CN100564489C - A kind of petroleum hydrocarbon catalytic pyrolysis catalyst and application thereof - Google Patents
A kind of petroleum hydrocarbon catalytic pyrolysis catalyst and application thereof Download PDFInfo
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- CN100564489C CN100564489C CNB200510114548XA CN200510114548A CN100564489C CN 100564489 C CN100564489 C CN 100564489C CN B200510114548X A CNB200510114548X A CN B200510114548XA CN 200510114548 A CN200510114548 A CN 200510114548A CN 100564489 C CN100564489 C CN 100564489C
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Abstract
The invention provides a kind of petroleum hydrocarbon catalytic pyrolysis catalyst and application thereof.Concrete, petroleum hydrocarbon catalytic pyrolysis catalyst of the present invention comprises following component: (1) rare earth element, weight content 0.1～25%; (2) phosphorus or boron, weight content 0.1～10%; (3) basic metal, alkaline-earth metal and transition metal, 0.1～15% of weight content; (4) all the other are carrier ZSM-5, ZRP.This catalyzer is used for heavy hydrocarbons such as cracking naphtha, diesel oil and decompression diesel oil and produces low-carbon alkene, gas space velocity 1～25hr
-1, can improve ethene, propylene, butylene and divinyl yield more than 5%.
Description
Technical field
The present invention relates to petroleum hydrocarbon catalytic pyrolysis and produce the catalyzer and the application thereof of olefine in low carbon number, more particularly, the present invention relates to catalyzer and application thereof that petroleum hydrocarbon catalytic pyrolysis is produced ethene and propylene.
Background technology
Ethene, propylene are basic raw materials important in the petrochemical complex, are the bases that produces various important organic chemical industry's products.Tube furnace steam heat cracking system alkene is still the main method that petroleum chemical industry is produced low-carbon alkene at present, but when obtaining higher ethene and propene yield by this method, temperature of reaction will arrive more than 800 ℃, owing to be subjected to the restriction of factors such as energy consumption, high temperature resistant tubing, the possibility of yield that further improves the ethene of tube furnace steam heat cracking process and propylene is very little.And adopt the method for heterogeneous catalyst producing olefin hydrocarbon by catalytic pyrolysis, can under lower temperature, improve the yield of cracking process ethene and propylene.
Patent JP06-346062 has proposed a kind of intermediate pore size Si-Al zeolite catalyzer, its SiO
2/ Al
2O
3Mol ratio is between 50～300, and used zeolite is ZSM-5 or ZSM-11, and cracking temperature is at 680 ℃, and raw material is a petroleum naphtha etc.Patent JP-06-346063 has also reported a kind of intermediate pore size Si-Al zeolite catalyzer of alkaline including earth metal, and the shortcoming of these two kinds of technology is mainly to generate aromatics, and the yield of ethene and propylene is on the low side.
Patent US4579997, US4621163, EP0211340 disclose the method that the hydrocarbon compound of C3, C4 is converted into low-carbon alkene.This catalyzer is the mixed oxide by magnesium and manganese; The ethene that its cracking generates, the yield of propylene is on the low side.
Patent JP99-180902 has developed a kind of method that suppresses aromatic hydrocarbons, produces ethene and propylene.Used catalyzer is a main component with the zeolite that contains rare earth element, and zeolite is based on the zeolite ZSM-5 or the ZSM-11 of supersiliceous zeolite type.Its SiO
2/ Al
2O
3Mol ratio between 25～800, best 100～300.This catalyzer contains 0.1～10% (weight) phosphorus, can also contain basic metal, alkaline-earth metal and transition metal, can make through the hydrocarbon behind the dehydrogenating technology and make light alkene by the cracking and catalyzing reaction, the lightweight hydrocarbon that its main hydrocarbon feed is ethane, propane, butane, crude oil or light oil, 600～700 ℃ of temperature of reaction can adopt fixed bed or fluidized-bed reactor.But the reactant gases air speed is little among all embodiment of this patent, and hydrocarbon feed is equivalent to react under very thin condition through nitrogen dilution, and industrial application value is little under this condition.
Nineteen ninety-five, basic industry office of MITI of Japan, Japan Chemical Industry Association are implemented petroleum naphtha catalytic pyrolysis technology as the part of " chemical process technology exploitation of new generation ".State-run material of Japan and chemical research institute connection and four tame petro-chemical corporations have participated in this research, the petroleum naphtha catalytic pyrolysis novel process of common Development and Production ethene, propylene.They have selected the petroleum naphtha catalytic pyrolysis catalyzer with premium properties, find that finally the 2%P-10%La/ZSM-5 catalyzer can obtain high olefin yields.650 ℃ of temperature of reaction, raw material is a light naphtha, steam/raw material ratio (weight) 0.64, and under the condition of material concentration 9.6% (volume) (using nitrogen dilution), the yield of ethene and propylene can reach 61%, has shown good crack characteristic.But this raw materials technology concentration is low, and the raw material treatment capacity of catalyzer is little, and industrial exploitativeness is little.
