CN106492859B - A kind of surface Modified Nickel system sulfur resistive hydrogenation catalyst and preparation method thereof - Google Patents
A kind of surface Modified Nickel system sulfur resistive hydrogenation catalyst and preparation method thereof Download PDFInfo
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- CN106492859B CN106492859B CN201611056159.0A CN201611056159A CN106492859B CN 106492859 B CN106492859 B CN 106492859B CN 201611056159 A CN201611056159 A CN 201611056159A CN 106492859 B CN106492859 B CN 106492859B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Abstract
A kind of surface Modified Nickel system sulfur resistive hydrogenation catalyst and preparation method thereof, belongs to nickel catalyst technical field.It is characterized by: the catalyst includes the complex compound shielded layer for having the surface of predetermined size and the inorganic oxide carrier of hole and being suitable for interacting with the surface and size is interacted by carrier and active metal.By applying on shielded layer to the surface and hole of carrier and active component, shielded layer complex compound is converted to or mixtures thereof metal, metal oxide by being calcined, sulfur resistive reduced state nickel series catalysts are prepared by hydrogen reducing.The activity of contained protection metal component in catalyst is greatly improved, the content of protection metal is reduced, ensure that the quantity in the activated centre of catalyst metals.
Description
Technical field
A kind of surface Modified Nickel system sulfur resistive hydrogenation catalyst and preparation method thereof, belongs to nickel catalyst technical field.
Background technique
Contain sulphur, nitrogen, oxygen and metal impurities in petroleum distillate, the presence of these impurity not only will affect the property of oil product
Matter, and the pernicious gas of pollution environment can be released during use, reduce activity and the service life of catalyst.With stone
Petroleum hydrocarbon class is in the hydroprocessing processes of raw material, and raw material is reacted under high-temperature and high-pressure conditions with hydrogen, to deviate from raw material
Harmful substance, such as organic sulfur compound, organic nitrogen compound and organo-metallic compound etc..
Sulphur is one of most important poisonous substance of reduction-state catalyst, and different amounts of sulphur is contained in petroleum.With adding hydrogen
Technology is popularized, and sulfur content of raw material is also further increasing.Desulfurization unit effect is deteriorated, and sulphur is made to enter follow-up hydrogenation system
Most direct sources are to be made the organic sulfur hydrogenolysis in raw material incomplete extremely due to hydroconversion condition most of the time, lead to reduction-state
Catalyst poisoning deactivation phenomenom；It may also be since substantial increase causes hydrodesulfurization energy to the sulfur content in raw material in a short time
Power deficiency causes sulfur poisoning.
Form existing for sulphur is sufficiently complex, is broadly divided into organic sulfur and inorganic sulfur.Common desulfurization process is first to use to add
Organic sulfur is decomposed into inorganic sulfur H by hydrogen catalyst2S.The desulfurization precision of existing commercial plant can generally be less than 0.5 × 10-6
Or less than 0.2 × 10-6Level, remaining Determination of Trace Sulfur enters follow-up hydrogenation system., with regard to currently used reduction-state catalyst
For, sulfur content is less than 0.1 × 10 in raw material-5When, it can guarantee that reduction-state hydrogenation catalyst normally plays activity, still, such as
The sulfur content that fruit enters hydrogenation system catalyst bed is exceeded, it will reforming catalyst is caused to be poisoned.
The poisoning of reduced state nickel series catalysts is commonly considered as hydrogen sulfide and is reacted with the active component nickel of catalyst:
3Ni+ 2H2S= Ni3S2+2H2
Hydrogen sulfide makes active nickel become inactive Ni3S2, thus inactivate the decline of reforming catalyst activity even.By
The experimental analysis of catalyst producer, under the high temperature conditions, the sulphur for containing only 0.005% has shown that poisoning to nickeliferous 15% catalyst
Sign, when sulphur reaches 0.015%, the coverage rate of nickel surface sulphur reaches 44%, and relative activity is only left 20%.Therefore, nickel poisoning
The new theory of mechanism is thought: entering after catalyst bed after first carrying out decomposition reaction containing sulfur feedstock and is decomposed into hydrogen sulfide, hydrogen sulfide
Strong chemisorption process occurs in catalyst surface:
Ni+ H2S =NiS+ H2
It is this be chemisorbed on sulphur concentration it is very low under conditions of can occur, Yao Yuanyuan is prior to generating solid Ni3S2Item
Part.The reactivity of catalyst can be reduced Catalyst Adsorption a small amount of sulphur.Because in petroleum distillate containing sulphur, nitrogen, oxygen and
Metal impurities exist, and catalyst activity gradually lowers, in a short time inactivation catalyst service life.
