CN101885980B - Preparation method and application of catalytic cracking metal passivant - Google Patents
Preparation method and application of catalytic cracking metal passivant Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 41
- 239000002184 metal Substances 0.000 title claims abstract description 38
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 14
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 239000002270 dispersing agent Substances 0.000 claims abstract description 13
- 239000003381 stabilizer Substances 0.000 claims abstract description 13
- 239000007800 oxidant agent Substances 0.000 claims abstract description 12
- 239000012535 impurity Substances 0.000 claims abstract description 8
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical class O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 5
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000005456 alcohol based solvent Substances 0.000 claims abstract description 4
- -1 methylcellulose compound Chemical class 0.000 claims abstract description 4
- 229920000609 methyl cellulose Polymers 0.000 claims abstract description 3
- 239000001923 methylcellulose Substances 0.000 claims abstract description 3
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 16
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 10
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 9
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 9
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 9
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 9
- 239000006078 metal deactivator Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 4
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 3
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 abstract description 6
- WUOBERCRSABHOT-UHFFFAOYSA-N diantimony Chemical compound [Sb]#[Sb] WUOBERCRSABHOT-UHFFFAOYSA-N 0.000 abstract 2
- CJJMLLCUQDSZIZ-UHFFFAOYSA-N oxobismuth Chemical class [Bi]=O CJJMLLCUQDSZIZ-UHFFFAOYSA-N 0.000 abstract 2
- 229940043237 diethanolamine Drugs 0.000 abstract 1
- 229960004418 trolamine Drugs 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 37
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 36
- 239000003054 catalyst Substances 0.000 description 20
- 239000003795 chemical substances by application Substances 0.000 description 19
- 239000007789 gas Substances 0.000 description 18
- 229910052759 nickel Inorganic materials 0.000 description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 15
- 239000000571 coke Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 229910001385 heavy metal Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 229910052787 antimony Inorganic materials 0.000 description 6
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 239000000295 fuel oil Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 229910000410 antimony oxide Inorganic materials 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- 239000003502 gasoline Substances 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000004231 fluid catalytic cracking Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910017850 Sb—Ni Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000008431 aliphatic amides Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000002010 green coke Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical group 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002683 reaction inhibitor Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a preparation method and application of a catalytic cracking metal passivant. The preparation method comprises the following steps of: preparing raw materials in the following percentage by weight: 20%-45% of dispersing agents, 30%-50% of oxidants, 15%-30% of metal oxides, 10%-30% of solvents and 2%-5% of stabilizing agents; sequentially adding the oxidants and the metal oxides to the dispersing agents during preparation; increasing temperature to 50-90 DEG C within 2-4 hours, keeping the temperature for 1-5 hours and then cooling; adding the solvents and the stabilizing agents, and then filtering to remove impurities so as to obtain the metal passivant, wherein the dispersing agents are diethanol amine and/or triethanol amine; the oxidants are hydrogen peroxide of 30-50 percent and/or nitric acids of 66-68 percent; the metal oxides are one of diantimony trioxide, rare earth oxides and bismuth oxides or mixtures of more than two of the diantimony trioxide, the rare earth oxides and the bismuth oxides in any proportion; the solvents are one of water or alcohol solvents or mixtures of more than two of the water or the alcohol solvents in any proportion; and the stabilizing agents are methylcellulose compound solutions.
Description
Technical Field
The invention relates to a preparation method and application of a catalytic cracking metal passivator.
Background
The catalytic cracking device occupies a leading position in the oil refining device, and the raw material is in contact cracking with a catalyst in the catalytic cracking reactor after heat exchange to obtain dry gas, liquefied gas, gasoline, diesel oil, coke and oil slurry. Under the influence of crude oil supply and quality, the content of metal elements in crude oil is increasing day by day, and various oil refining companies pursue high slag mixing ratio, lower coke yield and high light oil or total liquid yield so as to achieve the maximum economic benefit, and on the other hand, the metal element in the catalytic raw material is accelerated to rise. The metal elements in the catalytic raw material have great harm to the catalyst, particularly the nickel has serious harm to the catalyst, so that the distribution of catalytic cracking products is influenced. At home and abroad, a plurality of methods for improving the distribution of catalytic cracking products are reported.
