CN102941093A - Catalyst for decahydronaphthalene preparation by naphthalene hydrogenation - Google Patents
Catalyst for decahydronaphthalene preparation by naphthalene hydrogenation Download PDFInfo
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Abstract
A catalyst for decahydronaphthalene preparation by naphthalene hydrogenation is characterized by comprising 10wt%-50wt% of an active component, 0.1wt%-25wt% of an assistant and the balance of a carrier, calculated by metal. The catalyst has specific surface area of 80-400m<2> / g, and pore volume of 0.2-1.2 cm<3> / g; and apertures with diameter within 50-100nm account for 50-80% of the total aperture channel of the catalyst. The catalyst provided by the invention has advantages of good performance, high selectivity, long life and low price.
Description
Technical field
The invention belongs to a kind of hydrogenation catalyst and preparation method and application, be specifically related to catalyst and the preparation method and application of the standby decahydronaphthalene of a kind of naphthalene Hydrogenation.
Background technology
Decahydronaphthalene is a kind of good high boiling organic solvent, can dissolve some macromolecular compound, be the suitable solvent of ultra-high molecular weight polyethylene " dry-spinning process ", also can be used as the solvent of coating, be used for purification fat and wax, replace turpentine oil to be used for the manufacturing of shoe polish, floor wax.Because naphthalene can synthesize decahydronaphthalene by catalytic hydrogenation, the decahydronaphthalene that generates again can catalytic dehydrogenation under suitable condition, emit pure hydrogen, therefore, except doing the solvent, also can be used as the dehydrogenation, cracking " endothermic fuel " of hypersonic vehicle the best and as the good storage hydrogen media of automobile fuel battery, external more existing companies produce the decahydronaphthalene product, such as European Chemos GmbH, German Afflliated Company(Degussa AG), du pont company, Dow Chemical Ltd, Sigma-AldriCh etc., prices are rather stiff for it.
The method of the standby decahydronaphthalene of naphthalene Hydrogenation, the research report was just arranged before seven, 80 years, for example: J.Soc.Chem.Ind., 1927,46.454 and Rec.trav.chim., the effect of 1934,53.821 reaction mechanisms of having reported the standby decahydronaphthalene of naphthalene Hydrogenation, technological parameter, various catalyst etc., through the development of decades, there are a lot of new progresses in this field on the preparation of catalyst and process conditions.
The patent CN102320913A of Nanjing University of Technology has adopted Pd/ γ-Al
2O
3Be catalyst, normal heptane or cyclohexane are solvent, and its reaction condition is: temperature 100-280
oC, pressure 1.5-4.0MPa, liquid hourly space velocity (LHSV) 0.5-2.0h
-1, hydrogen-oil ratio is 80-100, and the conversion ratio of naphthalene is 99.92%, and the yield of decahydronaphthalene is 99.36%.
The patent CN 101602644A of Xiamen University adopts batch process, in autoclave naphthalene is hydrogenated to decahydronaphthalene, and its catalyst system therefor is Ni/ γ-Al
2O
3, solvent is cyclohexane, reaction condition is: temperature 80-200
oC, pressure 2-5MPa, liquid hourly space velocity (LHSV) 9-13h
-1, the conversion ratio of naphthalene is 100%, the yield of decahydronaphthalene is 99%.
The patent CN1733663A of China PetroChemical Corporation's Research Institute of Nanjing Chemical Industry Group has described the method for the synthetic decahydronaphthalene of a kind of continuous hydrogenation, and reactor used is stable state trickle bed reactor, and catalyst system therefor is Ni/ Al
2O
3Or Pt/ Al
2O
3, solvent is naphthane or decahydronaphthalene, reaction condition is: temperature 120-280
oC, pressure 2-15MPa, liquid hourly space velocity (LHSV) 0.1-5h
-1, hydrogen-oil ratio is 1-3000NL/L, and the conversion ratio of naphthalene is 70-99%, and the yield of decahydronaphthalene is 90%, accessory substance＜1%.
