediol is less than or equal to 1.0 percent, the content of 2-hydroxy-tetrahydrofuran is less than or equal to 2.0 percent, and the content of 2- (4' -hydroxybutoxy) -tetrahydrofuran is less than or equal to 2.0 percent, and the catalyst has excellent stability.
The invention has the advantages that:
1. the traditional path for inhibiting the content of acetal by-products in the BYD hydrogenation process is to promote the conversion of the by-products under high temperature and high pressure (the reaction temperature is 100-150 ℃ and the pressure is 10-20 MPa), the invention provides a path for inhibiting the isomeric conversion of 1, 4-butenediol serving as a hydrogenation intermediate species to 2-hydroxytetrahydrofuran (namely acetal precursor) by-products at the initial stage of the reaction by utilizing a functional synergistic catalyst, and the 1, 4-butynediol is efficiently and directly hydrogenated to the 1, 4-butanediol at low temperature and low pressure (the reaction temperature is 25-100 ℃ and the pressure is 0.5-5 MPa).
2. The core of the idea is to inhibit the conversion process of 1, 4-butylene glycol to 2-hydroxytetrahydrofuran, and the catalyst provided by the invention is used for low-temperature and low-pressure direct hydrogenation of coal-based 1, 4-butynediol, wherein the shell layer of the catalyst has a layered silicate structure consisting of nickel-silicon, and the active center of metal Ni is precipitated on the surface of a silicate carrier after being reduced, but still has an interaction with a part of unreduced Ni-PS to form Ni0-Ni2+Synergistically, electropositivity of the metal sites (fig. 2) favors stable adsorption of the C ═ C double bond in 1, 4-butenediol, inhibiting the conversion of intermediates to 2-hydroxytetrahydrofuran and acetals.
3. The first addition of the silicon precursor in step (2) of the preparation method of the present invention is intended to form dense SiO2The inner core is added, and the silicon precursor is added again after the silane coupling and pore-forming agent is added, so that SiO with loose structure is formed2The shell layer is further beneficial to the formation of the metal phyllosilicate structure and the porous structure of the shell layer.
4. In the preparation method, the silane coupling and pore-forming agent added in the step (2) has multiple functions, and on one hand, the silane coupling and pore-forming agent with long chain, long length and strong polarity is easy to be combined with the formed SiO2And (3) performing bonding growth on the seed crystal kernel to induce the formation of a coating structure monomer structure, on the other hand, removing the seed crystal kernel in the calcining process to form uniform mesopores, and adjusting the pore size of the ordered pore channel of the phyllosilicate of the shell layer by controlling the types of silane coupling and pore-forming agents.
5. The preparation method of the invention adopts a newThe multiple deposition process of urea dissolution-deposition of type forms a metal phyllosilicate shell: first, SiO2@SiO2SiO of the outer layer2Partially dissolved to form SiO under alkalescent condition4Tetrahedrally, nickel forms NiO under weakly alkaline conditionsx(OH)6-xOctahedron, two kinds of structural units are structurally assembled under the mild condition to form a nickel phyllosilicate shell layer with a 1:1 structure. Compared with the common nickel phyllosilicate with a 2:1 structure (the reduction temperature is 750 ℃), the nickel phyllosilicate with a 1:1 structure is easier to activate (the reduction temperature is 580 ℃, and the figure 3) and has stronger hydrogen overflow capacity, thereby being beneficial to low-temperature hydrogenation reaction.
6. The metal nickel sites are derived from the reduction growth of metal components in the nickel phyllosilicate, are decorated in a phyllosilicate shell layer framework, have strong metal-carrier interaction, can disperse and limit metal particles, and greatly improve the activity, the target product selectivity and the stability of the catalyst in the hydrogenation reaction of 1, 4-butynediol and an intermediate 1, 4-butenediol.
7. Different from the structure of common sheet or needle-shaped phyllosilicate, the phyllosilicate prepared by the invention has a loose porous sponge structure, large specific surface area and dense and uniform pore structure, and is beneficial to the dispersion of metal sites and the contact and adsorption of reaction materials.
