CN113292395B - Carbon-loaded Ni-based catalyst, preparation thereof and preparation of 1, 4-cyclohexanediol by hydrogenation of hydroquinone under catalysis of fixed bed - Google Patents

Carbon-loaded Ni-based catalyst, preparation thereof and preparation of 1, 4-cyclohexanediol by hydrogenation of hydroquinone under catalysis of fixed bed Download PDF

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CN113292395B
CN113292395B CN202110616568.6A CN202110616568A CN113292395B CN 113292395 B CN113292395 B CN 113292395B CN 202110616568 A CN202110616568 A CN 202110616568A CN 113292395 B CN113292395 B CN 113292395B
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hydroquinone
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CN113292395A (en
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黄家辉
任周
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Dalian Institute of Chemical Physics of CAS
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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • C07C29/19—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings
    • C07C29/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings in a non-condensed rings substituted with hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Abstract

The invention provides a high-surface-area porous-structure inorganic carbon carrier loaded Ni-based catalyst for preparing 1, 4-cyclohexanediol by selective hydrogenation of hydroquinone and a preparation method thereof. The catalyst comprises a main active component, an auxiliary agent and a carrier or the main active component and the carrier. The carrier is inorganic carbon carrier, or is treated by acid or alkali; the main active component is Ni, the content of Ni is 0.01-50.0 wt% of the weight of the catalyst, and the content of other auxiliary agents is 0-10.0 wt% of the catalyst; ni and an auxiliary agent are loaded on an inorganic carbon carrier by means of impregnation and the like, and the main active component is highly dispersed in the carrier. In a fixed bed reactor, hydroquinone can be converted into 1, 4-cyclohexanediol with high activity and high selectivity under the action of certain temperature and pressure and the catalyst.

Description

Carbon-loaded Ni-based catalyst, preparation thereof and preparation of 1, 4-cyclohexanediol by hydrogenation of hydroquinone under catalysis of fixed bed
Technical Field
The invention belongs to the technical field of hydrogenation of heterogeneous catalysts, and particularly relates to an inorganic carbon carrier-loaded Ni-based catalyst and application thereof in a reaction for preparing 1, 4-cyclohexanediol from hydroquinone through heterogeneous hydrogenation.
Background
The 1, 4-cyclohexanediol is an important fine chemical and an intermediate, and is widely applied to the fields of pesticides, organic synthesis, new materials of liquid crystals and the like. At present, the method is mainly used for synthesizing inositol phosphate cool inhibitors, benzotriazol medicaments, succinylsulfathiazole, HMGCoA reductase, tetracyanoquinodimethane and the like. The spectrally pure 1, 4-cyclohexanediol as a new material monomer can be used for synthesizing liquid crystal materials, biological controller markers, organic electric materials and the like. At present, with the improvement of national economy and the continuous progress of science and technology, the application field of the 1, 4-cyclohexanediol is wider and wider.
The synthesis method of 1, 4-cyclohexanediol generally adopts a catalytic benzene ring hydrogenation mode by taking hydroquinone as a raw material. In the fifties of the twentieth century, Adkins and the like use W-6Raney Ni catalyst, ethanol as solvent and hydroquinone as raw material to hydrogenate to obtain a cis-trans isomer mixture of 1, 4-cyclohexanediol, and start the research of the 1, 4-cyclohexanediol. At present, catalysts for preparing 1, 4-cyclohexanediol by hydrogenating hydroquinone mainly comprise Raney Ni and Ru supported catalysts.
The Ru-based catalyst mainly comprises diatomite and a molecular sieve (ZSM-5 and Y-type are main materials), but the catalyst generally has the problem of high cyclohexanol selectivity, because Ru species easily break C-O bonds, the selectivity is poor, and the selectivity of 1, 4-cyclohexanediol is generally 70-80%. 201019100011.6 to supercritical CO 2As a reaction medium, the Ru/C is used as a catalyst, hydroquinone and hydrogen react to generate the 1, 4-cyclohexanediol, but the selectivity is only about 80 percent. In the process of the Raney Ni catalyst, the activity is relatively poor, but the selectivity of the 1, 4-cyclohexanediol of the catalyst can reach more than 96 percent, and a large amount of alkali species is generally required to be added to improve the catalytic performance, so the problem of environmental pollution is aggravated by the addition of the alkali species. 200710061447.X and 200510112194.5 indicate that Raney Ni catalyst can catalyze hydroquinone to prepare 1, 4-cyclohexanediol by taking water and alkali solution as solvents under the conditions of certain temperature and pressure. At present, most of catalysts are applied to a kettle type reactor and a kettle type reaction system, the problems of poor operation continuity, complicated separation operation and the like are solved, and the application of the hydroquinone hydrogenation process to a continuously operated fixed bed system is a key means for simplifying the production process and promoting industrialization. On the other hand, since the selectivity of the Ru-based catalyst is poor, and the Ru species are expensive, and the Raney Ni catalyst generally requires the addition of an alkali species to cause serious environmental pollution, it is important to develop and design an inexpensive Ni-based hydrogenation catalyst for preparing 1, 4-cyclohexanediol from hydroquinone, which is another critical problem.
