CN107626344A - A kind of catalyst, preparation and the application of crude naphthalene Hydrogenation naphthane and decahydronaphthalene - Google Patents
A kind of catalyst, preparation and the application of crude naphthalene Hydrogenation naphthane and decahydronaphthalene Download PDFInfo
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Abstract
The present invention provides a kind of catalyst of crude naphthalene Hydrogenation naphthane and decahydronaphthalene, belongs to aromatic hydrocarbon hydrogenation catalyst technical field.The catalyst includes active component, binding agent, organic additive and inorganic assistant：The active component is two or three in Ni, Mo, W, based on metal oxide, accounts for the 35%~95% of catalyst gross mass；The organic additive is water-soluble oxygenatedchemicals, and its content is the 0.1%~1% of aggregate metal oxide；The inorganic assistant is one or more mixtures in P, B, F water soluble salt or oxyacid, and content accounts for the 0.1~2% of catalyst gross mass；Remaining as bonding agent.The present invention also provides preparation method and the application of the catalyst, and the catalyst is applied in crude naphthalene Hydrogenation naphthane and decahydronaphthalene.Catalyst activity of the present invention and stability are good, and crude naphthalene conversion ratio reaches 98%, and naphthane and decahydronaphthalene selectivity sum are more than 98%；The ratio of naphthane and decahydronaphthalene in product can be adjusted according to reaction condition simultaneously.
Description
Technical field
The invention belongs to aromatic hydrocarbon hydrogenation catalyst technical field, specially a kind of crude naphthalene Hydrogenation naphthane and decahydronaphthalene
Catalyst, preparation and application.
Background technology
Naphthane, decahydronaphthalene are important Organic chemical products, and its is widely used.Naphthane is as a kind of important fine
Chemical products, the industrial circles such as paint, coating, ink, hard alloy, medicine, papermaking are can be widely applied to, be also used for production four
Hydrogen naphthalenone.Decahydronaphthalene is both to produce in polyethylene fibre dry-spinning process most as a kind of excellent high boiling organic solvent
Good solvent, and improve the essential additive of aviation kerosine heat endurance.Because naphthane, decahydronaphthalene are widely used, need
The amount of asking is very big, and supply falls short of demand at this stage, needs a large amount of imports, therefore its is expensive.
Naphthane and decahydronaphthalene are mainly made by naphthalene catalytic hydrogenation.China's coal tar oil yield is very big, has abundant naphthalene money
Source.Therefore, the higher naphthane of naphthalene catalytic hydrogenation added value and decahydronaphthalene had into important industrial significance.Naphthalene is hydrogenated with present
Decahydronaphthalene technology is produced mainly to be monopolized by foreign countries.German Degussa AG, European Chemos GmbH, du pont company, Dow
Several companies such as Chemical Ltd, Sigma-Aldrich can produce decahydronaphthalene product, and the country there is no industrialized naphthalene
Hydrogen addition technology.
Existing crude naphthalene Hydrogenation is primarily present that product is single, ingredient requirement is harsh, catalyst for naphthane or decahydronaphthalene
The defects of manufacturing process is complicated, production cost is higher, operating condition is harsh, life cycle is shorter, is unfavorable for naphthalene industrialized production
Naphthane and decahydronaphthalene.
The content of the invention
It is an object of the invention to provide the catalyst of a kind of crude naphthalene Hydrogenation naphthane and decahydronaphthalene, preparation and answer
With Catalyst Production technique of the present invention is simple, operating condition is gentle, cost is cheap, stability is good, adds it to add applied to crude naphthalene
Hydrogen is prepared in naphthane and decahydronaphthalene, by changing the ratio of naphthane and decahydronaphthalene in operating condition i.e. adjustable product, energy
It is enough to realize simultaneously.
The object of the invention is realized by following technical proposals：
It is an object of the present invention to provide a kind of crude naphthalene Hydrogenation naphthane and the catalyst of decahydronaphthalene, its feature to exist
In the catalyst includes active component, binding agent, organic additive and inorganic assistant：
The active component is two or three in Ni, Mo, W, and based on metal oxide, it is total that active component accounts for catalyst
The 35%~95% of quality；
The organic additive is water-soluble oxygenatedchemicals, and its content is the 0.1%~1% of aggregate metal oxide；
The inorganic assistant is one or more mixtures in P, B, F water soluble salt or oxyacid, and its content, which accounts for, urges
The 0.1~2% of agent gross mass；
Remaining as bonding agent.
In catalyst of the present invention, activity component metal composite oxides mainly play hydrogenation；Organic additive is then main
Play reaming；The distribution that inorganic assistant can not only improve acidity of catalyst center can also reduce the reduction difficulty of metal；
Binding agent mainly plays molding bonded.The content of above each component optimizes to obtain by test of many times, in this scope
Outer content naphthalene conversion ratio is relatively low.
Inorganic assistant and organic additive are with the addition of in catalyst of the present invention, the conversion ratio of naphthalene can be significantly improved, is reduced secondary
Reaction, the total recovery of naphthane and decahydronaphthalene is improved, and the ratio of decahydronaphthalene and naphthane can be a wide range of according to process conditions
Regulation.
