CN107286985A - The method of C 4 olefin gasoline component coproduction ethene or propylene - Google Patents
The method of C 4 olefin gasoline component coproduction ethene or propylene Download PDFInfo
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- CN107286985A CN107286985A CN201610223851.1A CN201610223851A CN107286985A CN 107286985 A CN107286985 A CN 107286985A CN 201610223851 A CN201610223851 A CN 201610223851A CN 107286985 A CN107286985 A CN 107286985A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/36—Steaming
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/37—Acid treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/38—Base treatment
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38
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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
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- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The present invention relates to the method for C 4 olefin gasoline component coproduction ethene or propylene, mainly solve C 4 olefin oligomerisation gasoline component liquid in the prior art and receive the problem of low and ethylene, propylene content is low.The present invention comprises the following steps by using the method for C 4 olefin gasoline component coproduction ethene or propylene：In the presence of the catalyst of ZSM 35, C 4 olefin carries out reaction generation gasoline component coproduction ethene or propylene；The SiO of the catalyst of ZSM 352/Al2O3Mol ratio be 10~19, reaction temperature is 360~390 DEG C, and reaction pressure preferably solves the problem for 0~0.1MPa technical scheme, in the industrial production available for C 4 olefin gasoline component coproduction ethene or propylene.
Description
Technical field
The present invention relates to the method for C 4 olefin gasoline component coproduction ethene or propylene.
Background technology
C4 low-carbon alkenes and hydrocarbon mixture containing C4 low-carbon alkenes are the accessory substances of petrochemical industry and oil refining industry, originate from ethene work
The processes such as journey, oil plant and natural gas purification.Mix in C 4 olefin in addition to a small number of components are used as industrial chemicals by extracting, very
Major part is used as cheap fuel, and main cause is that fuel price is higher.With China's strategy to develop western regions and transfering natural gas from the west to the east
The smooth implementation of engineering, and from the large-scale use of coal dimethyl ether synthesis technology, mixing C 4 olefin is at last by pipeline
The more cheap fuel such as natural gas gradually extrudes commercial market.These are mixed into C 4 olefin by Catalytic processes and is converted into vapour
Oily component, can not only open up new raw material source for the production of gasoline, and can Optimum utilization lighter hydrocarbons resource, raising petroleum chemical enterprise warp
Ji benefit.
On the other hand, butyl ether (MTBE), ethyl tert-butyl ether (ETBE) (ETBE) are shown in reformulated gasoline and oxygenated gasoline
Go out higher octane number, low-steam pressure and good solubility in gasoline fraction hydro carbons and become excellent gasoline and add
Plus component, demand increases sharply in the whole world, causes many ether-based devices all to be expanded production.In production MTBE ether
Disguise in the outlet material put, separate after methanol and ether, normal olefine accounts for 40-100 weight %, and expanding production for device will
The n-butene resource after a large amount of ethers is produced, is burnt up at present mainly as liquefied gas, is badly in need of finding new purposes.
By carbon four after the ether of olefin-containing under special-purpose catalyst effect, occurs the reaction such as oligomerisation, isomerization, production is rich in different pungent
The high-knock rating gasoline cut of alkene, is also an effective utilization ways.
CN1597867A discloses a kind of alkene aromatisation being used in refinery's liquefied gas and alkylated reaction generation higher octane
It is worth the catalyst of clean gasoline component, the catalyst is by SiO2/Al2O3Mol ratio for 20~80 ZSM-5,
ZSM-11, MCM-22, one or more of mixed molecular sieves of ZSM-35 molecular sieve and inert fraction are mixed and made into Hydrogen point
Rare earth element is re-introduced into after son sieve to be made, wherein molecular sieve content is 15~70wt%, rare earth element content is 0~5wt%,
Remaining is inert component.Under the conditions of 250~450 DEG C, the gasoline component octane number of gained is high, but arene content is high (about
50%), to be unfavorable for environmental requirement.
The B of patent CN 103102235 disclose one kind and prepare isobutene co-production of gasoline with high octane for n-butene isomerization
The catalyst of component, is raw material to mix carbon four after ether using HZSM-35 as catalyst, passes through the control of dual temperature section and catalysis
Agent surface carbon deposition process is organically combined, and first paragraph reaction temperature is 200~300 DEG C, 300~350 DEG C of second segment reaction temperature,
Under the conditions of normal pressure, 0.5~1h-1, the highest yield of high octane gasoline component is 24.89%.Due to catalytic process gasoline group
Divide yield low, it is difficult to realize industrialized production.
