CN107376984A - One kind is used for C10+The preparation method of the non-precious metal catalyst of heavy aromatics lighting - Google Patents

One kind is used for C10+The preparation method of the non-precious metal catalyst of heavy aromatics lighting Download PDF

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Publication number
CN107376984A
CN107376984A CN201710461283.3A CN201710461283A CN107376984A CN 107376984 A CN107376984 A CN 107376984A CN 201710461283 A CN201710461283 A CN 201710461283A CN 107376984 A CN107376984 A CN 107376984A
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catalyst
nickel
warming
preparation
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CN107376984B (en
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臧甲忠
宫毓鹏
范景新
李健
于海斌
马明超
刘冠锋
潘月秋
隋芝宇
耿姗
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China National Offshore Oil Corp CNOOC
CNOOC Energy Technology and Services Ltd
CNOOC Tianjin Chemical Research and Design Institute Co Ltd
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China National Offshore Oil Corp CNOOC
CNOOC Energy Technology and Services Ltd
CNOOC Tianjin Chemical Research and Design Institute Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • B01J29/14—Iron group metals or copper
    • B01J29/146—Y-type faujasite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • B01J29/7615—Zeolite Beta
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1096—Aromatics or polyaromatics
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/30—Aromatics

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  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)

Abstract

The present invention relates to one kind to be used for C10 +The preparation method of the non-precious metal catalyst of heavy aromatics lighting.Catalyst of the present invention is with elemental nickel and nickel phosphide (Ni2P it is) active phase, using molecular sieve and aluminum oxide as carrier.The problem of generation aluminum phosphate being reacted using aluminum oxide in competitive adsorbate resolved vector and P elements so as to which catalyst reaction activity be greatly reduced；Nickel phosphide is reduced using the low-boiling-point organic compound with strong reducing property and mutually generates temperature, nickel phosphide particle buildup is reduced, greatly improves catalyst activity；Non-noble metal hydrogenation activity is used mutually to replace noble metal that catalyst cost is greatly reduced.

