CN1156417C - Method for producing propen of C4 and its above colefines catalytic cracking - Google Patents
Method for producing propen of C4 and its above colefines catalytic cracking Download PDFInfo
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- CN1156417C CN1156417C CNB01131947XA CN01131947A CN1156417C CN 1156417 C CN1156417 C CN 1156417C CN B01131947X A CNB01131947X A CN B01131947XA CN 01131947 A CN01131947 A CN 01131947A CN 1156417 C CN1156417 C CN 1156417C
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- Prior art keywords
- catalytic cracking
- molecular sieve
- zsm
- above olefin
- produce propylene
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Abstract
The present invention relates to a method for producing propylene by catalytically cracking C4 and above olefin. The present invention mainly solves the problems that the yield rate of propylene as a purpose product is low, and used raw material is only suitable for artificial preparation existing in the prior art. The present invention better solves the problems by adopting the technical scheme that a ZSM type molecular sieve is processed for 1 to 80 hours by water vapor under the temperature of 500 to 700 DEG C, and the ZSM type molecular sieve which is modified is used as a catalyst. The present invention can be used in industrial production for producing propylene by catalytically cracking olefin.
Description
Technical field
The present invention relates to the method for carbon four and above olefin catalytic cracking to produce propylene thereof.
Background technology
In the world wide, the appreciable C of quantity is arranged at present
4And C
4Above olefin feedstock.Be subjected to the influence of factors such as the variation in Chemicals market and transportation cost, it is a kind of approach that utilizes preferably that these raw materials are carried out deep processing on the spot.C wherein
4And C
4It is a kind of promising technology that above conversion of olefines becomes propylene.This technology can be utilized superfluous, that added value is lower relatively C on the one hand
4And C
4Above olefin feedstock can obtain broad-spectrum propylene product again on the other hand.
Proposed a kind of among the EP0109059A1 C
4～C
12Conversion of olefines is the technology of propylene.Catalyzer uses SiO in the document
2/ Al
2O
3Compare the ZSM-5 molecular sieve smaller or equal to 300, temperature of reaction is 400～600 ℃, and the alkene air speed was greater than 50 hours
-1Investigated the influence of the raw material, temperature of reaction, air speed of various artificial preparations in this patent in more detail to catalytic cracking reaction.Yet the ZSM-5 molecular sieve catalyst that uses in this patent does not carry out modification to be handled, so selectivity of catalyst and stable unsatisfactory.And the raw material that uses in the experiment is not from industrial installation, but the C of artificial preparation
4～C
12Raw material can not reflect really that trace impurity is to the influence of catalyzer in the industrial raw material.
Proposed a kind of among the US5981818 C
4～C
7Conversion of olefines is C
3And C
4The technology of alkene.Catalyzer uses SiO in the document
2/ Al
2O
3Mol ratio is 10～200 Pentasil type molecular sieve catalyst.The BET specific surface is 300～600 meters
2/ gram, particle diameter is 0.1～0.9 micron.Temperature of reaction is 380～500 ℃.Characteristics of above-mentioned patent are to sneak into a certain proportion of water vapour, wherein H in raw material
2O/HC is 0.5～3 (weight %).It is said to add the carbon distribution that water vapour can slow down catalyzer, improve the stability of catalyzer.The ZSM-5 molecular sieve catalyst that uses in same this patent does not carry out modification to be handled, so the yield of purpose product propylene is not high, and raw materials used also be artificial preparation.
Proposed a kind of among the WO 9,0/1 1338 C
4～C
12Alkane is converted into C
2～C
4The technology of alkene.A kind of technology of hydrocarbon polymer being produced gaseous olefin through catalyzed conversion has been proposed among the EP0305720.
Summary of the invention
Technical problem to be solved by this invention is to overcome in the past to exist purpose product propene yield lower in the document, and the raw materials used defective that only is suitable for artificial preparation, and a kind of new carbon four and the method for above olefin catalytic cracking to produce propylene thereof are provided.This method has raw material can be suitable for the full scale plant raw material, and the high characteristics of the yield of propylene.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: the method for a kind of carbon four and above olefin catalytic cracking to produce propylene thereof, with silica alumina ratio is that 38～500 ZSM type molecular sieve is a catalyzer, material carbon four and above alkene thereof are 400～600 ℃ in temperature of reaction, reaction pressure is 0～0.15MPa, and the liquid phase air speed is 10～50 hours
-1Under the condition scission reaction takes place, wherein earlier to use steam-treated, treatment temp be 500～700 ℃ to ZSM type molecular sieve, and the treatment time is 1～80 hour.