Summary of the invention
The technical problem to be solved by the present invention is it is long and active to overcome the deficiencies of the prior art and provide a kind of service life
A kind of good surface Modified Nickel system sulfur resistive hydrogenation catalyst and preparation method thereof.
The technical solution adopted by the present invention to solve the technical problems is: the surface Modified Nickel system sulfur resistive hydrogenation catalyst,
It is characterized by comprising carrier and the sulfur resistive shielded layer of load active component nickel thereon and catalyst coating, the sulfur resistive
Shielded layer includes the Zn composition of phosphorus element-containing, the copper composition of phosphorus element-containing or its mixed component, the zinc combination of phosphorus element-containing
The content of object, the copper composition of phosphorus element-containing or its mixed component is the 1% ~ 5% of catalyst gross mass.
Of the invention is exposed to catalyst used in the application under sulfur-containing impurities, catalyst in reduced state nickel series catalysts
Surface reaches sulfur resistive system by modification technology.Of the invention plus hydrogen sulfur resistant catalyst is a kind of with by the activated centre of catalyst
Make shielded layer by the high metal of close sulphur activity, the reaction probability of element sulphur in activated centre and raw material is reduced, to avoid living
Property center permanently inactivates, and extends the service life of catalyst.Exist under an atmosphere of hydrogen with element sulphur according to protection metal simultaneously
Reversible reaction under low temperature reduces the ability that sulfide enhances the anti-poisoning of catalyst in the deposition of catalyst surface.It is excellent
Choosing, or mixtures thereof the metallic zinc, copper metal component content are the 2% ~ 3% of catalyst gross mass.
The preparation method of a kind of above-mentioned surface Modified Nickel system sulfur resistive hydrogenation catalyst, it is characterised in that: pass through carrying method
Metallic solution containing modified body is applied on the surface and hole of carrier and active component and obtains shielded layer, incited somebody to action by being calcined
Shielded layer complex compound is converted to or mixtures thereof metal, metal oxide, prepares sulfur resistive hydrogenation catalyst by hydrogen reducing
Agent.The preparation method simple process, production cost are low, extend making for catalyst by load protection metallic shield laminar protective film
With period and active method.Improving catalyst sulfur resistive active material catalyst made from the dispersibility of matrix surface has
Very high catalytic activity, stronger catalytic stability, resistance to SO_2.
Specifically, the preparation steps of the metallic solution containing modified body are as follows: impregnate simple substance zinc, copper or its mixed component
In the mixed aqueous solution containing phosphorus component and citric acid, then mixed aqueous solution is continued to flow back, reflux temperature is controlled at 140 DEG C
~ 160 DEG C, return time 3h ~ 5h(to mixed aqueous solution is faint yellow in clear), co-impregnated solution is obtained by filtration.It distributes rationally
Protection metal in maceration extract forms stable complex structure, and load and catalyst surface can form stable with activated centre
Protect structure, it is long to the catalyst protection period, catalyst it is activity stabilized.
Preferably, the phosphorus component that contains is metaphosphoric acid.
Specifically, the carrying method are as follows: the temperature of control metallic solution containing modified body is at 140 DEG C ~ 160 DEG C, in ultrasound
Under the conditions of incipient impregnation load active component Raney nickel, be cooled to room temperature after taking-up, be dehydrated with centrifuge, to be catalyzed
Agent surface forms uniform film.
Preferably, the temperature of the metallic solution containing modified body is 150 DEG C.
