CN107286985B - The method of C 4 olefin gasoline component coproduction ethylene or propylene - Google Patents
The method of C 4 olefin gasoline component coproduction ethylene or propylene Download PDFInfo
- Publication number
- CN107286985B CN107286985B CN201610223851.1A CN201610223851A CN107286985B CN 107286985 B CN107286985 B CN 107286985B CN 201610223851 A CN201610223851 A CN 201610223851A CN 107286985 B CN107286985 B CN 107286985B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- hours
- propylene
- gasoline component
- olefin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000000034 method Methods 0.000 title claims abstract description 53
- 239000003502 gasoline Substances 0.000 title claims abstract description 42
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000005977 Ethylene Substances 0.000 title claims abstract description 28
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 27
- -1 C 4 olefin Chemical class 0.000 title claims abstract description 25
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 112
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 21
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 21
- 239000003513 alkali Substances 0.000 claims description 50
- 239000000203 mixture Substances 0.000 claims description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 34
- 239000002808 molecular sieve Substances 0.000 claims description 26
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 25
- 238000002360 preparation method Methods 0.000 claims description 18
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 17
- 229910052681 coesite Inorganic materials 0.000 claims description 17
- 229910052906 cristobalite Inorganic materials 0.000 claims description 17
- 229910017604 nitric acid Inorganic materials 0.000 claims description 17
- 239000000377 silicon dioxide Substances 0.000 claims description 17
- 229910052682 stishovite Inorganic materials 0.000 claims description 17
- 229910052905 tridymite Inorganic materials 0.000 claims description 17
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims 2
- 239000007788 liquid Substances 0.000 abstract description 18
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 45
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 40
- 229910052799 carbon Inorganic materials 0.000 description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 34
- 239000002994 raw material Substances 0.000 description 34
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 21
- 230000000694 effects Effects 0.000 description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 15
- 238000012986 modification Methods 0.000 description 15
- 230000004048 modification Effects 0.000 description 15
- 238000000465 moulding Methods 0.000 description 15
- 238000005453 pelletization Methods 0.000 description 15
- 239000000843 powder Substances 0.000 description 15
- 238000000967 suction filtration Methods 0.000 description 15
- 238000001035 drying Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- NUMQCACRALPSHD-UHFFFAOYSA-N tert-butyl ethyl ether Chemical compound CCOC(C)(C)C NUMQCACRALPSHD-UHFFFAOYSA-N 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 235000013847 iso-butane Nutrition 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000005672 tetraenes Chemical class 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Liquid Carbonaceous Fuels (AREA)
Abstract
The present invention relates to the method for C 4 olefin gasoline component coproduction ethylene or propylene, mainly solve the problems, such as that C 4 olefin oligomerisation gasoline component liquid is received low low with ethylene, propylene content in the prior art.The present invention by using C 4 olefin gasoline component coproduction ethylene or propylene method, comprising the following steps: in the presence of ZSM-35 catalyst, C 4 olefin carries out reaction and generates gasoline component coproduction ethylene or propylene；The SiO of ZSM-35 catalyst2/Al2O3Molar ratio be 10~19, reaction temperature be 360~390 DEG C, reaction pressure be 0~0.1MPa technical solution preferably solve the problems, such as this, can be used in the industrial production of C 4 olefin gasoline component coproduction ethylene or propylene.
Description
Technical field
The present invention relates to the methods of C 4 olefin gasoline component coproduction ethylene or propylene.
Background technique
C4 low-carbon alkene and hydrocarbon mixture containing C4 low-carbon alkene are the by-products of petrochemical industry and oil refining industry, originate from ethylene
The processes such as engineering, oil plant and natural gas purification.It mixes 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, C 4 olefin is mixed at last by pipeline
The more cheap fuel such as natural gas gradually squeezes out commercial market.These are mixed into C 4 olefin by Catalytic processes and is converted into vapour
Oily component not only can open up new raw material source for the production of gasoline, and can Optimum utilization lighter hydrocarbons resource, improve petroleum chemical enterprise's economy
Benefit.