Carbon four and above olefin feedstock thereof can be from the C-4-fractions of steam cracking device in the mixed c 4 of plant catalytic cracker or the ethylene plant in the technique scheme.The temperature of reaction preferable range is 540～580 ℃, and liquid phase air speed preferable range is 10～30 hours
-1, the silica alumina ratio preferable range is 80～300, and ZSM type molecular sieve preferred version is for being selected from ZSM-5 molecular sieve or ZSM-11 molecular sieve, and more preferably scheme is for being selected from the ZSM-5 molecular sieve.The treatment temp preferable range of steam-treated ZSM type molecular sieve is 550～650 ℃, and steam-treated time preferable range is 20～60 hours, and the water vapor weight concentration can be 40～100%.Can adopt water vapor and rare gas element He or N
2Mix in certain proportion and realize.
Can use Al in the moulding process of the catalyzer that uses among the present invention
2O
3Or SiO
2As binding agent, by extrusion moulding, the consumption of binding agent is generally 0～70% (weight).The silica alumina ratio of the ZSM type zeolite that uses in the catalyzer of the present invention has certain influence to reaction.In general, the catalyzer of low silica alumina ratio helps improving the conversion of olefines rate, and the catalyzer of high silica alumina ratio more helps improving the selectivity of propylene.
The present invention carries out steam-treated by the silica alumina ratio of employing control ZSM type molecular sieve and with ZSM type zeolite, make molecular sieve that framework dealumination to a certain degree take place, the strength of acid and the acid amount of molecular sieve have been reduced, thereby suppressed hydrogen transfer reactions, alkene can be kept as far as possible, improved the yield of propylene, the applicable full scale plant raw material of raw material has been obtained better technical effect simultaneously.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1～3]
Temperature of reaction has remarkable influence to the reaction of olefin catalytic cracking to produce propylene, in general, mentions the generation that temperature of reaction helps the reaction product propylene.
With the 5 commercial silica alumina ratios of gram (mol ratio) is 50 ZSM-5 molecular sieve, places 200 milliliters, 5% weight NH
4NO
3In the solution, exchange is 2 hours under 85～90 ℃ of temperature, repeats 3 times.Exchange is after washing, 120 ℃ of oven dry obtain the ZSM-5 molecular sieve of Hydrogen.After the ZSM-5 molecular sieve of 5 gram Hydrogens adds 5 milliliters of silicon sol mixing, extrusion moulding.Through 120 ℃ of oven dry, make the HZ-50 catalyzer after 400 ℃ of roastings again.The activation 2 hours under 500 ℃, nitrogen atmosphere of reaction procatalyst.The C that uses in the experiment
4Raw material is from the catalytic cracking unit in the refinery (FCC).
Change temperature of reaction, reaction result is as shown in table 1.
Table 1
| Project | Raw material is formed (weight %) | Product is formed (weight %) | ||
| 540℃ | 550℃ | 570℃ | ||
| C 2Below | - | 1.83 | 2.01 | 2.43 |
| Ethene | - | 4.44 | 4.79 | 5.80 |
| Propane | 0.20 | 9.09 | 8.85 | 8.09 |
| Propylene | 0.20 | 15.00 | 15.57 | 17.50 |
| Trimethylmethane | 28.64 | 34.21 | 33.52 | 33.27 |
| Normal butane | 7.53 | 9.93 | 9.82 | 9.90 |
| Anti-butylene | 16.29 | 4.41 | 4.48 | 3.77 |
| Butene-1 | 15.03 | 3.50 | 3.54 | 3.24 |
| Iso-butylene | 18.56 | 7.59 | 7.58 | 6.47 |
| Maleic | 11.73 | 3.35 | 3.45 | 3.28 |
| C 4More than | 1.68 | 6.61 | 6.36 | 6.25 |
Catalyzer: HZ-50 LHSV=15 hour
-1
[embodiment 4～7]
Air speed also has remarkable influence to the reaction of olefin catalytic cracking to produce propylene, in general, improves reaction velocity and helps the selectivity of reaction product propylene, but can reduce the conversion of olefines rate.
Synthesizing silica alumina ratio (mol ratio) according to US3702886 is 100 ZSM-5 molecular sieve, obtains the HZ-1 catalyzer according to the preparation method identical with embodiment 1～3 then.
Change the liquid air speed of raw material, reaction conditions and reaction result are as shown in table 2.
