CN104549304B

CN104549304B - A kind of catalyst of octenal gas phase hydrogenation octanol and preparation method thereof

Info

Publication number: CN104549304B
Application number: CN201410696302.7A
Authority: CN
Inventors: 苏发兵; 纪永军; 古芳娜
Original assignee: Institute of Process Engineering of CAS
Current assignee: Institute of Process Engineering of CAS
Priority date: 2014-11-26
Filing date: 2014-11-26
Publication date: 2017-06-06
Anticipated expiration: 2034-11-26
Also published as: CN104549304A

Abstract

The invention provides a kind of catalyst for octenal gas phase hydrogenation octanol and preparation method thereof, the method crushes the waste catalyst that direct method production methylchlorosilane is produced, screening, by roasting, acid dissolving, urea hydrothermal deposition step to its modifying and decorating, the catalyst of the octenal gas phase hydrogenation octanol is obtained, its composition contains copper, zinc active component and porous oxidation silicon carrier.The advantage of the invention is that：Solve the high-valued problem of complex utilization of solid residue waste catalyst in organosilicon compound probability；Low raw-material cost, operating method is simple, it is easy to accomplish industrialized production；Compared with infusion process, coprecipitation method, catalyst particle size prepared by urea water thermal precipitator method is smaller, and dispersiveness is preferable, therefore octanol selectivity and catalytic stability with hydrogenation activity and Geng Gao higher, the service life of catalyst can significantly be extended, and it is reproducible.

Description

A kind of catalyst of octenal gas phase hydrogenation octanol and preparation method thereof

Technical field

The invention belongs to technical field of chemical engineering catalysts, be related to a kind of catalyst of octenal gas phase hydrogenation octanol and its Preparation method.

Background technology

Octanol (2-Ethylhexyl Alcohol) is widely used in aliphatic acid and various as a kind of important solvent and Organic Chemicals The production of esters.The main method using octenal (EPA) catalytic hydrogenation of industry prepares octanol at present, and the method gas phase hydrogenation is main Using copper-based catalysts.The advantages of copper-based catalysts are active high, cheap, but easily sintered under its hot conditions, surely Qualitative difference, can also trigger some other side reactions to cause octanol selectively reduction.Therefore, at present to the research master of hydrogenation catalyst If stability and the suppression side reaction of catalyst are improved as auxiliary agent by adding other components.

Patent FR2489304A1 prepares copper oxide-zinc oxide-alumina series catalyst and carries out octene using coprecipitation technology Aldehyde gas phase hydrogenation, at 230~240 DEG C of reaction temperature, octanol yield is 94%.

Patent CN1255406A, in order to avoid the introducing of sodium ion, is 25~45 in temperature using organic acid as precipitating reagent DEG C, pH is that under conditions of 2~7, preparing copper-zinc system catalyst using co-precipitation carries out aldehyde Hydrogenation alcohol, is aoxidized in catalyst composition Copper is 30%~50wt%, and zinc oxide is 50%~70wt%.

Patent CN102407122A prepares octene aldehyde hydrogenating catalyst using the continuous coprecipitation of distribution：First in reactor The zinc salt and the mixing of certain density copper nitrate for having dissolved will be measured, is neutralized with alkali precipitation agent be co-precipitated under agitation；Then exist The aluminium salt that remaining zinc salt and metering have been dissolved is mixed in above-mentioned same reactor, and alkali precipitation agent is coprecipitated using cocurrent process Form sediment, ageing obtains filter cake, and graphite and deionized water are added after washing, filtering, dry, granulation and roasting, is molded on tablet machine Obtain catalyst.

Catalyst prepared by the above method improves the stability of catalyst and the yield of octanol to a certain extent, but by In complex catalyst system is prepared using coprecipitation, the catalyst dispersity for obtaining is poor and particle diameter is larger.Additionally, above-mentioned urge Agent preparation technology is cumbersome, the meeting generation environment pollution problem of high cost, preparation process, is restricted in actual applications.Therefore open Hair high activity, high selectivity, good stability and catalyst with low cost, and the environment-friendly and simple catalyst system of process Preparation Method is still octenal Hydrogenation for one of technological difficulties of octanol.

