CN106582628A - Selective ring-opening catalyst and preparation method thereof - Google Patents
Selective ring-opening catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN106582628A CN106582628A CN201510665167.4A CN201510665167A CN106582628A CN 106582628 A CN106582628 A CN 106582628A CN 201510665167 A CN201510665167 A CN 201510665167A CN 106582628 A CN106582628 A CN 106582628A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- aromatic hydrocarbon
- selective opening
- preparation
- polycyclic aromatic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The present invention relates to a selective ring-opening catalyst and a preparation method thereof. A purpose of the present invention is to mainly solve the problems of poor polycyclic aromatic hydrocarbon ring-opening selectivity, low monocyclic aromatic hydrocarbon yield and rapid catalyst deactivation in the prior art. The technical scheme of the present invention comprises that the selective ring-opening catalyst comprises, by weight, 63.5-68.4% of at least one selected from alumina, amorphous silicon aluminum and a zeolite molecular sieve, 20-30% of pseudo boehmite, 0.1-1.5% of a noble metal Ir, and 0.1-5% of at least one selected from Ba, Zn and Mg. With the technical scheme, the problems in the prior art are well solved. The selective ring-opening catalyst of the present invention has characteristics of high polycyclic aromatic hydrocarbon ring-opening selectivity, high monocyclic aromatic hydrocarbon yield and slow catalyst deactivation, and can be used in the aromatic hydrocarbon refining field.
Description
Technical field
The present invention relates to a kind of selective opening catalyst and preparation method thereof.
Background technology
Benzene,toluene,xylene (BTX) etc. is all important Organic Chemicals.Benzene is to prepare styrene, nylon, terylene
Deng the basic material of product；And toluene is used as the blending compound of gasoline to improve octane number, can also produce paint, glue
Knot agent, organic solvent etc. are in industry, agricultural and are medically widely used；Dimethylbenzene then more to be used to produce polyester, chemical fibre
Deng product, their clothing all with the national economic development and people, food, shelter, row are closely related, in strong demand in recent years, increase
Amount is rapid, and will produce the situation that supply falls short of demand, seeks aromatic hydrocarbons yield-increasing technology very urgent.However, with oil product heaviness
The continuous intensification of degree and the finiteness of world petroleum resource, are the growth for meeting the oil demand that economic development brings, and are led to
Development heavy oil deep conversion is crossed, the light-end products for increasing production high added value will be the significant development strategy of 21 century oil refining industry.
Through development for many years, as by the important technology hydrocracking technology of heavy polycyclic aromatic hydrocarbon lighting, although having at present
Have the advantages that adaptability to raw materials is wide, conversion level is big, but there is also that reaction temperature and pressure are high, air speed is low, consumption hydrogen is big, urge
The weak points such as agent short life, these also become the emphasis that domestic and international research institution breaks through.
Nippon Oil(Nippon Mitsubishi Oil) on January 21st, 2010 is reported, will develop with the technical matters of light diesel fuel (LCO) production aromatic hydrocarbon product.With
A large amount of traditional handicrafts for consuming hydrogen are compared, and the new technique can cut down production cost, be expected to realization and commercially produce.
USP4,341,622 discloses a kind of method that utilization heavy reformate produces BTX.The method adopt restricted index for
1～12, silica/alumina molar ratio (silica alumina ratio) be more than 12, low acid activity zeolite be catalyst, make reformate exist
React under conditions of 427～540 DEG C, then product separated is obtained into benzene, toluene and dimethylbenzene.Described catalyst contains
There is the VIII noble metal of hydro-dealkylation function, preferred platinum, the silica alumina ratio of zeolite used are preferably greater than 200, more preferably greatly
In 500, preferred zeolite is ZSM-5.Select the zeolite of high silica alumina ratio to reduce zeolite acidity, retain dimethylbenzene as far as possible
It is not converted in the reaction.
US2007062848A1 discloses one kind and first will carry out selective opening and de- alkyl after polycyclic aromatic hydrocarbon fractional saturation again
The method for obtaining light aromatics.The method can meet feed stream in polycyclic aromatic hydrocarbon content in more than 20wt%, saturation stage
Temperature at 300～500 DEG C, 2～10MPa of pressure；Open loop phase temperature at 200～600 DEG C, 1～12MPa of pressure.By
It is mounted in same reactor in two-stage catalytic agent, it requires that logistics needs to ensure that certain time of staying could obtain preferably
Conversion ratio, therefore air speed is relatively low.
CN1472181A discloses a kind of heavy aromatics lightening catalyst, including 0.01～2.0 weight % group VIII metal and
Complex carrier, described complex carrier include the ZSM-5 zeolite of 30～70 weight %, the modenite of 5～20 weight % and 10～
The aluminium oxide of 65 weight %.The catalyst is used for heavy aromatic hydrocarbon light, can improve C9 +Aromatics conversion rate and benzene and dimethylbenzene
Yield, and reduce carbon distribution.
