CN101912781B - Method for preparing dehydrogenizing nickel-base/kieselguhr catalyst - Google Patents
Method for preparing dehydrogenizing nickel-base/kieselguhr catalyst Download PDFInfo
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- CN101912781B CN101912781B CN2010102211545A CN201010221154A CN101912781B CN 101912781 B CN101912781 B CN 101912781B CN 2010102211545 A CN2010102211545 A CN 2010102211545A CN 201010221154 A CN201010221154 A CN 201010221154A CN 101912781 B CN101912781 B CN 101912781B
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Abstract
The invention relates to a method for preparing a dehydrogenizing nickel-base/kieselguhr catalyst, which comprises the following processes of: performing reaction of suspension obtained by mixing a soluble salt of nickel and kieselguhr and solution of precipitator to generate coprecipitate, and washing, drying, calcining, forming and modifying to prepare a catalyst used for the dehydrogenation of 1,2-cyclohexanediol for preparing pyrocatechol. 10 to 30 weight percent of solution of 1,2-cyclohexanediol is used as a raw material, the conversion rate of the 1,2-cyclohexanediol is over 98 percent, and the selectivity of the pyrocatechol serving as a target product is between 90 and 95 percent at the reaction temperature of between 280 and 350 DEG C.
Description
Technical field
The present invention relates to a kind of dehydrogenation Ni-based/diatomite Preparation of catalysts method, relate in particular to by 1, the dehydrogenation of 2-cyclohexanediol prepares the Catalysts and its preparation method of catechol.
Background technology
Catechol is an important chemical material, all has a wide range of applications at aspects such as medicine, agricultural chemicals, spices, chemical assistants.The main production method of catechol is a phenol hydrogen peroxide solution hydroxylating method at present, and phenol is at H
3PO
4/ HClO
4Or H
2SO
4Under the catalyst action, the hydrogen peroxide solution hydroxylating generates catechol and hydroquinones simultaneously, and this production method produces two kinds of diphenol simultaneously, and the product separating difficulty is bigger, and the purity of catechol is not high; Above-mentioned in addition these two kinds of catalyst are strong corrosive material, not only endanger environment, and serious to equipment corrosion, and operating condition is harsh.
1,2-cyclohexanediol catalytic dehydrogenation legal system be equipped with catechol by the initiation material cyclohexene through H
2O
2Hydroxylating obtains 1, and the 2-cyclohexanediol makes catechol through catalytic dehydrogenation again.This method has the feed stock conversion height, and the three wastes are few, and product is single, and advantages such as no catechol isomers generation are green synthetic routes with essential industry using value.
About by 1, the 2-cyclohexanediol is the research of feedstock production catechol catalyst, and scholar both domestic and external has carried out many useful explorations to this.Adopt Al among the JP 48-57934
2O
3At 1000 ℃ of N
2Roasting 10h in the atmosphere floods H again
2PtCl
6Aqueous acetone solution, and after washing, dry, H
2Reduction (350 ℃, 5h), under catalyst loading 2.0g cyclohexanediol/(g catalyst hour), normal pressure, 350 ℃ of conditions, react 2h, the cyclohexanediol conversion ratio is 99%, the catechol selectivity is 74.5%.JP 58-67636 discloses a kind of Pd-Te/C dehydrogenation preparation method, with palladium nitrate with telluric acid and ethanolamine treatment after, be carried on the absorbent charcoal carrier, using K
2SO
4Handle the final drying moulding.With 1 of 10wt%, 2-cyclohexanediol solution carries out catalytic dehydrogenation at 300 ℃, and the catechol selectivity is 95.9%, but 1,2-cyclohexanediol conversion ratio is merely 63.9%.It is active component with Pd and Fe, Ni, Co, Cr or Mn that JP56-169636 has adopted common immersion process for preparing, and by the catalyst of active carbon as carrier, the catechol selectivity is 68%.It is the Ni/ diatomite catalyst of 45～55wt% that CN 1160703A adopts common infusion process, the precipitation method to prepare Ni content, and the preceding interpolation auxiliary agent of moulding (column) improves.When cylindrical catalyst contains 2wt%Sn, 50wt%Ni, 1,2-cyclohexanediol conversion ratio 98.1%, catechol yield are 86.5%, but the active component nickel too high levels, the Catalyst Production cost increases, and has caused the production cost of whole process of production to rise.
Summary of the invention
The purpose of this invention is to provide a kind of dehydrogenation Ni-based/diatomite Preparation of catalysts method.