Summary of the invention
The purpose of this invention is to provide a kind of catalyzer that is different from above-mentioned production olefine in low carbon number and uses thereof.Use the rare earth class zeolite catalyst of the present invention's development to carry out the hydrocarbon catalytic cracking reaction, can the catalytic pyrolysis petroleum naphtha, heavy hydrocarbon such as diesel oil and decompression diesel oil, and raw material does not need nitrogen dilution, reactant gases air speed height, improved the treatment capacity of raw material and the yield of ethene, propylene, butylene and divinyl, good industrial application value and prospect have been arranged.
It is composed as follows that the present invention is used to produce the hydrocarbon pyrolysis catalyzer of low-carbon alkene:
(1) one or more rare earth element, content are 0.1～25% of catalyst weight; (2) phosphorus or boron, content are 0.1～10% of catalyst weight; (3) be selected from least a in basic metal, alkaline-earth metal and the transition metal, its content is 0.1～15% of catalyst weight; (4) all the other are carrier, and described carrier is a crystallinity silicic acid aluminium zeolite, preferred ZSM-5, ZRP zeolite.
Particularly, in the preferred technical solution of the present invention,
Component (4) support of the catalyst is a crystallinity silicic acid aluminium zeolite, preferred ZSM-5, and the ZRP zeolite, its silicon oxide and alumina molar ratio are 25～500, are preferably 90～300;
The content of component (1) rare earth element is preferably 5～15%;
The content of component (2) phosphorus or boron is preferably 1～5%;
The content of component (3) is preferably 1～10%.Component (3) is selected from one or more in basic metal, alkaline-earth metal and the rare earth metal transition metal in addition, and wherein basic metal comprises potassium, sodium, lithium; Alkaline-earth metal comprises magnesium, calcium, strontium, barium; Transition metal comprises manganese, vanadium, chromium, silver, zinc, copper, zirconium, palladium.
Content described in the catalyzer of the present invention is the weight content of metallic element.
The zeolite that described carrier ZSM-5, ZRP know for the public.
Catalyzer of the present invention can prepare by following two kinds of methods:
(1) can be with carrier and rare earth compound such as rare-earth oxide, nitrate etc., the oxide compound of boron and be selected from the compound of at least a metallic element of transition metal beyond the basic metal, alkaline-earth metal, rare earth metal, the pressed powder of acidic cpds such as oxide compound, nitrate, metavanadate or dihydrogen phosphate as them mixes, add tackiness agent commonly used, as starch, fully mediate, extruded moulding, dry under 100～140 ℃ of conditions, 600～900 ℃ of following roastings 3～5 hours, obtain final catalyst at last.
(2) can be with carrier and rare earth compound, as its oxide compound, nitrate etc., with the compound that is selected from least a metallic element in basic metal, alkaline-earth metal, the rare earth metal transition metal in addition, as their acidic cpds such as oxide compound, nitrate, metavanadate or dihydrogen phosphate, be placed on fully stirring in water or the acidic medium, dry, moulding.
The present invention also provides a kind of method of producing ethene and propylene, adopts catalyzer of the present invention recited above, and its processing condition are as follows:
(1) heavier hydrocarbon feeds weight ratios such as water and petroleum naphtha, diesel oil and decompression diesel oil are preferably in 0.4～1.5% 0.1～2%;
(2) the reactant gases air speed is 1～25hr
-1
(3) temperature of reaction is preferably in 550～800 ℃ at 500～850 ℃.
(4) reaction pressure can be normal pressure, decompression or pressurization, preferably pressurization.
Reactor can be fixed-bed reactor, also can be fluidized-bed reactor.Hydrocarbon raw material comprises petroleum naphtha, diesel oil, decompression diesel oil, also can be used for the shortening of ethane, propane, butane, lighter hydrocarbons.
