CN1102642C - Catalyst for small crystal granule ZSM-5 molecular sieve catalystic dewaxing - Google Patents
Catalyst for small crystal granule ZSM-5 molecular sieve catalystic dewaxing Download PDFInfo
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- CN1102642C CN1102642C CN97121843A CN97121843A CN1102642C CN 1102642 C CN1102642 C CN 1102642C CN 97121843 A CN97121843 A CN 97121843A CN 97121843 A CN97121843 A CN 97121843A CN 1102642 C CN1102642 C CN 1102642C
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- zsm
- catalyst
- molecular sieve
- catalyzer
- dewaxing
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- 239000003054 catalyst Substances 0.000 title claims abstract description 26
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 18
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000013078 crystal Substances 0.000 title abstract description 18
- 239000008187 granular material Substances 0.000 title 1
- 230000003197 catalytic effect Effects 0.000 claims abstract description 15
- 239000010687 lubricating oil Substances 0.000 claims abstract description 15
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 235000011089 carbon dioxide Nutrition 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 claims 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims 1
- 229910052721 tungsten Inorganic materials 0.000 claims 1
- 239000010937 tungsten Substances 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 8
- 238000001035 drying Methods 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000969 carrier Substances 0.000 abstract 3
- 239000011230 binding agent Substances 0.000 abstract 2
- 238000010000 carbonizing Methods 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- 229910021536 Zeolite Inorganic materials 0.000 description 14
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 14
- 239000010457 zeolite Substances 0.000 description 14
- 239000003921 oil Substances 0.000 description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 8
- 238000004517 catalytic hydrocracking Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000003657 tungsten Chemical class 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000003974 emollient agent Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- -1 small molecule hydrocarbon Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Abstract
The present invention relates to a catalytic dewaxing catalyst for lubricating oil. The catalyst is prepared by adding a small amount of binding agent into ZSM-5 molecular sieves, forming by extruding to obtain carriers, drying the carriers, roasting the carriers and carrying hydrogenating (dehydrogenating) metallic components on the carrier, wherein the ZSM-5 molecular sieves are small ZSM-5 hydrogen type crystal grains with the crystal granularity of 0.1 to 0.5 mum and the binding agent is aluminum oxide obtained in a carbonizing method. The catalyst is suitable for a hydrodecoagulation process of the fractions of the lubricating oil with high liquid yield.
Description
The present invention relates to particularly lubricating oil distillate catalytic dewaxing catalyst and preparation method thereof of distillate.
Need carry out dewaxing treatment when producing lubricant base and low-coagulation diesel oil, with low-temperature fluidity and the reduction diesel oil zero pour of improving lube product with waxy feeds oil.In lubricating oil dewaxing technology, catalytic dewaxing is a kind of than solvent dewaxing technology flexibly, its dewaxing principle is under certain operational condition, raw material is mixed with hydrogen pass through beds, in this bed, normal paraffin in the raw material and short-side chain isoparaffin generation hydrocracking reaction generate low molecular hydrocarbon, and other component does not change substantially, finally reaches the purpose that reduces pour point (or condensation point).
In order to improve the catalytic dewaxing selectivity, catalyst system therefor generally is a molecular sieve catalyst, and this molecular sieve can allow normal paraffin and short-side chain isoparaffin to enter in its duct, and hyperbranched isoparaffin, naphthenic hydrocarbon and aromatic hydrocarbons exclusion.Used molecular sieve has ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35 and ZSM-38 etc.U.S. Pat 3,894,938; 4,176,050; 4,181,598; 4,222,855; 4,229,282 and 4,247,388 pairs of above-mentioned molecular sieves should be used as detailed descriptionthe.
Because catalytic dewaxing is that the wax molecule is cracked into small molecule hydrocarbon gas in the stock oil, separates from oil product, certainly will cause certain liquid to receive (liquid product total recovery) and lubricating oil distillate loss like this.The liquid of WITH CATALYTIC DEWAXING TECHNIQUE process is received and yield of lubricating oil wax content and the operational condition, depends primarily on the essence of catalytic dewaxing catalyst in depending on raw material.
US 4,574,043 discloses the dewaxing process of a kind of hydrocracking unconverted oil (tail oil) on the 0.57%Pt/ZSM-22 catalyzer, though can improve liquid receives, but because catalyzer has used precious metal, cost is very high, and the impact resistance of poisoning easily is poor, environment for use is required harshness, make its practical application be subjected to great restriction.
The lubricating oil catalytic dewaxing catalyzer that the purpose of this invention is to provide a kind of activity, selectivity and have good stability, the characteristics of this catalyzer are to have adopted the ZSM-5 molecular sieve of little crystal grain, with this catalyzer hydrocracking tail oil is dewaxed, can obtain higher liquid yield and lubricating oil distillate yield.
