CN107597108A - A kind of naphthane Hydrogenation is for catalyst of decahydronaphthalene and its preparation method and application - Google Patents
A kind of naphthane Hydrogenation is for catalyst of decahydronaphthalene and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of naphthane Hydrogenation for catalyst of decahydronaphthalene and its preparation method and application.The catalyst is made up of active component, auxiliary agent and carrier, active component and auxiliary agent is more evenly distributed on carrier using equi-volume impregnating, improves the decentralization of active component and auxiliary agent, reduces the dosage of active component, improve decahydronaphthalene instead along than.Active component is Pt, Pd etc., auxiliary agent Zn, Ni, Mg, Ce, Zr, La, Fe, Cu, Co oxide, carrier Al2O3、SiO2、TiO2With one or several kinds of combinations in molecular sieves of ZSM 5 etc..The preparation-obtained catalyst of the present invention can be as the secondary hydrogenation catalyst of two-step method, and its bullion content is low, and catalytic activity is high, and reaction condition is moderate, and preparation method simple possible, economic benefit is good, has preferable prospects for commercial application.
Description
Technical field
The invention belongs to catalyst preparation technical field, and in particular to a kind of naphthane Hydrogenation for decahydronaphthalene catalyst
And its preparation method and application.
Background technology
Decahydronaphthalene is a kind of high-performance solvent, be mainly used in dry spinning polyethylene fibre, as aviation kerosine and
Battery hydrogen storage material etc..The heat endurance of trans-decalin is higher, is to improve the essential material of aviation kerosine heat endurance,
It is also used as preparing the raw material of high quality liquid crystal material；Cis-decaline mainly for the production of decanedioic acid so that produce nylon 6,
Nylon 10 and plasticizer.Existing market sells decahydronaphthalene instead along than between 2-4, decahydronaphthalene is instead along than its higher stability more
Height, price is also higher, but prepares also more difficult.The decahydronaphthalene of maturation is there is no at present instead along than the production technology higher than 4 and catalysis
Agent.
Crude naphthalene catalytic hydrogenation is the main technique of current production decahydronaphthalene, but in crude naphthalene containing a large amount of sulphur, nitrogen and
Beavy metal impurity, it is serious to catalyst poisoning effect, cause catalyst service life to shorten.China's crude naphthalene is mainly derived from coal
Tar, aboundresources, therefore its added value will be greatly improved for decahydronaphthalene by crude naphthalene Hydrogenation, while can also alleviate certain
Environmental protection pressure.
Prior art crude naphthalene Hydrogenation has two methods for decahydronaphthalene, and one kind is the step Deep catalytic of crude naphthalene one hydrogenation
Method.
Such as Chinese patent application CN102838439A discloses a kind of method of naphthalene hydrogenation production decahydronaphthalene, this method is adopted
With fixed bed continuously hydrogen adding technique, naphthalene carries out hydrogenation reaction under reduction-state nickel-base catalyst, and used hydroconversion condition is：Hydrogen
Qi leel presses 0.2MPa-10MPa, and 120 DEG C -320 DEG C of reaction temperature, liquid volume air speed is 0.5h-1-4.0h-1, hydrogen-oil ratio is
300-500.The technological process is shorter and catalyst cost is relatively low, but its poor catalyst stability, and accessory substance is more in product.
CN104645976A discloses a kind of catalyst for the step of naphthalene one hydrogenation production decahydronaphthalene and preparation method thereof, should
Catalyst is loaded catalyst, is made up of active component and carrier, and active component is platinum, carrier Al2O3、ZrO2Or TiO2,
Can be normal pressure~3.0MPa in pressure, temperature is 200~300 DEG C, and air speed is 1000~3000h using the catalyst-1Under carry
The selectivity and conversion ratio of high naphthalene Hydrogenation decahydronaphthalene.
Patent application CN102320913A discloses the method for decahydronaphthalene " a kind of synthesize ", this method with loading type Pd/γ-
Al2O3As catalyst, using fixed bed continuously hydrogen adding technique, used hydroconversion condition is：Reaction temperature is 100-280 DEG C,
Reaction pressure is 1.5-4.0MPa, and mass space velocity is 0.5-2.0h during liquid-1, hydrogen-oil ratio 80-1000.Although naphthalene turns in experiment
Rate is up to 99.92%, and decahydronaphthalene yield reaches 99.36%, but Pd contents are up to 1% in the catalyst, catalyst into
This costliness.Sulphur nitrogen content is higher in crude naphthalene simultaneously, and noble metal can be caused seriously to poison, reduce its service life.
CN102941093A is disclosed " naphthalene Hydrogenation is for decahydronaphthalene and preparation method and application ", and its catalyst composition is：
On the basis of the weight of catalyst, 10%-50% active component, 0.1%-25% promoter metal, remaining is carrier.China
Patent CN102836737A discloses " a kind of naphthalene hydrogenation catalyst and preparation method thereof ", and the composition of its catalyst is：With catalysis
On the basis of the weight of agent, the content of ZSM-5 molecular sieve is 10%-80%, and the content of alkali metal is 1%-10%, and group VIII is golden
The content of category is 0.1%-3.0%, content 0.1%-5% in terms of element of auxiliary agent and the silica of surplus, and the auxiliary agent is
One or more of compositions in tin, lead, rhenium.Above-mentioned two patent prepares decahydronaphthalene by naphthalene direct hydrogenation, although catalyst system
The simple use cost of Preparation Method is low, but side reaction is more in catalytic reaction, and resulting product purity is low, it is impossible to selective system
Standby anti-suitable decahydronaphthalene, limit the purposes of decahydronaphthalene.
The method of above-mentioned step decahydronaphthalene, universal impurity in products is more, simultaneously as technique limits, catalyst is easily poisoned
Inactivation, service life are shorter.
The method that another kind prepares decahydronaphthalene is two-step method, and naphthalene first hydrogenated into the higher naphthane of generation purity, then with four
Hydrogen naphthalene prepares decahydronaphthalene, and this method product purity is of a relatively high, but second step reaction is more difficult, it is necessary to improve the hydrogenation of catalyst
Performance.