On the other hand, butyl ether (MTBE), ethyl tert-butyl ether (ETBE) (ETBE) are shown in reformulated gasoline and oxygenated gasoline
Out higher octane number, low-steam pressure and good solubility in gasoline fraction hydro carbons and become excellent gasoline and add
Add component, demand increases sharply in the whole world, and many ether-based devices is caused all to be expanded production.In the ether-based device of production MTBE
Outlet material in, after separating methanol and ether, normal olefine accounts for 40-100 weight %, and expanding production for device will generate a large amount of ethers
N-butene resource afterwards is burnt up mainly as liquefied gas at present, is badly in need of finding new purposes.
By carbon four after the ether of olefin-containing under special-purpose catalyst effect, the reaction such as oligomerisation, isomerization occurs, production is rich in different
The high-knock rating gasoline fraction of octene and an effective utilization ways.
CN1597867A discloses a kind of alkene aromatisation in refinery's liquefied gas and alkylated reaction generates Gaoxin
The catalyst of alkane value clean gasoline component, which is by SiO2/Al2O3Molar ratio be 20~80 ZSM-5, ZSM-11,
MCM-22, one or more of mixed molecular sieves of ZSM-35 molecular sieve and inert fraction are re-introduced into after being mixed and made into hydrogen type molecular sieve
Rare earth element is made, and wherein molecular sieve content is 15~70wt%, and rare earth element content is 0~5wt%, remaining is inertia group
Point.Under the conditions of 250~450 DEG C, resulting gasoline component octane number is high, but arene content is high (about 50%), is unfavorable for ring
Guaranteed request.
103102235 B of patent CN discloses one kind and prepares isobutene co-production high-octane rating for n-butene isomerization
The catalyst of gasoline component is raw material to mix carbon four after ether, is controlled and be catalyzed by dual temperature section using HZSM-35 as catalyst
Agent surface carbon deposition process organically combine, first segment reaction temperature be 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.
Summary of the invention
The first technical problem to be solved by the present invention is that gasoline component liquid is received on molecular sieve catalyst in the prior art
The too low problem low with ethylene, propylene yield of rate, provides the method for C 4 olefin gasoline component coproduction ethylene or propylene.The party
Method has the advantages that gasoline component high income and ethylene, propylene content are high.
The second technical problem to be solved by the present invention is the preparation method of catalyst described in one of above-mentioned technical problem.
One of to solve above-mentioned technical problem, technical scheme is as follows:
The method of C 4 olefin gasoline component coproduction ethylene or propylene, comprising the following steps: deposited in ZSM-35 catalyst
Under, C 4 olefin carries out reaction and generates gasoline component coproduction ethylene or propylene；The SiO of ZSM-35 catalyst2/Al2O3Mole
Than being 10~19, 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/Al2O3Molar ratio is preferably 15~19.
In above-mentioned technical proposal, reaction temperature is preferably 370~380 DEG C.
In above-mentioned technical proposal, the alkatetraenes is preferably one of anti-butylene, maleic, butene-1, isobutene
Or it is a variety of.
To solve above-mentioned technical problem two, technical scheme is as follows:
The preparation method of catalyst described in any one of technical solution of one of above-mentioned technical problem, comprising the following steps:
A) by ZSM-35 molecular sieve under the conditions of temperature is 30~90 DEG C, alkali concentration is 1.0M below alkali process 0.1~
40 hours, obtain precursor I.The pressure of alkali process is not particularly limited, such as, but not limited to normal pressure.
B) 50~90 parts of ZSM-35 molecular sieves and 10~50 parts of binders are kneaded and formed, obtain preformed catalyst presoma
Mixtures II；
C) by mixtures II temperature is 200~700 DEG C, volume space velocity is 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 5 mol/Ls acid solution below with concentration, preferably
It is handled 0.1~24 hour under the conditions of temperature is 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 small
When-1, the 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 sour treatment temperature is preferably 30~85
DEG C, the time is preferably 1~20 hour.
Diene hydrocarbon content in C 4 olefin described in the method for the present invention is preferably shorter than 2%.
Conversion ratio and yield in the embodiment of the present invention are defined as follows:
The gasoline component yield of the method for the present invention is up to 64.5%, and ethylene, propylene yield is greater than 10%.
Below by comparative example and embodiment, the present invention is further elaborated.
