CN1176190C - Fraction oil catalytic dewaxing catalyst for increasing liquefied petroleum gas production - Google Patents
Fraction oil catalytic dewaxing catalyst for increasing liquefied petroleum gas production Download PDFInfo
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- CN1176190C CN1176190C CNB021096597A CN02109659A CN1176190C CN 1176190 C CN1176190 C CN 1176190C CN B021096597 A CNB021096597 A CN B021096597A CN 02109659 A CN02109659 A CN 02109659A CN 1176190 C CN1176190 C CN 1176190C
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Abstract
The present invention relates to a catalytic dewaxing catalyst for increasing the yield of liquefied petroleum gas and the yield of low-freezing diesel oil. In the catalyst, aluminosilicate molecular sieves are as substrates, a small amount of binding agent is added into the aluminosilicate molecular sieves to be extruded into a carrier, and VIII and/or VIB metals are used as hydrogen adding or removing ingredients. In the pore distribution of the catalyst, the volume of pores with the pore diameter of 1.7 to 5.0 nm accounts for less than 40% of the percentage of the total pore volume, the volume of pores with the pore diameter of 5.0 to 10.0 nm accounts for more than 40% of the percentage of the total volume, and the amount of acid at 380 DEGC is from 0.05 to 0.15mMol per gram. When the catalyst is used in ordinary catalytic dewaxing devices, the yield of the liquefied petroleum gas and the yield of the low-freezing diesel oil can be increased, wherein the yield of the liquefied petroleum gas to raw oil can reach 17m% and the yield of the low-freezing diesel oil to raw oil can reach 60m%.
Description
1, technical field
The present invention relates to a kind of catalytic dewaxing catalyst, particularly can voluminous liquefied petroleum gas (LPG) in the fraction oil catalytic dewaxing technology of routine and the catalytic dewaxing catalyst of diesel oil.
2, background technology
WITH CATALYTIC DEWAXING TECHNIQUE is meant that wax-containing distillate in the presence of hydrogen and catalyzer, selects the shape scission reaction, and main products is a low freezing point diesel fuel, by-product gasoline and a small amount of liquefied petroleum gas (LPG) (LPG).
In distillate dewaxing technology, the catalytic dewaxing technology is low because of its less investment, process cost, strong and operational condition relaxes, the oil product condensation point reduces advantages such as amplitude is big and receives much concern to adaptability to raw material.Its dewaxing principle be utilize molecular sieve catalyst select the shape cracking performance, normal paraffin in the raw material and short-side chain isoparaffin are cracked into small molecules, from raw material, remove, thereby reach the purpose that reduces oil pour point, improves low-temperature fluidity.
U.S. Patent No. 3,956,102,4,181,598,4,247,388,4,575,416,4,917,789 and 5,614,079 has described the catalytic dewaxing process of oil product.
Catalytic dewaxing is that the wax molecule in the stock oil is cracked into gasoline fraction and hydrocarbon gas, and gasoline fraction can also further be cracked into small molecules.The hydrocarbon gas that reaction generates mainly is C
3, C
4, and C
1, C
2Seldom, be ideal liquefied petroleum gas (LPG) component.Under certain process conditions, the degree of stock oil generation scission reaction depends primarily on the character of catalytic dewaxing catalyst.Less generation second pyrolysis reacted after conventional catalytic dewaxing catalyst was cracked into gasoline fraction with the wax molecule, thereby made that the liquid product yield of reaction process is higher.
Catalytic dewaxing catalyst is a dual-function catalyst, and adopting the mesopore aluminosilicate molecular sieves usually is matrix, adds a little binder and metal component and makes.Metal component provides and adds the dehydrogenation activity center, and molecular sieve provides suitable pore passage structure and acid sites, and these two kinds of active centre rational Match just can make activity of such catalysts, selectivity give full play to.
The special pore passage structure of molecular sieve only allows normal paraffin and a small amount of 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-35 and ZSM-38 etc.U.S. Patent No. 3,702,886,3,709,979,3,832,449,4,016,245 and 4,046,859 pairs of above-mentioned molecular sieves should be used as detailed descriptionthe.
