CN102614909B - Hydrodenitrogenation catalyst capable of removing nitrogen-containing compound from coal tar, and preparation method and application thereof - Google Patents
Hydrodenitrogenation catalyst capable of removing nitrogen-containing compound from coal tar, and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of catalysts for hydrodenitrogenation of coal tar. The technical problem to be solved is to provide a hydrodenitrogenation catalyst capable of deeply removing a nitrogen-containing compound from coal tar and provided with high mechanical strength, wear resistance and water resistance, and a preparation method and application thereof. The invention adopts the technical scheme that in the hydrodenitrogenation catalyst capable of removing nitrogen-containing compound from coal tar, active components consist of tungsten trioxide, nickel monoxide and chromium sesquioxide; aids comprise fluorine and phosphorus; and a carrier consists of aluminum oxide, zirconium oxide, a Hbeta molecular sieve, a binder and an extrusion aid. By adopting the hydrodenitrogenation catalyst capable of deeply removing the nitrogen-containing compound from the coal tar, the oil nitrogen content of the hydrogenation product can be reduced to be below 50 micrograms/gram; and the hydrodenitrogenation property is high, so that the oil sulfur content of the hydrogenation product can be reduced to be below 40 micrograms/gram.
Description
Technical field
The invention belongs to the catalyst technical field for coal tar hydrogenating denitrogenation.
Background technology
Coal tar is the fluid product that coal produces in pyrolytic process, according to pyrolysis temperature difference, can be divided into high temperature tar (900～1000 ℃), middle temperature tar (700～900 ℃), low temperature tar (500～700 ℃).Current, China's high temperature coal-tar annual production is about 1,000 ten thousand tons, mainly result from high-temperature coking industry, the annual production of middle coalite tar is also at millions of tons, the blue charcoal industry of the pyrolysis of coal system that mainly results from and coal gasification industry, in a foreseeable future, take pyrolysis as guide is rich produce in the development of extensive low-order coal clean and effective cascade utilization technology of coalite tar will produce more substantial middle coalite tar.
The composition of high temperature coal-tar, character and middle coalite tar have very big-difference: high temperature coal-tar density is high, are generally greater than 1.1 g/cm
3, bitumen content is high by approximately 50%～60%, is rich in valuable chemicals naphthalene, phenanthrene, anthracene, fluoranthene, fluorenes, acenaphthene, pyrene, carbazole, cresols etc.; And middle coalite tar bitumen content is low, be generally less than 30%, chemical composition concentration degree is very low, and except phenol, the content of most of component is less than 1%.The difference of composition, character has determined to adopt different processing modes from middle coalite tar to high temperature coal-tar.At present, the main processing mode of China's high temperature coal-tar is separated, the refining multi-chemical that obtains, for the industry such as medicine, agricultural chemicals, fiber, plastics, dyestuff, spices and material provide very important base stock, this has formed the main contents of traditional coal tar deep processing industry.And middle coalite tar many directly burnt or simple process after use, still lack and clean, utilize on a large scale technology, in the time of significant wastage resource, produced a large amount of pollutions.According to the compositing characteristic of middle coalite tar, its clean, efficient the most reasonable means of utilizing are catalytic hydrogenation clean fuels processed.Take a broad view domestic and international energy market, petroleum resources as fuel are more and more nervous, especially in China, net oil import accounts for the ratio of oil product consumption figure for successive years higher than 50%, the energy fuel that in utilization, coalite tar obtains alternative oil can reduce the consumption of petroleum resources, is national energy security power-assisted.Under above-mentioned background, the research and development of middle coalite tar Hydrogenation fuel oil technology are imperative, and just welcoming the period of strategic opportunity of great development.
