CN113402396A - Production method for m-xylylenediamine and co-production of 1, 3-diamine methylcyclohexane - Google Patents
Production method for m-xylylenediamine and co-production of 1, 3-diamine methylcyclohexane Download PDFInfo
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- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
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Abstract
The invention discloses a production method of m-xylylenediamine and co-production of 1, 3-diamine methylcyclohexane, which comprises the step of carrying out contact reaction on m-phthalonitrile and hydrogen in the presence of a catalyst to generate m-xylylenediamine and 1, 3-diamine methylcyclohexane, wherein the molar ratio of hydrogen to nitrile is 10-100, preferably 30-80. According to the invention, through optimization of hydrogen-nitrile ratio process conditions and modulation of a catalyst, the ratio of the target product m-xylylenediamine to 1, 3-diamine methylcyclohexane can be adjusted, and the molar ratio of the m-xylylenediamine to the 1, 3-diamine methylcyclohexane is about 9: 1-1: 1.
Description
Technical Field
The invention relates to a production method of m-xylylenediamine and co-produced 1, 3-diamine methylcyclohexane.
Background
M-xylylenediamine can be used as a raw material for an epoxy resin curing agent. The curing agent prepared by m-xylylenediamine can be used as a modified epoxy resin curing agent because of containing aromatic aliphatic amine, and is characterized in that the curing speed at normal temperature is accelerated, the heat resistance, the water resistance and the medicament resistance are good, and the wetting curing property and the surface gloss are good; widely used in coating, adhesive and electronic products.
The meta-xylylenediamine is also used as raw material for synthesizing MX-nylon and its derivatives, in particular MXD6 prepared together with nylon 6, and said nylon features high strength and elasticity in very high temp range, high deformation temp., low thermal expansion rate, same as alloy, suitable for precision forming and high-temp baking and coating.
The m-xylylenediamine can also be used as a raw material of polyurethane resin, m-xylylene phenyl diisocyanate is prepared from the m-xylylene phenyl diisocyanate, the polyurethane resin is further synthesized, the resin is comparable to hexamethylene diisocyanate, the yellowing resistance is superior to that of hexamethylene diisocyanate, the m-xylylene diamine can be used for light-colored coatings, the coating film hardness is high, the toxicity is low, and the m-xylylene diamine can also be used for synthetic leather.
CN200680036084.8 discloses a process flow for preparing MXDA by IPN through a fixed bed continuous hydrogenation method. At 170 ℃ and 200 ℃, IPN is melted and dissolved in liquid form (60 ℃) with liquid ammonia and recycle material. Under the condition of 60-130 ℃, under the catalysis of 150-200Bar and in a fixed bed reactor and a Mn-doped non-solid-supported Co catalyst, the conversion per pass is more than 99 percent, and the selectivity is more than 92 percent.
CN200680035201.9 describes the use of product MXDA recycle as IPN solvent, dissolved at 55-70 ℃. The technological processes provided in patents CN201010150757.0 and CN201010150725.0 are mainly: adding a modified Raney Ni catalyst into a stirring reaction kettle in advance, and pumping isophthalonitrile, a ternary mixed solvent (aromatic hydrocarbon, low-carbon alcohol and aliphatic halogenated derivative) and a secondary amine inhibitor into the reaction kettle by using a high-pressure pump. After dissolution, the reaction is carried out at the temperature of 40-120 ℃ and under the condition of 2-10MPa, and MXDA is prepared by intermittent hydrogenation in a stirring kettle.
Disclosure of Invention
The invention aims to solve the technical problems that in the prior art, the proportion of a target product is not adjustable and the total selectivity is low in the process of preparing m-xylylenediamine and coproducing 1, 3-diamine methylcyclohexane by one-step hydrogenation of intermediate phthalonitrile, and provides a novel method for preparing m-xylylenediamine and coproducing 1, 3-diamine methylcyclohexane.