The present inventor passes through early-stage Study, and a kind of two-step method work is disclosed in patent application CN106565398A
The method of industry naphthalene hydrogenation production decahydronaphthalene, using crude naphthalene as raw material, using Ni-Mo series catalysts as one-stage hydrogenation catalyst, adds
Sulphur nitrogen impurity in hydrogen removing raw material is tentatively hydrogenated to naphthane and decahydronaphthalene simultaneously, and then oxidized zinc absorption fine de-sulfur will
Sulfur content is taken off to below 1ppm, and resulting product then is carried out into secondary hydrogenation, the catalyst that the technique secondary hydrogenation uses
For nickel catalyst, catalyst shows stronger hydrogenation activity, is finally obtained with inexpensive, high conversion and in high yield high
The decahydronaphthalene of purity.
But prior art whether uses one-step method or two-step method, except each having catalyst to be easily poisoned, use
Short life, the purity deficiency such as low are outer, the problem of decahydronaphthalene is instead along than low (nearly all less than 4) also be present, can not meet market
To the demand of high stability decahydronaphthalene product.Therefore, based on existing two-step method, exploitation is a kind of have it is higher it is anti-along than, high turn
The decahydronaphthalene catalyst of rate and high selectivity is significant.
The content of the invention
The problem of existing for prior art, it is an object of the invention to provide a kind of naphthane Hydrogenation for decahydronaphthalene
Catalyst and its preparation method and application.Step of the catalyst for naphthane Hydrogenation in two-step method decahydronaphthalene for decahydronaphthalene
Suddenly, can effectively improve product decahydronaphthalene it is anti-along than, product is obtained higher stability, cost is low, high conversion rate, selection
Property is good.
The above-mentioned purpose of the present invention is achieved through the following technical solutions：
A kind of naphthane Hydrogenation for decahydronaphthalene catalyst, containing active component, catalyst promoter and catalyst carrier,
On the basis of the weight of catalyst, wherein, the active component is the noble metals such as Pt, Pd that mass content is 0.05%-0.3%
Middle one or more of combination；The catalyst promoter be mass content be 1%-6% Zn, Ni, Mg, Ce, Zr, La, Fe,
One or several kinds of combinations in Cu, Co etc. oxide；The catalyst carrier is that mass content is 93.7%-
98.95% Al2O3、SiO2、TiO2With combination one or more of in ZSM-5 molecular sieve.
According to some specific embodiments of the present invention, above-mentioned naphthane Hydrogenation is for the catalyst of decahydronaphthalene, the activity
Component is Pd the or Pt-Pd metallic combinations that mass content is 0.15%-0.3%, and Pd mass content is not less than 0.15%.
It was found by the inventors of the present invention that preparing the catalyst of two-step method using the preparation method of the present invention, its Pd content is higher, institute
Catalyst is obtained more to be advantageous to improve the anti-along than when Pd mass content is not less than 0.15%, energy is effective of decahydronaphthalene product
Ensure the anti-along than higher than 4 of decahydronaphthalene product.
According to some specific embodiments of the present invention, above-mentioned naphthane Hydrogenation is for the catalyst of decahydronaphthalene, the catalysis
Agent aid is CuO, MgO, ZnO, NiO, CeO, ZrO or Co that mass content is 1%-6%2O3In one or more.Catalyst
The species of auxiliary agent is to the anti-suitable than also having an impact of decahydronaphthalene product, when active component is identical, Co2O3＞ NiO ＞ CuO ＞ MgO ＞
ZnO ＞ CeO, ZrO.Preferable catalyst promoter is the Co that mass content is 1%-6%2O3, one kind in NiO, CuO, MgO or
It is combined.It is not less than 0.15%, Co in Pd mass content2O3, NiO, CuO, MgO make auxiliary agent, according to the inventive method be made urge
Agent, decahydronaphthalene product it is anti-along than higher than 5.
According to some specific embodiments of the present invention, above-mentioned naphthane Hydrogenation is for the catalyst of decahydronaphthalene, the activity
Component is the Pd that mass content is 0.3%, and the catalyst promoter is that mass content is 2%Co2O3+ 2%NiO+2%MgO groups
Close.The preferable technical scheme ensure in 1000h long period tests naphthane conversion ratio and decahydronaphthalene selectivity it is higher
While (being maintained at more than 99% for a long time), the anti-higher steady along having than being up to more than 7, product of decahydronaphthalene can be made for a long time
It is qualitative.And the anti-of the decahydronaphthalene that other catalysts obtain declines, substantially less than 7 along than that can increase with the reaction time.
According to some specific embodiments of the present invention, above-mentioned naphthane Hydrogenation is for the catalyst of decahydronaphthalene, the activity
Component is the Pd that mass content is 0.3%, and the catalyst promoter is mass content 6%Co2O3.The preferable technical scheme can
The conversion ratio of naphthane and the selectivity of decahydronaphthalene is set to reach 100%, and decahydronaphthalene is anti-along than reaching 12.7, effect is made us
It is pleasantly surprised.
Method of the above-mentioned naphthane Hydrogenation for the catalyst of decahydronaphthalene is prepared present invention also offers a kind of, including it is following
Step：
(1) by the catalyst carrier ball milling 5h, 200 mesh sieves are crossed, then in 400~500 DEG C of air atmospheres roasting 4~
6h, obtain carrier A；
(2) formulation aid precursor solution, it is 1~5 to adjust its pH value with acid solution, according to needed for incipient impregnation
Amount, take the maceration extract of respective amount；Carrier A is weighed again pour into and 20~40min is stirred and evenly mixed in maceration extract, then stand at room temperature
10~14h is aged, drying, 1~10h of roasting in 400~500 DEG C of air atmospheres is taken out, obtains carrier B；
(3) noble metal precursor liquid solution is prepared, it is 1~5 to adjust its pH value with acid solution, as needed for incipient impregnation
Amount, take the maceration extract of respective amount；Carrier B obtained by step (2) is fallen and stirs and evenly mixs 20~40min in maceration extract, then
Still aging 10~14h at room temperature, drying, add suitable quantity of water and binding agent and be squeezed into bar with its kneading, the column being molded
Particle diameter is 3~5mm, and particle length is 6~15mm, then by resulting cylindrical particle in 400~500 DEG C of air atmospheres
1~10h is calcined, obtains sample C；
(4) reductant solution is prepared, sample C is immersed in reductant solution, stands 2-24h, takes out sample C distilled water
Washing 1-5 times, dried in 90~120 DEG C of baking ovens and obtain the catalyst.
