CN100392047C - Method for preparing olefin by catalytic oxidation of petroleum hydrocarbon - Google Patents
Method for preparing olefin by catalytic oxidation of petroleum hydrocarbon Download PDFInfo
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- CN100392047C CN100392047C CNB2005100118911A CN200510011891A CN100392047C CN 100392047 C CN100392047 C CN 100392047C CN B2005100118911 A CNB2005100118911 A CN B2005100118911A CN 200510011891 A CN200510011891 A CN 200510011891A CN 100392047 C CN100392047 C CN 100392047C
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Abstract
The present invention relates to a method for preparing olefin by the catalytic oxidation cracking of petroleum hydrocarbon, particularly to a method for preparing low carbon olefin by catalytic oxidation cracking reaction under the function of a compound catalyst composed of solid acid and metal oxide. The solid acid is used as the catalytic cracking catalyst of the petroleum hydrocarbon, and the metal oxide is used as an oxidation catalyst, and a reaction product and the catalysts are separated after reaction. The catalysts are regenerated, namely that the inactivation solid acid catalyst burns out coke so as to restore activity, and simultaneously, the reduced metal oxide catalyst is oxidized. The reaction temperature is from 500 to 720 DEG C, the weight ratio of the solid acid catalyst to the metal oxide is 2 to 30: 1, and the weight ratio of the catalysts to the petroleum hydrocarbon is 5 to 30: 1. The petroleum hydrocarbon comprises low carbon hydrocarbon gasoline with different boiling ranges, diesel oil, vacuum gas oil, naphtha, crude oil, residual oil, etc. The present invention is particularly suitable for various heavy hydrocarbons. If the reaction is carried out in water vapour environment, the water and oil ratio of feed materials is 0.1 to 1: 1.
Description
Technical field
The invention belongs in the petrochemical complex with the hydrocarbon compound is that raw material is produced basic chemical raw materials low-carbon alkene technical field through catalytic oxidative cracking, relates in particular to a kind of method of preparing olefin by catalytic oxidation of petroleum hydrocarbon.
Background technology
Traditional olefins production is the tube furnace high temperature pyrolytic cracking, low-density oil hydrocarbon feeds such as only suitable petroleum naphtha, solar oil.Because light petroleum hydrocarbon output is restricted, and is paid attention to by people by the heavy petroleum hydrocarbon producing olefin hydrocarbon by catalytic pyrolysis.USP4,087,350 and USP4,111,793 have introduced a kind of MnO of containing
2/ TiO
2And MnO
2/ ZrO
2Being catalyzer, is raw material with Kuwait's wax oil or long residuum, producing olefin hydrocarbon by catalytic pyrolysis, and ethylene yield is 17.23%.EP0,490, the Deep Catalytic Cracking process that 435A1 introduces is catalyzer with the zeolite, and when being raw material with the hydrogenation wax oil, yield of ethene is 10.8%, and propene yield is 27.2%.CN1317543A adopts a kind of catalyzer that contains the ZSM-5 molecular sieve, and at temperature 650-750 ℃, reaction pressure 1.5-4.0MPa, agent-oil ratio are 15-40, and water-oil ratio is 03-1: under 1 the condition, ethene+propene yield is about 30%.The heavy oil catalytic pyrolysis of Beijing Research Institute of Petro-Chemical Engineering (RIPP) is produced low-carbon alkene technology (DCC, CPP, CN1218786A, CN1317547A, CN1031834A, " refining of petroleum and chemical industry ": v0125 in 1994, P30～34), wherein DCC branch art temperature of reaction is low, and reaction heat is provided by coke and heavy cycle oil.Exploitation HCC (the Heavy oil Contact Cracking) technology (CN97119048.8 of Luoyang Petrochemical engineering corporation (LPEG), " chemical industry and design ": nineteen ninety-fives 9 (5) P38-40) adopt fluidized-bed or plug flow reactor that the hydrocarbon raw material of preheating is contacted fast with the solid particulate contact substance with certain catalytic activity and carry out scission reaction, reacted contact substance to be generated is at high temperature regenerated.Dalian Chemical Physics Research Institute has developed a kind of fluid catalytic cracking mink cell focus that is used for and has produced the catalysis punishment of low-carbon alkene (Chinese patent 03141148.7), with molecular sieve as active constituent, with aluminum phosphate or silicon aluminium phosphate non-stoichiometric compound as matrix, through mixing making beating, the catalyzer of residual oil catalytic pyrolysis preparing Zhu Shi carbon olefin is made in spraying drying and roasting.
