CN108927204A - The catalyst and its preparation method of coal tar hydrogenating processing distillate selective hydrogenation cracking light aromatic hydrocarbons and application - Google Patents
The catalyst and its preparation method of coal tar hydrogenating processing distillate selective hydrogenation cracking light aromatic hydrocarbons and application Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
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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
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
- C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
- C10G45/54—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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Abstract
A kind of catalyst of coal tar hydrogenating processing distillate selective hydrogenation cracking light aromatic hydrocarbons is by HZSM-5-MgAPO-5 composite molecular screen carrier and active component Ni2P is formed, wherein active component Ni2The weight percentage of P is 12%~30%, and the weight percentage of composite molecular screen HZSM-5-MgAPO-5 is 70%~88%, and the weight percentage that the weight percentage of HZSM-5 is 11.2%~23.9%, MgAPO-5 in composite molecular screen is 76.1%~88.8%.The present invention has the advantages of catalyst that highly selective, high activity and high stability are provided using monocycle light aromatic hydrocarbons as purpose product.
Description
Technical field
The present invention relates to coal tar deep processings and field of comprehensive utilization, and in particular to a kind of coal tar hydrogenating processing distillate
The catalyst and its preparation method and application of selective hydrogenation cracking light aromatic hydrocarbons.
Background technique
Coal tar is a kind of by-product of coal gasification, pyrolysis or destructive distillation industry.It is fast with China's Modern Coal-based Chemical industry
Speed development, the yield of coal tar are also rapidly increasing.According to statistics, the yield of China's coal tar has reached nearly 20,000,000 at present
Ton/year.Coal tar complicated component, aromatic hydrocarbons therein especially polycyclic aromatic hydrocarbon content in 50% or more, especially high temperature coal-tar,
Polycyclic aromatic hydrocarbon content therein reaches 70% or more.Therefore, the clean utilization of coal tar becomes extremely important problem.
By the development of coal tar deep processing technology, producing clean fuel oil by hydrogenation of coal tar technology has realized industrialization
Using with popularization, this facilitate the clean utilizations of tar resource.But due to being influenced by international petroleum oil supply, cleaning combustion
Expect the market price continued jitters of oil, this has seriously affected the economic benefit of coal tar deep processing enterprise.So expanding coal tar
Comprehensive Utilization Ways, raising coal tar deep processing value-added content of product as far as possible, and then improve coal tar deep processing enterprise
Economic benefit is particularly critical.
Monocycle light aromatic hydrocarbons such as benzene, toluene, ethylbenzene, dimethylbenzene etc. are important basic fine chemical material, are widely used in poly-
Multiple industries such as ethylene, polyester fiber, nylon, coating, capsule, pesticide, demand is very big for many years, often in for not answering
The situation asked.Therefore, using selective hydrogenation cracking technology, by coal tar hydrogenating processing distillate be converted into including benzene, toluene,
High added value monocycle light aromatic hydrocarbons including dimethylbenzene etc., can both realize the comprehensive utilization of tar resource, be also beneficial to alleviate light
The imbalance between supply and demand of aromatic hydrocarbons has important reality and social effect.
The core that coal tar hydrogenating handles distillate selective hydrogenation cracking light aromatic hydrocarbons technology is catalyst, it is a kind of
Bifunctional catalyst need to have suitable hydrogenation activity and cracking activity simultaneously.The result of study of early period shows coal tar hydrogenating
Polycyclic aromatic hydrocarbon in processing distillate is hydrogenated to monocycle light aromatic hydrocarbons and mainly passes through two kinds of paths.One is coal tar hydrogenating processing
The side ring of polycyclic aromatic hydrocarbon in fraction first adds hydrogen, cracking open loop to generate the aromatic hydrocarbons of a few aromatic ring, generate the side ring of aromatic hydrocarbons again after
Continuous plus hydrogen, cracking open loop, until gradually generating monocycle light aromatic hydrocarbons.Another path is polycyclic in coal tar hydrogenating processing fraction
The intermediate ring of aromatic hydrocarbons first adds hydrogen, cracking open loop to generate the aromatic hydrocarbons of one or two few aromatic ring, and the polycyclic aromatic hydrocarbon of generation again can be into one
The intermediate ring of step generation adds hydrogen and cracking open loop, until the multiple monocycle light aromatic hydrocarbons of generation.Comparing both response paths can find,
Compared with the first path, the hydrogen that second of path not only consumes is less, but also the monocycle that can get higher yields is gently fragrant
Hydrocarbon.Therefore, it is removed for the property and compositing characteristic of coal tar hydrogenating processing distillate in order to improve the yield of monocycle light aromatic hydrocarbons
It develops outside coal tar hydrogenating processing distillate selective hydrogenation process, coal tar hydrogenating processing distillate selective hydrogenation is split
The development for changing catalyst also becomes the key of this technology with exploitation.