In order to solve the above technical problems, a first aspect of the present invention provides a catalyst for co-producing m-xylylenediamine and 1, 3-diaminomethylcyclohexane, comprising the following components:
a) an active component comprising Ni and/or an oxide thereof;
b) an adjuvant comprising Mg and/or an oxide thereof;
c) a support comprising at least one of alumina, silica and molecular sieves.
According to some embodiments of the invention, the promoter further comprises at least one selected from Mg, Fe, Cu, Co, Zn, Zr, Mo, La, Ce, Mn and/or oxides thereof, preferably at least one of Mg, Mn, Cu, Zn, Zr, Mo, Co, La and/or oxides thereof.
According to some embodiments of the invention, the composition comprises, in parts by weight:
the content of the active component is 5-70 parts, preferably 10-60 parts, and more preferably 20-40 parts;
the content of the auxiliary agent is 0.05-150 parts, preferably 0.1-100 parts, and more preferably 0.5-70 parts;
the content of the carrier is 0.05-50 parts, preferably 2-35 parts, and more preferably 5-25 parts.
The second aspect of the present invention provides a method for preparing a catalyst for the co-production of m-xylylenediamine and 1, 3-diaminomethylcyclohexane, comprising the steps of:
1) simultaneously adding an auxiliary agent salt solution and a precipitator solution into water containing a carrier to obtain a modified carrier;
2) adding the nickel salt solution and the precipitated salt solution into water containing the modified carrier at the same time, filtering and roasting to obtain the catalyst.
According to some embodiments of the invention, in step 1), the auxiliary salt is selected from Mg (NO)3)2、Fe(NO3)3、Cu(NO3)2、Co(NO3)2、Zn(NO3)2、Zr(NO3)4、(NH4)2MoO4、La(NO3)3、Ce(NO3)3And Mn (NO)3)2Preferably Mg (NO)3)2、Mn(NO3)2、Cu(NO3)2、Zn(NO3)2、Zr(NO3)4、(NH4)2MoO4、La(NO3)3And Co (NO)3)2One or more of (a).
According to some embodiments of the invention, in step 1), the precipitant is selected from one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and aqueous ammonia, preferably one or more of sodium carbonate, sodium hydroxide and aqueous ammonia.
According to some embodiments of the invention, in step 1), the support is selected from at least one of alumina, silica and molecular sieves, preferably alumina.
According to some embodiments of the invention, in step 1), the concentration of the adjuvant salt solution is 0.1 to 1.5mol/L, preferably 0.3 to 1.2 mol/L.
According to some embodiments of the invention, in step 1), the concentration of the precipitant solution is 0.4 to 2.0mol/L, preferably 0.6 to 1.6 mol/L.
According to some embodiments of the invention, in step 1), the carrier is present in the water in an amount of 5 to 20g/L, preferably 8 to 15 g/L.
According to some embodiments of the invention, in the step 1), the assistant salt solution and the precipitant solution are added into water containing a carrier at 50-90 ℃, the pH of the end point of the mixed solution is controlled to be 6.0-8.0, and the mixed solution is stirred for 3-6 hours.
According to some embodiments of the invention, in step 2), the nickel salt is selected from one or more of nickel sulfate and nickel nitrate, preferably nickel nitrate.
According to some embodiments of the invention, in step 2), the precipitating agent is selected from one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate and aqueous ammonia, preferably one or more of sodium hydroxide, sodium carbonate and sodium bicarbonate.
According to some embodiments of the invention, in step 2), the concentration of the nickel salt solution is 0.2 to 1.5mol/L, preferably 0.5 to 1.2 mol/L.
According to some embodiments of the invention, in step 2), the concentration of the precipitant solution is 0.4 to 2.0mol/L, preferably 0.6 to 1.5 mol/L.
According to some embodiments of the invention, in step 2), the content of the modified support in water is from 10 to 30g/L, preferably from 12 to 25 g/L.