Technical scheme of the present invention is: a kind of dehydrogenation is Ni-based/and diatomite Preparation of catalysts method, its concrete steps are following:
(1) takes by weighing the soluble-salt of diatomite, nickel, add entry and mix, this suspension and the precipitating reagent aqueous solution are carried out the coprecipitate that co-precipitation obtains nickel under ultrasonication, wherein supersonic frequency 20～60kHz, the ultrasonic sound intensity 100～3000W/m
2, ultrasonic time is 120～240min; Through washing, dry, roasting, obtain catalyst powder again;
(2) take by weighing the catalyst powder after (1) roasting, add entry and binding agent, mix moulding, drying;
The preformed catalyst that (3) will be made by (2) is in addition modification of dipping adjuvant water solution under the ultrasonication of 30～90min at supersonic frequency 10～50kHz, the ultrasonic sound intensity 100～2000W/m2, ultrasonic time, is drying to obtain final catalyst.
Wherein the soluble-salt of preferred described nickel be nickel nitrate, sulfate, acetate or halid any.
Described precipitating reagent is at least sodium acid carbonate, saleratus, carbonic hydroammonium, a kind of in sodium carbonate, potash, ammonium carbonate, oxalic acid or the ammonium oxalate; The soluble-salt of diatomite, nickel in the step (1); Add the addition that entry mixes water in the process and generally be controlled at the soluble-salt that can dissolve nickel, the overall control of the water in the suspension and the precipitating reagent aqueous solution is 1: 1～2.0: 145～152 at the soluble-salt of precipitating reagent, nickel and the mol ratio of water.The soluble-salt weight of nickel accounts for 10～40% of diatomite weight in the step (1).
The mass ratio of catalyst powder, water, binding agent is 1: 0.2～1.0: 0.01～0.3 in the preferred steps (2).
Described binding agent is at least a kind of in CMC, methylcellulose, citric acid, Ludox, aluminium colloidal sol or the soluble starch; Described auxiliary agent is at least a kind of in stannous chloride, sodium sulphate, copper sulphate, chromic nitrate or the cobalt nitrate; The mass ratio of preformed catalyst, auxiliary agent and water is 1: 0.02～0.1: 1.4～2.6 in the step (3).
Baking temperature in the preferred steps (2) is 80～150 ℃, and be 6～9h drying time.Catalyst described in the step (3) after the modification is at 60～100 ℃ of drying 3～5h.Conventional method is adopted in dry in the step (1), roasting, and generally controlling baking temperature is 100～180 ℃, drying time 4～10h, sintering temperature is 300～600 ℃, roasting time is 2～6h.The general employing fully of forming method extrudes or compression moulding after the kneading in the step (2).
Beneficial effect:
The present invention utilize ultrasonic technique prepare dehydrogenation Ni-based/the diatomite catalyst, changed the microscopic characteristics of catalyst, improved activity of such catalysts and selectivity; 1; 2-cyclohexanediol conversion ratio reaches more than 98%, and the catechol selectivity is more than 90%, and the catalyst activity amounts of components is few; Reduce the production cost of whole process, be applicable to suitability for industrialized production.Co-precipitation, the impregnation stage of the present invention in Preparation of Catalyst adds sonicated, and prepared catalyst reaction activity is good, and selectivity is high, simultaneously production equipment is not had corrosion, environment is had no adverse effects, and be a kind of environmentally friendly catalyst.
The specific embodiment
Further describe technical characterictic of the present invention through embodiment and comparative example below, but be not limited to embodiment.
Embodiment 1
Take by weighing diatomite 30g, Ni (CH
3COO)
24H
2O 14.1g adds deionized water 500ml stirring and dissolving; Take by weighing NaHCO
35.7g, be dissolved in the 150ml deionized water.At supersonic frequency 20kHz, ultrasonic sound intensity 100W/m
2, the ultrasonication time is under the ultrasound condition of 125min, adopts the ultrasound precipitation method to obtain the sediment of nickel, precipitation reaction finishes the back material through suction filtration, washing, 100 ℃ of dry 4h in baking oven, then 300 ℃ of roasting 3h get the catalyst powder siccative in Muffle furnace.Get the above-mentioned catalyst siccative of 10g, add the 5g deionized water, the 2g CMC mixes and fully mediate after extrude or compression moulding, then, obtain preformed catalyst A at 90 ℃ of dry 6h.
Take by weighing Na2SO4 0.31g and be dissolved in the 8ml deionized water, add above-mentioned preformed catalyst A 5g, in supersonic frequency 10kHz, ultrasonic sound intensity 100W/m
2, the ultrasonication time is under the ultrasound condition of 30min, adopts the ultrasonic immersing method to catalyst modification.Remove clear liquid with siphonage, behind 60 ℃ of dry 3h, obtain sample UPI1, its catalyst consists of 10wt%Ni, 2wt%Na (is benchmark with diatomite).