CN102847549B discloses a kind of coal tar hydrocracking catalyst and preparation method thereof, is by amorphous silica-alumina
The slurry that pH value is the .5 of 3 .0~5 is made, modified Y molecular sieve solid powder is uniformly mixed with amorphous silica-alumina slurry,
Then plastic paste is made in dehydration, and catalyst carrier is made through molding, drying, roasting, is finally added using infusion process load
Hydrogen metal component obtains final hydrocracking catalyst.
CN105562067A discloses middle coalite tar hydrocracking catalyst and its preparation method and application, low in this
Warm coal tar hydrocracking catalyst, including active component and Jie's micro porous molecular sieve, active component are supported on Jie's micro porous molecular sieve
On, two or more in active component Mo, Ni, Co and W, the quality of middle coalite tar hydrocracking catalyst presses 100%
Meter, the mass percent of Mo are 5% to 18%.
CN102728378B disclose it is a kind of using column clay as the novel coal tar hydrogenating Cracking catalyst of carrier and its
Preparation method.The hydrocracking catalyst is made of active component and carrier.Catalyst is made of carrier and active component, activity
Group is divided into WO3、MoO3With the mixture or WO of NiO3With the mixture of NiO, carrier is pillared montmorillonite clay.With oxidation
Object form calculus, active component account for total catalyst weight 15~35%, and carrier accounts for the 65~85% of catalyst gross mass.Catalyst
Preparation step includes the purification and modification, the preparation of pillared liquid, the preparation of pillared clay support and column clay catalysis of clay pit
Agent preparation.
CN102069004B discloses a kind of hydrocracking catalyst for preparing fuel oil from coal tar and its methods for making and using same.
The hydrocracking catalyst is by active component, auxiliary agent and carrier composition.Hydrocracking catalyst active component is WO3And NiO, it helps
Agent is ReO, and carrier is made of activated alumina, zeolite and BaO.It calculates in the form of an oxide, active component and auxiliary agent account for respectively
14-34%, 0.4-1.2% of catalyst gross mass.Catalyst preparation step includes the preparation of carrier, the pretreatment of carrier, leaching
Stain and catalyst post-processing etc. introduce ultrasonic wave and impregnate new technology.
It generally speaking, is with coal although coal tar hydrocracking catalyst disclosed above has the characteristics that respective
Tar is raw material, and production fuel oil is target product, rather than using coal tar hydrogenating processing fraction as raw material, nor with monocycle
Light aromatic hydrocarbons are purpose product.
CN101875017A also discloses a kind of condensed-nuclei aromatics hydrocracking catalyst and preparation method thereof.The catalyst by
Major catalyst and co-catalyst composition.Major catalyst is the alumino-silicate of carrying transition metal, and co-catalyst is selected from nitrogen-containing heterocycle
Compound, aromatic series nitrogenous compound, one or more compounds in acyl group nitrogenous compound.The catalyst aims heavy arene
It is higher to be hydrocracked rate, green coke is considered lower.But be not for coal tar hydrogenating processing distillate composition and property feature and open
The catalyst of hair, purpose product are also not to obtain the monocycle light aromatic hydrocarbons of high yield.