The inorganic carbon carrier loaded Ni-based catalyst for the reaction of preparing the 1, 4-cyclohexanediol by the selective hydrogenation of the heterogeneous hydroquinone has important significance for improving the selectivity and the production efficiency of the 1, 4-cyclohexanediol and reducing the cost.
Disclosure of Invention
The invention aims to provide a large-surface-area porous-structure inorganic carbon carrier loaded Ni-based catalyst for preparing 1, 4-cyclohexanediol by selective hydrogenation of hydroquinone and a preparation method thereof. The inorganic carbon carrier loaded Ni-based catalyst has large specific surface area and excellent thermal stability, so that the catalyst can meet the requirement of preparing 1, 4-cyclohexanediol by selective hydrogenation of hydroquinone under the heterogeneous catalysis condition. The inorganic carbon carrier loaded Ni-based catalyst shows high hydrogenation activity and 1, 4-cyclohexanediol selectivity.
The technical scheme of the invention is as follows:
the catalyst is used for the reaction of preparing 1, 4-cyclohexanediol by selectively hydrogenating hydroquinone, and comprises a main active component, an auxiliary agent and a carrier or a main active component and a carrier, wherein the main active component is Ni; the auxiliary agent is one of Na, Mg, Al, Ca and Fe; the carrier is inorganic carbon; the Ni accounts for 0.01-50.0 wt% of the total mass of the catalyst, and the auxiliary agent accounts for 0-10.0 wt% of the total mass of the catalyst.
Based on the scheme, preferably, the Ni accounts for 0.1-10.0 wt% of the total mass of the catalyst; the auxiliary agent accounts for 0-5.0 wt% of the total mass of the catalyst.
Based on the scheme, preferably, the Ni accounts for 0.1-5.0 wt% of the total mass of the catalyst; the auxiliary agent accounts for 0-3.0 wt% of the total mass of the catalyst.
Based on the scheme, preferably, the inorganic carbon is activated carbon with a porous structure, and the activated carbon is one or a mixture of coconut shell carbon and apricot shell carbon; the activated carbon is subjected to acid treatment or alkali treatment before use, and the pore volume range of the treated activated carbon is 0.1-10.0 cm3The pore diameter is 0.2-70.0 nm, the specific surface area is 20-2000 m2/g。
Based on the scheme, preferably, the acid is one of sulfuric acid, nitric acid and phosphoric acid, the concentration of acid species is 0.001-1.0mol/L, the treatment temperature is 30-100 ℃, and the pH value is washed after the treatment until the pH value is unchanged; the alkali is one of potassium hydroxide, sodium hydroxide and cesium hydroxide, the concentration of alkali species is 0.001-1.0mol/L, the treatment temperature is 30-100 ℃, and the pH value is unchanged after the treatment.
Based on the scheme, preferably, the hydrogenation reaction is carried out in a fixed bed reactor; the material of the reactor is 316L; the reaction temperature is 80-300 ℃, and preferably 100-200 ℃; the reaction pressure is 0.2-6.0 MPa, preferably 1.5-3.0 MPa.
Based on the scheme, preferably, in the hydrogenation reaction, the reaction raw material is hydroquinone solution, the solvent is one of water, isopropanol, ethanol, methanol and acetone, and the concentration of the hydroquinone solution is 0.01g/100g to 30g/100g, preferably 1g/100g to 15g/100 g; according to the volume space velocity of the reaction liquid of 0.1-500 h-1Preferably 1 to 10 hours-1；H2And hydroquinone in a molar ratio of 4000 to 3, preferably 100 to 1.
Based on the scheme, the catalyst is preferably subjected to H before use2Prereduction activation or no activation, H2The conditions for pre-reduction activation are as follows: GHSV of 2000--1，H2And (3) raising the temperature from room temperature to 200-700 ℃ at the temperature raising rate of 1-10 ℃/min under the atmosphere of 0.1-4.0 MPa, and keeping for 1-5 h to obtain the activated inorganic carbon carrier supported Ni-based catalyst.
