CN105728016A - Catalyst for preparing coal tar into diesel oil and preparation method thereof - Google Patents
Catalyst for preparing coal tar into diesel oil and preparation method thereof Download PDFInfo
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- CN105728016A CN105728016A CN201610123723.XA CN201610123723A CN105728016A CN 105728016 A CN105728016 A CN 105728016A CN 201610123723 A CN201610123723 A CN 201610123723A CN 105728016 A CN105728016 A CN 105728016A
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- catalyst
- attapulgite
- carrier
- supernatant
- mixed solution
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- 239000003054 catalyst Substances 0.000 title claims abstract description 80
- 239000011280 coal tar Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002283 diesel fuel Substances 0.000 title abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 38
- 229960000892 attapulgite Drugs 0.000 claims abstract description 36
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 36
- 238000003756 stirring Methods 0.000 claims abstract description 31
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 28
- 239000000243 solution Substances 0.000 claims abstract description 22
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 12
- 238000007598 dipping method Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000006228 supernatant Substances 0.000 claims description 30
- 229910002651 NO3 Inorganic materials 0.000 claims description 29
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 29
- 239000000295 fuel oil Substances 0.000 claims description 26
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 229910052593 corundum Inorganic materials 0.000 claims description 18
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 18
- 238000005984 hydrogenation reaction Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 15
- 239000012153 distilled water Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 239000002808 molecular sieve Substances 0.000 claims description 14
- 150000002497 iodine compounds Chemical class 0.000 claims description 13
- 238000001556 precipitation Methods 0.000 claims description 13
- 238000000227 grinding Methods 0.000 claims description 12
- 238000000746 purification Methods 0.000 claims description 12
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000000643 oven drying Methods 0.000 claims description 7
- 239000011697 sodium iodate Substances 0.000 claims description 7
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 230000010355 oscillation Effects 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 5
- 229910052738 indium Inorganic materials 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 4
- 239000002689 soil Substances 0.000 claims description 4
- 239000008187 granular material Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 abstract 1
- 238000000034 method Methods 0.000 description 11
- 239000003921 oil Substances 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000003245 coal Substances 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- 239000011269 tar Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 229910017318 Mo—Ni Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000000352 supercritical drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
- B01J23/8885—Tungsten containing also molybdenum
-
- 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
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/26—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/12—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing 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
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a catalyst for preparing coal tar into diesel oil and a preparation method thereof. The catalyst is obtained by a preparation method comprising the following steps: drying a carrier for 20 minutes at a temperature of 110-130 DEG C, dipping in a compound solution containing iodine, keeping for 1 hour at a temperature of 40-60 DEG C, taking out the carrier and drying for 1 hour in a baking oven at a temperature of 90-120 DEG C; adding acid-modified attapulgite with a mass percent of 2-5 percent of the carrier into a bitrate mixed solution of Co, Mo and W, uniformly stirring, dipping the dried carrier into the mixed solution, continuously dipping for 2-3 hours, controlling the temperature to be 30-45 DEG C, stirring and dispersing for 10-60 minutes, drying, roasting for 3-8 hours at a temperature of 170-420 DEG C, preparing catalyst powder and further preparing the catalyst powder into particles.
Description
Technical field
The present invention relates to a kind of producing diesel by coal tar catalyst.
Background technology
In China, petroleum import ratio surges year by year, and the breach such as fuel oil with it as raw material, diesel oil increases the most therewith.And I
The coal resources relative abundance of state, through exploring, producing fuel oil with coal becomes a kind of trend, in prior art, the direct liquid of coal
Changing or indirect liquefaction can be with output fuel oil, but the two Technology is considerably complicated, and running cost and difficulty are bigger.