The principal element that influences the catalytic dewaxing catalyst performance is the character of ZSM-5 molecular sieve.By intensive research, we find under the identical situation of character such as molecular sieve silica alumina ratio, degree of crystallinity, foreign matter content, and the zeolite crystal size is unusual significant effects factor.Since in lubricating oil distillate and the diesel oil bigger alkane molecule in the ZSM-5 molecular sieve pore passage velocity of diffusion much smaller than cracking speed, so reaction is by diffusion control.Because little crystal grain zeolite (grain size is 0.1～0.5 μ m) catalyst surface area is big, the active centre is many, the big crystal grain zeolite (grain size is generally 1～3 μ m) of alkane molecular diffusion required time to the active centre will be lacked, like this, the activity of little crystal grain zeolite catalyst is just higher, the duct of little crystal grain zeolite is short simultaneously, a crackate also is easier to spread out, avoid staying the long period and secondary cracking takes place, thereby cause aerogenesis to reduce, therefore can increase substantially liquid and receive and yield of lubricating oil.
Catalyzer of the present invention is to adopt ZSM-5 molecular sieve with small crystal grains and aluminum oxide caking agent and make, and the aluminum oxide caking agent can adopt general aluminum oxide, but adopts acid weak aluminum oxide better effects if.
The present invention in conjunction with prior art and by following measures to achieve the above object.
(1) selecting grain size is the ZSM-5 molecular sieve of 0.1～0.5 μ m, and silica alumina ratio is generally 50～120 because higher silica alumina ratio is arranged, its acidity a little less than.
(2) select a kind of acidity than common Al
2O
3Weak carborization aluminum oxide is as tackiness agent.This aluminum oxide is by making with sodium metaaluminate in the carbonic acid gas.
Because selected ZSM-5 molecular sieve and carborization aluminum oxide acidity are all lower, handle (purpose is to remove strong acid center) so need not to carry out high-temperature vapor behind the shaping of catalyst, take simple sinter process to get final product.
Catalyzer of the present invention consists of:
HZSM-5 (to carrier), 65-85m%
Al
2O
3(to carrier), 15-35m%
WO
3(to catalyzer), 10-18m%
NiO (to catalyzer), 2.0-6.0m%
Wherein: the crystal grain of HZSM-5 is 0.1～0.5 μ m, SiO
2/ Al
2O
3Than being 50～120;
Al
2O
3Aluminum oxide for carborization production.
The physico-chemical property of catalyzer of the present invention:
Pore volume, 0.10-0.30cm
3/ g
Specific surface, 180-300m
2/ g
Tap density, 0.88-0.95g/cm
3,
Preparation of catalysts method of the present invention
Appropriate amount of alumina and aqueous nitric acid are mixed, make tackiness agent, and add the ZSM-5 zeolite in proportion, mix and pinch evenly, extruded moulding, carrier is made in wet bar drying (80～120 ℃), roasting (480～580 ℃), and carrier floods (1～4 hour) in the aqueous solution that contains a certain amount of tungsten salt and nickel salt, filtration, dry (40～110 ℃), roasting (480～600 ℃) makes finished catalyst.
Said tungsten salt and nickel salt preferably are respectively ammonium metawolframate and nickelous nitrate.
In above-mentioned preparation method, used ZSM-5 zeolite crystal degree size is 0.1～0.5 μ m, SiO
2/ Al
2O
3(mol ratio) is 50～120.Aluminum oxide is the carborization aluminum oxide.
The character of catalyzer of the present invention is as follows:
| Form and character | Index |
| Component concentration HZSM-5 (to carrier), m% Al 2O 3(to carrier), m% WO 3(to carrier), m% NiO (to carrier), m% physico-chemical property: pore volume, cm 3/ g specific surface, m 2/ g tap density, g/cm 3 | 65-85 15-35 10-18 2.0-6.0 0.10-0.30 180-300 0.88-0.95 |
Catalyzer of the present invention can be used for especially hydrocracking unconverted oil of distillate (tail oil) catalytic dewaxing process, can be under than the demulcent processing condition, above-mentioned raw materials is processed into the low lubricant base that coagulates, keeps higher liquid yield and lubricating oil distillate yield simultaneously.
Embodiment 1
(1) gets carborization aluminum oxide 55.6g (moisture 30m%), add 65.5g water purification and 7.4ml concentrated nitric acid, mix, cook composite adhesives.
(2) getting HZSM-5 (silica alumina ratio is 110, grain size average out to 0.2 μ m) 100g and above-mentioned tackiness agent mixes and to pinch extruded moulding.
(3) wet bar is under 100 ± 10 ℃ of conditions dry 4 hours, and roasting is 3 hours under 540 ℃ of conditions, makes carrier.