Based on the above scheme, preferably, the catalyst is prepared by the following steps: dissolving a Ni metal precursor and an auxiliary agent precursor in water, soaking the obtained solution on an inorganic carbon carrier in an isometric manner or in an excessive manner, evaporating the solvent in a water bath at 30-80 ℃, drying for 5-15 h at 100-150 ℃ in an oven, and roasting for 2-8 h at 200-800 ℃ under the protection of Ar to obtain the catalyst.
Based on the above scheme, preferably, the Ni metal precursor is Ni (NO) 3)2·6H2O、 NiCl2·6H2O、NiSO4·6H2One or more than two of O; the precursor of the auxiliary agent is NaNO3、NaCl、Mg(NO3)2、MgCl2、Al(NO3)3、AlCl3、Ca(NO3)2、 CaCl2、Fe(NO3)3One or two or more of them.
The invention has the beneficial effects that:
compared with the existing kettle type hydrogenation technology of Raney Ni and Ru-based catalysts for hydrogenation of supported hydroquinone, the hydrogenation technology of the inorganic oxide supported Ni-based catalyst has the advantages that the selectivity of 1, 4-cyclohexanediol is good, the hydrogenation activity is high, a synergistic effect exists between alkali metal species and Ni components, the selectivity and the activity of the catalyst can be effectively improved by adding the alkali metal species auxiliary agent component, the process is environment-friendly, a continuous fixed bed system is efficiently used, the cost is greatly reduced, and the like.
Detailed Description
The following examples illustrate but do not limit the invention claimed, and the starting materials used in the following examples are commercially available conventional products, unless otherwise specified.
Example 1
Weighing 10.0g of coconut shell carbon, adding 20mL of concentrated nitric acid, heating to 40 ℃ for 10h, washing to be neutral, and drying to obtain acid-washing activated carbon-1. 0.58g of Ni (NO) was weighed3)2·6H2O and 0.20g MgCl2Dissolve in 6.0g of water. Then 3g of acid-washed activated carbon-1 was impregnated. Evaporating the solvent in a water bath at 70 ℃, drying in an oven at 150 ℃ for 10h, and roasting at 500 ℃ for 4h under the protection of argon to obtain the acid-washed activated carbon-1 loaded Ni-Mg-based catalyst, which is recorded as Ni-Mg/acid-washed activated carbon-1.
Example 2
0.29g of NiCl was weighed2·6H2O and 0.10g NaNO3Then dissolved in 10.0g of water. Then 3g of apricot shell carbon was impregnated. Evaporating the solvent in water bath at 50 ℃, drying in an oven at 120 ℃ for 10h, and roasting at 500 ℃ for 4h under the protection of argon to obtain the apricot shell carbon-loaded Ni-Na-based catalyst which is marked as Ni-Na/apricot shell carbon.
Example 3
Weighing 10.0g of coconut shell carbon, adding 20mL of concentrated phosphoric acid, heating to 40 ℃ for 10h, washing to be neutral, and drying to obtain acid-washing activated carbon-2. 0.29g of NiSO was weighed4·6H2O and 0.10g NaCl dissolved in 6.3g waterIn (1). Then 3g of acid-washed activated carbon-2 was impregnated. Evaporating the solvent in a water bath at 70 ℃, drying in an oven at 150 ℃ for 10h, and roasting at 500 ℃ for 4h under the protection of argon to obtain the acid-washed activated carbon-2 loaded Ni-Na-based catalyst, which is recorded as Ni-Na/acid-washed activated carbon-2.
Example 4
Weighing 10.0g of apricot shell carbon, adding 20mL of concentrated sulfuric acid, heating to 40 ℃ for 10h, washing to be neutral, and drying, wherein the mark is acid-washing active carbon-3. 0.58g of NiSO was weighed4·6H2O and 0.20 g Mg (NO)3)2Then dissolved in 10.0g of water. Then 3g of acid-washed activated carbon-3 was impregnated. Evaporating the solvent in a water bath at 70 ℃, drying in an oven at 150 ℃ for 10h, and roasting at 500 ℃ for 4h under the protection of argon to obtain the acid-washed activated carbon-3 loaded Ni-Mg-based catalyst, which is recorded as Ni-Mg/acid-washed activated carbon-3.
