CN106582779B - Polycyclic aromatic hydrocarbon ring opening catalyst and preparation method thereof - Google Patents
Polycyclic aromatic hydrocarbon ring opening catalyst and preparation method thereof Download PDFInfo
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- CN106582779B CN106582779B CN201510665166.XA CN201510665166A CN106582779B CN 106582779 B CN106582779 B CN 106582779B CN 201510665166 A CN201510665166 A CN 201510665166A CN 106582779 B CN106582779 B CN 106582779B
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Abstract
The present invention relates to a kind of polycyclic aromatic hydrocarbon ring opening catalysts and preparation method thereof.The excessive open loop of polycyclic aromatic hydrocarbon existing in the prior art is mainly solved, mononuclear aromatics yield is low, the fast problem of catalyst deactivation rate.The present invention is by using catalyst, it by weight percentage include: 45~60.9% selected from least one of FAU, BEA, MFI type zeolite or amorphous silica-alumina, 10~30% boehmite, 0.1~0.5% precious metals pd, the technical solution that 3~6% metal Co and 0.5~3% are selected from least one of metal Zn, Bi or Nb preferably solve the above problem.The catalyst is suitable for the refining field of lightweight mononuclear aromatics.
Description
Technical field
The present invention relates to a kind of polycyclic aromatic hydrocarbon ring opening catalysts and preparation method thereof.
Background technique
Benzene,toluene,xylene (BTX) etc. is all important Organic Chemicals.Benzene is to prepare styrene, nylon, terylene
The basic material of equal products；And toluene is used as the blending compound of gasoline to improve octane number, can also produce paint, bonding
Agent, organic solvent etc. are widely used in industrial, agricultural and medically；Then production polyester, chemical fibres etc. of being used to produce dimethylbenzene more
Product, they are all closely related with the food, clothing, housing and transportation of the national economic development and people, in strong demand in recent years, increment is rapid, and
The situation that supply falls short of demand will be generated, it is very urgent to seek aromatic hydrocarbons yield-increasing technology.However, as the continuous of oil product degree of heaviness adds
The finiteness of depth and world petroleum resource, it is deep by developing heavy oil for the growth for meeting economic development bring oil demand
Degree conversion, the light-end products for increasing production high added value will be the significant development strategy of 21 century oil refining industry.
By the development of many years, as by the important technology hydrocracking technology of heavy polycyclic aromatic hydrocarbon lighting, though at present
So have many advantages, such as that adaptability to raw materials is wide, conversion level is big, but that there is also reaction temperature and pressure is high, air speed is low, consumption hydrogen is big, urges
In place of the deficiencies of agent service life is short, these also become the emphasis that domestic and international research institution breaks through.
Nippon Oil(Nippon Mitsubishi Oil) on January 21st, 2010, exploitation, was produced the technical staff of aromatic hydrocarbon product by report with light diesel fuel (LCO)
Skill.Compared with the largely traditional handicraft of consumption hydrogen, which can cut down production cost, be expected to realize and commercially produce.
USP4,341,622 discloses a kind of method using heavy reformate production BTX.This method uses restricted index
It is catalyst for the zeolite that 1~12, silica/alumina molar ratio (silica alumina ratio) is 12 or more, low acid activity, reformate is made to exist
It is reacted under conditions of 427~540 DEG C, then product is distilled into isolated benzene, toluene and dimethylbenzene.The catalyst contains
The VIII group noble metal of hydro-dealkylation function, preferably platinum, the silica alumina ratio of zeolite used are preferably greater than 200, more preferably greater than
500, preferred zeolite is ZSM-5.Select the zeolite of high silica alumina ratio to reduce zeolite acidity, reservation dimethylbenzene as far as possible is reacting
In be not converted.
US2007062848A1, which is disclosed, a kind of first will carry out again selective opening and de- alkane after polycyclic aromatic hydrocarbon fractional saturation
Base is come the method that obtains light aromatics.This method can satisfy polycyclic aromatic hydrocarbon content in feed stream and be saturated in 20wt% or more
Phase temperature is at 300~500 DEG C, 2~10MPa of pressure；Open loop phase temperature is at 200~600 DEG C, 1~12MPa of pressure.Due to
Two-stage catalytic agent it requires that logistics needs to guarantee that certain residence time could obtain preferable turn in same reactor
Rate, therefore air speed is lower.