Specific embodiment
Four raw material of carbon used in the evaluating catalyst of specific embodiment is as shown in table 1.
[embodiment 1]
Catalyst preparation: by NaZSM-35 molecular screen primary powder (SiO2/Al2O3Than being removed 15) to be roasted 4 hours at 550 DEG C
Template.In 75 DEG C of alkali process 2h, suction filtration is dried to obtain alkali modification molecular sieve by resulting materials and 0.3M NaOH.Alkali process is changed
Property resulting materials are mixed with aluminium oxide with 1:0.5 weight ratio.Nitric acid solution is added into mixture, pinches even and extruded moulding,
The pelletizing after drying and roasting.After resulting materials are exchanged through ammonium, at 550 DEG C, air speed 2 hours-1Under conditions of at vapor
Catalyst is made in reason 2 hours.
Catalyst test: carbon four (n-butene content 93.1%) is mixed as raw material after using ether, 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, examination
Catalyst activity, the 1st day reaction result of catalyst are shown in Table 2.Gasoline component yield is 64.5%.Ethylene, propylene yield
11.3%.
[comparative example 1]
Catalyst preparation: by NaZSM-35 molecular screen primary powder (SiO2/Al2O3Than being removed 30) to be roasted 4 hours at 550 DEG C
Template.In 75 DEG C of alkali process 2h, suction filtration is dried to obtain alkali modification molecular sieve by resulting materials and 0.3M NaOH.Alkali process is changed
Property resulting materials are mixed with aluminium oxide with 1:0.5 weight ratio.Nitric acid solution is added into mixture, pinches even and extruded moulding,
The pelletizing after drying and roasting.After resulting materials are exchanged through ammonium, at 550 DEG C, air speed 2 hours-1Under conditions of at vapor
Catalyst is made in reason 2 hours.
Catalyst test: carbon four (n-butene content 93.1%) is mixed as raw material after using ether, 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, examination
Catalyst activity, the 1st day reaction result of catalyst are shown in Table 2.Gasoline component yield is 66.4%.Ethylene, propylene yield is less than
5%.
[comparative example 2]
Catalyst preparation: by NaZSM-35 molecular screen primary powder (SiO2/Al2O3Than being removed 15) to be roasted 4 hours at 550 DEG C
Template.In 75 DEG C of alkali process 2h, suction filtration is dried to obtain alkali modification molecular sieve by resulting materials and 0.3M NaOH.Alkali process is changed
Property resulting materials are mixed with aluminium oxide with 1:0.5 weight ratio.Nitric acid solution is added into mixture, pinches even and extruded moulding,
The pelletizing after drying and roasting.After resulting materials are exchanged through ammonium, at 550 DEG C, air speed 2 hours-1Under conditions of at vapor
Catalyst is made in reason 2 hours.
Catalyst test: carbon four (n-butene content 93.1%) is mixed as raw material after using ether, raw material composition is shown in Table 1；?
330 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, examination
Catalyst activity, the 1st day reaction result of catalyst are shown in Table 2.Gasoline component yield is 57.2%.Ethylene, propylene yield
1.99%.
[comparative example 3]
Catalyst preparation: by NaZSM-35 molecular screen primary powder (SiO2/Al2O3Than being removed 15) to be roasted 4 hours at 550 DEG C
Template.In 75 DEG C of alkali process 2h, suction filtration is dried to obtain alkali modification molecular sieve by resulting materials and 0.3M NaOH.Alkali process is changed
Property resulting materials are mixed with aluminium oxide with 1:0.5 weight ratio.Nitric acid solution is added into mixture, pinches even and extruded moulding,
The pelletizing after drying and roasting.After resulting materials are exchanged through ammonium, at 550 DEG C, air speed 2 hours-1Under conditions of at vapor
Catalyst is made in reason 2 hours.
Catalyst test: carbon four (n-butene content 93.1%) is mixed as raw material after using ether, raw material composition is shown in Table 1；?
420 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, examination
Catalyst activity, the 1st day reaction result of catalyst are shown in Table 2.Gasoline component yield is 22.5%.Ethylene, propylene yield
5.34%.
