CN109926052B

CN109926052B - Supported patina-based multi-metal hydroxide catalyst and preparation method thereof

Info

Publication number: CN109926052B
Application number: CN201910193269.9A
Authority: CN
Inventors: 李大鹏; 刘忠文
Original assignee: Individual
Current assignee: Individual
Priority date: 2019-03-14
Filing date: 2019-03-14
Publication date: 2021-08-17
Anticipated expiration: 2039-03-14
Also published as: CN109926052A

Abstract

The invention discloses a supported patina-based polymetallic hydroxide catalyst and a preparation method thereof, wherein the active component of the catalyst is layered polymetallic hydroxide, Fe³⁺And M²⁺、M^e+Forming a laminate host structure, and forming an object structure by anions between layers; the carrier of the catalyst is any one or more of carbon material, molecular sieve and inorganic oxide. The invention takes Fe (II) salt as raw material, takes other stable divalent and polyvalent metals as protective agents through process oxidation, and self-assembles into the supported patina-based polymetallic hydroxide catalyst in one step in the synthetic reaction under mild conditions.

Description

Supported patina-based multi-metal hydroxide catalyst and preparation method thereof

Technical Field

The invention belongs to the technical field of petroleum processing and coal chemical industry, and particularly relates to a high-activity supported type patina-based polymetallic hydroxide catalyst applied to a kerosene co-refining reaction, a direct coal liquefaction reaction, a heavy inferior oil lightening reaction and a coal tar hydrogenation reaction and a preparation method thereof.

Background

In recent years, FeOOH, which is widely used as a catalyst active component in direct coal liquefaction reactions and heavy and inferior oil lightening reactions, is mainly due to the fact that FeOOH has a low cost advantage and can show ideal reaction activity in the reactions, so that coal direct liquefaction, kerosene co-refining and other industrial devices in recent yearsGradually adopts a catalyst mainly comprising FeOOH. The intermediate product in the FeOOH synthesis process is green rust, which is a layered double hydroxide consisting of ferrous elements and ferric elements and belongs to anionic layered inorganic functional materials. Consists of a host layer plate containing Fe (II) and Fe (III) elements and interlayer object anions. Due to the unique structural property, the patina has unique catalyst performance, but the patina is extremely unstable in an oxygen-containing environment and difficult to obtain directly from a synthesis reaction, and the patina material can be obtained only in an extremely harsh environment in a laboratory. Patent 200810035857.1 discloses a method for preparing FeSO₄And Fe₂(SO₄)₃The synthesis method for preparing the patina under the anaerobic harsh condition by taking the ascorbic acid aqueous solution as the synthesis reaction liquid has the advantages of complex preparation process and difficult control of conditions, and obviously higher cost.

In addition, there have been many studies on modification of FeOOH catalysts in recent years to adjust the catalytic performance of FeOOH catalysts by doping with other elements. Patent CN 102380396 a discloses a catalyst using coal powder as carrier and gamma-FeOOH doped with molybdenum, nickel, tungsten or cobalt as active component; patent CN 104437492 a discloses a catalyst with coal powder as carrier and FeOOH doped with AlOOH as active component. The catalyst disclosed by the invention patent breaks through the traditional catalyst structure only taking FeOOH as an active component, so that the catalyst is superior to a catalyst taking pure FeOOH as an active component in respective application reactions, but because the doping amount of other elements is limited, the main body of the structure of the active component of the catalyst is still FeOOH, and therefore, the overall activity of the catalyst cannot be obviously improved.

Disclosure of Invention

The invention aims to provide a supported patina-based polymetallic hydroxide catalyst and a preparation method thereof.

The technical scheme provided by the invention is as follows: the active component of the catalyst is a layered multi-metal hydroxide with the chemical composition of [ M²⁺ _xFe²⁺ _xOHM^e+ _1-xFe³⁺ _1-xOH]^(1-x)+(A^n-)_(1-x)/n·mH₂O, wherein M²⁺Is Cu²⁺、Mg²⁺、Ni²⁺、Co²⁺、Fe²⁺、Zn²⁺、Ca²⁺、Mn²⁺、Pt²⁺、Ca²⁺Any one or more of, M^e+Is Al³⁺、Cr³⁺、Co³⁺、Mo⁶⁺、Mn⁴⁺、V⁵⁺、Ti⁴⁺Any one or more of A^n-Is Cl^-、Br^-、NO₃ ^-、ClO₃ ^-、IO₃ ^-、H₂PO₄ ^-、OH^-、CO₃ ^2-、SO₃ ^2-、SO₄ ^2-、PO₄ ^3-、CrO₄ ^2-、WO₄ ^2-X is (Fe)³⁺+M^e+) And (M)²⁺+Fe³⁺+M^e+) X is more than 0.5 and less than 1.0, m is the amount of crystal water, and m is 0-10; fe³⁺And M²⁺、M^e+Forming a laminate host structure, and forming an object structure by anions between layers; the carrier of the catalyst is one or more of carbon material, molecular sieve and inorganic oxide.