The graduate patent CN 1546442A of southization adopts batch process, in autoclave naphthalene is hydrogenated to decahydronaphthalene, and its catalyst system therefor is the Ni series catalysts, and solvent is naphthane, and reaction condition is: temperature 180-220
oC, pressure 6-12MPa, liquid hourly space velocity (LHSV) 0.5-1h
-1, the conversion ratio of naphthalene is greater than 98%, and the yield of decahydronaphthalene is greater than 98%.
Barbul, the people such as Marius Aurel have described a kind of tarry distillate generation naphthane of hydrogenated naphthalene content 90%, the method for decahydronaphthalene in patent " method and apparatus for purification of naphthalence from coking ", reaction condition is: temperature 350-510
oC, pressure 3-6MPa, hydrogen/ratio of solvent is 300-2500Nm
3/ m
3, solution feed rate is 1-10m
3/ h, catalyst for contain 12-16% molybdenum oxide and 3-5.5% cobalt oxide and (or) nickel oxide, carrier is Woelm Alumina.
In sum, all there is at present the problem of some in these synthetic methods, such as: adopt the noble metal catalysts such as palladium, platinum, although the noble metal catalyst hydrogenation activity is very high, usually can degree of depth hydrogenated naphthalene, expensive; Adopt the non-precious metal catalysts such as nickel, molybdenum, cobalt, although it is naphthane that these non-precious metal catalysts make naphthalene hydrogenation easily, it is but relatively more difficult that but naphthane continues to be hydrogenated into decahydronaphthalene, therefore, temperature, the pressure of reaction are relatively high, cause equipment investment and operating cost higher, accessory substance is also more.The mode of production that adopts mostly is batch (-type), and complex operation needs catalyst and separation of products after the reaction, and inefficiency is not suitable for producing in enormous quantities.
China every year is from a large amount of decahydronaphthalene of external import, and how especially highly purified decahydronaphthalene takes full advantage of the naphthalene resource of China's abundant, and the decahydronaphthalene of high-quality, the high added value of large-scale continuous production has great significance take naphthalene as raw material.
Summary of the invention
The object of the invention is to overcome problems of the prior art, good, the selective height of a kind of activity, long, cheap catalyst and preparation method and application of life-span are provided.
Catalyst of the present invention is comprised of active component, auxiliary agent, carrier three parts, and in metal, the quality percentage composition of activity component metal is 10wt%-50wt%, and the quality percentage composition of promoter metal is 0.1 wt%-25wt%, and all the other are carrier; The specific area of catalyst is 80-400m
2/ g; Pore volume is 0.2-1.2cm
3/ g, its mesoporous account for the 50-80% in the total duct of catalyst in the hole of 50-100nm.
Described active component is the oxide of Ni, and auxiliary agent is at least a in the oxide of Mg, Ca, Sr, Ba, Co, Fe, La, Mo, Zr, Ti, Mn, Cu, and carrier is Al
2O
3Or
The sial composite oxides
Aforesaid sial composite oxide carrier, aluminium oxide is 0.01～99:1 with the siliconoxide mass ratio.
Catalyst of the present invention adopts infusion process or precipitation method preparation, and wherein, the concrete steps of infusion process are:
(1) soluble-salt of active component, the soluble-salt of auxiliary agent are made into mixed solution, and add surfactant in the mixed solution and stir, total salt concentration is 0.3-2.0g/ml, and the concentration of surfactant is 0.01-0.5g/ml.
(2) solution (1) for preparing is poured into supersaturation dipping in the container that carrier is housed, constantly stirred in the process of dipping, solution is kept evenly, dip time is 2-10h.
(3) catalyst that (2) dipping is good leaches, and then natural drying 3-24h under room temperature places catalyst the drier inner drying with air blast, and drier slowly is elevated to 110 from room temperature
oC-130
oC, heating rate are 20-60
oC/h is 110
oC-130
oFreeze-day with constant temperature 6-24h under the C.
(4) with (3) dry good catalyst roasting, roasting condition is: 150-180
oRoasting 3-10h under the C, 200-250
oRoasting 3-6h under the C, 300-350
oRoasting 3-5h under the C, 400-450
oRoasting 3-8h namely gets required catalyst under the C.