[comparative example 4]
Catalyst preparation: by NaZSM-35 molecular screen primary powder (SiO2/Al2O3Than being removed 15) to be roasted 4 hours at 550 DEG C
Template.In 75 DEG C of alkali process 2h, suction filtration is dried to obtain alkali modification molecular sieve by resulting materials and 0.3M NaOH.Alkali process is changed
Property resulting materials are mixed with aluminium oxide with 1:0.5 weight ratio.Nitric acid solution is added into mixture, pinches even and extruded moulding,
The pelletizing after drying and roasting.After resulting materials are exchanged through ammonium, at 550 DEG C, air speed 2 hours-1Under conditions of at vapor
Catalyst is made in reason 2 hours.
Catalyst test: carbon four (n-butene content 93.1%) is mixed as raw material after using ether, raw material composition is shown in Table 1；?
250 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, examination
Catalyst activity, the 1st day reaction result of catalyst are shown in Table 2.Gasoline component yield is 35.1%.Ethylene, propylene yield
1.09%.
[comparative example 5]
Catalyst preparation: by beta-molecular sieve original powder (SiO2/Al2O3Than removing template agent removing 15) to roast 4 hours at 550 DEG C.
In 75 DEG C of alkali process 2h, suction filtration is dried to obtain alkali modification molecular sieve by resulting materials and 0.3M NaOH.By material obtained by alkali treatment modifying
Material is mixed with aluminium oxide with 1:0.5 weight ratio.Nitric acid solution is added into mixture, pinches even and extruded moulding, in dry and
Pelletizing after roasting.After resulting materials are exchanged through ammonium, at 550 DEG C, air speed 2 hours-1Under conditions of steam treatment 2 hours,
Catalyst is made.
Catalyst test: carbon four (n-butene content 93.1%) is mixed as raw material after using ether, 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, examination
Catalyst activity, the 1st day reaction result of catalyst are shown in Table 2.Gasoline component yield is 12.5%.Ethylene, propylene yield
5.65%.
[comparative example 6]
Catalyst preparation: by Y molecular sieve original powder (SiO2/Al2O3Than removing template agent removing 15) to roast 4 hours at 550 DEG C.
In 75 DEG C of alkali process 2h, suction filtration is dried to obtain alkali modification molecular sieve by resulting materials and 0.3M NaOH.By material obtained by alkali treatment modifying
Material is mixed with aluminium oxide with 1:0.5 weight ratio.Nitric acid solution is added into mixture, pinches even and extruded moulding, in dry and
Pelletizing after roasting.After resulting materials are exchanged through ammonium, at 550 DEG C, air speed 2 hours-1Under conditions of steam treatment 2 hours,
Catalyst is made.
Catalyst test: carbon four (n-butene content 93.1%) is mixed as raw material after using ether, 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, examination
Catalyst activity, the 1st day reaction result of catalyst are shown in Table 2.Gasoline component yield is 17.5%.Ethylene, propylene yield
4.63%.
[comparative example 7]
1 catalyst preparation: by NaZSM-5 molecular screen primary powder (SiO2/Al2O3Than being removed 15) to be roasted 4 hours at 550 DEG C
Template.In 75 DEG C of alkali process 2h, suction filtration is dried to obtain alkali modification molecular sieve by resulting materials and 0.3M NaOH.Alkali process is changed
Property resulting materials are mixed with aluminium oxide with 1:0.5 weight ratio.Nitric acid solution is added into mixture, pinches even and extruded moulding,
The pelletizing after drying and roasting.After resulting materials are exchanged through ammonium, at 550 DEG C, air speed 2 hours-1Under conditions of at vapor
Catalyst is made in reason 2 hours.
Catalyst test: carbon four (n-butene content 93.1%) is mixed as raw material after using ether, 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, examination
Catalyst activity, the 1st day reaction result of catalyst are shown in Table 2.Gasoline component yield is 46.3%.Ethylene, propylene yield
7.51%.