Embodiment 2
Get preformed catalyst A among the embodiment 1, according to the following steps operation:
Take by weighing SnCl
22H
2O 0.51g is dissolved in the 9ml deionized water, adds catalyst A 5g, in supersonic frequency 20kHz, ultrasonic sound intensity 200W/m
2, the ultrasonication time is under the ultrasound condition of 50min, adopts the ultrasonic immersing method to catalyst modification.Remove clear liquid with siphonage, behind 70 ℃ of dry 4h, obtain sample UPI 2, its catalyst consists of 10wt%Ni, 6wt%Sn (is benchmark with diatomite).
Embodiment 3
Take by weighing diatomite 30g, Ni (NO
3)
26H
2O 37.2g adds deionized water 600ml stirring and dissolving; Take by weighing (NH
4)
2CO
314.7g, be dissolved in the 345ml deionized water, at supersonic frequency 30kHz, ultrasonic sound intensity 600W/m
2, the ultrasonication time is under the ultrasound condition of 140min, adopts the ultrasound precipitation method to obtain the sediment of nickel, precipitation reaction finishes the back material through suction filtration, washing, 120 ℃ of dry 6h in baking oven, then 330 ℃ of roasting 4h get the catalyst powder siccative in Muffle furnace.Get the above-mentioned catalyst siccative of 10g, add the 8g deionized water, the 3g methylcellulose extrudes or compression moulding after mixing and fully mediating, and then at 100 ℃ of dry 7h, obtains preformed catalyst.
Take by weighing Cr (NO
3)
39H
2O 3.3g is dissolved in the 10ml deionized water, adds above-mentioned preformed catalyst 5g, in supersonic frequency 30kHz, ultrasonic sound intensity 500W/m
2, the ultrasonication time is under the ultrasound condition of 70min, adopts the ultrasonic immersing method to catalyst modification.Remove clear liquid with siphonage, behind 90 ℃ of dry 3h, obtain sample UPI 3, its catalyst consists of 20wt%Ni, 8wt%Cr (is benchmark with diatomite).
Embodiment 4
Take by weighing diatomite 30g, NiCl
26H
2O 52.1g adds deionized water 700ml stirring and dissolving; Take by weighing (NH
4)
2C
2O
4H
2O 37.4g is dissolved in the 590ml deionized water, at supersonic frequency 40kHz, ultrasonic sound intensity 1000W/m
2, the ultrasonication time is under the ultrasound condition of 160min, adopts the ultrasound precipitation method to obtain the sediment of nickel, precipitation reaction finishes the back material through suction filtration, washing, 150 ℃ of dried 8h in baking oven, then 400 ℃ of roasting 5h get the catalyst powder siccative in Muffle furnace.Get 10g catalyst siccative, add the 7g deionized water, the 0.5g citric acid extrudes or compression moulding after mixing and fully mediating, and then at 120 ℃ of dry 8h, obtains preformed catalyst.
Take by weighing Co (NO
3)
36H
2O 2.79g is dissolved in the 11ml deionized water, adds above-mentioned preformed catalyst 5g, in supersonic frequency 40kHz, ultrasonic sound intensity 1000W/m
2, the ultrasonication time is under the ultrasound condition of 70min, adopts the ultrasonic immersing method to catalyst modification.Remove clear liquid with siphonage, behind 90 ℃ of dry 4h, obtain sample UPI 4, its catalyst consists of 30wt%Ni, 10wt%Co (is benchmark with diatomite).
Embodiment 5
Take by weighing diatomite 30g, NiSO
46H
2O 44.8g adds deionized water 800ml stirring and dissolving; Take by weighing H
2C
2O
46.0g, be dissolved in the 150ml deionized water, at supersonic frequency 50kHz, ultrasonic sound intensity 1500W/m
2, the ultrasonication time is under the ultrasound condition of 180min, adopts the ultrasound precipitation method to obtain the sediment of nickel, precipitation reaction finishes the back material through suction filtration, washing, 160 ℃ of dry 9h in baking oven, then 500 ℃ of roasting 3h get the catalyst powder siccative in Muffle furnace.Get 10g catalyst siccative, add the 3g deionized water, the 2.5g soluble starch extrudes or compression moulding after mixing and fully mediating, and then at 130 ℃ of dry 8h, obtains preformed catalyst.
