CN106268792A - A kind of attapulgite clay basic weight is whole generates oil liquid-phase hydrogenatin olefinic hydrocarbon expelling catalyzer and its preparation method and application - Google Patents
A kind of attapulgite clay basic weight is whole generates oil liquid-phase hydrogenatin olefinic hydrocarbon expelling catalyzer and its preparation method and application Download PDFInfo
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- CN106268792A CN106268792A CN201610562881.5A CN201610562881A CN106268792A CN 106268792 A CN106268792 A CN 106268792A CN 201610562881 A CN201610562881 A CN 201610562881A CN 106268792 A CN106268792 A CN 106268792A
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
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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
- C10G45/10—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 platinum group metals or compounds thereof
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
Abstract
The present invention relates to a kind of attapulgite clay basic weight whole generation oil liquid-phase hydrogenatin olefinic hydrocarbon expelling catalyzer and application thereof.Attapulgite modified as carrier, containing the active component of 0.1～3.0wt%, the auxiliary agent of 0.05～2.0wt% with after mineral acid acidified of this catalyst.Catalyst prepared by the present invention is for reformed oil continuous liquid phase hydrogenation deolefination, in reaction temperature 120～180 DEG C, reaction pressure 1.0～2.0MPa, air speed 1～12h‑1, under the conditions of hydrogen-oil ratio 6:1～16:1, can effectively remove the trace amounts of olefin in reformed oil, the bromine index of product is less than 100mgBr/100g oil, and aromatic hydrocarbons loss is less than 0.5wt%.The invention have the advantages that this catalyst is environmentally friendly, do not have the pollution problem of traditional hargil technique, attapulgite is cheap, compares other catalyst cost and declines fairly obvious, and it is good to be catalyzed activity, and service life is long.
Description
Technical field
The invention belongs to oil product hydrofinishing field, especially relate to the catalysis of reformed oil liquid-phase hydrogenatin deolefination
The preparation method of agent and application.
Background technology
Catalytic reforming is the mistake that the hydrocarbon molecules structure in naphtha cut carries out being rearranged into new molecular structure
Journey, is to produce aromatic hydrocarbons and the important process process of solvent naphtha, and it specifically includes that cycloalkane dehydrogenation generates aromatic hydrocarbons, dehydrating alkanes ring
Metaplasia becomes aromatic hydrocarbons, chain hydrocarbon and cycloalkane isomerization, is hydrocracked.
Naphtha cut is after catalytic reforming, and it generates rich in aromatic hydrocarbons and spirit fraction in oil, the most also contains few
The alkene of amount.And in the continuous catalytic reforming device of high severity, the olefin(e) centent of generation oil, more than 1wt%, is raffinated oil
Olefin(e) centent possibly even reaches more than 2wt%.Produce qualified aromatic hydrocarbon product and solvent naphtha, except carrying out Aromatics Extractive Project
Outside with aromatics separation, it is necessary to remove alkene therein, otherwise after the bromine valency of product and pickling, color is defective.The bromine of solvent naphtha
Index and copper corrosion are defective.Generate the existence of alkene in oil simultaneously, can be polymerized in extraction solvent and pollute extraction solvent,
The organic acid that olefin oxidation generates will also result in the corrosion of extraction device.These problems are reformed in the higher Large Scale and Continuous of severity
The product of device becomes apparent from.
It is under facing hydrogen state that catalytic reforming generates the Main Function of oil liquid-phase hydrogenatin olefinic hydrocarbon expelling catalyzer, generates reforming
Oil under liquid phase state, carry out hydrogenation and removing alkene, aromatic hydrocarbons be not hydrogenated saturated in the case of, it is achieved deep hydrogenation removes it
In trace amounts of olefin.
In removing reformed oil, the conventional method of a small amount of alkene was to use clay-filtered method in the past.Through acidic treatment
Hargil, mainly by absorption or partially alkylated and olefinic hydrocarbon condensate reaction, thus reaches to remove the alkene in reformed oil
Purpose.The shortcoming of clay-filtered method is that it operates temperature drift so that in reformed oil, gum level uprises, and color adds
Deeply, when olefin(e) centent is more than 1wt%, clay-filtered method is difficult to touch the mark, and (bromine index is less than 100mgBr/100g in requirement
Oil), and hargil is shorter for service life, and the hargil after inactivation can not regenerate, general 2～within 3 months, be accomplished by changing once, discarded
Hargil environment can be caused severe contamination.
