CN115041222A - High-performance propylene additive and preparation method thereof - Google Patents
High-performance propylene additive and preparation method thereof Download PDFInfo
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- CN115041222A CN115041222A CN202210633652.3A CN202210633652A CN115041222A CN 115041222 A CN115041222 A CN 115041222A CN 202210633652 A CN202210633652 A CN 202210633652A CN 115041222 A CN115041222 A CN 115041222A
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 90
- 239000000654 additive Substances 0.000 title claims abstract description 46
- 230000000996 additive effect Effects 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000011268 mixed slurry Substances 0.000 claims abstract description 109
- 238000003756 stirring Methods 0.000 claims abstract description 50
- 239000002245 particle Substances 0.000 claims abstract description 45
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 38
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000002808 molecular sieve Substances 0.000 claims abstract description 33
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000002562 thickening agent Substances 0.000 claims abstract description 31
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 26
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 26
- 239000004005 microsphere Substances 0.000 claims abstract description 25
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 17
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims abstract description 13
- 238000000465 moulding Methods 0.000 claims abstract description 12
- 239000007921 spray Substances 0.000 claims abstract description 12
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 10
- 238000005470 impregnation Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 23
- 239000000126 substance Substances 0.000 claims description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 12
- 239000011574 phosphorus Substances 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- 238000000498 ball milling Methods 0.000 claims description 11
- 230000004913 activation Effects 0.000 claims description 7
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical group [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 7
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 7
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 7
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 238000004523 catalytic cracking Methods 0.000 abstract description 19
- 238000005299 abrasion Methods 0.000 abstract description 18
- 239000000295 fuel oil Substances 0.000 abstract description 10
- 239000002283 diesel fuel Substances 0.000 abstract description 9
- 239000012752 auxiliary agent Substances 0.000 description 20
- 239000000203 mixture Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 5
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 5
- 239000002671 adjuvant Substances 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000004230 steam cracking Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- -1 propylene-ethylene Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
Classifications
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- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/40—Special temperature treatment, i.e. other than just for template removal
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/42—Addition of matrix or binder particles
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
A preparation method of a high-performance propylene additive comprises the following steps: a) stirring kaolin and water uniformly, and then adding hydrochloric acid to obtain mixed slurry A; b) adding a molecular sieve into the mixed slurry A, and uniformly stirring to obtain mixed slurry B; c) adding aluminum sol and silica sol into the mixed slurry B, and uniformly stirring to obtain mixed slurry C; d) adding a thickening agent into the mixed slurry C, and uniformly stirring to obtain mixed slurry D; e) molding the mixed slurry D by adopting high-temperature spray centrifugal equipment to prepare microsphere particles with the particle size of D50 being 70-80 mu m; f) and (3) carrying out equal-volume impregnation treatment on the microsphere particles by adopting 0.1-5% tetrapropyl ammonium hydroxide solution, and then carrying out hydrothermal treatment and roasting to obtain the high-performance propylene additive. The high-performance propylene additive prepared by the preparation method has the capability of converting heavy oil and diesel oil fractions, has the advantages of high propylene yield, high additive activity, good stability, low abrasion, good sphericity and the like, and is suitable for the field of catalytic cracking and high propylene yield of refineries.
Description
Technical Field
The invention relates to the technical field of petroleum catalytic cracking, in particular to a high-performance propylene additive and a preparation method thereof.
Background
In recent years, with the rapid development of national economy, the demand of the chemical industry market for propylene is greatly increased, and the main sources of propylene in China at present are naphtha steam cracking and heavy oil catalytic cracking (FCC). Because crude oil in China is heavier, the increasing propylene demand is difficult to meet by adopting naphtha steam cracking. Compared with the steam cracking process, the FCC propylene production has the advantages of heavy raw materials, high propylene-ethylene ratio, low production cost and the like, and the FCC propylene yield increase becomes a hot spot for the development of the catalytic cracking technology.