The hydrodewaxing technology the exploitation at the beginning of, pursuit be the yield of low-coagulation diesel oil and byproduct raw gasline, promptly liquid product yield is high more good more.In China and many developing countries, diesel oil is main transport fuel, and market constantly increases the demand of intermediate oils such as diesel oil.Supply falls short of demand for China market diesel oil, and a part needs import, and seasonal overstocking often appears in gasoline, and drug on the market, therefore needs to improve the output of diesel oil distillate, reduces gasoline output.
In recent years, strictness day by day along with environmental regulation, basic orientation according to the energy strategy adjustment, implement the strategy of sustainable development, further optimize energy structure, promote rationally, effectively, cleanly to use the energy, the research of alternative fuel comes into one's own day by day, advantages such as liquefied petroleum gas (LPG) is few with its exhaust emission, dynamic performance good, production and storaging and transport technology maturation and become the ideal alternative fuel for cars are developed rapidly.This makes market increase fast the demand of liquefied petroleum gas (LPG), correspondingly increases production the LPG technology and comes into one's own gradually.
CN 1085885A discloses a kind of method of utilizing the fluid catalytic cracking technology increasing liquefied petroleum gas production.But the diesel oil distillate poor quality that fluid catalytic cracking technology is produced in increasing liquefied petroleum gas production.
U.S. Patent No. 5,961,818 to disclose a kind of be the Technology that raw material is produced LPG and aromatic hydrocarbons with aromatic hydrocarbons extract oil or light naphthar.
CN85100324B discloses a kind of distillate Hydrodewaxing catalyst and preparation method thereof.Adopting direct synthetic ZSM-5 zeolite molecular sieve is matrix, handle through modification, add tamanori and metal component, make Hydrodewaxing catalyst through steam-treated again, the physico-chemical property (as porous, acid amount and strength of acid etc.) of catalyzer is not made specific requirement; And the employing steam treatment process, length consuming time, energy consumption are big, and the catalyzer pore volume, the aperture that are produced are less, cause yield of liquefied gas low, are unfavorable for increasing production of liquid gas.
3, summary of the invention
The object of the present invention is to provide a kind of catalytic dewaxing catalyst, make its can be in the fraction oil catalytic dewaxing device of routine increasing liquefied petroleum gas production significantly, improve the yield of high-grade low-freezing diesel oil distillate simultaneously, reduce gasoline yield.In addition, the object of the invention also is to provide a kind of simple and convenient preparation method of this catalyzer.
Catalyzer of the present invention contains following component by weight:
Mesopore aluminosilicate molecular sieves: 50～90m% is preferably 50～85m%,
Tackiness agent: 9～49m%,
Hydrogenation active metals component: surplus.
The character of catalyzer is,
Pore volume: 0.10～0.30cm
3/ g, specific surface area: 180～300m
2/ g,
Pore distribution: 1.7～5.0nm,＜40%, 15-40% preferably,
5.0～10.0nm,＞40%, 40-65% preferably,
10.0～100.0nm, surplus,
380 ℃ of acid amount: 0.05～0.15mMol/g.
Said mesopore aluminosilicate molecular sieves is preferably selected for use has the ZSM series molecular sieve of selecting the shape effect, as ZSM-5, ZSM-8, ZSM-11, ZSM-22, ZSM-35, ZSM-38 etc., also can select erionite, mordenite for use.
The principal element that influences the catalytic dewaxing catalyst performance is the character of wherein contained molecular sieve.Discover that by intensive under the identical situation of character such as molecular sieve crystallinity, grain size, foreign matter content, the silica alumina ratio of molecular sieve is bigger to the acidity influence of catalyzer, silica alumina ratio is high more, and acidity is low more, therefore should adopt the high silica alumina ratio molecular sieve.But silica alumina ratio is too high, also can produce degree of crystallinity problem on the low side, and this shape selectivity to Hydrodewaxing catalyst can be very disadvantageous.The preferred silica alumina ratio of mesopore aluminosilicate molecular sieves is 25～120, particularly preferably is silica alumina ratio and is 40～70 ZSM-5 molecular sieve.
