CN104549304A - Catalyst for hydrogenating octenal gas phase to prepare octanol and preparation method of catalyst - Google Patents
Catalyst for hydrogenating octenal gas phase to prepare octanol and preparation method of catalyst Download PDFInfo
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Abstract
The invention provides a catalyst for hydrogenating an octenal gas phase to prepare octanol and a preparation method of the catalyst. The method comprises the following steps: breaking and sieving a waste contact generated by producing methyl chlorosilane with a direct method; and carrying out steps of roasting, dissolving with acid, and hydrothermally settling with urea to modify so as to obtain the catalyst for hydrogenating the octenal gas phase to prepare octanol. The components include copper and zinc active components and a porous silicon oxide carrier. The catalyst has the advantages that the problem of high-value comprehensive utilization of the solid residue waste contact in an organic silicon synthesizing industry is solved; the cost of raw materials is low, the operation method is simple and the industrial production is easy to realize; and compared with an impregnation method and a co-precipitation method, the grain diameter of the catalyst prepared by a urea hydrothermal settling method is smaller and the dispersity is better, so that the catalyst has higher hydrogenating activity and higher octanol selectivity and catalyzing stability, the service life of the catalyst can be greatly prolonged and the repeatability is good.
Description
Technical field
The invention belongs to chemical catalyst technical field, relate to a kind of Catalysts and its preparation method of octenal gas phase hydrogenation octanol.
Background technology
Octanol (2-Ethylhexyl Alcohol), as a kind of important solvent and Organic Chemicals, is widely used in the production of lipid acid and various ester class.Current industry mainly adopts the method for octenal (EPA) shortening to prepare octanol, and this method gas phase hydrogenation mainly adopts copper-based catalysts.Copper-based catalysts has the active advantage such as high, cheap, but easily sinters under its hot conditions, poor stability, also can cause some other side reactions and cause octanol selectivity to reduce.Therefore, at present mainly as auxiliary agent, the stability of catalyzer and suppression side reaction are improved by adding other component to the research of hydrogenation catalyst.
Patent FR2489304A1 employing coprecipitation technology is prepared copper oxide-zinc oxide-alumina series catalyzer and is carried out octenal gas phase hydrogenation, and at temperature of reaction 230 ~ 240 DEG C, octanol yield is 94%.
Patent CN1255406A is in order to avoid the introducing of sodium ion, using organic acid as precipitation agent, it is 25 ~ 45 DEG C in temperature, pH is under the condition of 2 ~ 7, adopt co-precipitation to prepare copper-zinc system catalyst and carry out aldehyde Hydrogenation alcohol, in catalyzer composition, cupric oxide is 30% ~ 50wt%, and zinc oxide is 50% ~ 70wt%.
Patent CN102407122A adopts the continuous coprecipitation method of distribution to prepare octenal hydrogenation catalyst: first will measure the zinc salt and the mixing of certain density cupric nitrate that have dissolved, under agitation with alkali precipitation agent neutral precipitation in reactor; The aluminium salt mixing of then in above-mentioned same reactor, remaining zinc salt and metering having been dissolved, cocurrent process co-precipitation is adopted with alkali precipitation agent, ageing obtains filter cake, washing, filters, adds graphite and deionized water after dry, granulation and roasting, shapingly on tablet machine obtains catalyzer.
Catalyzer prepared by aforesaid method improves the stability of catalyzer and the yield of octanol to a certain extent, but owing to adopting coprecipitation method to prepare complex catalyst system, the catalyst dispersity obtained is poor and particle diameter is larger.In addition, above-mentioned catalyst preparation process is loaded down with trivial details, cost is high, preparation process can produce problem of environmental pollution, restricted in actual applications.Therefore develop high reactivity, highly selective, good stability and catalyzer with low cost, and environmental friendliness and the simple method for preparing catalyst of process remain one of the technological difficulties of octenal Hydrogenation for octanol.