[embodiment 2]
Catalyst preparation: by NaZSM-35 molecular screen primary powder (SiO2/Al2O3Than being removed 10) to be roasted 4 hours at 550 DEG C
Template.In 75 DEG C of alkali process 2h, suction filtration is dried to obtain alkali modification molecular sieve by resulting materials and 0.3M NaOH.Alkali process is changed
Property resulting materials are mixed with aluminium oxide with 1:0.5 weight ratio.Nitric acid solution is added into mixture, pinches even and extruded moulding,
The pelletizing after drying and roasting.After resulting materials are exchanged through ammonium, at 550 DEG C, air speed 2 hours-1Under conditions of at vapor
Catalyst is made in reason 2 hours.
Catalyst test: carbon four (n-butene content 93.1%) is mixed as raw material after using ether, 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, examination
Catalyst activity, the 1st day reaction result of catalyst are shown in Table 2.Gasoline component yield is 64.5%.Ethylene, propylene yield
11.3%.
[embodiment 3]
Catalyst preparation: by NaZSM-35 molecular screen primary powder (SiO2/Al2O3Than being removed 19) to be roasted 4 hours at 550 DEG C
Template.In 75 DEG C of alkali process 2h, suction filtration is dried to obtain alkali modification molecular sieve by resulting materials and 0.3M NaOH.Alkali process is changed
Property resulting materials are mixed with aluminium oxide with 1:0.5 weight ratio.Nitric acid solution is added into mixture, pinches even and extruded moulding,
The pelletizing after drying and roasting.After resulting materials are exchanged through ammonium, at 550 DEG C, air speed 2 hours-1Under conditions of at vapor
Catalyst is made in reason 2 hours.
Catalyst test: carbon four (n-butene content 93.1%) is mixed as raw material after using ether, 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, examination
Catalyst activity, the 1st day reaction result of catalyst are shown in Table 2.Gasoline component yield is 61.5%.Ethylene, propylene yield
8.97%.
[embodiment 4]
Catalyst preparation: by NaZSM-35 molecular screen primary powder (SiO2/Al2O3Than being removed 15) to be roasted 4 hours at 550 DEG C
Template.In 75 DEG C of alkali process 2h, suction filtration is dried to obtain alkali modification molecular sieve by resulting materials and 0.3M NaOH.Alkali process is changed
Property resulting materials are mixed with aluminium oxide with 1:0.5 weight ratio.Nitric acid solution is added into mixture, pinches even and extruded moulding,
The pelletizing after drying and roasting.After resulting materials are exchanged through ammonium, at 550 DEG C, air speed 2 hours-1Under conditions of at vapor
Catalyst is made in reason 2 hours.
Catalyst test: carbon four (n-butene content 93.1%) is mixed as raw material after using ether, raw material composition is shown in Table 1；?
360 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, examination
Catalyst activity, the 1st day reaction result of catalyst are shown in Table 2.Gasoline component yield is 64.5%.Ethylene, propylene yield
11.3%.
[embodiment 5]
Catalyst preparation: by NaZSM-35 molecular screen primary powder (SiO2/Al2O3Than being removed 15) to be roasted 4 hours at 550 DEG C
Template.In 75 DEG C of alkali process 2h, suction filtration is dried to obtain alkali modification molecular sieve by resulting materials and 0.3M NaOH.Alkali process is changed
Property resulting materials are mixed with aluminium oxide with 1:0.5 weight ratio.Nitric acid solution is added into mixture, pinches even and extruded moulding,
The pelletizing after drying and roasting.After resulting materials are exchanged through ammonium, at 550 DEG C, air speed 2 hours-1Under conditions of at vapor
Catalyst is made in reason 2 hours.
Catalyst test: carbon four (n-butene content 93.1%) is mixed as raw material after using ether, raw material composition is shown in Table 1；?
390 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, examination
Catalyst activity, the 1st day reaction result of catalyst are shown in Table 2.Gasoline component yield is 51.6%.Ethylene, propylene yield
13.9%.
[embodiment 6]
Catalyst preparation: by NaZSM-35 molecular screen primary powder (SiO2/Al2O3Than being removed 15) to be roasted 4 hours at 550 DEG C
Template.In 75 DEG C of alkali process 2h, suction filtration is dried to obtain alkali modification molecular sieve by resulting materials and 0.3M NaOH.Alkali process is changed
Property resulting materials are mixed with aluminium oxide with 1:0.5 weight ratio.Nitric acid solution is added into mixture, pinches even and extruded moulding,
The pelletizing after drying and roasting.After resulting materials are exchanged through ammonium, at 550 DEG C, air speed 2 hours-1Under conditions of at vapor
Catalyst is made in reason 2 hours.