Preferably, catalyst is placed into humidity 78% ~ 82%, 48 DEG C ~ 52 DEG C of temperature of constant temperature and humidity after the completion of the dehydration
8h ~ 9h is aged in case, it is then dry at a temperature of 120 DEG C ~ 130 DEG C.Increase ageing process, can better ensure that catalyst
Stability.
Specifically, the calcination is placed in Muffle furnace for the catalyst that load is had shielded layer in 545 DEG C ~ 555 DEG C temperature
Lower calcination 4.5 h ~ 6h.Using after special technique calcination each component screen is greatly improved with the connection formed between carrier
The bond strength layer between substance and carrier is covered, so that so that the mechanical stability of catalyst is enhanced obtained catalyst has very
High catalytic activity, stronger mechanical strength and sulfur resistance.
Compared with prior art, a kind of surface Modified Nickel system sulfur resistive hydrogenation catalyst and preparation method thereof of the invention is had
Beneficial effect be:
1, preparation method simple process of the invention, by the way that close sulphur active metal substance to be directly loaded in active
The catalyst coating of the heart has broken traditional method by direct carrier and active material co-impregnation, has greatly improved catalysis
The activity of contained protection metal component, reduces the content of protection metal, ensure that the activated centre of catalyst metals in agent
Quantity.
2, form stable complex structure the present invention provides the protection metal in the maceration extract distributed rationally, load with
Catalyst surface can form stable protection structure with activated centre, long to the catalyst protection period, catalyst it is activity stabilized.
3, using after calcination each component greatly improve with the connection formed between carrier shielded layer substance and carrier it
Between bond strength, thus make the mechanical stability of catalyst enhance obtained catalyst have very high catalytic activity, compared with
Strong mechanical strength and sulfur resistance.
Specific embodiment
Below by specific embodiment, the present invention will be further described, and wherein embodiment 3 is most preferred embodiment.
Embodiment 1
Metaphosphoric acid 2.4g and citric acid 14.1g are dissolved in 40ml deionized water, moisturizing to 100ml, 20 DEG C of stirrings are molten
Solution.1.8g zinc powder is dissolved in above-mentioned solution, 152 DEG C of reflux 3h dissolutions.Limpid stable co-impregnated solution 100ml is obtained by filtration.It will
It is impregnated in above-mentioned pulp by pretreated nickel catalyst 97.3g in ultrasound condition volumetric, loads liquid temperature
It 150 DEG C, is cooled to room temperature after taking-up, is dehydrated with centrifuge, 180 revs/min of revolving speed, dewatering time 15 minutes；In catalyst
Surface forms uniform film；
Catalyst is placed into humidity 80% after the completion of dehydration, 8h is aged in temperature 50 C climatic chamber, takes out, in 120 DEG C
At a temperature of it is dry, finally catalyst that load has shielded layer is placed in Muffle furnace at a temperature of 550 DEG C and is calcined 5h surface is made
Modified Nickel system sulfur resistive hydrogenation catalyst C1.
Embodiment 2
Metaphosphoric acid 3.8g and citric acid 11.3g are dissolved in 40ml deionized water, moisturizing to 100ml, by 2.8g zinc powder
It is dissolved in above-mentioned solution, 148 DEG C of reflux 3.5h sufficiently dissolve.Limpid stable co-impregnated solution 100ml is obtained by filtration.It will be by pre- place
The nickel catalyst 95.7g of reason is impregnated in above-mentioned pulp in ultrasound condition volumetric, is loaded 146 DEG C of liquid temperature, is taken
It is cooled to room temperature after out, is dehydrated with centrifuge, 180 revs/min of revolving speed, dewatering time 15 minutes.To be formed in catalyst surface
Uniform film；
Catalyst is placed into humidity 80% after the completion of dehydration, 8h is aged in temperature 50 C climatic chamber, takes out, in 120 DEG C
At a temperature of it is dry, finally catalyst that load has shielded layer is placed in Muffle furnace at a temperature of 550 DEG C and is calcined 5h surface is made
Modified Nickel system sulfur resistive hydrogenation catalyst C2.
