CN1962574A - Process for producing cyclohexene - Google Patents
Process for producing cyclohexene Download PDFInfo
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- CN1962574A CN1962574A CN 200510110278 CN200510110278A CN1962574A CN 1962574 A CN1962574 A CN 1962574A CN 200510110278 CN200510110278 CN 200510110278 CN 200510110278 A CN200510110278 A CN 200510110278A CN 1962574 A CN1962574 A CN 1962574A
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- tetrahydrobenzene
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- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 title claims description 43
- 238000000034 method Methods 0.000 title claims description 33
- 230000008569 process Effects 0.000 title description 7
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 43
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000010457 zeolite Substances 0.000 claims abstract description 43
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052680 mordenite Inorganic materials 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 claims description 4
- 229910052676 chabazite Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 18
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- -1 chabasite Inorganic materials 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 238000006297 dehydration reaction Methods 0.000 description 20
- 239000000047 product Substances 0.000 description 15
- 208000005156 Dehydration Diseases 0.000 description 14
- 230000018044 dehydration Effects 0.000 description 14
- 239000002253 acid Substances 0.000 description 13
- 239000007791 liquid phase Substances 0.000 description 12
- 238000006555 catalytic reaction Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- 230000009466 transformation Effects 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000012805 post-processing Methods 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000009418 renovation Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a manufacturing method of cyclohexane, which is characterized by the following: adopting cyclohexanol as raw material; selecting at least one hydrogen zeolite or adhesive of ZSM zeolite, L-zeolite, beta-zeolite, MCM-typed zeolite, chabasite, mordenite or octahedra zeolite as catalyst; setting the reacting temperature at 120-240 Deg C and absolute reacting pressure at 0.01-1.0Mpa. The invention improves recovering rate, which shortens reacting time.
Description
Technical field
The present invention relates to a kind of method of producing tetrahydrobenzene, particularly the method that tetrahydrobenzene is produced in dehydration about the hexalin liquid-phase catalysis.
Background technology
Tetrahydrobenzene, have another name called tetrahydrobenzene, can be used for organic synthesis, the stablizer that also can be used for solvent and petroleum extn agent, stop bracket gasoline, be mainly used in and make L-Methionin, hexahydrobenzoic acid, epoxy cyclohexane etc., sealing admittedly at medicine intermediate, pesticide intermediate and microelectronics also has good application prospects aspect the polymkeric substance.
Traditional tetrahydrobenzene production method, adopting mineral acid mainly is the vitriol oil or organic acid as catalyst, the hexalin liquid-phase dehydration makes.It is catalyzer that the phosphoric acid of employing is also arranged, though slowed down corrodibility, carbide growing amount, cost has improved.Adopt vitriol oil homogeneous catalysis dewatering process to produce tetrahydrobenzene, yield only 81%.Thick product contains acid, SO in this technology
2, by-product carbide, must just obtain product through loaded down with trivial details postprocessing working procedures such as washing, neutralization, washing, rectifying.Exist that equipment corrosion is serious, spent acid environmental pollution, problems such as postprocessing working procedures is long, reaction yield is low, poor product quality.
In recent years, people explore the method that the hexalin gas-phase dehydration prepares tetrahydrobenzene, adopt modified alta-mud, solid super-strong acid SO
4 2-/ ZrO
2-Ce
2O
3Deng the preparation catalyzer.Xu Limin etc. " Fujian Normal University's journal " 1999, Vol.15, No.2 has studied among the p48 through the atlapulgite of 350 ℃ of acid activation processing, maturing temperature and has made catalyzer, charging air speed 2.5 hours
-1, 205 ℃ of hexalin gas-solid catalysis dehydrations, the tetrahydrobenzene productive rate is 98%.The catalyzer initial stage (continuous operation 26 hours) is activity stabilized 97.8%, and the catalyzer life-time service remains to be furtherd investigate.Li Yuanzhi " fine chemistry industry " 2000, Vol.17, No.2 has prepared in 550 ℃ of roastings among the p88 and has contained cerium solid super-strong acid SO
4 2-/ ZrO
2-Ce
2O
3(contain massfraction 1.5%Ce
2O
3) catalyzer, gas-solid catalysis dehydration reaction in the time of 140 ℃, hexalin transformation efficiency 95.3%, tetrahydrobenzene selectivity 100%.This only is the result of probe reaction.