8. The metal phyllosilicate has a rock structure, prevents water in a water-containing system from attacking a silicon carrier, effectively improves the hydrothermal stability of the catalyst, and prolongs the service life of the catalyst.
Drawings
FIG. 1 shows Ni-Si-PS @ SiO in example 2 of the present invention2Schematic transmission electron microscope of catalyst structure;
FIG. 2 shows Ni-Si-PS @ SiO in example 1 of the present invention2Catalyst Ni 2p orbital XPS spectra;
FIG. 3 shows Ni-Si-PS @ SiO in example 4 of the present invention2Catalyst H2And (5) heating the temperature program to restore the image.
Detailed Description
The invention is further described below with reference to the figures and examples.
Example 1
Preparing an ethanol-water solution with the volume ratio of ethanol to water being 0.5:1, and adjusting the pH value to 7.5 by using ammonia water; raising the temperature to 60 ℃, slowly adding 30mL/L methyl orthosilicate into the ethanol-water solution, stirring vigorously for 1h, continuously adding 27mL/L hexadecyl trimethoxy silane and 85mL/L methyl orthosilicate, and stirring vigorously the mixed solution for 1 h; centrifugally filtering the mixed solution, washing with ethanol and deionized water for 3 times, drying the filtered product at 90 deg.C for 10 hr to obtain uniformly layered SiO with coating structure2@SiO2Nanospheres.
② taking 2.0g of prepared SiO2@SiO2Dispersing nanospheres in 150mL of water, respectively dissolving 0.005mol of nickel acetylacetonate and 0.4mol of urea in the nanospheres, heating to 60 ℃, refluxing and stirring for 4h, centrifuging, filtering, washing with ethanol and deionized water for 5 times, drying the filtered product at 120 ℃ for 4h to obtain primary deposited Ni-Si-PS @ SiO2A precursor.
Thirdly, calcining the finally obtained solid in the air atmosphere at the temperature of 600 ℃ for 2h, then switching to the flowing hydrogen atmosphere for calcining for 2h, wherein the heating rate is 8 ℃/min, and obtaining the low-temperature low-pressure hydrogenation catalyst Ni-Si-PS @ SiO for preparing the coal-based 1, 4-butynediol by directly hydrogenating to 1, 4-butanediol in one step2And the number-1.
Example 2
Preparing an ethanol-water solution with the volume ratio of ethanol to water being 10:1, and adjusting the pH value to 8.5 by using ammonia water; raising the temperature to 40 ℃, slowly adding 80mL/L of ethyl orthosilicate into the ethanol-water solution, stirring vigorously for 2 hours, continuously adding 22mL/L of hexadecyl trimethoxy silane and 70mL/L of ethyl orthosilicate, and stirring vigorously the mixed solution for 1 hour; centrifugally filtering the mixed solution, washing with ethanol and deionized water for 3 times, drying the filtered product at 60 deg.C for 8 hr to obtain uniformly layered SiO with coating structure2@SiO2Nanospheres.
② taking 2.0g of prepared SiO2@SiO2Dispersing nanospheres in 500mL water, dissolving nickel acetate 0.006mol and urea 0.2mol respectively, heating to 120 deg.C, refluxing and stirring for 2 hr, centrifuging, washing with ethanol and deionized water for 3 times, and filteringDrying for 24h at 100 ℃ to obtain primary deposited Ni-Si-PS @ SiO2A precursor.
Thirdly, calcining the finally obtained solid in air atmosphere at 500 ℃ for 8h, then switching to flowing hydrogen atmosphere for calcining for 2h, wherein the heating rate is 8 ℃/min, and obtaining the low-temperature low-pressure hydrogenation catalyst Ni-Si-PS @ SiO for preparing the coal-based 1, 4-butynediol by directly hydrogenating to 1, 4-butanediol in one step2And the number-2.