Organosilicon material has the excellent specific property such as heatproof, electric insulation, corrosion-resistant and nonpoisonous and tasteless, is widely used in its people Economic every field, such as electronics, automobile, oil, chemical industry, building and aerospace field.Methylchlorosilane is to have prepared The most important organic silicon monomer of machine silicon materials, wherein, it is maximum with the consumption of dimethyldichlorosilane (M2).Industrial main use Direct method produces the monomer, because of its process is simple, high income, small without solvent and danger.I.e. in a fluidized bed reactor, silicon Powder and major catalyst copper powder, co-catalyst zinc powder are mixed to form active contact, with the extension in reaction time, contact surface it is heavy Product thing can be more and more, reduce contact activity, cause M2 to be selectively greatly lowered, and now this part of contact need to be discharged instead Device is answered, while add new contact to be beneficial to reaction continuous-stable carrying out.In addition, the gas solid separation system of fluid bed is continuously discharged The serious fine powder of surface contamination, this two parts waste residue is referred to as waste catalyst, its main component be silicon, copper, carbon, and containing a small amount of zinc, The components such as iron, aluminium, tin.Waste catalyst average grain diameter is thinner, and the copper containing high activity, and exposure can cause oxidation very in atmosphere To burning, environmental pollution is serious, while being also the hidden danger in safety in production.With the production-scale continuous expansion of organic silicon monomer Greatly, the amount of resulting waste catalyst is continuously increased, and the environmental pollution for causing and copper silicon waste problem and increasingly sharpen, therefore to useless The reasonable treatment of contact and utilization always China's silicone industry sustainable development problem demanding prompt solution.

Waste catalyst is passed through patent US5239102A hydrogen chloride and helium in the reactor, and temperature rises to 900 DEG C, there is 95% SiC_l4And HSiCl₃Generation.

Be put into 3Kg waste catalysts in nodulizer by patent US4892694A, a diameter of 1m of vibrating prilling device, and rotation number is 20r/min, adds 1Kg water in 1min, and nitrogen is protective gas, generates the particle that spherical particle diameter is 2~50mm.Then plus Enter the CaCO of 1Kg₃, the outer surface of spheric granules just adds has covered one layer of CaCO₃, center is active Si and SiO₂, its burning-point is reachable 400℃。

Patent US4724122A has invented a kind of technique of the particle or bead for waste catalyst being processed into stabilization.Making first Waste catalyst is processed into bead or formation particle in grain machine or caking machine, then makes bead saturation with organic bond, in order to Transport, the viscosity of organic bond is very low, it is easy to be impregnated with ball, and available organic bond includes that glucose, colloid are glued Mixture, asphalt, paraffin etc..

Although the treatment to waste catalyst has carried out substantial amounts of research, complex disposal process, secondary pollution is serious, product Added value than relatively low, therefore, product very must can be in the method for higher value application simultaneously to find a kind of simple, cleaning Will be with reality.

The content of the invention

The bad dispersibility of the octene aldehyde hydrogenating catalyst prepared for above-mentioned coprecipitation, particle diameter are big, preparation technology Cumbersome, high cost, preparation process can generation environment the problems such as pollute, and look for and a kind of production methylchlorosilane generation given up The processing method that contact is simple, cleaning, utilization rate are high, the invention provides a kind of catalyst of octenal gas phase hydrogenation octanol And preparation method thereof.

It is that, up to this purpose, the present invention uses following technical scheme：

A kind of catalyst of octenal gas phase hydrogenation octanol, the catalyst includes copper activity component, zinc active component With porous oxidation silicon carrier.

The composition of the catalyst includes following components by mass percentage：

Copper activity component 1~30%

Zinc active component 1~10%

Porous silica 60~98%

The each component mass percent sum is 100%.

Wherein, the content of copper activity component can for 1%, 3%, 5%, 7%, 10%, 13%, 15%, 17%, 20%, 23%th, 25%, 27% or 30% etc..

The content of zinc active component can be 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10% etc..

The content of porous silica can for 60%, 62%, 64%, 66%, 68%, 70%, 73%, 74%, 76%, 78%th, 80%, 82%, 84%, 86%, 88%, 90%, 92%, 94%, 96% or 98% etc..

The preparation method of the above catalyst, the described method comprises the following steps：

(A) solid residue waste catalyst is crushed and is sieved；

(B) the solid residue waste catalyst after crushing and sieve is calcined with organics removal, and silica is turned into oxidation Silicon；

(C) the solid residue waste catalyst acid solution after being calcined dissolves；

(D) step (C) resulting solution urea hydrothermal deposition, washing, dry and reduce, be obtained catalyst.

