CN100404484C - Method of preparing propylene by olefine containing gasoline catalytic cracking - Google Patents
Method of preparing propylene by olefine containing gasoline catalytic cracking Download PDFInfo
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Abstract
The present invention relates to a method for preparing propylene by using olefine-bearing gasoline through catalytic cracking reaction. Said method is characterized by that it makes the olefine-bearing gasoline be contacted and reacted with catalyst at 450-650deg.C in the presence of water vapour to make the olefine in the gasoline be cracked so as to obtain the propylene.
Description
Technical field
The present invention is a kind of method by olefine containing gasoline catalytic cracking system propylene, specifically, is the method that a kind of gasoline fraction that is produced by the crude oil secondary processing prepares propylene.
Background technology
Propylene is a kind of important Organic Chemicals, and the growth rate of demand has surpassed ethene its year in recent years.At present, the main method of industrial existing acquisition propylene has two classes, and a class is the steam heat cracking of petroleum naphtha in the blank pipe reactor, accounts for 66～70% of production of propylene; Second class is catalytic cracking and the catalytic pyrolysis of mink cell focus in fluidized-bed, accounts for 30～32% of production of propylene.
The steam heat cracking is to be raw material with the petroleum naphtha, and in the presence of water vapor, 750～850 ℃ of thermo-crackings generate the technology of light olefin.Main ethene, the propylene produced, propylene/ethylene about 0.65, is higher than this ratio than maximum limit, and the total olefin productive rate will descend.The high-quality feed naphtha that this process need consumption is a large amount of, market supply day is becoming tight, and is again the process of a high energy consumption simultaneously.Thereby the development of propylene produced restriction.
Fluid catalytic cracking (FCC) process is under 500～650 ℃, utilizes the mechanism of catalytic pyrolysis that the macromole hydrocarbon cracking in the stock oil is transformed into micromolecular hydrocarbon, obtains vapour, diesel oil distillate and alkene etc., as ethene, propylene and butylene.As raw material by the by-product propylene then of drastic cracking more.This process be in the refining of petroleum to the secondary processing of crude oil, handle raw material and be heavy product or even residual oil after the underpressure distillation, it mainly is the production of carrying out the oil fuel product.Producing propylene is the side reaction product, needs more degree of depth ground cracking stock, can reduce the production of oil fuel product.Catalytic pyrolysis is at 650～750 ℃, heavy petroleum hydrocarbon is contacted with the ZSM-5 zeolite catalyst that contains Ag or Cu modification, macromolecular heavy petroleum hydrocarbon is converted into small molecule hydrocarbon, reaches the purpose of voluminous ethene and propylene when obtaining vapour, diesel oil.
Existing other produced in the propylene technology, also has and passes through C
4 =, C
5 =Be cracked into CH
2Molecule, molecule is combined into C again in balanced reaction then
2 =, C
3 =, C
4 =(wherein, C
3 =Productive rate is higher) process produce.Its principal product is C
3 =, but the harsh just C of the raw material of this technical requirements
4 =, C
5 =Therefore also there is the problem of raw material supply in cut.In addition, CN1205154C is to be rich in C
4The hydrocarbon gas of cut and gasoline are raw material, contact propylene enhancing, ethene and butylene in the olefin(e) centent in reducing gasoline in fluidized-bed with the catalyzer that contains the five-ring supersiliceous zeolite in 500～650 ℃.
At present, along with the raising day by day of environmental requirement, require to reduce the content of alkene in the gasoline.As requiring the content of gasoline component alkene below 20 volume % in the world fuel oil standard II class gasoline standard.China on July 1st, 2002 requires that the content of alkene is lower than 35 volume % in the gasoline component in the gasoline standard that carry out in Beijing, Shanghai, three big cities, Guangzhou.Therefore, the FCC olefin content in gasoline is the main component of controlling in the clean fuel standards.