As a kind of crude naphthalene Hydrogenation naphthane of the present invention and a specific embodiment of the catalyst of decahydronaphthalene,
The active component is tri- kinds of systems of Ni-Mo/Ni-W/Ni-Mo-W；In Ni-Mo/Ni-W systems, nickel oxide accounts for metal oxidation
The 10%~20% of thing gross mass, remaining as molybdenum oxide or tungsten oxide；In Ni-Mo-W systems, nickel oxide accounts for metal oxide
The 8%~26% of gross mass, molybdenum oxide accounts for the 20%~40% of metal oxide gross mass, remaining as tungsten oxide.Work as activearm
When dividing in the above range, catalyst activity is best.
As a kind of crude naphthalene Hydrogenation naphthane of the present invention and a specific embodiment of the catalyst of decahydronaphthalene,
The water-soluble oxygenatedchemicals is organic acid, alcohol, aldehyde, ketone, ester, ether.It is still more preferably EDTA, PEG, PEO, PAM, second
Alcohol, polyethylene glycol, carboxylic acid etc..Organic additive mainly plays expanding agent, forms the passage of catalyst chemical reaction, preferably has
The advantages that machine aided agent has burns fully at 450 DEG C, and aperture is suitable, contributes to naphthalene Hydrogenation naphthane and decahydronaphthalene.
As a kind of crude naphthalene Hydrogenation naphthane of the present invention and a specific embodiment of the catalyst of decahydronaphthalene,
The bonding agent be boehmite, aluminum oxide, silica, ZSM-5 molecular sieve, modenite, X molecular sieve, Y molecular sieve,
Any one or more in MCM-41 molecular sieves.Binding agent mainly plays molding bonded, may also provide certain acidity in addition
Centre bit, so as to improve the yield of naphthalene Hydrogenation decahydronaphthalene and naphthane.
As a kind of crude naphthalene Hydrogenation naphthane of the present invention and a specific embodiment of the catalyst of decahydronaphthalene,
The inorganic assistant is preferably the one or more in phosphoric acid, potassium phosphate, tetraboric acid ammonium, potassium fluoride.Inorganic assistant not only can be with
Improve the distribution at acidity of catalyst center, the reduction difficulty of metal can also be reduced, so as to improve the activity of catalyst.
The two of the object of the invention are to provide a kind of preparation side of the catalyst of crude naphthalene Hydrogenation naphthane and decahydronaphthalene
Method, comprise the following steps：
1) preparation of composite oxide of metal：It is anti-that the presoma, auxiliary agent and deionized water of active metal are placed in high pressure
Answer in kettle, product washing drying is obtained into composite oxide of metal after reaction；
2) bonding agent and auxiliary agent shaping are added：Composite oxide of metal is pulverized last addition bonding agent, there is machine aided
Agent, inorganic assistant and deionized water, mud, extruded moulding after ageing are pinched after well mixed；
3) it is calcined：Catalyst precarsor after extruded moulding is dried, finished catalyst is prepared after roasting.
Relative to existing Hydrothermal Synthesiss naphthalene hydrogenation catalyst technology of preparing, preparation method of the present invention has the advantage that：Really
The optimum range of each component is determined；Inorganic assistant and organic additive are with the addition of, so as to significantly improve the conversion ratio of naphthalene, coproduction tetrahydrochysene
Naphthalene and decahydronaphthalene, reduce side reaction, improve the total recovery of naphthane and decahydronaphthalene, and the ratio of decahydronaphthalene and naphthane can
Adjusted on a large scale according to process conditions.
One as a kind of crude naphthalene Hydrogenation naphthane of the present invention and the preparation method of the catalyst of decahydronaphthalene
Specific embodiment, the active metal presoma are nickel nitrate, nickel sulfate, nickel acetate, ammonium tungstate, the tungstates of alkali metal, molybdenum
The molybdate of sour ammonium, alkali metal.
One as a kind of crude naphthalene Hydrogenation naphthane of the present invention and the preparation method of the catalyst of decahydronaphthalene
Specific embodiment, in the preparation process of composite oxide of metal, the auxiliary agent is urea or citric acid, the temperature of the reaction under high pressure
Spend for 120~220 DEG C, the time is 4~24h；The drying temperature is 100~120 DEG C；Add bonding agent and auxiliary agent forming process
In, the powder is 150~200 mesh, and digestion time is 1~6h；In roasting process, the drying temperature is 100~120 DEG C,
Sintering temperature is 350~500 DEG C, and the time is 3~6h.
The three of the object of the invention are to provide a kind of application of the catalyst of crude naphthalene Hydrogenation naphthane and decahydronaphthalene, institute
State application of the catalyst in crude naphthalene Hydrogenation naphthane and decahydronaphthalene.
One as the application of a kind of crude naphthalene Hydrogenation naphthane of the present invention and the catalyst of decahydronaphthalene is specific
Embodiment, the catalyst need to pre-process through sulfide before applying in crude naphthalene Hydrogenation naphthane and decahydronaphthalene, vulcanization behaviour
As：Catalyst handles 8~36h through sulfide at 240~360 DEG C, wherein, sulfide is DMDS, carbon disulfide, second
One or more combinations in mercaptan, isopropyl mercaptan, thioanisole.
Specifically, conditions of vulcanization is：1.5~6Mpa of hydrogen partial pressure, 240~360 DEG C of reaction temperature, volume space velocity 0.5~
4h-1, hydrogen-oil ratio 200~1000:1,8~36h of cure time.