CN1472181A discloses a kind of heavy aromatics lightening catalyst, the group VIII metal including 0.01~2.0 weight %
And complex carrier, the 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, and C can be improved9 +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.It is described to urge
Agent is boiled by the ZSM-5 of the platinum or palladium of 0.05~0.3 weight %, the zeolite with MOR structure of 20~59 weight %, 20~50 weight %
The aluminium oxide composition of stone and 20~40 weight %.By the raw material of the heavy arene containing C9+ in 350~450 DEG C, 0.3~3.5MPa item
Contacted under part with above-mentioned catalyst, gained lighting product by fractionation can be obtained BTX and mesitylene, pseudocumene,
The Organic Ingredients such as durol.
CN1048425C discloses a kind of heavy arenes lightening catalyst and lightening method.The catalyst is with 30~70
γ-or the η-Al of the ZSM-5 zeolite of weight % and 30~70 weight %2O3For carrier, load 0.1~0.5 weight % tin 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 active and stability with higher and lower hydrogen consumption.
Summary of the invention
The first technical problem to be solved by the present invention is to overcome polycyclic aromatic hydrocarbon existing in the prior art excessively to open
Ring, mononuclear aromatics yield is low, the fast problem of catalyst deactivation rate, provides a kind of new polycyclic aromatic hydrocarbon ring opening catalyst.This is urged
Agent has polycyclic aromatic hydrocarbon selectivity of ring-opening good, the high income of mononuclear aromatics, the slow advantage of catalyst deactivation rate.
The second technical problem to be solved by the present invention is to provide a kind of corresponding polycyclic with one of solution technical problem
The preparation method of aromatic hydrocarbons ring opening catalyst.
The third technical problem to be solved by the present invention is to provide a kind of corresponding polycyclic with one of solution technical problem
The operating method of aromatic hydrocarbons ring opening catalyst.
One of to solve above-mentioned technical problem, The technical solution adopted by the invention is as follows: a kind of polycyclic aromatic hydrocarbon open loop is catalyzed
Agent includes: based on catalyst weight percent
(a) 45~60.9% selected from least one of FAU, BEA, MFI type zeolite or amorphous silica-alumina；
(b) 10~30% boehmite；
(c) 0.1~0.5% precious metals pd；
(d) 3~6% metal Co；
(e) 0.5~3% selected from least one of metal Zn, Bi or Nb.
In above-mentioned technical proposal, the part (a) FAU zeolite in USY, HY, NTY or SSY molecular sieve at least
It is a kind of；BEA zeolite is selected from Hydrogen or ammonium type Beta molecular sieve；MFI zeolite is selected from Hydrogen or ammonium type ZSM-5 molecular sieve.
In above-mentioned technical proposal, metal preferably is selected from Zn and Bi in described part (e).
In above-mentioned technical proposal, metal preferably is selected from Nb in described part (e).
To solve above-mentioned technical problem two, The technical solution adopted by the invention is as follows: a kind of polycyclic aromatic hydrocarbon open loop is catalyzed
The preparation method of agent, comprising the following steps:
1. will selected from least one of FAU, BEA, MFI type zeolite or amorphous silica-alumina and boehmite through kneading,
Molding, extrusion, it is dry after, roast 0.5 in 450~650 DEG C~obtain catalyst carrier for 24 hours；
It is urged 2. the precursor solution containing at least one of metal Pd, Co, metal Zn, Bi or Nb is impregnated into 10~60 DEG C
Ageing 0.5 on agent carrier~for 24 hours, it is spare after dry；
3. after 400~650 DEG C of 1~10h of roasting of air atmosphere, after 300~650 DEG C of 3~10h of reduction of hydrogen atmosphere i.e.
Obtain finished catalyst.
In above-mentioned technical proposal, the presoma of the precious metals pd is at least one of palladium nitrate or palladium chloride；Gold
The presoma for belonging to Co is at least one of cobalt chloride or cobalt nitrate；The presoma of metal Zn be in zinc chloride or zinc nitrate extremely
Few one kind；The presoma of metal Bi is at least one of bismuth nitrate or bismuth chloride；The presoma of metal Nb is niobium pentaoxide.
In above-mentioned technical proposal, addition is by carrier dry basis 2~5% in the catalyst carrier preparation process
Extrusion aid, the gelatinizing agent of addition 3~6%.