According to some embodiments of the invention, in the step 2), the nickel salt solution and the precipitant solution are added into water containing the modified carrier at the same time at 50-90 ℃, the end point of the mixed solution is controlled to have a pH of 6.0-8.0, the mixed solution is stirred for 3-6 hours, and the catalyst is obtained by filtering, washing, drying and roasting at 300-600 ℃ in an air atmosphere.
In a third aspect, the present invention provides a use of the catalyst according to the first aspect or the catalyst prepared by the preparation method according to the second aspect of the present invention in the preparation of m-xylylenediamine by hydrogenation of m-phthalonitrile, preferably, m-phthalonitrile and m-xylylenediamine as diamine, and co-production of 1, 3-diaminomethylcyclohexane.
A process for co-producing m-xylylenediamine and 1, 3-diaminomethylcyclohexane, which comprises reacting m-xylylenenitrile with hydrogen in the presence of the catalyst according to the first aspect of the present invention or the catalyst prepared by the production process according to the second aspect to produce m-xylylenediamine and 1, 3-diaminomethylcyclohexane.
According to some embodiments of the invention, the reaction temperature is 50 to 120 ℃, preferably 60 to 80 ℃.
According to some embodiments of the invention, the reaction pressure is 4.0 to 12.0MPa, preferably 6.0 to 10.0 MPa.
According to some embodiments of the invention, the liquid phase volume space velocity is 1 to 12 hours-1Preferably 2 to 10 hours-1。
According to some embodiments of the invention, the ratio of m-xylylenediamine to 1, 3-diaminomethylcyclohexane is from 9:1 to 1: 1.
According to some embodiments of the invention, the hydrogen nitrile molar ratio is from 10 to 100, preferably the hydrogen/nitrile molar ratio is from 30 to 80.
In the concept used in the present invention, the conversion and selectivity of m-xylylenediamine prepared by hydrogenation of m-phthalonitrile are calculated as follows:
in the formula: the amount of n-substance in mol;
subscripts: IPN-isophthalonitrile MXDA-m-xylylenediamine 1-raw material 2-product.
The invention discloses a catalyst for preparing m-xylylenediamine and coproducing 1, 3-diamine methylcyclohexane from m-phthalonitrile, and mainly aims to solve the problems that the proportion of target products is not adjustable when the catalyst is used for preparing m-xylylenediamine and coproducing 1, 3-diamine methylcyclohexane from m-phthalonitrile, and the amount of available hydrogen species in a reaction system can be influenced by adjusting the hydrogen-nitrile ratio.
The catalyst for preparing m-xylylenediamine and co-producing 1, 3-diamine methylcyclohexane with m-phthalonitrile in high selectivity designed by the invention has the following advantages in the hydrogenation process: by optimizing the hydrogen-nitrile ratio process conditions and combining with catalyst modulation, the ratio of the target product intermediate xylylenediamine to the 1, 3-diamine methylcyclohexane can be adjusted, and the molar ratio of the xylylenediamine to the 1, 3-diamine methylcyclohexane is about 9: 1-1: 1. The technical scheme can better solve the problems that the proportion of target products is not adjustable and the total selectivity is low when m-xylylenediamine is prepared and 1, 3-diamine methylcyclohexane is co-produced by one-step hydrogenation of m-phthalonitrile.
Drawings
FIG. 1 is a gas chromatographic analysis of the product produced in example 1 of the present invention;
FIG. 2 is a gas chromatography analysis chart of the product produced in example 2 of the present invention.
Detailed Description
To further illustrate the specific features of the present invention, reference will be made to the accompanying drawings.
With reference to the attached drawing 1, the invention provides a catalyst for preparing m-xylylenediamine and coproducing 1, 3-diamine methylcyclohexane by one-step hydrogenation of m-phthalonitrile, and a preparation method and application thereof.
In the prior art, due to the modulation influence of the grain size, the acidity and the alkalinity of active components of a nickel-based catalyst system, m-xylylenediamine is mostly generated in the reaction process, and the amount of generated 1, 3-diamine methylcyclohexane is little; meanwhile, some side reactions are inevitable, and the total selectivity is low.