Refining relative to bleaching earth adsorption, gradually promoted now is " back end hydrogenation " process for refining, i.e. in reforming reaction system
One back end hydrogenation reactor of series connection after last reactor in system, uses conventional sulphided state base metal Co-Mo
Or Ni-Mo Hydrobon catalyst, at higher temperature (300～320 DEG C) and relatively low-speed (2～3h-1React under), be difficult to
Reach degree of depth deolefination (bromine index is less than 200mgBr/100g oil) and ensure that aromatic hydrocarbons does not loses (aromatic hydrocarbons loss in hydrogenation process
Less than 0.5wt%) requirement.But, due to not sulfur-bearing, sulphided state base metal in reformed oil and reformation by-product hydrogen
Co-Mo or Ni-Mo Hydrobon catalyst is easy to lose sulfur and cause inactivation.
Chinese patent CN85100760A describes a kind of hydrofining catalyst for hydrogenation of alkenes and preparation method thereof.This for oil
The catalyst of product hydrogenation of olefins by Pt or Pd or Pd and Pt of 0.2～1wt% and Sn or Pb of 0.05～2wt% support in
Made by fibrous alumina.Yet with threadiness Al at present2O3Forming technique not yet realize, threadiness Al2O3It is difficult to
It is shaped to the Industrial Catalysis agent carrier with certain mechanical strength, is permitted so the catalyst of this invention commercial Application to be realized also has
Many work to be done.
Chinese patent CN1250799A discloses a kind of reformed oil olefine saturation hydrogenation method, is included in catalyst and deposits
Under, being contacted with hydrogen by reformed oil, the condition of contact is temperature 50～200 DEG C, and pressure is more than 0.1MPa, liquid hourly space velocity (LHSV)
0.1～20h-1, hydrogen/oil ratio is more than 30；Described catalyst contains a kind of porous carrier materials, a kind of group VIII metal and is selected from
One or both element in boron, phosphorus, described group VIII metal is presented in amorphous alloy and is carried on porous load
In body material, the content of group VIII metal and boron and/or phosphorus is 0.1～60wt%, group VIII metal element and boron and/or phosphorus
Atomic ratio is 0.5～10.
Noble metal catalyst is high due to its activity, and treating capacity is big, and catalyst stability is good, and service life is long, easy and simple to handle
Etc. advantage, therefore it is more suitable for the alkene in selectively removing reformed oil than other catalyst.But it there is also catalyst
Expensive, the problems such as initial reaction stage catalyst activity is too high, and aromatic hydrocarbons loss is serious.
Summary of the invention
The present invention is directed to the problem that noble metal catalyst exists, develop a kind of with low cost, catalysis activity is good, selectivity
Height, service life length the catalyst for reformed oil liquid-phase hydrogenatin deolefination and its preparation method and application.
The present invention use mineral acid acidified after attapulgite modified as catalyst carrier, simultaneously containing 0.1～3.0wt%
Active component, the auxiliary agent of 0.05～2.0wt%, wherein, one or both in Pd, Pt, Sn of active component, auxiliary agent selects
One or both in Li, Na, K, Rb, Mg, Ca, Sr, Ba, the attapulgite modified carrier of preparation has the special knot of cage modle
Structure, without carrying out presulfurization when catalyst uses, effectively reduces the cost of catalyst, improves noble metal utilisation, in the degree of depth
While deolefination, reduce the loss of aromatic hydrocarbons as far as possible.