Coal tar hydrogenating diesel oil catalyst and utilize this catalyst to prepare the technique of diesel oil, application number: 200510012554.4
The applying date: 2005-05-25. invention is for coal tar hydrogenating diesel oil catalyst and utilizes the technique that this catalyst prepares diesel oil.Coal
Hydrogenation of tar diesel oil catalyst, including one stage catalyzing dose and second catalyst, urges for hydrogenation desulfurization and denitrogenation cracking for one stage catalyzing dose
Agent, second catalyst is hydrotreating deep dearomatizition catalyst.Described coal tar hydrogenating diesel oil catalyst is utilized to prepare the work of diesel oil
Skill include the air-distillation of coal tar, fuel oil one stage catalyzing, two grades of catalysis, air stripping, separation of fuel oil；The one of fuel oil
One stage catalyzing dose used by level catalysis is above-mentioned hydrotreating desulfurization and denitrogenation cracking catalyst, two grades used by two grades of catalysis of fuel oil
Catalyst is above-mentioned hydrotreating deep dearomatizition catalyst.The present invention substantially increases the heatproof of coal tar hydrogenating diesel oil catalyst
Performance, makes the expanded range of available feed coal tar, makes the arene content in diesel oil finished product be preferably minimized, improves hexadecane
Value, makes product be fully achieved the diesel oil standard of country.
CN1287152A discloses the production method of a kind of fuel oil, be by after coking produce tar through processed prepare essence
Tar, adds kerosene, crude benzol allotment forms, although its method is simple, but is intended to consume finished product kerosene, and in fuel oil
The crude benzol of 15-25wt% to be added is as diluent, to bad environmental.US4855037 describes a kind of hydrogenation treatment for coal tar
Catalyst And Method, the coal tar after hydrotreating is used for delayed coking, the method mainly by improve catalyst aperture,
Pore size distribution and metal component, and select suitable process conditions to improve the stability of catalyst, the method is mainly used for prolonging
The pretreatment of coking late, does not produce purpose product.Patent CN100348702C has invented a kind of method of producing fuel oil from coal tar,
Its by one stage catalyzing reaction with Mo-Ni/Al2O3For catalyst, S, the N in coal tar fraction is removed, enter back into two grades
Catalystic converter system is with W-Mo-Ni/Al2O3Carry out aromatic hydrocarbons saturated reaction for catalyst and remove the impurity such as S, N further,
To proper fuel oil product, but its shortcoming is reaction system is two grades of catalystic converter systems, complex, adds design difficulty
Degree and equipment cost.
Summary of the invention
Catalyst of a kind of preparing fuel oil by coal tar hydrogenation that the present invention provides and preparation method thereof.
A kind of method of coal tar hydrogenating diesel oil, hydrogen and coal tar fraction mixing with hydrogen to oil volume ratio as 850-1100 are laggard
Entering reactor, reaction temperature is 290-365 DEG C, and reaction pressure is 2-9MPa, and air speed is 2-4h-1, enter under catalyst action
Row reaction, goes out liquid product through gas-liquid separation and get final product.
The preparation method of preparing diesel from coal tar catalyst:
Carrier impregnates after being dried 20 minutes at 110-130 DEG C in containing iodine compound solution, and temperature is that 40-60 DEG C of holding 1 is little
Time, take out carrier 90-120 DEG C of oven drying 1 hour；Add the modified attapulgite of the acid of carrier quality 2-5% in Co,
In the nitrate mixed solution of Mo, W, after stirring, by above-mentioned dry carrier impregnation in this mixed solution, continue dipping
2-3 hour, temperature controlled at 30-45 DEG C, dispersed with stirring 10-60min, after drying, in 270-420 DEG C of roasting 3-8h, system
Obtain catalyst fines, it is possible to be prepared as granule further.
Described carrier is Y type molecular sieve, beta-molecular sieve, modenite, ZRP type molecular sieve or nanometer Al2O3In at least one.
By the beaded catalyst of made preformed catalyst or 8-16 mesh at 345-390 DEG C, 2-16MPa, air speed 0.5-4h-1, hydrogen oil
Volume ratio is to carry out activity rating of catalyst under 850-1100.
The soluble-salt of Co, Mo, W is nitrate.
The nitrate mixed solution of Co, Mo, W: above-mentioned three kinds of nitrate systems are prepared as mixed solution, each component in mixed solution
The weight concentration of nitrate is respectively Co 8-14wt%, Mo 10-16wt%, WO32-5wt%.
The described mixed solution containing iodine compound consists of, KI 3-8wt%, NaI 4-6wt%, NaIO36-10wt%.
Nanometer Al2O3The particle diameter of carrier is 5-20nm, preferably 5-10nm.
