CN104557397A - Method for producing propylene from n-butene - Google Patents

Method for producing propylene from n-butene Download PDF

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Publication number
CN104557397A
CN104557397A CN201310499342.8A CN201310499342A CN104557397A CN 104557397 A CN104557397 A CN 104557397A CN 201310499342 A CN201310499342 A CN 201310499342A CN 104557397 A CN104557397 A CN 104557397A
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molecular sieve
zsm
sapo
butene
catalyzer
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CN201310499342.8A
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CN104557397B (en
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周峰
马会霞
张海娟
翟庆铜
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention discloses a method for producing propylene from n-butene. Under the action of a catalyst, a raw material containing n-butene is subjected to cracking reaction under the reaction temperature of 500-600 DEG C, preferably 500-550 DEG C and the total reaction pressure (the absolute pressure) is 0-0.25MPa; the weight space velocity is 1-10h<-1>, preferably 1-5h<-1>; the catalyst comprises the following components in percentage by weight: 30-60 percent of a phosphorus-modified SAPO-11 molecular sieve, 20-30 percent of a hydrogen type ZSM-5 or ZSM-22 molecular sieve and the balance of an adhesive; the load of the phosphorus-modified SAPO-11 molecular sieve is 0.2-1 percent by weight (not including phosphorus in the SAPO-11 molecular sieve). The method used in the industrial process of producing propylene from the mixed carbon-4 raw material containing n-butene has the advantage of high once-through yield of propylene.