The hydrogenation active metals component is VIII family and/or group vib metal preferably, as Pt, Pd, Ni, Co, Mo, W etc., perhaps their mixture.Active metal component is preferably Ni, and NiO content (to catalyzer) is 1.0-6.0m%, can contain the WO of 0-15m% simultaneously
3
Described tackiness agent is meant what one or more and peptizing agent in the compounds such as activated alumina or its precursor, silicon oxide, magnesium oxide and water mixing and stirring formed.It accounts for the 9-49m% of catalyst weight.Described aluminum oxide is activated alumina or its precursor, is industrial aperture, mesopore or the macroporous aluminium oxide that generally adopts.Its pore volume is 0.2-1.0ml/g, and specific surface area is 100-400m
2/ g.Described peptizing agent refers to mineral acid and/or organic acid, the anionic salt of strongly-acid (as aluminum nitrate), mineral acid can be nitric acid, hydrochloric acid, sulfuric acid etc., organic acid is formic acid, acetate, oxalic acid, citric acid etc., also can be that several peptizing agents mix use, use simultaneously as nitric acid and acetate use simultaneously, acetate and citric acid.
Described extrusion aid is meant the material that helps extrusion molding, and as sesbania powder, carbon black, Graphite Powder 99, citric acid etc., the consumption of extrusion aid accounts for the 1-10m% of total material butt.
Preparation of catalysts method of the present invention is: molecular sieve, tackiness agent and extrusion aid are mixed in proportion pinch even, extruded moulding, carrier is made in wet bar drying, roasting; Carrier floods in the aqueous solution that contains VIII family and/or group vib metal-salt, and after filtration, drying, roasting makes finished catalyst.Wherein the maturing temperature of carrier is at 720～820 ℃, and the maturing temperature of catalyzer is 400～500 ℃, and it mainly acts on is the pore properties and the acid matter of regulating carrier, makes final catalyst pore distribution and acid amount meet the demands.The roasting condition of carrier depends primarily on factors such as the ratio, porous of kind, silica alumina ratio, consumption and the tamanori of used molecular sieve.
Catalyst metal components of the present invention is written into mode two kinds, and the one, adopt conventional mode of loading, at room temperature use the soluble metal salt solution impregnating carrier; The 2nd, carry out ion-exchange with soluble metal salt solution and molecular sieve, metal component is loaded on the molecular sieve, and then and the mixed pinching bar moulding of tamanori.
The pore distribution of catalytic dewaxing catalyst of the present invention is very important, and require: the aperture is that the hole of 1.7～5.0nm is not more than 40%, is preferably between 15～40%; The aperture is that the hole of 5.0～10.0nm is not less than 40%, is preferably between 40～65%; Have only the pore distribution of catalyzer to satisfy this requirement, just can make gasoline fraction minimizing in the product, the liquefied petroleum gas (LPG) productive rate improves.In catalyst preparation process,, catalyst pores is distributed concentrate in this scope by the roasting condition of control carrier.The mensuration of catalyst pores structure of the present invention is to carry out on the full-automatic physical adsorption appearance of the U.S. ASAP2400 of Mai Ke instrument company type.
Except that requiring catalyzer of the present invention to possess the above-mentioned pore structure, also require this catalyzer to have suitable acid amount and strength of acid, promptly 380 ℃ of acid amounts are 0.05～0.15mMol/g.The acid amount of catalyzer is to adopt the TPDE method to measure among the present invention, and this method is adsorbate with the pyridine, measures 380 ℃ of pyridines in the acid amount of chemisorbed on catalyst amount as catalyzer on recording quartz spring weight absorption instrument.
Advantage of the present invention is to adopt catalyzer of the present invention, on the fraction oil catalytic dewaxing device of routine, and under the catalytic dewaxing condition of routine, can increasing liquefied petroleum gas production, the low-coagulation diesel oil yield also increases simultaneously, and need not transform device.Conventional WITH CATALYTIC DEWAXING TECHNIQUE, the yield of liquefied petroleum gas (LPG) is generally less than 10%, adopts catalyzer of the present invention, and its liquefied petroleum gas (LPG) yield can be brought up to 17m%, and the diesel oil distillate yield improves 1-3 percentage point, reaches 60m%, and the gasoline fraction yield reduces.