CN1082539C discloses the separation method of a kind of heavy arenes lightening catalyst and lighting product.The catalysis
Agent by the platinum or palladium of 0.05～0.3 weight %, the zeolite with MOR structures of 20～59 weight %, 20～50 weight % ZSM-5
The aluminium oxide composition of zeolite and 20～40 weight %.By the raw material of the heavy arene containing C9+ in 350～450 DEG C, 0.3～3.5MPa
Under the conditions of carry out contacting with above-mentioned catalyst, gained lighting product through fractional distillation be obtained BTX and sym-trimethylbenzene., inclined three
The Organic Ingredientss such as toluene, durol.
CN1048425C discloses a kind of heavy arenes lightening catalyst and lightening method.The catalyst is with 30～70
γ-or η-Al of the ZSM-5 zeolite of weight % and 30～70 weight %2O3For carrier, load 0.1～0.5 weight % stannum and 0.05～
The palladium composition of the platinum of 0.3 weight % or 0.2～0.8 weight %.At 350～450 DEG C, 0.5～3.5MPa, weight space velocity 1～5-1、
Under conditions of hydrogen/hydrocarbon volume ratio is 500～1200, the catalyst has higher activity and stability and relatively low hydrogen consumption.
The content of the invention
One of the technical problem to be solved is to overcome polycyclic aromatic hydrocarbon selectivity of ring-opening present in prior art
Difference, mononuclear aromatics yield are low, the fast problem of catalyst deactivation rate, there is provided a kind of new polycyclic aromatic hydrocarbon selective opening catalysis
Agent.The catalyst has polycyclic aromatic hydrocarbon selectivity of ring-opening high, mononuclear aromatics high income, the slow advantage of catalyst deactivation rate.
The two of the technical problem to be solved be to provide it is a kind of with solve the corresponding selectivity of one of technical problem and open
The preparation method of ring catalyst.
The three of the technical problem to be solved be to provide it is a kind of with solve the corresponding selectivity of one of technical problem and open
The operational approach of ring catalyst.
To solve one of above-mentioned technical problem, the technical solution used in the present invention is as follows：A kind of selective opening catalyst, presses
Catalyst weight percent meter includes：
At least one of (a) 63.5～68.4% in aluminium oxide, amorphous silica-alumina or zeolite molecular sieve；
The boehmite of (b) 20～30%；
(c) 0.1～1.5% noble metal Ir；
At least one of (d) 0.1～5% in metal Ba, Zn or Mg；
To solve the two of above-mentioned technical problem, the technical solution used in the present invention is as follows：A kind of system of selective opening catalyst
Preparation Method, comprises the following steps：
1. by least one and boehmite in aluminium oxide, amorphous silica-alumina or the zeolite molecular sieve, peptizer,
Extrusion aid and water kneading, extruded moulding, after drying, catalyst carrier is obtained in 450～700 DEG C of 0.5～24h of roasting；
2. metal front liquid solution is impregnated into into 0.5～24h of ageing in catalyst carrier in 10～60 DEG C, it is standby after being dried；
3. after 300～550 DEG C of 1～10h of roasting of air atmosphere, after 250～550 DEG C of 1～10h of reduction of hydrogen atmosphere i.e.
Obtain finished catalyst.
In above-mentioned technical proposal, described zeolite molecular sieve be industrial conventional FAU types, BEA types, MOR types or
At least one in MFI type zeolite.
In above-mentioned technical proposal, the presoma of described noble metal Ir is iridium chloride or at least one in chloro-iridic acid.
In above-mentioned technical proposal, the presoma of described metal Ba is barium nitrate.
In above-mentioned technical proposal, the presoma of described metal Zn is zinc nitrate or at least one in zinc chloride.
In above-mentioned technical proposal, the presoma of described metal Mg is at least one in magnesium acetate, magnesium nitrate or magnesium carbonate.
In above-mentioned technical proposal, the extrusion aid of carrier dry basis 2～5% is pressed in addition in catalyst carrier preparation process, is added
Plus 3～6% gelatinizing agent.
In above-mentioned technical proposal, described extrusion aid is sesbania powder or at least one in Oleum Verniciae fordii.
In above-mentioned technical proposal, described gelatinizing agent is in hydrochloric acid, nitric acid, acetic acid, tartaric acid, citric acid or oxalic acid
The volume ratio of at least one and water be 1：1～1：5.
To solve the three of above-mentioned technical problem, the technical solution used in the present invention is as follows：A kind of polycyclic aromatic hydrocarbon selective opening
Method, Polycyclic Aromatic Hydrocarbon Mixture are mixed with hydrogen, pass through beds, 320～400 DEG C of reaction temperature,
3～10MPa of reaction pressure, 0.5～3hr of volume space velocity-1, under the conditions of hydrogen to oil volume ratio 300～1200 with it is above-mentioned any one
Catalyst is contacted, and carries out polycyclic aromatic hydrocarbon selective opening reaction.