Organosilicon material has heatproof, electric insulation, the excellent specific property such as corrosion-resistant and nonpoisonous and tasteless, is widely used in the every field of national economy, as electronics, automobile, oil, chemical industry, building and aerospace field etc.Methyl chlorosilane prepares the most important organosilane monomer of organosilicon material, wherein, maximum with the consumption of dimethyldichlorosilane(DMCS) (M2).Industrial main employing direct method produces this monomer, because its technique is simple, yield is high, without solvent and danger little.Namely in a fluidized bed reactor, silica flour and Primary Catalysts copper powder, promotor zinc powder are mixed to form active contact, along with the prolongation in reaction times, the settling on contact surface can get more and more, contact activity is reduced, cause M2 selectivity significantly to reduce, now this part of contact need discharge reactor, add simultaneously new contact be beneficial to reaction continous-stable carry out.In addition, the gas solid separation system of fluidized-bed discharges the serious fine powder of surface contamination continuously, and this two portions waste residue is called waste catalyst, and its main component is silicon, copper, carbon, and containing components such as a small amount of zinc, iron, aluminium, tin.Waste catalyst median size is comparatively thin, and containing highly active copper, exposes and oxidation can be caused in atmosphere even to burn, and environmental pollution is serious, is also the hidden danger in safety in production simultaneously.Along with the production-scale continuous expansion of organosilane monomer, the amount of consequent waste catalyst constantly increases, the environmental pollution caused and copper silicon waste problem are increasingly sharpened, and are therefore China's silicone industry sustainable development problem demanding prompt solutions to the reasonable disposal and utilization of waste catalyst always.
Waste catalyst is passed into hydrogenchloride and helium by patent US5239102A in the reactor, and temperature rises to 900 DEG C, has 95%SiC
l4and HSiCl
3generate.
3Kg waste catalyst is put into Fitz chilsonator by patent US4892694A, and the diameter of vibrating prilling device is 1m, and rotation number is 20r/min, adds 1Kg water in 1min, and nitrogen is shielding gas, creates the particle that spherical particle diameter is 2 ~ 50mm.Then the CaCO of 1Kg is added
3, the outside surface of spheroidal particle just adds and has covered one deck CaCO
3, center is active Si and SiO
2, its burning-point can reach 400 DEG C.
Patent US4724122A invents and a kind of waste catalyst is processed into stable particle or the technique of bead.First in tablets press or caking machine, waste catalyst be processed into bead or form particle; then make bead saturated with organic binder bond; so that transport; the viscosity of organic binder bond is very low; be easy to soak in ball, available organic binder bond comprises glucose, rubstick, petroleum pitch, paraffin etc.
Although carried out large quantifier elimination to the process of waste catalyst, complex disposal process, secondary pollution is serious, and value-added content of product is lower, and therefore, finding the method for all right higher value application of a kind of simple, clean product simultaneously, is very necessary and real.
Summary of the invention
Bad dispersibility, the particle diameter of the octenal hydrogenation catalyst prepared for above-mentioned coprecipitation method are large, preparation technology is loaded down with trivial details, cost is high, preparation process can produce the problems such as environmental pollution, and look for a kind for the treatment of process that waste catalyst is simple, clean, utilization ratio is high to producing methyl chlorosilane generation, the invention provides a kind of Catalysts and its preparation method of octenal gas phase hydrogenation octanol.
For reaching this object, the present invention by the following technical solutions:
A catalyzer for octenal gas phase hydrogenation octanol, described catalyzer comprises copper activity component, zinc active ingredient and porous oxidation silicon carrier.
The composition of described catalyzer comprises following component by mass percentage:
Copper activity component 1 ~ 30%
Zinc active ingredient 1 ~ 10%
Porous silica 60 ~ 98%
Described each constituent mass per-cent sum is 100%.
Wherein, the content of copper activity component can be 1%, 3%, 5%, 7%, 10%, 13%, 15%, 17%, 20%, 23%, 25%, 27% or 30% etc.
The content of zinc active ingredient can be 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10% etc.
The content of porous silica can be 60%, 62%, 64%, 66%, 68%, 70%, 73%, 74%, 76%, 78%, 80%, 82%, 84%, 86%, 88%, 90%, 92%, 94%, 96% or 98% etc.