Summary of the invention
The purpose of the present invention is the compositions and property feature for coal tar hydrogenating processing distillate, are with monocycle light aromatic hydrocarbons
Purpose product provides the coal tar hydrogenating processing distillate hydrocracking production of a kind of highly selective, high activity and high stability
The catalyst and its preparation method and application of monocycle light aromatic hydrocarbons.
Coal tar hydrogenating provided by the present invention handles distillate selective hydrogenation Cracking catalyst, by HZSM-5-
MgAPO-5 composite molecular screen carrier and active component Ni2P is formed, wherein active component Ni2The weight percentage of P be 12%~
The weight percentage of 30%, composite molecular screen HZSM-5-MgAPO-5 are 70%~88%, the weight of HZSM-5 in composite molecular screen
The weight percentage that percentage composition is 11.2%~23.9%, MgAPO-5 is 76.1%~88.8%.
The preparation method of catalyst of the present invention, includes the following steps:
(1) preparation of HZSM-5-MgAPO-5 composite molecular screen
Deionized water is added in the phosphoric acid (source P) that mass percentage concentration is 85%, magnesium nitrate (source Mg) then is added, stirs molten
Solution, then being added to boehmite (source Al) in above-mentioned solution, are vigorously stirred 0.5~1.5h, then organic mould is added dropwise
Plate agent triethylamine (TEA), and continue 3~4h of stirring, controlling each component molar ratio in above-mentioned material is Mg:Al2O3: P2O5: three second
Amine: total H2O=(0.02~0.06): 1.0:1.0:(0.5~1.5): (30~80), wherein total H2O is all in reaction system
Water, adds HZSM-5 molecular sieve in above-mentioned material, and the mass ratio for controlling HZSM-5 molecular sieve and boehmite is 0.2~
0.5, it is vigorously stirred 0.5~1h, obtained sol solutions are transferred in the stainless steel crystallizing kettle with polytetrafluoroethyllining lining, in 150
12~48 h of crystallization, product are centrifuged under the conditions of~230 DEG C, washing, 100~120 DEG C of 8~12 h of drying, finally in sky
500~600 DEG C of 4~8h of roasting, obtain HZSM-5-MgAPO-5 composite molecular screen, wherein the weight percent of HZSM-5 under gas atmosphere
The weight percentage that content is 11.2%~23.9%, MgAPO-5 is 76.1%~88.8%；
(2) Ni2The preparation of P/ HZSM-5-MgAPO-5 catalyst
First using nickel nitrate or nickelous carbonate as nickel source, using the HZSM-5-MgAPO-5 composite molecular screen of above-mentioned preparation as carrier, adopt
With equi-volume impregnating, HZSM-5-MgAPO-5 composite molecular screen is added in nickel source aqueous solution, is later 420 in maturing temperature
Roasted 2~6 hours at~520 DEG C, obtain Ni/ HZSM-5-MgAPO-5, wherein the weight percentage of NiO be 6.04m%~
The weight percentage of 15.10m%, HZSM-5-MgAPO-5 are 84.90m%~93.96m%；
Secondly Ni/ HZSM-5-MgAPO-5 obtained above is transferred in confined reaction furnace, in hydrogen atmosphere, furnace temperature control
System is 450~550 DEG C of reductase 12~6 hour；
Final reaction furnace is replaced with nitrogen, and red phosphorus is added, and control reacting furnace temperature is 350~450 DEG C, atmospheric reverse in nitrogen atmosphere
It answers 0.5~2 hour, obtains Ni2P/ HZSM-5-MgAPO-5 catalyst prod.
The application of coal tar hydrogenating processing distillate selective hydrogenation cracking light aromatic hydrocarbons catalyst provided by the present invention,
The following steps are included:
Catalyst is packed into fixed bed reactors, reactor is passed through hydrogen, and flow velocity is 700~2000m3/ (h*t catalyst), instead
Answering pressure in device is 8~16MPa, after temperature of reactor is first warming up to 550~750 DEG C with 1~3 DEG C/min, then is adjusted to anti-
Answer process conditions, reaction process condition are as follows: reaction raw materials are that coal tar hydrogenating handles distillate, and reaction temperature is 340~400
DEG C, liquid air speed is 0.3~1.0h-1, hydrogen to oil volume ratio is 800~2000, and pressure is 8~18MPa.