CN1245198A reports a preparation method of an antimony-containing metal passivator, wherein a water-soluble metal passivator is synthesized from antimony oxide, organic carboxylic acid, aliphatic amide and water at 80-180 ℃. The main mechanism is that antimony-containing compound is added into the raw material to passivate the influence of nickel on the catalytic cracking catalyst. At present, the metal passivators in a fluid catalytic cracking (hereinafter referred to as FCC) device are one or a mixture of water-soluble compounds of antimony, rare earth, tin and the like, and have the defects of easy precipitation at low temperature, low decomposition temperature, poor solubility in raw oil and poor dispersion performance. And one of the products requires that the content of effective metal antimony is more than 15%.
CN10121A5476A reports a preparation method and industrial application of a catalytic cracking coke-inhibiting yield-increasing auxiliary agent, wherein in the method, an oil-soluble dispersing agent, a thermal cracking active agent, a free radical chain reaction inhibitor, an oil-soluble metal passivator and a hydrocarbon solvent are heated to 50-150 ℃ within 1-3 hours, the temperature is kept for 1-5 hours, and the coke-inhibiting yield-increasing auxiliary agent is obtained by filtering to remove impurities after cooling. The main functions of the device are to improve the slag mixing ratio of the FCC device, improve the yield of light oil and reduce the yield of coke, and can reduce the consumption of metal passivators or stop injecting the metal passivators, thereby improving the overall benefit of the FCC device. The product can only replace metal passivator in part of catalytic cracking units, and is basically ineffective for heavy metal pollution of MIP-CGP (producing isoparaffin and increasing propylene) process catalytic cracking units.
Disclosure of Invention
The catalytic cracking metal passivator can improve the heavy metal nickel pollution resistance of a catalytic cracking device, reduce the yield of green coke and improve the yield of light oil.
The invention also provides the application of the catalytic cracking metal passivator prepared by the preparation method.
The preparation method of the catalytic cracking metal passivator comprises the following steps: 20-45% of dispersing agent, 30-50% of oxidant, 15-30% of metal oxide, 10-30% of solvent and 2-5% of stabilizing agent, wherein the mass percentages are respectively, when the catalytic cracking metal passivator is prepared, the oxidant and the metal oxide are sequentially added into the dispersing agent, the temperature is raised to 50-90 ℃ within 2-4 hours, the temperature is kept for 1-5 hours, the mixture is cooled, the solvent and the stabilizing agent are added, and then the impurities are filtered and removed to obtain the metal passivator;
wherein,
the dispersant is diethanolamine and/or triethanolamine, preferably triethanolamine;
the oxidant is hydrogen peroxide with the mass percent concentration of 30-50% and/or nitric acid with the mass percent concentration of 66-68%, and preferably the hydrogen peroxide with the mass percent concentration of 30-50%;
the metal oxide is one or a mixture of more than two of antimony trioxide, rare earth oxide and bismuth oxide in any proportion, and is preferably antimony trioxide or a mixture of antimony trioxide and rare earth oxide. The rare earth oxide is preferably cerium oxide and/or lanthanum oxide. In the case of a mixture of metal oxides, the content of antimony trioxide is preferably 70 to 80% by mass;
the solvent is one or a mixture of more than two of water or alcohol solvents in any proportion, preferably one or a mixture of more than two of water, glycol and glycerol in any proportion, and more preferably glycol and/or glycerol;
the stabilizer is one or a mixture of more than two of methylcellulose compound solutions in any ratio, more preferably a carboxymethyl cellulose solution, wherein the substitution degree of the carboxymethyl cellulose is 0.65-0.85, the polymerization degree is 200-1000, and the solution is an aqueous solution with the mass percentage concentration of 2% -5%.
As a preferred scheme of the invention, the raw materials are in the following ratio: 30-40% of a dispersant, 40-50% of an oxidant, 15-30% of a metal oxide, 10-15% of a solvent and 2-5% of a stabilizer, wherein the dosage of the metal oxide is more preferably 19-21%, the dosage of the solvent is more preferably 10-12% and the dosage of the stabilizer is more preferably 2-3%.
The catalytic cracking metal passivator obtained by the invention is directly added into a catalytic cracking raw material, has excellent dispersibility in the catalytic cracking raw material, and when the catalytic cracking metal passivator is applied, the addition amount is 10-80 ppm, preferably 15-60 ppm, and most preferably 20-30 ppm of the weight of the catalytic cracking raw material oil.
