CN100457857C - Method for producing olefin through catalytic cracking - Google Patents
Method for producing olefin through catalytic cracking Download PDFInfo
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- CN100457857C CN100457857C CNB2005101174355A CN200510117435A CN100457857C CN 100457857 C CN100457857 C CN 100457857C CN B2005101174355 A CNB2005101174355 A CN B2005101174355A CN 200510117435 A CN200510117435 A CN 200510117435A CN 100457857 C CN100457857 C CN 100457857C
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Abstract
This invention relates to a method for producing low-carbon olefins by catalytic cracking. The method comprises: performing catalytic cracking on raw materials containing naphtha, lightweight diesel oil and hydrogenation tail oil in two series catalyst bed layers filled with different catalysts to obtain low-carbon olefins. The method has such advantages as high conversion rate of raw materials, high reaction selectivity, high yield of ethylene and propylene, convenient operation of catalysts, and convenient maintenance of equipments. Preferentially, the method adopts two series fixed-bed reactors with two different catalyst beds, or one fixed-bed reactor with two different series catalyst beds. The method has such advantages as increased conversion rate of raw materials, improved reaction selectivity, increased yields of products (ethylene and propylene), convenient loading/deloading of catalysts, and convenient maintenance of equipment.
Description
Technical field
The present invention relates to a kind of catalytic cracking to prepare lower carbon and count the method for alkene.
Background technology
Olefine in low carbon number, particularly ethene and propylene are basic raw materials important in the petrochemical complex, are the bases that produces various important organic chemical industry's products.Set out by them, can synthesize macromolecular materials such as multiple plastics, rubber and fiber, also can produce other Chemicals by processes such as alkylations.So the ethene of a country, propone output and technology are to weigh the important symbol of this state's petrochemical complex developmental level.The method of producing olefine in low carbon number mainly contains methods such as steam heat cracking, catalytic cracking.Steam cracking method is mainly adopted in therein ethylene production, and its output surpasses 99% of ethene ultimate production.
Because the output of ethene and propylene is very big, small raising on the yield, and small saving all will bring considerable economic on the raw material and the energy.At present, steam cracking technology becomes better and approaching perfection day by day, and is the process of the mass consumption energy, is used the limitation of high temperature resistant tubing again, and in fact further improved potentiality very little.In order to improve the selectivity of cracking process alkene, reduce the temperature of scission reaction, further increase the yield of ethene, propylene, improve the diversity of raw material, developed multiple new ethylene production technology, as: catalytic pyrolysis preparing ethylene technology, methane oxidation coupling technology, oxidative dehydrogenation of ethane technology, natural gas via methyl alcohol or diether system alkene technology etc.Wherein the producing olefin hydrocarbon by catalytic pyrolysis technology is compared with the steam heat cracking, has and can reduce cracking temperature, improves ethene and the yield of propylene and the selectivity of scission reaction, saves the advantage of energy, thereby becomes the technology of very attractive.
Catalystic pyrolysis generally includes only a reactor and a kind of catalyzer of utilization.As the method for the fluidized-bed that adopts among the patent CN 1060755 be with petroleum hydrocarbon in reactor after the preheating, in the presence of high-temperature water vapor, contact the back catalytic cracking reaction takes place with the catalyzer of heat, reaction product, water vapor and band Jiao's reclaimable catalyst is drawn from reactor after quick gas solid separation, the product logistics is removed chilling and is isolated ethene, propylene and other products, and reclaimable catalyst Returning reactor after regenerating recycles.The method of using among the JP97-363675 is to use the reactor of forms such as fixed bed, fluidized-bed, and on reactor is filled catalyzer.Ratio between reactant and the thinner is 0.1-1wt%, and temperature of reaction is 350 ℃-780 ℃.Though aforesaid method has improved olefine in low carbon number, particularly the yield of ethene, propylene does not further utilize the product behind the catalytic cracking reaction.Patent US6,033,555 provides a kind of novel technology, and this technology is at first hydro carbons to be passed through catalytic pyrolysis, and then the product of catalytic pyrolysis is carried out thermo-cracking, thus voluminous ethene.In patent EP0262049, raw material carries out the steam heat cracking earlier, and product enters the fixed bed that catalyzer is housed again and carries out catalytic cracking reaction then, thereby improves the yield of olefine in low carbon number, particularly ethene, propylene.Patent WO 98/56740 carries out thermo-cracking with stock oil earlier, with the product cooling, contacts with catalyzer then again, carries out catalytic cracking reaction, produces light olefin.These patented technologies all are thermo-crackings and the combining of catalytic pyrolysis, but the wherein related relative catalytic pyrolysis of thermo-cracking step, the one, the temperature of reaction height; The 2nd, can not regulate the distribution of product.The present invention is the combination of two kinds of catalytic pyrolysis technology, promptly can increase the yield of ethene and propylene, can reduce temperature of reaction again, conservation and energy consumption.
