CN101885980A - 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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- CN101885980A CN101885980A CN2010102363406A CN201010236340A CN101885980A CN 101885980 A CN101885980 A CN 101885980A CN 2010102363406 A CN2010102363406 A CN 2010102363406A CN 201010236340 A CN201010236340 A CN 201010236340A CN 101885980 A CN101885980 A CN 101885980A
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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 present invention relates to a kind of preparation method and application thereof of catalytic cracking metal passivant.
Background technology
Catalytic cracking unit has occupied dominant position in oil refining apparatus, raw material through after the heat exchange with catalyst cracker in catalyzer contact cracking, obtain dry gas, liquefied gas, gasoline, diesel oil, coke and slurry oil.Be subjected to the influence of oil supply and quality, metal element content in the crude oil increases day by day, each oil refinery company is pursued is high intermingled dregs ratio, lower coking yield and high lightweight oil or total liquid yield, to reach maximum economic benefits, also quickened the metallic element in the fcc raw material from another point of view and risen.Metallic element in the fcc raw material is very large for the harm of catalyzer, and particularly nickel is particularly serious to catalyzer harm, thereby can influence the distribution of catalytic cracking product.At home and abroad, have many about improving the method report that the catalytic cracking product distributes.
CN1245198A has reported the preparation method who contains antimony metal passivator, with weisspiessglanz, organic carboxyl acid, aliphatic amide and water, under 80～180 ℃, has synthesized water-soluble metal passivator in this method.Dominant mechanism is to add antimony containing compounds in raw material, and passivation nickel is to the influence of catalytic cracking catalyst.One is one or more mixtures of compounds such as water-soluble antimony, rare earth, tin metal passivator in the device of fluid catalytic cracking (hereinafter to be referred as FCC) at present, its shortcoming is easily to separate out under the low temperature, decomposition temperature is low, poorly soluble in stock oil, and dispersing property is bad.And one requires the effective metal antimony content more than 15% in the product.
CN10121A5476A has reported a kind of preparation method and industrial application of assistant for catalytic cracking coking-inhibiting yield-increasing, in 1～3 hour, be warmed up to 50～150 ℃ with oil-soluble dispersant, thermo-cracking promoting agent, radical chain reaction inhibitor, oil soluble metal passivator, varsol in this method, be incubated 1～5 hour, the cooled and filtered removal of impurity promptly gets the coking-inhibiting yield-increasing auxiliary agent.Major function improves intermingled dregs ratio, the raising yield of light oil of FCC apparatus and reduces coke yield, and can reduce the consumption of device metal passivator or stop annotating metal passivator, improves the overall efficiency of FCC apparatus.This product only can be at part catalytic cracking unit alternative metals passivator, and is invalid substantially for the heavy metal contamination of MIP-CGP (voluminous isoparaffin and propylene enhancing) technology catalytic cracking unit.
Summary of the invention
The invention provides a kind of preparation method of catalytic cracking metal passivant, the gained catalytic cracking metal passivant can improve the pollution capacity of the preventing from heavy metal nickel of catalytic cracking unit, reduces the green coke productive rate and improves yield of light oil.
The present invention also provides the application of the catalytic cracking metal passivant that above-mentioned preparation method obtains.
The preparation method of described catalytic cracking metal passivant is, proportioning raw materials is: dispersion agent 20%～45%, oxygenant 30%～50%, metal oxide 15%～30%, solvent 10%～30%, stablizer 2%～5%, described per-cent is mass percent, during the preparation catalytic cracking metal passivant, in dispersion agent, add oxygenant, metal oxide successively, in 2～4 hours, be warmed up to 50～90 ℃, be incubated 1～5 hour, cooling adds the solvent and the removal of impurity of stablizer after-filtration and promptly gets metal passivator;
Wherein,
Described dispersion agent is diethanolamine and/or trolamine, is preferably trolamine;
Described oxygenant is that mass percent concentration is that 30%～50% hydrogen peroxide and/or mass percent concentration are 66%～68% nitric acid, is preferably mass percent concentration and is 30%～50% hydrogen peroxide;
Described metal oxide is the mixture of one or more arbitrary proportions in antimonous oxide, rare earth oxide, the bismuth oxide compound, is preferably the mixture of antimonous oxide or antimonous oxide and rare earth oxide.Rare earth oxide is preferably cerium oxide and/or lanthanum trioxide.For metal oxide is the situation of mixture, and the preferred wherein mass percentage content of antimonous oxide is 70%～80%;
Described solvent is the mixture of one or more arbitrary proportions in water or the alcoholic solvent, the mixture of one or more arbitrary proportions in preferably water, ethylene glycol, the glycerol, more preferably ethylene glycol and/or glycerol;
Described stablizer is the mixture of one or more any ratios in the methylcellulose gum compounds solution, cmc soln more preferably, the substitution value of described carboxymethyl cellulose is 0.65～0.85, the polymerization degree is 200～1000, and described solution is that mass percent concentration is 2%～5% the aqueous solution.