The method for increasing the yield of light olefins (propylene and butylene) by the FCC unit mainly comprises the following steps: firstly, improving a catalytic cracking base agent; adding a shape-selecting auxiliary agent; and thirdly, the operation severity of the catalytic cracking unit is improved (the outlet temperature of a lifting pipe is improved, the reaction time is shortened, and the catalyst-oil ratio is improved). Among them, addition of shape-selective aids is the most effective and most convenient method. The ZSM-5 molecular sieve is used as a main propylene yield increasing component in an FCC catalyst, determines the performance of the propylene yield increasing catalyst, and improves the activity of a propylene auxiliary agent mainly by adjusting the type and the content of the molecular sieve.
Chinese patent publication No. CN102049284A discloses a method for reducing wear of a propylene additive by using a phosphor-alumina sol as a binder, wherein the phosphor-alumina sol has good cohesiveness, the prepared propylene additive product has a low wear index, and the selectivity of the propylene additive can be improved. Chinese patent publication No. CN104888842A discloses a method for reducing wear index of an auxiliary agent by reacting inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, and the like as modifiers with conventional binders such as silica sol, alumina sol, or aluminum phosphate solution as modified binders. However, the increased levels of adjuvant actives prepared using the above patents result in a significant increase in the wear index.
The Chinese patent with publication number CN113262813A discloses a method for improving the strength of catalytic cracking propylene auxiliary agent and application thereof, wherein, the propylene auxiliary agent microspheres are mixed with a strength improver, filtered and roasted, and washed and dried to obtain the modified propylene auxiliary agent, the content of the propylene auxiliary agent ZSM-5 molecular sieve is 35-50 wt%, the main particle diameter after modification is 20-150 mu m, and the abrasion index is greatly reduced. However, the additional preparation step of the improved process of this patent is not conducive to product cost reduction.
In addition, chinese patent publication No. CN107971029A discloses a catalytic cracking assistant for increasing propylene yield and a preparation method thereof, wherein molecular sieves are modified and added with at least one metal additive selected from group viii metals and manganese, zinc, and gallium, and the prepared assistant can effectively improve propylene yield and propylene selectivity. Chinese patent publication No. CN107970998A discloses a catalytic cracking main agent for increasing propylene yield and a preparation method thereof, wherein IMF molecular sieves are mainly used, and propylene yield and propylene selectivity can be effectively improved. However, the above patents mainly improve propylene yield and selectivity, and cannot simultaneously achieve conversion of diesel oil and heavy oil.
Disclosure of Invention
In view of the above, the present invention aims to provide a high performance propylene additive and a preparation method thereof, and the high performance propylene additive prepared by the preparation method provided by the present invention has the capability of converting heavy oil and diesel oil fractions, and simultaneously has a high propylene yield, and is particularly suitable for the field of catalytic cracking and propylene yield increase in refineries.
The invention provides a preparation method of a high-performance propylene additive, which comprises the following steps:
a) stirring kaolin and water uniformly, and then adding hydrochloric acid to obtain mixed slurry A;
b) adding a molecular sieve into the mixed slurry A, and uniformly stirring to obtain mixed slurry B;
c) adding aluminum sol and silica sol into the mixed slurry B, and uniformly stirring to obtain mixed slurry C;
d) adding a thickening agent into the mixed slurry C, and uniformly stirring to obtain mixed slurry D;
e) molding the mixed slurry D by adopting high-temperature spray centrifugal equipment to prepare microsphere particles with the particle size of D50 being 70-80 mu m;
f) and (3) carrying out equal-volume impregnation treatment on the microsphere particles by adopting 0.1-5% tetrapropyl ammonium hydroxide solution, and then carrying out hydrothermal treatment and roasting to obtain the high-performance propylene additive.
Preferably, the mass ratio of the kaolin to the water to the hydrochloric acid to the molecular sieve to the aluminum sol to the silica sol to the thickener is 600: (600-1400): (1.2-12): (200-400): (250-300): (150-250): (2-5).
Preferably, the step a) further comprises:
carrying out high-temperature roasting activation on the kaolin, and then uniformly stirring the kaolin and water; the high-temperature roasting activation temperature is 700-900 ℃, and the time is 5-7 h.