Solid residue waste catalyst prepares organic silicon monomer methylchlorosilane for direct method fluidized-bed process in the step (A) The solid residue of generation.

Solid residue waste catalyst is crushed and the particle diameter after sieving is 0.5~100 μm in the step (A), such as 0.5 μm, 1 μm、5μm、10μm、15μm、20μm、25μm、30μm、35μm、40μm、45μm、50μm、55μm、60μm、65μm、70μm、75μm、 80 μm, 85 μm, 90 μm, 95 μm or 100 μm etc..

In the step (B) sintering temperature be 450~900 DEG C, such as 450 DEG C, 500 DEG C, 550 DEG C, 600 DEG C, 650 DEG C, 700 DEG C, 750 DEG C, 800 DEG C, 850 DEG C or 900 DEG C etc..

In the step (B) roasting time be 2~8h, such as 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h or 8h etc..

In the step (C) acid solution be hydrochloric acid, nitric acid or sulfuric acid in any one or at least two combination, the combination Typical but non-limiting examples have：The combination of the combination of hydrochloric acid and nitric acid, nitric acid and sulfuric acid, the combination of hydrochloric acid, nitric acid and sulfuric acid Deng.

In the step (C) concentration of acid solution be 0.5~6mol/L, such as 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, 3.5mol/L, 4mol/L, 4.5mol/L, 5mol/L, 5.5mol/L or 6mol/L etc..

In the step (C) acid solution solution temperature be 40~80 DEG C, such as 40 DEG C, 45 DEG C, 50 DEG C, 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C or 80 DEG C etc..

Acid solution dissolving is carried out under agitation in the step (C).

Acid solution dissolution time is 2~10h, such as 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10h etc. in the step (C).

Urea hydrothermal deposition step is in the step (D)：Precipitation is added after adding zinc salt in step (C) resulting solution Agent urea simultaneously adjusts pH value of solution, and be subsequently adding in water heating kettle carries out hydro-thermal reaction at autogenous pressures.

Zinc salt is any one in zinc nitrate, zinc chloride or zinc sulfate during urea hydrothermal deposition in the step (D) Or at least two combination, combination typical case but non-limiting examples have：The combination of zinc nitrate and zinc chloride, zinc chloride and sulphur The combination of sour zinc, combination of zinc nitrate, zinc chloride and zinc sulfate etc..

Addition≤the 0.05g/mL of zinc salt during the urea hydrothermal deposition, such as 0.05g/mL, 0.045g/mL, 0.04g/mL, 0.035g/mL, 0.03g/mL, 0.025g/mL, 0.02g/mL, 0.015g/mL, 0.01g/mL or 0.005g/mL Deng.

It is 9~14, such as 9,10,11,12,13 or 14 etc. that pH value of solution is adjusted during the urea hydrothermal deposition.

120~180 DEG C of the reaction temperature of the urea hydrothermal deposition process water thermal response, such as 120 DEG C, 125 DEG C, 130 DEG C, 135 DEG C, 140 DEG C, 145 DEG C, 150 DEG C, 155 DEG C, 160 DEG C, 165 DEG C, 170 DEG C, 175 DEG C or 180 DEG C etc..

The reaction time of the urea hydrothermal deposition process water thermal response be 8~16h, such as 8h, 8.5h, 9h, 9.5h, 10h, 10.5h, 11h, 11.5h, 12h, 12.5h, 13h, 13.5h, 14h, 14.5h, 15h, 15.5h or 16h etc..

The reduction of catalyst is using hydrogen reducing and with nitrogen as carrier gas, the wherein content of hydrogen in the step (D) It is 5~10%, such as 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5% or 10% etc..

In the step (D) reduction temperature of catalyst be 160~220 DEG C, such as 160 DEG C, 165 DEG C, 170 DEG C, 175 DEG C, 180 DEG C, 185 DEG C, 190 DEG C, 195 DEG C, 200 DEG C, 205 DEG C, 210 DEG C, 215 DEG C or 220 DEG C etc..

In the step (D) recovery time of catalyst be 2~10h, such as 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10h etc..

The above catalyst applications, it is applied to the reaction of octenal gas phase hydrogenation octanol.

Beneficial effect：

1st, using porous silica as catalyst carrier, copper and zinc are active component to the catalyst that the present invention is provided, and are had Hydrogenation activity higher and the octanol selectivity of Geng Gao and catalytic stability, in octenal gas phase hydrogenation reaction, octenal Conversion ratio >=95.0%, after octanol selectivity >=99.0%, and catalyst operation 250h, conversion ratio still >=94.0%, is selected Selecting property >=98.8%.Meanwhile, the service life of catalyst is significantly extended, and reproducible.