In above-mentioned technical proposal, the extrusion aid is at least one of sesbania powder or tung oil；Gelatinizing agent is selected from salt
The volume ratio of at least one of acid, nitric acid, acetic acid, tartaric acid, citric acid or oxalic acid and water is 1:1~1:5.
To solve above-mentioned technical problem three, The technical solution adopted by the invention is as follows: a kind of side of polycyclic aromatic hydrocarbon open loop
Method, Polycyclic Aromatic Hydrocarbon Mixture are mixed with hydrogen, pass through catalyst bed, in 350~450 DEG C of reaction temperature, reaction
4~8MPa of pressure, 0.5~5hr of volume space velocity-1, connect with any one of the above catalyst under the conditions of hydrogen to oil volume ratio 500~1600
Touching carries out heavy aromatics lighting reaction.
In above-mentioned technical proposal, preferred embodiment are as follows: 360~390 DEG C of reaction temperature, 5~7MPa of reaction pressure, volume space velocity
1~2hr-1, contacted with catalyst under conditions of hydrogen to oil volume ratio 600~1200.
The present invention carries out the Performance of polycyclic aromatic hydrocarbon ring-opening reaction, 12 milli of reactor inside diameter Ф using fixed bed reactors
Rice, 800 millimeters of length, stainless steel material.Using electric heating, temperature automatic control.Reactor bottom fills 2~3 millimeters of glass of Ф
Glass pearl is supporter, and 5 grams of catalyst filling in reactor, 2~3 millimeters of beades of Ф are filled on top, is made for raw material preheating and vapour
Change is used.Raw material Polycyclic Aromatic Hydrocarbon Mixture is mixed with hydrogen, passes through catalyst bed, is converted into polycyclic aromatic hydrocarbon
The mononuclear aromatics such as benzene,toluene,xylene.
Experimental data is calculated as follows:
The amount of mononuclear aromatics × liquid receives/100 in mononuclear aromatics yield=product
Catalyst provided by the invention is suitable for the refining field of lightweight mononuclear aromatics.
Due to having loaded various metals in catalyst carrier in the present invention, and merged various metals plus hydrogen characteristic, gold
Belong to atom to be reset, the metallic combination of generation is substantially better than single metal on hydrogenation activity, and stability is more preferable, sour with containing
The system with molecular sieve for preparing at center is standby at bifunctional catalyst, stronger to the cracking ability of polycyclic aromatic hydrocarbon, passes through and adjusts metal and acid carry
The ratio and operating procedure condition of body produce the mononuclear aromatics such as benzene,toluene,xylene to reach selective splitting polycyclic aromatic hydrocarbon
The selectivity of purpose, polycyclic aromatic hydrocarbon open loop is high, and the high income of mononuclear aromatics, catalyst deactivation rate is slow, achieves preferable skill
Art effect.
Below by embodiment, the present invention is further elaborated.
Specific embodiment
[embodiment 1]
It is the HY molecular sieve (commercially available) and (commercially available) the addition mixer of 30g boehmite that 60g silica alumina ratio is 10 by butt
To uniform, 3g sesbania powder, 5g volume ratio 1:1HNO are then added into mixture3Solution and 40g deionized water grind uniformly system
At the dough for being suitable for squeezing out.By its by mold squeeze out, shape be in elongated cylinder (diameter 1.7mm), 120 DEG C drying after in
550 DEG C of roasting 4h, it is spare to be then cut into the consistent carrier granular of size (1.7 × 4.0mm).
The mixed solution of palladium nitrate, cobalt nitrate, zinc nitrate impregnates carrier granular at 40 DEG C, is rolled in maceration extract
Contained carrier dry weight 0.2%Pd, 4%Co and 2%Zn are calculated, is aged 8h and after drying, in air 550 DEG C of oxidation 4h,
450 DEG C of reduction 4h (this step can be completed in the reactor) get product catalyst A in hydrogen again.
It is investigated on fixed bed reactors with catalyst A by Polycyclic Aromatic Hydrocarbon Mixture open loop ability.Table 1 is evaluation raw material group
At.Catalyst packing 5g, in 360 DEG C of reaction temperature, reaction pressure 5.0MPa, volume space velocity 1.0hr-1, hydrogen to oil volume ratio 800
It is contacted under part with catalyst, recycling is carried out to product and component detects, conversion results are shown in Table 2.