The content of the invention
One of technical problems to be solved by the invention are gasoline component liquid yield mistakes on molecular sieve catalyst in the prior art
There is provided the method for C 4 olefin gasoline component coproduction ethene or propylene for the problem of low and ethylene, propylene yield is low.This method has
Have the advantages that gasoline component high income and ethylene, propylene content are high.
The two of the technical problems to be solved by the invention are the preparation methods of one of above-mentioned technical problem catalyst.
To solve one of above-mentioned technical problem, technical scheme is as follows：
The method of C 4 olefin gasoline component coproduction ethene or propylene, comprises the following steps：Exist in ZSM-35 catalyst
Under, C 4 olefin carries out reaction generation gasoline component coproduction ethene or propylene；The SiO of ZSM-35 catalyst2/Al2O3Rub
You are than being 10~19, and reaction temperature is 360~390 DEG C, and reaction pressure is 0~0.1MPa.
In above-mentioned technical proposal, C 4 olefin liquid volume air speed is preferably 1~10 hour-1。
In above-mentioned technical proposal, the SiO of ZSM-35 catalyst2/Al2O3Mol ratio is preferably 15~19.
In above-mentioned technical proposal, reaction temperature is preferably 370~380 DEG C.
In above-mentioned technical proposal, described alkatetraenes be preferably one kind in anti-butylene, maleic, butene-1, isobutene or
It is a variety of.
To solve the two of above-mentioned technical problem, technical scheme is as follows：
The preparation method of catalyst, comprises the following steps any one of the technical scheme of one of above-mentioned technical problem：
A) by ZSM-35 molecular sieve temperature be 30~90 DEG C, alkali concn be alkali process 0.1~40 under conditions of below 1.0M
Hour, obtain precursor I.The pressure of alkali process is not particularly limited, such as, but not limited to normal pressure.
B) it is 50~90 parts of ZSM-35 molecular sieves and 10~50 parts of binding agents are kneaded and formed, obtain preformed catalyst presoma
Mixtures II；
C) by mixtures II temperature be 200~700 DEG C, volume space velocity be 0.1~20 hour-1Under the conditions of steam treatment 0.1~40
Hour, obtain catalyst.The pressure of steam treatment is not particularly limited, such as, but not limited to normal pressure.
In above-mentioned technical proposal, gained catalyst is preferably further the acid solution below 5 mol/Ls with concentration, preferably in temperature
Spend to handle 0.1~24 hour under the conditions of 20~95 DEG C.
In above-mentioned technical proposal, steam treatment temperature is preferably 300~600 DEG C, and volume space velocity is preferably 1~18 hour-1,
Processing time is preferably 1~30 hour.
In above-mentioned technical proposal, the acid preferably is selected from least one of oxalic acid, citric acid or nitric acid.
In above-mentioned technical proposal, the concentration of acid solution is preferably 0.2~4 mol/L, and acid treatment temperature is preferably 30~85 DEG C,
Time is preferably 1~20 hour.
Diene hydrocarbon content in C 4 olefin described in the inventive method is preferably shorter than 2%.
Conversion ratio and yield in embodiments of the invention are defined as follows：
The gasoline component high income of the inventive method is up to 64.5%, and ethylene, propylene yield is more than 10%.
Below by comparative example and embodiment, the present invention is further elaborated.
Embodiment
The raw material of carbon four used in the evaluating catalyst of embodiment is as shown in table 1.
【Embodiment 1】
Catalyst preparation：By NaZSM-35 molecular screen primary powders (SiO2/Al2O3Than 15) to be gone within 4 hours in 550 DEG C of roastings
Template agent removing.Resulting materials are with 0.3M NaOH in 75 DEG C of alkali process 2h, and suction filtration is dried to obtain alkali modification molecular sieve.By alkali
The modified resulting materials of processing are with aluminum oxide with 1:0.5 part by weight is mixed.Salpeter solution is added into mixture, pinches even and squeezes
Bar is molded, the pelletizing after drying and roasting.After resulting materials are exchanged through ammonium, in 550 DEG C, air speed 2 hours-1Bar
Steam treatment 2 hours under part, are made catalyst.