The preparation that acid is attapulgite modified: weigh particle diameter 300 mesh～the attapulgite of 1000 mesh, with distilled water wash, precipitation takes it
The supernatant, 500rpm takes its supernatant after being centrifuged 1min, continue 500rpm after adding a small amount of distilled water mix homogeneously in the supernatant
Centrifugal 1min, then takes its supernatant, after such cyclic washing supernatant 3～5 times, is finally centrifuged point with 4000rpm
From, take its precipitation, at 90 DEG C, be vacuum dried 24h, select the sieve of corresponding mesh number after grinding by size, obtain purification recessed
Convex rod soil.Configuration concentration is the hydrochloric acid solution of 0.5mol/L～3mol/L, takes purification attapulgite and mixes with hydrochloric acid solution stirring,
After 5min, heat the mixture to 70 DEG C～80 DEG C, stir 1h～2h, then sonic oscillation 30min～40min, sucking filtration, use
Distilled water wash is about about 6 to pH, is vacuum dried 24h at 90 DEG C, selects the sieve mistake of corresponding mesh number after grinding by size
Sieve, obtains sour attapulgite modified.
Described aluminium oxide can be that commercially available commodity also can be prepared by any one method in prior art, for example, it may be by selecting
After one or more mixture among Alumina hydrate, monohydrate alumina and amorphous hydroted alumina is fired
Prepare.
Described molecular sieve can be commercially available commodity, it would however also be possible to employ prepared by any one prior art.
The present invention has an advantage that
Invention having been surprisingly found that, the attapulgite rear catalyst performance of interpolation acid modification has had significantly improve.Significantly improve fuel oil
Middle sulfur and the content of other indexs.Can use as finished fuels oil；The catalyst of the present invention can remove coal tar in use and evaporate
The impurity such as S, N, O in Fen, reduce design difficulty and equipment cost；The catalyst of the present invention uses direct dipping process, preparation
Method is simple, and condition is easily controlled, catalyst reproducible so that active component disperses to be more uniformly distributed on carrier.
Detailed description of the invention
Be will assist in by following embodiment and understand the present invention, but be not intended to present disclosure.
Embodiment 1 contrast product:
The catalyst of a kind of preparing fuel oil by coal tar hydrogenation, active component is Co, Mo, W, and carrier is nanometer Al2O3Carrier, urges
Agent consists of the CoO of 5wt%, the MoO of 17.5wt%3, the WO of 20wt%3, remaining is nanometer Al2O3Carrier.Its preparation method,
Comprise the steps:
(1) by the Al (NO of metering3)3With in NaOH and gained Al (OH)3Aqueous solution, with ammonia as precipitant, controls pH=9,
Stirring is until precipitation is complete, and room temperature ageing 12h, washing, with the water in dehydrated alcohol displacement gained precipitate, through supercritical drying
Dry, in 950 DEG C of roasting 3.5h, obtain nanometer Al2O3Carrier, characterizes through TEM, nanometer Al2O3The particle diameter of carrier is at 5-20nm
Between, wherein most is between 5-10nm；
(2) by weight metal than Co, Mo, W for 1:4.45:4.02 nitrate aqueous solution mixing, after stirring, will
Nanometer Al2O3Carrier is immersed in mixed solution with equi-volume impregnating, and under stirring, ultrasonic disperse 30min, through microwave drying 10min
After, in 650 DEG C of roasting 5h, prepare catalyst fines.
According to the catalyst fines of step (2) gained, the type of being compressed into obtains preformed catalyst, after being crushed after molding again
Make beaded catalyst.
Gained pellet type catalyst at 370 DEG C, 10MPa, air speed 2h-1, hydrogen to oil volume ratio be 1000 times through activity rating, yield
Up to 99%, S content is 159 μ g, and N content is 228 μ g, and the content of aromatic hydrocarbons is 32.8%, can use as finished fuels oil.
Embodiment 2
Carrier impregnates after being dried 20 minutes at 120 DEG C in containing iodine compound solution, and temperature is 50 DEG C and keeps 1 hour, takes out
Carrier was 110 DEG C of oven dryings 1 hour；Add the attapulgite of acid modification of carrier quality 4% in the nitrate of Co, Mo, W
In mixed solution, after stirring, by above-mentioned dry carrier impregnation in this mixed solution, continuing dipping 2 hours, temperature controls
At 40 DEG C, dispersed with stirring 40min, after drying, in 370-390 DEG C of roasting 5h, prepare catalyst fines.