Catalyst test: carbon four (n-butene content 93.1%) is mixed as raw material after using ether, raw material composition is shown in Table 1；?
380 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, examination
Catalyst activity, the 1st day reaction result of catalyst are shown in Table 2.Gasoline component yield is 55.9%.Ethylene, propylene yield
11.7%.
[embodiment 7]
Catalyst preparation: by NaZSM-35 molecular screen primary powder (SiO2/Al2O3Than being removed 15) to be roasted 4 hours at 550 DEG C
Template.In 75 DEG C of alkali process 2h, suction filtration is dried to obtain alkali modification molecular sieve by resulting materials and 0.3M NaOH.Alkali process is changed
Property resulting materials are mixed with aluminium oxide with 1:0.5 weight ratio.Nitric acid solution is added into mixture, pinches even and extruded moulding,
The pelletizing after drying and roasting.After resulting materials are exchanged through ammonium, at 550 DEG C, air speed 2 hours-1Under conditions of at vapor
Catalyst is made in reason 2 hours.
Catalyst test: carbon four (n-butene content 93.1%) is mixed as raw material after using ether, raw material composition is shown in Table 1；?
370 DEG C of temperature, reaction pressure 0.03MPa, four liquid volume air speed of carbon 3 hours-1, under the conditions of loaded catalyst 10mL, examination
Catalyst activity, the 1st day reaction result of catalyst are shown in Table 2.Gasoline component yield is 61.0%.Ethylene, propylene yield
13.6%.
[embodiment 8]
Catalyst preparation: by NaZSM-35 molecular screen primary powder (SiO2/Al2O3Than being removed 15) to be roasted 4 hours at 550 DEG C
Template.In 75 DEG C of alkali process 2h, suction filtration is dried to obtain alkali modification molecular sieve by resulting materials and 0.3M NaOH.Alkali process is changed
Property resulting materials are mixed with aluminium oxide with 1:0.5 weight ratio.Nitric acid solution is added into mixture, pinches even and extruded moulding,
The pelletizing after drying and roasting.After resulting materials are exchanged through ammonium, at 550 DEG C, air speed 2 hours-1Under conditions of at vapor
Catalyst is made in reason 2 hours.
Catalyst test: carbon four (n-butene content 93.1%) is mixed as raw material after using ether, raw material composition is shown in Table 1；?
380 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, examination
Catalyst activity, the 1st day reaction result of catalyst are shown in Table 2.Gasoline component yield is 65.3%.Ethylene, propylene yield 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 (8)
1. the method for C 4 olefin gasoline component coproduction ethylene or propylene, comprising the following steps: exist in ZSM-35 catalyst
Under, C 4 olefin carries out reaction and generates gasoline component coproduction ethylene or propylene；The SiO of ZSM-35 catalyst2/Al2O3Molar ratio
It is 15~19, reaction temperature is 360~390 DEG C, and reaction pressure is 0~0.1MPa.
2. according to the method described in claim 1, it is characterized in that reaction temperature is 370~380 DEG C.
3. according to the method described in claim 1, it is characterized in that the C 4 olefin be anti-butylene, it is maleic, 1- butylene, different
One of butylene is a variety of.
4. according to the method described in claim 1, it is characterized in that, the preparation method of the catalyst, comprising the following steps:
A) by SiO2/Al2O3The ZSM-35 molecular sieve that molar ratio is 15~19 temperature be 30~90 DEG C, alkali concentration be 1.0M with
Alkali process 0.1~40 hour under conditions of lower, precursor I is obtained；
B) 50~90 parts of ZSM-35 molecular sieves and 10~50 parts of binders are kneaded and formed, obtain the mixing of preformed catalyst presoma
Object II；
C) by mixtures II temperature is 200~700 DEG C, volume space velocity is 0.1~20 hour-1Under the conditions of steam treatment 0.1
~40 hours, obtain catalyst.
