CN1038030C - Method for prepn. of cyclohexene by using natural mordenite as catalyst - Google Patents
Method for prepn. of cyclohexene by using natural mordenite as catalyst Download PDFInfo
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- CN1038030C CN1038030C CN93109228A CN93109228A CN1038030C CN 1038030 C CN1038030 C CN 1038030C CN 93109228 A CN93109228 A CN 93109228A CN 93109228 A CN93109228 A CN 93109228A CN 1038030 C CN1038030 C CN 1038030C
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- China
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- reaction
- catalyzer
- catalyst
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- raw material
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- 238000000034 method Methods 0.000 title claims abstract description 15
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 239000003054 catalyst Substances 0.000 title claims abstract description 9
- 229910052680 mordenite Inorganic materials 0.000 title claims abstract description 8
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 8
- 230000018044 dehydration Effects 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims description 9
- 238000011282 treatment Methods 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 5
- 238000010960 commercial process Methods 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 16
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005194 fractionation Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000003287 bathing Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 1
- 229930195722 L-methionine Natural products 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- -1 hexamethylene aldehyde Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a method for preparing cyclohexene from cyclohexanol through dehydration. In the method provided by the present invention, processed natural mordenite is used as catalysts for continuous feeding reaction for 3 to 20 hours at 80 to 250 DEG C; the purity of obtained products is higher than 90%, the yield is high, the catalysts have the advantages of long service life and easy preparation and can be regenerated, and the present invention is favorable for commercial process.
Description
The present invention relates to a kind of preparation method of tetrahydrobenzene.
Tetrahydrobenzene can be used for making multiple Chemicals such as L-Methionin, hexanodioic acid, oxysuccinic acid, cyclohexylenedinitrilotetraacetic acid and hexamethylene aldehyde, can also be as extraction agent and stop bracket gasoline stablizer in petroleum industry.
One of main method of preparation tetrahydrobenzene is the dehydration of cyclohexanol method, G.H.Coleaan and H.F.Johnstone make the dehydration of cyclohexanol synthesizing cyclohexene with sulfuric acid as catalyzer under heating condition, a large amount of carbonizations takes place in the reaction, cause and contain sulfurous gas in the product, must be in industrial production through neutralization, just can obtain product after loaded down with trivial details aftertreatment such as washing is purified,, also have problem of environment pollution caused simultaneously to the serious corrosion of instrument and equipment.Phosphoric acid method afterwards, though have only slight carbonization phenomenon in the reaction, the phosphoric acid consumption is too big, even accounts for 42% of raw material weight.The activated alumina method that E.B.Hersnberg and John R.Runoff propose, temperature of reaction is up to 450 ℃, and energy expenditure is also high.Fpetr is the method for dewatering agent with Tetra hydro Phthalic anhydride and Phenylsulfonic acid mixture, and the reaction times is shorter, but the dewatering agent consumption is 153% of a raw material weight, and raw material must be used anhydrous hexalin, and productive rate is lower, is difficult to realize modernization.Jiang Shuhua adopts cationic resin catalysis, and product purity can reach 87.7%, but the content of hexalin is higher in its product.When improving fractionation speed, hexalin content is higher, so that product purity reduces.N.W.Kostandyan etc. and G.V.Tsilsihvili etc. have generated difficult isolating tetrahydrobenzene isomerization by product with the catalytic dehydration of cyclohexanol reaction of natural zeolite, and productive rate is not high.
The objective of the invention is to propose a kind of low-cost catalyzer, make dehydration of cyclohexanol obtain the higher tetrahydrobenzene of purity productive rate.Be characterized in adopting through the peracid repeated treatments, add thermal bake-out and also use the natural mordenite catalyst of ammonia treatment, hexalin and catalyzer be equipped with in the flow reactor of thermometer, fractional column one carry out dehydration reaction, temperature of reaction is in 80-250 ℃ of scope, the one way reaction times is 3-20 hour, catalyzer can use 50-100 time, and the weight ratio of catalyzer and raw material is: catalyzer: raw material=1: 100～1: 1.After the reaction beginning, product is steamed through fractional column, steams after the thing layering removes water layer, obtains the product that purity is 90-94%, and productive rate is 90-95%, if product is further used the siccative drying, (used siccative is CaCl
2, MgSo
4, Na
2So
4, K
2Co
3, Na
2Co
3, CaO molecular sieve etc.) and filter the simple fractionation in back, purity can be brought up to 98%.Can constantly replenish raw material in the reaction and carry out continuous production, but the catalyzer life-time service.Iterative regenerable repeatedly behind the catalyst deactivation.This catalyzer adopts Chinese patent by natural mordenite zeolite: 86105408.3 provide the treatment process of natural system zeolite catalyst to make.Method provided by the present invention advantage compared with prior art is:
(1) used catalyzer natural mordenite zeolite is the China's abundant mineral products, is easy to preparation, and long service life can repeatedly be regenerated and be used repeatedly, and is cheap, free from environmental pollution.