Description

A kind of n-butene produces the method for propylene
Technical field
The present invention relates to a kind of method that n-butene produces propylene.
Background technology
Within 2011, China's propylene ultimate production is 1,468 ten thousand tons, and within 2011, China's propylene Apparent con-sumption is 1,643 ten thousand tons, and the degree of self-sufficiency is only 89.3%.It is expected that, within 2015, China's propylene Apparent con-sumption will reach 2,200 ten thousand tons.
Along with the lighting of ethylene cracking material, and by the impact of ethane cracking route and methanol-to-olefins project, in recent years, the output of the cracking of ethylene by-product propylene of originating as main propylene will reduce year by year.On the other hand, the fast development of methanol-to-olefins project, its by-product carbon four is again for market provides more n-butene resource.Therefore, with cheap and resourceful n-butene for raw material, by catalytic cracking reaction, n-butene cracking being converted into propylene, will be the less expensive approach solving propylene unbalanced supply-demand.
Existing for the method containing n-butene raw material production propylene, or be often called the method for carbon four and carbon more than four olefin catalytic cracking to produce propylene, usually adopt raw material and the technical scheme contacted under molecular sieve catalyst high-temperature low-pressure.
Catalyzer for this reaction mainly contains ZSM-5 molecular sieve (as CN1611470, CN1915928, CN1915929, CN1927786, CN102060648 etc.), also has and adopts ZSM-48(as CN1506343), SAPO-11(is as CN1927783) and SAPO-34(as CN1927783) molecular sieve is the technical scheme of catalyzer.
CN1413966 discloses a kind of method of carbon four and above olefin catalytic cracking to produce propylene, the process employs with the ZSM-5 molecular sieve of steam treatment as catalyzer, pass through steam-treated, inhibit the hydrogen transfer activity of catalyzer, make the one-pass yield of propylene bring up to 28.8% at most by 24.4%.
CN1506342 discloses a kind of method of carbon four and above olefin catalytic cracking to produce propylene, the process employs with alkali-earth metal modified ZSM-5 molecular sieve for catalyzer, and the one-pass yield of propylene can be made to bring up to 34%.
CN1704389 discloses a kind of method for olefin catalytic cracking to produce propylene, ethene, the process employs with rare-earth metal modified ZSM-5 molecular sieve for catalyzer, and the one-pass yield of propylene can be made to bring up to more than 34%.
CN103030501 discloses a kind of method of producing propylene, to the process employs with the metal-modified ZSM-5 molecular sieve of group VIII as catalyzer, makes the one-pass yield of propylene bring up to 32.9%.
CN1676499 discloses a kind of method of catalytic cracking to prepare lower carbon olefin, the process employs with the ZSM-5 molecular sieve of rare earth metal, alkaline-earth metal and phosphorous oxides modification for catalyzer, and adopts water vapour to dilute raw material, improves the one-pass yield of propylene.
CN101033166 discloses a kind of method of carbon four and carbon more than four preparing propylene by catalytic cracking olefin, to the process employs with the ZSM-5 molecular sieve of heteropolyacid modification as catalyzer, improves the one-pass yield of propylene.
CN102166529 discloses a kind of catalyzer and application method of C _ 4 alkene catalytic pyrolysis preparing ethylene and propylene, the process employs with the ZSM-5 molecular sieve of P Modification as catalyzer, and adopt water vapour to dilute raw material, there is certain promoter action to the raising of propylene one-pass yield.
Still there is the low deficiency of object product propylene once through yield in the ZSM-5 molecular sieve catalyzer adopted in prior art, by the catalyst modification method described in above-mentioned document, suitably can improve the one-pass yield of propylene, but productivity of propylene still needs the space of improving further.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of method of producing propylene for n-butene.The method, for containing in the commercial run of n-butene mixed c 4 raw material production propylene, has the advantage that propylene once through yield is high.
N-butene produces a method for propylene, and the raw material containing n-butene carries out scission reaction under the effect of catalyzer, and temperature of reaction is 500 ~ 600 DEG C, preferably 500 ~ 550 DEG C, reaction stagnation pressure (absolute pressure) is 0 ~ 0.5, and preferably 0 ~ 0.25MPa, weight space velocity is 1 ~ 10h -1, preferably 1 ~ 5h -1wherein said catalyst, the SAPO-11 molecular sieve of the P Modification containing 30 ~ 60%, the Hydrogen ZSM-5 of 20 ~ 30% or ZSM-22 molecular sieve, surplus is binding agent, in the SAPO-11 molecular sieve of described P Modification, the charge capacity of phosphorus is 0.2 ~ 1% by weight percentage, (not comprising the phosphorus in SAPO-11 molecular sieve).
In the inventive method, the described raw material containing n-butene is from the by-product carbon four of carbon four or methanol-to-olefins device after the ether of the methyl tertiary butyl ether device of refinery or petrochemical plant, and wherein n-butene mass content is 10 ~ 95%, and preferably 30 ~ 90%, more preferably 50 ~ 90%.
