CN1854256A - Method for decreasing by gasoline olefin and producing propylene - Google Patents
Method for decreasing by gasoline olefin and producing propylene Download PDFInfo
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- CN1854256A CN1854256A CN 200510066550 CN200510066550A CN1854256A CN 1854256 A CN1854256 A CN 1854256A CN 200510066550 CN200510066550 CN 200510066550 CN 200510066550 A CN200510066550 A CN 200510066550A CN 1854256 A CN1854256 A CN 1854256A
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Abstract
This invention published a method of catalyzing petrol to reduce olefin hydrocarbon and produce propene. The raw material of this method is from catalyzing petrol or light petrol, it is mixed with water, and then the mixture reacted with high silal zeolite in the fixed bed catalytic reactor, after cooling isolation, we can get propene, ethane and modified petrol. The composition of the zeolite catalyst that mentioned before is that 50% silica-rich zeolite (Sil\Al mol tatio is 50-300), 20-70% monox, 5-20% inorganic oxide. Using this method, not only can reduce the content of olefinic hydrocarbon in the catalytic petrol, and the octane level of the modified petroldoes not change, but also we can get the ethane and propane in the same time. It shows a very impotant industrialization way that we can possibly reduce the olefinic hydrocarbon contant of petrol.
Description
Technical field
The present invention relates to a kind of method that reduces olefin(e) centent in the gasoline, concrete, the present invention relates to the alkene in the catalytic gasoline is carried out catalyzed conversion, obtain the method for the propylene reformulated gasoline that octane value is constant substantially with falling alkene.
Background technology
Along with developing rapidly of automotive industry, the automobile exhaust pollution problem more and more is subjected to people's attention.Strict regulation have all been made to motor spirit quality and exhaust emissions by various countries, European III standard-required olefin(e) centent (volume fraction)≤18%, and US Basic Application Number requires olefin(e) centent≤10.8%, and California, USA requires olefin(e) centent≤6.0%.China issued in 1999 and the clean gasoline standard alkene in the gasoline, aromatic hydrocarbons, benzene and sulphur content proposed strict demand, wherein olefin(e) centent (volume fraction)≤35%.China's motor spirit is based on catalytically cracked gasoline, and catalytically cracked gasoline accounts for the amount of gasoline product up to 90%.The volume fraction of alkene is 45%-60% in the catalytically cracked gasoline, considerably beyond the gasoline standard of new prescription; And China's motor spirit standard is just progressively in line with international standards, and therefore, the decreasing by gasoline olefin new technology that exploitation is fit to China's national situation is very necessary.
The approach that reduces content of olefin in gasoline can be divided into two kinds, and a kind of is to improve from aspects such as catalytic cracking production process of gasoline, catalyzer and auxiliary agents, and another kind is that the catalytically cracked gasoline of producing is carried out post-treatment.
Processing condition, employing new catalyst or the auxiliary agent of patents such as CN 1298923A, CN 1356372A, CN 1465663A by improving or control the course of processing, improve activity of such catalysts, promote hydrogen transfer reactions, improve the saturation ratio of catalytically cracked gasoline, reach the purpose that reduces olefin(e) centent in the gasoline, but it is limited that olefin(e) centent descends, about 10%.
Patents such as CN 1390917A, CN 14423918A reach the purpose that reduces olefin(e) centent in the gasoline, improves quality of gasoline by methods such as hydrofining, superimposed, aromizing, etherificates.But present domestic most oil refining enterprises are not to lack hydrorefined means, are exactly the not enough or shortage hydrogen source of hydrorefined processing power.So it is unpractical that the catalytically cracked gasoline that accounts for commercial gasoline 90% all improves its quality by hydrofining, and hydrofining also can bring the loss of gasoline octane rating.
Petroleum naphtha etherificate, aromizing, alkylation, method such as superimposed can reduce the olefin(e) centent in the catalytic gasoline, some complex process of these methods and technology, investment are greatly, little refinery adopts still very big difficulty, and some Technology is immature, also has a segment distance from industrialization.
In sum, the of the prior art improvement from aspects such as catalytic cracking production process of gasoline, catalyzer and auxiliary agents reduces olefin(e) centent the gasoline, and the reduction amplitude is limited, can not satisfy new gasoline standard requirement; Carry out method and the technology that alkene falls in post-treatment from the catalytic gasoline of producing, some complex process in hydrogenation, etherificate, aromizing, the method such as superimposed, investment are big, and some Technology is immature.