Coal tar hydrogenating processing distillate of the present invention can be coalite tar hydrotreating distillate, medium temperature coal tar
Hydrotreating distillate, middle coalite tar hydrotreating distillate, hydrogenation of high temperature coal tar processing one of distillate or
The mixture of several fractions oil.
Compared with prior art, the present invention the following advantage having:
The catalyst is composition and the property feature for coal tar hydrogenating processing distillate and the catalyst developed, hydrogenation activity
Moderate with cracking activity, the selectivity of gained monocycle light aromatic hydrocarbons is greater than 64wt%, and catalyst service life is greater than 2 years, the list of acquisition
The yield of ring light aromatic hydrocarbons product is greater than 53wt%, and coal tar deep processing value-added content of product greatly improved.
Specific embodiment
Below with reference to embodiment, the present invention is further described.
Embodiment 1
Suitable deionized water is added in the phosphoric acid (source P) that mass percentage concentration is 85%, magnesium nitrate (source Mg) then is added,
Stirring and dissolving.Being added to boehmite (source Al) in above-mentioned solution again, is vigorously stirred 0.5h, then organic mould is added dropwise
Plate agent triethylamine (TEA), and continue to stir 3h.Controlling each component molar ratio in above-mentioned material is respectively Mg:Al2O3: P2O5:
TEA: total H2O=0.02:1.0:1.0:0.5:30.Then HZSM-5 molecular sieve is added in above-mentioned material.Control HZSM-5
The mass ratio of molecular sieve and boehmite is 0.2, is vigorously stirred 0.5h, and obtained sol solutions are transferred in band polytetrafluoroethylene (PTFE)
In the stainless steel crystallizing kettle of lining, 12 h of crystallization, product are centrifuged under the conditions of 150 DEG C, washing, 100 DEG C of 8 h of drying, most
500 DEG C of roasting 4h in air atmosphere afterwards, obtain HZSM-5-MgAPO-5 composite molecular screen, wherein the weight percent of HZSM-5 contains
The weight percentage that amount is 11.2%, MgAPO-5 is 88.8%.
Using nickel nitrate as nickel source, using the HZSM-5-MgAPO-5 composite molecular screen of above-mentioned preparation as carrier, using isometric
Infusion process prepares Ni/ HZSM-5-MgAPO-5, and the weight percentage for controlling wherein NiO is 6.04%, HZSM-5-MgAPO-5
Weight percentage be 93.96%, control catalyst maturing temperature be 420 DEG C, calcining time be 2 hours.It is made above-mentioned
Catalyst semi-finished product Ni/ HZSM-5-MgAPO-5 be transferred in confined reaction furnace, in hydrogen atmosphere, Control for Kiln Temperature is 450
DEG C reductase 12 hour.Reacting furnace is replaced with nitrogen, and red phosphorus is added, and control reacting furnace temperature is 350 DEG C, in nitrogen atmosphere under normal pressure
Reaction 0.5 hour, obtains Ni2P/ HZSM-5-MgAPO-5 catalyst prod.Ni in product2The weight percentage 12% of P,
The content of HZSM-5-MgAPO-5 is 88%.