In the inventive method, at the procatalyst preferably pre-treatment 1-3 hour in the inert atmosphere of 600 ~ 700 DEG C of charging, described inert atmosphere comprises argon gas, helium, neon, nitrogen etc., preferred nitrogen.
In the inventive method, described binding agent can be binding agent conventional in the catalyst preparing of this area, as one or more in aluminum oxide, silicon-dioxide or clay.Preferred binding agent is aluminum oxide, as pseudo-boehmite.
In the inventive method, described SAPO-11, ZSM-5 and ZSM-22 molecular sieve can adopt commercial goods or prepare by existing scheme.Wherein the Si/Al mol ratio of Hydrogen ZSM-5 or ZSM-22 molecular sieve is 50 ~ 500.
In the inventive method, described catalyst preparation process is as follows: first SAPO-11 and the ZSM-5 of P Modification or ZSM-22 molecular sieve are mixed, then mediates with binding agent and mix shaping, and drying, roasting obtain final catalyzer.Shaping of catalyst can adopt extrusion process, pressed disc method, drip ball or spin comminution granulation, and wherein preferably extrusion process is shaping.Catalyzer is dried 5 ~ 20 hours in 80 ~ 150 DEG C after shaping, roasting 2 ~ 15 hours at being 400 ~ 600 DEG C, maturing temperature preferably 450 ~ 650 DEG C.
In the preparation method of above-mentioned catalyzer, the preparation process of the SAPO-11 molecular sieve of P Modification is as follows: in a certain amount of solution containing phosphate, add SAPO-11 molecular sieve, dip treating 10 ~ 20 hours under room temperature, then evaporating water, through 100 ~ 150 DEG C of dryings, finally in 450 ~ 650 DEG C of roastings 2 ~ 24 hours.Wherein, described solution containing phosphate is selected from the mixed aqueous solution of one or more in phosphoric acid, ammonium phosphate, primary ammonium phosphate and Secondary ammonium phosphate, preferably phosphoric acid hydrogen two ammonium.
Effect of the present invention and benefit are, containing n-butene highly selective skeletal isomerization can be made to turn to the molecular sieve component of iso-butylene in catalyzer, adopt the catalyzer that the inventive method is obtained, produce in propylene process, can improve propylene one-pass yield for n-butene.
Embodiment
Below by embodiment, the present invention is set forth further.
SAPO-11 molecular sieve used in the following example, by Tianjin, Kai Meisi Chemical Co., Ltd. provides, wherein by weight percentage, P 2o 5content is 47.2%, SiO 2content is 11.2%, Al 2o 3content is 41.6%.Si/Al mol ratio used in the following example is NaZSM-5 and the NaZSM-22 molecular sieve of 50 ~ 100, is provided respectively by Tianjin Nan Hua catalyzer company limited and Dalian Ke Teli Chemical Co., Ltd..The chemical reagent used, as indicated without special, is analytical reagent.Catalyst preparing binding agent used is SW-17 type aluminium hydrate powder, and pore volume is 0.47-0.53 ml/g, is greater than 250 m than table 2/ g, mean pore size is 7.5-8.5 nm, and by Zibo, safe photoinitiator chemical company limited provides.
Embodiment 1 ~ 3
The preparation of the SAPO-11 molecular sieve of P Modification.
Take Secondary ammonium phosphate 0.43g, 1.07g and 2.13g, add 50g deionized water respectively, mix, then add SAPO-11 molecular sieve 50g respectively, flood 4 hours under room temperature.Then evaporating water in Rotary Evaporators, dries and 650 DEG C of roastings through 110 DEG C, obtains the SAPO-11 molecular sieve of P Modification process.Wherein, the charge capacity of phosphorus is respectively 0.2%, 0.5% and 1.0% by weight percentage, and the molecular sieve of corresponding P Modification is labeled as 0.2%P/SAPO-11,0.5%P/SAPO-11 and 1.0%P/SAPO-11.
Embodiment 4
HZSM-5 molecular sieve.
Be the NaZSM-5 molecular sieve of 56, the NH of 214 g by the Si/Al mol ratio of 200 g 4cl and 4000 g deionized waters mix making beating, stir 2 hours at 75 DEG C, filter, above-mentioned exchange process 3 ~ 5 times are repeated again at 75 DEG C, through filtering after exchange, gained filter cake 30 times of deionized water cleaning downs to ZSM-5 molecular sieve butt weight, through 110 DEG C of oven dry and 550 DEG C of roastings, obtain Hydrogen ZSM-5 molecular sieve, be designated as HZSM-5.
Embodiment 5
HZSM-22 molecular sieve.
Be the NaZSM-22 molecular sieve of 87, the NH of 214 g by the Si/Al mol ratio of 200 g 4cl and 4000 g deionized waters mix making beating, stir 2 hours at 75 DEG C, filter, above-mentioned exchange process 3 ~ 5 times are repeated again at 75 DEG C, through filtering after exchange, gained filter cake 30 times of deionized water cleaning downs to ZSM-5 molecular sieve butt weight, through 110 DEG C of oven dry and 550 DEG C of roastings, obtain Hydrogen ZSM-22 molecular sieve, be designated as HZSM-22.
Embodiment 6
The SW-17 aluminium hydrate powder of the HZSM-5 molecular sieve powder of 31 g of preparation in the 0.2%P/SAPO-11 molecular sieve powder of 62 g of preparation in embodiment 1 and embodiment 4 with 35 g is mixed.Then add 3 g sesbania powder and 100 g massfractions are the aqueous nitric acid of 1%, mediate at CD4X1TS type polyfunctional catalyst forming machine and form dense thick paste body, adopt the stainless steel moulded board extrusion molding in 1.5 mm holes.Gained extrudate prior to drying under room temperature 24 hours, then is dried 8 hours in 110 DEG C, finally in 650 DEG C of roastings 12 hours, obtains final catalyzer, is labeled as C-1.The final composition of catalyzer C-1 is the 0.2%P/SAPO-11 of 50% by weight percentage, the HZSM-5 of 25% and the binding agent of 25%.