One as the application of a kind of crude naphthalene Hydrogenation naphthane of the present invention and the catalyst of decahydronaphthalene is specific
Embodiment, the operating condition that the catalyst is applied in crude naphthalene Hydrogenation naphthane and decahydronaphthalene are：Reaction temperature 200~
400 DEG C, 2~9Mpa of hydrogen partial pressure, 1~10h of liquid air speed-1, hydrogen-oil ratio 300~1500:1.This operating condition is announced for the present invention
Catalyst optimum range：Under conditions of low temperature, low pressure, low hydrogen/gasoline ratio, high-speed, product is based on naphthane；And
Under conditions of high temperature, high pressure, high hydrogen-oil ratio, low-speed, product is based on decahydronaphthalene.The ratio of naphthane and decahydronaphthalene can pass through
The change of above operating condition and adjust.
One as the application of a kind of crude naphthalene Hydrogenation naphthane of the present invention and the catalyst of decahydronaphthalene is specific
Embodiment, the catalyst apply naphthane and decahydro in resulting product in crude naphthalene Hydrogenation naphthane and decahydronaphthalene
The mol ratio of naphthalene is 0.05~8.
Compared with prior art, the invention has the advantages that：
1st, catalyst activity of the present invention and stability are good, and life cycle was applicable to plurality of raw materials naphthalene more than 1 year, including
Crude naphthalene and refined naphthalene, naphthalene conversion ratio 98%, naphthane and decahydronaphthalene selectivity sum are more than 98%；It can be grasped simultaneously according to reaction
Make the ratio of naphthane and decahydronaphthalene in condition regulation product, make the mol ratio of naphthane and decahydronaphthalene between 0.05~8.
2nd, catalyst of the present invention solve in the prior art naphthalene Hydrogenation for naphthane and decahydronaphthalene conversion ratio be low, catalyst
The problem of life cycle is short, catalyst manufacturing process complexity, overcome that naphthalene hydrogenation products are single and the shortcomings that ingredient requirement harshness,
Make naphthalene hydrogenation products ratio adjustable, be advantageous to industrialized production.
3rd, the preparation technology of catalyst of the present invention is simple, science, and easy to operate, equipment is simple, and cost of investment is low.
Brief description of the drawings
Fig. 1 is that catalyst activity of the embodiment of the present invention determines schematic device.
Reference：1- stock bottles, 2- plunger pumps, 3- valves, 4- mass flowmenters, 5- triple valves, 6- pressure gauges, 7- are anti-
Answer device, 8- condensers, 9- gas-liquid separators, 10- counterbalance valves, 11- products, 12- Drexel bottles.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that specific embodiment described herein is only to explain the present invention, not
For limiting the present invention.
The present embodiment catalyst activity evaluating apparatus using micro fixed-bed reactor as shown in figure 1, evaluated.It is reacted
Primary product has the accessory substances such as naphthane, decahydronaphthalene and micro isopropylbenzene, ethyl cyclohexane, ethylbenzene.The evaluation of reaction product
Analyzed using the chromatograph of Agilent 7820, chromatographic column used is OV101 type chromatographic columns.In the present invention, wt.% is mass fraction.
The conversion ratio of naphthalene, naphthane selectivity and decahydronaphthalene selectivity calculation formula are as follows：
The quality of naphthalene point in the conversion ratio of naphthalene=(mass fraction of naphthalene in mass fraction-product of naphthalene in raw material)/raw material
Number * 100%
The molar fraction * 100% of the molar fraction of naphthane/naphthalene conversion in naphthane selectivity=product
The molar fraction * 100% of the molar fraction of decahydronaphthalene/naphthalene conversion in decahydronaphthalene selectivity=product
Raw material in the implementation case derives from commercially available.
Embodiment 1
The preparation of the present embodiment catalyst and application detailed process are as follows：
1st, the preparation of catalyst：Weigh basic nickel carbonate 5.01g (3g nickel oxide), (26g is aoxidized ammonium metatungstate 30.24g
Tungsten) deionized water 100g, citric acid 0.2g in autoclave, react 8h under the conditions of 140 DEG C.Reaction product is passed through into filtering
After taking-up, dried after being washed with deionized 3-4 times under the conditions of 120 DEG C.The metal oxide of drying is ground into 150-200
Mesh powder, add 0.22g ammonium phosphate, 0.3gPEO (polyoxyethylene), 2gZSM-5 molecular sieves, and a certain amount of deionization
Mud (amount of deionized water is depending on the requirement of extrusion) is pinched after water, kneaded walk is aged extrusion after 2h, and extrusion specification is ∮
1.3 × 2-8mm trifolium-shapeds.Extrusion is after 120 DEG C of conditions are dried, finally 500 DEG C of roasting 4h, i.e. finished product in Muffle furnace
Trifolium-shaped catalyst, catalyst gross mass is 30.9g.
Activity component metal oxide accounts for the 93.9% of catalyst total amount in the catalyst of above-mentioned preparation, elemental phosphorous to account for catalysis
The 0.11% of agent gross mass, remainder are binding agent.In metal oxide, nickel oxide accounts for aggregate metal oxide
10.3%, remaining as tungsten oxide, the PEO of addition accounts for the 1% of metal oxide component.