The preparation method of the above catalyzer, said method comprising the steps of:
(A) solid residue waste catalyst is broken and sieve;
(B) the solid residue waste catalyst after fragmentation also screening is carried out roasting with organics removal, silica is turned to silicon oxide;
(C) the solid residue waste catalyst acid fluid dissolves after roasting;
(D) step (C) gained solution urea water thermoprecipitation, washing, drying reducing, obtained catalyzer.
In described step (A), solid residue waste catalyst is the solid residue that direct method fluidized-bed process prepares the generation of organosilane monomer methyl chlorosilane.
Solid residue waste catalyst is broken and particle diameter after screening is 0.5 ~ 100 μm in described step (A), such as 0.5 μm, 1 μm, 5 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm or 100 μm etc.
Maturing temperature is 450 ~ 900 DEG C in described step (B), 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 described step (B), roasting time is 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.
Acid solution is the combination of any one or at least two kinds in hydrochloric acid, nitric acid or sulfuric acid in described step (C), described combination typical case but limiting examples have: the combination of hydrochloric acid and nitric acid, the combination of nitric acid and sulfuric acid, the combination etc. of hydrochloric acid, nitric acid and sulfuric acid.
In described step (C), the concentration of acid solution is 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.
Acid fluid dissolves temperature is 40 ~ 80 DEG C in described step (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.
In described step (C), acid fluid dissolves is carried out under agitation.
In described step (C), the acid fluid dissolves time is 2 ~ 10h, such as 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h or 10h etc.
In described step (D), urea water thermoprecipitation step is: add precipitation agent urea again and regulator solution pH after adding zinc salt in step (C) gained solution, then add in water heating kettle and carry out hydro-thermal reaction at autogenous pressures.
In urea water thermoprecipitation process, zinc salt is the combination of any one or at least two kinds in zinc nitrate, zinc chloride or zinc sulfate in described step (D), described combination typical case but limiting examples have: the combination of zinc nitrate and zinc chloride, the combination of zinc chloride and zinc sulfate, the combination etc. of zinc nitrate, zinc chloride and zinc sulfate.
Add-on≤the 0.05g/mL of zinc salt in described urea water thermoprecipitation process, 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 etc.
In described urea water thermoprecipitation process, regulator solution pH is 9 ~ 14, such as 9,10,11,12,13 or 14 etc.
The temperature of reaction 120 ~ 180 DEG C of described urea water thermoprecipitation 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 times of described urea water thermoprecipitation process water thermal response is 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 the middle catalyzer of described step (D) adopts hydrogen reducing and using nitrogen as carrier gas, wherein the content of hydrogen is 5 ~ 10%, and such as 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5% or 10% etc.
The reduction temperature of catalyzer is 160 ~ 220 DEG C in described step (D), 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 described step (D), the recovery time of catalyzer is 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:
1, catalyzer provided by the invention is using porous silica as support of the catalyst, copper and zinc are active ingredient, there is octanol selectivity and the catalytic stability of higher hydrogenation activity and Geng Gao, for in octenal gas phase hydrogenation reaction, octenal transformation efficiency >=95.0%, octanol selectivity >=99.0%, and after catalyzer operation 250h, transformation efficiency still >=94.0%, selectivity >=98.8%.Meanwhile, the work-ing life of catalyzer is significantly extended, and reproducible.
2, the present invention adopts urea water thermal precipitator method Kaolinite Preparation of Catalyst, make catalyst particle size less, better dispersed, be that porous silica is as support of the catalyst using the silicon direct oxidation contained in abandoned catalyst in direct synthesis methylchlorosilane, and using copper and zinc as active ingredient, for octenal gas phase hydrogenation octanol technique, solve the high-valued problem of complex utilization of the solid residue waste catalyst of organosilicon compound probability, meet the requirement of recycling economy and Green Chemistry.
3, the catalyzer as octenal gas phase hydrogenation octanol provided by the invention, low raw-material cost, working method is simple, is easy to realize suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the XRD figure without the catalyzer of reduction in the embodiment of the present invention 1;
Fig. 2 is that the embodiment of the present invention 1 controlling catalyst is for the performance test results figure in octenal gas phase hydrogenation reaction.