The method for preparing catalyst of the present invention is as follows:
(1) take a certain proportion of attapulgite and add sodium bicarbonate solution, with sodium hydroxide regulation pH between 8～9, super
Sound oscillation, dry, roasting, obtain having the attapulgite modified of cagelike structure, and recycling mineral acid is acidified, and obtains acidifying and changes
Property attapulgite, dry for standby；
(2) active component solubility predecessor, auxiliary agent solubility predecessor are made into mixed solution, mixed solution total concentration
Being 0.02～1mol/L, heating makes mixed solution temperature between 30～70 DEG C；
(3) with organic acid or mineral acid regulating step (2) gained mixed solution so that it is pH is between 5～7；
(4) by being placed in step (3) gained mixed solution with attapulgite modified after mineral acid acidified, stirring 4 is impregnated
～24h, filter, obtain catalyst sample；
(5) step (4) gained sample is added shaping assistant molding, at 90～120 DEG C, is dried 5～20h, 350～
At 650 DEG C, roasting 2.5～7.5h i.e. obtains required catalyst；
In solution described in step (1), attapulgite and sodium bicarbonate mass ratio are: 1:0.5～2；During described sonic oscillation
Between be: 6～16h；Described dry run temperature is: 90～120 DEG C, and drying time is: 5～12h；Described roasting process temperature
For: 400～700 DEG C, roasting time is: 2.5～7.5h；Described pH is between 8～9；Described mineral acid is sulphuric acid, hydrochloric acid, dense
Degree is 0.5～2.5mol/L.
Step (2) described active component predecessor includes: PdCl2、Pd(NO3)2、H2PdCl4、Pd(C3H5)2、Pd
(C5H7O2)2、[Pd(NH3)4]Cl2；H2PtCl6、Pt(C5H9)2、PtCl4；SnCl4, auxiliary agent derives from auxiliary agent solubility predecessor,
Adjuvant component predecessor includes its nitrate, sulfate, chlorate；
Organic acid or mineral acid described in step (3) are acetic acid, citric acid, oxalic acid, nitric acid, sulphuric acid.
Step (5) described shaping assistant is sesbania powder, boehmite and dust technology.
The application process of the present invention is as follows:
Under hydrogen atmosphere, through beds, there is hydrogenation and olefin hydrocarbon removal reaction in reformed oil, reaction condition is:
Reaction temperature 120～180 DEG C, reaction pressure 1.0～2.0MPa, air speed 1～10h-1, hydrogen-oil ratio 6:1～16:1；Preferably reaction
Temperature 130～160 DEG C, reaction pressure 1.2～1.8MPa, air speed 2～8h-1, hydrogen-oil ratio 8:1～14:1.
Wherein, catalyst need before use under hydrogen atmosphere reduce, temperature 130～210 DEG C, Hydrogen Vapor Pressure 1.0～
3.0MPa, gas agent volume ratio 100:1～500:1, the time 5～10h.
Advantages of the present invention is as follows:
The invention provides a kind of reformed oil liquid-phase hydrogenatin olefinic hydrocarbon expelling catalyzer and methods for making and using same thereof, according to
The catalyst that the present invention prepares, the Active components distribution frame of attapulgite modified carrier after caged is acidified and interior
Portion, This structure increases the contact area of raw oil and hydrogen so that the hydrogen that reaction needs reduces, moreover it is possible to ensure catalyst
Activity the most steadily eliminates pre-vulcanization process.The consumption of noble metal can be reduced, improve the utilization rate of noble metal, can protect again
While card olefin removal effect, effectively control the loss of aromatic hydrocarbons.And use that caged is attapulgite modified does carrier, make catalysis
The required hydrogen-oil ratio of agent catalysis, much smaller than other similar catalyst, greatly reduces hydrogen usage, has saved production cost, this catalysis
Agent can also under the volume space velocity higher than similar catalyst production and application.
Detailed description of the invention
It is further explained in detail the present invention below in conjunction with embodiment.
Embodiment 1:
Weighing a certain amount of attapulgite and sodium hydroxide by the mass ratio of 1:1, regulating pH after dissolving is 9, sonic oscillation 12h
After leach, at 110 DEG C after freeze-day with constant temperature 12h, roasting 4.5h at 550 DEG C.Weigh 10 grams of attapulgite modified addition 50ml
Concentration is in the dilution heat of sulfuric acid of 0.5mol/L, is heated to 60 DEG C, stirs 2h, and cooling is taken out.Weigh 0.18g Palladous chloride., 0.52g
Chloroplatinic acid, 6.36g sodium carbonate, make solution concentration be 0.8mol/L with deionized water dissolving, and be heated to 40 DEG C, molten to mixing
Liquid is slowly added citric acid so that it is pH is 5.0, adds the attapulgite modified dipping after acidifying, dipping process constantly stirs
Mix, after 12h, the catalyst that dipping completes is leached, freeze-day with constant temperature 12h at 110 DEG C.Pulverize last addition shaping assistant
Molding, freeze-day with constant temperature 12h at 120 DEG C, roasting 4.5h at 550 DEG C, obtains required catalyst afterwards.