According to some specific embodiments of the present invention, in above-mentioned preparation method, step (2) adjuvant used precursor solution is
Zn(NO3)2、Ni(NO3)2、Ce(NO3)3、Mg(NO3)2、Zr(NO3)4、La(NO3)3、Fe(NO3)3、Cu(NO3)2、Co(NO3)3In
Any one or several mixed solutions；Step (3) the noble metal precursor liquid solution is in chloroplatinic acid, palladium chloride
The mixed solution of any one or two kinds.
According to some specific embodiments of the present invention, in above-mentioned preparation method, step (2) and (3) described acid solution are
Any one in watery hydrochloric acid, dust technology, spirit of vinegar or several mixing.
According to some specific embodiments of the present invention, in above-mentioned preparation method, step (3) described binding agent is white for activity
One or two kinds of mixing in soil, kaolin, sesbania powder.
In above-mentioned preparation method, step (4) described reducing agent is one in formaldehyde, hydrazine hydrate, sodium borohydride and potassium borohydride
Kind or two kinds of mixing.According to some specific embodiments of the present invention, selection is sodium borohydride.
Catalyst answering in decahydronaphthalene is prepared invention further provides above-mentioned naphthane Hydrogenation for decahydronaphthalene
With, first by the catalyst 150-400 DEG C, hydrogen partial pressure be 0.5-5MPa conditions reduce 1-20h.
Further, in above-mentioned application, the reaction temperature of the catalyst is 150-400 DEG C, pressure 0.5-10MPa,
Volume space velocity is 0.5-8h during liquid-1, hydrogen-oil ratio 100-2000.
The positive effect of the present invention is：
1. the present invention uses equi-volume impregnating, active component and auxiliary agent is more evenly distributed on carrier, improve
The decentralization of active component and auxiliary agent, reduces the dosage of active component, and obtained catalyst is highly suitable for naphthane Hydrogenation
Standby decahydronaphthalene, the yield and purity of decahydronaphthalene can be effectively improved, especially improve the anti-along than increasing the stabilization of product of decahydronaphthalene
Property, particularly some preferred embodiments of the present invention, decahydronaphthalene more preferably reach more than 5, more instead along than that can reach more than 4
Reach 12.7 excellently, preferable technical foundation is provided to prepare the decahydronaphthalene product of high-quality.
It is 2. the patent application CN106565398A of the catalyst combination early-stage Study of present invention crude naphthalene Hydrogenation is standby
The method use in conjunction of naphthane, it is more beneficial for extending the service life of catalyst, reduces the use cost of catalyst.
3. the present invention also obtains the technological parameter of suitable catalyst application of the present invention through numerous studies, prepared for naphthane
Decahydronaphthalene provides preferable condition of work.
Brief description of the drawings
Fig. 1 is the structural representation for the catalysis detection means that the embodiment of the present invention is used；
Wherein, 1-mass flowmenter (gas and liquid), 2-tee ball valve, 3-ball valve, 4-gasification furnace, 5-catalysis
Agent reactor, 6-temperature indicator, 7-condenser, 8-plunger pump, 9-fluid reservoir, 10-counterbalance valve, 11-vent gas treatment
Tank.
Fig. 2 is that naphthane conversion ratios and decahydronaphthalene of the catalyst D7 and D11 in 1000h life experiments selectively change
Figure, wherein 1 is D7,2 be D11；
Fig. 3 is that catalyst D7 and D11 is catalyzed the anti-suitable than variation diagram of decahydronaphthalene in 1000h life experiments, wherein 1 is
D7,2 be D11.
Embodiment
Naphthane Hydrogenation provided by the invention containing active component, catalyst promoter and is urged for the catalyst of decahydronaphthalene
Agent carrier, wherein, the active component is one or more of in the noble metals such as Pt, Pd that mass content is 0.05%-0.3%
Combination；The catalyst promoter is Zn, Ni, Mg, Ce, Zr, La, Fe, Cu, Co that mass content is 1%-6% etc. oxidation
One or more of combination in thing；The catalyst carrier is the Al that mass content is 93.7%-98.95%2O3Powder, SiO2
Powder, TiO2One or more of combination in powder and ZSM-5 molecular sieve powder etc..
In some preferred embodiments, the active component is the Pd noble metals that mass content is 0.3%；The catalysis
Agent aid is the Co that mass content is 6%2O3Combination；More excellent, the active component is the Pd that mass content is 0.3%, described
Catalyst promoter is that mass content is 2%Co2O3+ 2%NiO+2%MgO is combined.The inventors found that the activearm
Point it is the Pd that mass content is 0.3%, the catalyst promoter is that mass content is 2%Co2O3+ 2%NiO+2%MgO combination
When the catalyst that is prepared into, in the experiment of 1000h long periods the conversion ratio of naphthane and the selectivity of decahydronaphthalene can be made to reach
More than 99%, and decahydronaphthalene is anti-along than reaching more than 7 for a long time.
The catalyst of the present invention is prepared by following preparation method：
(1) by the catalyst carrier ball milling 5h, 200 mesh sieves are crossed, then in 400~500 DEG C of air atmospheres roasting 4~
6h, obtain carrier A；
(2) formulation aid precursor solution, it is 1~5 to adjust its pH value with acid solution, according to needed for incipient impregnation
Amount, take the maceration extract of respective amount；Carrier A is weighed again pour into and 20~40min is stirred and evenly mixed in maceration extract, then stand at room temperature
10~14h is aged, drying, 1~10h of roasting in 400~500 DEG C of air atmospheres is taken out, obtains carrier B；
(3) noble metal precursor liquid solution is prepared, it is 1~5 to adjust its pH value with acid solution, as needed for incipient impregnation
Amount, take the maceration extract of respective amount；Carrier B obtained by step (2) is fallen and stirs and evenly mixs 20~40min in maceration extract, then
Still aging 10~14h at room temperature, drying, add suitable quantity of water and binding agent and be squeezed into bar with its kneading, the column being molded
Particle diameter is 3~5mm, and particle length is 6~15mm, then by resulting cylindrical particle in 400~500 DEG C of air atmospheres
1~10h is calcined, obtains sample C；
(4) reductant solution is prepared, sample C is immersed in reductant solution, stands 2-24h, takes out sample C distilled water
Washing 1-5 times, dried in 90~120 DEG C of baking ovens and obtain the catalyst.