Hexalin boiling point height, vapor phase process dehydration energy consumption is big, and conversion unit efficient is not as liquid phase method.These years, people continually develop the new catalyst that substitutes the vitriol oil to hexalin liquid-phase dehydration method, attempt to use NaHSO H
2O, SnCl
4, tosic acid, phospho-wolframic acid, solid super-strong acid SO
4 2-/ TiO
2-SiO
2, SO
4 2-/ ZrO
2, SO
4 2-/ TiO
2-SnO
2, SO
4 2-/ ZrO
2-flyash, natural mordenite zeolite, dealuminzation overstable gamma zeolite development catalyzer.Yang Kailian etc. " Zhejiang chemical industry " 2003, Vol.34, No.12, among the p1 with solid super-strong acid SO
4 2-/ TiO
2-SnO
2For the catalyzer dehydration of cyclohexanol prepares tetrahydrobenzene, catalyst levels is 8% of a hexalin quality, and temperature is 160 ℃, reacts 3 hours, and product yield is more than 78%, and catalyzer is reusable, but product yield is low.Gu Xupeng etc. " chemical industry progress " 2004, Vol.23, No.2 has prepared solid super-strong acid SO among the p195
4 2-/ ZrO
2-flyash catalyzer, catalyst levels are 10% of hexalin quality, and temperature of reaction is 180 ℃, dehydration of cyclohexanol reaction 1 hour, yield reaches 85%, product purity height, the easy and product separation of solid catalyst, reusable, but catalyst levels is too many, and product yield is not high.Chen Haisheng etc. " chemical reagent " 1997, Vol.19, No.4 uses treated natural mordenite zeolite to make catalyzer among the p242, and catalyst levels is 5～50%, 205 ℃ of hexalin quality, hexalin liquid-phase dehydration reaction 3 hours, the tetrahydrobenzene productive rate is 93%.Catalyzer 50 grams are through 28 secondary responses, and shared hexalin 3000 grams have long work-ing life.But exist catalyst levels many, the catalyzer life cycle is long, the temperature of reaction height, and the reaction times is than problems such as length.Zhang Min etc. " fine chemistry industry " 2000, Vol.17, No.5, adopting silica alumina ratio among the p287 is that 10.99 dealuminzation overstable gamma zeolite is made catalyzer, and catalyst levels is 7.5%, 180～190 ℃ of hexalin quality, hexalin liquid-phase dehydration reaction 1 hour, the tetrahydrobenzene productive rate is 87.8%.Catalyzer is reusable through the gas phase high-temperature roasting.But exist the reaction times to prolong catalyst activity reduction, problem such as the tetrahydrobenzene productive rate is low.
Summary of the invention
Technical problem to be solved by this invention be have in the prior art that equipment corrosion is serious, spent acid contaminate environment, problems such as postprocessing working procedures is long, reaction yield is low, poor product quality, perhaps catalyst levels is many, the temperature of reaction height, reaction times is longer, the tetrahydrobenzene productive rate is low, especially the reaction times prolongs problems such as catalyst activity reduction, the method that provides a kind of new hexalin liquid-phase catalysis dehydration to produce tetrahydrobenzene.This method not only have to equipment do not have corrosive nature, product postprocessing easily, advantage such as non-environmental-pollution, and it is simple to have flow process, product yield height, quality are good, the long and characteristics that can regenerate and use of catalyzer life cycle.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of producing tetrahydrobenzene, with the hexalin is raw material, in temperature of reaction is 120～240 ℃, the reaction absolute pressure is under 0.01～1.0MPa condition, reaction raw materials contacts with catalyzer and generates tetrahydrobenzene, and wherein used catalyzer comprises following component by weight percentage:
A) 30～90% be selected from least a h-type zeolite in ZSM type zeolite, L zeolite, β zeolite, MCM type zeolite, chabazite, mordenite or the faujusite;
B) 10～70% binding agent.
In the technique scheme, the temperature of reaction preferable range is 170～190 ℃, and reaction absolute pressure preferable range is normal pressure～0.5MPa.The consumption preferable range that is selected from h-type zeolite at least a in ZSM type zeolite, L zeolite, β zeolite, MCM type zeolite, chabazite, mordenite or the faujusite by weight percentage is 60～80%; The h-type zeolite preferred version is at least a for being selected from ZSM-5 zeolite, mordenite or the faujusite; ZSM-5 zeolite preferred version is that to be selected from silica alumina ratio be 10～1500 ZSM-5 zeolite, and the mordenite preferred version is that to be selected from silica alumina ratio be 8～150 mordenite, and the faujusite preferred version is that to be selected from silica alumina ratio be 0.8～30 faujusite.Preferred version is selected from least a in Ni, Zn, Cu, Pd or Pt element or its oxide compound for also containing in the catalyzer by weight percentage, and its consumption is＞0～5%, and preferable range is 0.01～3%.The preferred version of binding agent is for being selected from silicon oxide, aluminum oxide or its miscellany.