Catalyst is packed into fixed bed reactors, reactor is passed through hydrogen, flow velocity 700m3/ (h*t catalyst), reaction
Pressure is 8MPa in device.Temperature of reactor is warming up to after 550 DEG C with 1 DEG C/min and is adjusted to reaction process condition.Reaction process
Condition are as follows: reaction temperature is 340 DEG C, and liquid air speed is 0.3h-1, hydrogen to oil volume ratio 800, pressure 8MPa.Reaction raw materials are
Coalite tar hydrotreating distillate.Reaction result is that the feed stock conversion is 82.3wt%, monocycle light aromatic hydrocarbons selectivity
64.5wt%。
Embodiment 2
Suitable deionized water is added in the phosphoric acid (source P) that mass concentration is 85%, magnesium nitrate (source Mg) then is added, stirring
Dissolution.Being added to boehmite (source Al) in above-mentioned solution again, is vigorously stirred 1.5h, then organic formwork agent is added dropwise
Triethylamine (TEA), and continue to stir 4h.Controlling each component molar ratio in above-mentioned material is respectively Mg:Al2O3: P2O5: TEA: total
H2O=0.06:1.0:1.0:1.5:80.Then HZSM-5 molecular sieve is added in above-mentioned material.Control HZSM-5 molecular sieve with
The mass ratio of boehmite is 0.5, is vigorously stirred 1h, obtained sol solutions are transferred to the stainless steel with polytetrafluoroethyllining lining
In crystallizing kettle, 48 h of crystallization, product are centrifuged under the conditions of 230 DEG C, washing, 120 DEG C of 12 h of drying, finally in air
The lower 600 DEG C of roastings 8h removed template method of atmosphere, obtains HZSM-5-MgAPO-5 composite molecular screen, wherein the weight percent of HZSM-5
The weight percentage that content is 23.9%, MgAPO-5 is 76.1%.
Using nickelous carbonate as nickel source, using the HZSM-5-MgAPO-5 composite molecular screen of above-mentioned preparation as carrier, using isometric
Infusion process prepares Ni/ HZSM-5-MgAPO-5, and the weight percentage for controlling wherein NiO is 15.10%, HZSM-5-MgAPO-5
Weight percentage be 84.90%, control catalyst maturing temperature be 520 DEG C, calcining time be 6 hours.It is made above-mentioned
Catalyst semi-finished product Ni/ HZSM-5-MgAPO-5 be transferred in confined reaction furnace, in hydrogen atmosphere, Control for Kiln Temperature is 550
DEG C reduction 6 hours.Reacting furnace is replaced with nitrogen, and red phosphorus is added, and control reacting furnace temperature is 450 DEG C, in nitrogen atmosphere under normal pressure
Reaction 2 hours, can be prepared by Ni2P/ HZSM-5-MgAPO-5 catalyst prod.Control Ni in product2The weight percentage of P
The weight percentage of 30%, HZSM-5-MgAPO-5 are 70%.
Catalyst is packed into fixed bed reactors, reactor is passed through hydrogen, flow velocity 2000m3/ (h*t catalyst), reaction
Pressure is 16MPa in device.Reaction process condition is cooled to after temperature of reactor is warming up to 750 DEG C with 3 DEG C/min.Reaction process
Condition are as follows: reaction temperature is 400 DEG C, and liquid air speed is 1.0h-1, hydrogen to oil volume ratio 2000, pressure 18MPa.Reaction raw materials
Distillate is handled for hydrogenation of high temperature coal tar.The feed stock conversion is 92.5wt%, monocycle light aromatic hydrocarbons selectivity 74.5wt%.
Embodiment 3
Suitable deionized water is added in the phosphoric acid (source P) that mass concentration is 85%, magnesium nitrate (source Mg) then is added, stirring
Dissolution.Being added to boehmite (source Al) in above-mentioned solution again, is vigorously stirred 1.0h, then organic formwork agent is added dropwise
Triethylamine (TEA), and continue to stir 3.5h.Controlling each component molar ratio in above-mentioned material is respectively Mg:Al2O3: P2O5: TEA:
Total H2O=0.04:1.0:1.0:1.0:70.Then HZSM-5 molecular sieve is added in above-mentioned material.Control HZSM-5 molecular sieve
Mass ratio with boehmite is 0.3, is vigorously stirred 0.7h, obtained sol solutions are transferred to polytetrafluoroethyllining lining not
It becomes rusty in steel crystallizing kettle, 24 h of crystallization, product are centrifuged under the conditions of 200 DEG C, and washing, 110 DEG C of 10 h of drying finally exist
The lower 550 DEG C of roastings 6h of air atmosphere, obtains HZSM-5-MgAPO-5 composite molecular screen, wherein the weight percentage of HZSM-5 is
The weight percentage of 15.9%, MgAPO-5 are 84.1%.