The process that the process of middle coalite tar catalytic hydrogenation clean fuel processed is also its lighting, clean, the hydrogenation that comprises the unsaturated compounds such as alkene and part aromatic hydrocarbons is saturated, the large molecule cracking of part, the process such as remove of the harmful substances such as nitrogen, sulphur, oxygen, heavy metal, wherein hydrodenitrogeneration (HDN) and hydrodesulfurization (HDS) are that coal tar cleans part main in process.National environmental protection policy is more and more stricter, also more and more higher to the requirement of fuel clean-up performance, and its nitrogen of the fuel oil that coal tar hydrogenating makes, sulfur content must meet the requirement of national the present and the future to clean fuel.Because nitrogen content 0.45%～1.30% in middle coalite tar is generally higher than sulfur content 0.29%～0.40%, and the reaction difficulty of hydrodenitrogeneration (HDN) is greater than hydrodesulfurization (HDS), and HDN becomes one of key technology of coal tar hydrogenating clean fuel processed.HDN reaction need catalyst with under carry out, the research that meets HDN requirement catalyst becomes most important.CN1464031A has described a kind of coal tar hydrogenation process and catalyst, and its catalyst relating to is hydrofinishing and catalyst for hydro-upgrading, and the nitrogen content of hydrogenated diesel oil product is still greater than 180 μ g/g.CN1772846 discloses a kind of catalyst for coal tar hydrogenation modification and method is put in preparation, and under this catalyst action, hydrogenated oil nitrogen content is still greater than 200 μ g/g.
Summary of the invention
The present invention is in order to overcome the deficiencies in the prior art, provide a kind of can deep removal in nitrogen-containing compound and there is hydrodenitrogenation catalyst of better mechanical strength, wearability and resistance to water and its preparation method and application in coalite tar.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is: the hydrodenitrogenation catalyst that can remove coal tar nitrogen-containing compound, by active component, auxiliary agent and carrier, formed, it is characterized in that: active component is comprised of tungstic acid, nickel monoxide and chrome green, the 14wt%-18wt% that described tungstic acid content is catalyst, nickel monoxide content is the 4wt%-6wt% of catalyst, the 2wt%-4wt% that chrome green content is catalyst; Auxiliary agent is fluorine and phosphorus, calculates the 1wt%-4wt% that described fluorine content is catalyst, the 1wt%-2wt% that described phosphorus content is catalyst with simple substance; Carrier is comprised of aluminium oxide, zirconia, H beta-molecular sieve, binding agent and extrusion aid, with butt, calculate, described vector contg is the 66wt%-78wt% of catalyst, the weight part ratio of described aluminium oxide, zirconia and H beta-molecular sieve is 15-17:1-2:2-3, described weight of binder is the 3%-8% of described alumina weight, the 3wt%-7wt% that described extrusion aid content is carrier.
The predecessor of described aluminium oxide is that specific area is 350-450 m
2/ g, pore volume is 0.6-1.0 cm
3/ g, average pore size is the boehmite of 6-8 nm.
Described binding agent is pore volume 0.2-0.4 cm
3the boehmite of/g.
Described extrusion aid is by sesbania gum and organic acid composition, and its weight part ratio is 1:1-3, and described organic acid is a kind of in acetic acid, malonic acid, citric acid, tartaric acid and lactic acid.
Described organic acid is a kind of in acetic acid, malonic acid and citric acid.
Can remove the preparation method of the hydrodenitrogenation catalyst of coal tar nitrogen-containing compound, according to following steps, carry out:
The first step, prepares carrier
Described aluminum oxide precursor thing boehmite, zirconia, H beta-molecular sieve, ammonium fluoride, binding agent and extrusion aid are mixed, obtain mixture, the gouache ratio of take again adds distilled water as 0.5-0.7:1 in described mixture, in kneader, after kneading 60-150min, put into banded extruder extrusion molding, then at 15-40 ℃ of dry 4-6h, after 100 ℃ of dry 8-10h, with 1 ℃/min-5 ℃/min heating rate, be warming up to 450-650 ℃, roasting 6-8h, obtains carrier;
Second step, Kaolinite Preparation of Catalyst
By tungstic acid predecessor ammonium metatungstate (NH
4)
6w
7o
246H
2o, nickel monoxide predecessor nitric acid nickel (NO
3)
26H
2o, chrome green predecessor chromic nitrate Cr (NO
3)
39H
2o joins in distilled water, 15-60 ℃ of stirring, it is dissolved completely, then add phosphoric acid to continue to stir 0.5-1h, obtain active component solution, then with described active component solution, flood described carrier, dipping 3-5h, again in 20-30 ℃ of dry 5-8h, 100 ℃ of dry 6-8h, are then warming up to 450-550 ℃ with 2 ℃/min-6 ℃/min heating rate, roasting 6-8h, makes catalyst finished product.
In described active component solution, ammonium metatungstate weight percent concentration is 17%-19%, and nickel nitrate weight percent concentration is 16%-21%, and chromic nitrate weight percent concentration is 11%-19%, and phosphoric acid weight percent concentration is 3%-6%.
Can remove the application of the hydrodenitrogenation catalyst of coal tar nitrogen-containing compound, application process is: by catalyst, in fixed bed hydrogenation reactor, first to presulfiding of catalyst, then controlling reaction condition is H
2pressure 8.0-12.0Mpa, volume space velocity 0.3-0.8 h during liquid
-1, hydrogen/oil volume is than being 1200/1-1800/1, temperature is 380-420 ℃ and reacts.
The sulfuration liquid of described presulfurization is the kerosene containing DMDS 1.0-1.5 wt%, and conditions of vulcanization is: H
2pressure 1.5-2.5MPa, volume space velocity 0.5-0.8h during liquid
-1, hydrogen/oil volume is than being 700/1-900/1, temperature 200-230 ℃, cure time 35-50h.
The beneficial effect that the present invention compared with prior art has is: the present invention can deep removal in nitrogen-containing compound in coalite tar, hydrogenated products oil nitrogen content can be removed to below 50 μ g/g, there is good hydrodesulfurization performance simultaneously, can make hydrogenated products oil sulfur content can be removed to below 40 μ g/g.In catalyst of the present invention, auxiliary agent F and P introduce with kneading and dipping method respectively, make catalyst there is suitable acidity and pore-size distribution, make active component on carrier, obtain to greatest extent simultaneously and disperse, thereby make catalyst there is the performance of the especially de-basic nitrogen of good denitrogenation.Catalyst of the present invention also has good resistance to water, and in middle coalite tar, phenol content is higher, can produce more water, so the good resistance to water of catalyst of the present invention can adapt to this feature of coal tar hydrogenating process preferably in Hydrogenation fuel oil process.
The specific embodiment
With specific embodiment, the present invention will be described in detail below, but do not limit the scope of the invention.
Embodiment 1
Can remove the hydrodenitrogenation catalyst of coal tar nitrogen-containing compound, by active component, auxiliary agent and carrier, formed, active component is comprised of tungstic acid, nickel monoxide and chrome green, the 15wt% that described tungstic acid content is catalyst, nickel monoxide content is the 5wt% of catalyst, the 3.5wt% that chrome green content is catalyst; Auxiliary agent is fluorine and phosphorus, calculates the 3.2wt% that described fluorine content is catalyst, the 1.6wt% that described phosphorus content is catalyst with simple substance; Carrier is comprised of aluminium oxide, zirconia, H beta-molecular sieve, binding agent and extrusion aid, with butt, calculate, described vector contg is the 73wt% of catalyst, the weight part ratio of described aluminium oxide, zirconia and H beta-molecular sieve is 15.8:1.6:2.2, described weight of binder is 5% of described alumina weight, the 4.5wt% that described extrusion aid content is carrier.
Extrusion aid is comprised of sesbania gum and tartaric acid, and its weight part ratio is 1:2.
Can remove the preparation method of the hydrodenitrogenation catalyst of coal tar nitrogen-containing compound, according to following steps, carry out:
The first step, prepares carrier
Described aluminum oxide precursor thing boehmite, zirconia, H beta-molecular sieve, ammonium fluoride, binding agent and extrusion aid are mixed, obtain mixture, the gouache ratio of take again adds distilled water as 0.6:1 in described mixture, in kneader, after kneading 105min, put into banded extruder extrusion molding, then at 30 ℃ of dry 5h, after 100 ℃ of dry 9h, with 3.5 ℃/min heating rate, be warming up to 520 ℃, roasting 7h, obtains carrier;
Second step, Kaolinite Preparation of Catalyst
By tungstic acid predecessor ammonium metatungstate (NH
4)
6w
7o
246H
2o, nickel monoxide predecessor nitric acid nickel (NO
3)
26H
2o, chrome green predecessor chromic nitrate Cr (NO
3)
39H
2o joins in distilled water, 40 ℃ of stirrings, it is dissolved completely, then add phosphoric acid to continue to stir 0.6h, obtain active component solution, then with described active component solution, flood described carrier, dipping 4h, in 25 ℃ of dry 7h, 100 ℃ of dry 7h, are then warming up to 470 ℃ with 5 ℃/min heating rate again, roasting 7h, makes catalyst finished product.