2nd, the vulcanization of catalyst：Above-mentioned catalyst 10ml is loaded in fixed bed reactors, the paving each up and down of catalyst
Quartz sand thick one layer of 2cm.After filling catalyst, at the DMDS/cyclohexane solution vulcanization for being 5% with mass fraction
Reason, 240 DEG C of vulcanization 36h, vulcanization liquid air speed 1h-1, hydrogen/oil is than being 700:1, hydrogen partial pressure 4Mpa.
3rd, catalyst activity is evaluated：After vulcanization terminates, hydrogen is passed through to setting reaction pressure after nitrogen purging 1h.Naphthalene is molten
Naphthalene/cyclohexane solution that mass fraction is 10% is configured in hexamethylene, then squeezes into the fixed bed reaction with plunger pump
In device.Naphthalene used is crude naphthalene, and the content of naphthalene is with C10H895% is calculated as, the content of sulphur indene compounds is 3%, and inorganic salts contain
Measure as 2%.Reaction condition is as follows：300 DEG C of reaction temperature, hydrogen partial pressure 5Mpa, liquid air speed 1h-1, hydrogen-oil ratio 800:1.Reaction
After 24h, its product is analyzed, calculates the conversion ratio of naphthalene, the selectivity of naphthane, decahydronaphthalene selectivity.The experimental result such as institute of table 1
Show.
Embodiment 2
The preparation of the present embodiment catalyst and application detailed process are as follows：
1st, the preparation of catalyst：Weigh basic nickel carbonate 8.35g (5g nickel oxide), ammonium molybdate 26.97g (22g molybdenum oxides),
Deionized water 100g, urea 0.4g react 12h in autoclave under the conditions of 180 DEG C.Reaction product is taken out by filtering
Afterwards, dried after being washed with deionized 3-4 times under the conditions of 120 DEG C.The metal oxide of drying is ground into 150-200 purposes
Powder, 5.5g phosphoric acid (concentration 85%) is added, 0.03gPEG (polyvinyl alcohol), (400 DEG C of burn tinctuers are about for 65g boehmites
20%) mud, and after a certain amount of deionized water is pinched, kneaded walk is aged extrusion after 2h, and extrusion specification is 1.3 × 2- of ∮
8mm trifolium-shapeds.Extrusion after 120 DEG C of conditions are dried, finally in Muffle furnace 350 DEG C of roastings 4h, i.e. finished product three leaves
Careless type catalyst, catalyst gross mass are 76.8g.
Activity component metal oxide accounts for the 35.1% of catalyst total amount in the catalyst of above-mentioned preparation, elemental phosphorous to account for catalysis
The 1.9% of agent gross mass, remainder are binding agent.In metal oxide, nickel oxide accounts for aggregate metal oxide
18.5%, remaining as molybdenum oxide, addition organic additive PEG accounts for the 0.11% of metal oxide component.
2nd, the vulcanization of catalyst：Above-mentioned catalyst 10ml is loaded in fixed bed reactors, the paving each up and down of catalyst
Quartz sand thick one layer of 2cm.After filling catalyst, at the carbon disulfide/cyclohexane solution vulcanization for being 5% with mass fraction
Reason, 360 DEG C of vulcanization 8h, vulcanization liquid air speed 1h-1, hydrogen/oil is than being 700:1, hydrogen partial pressure 3Mpa.
3rd, catalyst activity is evaluated：After vulcanization terminates, hydrogen is passed through to setting reaction pressure after nitrogen purging 1h.Naphthalene is molten
Naphthalene/cyclohexane solution that mass fraction is 10% is configured in hexamethylene, then squeezes into the fixed bed reaction with plunger pump
In device.Naphthalene used is crude naphthalene, and the content of naphthalene is with C10H895% is calculated as, the content of sulphur indene compounds is 3%, and inorganic salts contain
Measure as 2%.Reaction condition is as follows：300 DEG C of reaction temperature, hydrogen partial pressure 5Mpa, liquid air speed 1h-1, hydrogen-oil ratio 600:1.Reaction
After 24h, its product is analyzed, calculates the conversion ratio of naphthalene, the selectivity of naphthane, decahydronaphthalene selectivity.The experimental result such as institute of table 1
Show.
Embodiment 3
The present embodiment is the comparative example of embodiment 2, does not add inorganic assistant phosphoric acid on the basis of embodiment 2 and has machine aided
Agent PEG, other operations are completely the same with embodiment 2, investigate organic and influence of the inorganic assistant to catalyst performance.
The preparation of the present embodiment catalyst and application detailed process are as follows：
1st, the preparation of catalyst：Weigh basic nickel carbonate 8.35g (5g nickel oxide), ammonium molybdate 26.97g (22g molybdenum oxides),
Deionized water 100g, urea 0.4g react 12h in autoclave under the conditions of 180 DEG C.Reaction product is taken out by filtering
Afterwards, dried after being washed with deionized 3-4 times under the conditions of 120 DEG C.The metal oxide of drying is ground into 150-200 purposes
Powder, 65g boehmites (400 DEG C of burn tinctuers about 20%) are being added, and mud is pinched after a certain amount of deionized water, it is kneaded
Walk ageing 2h after extrusion, extrusion specification is ∮ 1.3 × 2-8mm trifolium-shapeds.Extrusion finally exists after 120 DEG C of conditions are dried
350 DEG C of roastings 4h, i.e. finished product trifolium-shaped catalyst in Muffle furnace, catalyst gross mass is 74.9g.