Using nickel nitrate as nickel source, using the HZSM-5-MgAPO-5 composite molecular screen of above-mentioned preparation as carrier, using isometric
Infusion process prepares Ni/ HZSM-5-MgAPO-5, and the weight percentage for controlling wherein NiO is 10.07%, HZSM-5-MgAPO-5
Weight percentage be 89.93%, control catalyst maturing temperature be 480 DEG C, calcining time be 4 hours.It is made above-mentioned
Catalyst semi-finished product Ni/ HZSM-5-MgAPO-5 be transferred in confined reaction furnace, in hydrogen atmosphere, Control for Kiln Temperature is 500
DEG C reduction 3 hours.Reacting furnace is replaced with nitrogen, and a certain amount of red phosphorus is added, and control reacting furnace temperature is 400 DEG C, nitrogen atmosphere
It is reacted 1 hour under middle normal pressure, can be prepared by Ni2P/ HZSM-5-MgAPO-5 catalyst prod.Control Ni in product2The weight of P
Percentage composition 20%, the weight percentage of HZSM-5-MgAPO-5 are 80%.
Catalyst is packed into fixed bed reactors, reactor is passed through hydrogen, flow velocity 1500m3/ (h*t catalyst), reaction
Pressure is 12MPa in device.Reaction process condition is cooled to after temperature of reactor is warming up to 650 DEG C with 2 DEG C/min.Reaction process
Condition are as follows: reaction temperature is 380 DEG C, and liquid air speed is 0.5h-1, hydrogen to oil volume ratio 1500, pressure 13MPa.Reaction raw materials
For medium temperature coal tar hydrotreating distillate.The feed stock conversion is 89.7m%, monocycle light aromatic hydrocarbons selectivity 82.6m%.
Embodiment 4
Suitable deionized water is added in the phosphoric acid (source P) that mass concentration is 85%, magnesium nitrate (source Mg) then is added, stirring
Dissolution.Being added to boehmite (source Al) in above-mentioned solution again, is vigorously stirred 0.5h, then organic formwork agent is added dropwise
Triethylamine (TEA), and continue to stir 4h.Controlling each component molar ratio in above-mentioned material is respectively Mg:Al2O3: P2O5: TEA: total
H2O=0.02:1.0:1.0:1.5:30.Then HZSM-5 molecular sieve is added in above-mentioned material.Control HZSM-5 molecular sieve with
The mass ratio of boehmite is 0.4, is vigorously stirred 1h, obtained sol solutions are transferred to the stainless steel with polytetrafluoroethyllining lining
In crystallizing kettle, 48 h of crystallization, product are centrifuged under the conditions of 180 DEG C, washing, 120 DEG C of dry 8h, finally in air gas
The lower 600 DEG C of roastings 6h of atmosphere, obtains HZSM-5-MgAPO-5 composite molecular screen, and wherein the weight percentage of HZSM-5 is 20.1%,
The weight percentage of MgAPO-5 is 79.9%.
Using nickelous carbonate as nickel source, using the HZSM-5-MgAPO-5 composite molecular screen of above-mentioned preparation as carrier, using isometric
Infusion process prepares Ni/ HZSM-5-MgAPO-5, and the weight percentage for controlling wherein NiO is 9.06%, HZSM-5-MgAPO-5
Weight percentage be 90.94%, control catalyst maturing temperature be 510 DEG C, calcining time be 3 hours.It is made above-mentioned
Catalyst semi-finished product Ni/ HZSM-5-MgAPO-5 be transferred in confined reaction furnace, in hydrogen atmosphere, Control for Kiln Temperature is 490
DEG C reduction 5 hours.Reacting furnace is replaced with nitrogen, and red phosphorus is added, and control reacting furnace temperature is 440 DEG C, in nitrogen atmosphere under normal pressure
Reaction 1.5 hours, obtains Ni2P/ HZSM-5-MgAPO-5 catalyst prod.Ni in product2The weight percentage 18% of P,
The weight percentage of HZSM-5-MgAPO-5 is 82%.