In the catalyst, the loading amount of the active component is 0.5-50% calculated by the catalyst, the rest is the carrier, and the particle size of the carrier is 1-50000 mu m.

The carbon material is at least one of coal dust, semi coke, activated carbon, carbon nano tubes and ash with carbon content more than 40 wt.% in the coal gasification process; the molecular sieve is one or two of a silicon-aluminum molecular sieve and a catalytic cracking process waste molecular sieve catalyst; the inorganic oxide is one or more of silicon oxide, aluminum oxide and zinc oxide.

The preparation method of the supported patina-based polymetallic hydroxide catalyst comprises the following steps: mixing ferrous salt with M²⁺Soluble salt of (A), M^e+The soluble salt is dissolved in water, a carrier is added, the mixture is stirred and reacted for 0.5 to 24 hours at the temperature of 20 to 100 ℃, and the reaction process is reversedIntroducing air or oxygen into the reaction solution, and adding a precipitator to control the pH of the reaction solution to be 6-11; and dehydrating and drying after the reaction is finished to obtain the supported patina-based polymetallic hydroxide.

In the preparation method, the ferrous salt is more than one of ferrous sulfate, ferrous nitrate, ferrous chloride, ferrous bromide, ferrous sulfite and ferrous ammonium sulfate; the M is²⁺The soluble salt of (A) is M²⁺Sulfate, nitrate or chloride salts of (a); the M is^e+In soluble salt of (3) Al³⁺、Cr³⁺And Co³⁺The soluble salt is sulfate, nitrate or chloride, Ti⁴⁺And Mo⁵⁺The soluble salt of (A) is a chloride salt; the precipitator is NH₄HCO₃、(NH₄)₂CO₃Urea, ammonia water and NaHCO₃、Na₂CO₃、K₂CO₃、KHCO₃Sodium acetate, potassium acetate, NaOH, KOH, CaCO₃、Ca(OH)₂Any one or more of them.

In the preparation method, the drying temperature is 40-300 ℃.

The invention takes Fe (II) salt as raw material, takes other stable divalent and polyvalent metals as protective agent through process oxidation, takes carbon material, molecular sieve and inorganic oxide as carrier, and self-assembles into the load type patina-based polymetallic hydroxide catalyst in one step in the synthesis reaction under the mild condition. The patina-based catalyst can be applied to kerosene co-refining reaction, direct coal liquefaction reaction, heavy inferior oil lightening reaction and coal tar hydrogenation reaction, and has extremely wide application value.

Drawings

FIG. 1 is an X-ray diffraction pattern of the catalyst prepared in example 1.

Fig. 2 is an SEM image of the pulverized coal-supported patina-based catalyst prepared in example 1.

Figure 3 is an SEM image of the activated alumina-supported patina-based catalyst prepared in example 2.

Fig. 4 is an X-ray diffraction pattern of the catalysts prepared in examples 3 and 4.

Fig. 5 is an SEM image of the pulverized coal-supported patina-based catalyst prepared in example 3.

Fig. 6 is an SEM image of the pulverized coal-supported patina-based catalyst prepared in example 4.

Detailed Description

The invention is further illustrated with reference to the following figures and examples, but the scope of the invention is not limited to these examples.

Example 1

Based on the catalyst, 3.96g of analytically pure FeCl was added in an amount of 29.6% based on the Fe-Co-Mo loading₂·4H₂O、4.76g CoCl₂·6H₂O、2.73g MoCl₅Dissolving the mixture in 100mL of deionized water, adding 10g of bituminous coal powder with the particle size distribution of 20-120 mu m into the obtained solution, introducing oxygen and stirring, simultaneously dropwise adding a urea aqueous solution with the mass fraction of 5%, controlling the pH value of the solution to be 8.8, reacting at 60 ℃ for 18 hours, then performing suction filtration and discharging, and drying at 120 ℃ for 5 hours to obtain the Fe (II) Fe (III) patina-based catalyst loaded by coal powder and containing Co (II) Mo (IV), wherein an X-ray diffraction spectrum of the Fe (II) Fe (III) patina-based catalyst is shown in figure 1, and characteristic diffraction peaks of crystal faces of layered multi-metal hydroxides (003), (006), (012), (110) and (113) and the like and characteristic diffraction peaks of large broad peaks of coal powder carriers near 20 degrees can be obviously seen in the spectrum. The SEM photograph of the coal dust-supported Fe (II) Fe (III) patina-based catalyst containing Co (II), Mo (IV) is shown in figure 2, and the SEM (II) Fe (III) patina-based layered multi-metal hydroxide with a hexagonal sheet structure is obviously supported on the surface of the coal dust carrier particles uniformly.