Summary of the invention
The purpose of this invention is to provide a kind of easy to operately, can reduce in the catalytic gasoline olefin(e) centent greatly and obtain reformulated gasoline and the method for propylene.
Method of the present invention is to be raw material with catalytic gasoline or catalytic light gasoline, water is cooked thinner, alkene in the described raw material is converted into propylene, ethene in the presence of zeolite containing catalyst, alkane generates the product of isomerization and aromizing, can obtain ethene, propylene and reformulated gasoline after refrigerated separation.
Catalytic gasoline of the present invention is meant catalytically cracked gasoline, and catalytic light gasoline is the lighting end (＜80～100 ℃ of cuts) that catalytically cracked gasoline is isolated raw gasline and obtained.Other also can be used for method of the present invention as coker gasoline, pyrolysis gasoline etc.
Method of the present invention comprises:
With catalytic gasoline or catalytic light gasoline is raw material, with raw material with after water mixes, in fixed-bed reactor, contact and carry out the catalytic reforming reaction with zeolite containing catalyst, generation contains the reaction mixture of propylene and ethene, after refrigerated separation, obtain comprising the gas-phase product of ethene and propylene, comprise the liquid product of water and reformulated gasoline; Wherein said zeolite containing catalyst comprises following component: 50 parts of supersiliceous zeolites, silicon oxide 20-70 part, inorganic oxide 5-20 part.
The volume ratio of wherein said diluent water and raw material is 0.1-1.0, is preferably 0.2-0.8.
Described zeolite containing catalyst can be by the ordinary method preparation of catalyzer, as methods such as kneading method, pickling processes.Preferred described zeolite containing catalyst is mixed to pinch by following component and obtains: 50 parts of supersiliceous zeolites, silicon oxide 30-50 part, inorganic oxide 10-15 part.
At least a in the oxide compounds such as the optional autoxidation zirconium of preferred described inorganic oxide, titanium oxide, magnesium oxide, boron oxide; Described supersiliceous zeolite is selected from the zeolite of ZSM-5 type; Preferred its SiO
2With Al
2O
3Mol ratio be 50-300, more preferably 180-300.The zeolite of more preferably described supersiliceous zeolite commodity in use ZRP series by name, this zeolite is the ZSM-5 zeolite of modification.
Method of the present invention is to be raw material with catalytic gasoline or catalytic light gasoline, with after water mixes, in fixed-bed reactor, in the presence of above-mentioned zeolite containing catalyst, is that 450-600 ℃, pressure are 0.1-0.5MPa and 1-10h in temperature with raw material
-1Volumctric hourly space velocity under react.
The shape of the catalyzer that method of the present invention is used can be spherical, granular, strip, extrudate etc.
The used catalyzer of method of the present invention can adopt kneading method to prepare, and specifically comprises the following steps:
(1) supersiliceous zeolite, silicon oxide, extrusion aid, inorganic oxide are mixed in proportion used extrusion aid such as sesbania powder, polyacrylamide, silica gel etc.; (2) add an amount of nitric acid behind the mixing, stir evenly the back extrusion molding, wherein the weight percent concentration of nitric acid is less than 10%; (3) 60-140 ℃ dry 5-20 hour, 450-650 ℃ roasting 0.5-15 hour, obtain described catalyzer.
The used catalyzer of method of the present invention also can adopt earlier supersiliceous zeolite, silicon oxide kneading and compacting as carrier, use the method for salt solution impregnation on carrier of inorganic oxide to prepare with pickling process again, concrete comprising the following steps: (1) is mixed in proportion supersiliceous zeolite, silicon oxide, extrusion aid; (2) add an amount of nitric acid behind the mixing, stir evenly the back extrusion molding, wherein the weight percent concentration of nitric acid is less than 10%; (3) 60-140 ℃ dry 5-20 hour, 450-650 ℃ roasting 0.5-15 hour; (4) carrier that adopts the solution impregnation step (3) of inorganic salt to obtain preferably uses the solution of compounds such as zirconium oxychloride, magnesium nitrate, boric acid, and dry then, roasting obtain described catalyzer.
Method of the present invention has following beneficial effect:
1, uses method of the present invention, not only can reduce olefin content in gasoline, obtain olefin(e) centent and be less than 20% and the constant substantially reformulated gasoline of octane value, and can obtain about 6% ethene and about 16% propylene.
2, method of the present invention is a raw material with catalytic gasoline or catalytic light gasoline, and water is cooked thinner, uses fixed-bed reactor, and technology is simple, easy to operate;
3, the used catalyzer of method of the present invention combines supersiliceous zeolite and some oxide compounds and makes, and the preparation method is simple, long service life.