Embodiment
Technical scheme of the present invention is further illustrated by embodiment below in conjunction with accompanying drawing.
The solid residue of the waste catalyst that following examples use for producing in silicone industry production methyl chlorosilane monomer process, namely elemental silicon and methyl chloride are under the effect of copper Primary Catalysts and zinc promotor, unreacted silicon and copper beaded catalyst powder completely in production chlorosilane monomer commercial run, and the porous complex body that in this process, carbonaceous organic material pyrolysis and the carbon distribution produced form.
Embodiment 1:
Get abandoned catalyst in direct synthesis methylchlorosilane 10g, the particle diameter after its fragmentation, screening is 0.5 ~ 100 μm; Put into retort furnace, in 450 DEG C of roasting 2h, be cooled to room temperature; Place it in 1000mL beaker, add the nitric acid 200mL of 0.5mol/L, the lower 80 DEG C of reaction 2h of whipped state; Add 4gZn (NO
3)
26H
2o, then add urea soln, adjust ph, to 9, loads water heating kettle, hydro-thermal reaction 8h under 180 DEG C of autogenous pressures, and washing is dry.With nitrogen as carrier gas, control H
2content is 5%, reduces 10h at 160 DEG C.
X ' Pert PRO MPD type the Multi-functional X ray diffractometer produced Dutch Panalytical company (PANalytical) by the catalyzer of above-mentioned preparation carries out XRD test; U.S. Pekin-Elmer inductively coupled plasma atomic emission spectrometer carries out ICP test (lower same).
Fig. 1 is the XRD figure without the catalyzer of reduction in embodiment 1.Wherein 2 θ=21.9 ° are SiO
2diffraction peak, due to for amorphous intensity more weak, the acromion of 2 θ=35.5 ° and 2 θ=38.7 ° composition is the characteristic peak of CuO, and 2 θ=36.3 ° are the characteristic peaks of ZnO.
ICP test result shows, and copper content is 29.3%, and zinc element content is 6.3%.Embodiment 2:
Get abandoned catalyst in direct synthesis methylchlorosilane 10g, the particle diameter after its fragmentation, screening is 0.5 ~ 100 μm; Put into retort furnace, in 600 DEG C of roasting 4h, be cooled to room temperature; Place it in 1000mL beaker, add the sulfuric acid 200mL of 0.5mol/L, the lower 60 DEG C of reaction 6h of whipped state; Add 2gZn (NO
3)
26H
2o, then add urea soln, regulate pH to 12, load water heating kettle, hydro-thermal reaction 12h under 140 DEG C of autogenous pressures, washing, dry.With nitrogen as carrier gas, control H
2content is 7%, reduces 10h at 160 DEG C.
ICP test result shows, and copper content is 8.3%, and zinc element content is 3.2%.
Embodiment 3:
Get abandoned catalyst in direct synthesis methylchlorosilane 10g, the particle diameter after its fragmentation, screening is 0.5 ~ 100 μm; Put into retort furnace, in 900 DEG C of roasting 8h, be cooled to room temperature; Place it in 1000mL beaker, add the nitric acid 200mL of 6mol/L, the lower 40 DEG C of reaction 10h of whipped state; Add 10gZnSO
47H
2o, then add urea soln, adjust ph, to 14, loads water heating kettle, hydro-thermal reaction 16h under 120 DEG C of autogenous pressures, and washing is dry.With nitrogen as carrier gas, control H
2content is 8%, reduces 4h at 200 DEG C.
ICP test result shows, and copper content is 23.8%, and zinc element content is 9.0%.
Embodiment 4:
Get abandoned catalyst in direct synthesis methylchlorosilane 10g, the particle diameter after its fragmentation, screening is 0.5 ~ 100 μm; Put into retort furnace, in 600 DEG C of roasting 2h, be cooled to room temperature; Above-mentioned materials is placed in 1000mL beaker, adds 6mol/L sulfuric acid 200mL, the lower 80 DEG C of reaction 2h of whipped state; Add 2gZnSO
47H
2o, then add urea soln, regulate pH to 10, load water heating kettle, hydro-thermal reaction 2h under 180 DEG C of autogenous pressures, washing, dry.With nitrogen as carrier gas, control H
2content is 10%, reductase 12 h at 220 DEG C.