Above-mentioned technology has adopted fluidized-bed reaction technology, technical process that has and the conventional similar substantially reaction-regeneration system that comprises of catalytic cracking, separation system and absorbing-stabilizing system, raw material is sent into after steam atomizing in the riser tube fluidized-bed reactor, contact with the regenerated catalyst of heat and to carry out catalytic cracking reaction, further separate again after the product fractionation.Deposit the reclaimable catalyst coke burning regeneration of coke and be heated to high temperature.High-temperature regenerated catalyst carries reaction institute's heat requirement Returning reactor with suitable cycle rate and charging is reacted, and realization response-regeneration system rapidly circulation and thermal equilibrium.
Hydrocarbon cracking reaction is a strong endothermic reaction, and only under comparatively high temps reaction just can obtain high ethene and productivity of propylene.Raw material heats up and vaporization also needs a large amount of heats.This process institute heat requirement is taken reaction system to by regenerated catalyst.In order to carry enough heats, need to adopt high regeneration temperature (catalyst inlet temperature height) and high agent-oil ratio.High regeneration temperature is easily damaged catalyzer, and high agent-oil ratio reduces plant efficiency.If it is not enough to burn heat, then must adopt relative measures, add astatki as adopting, or mix refining heavy oil etc. to satisfy thermally equilibrated needs.
Summary of the invention
The objective of the invention is to propose a kind of method of preparing olefin by catalytic oxidation of petroleum hydrocarbon at problems such as high temperature fluidized technology, equipment complexity, energy consumption height.
For achieving the above object, the present invention is coupled by the petroleum hydrocarbon cracking reaction of selecting to have the oxidizing reaction of exothermic effect and endothermic effect is arranged, reaching oxidizing reaction provides the purpose of heat for scission reaction, mode with the heat supply of inside reactor original position provides part scission reaction institute heat requirement, burn temperature thereby reduce, prolong catalyzer work-ing life, reduce agent-oil ratio, improve plant efficiency.
The method of preparing olefin by catalytic oxidation of petroleum hydrocarbon provided by the invention, be with containing the solid acid of molecular sieve composition as hydrocarbon cracking catalyst, with the variable valence metal oxide as oxide catalyst, with two kinds of catalyzer uniform mixing, the petroleum hydrocarbon catalytic pyrolysis reaction of exothermic oxidation reaction between hydro carbons, hydrogen and the metal oxide and heat absorption is carried out simultaneously, and realization response device inside provides part required reaction heat.Solid acid catalyst behind the carbon distribution and the metal oxide catalyst that is reduced continue to recycle after being admitted to simultaneously and regenerating in the revivifier again.
Specifically, the method of preparing olefin by catalytic oxidation of petroleum hydrocarbon provided by the invention, be in fluidized-bed reactor, with the mixture of solid acid catalyst and variable valence metal oxide catalyst as composite catalyst, wherein the weight ratio of solid acid catalyst and variable valence metal oxide is 2-30: 1, optimum weight ratio is 5-20: 1, and the weight ratio of composite catalyst and petroleum hydrocarbon is 5-30: 1, temperature of reaction 500-720 ℃.If reaction is carried out under water vapor atmosphere, the weight ratio of water vapour and petroleum hydrocarbon is 0.1-1: 1.By above-mentioned reaction,, make oxidizing reaction provide a part of heat for scission reaction the hydro carbons of the hydrocarbon catalytic cracking system olefine reaction of heat absorption and heat release, oxidation of hydrogen reaction coupling.
Described solid acid catalyst is active constituent with the acidic molecular sieve, with aluminum phosphate, silicon aluminium phosphate or silicon oxide, aluminum oxide or its mixture as matrix.
Described acidic molecular sieve is Y zeolite, ZSM-5 molecular sieve, beta molecular sieve or mordenite.
Described variable valence metal oxide comprises single metal oxide and complex metal oxides.
Described variable valence metal oxide is that manganese oxide, cupric oxide, ferric oxide, silver suboxide, zirconium white are or/and uhligite.
Described petroleum hydrocarbon is low-carbon (LC) class hydro carbons, different boiling ranges gasoline, diesel oil, vacuum gas oil, petroleum naphtha, crude oil or residual oil and composition thereof.
That described fluidized-bed reactor comprises is fixed fluidized bed, fast bed, moving-bed and up riser tube fluidized-bed or descending riser tube fluidized-bed reactor.
The method that the present invention proposes, its advantage is: realization response device inside provides the part heat, can reduce regeneration temperature and agent-oil ratio, thermal equilibrium to reaction-regeneration system is easy to realize, improve process efficiency, reduce energy expenditure, productivity of low carbon olefin hydrocarbon is compared with catalystic pyrolysis simultaneously, does not reduce substantially.
Description of drawings
Fig. 1 is that catalyst A of the present invention, B, C, the following catalyst in reactor bed temperature of D effect are with the reaction times change curve.