Description

One kind is used for C10+The preparation method of the non-precious metal catalyst of heavy aromatics lighting
Technical field
The present invention relates to a kind of C10+The preparation method of heavy aromatics lightening catalyst, belongs to petrochemical industry.
Background technology
The heavy aromatics of plant catalytic reformation, ethylene cracker by-product a large amount of C9, C10 and the above.At present, C9 aromatic hydrocarbons is (few Amount C10 aromatic hydrocarbons) it is generally used for transalkylation reaction and prepares Mixed XYLENE, part C10 +And above heavy aromatics is isolated by rectifying A small amount of component for having economic value, but 20~30% C simultaneously10 +Heavy aromatics is converted into heavy oil residue, remaining C10+ heavy aromatics base This is used as low price fuel.According to existing C10 +The production management planning of heavy aromatics, raw material availability is low, both waste of resource, pollutes again Environment, it is difficult to play the due economic benefit of Heavy Aromatic Hydrocarbons.
A kind of method that CN101885663A discloses heavy aromatics lighting and transalkylation, it is beta nuclear shell-shaped using ZSM-5/ Molecular sieve catalyst, handle C9 +Heavy aromatics (C10 +For content less than 20%), conversion ratio reaches more than 40%, BTX selectivity 55% Left and right.The catalyst and technique that this method is provided have preferable heavy aromatics activity of conversion and BTX selectivity, but it can be handled C in raw material10 +Heavy aromatics ratio is relatively low, and industrial applicability is limited.
CN201410642474.6 discloses a kind of C10 +The method that heavy aromatics is hydrogenated with lighting, passed through using heavy aromatics raw material Cross after preheating furnace and hydrogen carries out air-fuel mixture, pass sequentially through that non-precious metal catalyst is hydrogenated with saturating reactor in advance and noble metal is urged Agent hydrocracking reactor, produce BTX and high-knock rating gasoline blend component.
CN201310512276.3 discloses a kind of heavy aromatics lightening catalyst and preparation method thereof, by using MCM- 41 molecular sieves and aluminum oxide are carrier, catalyst prepared by the noble metal such as supporting Pt, Pd, Ir, preferably resolve heavy aromatics and turn Change the problem of depth is low, and mononuclear aromatics yield is low with selectivity, and catalyst deactivation rate is fast.
CN200410006721.X discloses a kind of preparation method of transition metal phosphide, by transition metal salt and phosphoric acid Hydrogen diamino mixes after being dissolved in water respectively, and after being loaded to using equi-volume impregnating on carrier, drying and roasting obtains complex catalyst precursor Body.In a hydrogen atmosphere, 300~500 DEG C are risen to from room temperature with 2~10 DEG C/min of heating rate, is heated up with 0.5~2 DEG C/min 2~4 hours are incubated to 600~750 DEG C, loaded transitional metal phosphide catalyst is made.But traditional catalyst of phosphatizing nickel Because sintering temperature height causes active mutually aggregation, hydrogenation activity is relatively low, and the aluminum oxide in carrier can also react with P elements Generation aluminum phosphate can not meet C so as to which catalyst reaction activity be greatly reduced10 +The demand of heavy aromatics lighting.
From prior art as can be seen that main improve C using the high hydrogenation activity of noble metal10 +The conversion of heavy arene The stability of rate and catalyst, but the cost of catalyst can be greatly improved, the application of restriction technologies.And transition metal phosphide Turn into the developing direction of WeiLai Technology with its excellent Hydrogenation.
The content of the invention
The technical problems to be solved by the invention are to provide the excellent C of a kind of advantage of lower cost, Hydrogenation10 +Heavy The preparation method of arenes lightening catalyst.
Solve the above problems, the invention provides one kind to be used for C10 +The system of the non-precious metal catalyst of heavy aromatics lighting Preparation Method, wherein：The catalyst quality percentage forms：
1) molecular sieve 55~75%；Molecular sieve includes HY, H β, one kind or its mixture of ZSM series.
2) nickel phosphide Ni2P activity phase 5~15%；
3) elemental nickel activity phase 0.5~1%；
4) aluminum oxide 15~35%；
Said components gross mass content is 100%；
The catalyst preparation process is：
1) molecular sieve is mixed with aluminum oxide in proportion, adds extrusion aid, expanding agent or intensity no more than gross mass 5% Auxiliary agent, the dilute nitric acid solution for being 3~4% with mass percentage concentration are peptizing agent extruded moulding, and naturally dry is after 120~140 DEG C drying 12~24 hours, then temperature programming to 450~550 DEG C roasting 8~12 hours obtained catalyst carriers；
2) by obtained catalyst carrier and deionized water with mass ratio 1:3~5 mixing, stir lower add and be catalyzed in terms of nickel The Nickelous nitrate hexahydrate of agent carrier quality 5%~15%, warming-in-water stir 12~24h, are put into 80~90 DEG C to 45~60 DEG C It is dried in air dry oven without obvious raffinate, is warming up to 110~130 DEG C of 8~12h of insulation, is designated as modified support 1；
3) competitive adsorbate is loaded on modified support 1 using equi-volume impregnating, be warming up to after standing 8~12h 120~140 DEG C of 8~12h of drying, are designated as modified support 2；Wherein described competitive adsorbate is low molecular weight organic acid；
4) phosphorus source is loaded on modified support 2 using equi-volume impregnating, is put into 130~150 DEG C of air dry ovens and dries It is dry 2~4 hours, catalyst of phosphatizing nickel presoma is made；
5) catalyst of phosphatizing nickel presoma is fitted into fixed bed hydrogenation evaluating apparatus, 120~150 DEG C is warming up to, with body The nitrogen of product air speed 5~10 purges 2~8h；