The Performance that polycyclic aromatic hydrocarbon ring-opening reaction is carried out using fixed bed reactors of the invention, 12 millimeters of reactor inside diameter Ф,
800 millimeters of length, stainless steel.Using electrical heating, temperature automatic control.Reactor bottom fills 2～3 millimeters of glass of Ф
Glass pearl be supporter, 5 grams of catalyst filling in reactor, top filling 2～3 millimeters of beades of Ф, be made for raw material preheating and
Vaporization is used.Raw material Polycyclic Aromatic Hydrocarbon Mixture is mixed with hydrogen, passes through beds, converts polycyclic aromatic hydrocarbon
For alkyl benzene mononuclear aromatics.
The catalyst that the present invention is provided can be used for aromatic hydrocarbons refining field.
As noble metal Ir has been loaded in catalyst carrier in the present invention, Ir is stronger but common to the open loop ability of naphthenic ring
Carrying method causes metal Ir easily to reunite Jing after high-temperature process, declines the dispersion of active component, causes catalyst open loop
Ability declines, and rapid catalyst deactivation, the inventive method introduce auxiliary agent B a, Zn or Mg, can significantly inhibit metal
The reunion of Ir, so as to delay the deactivation rate of catalyst, and the introducing of auxiliary agent also improves the open loop efficiency of metal Ir,
Greatly increase the yield of mononuclear aromatics.
Below by embodiment, the present invention is further elaborated.
Specific embodiment
【Embodiment 1】
By butt be 70g macropore boehmites (commercially available) and butt 30g aperture boehmites it is (commercially available) addition blender extremely
Uniformly, then in mixture add 3g sesbania powders, 5g volume ratios 1:1HNO3Solution and 45g deionized waters, grinding
The dough for being suitable to extrude is made uniformly.By mould extrude, shape be in elongated cylinder (diameter 1.7mm), 120 DEG C
After 550 DEG C of roasting 4h, the carrier granular (1.7 × 4.0mm) for being then cut into consistent size is standby for drying.
Chloro-iridic acid, barium nitrate are made impregnation liquid in proportion at 40 DEG C to impregnate carrier granular, institute in impregnation liquid, is converted
The weight 1%Ir and 3%Ba of butt containing carrier, ageing 8h after drying, 350 DEG C aoxidize 4h in atmosphere, then in hydrogen
In 300 DEG C reduction 4h (this step can be completed in the reactor) get product catalyst 1.
With catalyst 1 on fixed bed reactors (highest response pressure 10MPa, using temperature be room temperature～600 DEG C) investigate will
Polycyclic Aromatic Hydrocarbon Mixture is converted into the ability of the mononuclear aromatics such as alkylbenzene.Table 1 is constituted to evaluate raw material.Catalyst packing 5g,
In 350 DEG C of reaction temperature, reaction pressure 5.0MPa, volume space velocity 1.0hr-1, under the conditions of hydrogen to oil volume ratio 600 with catalyst
Contacted, product is reclaimed and component detection, conversion results are shown in Table 2.
【Embodiment 2】
It is 70g amorphous silica-aluminas (commercially available) and (commercially available) the addition blender of butt 30g aperture boehmites to equal by butt
It is even, then in mixture add 3g sesbania powders, 5g volume ratios 1:1HNO3Solution and 45g deionized waters, grinding are equal
It is even to make the dough for being suitable to extrude.By mould extrude, shape be in elongated cylinder (diameter 1.7mm), 120 DEG C
After 550 DEG C of roasting 4h, the carrier granular (1.7 × 4.0mm) for being then cut into consistent size is standby for drying.
Chloro-iridic acid, barium nitrate are made impregnation liquid in proportion at 40 DEG C to impregnate carrier granular, institute in impregnation liquid, is converted
The weight 1%Ir and 3%Ba of butt containing carrier, ageing 8h after drying, 350 DEG C aoxidize 4h in atmosphere, then in hydrogen
In 300 DEG C reduction 4h (this step can be completed in the reactor) get product catalyst 2.
With catalyst 2 on fixed bed reactors (highest response pressure 10MPa, using temperature be room temperature～600 DEG C) investigate polycyclic aromatic hydrocarbon is mixed
Compound is converted into the ability of the mononuclear aromatics such as alkylbenzene.Table 1 is constituted to evaluate raw material.Catalyst packing 5g, in 350 DEG C of reaction temperature, instead
Contacted with catalyst under the conditions of answering pressure 5.0MPa, volume space velocity 1.0hr-1, hydrogen to oil volume ratio 600, product is reclaimed and component
Detection, conversion results are shown in Table 2.
