CN101274922B - A kind of method for preparing propylene oxide - Google Patents
A kind of method for preparing propylene oxide Download PDFInfo
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- CN101274922B CN101274922B CN2007100649801A CN200710064980A CN101274922B CN 101274922 B CN101274922 B CN 101274922B CN 2007100649801 A CN2007100649801 A CN 2007100649801A CN 200710064980 A CN200710064980 A CN 200710064980A CN 101274922 B CN101274922 B CN 101274922B
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- hydrogen peroxide
- molecular sieve
- adsorption
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- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 29
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 86
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 239000002808 molecular sieve Substances 0.000 claims abstract description 29
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 29
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 17
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 238000001179 sorption measurement Methods 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 3
- 238000003795 desorption Methods 0.000 claims abstract description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 3
- 239000007800 oxidant agent Substances 0.000 claims abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 51
- 238000006735 epoxidation reaction Methods 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 3
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 13
- 239000007795 chemical reaction product Substances 0.000 description 10
- 238000000465 moulding Methods 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 238000005070 sampling Methods 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- 229910052719 titanium Inorganic materials 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000007781 pre-processing Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000006004 Quartz sand Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 208000006558 Dental Calculus Diseases 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 239000004411 aluminium Substances 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
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229940001516 sodium nitrate Drugs 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
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- Epoxy Compounds (AREA)
Abstract
一种制备环氧丙烷的方法，是在溶剂存在下以过氧化氢为氧化剂，丙烯环氧化制备环氧丙烷，其特征在于该方法中催化剂的活性组元是一种具有MFI结构的钛硅分子筛，其晶粒为空心结构，该空心晶粒的空腔部分的径向长度为5～300nm，该分子筛样品在25℃、P/P0＝0.10、吸附时间1h的条件下测得的苯吸附量为至少70mg/g，分子筛的低温氮吸附的吸附等温线和脱附等温线之间存在滞后环。该方法催化剂稳定性好，环氧丙烷选择性高、过氧化氢利用率高，反应条件温和，便于操作。A method for preparing propylene oxide is to prepare propylene oxide by epoxidizing propylene with hydrogen peroxide as an oxidant in the presence of a solvent, which is characterized in that the active component of the catalyst in the method is a titanium silicon with MFI structure Molecular sieves, the grains of which are hollow structures, the radial length of the hollow portion of the hollow grains is 5-300nm, the molecular sieve sample is measured under the conditions of 25°C, P/P 0 =0.10, and adsorption time of 1h. The adsorption capacity is at least 70 mg/g, and there is a hysteresis loop between the adsorption isotherm and the desorption isotherm of the low-temperature nitrogen adsorption of the molecular sieve. The method has good catalyst stability, high propylene oxide selectivity, high hydrogen peroxide utilization rate, mild reaction conditions and convenient operation.
Description
Technical field
The present invention relates to a kind of method for preparing propylene oxide, more specifically to a kind of be the catalytic activity constituent element with the HTS, the method for catalyzing propone and hydrogen peroxide preparing epoxypropane by epoxidation.
Background technology
Propylene oxide (propylene oxide, be called for short PO), it is a kind of important basic Organic Chemicals, output is only second to polypropylene and vinyl cyanide in acryloyl derivative, maximum purposes is to produce polyether glycol, with further processing and manufacturing urethane, also can be used for producing broad-spectrum propylene glycol.In addition, propylene oxide also can be used for producing tensio-active agent, oil field emulsion splitter etc.
Along with the widespread use of polyurethane material and unsaturated polyester, the demand of propylene oxide is rising year by year.At present, industrial production propylene oxide is mainly based on chlorohydrination and common oxygen method.Wherein chlorohydrination is the method that extensively adopts.Though chlorohydrination technology is simple, the yield height, reduced investment, flexible operation, producing a large amount of waste water in the production process is its maximum shortcoming.
As can be seen, existing technology of producing propylene oxide exists drawback, does not especially meet the requirement of Green Chemistry chemical industry.Therefore, people press for the promptly economic and environment amenable again production method of exploitation.
The oxidation of the partial oxidation of the hydroxylation that is found to be alkene epoxidation, benzene and phenol of HTS, hexamethylene ketonize, alkane, alcohol etc. opens up a new way, and particularly aspect alkene epoxidation, has obtained good catalyzed oxidation effect.Be that oxygenant, methyl alcohol are in the reaction system of solvent with the hydrogen peroxide, HTS has advantages of high catalytic activity to propylene, but the propylene oxide that generates is easy to the open loop side reaction further takes place under the effect of catalyzer, thereby greatly reduces the selectivity of propylene oxide.