After a nickel compound in the raw oil is decomposed in a reactor, one strand of nickel oxide is formed, and 0-valent and + 1-valent nickel also exists; nickel is present in the +2, +3 valence form in the regenerator. The nickel is mainly in the form of nickel oxide, nickel aluminate or nickel aluminosilicate, and can be uniformly dispersed on the catalyst, so that the nickel poisoning causes the dehydrogenation activity of the catalyst to be increased, the yields of coke, dry gas and hydrogen to be increased, and the yield of light oil to be reduced, but the nickel has a small influence on the activity of the catalyst.
The nickel inhibitor designed according to the nickel poisoning mechanism is formed by using compounds of metal elements such as antimony, bismuth and the like and nickel to form a large-particle Sb-Ni or Bi-Ni alloy to prevent the nickel from dispersing, so that the aim of reducing the activity of the nickel is fulfilled.
The metal passivator synthesized by the invention contains high-valence antimony oxide, has the advantages of high thermal decomposition temperature and high antimony-hanging rate, and is preferentially combined with nickel under the condition of a catalytic system, so that the metal passivator loses the dehydrogenation activity and has good stability and is not easy to reduce. By adding a small amount of the metal passivator obtained by the invention into the catalytic raw material, the dispersant can change the surface property of the raw oil and reduce the viscosity and the surface tension thereof, thereby improving the atomization performance of the catalytic cracking raw material, reducing the diameter of fog drops, shortening the gasification time, increasing the diffusion speed of oil gas molecules on the catalyst and reducing the occurrence of condensation reaction and hydrogen transfer reaction; the high-valence antimony oxide or the mixture of high-valence antimony and cerium can improve the property of the equilibrium catalyst, convert Lewis acid (L acid) generated by alumina continuously removed from a molecular sieve framework into Bronsted acid (B acid), inhibit the generation of catalytic coke, and effectively passivate harmful heavy metals (nickel, vanadium, iron, sodium and the like).
The invention has the advantages of high decomposition temperature, stable low-temperature performance, good dispersion performance in raw oil and the like, and has high effective metal content (the content is more than 15 percent), effectively reduces the ratio of hydrogen to methane in dry gas and increases the total liquid yield under the condition of keeping the raw oil unchanged.
Through the industrial test of a heavy oil catalytic cracking device (MIP-CGP process) with the process of 100 ten thousand tons per year, the test result shows that the invention can ensure that the ratio of hydrogen to methane of the device is not increased under the conditions that the property of raw oil is deteriorated and the content of heavy metal is increased, and simultaneously, the yield of coke is not increased but is decreased by 0.2 percent, and the total liquid yield is increased by more than 0.5 percent. The invention is added into the raw material of the catalytic cracking device, can improve the heavy metal pollution resistance of the device, reduce the coke yield and improve the liquid yield of the device, and has simple operation, low auxiliary agent cost and obvious economic benefit of the device.
Detailed Description
The present invention will be further described with reference to the following examples.
In the following examples, carboxymethyl cellulose having a degree of substitution of 0.65 to 0.85 and a degree of polymerization of 200 to 1000 is used.
Example 1
Adding 1000kg of diethanolamine into a stainless steel reaction kettle, heating to 70-90 ℃ within 1 hour, stirring, sequentially adding 2300kg of hydrogen peroxide and 1000kg of antimony trioxide, preserving the temperature for 1-5 hours, cooling after the oxidation reaction is finished, adding 500kg of ethylene glycol and 100kg of carboxymethyl cellulose (2% aqueous solution), uniformly stirring, and filtering to remove impurities to obtain the water-soluble metal passivator A.
Example 2
Adding 1500kg of triethanolamine into a stainless steel reaction kettle, heating to 70-90 ℃ within 1 hour, stirring, sequentially adding 1600kg of hydrogen peroxide, 800kg of antimony trioxide, 100kg of cerium oxide, 100kg of lanthanum oxide and 300kg of 68% nitric acid, preserving heat for 1-5 hours, cooling after the oxidation reaction is finished, adding 500kg of glycerol and 100kg of carboxymethyl cellulose (2% aqueous solution), uniformly stirring, filtering and removing impurities to obtain the water-soluble metal passivator B.