2nd, the present invention prepares catalyst using urea water thermal precipitator method so that catalyst particle size is smaller, and dispersiveness preferably, will The silicon direct oxidation contained in abandoned catalyst in direct synthesis methylchlorosilane be porous silica as catalyst carrier, and using copper and zinc as activearm Point, for octenal gas phase hydrogenation octanol technique, solve organosilicon compound probability solid residue waste catalyst it is high-valued Problem of complex utilization, meets the requirement of recycling economy and Green Chemistry.

3rd, the present invention is provided as the catalyst of octenal gas phase hydrogenation octanol, low raw-material cost, operating method Simply, it is easy to accomplish industrialized production.

Brief description of the drawings

Fig. 1 is the XRD of the catalyst without reduction in the embodiment of the present invention 1；

Fig. 2 is the performance test results figure that the made catalyst of the embodiment of the present invention 1 is used in octenal gas phase hydrogenation reaction.

Specific embodiment

Further illustrate technical scheme below in conjunction with the accompanying drawings and by specific embodiment.

The waste catalyst that following examples are used is consolidating for being produced during silicone industry production methyl chlorosilane monomer Body residue, i.e. elemental silicon in the presence of copper major catalyst and zinc co-catalyst, produce chlorosilane monomer industry mistake with chloromethanes The complete silicon of unreacted and copper beaded catalyst powder in journey, and the carbon distribution institute that carbonaceous organic material is pyrolyzed and produces during this The porous complex of composition.

Embodiment 1：

Abandoned catalyst in direct synthesis methylchlorosilane 10g is taken, the particle diameter after its broken, screening is 0.5~100 μm；It is put into Muffle furnace, in 450 DEG C roasting 2h, be cooled to room temperature；Place it in 1000mL beakers, the nitric acid 200mL of 0.5mol/L is added, 80 under stirring DEG C reaction 2h；Add 4gZn (NO₃)₂·6H₂O, adds urea liquid, and regulation pH value to 9 loads water heating kettle, and 180 DEG C spontaneous Hydro-thermal reaction 8h under pressure, washing is dried.With nitrogen as carrier gas, H is controlled₂Content is 5%, in reducing 10h at 160 DEG C.

X ' Pert PRO MPD the types that the catalyst of above-mentioned preparation is produced in Dutch Panalytical companies (PANalytical) XRD tests are carried out on Multi-functional X ray diffractometer；In U.S.'s Pekin-Elmer inductively coupled plasma atomic emission spectrums ICP tests (similarly hereinafter) are carried out on instrument.

Fig. 1 is the XRD of the catalyst without reduction in embodiment 1.Wherein 2 θ=21.9 ° are SiO₂Diffraction maximum, by In for amorphous intensity it is weaker, 2 θ=35.5 ° and 2 θ=38.7 ° composition acromion be CuO characteristic peak, 2 θ=36.3 ° are ZnO Characteristic peak.

ICP test results show that copper coin cellulose content is 29.3%, and Zn-ef ficiency content is 6.3%.Embodiment 2：

Abandoned catalyst in direct synthesis methylchlorosilane 10g is taken, the particle diameter after its broken, screening is 0.5~100 μm；It is put into Muffle furnace, in 600 DEG C roasting 4h, be cooled to room temperature；Place it in 1000mL beakers, the sulfuric acid 200mL of 0.5mol/L is added, 60 under stirring DEG C reaction 6h；Add 2gZn (NO₃)₂·6H₂O, adds urea liquid, adjusts pH to 12, loads water heating kettle, 140 DEG C of spontaneous pressures Hydro-thermal reaction 12h under power, washing is dried.With nitrogen as carrier gas, H is controlled₂Content is 7%, in reducing 10h at 160 DEG C.

ICP test results show that copper coin cellulose content is 8.3%, and Zn-ef ficiency content is 3.2%.

Embodiment 3：

Abandoned catalyst in direct synthesis methylchlorosilane 10g is taken, the particle diameter after its broken, screening is 0.5~100 μm；It is put into Muffle furnace, in 900 DEG C roasting 8h, be cooled to room temperature；Place it in 1000mL beakers, add the nitric acid 200mL of 6mol/L, lower 40 DEG C of stirring Reaction 10h；Add 10gZnSO₄·7H₂O, adds urea liquid, and regulation pH value to 14 loads water heating kettle, 120 DEG C of spontaneous pressures Hydro-thermal reaction 16h under power, washing is dried.With nitrogen as carrier gas, H is controlled₂Content is 8%, in reducing 4h at 200 DEG C.