Explained below by way of specific embodiment is further to the content of the invention of the present invention, but should not be construed as the present invention
Scope be only limitted to following example, can will be each in following instance according to the invention thinking and entire contents of the present invention
Technical characteristic makes appropriate combination/replacement/adjustment/modification etc., and this is will be obvious to those skilled in the art that still
Belong to the category that the present invention protects.
Embodiment 1：
(1) by Al2O3Carrier ball milling 5h, 200 mesh sieves are crossed, then 5h is calcined in 450 DEG C of air atmospheres, obtains carrier A1；
(2) 11.5g magnesium nitrate hexahydrates are weighed it is dissolved in 50ml deionized waters and obtain compounding agent solution, it is adjusted with salpeter solution
PH value is 4, is placed in 2.5L plastic beakers；Weigh 28.11g carriers A1 and pour into plastic beaker rapidly and stir and evenly mix
30min, then still aging 12h at room temperature, dries 12h in 100 DEG C of baking ovens, takes out and be calcined in 450 DEG C of air atmospheres
5h, obtain carrier B 1；
(3) weigh 2g palladium chlorides to be dissolved in 200ml deionized waters, it is 4 that hydrochloric acid solution, which is added dropwise, and adjusts its pH value, is obtained
(a) solution.Measure 15ml (a) solution to be added in 2.5L plastic beakers, then add 35ml deionized waters and stir and evenly mix；Will
(2) carrier B 1 being prepared in, which is poured into rapidly, stirs and evenly mixs 30min in plastic beaker, then still aging 12h at room temperature,
12h is dried under the conditions of 120 DEG C.Weigh 1g sesbania powders to be dissolved in 5g deionized waters, by itself and the sample blending after drying, then
Pinching is pressed into bar, the cylindrical particle being molded a diameter of 4mm, particle length 8mm, then by resulting cylindrical particle 120
12h is dried under the conditions of DEG C, takes out and is calcined 5h in 450 DEG C of air atmospheres, obtains sample C1.
(4) 2g sodium borohydrides are weighed to be dissolved in 100ml deionized waters, are then placed in ice-water bath, by sample
C1 is added in sodium borohydride solution, stands 24h, takes out sample C1 with water washing is distilled 4 times, 12h is dried in 120 DEG C of baking ovens
Obtain catalyst D1.
Embodiment 2：
(1) by Al2O3Carrier ball milling 5h, 200 mesh sieves are crossed, then 5h is calcined in 450 DEG C of air atmospheres, obtains carrier A2；
(2) the water cerous nitrates of 4.5g six are weighed it is dissolved in 50ml deionized waters and obtain compounding agent solution, it is adjusted with salpeter solution
PH value is 4, is placed in 2.5L plastic beakers；Weigh 28.11g carriers A2 and pour into plastic beaker rapidly and stir and evenly mix
30min, then still aging 12h at room temperature, dries 12h in 100 DEG C of baking ovens, takes out and be calcined in 450 DEG C of air atmospheres
5h, obtain carrier B 2；
(3) measure (a) solution 15ml configured in case 1 to be added in 2.5L plastic beakers, then add 35ml
Deionized water stirs and evenly mixs；The carrier B 2 being prepared in (2) is poured into rapidly 30min is stirred and evenly mixed in plastic beaker, then
Still aging 12h at room temperature, 12h is dried under the conditions of 120 DEG C.1g sesbania powders are weighed to be dissolved in 5g deionized waters, by its with
Sample blending after drying, then pinching be pressed into bar, the cylindrical particle being molded a diameter of 4mm, particle length 8mm, then will
Resulting cylindrical particle dries 12h under the conditions of 120 DEG C, takes out and is calcined 5h in 450 DEG C of air atmospheres, obtains sample C2.
(4) 2g sodium borohydrides are weighed to be dissolved in 100ml deionized waters, are then placed in ice-water bath, by sample
C2 is added in sodium borohydride solution, stands 24h, takes out sample C2 with water washing is distilled 4 times, 12h is dried in 120 DEG C of baking ovens
Obtain catalyst D2.
Embodiment 3：
(1) by Al2O3Carrier ball milling 5h, 200 mesh sieves are crossed, then 5h is calcined in 450 DEG C of air atmospheres, obtains carrier A3；
(2) the water zirconium nitrates of 6.3g five, which are dissolved in 50ml deionized waters, obtains compounding agent solution, and its pH value is adjusted with salpeter solution
For 4, it is placed in 2.5L plastic beakers；Weigh 28.11g carriers A3 and pour into rapidly and 30min is stirred and evenly mixed in plastic beaker, so
Still aging 12h at room temperature afterwards, dries 12h in 100 DEG C of baking ovens, takes out and be calcined 5h in 450 DEG C of air atmospheres, carried
Body B3；
(3) measure and (a) solution 25ml is made in case 1 be added in 2.5L plastic beakers, then add 25ml go from
Sub- water stirs and evenly mixs；The carrier B 3 being prepared in (2) is poured into rapidly 30min is stirred and evenly mixed in plastic beaker, then in room
Still aging 12h under temperature, 12h is dried under the conditions of 120 DEG C.Weigh 1g sesbania powders to be dissolved in 5g deionized waters, by itself and drying
Sample blending afterwards, then pinching be pressed into bar, the cylindrical particle being molded a diameter of 4mm, particle length 8mm, then by gained
To cylindrical particle dry 12h under the conditions of 120 DEG C, take out and be calcined 5h in 450 DEG C of air atmospheres, obtain sample C3.
(4) 2g sodium borohydrides are weighed to be dissolved in 100ml deionized waters, are then placed in ice-water bath, by sample
C3 is added in sodium borohydride solution, stands 24h, takes out sample C3 with water washing is distilled 4 times, 12h is dried in 120 DEG C of baking ovens
Obtain catalyst D3.