4, embodiment
Further set forth the present invention with embodiment below, but the present invention is not limited thereto.
Embodiment 1
(1) gets little porous aluminum oxide (pore volume 0.49ml/g, specific surface area 229m
2/ g) 32.4g adds 51.2g water purification and 6.4ml concentrated nitric acid, mixes, and cooks composite adhesives.
(2) get HZSM-5 (silica alumina ratio is 40.0) 101.0g, sesbania powder 3.0g and above-mentioned tackiness agent mix and pinch extruded moulding.
(3) wet bar is under 100 ± 10 ℃ of conditions dry 4 hours, and roasting is 3 hours under 740 ℃ of conditions, makes carrier.
(4) get the 24.9g nickelous nitrate and dissolve, be made into 200ml solution with water purification.
(5) above-mentioned carrier 100g is put into steeping fluid, flooded 2 hours, filter then, under 100 ℃ of conditions dry 4 hours, 480 ℃ of roastings 3 hours, catalyst A, its character sees Table 1.
Embodiment 2
(1) gets little porous aluminum oxide (character is with embodiment 1) 54.0g, add 76.1g water purification and 10.7ml concentrated nitric acid, mix, cook composite adhesives.
(2) get HZSM-5 (silica alumina ratio is 45.2) 168.4g, carbon black 6.0g and above-mentioned tackiness agent mix and pinch extruded moulding.
(3) wet bar is under 110 ℃ of conditions dry 4 hours, and roasting is 3 hours under 800 ℃ of conditions, makes carrier.
(4) get the 27.9g nickelous nitrate and dissolve, be made into 200ml solution with water purification.
(5) above-mentioned carrier 100g is put into steeping fluid, flooded 2 hours, filter then, under 100 ℃ of conditions dry 4 hours, 500 ℃ of roastings 3 hours, catalyst B, its character sees Table 1.
Embodiment 3
(1) gets little porous aluminum oxide (character is with embodiment 1) 43.2g, add 67.6g water purification and 8.6ml concentrated nitric acid and 4.0g citric acid, mix, cook composite adhesives.
(2) getting HZSM-5 (silica alumina ratio is 46.1) 128.0g and above-mentioned tackiness agent mixes and to pinch extruded moulding.
(3) wet bar is under 110 ℃ of conditions dry 4 hours, and roasting is 4 hours under 750 ℃ of conditions, makes carrier.
(4) get the 25.7g nickelous nitrate and dissolve, be made into 200ml solution with water purification.
(5) above-mentioned carrier 100g is put into steeping fluid, flooded 2 hours, filter then, under 100 ℃ of conditions dry 4 hours, 480 ℃ of roastings 3 hours, catalyzer C, its character sees Table 1.
Embodiment 4
(1) preparation contains NiO3.5g/100ml solution, puts into water-bath and is heated to 60 ℃, puts into 160gHZSM-5 (silica alumina ratio is 46.1) constant temperature and stirs 2 hours, filtration, drying.
(2) get little porous aluminum oxide (character is with embodiment 1) 43.2g, add 60.6g water purification and 8.6ml concentrated nitric acid, mix, cook composite adhesives.
(3) getting in (1) molecular sieve 135.0g and above-mentioned tackiness agent mixes and pinches extruded moulding.
Wet bar under 110 ℃ of conditions dry 4 hours, roasting is 5 hours under 750 ℃ of conditions, makes catalyzer D, and its character sees Table 1.
Embodiment 5
(1) gets little porous aluminum oxide (pore volume 0.49ml/g, specific surface area 229m
2/ g) 81.1g adds 73.0g water purification and 10.7ml concentrated nitric acid, mixes, and cooks composite adhesives.
(2) get HZSM-5 (silica alumina ratio is 46.2) 140.0g, sesbania powder 3.0g and above-mentioned tackiness agent mix and pinch extruded moulding.