Summary of the invention
The purpose of this invention is to provide a kind of method by olefine containing gasoline catalytic cracking system propylene, this method can make the olefine selective cracking in the gasoline generate small-numerator olefin, thereby improves productivity of propylene.
Method by olefine containing gasoline catalytic cracking system propylene provided by the invention comprise with described olefine contained gasoline in the presence of water vapor with catalyzer 450～650 ℃ of contact reactss, make the olefin cracking in the gasoline generate propylene.
The inventive method makes the olefine selective in the content olefin gasolines be cracked into C by control reaction temperature
2～C
4Alkene, and make that wherein propone output is higher relatively, contain alkene gasoline production propylene thereby can utilize, for production of propylene provides a kind of new approach.Because described temperature of reaction is relatively low, also can suitably reduce the process energy consumption.
Embodiment
The inventive method makes the olefin cracking in the catalytically cracked gasoline become C in suitable temperature of reaction under the situation that has water vapor to exist
2～C
4Small-numerator olefin, and make productivity of propylene wherein higher relatively, thereby both can reduce olefin content in gasoline, can produce propylene again.
In the described method, alkene cracking in the presence of water vapor that gasoline contains, the mass ratio of water vapor and olefine contained gasoline preferred 0.2～3.0 during reaction.Reaction is preferably carried out in fixed bed, more preferably carries out in the ordered structure reactor.Described ordered structure reactor is a kind of novel fixed-bed reactor, is filling ordered structure catalyst and the fixed-bed reactor that form in fixed bed, has that bed pressure drop is little, the mass-and heat-transfer good effectiveness.Ordered structure catalyst is applied to purifying vehicle exhaust the earliest, is called for short cleaning catalyst for tail gases of automobiles, is that the slurry that will contain catalyst component is coated on the carrier with ordered structure, as has the catalyzer that forms on the cordierite carrier of honeycomb structure structure.
The inventive method is carried out in the presence of catalyzer, described catalyzer comprises the high-temperature inorganic oxide of 2～60 quality % and the modified ZSM-5 zeolite of 40～98 quality %, modifying element in the described modified ZSM-5 zeolite is selected from the combination of any one or two to three kinds of element in rare earth metal, IVB family metal, phosphorus, iron, zinc, tin and the vanadium, and modifying element content is 1～5 quality %.
Rare earth metal described in the catalyzer is selected from lanthanide series metal or yttrium, preferred titanium of IVB family metal or zirconium.The preferred aluminum oxide of described high-temperature inorganic oxide.
Catalyzer can be selected the used solid particle catalyst of general fixed bed, also can select ordered structure catalyst for use.
The preferred ordered structure catalyst of the present invention is the honeycomb-like cordierite that is coated with described catalyst coat, wherein trichroite content is 80～90 quality %, catalyst coat content is 10～20 quality %, described catalyst coat comprises the high-temperature inorganic oxide of 2～60 quality % and the modified ZSM-5 zeolite of 40～98 quality %, modifying element in the described modified ZSM-5 zeolite is selected from the combination of any one or two to three kinds of element in rare earth metal, IVB family metal, phosphorus, iron, zinc, tin and the vanadium, and modifying element content is counted 1～5 quality % with oxide compound.
The described olefine contained gasoline of the inventive method is a crude oil secondary processing product, and as catalytically cracked gasoline fraction, coker gasoline fraction etc., olefin(e) centent wherein is 30～55 quality %.
The ZSM-5 zeolite that Preparation of catalysts method of the present invention comprises preparation modification earlier mixes the ZSM-5 zeolite then with the precursor of aluminum oxide, moulding after drying, roasting promptly make catalyzer.
The preparation method of described ordered structure catalyst is as follows:
(1) with the soluble compound solution impregnation ZSM-5 zeolite that contains modifying element, dipping can adopt saturated or the supersaturation dipping, makes modified ZSM-5 after drying, the roasting.