6) 150~200 DEG C are warming up to, stops nitrogen purging, is passed through reducing agent, 0.5~2h of mass space velocity-1, the time 4~ 8h, finished catalyst is made；Wherein described reducing agent is that boiling point is 100~180 DEG C, has the low boiling of strong reducing property organic One or more of mixtures of thing.
In preparation method of the present invention, wherein competitive adsorbate load capacity is preferably modified support used in step 3) The 15~25% of quality of alumina in 1；Phosphorus source used in step 4) is preferably the metal salt-frees such as diammonium hydrogen phosphate, ammonium dihydrogen phosphate The phosphatic one or more of mixtures of ionically-soluble.
Competitive adsorbate used in step 3) is preferably the low molecular weight organic acids such as oxalic acid, formic acid, acetic acid.
Reducing agent used is preferably hydrazine or Dimethylhydrazine in step 6).
Preparation method of the present invention compared with prior art, has following characteristics and advantage：
The inventive method use in competitive adsorbate resolved vector aluminum oxide and P elements react generation aluminum phosphate from And the problem of catalyst reaction activity is greatly reduced；Nickel phosphide is reduced using the low-boiling-point organic compound with strong reducing property mutually to generate Temperature, nickel phosphide particle buildup is reduced, greatly improves catalyst activity；Use non-noble metal hydrogenation activity mutually replace noble metal with Catalyst cost is greatly reduced.
Embodiment
The inventive method is described further with reference to specific embodiment.
Catalyst is prepared by following embodiments and comparative example, and using the evaluation catalysis of fixed bed hydrogenation reaction evaluating device Agent, load the catalyst granules of the mesh of 20g 20~40 in the reactor, reaction condition is 400 DEG C of temperature, pressure 4MPa, C10 +Weight Aromatic feed amount 20g/h, hydrogen flowing quantity 330ml/min.
After stable reaction 24h, formed with gas-chromatography on-line analysis product, calculate C10 +Heavy aromatics conversion ratio, lightweight virtue Hydrocarbon-selective.
After stable reaction 120h, formed again with gas-chromatography on-line analysis product, calculate C10 +Heavy aromatics conversion ratio is simultaneously Convert the catalyst deactivation rate factor.
C10 +The definition of heavy aromatics conversion ratio, light aromatics selectivity and the catalyst deactivation rate factor is：
C10 +Heavy aromatics conversion ratio=(C in charging10 +C in quality-product of heavy aromatics10 +The quality of heavy aromatics)/charging in The quality * 100% of C10+ heavy aromatics
C in light aromatics selectivity=product6~C9Arene content/(C in charging10 +C in quality-product of heavy aromatics10 + The quality of heavy aromatics) * 100%
The deactivation rate factor (h-1)=(24h C10 +Heavy aromatics conversion ratio -120h C10 +Heavy aromatics conversion ratio)/96
The heavy aromatics that the present invention uses is technical grade C10 +Heavy aromatics.
Embodiment 1
(1) 65gHY molecular sieves (butt) are well mixed with 25g boehmites (butt) 4g sesbania powders, add quality Concentration is 3% dilute nitric acid solution, and product is extruded as into the extruded stock forms of Φ 2, and naturally dry is dried 15 hours after 125 DEG C, Temperature programming is to 550 DEG C of roastings, 8 hours obtained catalyst carriers again, while the water absorption rate for measuring the carrier is 105%.
(2) obtained catalyst carrier is added in 350ml deionized waters, warming-in-water adds the water of 39g six to 50 DEG C Nickel nitrate stirring 24h is closed, is put into 90 DEG C of air dry ovens and is dried to without obvious raffinate, 110 DEG C of insulation 12h is warming up to, obtains The modified support of nickel-loaded.
(3) 4g oxalic acid is added in 94.5g deionized waters, is poured into after being completely dissolved in the carrier obtained by step (2) and stand 8 120 DEG C are warming up to after hour to dry 12 hours.
(4) 10.7g diammonium hydrogen phosphates are added in 94.5g deionized waters, the load obtained by step (3) is poured into after being completely dissolved In body, 140 DEG C of oven for drying are put into 3 hours, obtain catalyst precursor.
(5) catalyst precursor of the mesh of 20g 20~40 is fitted into fixed bed hydrogenation reactor, is warming up to 120 DEG C, with 200ml/min nitrogen purging 3h.160 DEG C are warming up to, stops nitrogen purging, the hydrazine for being pumped into 20g/h reduces 4 hours, obtains into Product catalyst 1.
Embodiment 2
(1) 55gHY molecular sieves (butt) are well mixed with, 40g boehmites (butt) 3g sesbania powders, add quality Concentration is 4% dilute nitric acid solution, and product is extruded as into the extruded stock forms of Φ 2, and naturally dry is dried 20 hours after 120 DEG C, Temperature programming is to 500 DEG C of roastings, 10 hours obtained catalyst carriers again, while the water absorption rate for measuring the carrier is 95%.
(2) obtained catalyst carrier is added in 300ml deionized waters, warming-in-water adds the water of 51g six to 60 DEG C Nickel nitrate stirring 20h is closed, is put into 85 DEG C of air dry ovens and is dried to without obvious raffinate, 120 DEG C of insulation 10h is warming up to, obtains The modified support of nickel-loaded.
(3) 8g formic acid is added in 90.3g deionized waters, pours into the carrier obtained by step (2) and stand after being completely dissolved 130 DEG C are warming up to after 12 hours to dry 10 hours.
(4) 18.6g diammonium hydrogen phosphates are added in 90.3g deionized waters, the load obtained by step (3) is poured into after being completely dissolved In body, 145 DEG C of oven for drying are put into 3 hours, obtain catalyst precursor.