[embodiment 2]
It is the Beta molecular sieve (commercially available) and (commercially available) the addition mixing of 30g boehmite that 60g silica alumina ratio is 15 by butt
Then 3g sesbania powder, 5g volume ratio 1:1HNO is added to uniform in device into mixture3Solution and 40g deionized water, grinding are uniform
The dough suitable for squeezing out is made.It is squeezed out by mold, shape is in elongated cylinder (diameter 1.7mm), after 120 DEG C of drying
In 550 DEG C of roasting 4h, it is spare to be then cut into the consistent carrier granular of size (1.7 × 4.0mm).
The mixed solution of palladium nitrate, cobalt nitrate, zinc nitrate impregnates carrier granular at 40 DEG C, is rolled in maceration extract
Contained carrier dry weight 0.2%Pd, 4%Co and 2%Zn are calculated, is aged 8h and after drying, in air 550 DEG C of oxidation 4h,
450 DEG C of reduction 4h (this step can be completed in the reactor) get product catalyst B in hydrogen again.
It is investigated on fixed bed reactors with catalyst B by Polycyclic Aromatic Hydrocarbon Mixture open loop ability.Table 1 is evaluation raw material group
At.Catalyst packing 5g, in 360 DEG C of reaction temperature, reaction pressure 5.0MPa, volume space velocity 1.0hr-1, hydrogen to oil volume ratio 800
It is contacted under part with catalyst, recycling is carried out to product and component detects, conversion results are shown in Table 2.
[embodiment 3]
It is the ZSM-5 molecular sieve (commercially available) and (commercially available) the addition mixing of 30g boehmite that 60g silica alumina ratio is 40 by butt
Then 3g sesbania powder, 5g volume ratio 1:1HNO is added to uniform in device into mixture3Solution and 40g deionized water, grinding are uniform
The dough suitable for squeezing out is made.It is squeezed out by mold, shape is in elongated cylinder (diameter 1.7mm), after 120 DEG C of drying
In 550 DEG C of roasting 4h, it is spare to be then cut into the consistent carrier granular of size (1.7 × 4.0mm).
The mixed solution of palladium nitrate, cobalt nitrate, zinc nitrate impregnates carrier granular at 40 DEG C, is rolled in maceration extract
Contained carrier dry weight 0.2%Pd, 4%Co and 2%Zn are calculated, is aged 8h and after drying, in air 550 DEG C of oxidation 4h,
450 DEG C of reduction 4h (this step can be completed in the reactor) get product catalyst C in hydrogen again.
It is investigated on fixed bed reactors with catalyst C by Polycyclic Aromatic Hydrocarbon Mixture open loop ability.Table 1 is evaluation raw material group
At.Catalyst packing 5g, in 360 DEG C of reaction temperature, reaction pressure 5.0MPa, volume space velocity 1.0hr-1, hydrogen to oil volume ratio 800
It is contacted under part with catalyst, recycling is carried out to product and component detects, conversion results are shown in Table 2.
[embodiment 4]
It is 60g amorphous silica-alumina (commercially available) and (commercially available) the addition mixer of 30g boehmite to uniform by butt, then
3g sesbania powder, 5g volume ratio 1:1HNO are added into mixture3Solution and 40g deionized water, grinding, which is uniformly made, to be suitable for squeezing out
Dough.It is squeezed out by mold, shape is in elongated cylinder (diameter 1.7mm), is roasted after 120 DEG C of drying in 550 DEG C
Then it is spare to be cut into the consistent carrier granular of size (1.7 × 4.0mm) by 4h.
The mixed solution of palladium nitrate, cobalt nitrate, zinc nitrate impregnates carrier granular at 40 DEG C, is rolled in maceration extract
Contained carrier dry weight 0.2%Pd, 4%Co and 2%Zn are calculated, is aged 8h and after drying, in air 550 DEG C of oxidation 4h,
450 DEG C of reduction 4h (this step can be completed in the reactor) get product catalyst D in hydrogen again.
It is investigated on fixed bed reactors with catalyst D by Polycyclic Aromatic Hydrocarbon Mixture open loop ability.Table 1 is evaluation raw material group
At.Catalyst packing 5g, in 360 DEG C of reaction temperature, reaction pressure 5.0MPa, volume space velocity 1.0hr-1, hydrogen to oil volume ratio 800
It is contacted under part with catalyst, recycling is carried out to product and component detects, conversion results are shown in Table 2.