Embodiment 4：
(1) by Al2O3Carrier ball milling 5h, 200 mesh sieves are crossed, then 5h is calcined in 450 DEG C of air atmospheres, obtains carrier A4；
(2) weigh 5.44g nitrate trihydrate copper and be dissolved in 50ml deionized waters and obtain compounding agent solution, it is adjusted with salpeter solution
PH value is 4, is placed in 2.5L plastic beakers；Weigh 28.11g carriers A4 and pour into plastic beaker rapidly and stir and evenly mix
30min, then still aging 12h at room temperature, dries 12h in 100 DEG C of baking ovens, takes out and be calcined in 450 DEG C of air atmospheres
5h, obtain carrier B 4；
(3) measure (a) solution 15ml configured in case 1 to be added in 2.5L plastic beakers, then add 35ml
Deionized water stirs and evenly mixs；The carrier B 4 being prepared in (2) is poured into rapidly 30min is stirred and evenly mixed in plastic beaker, then
Still aging 12h at room temperature, 12h is dried under the conditions of 120 DEG C.1g sesbania powders are weighed to be dissolved in 5g deionized waters, by its with
Sample blending after drying, then pinching be pressed into bar, the cylindrical particle being molded a diameter of 4mm, particle length 8mm, then will
Resulting cylindrical particle dries 12h under the conditions of 120 DEG C, takes out and is calcined 5h in 450 DEG C of air atmospheres, obtains sample C4.
(4) 2g sodium borohydrides are weighed to be dissolved in 100ml deionized waters, are then placed in ice-water bath, by sample
C4 is added in sodium borohydride solution, stands 24h, takes out sample C4 with water washing is distilled 4 times, 12h is dried in 120 DEG C of baking ovens
Obtain catalyst D4.
Embodiment 5：
(1) by Al2O3Carrier ball milling 5h, 200 mesh sieves are crossed, then 5h is calcined in 450 DEG C of air atmospheres, obtains carrier A5；
(2) the water nickel nitrates of 7.0g six are weighed it is dissolved in 50ml deionized waters and obtain compounding agent solution, it is adjusted with salpeter solution
PH value is 4, is placed in 2.5L plastic beakers；Weigh 28.11g carriers A5 and pour into plastic beaker rapidly and stir and evenly mix
30min, then still aging 12h at room temperature, dries 12h in 100 DEG C of baking ovens, takes out and be calcined in 450 DEG C of air atmospheres
5h, obtain carrier B 5；
(3) measure (a) solution 15ml configured in case 1 to be added in 2.5L plastic beakers, then add 35ml
Deionized water stirs and evenly mixs；The carrier B 5 being prepared in (2) is poured into rapidly 30min is stirred and evenly mixed in plastic beaker, then
Still aging 12h at room temperature, 12h is dried under the conditions of 120 DEG C.1g sesbania powders are weighed to be dissolved in 5g deionized waters, by its with
Sample blending after drying, then pinching be pressed into bar, the cylindrical particle being molded a diameter of 4mm, particle length 8mm, then will
Resulting cylindrical particle dries 12h under the conditions of 120 DEG C, takes out and is calcined 5h in 450 DEG C of air atmospheres, obtains sample C5.
(4) 2g sodium borohydrides are weighed to be dissolved in 100ml deionized waters, are then placed in ice-water bath, by sample
C3 is added in sodium borohydride solution, stands 24h, takes out sample C3 with water washing is distilled 4 times, 12h is dried in 120 DEG C of baking ovens
Obtain catalyst D5.
Embodiment 6：
(1) by Al2O3Carrier ball milling 5h, 200 mesh sieves are crossed, then 5h is calcined in 450 DEG C of air atmospheres, obtains carrier A6；
(2) 6.61g zinc nitrate hexahydrates are weighed it is dissolved in 50ml deionized waters and obtain compounding agent solution, it is adjusted with salpeter solution
PH value is 4, is placed in 2.5L plastic beakers；Weigh 28.11g carriers A6 and pour into plastic beaker rapidly and stir and evenly mix
30min, then still aging 12h at room temperature, dries 12h in 100 DEG C of baking ovens, takes out and be calcined in 450 DEG C of air atmospheres
5h, obtain carrier B 6；
(3) measure (a) solution 15ml configured in case 1 to be added in 2.5L plastic beakers, then add 35ml
Deionized water stirs and evenly mixs；The carrier B 6 being prepared in (2) is poured into rapidly 30min is stirred and evenly mixed in plastic beaker, then
Still aging 12h at room temperature, 12h is dried under the conditions of 120 DEG C.1g sesbania powders are weighed to be dissolved in 5g deionized waters, by its with
Sample blending after drying, then pinching be pressed into bar, the cylindrical particle being molded a diameter of 4mm, particle length 8mm, then will
Resulting cylindrical particle dries 12h under the conditions of 120 DEG C, takes out and is calcined 5h in 450 DEG C of air atmospheres, obtains sample C6.
(4) 2g sodium borohydrides are weighed to be dissolved in 100ml deionized waters, are then placed in ice-water bath, by sample
C6 is added in sodium borohydride solution, stands 24h, takes out sample C6 with water washing is distilled 4 times, 12h is dried in 120 DEG C of baking ovens
Obtain catalyst D6.
Embodiment 7：
(1) by Al2O3Carrier ball milling 5h, 200 mesh sieves are crossed, then 5h is calcined in 450 DEG C of air atmospheres, obtains carrier A7；
(2) 6.3g cobalt nitrate hexahydrates are weighed it is dissolved in 50ml deionized waters and obtain compounding agent solution, it is adjusted with salpeter solution
PH value is 4, is placed in 2.5L plastic beakers；Weigh 28.11g carriers A7 and pour into plastic beaker rapidly and stir and evenly mix
30min, then still aging 12h at room temperature, dries 12h in 100 DEG C of baking ovens, takes out and be calcined in 450 DEG C of air atmospheres
5h, obtain carrier B 7；
(3) measure (a) solution 15ml configured in case 1 to be added in 2.5L plastic beakers, then add 35ml
Deionized water stirs and evenly mixs；The carrier B 7 being prepared in (2) is poured into rapidly 30min is stirred and evenly mixed in plastic beaker, then
Still aging 12h at room temperature, 12h is dried under the conditions of 120 DEG C.1g sesbania powders are weighed to be dissolved in 5g deionized waters, by its with
Sample blending after drying, then pinching be pressed into bar, the cylindrical particle being molded a diameter of 4mm, particle length 8mm, then will
Resulting cylindrical particle dries 12h under the conditions of 120 DEG C, takes out and is calcined 5h in 450 DEG C of air atmospheres, obtains sample C7.