As preferred version of the present invention, proportioning raw materials is: dispersion agent 30～40%, oxygenant 40～50%, metal oxide 15～30%, solvent 10～15%, stablizer 2%～5%, wherein, the consumption of metal oxide more preferably 19～21%, the consumption of solvent more preferably 10～12%, the consumption of stablizer more preferably 2%～3%.
Gained catalytic cracking metal passivant of the present invention directly joins in the catalytically cracked material, dispersed good in fcc raw material, when using above-mentioned catalytic cracking metal passivant, addition is 10～80ppm of catalytically cracked stock weight, be preferably 15～60ppm, most preferably be 20～30ppm.
After nickel compound in the stock oil decomposed in reactor, one formed nickel oxide, also had the nickel of 0 valency and+1 valency; Nickel is with+2 in revivifier, and+3 valency forms exist.The form of nickel mainly is nickel oxide, nickel aluminate or silicoaluminate nickel, nickel can be evenly dispersed on the catalyzer, has stronger dehydrogenation activity, therefore nickel poisoning causes the dehydrogenation activity of catalyzer to raise, coke, dry gas and hydrogen yield increase, light oil yield descends, but nickel is less to the activity of such catalysts influence.
According to the nickel inhibitor of nickel poisoning mechanism design, one is to adopt the compound of metallic elements such as antimony, bismuth and Sb-Ni or the Bi-Ni alloy that nickel forms larger particles, stops the dispersion of nickel, thereby reaches the active purpose that reduces nickel.
Synthetic metal passivator of the present invention contains the high price sb oxide, has the heat decomposition temperature height, hangs the high advantage of antimony rate, combines with nickel is preferential under the catalysis system condition, thereby it is lost dehydrogenation activity and good stability, is difficult for being reduced.By in fcc raw material, adding a small amount of gained metal passivator of the present invention, dispersion agent wherein can change the surface properties of stock oil, reduce its viscosity and surface tension, thereby improve the atomization of catalytically cracked material, reduce fogdrop diameter, shorten the gasification time, improve the velocity of diffusion of oil gas molecule on catalyzer, reduce the generation of condensation reaction and hydrogen transfer reactions; The mixture of high price sb oxide wherein or high price antimony and cerium can improve the character of equilibrium catalyst, the Lewis acid (L acid) that the aluminum oxide of constantly deviating from from framework of molecular sieve is generated is converted into Blang's acid (B acid), suppress catalysis Jiao's generation, effectively passivation harmful heavy metal (Ni-V-Fe, sodium etc.).
Advantage such as the present invention has the stable performance of decomposition temperature high and low temperature, dispersing property is good in stock oil, and effective metal content height (content one more than 15%), under the constant situation of stock oil, effectively reduce hydrogen and methane ratio in the dry gas, increase total liquid and receive.
Through 1,000,000 tons of/year technology heavy oil catalytically cracking equipments (MIP-CGP technology) industrial test, test-results shows that the present invention is under the situation of stock oil character variation and heavy metal content increase, hydrogen that can assurance device does not increase than with methane, the productive rate of coke does not rise simultaneously, descend 0.2% on the contrary, total liquid is received and is increased more than 0.5%.In the catalytic cracking unit raw material, add the present invention, can improve the preventing from heavy metal pollution ability of device, reduce coke yield and improve the liquid yield of device, simple to operate, the auxiliary agent cost is low, the remarkable in economical benefits of device.
Embodiment
Further specify content of the present invention below in conjunction with embodiment.
In following examples, the substitution value of used carboxymethyl cellulose is 0.65～0.85, and the polymerization degree is 200～1000.
Embodiment 1
Earlier diethanolamine 1000kg is joined in the stainless steel cauldron, in 1 hour, be warmed up to 70～90 ℃, stir, add hydrogen peroxide 2300kg, antimonous oxide 1000kg successively, be incubated 1～5 hour, after oxidizing reaction finished, cooling added that ethylene glycol 500kg, carboxymethyl cellulose (2% the aqueous solution) 100kg stir and filtering and impurity removing matter promptly gets water-soluble metal passivator A.