Each method of the system of the catalyzer that uses among the present invention is the preparation method of general zeolite catalyst.Use silicon source, aluminium source and auxiliary agent (for example ammonia, organic amine template) the former powder of synthetic zeolite, again through the roasting demoulding, the acid exchange, washing gets h-type zeolite.H-type zeolite is immersed in the salts solution of at least a Ni of being selected from, Zn, Cu, Pd or Pt element of requirement oven dry, roasting.To fully mediate through the zeolite and the binding agent of above-mentioned processing then, after the moulding, through super-dry, roasting and catalyzer.
Reaction raw materials is a hexalin among the present invention, can be various operational path synthetic hexalin, preferably lower boiling, impurity is few, cyclohexanone content is low hexalin.Raw material hexalin and catalyzer can directly add in the reactor, are warming up to preset temperature then and carry out the liquid-phase catalysis dehydration reaction; Also can add the raw material hexalin earlier, be warming up to preset temperature, add catalyzer again and carry out the liquid-phase catalysis dehydration reaction, catalyzer finishes after-filtration in reaction and reclaims, and joins in the reactor and reuses.Reaction times is 0.15～10 hour, and preferable range is 0.5～2 hour.After can also the catalyst dehydration of cyclohexanol being reacted to a certain degree, successively add after direct liquid phase cold conditions of hexalin or the preheating and be fed in the reactor, continue the liquid-phase catalysis dehydration reaction, descend, reach the effect that the catalyzer long period is used until catalyst performance.
Under general operational requirement(GOR), catalyzer can be reused 40～60 times, needn't regenerate.Under preferred reaction conditions, catalyzer can be reused 35～50 times, needn't regenerate.When catalyst performance descended, the renovation process of catalyzer had gas phase method of reproduction and liquid phase method of reproduction.Modal renovation process is the gas phase high-temperature roasting method.Using the air high-temperature roasting more than 500 ℃, regenerated catalyst effectively, catalyzer can be reused.
The present invention, reacted 0.15～10 hour under the condition of reaction pressure 0.01～1.0MPa (absolute pressure) 120～240 ℃ of temperature of reaction, and the hexalin transformation efficiency is more than 96%, and the tetrahydrobenzene yield is more than 95%.Under preferred reaction conditions: 170～190 ℃ of temperature of reaction, reaction pressure normal pressure～0.5MPa (absolute pressure) reacted 0.5～2 hour, and the hexalin transformation efficiency is more than 98%, and the tetrahydrobenzene yield is more than 97%, and product purity height, quality are good, do not contain acid, SO
2, by-product carbide etc., obtained better technical effect.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1～12]
H-type zeolite is immersed in the salts solution of at least a Ni of being selected from, Zn, Cu, Pd or Pt element of requirement 5～8 hours, filters back 120 ℃ of oven dry 10 hours, 550 ℃ of roastings 2 hours, and pulverize.To fully mediate through the zeolite and the binding agent aluminum oxide of above-mentioned processing then, behind the extruded moulding, 120 ℃ of bakings 10 hours, 550 ℃ of roastings 5 hours obtain catalyst A～L.The catalyzer composition sees Table 1.
Table 1
| Embodiment | Catalyzer | H-type zeolite | Metallic element weight % | ||
| Kind | SiO 2/Al 2O 3Mole | Weight % | |||
| 1 | A | ZSM-5 | 60 | 60 | Pd0.07 |
| 2 | B | ZSM-5 | 200 | 70 | Pd0.05、Pt0.03 |
| 3 | C | ZSM-5 | 800 | 80 | / |
| 4 | D | Faujusite | 2 | 40 | / |
| 5 | E | Faujusite | 8 | 60 | Ni2.6、Cu1.8 |
| 6 | F | Faujusite | 30 | 70 | Pd0.06 |
| 7 | G | Faujusite | 24 | 70 | Ni2.1、Zn2.8 |
| 8 | H | Faujusite | 20 | 80 | Ni1.2、Pt0.01 |
| 9 | I | Faujusite | 13 | 50 | / |
| 10 | J | Mordenite | 20 | 60 | Ni1.5、Zn1.3 |
| 11 | K | Mordenite | 70 | 70 | Ni1.8、Pt0.01 |
| 12 | L | Mordenite | 120 | 85 | / |
Add catalyzer 2.5 grams in 500 milliliters of reactors, hexalin 200 grams are warming up to temperature of reaction then, and catalytic dehydration generates tetrahydrobenzene, and reaction conditions and reaction result see Table 2.