The soluble-salt of the described active component of step (1) is nickel nitrate, nickel chloride, nickel acetate, nickel formate, and the soluble-salt of auxiliary agent is nitrate or chlorate, and surfactant is tartaric acid, AE03, AE09 or EDTA.
Adopt the concrete steps of precipitation method preparation as follows:
A. the soluble-salt of active component, the soluble-salt of auxiliary agent, the solubility predecessor of carrier are made into mixed solution with deionized water, and add surfactant in the mixed solution and stir, the concentration of surfactant is 0.01-0.5g/ml, and the solution total concentration is 0.5-2g/ml.
B. with the precipitating reagent wiring solution-forming.
C. a solution for preparing is added drop-wise in the b solution, or b solution is added drop-wise in a solution, or a, b solution co-precipitation, reaction temperature remains on 40-90 in the dropping process
oC, the pH value is controlled between the 7-9, the aging 1-5h of reinforced complete continuation.
D. step c gained catalyst is filtered, with deionized water washing 2-8 time.
E. steps d gained catalyst is placed the drier inner drying with air blast, drier slowly is elevated to 110 from room temperature
oC-130
oC, heating rate are 20-60
oC/h is 110
oC-130
oFreeze-day with constant temperature 6-24h under the C.
F. with the dry good catalyst roasting of step e, roasting condition is: 150-180
oRoasting 3-10h under the C, 200-250
oRoasting 3-6h under the C, 300-350
oRoasting 3-5h under the C, 400-450
oRoasting 3-8h namely gets required catalyst under the C.
The soluble-salt of the described active component of step a is nickel nitrate, nickel chloride, nickel acetate, nickel formate, and the soluble-salt of auxiliary agent is nitrate or chlorate.If carrier is aluminium oxide, then the solubility predecessor is aluminum nitrate, alchlor; If carrier is the sial composite oxides, then the solubility predecessor is the mixture of aluminum nitrate or alchlor and acidic silicasol.
Surfactant is tartaric acid, AE03, AE09 or EDTA.The described precipitating reagent of step b is one of sodium carbonate, NaOH, ammonium carbonate, carbonic hydroammonium, urea, ammoniacal liquor or its mixture.
The present invention also provides the process conditions of the synthetic decahydronaphthalene of naphthalene hydrogenation, and the employing decahydronaphthalene is solvent, and the concentration of naphthalene is 5wt%-50wt% in the raw material, and raw material is pumped into the fixed bed reactors reaction that catalyst is housed, and reaction condition is: temperature 100-250
oC, pressure 1-5MPa, the mass space velocity of naphthalene are 0.2-2.0h
-1, H
2/ naphthalene volume ratio is 50-1000.
According to reaction condition provided by the invention, the conversion ratio of raw naphthalene material is 100%, decahydronaphthalene selectively greater than 99.5 %.
Advantage of the present invention
A kind of catalyst for the synthetic decahydronaphthalene of naphthalene hydrogenation provided by the invention adopts base metal nickel as the active component of catalyst, and cost significantly is lower than noble metal catalyst.The present invention adopts special preparation method, makes catalyst have high activity, selective and stable.Adopt decahydronaphthalene to make solvent, product purity is high, does not need can obtain qualified products through separating-purifying again.The present invention adopts fixed bed reactors, and reaction condition is gentle, and is simple to operate, is fit to serialization industrial production in enormous quantities, reduces running cost.
Description of drawings
Fig. 1 is the stability test result of catalyst of the present invention
The specific embodiment
Further specify the present invention with following embodiment, but invention is not limited.
Embodiment 1:
Take by weighing 42.37g four water nickel oxalates, the 52.76g magnesium nitrate hexahydrate is used deionized water dissolving, and in mixed solution, add 15.8g tartaric acid, and add deionized water, making overall solution volume is 300ml, solution is stirred, add 85g alumina support dipping, constantly stir in the process of dipping, solution is kept evenly, to flood good catalyst behind the 2h leaches, then natural drying 3h under room temperature places catalyst the drier inner drying with air blast, and drier slowly is elevated to 110 from room temperature
oC, heating rate are 20
oC/h is 110
oFreeze-day with constant temperature 6h under the C.The catalyst roasting that drying is good, roasting condition is: 150
oRoasting 3h under the C, 250
oRoasting 3h under the C, 350
oRoasting 3h under the C, 420
oRoasting 3h namely gets required specific area 200 m under the C
2/ g, pore volume 0.6cm
3/ g, wherein the 50-100nm hole accounts for 50% catalyst.