Example 5
Weighing 10.0g of apricot shell carbon, adding 20mL of concentrated nitric acid, heating to 40 ℃ for 10h, washing to be neutral, and drying, wherein the mark is acid-washing active carbon-4. 0.58g of Ni (NO) was weighed 3)2·6H2O and 0.35gAl (NO)3)3Then dissolved in 10.0g of water. Then 3g of acid-washed activated carbon-4 was impregnated. Evaporating the solvent in 70 ℃ water bath, drying in a drying oven at 150 ℃ for 10h, and roasting at 500 ℃ for 4h under the protection of argon to obtain the acid-washed activated carbon-4 loaded Ni-Al-based catalyst, which is recorded as Ni-A1/acid-washed activated carbon-4.
Example 6
Weighing 10.0g of coconut shell charcoal, adding 20mL of 10mol/L NaOH solution, heating to 40 ℃ for 10h, washing to be neutral, and drying to record as alkaline washing activated carbon-5. 0.58g of Ni (NO) was weighed3)2·6H2O and 0.75g Ca (NO)3)2Then dissolved in 10.0g of water. Then 3g of alkali washing activated carbon-5 is impregnated. Evaporating the solvent in water bath at 70 ℃, drying in an oven at 150 ℃ for 10h, and roasting at 500 ℃ for 4h under the protection of argon to obtain the alkali washing activated carbon-5 loaded Ni-Ca-based catalyst which is marked as Ni-Ca/alkali washing activated carbon-5.
Example 7
Weighing 10.0g of coconut shell charcoal, adding 20mL of 10mol/L KOH solution, heating to 40 ℃ for 10h, washing to be neutral, and drying to record as alkaline washing activated carbon-6. 1.16g of Ni (NO) was weighed3)2·6H2O and 0.45g CaCl2Dissolve in10.0g of water. Then 3g of alkali washing activated carbon-6 was impregnated. Evaporating the solvent in a water bath at 70 ℃, drying in an oven at 150 ℃ for 10h, and roasting at 500 ℃ for 4h under the protection of argon to obtain the alkali washing activated carbon-6 loaded Ni-Ca-based catalyst which is marked as Ni-Ca/alkali washing activated carbon-6.
Example 8
Weighing 10.0g of coconut shell carbon, adding 20mL of concentrated nitric acid, heating to 40 ℃ for 10h, washing to be neutral, and drying to obtain acid-washing activated carbon-1. 0.58g of Ni (NO) was weighed3)2·6H2O and 0.20g Fe (NO)3)3Dissolve in 6.0g of water. Then 3g of acid-washed activated carbon-1 was impregnated. Evaporating the solvent in water bath at 70 ℃, drying in an oven at 150 ℃ for 10h, and roasting at 500 ℃ for 4h under the protection of argon to obtain the acid-washed activated carbon-1 supported Ni-Fe-based catalyst, which is recorded as Ni-Fe/acid-washed activated carbon-7.
Example 9
0.29g of Ni (NO) was weighed3)2·6H2Dissolved in 3.3g of water. Then 3g of coconut shell charcoal was impregnated. Evaporating the solvent in water bath at 40 ℃, drying in an oven at 120 ℃ for 10h, and roasting at 500 ℃ for 4h under the protection of argon to obtain the coconut shell carbon-loaded Ni-based catalyst which is marked as Ni/coconut shell carbon.
Example 10
0.29g of Ni (NO) was weighed3)2·6H2Dissolved in 3.3g of water. Then 3g of apricot shell charcoal was impregnated. Evaporating the solvent in water bath at 40 ℃, drying in an oven at 120 ℃ for 10h, and roasting at 500 ℃ for 4h under the protection of argon to obtain the apricot shell carbon-loaded Ni-based catalyst which is marked as Ni/apricot shell carbon.
Application example
The catalysts prepared in the above examples and comparative examples were used for the isopropanol solution of hydroquinone and H2Reaction for preparing 1, 4-cyclohexanediol as raw material.
Activation of the catalyst: GHSV of 6000h in the reactor before the catalyst is used-1In-situ reduction activation is carried out in a flow under the conditions: 0.1MPa, H 2And heating to 500 ℃ from room temperature at the speed of 10 ℃/min, and keeping for 3 hours to obtain the activated inorganic oxide supported Ni-based catalyst.
The activated catalyst was used in the above reaction, and the specific reaction conditions of each example and comparative example were as follows:
the reaction conditions are as follows: 160 ℃, 3.0MPa, H2The molar ratio of hydroquinone is 10: 1, and the LHSV of hydroquinone solution is 9h-1The catalyst volume was 0.2 mL.
And (3) performing off-line analysis on the liquid phase product, and analyzing the contents of hydroquinone and 1, 4-cyclohexanediol by using a DB-1701 capillary chromatographic column and a FID detector.