Catalyst test：Use and carbon four (n-butene content 93.1%) is mixed after ether for raw material, raw material composition is shown in Table 1；
370 DEG C of temperature, reaction pressure 0.05MPa, four liquid volume air speed of carbon 3 hours-1, under the conditions of loaded catalyst 10mL,
Catalyst activity is checked and rated, the catalyst reaction result of the 1st day is shown in Table 2.Gasoline component yield is 64.5%.Ethylene, propylene is received
Rate 11.3%.
【Comparative example 1】
Catalyst preparation：By NaZSM-35 molecular screen primary powders (SiO2/Al2O3Than 30) to be gone within 4 hours in 550 DEG C of roastings
Template agent removing.Resulting materials are with 0.3M NaOH in 75 DEG C of alkali process 2h, and suction filtration is dried to obtain alkali modification molecular sieve.By alkali
The modified resulting materials of processing are with aluminum oxide with 1:0.5 part by weight is mixed.Salpeter solution is added into mixture, pinches even and squeezes
Bar is molded, the pelletizing after drying and roasting.After resulting materials are exchanged through ammonium, in 550 DEG C, air speed 2 hours-1Bar
Steam treatment 2 hours under part, are made catalyst.
Catalyst test：Use and carbon four (n-butene content 93.1%) is mixed after ether for raw material, raw material composition is shown in Table 1；In temperature
370 DEG C of degree, reaction pressure 0.05MPa, four liquid volume air speed of carbon 3 hours-1, under the conditions of loaded catalyst 10mL,
Catalyst activity is checked and rated, the catalyst reaction result of the 1st day is shown in Table 2.Gasoline component yield is 66.4%.Ethylene, propylene is received
Rate is less than 5%.
【Comparative example 2】
Catalyst preparation：By NaZSM-35 molecular screen primary powders (SiO2/Al2O3Than 15) to be gone within 4 hours in 550 DEG C of roastings
Template agent removing.Resulting materials are with 0.3M NaOH in 75 DEG C of alkali process 2h, and suction filtration is dried to obtain alkali modification molecular sieve.By alkali
The modified resulting materials of processing are with aluminum oxide with 1:0.5 part by weight is mixed.Salpeter solution is added into mixture, pinches even and squeezes
Bar is molded, the pelletizing after drying and roasting.After resulting materials are exchanged through ammonium, in 550 DEG C, air speed 2 hours-1Bar
Steam treatment 2 hours under part, are made catalyst.
Catalyst test：Use and carbon four (n-butene content 93.1%) is mixed after ether for raw material, raw material composition is shown in Table 1；In temperature
330 DEG C of degree, reaction pressure 0.05MPa, four liquid volume air speed of carbon 3 hours-1, under the conditions of loaded catalyst 10mL,
Catalyst activity is checked and rated, the catalyst reaction result of the 1st day is shown in Table 2.Gasoline component yield is 57.2%.Ethylene, propylene is received
Rate 1.99%.
【Comparative example 3】
Catalyst preparation：By NaZSM-35 molecular screen primary powders (SiO2/Al2O3Than 15) to be gone within 4 hours in 550 DEG C of roastings
Template agent removing.Resulting materials are with 0.3M NaOH in 75 DEG C of alkali process 2h, and suction filtration is dried to obtain alkali modification molecular sieve.By alkali
The modified resulting materials of processing are with aluminum oxide with 1:0.5 part by weight is mixed.Salpeter solution is added into mixture, pinches even and squeezes
Bar is molded, the pelletizing after drying and roasting.After resulting materials are exchanged through ammonium, in 550 DEG C, air speed 2 hours-1Bar
Steam treatment 2 hours under part, are made catalyst.
Catalyst test：Use and carbon four (n-butene content 93.1%) is mixed after ether for raw material, raw material composition is shown in Table 1；In temperature
420 DEG C of degree, reaction pressure 0.05MPa, four liquid volume air speed of carbon 3 hours-1, under the conditions of loaded catalyst 10mL,
Catalyst activity is checked and rated, the catalyst reaction result of the 1st day is shown in Table 2.Gasoline component yield is 22.5%.Ethylene, propylene is received
Rate 5.34%.