【Embodiment 3】
By butt be 70gUSY (commercially available) and (commercially available) the addition blender of butt 30g aperture boehmites is to uniform, then
3g sesbania powders, 5g volume ratios 1 are added in mixture:1HNO3Solution and 45g deionized waters, grinding are uniformly made suitable
In the dough of extrusion.By mould extrude, shape be in elongated cylinder (diameter 1.7mm), 120 DEG C drying after
550 DEG C of roasting 4h, the carrier granular (1.7 × 4.0mm) for being then cut into consistent size are standby.
Chloro-iridic acid, barium nitrate are made impregnation liquid in proportion at 40 DEG C to impregnate carrier granular, institute in impregnation liquid, is converted
The weight 1%Ir and 3%Ba of butt containing carrier, ageing 8h after drying, 350 DEG C aoxidize 4h in atmosphere, then in hydrogen
In 300 DEG C reduction 4h (this step can be completed in the reactor) get product catalyst 3.
With catalyst 3 on fixed bed reactors (highest response pressure 10MPa, using temperature be room temperature～600 DEG C) investigate will
Polycyclic Aromatic Hydrocarbon Mixture is converted into the ability of the mononuclear aromatics such as alkylbenzene.Table 1 is constituted to evaluate raw material.Catalyst packing 5g,
In 350 DEG C of reaction temperature, reaction pressure 5.0MPa, volume space velocity 1.0hr-1, under the conditions of hydrogen to oil volume ratio 600 with catalyst
Contacted, product is reclaimed and component detection, conversion results are shown in Table 2.
【Embodiment 4】
By butt be 70gUSY (commercially available) and (commercially available) the addition blender of butt 30g aperture boehmites is to uniform, then
3g sesbania powders, 5g volume ratios 1 are added in mixture:1HNO3Solution and 45g deionized waters, grinding are uniformly made suitable
In the dough of extrusion.By mould extrude, shape be in elongated cylinder (diameter 1.7mm), 120 DEG C drying after
550 DEG C of roasting 4h, the carrier granular (1.7 × 4.0mm) for being then cut into consistent size are standby.
Chloro-iridic acid, zinc nitrate are made impregnation liquid in proportion at 40 DEG C to impregnate carrier granular, institute in impregnation liquid, is converted
The weight 1%Ir and 3%Zn of butt containing carrier, ageing 8h after drying, 350 DEG C aoxidize 4h in atmosphere, then in hydrogen
In 300 DEG C reduction 4h (this step can be completed in the reactor) get product catalyst 4.
With catalyst 4 on fixed bed reactors (highest response pressure 10MPa, using temperature be room temperature～600 DEG C) investigate will
Polycyclic Aromatic Hydrocarbon Mixture is converted into the ability of the mononuclear aromatics such as alkylbenzene.Table 1 is constituted to evaluate raw material.Catalyst packing 5g,
In 350 DEG C of reaction temperature, reaction pressure 5.0MPa, volume space velocity 1.0hr-1, under the conditions of hydrogen to oil volume ratio 600 with catalyst
Contacted, product is reclaimed and component detection, conversion results are shown in Table 2.
【Embodiment 5】
By butt be 70gUSY (commercially available) and (commercially available) the addition blender of butt 30g aperture boehmites is to uniform, then
3g sesbania powders, 5g volume ratios 1 are added in mixture:1HNO3Solution and 45g deionized waters, grinding are uniformly made suitable
In the dough of extrusion.By mould extrude, shape be in elongated cylinder (diameter 1.7mm), 120 DEG C drying after
550 DEG C of roasting 4h, the carrier granular (1.7 × 4.0mm) for being then cut into consistent size are standby.
Chloro-iridic acid, magnesium nitrate are made impregnation liquid in proportion at 40 DEG C to impregnate carrier granular, institute in impregnation liquid, is converted
The weight 1%Ir and 3%Mg of butt containing carrier, ageing 8h after drying, 350 DEG C aoxidize 4h in atmosphere, then in hydrogen
In gas, 300 DEG C of reduction 4h (this step can be completed in the reactor) get product catalyst 5.
With catalyst 5 on fixed bed reactors (highest response pressure 10MPa, using temperature be room temperature～600 DEG C) investigate will
Polycyclic Aromatic Hydrocarbon Mixture is converted into the ability of the mononuclear aromatics such as alkylbenzene.Table 1 is constituted to evaluate raw material.Catalyst packing 5g,
In 350 DEG C of reaction temperature, reaction pressure 5.0MPa, volume space velocity 1.0hr-1, under the conditions of hydrogen to oil volume ratio 600 with catalyst
Contacted, product is reclaimed and component detection, conversion results are shown in Table 2.