Preferably, the molecular sieve in step b) is a hydrogen type ZSM-5 molecular sieve.
Preferably, the step b) further comprises:
and uniformly stirring the mixed slurry A and a molecular sieve, and performing ball milling for 0.5-4 h to obtain mixed slurry B.
Preferably, the step c) further comprises:
adding aluminum sol and silica sol into the mixed slurry B, adding a phosphorus-containing substance, and uniformly stirring to obtain mixed slurry C; the phosphorus-containing substance is ammonium dihydrogen phosphate; the mass ratio of the phosphorus-containing substance to the aluminum sol to the silica sol is (1-2): (25-30): (15-25).
Preferably, the thickener in step d) is selected from one or more of a cellulose thickener, a polyacrylate thickener, an alkali-soluble acrylic thickener and a polyurethane thickener.
Preferably, the hydrothermal treatment in the step f) is carried out in a closed kettle at the temperature of 140-200 ℃ for 24-72 h.
Preferably, the roasting temperature in the step f) is 500-600 ℃, and the roasting time is 2-4 h.
The invention also provides a high-performance propylene additive which is prepared by the preparation method of the technical scheme.
The invention provides a high-performance propylene additive and a preparation method thereof; the preparation method comprises the following steps: a) stirring kaolin and water uniformly, and then adding hydrochloric acid to obtain mixed slurry A; b) adding a molecular sieve into the mixed slurry A, and uniformly stirring to obtain mixed slurry B; c) adding aluminum sol and silica sol into the mixed slurry B, and uniformly stirring to obtain mixed slurry C; d) adding a thickening agent into the mixed slurry C, and uniformly stirring to obtain mixed slurry D; e) molding the mixed slurry D by adopting high-temperature spray centrifugal equipment to prepare microsphere particles with the particle size of D50 being 70-80 mu m; f) and (3) carrying out equal-volume impregnation treatment on the microsphere particles by adopting 0.1-5% tetrapropyl ammonium hydroxide solution, and then carrying out hydrothermal treatment and roasting to obtain the high-performance propylene additive. Compared with the prior art, the preparation method provided by the invention adopts specific raw materials to match with specific process steps, so that the integral better interaction is realized, and the prepared high-performance propylene auxiliary agent has the capability of converting heavy oil and diesel oil fractions, and has the advantages of high propylene yield, high auxiliary agent activity, good stability, low abrasion, good sphericity and the like, and is particularly suitable for the field of high-yield propylene produced by refinery catalytic cracking.
Meanwhile, the preparation method provided by the invention has the advantages of simple and easily-controlled process, cheap and easily-obtained raw materials, economy, environmental protection and the like, so that the preparation method has good application prospect and potential in the technical field of petrochemical catalytic cracking catalyst production.
Drawings
FIG. 1 is a scanning electron microscope image of a high-performance propylene additive provided in example 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of a high-performance propylene additive, which comprises the following steps:
a) stirring kaolin and water uniformly, and then adding hydrochloric acid to obtain mixed slurry A;
b) adding a molecular sieve into the mixed slurry A, and uniformly stirring to obtain mixed slurry B;
c) adding aluminum sol and silica sol into the mixed slurry B, and uniformly stirring to obtain mixed slurry C;
d) adding a thickening agent into the mixed slurry C, and uniformly stirring to obtain mixed slurry D;
e) molding the mixed slurry D by adopting high-temperature spray centrifugal equipment to prepare microsphere particles with the particle size of D50 being 70-80 mu m;
f) and (3) carrying out equal-volume impregnation treatment on the microsphere particles by adopting 0.1-5% tetrapropyl ammonium hydroxide solution, and then carrying out hydrothermal treatment and roasting to obtain the high-performance propylene additive.
Firstly, kaolin and water are uniformly stirred and then hydrochloric acid is added to obtain mixed slurry A; adding a molecular sieve into the mixed slurry A, and uniformly stirring to obtain mixed slurry B; then adding aluminum sol and silica sol into the mixed slurry B, and uniformly stirring to obtain mixed slurry C; finally, adding a thickening agent into the mixed slurry C, and uniformly stirring to obtain mixed slurry D; the mixing process of the specific raw materials is completed.