Example 3
Preparing an ethanol-water solution with the volume ratio of ethanol to water being 1:1, and adjusting the pH value to 9.0 by using ammonia water; raising the temperature to 30 ℃, slowly adding 40mL/L of silica sol into the ethanol-water solution, vigorously stirring for 7 hours, continuously adding 30mL/L of dodecyl trimethoxy silane and 100mL/L of silica sol, and vigorously stirring the mixed solution for 4 hours; centrifugally filtering the mixed solution, washing with ethanol and deionized water for 3 times, drying the filtered product at 125 deg.C for 12 hr to obtain uniformly layered SiO with coating structure2@SiO2Nanospheres.
② taking 2.0g of prepared SiO2@SiO2Dispersing nanospheres in 300mL of water, respectively dissolving 0.01mol of nickel acetate and 0.2mol of urea in the nanospheres, heating to 70 ℃, refluxing and stirring for 5h, centrifuging and filtering, respectively washing with ethanol and deionized water for 5 times, drying the filtered product at 80 ℃ for 8h to obtain primary deposited Ni-Si-PS @ SiO2A precursor.
Thirdly, calcining the finally obtained solid in air atmosphere at 500 ℃ for 5h, then switching to flowing hydrogen atmosphere for calcining for 5h, wherein the heating rate is 5 ℃/min, and obtaining the low-temperature low-pressure hydrogenation catalyst Ni-Si-PS @ SiO for preparing the coal-based 1, 4-butynediol by directly hydrogenating to 1, 4-butanediol in one step2And the number-3.
Example 4
Preparing an ethanol-water solution with the volume ratio of ethanol to water being 5:1, and adjusting the pH value to be 8.0 by using ammonia water; raising the temperature to 35 ℃, slowly adding 80mL/L of ethyl orthosilicate into the ethanol-water solution, stirring vigorously for 1.5h, continuously adding 20mL/L of octadecyltrimethoxysilane and 65mL/L of ethyl orthosilicate, and stirring vigorously the mixed solution for 3 h; centrifuging and filtering the mixed solution, and respectively adding ethanol and deionized waterWashing for 4 times, drying the filtered material at 80 deg.C for 12h to obtain uniformly layered SiO with coating structure2@SiO2Nanospheres.
② taking 2.0g of prepared SiO2@SiO2Dispersing nanospheres in 250mL of water, respectively dissolving 0.006mol of nickel acetylacetonate and 0.25mol of urea in the nanospheres, heating to 80 ℃, refluxing and stirring for 3h, centrifuging, filtering, washing with ethanol and deionized water for 4 times, drying the filtered product at 90 ℃ for 12h to obtain primary deposited Ni-Si-PS @ SiO2A precursor.
Thirdly, replacing SiO in the step II with the obtained primary deposition precursor2@SiO2The nanospheres are repeatedly subjected to the same nickel deposition process to obtain secondary deposited Ni-Si-PS @ SiO2A precursor.
Fourthly, calcining the finally obtained solid in an air atmosphere at the temperature of 450 ℃ for 4h, then switching to a flowing hydrogen atmosphere for calcining for 3h, wherein the heating rate is 5 ℃/min, and obtaining the low-temperature low-pressure hydrogenation catalyst Ni-Si-PS @ SiO for preparing the coal-based 1, 4-butynediol by directly hydrogenating to 1, 4-butanediol in one step2Number-4
Example 5
Preparing an ethanol-water solution with the volume ratio of ethanol to water being 8:1, and adjusting the pH value to 7.5 by using ammonia water; raising the temperature to 40 ℃, slowly adding 90mL/L methyl orthosilicate into the ethanol-water solution, stirring vigorously for 4 hours, continuously adding 22mL/L dodecyl trimethoxy silane and 80mL/L methyl orthosilicate, and stirring vigorously the mixed solution for 10 hours; centrifugally filtering the mixed solution, washing with ethanol and deionized water for 5 times, and drying the filtered product at 90 deg.C for 6 hr to obtain uniformly layered SiO with coating structure2@SiO2Nanospheres.
② taking 2.0g of prepared SiO2@SiO2Dispersing nanospheres in 200mL of water, respectively dissolving 0.009mol of nickel acetylacetonate and 0.3mol of urea in the nanospheres, heating to 75 ℃, refluxing and stirring for 6h, centrifuging, filtering, washing with ethanol and deionized water for 3 times, drying the filtered product at 150 ℃ for 6h to obtain primary deposited Ni-Si-PS @ SiO2A precursor.