Embodiment 3
Metaphosphoric acid 4.8g and citric acid 12.3g are dissolved in 40ml deionized water, moisturizing to 100ml, by 2.8g zinc powder,
2.3g copper powder is dissolved in above-mentioned solution, and 140 DEG C of reflux 5h sufficiently dissolve.Limpid stable co-impregnated solution 100ml is obtained by filtration.It will be through
It crosses pretreated nickel catalyst 94g to be impregnated in above-mentioned pulp in ultrasound condition volumetric, loads liquid temperature 140
DEG C, it is cooled to room temperature after taking-up, is dehydrated with centrifuge, 180 revs/min of revolving speed, dewatering time 15 minutes.In catalyst surface
Form uniform film；
Catalyst is placed into humidity 78% after the completion of dehydration, 9h is aged in 48 DEG C of climatic chambers of temperature, takes out, in 125 DEG C
At a temperature of it is dry, finally catalyst that load has shielded layer is placed in Muffle furnace at a temperature of 545 DEG C and is calcined 6h surface is made
Modified Nickel system sulfur resistive hydrogenation catalyst C3.
Embodiment 4
Metaphosphoric acid 2.8g and citric acid 8.3g are dissolved in 40ml deionized water, moisturizing to 100ml, 1.2g copper powder is molten
In above-mentioned solution, 160 DEG C of reflux 3h sufficiently dissolve.Limpid stable co-impregnated solution 100ml is obtained by filtration.It will pass through pretreated
Nickel catalyst 98.5g is impregnated in above-mentioned pulp in ultrasound condition volumetric, loads 160 DEG C of liquid temperature, after taking-up
It is cooled to room temperature, is dehydrated with centrifuge, 180 revs/min of revolving speed, dewatering time 15 minutes.To be formed uniformly in catalyst surface
Film；The catalyst that load has shielded layer the obtained surface calcination 4.5h at a temperature of 555 DEG C is finally placed in Muffle furnace to change
Property nickel system sulfur resistive hydrogenation catalyst C4.
Comparative example 1
Orthophosphoric acid 2.4g is dissolved in 40ml deionized water, moisturizing to 100ml, 20 DEG C of stirring and dissolvings.1.8g zinc powder is molten
In above-mentioned solution, 152 DEG C of reflux 3h dissolutions.Limpid stable co-impregnated solution 100ml is obtained by filtration.Pretreated nickel system will be passed through
Catalyst 97.3g is impregnated in above-mentioned pulp in ultrasound condition volumetric, loads 150 DEG C of liquid temperature, cooling after taking-up
It to room temperature, is dehydrated with centrifuge, 180 revs/min of revolving speed, dewatering time 15 minutes；It is uniform thin to be formed in catalyst surface
Film；
Catalyst is placed into humidity 80% after the completion of dehydration, 8h is aged in temperature 50 C climatic chamber, takes out, in 120 DEG C
At a temperature of it is dry, finally catalyst that load has shielded layer is placed in Muffle furnace at a temperature of 550 DEG C and is calcined 5h surface is made
Modified Nickel system sulfur resistive hydrogenation catalyst C5.
Comparative example 2
Metaphosphoric acid 3.8g and citric acid 11.3g are dissolved in 40ml deionized water, moisturizing to 100ml, by 2.8g zinc powder
It is dissolved in above-mentioned solution, 148 DEG C of reflux 3.5h sufficiently dissolve.Limpid stable co-impregnated solution 100ml is obtained by filtration.It will be by pre- place
The nickel catalyst 95.7g of reason is impregnated in above-mentioned pulp in ultrasound condition volumetric, is loaded 146 DEG C of liquid temperature, is taken
It is cooled to room temperature after out, is dehydrated with centrifuge, 180 revs/min of revolving speed, dewatering time 15 minutes.To be formed in catalyst surface
Uniform film；
Catalyst is placed into humidity 80% after the completion of dehydration, 8h is aged in temperature 50 C climatic chamber, takes out, in 120 DEG C
At a temperature of it is dry, finally catalyst that load has shielded layer is placed in Muffle furnace at a temperature of 600 DEG C and is calcined 5h surface is made
Modified Nickel system sulfur resistive hydrogenation catalyst C6.