Take by weighing 5g20-40 order catalyst in the activation of fixed bed reactors Program heating reduction, activation condition is: Hydrogen Vapor Pressure is 0.5MPa, and volume space velocity is 1000h
-1, 150
oReductase 12 h is elevated to 300 with temperature under the C
oC reductase 12 h, heating rate are 10
oC/h.Reduction reduces the temperature to 100 after finishing
oC, pressure is elevated to 1MPa, is that the 5wt% raw material pumps into the fixed bed reactors reaction with naphthalene concentration, and solvent is decahydronaphthalene, and the mass space velocity of naphthalene is 0.2h
-1, H
2/ naphthalene volume ratio is 50, and catalyst composition and reaction result are as shown in table 1.
Embodiment 2
Take by weighing 247.7g six water nickel nitrates, the 0.2g barium nitrate is used deionized water dissolving, and in mixed solution, add 1.24gAE03, and add deionized water, making overall solution volume is 124ml, solution is stirred, add 49.9g alumina support dipping, constantly stir in the process of dipping, solution is kept evenly, to flood good catalyst behind the 10h leaches, then natural drying 24h under room temperature places catalyst the drier inner drying with air blast, and drier slowly is elevated to 110 from room temperature
oC, heating rate are 60
oC/h is 110
oFreeze-day with constant temperature 24h under the C.The catalyst roasting that drying is good, roasting condition is: 180
oRoasting 10h under the C, 200
oRoasting 6h under the C, 300
oRoasting 5h under the C, 450
oRoasting 8h namely gets required specific area 80 m under the C
2/ g, pore volume 0.2cm
3/ g, wherein the 50-100nm hole accounts for 60% catalyst.
Take by weighing 5g20-40 order catalyst in the activation of fixed bed reactors Program heating reduction, activation condition is: Hydrogen Vapor Pressure is 5MPa, and volume space velocity is 10000h
-1, 250
oReduce 10h under the C, temperature is elevated to 500
oC reduces 8h, and heating rate is 100
oC/h.Reduction reduces the temperature to 250 after finishing
oC, pressure is elevated to 5MPa, is that the 50wt% raw material pumps into the fixed bed reactors reaction with naphthalene concentration, and solvent is decahydronaphthalene, and the mass space velocity of naphthalene is 1.0h
-1, H
2/ naphthalene volume ratio is 500, and catalyst composition and reaction result are as shown in table 1.
Embodiment 3
Take by weighing 80.95g six water nickel chlorides, 9.13g strontium chloride, 5.7g molybdenum pentachloride, 24.13g ferric chloride (FeCl36H2O) deionized water dissolving, and in mixed solution, add 7.92gAE09, add deionized water, making overall solution volume is 79.19ml, and solution is stirred, and adds 70g sial composite oxide carrier (mass ratio of aluminium oxide and silica is 0.01:1) dipping, constantly stir in the process of dipping, solution is kept evenly, will flood good catalyst behind the 5h and leach natural drying 12h under room temperature, then catalyst is placed the drier inner drying with air blast, drier slowly is elevated to 120 from room temperature
oC, heating rate are 40
oC/h is 120
oFreeze-day with constant temperature 12h under the C.The catalyst roasting that drying is good, roasting condition is: 180
oRoasting 5h under the C, 230
oRoasting 4h under the C, 340
oRoasting 4h under the C, 440
oRoasting 5h namely gets required specific area 400 m under the C
2/ g, pore volume 1.2cm
3/ g, wherein the 50-100nm hole accounts for 55% catalyst.