Thirdly, replacing SiO in the step II with the obtained primary deposition precursor2@SiO2The nanospheres are repeatedly subjected to the same nickel deposition process to obtain secondary deposited Ni-Si-PS @ SiO2A precursor.
Fourthly, calcining the finally obtained solid in an air atmosphere at the temperature of 400 ℃ for 7h, then switching to a flowing hydrogen atmosphere for calcining for 4h, wherein the heating rate is 1 ℃/min, and obtaining the low-temperature low-pressure hydrogenation catalyst Ni-Si-PS @ SiO for preparing the coal-based 1, 4-butynediol by directly hydrogenating to 1, 4-butanediol in one step2And the number-5.
Example 6
Preparing an ethanol-water solution with the volume ratio of ethanol to water being 3:1, and adjusting the pH value to 8.5 by using ammonia water; raising the temperature to 45 ℃, slowly adding 60mL/L of ethyl orthosilicate into the ethanol-water solution, stirring vigorously for 5 hours, continuously adding 5mL/L of propylaminotrimethoxysilane and 50mL/L of ethyl orthosilicate, and stirring vigorously the mixed solution for 6 hours; centrifugally filtering the mixed solution, washing with ethanol and deionized water for 5 times, drying the filtered product at 140 deg.C for 15 hr to obtain uniformly layered SiO with coating structure2@SiO2Nanospheres.
② taking 2.0g of prepared SiO2@SiO2Dispersing nanospheres in 200mL of water, respectively dissolving 0.010mol of nickel nitrate and 0.2mol of urea in the nanospheres, heating to 90 ℃, refluxing and stirring for 2h, centrifuging and filtering, respectively washing with ethanol and deionized water for 3 times, drying the filtered product at 140 ℃ for 10h to obtain primary deposited Ni-Si-PS @ SiO2A precursor.
Thirdly, replacing SiO in the step II with the obtained primary deposition precursor2@SiO2The nanospheres are repeatedly subjected to the same nickel deposition process to obtain secondary deposited Ni-Si-PS @ SiO2A precursor.
Fourthly, calcining the finally obtained solid in an air atmosphere at the temperature of 420 ℃ for 10h, then switching to a flowing hydrogen atmosphere for calcining for 4h, wherein the heating rate is 10 ℃/min, and obtaining the low-temperature low-pressure hydrogenation catalyst Ni-Si-PS @ SiO for preparing the coal-based 1, 4-butynediol by directly hydrogenating to 1, 4-butanediol in one step2And the number-6.
Example 7
Preparing an ethanol-water solution with the volume ratio of ethanol to water being 7:1, and adjusting the pH value to be 8 by ammonia water0; raising the temperature to 35 ℃, slowly adding 80mL/L of ethyl orthosilicate into the ethanol-water solution, stirring vigorously for 1.5h, continuously adding 20mL/L of octadecyltrimethoxysilane and 65mL/L of ethyl orthosilicate, and stirring vigorously the mixed solution for 3 h; centrifugally filtering the mixed solution, washing with ethanol and deionized water for 4 times, drying the filtered product at 80 deg.C for 12 hr to obtain uniformly layered SiO with coating structure2@SiO2Nanospheres.
② taking 2.0g of prepared SiO2@SiO2Dispersing nanospheres in 250mL of water, respectively dissolving nickel nitrate 0.006mol and urea 0.25mol in the nanospheres, heating to 80 ℃, refluxing and stirring for 3h, centrifuging, filtering, washing with ethanol and deionized water for 4 times, drying the filtered product at 90 ℃ for 12h to obtain primary deposited Ni-Si-PS @ SiO2A precursor.
Thirdly, replacing SiO in the step II with the obtained primary deposition precursor2@SiO2The nanospheres are repeatedly subjected to the same nickel deposition process to obtain secondary deposited Ni-Si-PS @ SiO2A precursor; the obtained secondary deposition precursor is again substituted for SiO in step 22@SiO2The nanospheres are repeatedly subjected to the same nickel deposition process to obtain three times of deposited Ni-Si-PS @ SiO2A precursor.