In order to improve the selectivity of propylene oxide, in propylene ring oxidation reaction, add the organic compound that contains basic group come in and the acid site on the HTS can improve the selectivity (referring to EP0940393, CN1156463C) of propylene oxide.CN1062864C has disclosed a kind of certain density non-basic salt that adds in reaction system, as lithium chloride, SODIUMNITRATE, vitriolate of tartar and primary ammonium phosphate etc., improve optionally method of propylene oxide to improve.Though aforesaid method can improve the selectivity of propylene oxide to a certain extent, propylene oxide optionally improves the cost that is reduced to that is with the hydrogen peroxide utilization ratio.
Adopt metal salt solution pre-processing titanium si molecular sieves (referring to CN1555923A) to be used for propylene ring oxidation reaction, though the utilization ratio that can improve hydrogen peroxide can also improve the selectivity of propylene oxide, but along with the prolongation in reaction times, the selectivity of propylene oxide reduces gradually.Therefore, exist the problem of less stable through pretreated catalyzer.
In sum, in the technology of existing industrial production propylene oxide, exist environmental pollution, do not meet the requirement that contemporary green chemical industry is produced; And in the technology with titanium molecular sieve catalysis propylene and hydrogen peroxide epoxidation production propylene oxide of report, though solved the chlorohydrination environmental pollution problems, but it is lower to exist purpose product propylene oxide selectivity, when perhaps the propylene oxide selectivity improves, but exist the problem of poor catalyst stability.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of method of production propylene oxide of environmental protection is provided, catalyst system therefor does not need the modification pre-treatment or need not add inhibitor in reaction system, and the selectivity height and the catalyst stability of purpose product propylene oxide are better.
The method for preparing propylene oxide provided by the invention, be in the presence of solvent, to be oxygenant with the hydrogen peroxide, preparing epoxypropane by epoxidation of propene, it is characterized in that the activity of such catalysts constituent element that adopts is a kind of HTS of the MFI of having structure, its crystal grain is hollow structure, the radical length of the cavity part of this hollow crystal grain is 5～300nm, and this sieve sample is at 25 ℃, P/P
0=0.10, the benzene adsorptive capacity that records under the condition of adsorption time 1h is 70mg/g at least, has hysteresis loop between the adsorption isothermal line of the cryogenic nitrogen absorption of molecular sieve and the desorption isotherm.
In the method provided by the invention, the MFI structure titanium silicon molecular sieve that said crystal grain has hollow structure has had public publish in CN1301599A.
In the method provided by the invention, said solvent is selected from methyl alcohol, ethanol, n-propyl alcohol, Virahol, the trimethyl carbinol, isopropylcarbinol or acetone etc., and particular methanol is a solvent.
The reaction process of method provided by the invention can realize according to following A, B dual mode:
A, be reflected at intermittently on tank reactor or the slurry bed reactor and carry out, with former powdery HTS is catalyzer, its advantage is that molecular sieve needn't can use in moulding, preferred reaction conditions is to contain 0.001～0.01g molecular sieve in every milliliter of reaction solution, the mol ratio of solvent and hydrogen peroxide is 10～50, temperature is at 20～35 ℃, and pressure is 0.4～2.0MPa, 10～30 minutes reaction times.
B, be reflected on the fixed-bed reactor and carry out, the HTS that employing has after certain particle diameter, the moulding is a catalyzer, its advantage is, reaction product need not adopt extra separation circuit, the mol ratio that preferred reaction conditions is propylene and hydrogen peroxide is 1.0～4.0, the mol ratio of solvent and propylene is 20～100, and total liquid feeding volume space velocity is at 1.0～30.0h
-1, pressure is 0.4～2.0MPa, temperature is 20～60 ℃.Titanium-silicon molecular sieve catalyst after the said moulding is former powder of HTS and tackiness agent, mixes obtaining as silicon sol, aluminium colloidal sol, and preferred silicon sol is the tackiness agent of shaping of catalyst.
The method for preparing propylene oxide provided by the invention has good hydrogen peroxide utilization ratio, higher propylene oxide selectivity, and catalyst life is stable.With respect to traditional method, problems such as traditional processing technology complexity, equipment corrosion and noxious emission have been overcome; Solved to add inhibitor in HTS (TS-1) the catalytic epoxidation of propone reaction system, though the propylene oxide selectivity is higher, the problem that the hydrogen peroxide utilization ratio is lower; Though and the pre-processing titanium si molecular sieves the two all can take into account the problem that catalyst life is short.
Embodiment
By the following examples the present invention is further described, but content not thereby limiting the invention.
New titanium-silicone molecular sieve used among the embodiment is built the production of long company for the Sinopec Hunan, and trade names are HTS, are the Industrial products of the described HTS of Chinese patent CN1301599A.The HTS that Comparative Examples adopted (TS-1) is according to document Thangaraj A, Kumar R, Mirajkar SP, et al.[J]] .J.Catal.1991,130 (1): 1～8 described method preparation.
The analytical procedure of reaction product:
(1) organic constituent content in the gc analysis product is that internal standard substance carries out quantitative analysis calculating with the methyl tertiary butyl ether.Wherein chromatographiccondition is: Agilent-6890 type chromatographic instrument, 30m * 0.25mmFFAP capillary column, sample size 1.0uL, 180 ℃ of injector temperatures.Column temperature keeps 4min at 60 ℃, and then the speed with 20 ℃/min rises to 200 ℃, and keeps 4min.Fid detector, 240 ℃ of sensing chamber's temperature.
(2) concentration of hydrogen peroxide before and after iodimetric analysis reacts indirectly.
Activity of such catalysts is that the transformation efficiency with hydrogen peroxide is that index is investigated.
Comparative Examples 1
In this Comparative Examples explanation tank reactor, with the process of conventional TS-1 titanium molecular sieve catalysis epoxidation reaction.
Take by weighing the conventional former powder of HTS (TS-1) of 0.5g and the methyl alcohol of 60g and the mixed solution (wherein the mol ratio of methyl alcohol and hydrogen peroxide is 20:1) of hydrogen peroxide respectively, place the stainless steel autoclave reactor after Passivation Treatment.Air in the logical nitrogen replacement reactor, and guarantee that entire reaction system stopping property is intact, switch to propylene feed then.System pressure maintains 0.8MPa, and temperature of reaction is controlled to be 30 ℃.Behind the reaction 30min, place ice-water bath with termination reaction reactor rapidly.When treating that temperature in the kettle is reduced to below 15 ℃, open the still sampling, get supernatant liquor after the centrifugation and analyze its reaction product composition.Analytical results is: the transformation efficiency of hydrogen peroxide is 92.6%, and the selectivity of propylene oxide is 71.3%.
Comparative Examples 2
The explanation of this Comparative Examples is to carry out the process of epoxidation reaction behind the metal salt solution pre-processing titanium si molecular sieves.
The sodium sulfate of 2.0g is dissolved in the deionized water of 200mL, and the TS-1 molecular sieve of adding 5g. then under 40 ℃, magnetic agitation 5h, filtration washing, dry 2h in 120 ℃ of baking ovens again, with the mode of dried sample with temperature programming, 3h rises to 550 ℃ gradually by room temperature, roasting 5h in this temperature, air atmosphere makes the pretreated TS-1 sieve sample of modification then.According to comparative example's 1 described method, investigate the performance of its catalytic epoxidation of propone.The reaction product analytical results is: the transformation efficiency of hydrogen peroxide is 85.2%, and the selectivity of propylene oxide is 81.3%.
Embodiment 1
Take by weighing the methyl alcohol of former powder of 0.5g new titanium-silicone molecular sieve (HTS) and 60g and the mixed solution of hydrogen peroxide (wherein the mol ratio of methyl alcohol and hydrogen peroxide is 20:1) respectively, place the stainless steel autoclave reactor after Passivation Treatment.Air in the logical nitrogen replacement reactor, and guarantee that entire reaction system stopping property is intact, switch to propylene feed then.System pressure maintains 0.8MPa, and temperature of reaction is controlled to be 30 ℃.Behind the reaction 0.5h, place ice-water bath with termination reaction reactor rapidly.When treating that temperature in the kettle is reduced to below 15 ℃, open the still sampling, get supernatant liquor after the centrifugation and analyze its reaction product composition.Analytical results is: the transformation efficiency of hydrogen peroxide is 98.6%, and the selectivity of propylene oxide is 75.3%.
Embodiment 2
Take by weighing the methyl alcohol of former powder of 1.0g new titanium-silicone molecular sieve (HTS) and 60g and the mixed solution of hydrogen peroxide (wherein the mol ratio of methyl alcohol and hydrogen peroxide is 40:1), place the stainless steel autoclave reactor after Passivation Treatment.Air in the logical nitrogen replacement reactor, and guarantee that entire reaction system stopping property is intact, switch to propylene feed then.System pressure maintains 0.8MPa, and temperature of reaction is controlled to be 20 ℃.Behind the reaction 0.3h, place ice-water bath with termination reaction reactor rapidly.When treating that temperature in the kettle is reduced to below 15 ℃, open the still sampling, get supernatant liquor after the centrifugation and analyze its reaction product composition.Analytical results is: the transformation efficiency of hydrogen peroxide is 98.2%, and the selectivity of propylene oxide is 85.1%.
Comparative Examples 3
In this Comparative Examples explanation fixed-bed reactor, with the process of conventional TS-1 titanium molecular sieve catalysis epoxidation reaction.
(massfraction of HTS is 70% in the catalyzer to take by weighing conventional HTS (TS-1) catalyzer of 3.0g extruded moulding, with the silicon sol is binding agent), and add certain quartz sand and dilute, place the isothermal reaction district of fixed-bed tube reactor then, guarantee that entire reaction system stopping property is intact.System pressure maintains 0.6MPa, and temperature of reaction is controlled to be 30 ℃.Propylene and liquid phase feed (containing internal standard substance, hydrogen peroxide in methanol) adopt and the mode of the following charging of stream enters reaction zone, and its mass space velocity is 15h
-1, the mol ratio of propylene and hydrogen peroxide is 2:1, the mol ratio of methyl alcohol and hydrogen peroxide is 20:1.After question response is stablized 1 hour, the sampling analysis reaction product.The utilization ratio that obtains hydrogen peroxide is 95.6%, and the selectivity of propylene oxide is 71.3%.
Embodiment 3
According to Comparative Examples 3 described evaluation methods, under identical experiment condition, investigated the catalytic performance of moulding HTS molecular sieve catalyst (massfraction of HTS molecular sieve is 70%, is binding agent with the silicon sol).After question response is stablized 1 hour, the sampling analysis reaction product.The utilization ratio that obtains hydrogen peroxide is 96.6%, and the selectivity of propylene oxide is 72.5%.
Comparative Examples 4
The explanation of this Comparative Examples is in fixed-bed reactor, to carry out the process of epoxidation reaction behind the metal salt solution pre-processing titanium si molecular sieves.
With Comparative Examples 2 described method modifications pretreated TS-1 sample extruded mouldings (massfraction of TS-1 molecular sieve is 70% in the catalyzer).Take by weighing 3.0g modification TS-1 catalyzer, and add certain quartz sand and dilute, place the isothermal reaction district of fixed-bed tube reactor then, guarantee that entire reaction system stopping property is intact.System pressure maintains 0.6MPa, and temperature of reaction is controlled to be 30 ℃.Propylene and liquid phase feed (containing internal standard substance, hydrogen peroxide in methanol) adopt and the mode of the following charging of stream enters reaction zone, and its mass space velocity is 15h
-1, the mol ratio of propylene and hydrogen peroxide is 2:1, the mol ratio of methyl alcohol and hydrogen peroxide is 20:1.Behind the stable reaction 1h, the effective rate of utilization of hydrogen peroxide is 90%, and the selectivity of propylene oxide is 98.6%, and still along with the prolongation in reaction times, the selectivity of propylene oxide is tending towards descending; After 30h was carried out in reaction, the selectivity of propylene oxide reduced to 78.2%, and the utilization ratio of hydrogen peroxide rises to 95%.
Embodiment 4
According to Comparative Examples 4 described evaluation methods, under identical experiment condition, investigated the catalytic stability of moulding HTS molecular sieve catalyst (massfraction of HTS molecular sieve is 70%, is binding agent with the silicon sol).After the stable reaction 1 hour, the effective rate of utilization of hydrogen peroxide is 95.5%, and the selectivity of propylene oxide is 75.5%; After 30h is carried out in reaction, the sampling analysis reaction product, the utilization ratio that obtains hydrogen peroxide is 98.6%, the selectivity of propylene oxide is 75.3%.
Embodiment 5
(massfraction of HTS is 70% in the catalyzer to take by weighing conventional HTS (HTS) catalyzer of 3.0g extruded moulding, with the silicon sol is binding agent), and add certain quartz sand and dilute, place the isothermal reaction district of fixed-bed tube reactor then, guarantee that entire reaction system stopping property is intact.System pressure maintains 0.6MPa, and temperature of reaction is controlled to be 30 ℃.Propylene and liquid phase feed (containing internal standard substance, hydrogen peroxide in methanol) adopt and the mode of the following charging of stream enters reaction zone, and its mass space velocity is 25h
-1, the mol ratio of propylene and hydrogen peroxide is 2:1, the mol ratio of methyl alcohol and hydrogen peroxide is 20:1.Initial period after the stable reaction, the effective rate of utilization of hydrogen peroxide are 98.5%, and the selectivity of propylene oxide is 79.5%; After 30h is carried out in reaction, the sampling analysis reaction product, the utilization ratio that obtains hydrogen peroxide is 99.5%, the selectivity of propylene oxide is 80.3%.
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| RU2577850C2 (en) | 2010-10-11 | 2016-03-20 | Чайна Петролеум Энд Кемикал Корпорейшн | Raw propylene oxide refining method and propylene oxide production method |
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