(4) preparation steeping fluid is got ammonium metawolframate and nickelous nitrate is some, adds in the water purification WO in the solution
3Form definite by the catalyst metal of carrier water-intake rate and requirement with the concentration of NiO.
(5) above-mentioned carrier is put into steeping fluid, flooded 2 hours, solid-to-liquid ratio is 1: 2.Filter then, 100 ℃ of dryings, 540 ℃ of roastings, final catalyzer.With this catalyzer Maoming hydrocracking tail oil is carried out catalytic dewaxing test, catalyzer physico-chemical property, test conditions and test-results see Table 1 and table 2.
Embodiment 2
(1) gets carborization aluminum oxide 37.1g, add 69.7g water purification and the dense HNO3 of 7.4ml and mix, cook composite adhesives.
(2) getting HZSM-5 (silica alumina ratio is 120, grain size average out to 0.2 μ m) 114.3g and above-mentioned tackiness agent mixes and to pinch extruded moulding.
Following steps are with embodiment 1.
Embodiment 3
(1) gets carborization aluminum oxide 64.8g, add 63.0g water purification and the dense HNO3 of 7.4ml and mix, cook composite adhesives.
(2) getting HZSM-5 (silica alumina ratio is 70, grain size average out to 0.4 μ m) 92.8g and above-mentioned tackiness agent mixes and to pinch extruded moulding.
Following steps are with embodiment 1.
Embodiment 4
(1) gets carborization aluminum oxide 46.3g, add 67.7g water purification and the dense HNO3 of 7.4ml and mix, cook composite adhesives.
(2) getting HZSM-5 (silica alumina ratio is 80, grain size average out to 0.4 μ m) 107.1g and above-mentioned tackiness agent mixes and to pinch extruded moulding.
Following steps are with embodiment 1.
Comparative example 1
Identical with embodiment 1 catalyzer composition and preparation condition, just zeolite crystal varies in size, used around here ZSM-5 zeolite crystal size average out to 2.0 μ m, and silica alumina ratio is 100, makes reference catalyst.With this catalyzer Maoming hydrocracking tail oil is carried out the catalytic dewaxing test, see Table 1.
Table 1 catalyst property and evaluation result
| Catalyzer | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 |
| Zeolite type zeolite content (to carrier), m% average crystal grain size, SiO in the μ m zeolite 2/Al 2O 3NiO (to catalyzer), m% WO 3(to catalyzer), m% pore volume, cm 3/ g specific surface, m 2/ g mean pore size, the nm tap density, g/cm 3 | ZSM-5 72.0 0.2 110 5.40 12.82 0.189 242.8 2.31 0.89 | ZSM-5 81.5 0.2 120 5.38 14.85 0.180 229.7 2.40 0.92 | ZSM-5 67.2 0.4 70 4.15 13.81 0.183 239.2 2.29 0.91. | ZSM-5 76.8 0.4 80 3.41 16.09 0.193 247.8 2.45 0.94 | ZSM-5 72.0 2.0 100 4.82 15.25 0.157 206 2.26 0.95 |
Table 2 catalyst reaction The performance test results
| The activity rating processing condition | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 |
| Pressure, MPa temperature, ℃ air speed, h -1(v) product distributes hydrogen-oil ratio, m% C 1-C 4 C 5-180 ℃ of 180-320 ℃＞320 ℃ (lubricating oil distillate) liquid are received, m%＞320 ℃ cut oiliness pour point, ℃ kinematic viscosity, mm 240 ℃ of viscosity indexs of/s | 8.0 310 1.0 800 17.0 17.9 1.1 64.0 83.0 -15 19.21 122 | 8.0 310 1.0 800 16.8 18.3 1.2 63.7 82.8 -17 18.81 121 | 8.0 310 1.0 800 18.5 19.1 1.1 62.5 80.1 -16 19.01 120 | 8.0 310 1.0 800 17.7 18.8 1.4 62.1 80.4 -16 19.28 120 | 8.0 310 1.0 800 26.1 14.5 1.0 58.4 73.9 -18 22.60 119 |
As seen from Table 2, catalytic dewaxing catalyst C of the present invention
1-C
4Gas yield is low, and liquid is received and reached more than the 80m%, and than the high approximately 6～9m% of reference catalyst,＞320 ℃ of lubricating oil distillate yields also improve a lot, and the basic oiliness of lubricating oil distillate is suitable with reference catalyst gained data.The little crystal grain zeolite catalyst of this presentation of results is better than big crystal grain zeolite catalyst.