Example 2

Based on the catalyst, according to the load of Fe-Ni of 5.0 percent, 130 kilograms of industrial-grade FeSO is added into an industrial synthesis reaction kettle of 8 cubic meters₄·7H₂O, 120 kg NiSO₄·6H₂O was dissolved in 5 tons of deionized water, and 1 ton of active oxygen was added to the resulting solutionPreparing aluminum oxide powder into a suspension, introducing compressed air and stirring, adding ammonia water with the volume concentration of 3.7 percent through a distributor, controlling the pH value of the solution to be 7.5, stirring and reacting for 6 hours at 35 ℃, then performing plate-and-frame filter pressing discharging, and drying for 24 hours at 230 ℃ to obtain the active alumina supported Fe (II) Fe (III) patina-based catalyst containing Ni (II), wherein an SEM picture of the active alumina supported Fe (II) Fe (III) patina-based layered multi-metal hydroxide is shown in figure 3, and the active alumina surface is uniformly supported with Fe (II) Fe (III) patina-based layered multi-metal hydroxide with a hexagonal plate structure.

Example 3

Based on the catalyst, 130 kg of industrial-grade FeSO is added into an industrial synthesis reaction kettle of 8 cubic meters according to the load of Fe-Ni-Zn of 4.0 percent₄·7H₂O, 60 kg NiSO₄·6H₂O, 15 kg ZnSO₄·7H₂Dissolving O in 5 tons of tap water, adding 1 ton of activated carbon powder into the obtained solution to prepare a suspension, introducing the suspension into a factory instrument, stirring, simultaneously dropwise adding a 2 percent by mass aqueous solution of sodium hydroxide, controlling the pH of the solution to be 8.0, reacting at 50 ℃ for 4 hours, then performing plate-and-frame filter pressing discharging, and drying at 200 ℃ for 24 hours to obtain the activated carbon-supported Fe (II) Fe (III) patina-based catalyst containing Ni (II) Zn (II). The X-ray diffraction spectrum is shown in figure 4, and the characteristic diffraction peaks of crystal planes of the layered multi-metal hydroxides (003), (006), (012) and (015), etc., the large broad peak of the activated carbon carrier near 20 degrees and the characteristic diffraction peak of mineral ash in the carrier can be obviously seen. The SEM photograph of the Fe (II) Fe (III) patina-based catalyst containing Ni (II) Zn (II) is shown in figure 5, and the SEM photograph shows that Fe (II) Fe (III) patina-based layered multi-metal hydroxide with a hexagonal sheet structure is uniformly loaded on the surface of the activated carbon carrier.

Example 4

14.5g (NH) of analytically pure Fe-Mg-Al-Ti were used in an amount of 7.5% based on the catalyst, based on the Fe-Mg-Al-Ti loading₄)₂Fe(SO₄)₂·6H₂O、11.84g Mg(NO₃)₂、15.00g Al(NO₃)₃·9H₂O，7.59g TiCl₄Dissolving in 250mL deionized water, adding 85g of refined Yanan oilThe waste molecular sieve catalyst separated by the four-rotation of the catalytic cracking process of the factory is introduced with air and stirred, meanwhile, a mixed solution of potassium hydroxide with the mass fraction of 1% and potassium bicarbonate with the mass fraction of 4% is added dropwise, the pH of the solution is controlled to be 7.2, the solution reacts for 24 hours at the temperature of 75 ℃, then the discharged material is filtered and filtered, and dried for 12 hours at the temperature of 120 ℃, and the Fe (II) Fe (III) patina-based catalyst containing Mg (II) Al (III) Ti (IV) and loaded by the waste molecular sieve catalyst of the catalytic cracking process is obtained. The X-ray diffraction spectrum is shown in figure 4, the characteristic diffraction peaks of crystal faces of layered multi-metal hydroxides (003), (006), (012) and (015) can be obviously seen, and the characteristic diffraction peaks are characteristic diffraction peaks of waste molecular sieve catalyst carriers of the catalytic cracking process. SEM photographs of the Fe (II) Fe (III) patina-based catalyst loaded with the waste molecular sieve catalyst containing Mg (II), Al (III) Ti (IV) are shown in figure 6, and it is obvious that Fe (II) Fe (III) patina-based layered multi-metal hydroxide with a hexagonal sheet structure is uniformly loaded on the surfaces of the waste molecular sieve catalyst carrier particles in the catalytic cracking process.