The catalyst fines of gained, the type of being compressed into obtains preformed catalyst, makes particulate catalytic after molding after being crushed again
Agent.
Described carrier is Y type molecular sieve.
The soluble-salt of Co, Mo, W is nitrate.
The nitrate mixed solution of Co, Mo, W: above-mentioned three kinds of nitrate systems are prepared as mixed solution, each component in mixed solution
The weight concentration of nitrate is respectively Co 14wt%, Mo 16wt%, WO32wt%.
The described mixed solution containing iodine compound consists of, KI 3wt%, NaI 6wt%, NaIO310wt%.
Nanometer Al2O3The particle diameter of carrier is 7nm.
The attapulgite that acid is modified: weighing 1Kg particle diameter 600 mesh～the attapulgite of 1000 mesh, use 10L distilled water wash, precipitation takes
Its supernatant, 500rpm takes its supernatant after being centrifuged 1min, continue after adding a small amount of distilled water mix homogeneously in the supernatant
500rpm is centrifuged 1min, then takes its supernatant, after such cyclic washing supernatant 3～5 times, finally carries out with 4000rpm
Centrifugation, takes its precipitation, is vacuum dried 24h at 90 DEG C, selects the sieve of corresponding mesh number after grinding by size,
Purification attapulgite.Configuration concentration is the hydrochloric acid solution of 2mol/L, takes purification attapulgite and mixes with the stirring of 4500mL hydrochloric acid solution,
After 5min, heat the mixture to 75 DEG C, stir 1h, then sonic oscillation 30min, sucking filtration, be washed with distilled water to pH and be about
It is vacuum dried 24h at about 6,90 DEG C, selects the sieve of corresponding mesh number after grinding by size, obtain sour modified attapulgite
Soil.
Described molecular sieve can be commercially available commodity, it would however also be possible to employ prepared by any one prior art.
Gained pellet type catalyst at 370 DEG C, 10MPa, air speed 2h-1, hydrogen to oil volume ratio be 1000 times through activity rating, yield
Up to 99%, S content is 89 μ g, and N content is 148 μ g, and the content of aromatic hydrocarbons is 29.8%.
Embodiment 3
Catalyst of a kind of preparing fuel oil by coal tar hydrogenation that the present invention provides and preparation method thereof.
The preparation method of preparing diesel from coal tar catalyst:
2kg carrier impregnates after being dried 20 minutes at 110 DEG C in containing iodine compound solution, and temperature is 60 DEG C and keeps 1 hour,
Take out carrier 120 DEG C of oven dryings 1 hour；Add the modified attapulgite of the acid of carrier quality 2% in 10L volume Co,
In the nitrate mixed solution of Mo, W, after stirring, above-mentioned dry carrier is continued in this mixed solution dipping 3 hours,
Temperature controls at 45 DEG C, dispersed with stirring 60min, after drying, in 400-420 DEG C of roasting 8h, prepares catalyst fines.Institute
The catalyst fines obtained, the type of being compressed into obtains preformed catalyst, makes beaded catalyst after molding after being crushed again.
Described carrier is Y type molecular sieve and nanometer Al2O3In, Y type molecular sieve and nanometer Al2O3Mass ratio is 1:2.
By the beaded catalyst of made preformed catalyst or 8-16 mesh at 345-390 DEG C, 2-16MPa, air speed 0.5-4h-1, hydrogen oil
Volume ratio is to carry out activity rating of catalyst under 850-1100.
The soluble-salt of Co, Mo, W is nitrate.
The nitrate mixed solution of Co, Mo, W: above-mentioned three kinds of nitrate systems are prepared as mixed solution, each component in mixed solution
The weight concentration of nitrate is respectively Co 14wt%, Mo 16wt%, WO32wt%.
The described mixed solution containing iodine compound consists of, KI 8wt%, NaI 4wt%, NaIO310wt%.
Nanometer Al2O3The particle diameter of carrier is 10nm.