The sources of the kaolin, the water, the hydrochloric acid, the molecular sieve, the alumina sol, the silica sol and the thickening agent are not particularly limited, and commercial products well known to those skilled in the art can be adopted; wherein, the hydrochloric acid is hydrochloric acid with the mass fraction of 37 percent, which is well known by the technical personnel in the field.
In the present invention, the mass ratio of the kaolin, water, hydrochloric acid, molecular sieve, alumina sol, silica sol and thickener is preferably 600: (600-1400): (1.2-12): (200-400): (250-300): (150-250): (2-5), more preferably 600: 1200: 3: 300: 270: 200: 3.
in the present invention, the step a) preferably further comprises:
the kaolin is firstly roasted and activated at high temperature and then is evenly stirred with water.
In the present invention, the kaolin is a conventional kaolin well known to those skilled in the art.
In the invention, the temperature of the high-temperature roasting activation is preferably 700-900 ℃, and more preferably 80 ℃; the high-temperature roasting activation time is preferably 5 to 7 hours, and more preferably 6 hours. The invention carries out high-temperature roasting activation on the kaolin, and the silicon and the aluminum of the activated kaolin play a role in the recrystallization process (recrystallization, the silicon and the aluminum in the kaolin are recrystallized under the action of molecular sieve seed crystals and a template).
In the present invention, the stirring speed for uniformly stirring with water is preferably 300r/min to 500r/min, more preferably 400r/min, and the time is preferably 1h to 2h, more preferably 1.5 h.
In the present invention, the molecular sieve is preferably a hydrogen type ZSM-5 molecular sieve; is the main active component of the high-performance propylene additive.
In the present invention, the step b) preferably further comprises:
and uniformly stirring the mixed slurry A and a molecular sieve, and performing ball milling for 0.5-4 h to obtain mixed slurry B. In the present invention, the ball milling is preferably performed using a ball mill, and the ball milling time is preferably 1 h. The invention adopts the ball milling process, and the molecular sieve and the kaolin are ball milled together, so that the two components can be mixed more uniformly, the crystal grains of the molecular sieve can be reduced, and a better crystal seed guiding effect can be achieved.
In the present invention, said step c) preferably further comprises:
and adding the aluminum sol and the silica sol into the mixed slurry B, adding a phosphorus-containing substance, and uniformly stirring to obtain mixed slurry C.
In the present invention, the phosphorus-containing substance is preferably ammonium dihydrogen phosphate; the source of the phosphorus-containing substance is not particularly limited in the present invention, and commercially available products known to those skilled in the art can be used. The invention adds phosphorus-containing substances, and can improve the activity and stability of the auxiliary agent by cooperating with the combined action of the aluminum sol and the silica sol.
In the invention, the mass ratio of the phosphorus-containing substance to the aluminum sol and the silica sol is preferably (1-2): (25-30): (15-25), more preferably 1.5: 27: 20.
in the invention, the stirring speed for adding the phosphorus-containing substance and uniformly stirring is preferably 300r/min to 500r/min, more preferably 400r/min, and the time is preferably 1h to 2h, more preferably 1.5 h.
In the present invention, the thickener is preferably selected from one or more of a cellulose thickener, a polyacrylate thickener, an alkali-soluble acrylic thickener, and a polyurethane thickener, and more preferably a cellulose thickener; in a preferred embodiment of the invention, the thickener is a cellulosic thickener, in particular sodium carboxymethyl cellulose. The special thickening agent is added in the preparation process, so that the abrasion of the auxiliary agent can be effectively reduced.
In the present invention, the thickener is added to the mixed slurry C, and the mixed slurry D is obtained by stirring preferably for 0.5 to 2 hours, more preferably for 1 hour.
After the mixed slurry D is obtained, molding the mixed slurry D by adopting high-temperature spray centrifugal equipment to obtain microsphere particles with the particle size of D50 being 70-80 mu m; and finally, performing equal-volume impregnation treatment on the microsphere particles by adopting 0.1-5% tetrapropyl ammonium hydroxide solution, preferably 1% tetrapropyl ammonium hydroxide solution, and then performing hydrothermal treatment and roasting to obtain the high-performance propylene additive.