In order to prove the beneficial effects of the invention, the catalysts obtained in the above examples 1-4 and the pulverized coal-loaded Mo-FeOOH catalyst (prepared by the method of patent CN 102380396A, wherein the loading amount of metal (Mo-FeOOH) is 7.5%) are applied to the hydrocracking reaction of the suspension bed vacuum residue, the extra-heavy vacuum residue (fraction of over 525 ℃ accounts for 98 wt%, sulfur content is 4.3 wt%) is used as the raw material, and the reaction conditions are as follows: the reaction temperature is 460 ℃; the reaction pressure is 22 MPa; the addition of the catalyst is 1 wt% (dry basis ash-free coal); the reaction space velocity was 0.5 kg/(h.L). The main results of the heavy oil lightening reaction are shown in table 1.

TABLE 1

As can be seen from table 1, the catalyst of the present invention exhibited excellent performance in both catalyst activity and desulfurization.

Claims

1. A supported patina-based multimetal hydroxide catalyst characterized by: the catalystThe active component of (A) is a layered multi-metal hydroxide with a chemical composition [ M²⁺ _xFe²⁺ _xOHM^e+ _1-xFe³⁺ _1-xOH]^(1-x)+(A^n-)_(1-x)/n·mH₂O, wherein M² ⁺Is Cu²⁺、Mg²⁺、Ni²⁺、Co²⁺、Fe²⁺、Zn²⁺、Ca²⁺、Mn²⁺、Pt²⁺Any one or more of, M^e+Is Al³⁺、Cr³⁺、Co³⁺、Mo⁶⁺、Mn⁴⁺、V⁵⁺、Ti⁴⁺Any one or more of A^n-Is Cl^-、Br^-、NO₃ ^-、ClO₃ ^-、IO₃ ^-、H₂PO₄ ^-、OH^-、CO₃ ^2-、SO₃ ^2-、SO₄ ^2-、PO₄ ^3-、CrO₄ ^2-、WO₄ ^2-X is (Fe)³⁺+M^e+) And (M)²⁺+Fe³⁺+M^e+) X is more than 0.5 and less than 1.0, m is the amount of crystal water, and m = 0-10; fe³⁺And M²⁺、M^e+Forming a laminate host structure, and forming an object structure by anions between layers; the carrier of the catalyst is one or more of carbon material, molecular sieve and inorganic oxide.

2. The supported patina-based multimetal hydroxide catalyst of claim 1, characterized in that: the loading amount of the active component is 0.5-50% by the catalyst.

3. The supported patina-based multimetal hydroxide catalyst of claim 1, characterized in that: the carbon material is at least one of coal dust, semi coke, activated carbon, carbon nano tubes and ash with carbon content of more than 40 wt.% in the coal gasification process.

4. The supported patina-based multimetal hydroxide catalyst of claim 1, characterized in that: the molecular sieve is one or two of a silicon-aluminum molecular sieve and a catalytic cracking process waste molecular sieve catalyst.

5. The supported patina-based multimetal hydroxide catalyst of claim 1, characterized in that: the inorganic oxide is any one or more of silicon oxide, aluminum oxide and zinc oxide.

6. The supported patina-based multimetal hydroxide catalyst according to any one of claims 3 to 5, wherein: the particle size of the carrier is 1-50000 mu m.

7. A process for preparing the supported patina-based multimetal hydroxide catalyst of claim 1, characterized by: mixing ferrous salt with M²⁺Soluble salt of (A), M^e+Dissolving the soluble salt in water, adding a carrier, stirring and reacting for 0.5-24 hours at 20-100 ℃, introducing air or oxygen into the reaction liquid in the reaction process, and adding a precipitator to control the pH of the reaction liquid to be 6-11; and dehydrating and drying after the reaction is finished to obtain the supported patina-based polymetallic hydroxide.

8. The method of preparing a supported patina-based multimetal hydroxide catalyst of claim 7, characterized in that: the ferrous salt is more than one of ferrous sulfate, ferrous nitrate, ferrous chloride, ferrous bromide, ferrous sulfite and ferrous ammonium sulfate; the M is²⁺The soluble salt of (A) is M²⁺Sulfate, nitrate or chloride salts of (a); the M is^e+In soluble salt of (3) Al³⁺、Cr³⁺And Co³⁺The soluble salt is sulfate, nitrate or chloride, Ti⁴⁺And Mo⁵⁺The soluble salt of (a) is a chloride salt.

9. The method of claim 7 for preparing the supported patina-based multimetal hydroxide catalystThe method is characterized in that: the precipitator is NH₄HCO₃、(NH₄)₂CO₃Urea, ammonia water and NaHCO₃、Na₂CO₃、K₂CO₃、KHCO₃Sodium acetate, potassium acetate, NaOH, KOH, Ca (OH)₂Any one or more of them.

10. The method of preparing a supported patina-based multimetal hydroxide catalyst of claim 7, characterized in that: the drying temperature is 40-300 ℃.