Fourthly, calcining the finally obtained solid in an air atmosphere at the temperature of 450 ℃ for 4h, then switching to a flowing hydrogen atmosphere for calcining for 3h, wherein the heating rate is 5 ℃/min, and obtaining the low-temperature low-pressure hydrogenation catalyst Ni-Si-PS @ SiO for preparing the coal-based 1, 4-butynediol by directly hydrogenating to 1, 4-butanediol in one step2And the number-7.
Example 8
Preparing an ethanol-water solution with the volume ratio of ethanol to water being 7.5:1, and adjusting the pH value to be 7.5 by using ammonia water; raising the temperature to 50 ℃, slowly adding 100mL/L of silica sol into the ethanol-water solution, vigorously stirring for 10 hours, continuously adding 25mL/L of aminopropyltrimethoxysilane and 75mL/L of silica sol, and vigorously stirring the mixed solution for 8 hours; centrifugally filtering the mixed solution, washing with ethanol and deionized water for 3 times, drying the filtered product at 150 deg.C for 8 hr to obtain uniformly layered SiO with coating structure2@SiO2Nanospheres.
② taking 2.0g of prepared SiO2@SiO2Dispersing nanospheres in 400mL of water, respectively dissolving 0.008mol of nickel acetylacetonate and 0.2mol of urea in the nanospheres, heating to 100 ℃, refluxing and stirring for 5h, centrifuging and filtering, respectively washing with ethanol and deionized water for 4 times, drying filtered objects at 110 ℃ for 16h to obtain primary deposited Ni-Si-PS @ SiO2A precursor.
Thirdly, replacing SiO in the step II with the obtained primary deposition precursor2@SiO2The nanospheres are repeatedly subjected to the same nickel deposition process to obtain secondary deposited Ni-Si-PS @ SiO2A precursor; the obtained secondary deposition precursor is again substituted for SiO in step 22@SiO2The nanospheres are repeatedly subjected to the same nickel deposition process to obtain three times of deposited Ni-Si-PS @ SiO2A precursor.
Fourthly, calcining the finally obtained solid in an air atmosphere at the temperature of 400 ℃ for 3h, then switching to a flowing hydrogen atmosphere for calcining for 5h, wherein the heating rate is 2 ℃/min, and obtaining the low-temperature low-pressure hydrogenation catalyst Ni-Si-PS @ SiO for preparing the coal-based 1, 4-butynediol by directly hydrogenating to 1, 4-butanediol in one step2And the number is-8.
Example 9
Preparing an ethanol-water solution with the volume ratio of ethanol to water being 9:1, and adjusting the pH value to be 8.0 by using ammonia water; raising the temperature to 55 ℃, slowly adding 120mL/L of silica sol into the ethanol-water solution, stirring vigorously for 9 hours, continuously adding 10mL/L of octadecyltrimethoxysilane and 55mL/L of silica sol, and stirring vigorously the mixed solution for 5 hours; centrifugally filtering the mixed solution, washing with ethanol and deionized water for 4 times, drying the filtered product at 100 deg.C for 6 hr to obtain uniformly layered SiO with coating structure2@SiO2Nanospheres.
② taking 2.0g of prepared SiO2@SiO2Dispersing nanospheres in 350mL of water, respectively dissolving 0.01mol of nickel acetate and 0.25mol of urea in the nanospheres, heating to 85 ℃, refluxing and stirring for 4h, centrifuging and filtering, respectively washing with ethanol and deionized water for 3 times, drying the filtered product at 100 ℃ for 20h to obtain primary deposited Ni-Si-PS @ SiO2A precursor.
(iii) one time of obtainingDeposition precursor instead of SiO in step 22@SiO2The nanospheres are repeatedly subjected to the same nickel deposition process to obtain secondary deposited Ni-Si-PS @ SiO2A precursor; the obtained secondary deposition precursor is again substituted for SiO in step 22@SiO2The nanospheres are repeatedly subjected to the same nickel deposition process to obtain three times of deposited Ni-Si-PS @ SiO2A precursor.