Embodiment 2
Earlier trolamine 1500kg is joined in the stainless steel cauldron, in 1 hour, be warmed up to 70～90 ℃, stir, add hydrogen peroxide 1600kg, antimonous oxide 800kg, cerium oxide 100kg, lanthanum trioxide 100kg, 68% nitric acid 300kg insulation 1～5 hour successively, after oxidizing reaction finishes, cooling adds glycerol 500kg, carboxymethyl cellulose (2% the aqueous solution) the 100kg filtering and impurity removing matter that stirs and promptly gets water-soluble metal passivator B.
Embodiment 3
Earlier diethanolamine 1000kg, trolamine 900kg are joined in the stainless steel cauldron, in 1 hour, be warmed up to 70～90 ℃, stir, add hydrogen peroxide 1500kg, antimonous oxide 1000kg successively, be incubated 1～5 hour, after oxidizing reaction finished, cooling added ethylene glycol 300kg, glycerol 200kg, carboxymethyl cellulose (2% the aqueous solution) the 100kg filtering and impurity removing matter that stirs and promptly gets water-soluble metal passivator C.
Embodiment 4
Earlier trolamine 1500kg is joined in the stainless steel cauldron, in 1 hour, be warmed up to 70～90 ℃, stir, add hydrogen peroxide 1700kg, antimonous oxide 700kg, cerium oxide 200kg, bismuth oxide 100kg successively, 68% nitric acid 200kg insulation 1～5 hour, after oxidizing reaction finished, cooling added ethylene glycol 500kg, carboxymethyl cellulose (2% the aqueous solution) the 100kg filtering and impurity removing matter that stirs and promptly gets water-soluble metal passivator D.
Embodiment 5
This test is the fixed fluidized bed FCC tests device that certain catalyzer limited liability company buys from China Petroleum ﹠ Chemical Corporation Research Institute of Petroleum at the device that adopts, water-soluble metal passivator A, B, C, D are carried out Simulation evaluation, and the consumption of metal passivator is the 60ppm of stock oil quality.Experiment parameter and result are shown in table 1-5.
After adding the water-soluble metal passivator of 60ppm as can be seen in fcc raw material by table 1-5, the hydrogen in the dry gas has descended 24% with the methane ratio, and total liquid yield increases about 1%.
Table 1, stock oil main character
Table 2, equilibrium catalyst main character (the catalyzer model is DOCO)
| Project | Character |
| Settled density: the g/mL iron content: ppm contains vanadium: ppm is nickeliferous: the little index alive of ppm: % | ??0.83??3500??1160??14100??58.7 |
The analysis of table 3 test sample typical case performance perameter
Table 4 material balance
| Test number | ??0 # | ??1 # | ??2 # | ??3 # | ??4 # |
| Test period | ??2007.5.20 | ??2007.5.27 | ??2007.6.5 | ??2007.6.10 | ??2007.7.15 |
| Stock oil | Stock oil | Stock oil+A | Stock oil+B | Stock oil+C | Stock oil+D |
| Catalyzer | Poiser | Poiser | Poiser | Poiser | Poiser |
| Temperature of reaction, ℃ | ??505 | ??505 | ??505 | ??505 | ??505 |
| Agent-oil ratio (?) | ??6 | ??6 | ??6 | ??6 | ??6 |
| Test number | ??0 # | ??1 # | ??2 # | ??3 # | ??4 # |
| Air speed, l/h | ??15 | ??15 | ??15 | ??15 | ??15 |
| Material balance, m% | |||||
| Dry gas | ??3.5 | ??3.2 | ??3.2 | ??3.2 | ??3.1 |
| Gasoline+diesel oil | ??66.6 | ??69.2 | ??69.3 | ??69.1 | ??69.1 |
| Liquefied gas+gasoline+diesel oil | ??85.2 | ??87.3 | ??87.2 | ??87.3 | ??87.3 |
| Heavy oil+coke | ??10.6 | ??8.9 | ??9.1 | ??9.0 | ??9.0 |
| Loss, m% | ??0.7 | ??0.6 | ??0.5 | ??0.5 | ??0.6 |
| Amount to | ??100.00 | ??100.00 | ??100.00 | ??100.00 | ??100.00 |
Table 5 takes off preceding dry gas component mean value
| Test number | ??0 # | ??1 # | ??2 # | ??3 # | ??4 # |
| Test period | ??2004.8.31 | ??2004.9.1 | ??2004.9.2 | ??2004.9.4 | ??2004.9.5 |
| Stock oil | Heavily urge stock oil | Stock oil+A | Stock oil+B | Stock oil+C | Stock oil+D |
| Catalyzer | Poiser | Poiser | Poiser | Poiser | Poiser |
| Temperature of reaction, ℃ | ??505 | ??505 | ??505 | ??505 | ??505 |
| Agent-oil ratio | ??6 | ??6 | ??6 | ??6 | ??6 |
| Air speed, l/h | ??15 | ??15 | ??15 | ??15 | ??15 |
| Dry gas is formed, V% | |||||
| Methane | ??25.4 | ??29 | ??27 | ??28 | ??27 |
| Hydrogen | ??36.6 | ??31 | ??30 | ??30.4 | ??30 |
| Other | ??38 | ??40 | ??43 | ??41.6 | ??43 |
| Hydrogen first ratio | ??1.44 | ??1.06 | ??1.11 | ??1.09 | ??1.11 |