In the following examples, isophthalonitrile is used as an industrial grade, and is dissolved in liquid ammonia, wherein the mass fraction of isophthalonitrile is 10%, and the mass fraction of liquid ammonia is 90%; the hydrogen used was 99.9% by volume.
Example 1
In the present embodiment, reference is made to the attached drawings.
1) Preparation of the catalyst:
firstly, preparing a modified carrier, which comprises the following specific steps: (a) adding an auxiliary salt Mg (NO)3)2Preparing solution I with the concentration of 0.8mol/L, (b) preparing precipitator sodium hydroxide into solution II with the concentration of 1.0mol/L, (c) placing 12g of alumina carrier inIn 1L of water, under the condition of 70 ℃, the solution I and the solution II are precipitated in a cocurrent mode, the pH value of a terminal point is controlled to be 7.0, and stirring and aging are carried out for 4 hours;
secondly, preparing the catalyst by active component precipitation, which comprises the following steps: (d) preparing nickel nitrate salt into 0.8mol/L solution III, (e) preparing 1.2mol/L solution IV by precipitating salt sodium carbonate, (f) placing 40g of modified alumina into 2L water, precipitating the solution III and the solution IV in parallel flow at 70 ℃, controlling the pH value of a terminal point to be 7.5, stirring and aging for 4 hours, filtering, washing, drying and air atmosphere, wherein the space velocity is 600 hours-1And roasting at 500 ℃ to obtain a finished catalyst.
The carrier of the catalyst contains a small amount of Si, and the mass fraction of the Si is 1.2%.
2) And (3) catalyst reduction:
15g of catalyst, wherein the catalyst component contains MgO (3g), the loading amount of the catalyst is 15mL, and pure hydrogen is adopted to reduce for 24h at 500 ℃.
3) Catalytic hydrogenation by using a catalyst:
3000mL of isophthalonitrile liquid ammonia solution and pure hydrogen are taken as raw materials, the dosage of a catalyst is 15g, the reaction temperature is 80 ℃, the reaction pressure is 8.0MPa, the hydrogen/nitrile molar ratio is 30:1, and the liquid phase space velocity is 10h-1The hydrogenation test was carried out under the conditions of (1) and the results of the reaction are shown in Table 1, using gas chromatography (see FIG. 1). IPN conversion 99.9%, MXDA selectivity 49.3%, 1,3-BAC selectivity 48.5%.
As can be seen from FIG. 1, the formation ratio (molar ratio) of MXDA (peak at 18.9min in the figure is MXDA) and 1,3-BAC (peaks at 17.9min and 18.1min in the figure is 1,3-BAC) was about 1: 1.
Example 2
This example uses the catalyst prepared in example 1.
1) And (3) catalyst reduction:
15g of catalyst, wherein the catalyst component contains MgO (3g), the loading amount of the catalyst is 15mL, and pure hydrogen is adopted to reduce for 24h at 500 ℃.
2) Catalytic hydrogenation by using a catalyst:
using 3000mL of isophthalonitrile liquid ammonia solution and pure hydrogen as raw materials and catalyst15g of the catalyst is used, the reaction temperature is 80 ℃, the reaction pressure is 8.0MPa, the hydrogen/nitrile molar ratio is 10:1, and the liquid phase space velocity is 10h-1The hydrogenation test was carried out under the conditions of (1) and the results of the reaction are shown in Table 1, using chromatographic analysis (see FIG. 2). IPN conversion 99.7%, MXDA selectivity 80.2%, 1,3-BAC selectivity 16.5%.
As can be seen from FIG. 2, the formation ratio (molar ratio) of MXDA (peak at 18.9min in the figure is MXDA) and 1,3-BAC (peaks at 17.9min and 18.1min in the figure is 1,3-BAC) was about 4: 1.
Example 3
This example uses the catalyst prepared in example 1.