Table 3 stock oil character
| Title | Maoming petro-chemical corporation hydrocracking tail oil |
| Density (20 ℃), kg/m 3Boiling range, ℃ IBP/10% 30%/50% 70%/90% 95%/EBP sulphur, μ g/g nitrogen, μ g/g kinematic viscosity, mm 250 ℃ of 100 ℃ of pour points of/s, ℃ wax content, m% | 831.4 330/370 392/412 438/478 496/519 8.0 1.5 11.88 3.897 37 22.8 |
Claims (4)
1 one kinds of lubricating oil catalytic dewaxing catalyzer, its carrier chemical constitution are ZSM-5 molecular sieve 65～85m%, Al
2O
315～35m%, two kinds of metal components of load tungsten and nickel, the granular size that it is characterized in that said ZSM-5 molecular sieve is 0.1～0.5 μ m, SiO
2/ Al
2O
3Mol ratio is 50～120.
2 catalyzer according to claim 1 is characterized in that molecular sieve is Hydrogen ZSM-5.
3 catalyzer according to claim 1 or 2, it is characterized in that adopting by in the carbonic acid gas and sodium metaaluminate gained aluminum oxide be tackiness agent.
4 is according to claim 1, and its catalyst metal components is counted WO with catalyst quality
310～18m%, NiO2.0～6.0m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97121843A CN1102642C (en) | 1997-12-08 | 1997-12-08 | Catalyst for small crystal granule ZSM-5 molecular sieve catalystic dewaxing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97121843A CN1102642C (en) | 1997-12-08 | 1997-12-08 | Catalyst for small crystal granule ZSM-5 molecular sieve catalystic dewaxing |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1219571A CN1219571A (en) | 1999-06-16 |
| CN1102642C true CN1102642C (en) | 2003-03-05 |
Family
ID=5176490
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97121843A Expired - Lifetime CN1102642C (en) | 1997-12-08 | 1997-12-08 | Catalyst for small crystal granule ZSM-5 molecular sieve catalystic dewaxing |
Country Status (1)
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|---|---|
| CN (1) | CN1102642C (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1307132C (en) * | 2004-09-28 | 2007-03-28 | 中国石油化工股份有限公司 | Catalyst for producing diesel oil from tetracarbon olefin polymerization and its preparation method and uses |
| CN100425342C (en) * | 2005-04-21 | 2008-10-15 | 上海华谊丙烯酸有限公司 | Zeolite catalyst and its use for hydrolysis reaction of dihydropyran derivatives |
| CN1895776B (en) * | 2005-07-14 | 2012-07-25 | 中国科学院大连化学物理研究所 | Catalyst for producing dimethyl ether by methanol liquid-phase or mixed-phase dewatering method |
| CN101134910B (en) * | 2006-08-31 | 2011-06-15 | 中国石油化工股份有限公司 | Method for lowering lubricating oil fraction pour point and turbidity point |
| CN101134170B (en) * | 2006-08-31 | 2010-08-25 | 中国石油化工股份有限公司 | Catalytic dewaxing catalyst and its preparation thereof |
| CN100455511C (en) * | 2006-11-10 | 2009-01-28 | 南京工业大学 | Method for synthesizing molecular sieve of ZSM-5 zeolite in small crystal grain |
| CN101041442B (en) * | 2007-03-19 | 2010-08-25 | 天津元山科技开发有限公司 | Fine grain strong acid type molecular sieve and method for synthesizing same |
| CN112237947B (en) * | 2019-07-18 | 2023-06-30 | 国家能源投资集团有限责任公司 | Carrier and preparation method thereof, catalyst and preparation method thereof, and dewaxing method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4229282A (en) * | 1979-04-27 | 1980-10-21 | Mobil Oil Corporation | Catalytic dewaxing of hydrocarbon oils |
| US4247388A (en) * | 1979-06-27 | 1981-01-27 | Mobil Oil Corporation | Hydrodewaxing catalyst performance |
| US4305808A (en) * | 1980-04-14 | 1981-12-15 | Mobil Oil Corporation | Catalytic hydrocracking |
| CN87103258A (en) * | 1987-05-04 | 1988-11-23 | 金陵石油化工公司南京炼油厂 | A kind of method for preparation of zeolite catalyst that is used for superimposing production of gasoline with olefin |
-
1997
- 1997-12-08 CN CN97121843A patent/CN1102642C/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4229282A (en) * | 1979-04-27 | 1980-10-21 | Mobil Oil Corporation | Catalytic dewaxing of hydrocarbon oils |
| US4247388A (en) * | 1979-06-27 | 1981-01-27 | Mobil Oil Corporation | Hydrodewaxing catalyst performance |
| US4305808A (en) * | 1980-04-14 | 1981-12-15 | Mobil Oil Corporation | Catalytic hydrocracking |
| CN87103258A (en) * | 1987-05-04 | 1988-11-23 | 金陵石油化工公司南京炼油厂 | A kind of method for preparation of zeolite catalyst that is used for superimposing production of gasoline with olefin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1219571A (en) | 1999-06-16 |
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