[embodiment 5]
It is the HY molecular sieve (commercially available) and (commercially available) the addition mixer of 30g boehmite that 60g silica alumina ratio is 10 by butt
To uniform, 3g sesbania powder, 5g volume ratio 1:1HNO are then added into mixture3Solution and 40g deionized water grind uniformly system
At the dough for being suitable for squeezing out.By its by mold squeeze out, shape be in elongated cylinder (diameter 1.7mm), 120 DEG C drying after in
550 DEG C of roasting 4h, it is spare to be then cut into the consistent carrier granular of size (1.7 × 4.0mm).
The mixed solution of palladium nitrate, cobalt nitrate, bismuth nitrate impregnates carrier granular at 40 DEG C, is rolled in maceration extract
Contained carrier dry weight 0.2%Pd, 4%Co and 2%Bi are calculated, is aged 8h and after drying, in air 550 DEG C of oxidation 4h,
450 DEG C of reduction 4h (this step can be completed in the reactor) get product catalyst E in hydrogen again.
It is investigated on fixed bed reactors with catalyst E by Polycyclic Aromatic Hydrocarbon Mixture open loop ability.Table 1 is evaluation raw material group
At.Catalyst packing 5g, in 360 DEG C of reaction temperature, reaction pressure 5.0MPa, volume space velocity 1.0hr-1, hydrogen to oil volume ratio 800
It is contacted under part with catalyst, recycling is carried out to product and component detects, conversion results are shown in Table 2.
[embodiment 6]
It is the HY molecular sieve (commercially available) and (commercially available) the addition mixer of 30g boehmite that 60g silica alumina ratio is 10 by butt
To uniform, 3g sesbania powder, 5g volume ratio 1:1HNO are then added into mixture3Solution and 40g deionized water grind uniformly system
At the dough for being suitable for squeezing out.By its by mold squeeze out, shape be in elongated cylinder (diameter 1.7mm), 120 DEG C drying after in
550 DEG C of roasting 4h, it is spare to be then cut into the consistent carrier granular of size (1.7 × 4.0mm).
The mixed solution of palladium nitrate, cobalt nitrate, niobium pentaoxide impregnates carrier granular at 40 DEG C, maceration extract
Carrier dry weight 0.2%Pd, 4%Co and 2%Nb contained by middle conversion, ageing 8h and after drying are aoxidized for 550 DEG C in air
4h, then 450 DEG C of reduction 4h (this step can be completed in the reactor) get product catalyst F in hydrogen.
It is investigated on fixed bed reactors with catalyst F by Polycyclic Aromatic Hydrocarbon Mixture open loop ability.Table 1 is evaluation raw material group
At.Catalyst packing 5g, in 360 DEG C of reaction temperature, reaction pressure 5.0MPa, volume space velocity 1.0hr-1, hydrogen to oil volume ratio 800
It is contacted under part with catalyst, recycling is carried out to product and component detects, conversion results are shown in Table 2.
[embodiment 7]
It is the HY molecular sieve (commercially available) and (commercially available) the addition mixer of 30g boehmite that 60g silica alumina ratio is 10 by butt
To uniform, 3g sesbania powder, 5g volume ratio 1:1HNO are then added into mixture3Solution and 40g deionized water grind uniformly system
At the dough for being suitable for squeezing out.By its by mold squeeze out, shape be in elongated cylinder (diameter 1.7mm), 120 DEG C drying after in
550 DEG C of roasting 4h, it is spare to be then cut into the consistent carrier granular of size (1.7 × 4.0mm).
The mixed solution of palladium nitrate, cobalt nitrate, zinc nitrate impregnates carrier granular at 40 DEG C, is rolled in maceration extract
Calculate contained carrier dry weight 0.4%Pd, 4%Co and 1.8%Zn, ageing 8h and after drying is aoxidized for 550 DEG C in air
4h, then 450 DEG C of reduction 4h (this step can be completed in the reactor) get product catalyst G in hydrogen.