1) And (3) catalyst reduction:
15g of catalyst, wherein the catalyst component contains MgO (3g), the loading amount of the catalyst is 15mL, and pure hydrogen is adopted to reduce for 24h at 500 ℃.
2) Catalytic hydrogenation by using a catalyst:
3000mL of isophthalonitrile liquid ammonia solution and pure hydrogen are taken as raw materials, the dosage of a catalyst is 15g, the reaction temperature is 80 ℃, the reaction pressure is 8.0MPa, the hydrogen/nitrile molar ratio is 20:1, and the liquid phase space velocity is 10h-1The hydrogenation test was carried out under the conditions of (1), and the reaction results are shown in Table 1 by on-line chromatographic analysis. IPN conversion 99.8%, MXDA selectivity 61.2%, 1,3-BAC selectivity 36.5%.
Example 4
This example uses the catalyst prepared in example 1.
1) And (3) catalyst reduction:
15g of catalyst, wherein the catalyst component contains MgO (3g), the loading amount of the catalyst is 15mL, and pure hydrogen is adopted to reduce for 24h at 500 ℃.
2) Catalytic hydrogenation by using a catalyst:
3000mL of isophthalonitrile liquid ammonia solution and pure hydrogen are taken as raw materials, the dosage of a catalyst is 15g, the reaction temperature is 80 ℃, the reaction pressure is 8.0MPa, the hydrogen/nitrile molar ratio is 50:1, and the liquid phase space velocity is 10h-1The hydrogenation test was carried out under the conditions of (1), and the reaction results are shown in Table 1 by chromatographic analysis. IPN conversion 99.9%, MXDA selectivity 39.4%, 1,3-BAC selectivity 57.9%.
Example 5
This example uses the catalyst prepared in example 1.
1) And (3) catalyst reduction:
15g of catalyst, wherein the catalyst component contains MgO (3g), the loading amount of the catalyst is 15mL, and pure hydrogen is adopted to reduce for 24h at 500 ℃.
2) Catalytic hydrogenation by using a catalyst:
3000mL of isophthalonitrile liquid ammonia solution and pure hydrogen are taken as raw materials, the dosage of a catalyst is 15g, the reaction temperature is 80 ℃, the reaction pressure is 8.0MPa, the hydrogen/nitrile molar ratio is 100:1, and the liquid phase space velocity is 10h-1The hydrogenation test was carried out under the conditions of (1), and the reaction results are shown in Table 1 by chromatographic analysis. IPN conversion 99.9%, MXDA selectivity 35.1%, and 1,3-BAC selectivity 60.8%.
Example 6
This example differs from the catalyst prepared in example 1 in that: the catalyst component contained 15 wt% of MgO (15 g of catalyst, 2.25g of MgO in catalyst component).
1) And (3) catalyst reduction:
15g of catalyst, wherein the catalyst component contains MgO (2.25g) and the loading amount is 15mL, and pure hydrogen is adopted to reduce for 24h at 500 ℃.
2) Catalytic hydrogenation by using a catalyst:
3000mL of isophthalonitrile liquid ammonia solution and pure hydrogen are taken as raw materials, the dosage of a catalyst is 15g, the reaction temperature is 80 ℃, the reaction pressure is 8.0MPa, the hydrogen/nitrile molar ratio is 30:1, and the liquid phase space velocity is 10h-1The hydrogenation test was carried out under the conditions of (1), and the reaction results are shown in Table 1 by chromatographic analysis. IPN conversion 99.9%, MXDA selectivity 53.7%, 1,3-BAC selectivity 44.5%.
Example 7
The catalyst prepared in example 1 used in this example differs in that: the catalyst component contained 10 wt% of MgO (15 g of catalyst, 1.5g of MgO in catalyst component).
1) And (3) catalyst reduction:
15g of catalyst, wherein the catalyst component contains MgO (1.5g) and the loading amount is 15mL, and pure hydrogen is adopted to reduce for 24h at 500 ℃.