Take by weighing 5g20-40 order catalyst in the activation of fixed bed reactors Program heating reduction, activation condition is: Hydrogen Vapor Pressure is 2MPa, and volume space velocity is 5000h
-1, 200
oReduce 5h under the C, temperature is elevated to 400
oC reduces 5h, and heating rate is 50
oC/h.Reduction reduces the temperature to 200 after finishing
oC, pressure is elevated to 3MPa, is that the 30wt% raw material pumps into the fixed bed reactors reaction with naphthalene concentration, and solvent is decahydronaphthalene, and the mass space velocity of naphthalene is 2.0h
-1, H
2/ naphthalene volume ratio is 1000, and catalyst composition and reaction result are as shown in table 1.
Embodiment 4
Take by weighing 47.2g two water nickel formates, 3.8g nitrate trihydrate copper, 7.93g titanium tetrachloride, use deionized water dissolving, and in mixed solution, add 7.86gEDTA, add deionized water, making overall solution volume is 39.28ml, and solution is stirred, and adds 82g sial composite oxide carrier (mass ratio of aluminium oxide and silica is 99:1) dipping, constantly stir in the process of dipping, solution is kept evenly, will flood good catalyst behind the 8h and leach natural drying 16h under room temperature, then catalyst is placed the drier inner drying with air blast, drier slowly is elevated to 130 from room temperature
oC, heating rate are 30
oC/h is 130
oFreeze-day with constant temperature 18h under the C.The catalyst roasting that drying is good, roasting condition is: 160
oRoasting 8h under the C, 240
oRoasting 5h under the C, 320
oRoasting 3h under the C, 430
oRoasting 6h namely gets required specific area 300 m under the C
2/ g, pore volume 0.8cm
3/ g, wherein the 50-100nm hole accounts for 65% catalyst.
Take by weighing 5g20-40 order catalyst in the activation of fixed bed reactors Program heating reduction, activation condition is: Hydrogen Vapor Pressure is 3MPa, and volume space velocity is 8000h
-1, 220
oReduce 8h under the C, temperature is elevated to 450
oC reduces 3h, and heating rate is 80
oC/h.Reduction reduces the temperature to 220 after finishing
oC, pressure is elevated to 4MPa, is that the 40wt% raw material pumps into the fixed bed reactors reaction with naphthalene concentration, and solvent is decahydronaphthalene, and the mass space velocity of naphthalene is 1.5h
-1, H
2/ naphthalene volume ratio is 400, and catalyst composition and reaction result are as shown in table 1.
Embodiment 5
Take by weighing 198.16g six water nickel nitrates, 15.59g lanthanum nitrate hexahydrate, 7.44g five water zirconium nitrates, 294.22g nine water aluminum nitrates, 43.33g acidic silicasol (SiO
2Content is 30wt%), use the 450ml deionized water dissolving, add until completely dissolved 44.7g tartaric acid, adding deionized water, to make liquor capacity be 558ml, stirring obtains a solution.Get 600ml ammoniacal liquor, be made into 1000ml solution b, a, b solution and stream are added in the reactor that the 600ml deionized water is housed stir, reaction temperature is 40
oC, pH are controlled at about 7, and aging 1h after question response is finished filters, washs 2 times, then catalyst is leached, and places the drier inner drying with air blast, and drier slowly is elevated to 130 from room temperature
oC, heating rate are 20
oC/h is 130
oFreeze-day with constant temperature 6h under the C.The catalyst roasting that drying is good, roasting condition is: 170
oRoasting 3h under the C, 240
oRoasting 3h under the C, 340
oRoasting 3h under the C, 450
oRoasting 3h namely gets required specific area 150 m under the C
2/ g, pore volume 0.7cm
3/ g, wherein the 50-100nm hole accounts for 70% catalyst.
Get 5g20-40 order catalyst and carry out the temperature programmed reduction activation under hydrogen, activation condition is: pressure is 0.5MPa, and volume space velocity is 1000h
-1, 150
oReductase 12 h is elevated to 300 with temperature under the C
oC reductase 12 h, heating rate are 10
oC/h.Reduction reduces the temperature to 100 after finishing
oC, pressure is elevated to 2MPa, is that the 5wt% raw material pumps into the fixed bed reactors reaction with naphthalene concentration, and solvent is decahydronaphthalene, and the mass space velocity of naphthalene is 0.2h
-1, H
2/ naphthalene volume ratio is 50, and catalyst composition and reaction result are as shown in table 1.