It is investigated on fixed bed reactors with catalyst G by Polycyclic Aromatic Hydrocarbon Mixture open loop ability.Table 1 is evaluation raw material group
At.Catalyst packing 5g, in 360 DEG C of reaction temperature, reaction pressure 5.0MPa, volume space velocity 1.0hr-1, hydrogen to oil volume ratio 800
It is contacted under part with catalyst, recycling is carried out to product and component detects, conversion results are shown in Table 2.
[embodiment 8]
It is the HY molecular sieve (commercially available) and (commercially available) the addition mixer of 30g boehmite that 60g silica alumina ratio is 10 by butt
To uniform, 3g sesbania powder, 5g volume ratio 1:1HNO are then added into mixture3Solution and 40g deionized water grind uniformly system
At the dough for being suitable for squeezing out.By its by mold squeeze out, shape be in elongated cylinder (diameter 1.7mm), 120 DEG C drying after in
550 DEG C of roasting 4h, it is spare to be then cut into the consistent carrier granular of size (1.7 × 4.0mm).
The mixed solution of palladium nitrate, cobalt nitrate, zinc nitrate and bismuth nitrate impregnates carrier granular at 40 DEG C, soaks
Contained carrier dry weight 0.2%Pd, 4%Co, 1%Zn and 1%Bi are converted in stain liquid, 8h and after drying are aged, in air
In 550 DEG C of oxidation 4h, then 450 DEG C of reduction 4h (this step can be completed in the reactor) get product catalyst H in hydrogen.
It is investigated on fixed bed reactors with catalyst H by Polycyclic Aromatic Hydrocarbon Mixture open loop ability.Table 1 is evaluation raw material group
At.Catalyst packing 5g, in 360 DEG C of reaction temperature, reaction pressure 5.0MPa, volume space velocity 1.0hr-1, hydrogen to oil volume ratio 800
It is contacted under part with catalyst, recycling is carried out to product and component detects, conversion results are shown in Table 2.
[embodiment 9]
It is the HY molecular sieve (commercially available) and (commercially available) the addition mixer of 30g boehmite that 60g silica alumina ratio is 10 by butt
To uniform, 3g sesbania powder, 5g volume ratio 1:1HNO are then added into mixture3Solution and 40g deionized water grind uniformly system
At the dough for being suitable for squeezing out.By its by mold squeeze out, shape be in elongated cylinder (diameter 1.7mm), 120 DEG C drying after in
550 DEG C of roasting 4h, it is spare to be then cut into the consistent carrier granular of size (1.7 × 4.0mm).
The mixed solution of palladium nitrate, cobalt nitrate, zinc nitrate impregnates carrier granular at 40 DEG C, is rolled in maceration extract
Contained carrier dry weight 0.2%Pd, 5%Co and 1%Zn are calculated, is aged 8h and after drying, in air 550 DEG C of oxidation 4h,
450 DEG C of reduction 4h (this step can be completed in the reactor) get product catalyst I in hydrogen again.
It is investigated on fixed bed reactors with catalyst I by Polycyclic Aromatic Hydrocarbon Mixture open loop ability.Table 1 is evaluation raw material group
At.Catalyst packing 5g, in 360 DEG C of reaction temperature, reaction pressure 5.0MPa, volume space velocity 1.0hr-1, hydrogen to oil volume ratio 800
It is contacted under part with catalyst, recycling is carried out to product and component detects, conversion results are shown in Table 2.
[embodiment 10]
It is the HY molecular sieve (commercially available) and (commercially available) the addition mixer of 30g boehmite that 60g silica alumina ratio is 10 by butt
To uniform, 3g sesbania powder, 5g volume ratio 1:1HNO are then added into mixture3Solution and 40g deionized water grind uniformly system
At the dough for being suitable for squeezing out.By its by mold squeeze out, shape be in elongated cylinder (diameter 1.7mm), 120 DEG C drying after in
550 DEG C of roasting 4h, it is spare to be then cut into the consistent carrier granular of size (1.7 × 4.0mm).
The mixed solution of palladium nitrate, cobalt nitrate, zinc nitrate and bismuth nitrate impregnates carrier granular at 40 DEG C, soaks
Contained carrier dry weight 0.2%Pd, 4%Co, 1.5%Zn and 0.5%Bi are converted in stain liquid, are aged 8h and after drying,
550 DEG C of oxidation 4h in air, then 450 DEG C of reduction 4h (this step can be completed in the reactor) get product catalyst J in hydrogen.