2) Catalytic hydrogenation by using a catalyst:
3000mL of isophthalonitrile liquid ammonia solution and pure hydrogen are taken as raw materials, the dosage of a catalyst is 15g, the reaction temperature is 80 ℃, the reaction pressure is 8.0MPa, the hydrogen/nitrile molar ratio is 30:1, and the liquid phase space velocity is 10h-1The hydrogenation test was carried out under the conditions of (1), and the reaction results are shown in Table 1 by chromatographic analysis. IPN conversion 99.9%, MXDA selectivity 55.9%, and 1,3-BAC selectivity 42.1%.
Example 8
This example differs from the catalyst prepared in example 1 in that: the catalyst component contained 25 wt% of MgO (15 g of catalyst, 3.75g of MgO in catalyst component).
1) And (3) catalyst reduction:
15g of catalyst, wherein the catalyst component contains MgO (3.75g), the loading amount is 15mL, and pure hydrogen is adopted to reduce for 24h at 500 ℃.
2) Catalytic hydrogenation by using a catalyst:
3000mL of isophthalonitrile liquid ammonia solution and pure hydrogen are taken as raw materials, the dosage of a catalyst is 15g, the reaction temperature is 80 ℃, the reaction pressure is 8.0MPa, the hydrogen/nitrile molar ratio is 30:1, and the liquid phase space velocity is 10h-1The hydrogenation test was carried out under the conditions of (1), and the reaction results are shown in Table 1 by chromatographic analysis. IPN conversion 99.8%, MXDA selectivity 48.6%, and 1,3-BAC selectivity 47.3%.
Comparative example 1
This example uses the catalyst prepared in example 1.
1) And (3) catalyst reduction:
15g of catalyst, wherein the catalyst component contains MgO (3g) and the loading amount is 15mL, and pure hydrogen is adopted to reduce for 24h at 500 ℃.
2) Catalytic hydrogenation by using a catalyst:
3000mL of isophthalonitrile liquid ammonia solution and pure hydrogen are taken as raw materials, the dosage of a catalyst is 15g, the reaction temperature is 80 ℃, the reaction pressure is 8.0MPa, the hydrogen/nitrile molar ratio is 6:1, and the liquid phase space velocity is 10h-1The hydrogenation test was carried out under the conditions of (1), and the reaction results are shown in Table 1 by chromatographic analysis. IPN conversion 99.3%, MXDA selectionThe selectivity is 93.4 percent, and the selectivity of 1,3-BAC is 3.1 percent.
Comparative example 2
This example differs from the catalyst prepared in example 1 in that: the catalyst component does not contain MgO.
1) And (3) catalyst reduction:
15g of catalyst, wherein the catalyst component does not contain MgO, the loading amount is 15mL, and pure hydrogen is adopted to reduce for 24h at 500 ℃.
2) Catalytic hydrogenation by using a catalyst:
3000mL of isophthalonitrile liquid ammonia solution and pure hydrogen are used as raw materials, the dosage of a catalyst is 15g, a hydrogenation test is carried out under the conditions that the reaction temperature is 80 ℃, the reaction pressure is 8.0MPa, the hydrogen/nitrile molar ratio is 30:1, and the liquid phase space velocity is 10h < -1 >, and the reaction results are shown in Table 1 by adopting chromatographic analysis. IPN conversion 99.4%, MXDA selectivity 65.8%, 1,3-BAC selectivity 29.4%.
TABLE 1
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A process for the coproduction of m-xylylenediamine and 1, 3-diaminomethylcyclohexane, which comprises reacting m-xylylenenitrile with hydrogen in the presence of a catalyst in a contact manner to produce m-xylylenediamine and 1, 3-diaminomethylcyclohexane in a hydrogen/nitrile molar ratio of 10 to 100, preferably 30 to 80.