Embodiment 6
Take by weighing 60.72g six water nickel chlorides, 29.46g four water-calcium nitrate, 98.78g cobalt nitrate hexahydrate, 441.33g nine water aluminum nitrates are used the 500ml deionized water dissolving, add until completely dissolved 12.61gEDTA, adding deionized water, to make liquor capacity be 1260ml, and stirring obtains a solution.Get 200g NaOH, 100g sodium carbonate is made into 1000ml mixed solution b, under strong mixing a solution slowly is added drop-wise in the b solution, and reaction temperature is 90
oC, final pH is about 9, and aging 5h after question response is finished filters, washs 8 times, then catalyst is leached, and places the drier inner drying with air blast, and drier slowly is elevated to 120 from room temperature
oC, heating rate are 60
oC/h is 120
oFreeze-day with constant temperature 24h under the C.The catalyst roasting that drying is good, roasting condition is: 160
oRoasting 10h under the C, 240
oRoasting 6h under the C, 350
oRoasting 5h under the C, 450
oRoasting 8h namely gets required specific area 250 m under the C
2/ g, pore volume 0.9cm
3/ g, wherein the 50-100nm hole accounts for 75% catalyst.
Get 5g20-40 order catalyst and carry out the temperature programmed reduction activation under hydrogen, activation condition is: pressure is 5MPa, and volume space velocity is 10000h
-1, 150
oReduce 10h under the C, temperature is elevated to 500
oC reduces 8h, and heating rate is 100
oC/h.Reduction reduces the temperature to 250 after finishing
oC, pressure lifting are that the 10wt% raw material pumps into the fixed bed reactors reaction to 3MPa with naphthalene concentration, and solvent is decahydronaphthalene, and the mass space velocity of naphthalene is 2h
-1, H
2/ naphthalene volume ratio is 500, and catalyst composition and reaction result are as shown in table 1.
Embodiment 7
Take by weighing 17.33g two water nickel formates, the 4.55g manganese nitrate, the 128.11g alchlor is used the 100ml deionized water dissolving, adds until completely dissolved 8gAE03, and adding deionized water, to make liquor capacity be 145ml, and stirring obtains a solution.Get 100g sodium carbonate, be made into 500ml solution b, under strong mixing b solution slowly is added drop-wise in a solution, reaction temperature is 50
oC, pH are controlled at about 8, and aging 3h after question response is finished filters, washs 7 times, then catalyst is leached, and places the drier inner drying with air blast, and drier slowly is elevated to 110 from room temperature
oC, heating rate are 40
oC/h is 110
oFreeze-day with constant temperature 12h under the C.The catalyst roasting that drying is good, roasting condition is: 180
oRoasting 6h under the C, 250
oRoasting 4h under the C, 350
oRoasting 4h under the C, 400
oRoasting 5h namely gets required specific area 150 m under the C
2/ g, pore volume 0.8cm
3/ g, wherein the 50-100nm hole accounts for 80% catalyst.
Get 5g20-40 order catalyst and carry out the temperature programmed reduction activation under hydrogen, activation condition is: pressure is 3MPa, and volume space velocity is 5000h
-1, 150
oReduce 6h under the C, temperature is elevated to 400
oC reduces 6h, and heating rate is 80
oC/h.Reduction reduces the temperature to 210 after finishing
oC is that the 30wt% raw material pumps into the fixed bed reactors reaction with naphthalene concentration, and solvent is decahydronaphthalene, and the mass space velocity of naphthalene is 1.5h
-1, H
2/ naphthalene volume ratio is 400, and catalyst composition and reaction result are as shown in table 1.