Take by weighing Na
2SO
40.32g, Co (NO
3)
36H
2O 0.51g is dissolved in the 12ml deionized water, adds above-mentioned preformed catalyst 5g, in supersonic frequency 40kHz, ultrasonic sound intensity 1200W/m
2, the ultrasonication time is under the ultrasound condition of 80min, adopts the ultrasonic immersing method to catalyst modification.Remove clear liquid with siphonage, behind 90 ℃ of dry 5h, obtain sample UPI 5, its catalyst consists of 10wt%Ni, 2wt%Na, 2wt%Co (is benchmark with diatomite).
Comparative example 1
Take by weighing diatomite 30g, Ni (NO
3)
26H
2O 16.5g adds deionized water 500ml stirring and dissolving; Take by weighing (NH
4)
2C
2O
4H
2O 9.7g is dissolved in the 154ml deionized water, adopts the common precipitation method to obtain the sediment of nickel, and precipitation reaction finishes the back material through suction filtration, washing, and 140 ℃ of dry 5h in baking oven then get the catalyst powder siccative behind 450 ℃ of roasting 4h in Muffle furnace.Get 10g catalyst siccative, add the 8g deionized water, the 3g methylcellulose extrudes or compression moulding after mixing and fully mediating, and then at 90 ℃ of dry 8h, obtains preformed catalyst.
Take by weighing Na
2SO
40.31g be dissolved in the 8ml deionized water, add above-mentioned preformed catalyst 5g, adopt common infusion process to catalyst modification.Remove clear liquid with siphonage, behind 90 ℃ of dry 4h, obtain sample P I, its catalyst consists of 10wt%Ni, 6wt%Na (is benchmark with diatomite).
Comparative example 2
Take by weighing diatomite 30g, Ni (NO
3)
26H
2O 16.5g adds deionized water 500ml stirring and dissolving; Take by weighing (NH
4)
2C
2O
4H
2O 9.7g is dissolved in the 154ml deionized water, adopts the common precipitation method to obtain the sediment of nickel, and precipitation reaction finishes the back material through suction filtration, washing, and 140 ℃ of dry 5h in baking oven then get the catalyst powder siccative behind 450 ℃ of roasting 4h in Muffle furnace.Get 10g catalyst siccative, add the 8g deionized water, the 3g methylcellulose extrudes or compression moulding after mixing and fully mediating, and then at 90 ℃ of dry 8h, obtains preformed catalyst.
Take by weighing Na
2SO
40.31g be dissolved in the 8ml deionized water, add above-mentioned preformed catalyst 5g, in supersonic frequency 20kHz, ultrasonic sound intensity 500W/m
2, the ultrasonication time is under the ultrasound condition of 50min, adopts the ultrasonic immersing method to catalyst modification.Remove clear liquid with siphonage, behind 90 ℃ of dry 5h, obtain sample P-UI, its catalyst consists of 10wt%Ni, 6wt%Na (is benchmark with diatomite).
Comparative example 3
Take by weighing diatomite 30g, Ni (NO
3)
26H
2O 16.5g adds deionized water 500ml stirring and dissolving; Take by weighing (NH
4)
2C
2O
4H
2O 9.7g is dissolved in the 154ml deionized water, at supersonic frequency 40kHz, ultrasonic sound intensity 1000W/m
2, the ultrasonication time is under the ultrasound condition of 150min, adopts the ultrasound precipitation method to obtain the sediment of nickel, precipitation reaction finishes the back material through suction filtration, washing, 140 ℃ of dry 5h in baking oven, then in Muffle furnace behind 450 ℃ of roasting 4b the catalyst powder siccative.Get 10g catalyst siccative, add the 8g deionized water, the 3g methylcellulose extrudes or compression moulding after mixing and fully mediating, and then at 90 ℃ of dry 8h, obtains preformed catalyst.
Take by weighing Na
2SO
40.31g be dissolved in the 8ml deionized water, add above-mentioned preformed catalyst 5g, adopt common infusion process to catalyst modification.Remove clear liquid with siphonage, behind 90 ℃ of dry 5h, obtain sample UP-I, its catalyst consists of 10wt%Ni, 6wt%Na (is benchmark with diatomite).
In fixed bed reactors, estimate the above-mentioned reactivity worth that makes catalyst:
Catalyst is packed in the atmospheric fixed bed reactor, under 420 ± 10 ℃, use H
2Reduction 3～4h, with raw material 1, the 2-cyclohexanediol is mixed with 10～30% the aqueous solution, in N
2Carry out 1,2-cyclohexanediol dehydrogenation reaction under the atmosphere, 300 ± 10 ℃.