Activity component metal oxide accounts for the 36% of catalyst total amount in the catalyst of above-mentioned preparation, and remainder is bonding
Agent.In metal oxide, nickel oxide accounts for the 18.5% of aggregate metal oxide, remaining as molybdenum oxide.
2nd, the vulcanization of catalyst：With example 2.
3rd, catalyst activity is evaluated：With example 2.Activity evaluation is as shown in table 1.
Embodiment 4
The present embodiment is the comparative example of embodiment 2, does not add the other operations of inorganic assistant phosphoric acid on the basis of embodiment 2
It is completely the same with embodiment 2, investigate influence of the inorganic assistant to catalyst performance.
The preparation of the present embodiment catalyst and application detailed process are as follows：
1st, the preparation of catalyst：Weigh basic nickel carbonate 8.35g (5g nickel oxide), ammonium molybdate 26.97g (22g molybdenum oxides),
Deionized water 100g, urea 0.4g react 12h in autoclave under the conditions of 180 DEG C.Reaction product is taken out by filtering
Afterwards, dried after being washed with deionized 3-4 times under the conditions of 120 DEG C.The metal oxide of drying is ground into 150-200 purposes
Powder, add 0.03gPEG (polyvinyl alcohol), 65g boehmites (400 DEG C of burn tinctuers about 20%), and it is a certain amount of go from
Mud is pinched after sub- water, kneaded walk is aged extrusion after 2h, and extrusion specification is ∮ 1.3 × 2-8mm trifolium-shapeds.Extrusion is at 120 DEG C
Condition drying after, finally in Muffle furnace 350 DEG C roasting 4h, i.e. finished product trifolium-shaped catalyst, catalyst gross mass
For 75g.
Activity component metal oxide accounts for catalyst total amount 36% in the catalyst of above-mentioned preparation, and remainder is bonding
Agent.In metal oxide, nickel oxide accounts for the 18.5% of aggregate metal oxide, remaining as molybdenum oxide, addition organic additive PEG
Account for the 0.11% of metal oxide component.
2nd, the vulcanization of catalyst：With example 2
3rd, catalyst activity is evaluated：With example 2.Activity evaluation is as shown in table 1.
Embodiment 5
The present embodiment is the comparative example of embodiment 2, does not add organic additive PEG, other operations on the basis of embodiment 2
It is completely the same with embodiment 2, investigate influence of the organic additive to catalyst performance
Metal oxide accounts for the 35.2% of catalyst total amount, elemental phosphorous to account for the 1.9% of catalyst gross mass, and remainder is
Binding agent.In metal oxide, nickel oxide accounts for the 18.5% of aggregate metal oxide, remaining as molybdenum oxide.
The preparation of the present embodiment catalyst and application detailed process are as follows：
1st, the preparation of catalyst：Weigh basic nickel carbonate 8.35g (5g nickel oxide), ammonium molybdate 26.97g (22g molybdenum oxides),
Deionized water 100g, urea 0.4g react 12h in autoclave under the conditions of 180 DEG C.Reaction product is taken out by filtering
Afterwards, dried after being washed with deionized 3-4 times under the conditions of 120 DEG C.The metal oxide of drying is ground into 150-200 purposes
Powder, 5.5g phosphoric acid (concentration 85%), 65g boehmites (400 DEG C of burn tinctuers about 20%) are being added, and a certain amount of gone
Mud is pinched after ionized water, kneaded walk is aged extrusion after 2h, and extrusion specification is ∮ 1.3 × 2-8mm trifolium-shapeds.Extrusion is 120
After the drying of DEG C condition, finally in Muffle furnace 350 DEG C of roastings 4h, i.e. finished product trifolium-shaped catalyst, the total matter of catalyst
Measure as 76.6g.
Activity component metal oxide accounts for the 35.2% of catalyst total amount in the catalyst of above-mentioned preparation, elemental phosphorous to account for catalysis
The 1.9% of agent gross mass, remainder are binding agent.In metal oxide, nickel oxide accounts for aggregate metal oxide
18.5%, remaining as molybdenum oxide,.
2nd, the vulcanization of catalyst：With example 2.
3rd, catalyst activity is evaluated：With example 2.Activity evaluation is as shown in table 1.
Embodiment 6
The preparation of the present embodiment catalyst and application detailed process are as follows：
1st, the preparation of catalyst：Weigh nickel nitrate 19.39g (5g nickel oxide), ammonium molybdate 9.81g (8g molybdenum oxides), inclined tungsten
Sour ammonium 19.77g (17g tungsten oxides), deionized water 100g, urea 0.5g react 8h in autoclave under the conditions of 150 DEG C.
After reaction product is taken out by filtering, dried after being washed with deionized 3-4 times under the conditions of 120 DEG C.The metal oxygen of drying
Compound is ground into 150-200 mesh powders, is adding 2.2g phosphoric acid (concentration 85%), 0.3gPAM (polypropylene amine), 30g SB
Powder (400 DEG C of burn tinctuers about 20%), and mud is pinched after a certain amount of deionized water, extrusion after kneaded walk ageing 2h, squeeze
Bar specification is ∮ 1.3 × 2-8mm trifolium-shapeds.Extrusion is after 120 DEG C of conditions are dried, last 400 DEG C of roasting 4h in Muffle furnace,
That is the trifolium-shaped catalyst of finished product, catalyst gross mass are 51.6g.