In the present invention, the hydrothermal treatment is preferably carried out in a closed reactor at 140 to 200 ℃ for 24 to 72 hours, more preferably at 170 to 190 ℃ for 30 to 40 hours.
In the present invention, the temperature of the calcination is preferably 500 to 600 ℃, more preferably 540 ℃, and the time is preferably 2 to 4 hours, more preferably 3 hours.
The preparation method provided by the invention adopts specific raw materials and specific process steps to realize better overall interaction, and the prepared high-performance propylene additive has the capability of converting heavy oil and diesel oil fractions, and has the advantages of high propylene yield, high additive activity, good stability, low abrasion, good sphericity and the like, thereby being particularly suitable for the field of propylene production through catalytic cracking in refineries. Meanwhile, the preparation method provided by the invention has the advantages of simple and easily-controlled process, cheap and easily-obtained raw materials, economy, environmental protection and the like, so that the preparation method has good application prospect and potential in the technical field of petrochemical catalytic cracking catalyst production.
The invention also provides a high-performance propylene additive which is prepared by the preparation method of the technical scheme. The high-performance propylene additive provided by the invention has the capability of converting heavy oil and diesel oil fractions, has the advantages of high activity, good stability, low abrasion, good sphericity and the like of the prepared additive, has high propylene yield, and is particularly suitable for the field of catalytic cracking and high propylene yield of refineries.
The invention mainly aims at improving the yield and the selectivity of propylene by using a propylene auxiliary agent in the field of catalytic cracking, cannot simultaneously consider the conversion of diesel oil and heavy oil, has high activity and high abrasion, and provides a catalytic cracking auxiliary agent for increasing the yield of propylene and a preparation method thereof.
The invention provides a high-performance propylene additive and a preparation method thereof; the preparation method comprises the following steps: a) stirring kaolin and water uniformly, and then adding hydrochloric acid to obtain mixed slurry A; b) adding a molecular sieve into the mixed slurry A, and uniformly stirring to obtain mixed slurry B; c) adding aluminum sol and silica sol into the mixed slurry B, and uniformly stirring to obtain mixed slurry C; d) adding a thickening agent into the mixed slurry C, and uniformly stirring to obtain mixed slurry D; e) molding the mixed slurry D by adopting high-temperature spray centrifugal equipment to prepare microsphere particles with the particle size of D50 being 70-80 mu m; f) and (3) carrying out isometric impregnation treatment on the microsphere particles by adopting a 0.1-5% tetrapropyl ammonium hydroxide solution, and then carrying out hydrothermal treatment and roasting to obtain the high-performance propylene auxiliary agent. Compared with the prior art, the preparation method provided by the invention adopts specific raw materials to match with specific process steps, so that the overall better interaction is realized, and the prepared high-performance propylene auxiliary agent has the capability of converting heavy oil and diesel oil fractions, and has the advantages of high propylene yield, high auxiliary agent activity, good stability, low abrasion, good sphericity and the like, and is particularly suitable for the field of high-yield propylene in catalytic cracking of refineries.
Meanwhile, the preparation method provided by the invention has the advantages of simple and easily-controlled process, cheap and easily-obtained raw materials, economy, environmental protection and the like, so that the preparation method has good application prospect and potential in the technical field of petrochemical catalytic cracking catalyst production.
In order to further illustrate the present invention, the following examples are provided for illustrative purposes. The starting materials used in the following examples of the present invention are all commercially available.
Example 1
(1) Calcining kaolin at 800 ℃ for 6h to obtain activated kaolin; 600g of activated kaolin is weighed and dissolved in 1200g of deionized water under the stirring condition, the mixture is stirred for 1.5h at the speed of 400r/min, and then 3g of hydrochloric acid (the mass fraction is 37%) is added and stirred uniformly to obtain mixed slurry A.