【Comparative example 4】
Catalyst preparation：By NaZSM-35 molecular screen primary powders (SiO2/Al2O3Than 15) to be gone within 4 hours in 550 DEG C of roastings
Template agent removing.Resulting materials are with 0.3M NaOH in 75 DEG C of alkali process 2h, and suction filtration is dried to obtain alkali modification molecular sieve.By alkali
The modified resulting materials of processing are with aluminum oxide with 1:0.5 part by weight is mixed.Salpeter solution is added into mixture, pinches even and squeezes
Bar is molded, the pelletizing after drying and roasting.After resulting materials are exchanged through ammonium, in 550 DEG C, air speed 2 hours-1Bar
Steam treatment 2 hours under part, are made catalyst.
Catalyst test：Use and carbon four (n-butene content 93.1%) is mixed after ether for raw material, raw material composition is shown in Table 1；In temperature
250 DEG C of degree, reaction pressure 0.05MPa, four liquid volume air speed of carbon 3 hours-1, under the conditions of loaded catalyst 10mL,
Catalyst activity is checked and rated, the catalyst reaction result of the 1st day is shown in Table 2.Gasoline component yield is 35.1%.Ethylene, propylene is received
Rate 1.09%.
【Comparative example 5】
Catalyst preparation：By the former powder (SiO of beta-molecular sieve2/Al2O3Than 15) to remove template agent removing within 4 hours in 550 DEG C of roastings.
Resulting materials are with 0.3M NaOH in 75 DEG C of alkali process 2h, and suction filtration is dried to obtain alkali modification molecular sieve.By alkali treatment modifying institute
Material is obtained with aluminum oxide with 1:0.5 part by weight is mixed.Salpeter solution is added into mixture, even and extruded moulding is pinched, in
Pelletizing after drying and being calcined.After resulting materials are exchanged through ammonium, in 550 DEG C, air speed 2 hours-1Under conditions of vapor
Processing 2 hours, is made catalyst.
Catalyst test：Use and carbon four (n-butene content 93.1%) is mixed after ether for raw material, raw material composition is shown in Table 1；In temperature
370 DEG C of degree, reaction pressure 0.05MPa, four liquid volume air speed of carbon 3 hours-1, under the conditions of loaded catalyst 10mL,
Catalyst activity is checked and rated, the catalyst reaction result of the 1st day is shown in Table 2.Gasoline component yield is 12.5%.Ethylene, propylene is received
Rate 5.65%.
【Comparative example 6】
Catalyst preparation：By the former powder (SiO of Y molecular sieve2/Al2O3Than 15) to remove template agent removing within 4 hours in 550 DEG C of roastings.
Resulting materials are with 0.3M NaOH in 75 DEG C of alkali process 2h, and suction filtration is dried to obtain alkali modification molecular sieve.By alkali treatment modifying institute
Material is obtained with aluminum oxide with 1:0.5 part by weight is mixed.Salpeter solution is added into mixture, even and extruded moulding is pinched, in
Pelletizing after drying and being calcined.After resulting materials are exchanged through ammonium, in 550 DEG C, air speed 2 hours-1Under conditions of vapor
Processing 2 hours, is made catalyst.
Catalyst test：Use and carbon four (n-butene content 93.1%) is mixed after ether for raw material, raw material composition is shown in Table 1；In temperature
370 DEG C of degree, reaction pressure 0.05MPa, four liquid volume air speed of carbon 3 hours-1, under the conditions of loaded catalyst 10mL,
Catalyst activity is checked and rated, the catalyst reaction result of the 1st day is shown in Table 2.Gasoline component yield is 17.5%.Ethylene, propylene is received
Rate 4.63%.
【Comparative example 7】
1 catalyst preparation：By NaZSM-5 molecular screen primary powders (SiO2/Al2O3Than 15) to be gone within 4 hours in 550 DEG C of roastings
Template agent removing.Resulting materials are with 0.3M NaOH in 75 DEG C of alkali process 2h, and suction filtration is dried to obtain alkali modification molecular sieve.By alkali
The modified resulting materials of processing are with aluminum oxide with 1:0.5 part by weight is mixed.Salpeter solution is added into mixture, pinches even and squeezes
Bar is molded, the pelletizing after drying and roasting.After resulting materials are exchanged through ammonium, in 550 DEG C, air speed 2 hours-1Bar
Steam treatment 2 hours under part, are made catalyst.