Activity component metal oxide accounts for the 58.1% of catalyst total amount in the catalyst of above-mentioned preparation, elemental phosphorous to account for catalysis
The 1.1% of agent gross mass, remainder are binding agent.In metal oxide, nickel oxide accounts for aggregate metal oxide
16.7%, molybdenum oxide accounts for the 26.7% of aggregate metal oxide, and remaining as molybdenum oxide, addition organic additive PAM accounts for metal oxidation
The 1% of thing component.
2nd, the vulcanization of catalyst：Above-mentioned catalyst 10ml is loaded in fixed bed reactors, the paving each up and down of catalyst
Quartz sand thick one layer of 2cm.After filling catalyst, at the carbn disulfide/cyclohexane solution vulcanization for being 5% with mass fraction
Reason, 320 DEG C of vulcanization 24h, vulcanization liquid air speed 1h-1, hydrogen/oil is than being 700:1, hydrogen partial pressure 4Mpa.
3rd, catalyst activity is evaluated：After vulcanization terminates, hydrogen is passed through to setting reaction pressure after nitrogen purging 1h.Naphthalene is molten
Naphthalene/cyclohexane solution that mass fraction is 10% is configured in hexamethylene, then squeezes into the fixed bed reaction with plunger pump
In device.The content of the naphthalene is with C10H8It is calculated as 99%.Reaction condition is as follows：300 DEG C of reaction temperature, hydrogen partial pressure 5Mpa, liquid air
Fast 1h-1, hydrogen-oil ratio 600:1.After reacting 24h, its product is analyzed, calculates the conversion ratio of naphthalene, the selectivity of naphthane, decahydronaphthalene
Selectivity.Experimental result is as shown in table 1.
Embodiment 7
The preparation of the present embodiment catalyst and application detailed process are as follows：
1st, the preparation of catalyst：Weigh basic nickel carbonate 15.51g (4g nickel oxide), (10g is aoxidized ammonium molybdate 12.26g
Molybdenum), ammonium metatungstate 23.26g (20g tungsten oxides), deionized water 100g, urea 0.4g in autoclave, under the conditions of 150 DEG C
React 8h.After reaction product is taken out by filtering, dried after being washed with deionized 3-4 times under the conditions of 120 DEG C.Drying
Metal oxide is ground into 150-200 mesh powders, is adding 2.7g phosphoric acid (concentration 85%), 0.3gPAM (polyacrylamides
Amine), 20g SB powder (400 DEG C of burn tinctuers about 20%), and pinched after a certain amount of deionized water mud (amount of deionized water according to squeeze
Depending on the requirement of bar), kneaded walk ageing 2h after extrusion, extrusion specification is ∮ 1.3 × 2-8mm trifolium-shapeds.Extrusion exists
After 120 DEG C of condition drying, finally 400 DEG C of trifolium-shaped catalyst for being calcined 4h, i.e. finished product, catalyst are total in Muffle furnace
Quality is 48.2g.
Metal oxide accounts for the 70.5% of catalyst total amount in the catalyst of above-mentioned preparation, elemental phosphorous to account for catalyst gross mass
1.5%, remainder is binding agent.In metal oxide, nickel oxide accounts for the 11.8% of aggregate metal oxide, molybdenum oxide
The 29.4% of aggregate metal oxide is accounted for, residual metallic oxide is molybdenum oxide.Addition organic additive PAM accounts for metal oxide group
0.88% divided.
2nd, the vulcanization of catalyst：Above-mentioned catalyst 10ml is loaded in fixed bed reactors, the paving each up and down of catalyst
Quartz sand thick one layer of 2cm.After filling catalyst, at the carbn disulfide/cyclohexane solution vulcanization for being 5% with mass fraction
Reason, 320 DEG C of vulcanization 24h, vulcanization liquid air speed 1h-1, hydrogen/oil is than being 700:1, hydrogen partial pressure 4Mpa.
3rd, catalyst activity is evaluated：After vulcanization terminates, hydrogen is passed through to setting reaction pressure after nitrogen purging 1h.Naphthalene is molten
Naphthalene/cyclohexane solution that mass fraction is 10% is configured in hexamethylene, then squeezes into the fixed bed reaction with plunger pump
In device.Naphthalene used is crude naphthalene, and the content of naphthalene is with C10H895% is calculated as, the content of sulphur indene compounds is 3%, and inorganic salts contain
Measure as 2%.Reaction condition is as follows：300 DEG C of reaction temperature, hydrogen partial pressure 5Mpa, liquid air speed 1h-1, hydrogen-oil ratio 600:1.React 24h
Afterwards, its product is analyzed, calculates the conversion ratio of naphthalene, the selectivity of naphthane, decahydronaphthalene selectivity.Experimental result is as shown in table 1.
Embodiment 8
The present embodiment is comparative example, on the basis of embodiment 7, adjusts the addition of active metal component, makes preparation
Metal oxide content is the 25.1% of catalyst total amount in catalyst, investigates shadow of the reactive metal oxides to catalyst performance
Ring.