ICP test result shows, and copper content is 1.3%, and zinc element content is 3.9%.
Embodiment 5:
Get abandoned catalyst in direct synthesis methylchlorosilane 10g, the particle diameter after its fragmentation, screening is 0.5 ~ 100 μm; Put into retort furnace, in 600 DEG C of roasting 4h, be cooled to room temperature; Above-mentioned materials is placed in 1000mL beaker, adds the hydrochloric acid 200mL of 0.5mol/L, the lower 40 DEG C of reaction 10h of whipped state; Add 2gZnCl
2, add urea soln, regulate pH to 14, load water heating kettle, hydro-thermal reaction 16h under 120 DEG C of autogenous pressures, washing, dry.With nitrogen as carrier gas, control H
2content is 8%, reduces 4h at 200 DEG C.
ICP test result shows, and copper content is 29.3%, and zinc element content is 3.5%.
Embodiment 6:
Get abandoned catalyst in direct synthesis methylchlorosilane 10g, the particle diameter after its fragmentation, screening is 0.5 ~ 100 μm; Put into retort furnace, in 600 DEG C of roasting 4h, be cooled to room temperature; Place it in 1000mL beaker, add the hydrochloric acid 200mL of 6mol/L, the lower 60 DEG C of reaction 6h of whipped state; Add urea soln, regulate pH to 11, load water heating kettle, hydro-thermal reaction 12h under 140 DEG C of autogenous pressures, washing, dry.With nitrogen as carrier gas, control H
2content is 7%, reduces 10h at 160 DEG C.
ICP test result shows, and copper content is 8.3%, and zinc element content is 1.2%.
Embodiment 7: the evaluation of catalyzer
This example illustrates to generate in octanol reaction at octenal hydrogenation, the active testing result of catalyzer provided by the invention.
Reaction unit is continuous flow stainless steel fixed bed, and reactor inside diameter is 20mm, and the loadings of catalyzer is 1g.
Octenal liquid hourly space velocity is 0.3h
-1, hydrogen aldehyde mol ratio is 28:1, and temperature of reaction is 180 DEG C, and reaction pressure is 0.4, and the reaction times is 1h.
First make reactant octenal gasify, then enter beds continuously after mixing with hydrogen, reaction product is separated after cooling with excessive hydrogen, at set intervals, takes out condensed liquid product and carries out quantitative analysis by capillary gas chromatography.Chromatogram model is SHIMADZU GC-14B, and chromatographic column is HP-5 (30m × 0.25mm), fid detector, and external standard method calculates octenal transformation efficiency and octanol selectivity, and detected result is as shown in table 1.
Table 1: catalyst activity table with test results
| Catalyzer | Octenal transformation efficiency (%) | 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 |
Be used in octenal gas phase hydrogenation reaction by catalyzer obtained in embodiment 1, its reaction conditions is: catalyzer is 1g, and octenal liquid hourly space velocity is 0.3h
-1, hydrogen aldehyde mol ratio is 28:1, and temperature of reaction is 180 DEG C, and reaction pressure is 0.6MPa, and the reaction times is 250h, and its active testing result as shown in Figure 2.Can find out that the work-ing life of catalyzer is significantly extended, and reproducible.
From ICP result, take waste catalyst as catalyst metal content copper prepared by raw material be 1% ~ 30wt%, zinc is that these metal component grain diameters of 1 ~ 10wt%, XRD data presentation are less, good dispersion degree.
Experimental result shows, although be that catalyst activity component concentration prepared by raw material is different with waste catalyst, but catalytic activity and selectivity are all higher, octenal transformation efficiency >=95.0%, octanol selectivity >=99.0%, and catalyzer runs after 250h, transformation efficiency still >=94.0%, selectivity >=98.8%.Therefore take waste catalyst as raw material, after physical chemistry process, the octenal that can obtain better performances prepares the catalyzer of octanol.
Applicant states, the present invention illustrates method detailed of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned method detailed, does not namely mean that the present invention must rely on above-mentioned method detailed and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (10)
1. a catalyzer for octenal gas phase hydrogenation octanol, is characterized in that, described catalyzer comprises copper activity component, zinc active ingredient and porous oxidation silicon carrier.