Catalyst test：Use and carbon four (n-butene content 93.1%) is mixed after ether for raw material, raw material composition is shown in Table 1；In temperature
370 DEG C of degree, reaction pressure 0.05MPa, four liquid volume air speed of carbon 3 hours-1, under the conditions of loaded catalyst 10mL,
Catalyst activity is checked and rated, the catalyst reaction result of the 1st day is shown in Table 2.Gasoline component yield is 46.3%.Ethylene, propylene is received
Rate 7.51%.
【Embodiment 2】
Catalyst preparation：By NaZSM-35 molecular screen primary powders (SiO2/Al2O3Than 10) to be gone within 4 hours in 550 DEG C of roastings
Template agent removing.Resulting materials are with 0.3M NaOH in 75 DEG C of alkali process 2h, and suction filtration is dried to obtain alkali modification molecular sieve.By alkali
The modified resulting materials of processing are with aluminum oxide with 1:0.5 part by weight is mixed.Salpeter solution is added into mixture, pinches even and squeezes
Bar is molded, the pelletizing after drying and roasting.After resulting materials are exchanged through ammonium, in 550 DEG C, air speed 2 hours-1Bar
Steam treatment 2 hours under part, are made catalyst.
Catalyst test：Use and carbon four (n-butene content 93.1%) is mixed after ether for raw material, raw material composition is shown in Table 1；In temperature
370 DEG C of degree, reaction pressure 0.05MPa, four liquid volume air speed of carbon 3 hours-1, under the conditions of loaded catalyst 10mL,
Catalyst activity is checked and rated, the catalyst reaction result of the 1st day is shown in Table 2.Gasoline component yield is 64.5%.Ethylene, propylene is received
Rate 11.3%.
【Embodiment 3】
Catalyst preparation：By NaZSM-35 molecular screen primary powders (SiO2/Al2O3Than 19) to be gone within 4 hours in 550 DEG C of roastings
Template agent removing.Resulting materials are with 0.3M NaOH in 75 DEG C of alkali process 2h, and suction filtration is dried to obtain alkali modification molecular sieve.By alkali
The modified resulting materials of processing are with aluminum oxide with 1:0.5 part by weight is mixed.Salpeter solution is added into mixture, pinches even and squeezes
Bar is molded, the pelletizing after drying and roasting.After resulting materials are exchanged through ammonium, in 550 DEG C, air speed 2 hours-1Bar
Steam treatment 2 hours under part, are made catalyst.
Catalyst test：Use and carbon four (n-butene content 93.1%) is mixed after ether for raw material, raw material composition is shown in Table 1；In temperature
370 DEG C of degree, reaction pressure 0.05MPa, four liquid volume air speed of carbon 3 hours-1, under the conditions of loaded catalyst 10mL,
Catalyst activity is checked and rated, the catalyst reaction result of the 1st day is shown in Table 2.Gasoline component yield is 61.5%.Ethylene, propylene is received
Rate 8.97%.
【Embodiment 4】
Catalyst preparation：By NaZSM-35 molecular screen primary powders (SiO2/Al2O3Than 15) to be gone within 4 hours in 550 DEG C of roastings
Template agent removing.Resulting materials are with 0.3M NaOH in 75 DEG C of alkali process 2h, and suction filtration is dried to obtain alkali modification molecular sieve.By alkali
The modified resulting materials of processing are with aluminum oxide with 1:0.5 part by weight is mixed.Salpeter solution is added into mixture, pinches even and squeezes
Bar is molded, the pelletizing after drying and roasting.After resulting materials are exchanged through ammonium, in 550 DEG C, air speed 2 hours-1Bar
Steam treatment 2 hours under part, are made catalyst.
Catalyst test：Use and carbon four (n-butene content 93.1%) is mixed after ether for raw material, raw material composition is shown in Table 1；In temperature
360 DEG C of degree, reaction pressure 0.05MPa, four liquid volume air speed of carbon 3 hours-1, under the conditions of loaded catalyst 10mL,
Catalyst activity is checked and rated, the catalyst reaction result of the 1st day is shown in Table 2.Gasoline component yield is 64.5%.Ethylene, propylene is received
Rate 11.3%.