【Embodiment 6】
By butt be 70gUSY (commercially available) and (commercially available) the addition blender of butt 30g aperture boehmites is to uniform, then
3g sesbania powders, 5g volume ratios 1 are added in mixture:1HNO3Solution and 45g deionized waters, grinding are uniformly made suitable
In the dough of extrusion.By mould extrude, shape be in elongated cylinder (diameter 1.7mm), 120 DEG C drying after
550 DEG C of roasting 4h, the carrier granular (1.7 × 4.0mm) for being then cut into consistent size are standby.
Chloro-iridic acid, barium nitrate, zinc nitrate are made impregnation liquid in proportion at 40 DEG C to impregnate carrier granular, impregnation liquid
Carrier butt weight 1%Ir, 1.5%Ba, 1.5%Zn contained by middle conversion, are aged 8h after drying, and in atmosphere 350
DEG C oxidation 4h, then in hydrogen 300 DEG C reduction 4h (this step can be completed in the reactor) get product catalyst 6.
With catalyst 6 on fixed bed reactors (highest response pressure 10MPa, using temperature be room temperature～600 DEG C) investigate will
Polycyclic Aromatic Hydrocarbon Mixture is converted into the ability of the mononuclear aromatics such as alkylbenzene.Table 1 is constituted to evaluate raw material.Catalyst packing 5g,
In 350 DEG C of reaction temperature, reaction pressure 5.0MPa, volume space velocity 1.0hr-1, under the conditions of hydrogen to oil volume ratio 600 with catalyst
Contacted, product is reclaimed and component detection, conversion results are shown in Table 2.
【Embodiment 7】
By butt be 70gUSY (commercially available) and (commercially available) the addition blender of butt 30g aperture boehmites is to uniform, then
3g sesbania powders, 5g volume ratios 1 are added in mixture:1HNO3Solution and 45g deionized waters, grinding are uniformly made suitable
In the dough of extrusion.By mould extrude, shape be in elongated cylinder (diameter 1.7mm), 120 DEG C drying after
550 DEG C of roasting 4h, the carrier granular (1.7 × 4.0mm) for being then cut into consistent size are standby.
Chloro-iridic acid, barium nitrate, magnesium nitrate are made impregnation liquid in proportion at 40 DEG C to impregnate carrier granular, impregnation liquid
Carrier butt weight 1%Ir, 1.5%Ba, 1.5%Mg contained by middle conversion, are aged 8h after drying, and in atmosphere 350
DEG C oxidation 4h, then in hydrogen 300 DEG C reduction 4h (this step can be completed in the reactor) get product catalyst 7.
With catalyst 7 on fixed bed reactors (highest response pressure 10MPa, using temperature be room temperature～600 DEG C) investigate will
Polycyclic Aromatic Hydrocarbon Mixture is converted into the ability of the mononuclear aromatics such as alkylbenzene.Table 1 is constituted to evaluate raw material.Catalyst packing 5g,
In 350 DEG C of reaction temperature, reaction pressure 5.0MPa, volume space velocity 1.0hr-1, under the conditions of hydrogen to oil volume ratio 600 with catalyst
Contacted, product is reclaimed and component detection, conversion results are shown in Table 2.
【Embodiment 8】
By butt be 70gUSY (commercially available) and (commercially available) the addition blender of butt 30g aperture boehmites is to uniform, then
3g sesbania powders, 5g volume ratios 1 are added in mixture:1HNO3Solution and 45g deionized waters, grinding are uniformly made suitable
In the dough of extrusion.By mould extrude, shape be in elongated cylinder (diameter 1.7mm), 120 DEG C drying after
550 DEG C of roasting 4h, the carrier granular (1.7 × 4.0mm) for being then cut into consistent size are standby.
Chloro-iridic acid, zinc nitrate, magnesium nitrate are made impregnation liquid in proportion at 40 DEG C to impregnate carrier granular, impregnation liquid
Carrier butt weight 1%Ir, 1.5%Zn, 1.5%Mg contained by middle conversion, are aged 8h after drying, and in atmosphere 350
DEG C oxidation 4h, then in hydrogen 300 DEG C reduction 4h (this step can be completed in the reactor) get product catalyst 8.
With catalyst 8 on fixed bed reactors (highest response pressure 10MPa, using temperature be room temperature～600 DEG C) investigate will
Polycyclic Aromatic Hydrocarbon Mixture is converted into the ability of the mononuclear aromatics such as alkylbenzene.Table 1 is constituted to evaluate raw material.Catalyst packing 5g,
In 350 DEG C of reaction temperature, reaction pressure 5.0MPa, volume space velocity 1.0hr-1, under the conditions of hydrogen to oil volume ratio 600 with catalyst
Contacted, product is reclaimed and component detection, conversion results are shown in Table 2.