Using the inorganic carbon supported Ni-based catalysts prepared in the above examples and comparative examples, 1, 4-cyclohexanediols were prepared according to the above procedures, and the hydroquinone conversion and the 1, 4-cyclohexanediol selectivity are shown in Table 1.
TABLE 1 summary of the results of the selective hydrogenation of hydroquinone to 1, 4-cyclohexanediol in the examples and comparative examples
Figure BDA0003096975180000071
Figure BDA0003096975180000081
The results show that: comparison of examples 1 to 10 shows that Ni (NO) is added3)2·6H2O is a precursor and Mg (NO)3)2The catalyst used as the precursor of the auxiliary agent is better than other catalysts in both the hydrogenation activity of hydroquinone and the selectivity of 1, 4-cyclohexanediol.
The present invention has been described in detail above, but the present invention is not limited to the specific embodiments described herein. It will be understood by those skilled in the art that other modifications and variations may be made without departing from the scope of the invention. The scope of the invention is defined by the appended claims.

Claims (9)

1. The application of the inorganic carbon carrier loaded Ni-based catalyst is characterized in that: the catalyst is used for the reaction of preparing 1, 4-cyclohexanediol by selectively hydrogenating hydroquinone, and comprises a main active component, an auxiliary agent and a carrier, wherein the main active component is Ni; the auxiliary agent is one of Na and Mg; the carrier is inorganic carbon; the Ni accounts for 0.01-50.0 wt% of the total mass of the catalyst, the assistant accounts for 0-10.0 wt% of the total mass of the catalyst, and the mass of the assistant is not 0;
the inorganic carbon is activated carbon with a porous structure, and the activated carbon is one or a mixture of coconut shell carbon and apricot shell carbon; the active carbon is treated by acid before use;
the catalyst is prepared by the following steps: dissolving a Ni metal precursor and an auxiliary agent precursor in water, soaking the obtained solution on an inorganic carbon carrier in an isometric manner or in an excessive manner, evaporating the solvent in a water bath at 30-80 ℃, drying for 5-15 h at 100-150 ℃ in an oven, and roasting for 2-8 h at 200-800 ℃ under the protection of Ar to obtain the catalyst.
2. Use according to claim 1, characterized in that: the Ni accounts for 0.1-10.0 wt% of the total mass of the catalyst; the auxiliary agent accounts for 0-5.0 wt% of the total mass of the catalyst, and the mass of the auxiliary agent is not 0.
3. Use according to claim 2, characterized in that: the Ni accounts for 0.1-5.0 wt% of the total mass of the catalyst; the auxiliary agent accounts for 0-3.0 wt% of the total mass of the catalyst, and the mass of the auxiliary agent is not 0.
4. Use according to claim 1, characterized in that: the pore volume range of the treated active carbon is 0.1-10.0 cm3The pore diameter distribution is 0.2-70.0 nm, the specific surface area is 20-2000 m2/g。
5. Use according to claim 1, characterized in that: the acid is one of sulfuric acid, nitric acid and phosphoric acid, the concentration of the acid is 0.001-1.0mol/L, the treatment temperature is 30-100 ℃, and the pH value is unchanged after the treatment and washing.
6. Use according to claim 1, characterized in that: the hydrogenation reaction is carried out in a fixed bed reactor; the reaction temperature is 80-300 ℃; the reaction pressure is 0.2-6.0 MPa.
7. Use according to claim 1, characterized in that: the hydrogenation reaction adopts hydroquinone solution as a reaction raw material, one of water, isopropanol, ethanol, methanol and acetone as a solvent, the concentration of the hydroquinone solution is 0.01g/100 g-30 g/100g, and the volume space velocity of reaction liquid is 0.1-500 h-1；H2And the molar ratio of the hydroquinone to the hydroquinone is 4000-3.
8. Use according to claim 1, characterized in that: the catalyst is activated or not activated before use, and the activation conditions are as follows: GHSV of 2000--1，H2And (3) raising the temperature from room temperature to 200-700 ℃ at the temperature raising rate of 1-10 ℃/min under the atmosphere of 0.1-4.0 MPa, and keeping for 1-5 h to obtain the activated inorganic carbon carrier supported Ni-based catalyst.
9. Use according to claim 1, characterized in that: the Ni metal precursor is Ni (NO)3)2·6H2O、NiCl2·6H2O、NiSO4·6H2One or more than two of O; the precursor of the auxiliary agent is NaNO3、NaCl、Mg(NO3)2、MgCl2One or more than two of them.
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