(2) And adding 300g of hydrogen type ZSM-5 molecular sieve into the mixed slurry A, uniformly mixing, and then carrying out ball milling in a ball mill for 1h to obtain mixed slurry B.
(3) 270g of alumina sol, 200g of silica sol and 15g of ammonium dihydrogen phosphate were added to the mixed slurry B, and the mixture was stirred at 400r/min for 1.5 hours to obtain a mixed slurry C.
(4) And 3g of sodium carboxymethylcellulose is weighed and added into the mixed slurry C, and the mixed slurry D is obtained after stirring for 1 hour.
(5) And (3) molding the mixed slurry D by adopting high-temperature spray centrifugal equipment to obtain microsphere particles with the particle size of D50 being 70-80 mu m.
(6) Soaking the microsphere particles in 1% tetrapropylammonium hydroxide solution in the same volume, and treating in a 180 ℃ closed kettle for 36 h; and roasting the treated microspherical particles at 540 ℃ for 3 hours to obtain the high-performance propylene additive.
Through detection, a scanning electron microscope image of the high-performance propylene additive provided by the embodiment 1 of the invention is shown in fig. 1. As can be seen from the electron microscope analysis in FIG. 1, the high-performance propylene additive provided in example 1 of the present invention has uniform particles and good moldability.
Example 2
(1) 600g of kaolin (not activated) is weighed and dissolved in 1200g of deionized water under the stirring condition, the mixture is stirred for 1.5h at the speed of 400r/min, and then 3g of hydrochloric acid (the mass fraction is 37%) is added and stirred uniformly to obtain mixed slurry A.
(2) And adding 300g of hydrogen type ZSM-5 molecular sieve into the mixed slurry A, uniformly mixing, and then carrying out ball milling in a ball mill for 1h to obtain mixed slurry B.
(3) 270g of alumina sol, 200g of silica sol and 15g of ammonium dihydrogen phosphate were added to the mixed slurry B, and the mixture was stirred at 400r/min for 1.5 hours to obtain a mixed slurry C.
(4) And 3g of sodium carboxymethylcellulose is weighed and added into the mixed slurry C, and the mixed slurry D is obtained after stirring for 1 hour.
(5) And (3) molding the mixed slurry D by adopting high-temperature spray centrifugal equipment to obtain microsphere particles with the particle size of D50 being 70-80 mu m.
(6) Soaking the microsphere particles in 1% tetrapropylammonium hydroxide solution in the same volume, and treating in a 180 ℃ closed kettle for 36 h; and roasting the treated microspherical particles at 540 ℃ for 3 hours to obtain the high-performance propylene additive.
Example 3
(1) Calcining kaolin at 800 ℃ for 6h to obtain activated kaolin; 600g of activated kaolin is weighed and dissolved in 1200g of deionized water under the stirring condition, the mixture is stirred for 1.5h at the speed of 400r/min, and then 3g of hydrochloric acid (the mass fraction is 37%) is added and stirred uniformly to obtain mixed slurry A.
(2) And adding 300g of hydrogen type ZSM-5 molecular sieve into the mixed slurry A, uniformly mixing, and then carrying out ball milling to obtain mixed slurry B.
(3) 270g of alumina sol, 200g of silica sol and 15g of ammonium dihydrogen phosphate were added to the mixed slurry B, and the mixture was stirred at 400r/min for 1.5 hours to obtain a mixed slurry C.
(4) And 3g of sodium carboxymethylcellulose is weighed and added into the mixed slurry C, and the mixed slurry D is obtained after stirring for 1 hour.
(5) And (3) molding the mixed slurry D by adopting high-temperature spray centrifugal equipment to obtain microsphere particles with the particle size of D50 being 70-80 mu m.
(6) Soaking the microsphere particles in 1% tetrapropylammonium hydroxide solution in the same volume, and treating in a 180 ℃ closed kettle for 36 h; and roasting the treated microspherical particles at 540 ℃ for 3 hours to obtain the high-performance propylene additive.