(4) 2g sodium borohydrides are weighed to be dissolved in 100ml deionized waters, are then placed in ice-water bath, by sample
C7 is added in sodium borohydride solution, stands 24h, takes out sample C7 with water washing is distilled 4 times, 12h is dried in 120 DEG C of baking ovens
Obtain catalyst D7.
Embodiment 8：
(1) by Al2O3Carrier ball milling 5h, 200 mesh sieves are crossed, then 5h is calcined in 450 DEG C of air atmospheres, obtains carrier A8；
(2) 1.05g cobalt nitrate hexahydrates are weighed it is dissolved in 50ml deionized waters and obtain compounding agent solution, it is adjusted with salpeter solution
PH value is 4, is placed in 2.5L plastic beakers；Weigh 29.61g carriers A8 and pour into plastic beaker rapidly and stir and evenly mix
30min, then still aging 12h at room temperature, dries 12h in 100 DEG C of baking ovens, takes out and be calcined in 450 DEG C of air atmospheres
5h, obtain carrier B 8；
(3) measure (a) solution 15ml configured in case 1 to be added in 2.5L plastic beakers, then add 35ml
Deionized water stirs and evenly mixs；The carrier B 8 being prepared in (2) is poured into rapidly 30min is stirred and evenly mixed in plastic beaker, then
Still aging 12h at room temperature, 12h is dried under the conditions of 120 DEG C.1g sesbania powders are weighed to be dissolved in 5g deionized waters, by its with
Sample blending after drying, then pinching be pressed into bar, the cylindrical particle being molded a diameter of 4mm, particle length 8mm, then will
Resulting cylindrical particle dries 12h under the conditions of 120 DEG C, takes out and is calcined 5h in 450 DEG C of air atmospheres, obtains sample C8.
(4) 2g sodium borohydrides are weighed to be dissolved in 100ml deionized waters, are then placed in ice-water bath, by sample
C8 is added in sodium borohydride solution, stands 24h, takes out sample C8 with water washing is distilled 4 times, 12h is dried in 120 DEG C of baking ovens
Obtain catalyst D8.
Embodiment 9：
(1) by Al2O3Carrier ball milling 5h, 200 mesh sieves are crossed, then 5h is calcined in 450 DEG C of air atmospheres, obtains carrier A9；
(2) 6.3g cobalt nitrate hexahydrates are weighed it is dissolved in 50ml deionized waters and obtain compounding agent solution, it is adjusted with salpeter solution
PH value is 4, is placed in 2.5L plastic beakers；Weigh 28.11g carriers A9 and pour into plastic beaker rapidly and stir and evenly mix
30min, then still aging 12h at room temperature, dries 12h in 100 DEG C of baking ovens, takes out and be calcined in 450 DEG C of air atmospheres
5h, obtain carrier B 9；
(3) measure (a) solution 10ml configured in case 1 to be added in 2.5L plastic beakers, then add 40ml
Deionized water stirs and evenly mixs；The carrier B 9 being prepared in (2) is poured into rapidly 30min is stirred and evenly mixed in plastic beaker, then
Still aging 12h at room temperature, 12h is dried under the conditions of 120 DEG C.1g sesbania powders are weighed to be dissolved in 5g deionized waters, by its with
Sample blending after drying, then pinching be pressed into bar, the cylindrical particle being molded a diameter of 4mm, particle length 8mm, then will
Resulting cylindrical particle dries 12h under the conditions of 120 DEG C, takes out and is calcined 5h in 450 DEG C of air atmospheres, obtains sample C9.
(4) 2g sodium borohydrides are weighed to be dissolved in 100ml deionized waters, are then placed in ice-water bath, by sample
C9 is added in sodium borohydride solution, stands 24h, takes out sample C9 with water washing is distilled 4 times, 12h is dried in 120 DEG C of baking ovens
Obtain catalyst D9.
Embodiment 10：
(1) by Al2O3Carrier ball milling 5h, 200 mesh sieves are crossed, then 5h is calcined in 450 DEG C of air atmospheres, obtains carrier
A10；
(2) 6.3g cobalt nitrate hexahydrates are weighed it is dissolved in 50ml deionized waters and obtain compounding agent solution, it is adjusted with salpeter solution
PH value is 4, is placed in 2.5L plastic beakers；Weigh 28.11g carriers A10 and pour into plastic beaker rapidly and stir and evenly mix
30min, then still aging 12h at room temperature, dries 12h in 100 DEG C of baking ovens, takes out and be calcined in 450 DEG C of air atmospheres
5h, obtain carrier B 10；
(3) measure in case study on implementation 1 that each 3ml of (b) solution is added to 2.5L plastic beakers in (a) solution and case study on implementation 5
In, then add 47ml deionized waters and stir and evenly mix；The carrier B 10 being prepared in (2) is poured into plastic beaker rapidly
30min is stirred and evenly mixed, then still aging 12h at room temperature, 12h is dried under the conditions of 120 DEG C.Weigh 1g sesbania powders and be dissolved in 5g
In deionized water, by itself and the sample blending after drying, then pinching is pressed into bar, a diameter of 4mm of the cylindrical particle being molded,
Grain length is 8mm, then resulting cylindrical particle is dried into 12h under the conditions of 120 DEG C, takes out and is roasted in 450 DEG C of air atmospheres
5h is burnt, obtains sample C10.
(4) 2g sodium borohydrides are weighed to be dissolved in 100ml deionized waters, are then placed in ice-water bath, by sample
C10 is added in sodium borohydride solution, stands 24h, is taken out sample C10 with water washing is distilled 4 times, is dried in 120 DEG C of baking ovens
12h obtains catalyst D10.
