CN105688996A - Preparation method of modified pyrolysis catalyst - Google Patents
Preparation method of modified pyrolysis catalyst Download PDFInfo
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- CN105688996A CN105688996A CN201610119144.8A CN201610119144A CN105688996A CN 105688996 A CN105688996 A CN 105688996A CN 201610119144 A CN201610119144 A CN 201610119144A CN 105688996 A CN105688996 A CN 105688996A
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- medical stone
- stone powder
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- modified
- catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000000197 pyrolysis Methods 0.000 title abstract description 5
- 239000000843 powder Substances 0.000 claims abstract description 47
- 239000004575 stone Substances 0.000 claims abstract description 47
- 238000010438 heat treatment Methods 0.000 claims abstract description 40
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 35
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 24
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 18
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 14
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims abstract description 12
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims abstract description 12
- 238000005336 cracking Methods 0.000 claims description 32
- 238000010792 warming Methods 0.000 claims description 19
- 239000004115 Sodium Silicate Substances 0.000 claims description 17
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 17
- 229910019142 PO4 Inorganic materials 0.000 claims description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 15
- 239000010452 phosphate Substances 0.000 claims description 15
- 238000007598 dipping method Methods 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 11
- 238000009413 insulation Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 8
- 238000005245 sintering Methods 0.000 claims description 2
- 238000004939 coking Methods 0.000 abstract description 6
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 abstract 1
- 230000009849 deactivation Effects 0.000 abstract 1
- 238000004321 preservation Methods 0.000 abstract 1
- 239000013049 sediment Substances 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 abstract 1
- 235000015165 citric acid Nutrition 0.000 description 10
- 239000003921 oil Substances 0.000 description 6
- 241001274660 Modulus Species 0.000 description 5
- -1 palladium sulfates Chemical class 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000571 coke Substances 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000002010 green coke Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000010327 methods by industry Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical group [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/10—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing platinum group metals or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
- C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
- C10G45/40—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing platinum group metals or compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a modified pyrolysis catalyst. The method comprises the following steps that medical stone powder is put in a phosphoric acid aqueous solution for soaking, sodium water glass is added for uniform stirring, heating is conducted, heat preservation is conducted, the treated medical stone powder is taken out, water washing is conducted, and the modified medical stone powder is obtained; palladium sulfate, zirconium sulfate, nickel sulfate, citric acid, hexadecyl trimethyl ammonium bromide and absolute ethyl alcohol are mixed to be uniform, the pH is adjusted to be 9-10, the modified medical stone powder is added for water bath heating, and a mixed material is obtained; the mixed material is taken out for a hydrothermal reaction, washing is conducted on sediments, drying is conducted, heating calcining is conducted, and the modified pyrolysis catalyst is obtained. The preparation method of the modified pyrolysis catalyst is simple, the cost is low, and the obtained catalyst is good in hydrogenation property, high in stability and not prone to coking and deactivation.
Description
Technical field
The present invention relates to technical field of petrochemical industry, the preparation method particularly relating to a kind of modified catalyst for cracking。
Background technology