Example 4
(1) Calcining kaolin at 800 ℃ for 6h to obtain activated kaolin; 600g of activated kaolin is weighed and dissolved in 1200g of deionized water under the stirring condition, the mixture is stirred for 1.5h at the speed of 400r/min, and then 3g of hydrochloric acid (the mass fraction is 37%) is added and stirred uniformly to obtain mixed slurry A.
(2) And adding 300g of hydrogen type ZSM-5 molecular sieve into the mixed slurry A, uniformly mixing, and then carrying out ball milling in a ball mill for 1h to obtain mixed slurry B.
(3) 270g of alumina sol and 200g of silica sol were added to the mixed slurry B, and the mixture was stirred at 400r/min for 1.5 hours to obtain a mixed slurry C.
(4) And 3g of sodium carboxymethylcellulose is weighed and added into the mixed slurry C, and the mixed slurry D is obtained after stirring for 1 hour.
(5) And (3) molding the mixed slurry D by adopting high-temperature spray centrifugal equipment to prepare microsphere particles with the particle size of D50 being 70-80 mu m.
(6) Soaking the microsphere particles in 1% tetrapropylammonium hydroxide solution in the same volume, and treating in a 180 ℃ closed kettle for 36 h; and roasting the treated microspherical particles at 540 ℃ for 3 hours to obtain the high-performance propylene additive.
Comparative example 1
(1) Calcining kaolin at 800 ℃ for 6h to obtain activated kaolin; 600g of activated kaolin is weighed and dissolved in 1200g of deionized water under the stirring condition, the mixture is stirred for 1.5h at the speed of 400r/min, and then 3g of hydrochloric acid (the mass fraction is 37%) is added and stirred uniformly to obtain mixed slurry A.
(2) And adding 300g of hydrogen type ZSM-5 molecular sieve into the mixed slurry A, uniformly mixing, and then carrying out ball milling in a ball mill for 1h to obtain mixed slurry B.
(3) 270g of alumina sol, 200g of silica sol and 15g of ammonium dihydrogen phosphate were added to the mixed slurry B, and the mixture was stirred at 400r/min for 1.5 hours to obtain a mixed slurry C.
(4) And (3) molding the mixed slurry C by adopting high-temperature spray centrifugal equipment to obtain the microsphere particles with the D50 particle size of 70-80 microns.
(5) Soaking the microsphere particles in 1% tetrapropylammonium hydroxide solution in the same volume, and treating in a 180 ℃ closed kettle for 36 h; and roasting the treated microspherical particles at 540 ℃ for 3h to obtain the propylene auxiliary agent.
Comparative example 2
Domestic industrial agent.
And (3) performance testing:
the sphericity, particle size distribution, wear index and the like of the propylene additive are the basis for representing the long-period stable operation of the catalytic device; the invention utilizes a Quadrasorb evoTM full-automatic specific surface and porosity analyzer of Quantachrome company in the United states, adopts a GB/T21650.2-2008 method to analyze the propylene additives in examples 1-4 and comparative examples 1-2, and obtains specific surface area and pore volume data shown in Table 1.
TABLE 1 specific surface area and pore volume data for the propylene adjuvants of examples 1-4 and comparative examples 1-2
As can be seen from table 1, the high performance propylene aid prepared in example 1 has a higher specific surface area and pore volume than other propylene aids.
The wear index is detected by adopting a wear index instrument, and the method for detecting the wear index comprises the following steps:
taking 100g of a propylene auxiliary agent sample, placing the propylene auxiliary agent sample into a porcelain dish, and roasting the propylene auxiliary agent sample in a high-temperature furnace at 540 +/-10 ℃ for 3 hours; taking out, cooling for 5min, and cooling in a dryer to room temperature; the time from roasting to use of the sample should not exceed 24 hours.
Weighing 10 +/-0.02 g of the pretreated sample by using a weighing bottle, injecting 0.5 +/-0.005 mL of distilled water into the sample by using a burette, and gently stirring by using a glass rod; the particles are broken for use.
After leakage test and flow correction of the abrasion index instrument are normal, 10 +/-0.02 g of the prepared sample is placed into an abrasion straight pipe, blowing and grinding are carried out for 5 hours under constant air flow, and the abrasion index of the propylene additive is called after 4 hours of average abrasion percentage per hour except 1 hour.