Weighing 6g catalyst at fixed bed reactors Program heating reduction, reducing condition is: Hydrogen Vapor Pressure 2MPa, gas agent
Ratio 500:1, reduction 6h at 200 DEG C, heating rate is 25 DEG C/h.After reduction terminates, temperature 130 DEG C, under pressure 2.0MPa
Charging reaction, reaction volume air speed is 10h-1, hydrogen to oil volume ratio is 14:1, raw material 47wt% in aromatic hydrocarbons, and bromine index is
1470mgBr/100g oil, product 46.8wt% in aromatic hydrocarbons, bromine index is 82mgBr/100g oil.
Embodiment 2:
Weighing a certain amount of attapulgite and sodium hydroxide by the mass ratio of 1:1.5, regulating pH after dissolving is 9, sonic oscillation
Leach after 10h, at 100 DEG C after freeze-day with constant temperature 11h, roasting 3.5h at 450 DEG C.Weigh 10 grams of attapulgite modified additions
50ml concentration be the dilution heat of sulfuric acid of 1mol/L in beaker, be heated to 80 DEG C, stir 1.5h, cooling take out.Weigh 0.18g chlorine
Change palladium, 0.52g chloroplatinic acid, 2.86g magnesium chloride, make solution concentration be 0.5mol/L with deionized water dissolving, and be heated to 70
DEG C, in mixed solution, it is slowly added nitric acid so that it is pH is 6.0, adds the attapulgite modified dipping after acidifying, dipping process
In be stirred continuously, after 8h, the catalyst that dipping completes is leached, freeze-day with constant temperature 11h at 100 DEG C.Pulverize last addition into
Type auxiliary agent molding, freeze-day with constant temperature 9h at 130 DEG C, roasting 3.5h at 450 DEG C, obtains required catalyst afterwards.
Weighing 6g catalyst at fixed bed reactors Program heating reduction, reducing condition is: Hydrogen Vapor Pressure 2.5MPa, gas
Agent volume ratio 400:1, reduction 8h at 190 DEG C, heating rate is 25 DEG C/h.After reduction terminates, at temperature 180 DEG C, pressure
Charging reaction under 1.8MPa, reaction volume air speed is 6h-1, hydrogen to oil volume ratio is 12:1, raw material 47wt% in aromatic hydrocarbons, and bromine index is
1470mgBr/100g oil, product 46.9wt% in aromatic hydrocarbons, bromine index is 79mgBr/100g oil.
Embodiment 3:
Weighing a certain amount of attapulgite and sodium hydroxide by the mass ratio of 1:0.5, regulating pH after dissolving is 8, sonic oscillation
Leach after 14h, at 120 DEG C after freeze-day with constant temperature 8h, roasting 4h at 500 DEG C.Weigh 10 grams of attapulgite modified addition 50ml
Concentration be the dilution heat of sulfuric acid of 1.5mol/L in beaker, be heated to 70 DEG C, stir 2h, cooling take out.Weigh 0.23g nitric acid
Palladium, 0.34g platinum tetrachloride, 3.28g calcium nitrate, make solution concentration be 0.3mol/L with deionized water dissolving, and be heated to 50
DEG C, in mixed solution, it is slowly added oxalic acid so that it is pH is 5.0, adds the attapulgite modified dipping after acidifying, dipping process
In be stirred continuously, after 9h, the catalyst that dipping completes is leached, freeze-day with constant temperature 8h at 120 DEG C.Pulverize last addition into
Type auxiliary agent molding, freeze-day with constant temperature 10h at 120 DEG C, roasting 4h at 500 DEG C, obtains required catalyst afterwards.
Weighing 6g catalyst at fixed bed reactors Program heating reduction, reducing condition is: Hydrogen Vapor Pressure 1.5MPa, gas
Agent volume ratio 400:1, reduction 6h at 160 DEG C, heating rate is 25 DEG C/h.After reduction terminates, at temperature 140 DEG C, pressure
1.5MPa lower charging reaction, reaction volume air speed is 8h-1, hydrogen to oil volume ratio is 6:1, raw material 47wt% in aromatic hydrocarbons, and bromine index is
1470mgBr/100g oil, product 46.9wt% in aromatic hydrocarbons, bromine index is 89mgBr/100g oil.