Embodiment 11：
(1) by Al2O3Carrier ball milling 5h, 200 mesh sieves are crossed, then 5h is calcined in 450 DEG C of air atmospheres, obtains carrier
A11；
(2) 3.83g nitrate trihydrates magnesium, the water nickel nitrates of 2.33g six and 2.1g cobalt nitrate hexahydrates are weighed and is dissolved in 50ml deionizations
Compounding agent solution is obtained in water, it is 4 to adjust its pH value with salpeter solution, is placed in 2.5L plastic beakers；Weigh 29.67g loads
Body A11, which is poured into rapidly, stirs and evenly mixs 30min in plastic beaker, then still aging 12h at room temperature, is dried in 100 DEG C of baking ovens
Dry 12h, takes out and is calcined 5h in 450 DEG C of air atmospheres, obtain carrier B 11；
(3) measure in case study on implementation 1 that each 15ml of (b) solution is added to 2.5L plastic beakers in (a) solution and case study on implementation 5
In, then add 35ml deionized waters and stir and evenly mix；The carrier B 10 being prepared in (2) is poured into plastic beaker rapidly
30min is stirred and evenly mixed, then still aging 12h at room temperature, 12h is dried under the conditions of 120 DEG C.Weigh 1g sesbania powders and be dissolved in 5g
In deionized water, by itself and the sample blending after drying, then pinching is pressed into bar, a diameter of 4mm of the cylindrical particle being molded,
Grain length is 8mm, then resulting cylindrical particle is dried into 12h under the conditions of 120 DEG C, takes out and is roasted in 450 DEG C of air atmospheres
5h is burnt, obtains sample C10.
(4) 2g sodium borohydrides are weighed to be dissolved in 100ml deionized waters, are then placed in ice-water bath, by sample
C11 is added in sodium borohydride solution, stands 24h, is taken out sample C11 with water washing is distilled 4 times, is dried in 120 DEG C of baking ovens
12h obtains catalyst D11.
Embodiment 12：
(1) by Al2O3Carrier ball milling 5h, 200 mesh sieves are crossed, then 5h is calcined in 450 DEG C of air atmospheres, obtains carrier
A12；
(2) 6.3g cobalt nitrate hexahydrates are weighed it is dissolved in 50ml deionized waters and obtain compounding agent solution, it is adjusted with salpeter solution
PH value is 4, is placed in 2.5L plastic beakers；Weigh 28.11g carriers A12 and pour into plastic beaker rapidly and stir and evenly mix
30min, then still aging 12h at room temperature, dries 12h in 100 DEG C of baking ovens, takes out and be calcined in 450 DEG C of air atmospheres
5h, obtain carrier B 12；
(3) 1.66g chloroplatinic acids (platinum content 38%) are weighed to be dissolved in 100ml deionized waters, hydrochloric acid solution is added dropwise and adjusts it
PH value is 4, obtains (b) solution.Measure 15ml (b) solution to be added in 2.5L plastic beakers, then add 35ml deionizations
Water stirs and evenly mixs；The carrier B 12 being prepared in (2) is poured into rapidly 30min is stirred and evenly mixed in plastic beaker, then in room temperature
Under still aging 12h, dry 12h under the conditions of 120 DEG C.1g sesbania powders are weighed to be dissolved in 5g deionized waters, by its with after drying
Sample blending, then pinching be pressed into bar, the cylindrical particle being molded a diameter of 4mm, particle length 8mm, then will obtained by
Cylindrical particle dry 12h under the conditions of 120 DEG C, take out and be calcined 5h in 450 DEG C of air atmospheres, obtain sample C12.
(4) 2g sodium borohydrides are weighed to be dissolved in 100ml deionized waters, are then placed in ice-water bath, by sample
C12 is added in sodium borohydride solution, stands 24h, is taken out sample C12 with water washing is distilled 4 times, is dried in 120 DEG C of baking ovens
12h obtains catalyst D12.
Embodiment 13：
(1) by Al2O3Carrier ball milling 5h, 200 mesh sieves are crossed, then 5h is calcined in 450 DEG C of air atmospheres, obtains carrier
A13；
(2) 6.3g cobalt nitrate hexahydrates are weighed it is dissolved in 50ml deionized waters and obtain compounding agent solution, it is adjusted with salpeter solution
PH value is 4, is placed in 2.5L plastic beakers；Weigh 28.11g carriers A13 and pour into plastic beaker rapidly and stir and evenly mix
30min, then still aging 12h at room temperature, dries 12h in 100 DEG C of baking ovens, takes out and be calcined in 450 DEG C of air atmospheres
5h, obtain carrier B 13；
(3) measure in case study on implementation 1 that (c) solution 7.5ml is added to 2.5L modelings in (a) solution 7.5ml and case study on implementation 12
Expect in beaker, then add 35ml deionized waters and stir and evenly mix；The carrier B 13 being prepared in (2) is poured into rapidly plastics
30min is stirred and evenly mixed in beaker, then still aging 12h at room temperature, 12h is dried under the conditions of 120 DEG C.Weigh 1g sesbania powders
It is dissolved in 5g deionized waters, by itself and the sample blending after drying, then pinching is pressed into bar, and the cylindrical particle being molded is a diameter of
4mm, particle length 8mm, then resulting cylindrical particle is dried into 12h under the conditions of 120 DEG C, take out in 450 DEG C of air atmospheres
Middle roasting 5h is enclosed, obtains sample C13.
(4) 2g sodium borohydrides are weighed to be dissolved in 100ml deionized waters, are then placed in ice-water bath, by sample
C12 is added in sodium borohydride solution, stands 24h, is taken out sample C13 with water washing is distilled 4 times, is dried in 120 DEG C of baking ovens
12h obtains catalyst D13.
Comparative example
Pd/ γ-the Al that the load capacity prepared according to the method for patent application CN102320913A embodiments 2 is 0.3%2O3Urge
Agent.
Active testing：
The performance evaluation that carries out catalyst, catalysis detection are led directly in reaction tube in diameter 20mm and a length of 700mm tempering
Device is as shown in figure 1, the amount of fill of catalyst is 20ml.By embodiment under the conditions of being first 0.5MPa in 200 DEG C, hydrogen partial pressure
1~13 catalyst reduction 2h.Catalyst reaction temperatures are 230 DEG C, pressure 3MPa, liquid when volume space velocity be 2h-1, hydrogen-oil ratio
For 600.Comparative example carries out a step catalytic hydrogenation according to literature method to crude naphthalene, detect be made decahydronaphthalene it is anti-along than.Use D7
1000h life experiments are carried out with D11, the naphthane conversion ratio and decahydronaphthalene for detecting each catalyst selectively change with time,
Fig. 2 is made.The decahydronaphthalene of each catalyst is detected instead along than changing with time, Fig. 3 is made.