(2) the used ingredient requirement of present method is not harsh, need not anhydrous hexalin, and temperature of reaction is not high, and productive rate is higher.
(3) present method products obtained therefrom purity is higher is more than 90%, can shorten the reaction times by improving fractionation speed, can not reduce product purity.
(4) the non-isomerization by product generates in the reaction of present method.
Example 1:
In the there-necked flask that thermometer, fractional column are housed, add hexalin 100g and catalyzer 50g, in bathing under warm 180 ℃, reacted 5 hours, product is steamed by fractional column, steams the thing layering except that after anhydrating, and gets product 81.5g (content 90%), productive rate 91.3%.IR is consistent with the chemical reagent collection of illustrative plates.
Example 2:
In the there-necked flask of example one same apparatus, add hexalin 150g continuation and use former example one catalyst system therefor to react 5 hours down for 200 ℃ in bathing temperature, product steams by fractional column.Get product 117.8g (containing tetrahydrobenzene 93.88%), water 24.5g.
Example 3:
In with the reaction flask of example one same apparatus on, connect a feeder.After the reaction beginning,, replenish raw material, keep bottle interior liquid level on certain level by feeder along with steaming of product.Realize serialization, long-term production.
Claims (1)
1, a kind of dehydration of cyclohexanol prepares the method for tetrahydrobenzene, it is characterized by use through sour repeated treatments, add thermal bake-out and also use the mordenite catalyst of ammonia treatment, hexalin and treated natural mordenite catalyst, be equipped with in the flow reactor of thermometer, fractional column one and carry out dehydration reaction, temperature of reaction one way reaction times in 80-250 ℃ of scope is 3-20 hour, and the weight ratio of catalyzer and raw material is: catalyzer: raw material=1: 100-1: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93109228A CN1038030C (en) | 1993-08-06 | 1993-08-06 | Method for prepn. of cyclohexene by using natural mordenite as catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93109228A CN1038030C (en) | 1993-08-06 | 1993-08-06 | Method for prepn. of cyclohexene by using natural mordenite as catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1085886A CN1085886A (en) | 1994-04-27 |
| CN1038030C true CN1038030C (en) | 1998-04-15 |
Family
ID=4987549
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93109228A Expired - Fee Related CN1038030C (en) | 1993-08-06 | 1993-08-06 | Method for prepn. of cyclohexene by using natural mordenite as catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1038030C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1915517B (en) * | 2005-08-15 | 2010-04-28 | 中国石油化工股份有限公司 | Catalyst in use for producing cyclohexene |
| JP6409611B2 (en) * | 2015-02-23 | 2018-10-24 | 東レ株式会社 | Method for producing p-toluic acid |
| CN111253204B (en) * | 2018-11-30 | 2022-04-01 | 中国科学院大连化学物理研究所 | Method for preparing ethylene by ethanol dehydration |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3345425A (en) * | 1965-10-18 | 1967-10-03 | Union Oil Co | Preparation of cyclohexene |
| CN86105408A (en) * | 1986-08-26 | 1988-03-16 | 中国科学院广州化学研究所 | Catalytic synthesising of monoterpene ether from natural mordenite |
-
1993
- 1993-08-06 CN CN93109228A patent/CN1038030C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3345425A (en) * | 1965-10-18 | 1967-10-03 | Union Oil Co | Preparation of cyclohexene |
| CN86105408A (en) * | 1986-08-26 | 1988-03-16 | 中国科学院广州化学研究所 | Catalytic synthesising of monoterpene ether from natural mordenite |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1085886A (en) | 1994-04-27 |
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