Embodiment 6
Embodiment 2 described water-soluble metal passivator B carry out industrial application experiment (before the agent of the present invention of annotating at the water-soluble metal passivator with domestic certain auxiliary agent company) in 1,000,000 tons of/year heavy oil fluid catalytic cracking of certain refinery, joining day is that March 1 was to March 25, amount to 25 days, add-on is 60PPm/kg (raw material).Between the usage period, other main operating parameters and the feedstock property of device remain unchanged.Take off H in the preceding dry gas before and after using the present invention
2/ CH
4Changing conditions sees Table 6.
As can be seen from Table 6: after the device trial edition invention, before taking off in the dry gas volume ratio of hydrogen and methane occur significantly descending, and the same period live catalyst consumption slightly reduce, show that this agent effect aspect the dehydrogenation of inhibition heavy metal is better.
Embodiment 7
Embodiment 3 described water-soluble metal passivator C carry out industrial performance test at Sinopec branch office 2,800,000/year heavy-oil catalytic device (MIP-CGP technology), the intermingled dregs ratio of this device reaches 75%, heavy metal content height in the residual oil (Ni+V mean value is up to 13.7ppm), the agent of the present invention of annotating is preceding at the water-soluble metal passivator with domestic certain auxiliary agent company, processing condition remain unchanged before and after adding agent, 4.24～5.1 is the quick adding phase, add-on is 50ppm (to a stock oil), 5.1 begin to balance adds the phase, add-on is 30ppm (to a stock oil).Add the forward and backward feedstock property of agent and change and see Table 7, add the forward and backward material balance of agent and see Table 8, add that each change of component situation sees Table 9 in the forward and backward dry gas of agent.Wherein, the data that add after the agent are to record the balance adding phase.
As can be seen from Table 7: stock oil character becomes heavy before and after adding agent, and density increases, carbon residue is increased to 6.19 by 5.82, and heavy metal content increases.
As can be seen from Table 8: become under the situation about weighing at stock oil, add before and after the agent, device is found out from material balance, the slurry oil yield obviously descends, light liquid is received slightly and is risen, and the raising owing to catalyst activity is described, the cracking ability rises, but cause fcc raw material to change greatly because oil variety is changed, thereby cause green coke obviously slightly to rise.
Table 6: mean value in the dry gas before live catalyst consumes situation and takes off before and after using
| Project | Before using (on February 1 to 25) | Use back (on March 1 to 25) |
| Catalyst consumption | 112 tons | 111 tons |
| Catalyst consumption | 1.52kg/t raw material | 1.43kg/t raw material |
| Dry gas H before taking off 2 | ??36.6 | ??30.4 |
| Dry gas CH before taking off 4 | ??25.4 | ??28 |
| ??H 2/CH 4 | ??1.44 | ??1.08 |
Table 7: feedstock property
Table 8: material balance
Table 9: each change of component situation in the dry gas before taking off
| Project | Before the filling | After the filling |
| ??H 2 | ??29.01 | ??26.32 |
| ??CH 4 | ??20.33 | ??21.58 |
| ??CO | ??0.82 | ??1.77 |
| ??C 2H 6 | ??10.28 | ??10.48 |
| ??C 2H 4 | ??12.42 | ??12.86 |
| ??CO 2 | ??3.84 | ??4.27 |
| ??C 3H 8 | ??0.26 | ??0.27 |
| ??C 3H 6 | ??1.29 | ??1.33 |
| ??iC 4H 10 | ??0.14 | ??0.15 |
| ??nC 4H 10 | ??0.03 | ??0.02 |
| ??nC 4H 8 | ??0.03 | ??0.03 |
| ??iC 4H 8 | ??0.05 | ??0.04 |
| ??tC 4H 8 | ??0.03 | ??0.03 |
| ??cC 4H 8 | ??0.02 | ??0.02 |
| ??≥C 5 | ??0.03 | ??0.04 |
| ??H 2S | ??0.32 | ??0.29 |
| ??N 2 | ??14.62 | ??13.95 |
| ??≥C6 | ??0.01 | ??0.01 |
| ??H/CH4 | ??1.43 | ??1.22 |
From embodiment 5-7 as can be seen: metal passivator passivation effect of the present invention is remarkable, can reduce hydrogen/methane value in the catalytic cracked dry gas effectively, improves total liquid of device and receives, and filling is convenient, can improve the whole economic efficiency of catalytic cracking unit.