The preparation of the present embodiment catalyst and application detailed process are as follows：
1st, the preparation of catalyst：Weigh basic nickel carbonate 15.51g (4g nickel oxide), (10g is aoxidized ammonium molybdate 12.26g
Molybdenum), ammonium metatungstate 23.26g (20g tungsten oxides), deionized water 100g, urea 0.4g in autoclave, under the conditions of 150 DEG C
React 8h.After reaction product is taken out by filtering, dried after being washed with deionized 3-4 times under the conditions of 120 DEG C.Drying
Metal oxide is ground into 150-200 mesh powders, add 7.6g phosphoric acid (concentration 85%), 0.3gPAM (polypropylene amine),
130g SB powder (400 DEG C of burn tinctuers about 20%), and mud is pinched after a certain amount of deionized water (amount of deionized water is according to extrusion
Requirement depending on), kneaded walk ageing 2h after extrusion, extrusion specification is ∮ 1.3 × 2-8mm trifolium-shapeds.Extrusion is 120
After the drying of DEG C condition, finally in Muffle furnace 400 DEG C of roastings 4h, i.e. finished product trifolium-shaped catalyst, the total matter of catalyst
Measure as 135.4g.
Metal oxide accounts for the 25.1% of catalyst total amount in the catalyst of above-mentioned preparation, elemental phosphorous to account for catalyst gross mass
1.5%, remainder is binding agent.In metal oxide, nickel oxide accounts for the 11.8% of aggregate metal oxide, molybdenum oxide
The 29.4% of aggregate metal oxide is accounted for, residual metallic oxide is molybdenum oxide.Addition organic additive PAM accounts for metal oxide group
0.88% divided.
2nd, the vulcanization of catalyst：With example 7.
3rd, catalyst activity is evaluated：With example 7.Experimental result is as shown in table 1.
Embodiment 9
The preparation of the present embodiment catalyst and application detailed process are as follows：
1st, the preparation of catalyst：With example 7.
2nd, the vulcanization of catalyst：With example 7.
3rd, catalyst activity is evaluated：After vulcanization terminates, hydrogen is passed through to setting reaction pressure after nitrogen purging 1h.Naphthalene is molten
Naphthalene/cyclohexane solution that mass fraction is 10% is configured in hexamethylene, then squeezes into the fixed bed reaction with plunger pump
In device.The content of the naphthalene is with C10H895% is calculated as, the content of sulphur indene compounds is 3%, and the content of inorganic salts is 2%.Instead
Answer condition as follows：280 DEG C of reaction temperature, hydrogen partial pressure 3.5Mpa, liquid air speed 4h-1, hydrogen-oil ratio 500:1.After reacting 24h, analysis
Its product, calculate the conversion ratio of naphthalene, the selectivity of naphthane, decahydronaphthalene selectivity.Experimental result is as shown in table 1.
Embodiment 10
The preparation of the present embodiment catalyst and application detailed process are as follows：
1st, the preparation of catalyst：With example 7.
2nd, the vulcanization of catalyst：With example 7.
3rd, catalyst activity is evaluated：After vulcanization terminates, hydrogen is passed through to setting reaction pressure after nitrogen purging 1h.Naphthalene is molten
Naphthalene/cyclohexane solution that mass fraction is 10% is configured in hexamethylene, then squeezes into the fixed bed reaction with plunger pump
In device.The content of the naphthalene is with C10H895% is calculated as, the content of sulphur indene compounds is 3%, and the content of inorganic salts is 2%.Instead
Answer condition as follows：260 DEG C of reaction temperature, hydrogen partial pressure 3Mpa, liquid air speed 6h-1, hydrogen-oil ratio 300:1.After reacting 24h, it is analyzed
Product, calculate the conversion ratio of naphthalene, the selectivity of naphthane, decahydronaphthalene selectivity.Experimental result is as shown in table 1.
, will in order to further illustrate beneficial effect of the catalyst of the present invention in crude naphthalene Hydrogenation for naphthane and decahydronaphthalene
The Ni-Mo/Al of catalyst of the present invention and Hangzhou Refinery2O3Catalyst and RN10 catalyst are contrasted, according to this with implementation
The identical of example 4 vulcanizes and activity rating condition, and research different catalysts carry out the performance of crude naphthalene hydrogenation.Different catalysts are through sulphur
Activity evaluation is as shown in table 1 below after change.
The Activity evaluation of the different catalysts of table 1
From upper table 1 as can be seen that the inventive method be prepared catalyst (embodiment 1, embodiment 2, embodiment 6,
Embodiment 7, embodiment 9 and embodiment 10) conversion ratio of crude naphthalene can be made to reach more than 99.3%, even up to 100%.When not
Adding inorganic or organic additive (embodiment 3, embodiment 4 and embodiment 5) makes to be decreased obviously the activity of catalyst, meanwhile,
The addition of inorganic assistant and organic additive also has a significant impact to the selectivity of naphthane in product and decahydronaphthalene, mainly due to
Inorganic or organic additive addition can cause to change to the microstructure of catalyst, so as to influence the selection of naphthane and decahydronaphthalene
Property.Metal active oxide content, which reduces (embodiment 8), also can decline the conversion ratio of naphthalene, while influence the selectivity of product.
Identical catalyst is used from embodiment 9 and embodiment 10 as can be seen that working as, in the product that different reaction conditions is prepared,
The mol ratio of naphthane and decahydronaphthalene also has a large change, and the mol ratio of naphthane and decahydronaphthalene can be from product of the present invention
It is adjusted, can be selected according to the demand of specific product between 0.05~8.