(3) wet bar is under 100 ± 10 ℃ of conditions dry 4 hours, and roasting is 3 hours under 700 ℃ of conditions, makes carrier.
(4) get ammonium metawolframate 47.9g, nickelous nitrate 51.6g dissolves with water purification, is made into 200ml solution.
(5) above-mentioned carrier 100g is put into steeping fluid, flooded 2 hours, filter then, under 100 ℃ of conditions dry 4 hours, 480 ℃ of roastings 3 hours, catalyzer E, its character sees Table 1.
Embodiment 6
(1) gets little porous aluminum oxide (Wenzhou) 54.1g, add 76.0g water purification and 10.7ml concentrated nitric acid, mix, cook composite adhesives.
(2) get HZSM-5 (silica alumina ratio is 38) 168.4g, sesbania powder 3.0g and above-mentioned tackiness agent mix and pinch extruded moulding.
(3) wet bar is under 100 ± 10 ℃ of conditions dry 4 hours, and roasting is 3 hours under 730 ℃ of conditions, makes carrier.
(4) get nickelous nitrate 25.0g,, be made into 200ml solution with the water purification dissolving.
(5) above-mentioned carrier 100g is put into steeping fluid, flooded 2 hours, filter then, under 100 ℃ of conditions dry 4 hours, 480 ℃ of roastings 3 hours, catalyzer F, its character sees Table 1.
Embodiment 7
(1) gets little porous aluminum oxide (Wenzhou product) 32.4g, add 46.7g water purification and 6.4ml concentrated nitric acid, mix, cook composite adhesives.
(2) get HZSM-5 (silica alumina ratio is 33) 100g, carbon black 3.0g and above-mentioned tackiness agent mix and pinch extruded moulding.
(3) wet bar is under 100 ± 10 ℃ of conditions dry 4 hours, and roasting is 4 hours under 750 ℃ of conditions, makes carrier.
(4) get nickelous nitrate 25.0g,, be made into 200ml solution with the water purification dissolving.
(5) above-mentioned carrier 100g is put into steeping fluid, flooded 2 hours, filter then, under 100 ℃ of conditions dry 4 hours, 480 ℃ of roastings 3 hours, catalyzer G, its character sees Table 1.
Comparative example 1
Make conventional catalytic dewaxing catalyst H according to CN85100324B, do reference catalyst, its character sees Table 1.
Table 1 catalyzer physico-chemical property
Compile 380 ℃ of NiO WO of pore volume specific surface pore distribution
3
Number cm
3The long-pending 1.7-5.0 5.0-10.0 acid of/g amount m% m%
m
2/g nm nm mMol/g
A 0.217 288 39.4 44.1 0.145 0.94 -
B 0.240 287 28.5 40.4 0.112 1.35 -
C 0.228 280 30.8 43.2 0.141 1.44 -
D 0.224 271 31.8 45.3 0.122 2.33 -
E 0.219 237 17.9 64.5 0.149 1.95 10.93
F 0.242 293 35.7 41.2 0.149 1.51
G 0.211 286 36.7 46.1 0.142 1.45
H 0.229 276 54.5 27.6 0.100 1.72
Embodiment 8
With above-mentioned each catalyzer on the small-sized catalytic dewaxing unit of routine to the catalytic dewaxing of grand celebration straight run content of wax diesel oil distillate, stock oil character sees Table 2, and (except that temperature) other processing condition are identical during evaluation, i.e. reaction pressure 4.0MPa, hydrogen-oil ratio (v/v) 420, volume space velocity 1.0h
-1, product distributes and evaluation result sees Table 3, and the liquefied petroleum gas (LPG) composition sees Table 4.