Claims (7)
1. the preparation method of a catalytic cracking metal passivant, it is characterized in that, proportioning raw materials is: dispersion agent 20%～40%, oxygenant 30%～50%, metal oxide 15%～30%, solvent 10%～30%, stablizer 2%～5%, described per-cent is mass percent, during the preparation catalytic cracking metal passivant, in dispersion agent, add oxygenant, metal oxide successively, in 2～4 hours, be warmed up to 50～90 ℃, be incubated 1～5 hour, the cooling back adds solvent and stablizer filtering and impurity removing matter promptly gets metal passivator;
Wherein,
Described dispersion agent is diethanolamine and/or trolamine;
Described oxygenant is that mass percent concentration is that 30%～50% hydrogen peroxide and/or mass percent concentration are 66%～68% nitric acid;
Described metal oxide is the mixture of one or more arbitrary proportions in antimonous oxide, rare earth oxide, the bismuth oxide compound;
Described solvent is the mixture of one or more arbitrary proportions in water or the alcoholic solvent;
Described stablizer is the mixture of one or more any ratios in the methylcellulose gum compounds solution.
2. the preparation method of catalytic cracking metal passivant as claimed in claim 1 is characterized in that, proportioning raw materials is: dispersion agent 30～40%, oxygenant 40～50%, metal oxide 15～30%, solvent 10～15%, stablizer 2%～5%.
3. the preparation method of catalytic cracking metal passivant as claimed in claim 1 or 2 is characterized in that, described oxygenant is that mass percent concentration is 30%～50% hydrogen peroxide.
4. the preparation method of catalytic cracking metal passivant as claimed in claim 1 or 2 is characterized in that, described metal oxide is antimonous oxide and/or cerium oxide.
5. the preparation method of catalytic cracking metal passivant as claimed in claim 1 or 2 is characterized in that, described solvent is ethylene glycol and/or glycerol.
6. the preparation method of catalytic cracking metal passivant as claimed in claim 1 or 2, it is characterized in that, described stablizer is a cmc soln, the substitution value of described carboxymethyl cellulose is 0.65～0.85, the polymerization degree is 200～1000, and described solution is that mass percent concentration is 2%～5% the aqueous solution.
7. the application of each described catalytic cracking metal passivant in the claim 1～6 is characterized in that addition is 15～60ppm of catalytically cracked stock weight.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102229813A (en) * | 2011-05-23 | 2011-11-02 | 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 |
| CN102660317A (en) * | 2012-05-24 | 2012-09-12 | 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 |
| CN102974403A (en) * | 2012-12-11 | 2013-03-20 | 江苏汉光实业股份有限公司 | Catalytic-cracking metal passivator |
| 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 |
| CN103055916A (en) * | 2011-10-21 | 2013-04-24 | 中国石油化工股份有限公司 | Preparation method of catalytic cracking catalyst |
| 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 |
| CN106475155A (en) * | 2015-08-28 | 2017-03-08 | 江苏科创石化有限公司 | A kind of matal deactivator and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102229813A (en) * | 2011-05-23 | 2011-11-02 | 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 |
| 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 |
| CN103055916A (en) * | 2011-10-21 | 2013-04-24 | 中国石油化工股份有限公司 | Preparation method of catalytic cracking catalyst |
| 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 |
| CN102660317A (en) * | 2012-05-24 | 2012-09-12 | 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 |
| 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 |
| CN102974403A (en) * | 2012-12-11 | 2013-03-20 | 江苏汉光实业股份有限公司 | Catalytic-cracking metal passivator |
| 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 |
| 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 |
| CN106475155A (en) * | 2015-08-28 | 2017-03-08 | 江苏科创石化有限公司 | A kind of matal deactivator and preparation 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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