Embodiment 4
Weighing a certain amount of attapulgite and sodium hydroxide by the mass ratio of 1:2, regulating pH after dissolving is 9, sonic oscillation 12h
After leach, at 120 DEG C after freeze-day with constant temperature 12h, roasting 5h at 550 DEG C.Weigh 10 grams of attapulgite modified addition 50ml dense
The dilute hydrochloric acid solution that degree is 2mol/L, in beaker, is heated to 60 DEG C, stirs 1h, and cooling is taken out.Weigh 0.18g Palladous chloride.,
0.34g platinum tetrachloride, 2.86g magnesium chloride, make solution concentration be 0.5mol/L with deionized water dissolving, and be heated to 40 DEG C,
In mixed solution, it is slowly added citric acid so that it is pH is 5.0, adds the attapulgite modified dipping after acidifying, dipping process
In be stirred continuously, after 14h, the catalyst that dipping completes is leached, freeze-day with constant temperature 12h at 120 DEG C.Pulverize last addition
Shaping assistant molding, freeze-day with constant temperature 12h at 120 DEG C, roasting 5h at 550 DEG C, obtains required catalyst afterwards.
Weighing 6g catalyst at fixed bed reactors Program heating reduction, reducing condition is: Hydrogen Vapor Pressure 3.0MPa, gas
Agent volume ratio 300:1, reduction 10h at 200 DEG C, heating rate is 15 DEG C/h.After reduction terminates, at temperature 140 DEG C, pressure
Charging reaction under 1.0MPa, reaction volume air speed is 10h-1, hydrogen to oil volume ratio is 12:1, raw material 47wt% in aromatic hydrocarbons, bromine index
For 1470mgBr/100g oil, product 46.7wt% in aromatic hydrocarbons, bromine index is 92mgBr/100g oil.
Embodiment 5
Weighing a certain amount of attapulgite and sodium hydroxide by the mass ratio of 1:1, regulating pH after dissolving is 8, sonic oscillation 12h
After leach, at 110 DEG C after freeze-day with constant temperature 10h, roasting 3.5h at 450 DEG C.Weigh 10 grams of attapulgite modified addition 50ml
Concentration be the dilute hydrochloric acid solution of 0.5mol/L in beaker, be heated to 80 DEG C, stir 1.5h, cooling take out.Weigh 0.18g chlorination
Palladium, 0.26g stannic chloride, 3.73g magnesium chloride, make solution concentration be 0.7mol/L with deionized water dissolving, and be heated to 60 DEG C,
In mixed solution, it is slowly added citric acid so that it is pH is 6.0, adds the attapulgite modified dipping after acidifying, dipping process
In be stirred continuously, after 9h, the catalyst that dipping completes is leached, freeze-day with constant temperature 12h at 100 DEG C.Pulverize last addition into
Type auxiliary agent molding, freeze-day with constant temperature 10h at 130 DEG C, roasting 3.5h at 400 DEG C, obtains required catalyst afterwards.
Weighing 6g catalyst at fixed bed reactors Program heating reduction, reducing condition is: Hydrogen Vapor Pressure 1.5MPa, gas
Agent volume ratio 300:1, reduction 7h at 150 DEG C, heating rate is 25 DEG C/h.After reduction terminates, at temperature 130 DEG C, pressure
Charging reaction under 1.7MPa, reaction volume air speed is 5h-1, hydrogen to oil volume ratio is 8:1, raw material 47wt% in aromatic hydrocarbons, and bromine index is
1470mgBr/100g oil, product 46.8wt% in aromatic hydrocarbons, bromine index is 68mgBr/100g oil.