In recent years, crude quality is in poor quality increasingly, and the demand of light-weight fuel oil is constantly increased by market, and therefore RFCC develops quickly。Containing more more aromatic hydrocarbons than wax oil in heavy oil, so that RFCC coking yield is higher。How effectively suppressing catalyst green coke under the premise ensureing light oil yield is one of current people's target developing catalyst。For these green cokes, except needing to take measures in process engineering, such as good feed atomization, improve steam stripping efficiency, reduce beyond landing back-mixing etc., also to reduce the generation that catalysis is burnt。
For catalyst, coking is mainly determined by the acidity of catalyst and two factors of pore structure。But, the formation of coke is actually one and selects shape process, and the impact that the pore structure of catalyst and hole dimension generate for coke is much bigger compared with the density of acid strength and active sites。The coking process of catalyst actually carries out in micropore, and active component is relatively larger to green coke contribution。Active component does not reach desirable dispersion effect on carrier, and these catalyst often exist that hydrogenation activity is too high or activity is too low and stability is poor, the problem of easy coking。
Summary of the invention
Based on the technical problem that background technology exists, the preparation method that the present invention proposes a kind of modified catalyst for cracking, method is simple, low cost, and gained catalyst hydrogenation performance is good simultaneously, and stability is high, and not easily coking, non-easy in inactivation。
The preparation method of a kind of modified catalyst for cracking that the present invention proposes, comprises the steps:
S1, medical stone powder is placed in phosphate aqueous solution dipping, adds sodium silicate and stir, then heat up, insulation, to take out, washing obtains modified medical stone powder；
S2, by after palladium sulfate, Disulfatozirconic acid., nickel sulfate, citric acid, cetyl trimethylammonium bromide, dehydrated alcohol mix homogeneously, regulate pH to 9-10, add modified medical stone powder to carry out heating in water bath and obtain mixed material, then mixed material is taken out and carry out hydro-thermal reaction, then after precipitate being washed, dry, then the roasting that heats up obtains modified catalyst for cracking。
Preferably, in S1, the mass fraction of phosphate aqueous solution is 10-14wt%。
Preferably, in S1, the modulus of sodium silicate is 2.8-3.2。
Preferably, in S1, medical stone powder is placed in phosphate aqueous solution dipping 16-20h, add sodium silicate to stir, then it is warming up to 500-520 DEG C with average heating rate for 3-5 DEG C/min, then is warming up to 550-580 DEG C with average heating rate for 1-2 DEG C/min, be incubated 4-6h, taking out, washing obtains modified medical stone powder。
Preferably, in S1, by weight 30-40 part medical stone powder is placed in the phosphate aqueous solution dipping that 15-20 part mass fraction is 10-14wt%, add the sodium silicate that 30-40 part modulus is 2.8-3.2 to stir, then heat up, insulation, taking out, washing obtains modified medical stone powder。
Preferably, in S2, palladium sulfate, Disulfatozirconic acid., nickel sulfate, citric acid, cetyl trimethylammonium bromide, dehydrated alcohol mol ratio be 7-10:1-2:3-6:2-4:1-2:18-24。
Preferably, in S2, the weight ratio of modified medical stone powder and palladium sulfate is 10-15:4-6。
Preferably, in S2, the temperature of heating in water bath is 55-60 DEG C, and the time of heating in water bath is 50-90min。
Preferably, in S2, the temperature of hydro-thermal reaction is 200-220 DEG C, and the time of hydro-thermal reaction is 3-5h。
Preferably, in S2, sintering temperature is 380-400 DEG C, and roasting time is 90-150min。
The present invention adopts Maifanitum to add dipping in phosphate aqueous solution, make inside Maifanitum through phosphoric acid corrosion, the impurity of Partial Blocking micropore is eliminated, partial pore hole wall is destroyed or is changed into transitional pore, and expand the diameter of Maifanitum inner openings, reduce specific surface area, make average pore size increase, aperture broadens, and internal aperture can be made to be interconnected simultaneously；Add sodium silicate to be stirred, make sodium silicate molecule well in Maifanitum meso-hole structure, then pass through high temperature drying sodium silicate molecular conversion and become silicon dioxide molecules, and spread in the meso-hole structure of Maifanitum, not only reduce Maifanitum hole inner volume, prevent catalyst poisoning from inactivating, and also there is meso-hole structure due to silicon dioxide, and improve the specific surface area of modified Maifanitum, synergism can be produced with the active component of load simultaneously as carrier, thus promoting that active component is in the high degree