Table 2
| Project | Raw material is formed (weight %) | Air speed (LHSV) hour -1 | |||
| 10 | 20 | 30 | 50 | ||
| C 2Below | - | 1.69 | 0.92 | 0.58 | 0.34 |
| Ethene | - | 5.75 | 4.83 | 3.95 | 2.82 |
| Propane | 0.34 | 8.57 | 5.04 | 3.40 | 2.18 |
| Propylene | 0.31 | 16.36 | 17.62 | 17.27 | 15.32 |
| Trimethylmethane | 31.25 | 37.26 | 37.60 | 37.39 | 36.51 |
| Normal butane | 7.52 | 10.87 | 10.27 | 9.91 | 9.41 |
| Anti-butylene | 15.67 | 3.05 | 3.90 | 4.68 | 6.15 |
| Butene-1 | 14.56 | 2.38 | 3.02 | 3.66 | 4.80 |
| Iso-butylene | 18.69 | 5.32 | 6.75 | 8.04 | 10.09 |
| Maleic | 10.81 | 2.27 | 2.91 | 3.50 | 4.63 |
| C 4More than | 1.34 | 7.08 | 7.06 | 6.58 | 7.70 |
Catalyzer: 540 ℃ of HZ-1 temperature of reaction
[embodiment 8～10]
Get HZ-1 catalyzer 5 grams, at 650 ℃, 100% water vapor conditions was handled 20 hours down, made catalyzer HZ-2.Change the treatment condition of water vapor, obtain catalyzer HZ-3.Catalyzer HZ-2, HZ-3 and the catalyzer HZ-1 that obtains with embodiment 4～7 use the C that uses among the embodiment 1
4Raw material compares experiment, and reaction result is as shown in table 3.
Table 3
| Catalyzer | Olefin conversion (%) | The selectivity of propylene (%) | The yield of propylene (%) | |
| Title | The steam-treated condition | |||
| HZ-1 | Be untreated | 69.4 | 35.1 | 24.4 |
| HZ-2 | 650 ℃, 100% water vapour, 20 hours | 63.4 | 43.8 | 27.8 |
| HZ-3 | 550 ℃, 80% water vapour, 48 hours | 64.1 | 42.7 | 27.4 |
Temperature of reaction: 520 ℃ LHSV=15 hour
-1
[embodiment 11]
Synthesize silica alumina ratio (mol ratio) according to US3702886 and be respectively 80,200 and 300 ZSM-5 molecular sieve.With 5 gram silica alumina ratios is 80 ZSM-5 molecular sieve, places 200 milliliters, 5 weight %NH
4NO
3In the solution, exchange is 2 hours under 85～90 ℃ of temperature, repeats 3 times.Exchange is after washing, 120 ℃ of oven dry obtain the ZSM-5 molecular sieve of Hydrogen.After the ZSM-5 molecular sieve of 5 gram Hydrogens adds 5 milliliters of silicon sol mixing, extrusion moulding.Through 120 ℃ of oven dry, make the work in-process catalyzer after 400 ℃ of roastings again.The work in-process catalyzer feeds the water vapor of 40 volume % (all the other are nitrogen) under 600 ℃ temperature, handled 60 hours.Drying, roasting obtain the HZ-4 catalyzer.
Getting 5 gram silica alumina ratios more respectively is 200 and 300 ZSM-5 molecular sieve, adopts the method identical with embodiment 11 to make the work in-process catalyzer, adopts different steam-treated conditions then respectively, makes catalyzer HZ-5 and HZ-6.
[embodiment 12～13]
The activation 2 hours under 500 ℃, nitrogen atmosphere of reaction procatalyst.The C that uses in the experiment
4Raw material is formed with embodiment 1, for from the catalytic cracking unit in the refinery (FCC).The treatment condition and the reaction result of catalyzer see Table 4.
Table 4
| Catalyzer | Olefin conversion (%) | The selectivity of propylene (%) | The yield of propylene (%) | |
| Title | The steam-treated condition | |||
| HZ-4 | SiO 2/Al 2O 3=80 (mol ratios), 40% water vapor, 600 ℃, 60 hours | 65.0 | 41.1 | 26.7 |
| HZ-5 | SiO 2/Al 2O 3=200 (mol ratios), 100% water vapor, 650 ℃, 20 hours | 63.1 | 45.6 | 28.8 |
| HZ-6 | SiO 2/Al 2O 3=300 (mol ratios), 80% water vapor, 550 ℃, 48 hours | 51.3 | 48.4 | 24.8 |
Temperature of reaction: 527 ℃ of liquid air speeds (LHSV)=15 hour
-1
Claims (10)
1, the method for a kind of carbon four and above olefin catalytic cracking to produce propylene thereof, with silica alumina ratio is that 38～500 ZSM type molecular sieve is a catalyzer, material carbon four and above alkene thereof are 400～600 ℃ in temperature of reaction, and reaction pressure is 0～0.15MPa, and the liquid phase air speed is 10～50 hours
-1Under the condition scission reaction takes place, it is characterized in that it is 500～700 ℃ that ZSM type molecular sieve is used steam-treated, treatment temp earlier, the treatment time is 1～80 hour.