Embodiment 6
Weighing a certain amount of attapulgite and sodium hydroxide by the mass ratio of 1:1, regulating pH after dissolving is 9, sonic oscillation 12h
After leach, at 120 DEG C after freeze-day with constant temperature 8h, roasting 4h at 450 DEG C.Weigh 10 grams of attapulgite modified addition 50ml concentration
For the dilute hydrochloric acid solution of 1.5mol/L in beaker, being heated to 70 DEG C, stir 1.5h, cooling is taken out.Weigh 0.23g Palladous nitrate.,
0.52g chloroplatinic acid, 4.03g magnesium carbonate, make solution concentration be 0.8mol/L with deionized water dissolving, and be heated to 40 DEG C, to
Mixed solution is slowly added citric acid so that it is pH is 5.0, adds the attapulgite modified dipping after acidifying, in dipping process
It is stirred continuously, after 7h, the catalyst that dipping completes is leached, freeze-day with constant temperature 10h at 110 DEG C.Pulverize last addition molding
Auxiliary agent molding, freeze-day with constant temperature 8h at 120 DEG C, roasting 4.0h at 450 DEG C, obtains required catalyst afterwards.
Weighing 6g catalyst at fixed bed reactors Program heating reduction, reducing condition is: Hydrogen Vapor Pressure 2.0MPa, gas
Agent volume ratio 400:1, reduction 6h at 160 DEG C, heating rate is 20 DEG C/h.After reduction terminates, at temperature 160 DEG C, pressure
Charging reaction under 1.5MPa, reaction volume air speed is 8h-1, hydrogen to oil volume ratio is 12:1, raw material 47wt% in aromatic hydrocarbons, and bromine index is
1470mgBr/100g oil, product 46.6wt% in aromatic hydrocarbons, bromine index is 63mgBr/100g oil.
Embodiment 7
Weighing a certain amount of attapulgite and sodium hydroxide by the mass ratio of 1:1.5, regulating pH after dissolving is 9, sonic oscillation
Leach after 12h, at 120 DEG C after freeze-day with constant temperature 10h, roasting 5.5h at 500 DEG C.Weigh 10 grams of attapulgite modified additions
50ml concentration be the dilute hydrochloric acid solution of 2mol/L in beaker, be heated to 80 DEG C, stir 2h, cooling take out.Weigh 0.18g chlorination
Palladium, 0.34g platinum tetrachloride, 2.24g potassium chloride, make solution concentration be 0.5mol/L with deionized water dissolving, and be heated to 40
DEG C, in mixed solution, it is slowly added citric acid so that it is pH is 6.0, adds the attapulgite modified dipping after acidifying, impregnated
Journey is stirred continuously, after 12h, the catalyst that dipping completes is leached, freeze-day with constant temperature 11h at 100 DEG C.Pulverize last adding
Entering shaping assistant molding, freeze-day with constant temperature 10h at 130 DEG C, roasting 5.5h at 450 DEG C, obtains required catalyst afterwards.
Weighing 6g catalyst at fixed bed reactors Program heating reduction, reducing condition is: Hydrogen Vapor Pressure 2.0MPa, gas
Agent volume ratio 350:1, reduction 8h at 170 DEG C, heating rate is 25 DEG C/h.After reduction terminates, at temperature 150 DEG C, pressure
Charging reaction under 1.6MPa, reaction volume air speed is 6h-1, hydrogen to oil volume ratio is 10:1, raw material 47wt% in aromatic hydrocarbons, and bromine index is
1470mgBr/100g oil, product 46.9wt% in aromatic hydrocarbons, bromine index is 75mgBr/100g oil.
Embodiment 8
Catalyst stability is tested, and weighs the made catalyst of 6g embodiment 1 at fixed bed reactors Program heating reduction,
Reducing condition is: Hydrogen Vapor Pressure 1.6MPa, gas agent volume ratio 300:1, constant temperature reduction 7h, 20 DEG C/h of heating rate at 170 DEG C.
After reduction terminates, temperature 150 DEG C, charging reaction under pressure 1.5MPa, reaction volume air speed is 6h-1, hydrogen to oil volume ratio is 10:
1, raw material 47wt% in aromatic hydrocarbons, bromine index is 1470mgBr/100g oil, and result is as shown in table 1.As can be seen from Table 1, catalyst
Operate through 600h, product bromine index≤100mgBr/100g oil, and aromatic hydrocarbons loss≤0.5wt%.Therefore, catalyst of the present invention is fitted
Share in reformed oil liquid-phase hydrogenatin deolefination, the needs of the long-term operating of industry can be met.