According to Ni-Mo/Al2O3The contrast of catalyst and RN10 catalyst, it can be clearly seen that catalyst performance of the present invention
Better than existing catalyst, its conversion ratio to naphthalene significantly improves, while in the product prepared there is bigger mol ratio to adjust
Adjusting range, it is 4~7.5 that RN10 catalyst, which is used for the molar ratio range of naphthane and decahydronaphthalene in crude naphthalene hydrogenation, controllability
It is not high.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement made within refreshing and principle etc., should be included in the scope of the protection.
Claims (10)
1. the catalyst of a kind of crude naphthalene Hydrogenation naphthane and decahydronaphthalene, it is characterised in that the catalyst includes activearm
Point, binding agent, organic additive and inorganic assistant：
The active component is two or three in Ni, Mo, W, and based on metal oxide, active component accounts for catalyst gross mass
35%~95%；
The organic additive is water-soluble oxygenatedchemicals, and its content is the 0.1%~1% of aggregate metal oxide；
The inorganic assistant is one or more mixtures in P, B, F water soluble salt or oxyacid, in terms of element, its content
Account for the 0.1~2% of catalyst gross mass；
Remaining as bonding agent.
A kind of 2. catalyst of crude naphthalene Hydrogenation naphthane and decahydronaphthalene as claimed in claim 1, it is characterised in that the work
Property component is tri- kinds of systems of Ni-Mo/Ni-W/Ni-Mo-W；In Ni-Mo/Ni-W systems, nickel oxide accounts for the total matter of metal oxide
The 10%~20% of amount, remaining as molybdenum oxide or tungsten oxide；In Ni-Mo-W systems, nickel oxide accounts for metal oxide gross mass
8%~26%, molybdenum oxide accounts for the 20%~40% of metal oxide gross mass, remaining as tungsten oxide.
A kind of 3. catalyst of crude naphthalene Hydrogenation naphthane and decahydronaphthalene as claimed in claim 1, it is characterised in that the water
Dissolubility oxygenatedchemicals is organic acid, alcohol, aldehyde, ketone, ester, ether.
4. a kind of catalyst of crude naphthalene Hydrogenation naphthane and decahydronaphthalene as claimed in claim 1, it is characterised in that described viscous
Agent is connect as boehmite, aluminum oxide, silica, ZSM-5 molecular sieve, modenite, X molecular sieve, Y molecular sieve, MCM-41
Any one or more in molecular sieve.
5. a kind of preparation method of the catalyst of crude naphthalene Hydrogenation naphthane and decahydronaphthalene as claimed in claim 1, its feature
It is, comprises the following steps：
1) preparation of composite oxide of metal：By the presoma, auxiliary agent and deionized water of active metal as autoclave
In, product washing drying is obtained into composite oxide of metal after reaction；
2) bonding agent and auxiliary agent shaping are added：Composite oxide of metal is pulverized last addition bonding agent, organic additive, nothing
Machine aided agent and deionized water, mud, extruded moulding after ageing are pinched after well mixed；
3) it is calcined：Catalyst precarsor after extruded moulding is dried, finished catalyst is prepared after roasting.
6. a kind of preparation method of the catalyst of crude naphthalene Hydrogenation naphthane and decahydronaphthalene as claimed in claim 5, its feature
It is, in the preparation process of composite oxide of metal, the auxiliary agent is urea or citric acid, and the temperature of the reaction under high pressure is
120~220 DEG C, the time is 4~24h；The drying temperature is 100~120 DEG C；Add in bonding agent and auxiliary agent forming process,
The powder is 150~200 mesh, and digestion time is 1~6h；In roasting process, the drying temperature is 100~120 DEG C, roasting
Temperature is 350~500 DEG C, and the time is 3~6h.
A kind of 7. application of the catalyst of crude naphthalene Hydrogenation naphthane and decahydronaphthalene as claimed in claim 1, it is characterised in that
Application of the catalyst in crude naphthalene Hydrogenation naphthane and decahydronaphthalene.
A kind of 8. application of the catalyst of crude naphthalene Hydrogenation naphthane and decahydronaphthalene as claimed in claim 7, it is characterised in that
The catalyst needs to pre-process through sulfide before applying in crude naphthalene Hydrogenation naphthane and decahydronaphthalene, and vulcanisation operation is：Urge
Agent handles 8~36h through sulfide at 240~360 DEG C, wherein, sulfide is DMDS, carbon disulfide, ethyl mercaptan, different
One or more combinations in propanethiol, thioanisole.
A kind of 9. application of the catalyst of crude naphthalene Hydrogenation naphthane and decahydronaphthalene as claimed in claim 7, it is characterised in that
The operating condition that the catalyst is applied in crude naphthalene Hydrogenation naphthane and decahydronaphthalene is：200~400 DEG C of reaction temperature,
2~9Mpa of hydrogen partial pressure, 1~10h of liquid air speed-1, hydrogen-oil ratio 300~1500:1.
10. a kind of application of the catalyst of crude naphthalene Hydrogenation naphthane and decahydronaphthalene as claimed in claim 1, its feature exist
Naphthane and decahydronaphthalene in resulting product are applied in crude naphthalene Hydrogenation naphthane and decahydronaphthalene in, the catalyst
Mol ratio is 0.05~8.
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