4, used catalyzer anti-coking performance and the hydrothermally stable performance excellence of method of the present invention, catalyzer be seldom because therefore coking and inactivation need not to repeat continually regenerative operation, can be for a long time, operation expeditiously.
Description of drawings
Fig. 1 is experiment flow figure of the present invention.
1 volume pump, 2 volume pumps, 3 process furnace, 4 reactors, 5 water coolers, 6 gas-liquid separators
Below in conjunction with accompanying drawing method of the present invention is described.
Catalyzer is packed in the fixed-bed reactor 4 into logical N
2Behind the leak test, open process furnace 3 heating, temperature is opened volume pump 1 and 2 after rising to temperature of reaction, raw material and water enter reactor 4 through micro-plunger metering pump, reaction product after water cooler 5, gas-liquid separator 6 separates, gas phase wet test meter measurement volumes, liquid phase is collected with Erlenmeyer flask.Analyze the composition of gas phase and liquid phase with gas chromatograph.
Embodiment
Below example will illustrate further the present invention, but not thereby limiting the invention.
(provide SiO with 50g ZRP molecular sieve by economic technology trade center, Garden of Ten-Thousand Trees, Beijing
2/ Al
2O
3＞200), 50g silicon oxide (specific surface area＞200m
2/ g), the 2g extrusion aid mixes; It is an amount of to add rare nitric acid behind the mixing, is squeezed into the cylindrical type of 2mm after stirring evenly, and cuts into 2-3mm; 100 ℃ of dryings 10 hours, calcined then 6 hours, take out that to be cooled to room temperature standby.Zhi Bei catalyzer is expressed as catalyst A by this way.
With 50g ZRP molecular sieve (SiO
2/ Al
2O
3＞200), 40g silicon oxide, 10g magnesium oxide and 2g extrusion aid mix, it is an amount of to add rare nitric acid behind the mixing.Other working method is identical with embodiment 1.Zhi Bei catalyzer is expressed as catalyst B by this way.
With 50g ZRP molecular sieve (SiO
2/ Al
2O
3＞200), 50g silicon oxide, 5g magnesium oxide, 5g zirconium white and 2g extrusion aid mix, it is an amount of to add rare nitric acid behind the mixing.Other working method is identical with embodiment 1.Zhi Bei catalyzer is expressed as catalyzer C by this way.
With 50g ZRP molecular sieve (SiO
2/ Al
2O
3＞200), 35g silicon oxide, 5g magnesium oxide, 5g zirconium white 2g boron oxide and 2g extrusion aid mix, it is an amount of to add rare nitric acid behind the mixing.Other working method is identical with embodiment 1.Zhi Bei catalyzer is expressed as catalyzer D by this way.
Get the catalyst A of 30g moulding and use 22ml magnesium nitrate (0.6M), zirconium oxychloride (0.5M) and boric acid (0.1M) solution impregnation respectively, 100 ℃ of dryings 10 hours, calcine standby after 6 hours behind the airing.Zhi Bei catalyzer is expressed as catalyzer E by this way.
In the small stationary bed bioreactor, be raw material with catalytic light gasoline (＜90 ℃), it is formed as table 1, and its octane research method (RON) is 101.62, and motor method (MON) is 80.17.With catalyst A, B, C, D and E, at pressure 0.2MPa, air speed 3h
-1, water/oil ratio is to react under 0.6 the condition.Under the differential responses temperature, react after 6 hours the data of main olefins yield and octane research method (RON), motor method (MON) and list in table 2.The octane value of gasoline is constant substantially in the visible liquid product of result from table.
Reactor is the stainless steel tube of internal diameter Φ 16mm, wall thickness 2mm, interior dress 25ml catalyzer, and the particle diameter of catalyzer is about 2.0mm * 3.0mm.