Summary of the invention
The purpose of this invention is to provide a kind of catalytic pyrolysis and produce the method for alkene, can more effectively improve the yield and the utilization ratio of raw materials of ethene and propylene.
Concrete, catalytic pyrolysis of the present invention is produced the method for alkene, is to comprise the petroleum hydrocarbon cracking stock of petroleum naphtha, solar oil and hydrogenation tail oil, by the beds of placed in-line two filling different catalysts a and b up and down, carry out catalytic cracking reaction, obtain olefine in low carbon number.Described olefine in low carbon number is ethene, propylene etc.
Preferred described catalyzer a is a petroleum hydrocarbon catalytic pyrolysis catalyst; Described catalyzer b is carbon four, carbon pentaene hydrocarbon catalytic cracking catalyst.Described petroleum hydrocarbon catalytic pyrolysis catalyst can be selected from disclosed technology preparation such as CN1480255, SU910728, SU910729, SU968055, SU1011236 or use, and described carbon pentaene hydrocarbon catalytic cracking catalyst can be selected from disclosed technology preparation such as CN 1304440A, CN 1274342A, CN 1284109A, CN 1189433C or use.
More preferably, described catalyzer a obtains by the method for following solid mixture moulding and co-precipitation or dipping: by weight percentage, aluminum oxide is 10-70%, magnesium oxide is 5-30%, vanadic acid sodium is 5-30%, lime carbonate is 2-30%, and rare-earth oxide is 1-15%, and kaliophylite or potassium felspar sand are 10-20%; Described catalyzer b comprises following composition: with the total restatement of catalyzer, Al
2O
3Or SiO
2Be 20-45%, supersiliceous zeolite is 40-70%, and modified component is 8-20%.
In an optimal technical scheme double-reactor dual catalyst bed technology of the present invention, described catalyzer a is seated among the fixed-bed reactor A, and catalyzer b is seated among the fixed-bed reactor B; Described two reactor A and B connect up and down.Concrete, two fixed-bed reactor A and B are connected up and down, connect a valve in the middle of the two reactor, an end of valve is connected with the outlet of reactor A, and the other end is connected with the inlet of reactor B; Two reactors respectively load a kind of catalyzer, compare with existing single reactor list catalyst bed layer process, the running route of material does not change, reactant and thinner are through after the preheating, under the certain reaction condition, the reactor A of successively flowing through and B are after contacting with b with two kinds of catalyzer a and reacting, product separates obtaining ethene, propylene through over-quenching, condensation.
Wherein, the reaction conditions of preferred described reactor A is: temperature of reaction 650-850 ℃, the weight ratio of thinner and reactant is 0.5-2.0, residence time 0.05-2S, reaction pressure 0-0.5MPa; The temperature of reaction of described reactor B is 350-700 ℃.
In another optimal technical scheme single reactor dual catalyst bed technology of the present invention, catalyzer a that described filling is different and the beds of b are in fixed-bed reactor, and the beds of loading catalyst a is at the epimere of reactor.