(2) the ZSM-5 zeolite is made into the uniform sizing material that solid content is 30～50 quality %, again pseudo-boehmite is made into slurry, regulating the pH value is 2～6, stirs, and makes the slurry that alumina content is 10～25 quality %.Take out the part slurry, being adjusted to the pH value with diluted acid is 0.5～5.5, adds zeolite slurry and remaining pseudo-boehmite slurry, and the back that stirs adds the aluminium colloidal sol of 0.05～0.2 times of modified zeolite quality, obtains catalyst pulp after the stirring.
(3) with the catalyst pulp that makes of (2) step apply 100～400 holes/time
2The cordierite honeycomb carrier, dry roasting promptly obtains the catalyzer of ordered structure.
During described method (1) goes on foot, vitriol, muriate or the nitrate of the preferred rare earth metal of the soluble compound of modifying element, IVB family metal, phosphorus, iron, zinc, tin or vanadium.As modifying element is two or three o'clock, can be mixed with the steeping fluid that contains two or three modifying element, floods the ZSM-5 zeolite, makes required modified ZSM-5.
Institute's method (2) is in the step, and described diluted acid is selected from one or more in citric acid, hydrochloric acid, nitric acid and the phosphoric acid, and its concentration is 5～20 quality %.
Drying temperature described in the aforesaid method is 90～130 ℃, and maturing temperature is 350～500 ℃, and suitable roasting time is 0.5～3.0 hour.
Below by example in detail the present invention, but the present invention is not limited to this.
Example 1
The used catalyzer of preparation the present invention.
(1) preparation modified ZSM-5 zeolite.
Get 0.90 gram zinc chloride (chemical pure, Beijing sharp chemical of benefit company limited produces) be dissolved in 53 ml deionized water, heated and stirred is to dissolving fully, (the Shandong catalyst plant is produced to filter the saturated dipping 50 gram ZSM-5 zeolites in back, trade mark ZRP), 110 ℃ of dryings 3 hours, 500 ℃ of roastings 2 hours, obtain the ZSM-5 of zinc modification, wherein zinc oxide content is 1.0 quality %.
(2) preparation catalyst pulp
(the Shandong catalyst plant is produced, Al to add 235 gram pseudo-boehmites in 340 ml deionized water
2O
3Content is 32 quality %), 90 ℃ are stirred to evenly, make the slurries that solid content is 15.0 quality %.The ZSM-5 that gets the above-mentioned zinc modification of 50 grams is dissolved in 100 ml deionized water, makes the homogeneous slurry that solid content is 50 quality %.
Get 505 the gram above-mentioned pseudo-boehmite slurries half, to wherein adding an amount of 1: 1 hydrochloric acid, regulating slurry pH value is 2～3, stir the ZSM-5 slurries that add the zinc modification of above-mentioned preparation after 30 minutes, stirred 30 minutes, and added remaining half pseudo-boehmite slurries again, stirred 30 minutes, 0.1 times the aluminium colloidal sol (production of Shandong catalyst plant, the Al that add the modified ZSM-5 zeolite quality
2O
3Content is 22 quality %).60 ℃ are stirred an amount of decationizing water of adding after 40 minutes, obtain the catalyst pulp that solid content is 20 quality %.Wherein zinc modification ZSM-5 content is 40 quality % in the solids, Al
2O
3Content is 60 quality %.
(3) preparation ordered structure catalyst
Get (2) step catalyst pulp that makes 500 grams, apply 200 holes/time
2, φ 28 * 50 cordierite honeycomb carrier 16.5 gram, 120 ℃ of dryings 5 hours, 500 ℃ of roastings 2 hours obtain ordered structure catalyst A, its composition sees Table 1.
Example 2
Method by 1 (1) step of example prepares modified ZSM-5 zeolite, and different is to replace zinc chloride with 1.38 gram phosphoric acid, makes the ZSM-5 of phosphorus modification, wherein P
2O
5Content is 2.0 quality %.