Catalyst C1, C2, C3, C4 physico-chemical property is shown in Table 1.
The physico-chemical property of 1 catalyst of table
。
Evaluating feedstock oil is a kind of hydrogenated diesel oil and Aromatic raffinate miscella, the straight bavin of mixing ratio V(): V(aromatic naphtha)=3:
1, sulfur content is 236 μ gg-1.Evaluation condition: reaction pressure: 2.8 MPa, reaction temperature: 210 DEG C, volume space velocity 2.2h- 1,,
Hydrogen to oil volume ratio: 600.Evaluation result is shown in Table 2.
The evaluation result of 2 catalyst of table
。
The above described is only a preferred embodiment of the present invention, being not that the invention has other forms of limitations, appoint
What those skilled in the art changed or be modified as possibly also with the technology contents of the disclosure above equivalent variations etc.
Imitate embodiment.But without departing from the technical solutions of the present invention, according to the technical essence of the invention to above embodiments institute
Any simple modification, equivalent variations and the remodeling made, still fall within the protection scope of technical solution of the present invention.
Claims (7)
1. a kind of surface Modified Nickel system sulfur resistive hydrogenation catalyst, it is characterised in that: including the active group of carrier and load thereon
Divide the sulfur resistive shielded layer of nickel and catalyst coating, the sulfur resistive shielded layer includes the Zn composition of phosphorus element-containing, phosphorus element-containing
Copper composition or its mixed component, Zn composition, the copper composition of phosphorus element-containing or the content of its mixed component of phosphorus element-containing
It is the 1% ~ 5% of catalyst gross mass.
2. a kind of surface Modified Nickel system according to claim 1 sulfur resistive hydrogenation catalyst, it is characterised in that: the metal
Or mixtures thereof zinc, copper metal component content are the 2% ~ 3% of catalyst gross mass.
3. a kind of preparation method of surface Modified Nickel of any of claims 1 or 2 system sulfur resistive hydrogenation catalyst, it is characterised in that:
Metallic solution containing modified body is applied on the surface and hole of carrier and active component by carrying method and obtains shielded layer, is led to
Calcining is crossed so that shielded layer complex compound is converted to or mixtures thereof metal, metal oxide, is prepared by hydrogen reducing
Sulfur resistive hydrogenation catalyst；
The carrying method are as follows: the temperature of control metallic solution containing modified body is at 140 DEG C ~ 160 DEG C, in ultrasound condition volumetric
Load active component Raney nickel is impregnated, is cooled to room temperature after taking-up, is dehydrated with centrifuge, to be formed in catalyst surface
Even film；
The calcining is placed in Muffle furnace for the catalyst that load is had shielded layer in 545 DEG C ~ 555 DEG C temperature lower calcinations 4.5
h ~6h。
4. a kind of preparation method of surface Modified Nickel system according to claim 3 sulfur resistive hydrogenation catalyst, it is characterised in that:
The preparation steps of the metallic solution containing modified body are as follows: simple substance zinc, copper or its mixed component are immersed in containing phosphorus component and lemon
In the mixed aqueous solution of lemon acid, then mixed aqueous solution is continued to flow back, reflux temperature is controlled at 140 DEG C ~ 160 DEG C, reflux
Between 3h ~ 5h, co-impregnated solution is obtained by filtration.
5. a kind of preparation method of surface Modified Nickel system according to claim 4 sulfur resistive hydrogenation catalyst, it is characterised in that:
The phosphorus component that contains is metaphosphoric acid.
6. a kind of preparation method of surface Modified Nickel system according to claim 3 sulfur resistive hydrogenation catalyst, it is characterised in that:
The temperature of the metallic solution containing modified body is 150 DEG C.
7. a kind of preparation method of surface Modified Nickel system according to claim 3 sulfur resistive hydrogenation catalyst, it is characterised in that:
Catalyst is placed into the interior ageing 8h ~ 9h of humidity 78% ~ 82%, 48 DEG C ~ 52 DEG C of temperature of climatic chamber after the completion of the dehydration, so
It is dry at a temperature of 120 DEG C ~ 130 DEG C afterwards.
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