Concrete, two layers of different catalyzer about the filling in same fixed-bed reactor.During catalyst loading, load lower section catalyst b earlier, loaded epimere catalyzer a again; Preferably one section inert filler of filling between described two beds as porcelain ring, Stainless Steel Helices and quartz sand etc., connects two beds with inert filler; Be blank pipe between two beds perhaps, do not load any material, place a catalyzer screen to hold catalyzer a in the beds lower end of loading catalyst a.Inert filler and blank pipe can play the effect that reduces stream temperature, make the material of the beds that enters loading catalyst b reach the ideal temperature of reaction.
Preferred technical scheme is that reactant and thinner are entered into reactor together, and reactant of the present invention can also be selected from light naphtha, solar oil, hydrogenation tail oil etc.; Thinner can be selected from water, nitrogen, helium or hydrogen.
Compare with single reactor list catalyst process, the running route of material does not change, and reactant and thinner are through after the preheating, under the certain reaction condition, after successively contacting with b with two kinds of catalyzer a and reacting, product separates obtaining ethene, propylene through over-quenching, condensation.
The present invention adopts the dual catalyst bed to carry out the method for petroleum hydrocarbon catalytic pyrolysis system olefine in low carbon number, compares with existing single reactor list catalyst cracking technology, has added a beds, has the following advantages:
1, method of the present invention has improved the selectivity of petroleum hydrocarbon catalytic pyrolysis reaction, has particularly improved the yield of purpose product ethene, propylene;
2, method of the present invention combines petroleum hydrocarbon catalytic pyrolysis and carbon four, two catalytic pyrolysis technology of carbon pentaene hydrocarbon catalytic pyrolysis conversion, heavy component in the single reactor list beds technological reaction product in the prior art further can be converted into ethene and propylene, improve utilization ratio of raw materials;
3, use method of the present invention, catalyst filling, convenient disassembly, maintenance of equipment is convenient.
Description of drawings
Accompanying drawing one is a single reactor list beds process flow sheet
Accompanying drawing two is a single reactor dual catalyst bed process flow sheet of the present invention
Accompanying drawing three is a double-reactor dual catalyst bed process flow sheet of the present invention
1 stock oil volume pump; 2 thinner volume pumps; 3 preheaters; 4 reactors; 5 separation systems; 6 gas-phase products; 7 liquid products
Process description: shown in accompanying drawing two or three, with catalyst filling in fixed bed reactors 4, feedstock oil and diluent enter in the preheater 3 through measuring pump 1 and 2 respectively, enter in the reactor 4 through after the preheating, reacted product enters piece-rate system 5 (comprising water-cooled, ice-cold), obtains at last gas-phase product 6 and liquid product 7.
Specific embodiment
Below by the present invention of embodiment more detailed description, but the present invention is not limited to these embodiment.
1, Preparation of catalysts: catalyzer a among the embodiment makes according to the preparation method of catalyst A among the Chinese patent CN1480255A; Catalyzer b makes according to the preparation method of catalyzer D among the Chinese patent CN1189433C.
2, the rerum natura of the stock oil that uses sees Table one among the embodiment.
Table one
3, the employed reactor of embodiment is a tubular fixed-bed reactor, diameter 14 * 2mm, high 500mm.Two reactor specifications are identical.Reactor is vertical reactor.
4, the test product divides gas-phase product and liquid product two portions among the embodiment.Gas-phase product is analyzed by gas chromatograph (HP-6890), draws the composition of gas-phase product.Liquid product is through the distillation cutting, isolate initial boiling point-204 ℃, 204-288 ℃, 288 ℃ of-three kinds of cuts, and analyze the composition of aromatic hydrocarbons in the gasoline fraction (initial boiling point-204 ℃), carry out material balance then and calculate, draw the yield of variant production in the split product, the yield of product is represented with weight percent.