of dispersion on modified Maifanitum surface, improve the surface texture of catalyst；Modified medical stone powder is added palladium sulfate, Disulfatozirconic acid., nickel sulfate, citric acid, cetyl trimethylammonium bromide, in the mixed solution of dehydrated alcohol, citric acid and palladium ion form complex, the network of complex is by zirconium ion and nickel ion complexation simultaneously, complex is made to combine with modified medical stone powder by heating in water bath, carrying out hydro-thermal reaction again makes complex and cetyl trimethylammonium bromide hydrolyze to form stable active component, active constituent loading is on modified medical stone powder simultaneously, improve specific surface area and the stability of the present invention, the speed of heavy oil pyrolysis can be greatly improved, and selectivity is high, cetyl trimethylammonium bromide complete oxidation is made to obtain containing active constituent loading in the modified catalyst for cracking of modified medical stone powder by roasting afterwards。
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of the preparation method of a kind of modified catalyst for cracking that the present invention proposes。
Detailed description of the invention
As it is shown in figure 1, the schematic flow sheet of the preparation method that Fig. 1 is a kind of modified catalyst for cracking that the present invention proposes。
With reference to Fig. 1, the preparation method of a kind of modified catalyst for cracking that the present invention proposes, comprise the steps:
S1, medical stone powder is placed in phosphate aqueous solution dipping, adds sodium silicate and stir, then heat up, insulation, to take out, washing obtains modified medical stone powder；
S2, by after palladium sulfate, Disulfatozirconic acid., nickel sulfate, citric acid, cetyl trimethylammonium bromide, dehydrated alcohol mix homogeneously, regulate pH to 9-10, add modified medical stone powder to carry out heating in water bath and obtain mixed material, then mixed material is taken out and carry out hydro-thermal reaction, then after precipitate being washed, dry, then the roasting that heats up obtains modified catalyst for cracking。
Below, by specific embodiment, technical scheme is described in detail。
Embodiment 1
The preparation method of a kind of modified catalyst for cracking that the present invention proposes, comprises the steps:
S1, by weight 30 parts of medical stone powders are placed in the phosphate aqueous solution dipping 20h that 20 parts of mass fractions are 10wt%, add the sodium silicate that 30 parts of moduluses are 3.2 to stir, then it is warming up to 520 DEG C with average heating rate for 3 DEG C/min, it is warming up to 580 DEG C for 1 DEG C/min again with average heating rate, insulation 4h, taking out, washing obtains modified medical stone powder；
S2, by molar part by 10 parts of palladium sulfates, 1 part of Disulfatozirconic acid., 6 parts of nickel sulfate, 2 parts of citric acids, 2 parts of cetyl trimethylammonium bromide, after 18 parts of dehydrated alcohol mix homogeneously, regulate pH to 10, add modified medical stone powder to carry out heating in water bath and obtain mixed material, the weight ratio of modified medical stone powder and palladium sulfate is 5:3, the temperature of heating in water bath is 55 DEG C, the time of heating in water bath is 90min, then mixed material is taken out and carry out hydro-thermal reaction, the temperature of hydro-thermal reaction is 200 DEG C, the time of hydro-thermal reaction is 5h, then after precipitate being washed, dry, it is warming up to 380 DEG C again, roasting 150min obtains modified catalyst for cracking。
Embodiment 2
The preparation method of a kind of modified catalyst for cracking that the present invention proposes, comprises the steps:
S1, by weight 40 parts of medical stone powders are placed in the phosphate aqueous solution dipping 16h that 15 parts of mass fractions are 14wt%, add the sodium silicate that 40 parts of moduluses are 2.8 to stir, then it is warming up to 500 DEG C with average heating rate for 5 DEG C/min, it is warming up to 550 DEG C for 2 DEG C/min again with average heating rate, insulation 6h, taking out, washing obtains modified medical stone powder；
S2, by molar part by 7 parts of palladium sulfates, 2 parts of Disulfatozirconic acid .s, 3 parts of nickel sulfate, 4 parts of citric acids, 1 part of cetyl trimethylammonium bromide, after 24 parts of dehydrated alcohol mix homogeneously, regulate pH to 9, add modified medical stone powder to carry out heating in water bath and obtain mixed material, the weight ratio of modified medical stone powder and palladium sulfate is 15:4, the temperature of heating in water bath is 60 DEG C, the time of heating in water bath is 50min, then mixed material is taken out and carry out hydro-thermal reaction, the temperature of hydro-thermal reaction is 220 DEG C, the time of hydro-thermal reaction is 3h, then after precipitate being washed, dry, it is warming up to 400 DEG C again, roasting 90min obtains modified catalyst for cracking。