Example 3
Adding 1000kg of diethanolamine and 900kg of triethanolamine into a stainless steel reaction kettle, heating to 70-90 ℃ within 1 hour, stirring, sequentially adding 1500kg of hydrogen peroxide and 1000kg of antimony trioxide, preserving heat for 1-5 hours, cooling after the oxidation reaction is finished, adding 300kg of ethylene glycol, 200kg of glycerol and 100kg of carboxymethyl cellulose (2% aqueous solution), uniformly stirring, filtering and removing impurities to obtain the water-soluble metal passivator C.
Example 4
Adding 1500kg of triethanolamine into a stainless steel reaction kettle, heating to 70-90 ℃ within 1 hour, stirring, sequentially adding 1700kg of hydrogen peroxide, 700kg of antimony trioxide, 200kg of cerium oxide, 100kg of bismuth oxide and 200kg of 68% nitric acid, preserving heat for 1-5 hours, cooling after the oxidation reaction is finished, adding 500kg of ethylene glycol and 100kg of carboxymethyl cellulose (2% aqueous solution), uniformly stirring, filtering and removing impurities to obtain the water-soluble metal passivator D.
Example 5
The device adopted in the test is a fixed fluid catalytic cracking test device purchased from petrochemical engineering scientific research institute of China petrochemical company Limited by certain catalyst Limited liability company, and carries out simulation evaluation on the water-soluble metal deactivator A, B, C, D, wherein the dosage of the metal deactivator is 60ppm of the raw oil quality. The experimental parameters and results are shown in tables 1-5.
As can be seen from tables 1-5, after 60ppm of the water-soluble metal deactivator was added to the catalytic feedstock, the hydrogen to methane ratio in the dry gas decreased by 24%, and the total liquid yield increased by about 1%.
TABLE 1 Main Properties of the raw oils
TABLE 2 equilibrium catalyst key Properties (catalyst type DOCO)
| Item | Properties of |
| Settling density: g/mL iron-containing: ppm vanadium containing: ppm nickel: ppm micro-activity index: is based on | 0.83350011601410058.7 |
TABLE 3 analysis of typical Performance parameters of test samples
TABLE 4 Material balance
| Test number | 0# | 1# | 2# | 3# | 4# |
| Test time | 2007.5.20 | 2007.5.27 | 2007.6.5 | 2007.6.10 | 2007.7.15 |
| Raw oil | Raw oil | Raw oil + A | Raw oil + B | Raw oil + C | Raw oil + D |
| Catalyst and process for preparing same | Balancing agent | Balancing agent | Balancing agent | Balancing agent | Balancing agent |
| Reaction temperature of | 505 | 505 | 505 | 505 | 505 |
| Ratio of agent to oil ( | 6 | 6 | 6 | 6 | 6 |
| Space velocity l/h | 15 | 15 | 15 | 15 | 15 |
| Material balance, m% | |||||
| Dry gas | 3.5 | 3.2 | 3.2 | 3.2 | 3.1 |
| Gasoline and diesel oil | 66.6 | 69.2 | 69.3 | 69.1 | 69.1 |
| Liquefied gas, gasoline and diesel oil | 85.2 | 87.3 | 87.2 | 87.3 | 87.3 |
| Heavy oil plus coke | 10.6 | 8.9 | 9.1 | 9.0 | 9.0 |
| Loss, m% | 0.7 | 0.6 | 0.5 | 0.5 | 0.6 |
| Total of | 100.00 | 100.00 | 100.00 | 100.00 | 100.00 |
TABLE 5 average dry gas composition before dehydration
| Test number | 0# | 1# | 2# | 3# | 4# |
| Test time | 2004.8.31 | 2004.9.1 | 2004.9.2 | 2004.9.4 | 2004.9.5 |
| Raw oil | Heavy catalytic raw oil | Raw oil + A | Raw oil + B | Raw oil + C | Raw oil + D |
| Catalyst and process for preparing same | Balancing agent | Balancing agent | Balancing agent | Balancing agent | Balancing agent |
| Reaction temperature of | 505 | 505 | 505 | 505 | 505 |
| Ratio of agent to oil | 6 | 6 | 6 | 6 | 6 |
| Space velocity l/h | 15 | 15 | 15 | 15 | 15 |
| Composition of dry gas, V% | |||||
| Methane | 25.4 | 29 | 27 | 28 | 27 |
| Hydrogen gas | 36.6 | 31 | 30 | 30.4 | 30 |
| Others | 38 | 40 | 43 | 41.6 | 43 |
| Hydrogen to methyl ratio | 1.44 | 1.06 | 1.11 | 1.09 | 1.11 |
Example 6
The water-soluble metal passivator B described in example 2 is used for industrial application experiments in 100 ten thousand tons/year heavy oil catalytic cracking in a certain refinery (the water-soluble metal passivator of a certain auxiliary company in China is used before the agent of the invention is added), the adding time is 3 months and 1 day to 3 months and 25 days, the total time is 25 days, and the adding amount is 60PPm/kg (raw material). Other major operating parameters of the apparatus and the feedstock properties remain unchanged during use. H in dry gas before and after dehydration by using the invention2/CH4The changes are shown in Table 6.