Table 2 stock oil character
Title grand celebration straight run content of wax diesel oil
Density (20 ℃), kg/m
3834.9
Boiling range, ℃
IBP/10％ 250/298
30％/50％ 325/340
70％/90％ 353/374
95％/EBP 388/394
Sulphur, μ g/g 642
Nitrogen, μ g/g 120
Condensation point, ℃ 29
Wax content, m% 28.8
Table 3 grand celebration straight(-run) diesel distillate catalytic dewaxing evaluation result
Numbering reaction temperature product distributes m% diesel oil distillate character
Degree ℃ carburet hydrogen gasoline fraction diesel oil distillate condensation point, ℃ S, μ g/g N, μ g/g
A 360 24.8 18.9 56.3 -28 656 129
B 346 24.4 19.8 55.8 -44 678 131
C 348 22.2 18.4 59.4 -25 665 118
D 358 23.9 16.1 60.0 -20 672 121
E 370 18.9 22.3 58.8 -29 329 75
F 380 21.1 19.6 59.3 -11 673 136
G 345 25.1 18.0 56.9 -34 669 127
H 360 16.4 27.6 56.0 -20 672 123
Table 4 adopts the gas composition of each catalyzer
Form m% A C D F H
Methane 1.236 1.928 1.496 1.625 1.567
Ethene 0.030 0.054 0.025 0.047 0.034
Ethane 3.567 3.902 3.304 3.824 3.425
Propylene 0.389 0.366 0.375 0.345 0.396
Propane 33.029 34.047 34.527 33.515 32.954
Trimethylmethane 13.513 13.143 13.549 12.614 12.731
Just, iso-butylene 0.544 0.583 0.553 0.629 0.684
Normal butane 22.432 22.623 22.061 21.460 21.201
Pentane 15.968 15.198 16.445 16.170 16.031
C
6Total 9.206 8.031 10.237 9.635 10.834
Amylene 0.095 0.125 0.109 0.136 0.143
C wherein
3+ C
469.907 70.762 71.065 68.563 67.966
C
3+ C
4Yield 17.336 15.709 17.013 14.46 11.146
(to stock oil)
By table 3 and table 4 as seen, adopt catalyzer of the present invention, on the catalytic dewaxing unit of routine, the straight(-run) diesel distillate of processing paraffinic crude, under the suitable condition of diesel oil distillate condensation point, gaseous product yield height, C in the gaseous product
3+ C
4The content height can reach 71%, and mainly is alkane, and olefin(e) centent is few, is ideal liquefied petroleum gas (LPG) component.The low-coagulation diesel oil yield is than reference agent height simultaneously.
Adopt catalyzer of the present invention, liquefied petroleum gas (LPG) yield (to stock oil) reaches as high as 17m%, has improved 6 percentage points than reference catalyst (11m%).
Claims (8)
1, the application of a kind of catalytic dewaxing catalyst in the fraction oil catalytic dewaxing of increasing liquefied petroleum gas production is characterized in that the catalytic dewaxing catalyst that uses contains following component by weight:
Mesopore aluminosilicate molecular sieves: 50～90m%, tackiness agent: 9～49m%, all the other are the hydrogenation active metals component, it is characterized in that catalyst pores is distributed as: 1.7～5.0nm,＜40%;
5.0～10.0nm， ＞40％；
10.0～100.0nm, surplus.
2, according to the described application of claim 1, it is characterized in that catalyzer pore volume: 0.10～0.30cm
3/ g, specific surface area: 180～300m
2/ g, 380 ℃ of acid amount: 0.05～0.15mMol/g.
3,, it is characterized in that the pore distribution of catalyzer is according to the described application of claim 1:
1.7～5.0nm， 15-40％；
5.0～10.0nm，?40-65％；
10.0～100.0nm, surplus.
4,, it is characterized in that said mesopore aluminosilicate molecular sieves is a ZSM series molecular sieve according to the described application of claim 1.
5,, it is characterized in that said ZSM series molecular sieve is ZSM-5, ZSM-8, ZSM-11, ZSM-22, ZSM-35 or ZSM-38 according to the described application of claim 4.
6,, it is characterized in that said mesopore aluminosilicate molecular sieves silica alumina ratio is 25～120 according to the described application of claim 1.
7,, it is characterized in that said mesopore aluminosilicate molecular sieves silica alumina ratio is 40～70 according to the described application of claim 6.
8,, it is characterized in that 380 ℃ of acid amounts of said catalyzer are 0.112～0.149mMol/g according to the described application of claim 1.
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