Get the ZSM-5 of phosphorus modification, prepare ordered structure catalyst by example 1 (2), the method in (3) step, different is that used pseudo-boehmite slurries are 340 grams in (2) step, and phosphorous modified ZSM-5 content is 50 quality % in the gained catalyst pulp, Al
2O
3Content is 50 quality %, and the composition of the ordered structure catalyst B that finally obtains sees Table 1.
Example 3
Method by 1 (1) step of example prepares modified ZSM-5 zeolite, and different is to replace zinc chloride with 2.55 gram iron trichlorides, makes the ZSM-5 of iron modification, wherein Fe
2O
3Content is 2.5 quality %.
Get the ZSM-5 of iron modification, prepare ordered structure catalyst by example 1 (2), the method in (3) step, different is that used pseudo-boehmite slurries are 280 grams in (2) step, and iron modified ZSM-5 content is 55 quality % in the gained catalyst pulp, Al
2O
3Content is 45 quality %, and the composition of the ordered structure catalyst C that finally obtains sees Table 1.
Example 4
Method by 1 (1) step of example prepares modified ZSM-5 zeolite, and different is to replace zinc chloride with 3.92 gram zirconium oxychlorides, makes the ZSM-5 of modified zirconia, wherein ZrO
2Content is 3.0 quality %.
Get the ZSM-5 of modified zirconia, prepare ordered structure catalyst by example 1 (2), the method in (3) step, different is that used pseudo-boehmite slurries are 229 grams in (2) step, and iron modified ZSM-5 content is 60 quality % in the gained catalyst pulp, Al
2O
3Content is 40 quality %, and the composition of the ordered structure catalyst D that finally obtains sees Table 1.
Example 5
Method by 1 (1) step of example prepares modified ZSM-5 zeolite, and different is to replace zinc chloride with 3.03 gram anhydrous stannic chlorides, makes the ZSM-5 of tin modification, wherein SnO
2Content is 3.5 quality %.
Get the ZSM-5 of tin modification, prepare ordered structure catalyst by example 1 (2), the method in (3) step, different is that used pseudo-boehmite slurries are 186 grams in (2) step, and tin modification ZSM-5 content is 65 quality % in the gained catalyst pulp, Al
2O
3Content is 35 quality %, and the composition of the ordered structure catalyst E that finally obtains sees Table 1.
Example 6
Method by 1 (1) step of example prepares modified ZSM-5 zeolite, and different is to replace zinc chloride with 4.30 gram cerous chlorates, makes cerium modified ZSM-5, wherein CeO
2Content is 4.0 quality %.
Get cerium modified ZSM-5, prepare ordered structure catalyst by example 1 (2), the method in (3) step, different is that used pseudo-boehmite slurries are 149 grams in (2) step, and cerium modified ZSM-5 content is 70 quality % in the gained catalyst pulp, Al
2O
3Content is 30 quality %, and the composition of the ordered structure catalyst F that finally obtains sees Table 1.
Example 7
Method by 1 (1) step of example prepares modified ZSM-5 zeolite, and different is to replace zinc chloride with 4.88 gram Lanthanum trichlorides, makes the ZSM-5 of lanthanum modification, wherein La
2O
3Content is 4.5 quality %.
Get the ZSM-5 of lanthanum modification, prepare ordered structure catalyst by example 1 (2), the method in (3) step, different is that used pseudo-boehmite slurries are 87 grams in (2) step, and lanthanum modified ZSM-5 content is 80 quality % in the gained catalyst pulp, Al
2O
3Content is 20 quality %, and the composition of the ordered structure catalyst G that finally obtains sees Table 1.
Example 8
Method by 1 (1) step of example prepares modified ZSM-5 zeolite, and different is to replace zinc chloride with 3.2 gram ammonium meta-vanadates, makes the ZSM-5 of vanadium modification, wherein V
2O
5Content is 5.0 quality %.