2. catalyzer according to claim 1, is characterized in that, the composition of described catalyzer comprises following component by mass percentage:
3. a preparation method for octenal gas phase hydrogenation octanol catalyzer as claimed in claim 1 or 2, is characterized in that, said method comprising the steps of:
(A) solid residue waste catalyst is broken and sieve;
(B) the solid residue waste catalyst after fragmentation also screening is carried out roasting;
(C) the solid residue waste catalyst acid fluid dissolves after roasting;
(D) step (C) gained solution urea water thermoprecipitation, washing, drying reducing, obtained octenal gas phase hydrogenation octanol catalyzer.
4. preparation method according to claim 3, is characterized in that, in described step (A), solid residue waste catalyst is the solid residue that direct method fluidized-bed process prepares the generation of organosilane monomer methyl chlorosilane;
Preferably, the particle diameter in described step (A) after the broken also screening of solid residue waste catalyst is 0.5 ~ 100 μm.
5. the preparation method according to claim 3 or 4, is characterized in that, in described step (B), maturing temperature is 450 ~ 900 DEG C;
Preferably, in described step (B), roasting time is 2 ~ 8h.
6. the preparation method according to any one of claim 3-5, is characterized in that, acid solution is the combination of any one or at least two kinds in hydrochloric acid, nitric acid or sulfuric acid in described step (C);
Preferably, in described step (C), the concentration of acid solution is 0.5 ~ 6mol/L.
7. the preparation method according to any one of claim 3-6, is characterized in that, in described step (C), acid fluid dissolves temperature is 40 ~ 80 DEG C;
Preferably, in described step (C), acid fluid dissolves is carried out under agitation;
Preferably, in described step (C), the acid fluid dissolves time is 2 ~ 10h.
8. the preparation method according to any one of claim 3-7, it is characterized in that, in described step (D), urea water thermoprecipitation step is: add precipitation agent urea again and regulator solution pH after adding zinc salt in step (C) gained solution, then add in water heating kettle and carry out hydro-thermal reaction.
9. the preparation method according to any one of claim 3-8, is characterized in that, in urea water thermoprecipitation process, zinc salt is the combination of any one or at least two kinds in zinc nitrate, zinc chloride or zinc sulfate in described step (D);
Preferably, the add-on≤0.05g/mL of zinc salt in described urea water thermoprecipitation process;
Preferably, in described urea water thermoprecipitation process, regulator solution pH is 9 ~ 14;
Preferably, described urea water thermoprecipitation process is carried out at autogenous pressures;
Preferably, the temperature of reaction 120 ~ 180 DEG C of described urea water thermoprecipitation process water thermal response;
Preferably, the reaction times of described urea water thermoprecipitation process water thermal response is 8 ~ 16h.
10. the preparation method according to any one of claim 3-9, is characterized in that, the reduction of the middle catalyzer of described step (D) adopts hydrogen reducing and using nitrogen as carrier gas, wherein the content of hydrogen is 5 ~ 10%;
Preferably, in described step (D), the reduction temperature of catalyzer is 160 ~ 220 DEG C;
Preferably, in described step (D), the recovery time of catalyzer is 2 ~ 10h.
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| CN112246247A (en) * | 2020-10-15 | 2021-01-22 | 中国科学院过程工程研究所 | Organic silicon monomer synthesis reaction catalyst and preparation method and application thereof |
| CN114618491A (en) * | 2022-04-06 | 2022-06-14 | 北京石油化工学院 | Preparation method of copper-based catalyst and method for preparing alkanol by catalytic hydrogenation of copper-based catalyst |
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| CN112246247A (en) * | 2020-10-15 | 2021-01-22 | 中国科学院过程工程研究所 | Organic silicon monomer synthesis reaction catalyst and preparation method and application thereof |
| CN114618491A (en) * | 2022-04-06 | 2022-06-14 | 北京石油化工学院 | Preparation method of copper-based catalyst and method for preparing alkanol by catalytic hydrogenation of copper-based catalyst |
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