【Embodiment 9】
By butt be 70gUSY (commercially available) and (commercially available) the addition blender of butt 30g aperture boehmites is to uniform, then
3g sesbania powders, 5g volume ratios 1 are added in mixture:1HNO3Solution and 45g deionized waters, grinding are uniformly made suitable
In the dough of extrusion.By mould extrude, shape be in elongated cylinder (diameter 1.7mm), 120 DEG C drying after
550 DEG C of roasting 4h, the carrier granular (1.7 × 4.0mm) for being then cut into consistent size are standby.
Chloro-iridic acid, barium nitrate are made impregnation liquid in proportion at 40 DEG C to impregnate carrier granular, institute in impregnation liquid, is converted
The weight 1.5%Ir and 4%Ba of butt containing carrier, ageing 8h after drying, 350 DEG C aoxidize 4h in atmosphere, then in hydrogen
In gas, 300 DEG C of reduction 4h (this step can be completed in the reactor) get product catalyst 9.
With catalyst 9 on fixed bed reactors (highest response pressure 10MPa, using temperature be room temperature～600 DEG C) investigate will
Polycyclic Aromatic Hydrocarbon Mixture is converted into the ability of the mononuclear aromatics such as alkylbenzene.Table 1 is constituted to evaluate raw material.Catalyst packing 5g,
With catalyst under the conditions of 350 DEG C of reaction temperature, reaction pressure 5.0MPa, volume space velocity 1.0hr-1, hydrogen to oil volume ratio 600
Contacted, product is reclaimed and component detection, conversion results are shown in Table 2.
【Comparative example 1】
By butt be 70gUSY (commercially available) and (commercially available) the addition blender of butt 30g aperture boehmites is to uniform, then
3g sesbania powders, 5g volume ratios 1 are added in mixture:1HNO3Solution and 45g deionized waters, grinding are uniformly made suitable
In the dough of extrusion.By mould extrude, shape be in elongated cylinder (diameter 1.7mm), 120 DEG C drying after
550 DEG C of roasting 4h, the carrier granular (1.7 × 4.0mm) for being then cut into consistent size are standby.
Chloro-iridic acid is made impregnation liquid in proportion at 40 DEG C to impregnate carrier granular, contained carrier is converted in impregnation liquid and is done
Base weight 1%Ir, ageing 8h after drying, in atmosphere 350 DEG C of oxidation 4h, then in hydrogen 300 DEG C reduce 4h (this
Step can be completed in the reactor) get product catalyst A.
With catalyst A on fixed bed reactors (highest response pressure 10MPa, using temperature be room temperature～600 DEG C) investigate
Polycyclic Aromatic Hydrocarbon Mixture is converted into into the ability of the mononuclear aromatics such as alkylbenzene.Table 1 is constituted to evaluate raw material.Catalyst packing 5g,
With catalyst under the conditions of 350 DEG C of reaction temperature, reaction pressure 5.0MPa, volume space velocity 1.0hr-1, hydrogen to oil volume ratio 600
Contacted, product is reclaimed and component detection, conversion results are shown in Table 2.
【Comparative example 2】
By butt be 70gUSY (commercially available) and (commercially available) the addition blender of butt 30g aperture boehmites is to uniform, then
3g sesbania powders, 5g volume ratios 1 are added in mixture:1HNO3Solution and 45g deionized waters, grinding are uniformly made suitable
In the dough of extrusion.By mould extrude, shape be in elongated cylinder (diameter 1.7mm), 120 DEG C drying after
550 DEG C of roasting 4h, the carrier granular (1.7 × 4.0mm) for being then cut into consistent size are standby.
Chloroplatinic acid, zinc nitrate are made impregnation liquid in proportion at 40 DEG C to impregnate carrier granular, institute in impregnation liquid, is converted
Butt containing carrier weight 1%Pt, 3%Zn, ageing 8h after drying, 350 DEG C aoxidize 4h in atmosphere, then in hydrogen
In 300 DEG C reduction 4h (this step can be completed in the reactor) get product catalyst B.
With catalyst B on fixed bed reactors (highest response pressure 10MPa, using temperature be room temperature～600 DEG C) investigate
Polycyclic Aromatic Hydrocarbon Mixture is converted into into the ability of the mononuclear aromatics such as alkylbenzene.Table 1 is constituted to evaluate raw material.Catalyst packing 5g,
With catalyst under the conditions of 350 DEG C of reaction temperature, reaction pressure 5.0MPa, volume space velocity 1.0hr-1, hydrogen to oil volume ratio 600
Contacted, product is reclaimed and component detection, conversion results are shown in Table 2.
1 raw material of table is constituted
| Raw material is constituted | It is non-aromatic | Mononuclear aromatics | Polycyclic aromatic hydrocarbon |
| Content (wt%) | 0.1 | 24.54 | 75.45 |
2 polycyclic aromatic hydrocarbon conversion results of table
【Embodiment 10～13】
With catalyst 6 obtained in embodiment 6 on fixed bed reactors (highest response pressure 10MPa, using temperature be room
Temperature～600 DEG C) investigate the ability that Polycyclic Aromatic Hydrocarbon Mixture is converted into mononuclear aromatics.Catalyst packing 5g is anti-by changing
The conditions such as temperature, reaction pressure, volume space velocity and hydrogen to oil volume ratio are answered, product is reclaimed and component detection, will conversion
As a result it is shown in Table 3.