ICP test results show that copper coin cellulose content is 23.8%, and Zn-ef ficiency content is 9.0%.

Embodiment 4：

Abandoned catalyst in direct synthesis methylchlorosilane 10g is taken, the particle diameter after its broken, screening is 0.5~100 μm；It is put into Muffle furnace, in 600 DEG C roasting 2h, be cooled to room temperature；Above-mentioned material is placed in 1000mL beakers, 6mol/L sulfuric acid 200mL is added, under stirring 80 DEG C of reaction 2h；Add 2gZnSO₄·7H₂O, adds urea liquid, adjusts pH to 10, loads water heating kettle, 180 DEG C of spontaneous pressures Hydro-thermal reaction 2h under power, washing is dried.With nitrogen as carrier gas, H is controlled₂Content is 10%, in reductase 12 h at 220 DEG C.

ICP test results show that copper coin cellulose content is 1.3%, and Zn-ef ficiency content is 3.9%.

Embodiment 5：

Abandoned catalyst in direct synthesis methylchlorosilane 10g is taken, the particle diameter after its broken, screening is 0.5~100 μm；It is put into Muffle furnace, in 600 DEG C roasting 4h, be cooled to room temperature；Above-mentioned material is placed in 1000mL beakers, the hydrochloric acid 200mL of 0.5mol/L is added, shape is stirred The lower 40 DEG C of reactions 10h of state；Add 2gZnCl₂, urea liquid is added, pH to 14 is adjusted, load water heating kettle, 120 DEG C of self-generated pressures Lower hydro-thermal reaction 16h, washing is dried.With nitrogen as carrier gas, H is controlled₂Content is 8%, in reducing 4h at 200 DEG C.

ICP test results show that copper coin cellulose content is 29.3%, and Zn-ef ficiency content is 3.5%.

Embodiment 6：

Abandoned catalyst in direct synthesis methylchlorosilane 10g is taken, the particle diameter after its broken, screening is 0.5~100 μm；It is put into Muffle furnace, in 600 DEG C roasting 4h, be cooled to room temperature；Place it in 1000mL beakers, add the hydrochloric acid 200mL of 6mol/L, lower 60 DEG C of stirring Reaction 6h；Urea liquid is added, pH to 11 is adjusted, loads water heating kettle, hydro-thermal reaction 12h under 140 DEG C of self-generated pressures, washing is done It is dry.With nitrogen as carrier gas, H is controlled₂Content is 7%, in reducing 10h at 160 DEG C.

ICP test results show that copper coin cellulose content is 8.3%, and Zn-ef ficiency content is 1.2%.

Embodiment 7：The evaluation of catalyst

This example is illustrated in octenal is hydrogenated to octanol reaction, the active testing knot of the catalyst that the present invention is provided Really.

Reaction unit is continuous flowing stainless steel fixed bed, and reactor inside diameter is 20mm, and the loadings of catalyst are 1g.

Octenal liquid hourly space velocity is 0.3h^-1, hydrogen aldehyde mol ratio is 28:1, reaction temperature is 180 DEG C, and reaction pressure is 0.4, Reaction time is 1h.

Reactant octenal is gasified, then continuously enter beds, product and excess after mixing with hydrogen Hydrogen is separated after cooling, and at regular intervals, take out condensed liquid product carries out quantitative analysis by capillary gas chromatography. Chromatogram model SHIMADZU GC-14B, chromatographic column is HP-5 (30m × 0.25mm), and fid detector, external standard method calculates octene Aldehyde conversion ratio and octanol selectivity, testing result are as shown in table 1.

Table 1：Catalyst activity test result table

Catalyst	Octenal conversion ratio (%)	Octanol selectivity (%)
			Embodiment 1	99.8	99.5
Embodiment 2	99.9	99.8
			Embodiment 3	99.9	99.6
Embodiment 4	99.8	99.7
			Embodiment 5	99.9	99.7
Embodiment 6	95.0	99.0

Catalyst obtained in embodiment 1 is used in octenal gas phase hydrogenation reaction, its reaction condition is：Catalyst It is 1g, octenal liquid hourly space velocity is 0.3h^-1, hydrogen aldehyde mol ratio is 28:1, reaction temperature is 180 DEG C, and reaction pressure is 0.6MPa, Reaction time is 250h, and its active testing result is as shown in Figure 2.It can be seen that the service life of catalyst is significantly prolonged It is long and reproducible.