Embodiment
Embodiment 1:
Fixed-bed reactor, reaction raw materials are petroleum naphtha, form to see Table 1.Catalyst for cracking is solid acid catalyst A; Catalyst for cracking and 6.5: 1 by volume uniform mixing of three kinds of different metal oxides catalyzer difference obtain catalyst B, C and D, and catalyst property sees Table 2.Reaction tubes is internal diameter 6mm, and pipe range 300mm, reaction tubes have chuck outward, when reaction is carried out, is evacuated in the chuck, closes externally heated oven and stops heating (the reaction unit flow process is seen accompanying drawing 1).Granules of catalyst is the 40-60 order, and loaded catalyst is 6ml.The reaction carrier gas is a purity nitrogen, and flow rate of carrier gas is 22.5ml/min, reacts 1.5 minutes products and get gas method collection gaseous product with draining behind cold-trap, and reaction result sees Table 3.Reaction bed temperature is seen Fig. 1 with the reaction times variation tendency under catalyst A, B, C, D effect.
Table 1: raw material is formed (wt%)
| Normal paraffin | 30.82 |
| Isoparaffin | 20.63 |
| Naphthenic hydrocarbon | 33.79 |
| Alkene | 8.39 |
| Aromatic hydrocarbons | 3.61 |
| Other | 2.76 |
Table 2: catalyst property
| The catalyzer numbering | Active ingredient |
| A | HZSM-5 |
| B | HZSM-5，Mn 2O 3 |
| C | HZSM-5，CuO |
| D | HZSM-5，Mn 2O 3，CuO |
Table 3: fixed bed reaction result
Under the pure catalyst for cracking effect, bed temperature is to continue to reduce, and temperature drop is bigger, add metal oxide as coupled catalyst after, the bed temperature of catalyzer is fallen after rising, temperature drop also obviously reduces, show metal oxide and hydro carbons generation oxidizing reaction, emit heat.And behind the adding metal oxide, CO and CO
2The growing amount showed increased has also proved the generation of oxidizing reaction.In the reaction of catalyst B and D, productivity of low carbon olefin hydrocarbon is compared variation with catalytic pyrolysis less, and the heat coupling effect clearly.
Embodiment 2:
Fixed fluidized-bed reactor, reaction raw materials are the grand celebration long residuum, and the normal slag physico-chemical property of grand celebration sees Table 4.Composite catalyst E is the mixture of solid acid catalyst F (Chinese patent 03141148.7) and metal oxide catalyst G, and the rerum natura of catalyzer sees Table 5.F and G weight ratio are 10: 1.Under pure solid acid catalyst F and composite catalyst E effect, agent-oil ratio is 18: 1 respectively, and water-oil ratio is 0.3: 1, and the reaction times is 60 seconds, and temperature of reaction is 500 ℃, 600 ℃, 650 ℃, and reaction result sees Table 6.
Table 4: the physico-chemical property of raw material
| Density (kg/m 3) | Health formula carbon residue (m%) | Hydrogen richness (m%) | The averagemolecular wt amount |
| 0.9113 | 4.37 | 13.12 | 592 |
Table 5: catalyzer F, G physical and chemical indexes
| Catalyzer | Catalyst for cracking F | Oxide catalyst G |
| Molecular sieve Si/Al in the catalyzer | 38 | |
| The catalyst activity component | HZSM-5 | Mn 2O 3，CuO |
| Particle diameter (μ m) | 30-70 | 30-70 |
| Density (kg/m 3) | 0.72 | 0.85 |
Table 6: fixed fluidized bed reaction result
Scission reaction and oxicracking coupling reaction the results are shown in Table shown in 6 on fixed fluidized bed.Be added with on the catalyzer of metal oxide, during reaction, the beds temperature drop reduces, and coupling effect is obvious.Because the reactor thermal capacitance heats than Reaktionsofen in big and the reaction process always, it is less that the beds temperature drop reduces amplitude.And owing to there is the oxidative dehydrogenation (hydrogen increases to some extent) of raw material, olefin yields is constant substantially, has realized heat coupled purpose.
Embodiment 3:
Composite catalyst reacts back regeneration in reactor, the solid acid catalyst coke burning regeneration, and metal oxide passes through oxidation regeneration.Reaction result behind the catalyst regeneration sees Table 7.Reaction is E with catalyzer, and temperature of reaction is 650 ℃, and other reaction conditionss are with embodiment 2.
Table 7: pyrolysis oxidization catalyzer E regeneration afterreaction result
Claims (8)
1. the method for a preparing olefin by catalytic oxidation of petroleum hydrocarbon, in fluidized-bed reactor, with the mixture of solid acid catalyst and variable valence metal oxide catalyst as composite catalyst, wherein the weight ratio of solid acid catalyst and variable valence metal oxide is 2-30: 1, the weight ratio of composite catalyst and petroleum hydrocarbon is 5-30: 1, and temperature of reaction is 500-720 ℃; Be reflected under the water vapor atmosphere and carry out, the weight ratio of water vapour and petroleum hydrocarbon is 0.1-1: 1;
By above-mentioned reaction,, make oxidizing reaction provide a part of heat for scission reaction the hydro carbons of the hydrocarbon catalytic cracking system olefine reaction of heat absorption and heat release, oxidation of hydrogen reaction coupling.