Embodiment 8
Take by weighing 105.92g four water acetic acid nickel, 9.01g nitrate trihydrate copper, the 183.02g alchlor is used the 180ml deionized water dissolving, adds until completely dissolved 10.23gAE09, and adding deionized water, to make liquor capacity be 205ml, and stirring obtains a solution.Get the 200g ammonium carbonate, 50g ammoniacal liquor is made into 500ml mixed solution b, under strong mixing b solution slowly is added drop-wise in a solution, and reaction temperature is 80
oC, pH are controlled at about 7.5, and aging 4h after question response is finished filters, washs 3 times, then catalyst is leached, and places the drier inner drying with air blast, and drier slowly is elevated to 110 from room temperature
oC, heating rate are 50
oC/h is 110
oFreeze-day with constant temperature 8h under the C.The catalyst roasting that drying is good, roasting condition is: 170
oRoasting 4h under the C, 220
oRoasting 5h under the C, 320
oRoasting 4h under the C, 430
oRoasting 6h namely gets required specific area 95 m under the C
2/ g, pore volume 0.4cm
3/ g, wherein the 50-100nm hole accounts for 75% catalyst.
Take by weighing 5g20-40 order catalyst in the activation of fixed bed reactors Program heating reduction, activation condition is: Hydrogen Vapor Pressure is 1MPa, and volume space velocity is 8000h
-1, 220
oReduce 8h under the C, temperature is elevated to 450
oC reduces 3h, and heating rate is 80
oC/h.Reduction reduces the temperature to 180 after finishing
oC, pressure is elevated to 3MPa, is that the 50wt% raw material pumps into the fixed bed reactors reaction with naphthalene concentration, and solvent is decahydronaphthalene, and the mass space velocity of naphthalene is 1 h
-1, H
2/ naphthalene volume ratio is 400, and catalyst composition and reaction result are as shown in table 1.
Embodiment 9
The catalyst stability test takes by weighing 20g20-40 order embodiment 3 catalyst in the activation of fixed bed reactors Program heating reduction, and activation condition is: Hydrogen Vapor Pressure is 2MPa, and volume space velocity is 5000h
-1, 220
oReduce 8h under the C, temperature is elevated to 450
oC reduces 3h, and heating rate is 80
oC/h.Reduction reduces the temperature to 180 after finishing
oC, pressure is elevated to 3MPa, is that the 20wt% raw material pumps into the fixed bed reactors reaction with naphthalene concentration, and solvent is decahydronaphthalene, and the mass space velocity of naphthalene is 1 h
-1, H
2/ naphthalene volume ratio is 400, has carried out the 1500h stability test, and the result is shown in Figure 1.
Table 1 catalyst forms and reaction result
Claims (13)
1. the catalyst of the standby decahydronaphthalene of a naphthalene Hydrogenation, it is characterized in that catalyst is comprised of active component, auxiliary agent, carrier three parts, in metal, the quality percentage composition of activity component metal is 10wt%-50wt%, the quality percentage composition of promoter metal is 0.1 wt%-25wt%, and all the other are carrier; The specific area of catalyst is 80-400m
2/ g; Pore volume is 0.2-1.2cm
3/ g, its mesoporous account for the 50-80% in the total duct of catalyst in the hole of 50-100nm.
2. the catalyst of the standby decahydronaphthalene of a kind of naphthalene Hydrogenation as claimed in claim 1 is characterized in that described active component is the oxide of Ni.
3. the catalyst of the standby decahydronaphthalene of a kind of naphthalene Hydrogenation as claimed in claim 1 is characterized in that described auxiliary agent is at least a in the oxide of Mg, Ca, Sr, Ba, Co, Fe, La, Mo, Zr, Ti, Mn, Cu.
4. the catalyst of the standby decahydronaphthalene of a kind of naphthalene Hydrogenation as claimed in claim 1 is characterized in that described carrier is Al
2O
3Or
The sial composite oxides
5. the catalyst of the standby decahydronaphthalene of a kind of naphthalene Hydrogenation as claimed in claim 4 is characterized in that described sial composite oxide carrier, and aluminium oxide is 0.01～99:1 with the siliconoxide mass ratio.