Fourthly, calcining the finally obtained solid in an air atmosphere at the temperature of 450 ℃ for 6h, then switching to a flowing hydrogen atmosphere for calcining for 2h, wherein the heating rate is 2 ℃/min, and obtaining the low-temperature low-pressure hydrogenation catalyst Ni-Si-PS @ SiO for preparing the coal-based 1, 4-butynediol by directly hydrogenating to 1, 4-butanediol in one step2And the number-9.
Example 10
The No. 1-9 catalyst is suitable for kettle type direct hydroconversion with the raw material of 25-35 wt% of 1, 4-butynediol aqueous solution. Reaction conditions are as follows: the volume of the raw material is 15 mL-100 mL, the dosage of the catalyst is 0.05 g-0.4 g, the reaction temperature is 35-100 ℃, the hydrogen pressure is 0.5 MPa-5 MPa, and the hydrogenation time is 3 h. The conversion rate of 1, 4-butynediol in the net material phase after hydrogenation is more than or equal to 99.9 percent, the yield of 1, 4-butanediol is more than or equal to 94.0 percent, the byproduct 1, 4-butenediol is less than or equal to 1.0 percent, the 2-hydroxy-tetrahydrofuran is less than or equal to 2.0 percent, and the content of 2- (4' -hydroxybutoxy) -tetrahydrofuran is less than or equal to 3.0 percent.
Texture and structural parameters of catalysts Nos. 11-9 in Table
Catalyst numbering Ni content/wt% Diameter of inner core/nm Thickness of shell layer/nm Specific surface area/cm2/g Pore size/nm
1 5 200 55 315 2.9
2 6 430 50 272 3.3
3 10 550 70 400 2.7
4 12 330 65 276 3.1
5 18 320 78 297 2.5
6 20 295 52 200 4.0
7 18 280 85 261 3.0
8 24 305 115 278 3.2
9 30 360 80 265 3.4
Direct hydrogenation activity evaluation results of catalysts Nos. 21 to 9 in Table
Figure BDA0002806148920000111

Claims (10)

1. A low-temperature low-pressure direct hydrogenation catalyst for coal-based 1, 4-butynediol is characterized in that: the basic structural unit of the catalyst has a monodisperse spherical coating structure, and the catalyst consists of a uniform silicon oxide inner core and a metal phyllosilicate shell layer.
2. The catalyst for low-temperature low-pressure direct hydrogenation of coal-based 1, 4-butynediol according to claim 1, wherein: the silicon oxide inner core in the basic structural unit of the catalyst is solid, and the diameter is 250 nm-550 nm; the metal phyllosilicate shell is porous and spongy, the thickness of the shell is 50-115 nm, and the specific surface area is 200m2/g～400m2The pore diameter is 2.5 nm-4.0 nm, the chemical composition is Ni-Si-PS, and PS is layered phyllosilicate.