It is investigated on fixed bed reactors with catalyst J by Polycyclic Aromatic Hydrocarbon Mixture open loop ability.Table 1 is evaluation raw material group
At.Catalyst packing 5g, in 360 DEG C of reaction temperature, reaction pressure 5.0MPa, volume space velocity 1.0hr-1, hydrogen to oil volume ratio 800
It is contacted under part with catalyst, recycling is carried out to product and component detects, conversion results are shown in Table 2.
[comparative example 1]
It is the HY molecular sieve (commercially available) and (commercially available) the addition mixer of 30g boehmite that 60g silica alumina ratio is 10 by butt
To uniform, 3g sesbania powder, 5g volume ratio 1:1HNO are then added into mixture3Solution and 40g deionized water grind uniformly system
At the dough for being suitable for squeezing out.By its by mold squeeze out, shape be in elongated cylinder (diameter 1.7mm), 120 DEG C drying after in
550 DEG C of roasting 4h, it is spare to be then cut into the consistent carrier granular of size (1.7 × 4.0mm).
Palladium nitrate solution impregnates carrier granular at 40 DEG C, contained carrier dry weight is converted in maceration extract
0.2%Pd is aged 8h and after drying, in air 550 DEG C of oxidation 4h, then (this step can be anti-by 450 DEG C of reduction 4h in hydrogen
Answer in device and complete) get product catalyst.
It is investigated on fixed bed reactors with catalyst by Polycyclic Aromatic Hydrocarbon Mixture open loop ability.Table 1 is evaluation raw material group
At.Catalyst packing 5g, in 360 DEG C of reaction temperature, reaction pressure 5.0MPa, volume space velocity 1.0hr-1, hydrogen to oil volume ratio 800
It is contacted under part with catalyst, recycling is carried out to product and component detects, conversion results are shown in Table 2.
[comparative example 2]
It is the HY molecular sieve (commercially available) and (commercially available) the addition mixer of 30g boehmite that 60g silica alumina ratio is 10 by butt
To uniform, 3g sesbania powder, 5g volume ratio 1:1HNO are then added into mixture3Solution and 40g deionized water grind uniformly system
At the dough for being suitable for squeezing out.By its by mold squeeze out, shape be in elongated cylinder (diameter 1.7mm), 120 DEG C drying after in
550 DEG C of roasting 4h, it is spare to be then cut into the consistent carrier granular of size (1.7 × 4.0mm).
The mixed solution of palladium nitrate, cobalt nitrate impregnates carrier granular at 40 DEG C, in maceration extract contained by conversion
Carrier dry weight 0.2%Pd, 4%Co is aged 8h and after drying, in air 550 DEG C of oxidation 4h, then 450 in hydrogen
DEG C reduction 4h (this step can be completed in the reactor) get product catalyst.
It is investigated on fixed bed reactors with catalyst by Polycyclic Aromatic Hydrocarbon Mixture open loop ability.Table 1 is evaluation raw material group
At.Catalyst packing 5g, in 360 DEG C of reaction temperature, reaction pressure 5.0MPa, volume space velocity 1.0hr-1, hydrogen to oil volume ratio 800
It is contacted under part with catalyst, recycling is carried out to product and component detects, conversion results are shown in Table 2.
1 raw material of table composition
| Raw material composition | 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 11~15]
The catalyst A made from embodiment 1 is investigated on fixed bed reactors and is converted monocycle for Polycyclic Aromatic Hydrocarbon Mixture
The ability of aromatic hydrocarbons.Catalyst packing 5g, by changing the conditions such as reaction temperature, reaction pressure, volume space velocity and hydrogen to oil volume ratio,
Recycling and component detection are carried out to product, conversion results are shown in Table 3.
3 polycyclic aromatic hydrocarbon conversion results of table
Claims (10)
1. a kind of polycyclic aromatic hydrocarbon ring opening catalyst, composed of the following components based on catalyst weight percent:
(a) 45~60.9% selected from least one of FAU, BEA, MFI type zeolite or amorphous silica-alumina；
(b) 10~30% boehmite；
(c) 0.1~0.5% precious metals pd；
(d) 3~6% metal Co；
(e) 0.5~3% selected from least one of metal Zn, Bi or Nb.