3 polycyclic aromatic hydrocarbon conversion results of table
Claims (10)
1. a kind of selective opening catalyst, includes based on catalyst weight percent：
At least one of (a) 63.5～68.4% in aluminium oxide, amorphous silica-alumina or zeolite molecular sieve；
The boehmite of (b) 20～30%；
(c) 0.1～1.5% noble metal Ir；
At least one of (d) 0.1～5% in metal Ba, Zn or Mg.
2. the preparation method of the selective opening catalyst described in claim 1, comprises the following steps：
1. by least one and boehmite in aluminium oxide, amorphous silica-alumina or the zeolite molecular sieve, peptizer,
Extrusion aid and water kneading, extruded moulding, after drying, catalyst carrier is obtained in 450～700 DEG C of 0.5～24h of roasting；
2. metal front liquid solution is impregnated into into 0.5～24h of ageing in catalyst carrier in 10～60 DEG C, it is standby after being dried；
3. after 300～550 DEG C of 1～10h of roasting of air atmosphere, after 250～550 DEG C of 1～10h of reduction of hydrogen atmosphere i.e.
Obtain finished catalyst.
3. the preparation method of selective opening catalyst according to claim 2, it is characterised in that described zeolite point
Son sieve is at least one in industrial conventional FAU types, BEA types, MOR types or MFI type zeolite.
4. the preparation method of selective opening catalyst according to claim 2, it is characterised in that described noble metal
The presoma of Ir is iridium chloride or at least one in chloro-iridic acid.
5. the preparation method of selective opening catalyst according to claim 2, it is characterised in that described metal Ba
Presoma be barium nitrate.
6. the preparation method of selective opening catalyst according to claim 2, it is characterised in that described metal Zn
Presoma be at least one in zinc nitrate or zinc chloride；The presoma of metal Mg is magnesium acetate, magnesium nitrate or magnesium carbonate
In at least one.
7. the preparation method of selective opening catalyst according to claim 2, it is characterised in that catalyst carrier system
The extrusion aid of carrier dry basis 2～5% is pressed in addition during standby, adds 3～6% gelatinizing agent.
8. the preparation method of selective opening catalyst according to claim 7, it is characterised in that described extrusion aid
For at least one in sesbania powder or Oleum Verniciae fordii.
9. the preparation method of selective opening catalyst according to claim 7, it is characterised in that described gelatinizing agent
Be the volume ratio of at least one and water in hydrochloric acid, nitric acid, acetic acid, tartaric acid, citric acid or oxalic acid be 1：1～1：
5。
10. a kind of method of polycyclic aromatic hydrocarbon selective opening, Polycyclic Aromatic Hydrocarbon Mixture are mixed with hydrogen, pass through and urge
Agent bed, in 320～400 DEG C of reaction temperature, 3～10MPa of reaction pressure, 0.5～3hr of volume space velocity-1, hydrogen oil volume
Contact with any one catalyst in claim 1 under the conditions of than 300～1200, carry out polycyclic aromatic hydrocarbon selective opening reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510665167.4A CN106582628B (en) | 2015-10-15 | 2015-10-15 | Selective opening catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510665167.4A CN106582628B (en) | 2015-10-15 | 2015-10-15 | Selective opening catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106582628A true CN106582628A (en) | 2017-04-26 |
| CN106582628B CN106582628B (en) | 2019-07-05 |
Family
ID=58553307
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510665167.4A Active CN106582628B (en) | 2015-10-15 | 2015-10-15 | Selective opening catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106582628B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113333454A (en) * | 2021-05-12 | 2021-09-03 | 上海应用技术大学 | Method for reducing and degrading polycyclic aromatic hydrocarbons in soil by using glacial acetic acid and anhydrous ethanol to catalyze metal magnesium |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020043481A1 (en) * | 2000-07-21 | 2002-04-18 | Baird William C. | Ring opening with group VIII metal catalysts supported on modified substrate |
| CN1972748A (en) * | 2004-04-20 | 2007-05-30 | 环球油品公司 | Catalyst for selective opening of cyclic paraffins and process for using the catalyst |
| CN101254471A (en) * | 2008-04-17 | 2008-09-03 | 中国石油天然气集团公司 | Modified molecular screen base precious metal diesel oil deepness hydrogenation dearomatization catalyst and method of preparing the same |
| CN103121906A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Method for preparing mononuclear aromatics by using polycyclic aromatic hydrocarbon |
| CN103372459A (en) * | 2012-04-12 | 2013-10-30 | 中国石油化工股份有限公司 | Cyclane hydro-conversion catalyst, preparation method and applications |