Table 1 catalytic light gasoline (＜90 ℃) PONA mass percent report (wt%)
| Carbon number | Normal paraffin | Isoparaffin | Alkene | Naphthenic hydrocarbon | Aromatic hydrocarbons | By carbon number add and |
| 3456789 add up to | 0.00 1.04 6.75 2.29 0.56 0.05 0.00 10.70 | 0.00 0.53 21.59 10.86 2.18 0.49 0.17 35.81 | 0.00 3.13 23.48 13.70 3.90 0.66 0.05 44.91 | 0.00 0.00 0.00 2.60 1.77 0.33 0.02 4.71 | 0.00 0.00 0.00 1.45 1.70 0.00 0.00 3.15 | 0.00 4.71 51.82 30.90 10.11 1.52 0.23 99.28 |
Table 2 is main olefins yield (wt%) and octane value under the differential responses temperature
| Catalyzer | Temperature of reaction ℃ | 450℃ | 500℃ | 550℃ | |
| A | Olefin product content and octane number after the reaction | Content of olefin in gasoline % productivity of propylene % ethylene yield % octane value (RON, MON) | 23.26 13.22 5.66 99.60，80.21 | 21.19 14.60 6.25 100.01，80.06 | 20.11 16.33 7.06 99.68，80.16 |
| B | Content of olefin in gasoline % productivity of propylene % ethylene yield % octane value (RON, MON) | 23.86 13.98 5.67 99.18，79.21 | 21.55 15.16 6.58 100.03，80.11 | 20.63 16.76 8.21 100.00，80.65 | |
| C | Content of olefin in gasoline % productivity of propylene % ethylene yield % octane value (RON, MON) | 23.79 13.36 5.82 98.27，80.19 | 21.36 15.69 6.77 99.88，82.06 | 20.55 16.66 8.52 101.63，82.33 | |
| D | Content of olefin in gasoline % productivity of propylene % ethylene yield % octane value (RON, MON) | 22.18 13.27 5.89 97.63，79.52 | 20.65 16.23 6.88 100.15，82.03 | 18.36 20.12 9.03 102.06，82.05 | |
| E | Content of olefin in gasoline % productivity of propylene % ethylene yield % octane value (RON, MON) | 23.03 13.35 5.81 97.59，79.66 | 19.63 16.60 6.76 101.25，82.55 | 18.21 20.33 9.16 101.65，83.01 | |
Claims (9)
1, a kind of decreasing by gasoline olefin and the method for producing propylene is characterized in that this method is a raw material with catalytic gasoline or catalytic light gasoline, and raw material is mixed with water, carry out the catalytic reforming reaction in fixed-bed reactor with under zeolite containing catalyst contacts; After refrigerated separation, obtain comprising the gas-phase product of ethene and propylene, comprise the liquid product of water and reformulated gasoline; Wherein said zeolite containing catalyst comprises following component:
Supersiliceous zeolite is 50 parts, and silicon oxide is 20-70 part, and inorganic oxide is 5-20 part.
2, method according to claim 1, wherein said catalyzer comprises following component: supersiliceous zeolite is 50 parts, and silicon oxide is 30-50 part, and inorganic oxide is 10-15 part.
3, method according to claim 1, wherein said supersiliceous zeolite are selected from zeolite or the ZSM-5 class zeolite of commodity ZRP by name.
4, method according to claim 3, the SiO of wherein said supersiliceous zeolite
2With Al
2O
3Mol ratio be 50-300.
5, method according to claim 4, the SiO of wherein said supersiliceous zeolite
2With Al
2O
3Mol ratio be 180-300.
6, method according to claim 1, wherein said inorganic oxide are selected from least a in zirconium white, titanium oxide, magnesium oxide, the boron oxide.
7, method according to claim 1, the volume ratio of wherein said water and raw material are 0.1-1.0.
8, method according to claim 7, the volume ratio of wherein said water and raw material are 0.2-0.8.
9,, it is characterized in that the reaction of described catalytic reforming is is that 450-600 ℃, pressure are 0.1-0.5MPa and 1-10h in temperature according to the described method of one of claim 1-8
-1Weight hourly space velocity under carry out.
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|---|---|---|---|
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| CN100360646C CN100360646C (en) | 2008-01-09 |
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Cited By (1)
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|---|---|---|---|---|
| CN102872902A (en) * | 2011-07-12 | 2013-01-16 | 中国石油化工股份有限公司 | Catalytic cracking assistant for propylene yield increase |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4481105A (en) * | 1982-08-25 | 1984-11-06 | Mobil Oil Corporation | Processing of hydrocarbons in fixed catalyst bed with redistribution means |
| CN1056869C (en) * | 1996-03-21 | 2000-09-27 | 中国石油化工总公司 | Olefinpoducing-modified layered clay catalyst and its production and use |
| AU744826B2 (en) * | 1998-05-05 | 2002-03-07 | Exxonmobil Chemical Patents Inc | Hydrocarbon conversion to propylene with high silica medium pore zeolite catalysts |
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| CN102872902A (en) * | 2011-07-12 | 2013-01-16 | 中国石油化工股份有限公司 | Catalytic cracking assistant for propylene yield increase |
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