Table 1 catalyst stability test data table
Comparative example 1
Weigh 10 grams of refined attapulgites to add in the dilution heat of sulfuric acid that 50ml concentration is 0.5mol/L, be heated to 60 DEG C,
Stirring 2h, obtains bar-shaped acidifying attapulgite clay rod soil, and cooling is taken out.Weigh 0.18g radium chloride, 0.52g cobalt nitrate, 6.36g sodium carbonate,
Make solution concentration be 0.8mol/L with deionized water dissolving, and be heated to 40 DEG C, in mixed solution, be slowly added citric acid,
Making its pH is 5.0, adds the attapulgite dipping after acidifying, is stirred continuously, the catalysis completed by dipping after 12h in dipping process
Agent leaches, freeze-day with constant temperature 12h at 110 DEG C.Pulverize last addition shaping assistant molding, freeze-day with constant temperature at 120 DEG C
12h, roasting 4.5h at 550 DEG C, obtains required catalyst afterwards.
Weighing 6g catalyst at fixed bed reactors Program heating reduction, reducing condition is: Hydrogen Vapor Pressure 2.0MPa, gas
Agent volume ratio 350:1, reduction 8h at 170 DEG C, heating rate is 25 DEG C/h.After reduction terminates, at temperature 150 DEG C, pressure
Charging reaction under 1.6MPa, reaction volume air speed is 6h-1, hydrogen to oil volume ratio is 10:1, raw material 47wt% in aromatic hydrocarbons, and bromine index is
1470mgBr/100g oil, product bromine index is 192mgBr/100g oil, and arene content is reduced to 42.6wt%.
Comparative example 2
Weigh 0.18g radium chloride, 0.52g cobalt nitrate, 6.36g sodium carbonate, make the solution concentration to be with deionized water dissolving
0.8mol/L, and it is heated to 40 DEG C, in mixed solution, it is slowly added citric acid so that it is pH is 5.0, adds 10g spherical alumina
Alumina supporter impregnates, and is stirred continuously, is leached by the catalyst that dipping completes after 12h in dipping process, freeze-day with constant temperature at 110 DEG C
12h.Pulverize last addition shaping assistant molding, freeze-day with constant temperature 12h at 120 DEG C, afterwards roasting 4.5h at 550 DEG C,
Obtain required catalyst.
Weighing 6g catalyst at fixed bed reactors Program heating reduction, reducing condition is: Hydrogen Vapor Pressure 2.0MPa, gas
Agent volume ratio 350:1, reduction 8h at 170 DEG C, heating rate is 25 DEG C/h.After reduction terminates, at temperature 150 DEG C, pressure
Charging reaction under 1.6MPa, reaction volume air speed is 6h-1, hydrogen to oil volume ratio is 10:1, raw material 47wt% in aromatic hydrocarbons, and bromine index is
1470mgBr/100g oil, product bromine index is 218mgBr/100g oil, and arene content is reduced to 42.2wt%.
Claims (9)
1. an attapulgite clay basic weight whole generation oil liquid-phase hydrogenatin olefinic hydrocarbon expelling catalyzer, it is characterised in that: described catalyst is with mineral acid
Attapulgite modified for carrier after acidifying, simultaneously containing 0.1～3.0wt% active component, the auxiliary agent of 0.05～2.0wt%.
Attapulgite clay basic weight the most according to claim 1 is whole generates oil liquid-phase hydrogenatin olefinic hydrocarbon expelling catalyzer, it is characterised in that: described
Active component is selected from one or both in Pd, Pt, Sn, auxiliary agent one or two in Li, Na, K, Rb, Mg, Ca, Sr, Ba
Kind.
Attapulgite clay basic weight the most according to claim 1 is whole generates oil liquid-phase hydrogenatin olefinic hydrocarbon expelling catalyzer, it is characterised in that: described
Active component derives from active component solubility predecessor, including: PdCl2、Pd(NO3)2、H2PdCl4、Pd(C3H5)2、Pd
(C5H7O2)2、[Pd(NH3)4]Cl2；H2PtCl6、Pt(C5H9)2、PtCl4；SnCl4, described auxiliary agent derives from auxiliary agent solubility forerunner
Thing, including its nitrate, sulfate, chlorate；Mineral acid is hydrochloric acid, sulphuric acid, and inorganic acid concentration is 0.5～2.5mol/L.