| CN104117386A (en) * | 2013-04-24 | 2014-10-29 | 中国科学院大连化学物理研究所 | Catalyst used for hydrogenation ring opening reaction of polycyclic aromatic hydrocarbon, and preparation method and application thereof |
-
2015
- 2015-10-15 CN CN201510665167.4A patent/CN106582628B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020043481A1 (en) * | 2000-07-21 | 2002-04-18 | Baird William C. | Ring opening with group VIII metal catalysts supported on modified substrate |
| CN1972748A (en) * | 2004-04-20 | 2007-05-30 | 环球油品公司 | Catalyst for selective opening of cyclic paraffins and process for using the catalyst |
| CN101254471A (en) * | 2008-04-17 | 2008-09-03 | 中国石油天然气集团公司 | Modified molecular screen base precious metal diesel oil deepness hydrogenation dearomatization catalyst and method of preparing the same |
| CN103121906A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Method for preparing mononuclear aromatics by using polycyclic aromatic hydrocarbon |
| CN103372459A (en) * | 2012-04-12 | 2013-10-30 | 中国石油化工股份有限公司 | Cyclane hydro-conversion catalyst, preparation method and applications |
| CN104117386A (en) * | 2013-04-24 | 2014-10-29 | 中国科学院大连化学物理研究所 | Catalyst used for hydrogenation ring opening reaction of polycyclic aromatic hydrocarbon, and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| SILVANA A. D"IPPOLITO ET AL.: ""Selective ring opening of decalin with Pt-Ir/Al2O3 catalyst prepared by catalytic reduction"", 《CATALYSIS TODAY》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113333454A (en) * | 2021-05-12 | 2021-09-03 | 上海应用技术大学 | Method for reducing and degrading polycyclic aromatic hydrocarbons in soil by using glacial acetic acid and anhydrous ethanol to catalyze metal magnesium |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106582628B (en) | 2019-07-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103120955B (en) | Catalyst for converting polycyclic aromatic hydrocarbons into monocyclic aromatic hydrocarbons and preparation method thereof | |
| JP5298135B2 (en) | Selective hydrogenation catalyst and production thereof | |
| CN104399520B (en) | Catalyst for producing high-octane-number gasoline composition from heavy aromatic hydrocarbons and preparation method of catalyst | |
| CN106582668B (en) | Alloy-loaded hydrogenation saturation catalyst and preparation method thereof | |
| WO2021063345A1 (en) | Dearsenification adsorbent and preparation method therefor | |
| CN105732288A (en) | Selective hydrogenation method for C4 fraction | |
| CN104549465B (en) | Heavy aromatics lightening catalyst of voluminous dimethylbenzene and preparation method thereof | |
| WO2015172592A1 (en) | Catalyst suitable for production of aviation kerosene from biomass fischer-tropsch synthesis oil and preparation method therefor | |
| CN104549456B (en) | Heavy aromatic lightening catalyst and preparation method thereof | |
| CN1184289C (en) | Catalyst used for cracking gusoline selective hydrogenation, its preparation method and use | |
| CN1191331C (en) | Dual-function reforming catalyst containing Pt and Sn and its preparing process | |
| CN106582628A (en) | Selective ring-opening catalyst and preparation method thereof | |
| CN104549469A (en) | Reproducible catalyst for converting polycyclic aromatic hydrocarbon into monocyclic aromatic hydrocarbon and preparation method of reproducible catalyst | |
| CN102895993B (en) | Sulfur-containing alkane aromatization catalyst, preparation method and applications thereof | |
| CN107216230B (en) | Isobutane dehydrogenation method | |
| CN104549473B (en) | Polycyclic aromatic sulfur is converted into catalyst of mononuclear aromatics and preparation method thereof | |
| CN105732263A (en) | Selective hydrogenation method of trace amount of acetylene in methanol to olefin (MTO) apparatus | |
| CN104353486B (en) | C10+ heavy aromatic hydrocarbon hydrodealkylation catalyst and preparation method thereof | |
| CN104549471A (en) | Catalyst for converting C10<+> heavy aromatics into mononuclear aromatics and preparation method of catalyst | |
| CN103418379A (en) | Catalyst for removing alkadiene in C4 and preparation method thereof | |
| CN109022025A (en) | Full-cut fraction pyrolysis gasoline process for selective hydrogenation | |
| CN104383961A (en) | Catalyst for hydrocracking heavy aromatics for producing high-purity BTX aromatics and preparing method of catalyst | |
| CN106582779A (en) | Polycyclic aromatic hydrocarbon ring-opening catalyst and preparation method thereof | |
| CN1324392A (en) | Method for isomerization of hydrocarbon, andsolid acid catalyst and isomerization device for use therein | |
| CN109289868A (en) | Selective hydrogenation catalyst for pyrolysis gasoline and preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |