CN1162517C - Catalyst for producing diesel oil from Fischer-Tropsch synthetic wax and its prepn and use - Google Patents
Catalyst for producing diesel oil from Fischer-Tropsch synthetic wax and its prepn and use Download PDFInfo
- Publication number
- CN1162517C CN1162517C CNB011114398A CN01111439A CN1162517C CN 1162517 C CN1162517 C CN 1162517C CN B011114398 A CNB011114398 A CN B011114398A CN 01111439 A CN01111439 A CN 01111439A CN 1162517 C CN1162517 C CN 1162517C
- Authority
- CN
- China
- Prior art keywords
- zeolite
- oxide
- diesel oil
- catalyzer
- fischer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 27
- 239000002283 diesel fuel Substances 0.000 title claims abstract description 22
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 46
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000010457 zeolite Substances 0.000 claims abstract description 46
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000011148 porous material Substances 0.000 claims abstract description 7
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 6
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 4
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 230000003075 superhydrophobic effect Effects 0.000 claims description 14
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 11
- 230000004913 activation Effects 0.000 claims description 10
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 10
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 7
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 7
- 238000005984 hydrogenation reaction Methods 0.000 claims description 7
- 238000005342 ion exchange Methods 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 235000006408 oxalic acid Nutrition 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- 238000005096 rolling process Methods 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 6
- 239000004411 aluminium Substances 0.000 abstract description 2
- 229910052782 aluminium Inorganic materials 0.000 abstract description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000002485 combustion reaction Methods 0.000 abstract 1
- 229930195734 saturated hydrocarbon Natural products 0.000 abstract 1
- 229910052710 silicon Inorganic materials 0.000 abstract 1
- 239000010703 silicon Substances 0.000 abstract 1
- 239000001993 wax Substances 0.000 description 9
- 239000003921 oil Substances 0.000 description 7
- 238000005336 cracking Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- 206010003694 Atrophy Diseases 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- NBFQLHGCEMEQFN-UHFFFAOYSA-N N.[Ni] Chemical compound N.[Ni] NBFQLHGCEMEQFN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- LKTZODAHLMBGLG-UHFFFAOYSA-N alumanylidynesilicon;$l^{2}-alumanylidenesilylidenealuminum Chemical compound [Si]#[Al].[Si]#[Al].[Al]=[Si]=[Al] LKTZODAHLMBGLG-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000037444 atrophy Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000002101 lytic effect Effects 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000010742 number 1 fuel oil Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- -1 sulfur-bearing Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
Abstract
The present invention relates to a catalyst for producing diesel oil by using fischer-tropsch synthetic wax, which comprises (by weight percentage): 30 to 50w% of Y zeolite, 5 to 20% of tungsten oxide or molybdenum oxide, 1 to 10% of oxide and 30 to 60% of the mixture of aluminum oxide or silicon and aluminium. The specific surface area of the hydrocracking catalyst of the present invention is from 250 to 400m<2>/g, the pore volume is from 0.30 to 0.70 ml/g, and the TPD acidity is from 0.75 to 1.5 mmol/g. The present invention can carry out selectivity chain breaking operation for straight chain saturated hydrocarbons, and thereby, the yield of the cut fraction of diesel oil is improved; products are isomerized, cut fractions of the diesel oil in the products have a lower solidifying point, better combustion performance, good catalyst activity and high diesel oil selectivity.
Description
The invention belongs to a kind of catalyzer of producing diesel oil, relate in particular to a kind of Catalysts and its preparation method and purposes of producing diesel oil by Fischer-Tropsch synthetic wax.
In recent years, along with the atrophy of world's crude resources and raising up of crude oil price, energy consumption structure changes to oil, coal and Sweet natural gas alliance type gradually from oil dependent form, particularly SMDS (the Shell Middle Distillate Synthesis) technology of Shell company exploitation realizes industrial-scale production, makes coal/Sweet natural gas indirect liquefaction technology become one of the most attractive approach of back petroleum industry epoch liquid fuel.Also there is the research as the CO hydrogenation catalyst of a large amount of reports, particularly cobalt series catalyst domestic at present Fischer-Tropsch being synthesized.But the research to the deep processing of its product wax is still blank.
Fischer-Tropsch is synthetic can produce heavy hydrocarbon to greatest extent, its solid product---wax, and based on straight chain saturation alkane, impurity such as sulfur-bearing, nitrogen not, therefore aromatic free need not to carry out pre-treatment before further transforming, simplified technical process greatly.But the C-C key bond energy of straight chain saturation alkane makes comparatively difficulty of its selectivity scission of link than equalization, therefore, Preparation of catalysts is had higher requirement.
Hydrocracking technology is a kind of important refining of petroleum means, and it has good cracking selectivity, and can adapt to the variation of raw material and product demand neatly, therefore is Fischer-Tropsch synthetic wax is carried out the most effectively means of deep processing.With the amorphous silicon aluminium is the hydrocracking catalyst of cracking activity component, in cracking process to wax, show intermediate oil selectivity preferably, by the adjusting of acidity, specific surface and secondary pore, can obtain the diesel oil of highly selective, but products obtained therefrom is based on straight-chain paraffin, although such diesel oil has higher cetane value, but its condensation point height, combustionproperty is poor, needs further pour point depression and interpolation auxiliary agent to use.The use of zeolite is a qualitative leap of hydrocracking technology.It not only makes activity of such catalysts and stability significantly improve, and flexibility of operation is greatly strengthened, and the more important thing is that it makes in the alkane cracked product a certain amount of isomer is arranged.But present contain the processing that the zeolite hydrocracking catalyst all is applied to heavy crude, the cracking performance of these catalyzer is stronger relatively, is applied to the man-hour that adds of wax, and intermediate oil (comprising boat coal and diesel oil) selectivity is relatively poor.
The US4517074 patent disclosure a kind of hydrogenation crude cracking catalyst, produce 150-370 ℃ intermediate oil, this catalyzer is except using zeolite component, its characteristics are to use a kind of Al
2O
3-SiO
2Dispersion system, its SiO
2Content reaches 20-65%, though the amorphous aluminum silicide in the dispersion system has certain lytic activity, need be dispersed on the alumina substrate, to obtain the pore volume and the specific surface of a large amount of hydrogenation metal component of carrying.Though this catalyzer has higher middle distillates oil selectivity, generally more than 80%, activity is lower, reach 60v% and transform, and temperature of reaction is generally more than 400 ℃.
The object of the present invention is to provide a kind of activity good, isomery ratio height, the catalyzer that is used for the hydrocracking Fischer-Tropsch synthetic wax that the diesel oil selectivity is high.
The weight percent of catalyzer of the present invention consists of:
Y zeolite 30-50% cobalt oxide or nickel oxide 1-10%
Aluminum oxide or silicon-aluminum mixture 48.5-60%
Aforesaid catalyzer can also include Mo or the W oxide compound that weight percent is 5-20%.
Hydrocracking catalyst of the present invention has specific surface 250-400m
2/ g, pore volume 0.30-0.70ml/g, the feature of TPD acidity 0.75-1.5mmol/g.
Preparation of catalysts method of the present invention is as follows:
(1) NaY zeolite and ammonium nitrate solution are carried out ion-exchange 3～6 times, filtration, washing, oven dry obtain NH
4Y zeolite.
(2) with NH
4Y, ammonium nitrate, oxalic acid and handle after water mixes by 1: 1: 0.1～0.3: 10 weight ratio obtain super-hydrophobic Y zeolite.
(3) super-hydrophobic Y zeolite is contacted with the solution that contains Xiao Suangu or nickelous nitrate, obtain being impregnated with the Y zeolite (A) of hydrogenation metal.
(4) with (A) in 90～120 ℃ dry 4～6 hours down, in 400～600 ℃ down activation obtained (B) in 4～6 hours.
(5) with aluminum oxide with (B) mix after, add salpeter solution and prepare tackiness agent, become paste after rolling the enough time, use the banded extruder moulding, obtain the cylinder bar (C) of diameter 1.2～1.8mm.
(6) with (C) in 90～120 ℃ dry 4～6 hours down, in 400～600 ℃ of activation 4～6 hours down, obtain the catalyzer of the related use of hydrocracking process of the present invention.
Wherein the weight percent of each component consists of:
Y zeolite 30-50% cobalt oxide or nickel oxide 1-10%
Aluminum oxide or silicon-aluminum mixture 48.5-60%
Preparation of catalysts method of the present invention can also be as follows:
(1) NaY zeolite and ammonium nitrate solution are carried out ion-exchange 3～6 times, filtration, washing, oven dry obtain NH
4Y zeolite.
(2) with NH
4Y, ammonium nitrate, oxalic acid and handle after water mixes by 1: 1: 0.1～0.3: 10 weight ratio obtain super-hydrophobic Y zeolite.
(3) super-hydrophobic Y zeolite is contacted with the solution that contains metatungstic acid ammonia or molybdenum acid ammonia, obtain being impregnated with the Y zeolite (A) of promoter metal.
(4) with (A) in 90～120 ℃ dry 4～6 hours down, in 400～600 ℃ down activation obtained (B) in 4～6 hours.
(5) (B) contacted with the solution that contains Xiao Suangu or nickelous nitrate, obtains being impregnated with the Y zeolite of hydrogenation metal, with its in 90～120 ℃ dry 4～6 hours down, in 400～600 ℃ of activation 4～6 hours down.
(6) with aluminum oxide with (C) mix after, add salpeter solution and prepare tackiness agent, become paste after rolling the enough time, use the banded extruder moulding, obtain the cylinder bar (D) of diameter 1.2～1.8mm.
(7) with (D) in 90～120 ℃ dry 4～6 hours down, in 400～600 ℃ of activation 4～6 hours down, obtain the catalyzer of the related use of hydrocracking process of the present invention.
Wherein the weight percent of each component consists of:
Y zeolite 30-50% cobalt oxide or nickel oxide 1-10%
Aluminum oxide or silicon-aluminum mixture 48.5-60% Tungsten oxide 99.999 or molybdenum oxide 5-20%
The weight percent sum of each component is 100%.
Catalyzer of the present invention is used for Fischer-Tropsch synthetic wax production diesel oil processing condition: under the hydrogen existence condition, reaction pressure is 1.5-8.0MPa, hydrogen to oil volume ratio 800-5000, air speed 0.1-5.0h
-1, temperature of reaction 280-400 ℃.
The present invention compared with prior art has following advantage:
(1) catalyzer of the present invention can carry out the selectivity chain rupture to straight chain saturation alkane, thereby has improved the yield of diesel oil distillate.
(2) catalyzer of the present invention carries out isomerization to product in cracking stock, makes the condensation point of the diesel oil distillate in the product lower, and combustionproperty is better.
(3) good catalyst activity of the present invention, diesel oil selectivity height.
Embodiment 1
Catalyst A with the inventive method preparation
(1) gets 500gNaY zeolite (production of Wenzhou catalyst plant), be added to the NH that 2L concentration is 2M
4NO
3In the solution, stir down at 90 ℃, ion-exchange 2 hours exchanges 5 times altogether, filters then, washs to neutrality, oven dry.
(2) with product in (1) and ammonium nitrate, oxalic acid, water by 1: 1: 0.1: 10 mixed, stirred 1 hour under the room temperature, be warming up to 90 ℃ after, constant temperature stirred 1 hour, dried, and obtained super-hydrophobic Y zeolite.
(3) in the clean container of a 1L, add solid Ni (NO
3)
26H
2O 174 grams, with the less water dissolving, dropping ammonia is to forming the transparent nickel ammonia solution of mazarine, PH=12.
(4) super-hydrophobic Y zeolite involved in the present invention 300 grams be impregnated in the above-mentioned solution, stir and make it to form stable slurry, place more than 12 hours.
(5) descended dry 4 hours at 120 ℃, 500 ℃ of following roastings 4 hours.
(6) material that 700 gram aluminum oxide and (5) are obtained mixes, and adds salpeter solution, becomes paste after rolling the enough time, uses the banded extruder moulding, obtains the cylinder bar of diameter 1.2～1.8mm.
(7) with the bar that obtains in (6) in 120 ℃ dry 4 hours down, obtained the catalyzer of the related use of hydrocracking process of the present invention in 4 hours in 500 ℃ of following roastings.Catalyzer consists of: Y zeolite 28.7%, nickel oxide 4.2%, aluminum oxide 67.1%.
The physico-chemical property of catalyzer sees Table 1, and evaluation result sees Table 2.
Embodiment 2
Catalyst B with the inventive method preparation
(1) in the clean container of a 1L, adds metatungstic acid ammonia 93 grams, dissolve with less water.
(2) super-hydrophobic Y zeolite of the present invention 300 grams be impregnated in this solution, place more than 12 hours, 110 ℃ of dryings 6 hours, 400 ℃ of roastings 6 hours.
All the other preparation process are with embodiment 1.Catalyzer consists of: Y zeolite 27.3%, nickel oxide 5.9%, aluminum oxide 58.6%, Tungsten oxide 99.999 8.2%.
The physico-chemical property of catalyzer sees Table 1, and evaluation result sees Table 2.
Embodiment 3
Catalyzer C with the inventive method preparation.
(1) gets 500gNaY zeolite (production of Wenzhou catalyst plant), be added to the NH that 2L concentration is 2M
4NO
3In the solution, stir down at 90 ℃, ion-exchange 2 hours exchanges 6 times altogether, filters then, washs to neutrality, oven dry.
(2) with product in (1) and ammonium nitrate, oxalic acid, water by 1: 1: 0.3: 10 mixed, stirred 1 hour under the room temperature, be warming up to 90 ℃ after, constant temperature stirred 1 hour, dried, and obtained super-hydrophobic Y zeolite.
(3) all the other preparation process are with embodiment 2.Catalyzer consists of: Y zeolite 37.3%, nickel oxide 5.7%, aluminum oxide 48.5%, Tungsten oxide 99.999 8.5%.
The physico-chemical property of catalyzer sees Table 1, and evaluation result sees Table 2.
Embodiment 4
Catalyzer D with the inventive method preparation.
The Preparation of catalysts process is with embodiment 2.Catalyzer consists of: Y zeolite 46.9%, nickel oxide 8.3%, aluminum oxide 38.5%, molybdenum oxide 6.3%.
The physico-chemical property of catalyzer sees Table 1, and evaluation result sees Table 2.
Embodiment 5
Catalyzer E with the inventive method preparation.
(1) gets 500gNaY zeolite (production of Wenzhou catalyst plant), be added to the NH that 2L concentration is 2M
4NO
3In the solution, stir down at 90 ℃, ion-exchange 2 hours exchanges 6 times altogether, filters then, washs to neutrality, oven dry.
(2) with product in (1) and ammonium nitrate, oxalic acid, water by 1: 1: 0.2: 10 mixed, stirred 1 hour under the room temperature, be warming up to 90 ℃ after, constant temperature stirred 1 hour, dried, and obtained super-hydrophobic Y zeolite.
(3) in the clean container of a 1L, add metatungstic acid ammonia, dissolve with aquae destillata.
(4) super-hydrophobic Y zeolite of the present invention 300 grams be impregnated in this solution, place more than 12 hours, 90 ℃ of dryings 6 hours, 400 ℃ of roastings 6 hours.
(5) in the clean container of a 1L, add Xiao Suangu, dissolve with aquae destillata.
(6) material that obtains in the step (4) 300 grams be impregnated in this solution, place more than 12 hours, 90 ℃ of dryings 6 hours, 400 ℃ of roastings 6 hours.
(7) make shaping of catalyst by the step among the embodiment 1 (6) (7).Catalyzer consists of: Y zeolite 37.3%, cobalt oxide 5.7%, aluminum oxide 48.5%, Tungsten oxide 99.999 8.5%.
The physico-chemical property of catalyzer sees Table 1, and evaluation result sees Table 2.
The physico-chemical property of table 1 catalyzer
| Catalyzer | A | B | C | D | E |
| Specific surface (m 2/g) | 337 | 262 | 359 | 397 | 367 |
| Pore volume (ml/g) | 0.55 | 0.33 | 0.52 | 0.63 | 0.48 |
| ＞2.0nm pore distribution, % | 43 | 62 | 71 | 68 | 57 |
| TPD acidity, mmol/g | 1.2 | 1.0 | 0.8 | 0.9 | 1.1 |
The reaction evaluating result of table 2 catalyzer
| Catalyzer | A | B | C | D | E |
| Temperature of reaction (℃) | 320 | 320 | 320 | 320 | 320 |
| Transformation efficiency (w%) | 70 | 68 | 75 | 75 | 73 |
| Diesel oil selectivity (%) | 35.2 | 42.1 | 44.8 | 41.7 | 40.3 |
Claims (5)
1. produce the catalyzer of diesel oil by Fischer-Tropsch synthetic wax for one kind, it is characterized in that the weight percent of catalyzer consists of:
Y zeolite 30-50% cobalt oxide or nickel oxide 1-10%
Aluminum oxide or silicon-aluminum mixture 48.5-60%;
The specific surface area 250-400m of catalyzer
2/ g, pore volume 0.30-0.70ml/g, TPD acidity 0.75-1.5mmol/g.
2. a kind of catalyzer by Fischer-Tropsch synthetic wax production diesel oil according to claim 1 is characterized in that described catalyzer also includes Mo or the W oxide compound that weight percent is 5-20%, and the weight percent sum of each component is 100%.
3. a Preparation of catalysts method of producing diesel oil by Fischer-Tropsch synthetic wax is characterized in that the preparation method comprises the steps:
(1) NaY zeolite and ammonium nitrate solution are carried out ion-exchange 3～6 times, filtration, washing, oven dry obtain NH
4Y zeolite;
(2) with NH
4Y, ammonium nitrate, oxalic acid and handle after water mixes by 1: 1: 0.1～0.3: 10 weight ratio obtain super-hydrophobic Y zeolite;
(3) super-hydrophobic Y zeolite is contacted with the solution that contains Xiao Suangu or nickelous nitrate, obtain being impregnated with the Y zeolite (A) of hydrogenation metal;
(4) with (A) in 90～120 ℃ dry 4～6 hours down, in 400～600 ℃ down activation obtained (B) in 4～6 hours;
(5) with aluminum oxide with (B) mix after, add salpeter solution and prepare tackiness agent, become paste after rolling the enough time, use the banded extruder moulding, obtain the cylinder bar (C) of diameter 1.2～1.8mm;
(6) with (C) in 90～120 ℃ dry 4～6 hours down, in 400～600 ℃ of activation 4～6 hours down, obtain the catalyzer of the related use of hydrocracking process of the present invention;
Wherein the weight percent of each component consists of:
Y zeolite 30-50% cobalt oxide or nickel oxide 1-10%
Aluminum oxide or silicon-aluminum mixture 48.5-60%.
4. a Preparation of catalysts method of producing diesel oil by Fischer-Tropsch synthetic wax is characterized in that the preparation method comprises the steps:
(1) NaY zeolite and ammonium nitrate solution are carried out ion-exchange 3～6 times, filtration, washing, oven dry obtain NH
4Y zeolite;
(2) with NH
4Y, ammonium nitrate, oxalic acid and handle after water mixes by 1: 1: 0.1～0.3: 10 weight ratio obtain super-hydrophobic Y zeolite;
(3) super-hydrophobic Y zeolite is contacted with the solution that contains metatungstic acid ammonia or molybdenum acid ammonia, obtain being impregnated with the Y zeolite (A) of promoter metal;
(4) with (A) in 90～120 ℃ dry 4～6 hours down, in 400～600 ℃ down activation obtained (B) in 4～6 hours;
(5) (B) contacted with the solution that contains Xiao Suangu or nickelous nitrate, obtains being impregnated with the Y zeolite of hydrogenation metal, with its in 90～120 ℃ dry 4～6 hours down, in 400～600 ℃ of activation 4～6 hours down;
(6) with aluminum oxide with (C) mix after, add salpeter solution and prepare tackiness agent, become paste after rolling the enough time, use the banded extruder moulding, obtain the cylinder bar (D) of diameter 1.2～1.8mm;
(7) with (D) in 90～120 ℃ dry 4～6 hours down, in 400～600 ℃ of activation 4～6 hours down, obtain the catalyzer of the related use of hydrocracking process of the present invention;
Wherein the weight percent of each component consists of:
Y zeolite 30-50% cobalt oxide or nickel oxide 1-10%
Aluminum oxide or silicon-aluminum mixture 48.5-60% Tungsten oxide 99.999 or molybdenum oxide 5-20%
The weight percent sum of each component is 100%.