As can be seen from table 6: after the device uses the invention, the volume ratio of hydrogen to methane in the dry gas before dehydration is obviously reduced, and the consumption of fresh catalyst in the same period is slightly reduced, which shows that the agent has better effect in inhibiting the dehydrogenation of heavy metal.
Example 7
The water-soluble metal passivator C described in example 3 is subjected to an industrial application test in a heavy oil catalytic device (MIP-CGP process) of 280 ten thousand per year of a certain division of China petrochemical company, the slag doping ratio of the device reaches 75%, the heavy metal content in residual oil is high (the average value of Ni + V is as high as 13.7ppm), a water-soluble metal passivator of a certain auxiliary company in China is used before the agent is added, the process conditions before and after the agent is added are kept unchanged, 4.24-5.1 is a rapid addition period, the addition amount is 50ppm (for raw oil), 5.1 is an equilibrium addition period, and the addition amount is 30ppm (for raw oil). The change of the properties of the raw materials before and after adding the agent is shown in Table 7, the balance of the materials before and after adding the agent is shown in Table 8, and the change of each component in the dry gas before and after adding the agent is shown in Table 9. Wherein the data after dosing is measured as the equilibrium addition period.
As can be seen from table 7: before and after addition, the properties of the raw oil become heavier, the density is increased, the carbon residue is increased from 5.82 to 6.19, and the heavy metal content is increased.
As can be seen from table 8: under the condition that the raw oil is heavier, before and after the addition of the catalyst, the device shows from material balance that the yield of the slurry oil is obviously reduced, and the yield of light liquid is slightly increased, which shows that the cracking capability is increased due to the improvement of the activity of the catalyst, but the coke formation is obviously slightly increased due to the larger change of the catalytic raw material caused by the change of the variety of the crude oil.
Table 6: consumption of fresh catalyst before and after use and average value in dry gas before desorption
| Item | Before use (2 month 1 to 25 days) | After use (3 months, 1 to 25 days) |
| Catalyst consumption | 112 ton of | 111 ton of |
| Unit consumption of catalyst | 1.52kg/t of raw material | 1.43kg/t of raw material |
| Dry gas H before dehydration2 | 36.6 | 30.4 |
| Dry gas CH before dehydration4 | 25.4 | 28 |
| H2/CH4 | 1.44 | 1.08 |
Table 7: properties of the raw materials
Table 8: material balance
Table 9: change of each component in dry gas before dehydration
| Item | Before filling | After filling |
| H2 | 29.01 | 26.32 |
| CH4 | 20.33 | 21.58 |
| CO | 0.82 | 1.77 |
| C2H6 | 10.28 | 10.48 |
| C2H4 | 12.42 | 12.86 |
| CO2 | 3.84 | 4.27 |
| C3H8 | 0.26 | 0.27 |
| C3H6 | 1.29 | 1.33 |
| iC4H10 | 0.14 | 0.15 |
| nC4H10 | 0.03 | 0.02 |
| nC4H8 | 0.03 | 0.03 |
| iC4H8 | 0.05 | 0.04 |
| tC4H8 | 0.03 | 0.03 |
| cC4H8 | 0.02 | 0.02 |
| ≥C5 | 0.03 | 0.04 |
| H2S | 0.32 | 0.29 |
| N2 | 14.62 | 13.95 |
| ≥C6 | 0.01 | 0.01 |
| H/CH4 | 1.43 | 1.22 |
From examples 5-7 it can be seen that: the metal passivator has obvious passivation effect, can effectively reduce the hydrogen/methane value in the catalytic cracking dry gas, improves the total liquid yield of the device, is convenient to fill, and can improve the overall economic benefit of the catalytic cracking device.