The whole preparation method generating oil liquid-phase hydrogenatin olefinic hydrocarbon expelling catalyzer of attapulgite clay basic weight the most according to claim 1, it is special
Levy and be: described preparation method is as follows:
(1) take attapulgite and add sodium bicarbonate solution, regulate pH, sonic oscillation with sodium hydroxide, filter, be dried, roasting, must
To having the attapulgite modified of cagelike structure, recycling mineral acid is acidified, and obtains acidified modified attapulgite, dries standby
With；
(2) active component solubility predecessor, auxiliary agent solubility predecessor being made into mixed solution, mixed solution total concentration is
0.02～1mol/L, heating makes mixed solution temperature between 30～70 DEG C；
(3) with organic acid or mineral acid regulating step (2) gained mixed solution；
(4) by described for step (1) mineral acid acidified after attapulgite modified be placed in step (3) gained mixed solution, dipping
Stirring 4～24h, filtration, obtain catalyst sample；
(5) will add shaping assistant molding in step (4) gained sample, drying, roasting i.e. obtain catalyst.
The whole preparation method generating oil liquid-phase hydrogenatin olefinic hydrocarbon expelling catalyzer of attapulgite clay basic weight the most according to claim 4, it is special
Levy and be: in the solution described in step (1), attapulgite and sodium bicarbonate mass ratio are: 1:0.5～2；During described sonic oscillation
Between be: 6～16h；Described dry run temperature is: 90～120 DEG C, and roasting time is: 5～12h；Described roasting process temperature
For: 400～700 DEG C, roasting time is: 2.5～7.5h；Described pH is between 8～9；Described mineral acid is sulphuric acid, hydrochloric acid, dense
Degree is 0.5～2.5mol/L.
The whole preparation method generating oil liquid-phase hydrogenatin olefinic hydrocarbon expelling catalyzer of attapulgite clay basic weight the most according to claim 4, it is special
Levy and be: step (3) described organic acid is: acetic acid, citric acid, oxalic acid；Mineral acid is: nitric acid, sulphuric acid, described pH 5～7 it
Between.
The whole preparation method generating oil liquid-phase hydrogenatin olefinic hydrocarbon expelling catalyzer of attapulgite clay basic weight the most according to claim 4, it is special
Levy and be: step (5) described shaping assistant is sesbania powder, boehmite and dust technology；Described drying course temperature is: 90～
120 DEG C, drying time is: 5～20h；Described roasting process temperature is: 350～650 DEG C, and roasting time is: 2.5～7.5h.
The whole application generating oil liquid-phase hydrogenatin olefinic hydrocarbon expelling catalyzer of attapulgite clay basic weight the most according to claim 1, its feature exists
In: described application process is as follows:
Under hydrogen atmosphere, through beds, there is hydrogenation and olefin hydrocarbon removal reaction in reformed oil, described reaction condition is:
Reaction temperature 120～180 DEG C, reaction pressure 1.0～2.0MPa, volume space velocity 1～12h-1, hydrogen-oil ratio 6:1～16:1.
The whole application generating oil liquid-phase hydrogenatin olefinic hydrocarbon expelling catalyzer of attapulgite clay basic weight the most according to claim 8, its feature exists
In: need at 130～210 DEG C before the use of described catalyst, hydrogen reducing 5～10h, Hydrogen Vapor Pressure 1.0～3.0MPa；Reduction
After catalyst, be not required to through presulfurization be passivated, can directly apply.
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| CN106268797A (en) * | 2016-07-15 | 2017-01-04 | 常州大学 | A kind of attapulgite clay base precious metal reformed oil liquid-phase hydrogenatin olefinic hydrocarbon expelling catalyzer and its preparation method and application |
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| CN115709074A (en) * | 2022-11-07 | 2023-02-24 | 中国科学院山西煤炭化学研究所 | Preparation method of low-cost hydrogenation and olefin removal catalyst |
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| CN106268797A (en) * | 2016-07-15 | 2017-01-04 | 常州大学 | A kind of attapulgite clay base precious metal reformed oil liquid-phase hydrogenatin olefinic hydrocarbon expelling catalyzer and its preparation method and application |
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| CN115709074A (en) * | 2022-11-07 | 2023-02-24 | 中国科学院山西煤炭化学研究所 | Preparation method of low-cost hydrogenation and olefin removal catalyst |
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