Embodiment 1: adopt single reactor dual catalyst bed technology, load the catalyzer a of 5ml in the reactor earlier, the quartz sand of the 10ml that recharges, and then the catalyzer b of filling 5ml.
Light naphthar is at residence time 0.62S, water-oil ratio 0.6 (weight ratio), under normal pressure, react, earlier through catalyzer a bed is housed, its temperature of reaction is 750 ℃, arrives catalyzer b bed through quartz sand layer again, and its temperature of reaction is 650 ℃, reaction product is separated through separation system again, and products therefrom each component yield sees Table the embodiment 1 in two.
Embodiment 2: adopt single reactor dual catalyst bed technology, as method loading catalyst as described in the embodiment 1, unique different be not load quartz sand between catalyzer a bed and the catalyzer b bed, but be that the blank pipe of 10ml connects with the volume.
Raw material and reaction conditions such as embodiment 1, products therefrom each component yield sees Table the embodiment 2 in two.
Embodiment 3: adopt double-reactor dual catalyst bed technology, the catalyzer a of reactor A filling 5ml, the catalyzer b of filling 5ml in the reactor B.
Light naphthar is at residence time 0.62S, water-oil ratio 0.6 (weight ratio), reaction pressure is under the non-pressurized condition, through reactor A, its temperature of reaction is 750 ℃, passes through reactor B again, and its temperature of reaction is 650 ℃, after passing through separation system again, the yield of gained gas-phase product sees Table the embodiment 3 in 2.
The comparative example 1: adopt single reactor list catalyst bed layer process, the catalyzer a of filling 10ml in the reactor.
Raw material and reaction conditions such as embodiment 1, products therefrom each component yield sees Table the comparative example 1 in two.
The comparative example 2: adopt single reactor list catalyst bed layer process, the catalyzer b of filling 10ml in the reactor.
Raw material and reaction conditions such as embodiment 1, products therefrom each component yield sees Table the comparative example 2 in two.
Table two
| Product is formed | |
|
|
The comparative example 1 | The comparative example 2 |
| Hydrogen | 1.32 | 1.29 | 1.36 | 1.11 | 1.11 |
| Methane | 16.18 | 16.38 | 16.47 | 15.11 | 8.98 |
| Ethene | 29.35 | 28.97 | 29.41 | 26.23 | 20.07 |
| Propylene | 19.99 | 18.98 | 18.87 | 18.69 | 14.69 |
| Divinyl | 2.86 | 3.04 | 3.01 | 3.09 | 4.07 |
The result of comparing embodiment 1-3 and Comparative Examples 1,2 can see, adopts the technology of the beds of two different catalysts a of filling and b to carry out catalytic cracking reaction, and the yield of ethene and propylene is higher than the experimental result of single catalyst process in the product.
Claims (10)
1, a kind of catalytic pyrolysis is produced the method for alkene, it is characterized in that to comprise the petroleum hydrocarbon cracking stock of petroleum naphtha, solar oil and hydrogenation tail oil, by the beds of placed in-line two filling different catalysts a and b up and down, carry out catalytic cracking reaction, obtain olefine in low carbon number.
2, catalytic pyrolysis as claimed in claim 1 is produced the method for alkene, it is characterized in that described catalyzer a is a petroleum hydrocarbon catalytic pyrolysis catalyst; Described catalyzer b is C 4 olefin and/or carbon pentaene hydrocarbon catalytic cracking catalyst.
3, catalytic pyrolysis as claimed in claim 2 is produced the method for alkene, it is characterized in that described catalyzer a obtains by the method for following solid mixture moulding and co-precipitation or dipping: by weight percentage, aluminum oxide is 10-70%, magnesium oxide is 5-30%, vanadic acid sodium is 5-30%, lime carbonate is 2-30%, and rare-earth oxide is 1-15%, and kaliophylite or potassium felspar sand are 10-20%; Described catalyzer b comprises following composition: with the total restatement of catalyzer, Al
2O
3Or SiO
2Be 20-45%, supersiliceous zeolite is 40-70%, and modified component is 8-20%.