Levels of transition metals beyond basic metal, alkaline-earth metal and the rare earth metal during the present invention forms catalyzer limits.Because by discovering, have two kinds of acid sitess on acid molecular sieve catalyst, a kind of is the protonic acid center, i.e. the B acid site; Another kind of aprotic acid center, i.e. L acid site.The scission reaction of petroleum hydrocarbon on acidic molecular sieve undertaken by the carbonium ion reaction mechanism, and in the gas alkene that the carbonium ion reaction generates, the content of propylene and butylene is higher, the petroleum hydrocarbon that is adsorbed on the catalyzer can be intensified in the L acid site, the homolysis of aggravation hydro carbons C-C chain is quickened the formation and the splitting of chain of β position of free radical.Ethene and methane are more in the product that free radical reaction generates.Therefore, if select the acid molecular sieve catalyst in more L acid site, can also generate relatively large propylene simultaneously by voluminous ethene.Add basic metal, alkaline-earth metal and transition metal in the molecular sieve catalyst of supported rare earth element, can increase L acid/B acid, the increase of L acid can generate relatively large propylene in voluminous ethene.If the addition of basic metal, alkaline-earth metal and transition metal is too much, can obviously reduce the B acid amount of molecular sieve catalyst, influence activity of such catalysts, reduce the yield sum of ethene and propylene.
The rare earth class zeolite catalyst that hydrocarbon raw material of the present invention is developed by the present invention carries out the hydrocarbon catalytic cracking reaction, can the catalytic pyrolysis petroleum naphtha, heavy hydrocarbon such as diesel oil and decompression diesel oil, and raw material does not need nitrogen dilution, reactant gases air speed height, the yield that has improved the treatment capacity of raw material and ethene, propylene, butylene and divinyl has good industrial application value and prospect more than 5%.
Embodiment
The following examples will be further specified the present invention, but therefore not limit the present invention.
The raw materials used ZRP of embodiment and Comparative Examples buys from economic technology trade center, Garden of Ten-Thousand Trees, Beijing.
In the following example, the reactor of evaluate catalysts is fixed-bed reactor, and reactor is diameter of phi 14mm, the stainless steel tube of long 500mm.Reaction pressure is a normal pressure.
Embodiment 1
With ZRP (SiO
2/ Al
2O
3Mol ratio 200), lanthanum acetate, sodium metavanadate, potassium primary phosphate mix, and adds the distilled water of 200ml again, fully stirs under 40 ℃ condition, and be dry under 120 ℃ of conditions, made catalyzer in 4 hours 800 ℃ of following roastings.In the catalyzer (weight content) lanthanum account for 4.64%, vanadium 4.66%, phosphorus 0.85%.
Using above-mentioned catalyzer, is raw material with the petroleum naphtha, and water and petroleum naphtha weight ratio are 0.592, weight space velocity 5.12hr
-1, during 750 ℃ of temperature of reaction, the product yield of catalytic pyrolysis (raw material relatively) sees Table 1:
The test-results of table 1 embodiment 1
Embodiment 2
With ZRP (SiO
2/ Al
2O
3Mol ratio 200), lanthanum trioxide, barium oxide, potassium primary phosphate mix, adding tackiness agent again is starch, fully stirs, and mediates, then extrusion.The catalyzer of moulding is dry under 120 ℃ of conditions, makes catalyzer in 4 hours 800 ℃ of following roastings.In the catalyzer (weight content) lanthanum account for 10.41%, barium 5.33%, phosphorus 0.70%.Under the processing condition identical with embodiment 1, use above-mentioned catalyzer to carry out catalytic cracking reaction, product yield (raw material relatively) sees Table 2:
The test-results of table 2 embodiment 2
Embodiment 3
With ZRP (SiO
2/ Al
2O
3Mol ratio 180), lanthanum trioxide, sodium metavanadate, boron oxide mix, adding tackiness agent again is starch, fully stirs, and mediates, then extrusion.The catalyzer of moulding is dry under 120 ℃ of conditions, makes catalyzer in 4 hours 800 ℃ of following roastings.In the catalyzer (weight content) lanthanum account for 10.1%, vanadium 2.47%, boron 1.84%.
Using above-mentioned catalyzer, is raw material with the petroleum naphtha, and under the processing condition identical with embodiment 1, the product yield of catalytic pyrolysis (raw material relatively) sees Table 3:
The test-results of table 3 embodiment 3
Comparative Examples 1
With ZRP (SiO
2/ Al
2O
3Mol ratio 180), lanthanum trioxide, potassium primary phosphate mix, adding tackiness agent again is starch, fully stirs, and mediates, then extrusion.The catalyzer of moulding is dry under 120 ℃ of conditions, makes catalyzer in 4 hours 800 ℃ of following roastings.In the catalyzer (weight content) lanthanum account for 10.1%, phosphorus 2.01%.
Using above-mentioned catalyzer, is raw material with the petroleum naphtha, and water and petroleum naphtha weight ratio are 0.512, weight space velocity 2.65hr
-1, during 750 ℃ of temperature of reaction, the product yield of catalytic pyrolysis (raw material relatively) sees Table 4:
The test-results of table 4 Comparative Examples 1
Comparative Examples 2
With ZRP molecular sieve (SiO
2/ Al
2O
3Mol ratio 180), lanthanum trioxide mixes, adding tackiness agent again is starch, fully stirs, and mediates, then extrusion.The catalyzer of moulding is dry under 120 ℃ of conditions, makes catalyzer in 4 hours 800 ℃ of following roastings.(weight content) lanthanum accounts for 11.4% in the catalyzer.
Using above-mentioned catalyzer, is raw material with the petroleum naphtha, and under the condition identical with embodiment 1, the product yield of catalytic pyrolysis (raw material relatively) sees Table 5:
The test-results of table 5 Comparative Examples 2
Result by embodiment 1～3 compares with the result of Comparative Examples 1～2, added the catalyzer of alkaline-earth metal such as barium, vanadium and transition metal as can be seen and compared with the catalyzer that has only added rare earth metal, the yield of catalytic cracking petroleum naphtha gained ethene and propylene all increases to some extent.
Claims (8)
1, a kind of catalyzer that is used for hydrocarbon cracking raw material production low-carbon alkene, hydrocarbon raw material is petroleum naphtha, diesel oil, decompression diesel oil, this catalyzer comprises component: (1) more than one rare earth element, content is 5～25% of catalyst weight; (2) phosphorus or boron, content are 0.1～10% of catalyst weight; (3) be selected from least a in the transition metal beyond basic metal, alkaline-earth metal and the rare earth metal, its content is 0.1～15% of catalyst weight; (4) carrier, described carrier are ZSM-5, ZRP zeolite.
2, according to the described catalyzer of claim 1, the content that it is characterized in that described component (1) is 5～15% of catalyst weight.
3, according to the described catalyzer of claim 1, the content that it is characterized in that described component (2) is 1～5% of catalyst weight.
4, according to the described catalyzer of claim 1, the content that it is characterized in that described component (3) is 1～10% of catalyst weight.
5,, it is characterized in that the mol ratio of silicon oxide and aluminum oxide is 25～500 in described component (4) carrier according to the described catalyzer of claim 1.
6,, it is characterized in that the mol ratio of silicon oxide and aluminum oxide is 90～300 in described component (4) carrier according to the described catalyzer of claim 5.
7, the described catalyzer of one of claim 1-6 is used for the method for catalytic pyrolysis hydro carbons raw material production ethene and propylene, and hydrocarbon raw material is petroleum naphtha, diesel oil, decompression diesel oil, reacts in fixed-bed reactor or fluidized-bed reactor, and processing condition are as follows:
(1) water and hydrocarbon raw material weight ratio are 0.1～2%;
(2) the reactant gases air speed is 1～25hr
-1
(3) temperature of reaction is 500～850 ℃.
8,, it is characterized in that water and hydrocarbon raw material weight ratio are 0.4～1.5% in the described processing condition according to the method for the described catalytic pyrolysis hydro carbons of claim 7 raw material production ethene and propylene; Temperature of reaction is 550～800 ℃.
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| CN101314718B (en) * | 2007-05-31 | 2013-03-27 | 中国石油化工股份有限公司 | Method for improving productivity of low carbon olefin hydrocarbon in biological oil and fat catalytic conversion reaction |
| CN101314717B (en) * | 2007-05-31 | 2012-05-30 | 中国石油化工股份有限公司 | Catalytic conversion method for biological oil and fat |
| CN101348407B (en) * | 2007-07-18 | 2010-12-22 | 中国石油化工股份有限公司 | Method for preparing ethylene and propylene by catalytic pyrolysis |
| CN101898143B (en) * | 2009-05-27 | 2012-08-29 | 中国石油化工股份有限公司 | Inferior heavy oil cracking and gasifying catalyst |
| CN101992082B (en) * | 2009-08-31 | 2012-10-10 | 中国石油化工股份有限公司 | Catalyst for toluene methanol side-chain alkylation reaction and preparation method thereof |
| CN102059139B (en) * | 2010-12-28 | 2013-02-20 | 洛阳市科创石化科技开发有限公司 | Catalyst used for preparing propylene and ethylene by cracking and preparation method thereof |
| CN102863308B (en) * | 2011-07-07 | 2014-05-28 | 中国石油化工股份有限公司 | Method for preparing olefin by catalyzing and cracking naphtha |
| CN109174076B (en) * | 2018-09-25 | 2021-06-08 | 蚌埠知博自动化技术开发有限公司 | Catalyst for catalytic cracking of butylene into propylene and preparation method thereof |
| CN111068752B (en) * | 2018-10-18 | 2021-03-12 | 中国石油化工股份有限公司 | MFI structure molecular sieve rich in mesopores and preparation method thereof |
| CN111068758B (en) * | 2018-10-18 | 2021-03-12 | 中国石油化工股份有限公司 | Mesoporous-rich phosphorus-and-rare earth-containing MFI structure molecular sieve and preparation method thereof |
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