Adopt the performance of n-butene preparing propylene by catalytic cracking reaction evaluating catalyzer.Before each evaluating catalyst, by catalyzer first pre-treatment 2 hours in the High Purity Nitrogen atmosphere of 650 DEG C, then be cooled to temperature of reaction.With carbon after ether four for raw material, raw material composition is in table 1.Reaction product adopts the on-line analysis of Agilent 7890 type gas-chromatography.
Table 1
Component Raw material composition (% by weight)
Carbon three 0.12
Trimethylmethane 48.44
Iso-butylene 1.93
1-butylene 14.41
Cis-2-butene 10.33
Trans-2-butene 15.15
Normal butane 9.52
Carbon five 0.09
Take C-1 as catalyzer, with carbon four after above-mentioned ether for raw material, at 550 DEG C, weight space velocity is 3h -1, stagnation pressure (absolute pressure) is for reacting under 0.20MPa condition.React 200 constantly little, propylene one-pass yield is 34.9%.
Embodiment 7
The SW-17 aluminium hydrate powder of the HZSM-5 molecular sieve powder of 25 g of preparation in the 0.5%P/SAPO-11 molecular sieve powder of 72 g of preparation in embodiment 2 and embodiment 4 with 28 g is mixed.Then add 3 g sesbania powder and 100 g massfractions are the aqueous nitric acid of 1%, mediate at CD4X1TS type polyfunctional catalyst forming machine and form dense thick paste body, adopt the stainless steel moulded board extrusion molding in 1.5 mm holes.Gained extrudate prior to drying under room temperature 24 hours, then is dried 8 hours in 110 DEG C, finally in 650 DEG C of roastings 12 hours, obtains final catalyzer, is labeled as C-2.The final composition of catalyzer C-2 is the 0.5%P/SAPO-11 of 60% by weight percentage, the HZSM-5 of 20% and the binding agent of 20%.
Take C-2 as catalyzer, with carbon four after the ether described in embodiment 6 for raw material, at 530 DEG C, weight space velocity is 4h -1, stagnation pressure (absolute pressure) is for reacting under 0.15MPa condition, and reaction 200 is constantly little, and propylene one-pass yield is 35.6%.
Embodiment 8
The SW-17 aluminium hydrate powder of the HZSM-5 molecular sieve powder of 37 g of preparation in the 1.0%P/SAPO-11 molecular sieve powder of 36 g of preparation in embodiment 3 and embodiment 5 with 56 g is mixed.Then add 3 g sesbania powder and 100 g massfractions are the aqueous nitric acid of 1%, mediate at CD4X1TS type polyfunctional catalyst forming machine and form dense thick paste body, adopt the stainless steel moulded board extrusion molding in 1.5 mm holes.Gained extrudate prior to drying under room temperature 24 hours, then is dried 8 hours in 110 DEG C, finally in 650 DEG C of roastings 12 hours, obtains final catalyzer, is labeled as C-3.The final composition of catalyzer C-3 is the 1.0%P/SAPO-11 of 30% by weight percentage, the HZSM-5 of 30% and the binding agent of 40%.
Take C-3 as catalyzer, with carbon four after the ether described in embodiment 6 for raw material, at 540 DEG C, weight space velocity is 2h -1, stagnation pressure (absolute pressure) is for reacting under 0.25MPa condition, and reaction 200 is constantly little, and propylene one-pass yield is 34.2%.
comparative example 1
The SW-17 aluminium hydrate powder of the HZSM-5 molecular sieve powder of 94 g of preparation in embodiment 4 with 35 g is mixed.Then add 3 g sesbania powder and 100 g massfractions are the aqueous nitric acid of 1%, mediate at CD4X1TS type polyfunctional catalyst forming machine and form dense thick paste body, adopt the stainless steel moulded board extrusion molding in 1.5 mm holes.Gained extrudate prior to drying under room temperature 24 hours, then is dried 8 hours in 110 DEG C, finally in 650 DEG C of roastings 12 hours, obtains final catalyzer, is labeled as C-4.The final composition of catalyzer C-4 is the HZSM-5 of 75% and the binding agent of 25% by weight percentage.
Take C-4 as catalyzer, with carbon four after the ether described in embodiment 6 for raw material, at 550 DEG C, weight space velocity is 3h -1, stagnation pressure (absolute pressure) is for reacting under 0.20MPa condition, and reaction 200 is constantly little, and propylene one-pass yield is 21.7%.(condition is identical with embodiment 6)
comparative example 2
The SW-17 aluminium hydrate powder of the 0.2%P/SAPO-11 molecular sieve powder of 94 g of preparation in embodiment 1 with 35 g is mixed.Then add 3 g sesbania powder and 100 g massfractions are the aqueous nitric acid of 1%, mediate at CD4X1TS type polyfunctional catalyst forming machine and form dense thick paste body, adopt the stainless steel moulded board extrusion molding in 1.5 mm holes.Gained extrudate prior to drying under room temperature 24 hours, then is dried 8 hours in 110 DEG C, finally in 650 DEG C of roastings 12 hours, obtains final catalyzer, is labeled as C-5.The final composition of catalyzer C-5 is the 0.2%P/SAPO-11 of 75% and the binding agent of 25% by weight percentage.
Take C-4 as catalyzer, with carbon four after the ether described in embodiment 6 for raw material, at 550 DEG C, weight space velocity is 3h -1, stagnation pressure (absolute pressure) is for reacting under 0.20MPa condition, and reaction 200 is constantly little, and propylene one-pass yield is only 3.8%.