6. such as the preparation method of each described a kind of naphthalene Hydrogenation of claim 1-5 for the catalyst of decahydronaphthalene, it is characterized in that comprising the steps:
The soluble-salt of active component, the soluble-salt of auxiliary agent are made into mixed solution, and add surfactant in the mixed solution and stir, total salt concentration is 0.3-2.0g/ml, and the concentration of surfactant is 0.01-0.5g/ml;
Pour the solution (1) for preparing in the container that carrier is housed supersaturation dipping, constantly stir in the process of dipping, solution is kept evenly, dip time is 2-10h;
The catalyst that (2) dipping is good leaches, and then natural drying 3-24h under room temperature places catalyst the drier inner drying with air blast, and drier slowly is elevated to 110 from room temperature
oC-130
OC, heating rate is 20-60
oC/h is 110
oC-130
OCLower freeze-day with constant temperature 6-24h;
With (3) dry good catalyst roasting, roasting condition is: 150-180
oRoasting 3-10h under the C, 200-250
oRoasting 3-6h under the C, 300-350
oRoasting 3-5h under the C, 400-450
oRoasting 3-8h namely gets required catalyst under the C.
7. such as the preparation method of each described a kind of naphthalene Hydrogenation of claim 1-5 for the catalyst of decahydronaphthalene, it is characterized in that comprising the steps:
(a) soluble-salt of active component, the soluble-salt of auxiliary agent, the solubility predecessor of carrier are made into mixed solution with deionized water, and add surfactant in the mixed solution and stir, the concentration of surfactant is 0.01-0.5g/ml, and the solution total concentration is 0.5-2g/ml;
(b) with the precipitating reagent wiring solution-forming;
(c) a solution for preparing is added drop-wise in the b solution, or b solution is added drop-wise in a solution, or a, b solution co-precipitation, reaction temperature remains on 40-90 in the dropping process
oC, the pH value is controlled between the 7-9, the aging 1-5h of reinforced complete continuation;
Step c gained catalyst is filtered, with deionized water washing 2-8 time;
(e) steps d gained catalyst is placed drier inner drying with air blast, drier slowly is elevated to 110 from room temperature
oC-130
OC, heating rate is 20-60
oC/h is 110
oC-130
OCLower freeze-day with constant temperature 6-24h;
(f) with the dry good catalyst roasting of step e, roasting condition is: 150-180
oRoasting 3-10h under the C, 200-250
oRoasting 3-6h under the C, 300-350
oRoasting 3-5h under the C, 400-450
oRoasting 3-8h namely gets required catalyst under the C.
8. such as the preparation method of the catalyst of the standby decahydronaphthalene of claim 6 or 7 described a kind of naphthalene Hydrogenations, the soluble-salt that it is characterized in that described active component is nickel nitrate, nickel chloride, nickel acetate or nickel formate.
9. such as the preparation method of the catalyst of the standby decahydronaphthalene of claim 6 or 7 described a kind of naphthalene Hydrogenations, the soluble-salt that it is characterized in that described auxiliary agent is nitrate or chlorate.
10. such as the preparation method of the catalyst of the standby decahydronaphthalene of claim 6 or 7 described a kind of naphthalene Hydrogenations, it is characterized in that described surfactant is tartaric acid, AE03, AE09 or EDTA.
11. the preparation method such as the catalyst of the standby decahydronaphthalene of claim 6 or 7 described a kind of naphthalene Hydrogenations is characterized in that described carrier is aluminium oxide, the solubility predecessor is aluminum nitrate or alchlor; Carrier is the sial composite oxides, and the solubility predecessor is the mixture of aluminum nitrate or alchlor and acidic silicasol.
12. the preparation method of the catalyst of the standby decahydronaphthalene of a kind of naphthalene Hydrogenation as claimed in claim 7 is characterized in that described step b precipitating reagent is one of sodium carbonate, NaOH, ammonium carbonate, carbonic hydroammonium, urea, ammoniacal liquor or its mixture.
13. such as the application of each described a kind of naphthalene Hydrogenation of claim 1-5 for the catalyst of decahydronaphthalene, it is characterized in that adopting decahydronaphthalene is solvent, the concentration of naphthalene is 5wt%-50wt% in the raw material, raw material is pumped into the fixed bed reactors reaction that catalyst is housed, and reaction condition is: temperature 100-250
oC, pressure 1-5MPa, the mass space velocity of naphthalene are 0.2-2.0h
-1, H
2/ naphthalene volume ratio is 50-1000.
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