The attapulgite that acid is modified: weigh 900g particle diameter 300 mesh～the attapulgite of 1000 mesh, with distilled water wash, precipitation takes it
The supernatant, 500rpm takes its supernatant after being centrifuged 1min, continue 500rpm after adding a small amount of distilled water mix homogeneously in the supernatant
Centrifugal 1min, then takes its supernatant, after such cyclic washing supernatant 3～5 times, is finally centrifuged point with 4000rpm
From, take its precipitation, at 90 DEG C, be vacuum dried 24h, select the sieve of corresponding mesh number after grinding by size, obtain purification recessed
Convex rod soil.Configuration concentration is the hydrochloric acid solution of 2mol/L, takes purification attapulgite and mixes with the stirring of 2L hydrochloric acid solution, after 5min,
Heating the mixture to 70 DEG C～80 DEG C, stir 1h～2h, then sonic oscillation 30min～40min, sucking filtration, with distillation washing
Wash and be about about 6 to pH, at 90 DEG C, be vacuum dried 24h, select the sieve of corresponding mesh number after grinding by size, obtain sour
Attapulgite modified.
Gained catalyst at 370 DEG C, 10MPa, air speed 2h-1, hydrogen to oil volume ratio be 1000 times through activity rating, yield up to
99%, S content is 102 μ g, and N content is 169 μ g, and the content of aromatic hydrocarbons is 27.3%, can use as finished fuels oil.
Embodiment 4
Catalyst of a kind of preparing fuel oil by coal tar hydrogenation that the present invention provides and preparation method thereof.
The preparation method of preparing diesel from coal tar catalyst:
Carrier impregnates after being dried 20 minutes at 130 DEG C in containing iodine compound solution, and temperature is 40 DEG C and keeps 1 hour, takes
Go out carrier 90 DEG C of oven dryings 1 hour；Add the attapulgite of acid modification of carrier quality 2% in the nitrate of Co, Mo, W
In mixed solution, after stirring, above-mentioned dry carrier impregnation continuing in this mixed solution dipping 2 hours, temperature controls
35 DEG C, dispersed with stirring 10min, after drying, in 370-420 DEG C of roasting 4h, prepare catalyst fines.The catalyst of gained
Powder, the type of being compressed into obtains preformed catalyst, makes beaded catalyst after molding after being crushed again.
Described carrier is Y type molecular sieve and modenite and nanometer Al2O3, Y type molecular sieve and modenite and nanometer Al2The matter of O
Amount ratio is 1:2:1.
The soluble-salt of Co, Mo, W is nitrate.
The nitrate mixed solution of Co, Mo, W: above-mentioned three kinds of nitrate systems are prepared as mixed solution, each component in mixed solution
The weight concentration of nitrate is respectively Co 8wt%, Mo 14wt%, WO34wt%.
The described mixed solution containing iodine compound consists of, KI 3wt%, NaI 6wt%, NaIO36wt%.
Nanometer Al2O3The particle diameter of carrier is 8nm.
Gained catalyst at 370 DEG C, 10MPa, air speed 2h-1, hydrogen to oil volume ratio be 1000 times through activity rating, yield up to
99%, S content is 113 μ g, and N content is 187 μ g, and the content of aromatic hydrocarbons is 28.5%, can use as finished fuels oil.
Claims (10)
1. a catalyst for preparing fuel oil by coal tar hydrogenation, described catalyst is obtained by following preparation method:
Carrier impregnates after being dried 20 minutes at 110-130 DEG C in containing iodine compound solution, and temperature is that 40-60 DEG C of holding 1 is little
Time, take out carrier 90-120 DEG C of oven drying 1 hour；Add the modified attapulgite of the acid of carrier quality 2-5% in Co,
In the nitrate mixed solution of Mo, W, after stirring, by above-mentioned dry carrier impregnation in this mixed solution, continue dipping
2-3 hour, temperature controlled at 30-45 DEG C, dispersed with stirring 10-60min, after drying, in 270-420 DEG C of roasting 3-8h, system
Obtain catalyst fines, it is possible to be prepared as granule further.
The catalyst of a kind of preparing fuel oil by coal tar hydrogenation, it is characterised in that described carrier is Y type molecule
In sieve, beta-molecular sieve, modenite, ZRP type molecular sieve or nano-scale alumina at least one.
3. according to the catalyst of preparing fuel oil by coal tar hydrogenation a kind of described in claim 1 or 3, it is characterised in that Co, Mo, W's
In nitrate mixed solution, concentration is respectively Co 8-14wt%, Mo 10-16wt%, WO32-5wt%.