The catalyst activity evaluation result is as shown in table 1
| The catalyst sample numbering | 1,2-cyclohexanediol conversion ratio/% | Catechol selectivity/% |
| UPI?1 | 98.8 | 95.3 |
| UPI?2 | 98.2 | 93.1 |
| UPI?3 | 98.7 | 92.2 |
| UPI?4 | 97.5 | 89.9 |
| UPI?5 | 97.8 | 90.6 |
| PI | 95.5 | 83.3 |
| P-UI | 96.2 | 89.6 |
| UP-I | 97.1 | 88.7 |
Claims (7)
- A dehydrogenation Ni-based/diatomite Preparation of catalysts method, its concrete steps are following:(1) take by weighing the soluble-salt of diatomite, nickel, add entry and mix, with the aqueous solution of this suspension and precipitating reagent at supersonic frequency 20～60kHz, the ultrasonic sound intensity 100～3000W/m 2, the ultrasonication time is under the ultrasonication of 120～240min, carries out the coprecipitate that co-precipitation obtains nickel, through washing, dry, roasting, obtains catalyst powder again; Wherein said precipitating reagent is at least a kind of in sodium acid carbonate, saleratus, carbonic hydroammonium, sodium carbonate, potash, ammonium carbonate, oxalic acid or the ammonium oxalate;(2) take by weighing catalyst powder after step (1) roasting, add entry and binding agent, mix moulding, drying; The mass ratio of wherein said catalyst powder, water, binding agent is 1: 0.2～1.0: 0.01～0.3;(3) preformed catalyst that step (2) is made is at supersonic frequency 10～50kHz, the ultrasonic sound intensity 100～2000W/m 2, ultrasonic time is under the ultrasonication of 30～90min, the in addition modification of dipping adjuvant water solution, be drying to obtain dehydrogenation Ni-based/the diatomite catalyst.
- 2. preparation method according to claim 1, the soluble-salt that it is characterized in that described nickel be nickel nitrate, sulfate, acetate or halid any.
- 3. preparation method according to claim 1 is characterized in that described binding agent is at least a kind of in CMC, methylcellulose, citric acid, Ludox, aluminium colloidal sol or the soluble starch.
- 4. preparation method according to claim 1 is characterized in that precipitating reagent, the soluble-salt of nickel and the mol ratio of water are 1: 1～2.0: 145～152 in the step (1); The soluble-salt weight of nickel accounts for 10～40% of diatomite weight in the step (1).
- 5. preparation method according to claim 1 is characterized in that described auxiliary agent is at least a kind of in stannous chloride, sodium sulphate, copper sulphate, chromic nitrate or the cobalt nitrate; The mass ratio of preformed catalyst, auxiliary agent and water is 1: 0.02～0.1: 1.4～2.6 in the step (3).
- 6. preparation method according to claim 1 is characterized in that the baking temperature in the step (2) is 80～150 ℃, and be 6～9h drying time.
- 7. preparation method according to claim 1 is characterized in that the baking temperature in the step (3) is 60～100 ℃, and be 3～5h drying time.
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|---|---|---|---|
| CN2010102211545A CN101912781B (en) | 2010-07-08 | 2010-07-08 | Method for preparing dehydrogenizing nickel-base/kieselguhr catalyst |
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|---|---|---|---|
| CN2010102211545A CN101912781B (en) | 2010-07-08 | 2010-07-08 | Method for preparing dehydrogenizing nickel-base/kieselguhr catalyst |
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| CN101912781B true CN101912781B (en) | 2012-07-25 |
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| CN104069875B (en) * | 2013-03-28 | 2016-08-03 | 岳阳昌德化工实业有限公司 | A kind of dehydrogenation and preparation method thereof and a kind of method of dehydrogenating |
| CN105879874A (en) * | 2016-05-16 | 2016-08-24 | 连中博 | High-dispersion loaded nickel catalyst and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1160703A (en) * | 1996-03-27 | 1997-10-01 | 化学工业部大连化工研究设计院 | Production of catechol |
-
2010
- 2010-07-08 CN CN2010102211545A patent/CN101912781B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1160703A (en) * | 1996-03-27 | 1997-10-01 | 化学工业部大连化工研究设计院 | Production of catechol |
Non-Patent Citations (3)
| Title |
|---|
| 刘自力等.超声波对制备Co-Fe/硅藻土选择加氢催化剂的影响.《分子催化》.2009,第23卷(第3期),第203页右栏第2段以及第204页左栏第6段. * |
| 李林鹏等.制备邻苯二酚的镍-钠/硅藻土催化剂研究.《精细石油化工》.2009,第26卷(第6期),第52页最后1段以及第53页左栏第1-3段. * |
| 裴松鹏等.1，2－环己二醇脱氢制邻苯二酚镍基催化剂的研究.《石油化工》.2010,第39卷(第2期),第147页左栏第5，7段. * |
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