Embodiment 3
The preparation method of a kind of modified catalyst for cracking that the present invention proposes, comprises the steps:
S1, by weight 32 parts of medical stone powders are placed in the phosphate aqueous solution dipping 19h that 18 parts of mass fractions are 11wt%, add the sodium silicate that 33 parts of moduluses are 3.1 to stir, then it is warming up to 515 DEG C with average heating rate for 3.5 DEG C/min, it is warming up to 570 DEG C for 1.3 DEG C/min again with average heating rate, insulation 4.6h, taking out, washing obtains modified medical stone powder；
S2, by molar part by 9 parts of palladium sulfates, 1.3 parts of Disulfatozirconic acid .s, 5 parts of nickel sulfate, 2.8 parts of citric acids, 1.6 parts of cetyl trimethylammonium bromide, after 20 parts of dehydrated alcohol mix homogeneously, regulate pH to 10, add modified medical stone powder to carry out heating in water bath and obtain mixed material, the weight ratio of modified medical stone powder and palladium sulfate is 12:5.4, the temperature of heating in water bath is 58 DEG C, the time of heating in water bath is 60min, then mixed material is taken out and carry out hydro-thermal reaction, the temperature of hydro-thermal reaction is 215 DEG C, the time of hydro-thermal reaction is 3.8h, then after precipitate being washed, dry, it is warming up to 395 DEG C again, roasting 100min obtains modified catalyst for cracking。
Embodiment 4
The preparation method of a kind of modified catalyst for cracking that the present invention proposes, comprises the steps:
S1, by weight 38 parts of medical stone powders are placed in the phosphate aqueous solution dipping 17h that 16 parts of mass fractions are 13wt%, add the sodium silicate that 36 parts of moduluses are 2.9 to stir, then it is warming up to 505 DEG C with average heating rate for 4.5 DEG C/min, it is warming up to 560 DEG C for 1.8 DEG C/min again with average heating rate, insulation 5.4h, taking out, washing obtains modified medical stone powder；
S2, by molar part by 8 parts of palladium sulfates, 1.8 parts of Disulfatozirconic acid .s, 4 parts of nickel sulfate, 3.2 parts of citric acids, 1.2 parts of cetyl trimethylammonium bromide, after 22 parts of dehydrated alcohol mix homogeneously, regulate pH to 9, add modified medical stone powder to carry out heating in water bath and obtain mixed material, the weight ratio of modified medical stone powder and palladium sulfate is 14:4.5, the temperature of heating in water bath is 56 DEG C, the time of heating in water bath is 80min, then mixed material is taken out and carry out hydro-thermal reaction, the temperature of hydro-thermal reaction is 205 DEG C, the time of hydro-thermal reaction is 4.5h, then after precipitate being washed, dry, it is warming up to 385 DEG C again, roasting 140min obtains modified catalyst for cracking。
Embodiment 5
The preparation method of a kind of modified catalyst for cracking that the present invention proposes, comprises the steps:
S1, by weight 35 parts of medical stone powders are placed in the phosphate aqueous solution dipping 18h that 17 parts of mass fractions are 12wt%, add the sodium silicate that 35 parts of moduluses are 3 to stir, then it is warming up to 510 DEG C with average heating rate for 4 DEG C/min, it is warming up to 565 DEG C for 1.5 DEG C/min again with average heating rate, insulation 5h, taking out, washing obtains modified medical stone powder；
S2, by molar part by 8.5 parts of palladium sulfates, 1.5 parts of Disulfatozirconic acid .s, 4.5 parts of nickel sulfate, 3 parts of citric acids, 1.4 parts of cetyl trimethylammonium bromide, after 21 parts of dehydrated alcohol mix homogeneously, regulate pH to 9.5, add modified medical stone powder to carry out heating in water bath and obtain mixed material, the weight ratio of modified medical stone powder and palladium sulfate is 13:5, the temperature of heating in water bath is 57 DEG C, the time of heating in water bath is 70min, then mixed material is taken out and carry out hydro-thermal reaction, the temperature of hydro-thermal reaction is 210 DEG C, the time of hydro-thermal reaction is 4h, then after precipitate being washed, dry, it is warming up to 390 DEG C again, roasting 120min obtains modified catalyst for cracking。