【Embodiment 5】
Catalyst preparation：By NaZSM-35 molecular screen primary powders (SiO2/Al2O3Than 15) to be gone within 4 hours in 550 DEG C of roastings
Template agent removing.Resulting materials are with 0.3M NaOH in 75 DEG C of alkali process 2h, and suction filtration is dried to obtain alkali modification molecular sieve.By alkali
The modified resulting materials of processing are with aluminum oxide with 1:0.5 part by weight is mixed.Salpeter solution is added into mixture, pinches even and squeezes
Bar is molded, the pelletizing after drying and roasting.After resulting materials are exchanged through ammonium, in 550 DEG C, air speed 2 hours-1Bar
Steam treatment 2 hours under part, are made catalyst.
Catalyst test：Use and carbon four (n-butene content 93.1%) is mixed after ether for raw material, raw material composition is shown in Table 1；In temperature
390 DEG C of degree, reaction pressure 0.05MPa, four liquid volume air speed of carbon 3 hours-1, under the conditions of loaded catalyst 10mL,
Catalyst activity is checked and rated, the catalyst reaction result of the 1st day is shown in Table 2.Gasoline component yield is 51.6%.Ethylene, propylene is received
Rate 13.9%.
【Embodiment 6】
Catalyst preparation：By NaZSM-35 molecular screen primary powders (SiO2/Al2O3Than 15) to be gone within 4 hours in 550 DEG C of roastings
Template agent removing.Resulting materials are with 0.3M NaOH in 75 DEG C of alkali process 2h, and suction filtration is dried to obtain alkali modification molecular sieve.By alkali
The modified resulting materials of processing are with aluminum oxide with 1:0.5 part by weight is mixed.Salpeter solution is added into mixture, pinches even and squeezes
Bar is molded, the pelletizing after drying and roasting.After resulting materials are exchanged through ammonium, in 550 DEG C, air speed 2 hours-1Bar
Steam treatment 2 hours under part, are made catalyst.
Catalyst test：Use and carbon four (n-butene content 93.1%) is mixed after ether for raw material, raw material composition is shown in Table 1；In temperature
380 DEG C of degree, reaction pressure 0.05MPa, four liquid volume air speed of carbon 3 hours-1, under the conditions of loaded catalyst 10mL,
Catalyst activity is checked and rated, the catalyst reaction result of the 1st day is shown in Table 2.Gasoline component yield is 55.9%.Ethylene, propylene is received
Rate 11.7%.
【Embodiment 7】
Catalyst preparation：By NaZSM-35 molecular screen primary powders (SiO2/Al2O3Than 15) to be gone within 4 hours in 550 DEG C of roastings
Template agent removing.Resulting materials are with 0.3M NaOH in 75 DEG C of alkali process 2h, and suction filtration is dried to obtain alkali modification molecular sieve.By alkali
The modified resulting materials of processing are with aluminum oxide with 1:0.5 part by weight is mixed.Salpeter solution is added into mixture, pinches even and squeezes
Bar is molded, the pelletizing after drying and roasting.After resulting materials are exchanged through ammonium, in 550 DEG C, air speed 2 hours-1Bar
Steam treatment 2 hours under part, are made catalyst.
Catalyst test：Use and carbon four (n-butene content 93.1%) is mixed after ether for raw material, raw material composition is shown in Table 1；In temperature
370 DEG C of degree, reaction pressure 0.03MPa, four liquid volume air speed of carbon 3 hours-1, under the conditions of loaded catalyst 10mL,
Catalyst activity is checked and rated, the catalyst reaction result of the 1st day is shown in Table 2.Gasoline component yield is 61.0%.Ethylene, propylene is received
Rate 13.6%.
【Embodiment 8】
Catalyst preparation：By NaZSM-35 molecular screen primary powders (SiO2/Al2O3Than 15) to be gone within 4 hours in 550 DEG C of roastings
Template agent removing.Resulting materials are with 0.3M NaOH in 75 DEG C of alkali process 2h, and suction filtration is dried to obtain alkali modification molecular sieve.By alkali
The modified resulting materials of processing are with aluminum oxide with 1:0.5 part by weight is mixed.Salpeter solution is added into mixture, pinches even and squeezes
Bar is molded, the pelletizing after drying and roasting.After resulting materials are exchanged through ammonium, in 550 DEG C, air speed 2 hours-1Bar
Steam treatment 2 hours under part, are made catalyst.