Table 2
| Embodiment | Catalyzer | Temperature of reaction ℃ | Reaction pressure (absolute pressure) MPa | Reaction times minute | Hexalin transformation efficiency % | Tetrahydrobenzene yield % |
| 1 | A | 200 | 0.5 | 30 | 100 | 97.5 |
| 2 | B | 240 | 1.0 | 10 | 100 | 95.2 |
| 3 | C | 170 | 0.2 | 120 | 97.5 | 96.1 |
| 4 | D | 180 | 0.3 | 90 | 99.1 | 98.3 |
| 5 | E | 230 | 0.8 | 15 | 100 | 95.8 |
| 6 | F | 190 | 0.4 | 60 | 99.5 | 99.1 |
| 7 | G | 130 | 0.05 | 480 | 96.5 | 96.2 |
| 8 | H | 210 | 0.6 | 20 | 100 | 99.5 |
| 9 | I | 160 | 0.1 | 180 | 98.7 | 95.6 |
| 10 | J | 120 | 0.03 | 600 | 96.1 | 96.0 |
| 11 | K | 230 | 0.8 | 15 | 100 | 97.7 |
| 12 | L | 170 | 0.2 | 120 | 99.3 | 96.9 |
[embodiment 13]
Add catalyzer E 2.5 grams in 500 milliliters of reactors, hexalin 200 grams are warming up to 230 ℃ of temperature of reaction then, and under the condition of reaction pressure 0.8MPa (absolute pressure), catalytic dehydration generates tetrahydrobenzene.In reaction process, in order to control reaction pressure, some contain lower boiling tail gas to need continuous blow-down.Catalyzer joins in the reactor and reuses in each reaction filtered and recycled of lowering the temperature after 15 minutes.Catalyzer is reused 60 times under identical condition.In the time of the 60th time, the hexalin transformation efficiency is 100%, and the tetrahydrobenzene yield drops to 95.0%, and the product tetrahydrobenzene is except that the dissolved micro-moisture, and gas chromatographic analysis detects the olefin impurity peak and adds up to 800ppm.
[embodiment 14]
Add catalyzer H2.5 gram in 500 milliliters of reactors, hexalin 200 grams are warming up to 190 ℃ of temperature of reaction then, and under the condition of reaction pressure 0.4MPa (absolute pressure), catalytic dehydration generates tetrahydrobenzene.In catalytic reaction process,, need intermittently discharged to contain lower boiling tail gas in order to control reaction pressure.Catalyzer joins in the reactor and reuses in each reaction filtered and recycled of lowering the temperature after 60 minutes.Catalyzer is reused 45 times under identical condition.In the time of the 45th time, the hexalin transformation efficiency is 100%, and the tetrahydrobenzene yield drops to 97.1%, and the product tetrahydrobenzene is except that the dissolved micro-moisture, and gas chromatographic analysis detects the olefin impurity peak and adds up to 200ppm.The catalyzer that catalytic performance descends, roasting regeneration in 650 ℃ of air.In 500 milliliters of reactors, add catalyzer 2.5 grams after regenerating, hexalin 200 grams, be warming up to 190 ℃ of temperature of reaction then, under the condition of reaction pressure 0.4MPa (absolute pressure), catalytic dehydration generates tetrahydrobenzene, and the hexalin transformation efficiency is 100%, and the tetrahydrobenzene yield is 99.1%, the product tetrahydrobenzene is except that the dissolved micro-moisture, and gas chromatographic analysis detects the olefin impurity peak and adds up to 120ppm.
Claims (9)
1, a kind of method of producing tetrahydrobenzene, with the hexalin is raw material, is 120～240 ℃ in temperature of reaction, and the reaction absolute pressure is under 0.01～1.0MPa condition, reaction raw materials contacts with catalyzer and generates tetrahydrobenzene, and wherein used catalyzer comprises following component by weight percentage:
A) 30～90% be selected from least a h-type zeolite in ZSM type zeolite, L zeolite, β zeolite, MCM type zeolite, chabazite, mordenite or the faujusite;
B) 10～70% binding agent.
2,, it is characterized in that temperature of reaction is 170～190 ℃ according to the method for the described production tetrahydrobenzene of claim 1.
3, according to the method for the described production tetrahydrobenzene of claim 1, it is characterized in that reacting absolute pressure is normal pressure～0.5MPa.
4, according to the method for the described production tetrahydrobenzene of claim 1, the consumption that it is characterized in that being selected from by weight percentage h-type zeolite at least a in ZSM type zeolite, L zeolite, β zeolite, MCM type zeolite, chabazite, mordenite or the faujusite is 60～80%.
5, according to the method for the described production tetrahydrobenzene of claim 1, it is at least a to it is characterized in that h-type zeolite is selected from ZSM-5 zeolite, mordenite or the faujusite.
6, according to the method for the described production tetrahydrobenzene of claim 5, the silica alumina ratio that it is characterized in that the ZSM-5 zeolite is 10～1500, and the silica alumina ratio of mordenite is 8～150, and the silica alumina ratio of faujusite is 0.8～30.
7,, it is characterized in that by weight percentage also contain in the catalyzer and be selected from least a in Ni, Zn, Cu, Pd or Pt element or its oxide compound, its consumption is＞0～5% according to the method for the described production tetrahydrobenzene of claim 1.
8, the method for the described production tetrahydrobenzene of claim 7 is characterized in that by weight percentage, and at least a consumption that is selected from Ni, Zn, Cu, Pd or Pt element or its oxide compound is 0.01～3%.
9,, it is characterized in that binding agent is selected from silicon oxide, aluminum oxide or its miscellany according to the method for the described production tetrahydrobenzene of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101102785A CN100430350C (en) | 2005-11-11 | 2005-11-11 | Process for producing cyclohexene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101102785A CN100430350C (en) | 2005-11-11 | 2005-11-11 | Process for producing cyclohexene |
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| Publication Number | Publication Date |
|---|---|
| CN1962574A true CN1962574A (en) | 2007-05-16 |
| CN100430350C CN100430350C (en) | 2008-11-05 |
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|---|---|---|---|
| CNB2005101102785A Expired - Fee Related CN100430350C (en) | 2005-11-11 | 2005-11-11 | Process for producing cyclohexene |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103664534A (en) * | 2012-09-17 | 2014-03-26 | 埃克森美孚化学专利公司 | Process for producing phenol and/or cyclohexanone |
| CN103664533A (en) * | 2012-09-17 | 2014-03-26 | 埃克森美孚化学专利公司 | Process for producing phenol |
| US9260387B2 (en) | 2012-12-06 | 2016-02-16 | Exxonmobil Chemical Patents Inc. | Process for producing phenol |
| US9278897B2 (en) | 2012-09-17 | 2016-03-08 | Exxonmobil Chemical Patents Inc. | Process for producing phenol and/or cyclohexanone from cyclohexylbenzene |
| US9340474B2 (en) | 2012-12-06 | 2016-05-17 | Exxonmobil Chemical Patents Inc. | Process for producing phenol |
| CN109225281A (en) * | 2018-09-19 | 2019-01-18 | 中国天辰工程有限公司 | A kind of catalyst and preparation method and application of the component of copper activity containing multivalent state |
-
2005
- 2005-11-11 CN CNB2005101102785A patent/CN100430350C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103664534A (en) * | 2012-09-17 | 2014-03-26 | 埃克森美孚化学专利公司 | Process for producing phenol and/or cyclohexanone |
| CN103664533A (en) * | 2012-09-17 | 2014-03-26 | 埃克森美孚化学专利公司 | Process for producing phenol |
| US9278897B2 (en) | 2012-09-17 | 2016-03-08 | Exxonmobil Chemical Patents Inc. | Process for producing phenol and/or cyclohexanone from cyclohexylbenzene |
| CN103664534B (en) * | 2012-09-17 | 2016-03-16 | 埃克森美孚化学专利公司 | Produce the method for phenol and/or pimelinketone |
| CN103664533B (en) * | 2012-09-17 | 2016-08-24 | 埃克森美孚化学专利公司 | The method producing phenol |
| US9452965B2 (en) | 2012-09-17 | 2016-09-27 | Exxonmobil Chemical Patents Inc. | Process for producing phenol and/or cyclohexanone from cyclohexylbenzene |
| US9260387B2 (en) | 2012-12-06 | 2016-02-16 | Exxonmobil Chemical Patents Inc. | Process for producing phenol |
| US9340474B2 (en) | 2012-12-06 | 2016-05-17 | Exxonmobil Chemical Patents Inc. | Process for producing phenol |
| CN109225281A (en) * | 2018-09-19 | 2019-01-18 | 中国天辰工程有限公司 | A kind of catalyst and preparation method and application of the component of copper activity containing multivalent state |
| CN109225281B (en) * | 2018-09-19 | 2022-04-15 | 中国天辰工程有限公司 | Catalyst containing multivalent copper active component, preparation method and application |
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|---|---|
| CN100430350C (en) | 2008-11-05 |
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