2. a kind of preparation method of polycyclic aromatic hydrocarbon ring opening catalyst described in claim 1, comprising the following steps:
1. will selected from least one of FAU, BEA, MFI type zeolite or amorphous silica-alumina and boehmite through kneading, molding,
Extrusion, it is dry after, roast 0.5 in 450~650 DEG C~obtain catalyst carrier for 24 hours；
2. the precursor solution of precursor solution, at least one of Zn, Bi or Nb containing metal Pd, Co is impregnated in 10~60 DEG C
Ageing 0.5 on to catalyst carrier~for 24 hours, it is spare after dry；
3. urged after 300~650 DEG C of 3~10h of reduction of hydrogen atmosphere after 400~650 DEG C of 1~10h of roasting of air atmosphere to obtain the final product
Agent finished product.
3. the preparation method of polycyclic aromatic hydrocarbon ring opening catalyst according to claim 2, it is characterised in that the noble metal
The presoma of Pd is at least one of palladium nitrate or palladium chloride.
4. the preparation method of polycyclic aromatic hydrocarbon ring opening catalyst according to claim 2, it is characterised in that the metal Co
Presoma be at least one of cobalt chloride or cobalt nitrate.
5. the preparation method of polycyclic aromatic hydrocarbon ring opening catalyst according to claim 2, it is characterised in that the metal Zn
Presoma be at least one of zinc chloride or zinc nitrate；The presoma of metal Bi is at least one in bismuth nitrate or bismuth chloride
Kind；The presoma of metal Nb is niobium pentaoxide.
6. the preparation method of polycyclic aromatic hydrocarbon ring opening catalyst according to claim 2, it is characterised in that catalyst carrier system
The extrusion aid of carrier dry basis 2~5%, the gelatinizing agent of addition 3~6% are pressed in addition during standby.
7. the preparation method of polycyclic aromatic hydrocarbon ring opening catalyst according to claim 6, it is characterised in that the extrusion aid
For at least one of sesbania powder or tung oil.
8. the preparation method of polycyclic aromatic hydrocarbon ring opening catalyst according to claim 6, it is characterised in that the gelatinizing agent
It is 1:1~1 for the volume ratio selected from least one of hydrochloric acid, nitric acid, acetic acid, tartaric acid, citric acid or oxalic acid, and water:
5。
9. a kind of method of polycyclic aromatic hydrocarbon open loop, it is characterised in that Polycyclic Aromatic Hydrocarbon Mixture is mixed with hydrogen, is passed through
Catalyst bed, in 350~450 DEG C of reaction temperature, 4~8MPa of reaction pressure, 0.5~5hr of volume space velocity-1, hydrogen to oil volume ratio
It is contacted under the conditions of 500~1600 with catalyst described in claim 1, carries out polycyclic aromatic hydrocarbon ring-opening reaction.
10. the method for polycyclic aromatic hydrocarbon open loop according to claim 9, it is characterised in that 360~390 DEG C of reaction temperature, anti-
Answer 5~7MPa of pressure, 1~2hr of volume space velocity-1, contacted with catalyst under conditions of hydrogen to oil volume ratio 600~1200.
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| CN103120956A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Catalyst for converting polycyclic aromatic hydrocarbons into monocyclic aromatic hydrocarbons to produce more dimethylbenzene and preparation method thereof |
| CN104549465A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Heavy aromatics light catalyst for high-yield production of xylene and preparation method of catalyst |
| WO2015128017A1 (en) * | 2014-02-25 | 2015-09-03 | Saudi Basic Industries Corporation | Process for producing btx from a mixed hydrocarbon source using coking |
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| CN1351117A (en) * | 2000-10-26 | 2002-05-29 | 中国石油化工股份有限公司 | Hydrocatalyst for saturating arylhydrocarbon in diesel oil and its preparing process |
| CN103120956A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Catalyst for converting polycyclic aromatic hydrocarbons into monocyclic aromatic hydrocarbons to produce more dimethylbenzene and preparation method thereof |
| CN104549465A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Heavy aromatics light catalyst for high-yield production of xylene and preparation method of catalyst |
| WO2015128017A1 (en) * | 2014-02-25 | 2015-09-03 | Saudi Basic Industries Corporation | Process for producing btx from a mixed hydrocarbon source using coking |
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