The catalyst of a kind of preparing fuel oil by coal tar hydrogenation, it is characterised in that described mixed containing iodine compound
Conjunction solution composition is, KI 3-8wt%, NaI 4-6wt%, NaIO36-10wt%.
The catalyst of a kind of preparing fuel oil by coal tar hydrogenation, it is characterised in that nanometer Al2O3The grain of carrier
The a diameter of 5-20nm of son.
The catalyst of a kind of preparing fuel oil by coal tar hydrogenation, it is characterised in that acid is attapulgite modified
Preparation: weigh particle diameter 300 mesh～the attapulgite of 1000 mesh, with distilled water wash, precipitation takes its supernatant, 500rpm from
Take its supernatant after heart 1min, continue 500rpm after the supernatant adds a small amount of distilled water mix homogeneously and be centrifuged 1min, then
Take its supernatant, after such cyclic washing supernatant 3～5 times, finally be centrifuged separating with 4000rpm, take its precipitation,
It is vacuum dried 24h at 90 DEG C, selects the sieve of corresponding mesh number after grinding by size, obtain purification attapulgite.Configuration
Concentration is the hydrochloric acid solution of 0.5mol/L～3mol/L, takes purification attapulgite and mixes with hydrochloric acid solution stirring, after 5min, and will
Mixture is heated to 70 DEG C～80 DEG C, stirs 1h～2h, then sonic oscillation 30min～40min, and sucking filtration, with distillation washing
Wash and be about about 6 to pH, at 90 DEG C, be vacuum dried 24h, after grinding, select the sieve of corresponding mesh number by size,
Acid is attapulgite modified.
The catalyst of a kind of preparing fuel oil by coal tar hydrogenation, it is characterised in that described preparation method is as follows:
Carrier impregnates after being dried 20 minutes at 120 DEG C in containing iodine compound solution, and temperature is 50 DEG C and keeps 1 hour, takes out
Carrier was 110 DEG C of oven dryings 1 hour；Add the attapulgite of acid modification of carrier quality 4% in the nitrate of Co, Mo, W
In mixed solution, after stirring, by above-mentioned dry carrier impregnation in this mixed solution, continuing dipping 2 hours, temperature controls
At 40 DEG C, dispersed with stirring 40min, after drying, in 370-390 DEG C of roasting 5h, prepare catalyst fines.
8. according to the catalyst of preparing fuel oil by coal tar hydrogenation a kind of described in claim 1 or 7, it is characterised in that Co, Mo,
The nitrate mixed solution of W: in mixed solution, the weight concentration of each component nitrate is respectively Co 14wt%, Mo 16wt%,
WO32wt%.
The catalyst of a kind of preparing fuel oil by coal tar hydrogenation, it is characterised in that described containing iodate conjunction
Thing mixed solution consists of, KI 3wt%, NaI 6wt%, NaIO310wt%；The attapulgite that acid is modified: weigh 1Kg particle diameter 600
Mesh～the attapulgite of 1000 mesh, use 10L distilled water wash, precipitation to take its supernatant, and 500rpm takes it after being centrifuged 1min
The supernatant, continues 500rpm and is centrifuged 1min, then take its supernatant in the supernatant after adding a small amount of distilled water mix homogeneously,
So after the cyclic washing supernatant 3～5 times, finally being centrifuged separating with 4000rpm, take its precipitation, at 90 DEG C, vacuum is done
Dry 24h, is selected the sieve of corresponding mesh number, obtains purification attapulgite by size after grinding.Configuration concentration is 2mol/L
Hydrochloric acid solution, take the stirring of purification attapulgite and 4500mL hydrochloric acid solution and mix, after 5min, heat the mixture to 75 DEG C,
Stirring 1h, then sonic oscillation 30min, sucking filtration, it is washed with distilled water to pH and is about about 6, at 90 DEG C, be vacuum dried 24h,
Select the sieve of corresponding mesh number after grinding by size, obtain sour attapulgite modified.