Catalyst is packed into fixed bed reactors, reactor is passed through hydrogen, flow velocity 700m3/ (h*t catalyst), reaction
Pressure is 16MPa in device.Temperature of reactor is warming up to after 550 DEG C with 2.5 DEG C/min and is adjusted to reaction process condition.React work
Skill condition are as follows: reaction temperature is 380 DEG C, and liquid air speed is 1.0h-1, hydrogen to oil volume ratio 800, pressure 15MPa.Reaction raw materials
For middle coalite tar hydrotreating distillate.The feed stock conversion is 90.3m%, monocycle light aromatic hydrocarbons selectivity 88.1m%.
Embodiment 5
Suitable deionized water is added in the phosphoric acid (source P) that mass concentration is 85%, magnesium nitrate (source Mg) then is added, stirring
Dissolution.Being added to boehmite (source Al) in above-mentioned solution again, is vigorously stirred 1.5h, then organic formwork agent is added dropwise
Triethylamine (TEA), and continue to stir 3.5h.Controlling each component molar ratio in above-mentioned material is respectively Mg:Al2O3: P2O5: TEA:
Total H2O=0.05:1.0:1.0:1.5:60.Then HZSM-5 molecular sieve is added in above-mentioned material.Control HZSM-5 molecular sieve
Mass ratio with boehmite is 0.3, is vigorously stirred 0.7h, obtained sol solutions are transferred to polytetrafluoroethyllining lining not
It becomes rusty in steel crystallizing kettle, 48 h of crystallization, product are centrifuged under the conditions of 230 DEG C, and washing, 110 DEG C of 12 h of drying finally exist
The lower 600 DEG C of roastings 7h of air atmosphere, obtains HZSM-5-MgAPO-5 composite molecular screen, wherein the weight percentage of HZSM-5 is
The weight percentage of 15.8%, MgAPO-5 are 84.2%.
Using nickel nitrate as nickel source, using the HZSM-5-MgAPO-5 composite molecular screen of above-mentioned preparation as carrier, using isometric
Infusion process prepares Ni/ HZSM-5-MgAPO-5, and the weight percentage for controlling wherein NiO is 15.10%, HZSM-5-MgAPO-5
Weight percentage be 84.90%, control catalyst maturing temperature be 490 DEG C, calcining time be 5 hours.It is made above-mentioned
Catalyst semi-finished product Ni/ HZSM-5-MgAPO-5 be transferred in confined reaction furnace, in hydrogen atmosphere, Control for Kiln Temperature is 550
DEG C reductase 12 hour.Reacting furnace is replaced with nitrogen, and red phosphorus is added, and control reacting furnace temperature is 350 DEG C, in nitrogen atmosphere under normal pressure
Reaction 2 hours, can be prepared by Ni2P/ HZSM-5-MgAPO-5 catalyst prod.Control Ni in product2The weight percentage of P
The weight percentage of 30%, HZSM-5-MgAPO-5 are 70%.
Catalyst is packed into fixed bed reactors, reactor is passed through hydrogen, flow velocity 2000m3/ (h*t catalyst), reaction
Pressure is 10MPa in device.Temperature of reactor is warming up to after 750 DEG C with 3 DEG C/min and is adjusted to reaction process condition.Reaction process
Condition are as follows: reaction temperature is 400 DEG C, and liquid air speed is 0.5h-1, hydrogen to oil volume ratio 1000, pressure 12MPa.Reaction raw materials
For middle coalite tar and high temperature coal-tar miscella hydrotreating distillate, the two weight ratio is 2:3.The feed stock conversion
For 87.7m%, monocycle light aromatic hydrocarbons selectivity 85.2m%.