2,, it is characterized in that carbon four and above olefin feedstock thereof C-4-fraction from steam cracking device in the mixed c 4 of plant catalytic cracker or the ethylene plant according to the method for described carbon four of claim 1 and above olefin catalytic cracking to produce propylene thereof.
3,, it is characterized in that temperature of reaction is 540～580 ℃ according to the method for described carbon four of claim 1 and above olefin catalytic cracking to produce propylene thereof.
4,, it is characterized in that the liquid phase air speed is 10～30 hours according to the method for described carbon four of claim 1 and above olefin catalytic cracking to produce propylene thereof
-1
5,, it is characterized in that silica alumina ratio is 80～300 according to the method for described carbon four of claim 4 and above olefin catalytic cracking to produce propylene thereof.
6,, it is characterized in that ZSM type molecular sieve is ZSM-5 molecular sieve or ZSM-11 molecular sieve according to the method for described carbon four of claim 1 and above olefin catalytic cracking to produce propylene thereof.
7,, it is characterized in that ZSM type molecular sieve is the ZSM-5 molecular sieve according to the method for described carbon four of claim 6 and above olefin catalytic cracking to produce propylene thereof.
8,, it is characterized in that the steam-treated temperature is 550～650 ℃ according to the method for described carbon four of claim 1 and above olefin catalytic cracking to produce propylene thereof.
9, according to the method for described carbon four of claim 1 and above olefin catalytic cracking to produce propylene thereof, it is characterized in that the steam-treated time is 20～60 hours,
10,, it is characterized in that the water vapor weight concentration is 40～100% according to the method for described carbon four of claim 1 and above olefin catalytic cracking to produce propylene thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB01131947XA CN1156417C (en) | 2001-10-22 | 2001-10-22 | Method for producing propen of C4 and its above colefines catalytic cracking |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB01131947XA CN1156417C (en) | 2001-10-22 | 2001-10-22 | Method for producing propen of C4 and its above colefines catalytic cracking |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1413966A CN1413966A (en) | 2003-04-30 |
| CN1156417C true CN1156417C (en) | 2004-07-07 |
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ID=4671002
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100460369C (en) * | 2005-09-07 | 2009-02-11 | 中国石油化工股份有限公司 | Method for preparing propylene by catalytic cracking olefin with four carbon or above |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2859994B1 (en) * | 2003-09-19 | 2005-10-28 | Inst Francais Du Petrole | PROCESS FOR THE DIRECT CONVERSION OF A CHARGE COMPRISING FOUR AND / OR FIVE ATOMIC CARBON OLEFINS FOR THE PRODUCTION OF PROPYLENE |
| CN1312092C (en) * | 2004-02-02 | 2007-04-25 | 中国科学院大连化学物理研究所 | Method of preparing propylenel ethylene by using MCM-22 molecular sieve to catalyze C4-C6 olefine hydrocarbon |
| CN100457697C (en) * | 2006-03-09 | 2009-02-04 | 中国石油化工股份有限公司 | Method for preparing propylene by catalytic cracking olefin with four carbon atoms or above |
| CN101279280B (en) * | 2007-04-04 | 2010-07-28 | 中国石油化工股份有限公司 | Catalyst for preparing propylene transformed from methanol |
| CN101347745B (en) * | 2007-07-18 | 2010-10-27 | 中国石油化工股份有限公司 | Catalyst for producing ethylene and propylene by catalytic pyrolysis of naphtha |
| CN103121891B (en) * | 2011-11-18 | 2015-07-08 | 中国石油化工股份有限公司 | Method for producing low-carbon olefin |
| CN107915564A (en) * | 2016-10-10 | 2018-04-17 | 中国石油化工股份有限公司 | The method of four~carbon of carbon, eight olefins by catalytic cracking |
-
2001
- 2001-10-22 CN CNB01131947XA patent/CN1156417C/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100460369C (en) * | 2005-09-07 | 2009-02-11 | 中国石油化工股份有限公司 | Method for preparing propylene by catalytic cracking olefin with four carbon or above |
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|---|---|
| CN1413966A (en) | 2003-04-30 |
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