Claims (7)
1. The preparation method of the catalytic cracking metal passivator is characterized by comprising the following raw materials in parts by weight: 20-40% of dispersing agent, 30-50% of oxidant, 15-30% of metal oxide, 10-30% of solvent and 2-5% of stabilizing agent, wherein the mass percentages are respectively, when the catalytic cracking metal passivator is prepared, the oxidant and the metal oxide are sequentially added into the dispersing agent, the temperature is raised to 50-90 ℃ within 2-4 hours, the temperature is kept for 1-5 hours, the solvent and the stabilizing agent are added after cooling, and impurities are filtered and removed to obtain the metal passivator;
wherein,
the dispersant is diethanolamine and/or triethanolamine;
the oxidant is hydrogen peroxide with the mass percent concentration of 30-50% and/or nitric acid with the mass percent concentration of 66-68%;
the metal oxide is one or a mixture of more than two of antimony trioxide, rare earth oxide and bismuth oxide in any proportion;
the solvent is one or a mixture of more than two of water or alcohol solvents in any proportion;
the stabilizer is one or a mixture of more than one of methylcellulose compound solutions in any ratio.
2. The method for preparing the catalytic cracking metal deactivator according to claim 1, wherein the raw materials are in the following ratio: 30-40% of dispersing agent, 40-50% of oxidant, 15-30% of metal oxide, 10-15% of solvent and 2-5% of stabilizing agent.
3. The preparation method of the catalytic cracking metal passivator of claim 1 or 2, wherein the oxidant is hydrogen peroxide with a mass percentage concentration of 30-50%.
4. The method for preparing a catalytic cracking metal deactivator according to claim 1 or 2, wherein the metal oxide is antimony trioxide and/or cerium oxide.
5. The method for preparing a catalytic cracking metal deactivator according to claim 1 or 2, wherein the solvent is ethylene glycol and/or glycerol.
6. The preparation method of the catalytic cracking metal deactivator according to claim 1 or 2, wherein the stabilizer is a carboxymethyl cellulose solution, the substitution degree of the carboxymethyl cellulose is 0.65 to 0.85, the polymerization degree is 200 to 1000, and the solution is an aqueous solution with the mass percent concentration of 2% to 5%.
7. The application of the catalytic cracking metal deactivator according to any one of claims 1 to 6, wherein the addition amount is 15 to 60ppm of the weight of the catalytic cracking raw oil.
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| CN102229813B (en) * | 2011-05-23 | 2013-07-17 | 陕西超能石化科技有限公司 | Multifunctional desulphurization auxiliary agent of distillate of FCC device and preparation method thereof |
| CN103055916B (en) * | 2011-10-21 | 2015-06-17 | 中国石油化工股份有限公司 | Preparation method of catalytic cracking catalyst |
| CN102660317B (en) * | 2012-05-24 | 2014-04-16 | 沧州信昌化工有限公司 | Auxiliary for increasing yield of light oil in oil catalytic cracking device, and preparation method of auxiliary |
| CN102974399A (en) * | 2012-12-11 | 2013-03-20 | 江苏汉光实业股份有限公司 | Preparation method of catalytic cracking metal deactivator |
| CN102974403A (en) * | 2012-12-11 | 2013-03-20 | 江苏汉光实业股份有限公司 | Catalytic-cracking metal passivator |
| CN103285937A (en) * | 2013-05-22 | 2013-09-11 | 吴江市德佐日用化学品有限公司 | Catalytic cracking metal passivator and preparation method thereof |
| CN104162455A (en) * | 2014-07-02 | 2014-11-26 | 宜兴汉光高新石化有限公司 | A water-soluble catalytic cracking multifunctional deactivator and a preparing method thereof |
| CN106475155B (en) * | 2015-08-28 | 2019-09-20 | 江苏科创石化有限公司 | A kind of matal deactivator and preparation method thereof |
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