Catalyst test：Use and carbon four (n-butene content 93.1%) is mixed after ether for raw material, raw material composition is shown in Table 1；In temperature
380 DEG C of degree, reaction pressure 0.05MPa, four liquid volume air speed of carbon 3 hours-1, under the conditions of loaded catalyst 10mL,
Catalyst activity is checked and rated, the catalyst reaction result of the 1st day is shown in Table 2.Gasoline component yield is 65.3%.Ethylene, propylene is received
Rate 8.8%.
Table 1
| Raw material components | Iso-butane | Normal butane | Anti- butylene | Butene-1 | Isobutene | Maleic |
| Percentage composition (weight %) | 0.01 | 6.7 | 26.21 | 59.25 | 0.03 | 7.75 |
Table 2
Claims (9)
1. the method for C 4 olefin gasoline component coproduction ethene or propylene, comprises the following steps：In ZSM-35 catalyst
In the presence of, C 4 olefin carries out reaction generation gasoline component coproduction ethene or propylene；The SiO of ZSM-35 catalyst2/Al2O3
Mol ratio be 10~19, reaction temperature be 360~390 DEG C, reaction pressure be 0~0.1MPa.
2. according to the method described in claim 1, it is characterized in that the SiO of ZSM-35 catalyst2/Al2O3Mol ratio is 15~19.
3. according to the method described in claim 1, it is characterized in that reaction temperature is 370~380 DEG C.
4. according to the method described in claim 1, it is characterized in that described alkatetraenes be anti-butylene, maleic, butene-1,
One or more in isobutene.
5. the preparation method of catalyst described in claim 1, comprises the following steps：
A) by SiO2/Al2O3The ZSM-35 molecular sieve that mol ratio is 10~19 temperature be 30~90 DEG C, alkali concn be 1.0M
Alkali process 0.1~40 hour under conditions of below, obtains precursor I.
B) it is 50~90 parts of ZSM-35 molecular sieves and 10~50 parts of binding agents are kneaded and formed, obtain preformed catalyst presoma
Mixtures II；
C) by mixtures II temperature be 200~700 DEG C, volume space velocity be 0.1~20 hour-1Under the conditions of steam treatment 0.1~40
Hour, obtain catalyst.
6. preparation method according to claim 5, it is characterized in that gained catalyst is further 5 mol/Ls with concentration
Following acid solution, is handled 0.1~24 hour under the conditions of temperature is 20~95 DEG C.
7. preparation method according to claim 5, it is characterized in that steam treatment temperature is 300~600 DEG C, volume is empty
Speed is 1~18 hour-1, processing time is 1~30 hour.
8. preparation method according to claim 6, it is characterized in that the acid is in oxalic acid, citric acid or nitric acid
It is at least one.
9. preparation method according to claim 6, it is characterized in that the concentration of acid solution is 0.2~4 mol/L, at acid
It is 30~85 DEG C to manage temperature, and the time is 1~20 hour.
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Citations (4)
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|---|---|---|---|---|
| US20070015945A1 (en) * | 2005-06-28 | 2007-01-18 | Sylvain Louret | Process for preparing a gas oil by oligomerization |
| CN102276406A (en) * | 2010-06-11 | 2011-12-14 | 中国石油化工股份有限公司 | Method for increasing yield of propylene |
| CN102471702A (en) * | 2009-07-03 | 2012-05-23 | 英国石油国际有限公司 | Alkene oligomerization process |
| CN103301876A (en) * | 2012-03-13 | 2013-09-18 | 中国科学院大连化学物理研究所 | Method for preparing straight-chain olefin skeleton isomerization catalyst |
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2016
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070015945A1 (en) * | 2005-06-28 | 2007-01-18 | Sylvain Louret | Process for preparing a gas oil by oligomerization |
| CN102471702A (en) * | 2009-07-03 | 2012-05-23 | 英国石油国际有限公司 | Alkene oligomerization process |
| CN102276406A (en) * | 2010-06-11 | 2011-12-14 | 中国石油化工股份有限公司 | Method for increasing yield of propylene |
| CN103301876A (en) * | 2012-03-13 | 2013-09-18 | 中国科学院大连化学物理研究所 | Method for preparing straight-chain olefin skeleton isomerization catalyst |
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