2. in accordance with the method for claim 1, it is characterized in that described solid acid catalyst is active constituent with the acidic molecular sieve, with aluminum phosphate, silicon aluminium phosphate or silicon oxide, aluminum oxide or its mixture as matrix.
3. in accordance with the method for claim 2, it is characterized in that described acidic molecular sieve is Y zeolite, ZSM-5 molecular sieve, beta molecular sieve or mordenite.
4. in accordance with the method for claim 1, it is characterized in that described variable valence metal oxide comprises single metal oxide and complex metal oxides.
5. according to claim 1 or 4 described methods, it is characterized in that described variable valence metal oxide is that manganese oxide, cupric oxide, ferric oxide, silver suboxide, zirconium white are or/and uhligite.
6. in accordance with the method for claim 1, it is characterized in that the weight ratio of described solid acid catalyst and variable valence metal oxide is 5-20: 1.
7. in accordance with the method for claim 1, it is characterized in that described petroleum hydrocarbon is low-carbon (LC) class hydro carbons, different boiling ranges gasoline, diesel oil, vacuum gas oil, petroleum naphtha, crude oil or residual oil and composition thereof.
8. in accordance with the method for claim 1, it is characterized in that that described fluidized-bed reactor comprises is fixed fluidized bed, fast bed, moving-bed and up riser tube fluidized-bed or descending riser tube fluidized-bed reactor.
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| US11208599B2 (en) | 2017-05-10 | 2021-12-28 | Sabic Global Technologies B.V. | Process for catalytic cracking of naphtha using radial flow moving bed reactor system |
| US11905467B2 (en) | 2018-09-06 | 2024-02-20 | Sabic Global Technologies B.V. | Process for catalytic cracking of naphtha using multi-stage radial flow moving bed reactor system |
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| CN101337190B (en) * | 2007-07-04 | 2013-07-31 | 中国科学院大连化学物理研究所 | Catalyst for preparing low-carbon olefine by catalytic cracking using fluidized-bed and preparation method and use thereof |
| US11161101B2 (en) | 2017-05-31 | 2021-11-02 | Furukawa Electric Co., Ltd. | Catalyst structure and method for producing the catalyst structure |
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| CN110678263A (en) | 2017-05-31 | 2020-01-10 | 古河电气工业株式会社 | Catalyst structure for hydrodesulfurization, hydrodesulfurization apparatus provided with same, and method for producing catalyst structure for hydrodesulfurization |
| AU2018276618B2 (en) * | 2017-05-31 | 2021-05-27 | Furukawa Electric Co., Ltd. | Functional structure and production method for functional structure |
| WO2018221703A1 (en) | 2017-05-31 | 2018-12-06 | 古河電気工業株式会社 | Catalyst structure for catalytic cracking or hydrodesulfurization, catalytic cracking device and hydrodesulfurization device using said catalyst structure, and production method for catalyst structure for catalytic cracking or hydrodesulfurization |
| CN111065714A (en) * | 2017-08-28 | 2020-04-24 | 沙特阿拉伯石油公司 | Chemical looping process for catalytic hydrocarbon cracking |
| CN113680380A (en) * | 2021-08-30 | 2021-11-23 | 苏州拓诗迅科技有限公司 | High-efficiency olefin cracking catalyst and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4111793A (en) * | 1975-09-25 | 1978-09-05 | The British Petroleum Company Limited | Olefins production |
| CN1317543A (en) * | 2000-04-07 | 2001-10-17 | 中国石油化工集团公司 | Catalytic thermocracking process of hydrocarbons for higher output of ethylene and prpylene |
-
2005
- 2005-06-09 CN CNB2005100118911A patent/CN100392047C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4111793A (en) * | 1975-09-25 | 1978-09-05 | The British Petroleum Company Limited | Olefins production |
| CN1317543A (en) * | 2000-04-07 | 2001-10-17 | 中国石油化工集团公司 | Catalytic thermocracking process of hydrocarbons for higher output of ethylene and prpylene |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11208599B2 (en) | 2017-05-10 | 2021-12-28 | Sabic Global Technologies B.V. | Process for catalytic cracking of naphtha using radial flow moving bed reactor system |
| US11905467B2 (en) | 2018-09-06 | 2024-02-20 | Sabic Global Technologies B.V. | Process for catalytic cracking of naphtha using multi-stage radial flow moving bed reactor system |
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