The reaction performance was evaluated using a pilot riser, the feedstock properties are shown in table 2, and the pilot riser evaluation conditions are shown in table 3.
TABLE 2 Properties of the raw materials
Table 3 pilot riser evaluation conditions
The results are shown in Table 4.
TABLE 4 abrasion index and reactivity data for the propylene adjuvants of examples 1-4 and comparative examples 1-2
The abrasion index and the reaction performance of the propylene additive are shown in table 4, the abrasion index of an industrial propylene additive (comparative example 2) is generally controlled to be less than 3%/h, and the reaction result shows that the abrasion index of the high-performance propylene additive prepared in examples 1-4 is obviously reduced compared with that of the propylene additives in comparative examples 1-2, the conversion rate of diesel oil and heavy oil is improved by about 4%, the conversion rate of liquefied gas is improved by about 2%, the yield of propylene is improved by about 1%, and the high-performance propylene additive has the advantages of high reaction activity, high yield of propylene, low abrasion index and the like. At present, the applicant has completed the industrial production of 30 tons of high-performance propylene additives according to the preparation method provided by the above embodiment 1, and the prepared industrial high-performance propylene additives have the advantages of high activity, good stability, low abrasion, good sphericity and the like.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A preparation method of a high-performance propylene additive comprises the following steps:
a) stirring kaolin and water uniformly, and then adding hydrochloric acid to obtain mixed slurry A;
b) adding a molecular sieve into the mixed slurry A, and uniformly stirring to obtain mixed slurry B;
c) adding aluminum sol and silica sol into the mixed slurry B, and uniformly stirring to obtain mixed slurry C;
d) adding a thickening agent into the mixed slurry C, and uniformly stirring to obtain mixed slurry D;
e) molding the mixed slurry D by adopting high-temperature spray centrifugal equipment to prepare microsphere particles with the particle size of D50 being 70-80 mu m;
f) and (3) carrying out equal-volume impregnation treatment on the microsphere particles by adopting 0.1-5% tetrapropyl ammonium hydroxide solution, and then carrying out hydrothermal treatment and roasting to obtain the high-performance propylene additive.
2. The preparation method according to claim 1, wherein the mass ratio of the kaolin, the water, the hydrochloric acid, the molecular sieve, the alumina sol, the silica sol and the thickener is 600: (600-1400): (1.2-12): (200-400): (250-300): (150-250): (2-5).
3. The method of claim 1, wherein the step a) further comprises:
carrying out high-temperature roasting activation on the kaolin, and then uniformly stirring the kaolin and water; the high-temperature roasting activation temperature is 700-900 ℃, and the time is 5-7 h.
4. The method of claim 1, wherein the molecular sieve in step b) is a hydrogen form ZSM-5 molecular sieve.
5. The method of claim 1, wherein step b) further comprises:
and uniformly stirring the mixed slurry A and a molecular sieve, and performing ball milling for 0.5-4 h to obtain mixed slurry B.
6. The method of claim 1, wherein step c) further comprises:
adding aluminum sol and silica sol into the mixed slurry B, adding a phosphorus-containing substance, and uniformly stirring to obtain mixed slurry C; the phosphorus-containing substance is ammonium dihydrogen phosphate; the mass ratio of the phosphorus-containing substance to the aluminum sol to the silica sol is (1-2): (25-30): (15-25).
7. The method of claim 1, wherein the thickener in step d) is selected from one or more of a cellulose thickener, a polyacrylate thickener, an alkali-soluble acrylic thickener, and a polyurethane thickener.
8. The preparation method according to claim 1, wherein the hydrothermal treatment in step f) is carried out in a closed kettle at 140-200 ℃ for 24-72 h.
9. The preparation method according to claim 1, wherein the roasting temperature in step f) is 500-600 ℃ and the roasting time is 2-4 h.
10. A high-performance propylene additive, which is characterized by being prepared by the preparation method of any one of claims 1 to 9.
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