(5) catalyst precursor of the mesh of 20g20~40 is fitted into fixed bed hydrogenation reactor, is warming up to 150 DEG C, with 160ml/min nitrogen purging 3h.190 DEG C are warming up to, stops nitrogen purging, 32g/h Dimethylhydrazines is pumped into and reduces 4 hours, obtain Finished catalyst 2.
Embodiment 3
(1) 55gH beta-molecular sieves (butt) are well mixed with, 40g boehmites (butt) 3g sesbania powders, add quality Concentration is 4% dilute nitric acid solution, and product is extruded as into the extruded stock forms of Φ 2, and naturally dry is dried 20 hours after 120 DEG C, Temperature programming is to 500 DEG C of roastings, 10 hours obtained catalyst carriers again, while the water absorption rate for measuring the carrier is 102%.
(2) obtained catalyst carrier is added in 300ml deionized waters, warming-in-water adds the water of 51g six to 60 DEG C Nickel nitrate stirring 20h is closed, is put into 85 DEG C of air dry ovens and is dried to without obvious raffinate, 120 DEG C of insulation 10h is warming up to, obtains The modified support of nickel-loaded.
(3) 8g oxalic acid is added in 96.9g deionized waters, pours into the carrier obtained by step (2) and stand after being completely dissolved 130 DEG C are warming up to after 12 hours to dry 10 hours.
(4) 16.2g ammonium dihydrogen phosphates are added in 96.9g deionized waters, the load obtained by step (3) is poured into after being completely dissolved In body, 145 DEG C of oven for drying are put into 3 hours, obtain catalyst precursor.
(5) catalyst precursor of the mesh of 20g20~40 is fitted into fixed bed hydrogenation reactor, is warming up to 150 DEG C, with 200ml/min nitrogen purging 3h.190 DEG C are warming up to, stops nitrogen purging, 36g/h Dimethylhydrazines is pumped into and reduces 4 hours, obtain Finished catalyst 3.
Embodiment 4
(1) 75gHY molecular sieves (butt) are well mixed with, 15g boehmites (butt) 4g sesbania powders, add quality Concentration is 3% dilute nitric acid solution, and product is extruded as into the extruded stock forms of Φ 2, and naturally dry is dried 15 hours after 125 DEG C, Temperature programming is to 550 DEG C of roastings, 8 hours obtained catalyst carriers again, while the water absorption rate for measuring the carrier is 110%.
(2) obtained catalyst carrier is added in 450ml deionized waters, warming-in-water adds the water of 51g six to 50 DEG C Nickel nitrate stirring 24h is closed, is put into 90 DEG C of air dry ovens and is dried to without obvious raffinate, 110 DEG C of insulation 12h is warming up to, obtains The modified support of nickel-loaded.
(3) 2.5g acetic acid is added in 99g deionized waters, is poured into after being completely dissolved in the carrier obtained by step (2) and stand 8 120 DEG C are warming up to after hour to dry 12 hours.
(4) 14.0g ammonium dihydrogen phosphates are added in 99g deionized waters, the carrier obtained by step (3) is poured into after being completely dissolved In, it is put into 140 DEG C of oven for drying 3 hours, obtains catalyst precursor.
(5) catalyst precursor of the mesh of 20g20~40 is fitted into fixed bed hydrogenation reactor, is warming up to 120 DEG C, with 100ml/min nitrogen purging 3h.160 DEG C are warming up to, stops nitrogen purging, 34g/h hydrazines is pumped into and reduces 3 hours, obtain finished product Catalyst 4.
Comparative example 1
(1) 65gHY molecular sieves (butt) are well mixed with, 25g boehmites (butt) 4g sesbania powders, add quality Concentration is 3% dilute nitric acid solution, and product is extruded as into the extruded stock forms of Φ 2, and naturally dry is dried 15 hours after 125 DEG C, Temperature programming is to 550 DEG C of roastings, 8 hours obtained catalyst carriers again, while the water absorption rate for measuring the carrier is 105%.
(2) 39g Nickelous nitrate hexahydrates are weighed, 10.7g diammonium hydrogen phosphates are dissolved in 94.5g deionized waters, after being completely dissolved Pour into step (1) resulting vehicle, before 125 DEG C dry 15 hours, then temperature programming obtains catalyst in 8 hours to 550 DEG C of roastings Drive body.
(3) catalyst precursor of the mesh of 20g20~40 is fitted into fixed bed hydrogenation reactor, in a hydrogen atmosphere, with 10 DEG C/min of heating rate rises to 500 DEG C from room temperature, and being warming up to 750 DEG C with 2 DEG C/min is incubated 4 hours.Obtain finished product contrast medium 1。
Comparative example 2
(1) 65gHY molecular sieves (butt) are well mixed with, 25g boehmites (butt) 4g sesbania powders, add quality Concentration is 3% dilute nitric acid solution, and product is extruded as into the extruded stock forms of Φ 2, and naturally dry is dried 15 hours after 125 DEG C, Temperature programming is to 550 DEG C of roastings, 8 hours obtained catalyst carriers again, while the water absorption rate for measuring the carrier is 105%.
(2) 1.26g chloroplatinic acids are weighed to be dissolved in 94.5g deionized waters, step (1) resulting vehicle is poured into after being completely dissolved In, 120 DEG C dry 6 hours, then temperature programming to 400 DEG C of roastings obtain catalyst precursor in 4 hours.
(3) catalyst precursor of the mesh of 20g20~40 is fitted into fixed bed hydrogenation reactor, in a hydrogen atmosphere, with 10 DEG C/min of heating rate rises to 400 DEG C from room temperature, is incubated 4 hours.Obtain finished product contrast medium 2.
The evaluation result of catalyst is shown in Table 1 in 1-4 of the embodiment of the present invention and comparative example.It is from table 1 it follows that of the invention Catalyst prepared by method has high C10 +Conversion ratio, high light aromatics selectivity, relatively low catalyst deactivation rate, can be with Noble metal catalyst maintains an equal level, and is substantially superior to the catalyst of phosphatizing nickel activity of conventional method preparation.
The evaluation result of the different catalysts of table 1
Note：Reaction raw materials are industrial C10 +Heavy aromatics (durene isomers 28%, indan derivative 15%, biphenyl derivatives 3%, naphthalene and naphthalenes 45%, other aromatic hydrocarbons 9%).