Take the modified catalyst for cracking of 100g embodiment 5 gained as experimental group, take 100g palladium catalyst as a control group, with the hexamethylene presulfurization 3h containing dimethyl disulfide 70ppm, adiabatic reactor carries out activity rating, raw materials used for drippolene C in evaluation5-9Middle distillate, its diene value is 15.16gI2/ 100g oil, bromine valency is 50.02gBr2/ 100g oil, water content 150ppm。Reaction condition is: Hydrogen Vapor Pressure is 3MPa, and inlet temperature is 40 DEG C, and hydrogen to oil volume ratio is 80:1, and green oil air speed is 5h-1, Feed space velocities is 12h-1, run 1008h, wherein every 24h sampling detects, and averages as evaluation result using each sampling inspection results, as shown in the table:
From the numerical value of upper table it can be seen that use gained hydrocracking catalyst of the present invention, after hydrogenation in product diene value and bromine valency significantly lower than matched group, it was shown that the catalyst of the present invention has a better Hydrogenation relative to prior art, and not easy in inactivation。
The above; it is only the present invention preferably detailed description of the invention; but protection scope of the present invention is not limited thereto; any those familiar with the art is in the technical scope that the invention discloses; it is equal to replacement according to technical scheme and inventive concept thereof or is changed, all should be encompassed within protection scope of the present invention。
Claims (10)
1. the preparation method of a modified catalyst for cracking, it is characterised in that comprise the steps:
S1, medical stone powder is placed in phosphate aqueous solution dipping, adds sodium silicate and stir, then heat up, insulation, to take out, washing obtains modified medical stone powder；
S2, by after palladium sulfate, Disulfatozirconic acid., nickel sulfate, citric acid, cetyl trimethylammonium bromide, dehydrated alcohol mix homogeneously, regulate pH to 9-10, add modified medical stone powder to carry out heating in water bath and obtain mixed material, then mixed material is taken out and carry out hydro-thermal reaction, then after precipitate being washed, dry, then the roasting that heats up obtains modified catalyst for cracking。
2. the preparation method modifiying catalyst for cracking according to claim 1, it is characterised in that in S1, the mass fraction of phosphate aqueous solution is 10-14wt%。
3. the preparation method of modified catalyst for cracking according to claim 1 or claim 2, it is characterised in that in S1, the modulus of sodium silicate is 2.8-3.2。
4. the preparation method of modified catalyst for cracking according to any one of claim 1-3, it is characterized in that, in S1, medical stone powder is placed in phosphate aqueous solution dipping 16-20h, adds sodium silicate and stir, be then warming up to 500-520 DEG C with average heating rate for 3-5 DEG C/min, it is warming up to 550-580 DEG C for 1-2 DEG C/min again with average heating rate, insulation 4-6h, takes out, and washing obtains modified medical stone powder。
5. the preparation method of modified catalyst for cracking according to any one of claim 1-3, it is characterized in that, in S1, by weight 30-40 part medical stone powder is placed in the phosphate aqueous solution dipping that 15-20 part mass fraction is 10-14wt%, add the sodium silicate that 30-40 part modulus is 2.8-3.2 to stir, then heat up, insulation, taking out, washing obtains modified medical stone powder。
6. the preparation method of modified catalyst for cracking according to any one of claim 1-5, it is characterized in that, in S2, palladium sulfate, Disulfatozirconic acid., nickel sulfate, citric acid, cetyl trimethylammonium bromide, dehydrated alcohol mol ratio be 7-10:1-2:3-6:2-4:1-2:18-24。
7. the preparation method of modified catalyst for cracking according to any one of claim 1-6, it is characterised in that in S2, the weight ratio of modified medical stone powder and palladium sulfate is 10-15:4-6。
8. the preparation method of modified catalyst for cracking according to any one of claim 1-7, it is characterised in that in S2, the temperature of heating in water bath is 55-60 DEG C, and the time of heating in water bath is 50-90min。
9. the preparation method of modified catalyst for cracking according to any one of claim 1-8, it is characterised in that in S2, the temperature of hydro-thermal reaction is 200-220 DEG C, and the time of hydro-thermal reaction is 3-5h。
10. the preparation method of modified catalyst for cracking according to any one of claim 1-9, it is characterised in that in S2, sintering temperature is 380-400 DEG C, and roasting time is 90-150min。
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