From ICP results, for 1%~30wt%, zinc is 1 to the catalyst metal content copper prepared as raw material with waste catalyst These metal component grain diameters of~10wt%, XRD data display are smaller, good dispersion degree.

Test result indicate that, although it is different with the catalyst activity component content that waste catalyst is prepared as raw material, but catalysis Activity and selectivity is all higher, octenal conversion ratio >=95.0%, octanol selectivity >=99.0%, and catalyst runs After 250h, conversion ratio still >=94.0%, selectivity >=98.8%.Therefore with waste catalyst as raw material, after being processed through physical chemistry, The octenal that better performances can be obtained prepares the catalyst of octanol.

Applicant states that the present invention illustrates method detailed of the invention by above-described embodiment, but the present invention not office It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implement.Art Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosing.

Claims

1. a kind of preparation method of the catalyst of octenal gas phase hydrogenation octanol, it is characterised in that the catalyst includes copper Active component, zinc active component and porous oxidation silicon carrier；

Copper activity component 1~30%

Zinc active component 1~10%

Porous silica 60~98%

The each component mass percent sum is 100%；

The catalyst is prepared using urea water thermal precipitator method, and the silicon direct oxidation that will contain in abandoned catalyst in direct synthesis methylchlorosilane is many Hole silica as catalyst carrier, and using copper and zinc as active component；

Specifically the described method comprises the following steps：

(A) solid residue waste catalyst is crushed and is sieved；

(B) the solid residue waste catalyst after crushing and sieve is calcined；

(D) step (C) resulting solution urea hydrothermal deposition, washing, dry and reduce, octenal gas phase hydrogenation octanol is obtained Catalyst；

Solid residue waste catalyst is produced for direct method fluidized-bed process prepares organic silicon monomer methylchlorosilane in the step (A) Solid residue；

Urea hydrothermal deposition step is in the step (D)：Precipitating reagent urine is added after zinc salt is added in step (C) resulting solution Element simultaneously adjusts pH value of solution, and being subsequently adding in water heating kettle carries out hydro-thermal reaction；

120~180 DEG C of the reaction temperature of the urea hydrothermal deposition process water thermal response；

The reduction of catalyst is using hydrogen reducing and with nitrogen as carrier gas in the step (D), wherein the content of hydrogen be 5~ 10%；

The reduction temperature of catalyst is 160~220 DEG C in the step (D).

2. preparation method according to claim 1, it is characterised in that solid residue waste catalyst is crushed in the step (A) And the particle diameter after sieving is 0.5~100 μm.

3. preparation method according to claim 1, it is characterised in that sintering temperature is 450~900 in the step (B) ℃。

4. preparation method according to claim 1, it is characterised in that roasting time is 2~8h in the step (B).

5. preparation method according to claim 1, it is characterised in that acid solution is hydrochloric acid, nitric acid or sulphur in the step (C) In acid any one or at least two combination.

6. preparation method according to claim 1, it is characterised in that in the step (C) concentration of acid solution be 0.5~ 6mol/L。

7. preparation method according to claim 1, it is characterised in that in the step (C) acid solution solution temperature be 40~ 80℃。

8. preparation method according to claim 1, it is characterised in that acid solution is dissolved in stirring condition in the step (C) Under carry out.

9. preparation method according to claim 1, it is characterised in that in the step (C) acid solution dissolution time be 2~ 10h。

10. preparation method according to claim 1, it is characterised in that in the step (D) during urea hydrothermal deposition Zinc salt be zinc nitrate, zinc chloride or zinc sulfate in any one or at least two combination.

11. preparation methods according to claim 1, it is characterised in that zinc salt adds during the urea hydrothermal deposition Enter amount≤0.05g/mL.

12. preparation methods according to claim 1, it is characterised in that adjust solution during the urea hydrothermal deposition PH is 9~14.

13. preparation methods according to claim 1, it is characterised in that the urea hydrothermal deposition process is in self-generated pressure Under carry out.

14. preparation methods according to claim 1, it is characterised in that the urea hydrothermal deposition process water thermal response Reaction time is 8~16h.

15. preparation methods according to claim 1, it is characterised in that the recovery time of catalyst is in the step (D) 2~10h.