In active component solution, ammonium metatungstate weight percent concentration is 18%, and nickel nitrate weight percent concentration is 19%, and chromic nitrate weight percent concentration is 12%, and phosphoric acid weight percent concentration is 4%.
Embodiment 2
Can remove the hydrodenitrogenation catalyst of coal tar nitrogen-containing compound, by active component, auxiliary agent and carrier, formed, active component is comprised of tungstic acid, nickel monoxide and chrome green, the 17wt% that described tungstic acid content is catalyst, nickel monoxide content is the 5wt% of catalyst, the 2.5wt% that chrome green content is catalyst; Auxiliary agent is fluorine and phosphorus, calculates the 2.5wt% that described fluorine content is catalyst, the 1.5wt% that described phosphorus content is catalyst with simple substance; Carrier is comprised of aluminium oxide, zirconia, H beta-molecular sieve, binding agent and extrusion aid, with butt, calculate, described vector contg is the 69wt% of catalyst, the weight part ratio of described aluminium oxide, zirconia and H beta-molecular sieve is 16:1.5:2.5, described weight of binder is 7% of described alumina weight, the 4wt% that described extrusion aid content is carrier.
Extrusion aid is comprised of sesbania gum and lactic acid, and its weight part ratio is 1:2.
Can remove the preparation method of the hydrodenitrogenation catalyst of coal tar nitrogen-containing compound, according to following steps, carry out:
The first step, prepares carrier
Described aluminum oxide precursor thing boehmite, zirconia, H beta-molecular sieve, ammonium fluoride, binding agent and extrusion aid are mixed, obtain mixture, the gouache ratio of take again adds distilled water as 0.65:1 in described mixture, in kneader, after kneading 105min, put into banded extruder extrusion molding, then at 20 ℃ of dry 6h, after 100 ℃ of dry 10h, with 4 ℃/min heating rate, be warming up to 600 ℃, roasting 8h, obtains carrier;
Second step, Kaolinite Preparation of Catalyst
By tungstic acid predecessor ammonium metatungstate (NH
4)
6w
7o
246H
2o, nickel monoxide predecessor nitric acid nickel (NO
3)
26H
2o, chrome green predecessor chromic nitrate Cr (NO
3)
39H
2o joins in distilled water, 45 ℃ of stirrings, it is dissolved completely, then add phosphoric acid to continue to stir 0.8h, obtain active component solution, then with described active component solution, flood described carrier, dipping 3h, in 27 ℃ of dry 6h, 100 ℃ of dry 6.5h, are then warming up to 500 ℃ with 3 ℃/min heating rate again, roasting 6.5h, makes catalyst finished product.
In active component solution, ammonium metatungstate weight percent concentration is 19%, and nickel nitrate weight percent concentration is 20%, and chromic nitrate weight percent concentration is 14%, and phosphoric acid weight percent concentration is 4%.
Embodiment 3
Take aluminium oxide precursor boehmite 1000 g, zirconia 103 g, H beta-molecular sieve 162 g and NH
4f 25 g also mix, and then in said mixture, add boehmite binding agent 100 g, sesbania gum 16 g, and acetic acid 48 g, distilled water 774 g after kneading 150 min, put into banded extruder extrusion molding in kneader.Then at 40 ℃ of dry 4 h, after 100 ℃ of dry 10 h, with 1 ℃/min heating rate, be warming up to 650 ℃, roasting 8 h, obtain carrier finished product 1027 g, with butt, calculate, aluminium oxide accounts for total weight of carrier 75%, and zirconia accounts for total weight of carrier 10%, and H beta-molecular sieve accounts for total weight of carrier 15%.
By tungstic acid predecessor ammonium metatungstate 307 g, nickel monoxide predecessor nickel nitrate 343 g, chrome green predecessor chromic nitrate 309 g join in 575 g distilled water, 60 ℃ of stirrings, it are dissolved completely, then add phosphatase 79 3 g, continue to stir 1 h, obtain active component solution 1627 g, in active component solution, ammonium metatungstate weight percent concentration is 19%, and nickel nitrate weight percent concentration is 21%, chromic nitrate weight percent concentration is 19%, and phosphoric acid weight percent concentration is 6%.
Adopt saturated spray infusion process that the active component solution of above-mentioned preparation is sprayed onto on 1027 g carriers, flood 4 h, again in 20 ℃ of dry 8 h, 100 ℃ of dry 8 h, then with 2 ℃/min heating rate, be warming up to 550 ℃, roasting 8 h, obtain catalyst finished product 1435 g, be labeled as catalyst A, its composition and character are in Table 1.
The middle coalite tar I of take is raw material, and its density is 1.05 g/cm
3, sulfur content 0.40 wt%, nitrogen content 1.20 wt%, on 500 ml fixed bed hydrogenation reactors, investigate the hydrodenitrogeneration performance of catalyst A.Under these conditions, coal tar I hydrogenated products oil density is 0.87 g/cm
3, sulfur content 38 μ g/g, nitrogen content 49 μ g/g.
Embodiment 4
Take aluminium oxide precursor boehmite 1000 g, zirconia 66 g, H beta-molecular sieve 128 g and NH
4f 60 g also mix, and then in said mixture, add boehmite binding agent 70 g, sesbania gum 14 g, and malonic acid 28 g, distilled water 814 g after kneading 100 min, put into banded extruder extrusion molding in kneader.Then at 25 ℃ of dry 5 h, after 100 ℃ of dry 9 h, with 2 ℃/min heating rate, be warming up to 550 ℃, roasting 7 h, obtain carrier finished product 936 g, with butt, calculate, aluminium oxide accounts for total weight of carrier 80%, and zirconia accounts for total weight of carrier 7%, and H beta-molecular sieve accounts for total weight of carrier 13%.
By tungstic acid predecessor ammonium metatungstate 234 g, nickel monoxide predecessor nickel nitrate 245 g, chrome green predecessor chromic nitrate 198 g join in 580g distilled water, 40 ℃ of stirrings, it are dissolved completely, then add phosphoric acid 60 g, continue to stir 0.8h, obtain active component solution 1317g, in active component solution, ammonium metatungstate weight percent concentration is 18%, and nickel nitrate weight percent concentration is 18.5%, chromic nitrate weight percent concentration is 15%, and phosphoric acid weight percent concentration is 4.5%.
Adopt saturated spray infusion process that the active component solution of above-mentioned preparation is sprayed onto on 936g carrier, dipping 3h, again in 25 ℃ of dry 6h, 100 ℃ of dry 7h, then with 4 ℃/min heating rate, be warming up to 500 ℃, roasting 7h, obtains catalyst finished product 1232g, be labeled as catalyst B, its composition and character are in Table 1.
The middle coalite tar II of take is raw material, and its density is 1.02 g/cm
3, sulfur content 0.35 wt%, nitrogen content 0.67 wt%, on 500 ml fixed bed hydrogenation reactors, investigates the hydrodenitrogeneration performance of catalyst B.Under these conditions, coal tar II hydrogenated products oil density is 0.84 g/cm
3, sulfur content 30 μ g/g, nitrogen content 41 μ g/g.
Embodiment 5
Take aluminium oxide precursor boehmite 1000g, zirconia 43g, H beta-molecular sieve 91 g and NH
4f 91 g also mix, and then in said mixture, add boehmite binding agent 50 g, sesbania gum 12 g, and citric acid 28g, distilled water 858g after kneading 60min, puts into banded extruder extrusion molding in kneader.Then at 15 ℃ of dry 6h, after 100 ℃ of dry 8 h, with 5 ℃/min heating rate, be warming up to 450 ℃, roasting 6h, obtains carrier finished product 865g, with butt, calculates, aluminium oxide accounts for total weight of carrier 85%, and zirconia accounts for total weight of carrier 5%, and H beta-molecular sieve accounts for total weight of carrier 10%.
By tungstic acid predecessor ammonium metatungstate 357 g, nickel monoxide predecessor nickel nitrate 341 g, chrome green predecessor chromic nitrate 231 g join in 1107 g distilled water, 15 ℃ of stirrings, it is dissolved completely, then add phosphoric acid 69 g, continue to stir 0.5 h, obtain active component solution 2105 g, in active component solution, ammonium metatungstate weight percent concentration is 17%, nickel nitrate weight percent concentration is 16%, chromic nitrate weight percent concentration is 11%, and phosphoric acid weight percent concentration is 3%.
Adopt supersaturation infusion process, 865 g carriers are immersed in the active component solution of above-mentioned preparation, flood 3 h, elimination redundant solution, then in 30 ℃ of dry 5h, 100 ℃ of dry 6h, then with 6 ℃/min heating rate, be warming up to 450 ℃, roasting 6h, obtains catalyst finished product 1070g, be labeled as catalyst C, its composition and character are in Table 1.
The middle coalite tar III of take is raw material, and its density is 0.98 g/cm
3, sulfur content 0.32 wt%, nitrogen content 0.45 wt%, on 500 ml fixed bed hydrogenation reactors, investigates the hydrodenitrogeneration performance of catalyst C.Under these conditions, coal tar III hydrogenated products oil density is 0.80 g/cm
3, sulfur content 21 μ g/g, nitrogen content 32 μ g/g.
The method that solution is dipped on carrier can adopt supersaturation infusion process or saturated infusion process.Supersaturation infusion process is that carrier is immersed in excessive solution, and maceration extract consumption is much larger than carrier water absorption rate, and while therefore flooding, carrier is all submerged in maceration extract; Saturated infusion process refers to that maceration extract consumption equals carrier water absorption rate just, specifically can use saturated spray dipping.Supersaturation infusion process and saturated spray dipping are this area routine techniques.
Claims (9)
1. can remove the hydrodenitrogenation catalyst of coal tar nitrogen-containing compound, by active component, auxiliary agent and carrier, formed, it is characterized in that: active component is comprised of tungstic acid, nickel monoxide and chrome green, the 14wt%-18wt% that described tungstic acid content is catalyst, nickel monoxide content is the 4wt%-6wt% of catalyst, the 2wt%-4wt% that chrome green content is catalyst; Auxiliary agent is fluorine and phosphorus, calculates the 1wt%-4wt% that described fluorine content is catalyst, the 1wt%-2wt% that described phosphorus content is catalyst with simple substance; Carrier is comprised of aluminium oxide, zirconia, H beta-molecular sieve, binding agent and extrusion aid, with butt, calculate, described vector contg is the 66wt%-78wt% of catalyst, the weight part ratio of described aluminium oxide, zirconia and H beta-molecular sieve is 15-17:1-2:2-3, described weight of binder is the 3%-8% of described alumina weight, the 3wt%-7wt% that described extrusion aid content is carrier;
And adopt following method to prepare:
The first step, prepares carrier
Described aluminum oxide precursor thing boehmite, zirconia, H beta-molecular sieve, ammonium fluoride, binding agent and extrusion aid are mixed, obtain mixture, the gouache ratio of take again adds distilled water as 0.5-0.7:1 in described mixture, in kneader, after kneading 60-150min, put into banded extruder extrusion molding, then at 15-40 ℃ of dry 4-6h, after 100 ℃ of dry 8-10h, with 1 ℃/min-5 ℃/min heating rate, be warming up to 450-650 ℃, roasting 6-8h, obtains carrier;
Second step, Kaolinite Preparation of Catalyst
By tungstic acid predecessor ammonium metatungstate, nickel monoxide predecessor nitric acid nickel (NO
3)
26H
2o, chrome green predecessor chromic nitrate Cr (NO
3)
39H
2o joins in distilled water, 15-60 ℃ of stirring, it is dissolved completely, then add phosphoric acid to continue to stir 0.5-1h, obtain active component solution, then with described active component solution, flood described carrier, dipping 3-5h, again in 20-30 ℃ of dry 5-8h, 100 ℃ of dry 6-8h, are then warming up to 450-550 ℃ with 2 ℃/min-6 ℃/min heating rate, roasting 6-8h, makes catalyst finished product.
2. the hydrodenitrogenation catalyst that removes coal tar nitrogen-containing compound according to claim 1, the predecessor that it is characterized in that described aluminium oxide is that specific area is 350-450 m
2/ g, pore volume is 0.6-1.0 cm
3/ g, average pore size is the boehmite of 6-8 nm.
3. the hydrodenitrogenation catalyst that removes coal tar nitrogen-containing compound according to claim 1, is characterized in that described binding agent is pore volume 0.2-0.4 cm
3the boehmite of/g.
4. the hydrodenitrogenation catalyst that removes coal tar nitrogen-containing compound according to claim 1, it is characterized in that described extrusion aid is by sesbania gum and organic acid composition, its weight part ratio is 1:1-3, and described organic acid is a kind of in acetic acid, malonic acid, citric acid, tartaric acid and lactic acid.
5. the hydrodenitrogenation catalyst that removes coal tar nitrogen-containing compound according to claim 4, is characterized in that described organic acid is a kind of in acetic acid, malonic acid and citric acid.
6. a preparation method who removes the hydrodenitrogenation catalyst of coal tar nitrogen-containing compound claimed in claim 1, is characterized in that carrying out according to following steps:
The first step, prepares carrier
Described aluminum oxide precursor thing boehmite, zirconia, H beta-molecular sieve, ammonium fluoride, binding agent and extrusion aid are mixed, obtain mixture, the gouache ratio of take again adds distilled water as 0.5-0.7:1 in described mixture, in kneader, after kneading 60-150min, put into banded extruder extrusion molding, then at 15-40 ℃ of dry 4-6h, after 100 ℃ of dry 8-10h, with 1 ℃/min-5 ℃/min heating rate, be warming up to 450-650 ℃, roasting 6-8h, obtains carrier;
Second step, Kaolinite Preparation of Catalyst
By tungstic acid predecessor ammonium metatungstate, nickel monoxide predecessor nitric acid nickel (NO
3)
26H
2o, chrome green predecessor chromic nitrate Cr (NO
3)
39H
2o joins in distilled water, 15-60 ℃ of stirring, it is dissolved completely, then add phosphoric acid to continue to stir 0.5-1h, obtain active component solution, then with described active component solution, flood described carrier, dipping 3-5h, again in 20-30 ℃ of dry 5-8h, 100 ℃ of dry 6-8h, are then warming up to 450-550 ℃ with 2 ℃/min-6 ℃/min heating rate, roasting 6-8h, makes catalyst finished product.
7. the preparation method who removes the hydrodenitrogenation catalyst of coal tar nitrogen-containing compound according to claim 6, it is characterized in that in described active component solution, ammonium metatungstate weight percent concentration is 17%-19%, nickel nitrate weight percent concentration is 16%-21%, chromic nitrate weight percent concentration is 11%-19%, and phosphoric acid weight percent concentration is 3%-6%.
8. an application that removes the hydrodenitrogenation catalyst of coal tar nitrogen-containing compound claimed in claim 1, is characterized in that application process is: catalyst is contained in fixed bed hydrogenation reactor, and first to presulfiding of catalyst, then controlling reaction condition is H
2pressure 8.0-12.0MPa, volume space velocity 0.3-0.8 h during liquid
-1, hydrogen/oil volume is than being 1200/1-1800/1, temperature is 380-420 ℃ and reacts.
9. the application that removes the hydrodenitrogenation catalyst of coal tar nitrogen-containing compound according to claim 8, is characterized in that the sulfuration liquid of described presulfurization is the kerosene containing DMDS 1.0-1.5 wt%, and conditions of vulcanization is: H
2pressure 1.5-2.5MPa, volume space velocity 0.5-0.8h during liquid
-1, hydrogen/oil volume is than being 700/1-900/1, temperature 200-230 ℃, cure time 35-50h.
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| CN104001539B (en) * | 2014-05-14 | 2016-03-30 | 北京石油化工学院 | A kind of coal tar hydrocracking pretreatment catalyst and preparation method thereof |
| CN108906118A (en) * | 2018-08-17 | 2018-11-30 | 宁波敬业控股集团有限公司 | Coal tar hydro-denitrificatiocatalyst catalyst and preparation method thereof |
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| EP2256181B1 (en) * | 2005-01-07 | 2016-06-01 | Nippon Oil Corporation | Lubricant base oil and lubricant composition for an internal combustion engine and lubricant composition for a driving force transmitting device |
| US7247594B2 (en) * | 2005-04-13 | 2007-07-24 | Chevron Phillips Chemical Co. Lp | Catalysts for olefin polymerization |
| US7884163B2 (en) * | 2008-03-20 | 2011-02-08 | Chevron Phillips Chemical Company Lp | Silica-coated alumina activator-supports for metallocene catalyst compositions |
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