Claims (10)

1. n-butene produces a method for propylene, and it is characterized in that: the raw material containing n-butene carries out scission reaction under the effect of catalyzer, temperature of reaction is 500 ~ 600 DEG C, and reaction stagnation pressure (absolute pressure) is 0 ~ 0.5MPa, and weight space velocity is 1 ~ 10h -1wherein said catalyst, the SAPO-11 molecular sieve of the P Modification containing 30 ~ 60%, the Hydrogen ZSM-5 of 20 ~ 30% or ZSM-22 molecular sieve, surplus is binding agent, and in the SAPO-11 molecular sieve of described P Modification, the charge capacity of phosphorus is 0.2-1% by weight percentage.
2. method according to claim 1, is characterized in that: temperature of reaction is 500 ~ 550 DEG C, and reaction stagnation pressure (absolute pressure) is 0 ~ 0.25MPa, and weight space velocity is 1 ~ 5h -1.
3. method according to claim 1, is characterized in that: the described raw material containing n-butene is from the by-product carbon four of carbon four or methanol-to-olefins device after the ether of the methyl tertiary butyl ether device of refinery or petrochemical plant, and wherein n-butene mass content is 10 ~ 95%.
4. method according to claim 1, is characterized in that: at procatalyst pre-treatment 1-3 hour in the inert atmosphere of 600-700 DEG C of charging, described inert atmosphere comprises argon gas, helium, neon, nitrogen.
5. method according to claim 1, is characterized in that: described SAPO-11, ZSM-5 and ZSM-22 molecular sieve adopts commercial goods or by existing scheme preparation, wherein the Si/Al mol ratio of Hydrogen ZSM-5 or ZSM-22 molecular sieve is 50 ~ 500.
6. method according to claim 1, it is characterized in that: described catalyst preparation process is as follows: first SAPO-11 and the ZSM-5 of P Modification or ZSM-22 molecular sieve are mixed, mediate with binding agent and mix shaping, drying, roasting obtain final catalyzer.
7. method according to claim 6, is characterized in that: shaping of catalyst can adopt extrusion process, pressed disc method, drip ball or spin comminution granulation.
8. method according to claim 6, is characterized in that: catalyzer is dried 5 ~ 20 hours in 80 ~ 150 DEG C after shaping, roasting 2 ~ 15 hours at being 400 ~ 600 DEG C.
9. method according to claim 1, it is characterized in that: the preparation process of the SAPO-11 molecular sieve of P Modification is as follows: in a certain amount of solution containing phosphate, add SAPO-11 molecular sieve, dip treating 10 ~ 20 hours under room temperature, then evaporating water, through 100 ~ 150 DEG C of dryings, finally in 450 ~ 650 DEG C of roastings 2 ~ 24 hours.
10. method according to claim 9, is characterized in that: described solution containing phosphate is selected from the mixed aqueous solution of one or more in phosphoric acid, ammonium phosphate, primary ammonium phosphate and Secondary ammonium phosphate.
CN201310499342.8A 2013-10-23 2013-10-23 Method for producing propylene from n-butene Active CN104557397B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112679295A (en) * 2019-10-18 2021-04-20 中国石油化工股份有限公司 Method for producing propylene by converting tert-butyl alcohol
CN114308139A (en) * 2021-12-31 2022-04-12 中触媒新材料股份有限公司 Continuous production device for spherical catalyst particles and application method thereof

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CN102266793A (en) * 2011-06-21 2011-12-07 西北大学 Catalyst for producing propylene and producing method and application thereof
CN102285851A (en) * 2010-06-18 2011-12-21 中国石油化工股份有限公司 Method for increasing yields of ethylene and propylene
CN102463133A (en) * 2010-11-04 2012-05-23 中国石油化工股份有限公司 Catalyst for preparing olefin by catalytic cracking, preparation method and application thereof

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Cited By (4)

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Publication number Priority date Publication date Assignee Title
CN112679295A (en) * 2019-10-18 2021-04-20 中国石油化工股份有限公司 Method for producing propylene by converting tert-butyl alcohol
CN112679295B (en) * 2019-10-18 2022-11-04 中国石油化工股份有限公司 Method for producing propylene by converting tert-butyl alcohol
CN114308139A (en) * 2021-12-31 2022-04-12 中触媒新材料股份有限公司 Continuous production device for spherical catalyst particles and application method thereof
CN114308139B (en) * 2021-12-31 2023-10-24 中触媒新材料股份有限公司 Continuous production device for spherical catalyst particles and application method thereof

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