Get the ZSM-5 of vanadium modification, prepare ordered structure catalyst by example 1 (2), the method in (3) step, different is that used pseudo-boehmite slurries are 39 grams in (2) step, and lanthanum modified ZSM-5 content is 90 quality % in the gained catalyst pulp, Al
2O
3Content is 10 quality %, and the composition of the ordered structure catalyst H that finally obtains sees Table 1.
Example 9
Method by 1 (1) step of example prepares modified ZSM-5 zeolite, and different is to replace zinc chloride with 2.55 gram Cerium monophosphates, makes the ZSM-5 of cerium and phosphorus modification, wherein P
2O
5Content be 1.5 quality %, CeO
2Content be 3.5 quality %.
Get the ZSM-5 of cerium and phosphorus modification, prepare ordered structure catalyst by example 1 (2), the method in (3) step, different is that used pseudo-boehmite slurries are 88 grams in (2) step, and the ZSM-5 content of cerium and phosphorus modification is 80 quality % in the gained catalyst pulp, Al
2O
3Content is 20 quality %, and the composition of the ordered structure catalyst I that finally obtains sees Table 1.
Example 10
Method by 1 (1) step of example prepares modified ZSM-5 zeolite, different is to be mixed with solution impregnation ZSM-5 with 2.19 gram Lanthanum trichlorides, 1.53 gram tin chlorides and 1.10 gram zinc chloride and 53 ml deionized water, make the ZSM-5 of lanthanum, zinc and tin modification, wherein the content of ZnO is 1.25 quality %, SnO
2Content be 1.25 quality %, La
2O
3Content be 2.50 quality %.
Get the ZSM-5 of lanthanum, zinc and tin modification, prepare ordered structure catalyst by example 1 (2), the method in (3) step, different is that used pseudo-boehmite slurries are 62 grams in (2) step, and the ZSM-5 content of lanthanum, zinc and tin modification is 85 quality % in the gained catalyst pulp, Al
2O
3Content is 15 quality %, and the composition of the ordered structure catalyst J that finally obtains sees Table 1.
Example 11
Method by 1 (1) step of example prepares modified ZSM-5 zeolite, and different is to be mixed with solution impregnation ZSM-5 with 3.62 gram alum acid ceriums, 2.62 gram iron(ic) chloride and 53 ml deionized water, makes the ZSM-5 of cerium, iron and vanadium modification, wherein V
2O
5Content be 1.29 quality %, Fe
2O
3Content be 1.29 quality %, CeO
2Content be 2.44 quality %.
Get the ZSM-5 of cerium, iron and vanadium modification, prepare ordered structure catalyst by example 1 (2), the method in (3) step, different is that used pseudo-boehmite slurries are 39 grams in (2) step, and the ZSM-5 content of lanthanum, zinc and tin modification is 90 quality % in the gained catalyst pulp, Al
2O
3Content is 10 quality %, and the composition of the ordered structure catalyst K that finally obtains sees Table 1.
Example 12
Get the ZSM-5 of the lanthanum modification of 55 gram examples, 7 preparations, be mixed, add 75 milliliters of decationizing water and 3 milliliters of mixed pinching evenly of concentrated nitric acids with 45 gram pseudo-boehmites, extruded moulding then, 120 ℃ of dryings 6 hours, 500 ℃ of roastings 2 hours, make catalyzer L, its composition sees Table 1.
Example 13～21
Following example prepares propylene with the inventive method.
Filling 19 gram ordered structure catalysts or the non-ordered structure catalyst of 25 grams in 35 milliliters of fixed-bed reactor, the FCC gasoline that will contain alkene 31.2 quality %, in 250 ℃ of preheating injecting reactors, inject the water vapor of 250 ℃ of preheatings simultaneously, keeping FCC gasoline implantation quality air speed is 21.3 hours
-1, water/oily charging mass ratio is 0.46.Under 480 ℃, normal pressure, with catalyst for cracking contact reacts of the present invention, each example catalyst system therefor and reaction result see Table 2.C in the table 2
2 =～C
4 =Selectivity is meant C in the gas-phase product
2 =+ C
3 =+ C
4 =The mass percent of the shared gas-phase product of sum.