Claims (4)
1. a kind of catalyst of coal tar hydrogenating processing distillate selective hydrogenation cracking light aromatic hydrocarbons, it is characterised in that catalyst
By HZSM-5-MgAPO-5 composite molecular screen carrier and active component Ni2P is formed, wherein active component Ni2The weight percent of P contains
Amount is 12%~30%, and the weight percentage of composite molecular screen HZSM-5-MgAPO-5 is 70%~88%, in composite molecular screen
The weight percentage that the weight percentage of HZSM-5 is 11.2%~23.9%, MgAPO-5 is 76.1%~88.8%.
2. a kind of catalyst of coal tar hydrogenating processing distillate selective hydrogenation cracking light aromatic hydrocarbons as described in claim 1
Preparation method, it is characterised in that include the following steps:
(1) preparation of HZSM-5-MgAPO-5 composite molecular screen
Deionized water is added in the phosphoric acid that mass percentage concentration is 85%, magnesium nitrate, stirring and dissolving is then added, then will intend thin
Being added in above-mentioned solution for diaspore, is vigorously stirred 0.5~1.5h, then organic formwork agent triethylamine is added dropwise, and continue
3~4h is stirred, controlling each component molar ratio in above-mentioned material is Mg:Al2O3: P2O5: triethylamine: total H2O=(0.02~0.06):
1.0:1.0:(0.5~1.5): (30~80), wherein total H2O is all water in reaction system, is added in above-mentioned material
HZSM-5 molecular sieve, the mass ratio for controlling HZSM-5 molecular sieve and boehmite is 0.2~0.5, is vigorously stirred 0.5~1h,
Obtained sol solutions are transferred in the stainless steel crystallizing kettle with polytetrafluoroethyllining lining, under the conditions of 150~230 DEG C crystallization 12~
48 h, product are centrifuged, washing, 100~120 DEG C of 8~12 h of drying, finally 500~600 DEG C of roastings in air atmosphere
4~8h obtains HZSM-5-MgAPO-5 composite molecular screen；
(2) Ni2The preparation of P/ HZSM-5-MgAPO-5 catalyst
First using nickel nitrate or nickelous carbonate as nickel source, using the HZSM-5-MgAPO-5 composite molecular screen of above-mentioned preparation as carrier, adopt
With equi-volume impregnating, HZSM-5-MgAPO-5 composite molecular screen is added in nickel source aqueous solution, is later 420 in maturing temperature
It is roasted 2~6 hours at~520 DEG C, obtains Ni/ HZSM-5-MgAPO-5；
Secondly Ni/ HZSM-5-MgAPO-5 obtained above is transferred in confined reaction furnace, in hydrogen atmosphere, furnace temperature control
System is 450~550 DEG C of reductase 12~6 hour；
Final reaction furnace is replaced with nitrogen, and red phosphorus is added, and control reacting furnace temperature is 350~450 DEG C, atmospheric reverse in nitrogen atmosphere
It answers 0.5~2 hour, obtains Ni2P/ HZSM-5-MgAPO-5 catalyst prod.
3. a kind of catalyst of coal tar hydrogenating processing distillate selective hydrogenation cracking light aromatic hydrocarbons as described in claim 1
Application, it is characterised in that the following steps are included:
Catalyst is packed into fixed bed reactors, reactor is passed through hydrogen, and flow velocity is 700~2000m3/ (h*t catalyst), reaction
Pressure is 8~16MPa in device, after temperature of reactor is first warming up to 550~750 DEG C with 1~3 DEG C/min, then is adjusted to reaction
Process conditions, reaction process condition are as follows: reaction raw materials are that coal tar hydrogenating handles distillate, and reaction temperature is 340~400 DEG C,
Liquid air speed is 0.3~1.0h-1, hydrogen to oil volume ratio is 800~2000, and pressure is 8~18MPa.
4. a kind of catalyst of coal tar hydrogenating processing distillate selective hydrogenation cracking light aromatic hydrocarbons as claimed in claim 3
Application, it is characterised in that coal tar hydrogenating processing distillate is coalite tar hydrotreating distillate, medium temperature coal tar
One of oily hydrotreating distillate, middle coalite tar hydrotreating distillate, hydrogenation of high temperature coal tar processing distillate
Or the mixture of several fractions oil.
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