4, catalytic pyrolysis as claimed in claim 2 is produced the method for alkene, it is characterized in that described catalyzer a is seated among the fixed-bed reactor A, and catalyzer b is seated among the fixed-bed reactor B; Described two reactor A and B connect up and down.
5, catalytic pyrolysis as claimed in claim 4 is produced the method for alkene, the reaction conditions that it is characterized in that described reactor A is: temperature of reaction 650-850 ℃, the weight ratio of thinner and reactant is 0.5-2.0, residence time 0.05-2S, reaction pressure 0-0.5MPa; The temperature of reaction of described reactor B is 350-700 ℃.
6, catalytic pyrolysis as claimed in claim 2 is produced the method for alkene, it is characterized in that, catalyzer a that described filling is different and the beds of b are in fixed-bed reactor, and the beds of loading catalyst a is at the epimere of reactor.
7, catalytic pyrolysis as claimed in claim 6 is produced the method for alkene, it is characterized in that one section inert filler of filling between described two beds, connects two beds with inert filler.
8, catalytic pyrolysis as claimed in claim 7 is produced the method for alkene, the loading height that it is characterized in that described inert filler be loading catalyst b the catalyst bed layer height 1-3 doubly.
9, catalytic pyrolysis as claimed in claim 6 is produced the method for alkene, it is characterized in that being blank pipe between two beds, does not load any material, places a catalyzer screen to hold catalyzer a in the beds lower end of loading catalyst a.
10, catalytic pyrolysis as claimed in claim 9 is produced the method for alkene, the height that it is characterized in that described blank pipe be loading catalyst b the catalyst bed layer height 1-3 doubly.
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| CNB2005101174355A CN100457857C (en) | 2005-10-31 | 2005-10-31 | Method for producing olefin through catalytic cracking |
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| CNB2005101174355A CN100457857C (en) | 2005-10-31 | 2005-10-31 | Method for producing olefin through catalytic cracking |
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| CN100457857C true CN100457857C (en) | 2009-02-04 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101343557B (en) * | 2007-07-09 | 2012-08-29 | 中国石油化工股份有限公司 | Method for preparing high-quality ethylene raw material with petroleum naphtha hydrogenation |
| CN101684057B (en) * | 2008-09-28 | 2013-02-27 | 中国石油化工股份有限公司 | Method for producing low-carbon olefins by cracking petroleum hydrocarbon |
| CN102041083B (en) * | 2009-10-21 | 2016-06-22 | 中国石油化工股份有限公司 | A kind of hydrogenation modification method for coking gasoline/diesel fractions |
| CN102295284B (en) | 2010-06-28 | 2013-05-15 | 通用电气公司 | Method for converting carbon into carbon oxides and method and apparatus for cracking hydrocarbons |
| CN105582998B (en) * | 2014-10-21 | 2017-11-03 | 中国石油化工股份有限公司 | The method that naphtha catalytic cracking produces propylene |
| CN105585410B (en) * | 2014-10-21 | 2017-07-25 | 中国石油化工股份有限公司 | The method that naphtha catalytic cracking produces propylene |
| CN114516667A (en) * | 2020-11-20 | 2022-05-20 | 中国石油天然气集团有限公司 | Reaction device for fixed bed cracking of oily wastewater for laboratory |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1060755A (en) * | 1990-10-09 | 1992-04-29 | 中国科学院广州能源研究所 | Efficient electric heat tray |
| US6033555A (en) * | 1997-06-10 | 2000-03-07 | Exxon Chemical Patents Inc. | Sequential catalytic and thermal cracking for enhanced ethylene yield |
-
2005
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1060755A (en) * | 1990-10-09 | 1992-04-29 | 中国科学院广州能源研究所 | Efficient electric heat tray |
| US6033555A (en) * | 1997-06-10 | 2000-03-07 | Exxon Chemical Patents Inc. | Sequential catalytic and thermal cracking for enhanced ethylene yield |
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