10. the preparation method of the catalyst of a kind of preparing fuel oil by coal tar hydrogenation as described in claim 1-9,2kg carrier exists
110 DEG C are dried after 20 minutes and impregnate in containing iodine compound solution, and temperature is 60 DEG C and keeps 1 hour, takes out carrier at 120 DEG C
Oven drying 1 hour；The attapulgite of the acid modification adding carrier quality 2% mixes in the nitrate of Co, Mo, W of 10L volume
Closing in solution, after stirring, above-mentioned dry carrier continues in this mixed solution dipping 3 hours, temperature controls at 45 DEG C,
Dispersed with stirring 60min, after drying, in 400-420 DEG C of roasting 8h, prepares catalyst fines.The catalyst fines of gained,
The type of being compressed into obtains preformed catalyst, makes beaded catalyst after molding after being crushed again；
Described carrier is Y type molecular sieveWithNanometer Al2O3In, Y type molecular sieveWithNanometer Al2O3Mass ratio is 1:2；
In the nitrate mixed solution of Co, Mo, W, the weight concentration of each component nitrate is respectively Co 14wt%, Mo 16wt%,
WO32wt%；
The described mixed solution containing iodine compound consists of, KI 8wt%, NaI 4wt%, NaIO310wt%；
The attapulgite that acid is modified: weigh 900g particle diameter 300 mesh～the attapulgite of 1000 mesh, with distilled water wash, precipitation takes it
The supernatant, 500rpm takes its supernatant after being centrifuged 1min, continue 500rpm after adding a small amount of distilled water mix homogeneously in the supernatant
Centrifugal 1min, then takes its supernatant, after such cyclic washing supernatant 3～5 times, is finally centrifuged point with 4000rpm
From, take its precipitation, at 90 DEG C, be vacuum dried 24h, select the sieve of corresponding mesh number after grinding by size, obtain purification recessed
Convex rod soil.Configuration concentration is the hydrochloric acid solution of 2mol/L, takes purification attapulgite and mixes with the stirring of 2L hydrochloric acid solution, after 5min,
Heating the mixture to 70 DEG C～80 DEG C, stir 1h～2h, then sonic oscillation 30min～40min, sucking filtration, with distillation washing
Wash and be about about 6 to pH, at 90 DEG C, be vacuum dried 24h, select the sieve of corresponding mesh number after grinding by size, obtain sour
Attapulgite modified.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115254082A (en) * | 2021-04-29 | 2022-11-01 | 中国石油化工股份有限公司 | Catalyst carrier and preparation method thereof, catalyst and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050020445A1 (en) * | 2003-07-23 | 2005-01-27 | Choudhary Tushar V. | Desulfurization and novel process for same |
| CN101376816A (en) * | 2007-08-29 | 2009-03-04 | 汉能科技有限公司 | Method for preparing diesel from coal tar |
| CN102477310A (en) * | 2010-11-25 | 2012-05-30 | 邵素英 | Method using coal tar to produce fuel oil |
| CN103769179A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Preparation method of residual oil hydro-treatment catalyst |
| CN103769121A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Preparation method of catalyst for hydro-treatment |
| CN103769122A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Method for preparing hydro-treatment catalyst |
-
2016
- 2016-03-06 CN CN201610123723.XA patent/CN105728016A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050020445A1 (en) * | 2003-07-23 | 2005-01-27 | Choudhary Tushar V. | Desulfurization and novel process for same |
| CN101376816A (en) * | 2007-08-29 | 2009-03-04 | 汉能科技有限公司 | Method for preparing diesel from coal tar |
| CN102477310A (en) * | 2010-11-25 | 2012-05-30 | 邵素英 | Method using coal tar to produce fuel oil |
| CN103769179A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Preparation method of residual oil hydro-treatment catalyst |
| CN103769121A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Preparation method of catalyst for hydro-treatment |
| CN103769122A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Method for preparing hydro-treatment catalyst |
Non-Patent Citations (3)
| Title |
|---|
| 张培元: "《中国工业矿物和岩石》", 30 November 1987 * |
| 雷洋等: "凹凸棒石脱硫剂的性质与脱硫效果研究", 《矿物岩石》 * |
| 黎盛斯: "《海南地质论文专辑》", 30 November 1985 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115254082A (en) * | 2021-04-29 | 2022-11-01 | 中国石油化工股份有限公司 | Catalyst carrier and preparation method thereof, catalyst and preparation method and application thereof |
| CN115254082B (en) * | 2021-04-29 | 2024-03-26 | 中国石油化工股份有限公司 | Catalyst carrier, preparation method thereof, catalyst, preparation method thereof and application of catalyst |
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