5. one kind is used for the Application of Catalyst method that Fischer-Tropsch synthetic wax is produced diesel oil, it is characterized in that processing condition are: under the hydrogen existence condition, and reaction pressure 1.5-8.0MPa, hydrogen to oil volume ratio 800-5000, air speed 0.1-5.0h
-1, temperature of reaction 280-400 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011114398A CN1162517C (en) | 2001-03-09 | 2001-03-09 | Catalyst for producing diesel oil from Fischer-Tropsch synthetic wax and its prepn and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011114398A CN1162517C (en) | 2001-03-09 | 2001-03-09 | Catalyst for producing diesel oil from Fischer-Tropsch synthetic wax and its prepn and use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1374373A CN1374373A (en) | 2002-10-16 |
| CN1162517C true CN1162517C (en) | 2004-08-18 |
Family
ID=4659054
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011114398A Expired - Lifetime CN1162517C (en) | 2001-03-09 | 2001-03-09 | Catalyst for producing diesel oil from Fischer-Tropsch synthetic wax and its prepn and use |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1162517C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100345944C (en) * | 2005-09-08 | 2007-10-31 | 中科合成油技术有限公司 | Hydroconversion process of uncured Fisher-Tropsch process synthesized oil product |
| CN105618111B (en) * | 2014-11-03 | 2018-10-12 | 中国石油化工股份有限公司 | A kind of preparation method and hydrogenation technique of catalytic diesel oil hydrogenation conversion catalyst |
| CN105983407B (en) * | 2015-01-29 | 2018-07-13 | 中国石油天然气股份有限公司 | A kind of Co based Fischer-Tropsch synthesis catalyst and preparation method thereof for producing naphtha and drilling fluid |
-
2001
- 2001-03-09 CN CNB011114398A patent/CN1162517C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1374373A (en) | 2002-10-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1190473C (en) | Process for preparing a lubricating base oil | |
| CN100513531C (en) | Hydrocracking method of midbarrel oil circulation | |
| CN1119668A (en) | Hydrocarbon conversion catalysts | |
| CN1054153C (en) | Hydrocracking catalyst for producing intermediate fraction oil | |
| CN1955260A (en) | Hydrocracking method | |
| CN1778873A (en) | Inferior diesel hydrogenation catalyst | |
| CN112371167B (en) | Catalyst for producing high-octane component gasoline and preparation method and application thereof | |
| CN1814712A (en) | Modifying catalyst for naphtha processed maferial and method therefor | |
| CN1955262A (en) | Two-stage hydrocracking method | |
| CN1778872A (en) | Hydrogenation desulfurized catalyst containing molecular screen | |
| CN100497543C (en) | Combined hydrocracking method | |
| CN1352231A (en) | Hydrogenating and pour point depressing catalyst and its preparing method | |
| CN1043520A (en) | A kind of catalyst for cracking of producing low-carbon alkene | |
| CN1045462C (en) | Middle-pressure hydrocracking process for heavy fractional oil | |
| CN1159103C (en) | Low temperaure catalyst for producing intermediate fraction oil with heavy alkane and its preparation method | |
| CN100417713C (en) | Hydrocracking catalyst for Tscher-Topsch synthesis of heavy wax, its preparation method and application thereof | |
| CN1162517C (en) | Catalyst for producing diesel oil from Fischer-Tropsch synthetic wax and its prepn and use | |
| CN1504541A (en) | Catalyst for preparing olefin with arene as side product by hydrocarbon catalytic cracking, preparing method and uses thereof | |
| CN1212376C (en) | Light hydrocarbon non-hydrogenation modified catalyst, preparing process and application thereof | |
| CN1966617A (en) | Hydrocracking process for high yield producing intermediate distillate | |
| CN1955263A (en) | Combined processing method of faulty catalytic cracking diesel oil | |
| CN1966147A (en) | Catalyst for producing benzene, toluene and xylene and coupled production of low carbon olefin | |
| CN1955259A (en) | Parallel hydrocracking method | |
| CN1136298C (en) | Catalyst for producing middle fraction from Fischer-Tropsch synthetic heavy hydrocarbon and its prepn and use | |
| CN1955258A (en) | Hydrocracking method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: ZHONGKE SYNTHETIC OIL TECHNOLOGY CO., LTD., DISTR Free format text: FORMER OWNER: SHANXI INST. OF COAL CHEMISTRY, CHINESE ACADEMY OF SCIENCES Effective date: 20070119 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20070119 Address after: 030006, Taiyuan hi tech Zone, Shanxi, South Central Cyberport, port 4, 2, A and B Patentee after: Zhongke Synthetic Oil Technology Co., Ltd. Address before: 165 mailbox 030001, Shanxi City, Taiyuan Province Patentee before: Shanxi Institute of Coal Chemistry, Chinese Academy of Sciences |
|
| C56 | Change in the name or address of the patentee | ||
| CP02 | Change in the address of a patent holder |
Address after: 101407 Beijing city Huairou District Yanqi Economic Development Zone C District No. 1 south two Street Park Patentee after: Zhongke Synthetic Oil Technology Co., Ltd. Address before: 030006, Taiyuan hi tech Zone, Shanxi, South Central Cyberport, port 4, 2, A and B Patentee before: Zhongke Synthetic Oil Technology Co., Ltd. |
|
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20040818 |