2. The production method according to claim 1, wherein the reaction temperature is 50 to 120 ℃; the reaction pressure is 4.0-12.0 MPa; the liquid phase volume space velocity is 1-12 hours-1。
3. The production method according to claim 1 or 2, wherein the molar ratio of m-xylylenediamine to 1, 3-diaminomethylcyclohexane is 9:1 to 1: 1.
4. The production method according to any one of claims 1 to 3, wherein the catalyst comprises the following components:
a) an active component comprising Ni and/or an oxide thereof;
b) an adjuvant comprising Mg and/or an oxide thereof;
c) a support comprising at least one of alumina, silica and molecular sieves.
5. The production method according to claim 4, characterized in that the auxiliary agent further comprises at least one selected from Mg, Fe, Cu, Co, Zn, Zr, Mo, La, Ce, Mn and/or oxides thereof, preferably at least one selected from Mg, Mn, Cu, Zn, Zr, Mo, Co, La and/or oxides thereof.
6. The production process according to claim 4 or 5, characterized in that the catalyst is prepared by mixing, in parts by weight:
the content of the active component is 5-70 parts, preferably 10-60 parts, and more preferably 20-40 parts;
the content of the auxiliary agent is 0.05-150 parts, preferably 0.1-100 parts, and more preferably 0.5-70 parts;
the content of the carrier is 0.05-50 parts, preferably 2-35 parts, and more preferably 5-25 parts.
7. The production method according to any one of claims 1 to 6, characterized in that the preparation method of the catalyst comprises the steps of:
1) simultaneously adding an auxiliary agent salt solution and a precipitator solution into water containing a carrier to obtain a modified carrier;
2) adding the nickel salt solution and the precipitant solution into water containing the modified carrier at the same time, filtering and roasting to obtain the catalyst.
8. The production method according to claim 7,
in step 1), the auxiliary salt is selected from Mg (NO)3)2、Fe(NO3)3、Cu(NO3)2、Co(NO3)2、Zn(NO3)2、Zr(NO3)4、(NH4)2MoO4、La(NO3)3、Ce(NO3)3And Mn (NO)3)2Preferably Mg (NO)3)2、Mn(NO3)2、Cu(NO3)2、Zn(NO3)2、Zr(NO3)4、(NH4)2MoO4、La(NO3)3And Co (NO)3)2One or more of; the precipitant is selected from one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and ammonia water, preferably at least one of sodium carbonate, sodium hydroxide and ammonia water; the carrier is selected from at least one of alumina, silica and molecular sieve, preferably alumina;
in the step 2), the nickel salt is selected from one or more of nickel sulfate and nickel nitrate, preferably nickel nitrate; the precipitant is selected from one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate and ammonia water, preferably one or more of sodium hydroxide, sodium carbonate and sodium bicarbonate.
9. The production method according to claim 7 or 8,
in the step 1), the concentration of the assistant salt solution is 0.1-1.5mol/L, preferably 0.3-1.2mol/L, the concentration of the precipitant solution is 0.4-2.0mol/L, preferably 0.6-1.6mol/L, and the content of the carrier in water is 5-20g/L, preferably 8-15 g/L;
in the step 2), the concentration of the nickel salt solution is 0.2-1.5mol/L, preferably 0.5-1.2mol/L, the concentration of the precipitant solution is 0.4-2.0mol/L, preferably 0.6-1.5mol/L, and the content of the carrier in water is 10-30g/L, preferably 12-25 g/L.
10. The production method according to any one of claims 7 to 9,
in the step 1), adding the assistant salt solution and the precipitant solution into carrier-containing water at 50-90 ℃, controlling the pH of the mixed solution at the end point to be 6.0-8.0, and stirring for 3-6 h;
in the step 2), adding the nickel salt solution and the precipitated salt solution into water containing a modified carrier at the same time at 50-90 ℃, controlling the pH of the end point of the mixed solution to be 6.0-8.0, stirring for 3-6 h, filtering, washing, drying, and roasting at 300-600 ℃ in an air atmosphere to obtain the catalyst.
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