Claims (4)

1. one kind is used for C10 +The preparation method of the non-precious metal catalyst of heavy aromatics lighting, it is characterised in that：
The catalyst is with elemental nickel and nickel phosphide Ni2P is active phase, using molecular sieve and aluminum oxide as carrier；Each component accounts for catalysis The mass percent of agent forms：
1) molecular sieve 55~75%；Molecular sieve is HY, one kind or its mixture of H β, ZSM series；
2) nickel phosphide Ni2P activity phase 5~15%；
3) elemental nickel activity phase 0.5~1%；
4) aluminum oxide 15~35%；
The preparation method of the catalyst includes：
1) molecular sieve is mixed with aluminum oxide in proportion, extrusion aid, expanding agent or the intensity added no more than gross mass 5% helps Agent, the dilute nitric acid solution for being 3~4% with mass percentage concentration are peptizing agent extruded moulding, and naturally dry is after 120~140 DEG C Drying 12~24 hours, then temperature programming to 450~550 DEG C roasting 8~12 hours obtained catalyst carriers；
2) by obtained catalyst carrier and deionized water with mass ratio 1:3~5 mixing, stir lower addition catalyst in terms of nickel and carry The Nickelous nitrate hexahydrate of weight 5%~15%, warming-in-water stir 12~24h, are put into 80~90 DEG C of air blast to 45~60 DEG C It is dried in drying box without obvious raffinate, is warming up to 110~130 DEG C of 8~12h of insulation, is designated as modified support 1；
3) competitive adsorbate is loaded on modified support 1 using equi-volume impregnating, stand and be warming up to 120 after 8~12h~ 140 DEG C of 8~12h of drying, are designated as modified support 2；
4) phosphorus source is loaded on modified support 2 using equi-volume impregnating, be put into 130~150 DEG C of air dry ovens drying 2~ 4 hours, catalyst of phosphatizing nickel presoma is made；
5) catalyst of phosphatizing nickel presoma is fitted into fixed bed hydrogenation evaluating apparatus, is warming up to 120~150 DEG C, it is empty with volume The nitrogen of speed 5~10 purges 2~8h；
6) 150~200 DEG C are warming up to, stops nitrogen purging, is passed through reducing agent, 0.5~2h of mass space velocity-1, 4~8h of time, system Obtain finished catalyst；
Competitive adsorbate wherein described in step 3) is low molecular weight organic acid；
Reducing agent described in step 6) is the one kind for the low-boiling-point organic compound with strong reducing property that boiling point is 100~180 DEG C Or several mixtures.
2. according to the preparation method described in claim 1, it is characterised in that the load capacity of competitive adsorbate described in step 3) is The 15~25% of quality of alumina in modified support 1；
Phosphorus source described in step 4) is the phosphatic one or more of mixtures of metal salt-free ionically-soluble.
3. according to the preparation method described in claim 1, it is characterised in that described reducing agent is hydrazine, Dimethylhydrazine.
4. according to the preparation method described in claim 2, it is characterised in that described competitive adsorbate is oxalic acid, formic acid, second Acid, described phosphorus source are diammonium hydrogen phosphate, ammonium dihydrogen phosphate.
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Citations (6)

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