3. The preparation method of the coal-based 1, 4-butynediol low-temperature low-pressure direct hydrogenation catalyst according to claim 1 or 2, characterized by comprising the following steps: the method comprises the following steps:
(1) preparing an ethanol-water solution, and adjusting the pH value to 7.5-9.0 by ammonia water;
(2) raising the temperature to 30-60 ℃, firstly slowly adding 30-120 mL/L of silicon precursor into the ethanol-water solution, violently stirring for 1-10 h, continuously adding 5-30 mL/L of silane coupling and pore-forming agent and 50-100 mL/L of silicon precursor, and violently stirring the mixed solution for 1-10 h;
(3) after the mixed solution is centrifugally filtered, the mixed solution is washed by ethanol and deionized water for 3-5 times respectively, and filtered objects are dried for 6-15 hours at the temperature of 80-150 ℃ to obtain SiO with a uniformly layered coating structure2@SiO2Nanospheres;
(4) taking the SiO prepared in the step (3)2@SiO2Dispersing 2.0g of nanospheres in 150-500 mL of water, respectively dissolving 0.005-0.010 mol of metal nickel precursor and 0.2-0.4 mol of urea in the water, heating to 60-120 ℃, and performing reflux stirring for 2-6 h to perform nickel phyllosilicate deposition;
(5) after the solution is centrifugally filtered, washing the solution with ethanol and deionized water for 3-5 times respectively, and drying the filtered product at 80-150 ℃ for 4-24 h to obtain primary deposited Ni-Si-PS @ SiO2A precursor;
(6)calcining the obtained solid in an air atmosphere at 400-600 ℃ for 2-10 h, then switching to a flowing hydrogen atmosphere for reduction for 2-5 h, wherein the heating rate is 1-10 ℃/min, and obtaining a low-temperature low-pressure hydrogenation catalyst Ni-Si-PS @ SiO for preparing coal-based 1, 4-butynediol with the Ni content of 5-10 percent and directly hydrogenating the coal-based 1, 4-butynediol to 1, 4-butanediol in one step2。
4. The preparation method of the coal-based 1, 4-butynediol low-temperature low-pressure direct hydrogenation catalyst according to claim 3, characterized in that: the primary deposition Ni-X-Si-PS @ SiO obtained in the step (5)2Precursor is substituted for SiO used in step (4)2@SiO2Nanospheres, and repeating the operation of the step (4) and the step (5) to obtain secondary deposition Ni-Si-PS @ SiO2A precursor;
calcining the obtained solid in an air atmosphere at 400-600 ℃ for 2-10 h, then switching to a flowing hydrogen atmosphere for reduction for 2-5 h, wherein the heating rate is 1-10 ℃/min, and obtaining a low-temperature low-pressure hydrogenation catalyst Ni-Si-PS @ SiO for preparing coal-based 1, 4-butynediol with the Ni content of 10-20 percent and directly hydrogenating the coal-based 1, 4-butynediol to 1, 4-butanediol in one step2。
5. The preparation method of the coal-based 1, 4-butynediol low-temperature low-pressure direct hydrogenation catalyst according to claim 3, characterized in that: the primary deposition Ni-X-Si-PS @ SiO obtained in the step (5)2Precursor is substituted for SiO used in step (4)2@SiO2Nanospheres, and repeating the operation of the step (4) and the step (5) to obtain secondary deposition Ni-Si-PS @ SiO2A precursor; depositing the secondary Ni-X-Si-PS @ SiO obtained in the step (6)2Precursor is substituted for SiO used in step (4)2@SiO2Nanospheres, and repeating the operation of the step (4) and the step (5) to obtain three times of deposited Ni-Si-PS @ SiO2A precursor;
calcining the obtained solid in an air atmosphere at 400-600 ℃ for 2-10 h, then switching to a flowing hydrogen atmosphere for reduction for 2-5 h, wherein the heating rate is 1-10 ℃/min, and the obtained coal-based 1, 4-butynediol with the Ni content of 15-30 percent is directly hydrogenated to 1, 4-butylene glycol in one stepLow-temperature low-pressure hydrogenation catalyst Ni-Si-PS @ SiO for alcohol2。
6. The production method according to claim 3, characterized in that: the volume ratio of ethanol to water in the ethanol-water solution in the step (1) is 0.5-10: 1.
7. The production method according to claim 3, characterized in that: the silicon precursor in the step (2) is one of silica sol, ethyl orthosilicate or methyl orthosilicate; the silane coupling and pore-forming agent is one of octadecyl trimethoxy silane, hexadecyl trimethoxy silane, dodecyl trimethoxy silane or aminopropyl trimethoxy silane.
8. The production method according to claim 3, characterized in that: and (4) the metal nickel precursor is one of nickel nitrate, nickel acetylacetonate or nickel acetate, and the nickel acetylacetonate is preferred.
9. The production method according to claim 3, characterized in that: in the step (4), the upper limit of the nickel precursor deposited each time is 0.010mol, and if the upper limit exceeds the upper limit, multiple times of deposition are needed.
10. The production method according to claim 4 or 5, characterized in that: the upper limit of the nickel precursor is 0.010mol per deposition, and multiple depositions are needed if the upper limit is exceeded.
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