By table 2 data as can be known, yield of gasoline is higher in the liquid product that the inventive method obtains, and olefin(e) centent decline, and octane value still keeps high value.Productivity of propylene is far beyond the ethylene yield height in the gas-phase product.
Example 22
Press method loading catalyst I in fixed-bed reactor of example 13, will contain the FCC gasoline of alkene 37.9 quality %, in 250 ℃ of preheating injecting reactors, inject the water vapor of 250 ℃ of preheatings simultaneously, keeping stock oil implantation quality air speed is 36.5 hours
-1, water/oily charging mass ratio is 0.96.React under 530 ℃, normal pressure, the results are shown in Table 2.
Example 23
Press method loading catalyst J in fixed-bed reactor of example 13, will contain the FCC gasoline of alkene 43.6 quality %, in 250 ℃ of preheating injecting reactors, inject the water vapor of 250 ℃ of preheatings simultaneously, keeping stock oil implantation quality air speed is 56.2 hours
-1, water/oily charging mass ratio is 1.61.React under 590 ℃, normal pressure, the results are shown in Table 2.
Example 24
Press method loading catalyst K in fixed-bed reactor of example 13, will contain the FCC gasoline of alkene 51.9 quality %, in 250 ℃ of preheating injecting reactors, inject the water vapor of 250 ℃ of preheatings simultaneously, keeping stock oil implantation quality air speed is 88.3 hours
-1, water/oily charging mass ratio is 2.53.React under 620 ℃, normal pressure, the results are shown in Table 2.
Table 1
Table 2
Claims (6)
1. method by olefine containing gasoline catalytic cracking system propylene, comprise with described olefine contained gasoline in the presence of water vapor with catalyzer 450～650 ℃ of contact reactss, make the olefin cracking in the gasoline generate propylene, described catalyzer comprises the aluminum oxide of 2～60 quality % and the modified ZSM-5 zeolite of 40～98 quality %, modifying element in the described modified ZSM-5 zeolite is selected from the combination of any one or two to three kinds of element in rare earth metal, IVB family metal, phosphorus, iron, zinc, tin and the vanadium, and modifying element content is counted 1～5 quality % with oxide compound.
2. in accordance with the method for claim 1, the mass ratio that it is characterized in that described water vapor and olefine contained gasoline is 0.2～3.0.
3. in accordance with the method for claim 1, it is characterized in that described rare earth metal is selected from lanthanide series metal or yttrium, IVB family metal is selected from titanium or zirconium.
4. method by olefine containing gasoline catalytic cracking system propylene, comprise with described olefine contained gasoline in the presence of water vapor with catalyzer 450～650 ℃ of contact reactss, make the olefin cracking in the gasoline generate propylene, described catalyzer is an ordered structure catalyst, described ordered structure catalyst is the honeycomb-like cordierite that is coated with catalyst coat, wherein trichroite content is 80～90 quality %, catalyst coat content is 10～20 quality %, described catalyst coat comprises the aluminum oxide of 2～60 quality % and the modified ZSM-5 zeolite of 40～98 quality %, modifying element in the described modified ZSM-5 zeolite is selected from rare earth metal, IVB family metal, phosphorus, iron, zinc, the combination of any one or two to three kinds of element in tin and the vanadium, modifying element content is 1～5 quality %.
5. according to claim 1 or 4 described methods, it is characterized in that olefin(e) centent is 30～55 quality % in the described olefine contained gasoline.
6. according to claim 1 or 4 described methods, it is characterized in that described being reflected in the fixed bed carry out.
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| CN102451738B (en) * | 2010-10-22 | 2014-05-28 | 中国石油化工股份有限公司 | Regular structure catalyst for preparation of propylene by steam cracking, and application thereof |
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| CN1903808A (en) | 2007-01-31 |
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