The catalyst activity parameter of table 1
According to testing result, compared with prior art, when active component is identical, catalyst prepared by the inventive method is urged
The decahydronaphthalene of change is instead along than with significant advantage.Especially when active component is 0.3%Pd metals, adjuvant component is 6% Co2O3,
For the decahydronaphthalene that the catalyst made from the method for the present invention is catalyzed to obtain instead along than being up to 12.7, existing market sells decahydro
Naphthalene is instead along than between 2-4, decahydronaphthalene is anti-suitable higher than its higher stability, and price is higher, and the inventive method is prepared
Catalyst performance it is excellent, can meet to require the higher market demand.
Shown by 1000h life experiments in catalytic process, the naphthane conversion ratio and decahydronaphthalene of D7 and D11 catalyst
Selectivity is maintained at more than 99% for a long time, and the anti-of the decahydronaphthalene being catalyzed becomes along than overall in what is fallen before and then tend to be steady
Gesture, when steady, catalyst D7's is anti-along than being maintained at 5.8 or so, and catalyst D11's is anti-along than being maintained at 7.5 or so, advantage compared with
To be obvious.
Claims (10)
1. a kind of naphthane Hydrogenation is for the catalyst of decahydronaphthalene, containing active component, catalyst promoter and catalyst carrier, its
Be characterised by, on the basis of the weight of catalyst, wherein, the active component be mass content be 0.05%-0.3% Pt,
One or two kinds of combination in Pd；The catalyst promoter be mass content be 1%-6% Zn, Ni, Ce, Zr, Mg, La, Fe,
One or several kinds of combinations in Cu, Co oxide；The catalyst carrier is that mass content is 93.7%-98.95%
Al2O3、SiO2、TiO2With combination one or more of in ZSM-5 molecular sieve.
2. naphthane Hydrogenation according to claim 1 is for the catalyst of decahydronaphthalene, it is characterised in that the active component
It is Pd the or Pt-Pd metallic combinations that mass content is 0.15%-0.3%, and Pd mass content is not less than 0.15%.
3. naphthane Hydrogenation according to claim 1 is for the catalyst of decahydronaphthalene, it is characterised in that the catalyst helps
Agent is CuO, MgO, ZnO, NiO, CeO, ZrO or Co that mass content is 1%-6%2O3In one or more, be preferably
Co2O3, one or more in NiO, CuO, MgO.
4. naphthane Hydrogenation according to claim 1 is for the catalyst of decahydronaphthalene, it is characterised in that the active component
It is the Pd that mass content is 0.3%, the catalyst promoter is that mass content is 2%Co2O3+ 2%NiO+2%MgO is combined；Or
Active component described in person is the Pd that mass content is 0.3%, and the catalyst promoter is mass content 6%Co2O3。
5. a kind of naphthane Hydrogenation prepared described in Claims 1 to 4 any one is for the method for the catalyst of decahydronaphthalene, its
It is characterised by, comprises the following steps：
(1) by the catalyst carrier ball milling 5h, 200 mesh sieves are crossed, 4~6h is then calcined in 400~500 DEG C of air atmospheres,
Obtain carrier A；
(2) formulation aid precursor solution, it is 1~5 to adjust its pH value with acid solution, according to incipient impregnation aequum, is taken
The maceration extract of respective amount；Carrier A is weighed again pouring into, 20~40min is stirred and evenly mixed in maceration extract, it is then still aging at room temperature
10~14h, drying, 1~10h of roasting in 400~500 DEG C of air atmospheres is taken out, obtains carrier B；
(3) noble metal precursor liquid solution is prepared, it is 1~5 to adjust its pH value with acid solution, by incipient impregnation aequum, is taken
The maceration extract of respective amount；Carrier B resulting in step (2) is poured into 20~40min is stirred and evenly mixed in maceration extract, then in room
Still aging 10~14h under temperature, drying, add suitable quantity of water and binding agent and be squeezed into bar with its kneading, the cylindrical particle being molded
A diameter of 3~5mm, particle length are 6~15mm, then resulting cylindrical particle are calcined in 400~500 DEG C of air atmospheres
1~10h, obtain sample C；
(4) reductant solution is prepared, sample C is immersed in reductant solution, stands 2-24h, takes out sample C distillation water washings
1-5 times, dried in 90~120 DEG C of baking ovens and obtain the catalyst.
6. preparation method according to claim 5, it is characterised in that step (2) adjuvant used precursor solution is Zn
(NO3)2、Ni(NO3)2、Ce(NO3)3、Mg(NO3)2、Zr(NO3)4、La(NO3)3、Fe(NO3)3、Cu(NO3)2、Co(NO3)3In
Any one or several mixed solutions, step (3) the noble metal precursor liquid solution are appointing in chloroplatinic acid, palladium chloride
Anticipate one or two kinds of mixed solution.
7. preparation method according to claim 5, it is characterised in that step (2) and (3) described acid solution are dilute salt
Any one in acid, dust technology, spirit of vinegar or several mixing, step (3) described binding agent are atlapulgite, kaolinite
One or two kinds of mixing in soil, sesbania powder.
8. preparation method according to claim 5, it is characterised in that step (4) described reducing agent be formaldehyde, hydrazine hydrate,
One or two kinds of mixing in sodium borohydride and potassium borohydride.
9. naphthane Hydrogenation described in Claims 1 to 4 any one for decahydronaphthalene catalyst in decahydronaphthalene is prepared
Using, it is characterised in that it is first that 0.5-5MPa conditions reduce 1-20h in 150-400 DEG C, hydrogen partial pressure by the catalyst.
10. application according to claim 9, it is characterised in that the reaction temperature of the catalyst is 150-400 DEG C, pressure
Power is 0.5-10MPa, liquid when volume space velocity be 0.5-8h-1, hydrogen-oil ratio 100-2000.
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