5. according to the method described in claim 4, it is characterized in that it is that 5 mol/Ls are below that gained catalyst, which further uses concentration,
Acid solution is handled 0.1~24 hour under the conditions of temperature is 20~95 DEG C.
6. according to the method described in claim 4, it is characterized in that steam treatment temperature be 300~600 DEG C, volume space velocity 1
~18 hours-1, the processing time is 1~30 hour.
7. according to the method described in claim 5, it is characterized in that sour at least one in oxalic acid, citric acid or nitric acid
Kind.
8. according to the method described in claim 5, it is characterized in that the concentration of acid solution is 0.2~4 mol/L, sour treatment temperature
It is 30~85 DEG C, the time is 1~20 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610223851.1A CN107286985B (en) | 2016-04-12 | 2016-04-12 | The method of C 4 olefin gasoline component coproduction ethylene or propylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610223851.1A CN107286985B (en) | 2016-04-12 | 2016-04-12 | The method of C 4 olefin gasoline component coproduction ethylene or propylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107286985A CN107286985A (en) | 2017-10-24 |
| CN107286985B true CN107286985B (en) | 2019-04-12 |
Family
ID=60093225
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610223851.1A Active CN107286985B (en) | 2016-04-12 | 2016-04-12 | The method of C 4 olefin gasoline component coproduction ethylene or propylene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107286985B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 | Olefin 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2887555B1 (en) * | 2005-06-28 | 2009-06-26 | Inst Francais Du Petrole | PROCESS FOR THE PREPARATION OF A DIESEL CUTTING BY OLIGOMERISATION |
-
2016
- 2016-04-12 CN CN201610223851.1A patent/CN107286985B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102471702A (en) * | 2009-07-03 | 2012-05-23 | 英国石油国际有限公司 | Olefin 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107286985A (en) | 2017-10-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103157502A (en) | Catalyst of preparing ethylene and propylene by carbinol and / or dimethyl ether, preparing method and application thereof | |
| CN109012504A (en) | Co-production method is obtained the method and its system and device that high-content butene-1 prepares raw material by carbon four | |
| CN107286984B (en) | The method of n-butene gasoline component coproduction isobutene | |
| CN102872901B (en) | Preparation method of low-carbon hydrocarbon aromatization catalyst | |
| CN107286983B (en) | The method of C 4 olefin oligomerisation gasoline component | |
| CN107739291B (en) | Method for modifying FCC gasoline and producing chemical products simultaneously | |
| CN106967452A (en) | A kind of middle C that efficiently make use of liquefied petroleum gas3、C4The method that alkene synthesizes clean gasoline with high octane component with formaldehyde | |
| CN103785482A (en) | Olefin isomerization catalyst passivation treatment method | |
| CN106753506B (en) | Method for synthesizing high-octane component by formaldehyde and liquefied gas | |
| CN101165020B (en) | Method for increasing yield of propylene | |
| CN107286985B (en) | The method of C 4 olefin gasoline component coproduction ethylene or propylene | |
| CN103657707B (en) | Preparation method of low carbon hydrocarbon aromatization catalyst | |
| CN104557377B (en) | The method of oxygenatedchemicals and naphtha coupled reaction production ethylene and propylene | |
| CN107721791B (en) | Preparation system and preparation method for preparing propylene from methanol | |
| CN103539620A (en) | Method for preparing aromatic hydrocarbon from low-carbon hydrocarbon in aromatization mode | |
| CN212894505U (en) | A catalytic conversion device for producing light olefins and aromatics | |
| CN102464538A (en) | Low-carbon hydrocarbon aromatization method | |
| CN102372536B (en) | Method for producing aromatic hydrocarbons by methanol conversion | |
| CN112646598A (en) | Method for converting low-carbon alkane into aromatic hydrocarbon | |
| CN103420756B (en) | The method of preparing propylene from C 4 olefins | |
| CN101092326B (en) | Method for producing propylene | |
| CN111116282A (en) | Method for preparing olefin from tertiary butanol | |
| CN1915924A (en) | Method for producing propylene through catalytic cracking C4 olefin | |
| CN102267854A (en) | Method for preparing isobutylene by virtue of sulfuric acid extraction method | |
| CN103420762A (en) | Method for producing propylene from C4 and ethylene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |